JP2019119060A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having excellent heat resistance and moisture resistance. A gas barrier film obtained by forming an inorganic oxide layer and a photopolymerizable composition layer on at least one surface of a base material in this order, wherein the photopolymerizable composition layer is (a) unsaturated double. It is formed of a resin obtained by polymerizing a photopolymerizable composition containing a polyvalent metal salt of a carboxylic acid compound having a double bond and a compound having an unsaturated double bond other than (b) and (a). Then, the ratio of the absorbance A based on νC = O of the carboxylate ion near 1560 cm-1 and the absorbance A0 based on νC = O of the carboxylic acid group near 1700 cm-1 in the infrared absorption spectrum of the photopolymerizable composition layer. Provided is the gas barrier film having (A / A0) of 0.01 or more and less than 1.2. [Selection diagram] Fig. 1

Description

  The present invention relates to a barrier film in which the gas barrier performance hardly deteriorates even in a high temperature, high humidity and high temperature drying environment.

  In order to maintain the quality of food products, pharmaceuticals, chemical products, electronic components, industrial products, etc. for a long time, packaging materials and films with a barrier function that block or significantly reduce the amount of oxygen and water vapor transmission It has been demanded. For example, oxygen accelerates deterioration of quality such as oxidation and decay if the content is organic, and water vapor accelerates growth of various bacteria depending on the moisture content of the content if the content is deteriorated by drying or moisture absorption. From these, the barrier performance of each gas is required. In addition, with the globalization of supply chains in recent years, for example, products manufactured / processed and bagged in Southeast Asia may be placed under severe conditions in storage under high temperature and high humidity environment or in distribution process by ship etc. From the fact, it is required that the temperature and humidity dependency be sufficiently small to maintain high gas barrier performance even under such conditions.

  Moreover, in order to protect the electronic member and the building member from oxidation deterioration and moisture deterioration, a barrier material and a barrier film obtained by laminating them may be used by being incorporated into the member and stable even when exposed to high temperature and humidity Gas barrier performance is required.

  Conventionally, as a barrier material against oxygen or water vapor, an inorganic oxide such as silicon oxide or aluminum oxide is formed on a film substrate by vacuum evaporation, sputtering, ion plating, chemical vapor deposition, etc. Transparent gas barrier films have attracted attention. However, since such a transparent gas barrier film is a film in which an inorganic oxide is deposited on a substrate surface made of a biaxially stretched polyester film generally excellent in transparency and rigidity, the inorganic oxide layer is not It is weak, and when it is manufactured as a packaging film, there is a problem that the gas barrier performance is destabilized by cracks or the like in the inorganic oxide layer due to rubbing or elongation at the time of printing or laminating after processing or filling of contents. there were.

  Therefore, in order to protect the inorganic oxide layer from mechanical deterioration due to rubbing and elongation, and at the same time to improve the barrier performance, laminating of various coating type barrier materials is performed.

  For example, according to Patent Document 1, a solution comprising a polyacrylic acid polymer neutralized with ammonia, zinc oxide, etc. is formed into a film on a polyethylene terephthalate (PET) substrate, and heat-dried at 180 ° C. for 3 minutes. It is noted to form acrylic acid metal salts. However, this is limited to a heat-resistant substrate, and dimensional changes such as wrinkles and curls due to shrinkage of the laminated film are easily caused by heating, and degradation due to stress concentration on the barrier layer may be concerned. In addition, since ammonia gas is released or remains in the package during drying and subsequent circulation processes, there are concerns about working environment, deterioration of contents, odor and health of the human body.

  Further, according to Patent Document 2, it is described that a mixed solution comprising a zinc acrylate monomer and a photopolymerization initiator and the like is coated on a base material, and this is provided with a gas barrier layer by electron beam irradiation (EB, UV) There is.

  In the gas barrier films described in Patent Documents 1 to 3, how the oxygen permeability and the water vapor permeability change after a test of storing the laminated film having a layer under high temperature and humidity, for example, at 85 ° C. and 85% RH for 24 hours, There is no statement of whether it does not change.

  Further, according to the example of Patent Document 2, it is shown that the oxygen permeability is low (the oxygen barrier performance is good) at humidity RH 90%, and the oxygen permeability is high (the oxygen barrier performance is bad) at RH 0%. This indicates that the oxygen barrier performance changes by about one digit when the barrier material is in a low humidity or dry environment.

  From the above, the barrier performance is deteriorated by being exposed to the external environment (high temperature and humidity or drying), and the quality of the contents becomes shorter than expected along with it, and the packaging bag and packaging container, oxidation resistant It is expected that the requirements as a moistureproof member can not be satisfied.

JP, 2016-193509, A Patent No. 4808752 Patent No. 4373797 gazette

  An object of the present invention is to provide a gas barrier film which has excellent barrier performance against oxygen, water vapor and the like, and which is hardly deteriorated even under high temperature and humidity or high temperature drying.

As a result of various studies, the present inventor contains (a) a polyvalent metal salt of a carboxylic acid compound having a photopolymerizable functional group, and (b) a compound having a photopolymerizable functional group other than (a) provided a photopolymerizable composition layer on the inorganic oxide layer on the substrate layer, the light of the polymerizable composition layer near 1560 cm ^-1 in the infrared absorption spectrum carboxylate ion of νC = O based upon the absorbance a and 1700 cm ^{- The} above object is achieved by setting the ratio (A / A ₀ ) to the absorbance A ₀ based on C C O O of the carboxylic acid group in the vicinity of ^{1 to} a specific range of 0.01 or more and less than 1.2. I found out.
And this invention is characterized by the following points.

