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Mechanically Strengthened Multilayer, Multibarrier, Desiccant Interlaced Cold Formable Blister Laminates, Optionally Pvc Free

Abstract: ABSTRACT MECHANICALLY STRENGTHENED MULTILAYER, MULTIBARRIER, DESICCANT INTERLACED COLD FORMABLE BLISTER LAMINATES, OPTIONALLY PVC-FREE The present disclosure relates to multilayer, multibarrier, cold formable blister laminate. The present disclosure further relates to a compact blister pack made by cold forming of the multilayer, multibarrier, cold formable blister laminate. The laminate of the present disclosure incorporates or interlace mechanical cum impact strength enhancing materials, desiccant materials or both mechanical cum impact strength enhancing and desiccant materials. The laminate of the present disclosure has enhanced deep draw formability as well as is capable of yielding cold formed blisters of compact size along with improved mechanical and impact strength for cavities with large dimensions without any rupture after forming and at the same time providing requisite ultra high barrier with use of desiccant interlacing when required, against adverse environmental impact. The laminate of the present disclosure can be used for packaging of various products having large dimensions and which are fragile as well as sensitive or highly sensitive to moisture, temperature, and light.

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Patent Information

Application #
Filing Date
08 July 2023
Publication Number
33/2024
Publication Type
INA
Invention Field
POLYMER TECHNOLOGY
Status
Email
Parent Application

Applicants

BILCARE LIMITED
1028, Shiroli, Rajgurunagar Taluk Khed, Pune- 410505, Maharashtra, India

Inventors

1. NEMMANIWAR, Suhas
Bilcare ltd. 1028, Shiroli, Rajgurunagar Taluk Khed, Pune - 410505, Maharashtra, India
2. MUKHERJEE, Somenath
Bilcare ltd. 1028, Shiroli, Rajgurunagar Taluk Khed, Pune - 410505, Maharashtra, India
3. BHANDARI, Shreyans
Bilcare ltd. 1028, Shiroli, Rajgurunagar Taluk Khed, Pune - 410505, Maharashtra, India
4. BHANDARI, Mohan
Bilcare ltd. 1028, Shiroli, Rajgurunagar Taluk Khed, Pune - 410505, Maharashtra, India

