WO2014098069A1

WO2014098069A1 - Resin composition for use as vapor-barrier adhesive, and laminate

Info

Publication number: WO2014098069A1
Application number: PCT/JP2013/083727
Authority: WO
Inventors: 正憲林; 武田　博之; 加賀谷　浩之
Original assignee: Dic株式会社
Priority date: 2012-12-20
Filing date: 2013-12-17
Publication date: 2014-06-26
Also published as: TW201432006A; JPWO2014098069A1; TWI485219B; JP5761460B2

Abstract

The present invention provides a resin composition for use as a vapor-barrier adhesive. Said resin composition is obtained by reacting a polyol with a hardener, and either the polyol or the hardener has tricycloalkane structures that constitute 10-50% of the mass of the resin composition. Said resin composition makes it possible to provide a film that exhibits excellent adhesive strength and vapor-barrier performance. The present invention also provides a vapor-barrier film laminate obtained by curing the aforementioned resin composition on top of a film.

Description

Resin composition for water vapor barrier adhesive and laminate

The present invention relates to a resin composition capable of providing a film having excellent adhesive strength and water vapor barrier property, and a water vapor barrier film laminate obtained by curing the resin composition on the film.

Food packaging materials are required to have gas or water vapor barrier properties in order to protect their contents and extend their shelf life, and have been studied in many ways, including various plastic films, metals, glass-deposited films, metal foils, etc. Materials that have been laminated into composite films have been used. In order to satisfy the needs for the material having the gas barrier property, a transparent vapor-deposited film on which inorganic materials such as silica and alumina are vapor-deposited is used as the packaging material, but it is expensive and has poor bending resistance. There was a problem.

When aluminum foil or the like is used, gas barrier properties are strong, but there are problems such as being difficult to use and expensive from the viewpoint of recycling.

As materials having water vapor barrier properties, halogenated materials such as polyvinylidene chloride and cycloolefin copolymer systems were mainly used.

In addition, as a method of laminating these various barrier films, metals, glass-deposited films, metal foils, etc., after applying an adhesive on one material surface, the solvent is evaporated to dryness, and the other There is a technique called dry lamination in which the above materials are laminated while heating and pressure bonding. This technology is widely used in the manufacture of food packaging materials that require high performance because any film can be bonded together freely and a composite film having performance according to the purpose can be obtained. Yes.

The adhesive used here is (1) adhesiveness to plastic film, aluminum vapor deposition film, alumina vapor deposition film, silica vapor deposition film, and aluminum foil, (2) initial adhesiveness to prevent tunneling, (3) adhesion High performance is required for the curing rate of the agent, (4) pot life, (5) content resistance, (6) boil, retort resistance and the like. More recently, various impurities derived from adhesives do not migrate to the contents and do not adversely affect the scent or taste. (7) Low odor properties have become important, but water vapor barrier properties The present condition is that the adhesive which has this is not known.

As a sheet having a water vapor barrier property, for example, Patent Document 1 discloses a sheet excellent in water vapor barrier property, impact resistance, rigidity, and heat resistance containing a cyclic olefin in a resin composition, and a container formed of the sheet. ing.

Further, Patent Document 2 describes a material that is a film or sheet containing a vinylidene chloride copolymer.

Regarding a material having a tricyclodecane skeleton, for example, Patent Document 3 has an example using a maleimide compound having a condensed alicyclic structure, and describes that a water vapor barrier property can be imparted to the resulting sealant. .

Patent Document 4 discloses that polyurethane is developed as an adhesive for transparent inorganic vapor-deposited film and an anchor coating agent, polyester polyol is used as a polyurethane raw material, and tricyclodecane dimethanol is used as a glycol component. Are listed.

JP 2001-316558 A JP 2011-212983 PR Japanese Laid-Open Patent Publication No. 2006-176576 Japanese Laid-Open Patent Publication No. 2006-213860

The problem to be solved by the present invention is to provide a resin composition capable of providing a film having excellent adhesive strength and water vapor barrier property, and a water vapor barrier film laminate obtained by curing the resin composition on the film. There is to do.

The present inventors are a resin composition for a water vapor barrier adhesive obtained by reacting a polyol and a curing agent,
The above problems have been solved by providing a resin composition for a water vapor barrier adhesive, wherein the polyol or the curing agent has a tricycloalkane structure.

That is, the present invention comprises the following items.
1. A resin composition for a water vapor barrier adhesive obtained by reacting a polyol and a curing agent,
A resin composition for a water vapor barrier adhesive, which has a tricycloalkane structure in a polyol or a curing agent,
2.1. In the water vapor barrier adhesive resin composition described in
A resin composition for a water vapor barrier adhesive, wherein the proportion of the tricycloalkane structure contained in the resin composition is 10% by mass to 50% by mass;
3. The polyol is a polyester polyol obtained by reacting a tricycloalkane having a hydroxyl group with a polyvalent carboxylic acid or acid anhydride thereof and a polyhydric alcohol. Or 2. A resin composition for a water vapor barrier adhesive according to claim 1,
4). 1. The curing agent is an isocyanate compound. ~ 3. The adhesive resin composition for water vapor barrier according to any one of
5. 1. The isocyanate compound is a reaction product of metaxylene diisocyanate or metaxylene diisocyanate and a polyhydric alcohol having at least two hydroxyl groups in the molecule. ~ 4. A resin composition for a water vapor barrier adhesive according to any one of
6). 1. The isocyanate compound is a reaction product of a tris-cycloalkane having at least two or more hydroxyl groups in the molecule or a polyester polyol comprising tricycloalkane and isocyanate. ~ 4. A resin composition for a water vapor barrier adhesive according to any one of
7). 1. The tricycloalkane is tricyclodecane ~ 6. A resin composition for a water vapor barrier adhesive according to any one of
8.1. ~ 7. A water vapor barrier film laminate obtained by curing the resin composition for water vapor barrier adhesive according to any one of the above on a film.

