JP6745096B2 - Anchor coating agent for transparent vapor deposition and laminated body - Google Patents

Description

The present invention relates to an anchor coating agent for transparent vapor deposition and a laminate.

As a gas barrier film, a packaging material, or the like, there is known a laminated body in which a sealant layer is laminated on the surface of a barrier layer. In such a laminate, an anchor coat layer (adhesion layer) is generally included between the barrier layer and the sealant layer. For example, Patent Document 1 describes a packaging material in which a barrier layer, an anchor coat layer, and a sealant layer are laminated in this order.

A transparent vapor deposition base material is known as a barrier layer used for a packaging material. The transparent vapor deposition substrate is one in which alumina or silica or the like is vapor deposited on a substrate such as a thermoplastic resin to form a transparent vapor deposition layer, which is excellent in transparency and does not impair the design of the substrate, Widely used. Since the transparent vapor deposition layer is easily cracked, a protective layer (crack prevention layer) for preventing cracking may be provided on the transparent vapor deposition layer (see Patent Document 2).

JP, 2008-229971, A JP, 2011-042725, A

However, the anchor coat layer described in Patent Document 1 has poor adhesion and adhesiveness to the crack prevention layer as described in Patent Document 2, and further has insufficient boiling resistance.

The present invention solves the above problems. That is, it is an object of the present invention to provide an anchor coat agent that can form an anchor coat layer having excellent adhesion and adhesiveness to a crack prevention layer formed on a transparent vapor-deposited layer and further excellent in boil resistance.

As a result of intensive studies, the present inventors have found that an anchor coating agent for transparent vapor deposition containing an acid-modified polyolefin resin and an epoxy silane coupling agent is cracked when a crack prevention layer is formed on the transparent vapor deposition layer. The inventors have found that an anchor coat layer having excellent adhesion and adhesiveness to the prevention layer and further having excellent boil resistance can be formed, and arrived at the present invention.

That is, the gist of the present invention is the following (1) to (6).
(1) The content of the unsaturated carboxylic acid component is 1 to 8% by mass, the acid-modified polyolefin resin (A), the epoxy-based silane coupling agent (B) and the aqueous medium are contained, and the content of (B) is (A) An anchor coating agent for transparent vapor deposition, which is 0.2 to 2 parts by mass with respect to 100 parts by mass.

(2) The anchor coating agent for transparent vapor deposition of (1), wherein the epoxy-based silane coupling agent (B) is 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropylmethyldimethoxysilane.

(3) A laminate in which a base material (a), a transparent vapor deposition layer (b), a crack prevention layer (c), an anchor coat layer (d), and a sealant layer (e) are laminated in this order, wherein the anchor is The coating layer (d) contains an acid-modified polyolefin resin (A) having an unsaturated carboxylic acid component content of 1 to 8% by mass , an epoxy silane coupling agent (B), and the content of (B) is (A) 0.2 to 2 parts by mass relative to 100 parts by mass, a laminate.

(4) The laminate of (3), wherein the base material (a) is composed of a thermoplastic resin.

(5) The laminate of (3) or (4), wherein the transparent vapor deposition layer (b) contains alumina or silica.

INDUSTRIAL APPLICABILITY The anchor coating agent for transparent vapor deposition of the present invention is capable of obtaining an anchor coat layer having excellent adhesion and adhesion to a crack prevention layer and boil resistance, and is also extremely excellent in liquid stability. Further, the anchor coat layer formed from the anchor coating agent for transparent vapor deposition of the present invention has high transparency, and has an effect of not impairing the design of the base material.

Hereinafter, the present invention will be described in detail.
<Anchor coating agent for transparent vapor deposition>
The anchor coating agent for transparent vapor deposition of the present invention (hereinafter sometimes simply referred to as “anchor coating agent”) comprises an acid-modified polyolefin resin (A), an epoxy silane coupling agent (B), and an aqueous medium. contains. The acid-modified polyolefin resin (A) is dispersed and present in an aqueous medium.

(Acid-modified polyolefin resin (A))
The acid-modified polyolefin resin (A) has an olefin component as a main component and is acid-modified with an unsaturated carboxylic acid component. Since the acid-modified polyolefin resin (A) is stably and sufficiently dispersed in an aqueous medium, the anchor coating agent of the present invention is uniform and easy to apply. When a non-acid-modified polyolefin resin is used, the dispersion in an aqueous medium becomes insufficient and only a non-uniform anchor coating agent can be obtained.