Specification

DESC:This application is a cognate application of the provisional specification filed at the Indian Patent Office under Application No. 202321046025 on 08/07/2023 and Provisional Specification filed at the Indian Patent Office under Application No. 202421005315 on 25/01/2024.
FIELD
The present disclosure relates to a multilayer, multibarrier, mechanically strengthened desiccant interlaced, optionally PVC free cold formable blister laminate. The present disclosure further relates to a compact blister pack made of the multilayer, multibarrier, mechanically strengthened desiccant interlaced, optionally PVC free cold formable blister laminate.
DEFINITIONS
As used in the present disclosure, the following terms are generally intended to have the meaning as set forth below, except to the extent that the context in which they are used, indicate otherwise.
The term “Multilayer laminate” refers to a laminate comprising at least two layers made from different combinations of polymer films such as PVC, PP, PE, COC, PET, nylon, other polymeric films and foils, more particularly foils made from metals like aluminum or other metals juxtaposed in layer formation and infused with specialty materials having moisture barrier/adsorption, desiccant properties and/or having mechanical strengthening properties; wherein layers were adhesively laminated or extrusion laminated to meet special requirements of moisture barrier and mechanical properties like stiffness, stretchability, drawability, impact strength, tensile strength, peak elongation.
The term “Mechanically strengthened” refers to enhancement and improvement in key mechanical properties like stretchability, drawability, stiffness, tensile strength, impact strength and peak elongation of the individual polymer film layer and/or foil layer by infusion, introduction, inclusion or adhesion of specialty material in the polymer resin during film formation or during the lamination process of the polymer film/foil layer over an existing film, foil or laminate leading to the making of the multilayer laminate.
The term “Impact strength” is the measure of ability of a multilayer laminate to resist cracking, fracturing, or deformation under impact or shock loads. It is a critical property that determines the multilayer laminate’s ability to withstand external forces.
The term “Drawability” refers to the ability of a multilayer laminate in formation of a cavity of desired depth without having any micro cracks, pinholes and retaining desired barrier and mechanical properties when subjected to the blister formation process using cold forming process.
The term “Stretchability” refers to the ability of some polymer films to improve the stretching property of a multilayer laminate such that the multilayer laminate does not break or fracture during the blister cavity formation process.
The term “Tensile strength at peak” is defined as the maximum stress that a multilayer laminate can bear before breaking or fracturing when it is allowed to be stretched or pulled.
The term “Percent Elongation at peak” is defined as a measurement of the amount in percentage a multilayer laminate will plastically and elastically deform upto its breaking or fracturing.
The term “Stiffness” refers to a measured value which is directly proportional to increase in the tensile strength of multilayer laminates which is accomplished by incorporation of additional polymer layers in the laminates.
The term “Cold forming process” refers to the stamping of the solid material or multi-layer laminates to force it into a form and impart a desired shape and size at or near room temperature. In the case of blister packaging, it is achieved by the application of force on a multilayer laminate in a perpendicular direction to its parting line. The laminate stretches and retains the imparted shape and form after the stamp has been removed.
The term “blister pack” or package (pkg) refers to a formable web/multilayer laminate into which blisters or cavities are formed, wherein after placing the product into these blisters or cavities, a lid or a sealing layer, is employed as a seal/ cover/ support. It is thus a pre-formed package used for packaging of consumer goods, foods, and for pharmaceuticals.
The terms “blister cups” or “blisters” or “cavities” refer to a recess or a pocket in a laminate made by thermoforming or cold forming process to accommodate a product.
The term “product” refers to a product comprising but not limited to pharmaceuticals, nutraceuticals, healthcare, medical devices, medical diagnostics, electronic components, electronic products, consumable products in either unit, multi or aggregated formats
The term “support” refers to a layer of a film, paper, metal foil or laminate comprising a polymer film, paper, aluminium foil or a laminate which is used for covering/ protecting the blister pockets or cavities and the term “base” refers to the plane surface of the laminate sheet from where the stretching takes place to form the cavity or a recess. A recess is thus formed within the laminate, and with a shoulder defining the base material in between the recesses; the recesses of the base are filled with the products; and the base, with the filled recesses, is then covered with the support in the form of a lid, wherein the lid is sealed or otherwise adhered to the shoulder of the base. The lid material provides a structural component upon which the final blister package is built. Lid material is made of a paper, a polymer, a metal foil or an aluminium laminate and combination of any of these materials is often called push through, peelable, or peel–push foil.
The term “Polymer film” refers to thin continuous polymeric material prepared from polymer resins and their variants including but not limited to Polyvinyl Chloride (PVC), Polyvinylidene chloride (PVdC), Polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), Cyclic olefin co-polymer (COC) by methods such as coating, cast, extrusion and/or blown film manufacturing processes.
The term “Polyolefin” refers to the polymer with general formula (CH2CHR) n where is R is an alkyl group. They are generally derived from small set of simple molecules such as Olefins, for example ethane, propene, n-butane and iso-butene to form for example polyethylene (PE) or polypropylene (PP).
The term “Modified Polyolefin” refers to the polyolefin produced using metallocene or incorporating desiccant during production.
The term “Polyamide” refers to a type of polymer with repeating units linked by amide bonds –CONH-.
The term “Polyethylene terephthalate” (PET) refers to the type of polymer from the family of polyesters, that are formed by reaction between terephthalic acid and monoethylene glycol.
The term “Cyclic Olefin Copolymer (COC)” refers to the group of copolymers produced by chain copolymerization of cyclic monomers such as 8,9,10-trinorborn-2-ene(norbornene) or 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8 dimethanonaphthalene (tetracyclododecene) with ethene or by ring-opening metathesis polymerization of various cyclic monomers followed by hydrogenation.
The term “Polyvinyl Chloride polymer” refers to the polymer produced by polymerization of Vinyl Chloride monomer.
The term “Polyvinylidene Chloride (PVdC)” refers to a polymer formed by polymerization Vinylidene Chloride monomer. This polymer shows good water and gas barrier properties.
The Term “Metal Foil” refers to a thin foil of metal such as Aluminum, Gold, silver, Copper, Platinum and Palladium obtained after rolling the sheet several times till desired thickness is achieved.
The term “Aluminium foil” refers to a soft form of aluminium metal obtained after rolling the aluminium sheet several times till a desired thickness is achieved and then heating in an oven for several hours which transforms hard aluminium foil in to its soft form. It is mainly used in preparation of laminates
The term “Heat seal lacquer” (HSL) refers to a solvent based or water-based polymer dispersion/ solution which becomes soft after heating and bonds strongly between two same or different substrates and acts as a sealant between them and it helps protect a packaged product from external conditions.
The term “Adhesive” refers to a compound which is any non-metallic substance applied to one or both surfaces of two separate items that binds them together and resists their separation. It provides ability to bond different materials together, and results in a more efficient distribution of stress across a joint.
The term “Desiccant” refers to a compound which is hygroscopic in nature and has the capability to absorbing and/or adsorbing moisture or water.
The term “Oriented polymeric film” refers to an alignment or a position of a polymeric film in a specified direction along the axis relative to the direction of stretching.
The term “Metallized polymeric film” refers to the deposition of aluminium or other metals on polymeric film using vacuum metallization or plating process.
The term “Barrier-coated polymeric film” refers to a modified polymeric film wherein the polymeric film is coated with a barrier material such as polymeric material like PVdC or deposition of metal oxides such as AlOx or SiOx on the polymeric film.
The term “Metallocene” refers to a compound typically consisting of two cyclopentadienyl anions (C.5H -5., abbreviated Cp) bound to a metal centre (M) in the oxidation state II, with the resulting general formula (C5H5)2M, wherein the metal is selected from Fe, Cr, Ti, Mn, etc. Thus, metallocenes are organometallic compounds that contain a metal atom “sandwiched” between two aromatic cyclopentadienyl (Cp) rings.
Inner operative side of the polymeric film refers to side of the polymeric film which is near to or in immediate contact with the packaged product or to a side of the foil which is near to polymeric layer below it.
Outer operative side of the polymeric film refers to the side of polymeric film which is opposite to the inner operative side and not in contact with the packaged product.
The term “Desiccant interlacing” refers to the incorporation of desiccant material in one of the strata of the modified polyolefin.
The term “Metallocene modified” refers to the incorporation of metallocene in a sub layer of the polymer layer.
The term “Parting line” refers to a plane in which the two halves of a mold are set to meet in which all features are oriented perpendicular to the parting line to facilitate removal from the mold.
The term “Draft” refers to an amount of taper provided for molded or cast parts perpendicular to the parting line.
The term “Draft angle” refers to a draft provided to an article or sheet which is measured in degrees.
The term “Normal” refers to a direction perpendicular to the plane of a given surface or object.
The term “Test Method 671” refers to the test method detailed in the general chapter 671 titled “Containers – Performance Testing” in the United States Pharmacopoeia 40 (USP 40, print version) and United State Pharmacopoeia online version official as of 01st December 2020. This test method details the process for determining the level of barrier protection provided by packaging systems.
The term “gm/pkg/day” refers to rate of weight gain by a package containing a product to determine the moisture vapor transmission rate (MVTR) or water vapor transmission rate (WVTR). Further, the “pkg” in the unit gm/pkg/day refers to atleast 2 cold formed blister packs with each blister pack containing 10 or more blister cavities for packaging of a product in these cavities.
The term “Optical Density” refers to the degree at which an object or material reduces the intensity of light passing through it.
The term “Moisture vapor transmission rate” (“MVTR”) or “Water vapor transmission rate” (“WVTR”) refers to the steady-state moisture vapor transmission (in unit time) through a packaging system, under specific conditions of temperature and humidity. These test methods use gravimetric measurement to determine the rate of weight gain as a result of moisture vapor transmission into the packaging system and subsequent uptake by a desiccant product enclosed within the packaging system.
The term “Barrier” refers to a property of blister laminates of separating a packed “products”, from the environment. Barrier properties include permeability of gases (such as O2, CO2, and N2), water vapour, aroma compounds and light. These are vital factors for maintaining the quality of the packaged products.
The Term “Multi barrier packs” refers to blister packs made from ultra-high barrier or high barrier multilayer thermoformable or cold formable laminates.
The term “High barrier packs” refers to blister packs made from high-barrier multi-layer laminate material and when formed and sealed have moisture vapor transmission rate of less than 1.00 mg/cavity-day when tested at 40°/75% RH.
The term “Ultra high barrier” is for blister packs made from ultra high-barrier multi-layer laminate material and when formed and sealed have moisture vapor transmission rate of less than 0.01 mg/cavity-day when tested at 40°/75% RH.
The term “Capsule” refers to a solid dosage form, in which the drug/supplement, a mixture of drugs/supplements, a consumable constituent or a mixture of consumable constituents is enclosed in a gelation shell or any other suitable material to form a capsule in various shapes and sizes.
The term “Tablet” refers to a solid dosage form, in which the drug/supplement, a mixture of drugs/supplements, a consumable constituent or a mixture of consumable constituents where such ingredients along with suitable and compatible excipients and binders are compressed to form a tablet with different sizes and shapes.
The term “Blown” refers to polymer blown films, sometimes referred to as “tubular films”, and are manufactured by extruding molten resin vertically through a circular die. Air is introduced through the center of the die creating a bubble. The air drives the bubble upwards and slowly cools the material. Nip rollers flatten the material into a tube that can be reeled for creating bags and pouches, or slit and then reeled as a flat sheet of film.
The term “Cast” or “cast films” refers to polymer films made by extruding melted resin horizontally through a flat die to create a sheet of material that is pinned to a highly polished chilled roller by means of an air curtain or vacuum box.
The term “Sealable” refers to a property of lidding material to be adapted to seal with the laminate with the desired seal strength and seal integrity by heat and pressure, so as to form a closed blister pack to make it impervious to gases, moisture and the like.
The term “Tearable” refers to a property of a lidding material, wherein a polymer material present therein is adapted to tear easily with a desired force either in a machine direction or in a transverse direction or in both directions.
The term “First polymer layer” for a multi-layered laminate refers to a layer in contact or in close proximity to the packaged product and in contact with the sealing layer of lidding laminate.
The term “Second polymer layer” for a multi-layered laminate refers to a layer opposite to the first polymer layer which is in contact or in close proximity to the ambient.
The term “Outer layer” for a multi-layered film laminate refers to a layer opposite to the inner layer which is in contact or in close proximity to the ambient.
The term “Inner layer” for a lidding foil or lidding laminate refers to a layer in contact or in close proximity to the packaged product and in contact with inner layer of the formed multi layered film laminate.
The term “Outer layer” for a lidding foil or lidding laminate refers to a layer opposite to the inner layer which is in contact or in close proximity to the ambient.
BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.
Blister packages are employed for packaging numerous products including, but not limited to, consumer goods, foods, nutraceutical products, veterinary products, electronic gadgets and pharmaceutical products. Further, many of these products may be sensitive and/or highly sensitive to moisture in the ambient environment and may deteriorate or get adversely impacted from the moisture and therefore require protection against the same. These blister packages made from specially designed multi-layer laminates with improved barrier, tensile strength and stiffness of blisters, having enhanced cavity size formation, protect the sealed product, from external factors such as humidity, light, temperature, contamination, direct physical impact, physical damage during transportation, handling and storage and any other factors which may affect the quality of the sealed packaged products.
The blister pack comprises a formable web/multilayer laminate into which blisters or cavities are formed, and a lid or a sealing layer or a support, which is employed as a seal, the product being placed within the blisters or cavities. Generally, the blisters or blister cups or cavities are formed by a thermal or a cold forming process. Typically, a blister (also known as a “blister cup”) is a cavity structure formed on a multilayer laminate by the action of force acting on the multilayer laminate. A die is used for thermoforming or cold forming the blister cups or cavities on the multilayer laminate.
Typically, the multilayer laminate used in cold forming process can comprise a first polymer layer, a metal layer, and a structural strengthening layer which can be a second polymer layer. The first polymer layer typically comprises polyvinyl chloride (PVC), with aluminum as the metal layer and polyamide polymer as the second polymer layer which imparts structural strengthening to the laminate. The product placed within the blister is in contact with the inner layer of the multilayer laminate which is generally the PVC layer.
In the multilayer laminate comprising PVC as the inner layer (that is in contact with the product), the intermediate layer which can be an aluminum layer, and the structural strengthening layer (polyamide polymer) as the outer layer, it is observed that it is difficult to cold form cavities with deep draw wherein products with larger dimensions are to be packaged, due to the fact that PVC layer is not stretchable enough. This leads to cracking or rupturing of cavities during cold forming process. Therefore, there is need of multilayer laminate which can offer deep draw cavity forming ability with good mechanical and impact strength which will facilitate not only forming of deep cavities but also retention of good mechanical and impact strength by the formed deep cavities to accomplish protection of the packaged product against environmental impact as well as physical impact and damage during transportation, handling and storage.
Further, the disadvantages of using PVC layers include poor barrier against moisture ingress and oxygen ingress. Typical values for the Water Vapor Transmission Rate of 250µ PVC film are around 3.0 g/m2/day to 3.5 g/m2/day measured at 37.8?C and 90% RH. This results in negligible or very low moisture barrier property of the individual cavities of a formed blister from such laminates. Thus, there is a need of a multilayer laminate wherein the components of the formable laminates are infused or integrated with suitable materials to offer substantially better moisture barrier property by the cavities of the cold formed blister upon cold forming of such laminate. Further the mechanical and impact strength along with the moisture barrier property of the laminates deteriorate incrementally with the increase in size and depth of the cavities of cold formed blister which necessitates a further need of custom infusion or integration of suitable mechanical and impact strength providing materials along with the moisture barrier providing materials into the laminate.
There is, therefore, a need felt for a multilayer, multibarrier, cold formable blister laminate that mitigates the drawbacks mentioned herein above or at least provide a useful alternative.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows:
It is an object of the present disclosure to ameliorate one or more problems of background or to at least provide a useful alternative.
An object of the present disclosure is to provide a multilayer, multibarrier, cold formable blister laminate.
Another object of the present disclosure is to provide a multilayer, multibarrier, cold formable blister laminate which has improved mechanical and impact properties.
Still another object of the present disclosure is to provide a multilayer, multibarrier, cold formable blister laminate which has an enhanced barrier to moisture, light and gas.
Yet another object of the present disclosure is to provide a multilayer, multibarrier, cold formable blister laminate with significantly improved mechanical and impact properties for making compact size blister packs comprising cavities with larger size and depth for packaging of environmentally sensitive to highly sensitive and physically fragile products of large dimensions.
Still another object of the present disclosure is to provide a multilayer, multibarrier, cold formable blister laminate having better mechanical and impact properties over conventional cold formable laminate, thus, providing protection to the packaged product against physical impact during transportation, handling and storage.
Yet another objective of the present disclosure is to provide a multilayer, multibarrier cold formable laminate with improved mechanical and impact properties thereby resulting in reduction in the pinhole formation and rupturing of the cavities during cold formable process.
Still another object of the present disclosure is to provide a multilayer, multibarrier, cold formable blister laminate which enhances the overall shelf life of the product that is packaged.
Yet another object of the present disclosure is to provide a compact, multilayer, multibarrier, cold formable blister laminate with MVTR less than 0.02 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH which in turn corresponds to less than 0.8 mg/blister cavity/day. The pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90 mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Still another object of the present disclosure is to provide a compact, multilayer, ultra multibarrier, cold formable blister laminate with MVTR less than 0.0002 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH which in turn corresponds to less than 0.008 mg/blister cavity/day. The pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90 mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Yet another object of the present disclosure is to provide a multilayer, multibarrier, cold formable blister laminate which provides improved mechanical and impact properties along with improved stiffness to the blisters which in turn reduces deformation of blisters and blister pockets during transportation, handling and storage.
Still another object of the present disclosure is to provide a compact blister pack.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.
SUMMARY
In an aspect, the present disclosure provides a multilayer, multibarrier, cold formable blister laminate comprising:
at least one first polymer layer having thickness in the range of 10 microns to 300 microns;
wherein the first polymer layer is selected from the group consisting of polyethylene (PE) layer, modified polyethylene (m-PE) layer, polypropylene (PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, and modified cyclic olefin co-polymer (m-COC) layer;
at least one intermediate metal layer having thickness in the range of 10 microns to 200 microns having a first operative surface and a second operative surface; and
at least one second polymer layer having thickness in the range of 10 microns to 300 microns;
wherein the second polymer layer is selected from the group consisting of polyethylene (o-PE) layer, modified polyethylene (m-PE) layer, polypropylene (o-PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, modified cyclic olefin co-polymer (m-COC) layer, polyethylene terephthalate layer (PET), and modified polyethylene terephthalate (m-PET) layer;
wherein the at least one first polymer layer is disposed on the first operative surface and the at least one second polymer layer is disposed on the second operative surface; and
wherein the water vapour transmission rate (WVTR) of the laminate is in the range of 0.00009 gm/pkg/day to 0.02 gm/pkg/day at 40°C and 75% RH.
In accordance with the embodiments of the present disclosure, the at least one first polymer layer, the at least one intermediate layer and the at least one second polymer layer are adhered to each other by a method selected from extrusion lamination and adhesive lamination.
In accordance with the embodiments of the present disclosure, the adhesive lamination is performed by forming an adhesive layer on the layers selected from the first polymer layer, the intermediate metal layer and the second polymer layer, having thickness in the range of 1 gsm to 10 gsm; the adhesive layer is selected from the group consisting of polyester based adhesive layer, polyurethane based adhesive layer, and polyacrylic based adhesive layer.