[1] A gas barrier film obtained by forming an inorganic oxide layer and a photopolymerizable composition layer in this order on at least one side of a substrate,
The photopolymerizable composition layer is
(A) a polyvalent metal salt of a carboxylic acid compound having a photopolymerizable functional group,
(B) It is formed of a resin obtained by polymerizing a photopolymerizable composition containing a compound having a photopolymerizable functional group other than (a),
Then, the ratio between the absorbance A ₀ based on νC = O of 1560 cm ^-1 vicinity of carboxylate absorbance A and 1700 cm ^-1 vicinity of the carboxylic acid groups based on νC = O ions in the infrared absorption spectrum of the gas barrier layer (A The said gas barrier film whose / _A0 ) is 0.01 or more and less than 1.2.

[2] The gas barrier film according to the above [1], wherein A / A ₀ is 0.01 to 1.0.

  [3] The gas barrier film according to the above [1] or [2], wherein the carboxylic acid compound of the compound (a) is a monomer having an unsaturated double bond or a carboxylic acid compound having a polymerization degree of 10 or less.

[4] The carboxylic acid compound of the compound (a) is at least one selected from the group consisting of (meth) acrylic acid, α-ethyl acrylic acid, maleic acid, fumaric acid and itaconic acid, and the compound (a) The polyvalent metal according to any one of the above [1] to [3], which is at least one selected from the group consisting of Mg, Ca, Ba, Zn, Cu, Co, Ni, Al and Fe Gas barrier film.

  [5] The gas barrier film according to any one of the above [1] to [4], wherein the compound (b) is a monomer having an unsaturated double bond or a carboxylic acid compound having a degree of polymerization of 100 or less.

  [6] Compound (b) is pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, triethylene glycol diacrylate, isocyanuric acid EO modified The gas barrier film according to any one of the above [1] to [5], which is at least one selected from the group consisting of diacrylate, isocyanuric acid EO modified triacrylate and 2-hydroxy-3-acryloyloxypropyl methacrylate. .

  [7] The gas barrier film according to any one of the above [1] to [4], wherein the compound (b) is a reactive polymer having an unsaturated double bond.

  [8] The gas barrier film according to the above [5] or [6], further containing a reactive polymer having a photopolymerizable functional group as the compound (b).

  [9] The reactive polymer is a homopolymer or copolymer obtained from alkyl (meth) acrylate, and is a homopolymer or copolymer having an unsaturated double bond in the main chain or side chain, The gas barrier film as described in said [7] or [8].

  [10] A laminated material for packaging using the gas barrier film according to any one of the above [1] to [9], wherein an intermediate layer and a heat sealable resin layer are provided in order on the barrier film of the laminated film. Packaging laminate material characterized by

  [11] A packaging bag using the packaging laminate according to the above [10], wherein the heat sealing resin layer side of one packaging laminate and the heat sealing resin layer of the other packaging laminate A packaging bag characterized by being stacked so as to be opposed to the side, and heat sealing the end.

  It is an object of the present invention to provide a gas barrier film having excellent barrier performance against oxygen, water vapor, etc., and to which the barrier performance hardly deteriorates even when exposed to high temperature and humidity and high temperature drying, and a laminate thereof. The packaging bag / packaging container using the gas barrier film of the present invention, the oxidation-resistant, moisture-proof member is less likely to deteriorate the barrier layer due to high temperature and humidity than before, and can be expected as maintaining the quality of contents and prolonging the life It is a thing.

It is a schematic sectional drawing which shows the example about the gas barrier film of this invention. It is a schematic sectional drawing which shows the example about the laminated material for packaging containing the gas barrier film of this invention.

The above invention will be described in more detail below.
<Layer constitution of gas barrier film and laminated material for packaging including the same>
The gas barrier film of the present invention and a packaging laminated material containing the same will be described.

  FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier film of the present invention.

  The gas barrier film of the present invention is based on a structure in which an inorganic oxide layer 2 and a photopolymerizable composition layer 3 are laminated in this order on a base material layer 1 as shown in FIG.

  FIG. 2 is a schematic cross-sectional view showing an example of a packaging laminate including the gas barrier film of the present invention. As shown in FIG. 2, the above-mentioned packaging laminate material is based on a configuration in which an intermediate layer 4 and a sealant layer 5 are sequentially laminated on the photopolymerizable composition layer 3 of the gas barrier film.

  Hereinafter, each layer which comprises the gas barrier film of this invention and the laminated material for packaging containing this is demonstrated.

<Base layer>
The base material layer constituting the above-mentioned gas barrier film may be any resin film or sheet which satisfies mechanical, physical and chemical strength, heat resistance and texture required for packaging material of contents to be filled and packaged. Can be selected.

  Specifically, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), Polyester resins such as polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, polyethylene flanolate, etc., various nylons, etc. Polyamide resins, polyimide resins, polyamideimide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfone resins, and polycarbonates. Tan resin, acetal resin, cellulose resin, and a film or sheet of various resins such as mixtures thereof. As films or sheets of these various resins, for example, films or sheets of various resins formed by stretching in one or two axial directions by using a tenter system or a tubular system can be used. .

  In the above plastic film, the film thickness of films or sheets of various resins is preferably 3 to 200 μm, more preferably 9 to 100 μm.

<Inorganic oxide layer>
As the inorganic oxide layer, a deposited film of an inorganic oxide such as silicon oxide or alumina can also be used. As the above-mentioned vapor deposition film, inorganic oxides such as silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron ( B) Oxides such as titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and the like, preferably alumina, and a deposited film of silica can be mentioned. The film thickness of the vapor-deposited film of the inorganic oxide varies depending on the type of inorganic oxide used, etc., but is arbitrarily selected within the range of, for example, 20 to 2000 Å, preferably 50 to 500 Å, from the viewpoint of gas barrier performance. Can. Moreover, the vapor deposition film of the said inorganic oxide can be provided on a film by a physical vapor deposition method or a chemical vapor deposition method.