The content of the olefin component in the acid-modified polyolefin resin (A) is preferably 50% by mass or more, and more preferably 70% by mass or more. When the content of the olefin component is less than 50% by mass, the properties (for example, adhesion) derived from the polyolefin resin may be lost.

The olefin component, which is the main component of the acid-modified polyolefin resin (A), is not particularly limited, but is, for example, ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, or 1-hexene having 2 carbon atoms. ~6 alkenes. You may use these mixtures. Among them, since the anchor coat layer formed from the anchor coating agent of the present invention has excellent adhesion and adhesion to the crack prevention layer described below, ethylene, propylene, isobutylene, 1-butene or the like having 2 to 4 carbon atoms is used. Alkenes are more preferred, ethylene or propylene are even more preferred, and ethylene is most preferred.

As the unsaturated carboxylic acid or its anhydride for introducing the unsaturated carboxylic acid component into the polyolefin resin, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, or crotonic acid. In addition to the above, a half ester or a half amide of an unsaturated dicarboxylic acid can be used. Of these, acrylic acid, methacrylic acid, maleic acid, or maleic anhydride is preferable, and acrylic acid or maleic anhydride is particularly preferable. Further, the unsaturated carboxylic acid component may be copolymerized in the acid-modified polyolefin resin. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization (graft modification).

The content of the unsaturated carboxylic acid component in the acid-modified polyolefin resin (A) is preferably 0.1 to 25% by mass, from the viewpoint of adhesion and adhesiveness to a crack prevention layer described later, and 0.5 to 15 mass% is more preferable, 1-8 mass% is still more preferable, 1-5 mass% is especially preferable.

The acid-modified polyolefin resin (A) preferably contains a (meth)acrylic acid ester component because the anchor coat layer formed from the anchor coat agent of the present invention has excellent adhesion and adhesion to the crack prevention layer. .. The content of the (meth)acrylic acid ester component in the acid-modified polyolefin resin (A) is preferably 0.5 to 40% by mass, more preferably 1 to 35% by mass, and 3 to 30% by mass. Is more preferable, 5 to 25 mass% is particularly preferable, and 6 to 20 mass% is the most preferable. When the content is less than 0.5% by mass, the adhesion and the adhesion to the crack prevention layer may be insufficient. On the other hand, if it exceeds 40% by mass, the properties derived from the olefin resin may be lost, and the adhesiveness and the adhesiveness may rather deteriorate.

Examples of the (meth)acrylic acid ester component include esterified products of (meth)acrylic acid and an alcohol having 1 to 30 carbon atoms. Among them, an esterified product of (meth)acrylic acid and an alcohol having 1 to 20 carbon atoms is preferable from the viewpoint of easy availability. Specific examples of such compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylic acid. Examples thereof include octyl, decyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. You may use these mixtures. Among them, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl acrylate, or octyl acrylate is more preferable from the viewpoint of adhesion and adhesiveness to the crack prevention layer, and acrylic Ethyl acrylate or butyl acrylate is more preferable, and ethyl acrylate is particularly preferable. In addition, "(meth)acrylic acid ~" means "acrylic acid ~ or methacrylic acid ~".

Moreover, the acid-modified polyolefin resin (A) may contain other components. Other components include dienes, dimethyl maleate, maleic acid esters such as diethyl maleate or dibutyl maleate, (meth)acrylic acid amides, alkyl vinyl ethers such as methyl vinyl ether or ethyl vinyl ether, vinyl formate, Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, etc., vinyl alcohol obtained by saponifying vinyl esters with a basic compound, 2-hydroxyethyl acrylate, glycidyl (meth)acrylate, ( Examples thereof include (meth)acrylonitrile, styrene, substituted styrene, carbon monoxide, and sulfur dioxide. It is also possible to use mixtures of these. The content of these components is preferably 10% by mass or less based on 100% by mass of the acid-modified polyolefin resin (A).

Examples of the acid-modified polyolefin resin (A) include ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid-maleic anhydride copolymer, ethylene-acrylic acid ester-maleic anhydride copolymer. , Acid-modified polyethylene, acid-modified polypropylene, acid-modified ethylene-propylene resin, acid-modified ethylene-butene resin, acid-modified propylene-butene resin, or acid-modified ethylene-propylene-butene resin, or acrylic acid added to these acid-modified resins. Examples thereof include those that have been acrylic-modified with an ester or the like. Furthermore, the acid-modified polyolefin resin (A) may be chlorinated in the range of 5 to 40% by mass.

