[0001]The present invention, at least a substrate layer and (A), the gas barrier properties of the adhesive layer (B), and a gas barrier inorganic vapor-deposited layer (C), and a gas barrier laminate having a sealant layer (D).
[0002]The gas barrier layered product of the present invention has a configuration in which a gas barrier inorganic vapor-deposited layer (C) and adhesive layer (B) and is laminated adjacently, thickness 0.5 to adhesive layer (B) 6. the gas barrier layered product is 0 .mu.m, further, the gas barrier laminate having a gas barrier coating film layer (E) and or printed layer and a (F), and relates to a gas barrier packaging material and the pillow packaging bag made of the gas barrier laminate, in particular, it relates to a packaging material and a pillow packaging bag made of excellent flexibility and easy-open performance and oxygen barrier property and water vapor barrier properties (permeability of oxygen and water vapor are reduced) laminate and laminate .
　Further, the packaging material of the present invention are ideal for various packaging bags or retort pouch.
BACKGROUND
[0003]
　Generally, packaging materials with gas barrier properties, at least, the base layer, a gas barrier layer, an adhesive layer, and a multilayer body having a sealant layer, in particular, as a gas barrier layer for improving the oxygen barrier property, metal foil, deposited film of metal or metal oxide is used.
　However, the metal foil as the gas barrier layer, can achieve high oxygen barrier property, thicker than are deposited film, as a result, packaging materials using metal foil becomes thicker, it is inferior in bending resistance It has been known.
　In contrast, it is possible to reduce the thickness by using the deposited film of a metal or a metal oxide is excellent in bending resistance, or since the deposited film surface having unevenness, sufficient oxygen barrier property it is achieved had the problem that it is difficult.
[0004]
　Patent Document 1, as an oxygen barrier material, is described active hydrogen-containing compound (A) and the organic polyisocyanate compound (B) thermosetting gas containing resin cured product obtained by reacting (oxygen) barrier polyurethane resin ing.
　The the resin cured product, backbone structure derived from meta-xylene diisocyanate are contained 20% by mass or more, and wherein among the (A) and (B), the proportion of compounds of trifunctional or more is a (A) ( gas using a thermosetting oxygen barrier polyurethane resin characterized in that the total amount of B) is 7 mass% or more (oxygen) barrier composite film (base film layer and the thermosetting gas barrier polyurethane resin It is described and a layer) containing.
[0005]
　Further, Patent Document 2, on at least one side of a polymer film substrate, and the thin film layer surface of the coating film having transparency forming a thin layer of silicon oxide or aluminum oxide, and a heat sealable resin film, an inorganic barrier laminate, characterized in that adhered by dry lamination via a silicon oxide and one or more particles selected from materials aluminum oxide and a polyester polyol and a barrier adhesive containing isocyanate compound, and this It described packaging material using the.
[0006]
　However, in Patent Document 1, the composition since it must use a highly polar solvent, poor workability. For example in the case of using a highly soluble solvents such as acetone, since the boiling point is likely to take in low and ambient air of water, adjusting the viscosity by the reaction of water with isocyanate there is a problem easily increased.
[0007]
　Further, in Patent Document 2, since the particle size of the inorganic compound contained in the adhesive is spherical or amorphous inorganic compound nano-order, the oxygen barrier property of the adhesive itself, especially given the load of bending oxygen barrier property of the case there is a problem that not high.
CITATION
Patent Document
[0008]
Patent Document 1: Patent No. 4054972 Patent specification
Patent Document 2: Patent No. 3829526
Summary of the Invention
Problems that the Invention is to Solve
[0009]
　The present invention is to solve the above problems, the total structure layer number is small, a laminate excellent in workability during production, easy-open performance and gas barrier properties and laminate and laminate excellent in flex resistance an object of the present invention is to provide a made packaging material and a pillow packaging bag.
Means for Solving the Problems
[0010]
　The present inventors, as a result of various studies, at least, a gas barrier laminate having a substrate layer and (A), the gas barrier properties of the adhesive layer (B), and a gas barrier inorganic vapor-deposited layer (C), and the sealant layer and (D) a body having a configuration in which a gas barrier inorganic vapor-deposited layer (C) and adhesive layer (B) and are adjacent, the gas barrier laminate thickness is 0.5 ~ 6.0 .mu.m adhesive layer (B), Furthermore, a gas barrier laminate having a gas barrier coating film layer (E) and the print layer (F), and said barrier gas barrier packaging material made of a laminate were found to achieve the above object.
[0011]
　The present invention is characterized in the following points.
1. At least, the base layer and (A), the gas barrier properties of the adhesive layer (B), and a gas barrier inorganic vapor-deposited layer (C), and a gas barrier laminate having a sealant layer (D), the gas barrier properties of the adhesive the thickness of the layer (B) and the gas barrier inorganic vapor-deposited layer and (C) are laminated adjacently, gas barrier properties of the adhesive layer (B) is a 0.5 ~ 6.0 .mu.m, the gas barrier laminate.
2. The gas barrier properties of the adhesive layer (B) is a solventless gas barrier organic adhesive layer, the inorganic solvent type gas barrier organic adhesive layer, two-component curing type non solvent bonding agent is applied, it is further cured a formed layer, the solvent content of the solvent-free gas barrier organic adhesive layer is zero or 6 mg / m 2 gas barrier laminate according to claim 1 or less.
3. Sealant layer (D) is an easy-open sealant layer, a gas barrier laminate according to the above 1 or 2.
4. Between the substrate layer (A) and the gas barrier properties of the adhesive layer (B), and a gas barrier laminate having a gas barrier coating film layer (E), the gas barrier coating film layer (E) is a metal alkoxide those containing sol-gel method hydrolytic polycondensate of a mixture of a water-soluble polymer, the gas barrier laminate according to any of the above 1-3.
5. Between the substrate layer (A) and the gas barrier properties of the adhesive layer (B), and having a printing layer (F), the gas barrier laminate according to any of the above 1-4.
6. Gas barrier inorganic vapor-deposited layer (C) is vapor-deposited aluminum layer, alumina vapor deposited layer, and, a silica vapor deposited layer is one or a layer having two or more selected from the group consisting, according to any of the above 1 to 5, gas barrier laminate.
7. Gas barrier inorganic vapor-deposited layer (C) is a layer having a vapor-deposited aluminum layer, a gas barrier laminate according to any of the above 1-6.
8. Gas barrier thickness of the inorganic deposited layer (C) is 1 ~ 100 nm, the gas barrier laminate according to any of the above 1-7.
Oxygen permeability under 9.23 ° C. 90% RH environment, 0.05 ~ 2.0 cc / m 2 was / day / atm, the water vapor permeability under 40 ° C. 90% RH environment, 0.01-2 .0G / m 2 is / day / atm, the oxygen barrier for and water vapor barrier, a gas barrier laminate according to any of the above 1-8.
10. After giving five bending load Gelbo flex tester, the oxygen permeability under 23 ° C. 90% RH environment, increasing values from prior to applying the bending load, zero or 20.0 cc / m 2 / day / atm or less, the gas barrier laminate according to any of the above 1-8.
11. After giving five bending load Gelbo flex tester, the oxygen permeability under 23 ° C. 90% RH environment, increasing values from prior to applying the bending load, zero or 10.0 cc / m 2 / day / atm or less, the gas barrier laminate according to any of the above 1-8.
12. After received a single filling load longitudinal pillow packing machine, the oxygen permeability under 23 ° C. 90% RH environment, increasing values from prior to applying the bending load, zero or 10.0 cc / m 2/ Day / atm or less, the water vapor permeability under 40 ° C. 90% RH environment, increasing values from prior to applying the bending load, zero or 5.0 g / m 2 or less / day / atm, the the gas barrier laminate according to any one of 1-8.