According to the present invention, it is possible to provide a resin composition capable of providing a film having excellent adhesive strength and water vapor barrier properties, and a water vapor barrier film laminate obtained by curing the resin composition on the film.

The resin composition for water vapor barrier adhesive used in the present invention is a resin composition for water vapor barrier adhesive obtained by reacting a polyol and a curing agent,
It is characterized by having a tricycloalkane structure in the polyol or the curing agent and having a tricycloalkane structure in the resin composition. Since the hydrophobicity of the resin composition by containing this structure is improved and the solubility of water vapor can be reduced, water vapor barrier properties are exhibited.
In the present invention, a resin composition that can be used as an adhesive having a water vapor barrier property is referred to as a resin composition for a water vapor barrier adhesive.

The polyol used in the present invention is not particularly limited as long as it reacts with a curing agent, but a tricycloalkane having a hydroxyl group and a polyvalent carboxylic acid or an acid anhydride thereof, or a tricycloalkane having a hydroxyl group and a polyvalent carboxylic acid. Or the polyol formed by making the acid anhydride and polyhydric alcohol react is mentioned.

(Tricycloalkane having a hydroxyl group)
Examples of the tricycloalkane having a hydroxyl group used in the present invention include known and commonly used tricycloalkanes having a hydroxyl group. Examples of the tricycloalkane include tricyclononane, tricyclononene, tricyclodecane, and tricycloalkane. Examples include cyclodecene, tricycloundecane, tricyclododecane, tricyclotetradecane, tricyclopentadecane, and tricyclohexadecane.

(Polyvalent carboxylic acid)
Specifically, as the polyvalent carboxylic acid component used in the present invention, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like are used, and alicyclic polyvalent carboxylic acid. 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and aromatic polyvalent carboxylic acids include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4 -Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and the dicarboxylic acids Anhydrides or ester-forming derivatives; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) an Polybasic acids such as benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more. These acid anhydrides can also be used. Among these, in order to obtain barrier properties, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable.

(Polyhydric alcohol component)
Specific examples of the polyhydric alcohol used in the present invention include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, and 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenol , Hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide De extension product, there can be mentioned hydrogenated alicyclic. Among them, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane dimethanol are preferred, because it is estimated that the smaller the number of carbon atoms between oxygen atoms, the more difficult the molecular chain becomes excessively flexible. More preferred is ethylene glycol. The polycondensation reaction between the polyvalent carboxylic acid and the polyhydric alcohol can be performed by a known and usual method.

Examples of the polyester polyol according to the present invention include, but are not limited to, the following.
(I); General formula (1)

(1)

(However, A is a polyvalent carboxylic acid or its anhydride, B is a polyhydric alcohol having a tricyclodecane skeleton, and A and B are bound by an ester group obtained by reaction with A and B. , N is an integer from 1 to 100.)
Polyester polyol represented by

(II); general formula (2)

(2)

(However, A is a polyhydric carboxylic acid or its anhydride, B is a polyhydric alcohol having a tricyclodecane skeleton, C is a polyhydric alcohol other than a polyhydric alcohol having a tricyclodecane skeleton, A and C are bonded with an ester group obtained by reaction with A and B, A and C, and m and n are integers of 1 to 100.)
Polyester polyol represented by

(III); General formula (3)

(3)

(However, A is a polyvalent carboxylic acid or its anhydride, B is a polyhydric alcohol having a tricyclodecane skeleton, C is a monovalent or polyhydric alcohol having a tricyclodecane skeleton, and D is a polyhydric having a tricyclodecane skeleton. A polyhydric alcohol other than a monohydric alcohol, wherein A and B, A and C, A and D are bonded with an ester group obtained by reaction with A and B, A and C, A and D, m , N is an integer from 1 to 100.)
Polyester polyol represented by

(IV); General formula (4)

(4)

(Where A is a polyvalent carboxylic acid or anhydride thereof, B is a polyhydric alcohol having a tricyclodecane skeleton, C is a linear or branched alkyl group having 1 to 30 carbon atoms and having a hydroxyl group, And B, A and C are bonded with an ester group obtained by reaction with A and B, A and C, and n is an integer of 1 to 100.)
Polyester polyol represented by

(V); General formula (5)

(5)