The acid-modified polyolefin resin (A) preferably has a melt flow rate of 0.01 to 5000 g/10 minutes, more preferably 0.1 to 1000 g/10 minutes at 190° C. and a load of 2160 g, which is a measure of the molecular weight. , 1 to 500 g/10 minutes are more preferable, 2 to 300 g/10 minutes are even more preferable, and 2 to 200 g/10 minutes are particularly preferable. When the melt flow rate of the acid-modified polyolefin resin (A) is less than 0.01 g/10 minutes, the adhesion and the adhesiveness to the crack prevention layer may decrease. On the other hand, when it exceeds 5000 g/10 minutes, the formed anchor coat layer becomes hard and brittle, and the adhesion and the adhesiveness to the crack prevention layer may rather deteriorate.

Examples of commercially available acid-modified polyolefin resin (A) include HX-8290, TX-8030, and HX-8210 manufactured by Arkema.

The content of the acid-modified polyolefin resin (A) in the anchor coating agent of the present invention is appropriately selected according to the conditions for forming the anchor coating layer as a coating film, the target coating film thickness, or the required performance. be able to. For example, the content of the acid-modified polyolefin resin (A) is preferably from 1 to 60% by mass, and from 3 to 55, in order to maintain the viscosity of the anchor coating agent to an appropriate level and to develop a good film-forming ability. It is more preferably mass%, further preferably 5 to 50 mass%, particularly preferably 5 to 45 mass%.

(Epoxy silane coupling agent (B))
The anchor coating agent for transparent vapor deposition of the present invention needs to contain an epoxy silane coupling agent (B). By using the acid-modified polyolefin resin (A) and the epoxy-based silane coupling agent (B) together, a polyolefin resin which is not modified or a silane coupling agent other than the epoxy-based one (for example, an amino-based silane coupling agent, Or an isocyanate-based silane coupling agent), the anchor coating agent of the present invention is capable of forming an anchor coating layer that is remarkably excellent in adhesion and adhesion to the crack prevention layer, and boil resistance. it can.

The content of the epoxy silane coupling agent (B) in the anchor coating agent of the present invention is 0.2 to 2 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), and 0.2 to 1. It is preferably 5 parts by mass, and particularly preferably 0.5 to 1 part by mass. When the content of the epoxy-based silane coupling agent (B) is less than 0.2 parts by mass, the adhesion or the adhesiveness to the crack prevention layer or the boil resistance is not exhibited. On the other hand, if it exceeds 2 parts by mass, the liquid stability of the anchor coating agent is poor and it cannot be uniformly coated on the substrate. Alternatively, even if it can be applied uniformly, only an anchor coat layer having poor adhesion or adhesiveness or boil resistance can be obtained.

Examples of the compound that can be used as the epoxy-based silane coupling agent (B) include 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxy. Examples include propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, or 3-glycidoxypropyltriethoxysilane. Among them, 3-glycidoxypropylmethyldimethoxysilane or 3-glycidoxypropyltrimethoxysilane is preferred because an anchor coat layer having excellent adhesion and adhesion to the crack prevention layer and excellent boiling resistance can be formed. Is preferred.

Examples of commercially available epoxy silane coupling agents include silane coupling agent series manufactured by Shin-Etsu Chemical Co., Ltd. Specifically, water-soluble type "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403", etc. are mentioned.

(Aqueous medium)
The anchor coating agent for transparent vapor deposition of the present invention contains an aqueous medium. In the present invention, the aqueous medium means water or a mixed liquid of water and an organic solvent. Among them, those containing water as a main component are preferable from the viewpoint of safety to the operator or the working environment. Further, a mixed solution of water and an organic solvent is preferable in order to facilitate the aqueous dispersion or dissolution of the acid-modified polyolefin resin (A) or the epoxy silane coupling agent (B) and further reduce the drying load.

The content of the organic solvent in the aqueous medium is preferably 40% by mass or less, more preferably 1 to 40% by mass, further preferably 2 to 35% by mass, particularly preferably 3 to 30% by mass. When the content of the organic solvent exceeds 40% by mass, it cannot be regarded as an aqueous medium substantially, and the stability of the anchor coating agent may decrease depending on the organic solvent used.

The organic solvent added at the time of aqueous dispersion may be appropriately reduced by distilling it out of the system by a solvent removal operation called stripping. Even if the amount of organic solvent is lowered, there is no particular effect on the performance.

