JPH0680948A - Water-base adhesive composition for laminating and method for laminating therewith - Google Patents

Abstract

PURPOSE:To obtain the title adhesive having improved adhesive properties by compounding a water-sol. or dispersible isocyanate-reactive resin with a water-dispersible polyisocyanate compd. CONSTITUTION:A water-dispersible polyisocyanate compd. such as an isocyanate- terminated prepolymer is obtd. by reacting a polyisocyanate such as 2,4-tolylene diisocyanate with a hydrophilic compd. such as a polyol. The title compsn. is obtd. by mixing the obtd. compd. with an isocyanate-reactive water-sol. or dispersible resin such as a polyurethane resin, a polyester resin, or a polyacrylic resin in an equivalent ratio of the groups in the polyisocyanate compd. to the isocyanate-reactive groups in the resin of (10:100)-(500:100). A laminated sheet is obtd. by applying the compsn. to a flexible substrate, drying the resulting adhesive layer, and pressing another flexible substrate to the adhesive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous laminating adhesive composition having excellent water resistance and hot water resistance which can be used for boiling and retort applications, and a laminating method using the same.

More particularly, it relates to an aqueous laminating adhesive composition which exhibits excellent adhesiveness, water resistance and hot water resistance when a composite film is produced by laminating various films, metal foils, papers and the like, and a laminating method thereof.

[0003]

2. Description of the Related Art Water-based adhesives for laminating various films made of water-soluble or water-dispersible resins are water-based and therefore have no risk of fire or contamination of the working environment. In order to make it water-dispersible, a large amount of hydrophilic groups have to be contained in the resin and the water resistance is inferior, so it has been used only in applications where water resistance is not required.

[0004]

In recent years, in order to solve the above drawbacks, as a crosslinking system, amine and epoxy system, carboxyl group and epoxy system, carboxyl group and aziridine system, carboxyl group and carbodiimide system, acetoacetate and ketimine system are used. Attempts have been made to improve the water resistance of water-based adhesives composed of water-soluble or water-dispersible resins by using carboxylic acids and metal ion systems, but they are still insufficient in terms of water resistance, hot water resistance and hygiene. The current situation is that no good results have been obtained.

[0005]

In view of the above situation, the present inventors have conducted research to develop an aqueous laminating adhesive composition having excellent water resistance and hot water resistance capable of withstanding boiling and retort applications. As a result of stacking, an aqueous laminate adhesive composition comprising a water-soluble or water-dispersible resin (A) having a functional group capable of reacting with an isocyanate group and a water-dispersible polyisocyanate compound (B) can achieve the above object. The present invention has been completed and the present invention has been completed.

That is, the present invention provides a water-soluble or water-dispersible resin (A) having a functional group capable of reacting with an isocyanate group.
And a water-dispersible polyisocyanate compound (B), which is a water-based laminating adhesive composition and a laminating method performed using the same.

Examples of the water-soluble or water-dispersible resin (A) having a functional group capable of reacting with an isocyanate group of the present invention include polyurethane resins. It can also be used in an isocyanate compound. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane. Diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-
4,4'-biphenylene diisocyanate, 3,3'-
Dichloro-4,4'-biphenylene diisocyanate,
1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene Diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-
Examples thereof include dicyclohexylmethane diisocyanate.

In producing the polyurethane resin of the present invention, any polyol can be used. Examples thereof include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols and polythioether polyols.

As the polyester polyol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, glycol components such as hydroquinone and alkylene oxide adducts thereof, succinic acid,
Adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic 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 these dicarboxylic acids Polyesters obtained by dehydration condensation reaction with acid components such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these hydryloxycarboxylic acids. And polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, and copolyesters thereof.

As the polyether polyol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. One or two of the compounds having two active hydrogen atoms of
One or more kinds of monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, and the like, which are obtained by addition polymerization of one or more kinds by an ordinary method, can be used as an initiator. According to the above, an alkyl alcohol having 1 to 4 carbon atoms as an initiator, ethylene oxide as an essential component, and at least one of monomers such as propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene and the like, or a block or A polyoxyalkylene monoalkyl ether obtained by random copolymerization may be used in combination.

As the polycarbonate polyol,
1,4-butanediol, 1,6-hexanediol,
Examples thereof include compounds obtained by reacting a glycol such as diethylene glycol with diphenyl carbonate or phosgene.