(Where A is a polyvalent carboxylic acid or its anhydride, B is a polyhydric alcohol other than a polyhydric alcohol having a tricyclodecane skeleton, C is a monovalent or polyhydric alcohol having a tricyclodecane skeleton, And B, A and C are bonded with an ester group obtained by reaction with A and B, A and C, and n is an integer of 1 to 100.)
Polyester polyol represented by

The polyvalent carboxylic acid used in the present invention preferably contains a benzene ring, and particularly preferably includes orthophthalic acid and its anhydride. The orthophthalic acid and its anhydride skeleton have an asymmetric structure. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and it is presumed that this provides excellent gas barrier properties, particularly water vapor barrier properties. Further, it is presumed that the non-crystalline structure is exhibited due to this asymmetric structure, sufficient adhesion to the base material is imparted, and excellent adhesion and gas barrier properties, particularly water vapor barrier properties. Furthermore, when used as a dry laminate adhesive, the solvent solubility, which is essential, is also high, so that it has excellent handling characteristics. Moreover, when the polyvalent carboxylic acid containing the cyclohexane skeleton which hydrogenated the benzene ring is used, since hydrophobicity improves and the solubility of water vapor | steam can be reduced, it can use preferably.

(Polyvalent carboxylic acid and other components)
When synthesizing a polyester polyol having three or more hydroxyl groups, when a branched structure is introduced by a polyvalent carboxylic acid component, it is necessary to have at least part of a trivalent or higher carboxylic acid. Examples of these compounds include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride, etc. In order to prevent gelation during synthesis, trivalent or higher polyvalent carboxylic acids include three. Divalent carboxylic acids are preferred.

As other components, the polyester polyol of the present invention may be copolymerized with other polyvalent carboxylic acid components as long as the effects of the present invention are not impaired. Specifically, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc., as the unsaturated bond-containing polyvalent carboxylic acid, maleic anhydride, maleic acid, Fumaric acid, etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc. as alicyclic polyvalent carboxylic acid, terephthalic acid, isophthalic acid, pyromellitic as aromatic polyvalent carboxylic acid Acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p '-Dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- ( - it can be used in hydroxyethoxy) benzoic acid and alone or in mixture of two or more polybasic acids such as ester-forming derivatives of these dihydroxy carboxylic acids. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.

(Polyhydric alcohol and other ingredients)
When synthesizing a polyester polyol having three or more hydroxyl groups, when a branched structure is introduced by a polyhydric alcohol component, it is necessary to have at least part of a trihydric or higher polyhydric alcohol. Examples of these compounds include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, and dipentaerythritol. In order to prevent gelation, trihydric alcohol is preferable as the trihydric or higher polyhydric alcohol.

In the present invention, other polyhydric alcohol components may be copolymerized with other polyhydric alcohol components as long as the effects of the present invention are not impaired. Specifically, aliphatic diols include 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenols, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and their ethylene oxides An elongated product and a hydrogenated alicyclic group can be exemplified.

Next, the synthesis of the polyester polyol can be performed using a known and commonly used method (for details, refer to Examples).

In the present invention, the polyester polyol preferably has a hydroxyl value of 20 to 250 and an acid value of 20 to 200. The hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070. When the hydroxyl value is smaller than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and good coating suitability cannot be obtained. On the other hand, when the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinking density of the cured coating film becomes too high, and good adhesive strength cannot be obtained. When the acid value is less than 20 mgKOH / g, the interaction between molecules becomes small, and good barrier properties and good initial cohesive force cannot be obtained. On the other hand, when the acid value exceeds 200 mgKOH / g, the reaction with the isocyanate compound as the curing agent becomes too fast, and good coating suitability cannot be obtained.

In addition, the ratio (mass%) of the tricycloalkane structure contained in the resin composition for water vapor | steam barrier adhesives in this application is computable as follows. That is,

However,
TMW: Tricycloalkane molecular weight n: Degree of polymerization (in the case of containing a tricycloalkane structure at the terminal, n + 1)
NMW: repeating unit molecular weight EMW: terminal monomer molecular weight W: main agent or curing agent blending amount containing tricycloalkane structure, or main agent + curing agent blending amount AW: main agent + curing agent blending amount.

For example, as a specific compound example in [Chemical Formula 5], when A is trimellitic acid, B is ethylene glycol, C is a monohydric alcohol having a tricyclodecane skeleton, and Takenate D110N is used as a curing agent. It becomes as follows.

In the present invention, in order to maintain a sufficient water vapor barrier property, the ratio of the tricycloalkane structure contained in the resin composition for a water vapor barrier adhesive of the present invention is preferably 10% by mass to 50% by mass.

(Adhesive hardener)
The curing agent used in the present invention is not particularly limited as long as it can react with the hydroxyl group of the polyol, and known curing agents such as diisocyanate compounds, polyisocyanate compounds, and epoxy compounds can be used. Especially, it is preferable to use a polyisocyanate compound from a viewpoint of adhesiveness or retort resistance.

Polyisocyanate compounds include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanate compounds, which may be either low molecular compounds or high molecular compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amount and, for example, ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, Diethanolamine, triethanol Examples include adducts obtained by reacting low molecular active hydrogen compounds such as amines and metaxylylenediamines and their alkylene oxide adducts, various polyester resins, polyether polyols, and high molecular active hydrogen compounds of polyamides. .