13. Total configuration layer number is 6 or less, the gas barrier laminate according to any of the above 1 to 12.
14. According to any of the 3-12, the easy-open gas-barrier laminate having an easy-open sealant layer.
15. In any one of 1 to 14 using a gas barrier laminate according, the gas barrier packaging material.
16. Using a gas barrier laminate according to any of the above 1 to 15, pillow packaging bags.
The invention's effect
[0012]
　本発明のガスバリア積層体および該ガスバリア積層体からなるガスバリア包装材料は、少なくとも、基材層（Ａ）、無溶剤型ガスバリア有機接着剤層（Ｂ）、ガスバリア無機蒸着層（Ｃ）、及びシーラント層（Ｄ）とを有し、ガスバリア無機蒸着層（Ｃ）と無溶剤型ガスバリア有機接着剤層（Ｂ）とが接した構成を有する。
　そして、無溶剤型ガスバリア有機接着剤層（Ｂ）は、２液硬化型無溶剤接着剤が塗布され、硬化されて形成された層であり、無溶剤型ガスバリア有機接着剤層（Ｂ）の溶剤含有率はゼロまたは６ｍｇ／ｍ 2以下である、ガスバリア積層体、あるいは、更に、ガスバリア性塗布膜層（Ｅ）及び又は印刷層（Ｆ）とを有するものであり、ガスバリア無機蒸着層（Ｃ）と無溶剤型ガスバリア有機接着剤層（Ｂ）とを隣接して組み合わせることで、ガスバリア無機蒸着層（Ｃ）表面に生じている凹凸の凹部が、無溶剤型ガスバリア有機接着剤層（Ｂ）により埋められて平坦化されて面方向のガスバリア性が均一化され、ガスバリア無機蒸着層の層厚を薄くして耐屈曲性を保持しつつ、従来では成し得なかった高いガスバリア性を発現することができる。
　また、無溶剤型ガスバリア有機接着剤層（Ｂ）が無溶剤型であり溶剤含有率はゼロまたは６ｍｇ／ｍ 2以下であることにより、ガスバリア性の更なる向上と、内容物への溶剤臭転移の低減化を発現することができる。
　Also, the easy-open gas-barrier packaging material made of the easy-open gas-barrier laminate and the easily openable barrier laminate of the present invention, at least a substrate layer and (A), the gas barrier properties of the adhesive layer (B), and gas barrier inorganic deposited layer and (C), those having an easy-open sealant layer (D), has a configuration in which a gas barrier inorganic vapor-deposited layer and (C) and adhesive layer (B) are adjacent, the adhesive the thickness of the layer (B) is 0.5 ~ 6.0 .mu.m, or further, which has a gas barrier coating film layer (E) and the print layer (F), the gas barrier inorganic vapor-deposited layer (C) and the gas barrier by combining sex of the adhesive layer and (B) adjacent, the recess of irregularities occurring in the gas barrier inorganic vapor-deposited layer (C) surface planarization is filled with the adhesive layer (B) having gas barrier properties gas barrier properties Hitoshi has been surface direction Ized, while retaining flexibility by reducing the thickness of the gas barrier inorganic vapor-deposited layer (C), with a small total structure layer number, it is possible to exert a conventional equal or gas barrier properties.
　Moreover, since it has easy-open sealant layer (D), it is possible to express the easily openable.
　Also, the easy-open gas-barrier packaging material made of the easy-open gas-barrier laminate and the easily openable barrier laminate of the present invention, at least a base material layer (A), solventless gas barrier organic adhesive layer (B), gas barrier inorganic vapor-deposited layer (C), and has easy-open sealant layer and (D), has a structure in which a gas barrier inorganic vapor-deposited layer and (C) a solvent-free gas barrier organic adhesive layer (B) are in contact.
　The solvent-free gas barrier organic adhesive layer (B), two-component curing type non solvent bonding agent is applied, a layer that is formed by curing, the thickness is 0.5 ~ 6 mm, solvent content is zero or 6 mg / m 2Or less, the easy-open gas-barrier laminate preferably further is one having a gas barrier coating film layer (E) and or printed layer (F), the gas barrier inorganic vapor-deposited layer and (C) a solvent-free gas barrier organic adhesive layer and (B) by combining adjacent, recesses of irregularities occurring in the gas barrier inorganic vapor-deposited layer (C) surface, planarized buried by solvent-free gas barrier organic adhesive layer (B) been equalized gas barrier properties in the plane direction is, while retaining flexibility by reducing the thickness of the gas barrier inorganic vapor-deposited layer, with less total structure layer number, to express a conventional equal or higher gas barrier properties can.
　Also, solventless gas barrier organic adhesive layer (B) is a solvent-free type solvent content is zero or 6 mg / m 2 by at most, a further improvement in gas barrier properties, solvent odor transfer to the contents of capable of expressing the reduction. Moreover, since it has easy-open sealant layer (D), packaging can express easily openable.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013]
FIG. 1 is a schematic sectional view showing an example thereof the layer structure of the gas barrier laminate having a solvent-free gas barrier organic adhesive layer of the present invention.
FIG. 2 is a schematic sectional view showing other example for the layer structure of the gas barrier layered product of the present invention.
3 is a schematic sectional view showing an example yet another for the layer structure of the gas barrier layered product of the present invention.
4 is a schematic sectional view showing an example of the layer structure of the easy-open gas-barrier laminate of the present invention.
FIG. 5 is a schematic sectional view showing another example for the layer structure of the easy-open gas-barrier laminate of the present invention.
6 is a schematic sectional view showing still other example for a layer structure of the easy-open gas-barrier laminate of the present invention.
7 is a schematic sectional view showing an example of the layer structure of the easy-open gas-barrier laminate having a solvent-free gas barrier organic adhesive layer of the present invention.
8 is a schematic sectional view showing another example for the layer structure of the gas barrier layered product of the present invention.
9 is a schematic sectional view showing an example yet another for the layer structure of the gas barrier layered product of the present invention.
DESCRIPTION OF THE INVENTION
[0014]
　For the gas barrier laminate and a gas barrier packaging material and the pillow packaging bag made of a gas barrier laminate of the present invention will be described in detail below with reference to the drawings.
　In the present invention, the total structure layer number, constituting the laminate, the base material layer, a gas barrier layer, an adhesive layer, and a detailed number of layers of the sealant layer such as a vapor deposition layer in each layer or AC coating or the like of is that of the number of layers also includes a special processing coat layer. For example, with aluminum deposited layer PET film layer, it counted as two layers.
　Figure 1-9 is a schematic sectional view showing an example of the layer structure of the gas barrier layered product of the present invention.
[0015]
　The gas barrier layered product of the present invention, as shown in FIG. 1, substrate layer and (A), solventless gas barrier organic adhesive layer (B), and a gas barrier inorganic vapor-deposited layer (C), and a sealant layer (D) preparative, a laminated comprising construction in which a basic structure.
[0016]
　Other aspects of the gas barrier layered product of the present invention, as shown in FIG. 2, between the substrate layer (A) and solvent-free gas barrier organic adhesive layer (B), further, the gas barrier inorganic vapor-deposited layer ( a separate gas barrier inorganic deposited layer and C), may be configured to a gas barrier coating film layer and (E) are laminated.
[0017]
　Yet another embodiment of the laminate of the present invention, as shown in FIG. 3, stacked between the substrate layer (A) and solvent-free gas barrier organic adhesive layer (B), and the printing layer (F) it may be a configuration.
　Also, the easy-open gas-barrier laminate of the present invention, as shown in FIG. 4, the substrate layer and (A), the gas barrier properties of the adhesive layer (B), and a gas barrier inorganic vapor-deposited layer (C), and the easy-open sexual sealant layer and (D), the stacked formed by configuration in which a basic structure.
　Other aspects of the easy-open gas-barrier laminate of the present invention, as shown in FIG. 5, between the substrate layer (A) and adhesive layer (B), and further, the gas barrier inorganic vapor-deposited layer (C) a separate gas barrier inorganic deposited layer and the gas barrier coating film layer (E) and may be a laminated structure of.
　Yet another embodiment of the laminate of the present invention, as shown in FIG. 6, between the substrate layer (A) and gas barrier adhesive layer (B), and there in stacked configuration printed layer (F) it may be.
　Also, the easy-open gas-barrier laminate of the present invention, as shown in FIG. 7, the base layer and (A), solventless gas barrier organic adhesive layer (B), and a gas barrier inorganic vapor-deposited layer (C), and peelable sealant layer and (D), the stacked formed by configuration in which a basic structure.
　Other aspects of the easy-open gas-barrier laminate of the present invention, as shown in FIG. 8, between the substrate layer (A) and solvent-free gas barrier organic adhesive layer (B), further, the gas barrier inorganic a separate gas barrier inorganic vapor deposition layer deposited layer and (C) is a gas barrier coating film layer (E) and may be a laminated structure of.
　Yet another embodiment of the easy-open gas-barrier laminate of the present invention, as shown in FIG. 9, between the substrate layer (A) and solvent-free gas barrier organic adhesive layer (B), the print layer ( F) may be a laminated structure of.
[0018]
　The above example is an example of the easy-open gas-barrier laminate of the present invention, the present invention is not limited thereto.
[0019]
　Next, the material of the easy-open gas-barrier laminate according to the present invention, its manufacturing method will be described.
　Resins names used in the present invention is the use of what is customary in the industry. Further, the present invention is not limited to various specific examples listed later.