As the chain extender for the above polyurethane resin, a compound having two or more active hydrogen atoms can be used. For example, glycol component used as a raw material for polyester polyol; ethylenediamine, 1,6
-Hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-
4,4'-dicyclohexylmethanediamine, 1,2-
Examples include diamine compounds such as cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-propanediamine, and hydrazine.

In principle, the polyurethane resin of the present invention is preferably one having a linear structure because it is excellent not only in initial adhesiveness to substrates such as various films but also in normal adhesiveness and durability after crosslinking. However, polyhydroxy compounds such as glycerin, trimethylolethane, trimethylolpropane, sorbitol and pentaerythritol;
Trifunctional or higher polyisocyanate compounds; polyamine compounds such as diethylenetriamine and triethylenetetramine may be used in combination.

The polyurethane resin of the present invention has a hydroxyl group, a phenolic hydroxyl group, a carboxyl group and its base, an amino group and a sulfone as a functional group capable of reacting with the isocyanate group of the compound (B) in order to impart water resistance and hot water resistance. It has an acid group and its salt, and a mercapto group, but from the viewpoint of hygiene, a hydroxyl group, a carboxyl group or a combination thereof is preferable. As a method for introducing such a hydroxyl group or a carboxyl group, any known method can be used. For example, an introduction method using a terminal hydroxyl group obtained by reacting an excess amount of a polyol and polyisocyanate, a polyurethane resin having a terminal isocyanate group obtained by a reaction of an excess amount of a polyisocyanate and 2-aminoethanol, 2,
There is a method of introducing a hydroxyl group by reacting with amino alcohols such as 2'dihydroxydiethylamine and aminophenols such as 0, m, p-aminophenol.

As a method of introducing a carboxyl group, for example, 2,2-dimethylolpropionic acid or 2,2 is used as a part of the polyol component of the polyurethane resin.
-Dimethylol butyric acid, 2,2-dimethylol valeric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4
-A method of using a carboxylic acid-containing compound such as diaminobenzoic acid and a derivative thereof and a salt thereof, or a polyester polyol obtained by using the same and a salt thereof,
Polyurethane resin of terminal isocyanate obtained by reaction of excess polyisocyanate and polyol, alanine, aminobutyric acid, aminocaproic acid, glycine, histidine, leucine, isoleucine, proline, serine,
Neutral amino acids such as tyrosine or acidic amino acids such as glutamic acid and aspartic acid, or amino acids such as basic amino acids such as glutamine, asparagine, citrulline, arginine, cystine and histidine or succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane Dicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic 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, etc. There is a method of introducing a carboxyl group by reacting with a polycarboxylic acid.

In the method of the present invention, it is preferable not to use an emulsifier, but a small amount of an emulsifier may be used in combination for the purpose of improving the mechanical stability of the urethane aqueous dispersion. Examples of such emulsifiers include alkylphenyl ether type such as polyoxyethylene nonylphenyl ether, alkyl ether type such as polyoxyethylene lauryl ether, alkyl ester type such as polyoxyethylene laurate, polyoxyethylene styrenated phenyl ether and the like. Alkylphenyl condensate ether type, sorbitan derivative such as polyoxyethylene sorbitol tetraoleate, alkylamine type such as polyoxyethylene lauryl amino ether, monool type such as polyoxyalkylene alkyl ether, alkanolamide type such as lauric acid diethanolamide Nonionic emulsifiers such as; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates,
Examples thereof include anionic emulsifiers such as alkyl sulfosuccinate, naphthalene sulfonate, polyoxyethylene alkyl sulfate, sodium alkane sulfonate, sodium alkyl diphenyl ether sulfonate, and phosphoric acid ester.

The polyurethane resin mentioned as the water-soluble or water-dispersible resin (A) having a functional group capable of reacting with the isocyanate group of the present invention can be widely used as long as it is known. For example, Sofranate AE-10, Sofranate AE-10 (all manufactured by Nippon Sofranate Kako Co., Ltd.), Hydran HW-111, Hydran HW
-131, Hydran HW-311, Hydran HW-
340, AP-30 (both manufactured by Dainippon Ink and Chemicals, Inc.) Poise 710, Poise 720 (both manufactured by Kao Co., Ltd.) Mercy 525, Mercy 455 (both manufactured by Toyo Polymer Co., Ltd.), Dispacol KA8464
(Sumitomo Bayer Urethane Co., Ltd.) and the like can be mentioned.