The organic solvent preferably has a boiling point of 30 to 250°C, more preferably 50 to 200°C. When the boiling point of the organic solvent is lower than 30° C., the rate of volatilization during aqueous dispersion of the acid-modified polyolefin resin (A) increases, and the aqueous dispersion may be insufficient. On the other hand, an organic solvent having a boiling point of more than 250° C. is difficult to be scattered by drying or the like, and only an anchor coat layer having poor water resistance may be obtained. You may use these organic solvents in mixture of 2 or more types.

Among the above-mentioned organic solvents, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone can be sufficiently promoted in aqueous dispersion and the organic solvent can be easily removed from the aqueous medium. , Tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, or ethylene glycol monobutyl ether are preferable, and ethanol, n-propanol, or isopropanol is particularly preferable from the viewpoint of low-temperature drying property.

The aqueous medium may contain a basic compound. When the carboxyl group in the acid-modified polyolefin resin (A) is neutralized by the basic compound, aggregation between the fine particles is suppressed by the electric repulsive force between the carboxyl anions generated by the neutralization. This improves the stability of the anchor coating agent. Any such basic compound may be used as long as it can neutralize a carboxyl group and can be said to be an aqueous hydration aid. In order not to impair the effects of the present invention, it is preferable to use a volatile basic compound.

As the basic compound, ammonia or an organic amine compound is preferable because it is water resistant and easily volatilizes when the anchor coat layer is formed. Among them, those having a boiling point of 30 to 250°C are preferable, and those having a boiling point of 50 to 200°C are more preferable. When a basic compound having a boiling point of less than 30° C. is used, the rate of volatilization during aqueous dispersion increases, and the aqueous dispersion may become insufficient. If the one having a boiling point of more than 250° C. is used, it becomes difficult to scatter due to drying or the like, and only an anchor coat layer having poor water resistance may be obtained.

Specific examples of the organic amine compound include triethylamine, N,N-dimethylethanolamine, aminoethanolamine, N-methyl-N,N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like.

The addition amount of the basic compound is preferably 0.5 to 3.0 times equivalent, more preferably 0.8 to 2.5 times equivalent to the carboxyl group in the acid-modified polyolefin resin (A), more preferably 1 0.01 to 2.0 equivalents are particularly preferable. If it is less than 0.5 times the equivalent, the effect of adding the basic compound may not be exhibited. If it exceeds 3.0 times equivalent, it may be necessary to lengthen the drying time when forming the anchor coat layer, or the anchor coat agent may be colored.

In the anchor coating agent of the present invention, in addition to a volatile hydration aid, a non-volatile hydration aid such as an emulsifier may be used. From the viewpoint of adhesion and adhesiveness to the crack prevention layer, the content of the non-volatile hydration aid is preferably 5 parts by mass or less with respect to 100 parts by mass of the acid-modified polyolefin resin, and most preferably not used. preferable. Examples of the non-volatile aqueous auxiliaries include emulsifiers, compounds having a protective colloid action, modified waxes, acid-modified compounds having a high acid value, and water-soluble polymers.

Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. Further, in addition to those generally used for emulsion polymerization, surfactants are also included.

Examples of the anionic emulsifier include sulfuric acid ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulphates, polyoxyethylene alkyl phenyl ether sulphates, or vinyl sulfosuccinates. Etc.

Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide copolymer and the like. Examples thereof include compounds having an oxyethylene structure, sorbitan derivatives such as polyoxyethylene sorbitan fatty acid ester, and the like.

Examples of the amphoteric emulsifier include lauryl betaine and lauryl dimethylamine oxide.

Examples of compounds having a protective colloid action, modified waxes, acid-modified compounds having a high acid value, or water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinylpyrrolidone. , Polyacrylic acid and its salts, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax, and other acid-modified polyolefin waxes having a number average molecular weight of usually 5,000 or less and salts thereof, acrylic acid- Maleic anhydride copolymer and its salt, styrene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth)acrylic acid-(meth ) A carboxyl group-containing polymer having an unsaturated carboxylic acid content such as an acrylic acid ester copolymer of 10% by mass or more and a salt thereof, polyitaconic acid and a salt thereof, a water-soluble acrylic copolymer having an amino group, gelatin, and Arabic. Examples thereof include rubber and casein, which are generally used as a dispersion stabilizer for fine particles.

