TWI485219B - A resin composition for steam barrier-related adhesive and laminate - Google Patents

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 adhesion and water vapor barrier properties, and a water vapor barrier film laminate which is obtained by curing the resin composition on a film.

Food packaging materials require gas or water vapor barrier properties due to the need for content protection, extension of taste period, etc. Many studies have been conducted so far, and various layers of plastic films, metals, glass vapor deposited films, and metal foils have been used. Wait for the composite filming material. In order to satisfy the need for the above-described material having gas barrier properties, the packaging material uses a transparent vapor-deposited film of a vapor-deposited inorganic material such as silica or alumina, but has a problem of high cost, lack of bending resistance, and the like. .

When aluminum foil or the like is used, the gas barrier property is strong, but from the viewpoint of recycling, there is a problem that it is difficult to use and expensive.

As a material having a water vapor barrier property, a halogenated material such as polyvinylidene chloride or a cycloolefin copolymer system is mainly used.

Moreover, a method of producing a laminate by bonding various barrier films, metals, glass vapor deposited films, metal foils, and the like to these is In other words, there is a technique called dry lamination in which an adhesive is applied to one side of a material surface, and the solvent is evaporated and dried, and other materials are heated and pressed while laminating. This technology has been widely used for the production of food packaging materials requiring high performance because it is possible to freely bond any of the films to each other and to obtain a composite film having properties according to the purpose.

The adhesive used herein is for (1) adhesion to plastic film, aluminum vapor deposited film, alumina vapor deposited film, yttria vapor deposited film, and aluminum foil, and (2) for preventing tunneling (tunneling) High performance is required for the initial adhesion, (3) curing rate of the adhesive, (4) pot life, (5) resistance to physical properties, (6) boiling, retort resistance, and the like. In addition, (7) low odor which does not affect the sense of smell and taste is not caused by the transfer of various impurities derived from the adhesive to the contents, but it is not known that there is a water vapor barrier.

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

Further, Patent Document 2 describes a material containing a film or sheet of a vinylidene chloride-based copolymer.

For the material having a tricyclodecane skeleton, for example, Patent Document 3 describes an example in which a maleic acid imide compound having a condensed alicyclic structure is used, and water vapor barrier properties can be imparted to the obtained sealing agent.

Further, Patent Document 4 describes the development of a polyurethane as an adhesive for a transparent inorganic vapor deposited film, an anchor coat agent, and a polyester polyol as a raw material of a polyurethane, and a tricyclic fluorene is used. Alkanediethanol is used as the diol component.

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2001-316558

Patent Document 2 Japanese Patent Laid-Open Publication No. 2011-212983

Patent Document 3 Japanese Patent Laid-Open Publication No. 2006-176576

Patent Document 4 Japanese Patent Laid-Open Publication No. 2006-213860

An object of the present invention is to provide a resin composition capable of providing a film having excellent adhesion and water vapor barrier properties, and a water vapor barrier film laminate which is obtained by curing the resin composition on a film.

The present inventors have a resin composition for a water vapor barrier adhesive which is obtained by reacting a polyhydric alcohol with a curing agent, that is, The above-mentioned problem is solved by the provision of a resin composition for a water vapor barrier adhesive having a tricycloalkane structure in which a polyalcohol or a curing agent is used.

That is, the present invention encompasses the following items.

1. A resin composition for a water vapor barrier adhesive, which is a resin composition for a water vapor barrier adhesive which is obtained by reacting a polyol with a curing agent, It is characterized in that the polyol or the hardener has a tricycloalkane structure; 2. The resin composition for a water vapor barrier adhesive according to 1. The ratio of the tricycloalkane structure contained in the resin composition is 10% by mass. The resin composition for a water vapor barrier adhesive according to the above aspect, wherein the polyalcohol is a reaction of a tricycloalkane having a hydroxyl group with a polyvalent carboxylic acid or an anhydride thereof, and a polyhydric alcohol. The polyester resin for a water vapor barrier according to any one of claims 1 to 3, wherein the hardener is an isocyanate compound; 5. any one of 1. to 4. The resin composition for a water vapor barrier adhesive according to the invention, wherein the isocyanate compound is meta-xylene diisocyanate or m-xylene diisocyanate and a polyhydric alcohol having at least two hydroxyl groups in the molecule. The resin composition for a water vapor barrier adhesive according to any one of the above aspects, wherein the isocyanate compound is a tricycloalkane having at least two or more hydroxyl groups in the molecule or a tricyclic ring. Polyester polyol The resin composition for a water vapor barrier adhesive according to any one of the above aspects, wherein the tricycloalkane is tricyclodecane; 8. a water vapor barrier The film laminate of the present invention is obtained by curing a resin composition for a water vapor barrier adhesive according to any one of the items 1 to 7.

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

[Formation for implementing the invention]

The resin composition for a water vapor barrier adhesive used in the present invention is a resin composition for a water vapor barrier adhesive which is obtained by reacting a polyhydric alcohol with a curing agent, and is characterized in that the polyalcohol or the curing agent has a tricycloalkane structure. The resin composition has a tricycloalkane structure. Since the solubility of the resin composition due to the present structure is improved, the solubility of water vapor can be lowered, thereby exhibiting water vapor barrier properties.

Further, in the present invention, a resin composition as a water vapor barrier adhesive can be used, and it is called a resin composition for a water vapor barrier adhesive.

The polyalcohol used in the present invention is not particularly limited as long as it can react with a curing agent, and examples thereof include a tricycloalkane having a hydroxyl group and a polyvalent carboxylic acid or an anhydride thereof, or a tricycloalkane having a hydroxyl group and a polyvalent carboxylic acid or an anhydride thereof. Polyols obtained by reacting with a polyol.