  By providing such an inorganic oxide layer between the base material layer and the photopolymerizable composition, the barrier performance of the obtained barrier film is dramatically improved.

<Photopolymerizable Composition Layer>
The photopolymerizable composition layer is formed by coating on the inorganic oxide surface of the base material layer.

  Examples of the method for applying the liquid composition include application methods such as roll coating, bar coating, gravure coating, and slit coating. After application of the liquid composition, drying and UV curing are performed.

  Specific examples of the ultraviolet light source include light sources of ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc lamp, black light fluorescent lamp and metal halide lamp. As a wavelength, a wavelength range of 190 to 450 nm can be used.

In the photopolymerizable composition layer, and the absorbance A ₀ based on νC = O absorbance A and 1700 cm ^-1 vicinity of the carboxylic acid groups based on νC = O of carboxylate ions in the vicinity of 1560 cm ^-1 in the infrared absorption spectrum The ratio (A / A ₀ ) is at least 0.01 and less than 1.2, preferably 0.01 to 1.19, and more preferably 0.01 to 1.1.

In the present invention, the ratio of the absorbance A ₀ based on ν C O O of the carboxylic acid group around 1700 cm ⁻¹ to the absorbance A based on ν C O O of carboxylate ion around 1560 cm ⁻¹ in the infrared absorption spectrum (A / A ₀ 1) cut out a 1 cm × 3 cm measurement sample from the gas barrier film, measure the infrared absorption spectrum of the surface (photopolymerizable composition layer) by infrared total reflection measurement (ATR method), and measure the absorbance according to the following procedure A and absorbance A ₀ are determined, and the ratio (A / A ₀ ) calculated therefrom is meant.

In the above, the absorbance A, based on the νC = O of carboxylate ions in the vicinity of 1560 cm ^-1, signed and absorbance at 1500 cm ^-1 and 1600 cm ^-1 in the infrared absorption spectrum by a straight line (L), between 1500～1600Cm ^-1 A straight line (M) is drawn vertically from the maximum absorbance of ¹ (in the vicinity of 1560 cm ^-1 ), and the distance (length) of the absorbance at the point of intersection between the straight line (M) and the straight line (L) and the maximum absorbance.

In the above, the absorbance A ₀ based on νC = O of the carboxylic acid groups in the vicinity of 1700 cm ^-1, signed and absorbance at 1600 cm ^-1 and 1800 cm ^-1 in the infrared absorption spectrum by a straight line (N), 1600~1800cm ^-1 A straight line (O) is drawn vertically from the maximum absorbance (near 1700 cm ^-1 ), and the distance (length) of the absorbance between the point of intersection of the straight line (O) and the straight line (N) and the maximum absorbance.

  The thickness of the photopolymerizable composition layer is 0.05 to 20 μm, more preferably 0.1 to 10 μm.

<Photopolymerizable composition>
In the present invention, the photopolymerizable composition comprises (a) a polyvalent metal salt of a carboxylic acid compound having a photopolymerizable functional group (hereinafter also referred to as "compound (a)") and (b) (a) And a compound having a photopolymerizable functional group (hereinafter, also referred to as "compound (b)").

Since the ratio (A / A ₀ ) of the absorbance A to the absorbance A ₀ is based on the amount of carboxylic acid and carboxylate ion in the photopolymerizable composition, the compound (a) and the compound (b) The ratio (A / A ₀ ) of the absorbance A to the absorbance A ₀ can be made to fall within the above specific range by adjusting the mixing ratio of The mixing ratio of the compound (a) to the compound (b) depends on the kind of the compound, but the mass ratio is more than 1: 1 and 1:15 or less, preferably 1: 1.05 to 1 : 13.

  Hereinafter, each component contained in said photopolymerizable composition is demonstrated.

<(A) Polyvalent Metal Salt of Carboxylic Acid Compound Having Photopolymerizable Functional Group>
A polyvalent metal salt of a carboxylic acid compound having a photopolymerizable functional group (hereinafter, also referred to as “compound (a)”) is formed from a compound having a photopolymerizable functional group and a carboxylic acid group and a polyvalent metal Salt. In the carboxylic acid compound having a photopolymerizable functional group, which is one of the components forming the compound (a), the “photopolymerizable functional group” can exemplify, for example, an unsaturated double bond, and In particular, ethylenic double bonds such as (meth) acryloyl group, vinyl group and allyl group can be mentioned. In addition, "(meth) acryloyl group" means at least any one of "acryloyl group" and "methacryloyl group."

  Examples of the carboxylic acid compound of the compound (a) include monomers having unsaturated double bonds or carboxylic acid compounds having a polymerization degree of 10 or less, and specifically, (meth) acrylic acid, α-ethyl acrylic acid It is preferred to use at least one selected from the group consisting of acid, maleic acid, fumaric acid and itaconic acid. In addition, "(meth) acrylic acid" means at least one of "acrylic acid" and "methacrylic acid."

  As a polyvalent metal which is one of the components to form the compound (a), magnesium (Mg), calcium (Ca), barium (Ba), zinc (Zn), copper (Cu), cobalt (Co), nickel And metals such as (Ni), aluminum (Al), iron (Fe) and the like, and more preferably at least one metal selected from the group consisting of Mg, Ca, Ba, Zn and Al. It is preferable to do.

  In the present invention, at least one selected from the group consisting of zinc (meth) acrylate, magnesium (meth) acrylate, calcium (meth) acrylate and aluminum (meth) acrylate as the above compound (a) It is preferred to use. In the present invention, commercially available polyvalent metal salts of carboxylic acid compounds having unsaturated double bonds can also be used, and examples thereof include zinc acrylate manufactured by Wako Pure Chemical Industries, Ltd.