In accordance with the embodiments of the present disclosure, the intermediate metal layer comprises at least one metal selected from the group consisting of aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a polyethylene layer, and the polyethylene layer being at least one selected from the group consisting of high density polyethylene (HDPE) polymer layer, medium density polyethylene polymer layer, low density polyethylene (LDPE) polymer layer, linear low-density polyethylene (LLDPE) polymer layer, linear polyethylene polymer layer, chlorinated polyethylene polymer layer, cross-linked polyethylene polymer layer, ultra-high molecular weight polyethylene (UHMWPE) polymer layer and polyethylene copolymer with styrene-butadiene layer.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a modified polyethylene layer; the modified polyethylene layer being selected from a metal oxide coated polyethylene layer, a barrier polymer coated polyethylene layer, a metallized polyethylene layer, a metallocene modified polyethylene polymer layer and a desiccant modified polyethylene polymer layer; the modified polyethylene layer being obtained by a method selected from; coating a metal oxide on a polyethylene sheet to obtain the metal oxide coated polyethylene layer, wherein the metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx; coating a barrier polymer on a polyethylene sheet to obtain the barrier polymer coated polyethylene layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm; wherein the barrier polymer being selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and Heat seal lacquer (HSL); depositing a metal on a polyethylene sheet to obtain the metallized polyethylene layer having an optical density in the range of 0.5 to 2.5; wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag); adding metallocene to a polyethylene polymer in an amount in the range of 1 mass% to 90 mass% followed by extruding or laminating to obtain the metallocene modified polyethylene polymer layer; and adding desiccant to a polyethylene polymer in an amount in the range of 1 mass% to 70 mass% followed by extruding or laminating to obtain the desiccant modified polyethylene polymer layer; the desiccant being at least one selected from the group consisting of silica, calcium chloride, calcium carbonate, calcium oxide, magnesium oxide, magnesium chloride, sodium sulphate, dry aluminum chloride, aluminum oxide, molecular sieves, and activated charcoal.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a polypropylene layer, the polypropylene layer being at least one selected from the group consisting of polypropylene homopolymer layer, polypropylene random copolymer layer and polypropylene impact copolymer layer.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a modified polypropylene layer; the modified polypropylene layer being selected from a metal oxide coated polypropylene layer, a polymer coated polypropylene layer, a metallized polypropylene layer, a metallocene modified polypropylene polymer, and desiccant modified polypropylene polymer; the modified polypropylene layer being obtained by a method selected from; coating a metal oxide on a polypropylene sheet to obtain the metal oxide coated polypropylene layer, wherein the metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx; coating a barrier polymer on a polypropylene sheet to obtain the barrier polymer coated polypropylene layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm; wherein the barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc) polyvinyl alcohol (PVOH) and heat seal lacquer (HSL); depositing a metal on a polypropylene sheet to obtain the metallized polypropylene layer having an optical density in the range of 0.5 to 2.5; wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag); adding metallocene to a polypropylene polymer in an amount in the range of 1 mass% to 90 mass% followed by extruding or laminating to obtain the metallocene modified polypropylene polymer layer; and adding desiccant to a polypropylene polymer in an amount in the range of 1 mass% to 70 mass% followed by extruding or laminating to obtain the desiccant modified polypropylene polymer layer; the desiccant being at least one selected from the group consisting of silica, calcium chloride, calcium carbonate, calcium oxide, magnesium oxide, magnesium chloride, sodium sulphate, dry aluminum chloride, aluminum oxide, molecular sieves, and activated charcoal.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is selected from a modified polyethylene layer and a modified polypropylene layer, wherein the modified polyethylene layer has a plurality of strata selected from the group consisting of virgin polyethylene stratum, desiccant modified polyethylene stratum, metallocene modified polyethylene stratum, metal oxide coated polyethylene stratum, polymer coated polyethylene stratum, and metallized polyethylene stratum; and the modified polypropylene layer has a plurality of strata selected from the group consisting of virgin polypropylene stratum, desiccant modified polypropylene stratum, metallocene modified polypropylene stratum, metal oxide coated polypropylene stratum, polymer coated polypropylene stratum, and metallized polypropylene stratum.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is an oriented polyamide layer, the oriented polyamide layer being selected from semi-crystalline polyamide layer, amorphous polyamide layer, and a copolymer thereof; the semi-crystalline polyamide layer is at least one selected from the group consisting of Nylon 6, Nylon 6,6, Nylon 6,9, Nylon 6,12, Nylon 12,12, and a copolymer thereof.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a modified oriented polyamide (OPA) layer; the modified oriented polyamide (OPA) layer being selected from a metallized oriented polyamide layer, a metal oxide coated oriented polyamide layer, and a barrier polymer coated oriented polyamide layer; the modified oriented polyamide (OPA) layer being obtained by a method selected from; depositing a metal on an oriented polyamide (OPA) sheet to obtain the metallized oriented polyamide layer having an optical density in the range of 0.5 to 2.5; wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag); coating of a metal oxide on an oriented polyamide (OPA) sheet to obtain the metal oxide coated oriented polyamide layer, wherein the metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx; and coating a barrier polymer on an oriented polyamide (OPA) sheet to obtain the barrier polymer coated oriented polyamide layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm; wherein the barrier polymer being selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and Heat seal lacquer (HSL).
In accordance with the embodiments of the present disclosure, the second polymer layer is a polyethylene terephthalate (PET) layer, and the polyethylene terephthalate (PET) layer is at least one selected from group comprising of amorphous polyethylene terephthalate (APET) layer, polyethylene terephthalate (PET) layer, glycol modified PET (PETg) layer, poly (1,3- propylene) terephthalate layer, poly (1,4- butylenes) terephthalate layer, elastomeric polyester comprising poly (1,4-butylene) terephthalate layer and poly (tetramethylene ether) glycol layer.
In accordance with the embodiments of the present disclosure, the second polymer layer is a modified polyethylene terephthalate (o-PET) layer; the modified polyethylene terephthalate (o-PET) layer being selected from a metallized polyethylene terephthalate layer, a metal oxide coated polyethylene terephthalate layer and a barrier polymer coated polyethylene terephthalate layer; the modified polyethylene terephthalate (o-PET) layer being obtained by a method selected from; depositing a metal on a polyethylene terephthalate (o-PET) sheet to obtain the metallized polyethylene terephthalate layer having an optical density in the range of 0.5 to 2.5; wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag); coating of a metal oxide on a polyethylene terephthalate (o-PET) sheet to obtain the metal oxide coated polyethylene terephthalate layer, wherein the metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx; and coating a barrier polymer on a polyethylene terephthalate (o-PET) sheet to obtain the barrier polymer coated polyethylene terephthalate layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm; wherein the barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), and polyvinyl alcohol (PVOH), and heat seal lacquer (HSL).
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a modified cyclic olefin co-polymer layer; the modified cyclic olefin co-polymer layer being selected from a metal oxide coated cyclic olefin co-polymer layer, a barrier polymer coated cyclic olefin co-polymer layer and a metallized cyclic olefin co-polymer layer; the modified cyclic olefin co-polymer layer being obtained by a method selected from; coating a metal oxide on a cyclic olefin co-polymer sheet to obtain the metal oxide coated cyclic olefin co-polymer layer, wherein the metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx; coating a barrier polymer on a cyclic olefin co-polymer sheet to obtain the barrier polymer coated cyclic olefin co-polymer layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm; wherein the barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and Heat seal lacquer (HSL); and depositing a metal on a cyclic olefin co-polymer sheet to obtain the metallized cyclic olefin co-polymer layer having an optical density in the range of 0.5 to 2.5; wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a polyvinyl chloride (PVC) polymer layer, and the polyvinyl chloride (PVC) polymer layer is selected from flexible PVC layer, rigid PVC layer, chlorinated PVC layer, oriented PVC layer and modified PVC layer.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a modified polyvinyl chloride layer; the modified polyvinyl chloride layer being selected from a metal oxide coated polyvinyl chloride layer, a barrier polymer coated polyvinyl chloride layer, and metallized polyvinyl chloride layer; the modified polyvinyl chloride layer being obtained by a method selected from; coating a metal oxide on a polyvinyl chloride sheet to obtain the metal oxide coated polyvinyl chloride layer, wherein the metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx; coating a barrier polymer on a polyvinyl chloride sheet to obtain the barrier polymer coated polyvinyl chloride layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm; wherein the barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and Heat seal lacquer (HSL); and depositing a metal on a polyvinyl chloride sheet to obtain the metallized polyvinyl chloride layer having an optical density in the range of 0.5 to 2.5; wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In accordance with the embodiments of the present disclosure, the at least one first polymer layer is prepared by a method selected from cast extrusion and blow extrusion; and the at least one second polymer layer is prepared by a method selected from cast extrusion and blow extrusion.
In accordance with the embodiments of the present disclosure, a primer layer having thickness in the range of 1 gsm to 3 gsm is applied on the first operative surface or the second operative surface OR the surface of the first polymer layer or the second polymer layer in contact with the first operative surface or the second operative surface; and wherein the primer layer is at least one selected from the group consisting of acrylic based primer layer, polyurethane based primer layer and polyester based primer layer.
In accordance with the embodiments of the present disclosure, the first polymer layer comprises a polypropylene layer having thickness of 60 microns; and a metallocene modified polyethylene layer having thickness of 100 microns, wherein the polypropylene layer and the metallocene modified polyethylene layer are bonded together, the intermediate metal layer is an aluminum layer having thickness of 50 microns; and the second polymer layer comprises a modified oriented polyamide layer having a thickness of 25 microns; a layer of a combination of a metallocene modified polyethylene and a desiccant modified polyethylene having thickness of 60 microns, wherein the modified oriented polyamide layer and the layer of the combination of the metallocene modified polyethylene and the desiccant modified polyethylene, are bonded together.
In accordance with the embodiments of the present disclosure, the first polymer layer is a polypropylene having thickness of 60 microns; the intermediate metal layer is an aluminum layer having thickness of 50 microns; and the second polymer layer comprises a metallized oriented polyamide layer having a thickness of 25 microns; and a PVC layer having thickness of 60 microns, wherein the metallized oriented polyamide layer and the PVC layer are bonded together.
In accordance with the embodiments of the present disclosure, the first polymer layer is a metallocene modified polyethyelene layer having thickness of 50 microns; the intermediate metal layer is an aluminum layer having thickness of 50 microns; and the second polymer layer comprises a metallized oriented polyamide layer having a thickness of 25 microns; and a PVC layer having thickness of 30 microns, wherein the metallized oriented polyamide layer and the PVC layer are bonded together.
In accordance with the embodiments of the present disclosure, the first polymer layer is a metallocene modified polyethylene layer having thickness of 100 microns; the intermediate metal layer is an aluminum layer having thickness of 50 microns; and the second polymer layer is a PVdC coated oriented polyamide layer having a thickness of 25 microns.
In accordance with the embodiments of the present disclosure, the first polymer layer is a metallocene modified polyethylene layer having thickness of 50 microns; the intermediate metal layer is an aluminum layer having thickness of 50 microns; and the second polymer layer is a PVdC coated oriented polyamide layer having a thickness of 25 microns.
In accordance with the embodiments of the present disclosure, the first polymer layer is a metallocene modified polyethylene layer having thickness of 50 microns; the intermediate metal layer is an aluminum layer having thickness of 50 microns; and the second polymer layer is an AlOx coated oriented polyamide layer having a thickness of 25 microns.
In accordance with the embodiments of the present disclosure, the first polymer layer is a metallocene modified polyethylene layer having thickness of 50 microns; the intermediate metal layer is an aluminum layer having thickness of 50 microns; and the second polymer layer is a metallized oriented polyamide layer having a thickness of 25 microns.
In accordance with the embodiments of the present disclosure, the multilayer, multibarrier cold formable blister is characterized by having a tensile strength in the range of 400 kg/cm2 to 1200 kg/cm2; a percent elongation at peak in the range of 12% to 40%; an impact strength in the range of 1400 g to 2500 g; and a cavity height at bursting of more than 24 mm.
In another aspect, the present disclosure provides a compact blister pack comprising:
at least one blister shaped cup made by cold forming of a multilayer, multibarrier, cold formable blister laminate having:
at least one first polymer layer having a thickness in the range of 10 microns to 300 microns;
wherein the first polymer layer is selected from the group consisting of polyethylene (PE) layer, modified polyethylene (m-PE) layer, polypropylene (PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, and modified cyclic olefin co-polymer (m-COC) layer;
at least one intermediate metal layer having a thickness in the range of 10 microns to 200 microns having a first operative surface and a second operative surface; and
at least one second polymer layer having a thickness in the range of 10 microns to 300 microns;
wherein the second polymer layer is selected from the group consisting of polyethylene (PE) layer, modified polyethylene (m-PE) layer, polypropylene (o-PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, modified cyclic olefin co-polymer (m-COC) layer, polyethylene terephthalate layer (PET), and modified polyethylene terephthalate (m-PET) layer;
wherein the at least one first polymer layer is disposed on the first operative surface and the at least one second polymer layer is disposed on the second operative surface;
wherein the water vapour transmission rate (WVTR) of the laminate is in the range of 0.00009 gm/pkg/day to 0.02 gm/pkg/day at 40°C and 75% RH; and
a sealable and tearable lid defining an operative outer surface and an operative inner surface, compatible to bond with the first polymer layer in the laminate and to seal the at least one cup.
In accordance with the embodiments of the present disclosure, a primer layer having thickness in the range of 1 gsm to 3 gsm is applied on the first operative surface or the second operative surface OR the surface of the first polymer layer or the second polymer layer in contact with the first operative surface or the second operative surface; and wherein the primer layer is at least one selected from the group consisting of acrylic based primer layer, polyurethane based primer layer and polyester based primer layer.
In accordance with the embodiments of the present disclosure, the operative inner surface of the sealable and tearable lid is coated by using a heat seal lacquer compatible to bond with the first polymer layer in the blister laminate, in an amount in the range of 3 gsm to 10 gsm; and the sealable and tearable lid comprises an aluminum foil having an operative inner surface and an operative outer surface, laminated with polyethylene film compatible to bond with the first polymer layer of the cold formable multilayer blister laminate, wherein thickness of the aluminum foil is in the range of 15 microns to 40 microns, and thickness of the polyethylene film is in the range of 15 microns to 40 microns.
In accordance with the embodiments of the present disclosure, the blister shaped cup being defined by a first slanted wall having a first slanted edge and a second slanted edge; the first slanted wall extending in an operative direction from a flat wall abutting on a mouth of the at least one cup and slanted at an angle ? with respect to a normal to the lid; the flat wall being parallel to the lid; a second slanted wall joining the second slanted edge and a third slanted edge; the second slanted wall extending in an operative direction from the flat wall abutting on the mouth of the at least one cup, and slanted at an angle ? with respect to a normal to the lid; a third slanted wall joining the third slanted edge and a fourth slanted edge; the third slanted wall extending in an operative direction from the flat wall abutting on the mouth of the at least one cup, and slanted at an angle ? with respect to a normal to the lid; and a fourth slanted wall joining the first slanted edge and the fourth slanted edge; the fourth slanted wall extending from an operative direction from the flat wall abutting on the mouth of the at least one cup, and slanted at an angle ? with respect to a normal to the lid, wherein the angle ? is in the range of 15° to 30°.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
The present disclosure will now be described with the help of the accompanying drawing, in which:
Fig. 1 illustrates a seven layered laminate (1000), an intermediate metal layer (10) with three first polymer layers (20, 40, 60), three second polymer layer (30, 50, 70), and six adhesive layers (5A) in accordance with the present disclosure;
Fig. 2a illustrates a modified polyolefin (PE or PP) layer having two strata (02, 06) comprising a stratum of virgin polyolefin (20) and a stratum of metallocene modified polyolefin (06), in accordance with the present disclosure;
Fig. 2b illustrates a modified polyolefin (PE or PP) layer having three strata (02, 04, 06) comprising a layer of virgin polyolefin (02), a layer of desiccant modified polyolefin (04), and a layer of metallocene modified polyolefin (06), in accordance with the present disclosure;
Fig. 2c illustrates a modified polyolefin (PE or PP) layer of having five strata (02, 04, 06, 04, 06) comprising a layer of virgin polyolefin (02), a layer of desiccant modified polyolefin (04), a layer of metallocene modified polyolefin (06), a layer of desiccant modified polyolefin (04), and a layer of metallocene modified polyolefin (06), in accordance with the present disclosure;
Fig. 2d illustrates a modified polyolefin (PE or PP) layer having seven strata (02, 04, 06, 04, 06, 02, 06) comprising a layer of virgin polyolefin (02), a layer of desiccant modified polyolefin (04), a layer of metallocene modified polyolefin (06), a layer of desiccant modified polyolefin (04), a layer of metallocene modified polyolefin (06), a layer of virgin polyolefin (02) and a layer of metallocene modified polyolefin (06), in accordance with the present disclosure;
Fig. 3 illustrates three layered laminate comprising a first polymer layer (20), an adhesive layer (5A), an intermediate layer (10), an adhesive layer (5A), and a second polymer layer (30), in accordance with the present disclosure;
Fig. 4 illustrates four layered laminate comprising a first polymer layer (20), an adhesive layer (5A), an intermediate layer (10), an adhesive layer (5A), a second polymer layer (30), an adhesive layer (5A), a second polymer layer (50) in accordance with the present disclosure;
Fig. 5 illustrates five layered laminate comprising a first polymer layer (20), an adhesive layer (5A), a first polymer layer (40), an intermediate layer (10), an adhesive layer (5A), a second polymer layer (30), an adhesive layer (5A), a second polymer layer (50) in accordance with the present disclosure;
Fig. 6 illustrates the draft angle of the blister cups formed in a multilayer laminate of a conventional blister pack (prior art);
Fig. 7A illustrates the draft angle of the blister cups formed in a multilayer laminate of a blister pack in accordance with one embodiment of the present disclosure;
Fig. 7B illustrates the top view of the blister cup in accordance with one embodiment of the present disclosure;
Fig. 8 illustrates an image of lidding Al/PE laminate sealed to blister, Al Foil 25 microns/ PE film 25 microns in accordance with one embodiment of the present disclosure;
Fig. 9 illustrates an image of lidding foil with HSL coating sealed to blister, Al foil of 25 microns coated with polyethylene (PE) based heat seal lacquer (HSL) of thickness 3 gsm in accordance with one embodiment of the present disclosure;
Fig. 10A illustrates micrograph of section of multilayer laminate in flat film form Flat film-25 µ mOPA/ 50µ Al Foil/ 50µ PE (Three-layer structure) (Example 1 and 4) in accordance with the present disclosure; wherein (i), (ii) and (iii) illustrates thickness of the layers;
Fig. 10B illustrates micrograph of section of multilayer laminate in dome of the formed cavity of 25µ mOPA/ 50µ Al foil/ 50µ PE (Three-layer structure) (Example 1 and 4) in accordance with the present disclosure; wherein (i), (ii) and (iii) illustrates thickness of the layers;
Fig. 10C illustrates micrograph of section of multilayer laminate in Flat surface of the laminate 25µ m OPA/ 25µ OPA/ 50µ Al foil/ 50 µ PE metallocene modified (60%) (4-layer structure) (Example 23) in accordance with the present disclosure; wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers;
Fig. 10D illustrates micrograph of section of multilayer laminate in dome of the formed cavity in 25µ m OPA/ 25µ OPA/ 50µ Al foil/ 50µ PE metallocene modified (60%) (4 layer structure) (Example 23) in accordance with the present disclosure; wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers;
Fig. 10E illustrates micrograph of section of multilayer laminate in Flat surface of the laminate 60µPVC/ 25µ m-OPA/50µ Al foil/ 50µ PE (60% metallocene modified) (4 layer structure) (Example 24) in accordance with the present disclosure; wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers;
Fig. 10F illustrates micrograph of section of multilayer laminate in Dome of the formed cavity in 60µ PVC/25µ m-OPA/ 50µ Al foil/ 50µ PE (4 layer structure) (60% metallocene modified) (Example 24) in accordance with the present disclosure; wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers;
Fig. 10G illustrates micrograph of section of multilayer laminate in Flat surface of 250µ APET/ 25µ mOPA/ 50µ Al foil/ 50µ PE metallocene modified (60%) (4 layer structure) (Example 26) in accordance with the present disclosure; wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers;
Fig. 10H illustrates micrograph of section of multilayer laminate in dome of the cavity of the 250µ APET/ 25µ m OPA/ 50µ Al foil/ 50µ PE metallocene modified (60%) (4-layer structure) (Example 26) in accordance with the present disclosure; wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers;
Fig. 10I illustrates micrograph of section of multilayer laminate in flat surface of 150µ APET/ 25 µ PVdC coated OPA/ 50µ Al foil/ 50µ PE metallocene modified (60%) (4-layer structure) (Example 29) in accordance with the present disclosure; wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers;
Fig. 10J illustrates micrograph of section of multilayer laminate in dome of the cavity of 150µ APET/ 25µ PVdC coated OPA/ 50µ Al foil/ 50µ PE metallocene modified (60%) (4 layer structure) (Example 29) in accordance with the present disclosure; wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers;
Fig. 10K illustrates micrograph of section of multilayer laminate in flat surface of 25µ OPA/ 150µ Al foil/ 50µ PE metallocene modified (60%) (3 layer structure) (Example 21) in accordance with the present disclosure; wherein (i), (ii), and (iii) illustrates thickness of the layers; and
Fig. 10L illustrates micrograph of section of multilayer laminate in dome of cavity of 25µ OPA/ 150µ Al foil/ 50µ PE metallocene modified (60%) (Example 21), wherein (i), (ii), (iii) and (iv) illustrates thickness of the layers in accordance with the present disclosure.
LIST OF REFERENCE NUMERALS USED IN DETAILED DESCRIPTION AND DRAWINGS
1000- Multi layered laminate with layers involved in it
10- Intermediate metal layer
20- First polymer layer laminated on the inner operative surface of intermediate metal layer
30- Second polymer layer laminated on the outer operative surface of intermediate metal layer
40- First polymer layer laminated on the first polymer layer 20
50- Second polymer layer laminated on the second polymer layer 30
60- First polymer layer laminated on the first polymer layer 40
70- Second polymer layer laminated on the second polymer layer 50
5A- Adhesive layer
02 – a stratum of virgin polyolefin (PE or PP)
04 – a stratum of desiccant modified polyolefin (PE or PP)
06 - a stratum of metallocene modified polyolefin (PE or PP)
600 – blister pack in accordance with the prior art
602– blister cup
604- draft angle of the blister cup 602
700 – blister pack in accordance with an embodiment of the present disclosure
702 – blister cup
704 - a first slanted wall
706 - a first slanted edge
708 - a second slanted edge
710 - a flat wall
712 - a mouth
714 - a second slanted wall
716 - a third slanted edge
718 - a third slanted wall
720 - a fourth slanted edge
722 - a fourth slanted wall
750 - a lid
DETAILED DESCRIPTION
The present disclosure relates to a multilayer, multibarrier, mechanically strengthened desiccant interlaced, optionally PVC free cold formable blister laminate. The present disclosure further relates to a compact blister pack made of the multilayer, multibarrier, mechanically strengthened desiccant interlaced, optionally PVC free cold formable blister laminate.
Embodiments, of the present disclosure, will now be described with reference to the accompanying drawing.
Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.
The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms “a,” “an,” and “the” may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms “comprises,” “comprising,” “including,” and “having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
The conventionally available blister packs are associated with the drawbacks such as a low barrier against water vapours and a comparatively larger draft angle. The conventional blister cups having a larger draft angle need to be spaced apart in the blister pack and hence result in the blister pack with a larger size and/or volume, which is not desired.
The present disclosure relates to packaging of “Products” which are sensitive or highly sensitive to environment factors, particularly to moisture present in atmospheric ambient air as well as light. Such “Products” which may be large in dimensions and fragile, are also prone to physical damage during transportation, handling and storage. Such “Products” comprise but are not limited to pharmaceuticals, nutraceuticals, healthcare, medical devices, medical diagnostics, electronic components, electronic products, consumable products in either unit, multi or aggregated formats and requiring larger and deeper cavities or containment area for providing effective protection and barrier against adverse environmental as well as transportation, handling and storage impact. In particular, the present disclosure relates to a mechanically strengthened, multilayer, multi barrier, cold formable blister laminates enabled with desiccant interlacing capability, wherein the blisters formed have lower draft angle and improved stiffness cum impact strength leading to formation of cavities with large size and dimensions for imparting the required functional and physical protection to the packaged products.