(tricycloalkane having a hydroxyl group)

The tricycloalkane having a hydroxyl group used in the present invention may, for example, be a tricycloalkane having a hydroxyl group which is conventionally used. As the tricycloalkane, tricyclodecane, tricyclodecene, tricyclodecane or tricyclic fluorene can be exemplified. Alkene, tricycloundecane, tricyclododecane, tricyclotetradecane, tricyclopentadecane, tricyclohexadecane, and the like.

(polycarboxylic acid)

Specific examples of the polyvalent carboxylic acid component to be used in the present invention include succinic acid, adipic acid, sebacic acid, sebacic acid, and ten, as the aliphatic polyvalent carboxylic acid, alone or in combination of two or more. Dialkyldicarboxylic acid or the like; as the alicyclic polycarboxylic acid, 1,3-cycloheptadicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, or the like can be used singly or in combination of two or more kinds; The polyvalent carboxylic acid may be used alone or in combination of two or more kinds of o-nonanoic acid, p-nonanoic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalene dicarboxylic acid, 2,5- Naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalene dicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-pair, p-dicarboxylic acid and An acid anhydride or ester-forming derivative of the dicarboxylic acid; a polybasic acid such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid or an ester-forming derivative of the dihydroxycarboxylic acid. Further, these acid anhydrides can also be used. In particular, in order to obtain barrier properties, it is preferably succinic acid, 1,3-cyclopentanedicarboxylic acid, o-decanoic acid, an acid of o-decanoic acid, isodecanoic acid, further preferably phthalic acid and Anhydride.

(polyol component)

The polyol used in the present invention, specifically, an aliphatic diol can be exemplified by ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexane dimethanol, 1,5-pentanediol, and 3- Methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethyl Glycol, dipropylene glycol, and tripropylene glycol; examples of the aromatic polyhydric phenol include hydroquinone, resorcin, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, and tetramethylbiphenol. These ethylene oxide extensions, hydrogenated alicyclic groups. In particular, it is inferred that the fewer the number of carbon atoms between oxygen atoms, the less the molecular chain becomes too soft, and the preferred ones are ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and cyclohexane. Methanol is further more preferably ethylene glycol. The polycondensation reaction of a polyvalent carboxylic acid with a polyhydric alcohol can be carried out by a well-known conventional method.

The aspect of the polyester polyol of the present invention is, for example, the following, but is not limited thereto.

(I); with the general formula (1)

(A, A is a polycarboxylic acid or an anhydride thereof, B is a polyol having a tricyclodecane skeleton, and A and B are ester-bonded by a reaction of A and B, and n is 1 to 100. Integer.)

The polyester polyol represented.

(II); with the general formula (2)

(A is a polyvalent carboxylic acid or an anhydride thereof, B is a polyhydric alcohol having a tricyclodecane skeleton, C is a polyhydric alcohol other than a polyhydric alcohol having a tricyclodecane skeleton, and A and B, A and C are borrowed The ester group bond obtained by the reaction of A and B, A and C, m and n are integers of 1 to 100.)

The polyester polyol represented.

(III); with the general formula (3)

(A is a polycarboxylic acid or an anhydride thereof, B is a polyhydric alcohol having a tricyclodecane skeleton, C is a monohydric or polyhydric alcohol having a tricyclodecane skeleton, and D is a polyhydric alcohol having a tricyclodecane skeleton. In addition to the polyols, A and B, A and C, A and D are ester-bonded by the reaction of A and B, A and C, A and D, and m and n are integers of 1 to 100. .)

The polyester polyol represented.

(IV); with the general formula (4)

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

The polyester polyol represented.

(V); with the general formula (5)

(A is a polyvalent carboxylic acid or an anhydride thereof, B is a polyhydric alcohol other than a polyhydric alcohol having a tricyclodecane skeleton, C is a monohydric or polyhydric alcohol having a tricyclodecane skeleton, and A and B, A and C The ester group is bonded by the reaction of A and B, A and C, and n is an integer of 1 to 100.)

The polyester polyol represented.

The polyvalent carboxylic acid used in the present invention is preferably a benzene ring, and particularly preferably an ortho ic acid or an acid anhydride thereof. The ortho-acid and its anhydride skeleton have an asymmetric structure. Therefore, it is inferred that the rotation inhibition of the molecular chain of the obtained polyester polyol is caused, and it is inferred that the gas barrier property, particularly the water vapor barrier property is good. Moreover, the amorphous structure is exhibited by the asymmetrical structure, and it is inferred that sufficient substrate adhesion, adhesion force, gas barrier property, and particularly water vapor barrier property are provided. Further, when it is used as a dry laminate adhesive, it has a characteristic that the solvent solubility is high and the handleability is also good. Further, when a polyvalent carboxylic acid containing a cyclohexane skeleton having a hydrogenated benzene ring is used, it is preferably used because it can improve the hydrophobicity and reduce the solubility of water vapor.

(polycarboxylic acid other components)

When a polyester polyol having three or more hydroxyl groups is synthesized, when a branched structure is introduced by a polyvalent carboxylic acid component, at least a part of a carboxylic acid having a ternary or higher amount is required. As such compounds, although benzene can be mentioned The tricarboxylic acid and its anhydride, pyromellitic acid, an acid anhydride thereof and the like are preferable, but in order to prevent gelation during synthesis, a trivalent carboxylic acid is preferred as the trivalent or higher polyvalent carboxylic acid.