As the water-soluble or water-dispersible resin (A) of the present invention having a functional group capable of reacting with an isocyanate group, a polyester resin can be mentioned. Any known polyester resin can be widely used. For example, Bayronal MD-120
0, Bayronal MD-1400, Bayronal MD-
1930 (all manufactured by Toyobo Co., Ltd.), WD365
2, WJL6342 (all manufactured by Eastman Chemical Company), Finetex ES-650, Finetex ES-850 (all Dainippon Ink and Chemicals, Inc.)
Manufactured) and the like.

As the water-soluble or water-dispersible resin (A) having a functional group capable of reacting with the isocyanate group of the present invention, a polyacrylic resin can also be mentioned. The polyacrylic resin of the present invention can be widely used as long as it is known. For example, AE120, AE316, AE33
2 (all manufactured by Japan Synthetic Rubber Co., Ltd.), acronal 8
0DN, ACRONAL 81DN, ACRONAL YJ30
31D (all manufactured by Mitsubishi Yuka Birdish Co., Ltd.) and the like.

The water-soluble or water-dispersible resin (A) having a functional group capable of reacting with an isocyanate group according to the present invention is not limited to a polyurethane resin, a polyester resin and a polyacrylic resin, but can react with an isocyanate group. Any functional group can be used as long as it has a functional group capable of controlling.

As the water-dispersible polyisocyanate compound (B) of the present invention, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and 4,4'- Diphenylmethane diisocyanate,
2,4'-diphenylmethane diisocyanate, 2,
2'-diphenylmethane diisocyanate, 3,3'-
Dimethyl-4,4'-biphenylene diisocyanate,
3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate , 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,
4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,
4'-dicyclohexylmethane diisocyanate, 3,
Polyisocyanate compounds such as 3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate, or isocyanurate-type or buret-type trifunctional polyisocyanates, or terminal isocyanates obtained by reaction with bifunctional or higher-functional polyol compounds Examples thereof include a substantially hydrophobic polyisocyanate such as a group-containing prepolymer which is mixed with an emulsifier so that it can be dispersed in water.

Examples of the emulsifier include alkyl phenyl ether type such as polyoxyethylene nonyl phenyl ether, alkyl ether type such as polyoxyethylene lauryl ether, alkyl ester type such as polyoxyethylene laurate and polyoxyethylene styrenated phenyl. Alkylphenyl condensate ether type such as ether,
Nonionic emulsifiers such as sorbitan derivative type such as polyoxyethylene sorbitol tetraoleate, alkylamine type such as polyoxyethylene lauryl amino ether, monool type such as polyoxyalkylene alkyl ether, and alkanolamide type such as lauric acid diethanolamide. Fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates,
Examples thereof include anionic emulsifiers such as alkyl sulfosuccinate, naphthalene sulfonate, polyoxyethylene alkyl sulfate, sodium alkane sulfonate, sodium alkyl diphenyl ether sulfonate, and phosphoric acid ester.

Water-dispersible polyisocyanate compound (B)
More preferably, a self-emulsifiable polyisocyanate compound obtained by copolymerizing a hydrophilic group-containing compound containing a repeating unit of alkylene oxide with the above-mentioned polyisocyanates can be mentioned. Examples of commercially available self-emulsifiable polyisocyanate compounds include CR-60N manufactured by Dainippon Ink and Chemicals, Coronate C3062 and C3053 manufactured by Nippon Polyurethane Co., and Dismodur DA manufactured by Sumitomo Bayer Urethane.

When the mixed solution of the water-soluble or water-dispersible resin (A) having a functional group capable of reacting with an isocyanate group and the water-dispersible polyisocyanate compound (B) of the present invention is used as an aqueous adhesive, , Other aqueous resins such as vinyl acetate-based, ethylene vinyl acetate-based, and acrylic styrene-based emulsions; styrene-butadiene-based, acrylonitrile-butadiene-based, acrylic-butadiene-based, polychloroprene-based, vinylpyridine-based, butyl rubber-based, It can be used by blending with a latex such as natural rubber; an ionomer such as polyethylene or polyolefin; an aqueous dispersion of epoxy or the like at an arbitrary ratio.