The isocyanate compound may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime oximes, methanol, Alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Examples include lactams such as caprolactam, δ-valerolactam, γ-butyrolactam, β-propylolactam, and other aromatic amines, imides, acetylacetate. , Acetoacetic ester, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, ureas, and also such as diaryl compounds sodium bisulfite. The blocked isocyanate can be obtained by subjecting the above isocyanate compound and the isocyanate blocking agent to an addition reaction by a known and appropriate method.

Among them, in order to obtain good barrier properties, metaxylene diisocyanate or a reaction product of metaxylene diisocyanate and a polyhydric alcohol having at least two hydroxyl groups in the molecule is preferable.

The glass transition temperature of the cured coating film of the polyol of the present invention and the curing agent is preferably in the range of −30 ° C. to 80 ° C. More preferably, it is 0 ° C to 70 ° C. More preferably, it is 25 ° C to 70 ° C. When the glass transition temperature is higher than 80 ° C., the flexibility of the cured coating film near room temperature becomes low, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate. On the other hand, when the temperature is lower than −30 ° C., there is a fear that sufficient barrier properties may not be obtained due to intense molecular motion of the cured coating film at around room temperature, and there is a possibility that adhesive strength may be reduced due to insufficient cohesive force.

Also, when carboxylic acid remains at the end of the resin composition used in the present invention, an epoxy compound can be used as a curing agent. Epoxy compounds include bisphenol A diglycidyl ether and oligomers thereof, hydrogenated bisphenol A diglycidyl ether and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid diglyceride. Glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol Cole diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like.

In the case of using an epoxy compound as a curing agent, a general-purpose known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing as long as the barrier property which is the object of the present invention is not impaired.

Among them, the curing agent is preferably a polyisocyanate compound having an aromatic ring. If the polyisocyanate compound includes the metaxylene skeleton, the barrier is not only caused by hydrogen bonding of the urethane group but also by π-π stacking of aromatic rings. It is preferable because the property can be improved.

Examples of the polyisocyanate compound containing the meta-xylene skeleton include a trimer of xylylene diisocyanate, a burette synthesized by reaction with an amine, and an adduct obtained by reacting with an alcohol. The adduct body is more preferable because the solubility of the polyisocyanate compound in the organic solvent used for the dry laminate adhesive is easily obtained as compared with the body. As the adduct, an adduct obtained by reacting with an alcohol appropriately selected from the above low molecular active hydrogen compounds can be used. Among them, addition of ethylene oxide of trimethylolpropane, glycerol, triethanolamine, metaxylenediamine, etc. Adduct bodies with objects are particularly preferred.

The resin composition and the curing agent are such that the ratio of the resin composition to the curing agent is such that the hydroxyl group of the resin composition and the reaction component of the curing agent are 1 / 0.5 to 1/10 (equivalent ratio). It is preferably blended in, more preferably 1/1 to 1/5. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength is insufficient. There is a fear.

The above-mentioned curing agent can be used in combination with a known curing agent or accelerator selected according to the type. Examples of the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are also preferred in terms of improving the adhesive to various film materials.

(Adhesive and other ingredients)
The adhesive of the present invention may contain various additives as long as the adhesive strength and the barrier property are not impaired. Examples of additives include inorganic fillers such as silica, alumina, aluminum flakes, and glass flakes, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, and antiblocking agents. Examples include agents, colorants, fillers, crystal nucleating agents and the like.

(Plate-like inorganic compound)
In the resin composition for adhesives of this invention, you may contain a plate-shaped inorganic compound.
The plate-like inorganic compound used in the present invention has an effect of improving the laminate strength and barrier properties of an adhesive obtained by curing a resin composition for an adhesive.

The plate-like inorganic compound used in the present invention has a feature that the laminate strength and barrier properties are improved by the plate-like shape. The charge between the layers of the plate-like inorganic compound does not greatly affect the barrier property directly, but the dispersibility to the resin composition is greatly inferior with the ionic inorganic compound or the swellable inorganic compound with respect to water, and the amount added is increased. As a result, the resin composition becomes thicker and thixotropic. On the other hand, in the case of being uncharged (nonionic) or non-swelling with respect to water, even if the addition amount is increased, it is difficult to become thickened or thixotropic, so that the coating suitability can be secured. Examples of the plate-like inorganic compound used in the present invention include, for example, hydrous silicate (phyllosilicate mineral etc.), kaolinite-serpentine clay mineral (halloysite, kaolinite, ende Light, dickite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kellorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, Sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite etc.), mica or mica group clay minerals (muscovite, phlogopite etc. mica, margarite, tetrasilic mica, teniolite, etc.), chlorite group (kukeite, sudite) , Clinocroix, sha Site Nimaito etc.), hydrotalcite, tabular barium sulfate, boehmite, and aluminum polyphosphate and the like. These minerals may be natural clay minerals or synthetic clay minerals. An inorganic layered compound is used individually or in combination of 2 or more types.

Further, the plate-like inorganic compound used in the present invention is preferably nonionic without intercalation.

Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.), pyrophyllite, and the like. -The talc family (pyrophyllite, talc, kerolai, etc.) can be mentioned.

The plate-like inorganic compound used in the present invention is preferably non-swellable with respect to water.

Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.), pyrophyllite, and the like. -Talc (pyrophyllite, talc, kerolai, etc.), mica or mica clay minerals (mica, muscovite, phlogopite, etc.), margarite, tetrasilic mica, teniolite, etc., chlorite (kukeite, sudite, (Clinochlor, chamosite, nimite, etc.), hydrotalcite, plate-like barium sulfate and the like.

The average particle size in the present invention means a particle size having the highest appearance frequency when the particle size distribution of a certain plate-like inorganic compound is measured with a light scattering type measuring device. The average particle diameter of the plate-like inorganic compound used in the present invention is not particularly limited, but is preferably 0.1 μm or more, and more preferably 1 μm or more. If the average particle size is 0.1 μm or less, the length of the long side is short, so that there are problems that the detour path of the molecule does not become long and the barrier ability is difficult to improve and the adhesive force is difficult to improve. The side with a large average particle diameter is not particularly limited. When defects such as streaks occur on the coated surface by containing a large plate-like inorganic compound by the coating method, a material having an average particle diameter of 100 μm or less, more preferably 20 μm or less is preferably used.

The aspect ratio of the plate-like inorganic compound used in the present invention is preferably higher in order to improve the barrier ability due to the gas maze effect. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

As a method for dispersing the inorganic compound used in the present invention in a resin composition or a resin composition for a water vapor barrier adhesive, a known dispersion method can be used. For example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint conditioner, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, a nano mill, an SC mill, a nanomizer, and the like can be mentioned, and even more preferably, a high shear force is generated. Examples of equipment that can be used include Henschel mixer, pressure kneader, Banbury mixer, planetary mixer, two-roll, three-roll. One of these may be used alone, or two or more devices may be used in combination.

The adhesive and film laminate of the present invention can also block gases other than water vapor. Examples of the target gas include oxygen, alcohol, inert gas, and volatile organic substances (fragrance).

(Target alcohol)
The alcohol targeted for blocking by the adhesive and multilayer film of the present invention is a material generally classified as an alcohol having a structure in which a hydroxyl group is bonded to an alkyl chain in at least one place. If there is no particular limitation. Moreover, monohydric alcohol or polyhydric alcohol can be used. Examples of the monohydric alcohol include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, neopentyl glycol, hexanol, benzyl alcohol, allyl alcohol, and cyclohexanol. Examples of the polyhydric alcohol include ethylene glycol, propanediol, butanediol, glycerin, and trimethylpropane. Furthermore, in addition to aminoalcohols such as N, N-diethylethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine and N-ethylethanolamine, alcohol compounds containing ether groups such as diethylene glycol and triethylene glycol Etc. can also be used.

In addition, as the state of the alcohol compound, a material that is a gas to a liquid in a normal temperature region is preferable because of high effectiveness of the present invention.

(Target inert gas)
The inert gas that is intended to be blocked by the adhesive and multilayer film of the present invention is inert to foods and is unlikely to cause a general chemical change. It is a gas useful for maintaining the flavor of food, maintaining its contents, and preventing oxidation by functions such as preventing contact. Specifically, in addition to nitrogen and carbon dioxide, helium, neon, argon, krypton, xenon, and radon rare gases can be exemplified. Of these, nitrogen, argon, and carbon dioxide are widely used as the inert gas.

(fragrance)
Volatile organic substances (fragrances) targeted for blocking by the adhesive and multilayer film of the present invention are cocoa, soy sauce, sauce, miso, coffee, lemonene, methyl salicylate, menthol, cheese, flavors, shampoo, rinse Sanitary field containing scent components such as detergents, softeners, soaps, pet foods, insect repellents, fragrances, hair dyes, perfumes, agricultural chemicals and the like.

Since the adhesive and multilayer film of the present invention can block gas, adsorbents such as activated carbon and zeolite, deodorants, water purifier cartridges, rice grains, instant noodles, mineral water, somen, cotton, etc. It is also suitably used for applications where it is desired to prevent the entry of fragrance from the outside and for applications where it is desired to prevent leakage of the fragrance to the outside.

(Adhesive form)
The adhesive of the present invention may be either a solvent type or a solventless type. In the case of a solvent type, the solvent may be used as a reaction medium during the production of the polyester polyol and the curing agent. Furthermore, it is used as a diluent during painting. Solvents that can be used include, for example, esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene. , Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. Of these, it is usually preferable to use ethyl acetate or methyl ethyl ketone. In addition, when used without a solvent, it is not always necessary to be soluble in an organic solvent. However, in consideration of washing of a reaction kettle during synthesis and washing of a coating machine during lamination, it is soluble in an organic solvent. Sex is necessary.