As the components other than these, the polyester polyol of the present invention may copolymerize other polyvalent carboxylic acid components in a range that does not impair the effects of the present invention. Specifically, as the aliphatic polycarboxylic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, dodecanedicarboxylic acid, or the like can be used singly or in combination of two or more kinds; As the carboxylic acid, maleic anhydride, maleic acid, fumaric acid or the like can be used singly or in combination of two or more kinds; and the alicyclic polycarboxylic acid can be used singly or in combination of two or more. 3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc.; as the aromatic polycarboxylic acid, phthalic acid, isodecanoic acid, pyromellitic acid, and benzene may be used singly or in combination of two or more kinds. Triacid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy) Ethyl-p-, p-dicarboxylic acid and such dicarboxylic anhydride or ester-forming derivatives; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and esters of such dihydroxycarboxylic acids A polybasic acid such as a forming derivative. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are particularly preferred.

(polyol other ingredients)

When a polyester polyol having three or more hydroxyl groups is synthesized, at least a part of a polyol having three or more members is required in the case where a polyol component is introduced into a branched structure. Examples of such compounds include glycerin, trimethylolpropane, trimethylolethane, and tris(2-hydroxyethyl)isocyanurate. 1,2,4- Butanetriol, pentaerythritol, dipentaerythritol, etc., but in order to prevent gelation during synthesis, it is preferred to use a triol as a trihydric or higher polyhydric alcohol.

As the other components, the polyol component of the present invention can also copolymerize other polyol components in a range that does not impair the effects of the present invention. Specifically, as the aliphatic diol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethyl group can be exemplified. Butylene glycol, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol; as aromatic polyhydric phenol, hydroquinone, resorcinol, catechol can be exemplified , naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, such ethylene oxide extensions, hydrogenated alicyclic groups.

Next, the synthesis of the above polyester polyol can be carried out by a well-known conventional method (refer to the examples for details).

In the present invention, the polyester polyol has a hydroxyl group value of 20 to 250 and an acid value of 20 to 200. The hydroxyl value can be measured by the hydroxyl value measurement method described in JIS-K0070, and the acid value can be measured by the acid value measurement method described in JIS-K0070. When the valence of the hydroxyl group is less than 20 mgKOH/g, since the molecular weight is too large, the viscosity becomes high, and good coatability cannot be obtained. On the contrary, when the valence of the hydroxyl group is more than 250 mgKOH/g, the crosslinking density of the hardened coating film becomes too high because the molecular weight is too small, and good adhesion strength cannot be obtained. When the acid value is less than 20 mgKOH/g, the intermolecular interaction becomes small, and good barrier properties and good initial cohesive force cannot be obtained. Conversely, when the acid value is more than 200 mgKOH/g, the reaction with the isocyanate compound as a hardener becomes too fast, and good coatability cannot be obtained.

In addition, the ratio (% by mass) of the tricycloalkane structure contained in the resin composition for a water vapor barrier adhesive in the present application can be calculated as follows. That is, TMW × n (or n + 1) / (NWM × n + EMW) × W / AW × 100

However, represents the molecular weight of TMW: tricycloalkane

n: degree of polymerization (n+1 when the terminal contains a tricycloalkane structure)

NMW: repeating unit molecular weight

EMW: terminal monomer molecular weight

W: a blending amount of a main agent or a hardener containing a tricycloalkane structure, or a blending amount of a main agent + a hardener

AW: main agent + hardener blending amount.

For example, as an example of a specific compound of the formula (5), in the main polyester polyol, A is trimellitic acid, B is ethylene glycol, C is a monohydric alcohol having a tricyclodecane skeleton, and Takenate D110N is used. When the hardener is used, it is as follows.

136.2 (tricyclodecane molecular weight) × 1.4 (degree of polymerization n) / {384.4 (repeating unit molecular weight) / 1.4 (degree of polymerization n) + 62.1 (molecular weight of ethylene glycol)} × 100 (mixing amount of main agent) / 210.8 (main agent + hardener blending amount) × 100 = 15.1 [%]

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 is a curing agent which reacts with the hydroxyl group of the above-mentioned polyol, and a known curing agent such as a diisocyanate compound, a polyisocyanate compound or an epoxy compound can be used. Among them, a polyisocyanate compound is preferably used from the viewpoint of adhesion and retort resistance.

The polyisocyanate compound may be any of an aromatic, an aliphatic diisocyanate, a trivalent or higher polyisocyanate compound, a low molecular compound or a polymer compound. Examples of tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, benzodimethyl diisocyanate, hydrogenated dimethyl diisocyanate, and isophora a mercapto diisocyanate or a trimer of the isocyanate compound, and an excess of the isocyanate compound such as ethylene glycol, propylene glycol, meta-xylylene alcohol, 1,3-dihydroxypropyl Benzobenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, neopentyl alcohol, erythritol, sorbitol, ethylenediamine, monoethanolamine, two Low molecular weight active hydrogen compounds such as ethanolamine, triethanolamine, meta-xylylene diamine, and alkylene oxide adducts thereof, various polyester resins, polyether polyols, polyamines An adduct obtained by a reaction of a polymer active hydrogen compound or the like.

The isocyanate compound may also be a blocked isocyanate. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcin, nitrophenol, and chlorophenol; Methyl ethyl ketone oxime, cyclohexyl Anthraquinones such as ketone oxime; alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as chlorohydrin and 1,3-dichloro-2-propanol; tertiary butanol and tertiary pentane Tertiary alcohols such as alcohol; decylamines such as ε-caprolactam, δ-valeroguanamine, γ-butylide, β-propionamide, and aromatic amines Active methylene compounds such as hydrazines, acetoacetones, acetamidine acetates, ethyl malonate, etc.; mercaptans, imines, ureas, diaryl compounds, sodium hydrogen sulfite Wait. The blocked isocyanate can be obtained by subjecting the above isocyanate compound and an isocyanate blocking agent to an addition reaction by a known method.