Various agents such as a crosslinking agent, an antiblocking agent, a leveling agent, an antifoaming agent, an anti-armpitting agent, a pigment dispersant, or an ultraviolet absorber may be added to the anchor coating agent of the present invention, if necessary. ..

The anchor coating agent of the present invention may contain other polymer (or resin), if necessary. Examples of other polymers include polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, styrene-maleic acid resin, styrene-butadiene resin, acrylonitrile-butadiene resin, (meth)acrylamide resin. , Polyurethane resin, acrylic resin, polyester resin, modified nylon resin, or phenol resin. You may use 2 or more types of these. The timing of adding the other polymer to the anchor coating agent is not particularly limited, and for example, a liquid material of the above polymer may be appropriately added.

<Method of manufacturing anchor coating agent for transparent vapor deposition>
The method for producing the anchor coating agent for transparent vapor deposition of the present invention is a method capable of uniformly dispersing or dissolving the acid-modified polyolefin resin (A) and the epoxy silane coupling agent (B) in an aqueous medium. If there is, it is not particularly limited. For example, a method may be mentioned in which an aqueous dispersion of the acid-modified polyolefin resin (A) is mixed with a liquid substance of the epoxy silane coupling agent (B) and, if necessary, water or an organic solvent is added.

Examples of the method for obtaining an aqueous dispersion of the acid-modified polyolefin resin (A) include a method of heating and stirring the acid-modified polyolefin resin together with an aqueous medium and a basic compound. At this time, an aqueous emulsifying agent such as an emulsifier may be added if necessary.

A commercially available product may be used as the aqueous dispersion of the acid-modified polyolefin resin (A). Specific examples thereof include Chemipearl SA-100 or Chemipearl S-75N manufactured by Mitsui Chemicals, Inc., Supercron E-723 manufactured by Nippon Paper Industries Co., Ltd., and the like.

Further, a method of mixing the acid-modified polyolefin resin (A) and the epoxy-based silane coupling agent (B) and then mixing with water or an organic solvent to disperse or dissolve in water is also exemplified. Also in this case, a basic compound or an emulsifier may be used if necessary.

In any of the production methods, the concentration can be arbitrarily adjusted by distilling off water or an organic solvent or diluting with water or an organic solvent after or during the step.

<Laminate>
The laminate of the present invention has a structure in which a substrate (a), a transparent vapor deposition layer (b), a crack prevention layer (c), an anchor coat layer (d), and a sealant layer (e) are laminated in this order. The anchor coat layer (d) is formed by applying the anchor coating agent for transparent vapor deposition of the present invention on the crack prevention layer (c) and then removing the aqueous medium by drying or the like. That is, the anchor coat layer (d) is a coating film containing the acid-modified polyolefin resin (A) and the epoxy silane coupling agent (B).

Examples of the base material (a) include polyolefin resins such as polyethylene or polypropylene, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate or polycarbonate, and polymethyl methacrylate. Acrylic resin, polystyrene, or styrene resin such as ABS, polyvinyl chloride resin, metal, paper, or thread can be used. From the viewpoint of moldability and heat resistance, it is preferably formed using a thermoplastic resin, and particularly preferably formed using polyethylene terephthalate or polypropylene. The form of the substrate (a) is preferably a film.

The thickness of the substrate (a) is not particularly limited, but is usually 0.5 to 1000 μm, preferably 1 to 500 μm, more preferably 1 to 100 μm, and particularly preferably 1 to 50 μm.

The transparent vapor-deposited layer (b) is made of an inorganic substance such as alumina, silica, or tin, and is preferably made of alumina or silica because it is excellent in transparency or strength. The laminate of the present invention is used as a packaging material or the like. When used, silica is particularly preferred because it has excellent performance of suppressing corrosion from the contents. The transparent vapor deposition layer (b) is formed by vapor deposition on the base material (a), and the vapor deposition method is not particularly limited, and known ones can be used.

The thickness of the transparent vapor deposition layer (b) is not particularly limited, but is usually 0.02 to 0.1 μm, preferably 0.02 to 0.09 μm, more preferably 0.03 to 0.08 μm, and particularly preferably. Is 0.03 to 0.07 μm.

The crack prevention layer (c) prevents and protects the transparent vapor deposition layer (b) from cracking. The crack prevention layer (c) is made of a resin, and examples of such a resin include polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, styrene-maleic acid resin, styrene-butadiene. Examples thereof include resins, acrylonitrile-butadiene resins, polyvinyl alcohol, (meth)acrylamide resins, polyurethane resins, acrylic resins, polyester resins, modified nylon resins, and phenol resins. You may use these 2 or more types together.