The adhesive of the present invention can be used by being applied to a substrate film or the like. The coating method is not particularly limited and may be performed by a known method. For example, in the case of a solvent type whose viscosity can be adjusted, it is often applied by a gravure roll coating method or the like. Moreover, when it is a solventless type and has a high viscosity at room temperature and is not suitable for gravure roll coating, it can be coated with a roll coater while heating. In the case of using a roll coater, it is preferable to coat the adhesive of the present invention in a state heated to about room temperature to about 120 ° C. so that the viscosity of the adhesive of the present invention is about 500 to 2500 mPa · s.

The adhesive of the present invention can be used as a water vapor barrier adhesive for various applications that require gas barrier properties, particularly water vapor barrier properties, for polymers, paper, metals, and the like.

Hereinafter, an adhesive for film lamination will be described as one of specific applications.

The adhesive of the present invention can be used as an adhesive for film lamination. Since the laminated film is excellent in gas barrier property, particularly water vapor barrier property, it can be used as a gas barrier property, particularly water vapor barrier laminated film.

The film for lamination used in the present invention is not particularly limited, and a thermoplastic resin film can be appropriately selected according to a desired application. For example, for food packaging, PET film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched polypropylene film, OPP: Examples thereof include polyolefin films such as biaxially stretched polypropylene film), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films. These may be subjected to stretching treatment. As the stretching treatment method, it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.

The adhesive of the present invention can be preferably used as an adhesive for a laminated film formed by bonding a plurality of the same or different resin films. The resin film may be appropriately selected depending on the purpose. For example, when used as a packaging material, the outermost layer is a thermoplastic resin film selected from PET, OPP, and polyamide, and the innermost layer is unstretched polypropylene. (Hereinafter abbreviated as CPP), a composite film consisting of two layers using a thermoplastic resin film selected from a low density polyethylene film (hereinafter abbreviated as LLDPE), or an outermost layer selected from, for example, PET, polyamide and OPP A three-layer composite using a thermoplastic resin film, a thermoplastic resin film that forms an intermediate layer selected from OPP, PET, and polyamide, and a thermoplastic resin film that forms an innermost layer selected from CPP and LLDPE Heat to form an outermost layer selected from a film, for example, OPP, PET, polyamide Selected from a plastic film, a thermoplastic film forming a first intermediate layer selected from PET and nylon, and a thermoplastic film forming a second intermediate layer selected from PET and polyamide, LLDPE, and CPP A four-layer composite film using a thermoplastic resin film that forms the innermost layer can be preferably used as a food packaging material as a gas barrier property, particularly as a water vapor barrier film.

In addition, the surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer free from defects such as film breakage and repellency is formed.

The water vapor barrier laminate film of the present invention is obtained by applying the adhesive of the present invention to one of the thermoplastic resin films and then laminating the other thermoplastic resin film and laminating them by lamination. As the lamination method, known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.

Specifically, in the dry lamination method, the adhesive of the present invention is applied to one of the base films by a gravure roll method, and the other base film is stacked and bonded by dry lamination (dry lamination method). The temperature of the laminate roll is preferably about room temperature to 60 ° C.

In addition, non-solvent lamination is applied to the surface immediately after applying the adhesive of the present invention, which has been heated to room temperature to about 120 ° C., with a roll such as a roll coater heated to room temperature to about 120 ° C. A laminate film can be obtained by laminating various film materials. The laminating pressure is preferably about 10 to 300 kg / cm ² .

In the case of the extrusion laminating method, the organic solvent solution of the adhesive of the present invention is applied to the base film as an adhesion aid (anchor coating agent) by a roll such as a gravure roll, and the solvent is dried and cured at room temperature to 140 ° C. After the reaction, a laminate film can be obtained by laminating the polymer material melted by the extruder. The polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.

The water vapor barrier laminate film of the present invention is preferably subjected to aging after production. If polyisocyanate is used as a curing agent, the aging condition is from room temperature to 80 ° C. for 12 to 240 hours, during which adhesive strength is generated.

Since the adhesive of the present invention is characterized by having a gas barrier property, particularly a water vapor barrier property, a laminate film formed from the adhesive may be a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, or ethylene-vinyl alcohol. Very high level barrier without using commonly used barrier materials such as copolymer (EVOH) film layer, metaxylylene adipamide film layer, inorganic vapor deposited film layer deposited with alumina, silica, etc. Sex is expressed.

In the present invention, in order to provide an even higher barrier function, a film in which a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina is laminated, polyvinyl alcohol, or ethylene / vinyl alcohol as necessary. A barrier film containing a gas barrier layer such as a polymer or vinylidene chloride may be used in combination.

(Synthesis Example 1 TCDoPA)
In a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a water separator, etc., 100 parts of phthalic anhydride, 155 parts of tricyclodecane dimethanol, and titanium tetraisopropoxide are mixed with a polycarboxylic acid and a polyhydric alcohol. 100 ppm was added to the total amount, and the internal temperature was stored at 220 ° C. by gradually heating so that the temperature of the upper part of the rectification column did not exceed 100 ° C. When the acid value became 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (TCDoPA) having a number average molecular weight of 2000, an acid value of 1.13 mgKOH / g, and a hydroxyl value of 58.8 mgKOH / g.