Among them, in order to obtain good barrier properties, a reaction product of m-xylene diisocyanate or m-xylene diisocyanate and a polyol having at least two or more hydroxyl groups in the molecule is particularly preferable.

The glass transition temperature of the cured coating film of the polyalcohol and the hardener of the present invention is preferably in the range of -30 ° C to 80 ° C. It is preferably 0 ° C ~ 70 ° C. More preferably 25 ° C ~ 70 ° C. When the glass transition temperature is higher than 80 ° C, the adhesion to the substrate is deteriorated due to a decrease in the flexibility of the cured coating film near the room temperature, and the adhesion may be lowered. Further, when the temperature is lower than -30 ° C, the molecular motion of the hardened coating film near the normal temperature may be insufficient to exhibit sufficient barrier properties, and the adhesion may be lowered due to insufficient cohesive force.

Further, when a carboxylic acid remains at the end of the resin composition used in the present invention, an epoxy compound can be used as the curing agent. Examples of the epoxy compound include diglycidyl ether of bisphenol A and oligomers thereof, diepoxypropyl ether of hydrogenated bisphenol A, oligomers thereof, and diepoxypropyl o-ruthenate. , diepoxypropyl isophthalate, diepoxypropyl p-nonanoate, diepoxypropyl p-oxybenzoate, diepoxypropyl tetrahydrophthalate Ester, diglycidyl hexahydrophthalate, diepoxypropyl succinate, diepoxypropyl adipate, diepoxypropyl sebacate, ethylene glycol diepoxypropyl Ether, propylene glycol diepoxypropyl ether, 1,4-butanediol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether and polyolefin-based diol diepoxypropyl ether Classes; triglycidyl trimellitate, triglycidyl isocyanurate, 1,4-diepoxypropyloxybenzene, diepoxypropyl propylene urea, C Triol triepoxypropyl ether, trimethylolethane triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, neopentyl alcohol tetraepoxypropyl ether, glycerol epoxy A triepoxypropyl ether of an alkane adduct or the like.

When an epoxy compound is used as the curing agent, a well-known epoxy curing accelerator may be suitably added in the range of barrier properties which do not impair the object of the present invention for the purpose of promoting the curing.

Among them, a polyisocyanate compound having an aromatic ring of a curing agent is particularly preferable, and a polyisocyanate compound containing the above-mentioned meta-xylene skeleton can be bonded not only by a hydrogen bond of a urethane group but also by an aromatic ring. The reason for the π-π overlap is to improve the barrier properties.

The polyisocyanate compound containing a meta-xylene skeleton has an adduct of a benzene dimethylene diisocyanate, a diurea synthesized by a reaction with an amine, and an adduct which reacts with an alcohol. The reason for the solubility of the organic solvent used for the dry laminate adhesive of the polyisocyanate compound is easily obtained as compared with the trimer or the burette body, and an adduct is preferable. As the adduct, an adduct which is reacted with an alcohol selected from the above-mentioned low molecular weight active hydrogen compounds can be used, and among them, trimethylolpropane and c are particularly preferable. An adduct of a triol, triethanolamine, m-xylene diamine and an ethylene oxide adduct product.

The resin composition and the curing agent are preferably a ratio of the blended resin composition to the curing agent, and the reaction component of the hydroxyl group of the resin composition and the curing agent is preferably 1/0.5 to 1/10 (equivalent ratio), more preferably 1/1~1/5. When it exceeds this range and the hardener component is excessive, since the remaining hardener component remains, it may ooze out from the adhesive layer afterwards, and when the hardener component is insufficient, the strength may be insufficient.

The aforementioned hardener can also be used in combination with a well-known hardener or accelerator selected according to the kind. For example, a decane coupling agent such as a hydrolyzable alkoxydecane compound, a titanate coupling agent, a coupling agent such as aluminum, or an epoxy resin can be used. The decane coupling agent or the titanate coupling agent is also preferably expressed to mean that the adhesion to various film materials is improved.

(adhesive other ingredients)

The adhesive of the present invention may be blended with various additives without impairing the adhesion and barrier properties. Examples of the additive include inorganic fillers such as cerium oxide, aluminum oxide, aluminum flakes, and glass shards, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, and anti-static agents. Agglomeration agents, colorants, fillers, nucleating agents, and the like.

(plate-like inorganic compound)

The resin composition for an adhesive of the present invention may also contain a plate-like inorganic compound.

The plate-like inorganic compound used in the present invention has an effect of increasing the layering strength and barrier properties of the adhesive which is a resin composition for curing the adhesive.