In an aspect, the present disclosure provides a multilayer, multibarrier, cold formable blister laminate. The multilayer, multibarrier, cold formable blister laminate comprises at least one first polymer layer, at least one intermediate layer and at least one second polymer layer.
In accordance with the embodiments of the present disclosure, the at least one first polymer layer having thickness in the range of 10 microns to 300 microns.
In accordance with the embodiments of the present disclosure, the first polymer layer is selected from the group consisting of polyethylene (o-PE) layer, modified polyethylene (m-PE) layer, polypropylene (PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, and modified cyclic olefin co-polymer (m-COC) layer.
In accordance with the embodiments of the present disclosure, the at least one intermediate metal layer has thickness in the range of 10 microns to 200 microns having a first operative surface and a second operative surface.
In accordance with the embodiments of the present disclosure, the at least one second polymer layer having thickness in the range of 10 microns to 300 microns.
In accordance with the embodiments of the present disclosure, the second polymer layer is selected from the group consisting of polyethylene (o-PE) layer, modified polyethylene (m-PE) layer, polypropylene (o-PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, modified cyclic olefin co-polymer (m-COC) layer, polyethylene terephthalate layer (PET), and modified polyethylene terephthalate (m-PET) layer.
In accordance with the embodiments of the present disclosure, the at least one first polymer layer is disposed on the first operative surface and the at least one second polymer layer is disposed on the second operative surface.
In accordance with the present disclosure, the layer adhered to the operative outer surface of the aluminum layer provides structural strength to the multibarrier multilayer laminate for cold formable blisters and blister pack made therefrom.
In accordance with the embodiments of the present disclosure, a count of the first polymer layer in the laminate may be at least one layer and maximum up to seven layers.
In accordance with the embodiments of the present disclosure, a count of the second polymer layer in the laminate may be at least one layer and maximum up to seven layers.
In accordance with the embodiments of the present disclosure, the laminate has the water vapour transmission rate (WVTR) of the laminate is in the range of 0.00009 gm/pkg/day to 0.02 gm/pkg/day at 40°C and 75% RH, when tested using Test Method 671 at 40?C and 75% RH which in turn corresponds to less than 0.8 mg/blister cavity/day. The pkg (package) used for test, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90 mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Ultra high barrier property is obtained from incorporation of additional layers to produce the ultra-high barrier multilayer cold formable blister laminates. Cold formed blister packs made from such a multilayer, ultra high barrier, cold formable blister laminate has MVTR less than 0.0002 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH which in turn corresponds to less than 0.008 mg/blister cavity/day. The pkg (package) used for test, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90 mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
In an embodiment of the present disclosure, the moisture vapor transmission rate (MVTR) of the formed blister from a multibarrier laminate is in the range of 0.0006 gm/pkg/day to 0.02 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
In accordance with the embodiments of the present disclosure, the at least one first polymer layer and the at least one second polymer layer may be a similar polymer layers or different polymer layers. The first polymer layer and the second polymer layer being used for incorporation or interlacing of desiccant or mechanical cum impact strength enhancing materials or both desiccant and mechanical cum impact strength enhancing materials. The first polymer layer is a contact layer with the product to be packaged.
In accordance with an exemplary embodiment of the present disclosure, the multilayer laminate comprises at least three layers wherein the intermediate layer comprising Al foil is sandwiched between a first polymer layer and a second polymer layer and of which first polymer layer may be a modified polyolefin layer.
In accordance with the embodiments of the present disclosure, the at least one first polymer layer, the at least one intermediate layer, and the at least one second polymer layer are adhered to each other by a method selected from extrusion lamination and adhesive lamination. In case of multiple first polymer layers, the first polymer layers are adhered to each other by the method selected from extrusion lamination and adhesive lamination. In case of multiple second layers, the second layers are adhered to each other by the method selected from extrusion lamination and adhesive lamination.
In accordance with the embodiments of the present disclosure, the adhesive lamination is performed by forming an adhesive layer on the layers selected from the first polymer layer, the intermediate metal layer and the second polymer layer, having thickness in the range of 1 gsm to 10 gsm. The adhesive layer is selected from the group consisting of polyester based adhesive layer, polyurethane based adhesive layer, and polyacrylic based adhesive layer.
In accordance with the embodiments of the present disclosure, the intermediate metal layer comprises at least one metal selected from the group consisting of aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a polyethylene layer, the first polymer layer and/or the second polymer layer is at least one selected from the group consisting of high density polyethylene (HDPE) polymer layer, medium density polyethylene polymer layer, low density polyethylene (LDPE) polymer layer, linear low-density polyethylene (LLDPE) polymer layer, linear polyethylene polymer layer, chlorinated polyethylene polymer, cross-linked polyethylene polymer layer, ultra-high molecular weight polyethylene (UHMWPE) polymer layer and polyethylene copolymer with styrene-butadiene layer.
In accordance with the embodiments of the present disclosure, wherein the first polymer layer and/or the second polymer layer is a modified polyethylene layer.
The modified polyethylene layer is being selected from a metal oxide coated polyethylene layer, a barrier polymer coated polyethylene layer, a metallized polyethylene layer, a metallocene modified polyethylene polymer layer and a desiccant modified polyethylene polymer layer.
The modified polyethylene layer being obtained by at least one of the following methods.
In a first method, a metal oxide is coated on a polyethylene sheet to obtain the metal oxide coated polyethylene layer, wherein the metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx.
In a second method, a barrier polymer is coated on a polyethylene sheet to obtain the barrier polymer coated polyethylene layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm; wherein the barrier polymer being selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc) and polyvinyl alcohol (PVOH). In an exemplary embodiment, the thickness of the polymer coating is 3 gsm.
In a third method, a metal is deposited on a polyethylene sheet to obtain the metallized polyethylene layer having an optical density in the range of 0.5 to 2.5; wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In a fourth method, metallocene is added to a polyethylene polymer in an amount in the range of 1 mass% to 90 mass% followed by extruding or laminating to obtain the metallocene modified polyethylene polymer.
In a fifth method, a desiccant is added to a polyethylene polymer in an amount in the range of 1 mass% to 70 mass% followed by extruding or laminating to obtain the desiccant modified polyethylene polymer. The desiccant being at least one selected from the group consisting of silica, calcium chloride, calcium carbonate, calcium oxide, magnesium oxide, magnesium chloride, sodium sulphate, dry aluminum chloride, aluminum oxide, molecular sieves, and activated charcoal.
The modified polyolefin layer on the operative inner surface of the intermediate metal layer provides enhanced stretchability. The modification of polyolefin polymer with metallocene imparts better mechanical and impact properties and improved stretchability and also avoids rupturing of blister pockets during the cold forming process and leads to lowering of chances of deformation of blister pockets during transportation, handling and storage. The modification of polyethylene polymer (PE) with desiccant material improves water vapour adsorption capacity, thereby improving the shelf life of the packaged product. In an exemplary embodiment, the thickness of the modified polyethylene layer is 40 microns. In another exemplary embodiment, the thickness of the modified polyethylene layer is 60 microns. In another exemplary embodiment, the thickness of the modified polyethylene layer is 100 microns.
In an embodiment of the present disclosure, the polyethylene polymer layer is modified by using metallocene in an amount in the range of 1 mass% to 90 mass% with respect to the total mass of the modified polyethylene polymer. In an exemplary embodiment, the metallocene in the polyethylene layer is present in an amount of 50 mass% with respect to the total mass of the modified polyethylene polymer layer. In an exemplary embodiment, the metallocene in the polyethylene layer is present in an amount of 60 mass% with respect to the total mass of the modified polyethylene polymer layer.
In accordance with an embodiment of the present disclosure, the polyethylene polymer is modified by using desiccant in an amount in the range of 1 mass% to 70 mass% with respect to the total mass of the modified polyethylene polymer. In an exemplary embodiment, the desiccant in the polyethylene is present in an amount of 33 mass% with respect to the total mass of the modified polyethylene polymer layer. In normal polyethylene (PE) based laminate, during cold forming operation, pin holes were observed due to a low impact strength of PE (below 300 g) present in the laminate. Metallocene in LDPE in turn extruded PE film improves the impact strength of modified PE film which is evident after measuring the impact strength of metallocene LDPE. Due to the addition of metallocene in LDPE, the impact strength increases from below 300 g to above 425 g, which in turn lowers the pin hole appearance in the laminate during the cold forming process. It is further observed that the deformation of blister pockets during transportation, handling and storage is lower when compared to the laminate with PE without metallocene.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a polypropylene layer. The polypropylene layer is at least one selected from the group consisting of polypropylene homopolymer layer, polypropylene random copolymer layer and polypropylene impact copolymer layer.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a modified polypropylene layer.
The modified polypropylene layer being selected from a metal oxide coated polypropylene layer, a polymer coated polypropylene layer, a metallized polypropylene layer, a metallocene modified polypropylene polymer, and a desiccant modified polypropylene polymer.
In accordance with the embodiments of the present disclosure, the modified polypropylene layer is obtained by at least one of the following methods.
In a first method, a metal oxide is coated on a polypropylene sheet to obtain the metal oxide coated polypropylene layer, wherein the metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx.
In a second method, a barrier polymer is coated a polypropylene sheet to obtain the polymer coated polypropylene sheet having thickness of the polymer coating is in the range of 1 gsm to 10 gsm; wherein the barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc) and polyvinyl alcohol (PVOH). In an exemplary embodiment, the thickness of the polymer coating is 3 gsm.
In a third method, a metal is deposited a polypropylene sheet to obtain the metallized polypropylene layer having an optical density in the range of 0.5 to 2.5, preferably in the range of 1.5 to 2.5 optical density (OD); wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag). In an exemplary embodiment, the metallized oriented polyamide layer has an optical density of 2.4. In another exemplary embodiment, the metallized oriented polyamide layer has an optical density of 2.2. Yet another exemplary embodiment, the metallized oriented polyamide layer has an optical density of 1.96.
In a fourth method, metallocene is added to a polypropylene polymer in an amount in the range of 1 mass% to 90 mass% followed by extruding or laminating to obtain the metallocene modified polypropylene polymer layer.
In a fifth method, a desiccant is added a polypropylene polymer in an amount in the range of 1 mass% to 70 mass% followed by extruding or laminating to obtain the desiccant modified polypropylene polymer. The desiccant is at least one selected from the group consisting of silica, calcium chloride, calcium carbonate, calcium oxide, magnesium oxide, magnesium chloride, sodium sulphate, dry aluminum chloride, aluminum oxide, molecular sieves, and activated charcoal.
In accordance with the embodiments of the present disclosure, wherein the first polymer layer and/or the second polymer layer is selected from a modified polyethylene layer and a modified polypropylene layer,
The modified polyethylene layer has a plurality of strata selected from the group consisting of virgin polyethylene stratum, desiccant modified polyethylene stratum, metallocene modified polyethylene stratum, metal oxide coated polyethylene stratum, polymer coated polyethylene stratum, and metallized polyethylene stratum. In accordance with the embodiments of the present disclosure, the modified polypropylene layer has a plurality of strata selected from the group consisting of virgin polypropylene stratum, desiccant modified polypropylene stratum, metallocene modified polypropylene stratum, metal oxide coated polypropylene stratum, polymer coated polypropylene stratum, and metallized polypropylene stratum. In an embodiment of the present disclosure, the modified polypropylene layer is obtained by co extruding metallocene polypropylene layer, desiccated PP layer and polypropylene random copolymer.
In a blister pack formed with the multilayer laminate of the present disclosure, any moisture present in the cavity or any moisture generated during shelf-life of the product is absorbed and/or adsorbed by desiccant modified polymer layer which comes into contact with the packaged product.
In accordance with the embodiments of the present disclosure, wherein the first polymer layer and/or the second polymer layer is an oriented polyamide layer.
The oriented polyamide layer being selected from semi-crystalline polyamide layer, amorphous polyamide layer, and a copolymer layer thereof; the semi-crystalline polyamide is at least one selected from the group consisting of Nylon 6, Nylon 6,6, Nylon 6,9, Nylon 6,12, Nylon 12,12, and a copolymer thereof.
In an exemplary embodiment, the thickness of the oriented polyamide layer is 25 microns. In another exemplary embodiment, the thickness of the oriented polyamide layer is 50 microns.
In accordance with the embodiments of the present disclosure, wherein the first polymer layer and/or the second polymer layer is a modified oriented polyamide (OPA) layer.
The modified oriented polyamide (OPA) layer being selected from a metallized oriented polyamide layer, a metal oxide coated oriented polyamide layer, and a barrier polymer coated oriented polyamide layer.
The modified oriented polyamide (OPA) layer is obtained by at least one of the following methods.
In a first step, a metal is deposited on an OPA sheet to obtain the metallized oriented polyamide layer having an optical density in the range of 0.5 to 2.5, preferably in the range of 1.5 to 2.5 optical density (OD); wherein the metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In a second method, metal oxide is coated an OPA sheet to obtain the metal oxide coated oriented polyamide layer. The metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx.
In a third method, a barrier polymer is coated on an OPA sheet to obtain a polymer coated oriented polyamide layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm. The barrier polymer being selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and heat seal lacquer (HSL). In an exemplary embodiment, the thickness of the polymer coating is 3 gsm.
In accordance with the embodiments of the present disclosure, wherein the second polymer layer is a polyethylene terephthalate (PET) layer. The polyethylene terephthalate (PET) layer is at least one selected from group comprising of amorphous polyethylene terephthalate (APET) layer, polyethylene terephthalate (PET) layer, glycol modified PET (PETg) layer, poly (1,3- propylene) terephthalate, poly (1,4- butylenes) terephthalate layer, elastomeric polyester comprising poly (1,4-butylene) terephthalate layer and poly (tetramethylene ether) glycol layer. PET polymer layer may be uniaxially oriented or biaxially oriented.
In accordance with the embodiments of the present disclosure, wherein the second polymer layer is a modified polyethylene terephthalate (o-PET) layer.
The modified polyethylene terephthalate (o-PET) layer being selected from a metallized polyethylene terephthalate layer, a metal oxide coated polyethylene terephthalate layer and a barrier polymer coated polyethylene terephthalate layer.
The modified polyethylene terephthalate (o-PET) layer is obtained by at least one of the following methods:
In a first method, a metal is deposited on an o-PET sheet to obtain the metallized polyethylene terephthalate layer having an optical density in the range of 0.5 to 2.5, preferably in the range of 1.5 to 2.5 optical density (OD). The metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In a second method, metal oxide is coated on an o-PET sheet to obtain the metal oxide coated polyethylene terephthalate layer. The metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx.
In a third method, a barrier polymer is coated on an o-PET sheet to obtain the polymer coated polyethylene terephthalate layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm. The barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), and Heat seal lacquer (HSL). In an exemplary embodiment, the thickness of the polymer coating is 3 gsm.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a modified cyclic olefin co-polymer layer. S
The modified cyclic olefin co-polymer layer being selected from a metal oxide coated cyclic olefin co-polymer layer, a barrier polymer coated cyclic olefin co-polymer layer and a metallized cyclic olefin co-polymer layer.
The modified cyclic olefin co-polymer layer is obtained by at least one of the following method.
In a first method, a metal oxide is coated on a COC sheet to obtain the metal oxide coated cyclic olefin co-polymer layer. The metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx.
In a second method, a barrier polymer is coated on an COC sheet to obtain the polymer coated cyclic olefin co-polymer layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm. The barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), and Heat seal lacquer (HSL). In an exemplary embodiment, the thickness of the polymer coating is 3 gsm.
In a third method, a metal is deposited on an COC to obtain the metallized cyclic olefin co-polymer layer having an optical density in the range of 0.5 to 2.5, preferably in the range of 1.5 to 2.5 optical density (OD). The metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In accordance with the embodiments of the present disclosure, wherein the first polymer layer and/or the second polymer layer is a polyvinyl chloride (PVC) polymer layer. The polyvinyl chloride (PVC) polymer layer is selected from flexible PVC layer, rigid PVC layer, chlorinated PVC layer, and oriented PVC layer.
In accordance with the embodiments of the present disclosure, the first polymer layer and/or the second polymer layer is a modified polyvinyl chloride layer.
The modified polyvinyl chloride layer being selected from a metal oxide coated polyvinyl chloride layer, a barrier polymer coated polyvinyl chloride layer, and metallized polyvinyl chloride layer.
The modified polyvinyl chloride layer is obtained by at least one of the following method.
In a first method, a metal oxide is coated on a polyvinyl chloride sheet to the obtain a metal oxide coated polyvinyl chloride layer. The metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx.
In a second method, a barrier polymer is coated on a PVC sheet to obtain the polymer coated polyvinyl chloride layer having thickness of the polymer coating is in the range of 1 gsm to 10 gsm. The barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), and Heat seal lacquer (HSL). In an exemplary embodiment, the thickness of the polymer coating is 3 gsm.
In a third method, a metal is deposited on a PVC sheet to obtain the metallized polyvinyl chloride layer having an optical density in the range of 0.5 to 2.5, preferably in the range of 1.5 to 2.5 optical density (OD). The metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
In accordance with the embodiments of the present disclosure, the at least one first polymer layer is prepared by a method selected from cast extrusion and blow extrusion. In accordance with the embodiments of the present disclosure, the at least one second polymer layer is prepared by a method selected from cast extrusion and blow extrusion.
In accordance with the present disclosure, the metalized Polyamide or metalized PET or metalized PP or metalized PE or metalized COC layer or metalized PVC layer or metal oxide such as AlOx or SiOx coated OPA or AlOx or SiOx coated PET or AlOx or SiOx coated PP or AlOx or SiOx coated PE or AlOx or SiOx coated COC or AlOx or SiOx coated PVC layer or polymer such as PVdC coated polyamide or PVdC coated PET or PVdC coated PP or PVdC coated PE or PVdC coated COC layer or PVdC coated PVC layer is printable as per the design requirements.
The modified oriented polyamide polymer or PET or PP or PE or COC polymer layer is biaxially oriented. The biaxially oriented modified polyamide provides the structural strengthening property to the multilayer laminate. The modified oriented polyamide or PET or PP or PE or COC provides high durability, high strength, abrasion resistance, and resilience, and provides a good balance between mechanical and impact strength and barrier properties against oxygen, smell and oils.
Generally, the oriented polyamide or PET or PE or PP polymer has a poor barrier against water vapour. This leads to the ingression of water vapour through the oriented polyamide or PP or PE polymer film which results into the weakening of the bond between the intermediate aluminum foil and the oriented polyamide or PP or PE or COC polymer layer and delaminates oriented polyamide or PP or PE or COC polymer from aluminum foil at the edges of the pocket. Coating of the polymer layer or metal oxide or deposition of metal layer prevents the ingression of moisture through oriented polyamide polymer and prevents delamination. Further, this barrier layer offers a better printing surface.
The inventors of the present disclosure have observed that an increase in the metallization increases the optical density of the metallized layer. The inventors have also found that the optical density below 1.5 does not significantly contribute to the desired water vapour barrier. Further, if the optical density is higher than 2.4, then there are chances of flaking/ cracking of the metallized layer due to higher deposition of metal, and also not adding to enhancement in barrier property. In one embodiment, the metallized oriented polyamide layer has thickness of 25 microns having metallization in the range of 0.5 to 2.5 optical density (OD), preferably in the range of 1.5 to 2.5 optical density (OD).
In accordance with the embodiments of the present disclosure, a primer layer having thickness in the range of 1 gsm to 3 gsm is applied on the first operative surface or the second operative surface OR the surface of the first polymer layer or the second polymer layer in contact with the first operative surface or the second operative surface. The primer layer is at least one selected from the group consisting of acrylic based primer layer, polyurethane based primer layer and polyester based primer layer.
In accordance with the embodiments of the present disclosure, the laminate comprises:
o the first polymer layer is a polypropylene layer of a thickness 60 microns, and a metallocene modified polyethylene layer having thickness of 100 microns;
o the intermediate metal layer as the aluminum layer having thickness of 50 microns; and
o the second polymer layer having a modified oriented polyamide layer of a thickness of 25 microns, and a layer having a combination of a metallocene modified PE and desiccant modified PE having thickness of 60 microns.
In accordance with the embodiments of the present disclosure, the laminate comprises:
o the first polymer layer is a polypropylene having thickness of 60 microns;
o the intermediate metal layer is an aluminum layer having thickness of 50 microns; and
o the second polymer layer having a metallized oriented polyamide layer having a thickness of 25 microns, and a PVC layer having thickness of 60 microns.
wherein the metallized oriented polyamide layer and the PVC layer are bonded together. The polypropylene layer and the metallocene modified polyethylene layer are bonded together by heat lamination or extrusion lamination or by adhesive lamination.
In accordance with the embodiments of the present disclosure, the laminate comprises:
o the first polymer layer is a metallocene modified polyethylene having thickness of 50 microns;
o the intermediate metal layer is an aluminum layer having thickness of 50 microns; and
o the second polymer layer having a metallized oriented polyamide layer having a thickness of 25 microns, and a PVC layer having thickness of 30 microns.
The metallized oriented polyamide layer and the PVC layer are bonded together by heat lamination or extrusion lamination or by adhesive lamination.
In accordance with the embodiments of the present disclosure, the laminate comprises
o the first polymer layer of a metallocene modified polyethylene layer having thickness of 100 microns;
o the intermediate metal layer of an aluminum layer having thickness of 150 microns; and
o the second polymer layer is oriented polyamide layer having a thickness of 25 microns.