(Synthesis Example 2 TCDHH)
In a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a water separator, etc., 100 parts of hexahydroxyphthalic anhydride, 150 parts of tricyclodecane dimethanol, and titanium tetraisopropoxide are mixed with polyvalent carboxylic acid. 100 ppm was added to the total amount of alcohol, and the inner temperature was stored at 220 ° C. by gradually heating so that the temperature of the upper part of the rectification column did not exceed 100 ° C. When the acid value became 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (TCDHH) having a number average molecular weight of 2000, an acid value of 3.35 mgKOH / g, and a hydroxyl value of 60.7 mgKOH / g.

(Synthesis Example 3 EGTMATCD)
A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a water separator, etc. is charged with 100 parts of trimellitic anhydride and 90 parts of tricyclodecane monomethanol, and is refluxed using methyl ethyl ketone as a solvent. Was 315 mgKOH / g, the reaction was terminated and the solvent was removed. 60 parts of ethylene glycol and titanium tetraisopropoxide were charged at 100 ppm with respect to the total amount of polycarboxylic acid and polyhydric alcohol, and gradually heated so that the upper temperature of the rectification column did not exceed 100 ° C. Was stored at 220 ° C. When the acid value became 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (EGTMATCD) having a number average molecular weight of 600, an acid value of 1.32 mgKOH / g, and a hydroxyl value of 161.8 mgKOH / g.

(Synthesis Example 4 CHDMTMATCD)
A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a water separator, etc. is charged with 100 parts of trimellitic anhydride and 90 parts of tricyclodecane monomethanol, and is refluxed using methyl ethyl ketone as a solvent. Was 315 mgKOH / g, the reaction was terminated and the solvent was removed. Add 150 parts of cyclohexanedimethanol and titanium tetraisopropoxide to the total amount of polycarboxylic acid and polyhydric alcohol to 100 ppm, and gradually heat the rectifying tower so that the upper temperature does not exceed 100 ° C. The temperature was stored at 220 ° C. When the acid value reached 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (CHDMTMATCD) having a number average molecular weight of 640, an acid value of 0.2 mgKOH / g, and a hydroxyl value of 184.4 mgKOH / g.

(Synthesis Example 5 TCDTMATCD)
A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a water separator, etc. is charged with 100 parts of trimellitic anhydride and 90 parts of tricyclodecane monomethanol, and is refluxed using methyl ethyl ketone as a solvent. Was 315 mgKOH / g, the reaction was terminated and the solvent was removed. Charge 210 parts of tricyclodecane dimethanol and titanium tetraisopropoxide to 100 ppm with respect to the total amount of polycarboxylic acid and polyhydric alcohol, and gradually heat the rectifying tower so that the upper temperature does not exceed 100 ° C. The internal temperature was stored at 220 ° C. When the acid value became 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (TCTDMATCD) having a number average molecular weight of 720, an acid value of 1.09 mgKOH / g, and a hydroxyl value of 160.5 mgKOH / g.

(Comparative Example 1 NDoPA)
Total amount of polyhydric carboxylic acid and polyhydric alcohol containing 100 parts of phthalic anhydride, 127 parts of nonanediol, and titanium tetraisopropoxide in a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, moisture separator, etc. The inner temperature was stored at 220 ° C. by gradually heating the rectifying tower so that the temperature at the upper part of the rectification column did not exceed 100 ° C. When the acid value became 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (NDoPA) having a number average molecular weight of 2000, an acid value of 0.12 mgKOH / g, and a hydroxyl value of 50.4 mgKOH / g.

(Comparative Example 2 NDHH)
In a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a water separator, etc., 100 parts of hexahydroxyphthalic anhydride, 122 parts of nonanediol, and titanium tetraisopropoxide are mixed with polyhydric carboxylic acid and polyhydric alcohol. 30 ppm was charged with respect to the total amount, and the internal temperature was stored at 220 ° C. by gradually heating so that the temperature of the upper part of the rectification column did not exceed 100 ° C. When the acid value reached 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (NDHH) having a number average molecular weight of 2000, an acid value of 1.94 mgKOH / g, and a hydroxyl value of 62.2 mgKOH / g.

(Comparative Example 3 CHDMODA)
In a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a water separator, etc., 100 parts of octanedioic acid, 97 parts of cyclohexanedimethanol, and titanium tetraisopropoxide are the sum of polycarboxylic acid and polyhydric alcohol. 30 ppm was charged with respect to the amount, and the upper temperature of the rectifying column was gradually heated so as not to exceed 100 ° C., and the internal temperature was stored at 220 ° C. When the acid value became 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (CHDMODA) having a number average molecular weight of 2000, an acid value of 0.91 mgKOH / g, and a hydroxyl value of 54.5 mgKOH / g.

(Comparative Example 4 EGOSA)
In a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a water separator, etc., 100 parts of octenyl succinic anhydride, 45 parts of ethylene glycol, and titanium tetraisopropoxide are added to the polycarboxylic acid and polyhydric alcohol. 30 ppm with respect to the amount, and 100 ppm of t-butylcatechol with respect to the total amount of polyvalent carboxylic acid and polyhydric alcohol, and gradually heated so that the upper temperature of the rectification column does not exceed 100 ° C. Stored at 220 ° C. When the acid value became 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (EGOSA) having a number average molecular weight of 600, an acid value of 0.55 mgKOH / g, and a hydroxyl value of 190.8 mgKOH / g.