The plate-like inorganic compound used in the present invention is characterized in that the laminate strength and the barrier properties are improved by the shape of the plate. The interlayer charge of the plate-like inorganic compound does not directly have a large influence on the barrier property, but the dispersibility of the resin composition causes a large deterioration of the ionic inorganic compound or the water-swellable inorganic compound, and the addition amount is increased by the resin. The adhesion of the composition and thixotropy make coating suitability a problem. On the other hand, when it is non-charged (nonionic) or water is non-swellable, even if the amount of addition is increased, it is difficult to increase the viscosity and become thixotropic, and the coating suitability can be ensured. The plate-like inorganic compound used in the present invention, for example, as a plate-like inorganic compound, can be exemplified by aqueous citrate (phyllosilicate mineral, etc.), kaolin-serpentine clay mineral (polyhydrate kaolin). (halloysite), kaolin, endellite, dickite, nacrite, etc.; antigorite, chrysotile, etc., pyrophyllite - talc (pyramite, talc, kerolite, etc.), smectite clay minerals (montmorillonite, bemidelite, multi-iron montmorillonite (nontronite) ), saponite, hectorite, sauconite, stevensite, etc., vermiculite clay minerals (meteorites, etc.), mica or mica (mica) Group clay minerals (mica, phlogopic mica, margarite, tetra cyrillic mica, mica (taeniolite), etc., chlorite family (cookeite, sudoite, clinochlore, chamosite, nickel chlorite (nimite) Etc.), hydrotalcite, platy barium sulfate, boehmite, aluminum polyphosphate, and the like. These minerals may be natural clay minerals or may be synthetic clay minerals. The inorganic layered compound can be used singly or in combination of two or more.

Further, the plate-like inorganic compound used in the present invention is preferably nonionic having no interlayer charge.

As the platy inorganic compound used in the present invention, kaolin-serpentine clay minerals (polyhydrate kaolin, kaolin, Ander Stone, double kaolin, pearlite, etc., serpentine, serpentine, etc.) can be exemplified. ), pyrophyllite-talc (leaf stone, talc, disordered talc, etc.).

Further, the plate-like inorganic compound used in the present invention is preferably non-swellable to water.

As the platy inorganic compound used in the present invention, kaolin-serpentine clay minerals (polyhydrate kaolin, kaolin, Ander Stone, double kaolin, pearlite, etc., serpentine, serpentine, etc.) can be exemplified. ), pyrophyllite-talcite (pyramite, talc, disordered talc, etc.), mica or mica clay minerals (mica, phlogopic mica, pearl mica, Sicilil mica, mica, etc.), Chlorite family (lithium chlorite, aluminum chlorite, oblique chlorite, chlorite, nickel chlorite, etc.), hydrotalcite, platy barium sulfate, etc.

The average particle diameter of the present invention means the frequency of occurrence when the particle size distribution of a plate-like inorganic compound is measured by a light scattering type measuring device. The meaning of the highest particle size. The average particle diameter of the plate-like inorganic compound used in the present invention is not particularly limited, and is preferably 0.1 μm or more, and more preferably 1 μm or more. When the average particle diameter is 0.1 μm or less, since the length of the long side is short, the bypass path of the molecules does not become long, and there is a problem that it is difficult to raise the barrier ability and it is difficult to increase the adhesion force. The side having a large average particle diameter is not particularly limited. When uneven coating defects occur on the coated surface due to the inclusion of a large plate-like inorganic compound by a coating method, a material having an average particle diameter of 100 μm or less, more preferably 20 μm or less can be 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 of the gas labyrinth effect. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

As a method of dispersing the inorganic compound used in the present invention in a resin composition or a resin composition for a water vapor barrier adhesive, a well-known dispersion method can be used. Examples of ultrasonic homogenizers, high pressure homogenizers, paint blenders, ball mills, roller mills, sanders, sand mills, ultrafine mills (DYNO-MILL), high speed dispersers (DISPERMAT), nanomills (NanoMill), SC type mill, wet type ultra atomizer (Nanomizer), etc., and further preferably Henschel mixer, pressure kneader, Banbury mixer (Banbury mixer) ), a planetary mixer, a twin roll machine, a three-roll machine, etc., as a machine capable of generating high shear force. One of these may be used alone, or two or more types of devices may be used in combination.

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

(target alcohol)

The alcohol which is the target of the adhesive of the present invention and the multilayer film is not particularly limited as long as it has at least one structure in which an alkyl group is bonded to a hydroxyl group and is generally classified into an alcohol. Also, it may be a monohydric or polyhydric alcohol. Examples of the monohydric alcohol include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, neopentyl glycol, hexanol, benzyl alcohol, allyl alcohol, and cyclohexanol. Further, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, glycerin, and trimethylpropane. Further, in addition to the amino alcohols such as N,N-diethylethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine, and N-ethylethanolamine, diethylene glycol can also be used. An alcohol compound containing an ether group such as triethylene glycol.

Further, as the state of the alcohol compound, it is preferable that the material having a normal temperature range from gas to liquid is high in the effectiveness of the present invention.

(target inert gas)

The inert gas which is the target of the adhesive of the present invention and the multilayer film is not inert to foods and the like, and it is not easy to cause ordinary chemical changes, and the food is flavored by preventing the contact of oxygen and water vapor around the food. It is maintained, the content is kept, and the antioxidant is effective. Specifically, in addition to nitrogen gas and carbon dioxide, rare gases of ruthenium, rhodium, argon, krypton, xenon, and krypton can be exemplified. Among them, nitrogen, argon, and carbon dioxide are widely used as inert gases.

(fragrance)

The volatile organic substance (fragrance) which is the target of the adhesive of the present invention and the multilayer film can be exemplified by cocoa, soy sauce, sauce, miso, coffee, limonene, methyl salicylate, menthol, Cheese, spices, shampoo, moisturizing essence, detergents, softeners, soaps and other health products containing fragrance ingredients; pet foods, insecticides, fragrances, hair dyes, perfumes, pesticides, etc.

Since the adhesive and the multilayer film of the present invention can block gas, it is also suitable for adsorbents, deodorants, water purifiers, rice, instant noodles, bottled water, plain noodles, cotton, etc. of activated carbon and zeolite. It is desirable to prevent the use of the fragrance from the outside and to prevent the fragrance from leaking to the outside.