<(B) (a) Compound Having Photopolymerizable Functional Group Other Than (a)>
The compound having a photopolymerizable functional group other than (a) (hereinafter, also referred to as “compound (b)”) is a compound other than the compound (a), and a photopolymerizable functional group such as unsaturated It may be any one having a double bond, and can be widely used regardless of, for example, the number of functional groups of the ethylenic double bond, and the properties of the compound such as hydrophilicity and hydrophobicity. As the compound (b), usually, a compound having a photopolymerizable functional group and a carboxylic acid group may be used as long as it is a compound which does not contain a polyvalent metal salt or a polyvalent metal oxide.

As the compound (b), for example, a monomer having an unsaturated double bond or a compound having a polymerization degree of 100 or less, or a reactive polymer having an unsaturated double bond can be used alone or in combination. . Examples of the monomer having a unsaturated double bond or the compound having a degree of polymerization of 100 or less include (meth) acrylic acid, α-ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid and pentaerythritol triacrylate. , Pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, triethylene glycol diacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified triacrylate and 2-hydroxy It is possible to use at least one member selected from the group consisting of -3-acryloyloxypropyl methacrylate, among which pentaerythritol triacrylate, dipentaerythritol hexaacrylate, Ethylene glycol diacrylate, it is preferred to use 2-hydroxy-3-acryloyloxy propyl methacrylate.

  In the present invention, commercially available products can be used. For example, pentaerythritol triacrylate (trade name: M-306) manufactured by Toagosei Co., Ltd., dipentaerythritol hexaacrylate manufactured by Toagosei Co., Ltd. (trade name: M-405) , Shin-Nakamura Chemical Co., Ltd. dipentaerythritol hexaacrylate EO modified product (trade name: NK ester A-DPH-6EL), Kyoeisha Chemical Co., Ltd. triethylene glycol diacrylate (trade name: light acrylate 3EG-A), new Nakamura Chemical's 2-hydroxy-3-acryloyloxypropyl methacrylate (trade name: 701A), Toagosei Co., Ltd. isocyanurate EO modified diacrylate (trade name; M-215), Toagosei Co., Ltd. ω-carboxy-poly Examples include caprolactone (n22) monoacrylate (trade name; M-5300).

  Moreover, as the above-mentioned reactive polymer having unsaturated double bond, for example, (meth) acrylic acid, α-ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, methyl (meth) acrylate, ethyl (meth) Acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, C8-22 straight chain aliphatic alkyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , 2-hydroxy-3 Acrylic monomers such as phenoxypropyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate; styrene-based monomers such as styrene, α-methylstyrene, p-hydroxystyrene; ethyl vinyl ether, hydroxyethyl vinyl ether And vinyl monomers such as vinyl acetate may be used alone or in combination of two or more. When 2 or more types of monomers constitute a copolymer, the arrangement thereof is not particularly limited, and may be any of a random copolymer, a block copolymer, and the like. By subjecting these copolymers to a compound having a glycidyl group, an isocyanate group or a compound having an unsaturated double bond having a carboxylic acid group, a reactive polymer having an unsaturated double bond can be obtained.

  When a mixture of a reactive polymer having the above unsaturated double bond and a monomer having the unsaturated double bond or a carboxylic acid compound having a degree of polymerization of 100 or less is used as the compound (b), the oxygen permeability and water vapor The permeability, oxygen permeability and water vapor permeability after the moist heat test become even better.

<Photoinitiator>
There is no restriction | limiting in particular as a photoinitiator, It can select suitably from what is conventionally used conventionally. For example, alkylphenones, acetophenones, benzophenones, ketals, anthraquinones, disulfide compounds, thiuram compounds, fluoroamine compounds and the like can be mentioned. More specifically, there is no particular limitation, and it can be appropriately selected from various conventionally known photoinitiators. For example, aromatic ketones such as benzophenone, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin ethers, benzoin such as methylbenzoin, ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-tria Reyl imidazole dimer 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butanone, 2-
Trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p Halomethyl oxadiazole compounds such as -methoxystyryl) -1,3,4-oxadiazole; 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine; Trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2- (naphtho) -1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl Halomethyl-S-triazine compounds such as -S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2 -Diphenylethan-1-one, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate , 2-n-butoxyethyl-4-dimethylaminobenzoate, 2 -Chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- 1 (O-acetyl oxime), 4-benzoyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1- Butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenyl bis ( 2,4,6-trimethyl benzoyl) phosphine oxide, 2- And ethyl 1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone. One of these photoinitiators may be used alone, or two or more thereof may be used in combination.

<Other ingredients>
In the photopolymerizable composition of the present invention, in addition to the above components, a solvent and various additives may be added as needed.

  Examples of the additive include an antioxidant, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion promoter, and the like.

  Examples of the solvent include alcohols such as water, methanol, ethanol and isopropyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate and butyl acetate; halogenated hydrocarbons; Aromatic hydrocarbons such as toluene and xylene may be mentioned, and one obtained by mixing one or more of these may be used.

As the surfactant, for example, silicone type, fluorine type, cellulose type leveling agent and lubricant of natural wax type, nonylphenol polyethylene oxide adduct, block polymer of ethylene oxide and propylene oxide, sorbitan fatty acid ester, glycerin fatty acid ester, poly Oxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, alkyl alkanolamide, etc. These may be used alone or in combination of two or more.

  As a silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Trimethoxysilane, 1,3,5-tris (3-methoxysilylpropyl) isocyanurate and the like may be mentioned, and one or a mixture of these may be used.