If necessary, the crack preventing layer (c) may contain other additives such as a crosslinking agent, an antiblocking agent, a leveling agent, an antifoaming agent, an anti-armpitting agent, a pigment dispersant, or an ultraviolet absorber. May be.

The thickness of the crack prevention layer (c) is not particularly limited, but is preferably 1 to 3 μm. The method for forming the crack prevention layer (c) is not particularly limited, and for example, the above-described resin emulsion or the like is applied onto the transparent vapor deposition layer (b) by a known coating method, and dried to form a coating film. Method etc. are mentioned.

The anchor coating layer (d) is formed by applying the anchor coating agent of the present invention on the crack preventing layer (c) and removing the aqueous medium by, for example, performing a drying treatment or the like. The anchor coat layer (d) formed from the anchor coat agent of the present invention is excellent in adhesion and adhesion to the crack prevention layer (c) and boil resistance.

The content of the epoxy silane coupling agent (B) in the anchor coat layer (d) is 0.2 to 2 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), and 0.2 to 1. It is preferably 5 parts by mass, and particularly preferably 0.5 to 1 part by mass. When the content of the epoxy silane coupling agent (B) is less than 0.2 parts by mass, the adhesion or the adhesiveness to the crack prevention layer or the boil resistance is not exhibited. On the other hand, when it exceeds 2 parts by mass, the uniformity becomes poor.

The method for applying the anchor coating agent is not particularly limited, and may be gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, or brush coating. Can be adopted. The coating amount of the anchor coating agent can be appropriately adjusted depending on the type of the base material (a) used and the like.

The drying treatment conditions after applying the anchor coating agent are not particularly limited and can be appropriately adjusted in consideration of the heat resistance of the substrate, for example, a temperature of 100 to 180° C., a treatment time of 10 seconds to 10 minutes. Is.

The thickness of the coating film of the anchor coat layer (d) is not particularly limited. For example, when a thermoplastic resin film is used as the substrate (a), it is 0.1 μm or more in order to sufficiently enhance the heat sealability. The thickness is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm, particularly preferably 0.3 to 7 μm.

Examples of the sealant layer (e) include polyethylene such as low-density polyethylene (LDPE) or high-density polyethylene (HDPE), acid-modified polyethylene, polypropylene, acid-modified polypropylene, copolymerized polypropylene, ethylene-vinyl acetate copolymer, Examples thereof include those made of a sealant resin such as an ethylene-(meth)acrylic acid ester copolymer, an ethylene-(meth)acrylic acid copolymer, or a polyolefin resin such as an ionomer. Among them, those made of polyethylene resin are preferable because they are excellent in sealing property at low temperature, and those made of polyethylene are particularly preferable because they are inexpensive.

The anchor coat layer contained in the laminate of the present invention is formed from the anchor coat agent of the present invention as described above, and has excellent adhesion and adhesiveness to the crack prevention layer, boil resistance, and transparency. .. Therefore, the laminate of the present invention provided with such an anchor coat layer can be suitably used as a barrier film or a packaging material.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Various properties were measured or evaluated by the following methods.

1. Characteristics of acid-modified polyolefin resin (1) Composition
^{It was determined from 1} H-NMR analysis (Varian, 300 MHz). Ortho-dichlorobenzene (d ₄ ) was used as a solvent, and the measurement was performed at 120°C.

(2) Melt Flow Rate The melt flow rate was measured by the method described in JIS 6730 (190° C., 2160 g load).

(3) Melting point Using a DSC (Differential Scanning Calorimetry) device (DSC-7, manufactured by Perkin Elmer), measurement was performed at a temperature rising rate of 10°C/min, and the melting point was determined from the obtained temperature rising curve. It was

2. Characteristics of Aqueous Dispersion of Acid-Modified Polyolefin Resin (1) Solid Content Concentration An appropriate amount of the aqueous dispersion is weighed, and this is heated at 150° C. until the mass of the residue (solid content) reaches a constant amount to determine the solid content concentration. It was

(2) Average particle size of acid-modified polyolefin resin particles A number average particle size (mn) and a weight average particle size (mw) were determined using a Microtrac particle size distribution analyzer UPA150 (manufactured by Nikkiso Co., Ltd., MODEL No. 9340).

