A Glycerol Derivative For Polymer Applications.

FORM 2 THE PATENTS ACT, 1970 (39 OF 1970) & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION (See section 10; rule 13) A GLYCEROL DERIVATIVE FOR POLYMER APPLICATIONS FINE ORGANIC INDUSTRIES LTD A company incorporated under the laws of India having their office at Plot A 28, Millennium Business Park, Mahape MIDC, Navi Mumbai 400 710. The following specification particularly describes the invention and the manner in which it is to be performed

A GLYCEROL DERIVATIVE FOR POLYMER APPLICATIONS The present invention relates to a glycerol derivative or a polyglycerol for polymers wherein the polymer is thermoplastic elastomer. BACKGROUND OF THE INVENTION United States patent no. 4426477 (referred to herein as '477 patent, assigned to M/s Riken Vitamin Co., Ltd.) claims thermoplastic resin compositions obtained by blending to a vinyl chloride resin composition a glycerin ester. The results show that the composition of the invention demonstrates improved processibility, transparency, % haze, bleeding and anti-fogging. However, the '477 patent does not disclose reduction in opening torque of thermoplastic elastomers. International application publication no. 2001/14466 (referred to herein as '466 publication, assigned to M/s Danisco) discloses thermoplastic polymer compositions comprising a compound with formula

wherein at least one of R1, R2 and R3 is a branched chain acyl group consisting of a saturated chain having 10 to 20 carbon atoms and a hydrophilic branch group; wherein the compound of the invention is used as a plasticizer and the thermoplastic polymer is or comprises a vinyl chloride polymer or a vinyl chloride copolymer and a copolymer prepared by grafting vinyl chloride onto ethylene/vinyl acetate copolymer and mixtures thereof. However, the '466 publication does not disclose the glycerol derivative or a polyglycerol of the present invention and its polymer applications. International application publication no. 2016/058927 (referred to herein as '927 publication, assigned to M/s DuPont Nutrition Biosciences) claims a polymer composition comprising poly(ethylene

terphthalate) and polyglycerol fatty acid ester as an internal additive wherein the composition enables reduced torque during processing and reduced surface friction during its use as a packaging material. However, the '927 publication does not disclose use of the polyglycerol fatty acid ester in thermoplastic elastomers. OBJECT OF THE INVENTION The object of the present invention is to provide thermoplastic elastomer compositions which enable reduced opening torque. SUMMARY OF THE INVENTION A thermoplastic elastomer comprising 0.1 to 0.5% of a glycerol derivative, compound of formula I,

Compound of formula I wherein R1; R2 and R3 represent each an acyl group or a hydrogen atom, said acyl group comprises at least one with 2 carbon atoms and one with more than 12 carbon atoms. A thermoplastic elastomer comprising 0.1 to 0.5% of a polyglycerol, compound of formula II,

wherein R1, R2 and R3 represent each a fatty acyl group, said fatty acyl group comprises at least 12 carbon atoms.

DESCRIPTION OF THE INVENTION Thermoplastic elastomers (TPE) sometimes referred to as thermoplastic rubbers have been created as an alternative to natural rubber are a class of copolymers or a physical mixture of polymers (usually a plastic and a rubber) which consists of materials with both thermoplastic and elastomeric properties. Thermoplastic elastomers have the properties and performance of rubber but are processed like plastic. TPEs are flexible materials with varied applications such as in sealants, molded flexible parts and adhesives for use in automobile manufacturing, food packaging and allied industries. Various additives are added to thermoplastic elastomers to improve its performance such as plasticizers, colorants, flavours, torque reducing agents, coefficient of friction reducing agents etc. We have developed thermoplastic elastomers with torque reducing agent, compound of formula I, which is a glycerol derivative. According to one embodiment of the present invention is a thermoplastic elastomer comprising a glycerol derivative, compound of formula I,

Compound of formula I wherein Rlf R2 and R3 represent each arvacyl group or a hydrogen atom, said acyl group comprises at least one with 2 carbon atoms and one with more than 12 carbon atoms. The compound of formula I may be used in about 0.1 to 1%, preferably 0.1 to 0.5%, most preferred being about 0.25% by weight of the polymer.

The thermoelastic elastomer of the present invention may be ethylene vinyl acetate. The thermoelastic elastomer of the present invention may be used as a sealant for liquid containers. The glycerol derivative of the present invention enables the opening torque of the sealant for liquid containers to be reduced by at least 50%. The glycerol derivative of the present invention also retains the organoleptic properties of the liquid. The glycerol derivative of the present invention does not scuff the seal during opening of the liquid container. According to another embodiment of the present invention is a Thermoplastic elastomer comprising a polyglycerol, compound of formula II,

Compound of formula II wherein R1; R2 and R3 represent each a fatty acyl group, said fatty acyl group comprises at least 12 carbon atoms. The compound of formula II may be used in about 0.1 to 1%, preferably 0.1 to 0.5%, most preferred being about 0.25% by weight of the polymer. The thermoelastic elastomer of the present invention may be ethylene vinyl acetate. The thermoplastic elastomer of the present invention may be used as a sealant for liquid containers. The polyglycerol of the present invention enables the opening torque of the sealant for liquid containers to be reduced by at least 50%.