<Laminated material for packaging>
As a laminate for packaging using the gas barrier film of the present invention, for example, as shown in FIG. 2, one in which an intermediate layer and a sealant layer are sequentially laminated on the gas barrier layer of the above gas barrier film can be mentioned.

<Middle class>
The intermediate layer has excellent mechanical, physical and chemical strength, is excellent in puncture resistance, etc., and is excellent in heat resistance, moisture resistance, pinhole resistance, transparency etc. Films or sheets can be used.

  Specifically, for example, polyester resins, polyamide resins, polyaramid resins, polypropylene resins, polycarbonate resins, polyacetal resins, fluorine resins, and other tough resin films or sheets can be used.

  As the film or sheet of the above-mentioned resin, any of an unstretched film or a stretched film stretched uniaxially or biaxially can be used. In the present invention, the thickness of the film or sheet of the resin is preferably 10 to 100 μm, particularly 12 to 50 μm.

<Sealant layer>
The heat-sealable resin constituting the sealant layer may be any resin that can be melted by heat and fused with each other, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low Density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene One or more of resins such as polymers, polyolefin resins such as polyethylene and polypropylene, or acid-modified polyolefin resins modified with these resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid Film or sheet of resin It is possible.

  The film or sheet of the above resin can be used in a single layer or multiple layers, and its thickness is 5 to 300 μm, preferably 10 to 150 μm.

<Other layers>
The above-mentioned packaging laminate may further have other layers in addition to the base material layer, the inorganic oxide layer, the photopolymerizable composition layer, the intermediate layer and the sealant layer. As another layer, the layer which consists of metal foils obtained by rolling a metal, an adhesive bond layer, a printing layer etc. can be mentioned, for example. When two or more other layers are provided, each may have the same composition or different compositions. Another layer may be formed between the photopolymerizable composition and the intermediate layer, between the intermediate layer and the sealant layer, on the side opposite to the side on which the metal oxide layer of the base layer is provided. it can.

As metal foil, conventionally well-known metal foil can be used. From the viewpoints of oxygen barrier property, water vapor barrier property, light blocking property for blocking transmission of visible light, ultraviolet light and the like, and a design property of gloss, an aluminum foil or the like is preferable.

The printing layer can be formed by a conventionally known method using a conventionally known pigment or dye. Moreover, an adhesive bond layer is an adhesive bond layer formed in order to bond two layers by lamination. The adhesive for laminating includes, for example, one-component or two-component cured or non-cured vinyl-based, (meth) acrylic, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, Other solvent-based, water-based or emulsion-type laminating adhesives may be used. As a coating method of said adhesive agent, it can apply by the direct gravure roll coat method, the gravure roll coat method, the kiss coat method, the reverse roll coat method, the Fonten method, the transfer roll coat method, and other methods, for example. As the coating amount is preferably from 0.1 to 10 g / m ² (dry), 1 to 5 g / m ² (dry) is more preferable.

<Method of manufacturing packaging bag and packaging container>
The packaging bag using said laminated material is demonstrated. The bag-like container main body made of a mounting bag is formed by folding the laminated material in two using the laminated material made of the above-mentioned gas barrier film, making the surface of the heat sealable resin layer opposite and laminating them, The package can be manufactured by heat sealing to form a cylindrical package, then sealing the bottom to fill the contents, and sealing the top.

  As the bag making method, the laminated material as described above is folded or stacked, and the inner layer faces are made to face each other, and further, the peripheral edge portion is, for example, side seal type, two side seal type, three way seal Heat-seal by heat seal form such as mold, four-sided seal type, envelope-sealed seal type, combined palm-sealed seal type (pillow seal type), crimped seal type, flat bottom seal type, square bottom seal type, gusset type etc. A form of wear bag can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch) or the like is also possible.

  In the above, as a method of heat sealing, it can carry out by publicly known methods, such as bar seal, rotation roll seal, belt seal, impulse seal, high frequency seal, ultrasonic seal etc., for example.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the scope of the present invention.

  Physical property values and the like in Examples and Comparative Examples were determined by the following evaluation methods.

<Evaluation method>
(1) Oxygen Permeability [cc / m ² / day]: After conditioning for 1 hour according to JIS K7126-2 using OX-TRAN 2 / 22H manufactured by MOCON, oxygen permeability was measured. However, the measurement conditions of the oxygen permeability were temperature: 23 ° C., humidity: 90% RH. In addition, since the lower limit of the standard test range of the said apparatus is 0.1 cc / m < ² > / day, about all the values below it, it describes with <0.1.

(2) Water vapor transmission rate [g / m ² / day]: After conditioning for 1 hour according to JIS K 7129 B using PERMATRAN-W 3 / 34G manufactured by MOCON, the water vapor transmission rate was measured. However, the measurement conditions of the water vapor permeability were temperature: 40 ° C., humidity: 100% RH. The lower limit value of the standard test range of the device is 0.01 g / m ² / day.

(3) Absorbance ratio (A / A ₀₎ Measurement: based on C = O stretching vibration of carboxylic acid groups in the vicinity of absorbance A and 1700 cm ^-1 based on the carboxylate ion in the vicinity of 1560 cm ^-1 in the infrared absorption spectrum in the present invention The ratio (A / A ₀ ) to the absorbance A ₀ is obtained by cutting out a 1 cm × 3 cm measurement sample from the gas barrier film (gas barrier laminate), and measuring the infrared absorption spectrum of the surface (gas barrier layer) by infrared total reflection The spectrum was measured by (ATR method), and the absorbance A and the absorbance A ₀ were first determined by the following procedure. Absorbance peak A (1560 cm around ^-1), the connecting it straight two points absorbance absorbance and 1600 cm ^-1 in 1500 cm ^-1 as the baseline, was determined from the height of the absorption maximum in the range of 1500～1600Cm ^-1 . The peak A ₀ (1700cm ^-1) is a connecting it straight two points absorbance absorbance and 1800 cm ^-1 in 1600 cm ^-1 as the baseline, was determined from the height of the absorption maximum in the range of 1600~1800cm ^-1. The measurement of the infrared spectrum in the present invention (infrared total reflection measurement: ATR method) is carried out using an FT-IR 6100 apparatus manufactured by JASCO Corporation at an incident angle of 45 degrees, room temperature, resolution of 4 cm ^-1 and integration number of 32 times. It went on condition.