(form of the adhesive)

The adhesive of the present invention may be either a solvent type or a solventless type. When it is a solvent type, the solvent can also be used as a reaction medium in the production of a polyester polyol and a hardener. In addition, it can be used as a diluent when painting. Examples of the solvent that can be used include esters of ethyl acetate, butyl acetate, celecoxib acetate, and the like; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; tetrahydrofuran, An ether such as an alkane; an aromatic hydrocarbon such as toluene or xylene; a halogenated hydrocarbon such as dichloromethane or dichloroethane; dimethyl hydrazine or dimethylsulfonamide. Of these, ethyl acetate and methyl ethyl ketone are usually used. Further, when it is used in the absence of a solvent, it is considered that it is not necessarily soluble in an organic solvent. However, in consideration of washing of the reaction vessel during the synthesis and washing of the coater at the time of lamination, the solubility in the organic solvent is need.

The adhesive of the present invention can be applied to a substrate film or the like. The coating method can be carried out by a well-known method without particular limitation. For example, when a solvent type capable of adjusting the viscosity is used, it is often applied by a gravure roll coating method or the like. Also as a solvent-free type, the viscosity at room temperature is high and When it is not suitable for gravure roll coating, it can also be heated while being coated by a roll coater. When a roll coater is used, the adhesive viscosity of the present invention is 500~2500 mPa by heating to room temperature to about 120 °C. It is better to coat the state around s.

The adhesive agent of the present invention can be used as a water vapor barrier adhesive, and can be used as an adhesive for various applications requiring a gas barrier property, particularly a water vapor barrier property, such as a polymer, paper, or metal.

An adhesive for a film laminate is described as one of the following specific uses.

The adhesive agent of the present invention can be used as an adhesive for film laminate. The laminated film which has been laminated has good gas barrier properties, particularly water vapor barrier properties, and thus can be used as a gas barrier property, particularly a 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 depending on the intended use. For example, as a food packaging, a PET film, a polystyrene film, a polyamide film, a polyacrylonitrile film, a polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film), and polypropylene can be given. A polyolefin film such as a film (CPP: non-stretched polypropylene film, OPP: biaxially oriented polypropylene film), a polyvinyl alcohol film, an ethylene-vinyl alcohol copolymer film, or the like. These can also be extended. As the elongation treatment method, the resin is usually melt-extruded into a sheet shape by an extrusion film forming method or the like, and then simultaneous biaxial stretching or sequential biaxial stretching is performed. Also, when successively biaxially extending, the longitudinal stretching process is usually first performed, followed by lateral extension. Specifically, a method of using a longitudinal extension using a difference in speed between rolls and a lateral extension using a tenter is often used in combination.

The adhesive agent of the present invention is preferably an adhesive which can be used for a laminated film obtained by laminating a plurality of resin films of the same type or different types. Although the resin film can be suitably selected according to the purpose, for example, when used as a packaging material, the thermoplastic resin film containing the outermost layer selected from the group consisting of PET, OPP, and polyamine is used, and the innermost layer is selected from the non-stretched polypropylene (below a composite film of a double layer of a thermoplastic resin film of a low density polyethylene film (hereinafter referred to as LLDPE); or, for example, comprising a thermoplastic resin film formed using an outermost layer selected from the group consisting of PET, polyamide, OPP, and selected from the group consisting of a thermoplastic resin film of an intermediate layer of OPP, PET, polyamide, and a three-layer composite film forming a thermoplastic resin film selected from the group consisting of CPP and LLDPE; and, for example, comprising a composition selected from OPP, PET, a thermoplastic resin film of the outermost layer of polyamine, a thermoplastic film formed of a first intermediate layer selected from the group consisting of PET and nylon, a thermoplastic film formed of a second intermediate layer selected from the group consisting of PET and polyamide, and formed A four-layer composite film of a thermoplastic resin film selected from the group consisting of LLDPE and CPP can be used as a gas barrier, particularly a water vapor barrier film, and is preferably used as a food packaging material.

Further, the surface of the film is an adhesive layer for forming defects such as no breakage or breakage, and various surface treatments such as flame treatment and corona discharge treatment may be performed as needed.

After applying the adhesive of the present invention to one of the thermoplastic resin films, the other thermoplastic resin film is laminated and laminated by lamination to obtain the water vapor barrier laminated film of the present invention. The lamination method can use well-known lamination methods such as dry lamination, solventless lamination, and extrusion lamination.

In the dry lamination method, specifically, the adhesive of the present invention is applied to one of the base films by a gravure roll, and the other base film is superposed and bonded by dry lamination (dry lamination). The temperature of the build-up rolls is preferably from room temperature to about 60 °C.

Further, the solvent-free laminate can be applied to the substrate film by directly applying the adhesive of the present invention heated to room temperature to about 120 ° C by a roller such as a roll coater heated to room temperature to about 120 ° C. A laminate film is obtained by bonding a new film material to the surface. The lamination pressure is preferably about 10 to 300 kg/cm ² .

When the laminate method is used, the organic solvent solution of the adhesive of the present invention can be applied as a binder (bonding agent) to the substrate film by a roller such as a gravure roll, and the solvent can be dried at room temperature to 140 ° C. After the hardening reaction, a laminated film is obtained by laminating a polymer material melted by an 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.

Further, the water vapor barrier laminated film of the present invention is preferably cured after production. The aging condition is such that when polyisocyanate is used as the curing agent, it is room temperature to 80 ° C for 12 to 240 hours, and the bonding strength is generated during this period.