[Substrate layer (A)]
　As the base material layer (A), excellent chemical or physical strength to withstand the conditions of forming an inorganic vapor deposition film, good without impairing the properties such as those inorganic vapor-deposited film metal can be retained, it is possible to use organic materials such as inorganic materials and resins such as metal oxides such as a film or sheet.
　As the base material layer (A), a single-layer film or it multilayered film is used, it can be used is not particularly limited, any film for use in various packaging materials. From these, according to the use conditions of the presence or absence of heat treatment after the type and filling of the contents to be packaged, selected and used freely those suitable.
[0020]
　Specific examples of the film which is preferably used as the base material layer (A), paper, aluminum foil, cellophane, polyamide resin film, polyester resin film, an olefin resin film, the acid-modified polyolefin resin film, polystyrene resin film, polyurethane resin film, acetal resin film, they were uniaxially or biaxially oriented film, K-coated film, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene, polyvinyl alcohol, ethylene - vinyl acetate copolymer, ionomer, ethylene - (meth) acrylic acid copolymer, ethylene - (meth) acrylic acid ester copolymer, ethylene - propylene copolymer, methylpentene, Polyacrylonitrile, acrylonitrile - styrene copolymers, acrylonitrile - butadiene - styrene copolymer, polycarbonate, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), ethylene - tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene terephthalate, a resin film made of polyethylene naphthalate, K coated oriented polypropylene film, K-coated stretched nylon film, these two or more films laminated composite films.
[0021]
　Among them, polyethylene terephthalate, uniaxially or biaxially stretched polyester film, nylon 6, nylon 66, MXD6 (poly-m-xylylene adipamide) uniaxially or biaxially stretched polyamide film of polyamide, such as polyethylene naphthalate, and, biaxial oriented polypropylene film (OPP) or the like can be suitably used. Further, silica-deposited PET, transparent deposited PET such as alumina-deposited PET, aluminum deposited biaxially oriented polypropylene film (OPP), etc. are also suitable.
(Thickness)
　The thickness of the substrate layer (A) is may be selected arbitrarily, in view of moldability and transparency, it can be used by selecting from a range of 1μm to 300μm position, preferably 1 it is in the range of ~ 100μm. If the thickness is less than this, the strength is insufficient, and when the thickness is larger than this, rigidity becomes too high, processing may be difficult.
[0022]
(Surface treatment)
　film or sheet constituting the base material layer (A) and substrate layer (A), each adhesive layer or a gas barrier inorganic vapor deposition layer, such as an adhesive layer (B) (C) each inorganic vapor deposition such as in order to improve the adhesion between the layers, the laminate or substrate layer prior to the deposition (a) and constituting the base material layer (a) a film or sheet close contact to the surface of, if necessary, previously, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas or the like, physical procedures such as when a glow discharge treatment, chemical treatment and the like oxidation treatment using chemicals, adhesive layer, primer coat agent layer, undercoat layer, or treatment for forming a deposition anchor coating agent layer or the like, and may be subjected to other processing, the inorganic vapor deposition layer formed after surface treatment, further, on the inorganic deposited layer, which will be described later gas It may be configured to provide a barrier coating layer, such as a rear coating film layer (E).
(Molding of the film)
　The film or sheet of the resin used for the base material layer (A), for example, using one or more resins selected from the group of the resin, the extrusion method, a cast molding method , T-die method, a cutting method, a film of methods have been used inflation method conventionally or can use two or more resins prepared by multi-layer co-extrusion film forming method. Furthermore, the strength of the film, dimensional stability, in view of heat resistance, for example, a tenter method or can be stretched to biaxially uniaxial not using the tubular method or the like.
(Additive)
　Film or sheet of the resin used for the base material layer (A), if necessary, workability, heat resistance, weather resistance, mechanical properties, dimensional stability, oxidation resistance, slip properties, releasability, flame retardant sex, antifungal, electrical properties, improved strength, etc., in the reforming purposes, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. plastic compounding agents or additives and the like can be added, as the amount added, depending on the purpose within a range that does not adversely affect the other performance, it can be optionally added.
[Gas barrier properties of the adhesive layer (B)]
　The adhesive layer in the gas barrier layered product (B) of the present invention, gas barrier properties, in particular oxygen and water vapor barrier properties.
　The thickness of the adhesive layer (B) is 0.5 ~ 6.0 .mu.m, preferably 0.8 ~ 5.0 .mu.m, more preferably from 1.0 ~ 4.5 [mu] m. Tends to thin the gas barrier property inadequate than the above range, easily inferior thicker folding resistant than the above range, the gas barrier property tends to lead to a reduction of the post-bending.
　The adhesive resin composition for forming an adhesive layer (B), for example, a polyol having two or more hydroxyl groups in the molecule (J), an isocyanate compound having two or more isocyanate groups in one molecule (K ) and contains a phosphoric acid-modified compound (L), polyol (J), the main skeleton is a polyester structure, a polyester polyurethane structure, a polyether structure, and one or two elements selected from polyether polyurethane structure comprising the group those having more than include adhesive resin composition. Adhesive resin composition may contain further plate-like inorganic compound (M).
[0023]
　Glass transition temperature of cured coating film of the adhesive resin composition is preferably in the range of -30 ℃ ~ 80 ℃. More preferably from 0 ℃ ~ 70 ℃. More preferably 25 ℃ ~ 70 ℃. If the glass transition temperature is higher than 80 ° C., by the lower flexibility of the cured coating in the vicinity of room temperature, the adhesive strength may be reduced by the adhesion to the substrate is poor. If on the other hand lower than -30 ° C., there is sufficient possibility and the oxygen barrier properties does not come out, the risk of adhesion decreases due to an insufficient cohesive strength by vigorous molecular motion of the cured coating film at about room temperature.
[0024]
　Such polyols (J), isocyanate compound (K), and specific examples of the adhesive resin composition containing a phosphoric acid-modified compound (L), available from DIC Corporation, the oxygen barrier property Series of adhesives Pasurimu (PASLIM) can be used, in particular, a main skeleton polyester, curing agent PASLIM vM001 / VM102CP such a compound is having two or more isocyanate groups is preferably used.
[0025]
(Polyol (J))
　in the polyol (J), wherein the polyester structure was obtained by polycondensation reaction of a polyhydric alcohol polycarboxylic acids by known conventional methods.
　Examples of the polyvalent carboxylic acids include aliphatic polycarboxylic acids and aromatic polycarboxylic acids.
　Specific aliphatic polycarboxylic acids, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like.
[0026]
　Specific aromatic polycarboxylic acids, orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl dicarboxylic acid, 1,2-bis (phenoxy) ethane -p, p'-dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy) such polybasic acids such as benzoic acid and ester-forming derivatives of these dihydroxy carboxylic acids .
[0027]
　Specific ortho-oriented aromatic dicarboxylic acids, orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene dicarboxylic acid, and anhydrides or ester-forming of these dicarboxylic acids derivatives, and the like.
　Examples of the polyvalent carboxylic acids may be used in combination of these singly or two or.
　The polyhydric alcohols include aliphatic polyhydric alcohols and aromatic polyhydric phenol.
[0028]
　Examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, 6-hexanediol, methyl pentanediol, dimethyl butanediol, butyl ethyl propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, can be exemplified tripropylene glycol.
[0029]
　The aromatic polyhydric phenols, specifically, hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, His phenol F, and tetramethyl biphenol, these, ethylene oxide extension product, hydrogenated alicyclic it can be exemplified, and the like.
[0030]
(Isocyanate compound (K))
　the isocyanate compound (K) has two or more isocyanate groups in the molecule may be either aromatic or aliphatic and may be either a low molecular compound or a high molecular compound, an isocyanate group There and two diisocyanate compounds, known compounds such as 3 or more polyisocyanate compounds can be used. Examples of the isocyanate compound (K), may be a blocked isocyanate compound obtained by addition reaction from appropriate method known conventionally using known isocyanate blocking agents.
[0031]
　Among them, from the viewpoint of adhesiveness and retort resistance, the polyisocyanate compound is preferred, in terms of oxygen barrier property imparting, preferably has an aromatic ring, in particular, an isocyanate compound containing meta-xylene skeleton, a urethane group preferred for the reason that it is possible to improve the oxygen barrier property by [pi-[pi stacking of aromatic rings as well as hydrogen bonding.
[0032]
　Specific compounds of the isocyanate compound (K), for example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or their trimer of isocyanate compound, and an excess amount of these isocyanate compounds, such as ethylene glycol, propylene glycol, meta-xylylene alcohol, 1,3-bis hydroxy ethyl benzene, 1,4-bis-hydroxy ethyl benzene, trimethylolpropane, glycerol , pentaerythritol, erythritol, sorbitol, ethylene diamine Monoethanolamine, diethanolamine, triethanolamine, low molecular weight active hydrogen compound and alkylene oxide adducts thereof, such as m-xylylenediamine, various polyester resins, polyether polyols, are reacted with such high molecular active hydrogen compound polyamides adducts obtained Te, biuret, allophanate and the like can be mentioned.