The polyglycerol of the present invention also retains the organoleptic properties of the liquid. The polyglycerol of the present invention does not scuff the seal during opening of the liquid container. DEFINITION OF TERMS Organoleptic property The term Organoleptic Property is the result of adverse effect of substance/material on smell and taste. It can be assessed by human panel measured as organolepticity index or by using sophisticated analytical tools. Scuffing Wear marks or scratches on outside surface of the caps after friction with other adjacent bottle or other substrate. Scuffing is a defect which impairs appearance but not function. Opening Torque Release The term torque release is the moment of a force tending to cause rotation of an appropriate closure in a direction opposite to that of closing, causing the closure to be unsecured from its position on the neck finish of an appropriate container. Coefficient of Friction Coefficient of friction is the ratio of the force required to move one surface over another to the total force applied normal to those surfaces. The following examples illustrate preferred embodiments in accordance with the present invention without limiting the scope of the invention.

EXAMPLES The sample details are as follows - Finawax-B is behenamide Finawax-E is Erucamide Finawax-0 is Oleamide Finaslip - EZY is mixture of linear saturated fatty amide(s) and glycerol monostearate Finaslip - PEX2 is an ester additive prepared from a 1,3-propanediol and succinic acid Finaslip - PEX is an ester additive prepared from diol and dicarboxylic acid EV-4 is hexanediol disuccinate EV-5 is hexanediol mixed ester of stearate-succinate EV-6 is hexanediol distearate EV-7 is polyglycerol fatty acid ester EV-8 is acetyl ester of monoglycerin fatty acid ester EV-9 is Polyglycerol Stearate Test Methods Release or opening torque Measurement: Firmly position the bottle in the holder. Fix the fixer containing test cap to the bottle (avoid contact with bottle). Position the torque meter with needle to left hand side & rotate clockwise slowly, at constant rate, until the desired/predetermined constant torque (called as closing torque) is indicated on the needle. Keeping the torque meter in its place, bring the needle to the right hand side and rotate anticlockwise, slowly avoiding contact with the container. The torque indicated by needle is release or opening torque of the closure. Application Angle: Draw a vertical line on test cap from start of the thread and continue to the outside, use red pen. Draw a vertical line from the start of the thread on the neck finish of the bottle & continue down for 1-2 cm, use

red pen. Screw the cap on bottle until the desired closing torque indicated on torque meter needle. Draw a vertical line from the top of the cap down the side of the bottle, use blue pen. Measure the opening torque. Re-screw the cap onto the bottle and align the 2 lines drawn with the blue pen. Place the Protractor on the neck of the bottle. Align the red line on the bottle with the red line on the protractor. The application angle is indicated by the value on the protractor where it meets the red line on the closure. Thus the application angle is the angle between the marked threads on cap & on the bottle Coefficient of Friction (CoF) {Ref. ASTM D-1894 (1963)}: Film to Metal measurement: Position the test film or sheet specimen to the platform (stainless steel plane). Smoothen the film specimen, gently with your fingers, to eliminate wrinkles. Attach the filament to the sled & lightly place the sled in position on the test specimen. Start the test & calculate the CoF with the help of attached software. For Film to film measurement: Wrap the film specimen to the back of the sled, using adhesive tape. Pull the specimen tight to eliminate wrinkles, if any. Repeat the same procedure as film to metal. Organoleptic Property: Fill 500ml glass bottles with potable water & fit with test caps. Expose these bottles to sunlight for 72 hrs, horizontally. To ensure constant contact between water and the cap the bottles are shaken thrice in a day. After 72 hrs, cool to ambient temperature. Then, test the water for taste and flavour by a panel of 10-12 individuals drawn from a pool of the employees. This panel rates the test samples on a scale of 1 to 2.5 [higher rank attributed to bad taste / odour. Average of the marks gives the Organoleticity Index (01) for a test sample. Conditioning: Condition the test specimens at 23 ± 2° C and 50 ± 5 % relative humidity. Test Conditions: Conduct tests in the standard laboratory atmosphere of 23 ± 2° C and 50 ± 5 % R.H.