In accordance with the embodiments of the present disclosure, the laminate comprises:
o the first polymer layer is a metallocene modified polyethylene layer of a thickness 50 microns;
o the intermediate metal layer is an aluminum layer having thickness of 50 microns; and
o the second polymer layer is a PVdC coated oriented polyamide layer having a thickness of 25 microns.
In accordance with the embodiment of the present disclosure, the laminate comprises:
o the first polymer layer is a metallocene modified polyethylene layer of a thickness of 50 microns;
o the intermediate metal layer is an aluminum layer of thickness of 50 microns; and
o the second polymer layer is an AlOx coated oriented polyamide layer of a thickness of 25 microns.
In accordance with the embodiment of the present disclosure, the laminate comprises:
o the first polymer layer is a metallocene modified polyethylene layer of a thickness of 50 microns;
o the intermediate metal layer is an aluminum layer of thickness of 50 microns; and
o the second polymer layer is a metallized oriented polyamide layer of a thickness of 25 microns.
In accordance with the embodiments of the present disclosure, the multilayer, multibarrier cold formable blister is characterized by having a tensile strength in the range of 400 kg/cm2 to 1200 kg/cm2, a percent elongation at peak in the range of 12% to 40%, an impact strength in the range of 1400 g to 2500 g, and a cavity height at bursting of more than 24 mm. In an exemplary embodiment, the tensile strength is 978 kg/cm2, elongation at peak is 26%, impact strength is 1960 g, and a cavity height at bursting is 27.6 mm.
Based on evaluation of experimental samples subjected to deformation and cavity height evaluation, it is found that, multilayer laminate having thickness of 160 microns is able to form cavity height of 25 mm, and multilayer laminate having thickness of 265 microns is able to form cavity height 28.2 mm. With increase of 100-micron thickness of multilayer laminate, there is around 10% to 15% increase in the cavity height. Accordingly a multilayer laminate having thickness of 2000 microns would have capability of accomplishing the cavity height at bursting is in the range of 60 mm to 65 mm. The laminate of the present disclosure has enhanced deep draw formability as well as is capable of yielding cold formed blisters of compact size along with improved mechanical and impact strength for cavities with large dimensions without any rupture after forming and at the same time providing requisite ultra multibarrier against adverse environmental impact. Such a multi-layer cold formable laminate can be used for packaging of various products having large dimensions and which are fragile as well as sensitive or highly sensitive to moisture, temperature, light such as consumer goods, food, nutraceuticals, veterinary products, electronic goods and gadgets, pharmaceutical products, medical devices and the like.
In accordance with an embodiment of the present disclosure, the structure of the multi layered laminate (100) as described above is depicted in Fig. 1 wherein an intermediate layer (10) in the form of metal foil comprising of Al. Pd, Pt, Cu, Ni, Au and Ag, preferably Al foil having thickness in the range of 10 to 150 microns. The intermediate layer has outer operative surface and inner operative surface. The intermediate layer in the multilayer is sandwiched between two polymer layers, polymer layer adhesively laminated or extrusion laminated on the outer operative surface of the intermediate layer (10) called as second polymer layer (30), comprising OPA or o-PET or o-PE or o-PP or COC, having thickness in the range of 10 to 100 microns, while the polymer layer on the inner operative surface of intermediate layer (10) is adhesively laminated or extrusion laminated called as first polymer layer (20), comprising OPA or o-PE or o-PP, or COC having thickness in the range of 10 to 300 microns. Further, optional additional polymer layer (40 and 60) above second polymer layer adhesively laminated or extrusion laminated comprising PVC or OPA or o-PET or o-PE or o-PP or COC, having thickness in the range of 10 to 300 microns. And optional additional polymer layers (40 and 60) below first polymer layer adhesively laminated or extrusion laminated comprising PVC or OPA or PE or PP or COC, having thickness in the range of 10 to 300 microns.
In case of a modified layer polyolefin (PE or PP) having two strata, the innermost product contact layer comprising a stratum of virgin polymer (02) and the second strata (04) polyolefin interlaced with desiccant material (Fig. 2a).
In case of a modified layer polyolefin (PE or PP) of three strata, product contact layer or innermost layer is of a stratum of virgin polyolefin (02), a stratum of desiccant polyolefin layer (04) and a stratum of metallocene polyolefin (06) (Fig. 2b) wherein the order of layers can be arranged as per desire and requirement.
In case of a modified layer polyolefin (PE or PP) of five strata, the order of the layers is virgin polyolefin (02), two layers of desiccant polyolefin (04, 04) and two layers of metallocene polyolefin (06, 06) (Fig. 2c) wherein the order of layers can be arranged as per desire and requirement, likewise up to seven layer first layer of modified polyolefin can be prepared by two strata of virgin polyolefin, two strata of desiccant polyolefin and three strata of metallocene polyolefin. (Fig. 2d) wherein the order of layers can be arranged as per desire and requirement. Fig. 2d illustrates a modified layer polyolefin (PE or PP) of seven strata comprising a stratum of virgin polyolefin (02), a stratum of desiccant modified polyolefin (04), a stratum of metallocene modified polyolefin (06), a stratum of desiccant modified polyolefin (04), a stratum of metallocene modified polyolefin (06), a stratum of virgin polyolefin (02) and a stratum of metallocene modified polyolefin (06), in accordance with the present disclosure.
In an embodiment of the present disclosure, the multilayer laminate (Fig. 3) comprises a first polymer layer (20), an adhesive layer (5A), an intermediate layer (10), an adhesive layer (5A), and a second polymer layer (30). In an embodiment, the multilayer laminate comprises layers in order of a first polymer layer of modified PE, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of OPA. In another embodiment, the multilayer laminate comprises layers in order of a first polymer layer of modified PP, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of OPA. In still another embodiment, the multilayer laminate comprises layers in order of a first polymer layer of modified PE, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of modified PE. In yet another embodiment, the multilayer laminate comprises the layers in order of a first polymer layer of modified PP, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of modified PP. In still another embodiment, the multilayer laminate comprises the layers in order of a first polymer layer of modified PE, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of modified PP. In yet another embodiment, the multilayer laminate comprises the layers in order of a first polymer layer of modified PP, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of modified PE. In still another embodiment, the multilayer laminate comprises the layers in order of a first polymer layer of modified PP, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of modified PP. In yet another embodiment, the multilayer laminate comprises the layers in order of a first polymer layer of OPA, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of OPA or PET. In still another embodiment, the multilayer laminate comprises the layers in order of a first polymer layer of COC, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of COC. In yet another embodiment, the multilayer laminate comprises the layers in order of a first polymer layer of COC, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of modified OPA or modified PE or modified PP or modified PET. In still another embodiment, the multilayer laminate comprises the layers in order of a first polymer layer of modified OPA or modified PE or modified PP, an adhesive layer, an intermediate Al layer, an adhesive layer, and a second polymer layer of COC.
When both the desiccant and metallocene are present in a layer, another layer is introduced for infusing or incorporating the layer with metallocene or desiccant. The modified PE or PP layers may be uniaxially oriented or bi-axially oriented.
When the second polymer layer of oriented polyamide (OPA) layer or o-PET or polyolefin or COC or PVC layer on the outer operative surface on Al foil layer where in the OPA or o-PET layer is modified by any of methods selected from a) a layer of metal deposited on OPA or PET or polyolefin or COC layer to obtain metallized OPA or PET or polyolefin or COC or PVC layer, metal is selected from the group comprising of Al, Cu, Pd, Pt, Au and Ag, preferably Al; b) a barrier polymer layer coating applied on OPA or PET or polyolefin or COC or PVC layer to obtain barrier polymer coated OPA or PET or polyolefin or COC or PVC in barrier polymer selected from group comprising of PVdC, PVAc, PVOH; c) a coating of metal oxide deposited on OPA or PET to obtain metal oxide coated OPA or PET or polyolefin or COC or PVC layer wherein metal oxide selected from group comprising of AlOx, SiOx, CuOx, NiOx, CoOx Preferably AlOx. The first layer of oriented polyamide or PET or polyolefin or COC or PVC layer on the inner operative surface of Al foil wherein the product contact side of OPA layer is PVdC coated or HSL layer coated compatible for sealing with the lidding foil used for packaging of product.
When the first layer of COC layer is on the inner operative surface of Al foil, the product contact side of COC layer is PVdC coated or HSL layer coated compatible for sealing with the lidding foil used for packaging of product.
Similarly, the first polymer layer and the second polymer layers could be modified as per the combination specified in Table 1.
Table 1: Combination of the first polymer layer and the second polymer layers for a three layered laminate structure
Outer Layer Intermediate layer Inner Layer
1 OPAa Al Foil Polyolefinb
2 Polyolefinc Al Foil OPAd
3 Polyolefinc Al Foil Polyolefinb
4e OPAa Al foil OPAd
5 COCf Al COCg
6 OPA or PE or PP or PETh Al COCg
7 COCf Al OPA or PP or PEi
a OPA transparent or metallized or PVdC coated or AlOx coated, b polyolefin modified by metallocene and/ or desiccant, c metallocene and/ or desiccant polyolefin with transparent or metallization or AlOx coating or PVdC coating, d OPA modified by PVdC or HSL coating, e In this structure an additional layer of modified PE or modified PP with metallocene and/or desiccant is adhered / laminated on either outer or inner OPA layers, f COC transparent or metallized or AlOx coated or PVdC coated, g COC PVdC coated or HSL coated, h OPA or PP or PE or PET transparent or metallized or AlOx coated or PVdC coated and PP or PE additionally modified by metallocene and/ or desiccant, i OPA or PP or PE wherein PE or PP modified by metallocene and/or desiccant and OPA is PVdC coated or HSL coated.
In an embodiment of the present disclosure, the multilayer laminate (Fig. 4) comprises the three layers as described for the multilayer laminate as per the combination specified in Table 1 along with a PVC layer laminated on the second polymer layer to form four-layer structure. Fig. 4 illustrates four layered laminate comprising a first polymer layer (20), an adhesive layer (5A), an intermediate layer (10), an adhesive layer (5A), a second polymer layer (30), an adhesive layer (5A), a second polymer layer (50) in accordance with the present disclosure. In an embodiment, the four layered laminate comprising the layers in order of a first polymer layer (20) of modified polyolefin or OPA or COC, an adhesive layer (5A), an intermediate layer (10) of Al foil, an adhesive layer (5A), a second polymer layer (30) of modified OPA or PET or COC or polyolefin, an adhesive layer (5A), a second polymer layer (50) of PVC in accordance with the present disclosure. In another embodiment, the four layered laminate comprising the layers in order of a first polymer layer (20) of OPA or PP or PE or COC, an adhesive layer (5A), an intermediate layer (10) of Al foil, an adhesive layer (5A), a second polymer layer (30) of OPA or PET or PP or PE or COC, an adhesive layer (5A), a second polymer layer (50) of OPA or PET or PP or PE or COC in accordance with the present disclosure. In still another embodiment, the four layered laminate comprising the layers in order of a first polymer layer (20) of OPA or PP or PE or COC, an adhesive layer (5A), a first polymer layer (40) of OPA or PE or PP, an intermediate layer (10) of Al foil, an adhesive layer (5A), a second polymer layer (30) of OPA or PET or PP or PE or COC, in accordance with the present disclosure. When this layer comprises OPA or PET or PP or PE or COC on outer surface then it is optionally modified by one of the methods selected from: a) Deposition of metal layer to obtain metallized polymer layer wherein metal was selected from group comprising of Al, Cu, Pd, Pt, Au and Ag, preferably Al b). Coating OPA or PET or PP or PE or COC layer by a barrier polymeric layer to obtained barrier coated OPA or PET or PP or PE or COC wherein barrier polymer is selected from group comprising of PVdC, PVAc, PVOH and c). Deposition of barrier layer of metal oxide selected from group comprising of AlOx, SiOx, CuOx, NiOx, CoOx to obtain metal oxide coated OPA or PET or PP or PE or COC preferably AlOx while OPA layer on the inner operative surface is coated either with PVdC or HSL coating to facilitate sealing. Polyethyelene or polypropylene or PET or COC layers above second polymer layer or below first polymer layer may be uni-axially or bi-axially oriented.
Fig. 5 illustrates five layered laminate comprising a first polymer layer (20) OPA or PP or PE or COC, an adhesive layer (5A), a first polymer layer (40) of OPA or PP or PE or COC, an intermediate layer (10), an adhesive layer (5A), a second polymer layer (30) of OPA or PET or PP or PE or COC, an adhesive layer (5A), a second polymer layer (50) of PVC or OPA or PET or PP or PE or COC in accordance with the present disclosure. In an embodiment, five layered laminate comprising a first polymer layer (20), an adhesive layer (5A), a first polymer layer (40), an intermediate layer (10), an adhesive layer (5A), a second polymer layer (30), an adhesive layer (5A), a second polymer layer (50)
In still another embodiment of the present disclosure, a cold formable multilayer laminate (Fig. 5) comprises a five layers with an optional innermost polymer layer having thickness in the range of 10 to 300 microns which may become the 6th layer as a product contact layer (the first polymer layer) comprising body strengthening polymers selected from polymers approved for direct contact with consumables products comprising virgin polymers such as PVC, polyamide, polyolefin, COC and the like. An additional optional second polymer layer having thickness in the range of 10 to 300 microns, which may be laminated or adhesioned to the second polymer layer towards the outer operative side of Al Foil or replacing one of the outer polymer layers towards the outer operative side of Al Foil. Such a layer comprises polymers from PVC, Polyolefin, polyamide, PET or COC (Fig. 5).
In an embodiment of the present disclosure, the laminate comprises
a. the polyethylene (PE) layer modified by using metallocene (60%) and has a thickness of 50 microns;
b. the intermediate aluminum layer has thickness of 45 microns; and
c. the oriented polyamide layer is metallized and has thickness of 25 microns and optical density of 1.96,
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.0002 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
In another embodiment of the present disclosure, the laminate comprises
a. the polyethylene layer modified by using metallocene (60%) and has thickness of 50 microns;
b. the intermediate aluminum layer has thickness of 50 microns; and
c. the oriented polyamide layer is modified by polymer coating such as PVdC (3 gsm thickness) and has thickness of 25 microns,
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.002 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
In still another embodiment of the present disclosure, the laminate comprises
a. the polyethylene (PE) layer modified by using metallocene (60%) and has a thickness of 100 microns;
b. the intermediate aluminum layer has thickness of 50 microns; and
c. the oriented polyamide layer is metallized and has thickness of 25 microns and optical density of 2.4,
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.00009 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
Still another embodiment of the present disclosure, the laminate comprises
a. the polypropylene (PP) layer has thickness 60 microns;
b. Aluminum layer has thickness 50 microns
c. oriented polyamide layer is metallized and has thickness 25 microns and optical density 2.4,
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.00008 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
Yet another embodiment of the present disclosure, the laminate comprises
a. the polyethylene (PE) layer modified by metallocene (60%) has thickness 60 microns;
b. Aluminum layer has thickness 50 microns
c. oriented polyamide layer has thickness 25 microns where in AlOx coating deposited on OPA layer,
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.008 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
In yet another embodiment of the present disclosure a laminate formed by
a. the polyethylene (PE) layer modified by metallocene (60%) has thickness 60 microns;
b. Aluminum layer has thickness 50 microns
c. oriented polyamide layer has thickness 25 microns
d. and PVC layer of thickness 30 microns and is metallized having optical density 2.2
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.0006 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
Yet another embodiment of the present disclosure, the multilayer laminate comprises
a. Polyethylene layer modified by metallocene (60%) and desiccant (40%) in the form of multistrata having thickness 50 microns
b. Aluminum layer has thickness 50 microns
c. Oriented polyamide layer of thickness 25 microns and is metallized having optical density 2.2
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.0006 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
Still yet another embodiment of the present disclosure, the multilayer laminate comprises of
a. Polyethylene layer metallocene modified, (60%) of thickness 100 microns
b. Polypropylene layer having thickness 60 microns
c. Aluminum layer having thickness 50 microns
d. Oriented polyamide layer of thickness 25 microns, is metallized and having optical density 2.2
e. Polypropylene layer of thickness 60 microns
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.0006 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
Still yet another embodiment of the present disclosure, the multilayer laminate comprises of
a. Polyethylene layer modified with metallocene (60%)
b. Aluminum layer of thickness 50 microns
c. Barrier polymer layer (3 gsm) coated oriented polyamide layer has thickness 25 microns
d. Amorphous polyethylene terephthalate layer having thickness 150 microns
wherein the laminate, when cold formed into blisters having cavity dimensions 23.7mm x 15.5mm x 6.9mm has MVTR of 0.008 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions.
It has been found that lamination of additional polymer layer above OPA or PET or PP or PE or COC layer improved the stiffness and mechanical and impact strength of the blisters without compromising compactness of the blister, that were formed from the structure. Improved stiffness, mechanical and impact strength found to be beneficial as blisters cannot be easily deformed.
Improvement in stiffness, tensile strength, impact strength and other mechanical properties including stretchability and drawability were observed in the multilayer laminates of the present disclosure after mechanical properties such as Tensile Strength at Peak, Percent Elongation at Peak, Dome Height of formed Cavity at Bursting and Impact strength are tested using methods prescribed in international testing standards.
Tensile strength displays the ability of the material to withstand the maximum tensile stress and % Elongation shows ability of material when stretched at the maximum load at the yield point before breaking. The Tensile strength at peak (in Kg/cm2) and Percent Elongation at peak (in %) of the multilayer laminates in present disclosure were tested according to the following methodology.
Testing was done in accordance to and specified in International Standard ASTM D 822. Samples of multilayer laminates were subjected to Tensile strength at peak (in Kg/cm2) and % Elongation at peak (in %) tests in both machine direction (MD) as well as transverse direction (TD). According to the method, samples taken from the multilayer laminates were tested on Computerized single screw Tensile tester (NX International Equipment Ltd.) with International Equipments Limited make load indicator and Sensortronics make load cell. Sample strips of 10 mm (width) x 100 mm (length) from the multilayer laminates were taken and subjected to test with testing machine parameters set at load limit 22.5 Kg and travelling limit 900 mm.
Impact strength is a measure of materials ability to resist impact. The impact strength was tested in accordance to International Standard ASTM D 1709. Impact strength of multilayer laminates was measured using equipment from International Equipments Limited. Circular Samples of 16 cm diameter were subjected to impact of known amount of weight from a height of 660 mm ± 10mm.
Height of the formed cavity at bursting provides information about the ability of Laminate drawability and forming a cavity at pressure of 6 bar before bursting. The height of dome of the formed cavity is measured which gives the maximum bulge (dome) height of the formed cavity. Testing was carried out in accordance to Standard DIN 51220 using equipment S-18623 from Frank PTI Germany with sample testing area of 50 cm2 and maximum bulging (formed cavity) height of 30 mm.
Mechanical properties of 4 or more layered laminates of the present disclosure were observed to be better and higher than the 3 layered laminates by virtue of having additional layer over three layer laminates. The enhanced mechanical properties of the multilayered laminates of present disclosure in comparison to commercially available, conventional 3 layered Alu-Alu cold formable blister laminate showcases significantly lower deformation of the blisters formed from the mechanically strengthened multilayer laminates which in turn will lead to better protection of the fragile products packaged in these blisters during transportation, handling and storage.
It is observed that the multibarrier multilayer laminate for cold formable blisters of the present disclosure, described herein above, is characterized by having high stretchability and high impact strength as compared to the multilayer laminate with the polymer adhered to the inner surface of the aluminum layer being PVC.
The laminates of the present disclosure can provide for a cold formed blister wherein the cavities of the cold formed blister retain high or ultra high barrier against water vapour along with high mechanical and impact strength wherein a significantly compact blister size is accomplished with deep draw and large dimensions of the cavities and which in turn provides appropriate protection to environmentally sensitive and/or highly sensitive products with large dimensions. Also, Products, particularly physically fragile products having large dimensions which are susceptible or highly susceptible to deterioration from environmental factors like temperature, humidity, light, as well as physical damage and deterioration from physical impact during transportation, handling and storage requires such products to be adequately protected against such environment and physical impact when packaged in cold formed blister format. These limitations necessitates the laminates of the present disclosure, capable of significantly increased depth and size of the formed cavities for containing such products and simultaneously maintaining the high or ultra-high barrier property, compactness of the cold formed blister and retention of high mechanical and impact strength by the cavities and stiffness of the blister packs after formation, leading to a viable alternative for overcoming the existing limitations and drawbacks for blister packaging of such products.
In another aspect, the present disclosure provides a compact blister pack. The compact blister pack comprising at least one blister shaped cup by cold forming of a multilayer, multibarrier, and a sealable and tearable lid. The sealable and tearable lid compatible to seal with the multilayer laminate of the present disclosure.
The multilayer, multibarrier, cold formable blister laminate comprises at least one first polymer layer, at least one intermediate layer and at least one second polymer layer.
In accordance with the embodiments of the present disclosure, the at least one first polymer layer having a thickness in the range of 10 microns to 300 microns.
In accordance with the embodiments of the present disclosure, the first polymer layer is selected from the group consisting of polyethylene (o-PE) layer, modified polyethylene (m-PE) layer, polypropylene (o-PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, and modified cyclic olefin co-polymer (m-COC) layer.
In accordance with the embodiments of the present disclosure, the at least one intermediate metal layer having thickness in the range of 10 microns to 200 microns having a first operative surface and a second operative surface.
In accordance with the embodiments of the present disclosure, the at least one second polymer layer having thickness in the range of 10 microns to 300 microns.
In accordance with the embodiments of the present disclosure, the second polymer layer is selected from the group consisting of polyethylene (o-PE) layer, modified polyethylene (m-PE) layer, polypropylene (o-PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, modified cyclic olefin co-polymer (m-COC) layer, polyethylene terephthalate layer (PET), and modified polyethylene terephthalate (m-PET) layer.
In accordance with the embodiments of the present disclosure, the at least one first polymer layer is disposed on the first operative surface and the at least one second polymer layer is disposed on the second operative surface.
In accordance with the embodiments of the present disclosure, the laminate has the water vapour transmission rate (WVTR) of the laminate is in the range of 0.00009 gm/pkg/day to 0.02 gm/pkg/day at 40°C and 75% RH, when tested using Test Method 671 at 40?C and 75% RH which in turn corresponds to less than 0.8 mg/blister cavity/day. The pkg (package) used for test, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90 mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
In accordance with the embodiments of the present disclosure, the sealable and tearable lid is defined by an operative outer surface and an operative inner surface, compatible to bond with the first polymer layer in the laminate and to seal the at least one cup.
In accordance with the embodiments of the present disclosure, a primer layer having thickness in the range of 1 gsm to 3 gsm is applied on the first operative surface or the second operative surface OR the surface of the first polymer layer or the second polymer layer in contact with the first operative surface or the second operative surface. The primer layer is at least one selected from the group consisting of acrylic based primer layer, polyurethane based primer layer and polyester based primer layer.
In accordance with the embodiments of the present disclosure, the inner operative surface of the sealable and tearable lid is coated by using a heat seal lacquer compatible to bond with the first polymer layer in the blister laminate. The heat seal lacquer layer is in an amount in the range of 3 gsm to 10 gsm.
In accordance with the embodiments of the present disclosure, the sealable and tearable lid comprises an aluminum foil having an operative inner surface and an operative outer surface, laminated with polyethylene film compatible to bond with the first polymer layer of the cold formable multilayer blister laminate, wherein the thickness of the aluminum foil is in the range of 15 microns to 40 microns, and the thickness of the polyethylene film is in the range of 15 microns to 40 microns.
In accordance with an embodiment of the present disclosure, the sealable and tearable lid defines an operative outer surface and operative inner surface comprises a laminated Al-PE foil having a total thickness in the range of 30 microns to 80 microns, wherein the sealable and tearable PE film is compatible with the bond to the PE side of the cold formable blister laminate.
In accordance with an embodiment of the present disclosure, the tearable and sealable PE film in the Al-PE laminate of the lid foil has thickness in the range of 15 microns to 40 microns.
In accordance with an embodiment of the present disclosure, the Al-PE laminate of the lid foil showed a higher sealing property of about 0.85 kg/cm while the heat seal based lacquer (HSL) lid foil shows 0.64 kg/cm. The same is evident from Fig. 8 and Fig. 9.
The compact blister pack 700 of the present disclosure will now be described with reference to Fig. 6, Fig. 7A and Fig. 7B. The preferred embodiment does not limit the scope and ambit of the present disclosure.
Fig. 6 illustrates (cross sectional view) the draft angle ? 604 of blister cups 602 formed in a multilayer laminate of a conventional blister pack 600.
Fig. 7A illustrates (cross sectional view) the draft angle ? of the blister cups 702 formed in a multilayer laminate of a blister pack 700 in accordance with one embodiment of the present disclosure.
Fig. 7B illustrates the blister cup (700). The compact blister pack (700) comprises a blister shaped cup (702) and a lid (750). The blister shaped cup being defined four slanted walls (704, 714, 718, 722) and a flat wall (710).
A first slanted wall (704) having a first slanted edge (706) and a second slanted edge (708). The first slanted wall is extended in an operative direction from a flat wall (710) abutting on a mouth (712) of the at least one cup and slanted at an angle ? with respect to a normal to the lid (750). The flat wall (710) being parallel to the lid.
A second slanted wall (714) joining the second slanted edge (708) and a third slanted edge (716). The second slanted wall (714) is extended in an operative direction from the flat wall (710) abutting on the mouth (712) of the at least one cup (702), and slanted at an angle ? with respect to a normal to the lid (750);
A third slanted wall (718) joining the third slanted edge (716) and a fourth slanted edge (720); the third slanted wall (718) extending in an operative direction from the flat wall (710) abutting on the mouth (712) of the at least one cup, and slanted at an angle ? with respect to a normal to the lid (750).
A fourth slanted wall (722) joining the first slanted edge and the fourth slanted edge. The fourth slanted wall extending from an operative direction from the flat wall (710) abutting on the mouth (712) of the at least one cup, and slanted at an angle ? with respect to a normal to the lid (750),
wherein the angle ? is in the range of 15° to 30°.