[0033]
(Phosphoric acid-reactive compound (L))
　phosphoric acid-reactive compound (L) are those having an effect of improving adhesive strength to an inorganic member, it can be used conventionally known.
　Specifically, phosphoric acid, pyrophosphoric acid, triphosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid, etc., and may be used alone or two or more thereof.
[0034]
(Solvent)
　was dissolved polyol (J) isocyanate compound and (K), phosphate-modified compound (L) or a plate-like inorganic compounds (M) are uniformly dispersible, and the easy-open gas-barrier laminate of the present invention if those having a suitable boiling point and volatility of the manufacturing process is not particularly restricted.
[0035]
(Plate-like inorganic compounds (M))
　plate-like inorganic compounds (M) has the effect of improving the laminate strength and gas barrier formed by curing the adhesive resin composition barrier adhesive layer (B) .
　The plate-like inorganic compounds (M), specifically, kaolinite - serpentine group clay minerals (halloysite, kaolinite, Ende light, dickite, nacrite and the like, antigorite, chrysotile, etc.), pyrophyllite - Talc Group (pyrophyllite, talc, Kerorai etc.) and the like, may be used alone or two or more thereof.
　Also, solventless gas barrier organic adhesive layer in the gas barrier layered product of the present invention (B) is formed by a solventless, gas barrier properties, in particular oxygen and water vapor barrier properties.
　Solvent content of solvent-free gas barrier organic adhesive layer (B) is zero or 6 mg / m 2 or less. To suppress the solution agent content, curable isocyanate resin composition for forming a solvent-free gas barrier organic adhesive layer (B) is required to have a two-component curing type non solvent adhesive. The two-component curing type non solvent adhesive remains solventless during lamination, used in low viscosity by heating.
[0036]
　If polarity curable isocyanate resin composition using high solvent is poor in workability, for example, in the case of using a highly soluble solvents such as acetone, it has a low boiling point and takes in outside air water easy for the viscosity of the curable isocyanate resin composition by the reaction of water with isocyanate cause problems such easily increased.
[0037]
　Further, when the solvent solventless gas barrier organic adhesive layer (B) is contained in a large amount, it is concerned that adhesion between the layers of the laminate with a solvent is weakened, further, using the obtained laminate a packaging body produced by the packaging material, there is a concern that solvent odor is transferred to the contents. Still further, for the drying time of the volume shrinkage, the gas barrier inorganic vapor-deposited layer (C) solventless embedded in the recess of the irregularities are generated on the surface barrier organic adhesive layer (B) is a defect in peeling liable deterioration of gas barrier properties by causing peeling of the recess becomes larger when bending the laminate easily lead to the gas barrier properties are deteriorated.
[0038]
　The thickness of the solvent-free gas barrier organic adhesive layer (B) is 0.5 ~ 6.0 .mu.m, preferably 0.8 ~ 5.0 .mu.m, more preferably from 1.0 ~ 4.5 [mu] m. Tends to thin the gas barrier property inadequate than the above range, easily inferior thicker folding resistant than the above range, the gas barrier property tends to lead to a reduction of the post-bending.
[0039]
(Two-component curing type non solvent adhesive)
　gas barrier organic adhesive layer (B) two-component curing type non solvent adhesive forming a, for example, with the polyol having two or more hydroxyl groups in the molecule (J), the isocyanate compound having two or more isocyanate groups in one molecule and (K), the phosphoric acid-modified compound (L) and two-component curing type non solvent adhesives containing the like.
[0040]
　Here, the main skeleton of a polyol having two or more hydroxyl groups in the molecule (J) is a polyester structure or polyester polyurethane structure, 70 of polycarboxylic acids derived structural moiety in the polyester structure or the polyester polyurethane structure to 100% by weight is derived from ortho-oriented aromatic dicarboxylic acids.
[0041]
　The polycarboxylic acids refers to polycarboxylic acids and anhydrides and ester-forming derivatives, and the ortho-oriented aromatic dicarboxylic acids refers to ortho-oriented aromatic dicarboxylic acids and their anhydrides or ester-forming derivatives .
[0042]
　Further, the two-liquid curing type non solvent adhesive, further plate-like inorganic compounds (M), a polyester polyol having 2 or more hydroxyl groups in one molecule (P), 1 or 2 or more in one molecule carboxyl groups and may contain one or more of the group consisting of polycarboxylic acid-modified polyester polyol (N) and a least two hydroxyl groups.
[0043]
　In particular, a polyvalent carboxylic acid-modified polyester polyol (N), containing an isocyanate compound having two or more isocyanate groups in one molecule (K), is an acid value of 20 mgKOH / g or more, two-component curing type non solvent adhesives are preferred.
[0044]
　The glass transition temperature of the cured coating film of the two-component curing type non solvent bonding agent is preferably in the range of -30 ° C. ~ 80 ° C., more preferably 0 ° C. ~ 70 ° C., more preferably 25 ℃ ~ 70 ℃. If the glass transition temperature is higher than 80 ° C., by the lower flexibility of the cured coating in the vicinity of room temperature, the adhesive strength may be reduced by the adhesion to the substrate is poor.
[0045]
　If on the other hand lower than -30 ° C., there is sufficient possibility and the oxygen barrier properties does not come out, the risk of adhesion decreases due to an insufficient cohesive strength by vigorous molecular motion of the cured coating film at about room temperature.
[0046]
　There is a type which contains a solvent, but specific examples of the curable isocyanate resin composition for the adhesive layer having an oxygen barrier property, sold by DIC Corporation, the oxygen barrier adhesive Pasurimu (PASLIM) of the series, and the like PASLIMVM001 / VM102CP.
　Here, the polyol (J), isocyanate compound (K), phosphate-modified compound (L), used as the above as a plate-like inorganic compound (M).
(Polycarboxylic acid-modified polyester polyol (N)) 1
　1 or 2 or more carboxyl groups in the molecule and a polycarboxylic acid-modified polyester polyol having 2 or more hydroxyl groups (N) is 3 in one molecule some of the hydroxyl groups of the polyester polyol having a number more hydroxyl groups, is obtained by reacting a polyvalent carboxylic acid.
[Gas barrier inorganic vapor-deposited layer (C)]
　The gas barrier inorganic vapor-deposited layer (C) is a barrier film having a gas barrier property to prevent permeation such as oxygen gas and water vapor, and a vapor deposition film of an inorganic material or an inorganic oxide.
　In general, the inorganic vapor deposition layer surface has occurred ultra fine irregularities, in the ultra-fine levels, the thickness of the inorganic vapor-deposited layer is not uniform, thin portion is weak gas barrier properties in the surface direction.
[0047]
　However, the laminate of the present invention, by having the configuration in contact gas barrier inorganic vapor-deposited layer (C) and adhesive layer and (B) is a super-fine irregularities caused in the gas barrier inorganic vapor-deposited layer (C) the surface by the recess has a flattened structure is filled with an adhesive layer (B) having gas barrier properties, gas barrier properties in the plane direction is made uniform, by reducing the thickness of the gas barrier inorganic vapor-deposited layer (C) while maintaining the flexibility, it is possible to exert a conventional equal or higher gas barrier properties.
[0048]
　Gas barrier inorganic vapor-deposited layer (C) is vapor-deposited aluminum layer, alumina vapor deposited layer, and, a silica vapor deposition layer is preferably a layer having one or more selected from the group consisting of, in particular, an aluminum deposited layer it is preferable.
　Gas barrier inorganic vapor-deposited layer (C), directly on the sealant layer (D), can be provided without using the adhesive layer such as an adhesive layer (B).
[0049]
　If necessary, it is also possible to impart light-blocking properties to prevent the transmission of such visible light and ultraviolet light. Further, the gas barrier inorganic vapor-deposited layer (C) may be composed of one or more layers. When composed of two or more layers, each may be the same composition or a different composition.
[0050]
　The thickness of the gas barrier inorganic vapor-deposited layer (C) is preferably 1 ~ 200 nm, but more preferred thickness varies depending deposition species, in the case of aluminum deposited layer is more preferably 1 ~ 100 nm, still further preferably it is 15 ~ 60 nm, particularly preferably 10 ~ 40 nm.
　In the case of silicon oxide or alumina-deposited film is more preferably from 1 ~ 100 nm, still further preferably 10 ~ 50 nm, particularly preferably 20 ~ 30 nm.