(Comparative Example 5 PDTMAOcOH)
A polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a water separator, and the like was charged with 100 parts of trimellitic anhydride and 70 parts of octyl alcohol, and was refluxed using methyl ethyl ketone as a solvent. The acid value was 315 mgKOH / When g was reached, the reaction was terminated and the solvent was removed. Charge 103 parts of 1,2-pentanediol and titanium tetraisopropoxide to 100 ppm with respect to the total amount of polycarboxylic acid and polyhydric alcohol, and gradually heat the rectifying column top temperature not to exceed 100 ° C. The internal temperature was stored at 220 ° C. When the acid value reached 5 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol (PDTMAOcOH) having a number average molecular weight of 600, an acid value of 0.43 mgKOH / g, and a hydroxyl value of 187.4 mgKOH / g.

(Adhesive resin)
The polyester polyol of (Synthesis Example 1) to (Synthesis Example 5), a curing agent, and an organic solvent were mixed to obtain an adhesive. The configuration is shown in Table 1.

(Coating method)
Using a bar coater, the solvent-type adhesive is subjected to corona treatment of a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm so that the coating amount is about 5 g / m ² (solid content). It is applied to the surface, the solvent is evaporated and dried with a dryer set at a temperature of 70 ° C., and the adhesive surface of the PET film to which the adhesive is applied, and a nylon film with a thickness of 15 μm (“Emblem ON” manufactured by Unitika Ltd.) -BC ") was laminated with a corona-treated surface to prepare a composite film having a layer structure of PET film / adhesive layer / nylon film. Next, this composite film was aged at 40 ° C. for 5 days to cure the adhesive, and the laminated film of the present invention was obtained.

(Evaluation methods)
(1) Water vapor transmission rate (MVTR)
The laminated film after aging was evaluated in an atmosphere of 40 ° C. and 90% RH using a measuring apparatus model 7000 manufactured by Illinois in accordance with a water vapor permeability test method conductivity method “ISO-15106-3”. . Note that RH represents humidity.

Also, the water vapor barrier property of the adhesive cured coating film alone was calculated using the formula (a) from the measurement results of the water vapor barrier laminated film, PET film and nylon film.

P: Water vapor transmission rate of water vapor barrier laminate film P1: Water vapor transmission rate of coating film alone P2: Water vapor transmission rate of 12 μm PET film (calculated as 49 g / m ² · 24 hours)
P3: Water vapor permeability of 15 μm nylon film (calculated as 300 g / m ² · 24 hours)

(Examples 1 to 5)
Using the resins of Synthesis Examples 1 to 5, a curing agent and a solvent were mixed to obtain an adhesive.
The coating method and the evaluation method are as described above. The results are shown in Table 1.

Table 2 shows the results using the resin compositions obtained in Comparative Examples 1 to 5.

-Takenate D-110N: Takenate D-110N (Mitsui Chemicals Co., Ltd .: XDI polyisocyanate, non-volatile content / about 75%)
・ AcOET: Ethyl acetate ・ MEK: Methyl ethyl ketone

Since the adhesive of the present invention has good adhesive strength and water vapor barrier properties, in addition to the adhesive for film laminate for the packaging material, for example, an adhesive for a protective film for solar cells and a barrier substrate for display elements. It can be suitably used in applications where water vapor barrier properties are desired, such as adhesives for electronic materials such as adhesives, adhesives for building materials, and adhesives for industrial materials.

Claims

A water vapor barrier adhesive resin composition obtained by reacting a polyol and a curing agent,
A resin composition for a water vapor barrier adhesive, wherein the polyol or curing agent has a tricycloalkane structure.
In the resin composition for water vapor | steam barrier adhesives of Claim 1,
A resin composition for a water vapor barrier adhesive wherein the proportion of the tricycloalkane structure contained in the resin composition is 10% by mass to 50% by mass.
The water vapor barrier adhesive resin according to claim 1 or 2, wherein the polyol is a polyester polyol obtained by reacting a tricycloalkane having a hydroxyl group with a polyvalent carboxylic acid or acid anhydride thereof and a polyhydric alcohol. Composition.
The water vapor barrier adhesive resin composition according to any one of claims 1 to 3, wherein the curing agent is an isocyanate compound.
5. The water vapor barrier adhesive according to claim 1, wherein the isocyanate compound is metaxylene diisocyanate or a reaction product of metaxylene diisocyanate and a polyhydric alcohol having at least two hydroxyl groups in the molecule. Agent resin composition.
The water vapor barrier according to any one of claims 1 to 4, wherein the isocyanate compound is a tricycloalkane having at least two hydroxyl groups in the molecule or a reaction product of a polyester polyol comprising tricycloalkane and an isocyanate. Resin composition for adhesive.
7. The water vapor barrier adhesive resin composition according to claim 1, wherein the tricycloalkane is tricyclodecane.
A water vapor barrier film laminate obtained by curing the resin composition for water vapor barrier adhesive according to any one of claims 1 to 7 on a film.