The adhesive of the present invention is characterized by having a gas barrier property, particularly a water vapor barrier property, and a laminate film formed by the adhesive without using a PVDC coating and a polyvinyl alcohol (PVA) coating, ethylene. -Inorganic vapor deposited film of vinyl alcohol copolymer (EVOH) film layer, m-xylylene hexamethylenediamine film layer, vapor deposited alumina and cerium oxide Under the barrier material commonly used for layers, etc., a very high degree of barrier properties are exhibited.

In order to impart a higher barrier function, the present invention may also be used in combination with a film of a metal such as aluminum, or a vapor deposited layer of a metal oxide such as cerium oxide and aluminum oxide, and a polyvinyl alcohol and ethylene. A barrier film of a gas barrier layer such as a vinyl alcohol copolymer or a vinylidene chloride.

[Examples] [Synthesis Example 1 TCDoPA]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a moisture separator, or the like, 100 parts of phthalic anhydride, 155 parts of tricyclodecane dimethanol, and 100 ppm of the total amount of the polycarboxylic acid and the polyol are placed. Titanium tetraisopropoxide is slowly heated to maintain the internal temperature at 220 ° C in such a manner that the temperature of the upper portion of the rectification column does not exceed 100 ° C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol (TCDoPA) having a number average molecular weight of 2,000, an acid value of 1.13 mgKOH/g, and a hydroxyl value of 58.8 mgKOH/g was obtained.

[Synthesis Example 2 TCDHH]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a moisture separator, or the like, 100 parts of hexahydroxyphthalic anhydride, 150 parts of tricyclodecane dimethanol, and the total amount of the polycarboxylic acid and the polyol are placed. The titanium tetraisopropoxide was slowly heated in such a manner that the temperature of the upper portion of the rectification column did not exceed 100 ° C to maintain the internal temperature at 220 ° C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol (TCDHH) having a number average molecular weight of 2,000, an acid value of 3.35 mgKOH/g, and a hydroxyl value of 60.7 mgKOH/g was obtained.

[Synthesis Example 3 EGTMATCD]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a water separator, or the like, 100 parts of trimellitic anhydride and 90 parts of tricyclodecane-methanol were placed, and the solvent was methyl ethyl ketone and refluxed, and the acid value was 315 mgKOH/ When g is completed, the reaction is carried out and the solvent is removed. 60 parts of ethylene glycol and 100 ppm of tetraisopropoxy titanium relative to the total amount of the polycarboxylic acid and the polyhydric alcohol are placed, and the temperature is gradually increased by not exceeding 100 ° C in the upper portion of the rectification column. The temperature is maintained at 220 °C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and 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 was obtained.

[Synthesis Example 4 CHDMTMATCD]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a water separator, or the like, 100 parts of trimellitic anhydride and 90 parts of tricyclodecane-methanol were placed, and the solvent was methyl ethyl ketone and refluxed, and the acid value was 315 mgKOH/ When g is completed, the reaction is carried out and the solvent is removed. 150 parts of cyclohexanedimethanol and 100 ppm of titanium tetraisopropoxide with respect to the total amount of the polycarboxylic acid and the polyol, and slowly heating in such a manner that the upper temperature of the distillation column does not exceed 100 ° C The internal temperature was maintained at 220 °C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol (CHDMTMATCD) having a number average molecular weight of 640, an acid value of 0.2 mgKOH/g, and a hydroxyl group of 184.4 mgKOH/g was obtained.

[Synthesis Example 5 TCDTMATCD]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a moisture separator, or the like, 100 parts of trimellitic anhydride and 90 parts of tricyclic ruthenium were placed. Alkyl-methanol was used as a solvent, and methyl ethyl ketone was used for the reflux reaction. When the acid value became 315 mgKOH/g, the reaction was terminated and the solvent was removed. 210 parts of tricyclodecane dimethanol and 100 ppm of tetraisopropoxy titanium relative to the total amount of the polycarboxylic acid and the polyhydric alcohol, and slowly heated in such a manner that the upper temperature of the rectification column does not exceed 100 ° C The internal temperature was maintained at 220 °C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol (TCDTMATCD) 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 was obtained.

[Comparative Example 1 NDoPA]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a moisture separator, or the like, 100 parts of phthalic anhydride, 127 parts of decane diol, and 30 ppm of tetrahydric alcohol based on the total amount of the polycarboxylic acid and the polyol are placed. The titanium propoxide was slowly heated in such a manner that the upper temperature of the rectification column did not exceed 100 ° C to maintain the internal temperature at 220 ° C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyalcohol (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 was obtained.

[Comparative Example 2 NDHH]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a moisture separator, or the like, 100 parts of hexahydroxyphthalic anhydride, 122 parts of decanediol, and 30 ppm of the total amount of the polycarboxylic acid and the polyol are placed. Titanium tetraisopropoxide was slowly heated to maintain the internal temperature at 220 ° C in such a manner that the temperature of the upper portion of the rectification column did not exceed 100 ° C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol (NDHH) having a number average molecular weight of 2,000, an acid value of 1.94 mgKOH/g, and a hydroxyl group value of 62.2 mgKOH/g was obtained.

[Comparative Example 3 CHDMODA]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a moisture separator, or the like, 100 parts of suberic acid, 97 parts of cyclohexane dimethanol, and 30 ppm of the total amount of the polycarboxylic acid and the polyol are placed. The titanium tetraisopropoxide was slowly heated in such a manner that the temperature of the upper portion of the rectification column did not exceed 100 ° C to maintain the internal temperature at 220 ° C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol (CHDMODA) having a number average molecular weight of 2,000, an acid value of 0.91 mgKOH/g, and a hydroxyl value of 54.5 mgKOH/g was obtained.