[0051]
　Gas barrier inorganic vapor-deposited layer (C), using a conventionally known inorganic or inorganic oxide, can be formed by a conventionally known method, the composition and forming method is not particularly limited.
　As a formation method, for example, vacuum deposition, sputtering, and ion plating method physical vapor deposition method such as (PhysicalVaporDeposition method, PVD method), or plasma enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition chemical vapor deposition method such as (ChemicalVaporDeposition method, CVD method), and the like.
[0052]
　In the present invention, the gas barrier inorganic vapor-deposited layer (C) sealant layer (D), may be provided on the surface of the adhesive layer (B) side.
　Also, at that time, but it may be pretreated if necessary to the sealant layer (D) surface, specifically, a corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas or the like, glow physical treatment and such discharge treatment, may be subjected to chemical treatment such as oxidation treatment is treated with such chemicals.
[0053]
　In the gas barrier layered product of the present invention, in order to further improve the gas barrier properties against oxygen gas and water vapor, etc., the gas barrier inorganic vapor-deposited layer similar gas barrier inorganic vapor-deposited layer (C), and the adhesive layer of the base material layer (A) ( may also be provided on the side in contact with B). Pretreatment, the deposition species, deposition film forming method and the like are the same as the gas barrier inorganic vapor-deposited layer (C).
[0054]
[Sealant layer (D) (heat-sealing layer)
　sealant layer (D) is a gas barrier laminate and heat-sealable packaging material made of the gas barrier layered product of the present invention, further, bending resistance, impact resistance it is intended to impart a function of equal. In particular, by bending resistance is imparted, it is desirable that it is possible to suppress a decrease in gas barrier properties after bending.
[0055]
　In the present invention, it may optionally be used a material satisfying the conditions as described above.
　In the present invention, the sealant layer (D) preferably has a heat-sealable resin layer. Heat sealable resin layer may be any of those capable of being fused to each other and melted by heat.
　Suitable resin sealant layer (D), polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene - vinyl acetate copolymer, ionomer resin, ethylene - (meth) acrylate copolymer, ethylene - (meth) acrylic acid copolymer, ethylene - propylene copolymer, methylpentene polymer, acrylic acid a polyolefin resin such as polyethylene or polypropylene, methacrylic acid, anhydride maleic acid, modified polyolefin resin with an unsaturated carboxylic acid and other fumaric acid, ethylene - (meth) acrylic acid ester - terpolymer resin of an unsaturated carboxylic acid, cyclic polyolefin resin, cyclic olefin copolymers, polyethylene terephthalate ( ET), polyacrylonitrile (PAN), one or of two or more films or sheets, or other coating film such as a resin of a resin other like can be used.
[0056]
　The film or sheet forming the layer of the resin, can be used but any of the stretched film or sheet or the like was stretched unstretched film or sheet, or uniaxially or biaxially.
[0057]
　Stretched film was stretched in two axial directions is, for example, 50 to longitudinally stretched 2 to 4 times by ~ 100 ° C. of roll stretching machine, brought further transversely stretched 3-5 times by a tenter stretching machine of the atmosphere 90 ~ 0.99 ° C., the same tenter can be obtained by heat treatment at 100 ~ 240 ° C. in an atmosphere. In addition, the stretched film, simultaneous biaxial stretching, may be a sequential biaxial stretching.
　Further, the sealant layer (D) is a heat sealable and peelable in the easy-open gas-barrier laminate of the present invention, further, it may be one which imparts flexibility, functionality such as impact resistance easy peel film is used.
　In particular, by bending resistance is imparted, it is desirable that it is possible to suppress a decrease in gas barrier properties after bending.
　The easy peel film, interfacial peeling type, cohesive failure type is applicable any of delamination type, can be suitably selected depending on the type and required characteristics of the package.
　As an index of easy-open, it is preferable that the sealing strength of the package is in the range of 2 ~ 20 N / 15 mm, it is easy peel film capable of providing a seal strength of the range is used.
　In the present invention, it may optionally be used a material satisfying the conditions as described above.
[0058]
　In the present invention, the sealant layer (D) preferably has a heat-sealable resin layer. Heat sealable resin layer may be any of those capable of being fused to each other and melted by heat.
　Suitable resin sealant layer (D), polyethylene, low density polyethylene, linear low density polyethylene, metallocene polyethylenes, such as cast polypropylene and the like, one or resin composed of two or more of these resin films or it may be used a sheet or other coating film.
　The layer configuration of the sealant layer (D), a multilayer film of polyethylene / polypropylene + polyethylene / polypropylene are preferred. Further, an aluminum film heat sealable unstretched polypropylene (CPP), low density polyethylene, can also be used a film deposited on linear low density polyethylene.
　The above resin may be blended as needed, known bending resistance-improving agent, an inorganic or organic additives.
[0059]
(Thickness of the sealant layer (D))
　The thickness of the sealant layer (D) is capable of arbitrarily selected, from the viewpoint of strength as a packaging material, be selected for use from the range of 5 ~ 500 [mu] m-position It can be, preferably in the range of 10 ~ 250 [mu] m, more preferably 15 ~ 100 [mu] m. Thinner than this without sufficient lamination strength can be obtained even if heat-sealing, penetration resistance, etc. do not function as wrapping material is抵下. In addition, when thicker than this, the film becomes hard workability is deteriorated with the cost is increased.
[0060]
[Gas barrier coating film layer (E)]
　In the present invention, between the substrate layer (A) and the adhesive layer (B), to improve the barrier property to gases such as oxygen gas and water vapor, further, it can be provided a gas barrier coating film layer (E). The gas barrier coating film layer (E) may be provided on the laminated on the base material layer (A) a gas barrier inorganic vapor deposited layer.
　The gas barrier coating film layer (E) is a mixture of a metal alkoxide and a water-soluble polymer, a sol-gel method the catalyst in the presence of such water and an organic solvent, a hydrolyzate of a metal alkoxide obtained by polycondensation by the sol-gel method or it is preferably a layer formed from the resin composition, such as hydrolysis condensates metal alkoxide.
[0061]
　As the metal alkoxide is represented by the following general formula can be preferably used alone or in combination.
　　　　R 1 n M (OR 2 ) m
　(In the formula, R 1 , R 2 represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, n + m represents the valence of M.)
　here, as the metal atom M can be used silicon, zirconium, titanium, aluminum and other. Further, R 1 and R 2 Specific examples of the organic groups represented by, for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, an alkyl group such as i- butyl it can be mentioned. In the same molecule, even these alkyl groups the same or may be different.
[0062]
　Examples of such a metal alkoxide, for example, tetramethoxysilane Si (OCH 3 ) 4 , tetraethoxysilane Si (OC 2 H 5 ) 4 , tetrapropoxysilane Si (OC 3 H 7 ) 4 , tetrabutoxysilane Si (OC 4 H 9 ) 4 , etc., and a silane coupling agent having a functional group that binds to organic matter and the like.
　Metal alkoxide may be used as a mixture of two or more to one without.
[0063]
　The silane coupling agent may be a known organic reactive group-containing organoalkoxysilane, in particular, organoalkoxysilane having an epoxy group is preferred, for example, .gamma.-glycidoxypropyltrimethoxysilane, γ- glycidoxypropylmethyldiethoxysilane or can be used beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
　Silane coupling agents as described above may be used in admixture of two or more to one without. In the present invention, a silane coupling agent as described above can be contained in the range of about 1 to 20 parts by mass relative to the total 100 parts by weight of the alkoxide.
[0064]
　The water-soluble polymer can be preferably used one or both of polyvinyl alcohol resin or ethylene-vinyl alcohol copolymer. These resins may be commercially available ones, for example as the ethylene-vinyl alcohol copolymer, manufactured by Kuraray Co., EVAL EP-F101 (ethylene content: 32 mol%), manufactured by The Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%), or the like can be used.
[0065]
　As the polyvinyl alcohol resin, RS-110 is a RS polymer manufactured by Kuraray Co., Ltd. (saponification degree = 99%, degree of polymerization = 1,000), manufactured by the same company Kuraray Poval LM-20SO (saponification degree = 40%, degree of polymerization = 2,000), the Nippon Synthetic Chemical Industry GOSENOL NM-14 (saponification degree = 99% Co., Ltd., polymerization degree = 1,400), or the like can be used.
[0066]
　The content of the water-soluble polymer is preferably in the range of 5 to 500 parts by weight per 100 parts by weight metal alkoxide. When less than 5 parts by weight, brittleness increases inferior film forming properties of the gas barrier coating film layer (E), weather resistance and the like becomes liable to decrease, if it exceeds 500 parts by weight, the gas barrier property improvement effect is low It becomes trend.