  (4) Wet heat test: The film is exposed to a constant temperature and humidity oven (Humidic Chamber IH401 manufactured by YAMATO) at 85 ° C. and 85% RH for 24 hours, and then oxygen permeation is carried out by the method described in the above (1) and (2). Degree, water vapor permeability was measured.

  (5) Drying test: The film was exposed to a constant temperature and humidity chamber at 85 ° C. and 0% RH (Humidic Chamber IH 401 manufactured by YAMATO Co., Ltd.) for 24 hours, and then the oxygen permeability was measured by the apparatus described in (1) above. . However, the measurement conditions of the oxygen permeability were changed to temperature: 23 ° C., humidity: 0% RH.

(1) Preparation of coating solution 1 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g of methanol (manufactured by Kanto Chemical Co., Ltd.) were added to a 100 ml eggplant flask, and then 0.28 g of zinc oxide (manufactured by Junsei Chemical Co., Ltd.) was gradually added. .
Then, it heated at 60 degreeC for 10 minutes, and obtained the colorless and transparent liquid.

Subsequently, methanol and excess acrylic acid were volatilized with an evaporator to obtain 0.71 g of white crystals. To this was added 1.66 g of methanol to make a 30% solution.
A photopolymerization initiator (trade name; IRGACURE 184, manufactured by BASF) diluted to 30% with methanol is added to this zinc acrylate solution so that the solid content ratio to the zinc acrylate solution is 10%. This was taken as solution (a).

  Pentaerythritol triacrylate (trade name: M-306, manufactured by Toagosei Co., Ltd.) was diluted to 30% with methyl isobutyl ketone (manufactured by Kanto Chemical Co., Inc.) to obtain a solution (b).

  The solution (a) and the solution (b) were mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 was obtained, to prepare a coating liquid of the photopolymerization composition. The compound (b) / the compound (a) = 1.22 was obtained.

(2) Preparation of Inorganic Oxide Layer A 12 μm thick biaxially stretched polyethylene terephthalate (PET) film is attached to the take-up roll of a take-up type vacuum deposition apparatus, and then it is fed out to form a deposited layer of the substrate film. The surface to be formed is subjected to corona discharge treatment or to form a corona-treated surface of a substrate film subjected to corona treatment, and the substrate film having the corona-treated surface is attached to a delivery roll of a plasma chemical vapor deposition apparatus. Then, a deposited layer of metal oxide such as silicon oxide having a thickness of 100 Å was formed on the corona-treated surface of the base film under the conditions described below.
Deposition conditions: Conditions for forming a silicon oxide deposition layer Reaction gas mixture ratio; Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 [Slm]
Ultimate pressure: 5.0 × 10 ^ -5 [mbar]
Film forming pressure: 7.0 × 10 ^ -2 [mbar]
Line speed: 150 [m / min]
Power: 35 [kW]

  Next, immediately after forming the deposited layer of silicon oxide with a thickness of 100 Å as described above, a glow discharge plasma generator is used on the deposited layer surface of silicon oxide, power 9 kW, oxygen gas: argon gas = 7.0: An oxygen / argon mixed gas plasma treatment is performed using a mixed gas consisting of 2.5 [Slm] at a processing speed of 420 [m / min] with a mixed gas pressure of 6 × 10 ^ -2 [mbar] to obtain silicon oxide Plasma treatment was performed so that the surface tension of the deposition layer surface was 54 [dyn / cm] or more.

(3) Preparation of gas barrier film The coating liquid of the above (1) is applied to the deposition surface of the biaxially oriented polyethylene terephthalate (PET) film having the above silicon oxide deposition layer with an applicator, and the temperature is: It dried on condition of 85 degreeC and time: 60 second. From this state, the coated surface is turned up immediately and fixed to a stainless steel plate, and after nitrogen purge is performed, using a UV irradiation device (Hereus Fusion UV lamp, model DRS-10 / 12QN, H bulb), The polymerization was carried out by irradiation with ultraviolet light under the conditions of a cumulative light quantity of 1000 mJ / cm ² to obtain a gas barrier film having a thickness of 1 μm of the photopolymerizable composition.

The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 1 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the coating liquid of the photopolymerization composition is Formulated. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 5.56 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 1 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the coating liquid of the photopolymerization composition is Formulated. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 11.1 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.
The

The solution (b) described in Example 1 was changed to dipentaerythritol hexaacrylate (trade name: M-405, manufactured by Toagosei Co., Ltd.) diluted to 30% with methyl isobutyl ketone, and compounds as shown in Table 1 ( The solution (a) and the solution (b) were mixed so that the mass composition ratio of a) and the compound (b) was reached, and a coating liquid of the photopolymerization composition was prepared. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 1.22 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 4 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 5.56 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 4 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 11.1 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (b) described in Example 1 is changed to a dipentaerythritol hexaacrylate EO modified product (trade name; NK ester A-DPH-6EL, manufactured by Shin-Nakamura Chemical Co., Ltd.) diluted to 30% with methyl isobutyl ketone, The solution (a) and the solution (b) were mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 was obtained, to prepare a coating liquid of the photopolymerization composition. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 1.22 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

Incidentally, it refers to the "EO" and "ethylene oxide", an "EO-modified" means having a repeating structure of ethylene oxide units (-CH ₂ -CH ₂ -O-).