In case of a conventional cold formable laminate (Fig, 6), the multilayer laminate comprises a first polymer layer, a metal layer, and a structural strengthening layer which can be a second polymer layer. Further, the first polymer layer can be polyvinyl chloride (PVC), the metal employed can be aluminium and the structural strengthening layer can comprise a polymer such as a polyamide polymer component (the second polymer). The product placed within the blister is in contact with the inner layer of the multilayer laminate which is generally the PVC layer. It is observed that the draft angle that can be achieved is in the range of 30o to 75o. The blister cups having a larger draft angle are required to be spaced apart in the blister pack and hence result in a blister pack with a larger size and/or volume, which is not desired.
The multilayer, multibarrier, cold formable blister laminate of the present disclosure has reduced volume, and effectively provides a significantly better water vapour barrier along with mechanical cum impact strength, thereby enhancing the shelf life of the product being packaged with improved barrier against moisture resulting from desiccant infused polymer layer, improved barrier against gases and light; and improved stiffness, mechanical and impact strength resulting from metallocene infused polymer layer which results in significantly lesser deformation of blister cavities during transportation, handling and storage. Also, the multilayer laminate with desiccant enhances the shelf life of certain sensitive products including drug formulations by absorbing and/or adsorbing moisture liberated by the products/ drug formulations during storage as well as the absorbing and/or adsorbing any moisture from ambient air ingression into the packs during storage.
The inventors of the present disclosure have discovered that if the multilayer laminate has good stretchability, it is possible to form blister cups having draft angle ? starting from 15? (as seen in Fig. 7A) in comparison to the conventional multilayer laminates where draft angle ? could not be reduced below 30? and would go upto 75? (as seen in Fig. 6).
It is evident from Fig. 6 and 7A that the size of the blister pack prepared by using the multilayer laminate of the present disclosure is small, wherein the draft angle ? of the blister cups is significantly lesser in comparison to that in the blister cups of the conventional blister pack. In other words, a relatively more number of blister cups are formable in a given area when using the multilayer laminate of the present disclosure in comparison to the number of blister cups formable using the conventional laminate of the same area. This results in a significant reduction in the blister pack size and the total amount (in area) of laminate required for accommodating same number of blister cups when using the multilayer laminate of the present disclosure in comparison to the conventional laminate.
It is found that the use of the modified polyethylene layer leads to improvement in the stretchability of the multilayer laminate and the multilayer laminate does not break or rupture during the cold forming process even when the angle ? is of less than 30? are attempted, typically in the range of 15? to 30?.
The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment, but, are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.
The present disclosure is further described in light of the following experiments which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure. The following experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial scale.
EXPERIMENTAL DETAILS
Example 1: Multilayer, ultra high barrier, cold forming, blister laminate; in accordance with the present disclosure [Metalized OPA/Al/metallocene based PE]
A master batch of Metallocene (1% to 90%) in LLDPE was prepared and extruded with LDPE and HDPE to obtain a film of modified polyethylene layer of thickness 50 µ. The modified polyethylene layer was then laminated on Al foil of thickness 50 µ with ester acrylic adhesive of thickness 5 gsm on inner operative surface of Al foil. The outer operative surface of the Al foil was laminated with metalized OPA (25µ) with the ester acrylic adhesive of thickness 5 gsm having optical density 2.2.
The properties of the resulting laminated material are mentioned in Table 2:
Table 2: Properties of the resulting laminated material of example 1:
Material % Metallocene Impact strength Pin holes
LLDPE (without modification) - LDPE - HDPE film 50 µ 0% Below
300 g Out of 50 blisters, 35 blisters with pin holes and cracking of laminate observed
LLDPE (modified with Metallocene) - LDPE - HDPE 50 µ 50% Between 350 g to 400 g Out of 50 blisters, 5 blisters with pin holes. No cracking of laminate observed.
LLDPE (modified with Metallocene) – LDPE - HDPE 50 µ 60% Between 400 g to 425 g Out of 50 blisters, 0 blisters with pin holes. No cracking of laminate observed.
LLDPE- Linear low-density polyethylene, LDPE- low-density polyethylene, HDPE- High-density polyethylene
From Table 2 it is clear that as % of metallocene increases (up to 60 mass %), the impact strength of PE film was significantly increased, moreover, there was a significant reduction in the number of pinholes in blisters with increase in metallocene content in the PE film.
In another variant of example 1, a multilayer laminate was formed by laminating 50 microns of metallocene modified PE with 50 microns of Aluminum foil on the inner operative surface of aluminum foil and laminating 25 microns of metalized OPA film on the outer operative surface of Aluminum foil.
The optical density of multilayer laminate was found to 2.4.
The moisture vapor transmission rate (MVTR) of the formed blister from this ultra high barrier laminate was 0.0001 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
This blister showed improved stiffness, mechanical and impact strength.
Example 2: Multilayer, ultra high barrier, cold forming, blister laminate, in accordance with the present disclosure [Metalized OPA/Al/Desiccant based PE]
Desiccant material like CaCO3 was mixed with LDPE to form a master batch of desiccant PE. Desiccant PE (50 µ) film was co-extruded with LDPE, LLDPE and HDPE. In the middle layer, a desiccant master batch (1 mass% to 70 mass%) was added.
To study the effect of desiccant on the performance of PE, laminate consisting of unmodified PE 50µ/ Al foil 50µ/ metalized OPA, 25µ PE modified with 2% desiccant 50µ/ Al foil 50µ/ metalized OPA 25µ and PE modified with 33% desiccant 50µ/ Al foil 50µ/ metalized OPA 25µ were tested both as flat laminate 10cm x 10 cm (5 no.) and blisters (5 no.) formed from the laminate. Flat laminate and blisters without sealing were exposed to 40% RH and 75°C in the humidity chamber. The weight of the flat films and blisters were recorded before exposure and the weight of the flat films and the blisters was recorded after 1 day and 6 day exposure and also continued till it reached 70% of the saturation.
Table 3: Percent weight gain studies on desiccant infused laminate of example 2 along with its cold formed blisters
Material % desiccant master batch Weight gain (%)
Flat laminate Weight gain (%)
Cold formed laminate
PE 50µ/ AL foil 50 µ/ metalized OPA 25µ 0% 0.15% after 1 day 0.08% after 1 day
PE 50µ/ AL foil 50µ/ metalized OPA 25µ 0% 0.20% after 6 days 0.12% after 6 days
Desiccant PE 50 µ/ AL foil 50µ/ metalized OPA 25µ 2% 0.19% after 1 day 0.09% after 1 day
Desiccant PE 50 µ/ AL foil 50µ/ metalized OPA 25µ 2% 0.29% after 6 days 0.15% after 6 days
Desiccant PE 50 µ/ AL foil 50 µ/ metalized OPA 25µ 33% 1.65% after 1 day 1.53% after 1 day
Desiccant PE 50 µ/ AL foil 50 µ/ metalized OPA 25µ 33% 1.85% after 6 days 1.74% after 6 days
OPA- Oriented polyamide, m-OPA- metallized oriented polyamide, PE- Polyethylene
From the examples, it was observed that blisters formed from desiccant modified multilayer blister laminate showed a significantly higher weight gain compared to blisters formed from multilayer laminate with unmodified PE. Multilayer laminate with PE containing 2% desiccant did not show any appreciable weight gain as compared to multilayer laminate with 33% of desiccant in PE.
The moisture vapor transmission rate (MVTR) of the formed blister from this ultra high barrier laminate was 0.0001 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Table 4: Weight gain studies of desiccant modified cold formable laminate when exposed to 40?C and 75% RH
Week % weight gain for flat film % weight gain for formed blister
1 16.25 19.79
2 17.48 22.41
3 18.69 25.28
4 19.92 28.17
5 21.3 31.01
6 22.37 33.79
7 23.57 36.54
8 24.79 39.22
9 25.99 41.87
10 27.23 44.53
11 28.44 47.15
12 29.67 49.74
13 30.83 52.32
14 32 54.91
15 33.54 57.43
20 38.78 68.91
25 44.34
30 49.89
35 55.28
40 60.61
45 66.95
Weight gain studies of desiccant in cold formable laminate of the present disclosure at accelerated conditions of 40?C and 75% RH showed that Flat film of the laminate required more number of weeks to reach 70% weight gain compared to formed blister from the same material. When material formed into blisters, desiccant material actively absorbed and/or adsorbed moisture due to thinning of the laminate during cold forming and showed weight gain higher than flat sheet of same material.
Example 3: Multilayer, multibarrier, cold formable blister laminate, in accordance with the present disclosure [barrier coated transparent OPA/Al/ Modified PE with metallocene]
Multilayer laminate was formed from 50 microns of transparent modified polyethylene infused with metallocene laminated on the first operative side of aluminum foil of 50 microns and 25 microns of transparent bi-axially oriented polyamide (OPA) was laminated with the second operative side of aluminum foil. The outer side of transparent OPA was coated with a PVDC coating of 3 gsm. Multilayer laminate was then formed in blisters of cavity dimensions 35mm x 21 mm x 8.2 mm.
The moisture vapor transmission rate (MVTR) of the formed blister from this multibarrier laminate was 0.0008 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Example 4: Multilayer, multibarrier, cold formable blister laminate, in accordance with the present disclosure [barrier coated OPA/Al/ Modified PE with metallocene and desiccant]
Multilayer laminate was formed from 50 microns of transparent modified polyethylene infused with both 60% metallocene and 40 % desiccant wherein the metallocene sublayer was on the inner side which sealed with lidding foil and the desiccant sub layer was below the metallocene sublayer. This modified Polyethylene was laminated on the inner operative side of aluminum foil of 50 microns and 25 microns of transparent bi-axially oriented polyamide (OPA) was laminated with the outer operative side of aluminum foil. The outer side of transparent OPA was coated with a PVdC coating of 3 gsm. Multilayer laminate was then formed in blisters of cavity dimensions 35mm x 21 mm x 8.2 mm.
The moisture vapor transmission rate (MVTR) of the formed blister from this multibarrier laminate was 0.002 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Examples 5 to 18: Effect of Optical density of the metalized oriented polyamide on WVTR of the multilayer, ultra multibarrier, cold forming, multilayer blister laminates, in accordance with the present disclosure:
Multilayer laminates were formed in accordance with the details of each layer as provided in below Table 5.
Table 5: Details of Multilayer laminates for examples 5 to 18:
Example No. Thickness of polyethylene (modified with metallocene) layer (microns) Thickness of aluminum layer (microns) Thickness of metallized OPA layer (microns) Optical Density of the laminate MVTR gm/pkg/day of the laminate
5 100 50 25 2.18 0.0001
6 50 50 25 1.96 0.0002
7 50 50 50 2.25 0.0001
8 50 50 15 2.4 0.00009
9 30 50 25 2.3 0.00009
10 75 50 25 2.2 0.0001
11 150 50 25 2.4 0.00009
12 50 40 25 2.4 0.00009
13 50 60 25 2.2 0.0001
14 50 45 25 1.96 0.0002
15 100 45 25 2.4 0.00009
16 180 50 25 2.3 0.00009
17 50 50 75 2.35 0.00009
18 50 50 30 2.4 0.0002
OPA- Oriented polyamide, m-OPA- metallized oriented polyamide, MVTR-moisture vapour transmission rate
From Table 5, it is observed that when the optical density of the oriented polyamide increases from 1.96 to 2.4, WVTR value of laminate showed improvement from gm/pkg/day of the laminate to 0.00009 gm/pkg/day of the laminate.
Example 19: Multilayer, multibarrier cold formable blister laminate according to present disclosure (AlOx coated OPA/Al foil/ PE)
A multilayer cold forming laminate was formed by laminating 50 microns of metallocene modified PE to Al foil on the inner operative surface of Al foil and AlOx coated OPA of 25 microns thickness on the outer operative surface of Al foil.
The moisture vapor transmission rate (MVTR) of the formed blister from this multibarrier laminate was 0.01 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Example 20: Multilayer, multibarrier cold formable blister laminate according to present disclosure (PVC/ AlOx coated OPA/Al foil/ PE)
A multilayer cold formable blister laminate was formed by laminating on outer operative surface of Al foil of 50 microns with AlOx coated OPA of 25 microns and 50 microns PE (60% metallocene) on the inner operative surface of Al foil. PVC of 60 microns thickness is then laminated on AlOx coated OPA.
The moisture vapor transmission rate (MVTR) of the formed blister from this multibarrier laminate was 0.009 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Example 21 to 32: Multilayer, multibarrier, cold formable blister laminate having plurality of polymer layers in accordance with the present disclosure
Table 6: Multilayer laminate formed as per examples 20 to 32
Sr. No. Additional second polymer layer Additional second polymer layer Second polymer layer (above intermediate layer) Intermediate metal layer First polymer layer (below intermediate layer) Additional first polymer layer below first polymer layer
21 ----- ----- OPA 25 microns Al foil 150 microns PE 50 microns, Metallocene modified (60%) -------
22 ----- ----- APET 250 microns Al foil 50 microns PE 50 microns Metallocene modified (60%) ------
23 --------- OPA 25 microns metallized OPA 25 microns Al Foil 50 microns PE 50 microns Metallocene modified (60%) ---------
24 ------ PVC 60 microns metallized OPA 25 microns Metallized Al foil 50 microns PE 50 microns, metallocene modified (60%)
25 ------ PVC 60 microns OPA 25 microns Metallized Al Foil 50 microns PP 60 microns
26 ------ APET 250 microns OPA 25 microns Metallized Al foil 50 PE 50 microns Metallocene modified (60%) ----------
27 ------- APET 250 microns OPA 25 microns Metallized Al foil 50 microns PP 60 microns ---------
28 -------- --------- APET 250 microns Al Foil 50 microns PE (metallocene modified) 50 microns (60%) PVC 60 microns
29 ------- APET 150 microns OPA (PVdC coated 3 GSM) Al foil 50 microns PE (60% metallocene modified) 60 microns
30 ------- PE (metallocene and desiccant modified) 60 microns OPA 25 (metallized) Al foil 50 microns PE (60% metallocene modified) 100 microns PP (metallocene modified) 60 microns
31 ------- PP 60 microns OPA 25 microns metallized Al foil 50 microns PP 60 microns PE 100 microns metallocene (60%)
32 PP (40% desiccant modified) 60 microns PVC 60 microns metallized OPA 25 microns Al Foil 50 microns PP (60% metallocene modified) 60 microns PE (40% desiccant modified) 50 microns
MD- Machine Direction, TD- Transverse Direction, OPA- Oriented polyamide, m-OPA- metallized oriented polyamide, AlOx coated OPA- Aluminum Oxide coated OPA, Al foil- Aluminum foil, PVC- polyvinyl chloride, mPVC- metallized PVC film, PE- Polyethylene, PP- Polypropylene, PET- Polyethylene terephthalate, APET- Amorphous Polyethylene terephthalate, COC- Cycloolefin copolymer, Number beside the polymer or Aluminum foil in Table indicate thickness of the polymer layer or intermediate metal foil
Example 33: Multilayer, ultra high barrier, cold formable blister laminate, in accordance with the present disclosure [metallized OPA/Al/metallocene modified PP]
Multilayer laminate was formed from 60 microns of transparent modified polypropylene infused with metallocene was laminated to first operative side of aluminum foil of thickness 50 microns and with 25 microns of metallized bi-axially oriented polyamide (OPA) laminated to the outer operative side of aluminum foil.
The moisture vapor transmission rate (MVTR) of the formed blister from this ultra high barrier laminate was 0.0001 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Example 34: Multilayer cold formable ultra high barrier blister laminate in accordance with the present disclosure [Metallized PVC/ OPA/ Al foil/ PE (metallocene modified)]
A multilayer cold formable blister laminate was formed by laminating transparent OPA of thickness 25 microns to second operative surface of Al foil of thickness 50 microns and metallocene modified PE of thickness laminated to first operative surface of the Al foil. Further, metallized PVC film of thickness 30 microns laminated above transparent OPA.
The moisture vapor transmission rate (MVTR) of the formed blister from an ultra-high barrier laminate is 0.00009 gm/pkg/day when tested using Test Method 671 at 40?C and 75% RH wherein the pkg (package) tested, comprises 3 blister packs, wherein each blister pack with dimensions 105mm x 90mm x 6.9mm comprises 10 blister cavities with each blister cavity having dimensions 23.7mm x 15.5mm x 6.9mm.
Evaluation and Testing of mechanical properties of experimental examples
Mechanical properties – Tensile strength at Peak, Percent elongation at Peak, Impact strength and Cavity dome height at bursting of experimental examples:
Multilayer Laminates of the present disclosure were tested for mechanical properties comprising Tensile strength, Percent Elongation, Impact strength and Cavity dome height at bursting using methods prescribed in international testing standards.
Tensile strength at Peak and Percent Elongation at Peak testing methodology:
Tensile strength displays the ability of the material to withstand the maximum tensile stress and % Elongation shows ability of material when stretched at the maximum load at the yield point before breaking. The Tensile strength at peak (in Kg/cm2) and Percent Elongation at peak (in %) of the multilayer laminates in present disclosure were tested according to the following methodology.
Testing was done in accordance to and specified in International Standard ASTM D 822. Samples of multilayer laminates were subjected to Tensile strength at peak (in Kg/cm2) and % Elongation at peak (in %) tests in both machine direction (MD) as well as transverse direction (TD). According to the method, samples taken from the multilayer laminates were tested on Computerized single screw Tensile tester (NX International Equipment Ltd.) with International Equipments Limited make load indicator and Sensortronics make load cell. Sample strips of 10 mm (width) x 100 mm (length) from the multilayer laminates were taken and subjected to test with testing machine parameters set at load limit 22.5 Kg and travelling limit 900 mm.
Impact strength testing methodology:
Impact strength is a measure of materials ability to resist impact. The impact strength was tested in accordance to International Standard ASTM D 1709. Impact strength of multilayer laminates was measured using equipment from International Equipments Limited. Circular Samples of 16mm diameter were subjected to impact of known amount of weight from a height of 660 mm ± 10 mm.
Testing methodology for Laminate drawability by measuring height of cavity formed at Bursting pressure:
Height of the formed cavity at bursting provides information about the ability of material drawability and forming a cavity at pressure of 6 bar before bursting. The height of dome of the formed cavity is measured which gives the maximum bulge (dome) height of the formed cavity. Testing was carried out in accordance to Standard DIN 51220 using equipment S-18623 from Frank PTI Germany with sample testing area of 50 cm2 and maximum bulging (formed cavity) height of 30 mm.
Laminates from above experimental examples were tested for the following mechanical properties:
1. Tensile strength at Peak in machine direction (MD) using ASTM D 822, Samples were prepared in strip form of dimensions 10mm x 100 mm strips
2. Tensile strength at Peak in Transverse direction (TD) using ASTM D 822, Samples were prepared 10mm x 100 mm strips and subjected to load.
3. % Elongation at Peak in Machine Direction (MD) using ASTM D 822, Samples were prepared 10mm x 100 mm strips and subjected to load.
4. % Elongation at Peak in transverse Direction (TD) using ASTM D 822, Samples were prepared 10mm x 100 mm strips and subjected to load.
5. Impact Strength determined using ASTM D 1709 by cutting samples of diameter of 60 mm and subjected to load from 600 mm± 10 mm height.
6. Height of the formed cavity at bursting provides information about the ability of material drawability and forming a cavity at pressure of 6 bar before bursting carried out using DIN 51220 by preparing samples of 50 cm2 and subjecting them to 6 bar pressure and formation of cavity depth of up to 30 mm
Results of the testing of samples of experimental examples are depicted in Table 7.
Table 7: Test Results of Mechanical properties of Multilayer laminates in accordance with the present disclosure (experimental examples)
Ex. No Additional second polymer layer
601 (µ) Additional second polymer layer
401 (µ) Second polymer layer
201 (µ) Inter-mediate layer
101 (µ) First polymer layer
301 (µ) Additional first polymer layer
501 (µ) Additional first polymer layer
701 (µ) Tensile property at MD Kg/cm2 Tensile property at TD Kg/cm2 Percent Elongation at Peak in MD Percent Elongation at Peak in TD Impact strength (g) Cavity
Height
at
bursting
(mm)
1 No No 25 mOPA 50 Al 50 PE (60% metallocene modified) No No 665 634 23.48 23.48 1620 26.3
2 No No 25 OPA 50 Al 50 PE desiccant modified No No 600 600 22.48 17.23 1425