　The sol-gel method catalysts, acid or amine-based compounds are preferable.
[0067]
　Examples of the amine compound is substantially insoluble in water and tertiary amines soluble in organic solvent is preferred. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, may be used tripentylamine like. In particular, N, N-dimethyl base Njiruamin are preferred, metal alkoxides weight per 100 parts by weight, for example, from 0.01 to 1.0 part by weight, it is particularly preferable to contain 0.03 to 0.3 part by weight. Catalytic effect is too small and smaller than 0.01 part by weight, often a catalytic effect is too strong too the reaction rate faster than 1.0 part by weight, the tendency to become uneven.
[0068]
　As the acid, for example, sulfuric, hydrochloric, mineral acids such as nitric acid, and acetic acid, or the like can be used organic acids tartaric such like. The content of the acid, based on the total molar amount of the alkoxy group of the metal alkoxide, preferably 0.001 to 0.05 mole, more preferably 0.01 to 0.03 mol. 0.001 mole catalytic effect is too small and smaller than the greater the catalytic effect is too strong too the reaction rate faster than 0.05 molar parts, the tendency to become uneven.
[0069]
　As the organic solvent, it can be used methyl alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, n- butanol. The gas barrier coating film layer (E) is a coating liquid composed of the resin composition is usually employed, roll coating such as gravure roll coater, spray coating, spin coating, dipping, brushing, bar codes, conventional such applicators by known means, it is formed by coating one or more times.
[0070]
　A specific example of the method of forming the gas barrier coating film layer (E) will be described below.
　First, a metal alkoxide, water-soluble polymer, sol-gel method the catalyst, water, organic solvents, and, by mixing the silane coupling agent, if necessary, to prepare a coating liquid comprising the resin composition. Gradually polycondensation reaction in coating solution in proceeds.
　Then, on the gas barrier inorganic vapor-deposited layer laminated on the base material layer (A), by a conventional method, the coating liquid was coated in a conventional manner and dried. Dried, the alkoxide and vinyl alcohol polymers (and a silane coupling agent) polycondensation is further progress of the layers of the composite polymer is formed. Preferably, it is also possible to repeat the above operation, stacking a plurality of composite polymer layer.
[0071]
　Finally, the laminate formed by coating a coating liquid 20 - 250 ° C., preferably at temperatures of 50 - 220 ° C., it is heated for 1 second to 10 minutes. Thus, it is possible to form on the gas barrier inorganic vapor-deposited layer gas barrier coating film layer (E).
[0072]
　The gas barrier coating film layer (E) may be a composite polymer layer overlaid with one or more layers. The thickness of the gas barrier coating film layer after drying (E) is preferably in the range of 0.01 ~ 100 [mu] m, more preferably from 0.1 ~ 50 [mu] m. Improved dry thickness of the 0.01μm smaller and the gas barrier property is too small, and 100μm larger, cracks are likely to occur.
[0073]
Print layer (F)]
　the easy-open gas-barrier laminate of the present invention, if necessary, for example, between the substrate layer (A) and the adhesive layer (B), in particular, for example, shown in FIG. 3 as, during the gas barrier coating film layer and the (E) and the adhesive layer (B), characters, figures, symbols, print layer formed on any at other desired pattern normal printing scheme (F) it can be provided.
[0074]
[A laminate and the laminate packaging material]
　conventional gas barrier laminates, the inclusion of AC coating or metal deposition layer, etc., the total structure layer number is required than about 8 layers, long manufacturing process for the , had complicated, the gas barrier laminate of the present invention, the total structure layer number it is possible to less than the prior art, it is possible to express an equivalent or more gas barrier properties in the following six layers. It is also possible to 7 or more layers, it is possible to express an equivalent or more gas barrier properties in the total structure layer number less than a relatively conventional materials. The total structure layer number is small, the ability to thin the inorganic vapor deposition layer, the steps can be simplified and shortened, it is possible to reduce the thickness of the laminate, improved flexibility of the laminate, bending resistance There is improved.
[0075]
　Packaging material made of the easy-open gas-barrier laminate and the easily openable barrier laminate of the present invention, as shown in FIG. 4, the substrate layer and (A), the gas barrier inorganic disposed on one side of the sealant layer (D) a deposition layer (C), also, as in Figure 5, and the gas barrier coating film layer (E) the surface of one side gas barrier inorganic vapor-deposited layer and the gas barrier coating film layer (E) is the base layer which is provided (a) , the gas barrier inorganic vapor-deposited layer provided on one surface of the sealant layer (D) and (C) plane, furthermore, as was provided a printed layer as necessary (F) substrate layer shown in FIG. 6 (a) can be manufacturing a gas barrier inorganic vapor-deposited layer provided on one side and (C) plane, respectively laminated via the above adhesive layer (B) of the printed layer (F) surface and the sealant layer (D) .
[0076]
　Packaging material comprising a gas barrier laminate and laminate of the present invention is excellent in gas barrier properties, preferably, an oxygen permeability under 23 ° C. 90% RH environment, 0.05 ~ 2.0 cc / m 2 / day / atm , and the water vapor permeability under 40 ° C. 90% RH environment, 0.01 ~ 2.0 g / m 2 is / day / atm.
[0077]
　Generally, when the vertical pillow filled with contents were prepared packaging bag using the packaging material, the gas barrier properties of the packaging bag the packaging bag is to be exposed to physical load by heat or friction or pressure, etc. Although decreases, packaging bag prepared by using the easy-open gas-barrier packaging material of the present invention has less vertical pillow decrease in gas barrier properties after filling, preferably, one of the filling load longitudinal pillow packing machine It gave after, the oxygen permeability under 23 ° C. 90% RH environment, increasing values from prior to applying the bending load is zero or 10.0 cc / m 2 or less / day / atm, 40 ℃ 90 % RH the water vapor permeability in environment, increase value before providing the bending load, zero or 2.0 g / m 2 or less / day / atm.
　Also, in general, bent with packaging material, heated, to prepare a bonding to packaging bag, upon vertical pillow filled with contents, the packaging bag physical load by heat or friction or pressure, etc. While the gas barrier properties of the packaging bag falls to be exposed to, packaging bag which is manufactured using a gas barrier packaging material of the present invention has less decrease in gas barrier properties, preferably, 5 times Gelbo flex tester after giving a bending load, 23 ° C. of oxygen permeability under 90% RH environment, the increasing value from before giving bending load zero or 20.0 cc / m 2 or less / day / atm, or 10.0cc / m 2 is / day / atm or less.
[Package]
　pillow packaging bag of the present invention is a packaging body obtained by pillow packaging the laminate obtained above, is excellent in gas barrier properties and easy-open performance and flex resistance.
　The present invention will be specifically described by way of examples.
Example
[0078]
Example: Type 1]
[2-component curing type non Preparation of a solvent adhesive A]
　in the polyester reaction vessel equipped with a rectifying tube and water separator was charged with the following raw material is heated gradually under a nitrogen atmosphere, liquid temperature 220 ° C. of the reaction mixture, while maintaining the 100 ° C. vapor temperature was allowed to proceed an esterification reaction, the acid value of the reaction solution is complete the esterification reaction was equal to or less than 1 mgKOH / g, the liquid temperature up to 120 ° C. It cooled.
　　Phthalic anhydride 241.9 parts by weight
　　of ethylene glycol 105.4 parts by
　　Glycerin 75.2 parts by weight
　　of titanium tetraisopropoxide 0.042 parts by
[0079]
　Then, the following raw materials in the reaction solution was poured, while maintaining the liquid temperature 120 ° C., allowed to proceed for polycarboxylic acid-modified reaction, the acid value becomes approximately half of the acid value as calculated from the charged amount of maleic acid It was completed esterification reaction at, and then cooled to obtain a polycarboxylic acid-modified polyester polyols a.
　　77.5 parts by weight of maleic anhydride
characteristics as follows polyvalent carboxylic acid-modified polyester polyol A was obtained.
　　The number average molecular weight: about 520
　　hydroxyl value: 216.6mgKOH / g
　　acid value: 96.2MgKOH / g
　　1 hydroxyl group per molecule: 2 (design value)
　　carboxyl groups per molecule: 1 (design value)
[0080]
　Then, as an isocyanate compound, (number of isocyanate groups biuret .1 per molecule of hexamethylene diisocyanate: Sumika Bayer Urethane Co., "Desmodur N3200" 2 ) and, manufactured by Mitsui Chemicals, Inc. "Takenate 500" (m-xylylene diisocyanate .1 isocyanate groups per molecule: 2) and with a polycarboxylic acid-modified polyester polyol a obtained above, and uniformly mixed and heated to 80 ° C. in the following formulation ratios, cooled, two-component curing to obtain a type non-solvent adhesive a.