[Comparative Example 4 EGOSA]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a moisture separator, or the like, 100 parts of octenyl succinic anhydride, 45 parts of ethylene glycol, and the total amount of the polycarboxylic acid and the polyol are used. 30 ppm of titanium tetraisopropoxide, 100 ppm of tertiary catechol relative to the total amount of the polycarboxylic acid and the polyhydric alcohol, and slowly heating in such a manner that the temperature of the upper portion of the rectification column does not exceed 100 ° C The internal temperature was maintained at 220 °C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and 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 was obtained.

[Comparative Example 5 PDTMAOcOH]

In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a moisture separator, or the like, 100 parts of trimellitic anhydride and 70 parts of octanol are placed, and the solvent is refluxed using methyl ethyl ketone, and the reaction is terminated when the acid value becomes 315 mgKOH/g. , remove the solvent. 103 parts of 1,2-pentanediol, and relative to the total amount of polycarboxylic acid and polyol 100 ppm of titanium tetraisopropoxide was gradually heated in such a manner that the temperature of the upper portion of the rectification column did not exceed 100 ° C to maintain the internal temperature at 220 ° C. When the acid value was 5 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol (PDTMAOcOH) having a number average molecular weight of 600, an acid value of 0.43 mgKOH/g, and a hydroxyl group value of 187.4 mgKOH/g was obtained.

(adhesive resin)

The polyester polyol of the above [Synthesis Example 1] to [Synthesis Example 5], a curing agent, and an organic solvent were mixed to obtain an adhesive. The structure is shown in Table 1.

(coating method)

The solvent-based adhesive was applied to a corona-treated surface of a PET film ("E-5102" manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm at a coating amount of 5 g/m ² (solid content) using a roll coater. The dryer was set to a temperature of 70 ° C to evaporate and dilute the solvent to dry, and the adhesive surface of the PET film to which the adhesive was applied and the nylon film ("EMBLEM ON-BC" manufactured by Unitika Co., Ltd.) having a thickness of 15 μm were charged. The halo-treated surface was laminated to prepare a composite film having a layer of a PET film/adhesion layer/nylon film. Next, the composite film was aged at 40 ° C/5, and the adhesive was cured to obtain a laminated film of the present invention.

(evaluation method) (1) Water vapor transmission rate (MVTR)

The laminated film which has been aged is evaluated in accordance with the water vapor transmission test method "ISO-15106-3" and in an atmosphere of 40 ° C and 90% RH using a measuring device Model 7000 manufactured by Illinois. Further, the term "RH" means humidity.

Moreover, the water vapor barrier property of the adhesive agent coating film monomer is calculated from the measurement results of the water vapor barrier laminated film, the PET film, and the nylon film, using the formula (a).

1/P=1/P1+1/P2+1/P3 (a)

P: Water vapor transmission rate of water vapor barrier laminated film

P1: water vapor transmission rate of film-coated monomer

Water vapor transmission rate of P2: 12μm PET film (calculated at 49g/m ² .24 hours)

P3: water vapor transmission rate of 15μm nylon film (calculated at 300g/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 evaluation method are as described above. The results are shown in Table 1.

The results of using the resin compositions obtained in Comparative Examples 1 to 5 are shown in Table 2.

. TAKENATE D-110N: TAKENATE D-110N (manufactured by Mitsui Chemicals, Inc.: XDI polyisocyanate, nonvolatile content / approximately 75%)

. AcOET: ethyl acetate

. MEK: methyl ethyl ketone

[Industry use possibility]

The adhesive agent of the present invention can be suitably used for, for example, an adhesive for a solar cell protective film and a display member, in addition to the above-mentioned adhesive for film laminate for packaging materials, because it has good adhesive strength and water vapor barrier properties. The use of an adhesive for an electronic material such as an adhesive for a barrier substrate, an adhesive for a building material, an adhesive for an industrial material, or the like, which is desired to have a water vapor barrier property.

Claims (8)

A resin composition for a water vapor barrier adhesive, which is a water vapor barrier adhesive resin composition obtained by reacting a polyhydric alcohol and a curing agent, wherein the polyalcohol or the curing agent has a tricycloalkane structure. The resin composition for a water vapor barrier adhesive according to claim 1, wherein the ratio of the tricycloalkane structure contained in the resin composition is from 10% by mass to 50% by mass. The resin composition for a water vapor barrier adhesive according to claim 1 or 2, wherein the polyalcohol is a polyester polyol obtained by reacting a tricycloalkane having a hydroxyl group with a polyvalent carboxylic acid or an anhydride thereof, and a polyhydric alcohol. A resin composition for a water vapor barrier adhesive according to claim 1 or 2, wherein the hardener is an isocyanate compound. The resin composition for a water vapor barrier adhesive according to claim 4, wherein the isocyanate compound is a reaction product of m-xylene diisocyanate or m-xylene diisocyanate with a polyol having at least two hydroxyl groups in the molecule. The resin composition for a water vapor barrier adhesive according to claim 4, wherein the isocyanate compound is a reaction of a tricycloalkane having at least two hydroxyl groups in a molecule or a polyester polyol comprising a tricycloalkane and an isocyanate. Things. A resin composition for a water vapor barrier adhesive according to claim 1 or 2, wherein the tricycloalkane is tricyclodecane. A water vapor barrier film laminate which is obtained by hardening a resin composition for a water vapor barrier adhesive according to any one of claims 1 to 7 on a film.