25.2
3 No No 25 OPA (PVdC coated) 50 Al 50 PE (60% metallocene modified) No No 632 632 23.12 23.12 1580 25.2
4 No No 25 OPA (PVdC coated 50 Al 50 PE (60% metallocene modified and 40% desiccant) No No 615 597 22.88 23.71 1540
25
5 No No 25 mOPA 50 Al 100 PE (60% metallocene modified) No No 710 680 24.67 24.56
1660 26.8
7 No No 50 mOPA 50 Al 50 PE (60% metallocene modified) No No 694 679 22.89 23.89 1680 27.2
8 No No 15 m OPA 50 Al 50 PE metallocene modified No No 635 623 22.34 22.32 1610 26
9 No No 25 m OPA 50 Al 30 PE metallocene modified No No 643 643 22.89 22.56 1610 26
10 No No 25 m OPA 50 Al 75 PE metallocene modified No No 689

665 23.78 23.64 1640 27.2
11 No No 25 mOPA 50 Al 150 PE metallocene modified No No 815 788 26.24 26.05 1775 27.6
12 No No 25 m OPA 40 Al 50 PE metallocene modified No No 634 632 23.36 23.23 1620 26.1
13 No No 25 m OPA 60 Al 50 PE metallocene modified No No 678
653 24.24 24.03 1620 26.6
14 No No 25 m OPA 45 Al 50 PE metallocene modified No No 667 667 23.48 23.48 1620 26.3
15 No No 25 m OPA 45 Al 100 PE metallocene modified No No 688 675 23.92 24.01 1650 26.6
16 No No 25 m OPA 50 Al 180 PE metallocene modified No No 868 865 27.47 27.31 1700 28.2
17 No No 75 m OPA 50 Al 50 PE metallocene modified No No 725 725 22.56 22.56 1725 27.6
18 No No 30 OPA 50 Al 50 PE (60% metallocene modified) No No 645 645 22.98 22.73
1700 26.5
19 No No 25 OPA (AlOx coated) 50 Al 50 PE (60% metallocene) No No 645 645 22.92 22.72 1580 25
20 No 60 PVC 25 OPA (AlOx coated) 50 Al 50 PE (60% metallocene) No No 640 643 23.46 23.34 1640 25.7
21 No No 25 OPA 150 Al 50 PE (60% metallocene modified) No No 945 945 19.67 20.51 1920
>30
22 No No 250 APET 50 Al 50 PE
(metallocene modified) N0 No 595 567 18.43 18.43 1700 >30
23 No 25 m OPA 25 OPA 50 Al 50 PE (60% metallocene modified) No No 689 673 23.48 23.48 1725 27.2
24 No 60 m PVC 25 m OPA 50 Al 50 PE metallocene modified No No 745 734 23.82 23.67 1660 26.1
25 No 60 PVC 25 m OPA 50 Al 60 PP No No 697 683 22.88 22.73 1680 25.6
26 No 250 APET 25 m OPA 50 Al 50 metallocene modified PE No No 689 676 17.48 17.33 1960 >30
27 No 250 APET 25 m OPA 50 Al 60 PP No No 676 676 16.23 16.21 1740 >30
28 No No 250 APET 50 Al 50 metallocene modified PE 60 PVC No 715 715 16.83 16.83 1740 >30
29 No 150 APET 25 OPA (PVdC coated) 50 Al 50 PE (60% metallocene modified) No No 656
645 16.14 16.14 1700 >30
30 60 PE (metallocene and desiccant modified) 25 m OPA 50 Al 100 PE (metallocene modified) 60 PP (metallocene modified) No 765 745 20.45 20.45 1760 26.6
31 No 60 PP 25 m OPA 50 Al 60 PP 100 PE metallocne modified No 878 853 25.67 25.56 1760 27.3
32 60 PP (40% desiccant modified) 60 metallized PVC 25 OPA 50 Al 60 PP (60% metallocene modified) 50 PE (60% metallocene and 40% desiccant modified) No 951 942 28.71 28.53 1940 27.8
33 No No 25 m OPA 50 Al 60 PP No No 532 518 19.16 19.02 1440 25.2
34 No 30 mic PVC 25 mOPA 50 Al 50 PE (60% metallocene modified) No No 688 673 24.54 2.4.34 1780 >30
35 No No 23 PET 50 Al 50 PE (60% metallocene modified) No No 697 676 23.48 23.34 1620 26.1
36 No 60 PE (metallocene modified) 25 m OPA 50 Al 100 PE (metallocene modified) 60 PP No 978 957 26.57 26.43 1960
27.6
37 No 40 PP 25 OPA 50 Al 50 PE No No 738
723 20.34 20.34 1640 27.6
MD- Machine Direction, TD- Transverse Direction, OPA- Oriented polyamide, m-OPA- metallized oriented polyamide, AlOx coated OPA- Aluminum Oxide coated OPA, Al foil- Aluminum foil, PVC- polyvinyl chloride, mPVC- metallized PVC film, PE- Polyethylene, PP- Polypropylene, PET- Polyethylene terephthalate, APET- Amorphous Polyethylene terephthalate, COC- Cycloolefin copolymer, Number beside the polymer or Aluminum foil in Table indicate thickness of the polymer layer or intermediate metal foil
For understanding the improvement in the mechanical properties of Multilayer laminates of present disclosure, same tests were replicated on samples taken from commercially available conventional Alu-Alu cold formable blister multilayer laminate. Test results of the mechanical properties tested for the conventional multilayer laminate are tabulated in Table 8.
Table 8: Test Results of Mechanical properties of commercially available conventional Multilayer laminate (Alu-Alu old formable blister laminate)
Sr.
No Additional second polymer layer 601
(µ) Additional second polymer layer
401 (µ) Second polymer layer 201 (µ) Inter-
mediate layer 101 (µ) First polymer layer 301 (µ) Additional first polymer layer 501 (µ) Additional first polymer layer 701 (µ) Tensile property at MD Kg/cm2 Tensile property at TD Kg/cm2 Percent Elong-ation at MD Percent Elong-ation at TD Impact strength (g) Height at bursting (mm)
1 No No 25 OPA 50 Al 60 PVC No No 485 475 12.45 12.45 1440 24
MD- Machine Direction, TD- Transverse Direction, OPA- Oriented polyamide, m-OPA- metallized oriented polyamide, AlOx coated OPA- Aluminum Oxide coated OPA, Al foil- Aluminum foil, PVC- polyvinyl chloride, mPVC- metallized PVC film, PE- Polyethylene, PP- Polypropylene, PET- Polyethylene terephthalate, APET- Amorphous Polyethylene terephthalate, COC- Cycloolefin copolymer, Number beside the polymer or Aluminum foil in Table indicate thickness of the polymer layer or intermediate metal foil