Example 1: Torque, Coefficient of Friction Dosage level: 2000 ppm. Polymer: TPE sealing compound Compounding: Using Haake Polylab QC single screw extruder (L/D- 25) @155°C. Compression Molding: at 105°C, thickness 0.7mm (water cooling). Sealing discs of 26mm diameter were cut & fitted into caps. These caps were tested for Opening Torque (OT, in Nm), application angle (degrees), scuffing & organoleptic property. CoF Film was blown followed by CoF measurement, thickness 60-80µ Torque Release & Application Angle-Closing Torque = 1.6Nm

Sample Opening Torque(Nm) Application Angle, ° CoF* Exudation

Ambient at 4°C Ambient at 4°C

Without additive 1.3 1.33 676 675 2.529 - Finawax-B 1.31 1.31 676 675 0.944 yes Finawax-E 0.88 0.89 688 693 0.238 yes Finawax-O 0.92 0.90 693 686 0.167 yes Finaslip-EZY 1.05 0.99 661 684 0.554 yes Finaslip-PEX2 1.3 1.26 680 682 1.094 No Finaslip-PEX 1.43 1.48 675 668 - No EV-4 1.12 1.00 684 690 - No EV-5 0.94 1.00 662 690 - No EV-6 1.08 0.96 691 684 - No EV-7 0.90 0.86 678 680 1.375 Less EV-8 0.92 0.86 672 666 2.324 No EV-9 1.1 1.0 670 675 - - Isostearamide 0.79 0.75 699 701 0.268 Yes * Except samples O, E & Isostearamide, for all other samples too much variation in CoF readings observed as sledge sticks to films. Application angle of all samples is almost same & ranges from 660 - 700°. Based on Opening Torque results, good performance additives are as EV8 ≈ EV7 ≤ EV5

Opening Torque of FW-E, O, EV-5, EV-7, EV-8 & Isostearamide is better compared to other additives. Example 2 : Organoleptic Property (01) Glass Bottles Ex. Actega ( Capacity : 700 ml) containing potable water fitted with Actega caps & TPE disc/insert with additive level 2000 ppm, were exposed to sunlight for 72 hrs, horizontally. Exposed water was tested for flavour. Organolepticity index, as 1 to 2.5, was calculated from the panelist ratings. Higher ratings correspond to bad taste.

Sample 01*

Ave rating Without additive 2.0 Finawax-B 1.2 Finawax-E 2.4 Finawax-0 2.6 Finaslip-EZY 2.3 Finaslip-PEX2 - Finaslip-PEX - EV-4 - EV-5 1.9 EV-6 - EV-7 2.5 EV-8 1.8 EV-9 - Isostearamide 1.9 Organoleptic property of Finawax-B is good, and that of EV5, EV8 & Isostearamide is Fair. From new/developed samples, O1 of EV5, EV8 is better & same as without additive sample. *Rating:

1 Good 1.5 OK 2.0 Fair 2.5 Bad Example 3: Scuffing: No scuffing observed visually for all samples

We claim 1. A thermoplastic elastomer comprising 0.1 to 0.5% of a glycerol derivative, compound of formula I,

Compound of formula I wherein R1, R2 and R3 represent each an acyl group or a hydrogen atom, said acyl group comprises at least one with 2 carbon atoms and one with more than 12 carbon atoms. 2. A thermoplastic elastomer as claimed in claim 1 wherein the thermoplastic elastomer is ethylene vinyl acetate. 3. A thermoplastic elastomer as claimed in claim 1 wherein the thermoplastic elastomer is used in polymer applications such as a sealant for liquid containers. 4. A thermoplastic elastomer as claimed in claim 1 wherein the compound of formula I helps in reducing opening torque of sealant of liquid containers by at least 50%. 5. A thermoplastic elastomer as claimed in claim 1 wherein the compound of formula I retains the organoleptic properties of the liquid containers. 6. A thermoplastic elastomer as claimed in claim 3 wherein the sealant is not scuffed during opening o f the liquid container. 7. A thermoplastic elastomer comprising 0.1 to 0.5% of a polyglycerol, compound of formula II,

wherein R1, R2 and R3 represent each a fatty acyl group, said fatty acyl group comprises at least 12 carbon atoms. 8. A thermoplastic elastomer as claimed in claim 7 wherein the thermoplastic elastomer is ethylene vinyl acetate.

9. A thermoplastic elastomer as claimed in claim 7 wherein the thermoplastic elastomer is used in polymer applications such as a sealant for liquid containers. 10. A thermoplastic elastomer as claimed in claim 7 wherein the compound of formula I helps in reducing opening torque of sealant of liquid containers by at least 50%. 11. A thermoplastic elastomer as claimed in claim 7 wherein the compound of formula I retains the organoleptic properties of the liquid containers. 12. A thermoplastic elastomer as claimed in claim 7 wherein the sealant is not scuffed during opening of the liquid container.