　　Polycarboxylic acid-modified polyester polyol A 100 weight parts
　　Desmodur N3200 49.5 parts by
　　Takenate 500 28.9 parts by weight
[0081]
[Example 1]
　one-side corona-treated 20μm of OPP (2 biaxially stretched polypropylene) film as the substrate layer (Toyobo Co., Ltd., P-2171) and the corona treated surface of a single-sided aluminum deposition as a sealant layer processing (40 nm thick) has been 25μm of CPP (non-oriented polypropylene) film (Toray Advanced film Co., Ltd., 2703) and aluminum-deposited surface of the via two-component curing type non solvent adhesive a, nonsolvent It was laminated.
[0082]
　The coating amount of the adhesive in this case, the thickness after curing of the adhesive layer is an amount to be 3 [mu] m. After the lamination, and one day aging process at 40 ° C., to obtain a laminate. About the obtained layered product, the gas barrier property, lamination strength was evaluated containing solvent amount. The results are shown in Table 1.
[0083]
　　Layer structure: OPP (20μm) / solventless gas barrier organic adhesive (3 [mu] m) / aluminum vapor deposition (40nm) / CPP (25μm)
[0084]
Example 2
　as a sealant layer, instead of the CPP thickness 25 [mu] m, which is one side aluminized, thickness 25 [mu] m CPP (Toyobo Co., Ltd., P1128. Sided corona treated.) One side alumina deposition process ( except for using 20nm thick) that were performed in the same manner as in example 1, to obtain a laminate was evaluated in the same manner. One side alumina deposition process conditions are as follows.
[0085]
　　Layer structure: OPP (20 [mu] m) / solventless gas barrier organic adhesive (3 [mu] m) / alumina deposition (20 nm) / CPP (25 [mu] m)

　deposition surface: corona-treated surface
　vacuum chamber - vacuum in; 2-6 × 10 -6 mBar
　deposition chamber - the degree of vacuum: 2 ~ 5 × 10 -3 mBar
　cooling-electrode drum supply power: 10 kW
　line speed: 100 m / min
　Next, the deposition of the alumina film thickness 200 Å (20 nm) in the above immediately after forming the film, the deposited film surface of the alumina using a glow discharge plasma generating apparatus, power 9 kW, oxygen gas: a mixed gas of argon gas = 7.0:: 2.5 (S1M units) use a mixed gas pressure of 6 × 10 -3 subjected to oxygen / argon mixed gas plasma treatment at Torr, thereby improving the surface tension of the vapor deposited film surface of the alumina 54 dyne / cm or more flop To form a plasma-treated surface.
[0086]
[Example 3]
　as a sealant layer, instead of the CPP thickness 25 [mu] m, which is one side aluminized, thickness 25 [mu] m CPP (Toyobo Co., Ltd., P1128. Sided corona treated.) One side of silicon oxide deposition process except for using (20 nm thick) that performed in the same manner as in example 1, to obtain a laminate was evaluated in the same manner. Single-sided silicon oxide deposition process conditions are as follows.
[0087]
　　Layer structure: OPP (20 [mu] m) / solventless gas barrier organic adhesive (3 [mu] m) / silicon oxide deposition (20 nm) / CPP (25 [mu] m)

　deposition surface: corona-treated surface
　of introduced gas: hexamethyldisiloxane / oxygen gas / helium = 1.0 / 3.0 / 3.0 (unit: S1M)
　vacuum chamber - vacuum in; 2 ~ 6 × 10 -6 mBar
　deposition chamber - the degree of vacuum: 2 ~ 5 × 10 -3 mBar
　cooling-electrode drum supply power: 10kW
　line speed: 100m / min
[0088]
　Then, immediately after forming the deposited film of silicon oxide film thickness 200 Å (20 nm) above, the vapor deposited film surface of the silicon oxide, using a glow discharge plasma generating apparatus, power 9 kW, oxygen gas: argon gas = 7.0: 2.5 (unit: S1M) using a mixed gas consisting of a mixed gas pressure of 6 × 10 -3 subjected to oxygen / argon mixed gas plasma treatment at Torr, the surface tension of the vapor deposited film surface of silicon oxide was to form a plasma treated surface with improved 54 dyne / cm or more.
[0089]
[Comparative Example 1]
　2-component curing type non-solvent adhesive A, 2 part curing urethane adhesive (Toyo Morton Co., Ltd., Tomo flex TM-340 / Toyo Morton Co., Ltd. CAT-29) in place, the aging conditions the same manner as in example 1 except that the 25 ° C. 1 day to obtain a laminated body, was evaluated in the same manner.
[0090]
　　Layer structure: OPP (20μm) / 2-component curing type urethane adhesive (3 [mu] m) / aluminum vapor deposition (40nm) / CPP (25μm)
[0091]
[Comparative Example 2]
　to form a film of the multilayer film of polyethylene / polypropylene + polyethylene / polypropylene, to give easy peel CPP film having a thickness of 25 [mu] m.
[0092]
　Moreover, for easy peel CPP film obtained by winding type vacuum deposition apparatus, aluminum was induction heating, 5 × 10 -4 performs aluminum vapor deposition treatment under Torr, as a gas barrier inorganic vapor-deposited layer (C) having a single-sided aluminum deposition layer of 40nm thickness, to obtain easy peel CPP (non-oriented polypropylene) film a having a thickness of 25 [mu] m.
[0093]
　One side corona-treated 20μm of OPP (2 biaxially stretched polypropylene) film (Toyobo Co., Ltd., P-2171) of the AC coat (DICG Co., Ltd. P-1000 to the corona-treated surface, the coating coating, after drying thickness 3 g / m 2 ), and said the AC coated surface, a PET film of 12 [mu] m, which is one side aluminized by the following deposition conditions (Toyobo Co., Ltd., biaxially oriented PET film, E-5100. thickness 12 [mu] m, an aluminum vapor deposition surface of the one-side corona-treated.), low density polyethylene (Nippon polyethylene Co., Ltd., was laminated by extrusion lamination through LC600A.). The thickness of the polyethylene was adjusted to 7 [mu] m.
[0094]
　Next, by AC-coated non-deposition surface of the laminated the aluminum deposited PET, and the AC-coated surface, and easy peel CPP film A of 25μm which has easy-open, low-density polyethylene (Nippon Polyethylene Co. Ltd., was extrusion lamination through the LC600A.). The thickness of the polyethylene was adjusted to 7 [mu] m. After the lamination, and aged for 1 day at 25 ° C., to obtain a laminate was evaluated in the same manner.
[0095]
　　Layer structure: OPP (20μm) / AC coat / PE (7μm) / aluminum vapor deposition (40nm) / PET (12μm) / AC coat / PE (7μm) / CPP (25 [mu] m)

　deposition surface: corona-treated surface
　vacuum chamber - vacuum in; 2 ~ 6 × 10 -6 mBar
　deposition chamber - the degree of vacuum: 2 ~ 5 × 10 -3 mBar
　cooling-electrode drum supply power: 10 kW
　line speed: 100 m / min
[0096]
　Then, immediately after forming the deposited film of aluminum having a thickness 400 Å (40 nm) above, the vapor deposited film surface of the aluminum, using a glow discharge plasma generating apparatus, power 9 kW, oxygen gas: argon gas = 7. 0: 2.5 (unit: S1M) using a mixed gas consisting of a mixed gas pressure of 6 × 10 -3 subjected to oxygen / argon mixed gas plasma treatment Torr, the surface tension of the vapor deposited film surface of aluminum 54 dyne / to form a plasma treated surface with improved or more cm.
[0097]
[Comparative Example 3]
　The solvent-free gas barrier organic adhesive, was replaced by含溶agent gas barrier organic adhesive following the same manner as in Example 1, to obtain a laminate was evaluated in the same manner.
[0098]
　　Layer structure: OPP (20μm) / 含溶 agent gas barrier organic adhesive (3 [mu] m) / aluminum vapor deposition (40nm) / CPP (25μm)
[0099]
(Preparation of含溶agent gas barrier organic adhesive)
　by mixing the adhesive and a solvent described below were prepared含溶agent gas barrier organic adhesive.
[0100]
　　Adhesive: PASLIM VM001 / VM102CP (DIC (Co.) Ltd.) 19 parts by weight
　　agent: ethyl acetate 15 parts by weight
[0101]

[laminating property]
　Each Example and each laminate obtained in the Comparative Examples, respectively cut a strip to the width of the specimen of 15 mm, Tensilon tensile tester (KK Orientech manufactured RTC-1310A) with under 25 ° C. atmosphere, the T-peel method (pulling rate 50 mm / min), to measure the maximum load when peeling the substrate layer and the sealant layer, and the laminate strength (N / 15 mm). Furthermore, it was confirmed peeling boundary site. Notation in Table 1 are the following meanings.