The solution (a) and the solution (b) of Example 7 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. Compound (b) / compound (a) = 3.33 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 7 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 11.1 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (b) described in Example 1 is changed to triethylene glycol diacrylate (trade name; light acrylate 3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) diluted to 30% with methyl isobutyl ketone, as shown in Table 1. The solution (a) and the solution (b) were mixed so that the mass composition ratio of the compound (a) and the compound (b) was achieved, to prepare a coating liquid of the photopolymerization composition. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 1.22 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 10 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. Compound (b) / compound (a) = 3.33 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 10 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 11.1 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (b) described in Example 1 is changed to 2-hydroxy-3-acryloyloxypropyl methacrylate (trade name: 701A, manufactured by Shin-Nakamura Chemical Co., Ltd.) diluted to 30% with methyl isobutyl ketone, as shown in Table 1. The solution (a) and the solution (b) were mixed such that the mass composition ratio of the compound (a) and the compound (b) was obtained, to prepare a coating liquid of the photopolymerization composition. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 1.22 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 13 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. Compound (b) / compound (a) = 3.33 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 13 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 11.1 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (b) described in Example 1 was changed to an isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toagosei Co., Ltd.) diluted to 30% with methyl isobutyl ketone, and compounds as shown in Table 1 ( The solution (a) and the solution (b) were mixed so that the mass composition ratio of a) and the compound (b) was reached, and a coating liquid of the photopolymerization composition was prepared. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 1.22 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 16 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. It was compound (b) / compound (a) = 2.22. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 16 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 11.1 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (b) described in Example 1 was changed to ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate (trade name; M-5300, manufactured by Toagosei Co., Ltd.) diluted to 30% with methyl isobutyl ketone, The solution (a) and the solution (b) were mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in 1 was obtained, to prepare a coating liquid of the photopolymerization composition. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 1.22 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 19 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. It was compound (b) / compound (a) = 2.22. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) and the solution (b) of Example 19 are mixed so that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is prepared, and a coating liquid of the photopolymerization composition is prepared. did. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 11.1 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

Comparative Example 1

A gas barrier film was obtained in the same manner as in Example 1 except that only the solution (a) described in Example 1 was used as a coating solution. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

Comparative example 2

A photopolymerization initiator (trade name; IRGACURE 184, manufactured by BASF) diluted to 30% with methanol was added to the solution (b) described in Example 1 at a solid content ratio of 10% based on the solution (b). A gas barrier film was obtained in the same manner as in Example 1 except that only the solution prepared was used as a coating solution. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

As described in Tables 1 and 2, when the absorbance ratio (A / A ₀ ) is in the specific range of 0.01 or more and less than 1.2, the number of functional groups of unsaturated carboxylic acid, the hydrophilicity or By adding the solution (b) regardless of the hydrophobicity, it was confirmed that a clear and good oxygen gas barrier property and water vapor gas barrier property can be obtained, and the water vapor gas barrier property after the wet heat test is not deteriorated. On the other hand, when the absorbance ratio (A / A ₀ ) deviates from the above range as in Comparative Example 1, it was confirmed that the gas barrier film has a high water vapor permeability after the wet heat test and is inferior in the gas barrier properties.

  As described above, by mixing the unsaturated carboxylic acid with the unsaturated carboxylic acid polyvalent metal salt, it is possible to produce a gas barrier film in which the water vapor transmission rate after the wet heat test does not deteriorate.

In addition, if the absorbance ratio (A / A ₀ ) is 0.01 or more and less than 1.2, good results are obtained even if the solution (b) is changed to a reactive polymer or oligomer to produce a gas barrier film Be An example is shown below.

Preparation of Solution (b) Mass of acrylic polymer having unsaturated double bond (trade name: SMP-250A, manufactured by Kyoeisha Chemical Co., Ltd.) and pentaerythritol triacrylate (trade name: M-306, manufactured by Toagosei Co., Ltd.) The mixture was mixed in a ratio of 2: 3 and the mixture was diluted to a concentration of 30% with methyl isobutyl ketone.

The solution (a) of Example 1 and the solution (b) of Example 22 are mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the photopolymerization composition is obtained The coating liquid was prepared. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 1.11 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) of Example 1 and the solution (b) of Example 22 are mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the photopolymerization composition is obtained The coating liquid was prepared. A gas barrier film was produced in the same manner as in Example 1. It was compound (b) / compound (a) = 2.22. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) of Example 1 and the solution (b) of Example 22 are mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the photopolymerization composition is obtained The coating liquid was prepared. A gas barrier film was produced in the same manner as in Example 1. Compound (b) / compound (a) = 3.33 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) of Example 1 and the solution (b) of Example 22 are mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the photopolymerization composition is obtained The coating liquid was prepared. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 5.56 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

The solution (a) of Example 1 and the solution (b) of Example 22 are mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the photopolymerization composition is obtained The coating liquid was prepared. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) = 11.1 was obtained. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

  The heat and moisture test of the gas barrier film obtained in Example 22 was further extended to 72 hours. The oxygen permeability and the water vapor permeability of the obtained gas barrier film after the wet heat test are shown in Table 2.

  The heat and moisture test of the gas barrier film obtained in Example 25 was further extended to 72 hours. The oxygen permeability and the water vapor permeability of the obtained gas barrier film after the wet heat test are shown in Table 2.

  The wet heat test was further extended to 72 hours for the gas barrier film obtained in Example 26. The oxygen permeability and the water vapor permeability of the obtained gas barrier film after the wet heat test are shown in Table 2.