3. Characteristics of anchor coating agent (1) Liquid stability of anchor coating agent The anchor coating agent was visually confirmed and evaluated according to the following criteria.
◯: No gelation or generation of spots.
Δ: There is some gelation or generation of spots.
X: There is a large amount of gelation or lumps.

4. Properties of Anchor Coat Layer In the following evaluation, a transparent vapor-deposited PET film (“TL-HP”, 12 μm thick, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) in which alumina was vapor-deposited on a polyethylene terephthalate (PET) film was used. The PET film corresponds to the base material (a), and the vapor deposition layer of alumina corresponds to the transparent vapor deposition layer (b).
A polyester resin emulsion (“Elitel KT-8803” manufactured by Unitika Ltd., solid content concentration 30% by mass) was placed on the alumina deposited layer of this transparent deposited PET film with a Meyer bar so that the film thickness after drying was 2 μm. After application, it was dried at 120° C. for 90 minutes to form a crack prevention layer (c). The anchor coating agents obtained in Examples and Comparative Examples were applied to this crack prevention layer using a Meyer bar so that the film thickness after drying would be 0.5 μm. Then, it was dried at 100° C. for 2 minutes to remove the aqueous medium to form an anchor coat layer (film thickness 1 μm), and a laminated film was obtained. The following characteristics were evaluated using these laminated films.

(1) Adhesion (tape peeling test)
After the laminated film was left at room temperature for 1 day, cellophane tape (“TF-12” manufactured by Nichiban Co., Ltd.) was attached to the surface of the anchor coat layer, and the degree of peeling when the tape was peeled off at a stretch was visually confirmed, and the following criteria were used. It was evaluated by.
◯: No peeling at all.
X: Part or all was peeled off.

(2) Boil resistance After the laminated film was immersed in hot water at 98°C for 2 hours, the state of the anchor coat layer was visually confirmed and evaluated according to the following criteria.
◯: No change.
X: Whitening was observed.

(3) Adhesion A polyethylene resin was extruded and laminated on the anchor coat layer of the laminated film so as to have a film thickness of 35 μm to form a sealant layer to obtain a laminate. A test piece having a width of 15 mm was sampled from this laminate, and the tensile tester (manufactured by Intesco, precision universal material tester 2020) was used to peel the interface of the sealant layer from the end of the test piece by the T peel method. The laminate strength was measured. The measurement was performed in an atmosphere of 20° C. and 65% RH at a tensile rate of 200 mm/min. It was determined that the adhesive strength was remarkably excellent when the laminate strength was 3.0 N/15 mm or more.
When the laminate strength is high, the sealant layer may be broken during the measurement, but such a phenomenon is an index of superior adhesiveness.

Table 1 shows the compositions of the acid-modified polyolefin resins (A) to (C) used.

Production of Aqueous Dispersion (E-1) of Acid-Modified Polyolefin Resin (A) 125.0 g of acid-modified polyolefin resin (A) (Arkema Co. "Bondaine HX-8290"), 75.0 g of isopropanol (hereinafter, IPA), 7.0 g of triethylamine (hereinafter, TEA) and 293 g of distilled water were charged in a glass container, and the rotation speed of the stirring blade was 300 rpm. It was stirred. No precipitation of resin granules was observed at the bottom of the container, confirming that it was in a floating state.

While maintaining this state, the heater was turned on and heated after 10 minutes. Then, the temperature in the system was kept at 130° C., and stirring was continued for 30 minutes. Then, while stirring at a rotation speed of 300 rpm, it was cooled to room temperature (about 25° C.) by air cooling. Then, pressure filtration (air pressure 0.2 MPa) was performed with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform aqueous dispersion of an acid-modified polyolefin resin (E-1). Various properties of this aqueous dispersion are shown in Table 2.

Production of Aqueous Dispersion of Acid-Modified Polyolefin Resin (A) (E-2) Using a stirrer equipped with a pressure-resistant 1L glass container with a heater, 100.0 g of the acid-modified polyolefin resin (A) (Arkema) "Bondaine TX-8030"), 150.0 g of IPA, 6.0 g of TEA, and 244.0 g of distilled water were charged in a glass container and stirred at a rotation speed of a stirring blade of 300 rpm. No precipitation of resin particles was observed at the bottom of the container, confirming that it was in a floating state.

While maintaining this state, the heater was turned on and heated after 10 minutes. Then, the temperature in the system was kept at 130° C., and stirring was continued for 30 minutes. Then, while stirring at a rotation speed of 300 rpm, it was cooled to room temperature (about 25° C.) by air cooling. Then, pressure filtration (air pressure 0.2 MPa) was carried out with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform aqueous dispersion of an acid-modified polyolefin resin (E-2). Various properties of this aqueous dispersion are shown in Table 2.