　　VM / CPP: Peeling at the interface between the deposited layer and the CPP layer
　　PE / VM: Peeling at the interface between the polyethylene layer and the deposited layer
　　contact / VM: Peeling at the interface between the adhesive layer and the vapor deposition layer
[0102]
[Gas
barrier] (1) oxygen permeability
　of each laminate was cut into A4 size, using the American manufactured by MOCON OXTRAN2 / 20, 23 ℃, oxygen permeability under the conditions of 90% RH (cc / m 2 / day / atm) was measured.
(2) water vapor transmission rate
　of each laminate was cut into A4 size, using the American manufactured by MOCON PERMATRAN3 / 31, 40 ℃, water vapor permeability under conditions of 90% RH (g / m 2 / day / atm ) was measured.
(3) bending load after
　after giving the five bending load Gelbo flex tester, the oxygen permeability was measured by the same method and conditions as described above.
[Containing solvent
　amount] in the DNP method, in the film, toluene, ethyl acetate, IPA, methanol, the total amount of MEK (mg / m 2 was measured). The total amount is zero or 6 mg / m 2 was evaluated as acceptable or less.
[0103]
[Table 1]

[0104]
[Result Conclusion
　Examples 1-3 with the solvent-free gas barrier organic adhesive layer (B), the laminate strength is equivalent to Comparative Example 1 using a conventional two-liquid curing type urethane adhesive, Comparative Example 2 is better than 3, and gas barrier property after bending was higher than Comparative example 3 using a conventional Comparative examples 1 and 2, and含溶agent gas barrier adhesive.
[0105]
Example: Type 2
(Preparation of adhesive resin composition)
　were mixed adhesive and a solvent described below, adhesive resin composition (A) was prepared.
　　Adhesive: PASLIM VM001 / VM102CP (DIC (Co.) Ltd.) 19 parts by mass
　　Solvent: ethyl acetate 15 parts by weight
[0106]
(Preparation of aluminum deposited easy peel CPP)
　Next, to form a film of the multilayer film of polyethylene / polypropylene + polyethylene / polypropylene, to give easy peel CPP film having a thickness of 25 [mu] m.
　Moreover, for easy peel CPP film obtained by winding type vacuum deposition apparatus, aluminum was induction heating, 5 × 10 -4 performs aluminum vapor deposition treatment under Torr, as a gas barrier inorganic vapor-deposited layer (C) having a single-sided aluminum deposition layer of 40nm thickness, to obtain easy peel CPP (non-oriented polypropylene) film a having a thickness of 25 [mu] m.
[0107]
[Example 4]
　20 [mu] m of OPP (2 biaxially oriented polypropylene) which is one side corona treated as a base material layer (A) Film (Toyobo Co., Ltd., P-2171) and the corona treated surface of a sealant layer (D as the aluminum-deposited surface of the easy peel CPP film a single-sided aluminum deposition), via the adhesive resin composition as a gas barrier adhesive layer (B) to (a), and dry lamination.
　The coating amount of the adhesive resin composition of this case (A), the thickness after curing of the adhesive layer is an amount to be 3 [mu] m. After the lamination, and 3 days aged at 40 ° C., to obtain a laminate. About the obtained layered product, the vertical pillow filling test, gas barrier property, lamination strength was evaluated packaging material seal strength. The results are shown in Table 2.
　　Layer structure: OPP (20μm) / gas barrier adhesive (3 [mu] m) / aluminum vapor deposition (40nm) / CPP (25μm)
[0108]
[Example 5-8]
　except that the thickness of the adhesive resin composition (A) was changed to a value in the table (1.1,2.2,3.3,4.4Myuemu), performed to prepare a laminate in the same manner as in example 4, it was evaluated gas barrier property.
Layer structure of Example 5: OPP (20μm) / gas barrier adhesive (1.1 .mu.m) / aluminum vapor deposition (40nm) / CPP (25μm)
layer of Example 6 configuration: OPP (20μm) / gas barrier adhesive (2.2 .mu.m ) / aluminum vapor deposited (40 nm) / CPP (25 [mu] m)
layer of example 7 Composition: OPP (20 [mu] m) / gas barrier adhesive (3.3 [mu] m) / aluminum vapor deposited (40 nm) / CPP (25 [mu] m)
layer of example 8 Composition: OPP (20 [mu] m) / gas barrier adhesive (4.4 [mu] m) / aluminum vapor deposition (40nm) / CPP (25μm)

claims

At least, the base layer and (A), the gas barrier properties of the adhesive layer (B), and a gas barrier inorganic vapor-deposited layer (C), and a gas barrier laminate having a sealant layer (D),
　the gas barrier properties of the adhesive layer (B) and the gas barrier inorganic vapor-deposited layer and (C) are laminated adjacently,
　the thickness of the gas barrier properties of the adhesive layer (B) is a 0.5 ~ 6.0 .mu.m,
the gas barrier laminate.
[Requested item 2]
　The gas barrier properties of the adhesive layer (B) is a solventless gas barrier organic adhesive layer, the inorganic solvent type gas barrier organic adhesive layer, two-component curing type non solvent bonding agent is applied, it is further cured a formed layer, the solvent content of the solvent-free gas barrier organic adhesive layer is zero or 6 mg / m 2 or less,
the gas barrier laminate according to claim 1.
[Requested item 3]
　It said sealant layer (D) is an easy-open sealant layer, a gas barrier laminate according to claim 1 or 2.
[Requested item 4]
　Between the substrate layer (A) and the gas barrier properties of the adhesive layer (B), and a gas barrier laminate having a gas barrier coating film layer (E), the gas barrier coating film layer (E) is a metal alkoxide and those containing sol-gel method hydrolytic polycondensate of a mixture of a water-soluble polymer, the gas barrier laminate according to any one of claims 1-3.
[Requested item 5]
　Between the substrate layer (A) and the gas barrier properties of the adhesive layer (B), and having a printing layer (F), the gas barrier laminate according to any one of claims 1-4.
[Requested item 6]
　The gas barrier inorganic vapor deposited layer (C) is vapor-deposited aluminum layer, alumina vapor deposited layer, and, a silica vapor deposited layer is one or a layer having two or more selected from the group consisting of any one of claims 1 to 5, the gas barrier laminate according to claim.
[Requested item 7]
　The gas barrier inorganic vapor deposited layer (C) is a layer having a vapor-deposited aluminum layer, a gas barrier laminate according to any one of claims 1-6.
[Requested item 8]
　The gas barrier thickness of the inorganic deposited layer (C) is 1 ~ 100 nm, the gas barrier laminate according to any one of claims 1 to 7.
[Requested item 9]
　Oxygen permeability under 23 ° C. 90% RH environment, 0.05 ~ 2.0 cc / m 2 was / day / atm, the water vapor permeability under 40 ° C. 90% RH environment, 0.01 ~ 2.0 g / m 2 is / day / atm, the oxygen barrier for and water vapor barrier, a gas barrier laminate according to any one of claims 1-8.
[Requested item 10]
　After giving five bending load Gelbo flex tester,
　the oxygen permeability under 23 ° C. 90% RH environment, increasing values from prior to applying the bending load, zero or 20.0 cc / m 2 / day / atm or less, the gas barrier laminate according to any one of claims 1-8.
[Requested item 11]
　After giving five bending load Gelbo flex tester,
　the oxygen permeability under 23 ° C. 90% RH environment, increasing values from prior to applying the bending load, zero or 10.0 cc / m 2 / day / atm or less, the gas barrier laminate according to any one of claims 1-8.
[Requested item 12]
　After it received a single filling load longitudinal pillow packing machine,
　the oxygen permeability under 23 ° C. 90% RH environment, increasing values from prior to applying the bending load, zero or 10.0 cc / m 2 / day / atm or
　less, the water vapor permeability under 40 ° C. 90% RH environment, increasing values from prior to applying the bending load, zero or 5.0 g / m 2 or less / day / atm,
claim the gas barrier laminate according to any one of 1-8.
[Requested item 13]
　Total configuration layer number is 6 or less, the gas barrier laminate according to any one of claims 1 to 12.
[Requested item 14]
　Either according to item 1, the easy-open gas-barrier laminate having an easy-open sealant layer of claim 3-12.
[Requested item 15]
　Using a gas barrier laminate according to any one of claims 1 to 14, a gas barrier packaging material.
[Requested item 16]
　Using a gas barrier laminate according to any one of claims 1 to 15, pillow packaging bags.