Based on comparative analysis of mechanical properties of multilayer laminates of present disclosure with the mechanical properties of commercially available, conventional multilayer laminates, it can be easily deduced that the multilayer laminates of the present disclosure have significantly enhanced mechanical properties.

Sealable and tearable Lid foil development for sealing with multilayer, Metallized OPA and PE based ultra high barrier cold formable blister laminate, in accordance with the present disclosure
Sealable and tearable PE film (25µ) made by extruding a mixture of HDPE, LLDPE and LDPE. One of the mixture comprised co-extrusion with 50% HDPE, 30 % LLDPE and 20% LDPE. 25 microns tearable and sealable PE formed by co-extrusion the mixture was laminated with Al foil 25 microns using polyurethane based adhesive of thickness 3 gsm. This laminate acts as a lidding material for PE-based cold-forming laminate as per one of the embodiments of present disclosure (PE 50 microns/ Al 45 microns/ 25 microns metalized OPA) which makes the blister pack completely free of PVC. Because of the presence of PE in the lidding material, it had a very good sealing property with PE based cold forming laminate.
A conventional PE based HSL (heat seal lacquer) of 3 gsm thickness was coated on Al foil to create the lidding foil which was then used to seal the blister pack formed with PE-based cold-forming laminate as per one of the embodiments of present disclosure (PE 50 microns/ Al 45 microns/ 25 microns metalized OPA).
The conventional PE based HSL (heat seal lacquer) coated Al foil exhibited sealing strength of 0.64 Kg/cm with PE 50 microns/ Al 45 microns/ 25 microns metalized OPA cold formable multi-layer laminate, whereas sealable and tearable Al 25 microns/25 microns PE laminate as lidding foil exhibited superior sealing strength of 0.85 Kg/cm with 50 microns PE/ Al 45 microns/ 25 microns metalized OPA cold formable multi-layer laminate
An experiment comprising blister packs wherein moisture laced dummy placebo tablets were blister packaged in the above described multi layered laminate and sealed using the PE based HSL (heat seal lacquer) coated Al foil as well as sealable and tearable Al 25 microns/25 microns PE laminate lidding foil and subjected to 40°C / 75% RH for 24 hours which led to ballooning of packs. Figure 9 illustrates an image of sealing integrity of blister pack with sealable and tearable Al Foil 25 microns/ PE film 25 microns used as lidding foil. Figure 10 illustrates an image of sealing integrity of blister pack with cm with PE based HSL lacquer based lidding foil. A comparison of the seal strength of PE based HSL coated Al lidding foil and Al foil (25 microns)/ PE film (25 microns) is provided in below Table 9.
Sealable and tearable Al foil 25µ/ PE 25µ not only exhibited better seal strength over conventional PE based HSL coated Al lidding foil but also superior sealing integrity of the blister pack subsequent to ballooning test of the packs where the bulging of the packs resulted into opening of sealed areas in case of blister packs sealed with the conventional HSL coated Al lidding foil.
Table 9: Comparison of seal strength of PE based HSL coated Al lidding foil and Al foil (25 microns)/ PE film (25 microns):
Sr. No. Complex Lidding material complex Seal strength (Kg/cm)
1 50 microns PE/ 45 microns Al foil/ 25 microns metalized OPA 25 microns Al foil/ 25 microns PE compatible to seal with PE 0.85
2 50 microns PE/45 microns Al foil/ 25 microns metalized OPA Al foil coated with PE based HSL 0.64
Fig. 10A to 10B illustrates micrographs of sections of multilayer laminate in Flat film form and Dome forms. Micrograph study provide thickness determination of individual layer in the laminate. These graphs indicate thickness of individual layer in the laminate. Micrograph analysis was done by cutting thin section of laminate along thickness side and then viewed under microscope, for example- Fig. 10A represent laminate structure 25 m OPA/ 50 Al/ 50 PE, so first micrograph represents for PE which is showing thickness 55 microns likewise each layer thickness was found out. Fig. 10A illustrates micrograph of section of multilayer laminate in flat film form Flat film-25 µ mOPA/ 50µ Al Foil/ 50µ PE (Three-layer structure) (Example 1 and 4) in accordance with the present disclosure. Fig. 10B illustrates micrograph of section of multilayer laminate in dome of the formed cavity of 25µ mOPA/ 50µ Al foil/ 50µ PE (Three-layer structure) (Example 1 and 4) in accordance with the present disclosure. Fig. 10C illustrates micrograph of section of multilayer laminate in Flat surface of the laminate 25µ m OPA/ 25µ OPA/ 50µ Al foil/ 50 µ PE (4-layer structure) (Example 23) in accordance with the present disclosure. Fig. 10D illustrates micrograph of section of multilayer laminate in dome of the formed cavity in 25µ m OPA/ 25µ OPA/ 50µ Al foil/ 50µ PE (4-layer structure) (Example 23) in accordance with the present disclosure. Fig. 10E illustrates micrograph of section of multilayer laminate in Flat surface of the laminate 60µPVC/ 25µ OPA/50µ Al foil/ 50µ PE (4-layer structure) (Example 24) in accordance with the present disclosure. Fig. 10F illustrates micrograph of section of multilayer laminate in Dome of the formed cavity in 60µ PVC/25µ OPA/ 50µ Al foil/ 50µ PE (4-layer structure) (Example 24) in accordance with the present disclosure. Fig. 10G illustrates micrograph of section of multilayer laminate in Flat surface of 250µ APET/ 25µ m OPA/ 50µ Al foil/ 50µ PE (4-layer structure) (Example 26) in accordance with the present disclosure. Fig. 10H illustrates micrograph of section of multilayer laminate in dome of the cavity of the 250µ APET/ 25µ m OPA/ 50µ Al foil/ 50µ PE (4-layer structure) (Example 26) in accordance with the present disclosure. Fig. 10I illustrates micrograph of section of multilayer laminate in flat surface of 150µ APET/ 25 µ PVdC coated OPA/ 50µ Al foil/ 50µ PE (4-layer structure) (Example 29) in accordance with the present disclosure. Fig. 10J illustrates micrograph of section of multilayer laminate in dome of the cavity of 150µ APET/ 25µ PVdC coated OPA/ 50µ Al foil/ 50µ PE (4-layer structure) (Example 29) in accordance with the present disclosure. Fig. 10K illustrates micrograph of section of multilayer laminate in flat surface of 25µ OPA/ 150µ Al foil/ 50µ PE (3-layer structure) (Example 21) in accordance with the present disclosure. Fig. 10L illustrates micrograph of section of multilayer laminate in dome of cavity of 25µ OPA/ 150µ Al foil/ 50µ PE (Example 21) in accordance with the present disclosure.
TECHNICAL ADVANCEMENTS
The present disclosure described herein above has several technical advantages including, but not limited to, the realization of a multilayer, multibarrier, cold forming, blister laminate that has
• reduced volume resulting from compactness of blister dimensions accomplished from the improved stretchability;
• effectively provides water vapour barrier against both the internally liberated moisture including residual moisture within the product and blister cavity as well as from any moisture ingression from the outside ambient environment depending upon the layer combination in the multilayer laminate,
• has improved barrier against moisture, gases and light;
• enhanced blister pocket size formation and dimensions including increased depth of blister cavities accomplished from improved laminate drawability
• has improved stiffness, mechanical and impact strength resulting in lower deformation of blister cavities during transportation, handling and storage in turn resulting in lower damage to the product, particularly fragile products with large dimensions; and
• enhances the shelf life of certain products which are highly sensitive to moisture by dual mechanism comprising a) absorbing and/or adsorbing the residual moisture within the blister cups or absorption and/or adsorption of the moisture liberated from within the product and b) capturing the moisture ingression which may happen from the outside through any sections of improper sealing between the cold formable blister and lid component.
Throughout this specification the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results. While certain embodiments of the disclosure have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosure. Variations or modifications to the formulation of this disclosure, within the scope of the disclosure, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this disclosure.
The numerical values given for various physical parameters, dimensions and quantities are only approximate values and it is envisaged that the values higher than the numerical value assigned to the physical parameters, dimensions and quantities fall within the scope of the disclosure unless there is a statement in the specification to the contrary.
While considerable emphasis has been placed herein on the specific features of the preferred embodiment, it will be appreciated that many additional features can be added and that many changes can be made in the preferred embodiment without departing from the principles of the disclosure. These and other changes in the preferred embodiment of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation. ,CLAIMS:WE CLAIM:
1. A multilayer, multibarrier, cold formable blister laminate comprising:
(a) at least one first polymer layer having thickness in the range of 10 microns to 300 microns;
wherein said first polymer layer is selected from the group consisting of polyethylene (PE) layer, modified polyethylene (m-PE) layer, polypropylene (PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, and modified cyclic olefin co-polymer (m-COC) layer;
(b) at least one intermediate metal layer having thickness in the range of 10 microns to 200 microns having a first operative surface and a second operative surface; and
(c) at least one second polymer layer having thickness in the range of 10 microns to 300 microns;
wherein said second polymer layer is selected from the group consisting of polyethylene (o-PE) layer, modified polyethylene (m-PE) layer, polypropylene (o-PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, modified cyclic olefin co-polymer (m-COC) layer, polyethylene terephthalate layer (PET), and modified polyethylene terephthalate (m-PET) layer;
wherein said at least one first polymer layer is disposed on said first operative surface and said at least one second polymer layer is disposed on said second operative surface; and
wherein the water vapour transmission rate (WVTR) of said laminate is in the range of 0.00009 gm/pkg/day to 0.02 gm/pkg/day at 40°C and 75% RH.
2. The laminate as claimed in claim 1, wherein said at least one first polymer layer, said at least one intermediate layer and said at least one second polymer layer are adhered to each other by a method selected from extrusion lamination and adhesive lamination.
3. The laminate as claimed in claim 2, wherein said adhesive lamination is performed by forming an adhesive layer on the layers selected from said first polymer layer, said intermediate metal layer and said second polymer layer, having thickness in the range of 1 gsm to 10 gsm; said adhesive layer is selected from the group consisting of polyester based adhesive layer, polyurethane based adhesive layer, and polyacrylic based adhesive layer.
4. The laminate as claimed in claim 1, wherein said intermediate metal layer comprises at least one metal selected from the group consisting of aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
5. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is a polyethylene layer, and said polyethylene layer being at least one selected from the group consisting of high density polyethylene (HDPE) polymer layer, medium density polyethylene polymer layer, low density polyethylene (LDPE) polymer layer, linear low-density polyethylene (LLDPE) polymer layer, linear polyethylene polymer layer, chlorinated polyethylene polymer layer, cross-linked polyethylene polymer layer, ultra-high molecular weight polyethylene (UHMWPE) polymer layer and polyethylene copolymer with styrene-butadiene layer.
6. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is a modified polyethylene layer;
said modified polyethylene layer being selected from a metal oxide coated polyethylene layer, a barrier polymer coated polyethylene layer, a metallized polyethylene layer, a metallocene modified polyethylene polymer layer and a desiccant modified polyethylene polymer layer;
said modified polyethylene layer being obtained by a method selected from
(a) coating a metal oxide on a polyethylene sheet to obtain said metal oxide coated polyethylene layer, wherein said metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx;
(b) coating a barrier polymer on a polyethylene sheet to obtain said barrier polymer coated polyethylene layer having thickness of said polymer coating is in the range of 1 gsm to 10 gsm; wherein said barrier polymer being selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and Heat seal lacquer (HSL);
(c) depositing a metal on a polyethylene sheet to obtain said metallized polyethylene layer having an optical density in the range of 0.5 to 2.5; wherein said metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag);
(d) adding metallocene to a polyethylene polymer in an amount in the range of 1 mass% to 90 mass% followed by extruding or laminating to obtain said metallocene modified polyethylene polymer layer; and
(e) adding desiccant to a polyethylene polymer in an amount in the range of 1 mass% to 70 mass% followed by extruding or laminating to obtain said desiccant modified polyethylene polymer layer; said desiccant being at least one selected from the group consisting of silica, calcium chloride, calcium carbonate, calcium oxide, magnesium oxide, magnesium chloride, sodium sulphate, dry aluminum chloride, aluminum oxide, molecular sieves, and activated charcoal.
7. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is a polypropylene layer, said polypropylene layer being at least one selected from the group consisting of polypropylene homopolymer layer, polypropylene random copolymer layer and polypropylene impact copolymer layer.
8. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is a modified polypropylene layer;
said modified polypropylene layer being selected from a metal oxide coated polypropylene layer, a polymer coated polypropylene layer, a metallized polypropylene layer, a metallocene modified polypropylene polymer, and desiccant modified polypropylene polymer;
said modified polypropylene layer being obtained by a method selected from
(a) coating a metal oxide on a polypropylene sheet to obtain said metal oxide coated polypropylene layer, wherein said metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx;
(b) coating a barrier polymer on a polypropylene sheet to obtain said barrier polymer coated polypropylene layer having thickness of said polymer coating is in the range of 1 gsm to 10 gsm; wherein said barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc) polyvinyl alcohol (PVOH) and heat seal lacquer (HSL);
(c) depositing a metal on a polypropylene sheet to obtain said metallized polypropylene layer having an optical density in the range of 0.5 to 2.5; wherein said metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag);
(d) adding metallocene to a polypropylene polymer in an amount in the range of 1 mass% to 90 mass% followed by extruding or laminating to obtain said metallocene modified polypropylene polymer layer; and
(e) adding desiccant to a polypropylene polymer in an amount in the range of 1 mass% to 70 mass% followed by extruding or laminating to obtain said desiccant modified polypropylene polymer layer; said desiccant being at least one selected from the group consisting of silica, calcium chloride, calcium carbonate, calcium oxide, magnesium oxide, magnesium chloride, sodium sulphate, dry aluminum chloride, aluminum oxide, molecular sieves, and activated charcoal.
9. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is selected from a modified polyethylene layer and a modified polypropylene layer, wherein
(a) said modified polyethylene layer has a plurality of strata selected from the group consisting of virgin polyethylene stratum, desiccant modified polyethylene stratum, metallocene modified polyethylene stratum, metal oxide coated polyethylene stratum, polymer coated polyethylene stratum, and metallized polyethylene stratum; and
(b) said modified polypropylene layer has a plurality of strata selected from the group consisting of virgin polypropylene stratum, desiccant modified polypropylene stratum, metallocene modified polypropylene stratum, metal oxide coated polypropylene stratum, polymer coated polypropylene stratum, and metallized polypropylene stratum.
10. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is an oriented polyamide layer, said oriented polyamide layer being selected from semi-crystalline polyamide layer, amorphous polyamide layer, and a copolymer thereof; said semi-crystalline polyamide is at least one selected from the group consisting of Nylon 6, Nylon 6,6, Nylon 6,9, Nylon 6,12, Nylon 12,12, and a copolymer thereof.
11. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is a modified oriented polyamide (OPA) layer;
said modified oriented polyamide (OPA) layer being selected from a metallized oriented polyamide layer, a metal oxide coated oriented polyamide layer, and a barrier polymer coated oriented polyamide layer;
said modified oriented polyamide (OPA) layer being obtained by a method selected from
(a) depositing a metal on an oriented polyamide (OPA) sheet to obtain said metallized oriented polyamide layer having an optical density in the range of 0.5 to 2.5; wherein said metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag);
(b) coating of a metal oxide on an oriented polyamide (OPA) sheet to obtain said metal oxide coated oriented polyamide layer, wherein said metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx; and
(c) coating a barrier polymer on an oriented polyamide (OPA) sheet to obtain said barrier polymer coated oriented polyamide layer having thickness of said polymer coating is in the range of 1 gsm to 10 gsm; wherein said barrier polymer being selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and Heat seal lacquer (HSL).
12. The laminate as claimed in claim 1, wherein said second polymer layer is a polyethylene terephthalate (PET) layer, and said polyethylene terephthalate (PET) layer is at least one selected from group comprising of amorphous polyethylene terephthalate (APET) layer, polyethylene terephthalate (PET) layer, glycol modified PET (PETg) layer, poly (1,3- propylene) terephthalate layer, poly (1,4- butylenes) terephthalate layer, elastomeric polyester comprising poly (1,4-butylene) terephthalate layer and poly (tetramethylene ether) glycol layer.
13. The laminate as claimed in claim 1, wherein said second polymer layer is a modified polyethylene terephthalate (o-PET) layer;
said modified polyethylene terephthalate (o-PET) layer being selected from a metallized polyethylene terephthalate layer, a metal oxide coated polyethylene terephthalate layer and a barrier polymer coated polyethylene terephthalate layer;
said modified polyethylene terephthalate (o-PET) layer being obtained by a method selected from
(a) depositing a metal on a polyethylene terephthalate (o-PET) sheet to obtain said metallized polyethylene terephthalate layer having an optical density in the range of 0.5 to 2.5; wherein said metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag);
(b) coating of a metal oxide on a polyethylene terephthalate (o-PET) sheet to obtain said metal oxide coated polyethylene terephthalate layer, wherein said metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx; and
(c) coating a barrier polymer on a polyethylene terephthalate (o-PET) sheet to obtain said barrier polymer coated polyethylene terephthalate layer having thickness of said polymer coating is in the range of 1 gsm to 10 gsm; wherein said barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), and polyvinyl alcohol (PVOH), and heat seal lacquer (HSL).
14. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is a modified cyclic olefin co-polymer layer;
said modified cyclic olefin co-polymer layer being selected from a metal oxide coated cyclic olefin co-polymer layer, a barrier polymer coated cyclic olefin co-polymer layer and a metallized cyclic olefin co-polymer layer;
said modified cyclic olefin co-polymer layer being obtained by a method selected from
(a) coating a metal oxide on a cyclic olefin co-polymer sheet to obtain said metal oxide coated cyclic olefin co-polymer layer, wherein said metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx;
(b) coating a barrier polymer on a cyclic olefin co-polymer sheet to obtain said barrier polymer coated cyclic olefin co-polymer layer having thickness of said polymer coating is in the range of 1 gsm to 10 gsm; wherein said barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and Heat seal lacquer (HSL); and
(c) depositing a metal on a cyclic olefin co-polymer sheet to obtain said metallized cyclic olefin co-polymer layer having an optical density in the range of 0.5 to 2.5; wherein said metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
15. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is a polyvinyl chloride (PVC) polymer layer, and said polyvinyl chloride (PVC) polymer layer is selected from flexible PVC layer, rigid PVC layer, chlorinated PVC layer, and oriented PVC layer r.
16. The laminate as claimed in claim 1, wherein said first polymer layer and/or said second polymer layer is a modified polyvinyl chloride layer;
said modified polyvinyl chloride layer being selected from a metal oxide coated polyvinyl chloride layer, a barrier polymer coated polyvinyl chloride layer, and metallized polyvinyl chloride layer;
said modified polyvinyl chloride layer being obtained by a method selected from
(d) coating a metal oxide on a polyvinyl chloride sheet to obtain said metal oxide coated polyvinyl chloride layer, wherein said metal oxide is selected from AlOx, SiOx, CuOx, NiOx, and CoOx;
(e) coating a barrier polymer on a polyvinyl chloride sheet to obtain said barrier polymer coated polyvinyl chloride layer having thickness of said polymer coating is in the range of 1 gsm to 10 gsm; wherein said barrier polymer is selected from polyvinylidene chloride (PVdC), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and Heat seal lacquer (HSL); and
(f) depositing a metal on a polyvinyl chloride sheet to obtain said metallized polyvinyl chloride layer having an optical density in the range of 0.5 to 2.5; wherein said metal is selected from aluminum (Al), palladium (Pd), platinum (Pt), copper (Cu), nickel (Ni), gold (Au) and silver (Ag).
17. The laminate as claimed in claim 1, wherein
(a) said at least one first polymer layer is prepared by a method selected from cast extrusion and blow extrusion; and
(b) said at least one second polymer layer is prepared by a method selected from cast extrusion and blow extrusion.
18. The laminate as claimed in claim 1, wherein a primer layer having thickness in the range of 1 gsm to 3 gsm is applied on the first operative surface or the second operative surface OR the surface of the first polymer layer or the second polymer layer in contact with the first operative surface or the second operative surface; and wherein said primer layer is at least one selected from the group consisting of acrylic based primer layer, polyurethane based primer layer and polyester based primer layer.
19. The laminate as claimed in claim 1, wherein
(a) said first polymer layer comprises
(i) a polypropylene layer having thickness of 60 microns; and
(ii) a metallocene modified polyethylene layer having thickness of 100 microns,
wherein said polypropylene layer and said metallocene modified polyethylene layer are bonded together,
(b) said intermediate metal layer is an aluminum layer having thickness of 50 microns; and
(c) said second polymer layer comprises
(i) a modified oriented polyamide layer having a thickness of 25 microns;
(ii) a layer of a combination of a metallocene modified polyethylene and a desiccant modified polyethylene having thickness of 60 microns,
wherein said modified oriented polyamide layer and said layer of said combination of said metallocene modified polyethylene and said desiccant modified polyethylene, are bonded together.
20. The laminate as claimed in claim 1, wherein
(a) said first polymer layer is a polypropylene having thickness of 60 microns;
(b) said intermediate metal layer is an aluminum layer having thickness of 50 microns; and
(c) said second polymer layer comprises
(i) a metallized oriented polyamide layer having a thickness of 25 microns; and
(ii) a PVC layer having thickness of 60 microns,
wherein said metallized oriented polyamide layer and said PVC layer are bonded together.
21. The laminate as claimed in claim 1, wherein
(a) said first polymer layer is a metallocene modified polyethyelene layer having thickness of 50 microns;
(b) said intermediate metal layer is an aluminum layer having thickness of 50 microns; and
(c) said second polymer layer comprises
(i) a metallized oriented polyamide layer having a thickness of 25 microns; and
(ii) a PVC layer having thickness of 30 microns,
wherein said metallized oriented polyamide layer and said PVC layer are bonded together.
22. The laminate as claimed in claim 1, wherein
(a) said first polymer layer is a metallocene modified polyethylene layer having thickness of 100 microns;
(b) said intermediate metal layer is an aluminum layer having thickness of 50 microns; and
(c) said second polymer layer is a PVdC coated oriented polyamide layer having a thickness of 25 microns.
23. The laminate as claimed in claim 1, wherein
(a) said first polymer layer is a metallocene modified polyethylene layer having thickness of 50 microns;
(b) said intermediate metal layer is an aluminum layer having thickness of 50 microns; and
(c) said second polymer layer is a PVdC coated oriented polyamide layer having a thickness of 25 microns.
24. The laminate as claimed in claim 1, wherein
(a) said first polymer layer is a metallocene modified polyethylene layer having thickness of 50 microns;
(b) said intermediate metal layer is an aluminum layer having thickness of 50 microns; and
(c) said second polymer layer is an AlOx coated oriented polyamide layer having a thickness of 25 microns.
25. The laminate as claimed in claim 1, wherein
(a) said first polymer layer is a metallocene modified polyethylene layer having thickness of 50 microns;
(b) said intermediate metal layer is an aluminum layer having thickness of 50 microns; and
(c) said second polymer layer is a metallized oriented polyamide layer having a thickness of 25 microns.
26. The laminate as claimed in claim 1, wherein said multilayer, multibarrier cold formable blister is characterized by having
(a) a tensile strength in the range of 400 kg/cm2 to 1200 kg/cm2;
(b) a percent elongation at peak in the range of 12% to 40%;
(c) an impact strength in the range of 1400 g to 2500 g; and
(d) a cavity height at bursting of more than 24 mm.
27. A compact blister pack comprising:
(i) at least one blister shaped cup made by cold forming of a multilayer, multibarrier, cold formable blister laminate having:
(a) at least one first polymer layer having a thickness in the range of 10 microns to 300 microns;
wherein said first polymer layer is selected from the group consisting of polyethylene (PE) layer, modified polyethylene (m-PE) layer, polypropylene (PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, and modified cyclic olefin co-polymer (m-COC) layer;
(b) at least one intermediate metal layer having a thickness in the range of 10 microns to 200 microns having a first operative surface and a second operative surface; and
(c) at least one second polymer layer having a thickness in the range of 10 microns to 300 microns;
wherein said second polymer layer is selected from the group consisting of polyethylene (PE) layer, modified polyethylene (m-PE) layer, polypropylene (o-PP) layer, modified polypropylene (m-PP) layer, oriented polyamide (OPA) layer, modified oriented polyamide (m-OPA) layer, polyvinyl chloride (PVC) layer, modified polyvinyl chloride (m-PVC) layer, cyclic olefin co-polymer (COC) layer, modified cyclic olefin co-polymer (m-COC) layer, polyethylene terephthalate layer (PET), and modified polyethylene terephthalate (m-PET) layer;
wherein said at least one first polymer layer is disposed on said first operative surface and said at least one second polymer layer is disposed on said second operative surface;
wherein the water vapour transmission rate (WVTR) of said laminate is in the range of 0.00009 gm/pkg/day to 0.02 gm/pkg/day at 40°C and 75% RH;
and
(ii) a sealable and tearable lid defining an operative outer surface and an operative inner surface, compatible to bond with said first polymer layer in the laminate and to seal said at least one cup.
28. The compact blister pack as claimed in claim 27, wherein a primer layer having thickness in the range of 1 gsm to 3 gsm is applied on the first operative surface or the second operative surface OR the surface of the first polymer layer or the second polymer layer in contact with the first operative surface or the second operative surface; and wherein said primer layer is at least one selected from the group consisting of acrylic based primer layer, polyurethane based primer layer and polyester based primer layer.

29. The compact blister pack as claimed in claim 27, wherein
(a) said operative inner surface of said sealable and tearable lid is coated by using a heat seal lacquer compatible to bond with the first polymer layer in the blister laminate, in an amount in the range of 3 gsm to 10 gsm; and
(b) said sealable and tearable lid comprises an aluminum foil having an operative inner surface and an operative outer surface, laminated with polyethylene film compatible to bond with the first polymer layer of said cold formable multilayer blister laminate, wherein thickness of said aluminum foil is in the range of 15 microns to 40 microns, and thickness of said polyethylene film is in the range of 15 microns to 40 microns.

30. The compact blister pack as claimed in claim 27, wherein said blister shaped cup being defined by
a first slanted wall (704) having a first slanted edge (706) and a second slanted edge (708); said first slanted wall extending in an operative direction from a flat wall (710) abutting on a mouth (712) of said at least one cup and slanted at an angle ? with respect to a normal to said lid (750);
said flat wall (710) being parallel to said lid (750);
a second slanted wall (714) joining said second slanted edge (708) and a third slanted edge (716); said second slanted wall (714) extending in an operative direction from said flat wall (710) abutting on said mouth (712) of said at least one cup, and slanted at an angle ? with respect to a normal to said lid (750);
a third slanted wall (718) joining said third slanted edge (716) and a fourth slanted edge (720); said third slanted wall (718) extending in an operative direction from said flat wall (710) abutting on said mouth (712) of said at least one cup, and slanted at an angle ? with respect to a normal to said lid (750); and
a fourth slanted wall (722) joining said first slanted edge and said fourth slanted edge; said fourth slanted wall extending from an operative direction from said flat wall (710) abutting on said mouth (712) of said at least one cup, and slanted at an angle ? with respect to a normal to said lid (750),
wherein said angle ? is in the range of 15° to 30°.

Dated this 08th day of July, 2024

_______________________________
MOHAN RAJKUMAR DEWAN, IN/PA – 25
OF R. K. DEWAN & CO.
AUTHORIZED AGENT OF APPLICANT

TO,
THE CONTROLLER OF PATENTS
THE PATENT OFFICE, AT MUMBAI

Documents

Application Documents

# Name Date
1 202321046025-STATEMENT OF UNDERTAKING (FORM 3) [08-07-2023(online)].pdf 2023-07-08
2 202321046025-PROVISIONAL SPECIFICATION [08-07-2023(online)].pdf 2023-07-08
3 202321046025-PROOF OF RIGHT [08-07-2023(online)].pdf 2023-07-08
4 202321046025-FORM 1 [08-07-2023(online)].pdf 2023-07-08
5 202321046025-DECLARATION OF INVENTORSHIP (FORM 5) [08-07-2023(online)].pdf 2023-07-08
6 202321046025-FORM-26 [10-07-2023(online)].pdf 2023-07-10
7 202321046025-MARKED COPIES OF AMENDEMENTS [11-07-2023(online)].pdf 2023-07-11
8 202321046025-FORM 13 [11-07-2023(online)].pdf 2023-07-11
9 202321046025-AMENDED DOCUMENTS [11-07-2023(online)].pdf 2023-07-11
10 202321046025-Proof of Right [10-08-2023(online)].pdf 2023-08-10
11 202321046025-Proof of Right [10-08-2023(online)]-1.pdf 2023-08-10
12 202321046025-ENDORSEMENT BY INVENTORS [08-07-2024(online)].pdf 2024-07-08
13 202321046025-DRAWING [08-07-2024(online)].pdf 2024-07-08
14 202321046025-COMPLETE SPECIFICATION [08-07-2024(online)].pdf 2024-07-08
15 202321046025-Request Letter-Correspondence [17-07-2024(online)].pdf 2024-07-17
16 202321046025-Power of Attorney [17-07-2024(online)].pdf 2024-07-17
17 202321046025-Covering Letter [17-07-2024(online)].pdf 2024-07-17
18 202321046025-CORRESPONDENCE(IPO)-(WIPO DAS)-22-07-2024.pdf 2024-07-22
19 202321046025-FORM-9 [24-07-2024(online)].pdf 2024-07-24
20 202321046025-FORM 18A [24-07-2024(online)].pdf 2024-07-24
21 202321046025-FER.pdf 2025-01-24
22 202321046025-FORM 3 [03-03-2025(online)].pdf 2025-03-03
23 202321046025-Information under section 8(2) [31-03-2025(online)].pdf 2025-03-31
24 202321046025-FORM-26 [22-07-2025(online)].pdf 2025-07-22
25 202321046025-MARKED COPIES OF AMENDEMENTS [23-07-2025(online)].pdf 2025-07-23
26 202321046025-FORM 13 [23-07-2025(online)].pdf 2025-07-23
27 202321046025-FER_SER_REPLY [23-07-2025(online)].pdf 2025-07-23
28 202321046025-CLAIMS [23-07-2025(online)].pdf 2025-07-23
29 202321046025-AMMENDED DOCUMENTS [23-07-2025(online)].pdf 2025-07-23
30 202321046025-US(14)-HearingNotice-(HearingDate-19-08-2025).pdf 2025-07-29
31 202321046025-Correspondence to notify the Controller [11-08-2025(online)].pdf 2025-08-11
32 202321046025-US(14)-HearingNotice-(HearingDate-09-10-2025).pdf 2025-09-19
33 202321046025-Correspondence to notify the Controller [03-10-2025(online)].pdf 2025-10-03
34 202321046025-Written submissions and relevant documents [17-10-2025(online)].pdf 2025-10-17
35 202321046025-MARKED COPIES OF AMENDEMENTS [17-10-2025(online)].pdf 2025-10-17
36 202321046025-FORM 13 [17-10-2025(online)].pdf 2025-10-17
37 202321046025-AMMENDED DOCUMENTS [17-10-2025(online)].pdf 2025-10-17

Search Strategy

1 202321046025_SearchStrategyNew_E_SearchHistoryE_23-01-2025.pdf