Production of Aqueous Dispersion (E-3) of Acid-Modified Polyolefin Resin (C) Other than Using Acid-Modified Polyolefin Resin (C) (Arkema “Bondaine HX-8210”) Instead of Acid-Modified Polyolefin Resin (A) In the same manner as in (E-1), an acid-modified polyolefin resin aqueous dispersion (E-3) was obtained. Various properties of this aqueous dispersion are shown in Table 2.

Epoxy silane coupling agent solution (S-1)
A solution in which 3-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 100%) as an epoxy-based silane coupling agent is dissolved in water and the active ingredient is 1% (S -1) was obtained.

Amino-based silane coupling agent solution (S-2)
N-2-(aminoethyl)-3-aminopropylmethyltrimethoxysilane (“KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 100%) as an amino-based silane coupling agent was dissolved in water to prepare an active ingredient. To obtain a solution (S-2) having 1%.

Isocyanate silane coupling agent (S-3)
A solution of 3-isocyanatepropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 100%) as an isocyanate-based silane coupling agent in isopropanol, and the active ingredient is 1% (S-3 ) Got.

Example 1
(E-1) and (S-1) are stirred and mixed with a mechanical stirrer at room temperature so that (S-1) becomes 1 part by mass with respect to 100 parts by mass of the solid content of (E-1). (Agitation speed 100 rpm) to prepare an anchor coating agent (J-1).

Examples 2-9, Comparative Examples 1-15
As shown in Tables 3-5, the same operation as in Example 1 was performed except that the kind or content of the aqueous dispersion of the acid-modified polyolefin resin or the silane coupling agent was changed, and Examples 2-9 were performed. The anchor coating agents (J-2) to (J-9) and Comparative Examples 1 to 15 (H-1) to (H-15) were obtained. The evaluation results are shown in Tables 3-5.

In Table 3, “PE break” indicates that the sealant layer was cut.

As is clear from Table 3, the anchor coating agents for transparent vapor deposition of the present invention obtained in Examples 1 to 9 were excellent in liquid stability. Furthermore, the anchor coat layer formed by using this anchor coat agent was excellent in adhesion and adhesion to the crack prevention layer and boil resistance, and was also excellent in transparency.

As is clear from Table 4, the anchor coating agents obtained in Comparative Examples 1 to 3 did not contain the silane coupling agent (B), and thus were obtained in Comparative Examples 4, 6, or 8. The anchor coating agent was good in liquid stability because the content of the epoxy silane coupling agent (B) was too small, but only an anchor coating layer having poor adhesion and adhesiveness and boil resistance was obtained. I couldn't.

The anchor coating agent obtained in Comparative Example 5, 7, or 9 had an excessive amount of the epoxy silane coupling agent (B) and thus was poor in liquid stability and could not be applied to the substrate. ..

As is clear from Table 5, since the anchor coating agents obtained in Comparative Examples 10 to 15 used a silane coupling agent other than the epoxy silane coupling agent, the liquid stability was good, Only an anchor coat layer having poor adhesion and adhesion and boil resistance was obtained.

Claims (5)

It contains an acid-modified polyolefin resin (A) having an unsaturated carboxylic acid component content of 1 to 8% by mass , an epoxy silane coupling agent (B) and an aqueous medium, and the content of (B) is (A). An anchor coating agent for transparent vapor deposition, which is 0.2 to 2 parts by mass with respect to 100 parts by mass. The anchor coat for transparent vapor deposition according to claim 1, wherein the epoxy-based silane coupling agent (B) is 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropylmethyldimethoxysilane. Agent. A laminated body in which a base material (a), a transparent vapor deposition layer (b), a crack prevention layer (c), an anchor coat layer (d), and a sealant layer (e) are laminated in this order,
The anchor coat layer (d) contains an acid-modified polyolefin resin (A) having an unsaturated carboxylic acid component content of 1 to 8 mass% and an epoxy silane coupling agent (B), and contains (B). The laminated body is characterized in that the amount is 0.2 to 2 parts by mass with respect to 100 parts by mass of (A). The laminate according to claim 3, wherein the base material (a) is composed of a thermoplastic resin. The layered product according to claim 3 or 4, wherein the transparent vapor deposition layer (b) contains alumina or silica.