Comparative example 3

The solution (a) of Example 1 and the solution (b) of Example 22 are mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the photopolymerization composition is obtained The coating liquid was prepared. A gas barrier film was produced in the same manner as in Example 1. It was compound (b) / compound (a) = 0.56. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

Comparative example 4

The solution (a) of Example 1 and the solution (b) of Example 22 are mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the photopolymerization composition is obtained The coating liquid was prepared. A gas barrier film was produced in the same manner as in Example 1. The compound (b) / the compound (a) was 0.22. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

Comparative example 5

The solution (a) of Example 1 and the solution (b) of Example 22 are mixed such that the mass composition ratio of the compound (a) and the compound (b) as shown in Table 1 is obtained, and the photopolymerization composition is obtained The coating liquid was prepared. A gas barrier film was produced in the same manner as in Example 1. It was compound (b) / compound (a) = 22.2. The absorbance ratio (A / A ₀ ) of the obtained gas barrier film is shown in Table 1. The oxygen permeability and the water vapor permeability, and the oxygen permeability and the water vapor permeability after the wet heat test are shown in Table 2.

As described in Tables 1 and 2, if the absorbance ratio (A / A ₀ ) is 0.01 or more and less than 1.2, it is good even if the solution (b) is changed to a reactive polymer or oligomer While oxygen gas barrier property and water vapor gas barrier property were obtained, it was confirmed that the water vapor gas barrier property after the wet heat test is not deteriorated. On the other hand, in Comparative Examples 3 to 5 in which the absorbance ratio (A / A ₀ ) is out of the range of 0.01 or more and less than 1.2, the water vapor permeability after the moist heat test is high, and the gas barrier property is deteriorated. confirmed.
(Result of drying test)

  The gas barrier film obtained in Example 25 was evaluated by a drying test. The oxygen permeability after the drying test is shown in Table 2.

  The gas barrier film obtained in Example 26 was evaluated by a drying test. The oxygen permeability after the drying test is shown in Table 2.

Comparative example 6

  The gas barrier film obtained in Comparative Example 1 was evaluated by a drying test. The oxygen permeability after the drying test is shown in Table 2.

  From the results of Examples 30 and 31 shown in Table 2, even if an acrylic polymer having unsaturated double bond is added to the solution (b), it comprises the composition containing the solution (a) and the solution (b) By forming the barrier film, it was confirmed that good oxygen gas barrier properties and water vapor gas barrier properties are obtained, and that the oxygen gas barrier properties after the drying test are not deteriorated. On the other hand, it was confirmed from the results of Comparative Example 6 that the oxygen permeability after the drying test was high only with the solution (a) and the gas barrier performance was deteriorated.

1: base material layer 2: inorganic oxide layer 3: photopolymerizable composition layer 4: intermediate layer 5: sealant layer

Claims (11)

A gas barrier film obtained by forming an inorganic oxide layer and a photopolymerizable composition layer in this order on at least one side of a substrate,
The photopolymerizable composition layer is
(A) a polyvalent metal salt of a carboxylic acid compound having a photopolymerizable functional group,
(B) It is formed of a resin obtained by polymerizing a photopolymerizable composition containing a compound having a photopolymerizable functional group other than (a),
Then, the absorbance A ₀ based on νC = O of the carboxylic acid groups in the vicinity of absorbance A and 1700 cm ^-1 based on νC = O of 1560 cm ^-1 vicinity carboxylate ions in the infrared absorption spectrum of the photopolymerizable composition layer Said gas barrier film whose ratio (A / _A0 ) is 0.01 or more and less than 1.2. The gas barrier film according to claim 1, wherein A / A ₀ is 0.01 to 1.1.   The gas barrier film according to claim 1, wherein the carboxylic acid compound of the compound (a) is a monomer having an unsaturated double bond or a carboxylic acid compound having a degree of polymerization of 10 or less.   The carboxylic acid compound of the compound (a) is at least one selected from the group consisting of (meth) acrylic acid, α-ethyl acrylic acid, maleic acid, fumaric acid and itaconic acid, and the polyvalent compound of the compound (a) The gas barrier film according to any one of claims 1 to 3, wherein the metal is at least one selected from the group consisting of Mg, Ca, Ba, Zn, Cu, Co, Ni, Al and Fe.   The gas barrier film according to any one of claims 1 to 4, wherein the compound (b) is a monomer having an unsaturated double bond and containing no polyvalent metal or polyvalent metal oxide.   Compound (b) is pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, triethylene glycol diacrylate, isocyanuric acid EO modified diacrylate, The gas barrier film according to any one of claims 1 to 5, which is at least one selected from the group consisting of isocyanuric acid EO modified triacrylate and 2-hydroxy-3-acryloyloxypropyl methacrylate.   The gas barrier film according to any one of claims 1 to 4, wherein the compound (b) is a reactive polymer having an unsaturated double bond.   The gas barrier film according to claim 5 or 6, further comprising a reactive polymer having an unsaturated double bond as the compound (b).   The reactive polymer is a homopolymer or copolymer obtained from an alkyl (meth) acrylate, and is a homopolymer or copolymer having an unsaturated double bond in the main chain or side chain. Or the gas barrier film as described in 8.   It is a laminated material for packaging using the gas-barrier laminated film of any one of Claims 1-9, Comprising: An intermediate | middle layer and a heat sealable resin layer are provided in order on the barrier film of the said laminated film. Packaging material for packaging. A packaging bag using the packaging laminate material according to claim 10, wherein the heat sealable resin layer side of one packaging laminate material and the heat sealable resin layer side of the other packaging laminate material are opposed A packaging bag characterized in that the end portions are heat sealed.

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