When the mixed solution of the water-soluble or water-dispersible resin (A) having a functional group capable of reacting with an isocyanate group and the water-dispersible polyisocyanate compound (B) of the present invention is used as an aqueous adhesive. In addition to the above components, known fillers, softeners, antiaging agents, stabilizers, adhesion promoters, leveling agents, defoamers, plasticizers, inorganic fillers, tackifying resins, fibers, pigments, etc. The colorants, the usable time extenders and the like can be used. As the adhesion promoting agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. are preferably used. A rosin derivative or the like is preferably used as the tackifying resin.

The water-soluble or water-dispersible resin (A) having a functional group capable of reacting with these isocyanate groups and the water-dispersible polyisocyanate compound (B) are blended before use. The water-soluble or water-dispersible resin (A) is
Although the solvent is water, a small amount of an organic solvent may be added and used for improving the emulsion properties. The water-dispersible polyisocyanate compound (B) has a resin solid content of 100
%, Or in order to improve the mixing efficiency at the time of compounding with the water-soluble or water-dispersible resin (A), it may be diluted with an organic solvent before use.

The compounding ratio of the water-soluble or water-dispersible resin (A) and the water-dispersible polyisocyanate compound (B) is such that the functional group capable of reacting with the isocyanate group contained in the water-soluble or water-dispersible resin (A). The equivalent amount of the isocyanate group of the water-dispersible polyisocyanate compound (B) can be used in an amount of 10 to 500, and preferably 50 to 300.

The water-based adhesive of the present invention comprising a mixture of a water-soluble or water-dispersible resin (A) having a functional group capable of reacting with an isocyanate group and a water-dispersible polyisocyanate compound (B) is a resin (A). A reaction catalyst can be used to promote the reaction between the functional group capable of reacting with the isocyanate group in () and the isocyanate in the resin (B).

The water-based adhesive obtained by blending the water-soluble or water-dispersible resin (A) having a functional group capable of reacting with the isocyanate group of the present invention with the water-dispersible polyisocyanate compound (B) is various plastics. Various plastics are formed by applying the present compounding liquid onto one or more types of base materials selected from various base materials such as films, various metal vapor deposition films, metal foils, papers, and synthetic papers, and drying to form an adhesive layer. the film,
Applied to a method of laminating at least one kind of base material selected from various base materials such as various metal vapor deposition films, metal foils, papers, synthetic papers and the base material on which the adhesive layer is formed. To be done.

For example, by a dry laminator having a dryer, PVC, PET, biaxially stretched PP, unstretched PP, PE, nylon, polyvinyl alcohol, vinyl chloride, vinylidene chloride OPP, polystyrene, E
Various plastic films such as VOH, polycarbonate and cellophane, aluminum evaporated PET, biaxially stretched PP, non-stretched PP, various metal evaporated films such as PE, metal foil, paper,
The water-soluble or water-dispersible resin (A) and the water-dispersible polyisocyanate compound (of the present invention) (rolling coating, gravure coating, knife coating, etc. are applied to various base materials such as synthetic paper. A method of applying the compounded solution with B), drying it, and laminating the adhesive application surface on at least one other substrate is used. Further, various base materials can be laminated in multiple layers by using the present laminating method. The adhesive of the present invention crosslinks even at room temperature, but preferably it can be heated to accelerate the crosslinking.

Thus, the aqueous adhesive obtained by blending the water-soluble or water-dispersible resin (A) having a functional group capable of reacting with the isocyanate group of the present invention with the water-dispersible polyisocyanate compound (B) is used. The produced laminate exhibits strong adhesion, water resistance or hot water resistance. When these laminates are used for packaging containers such as retort pouches, boiled pouches, lids, etc., the film does not peel off due to high temperature sterilization performed at 80 ° C or higher in the manufacturing process, and the long-term content of the food product It enables the production of packaging materials with excellent storage stability and safety.

[0032]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples without departing from the technical idea of the present invention.

Example 1 52.3 parts of polypropylene glycol having an OH value of 280,
329.1 parts of polypropylene glycol having an OH value of 56,
Neopentyl glycol 8.8 parts, dimethylolpropionic acid 35.2 parts, polyoxyethylene polyoxypropylene copolymer (molecular weight about 3000, EO / PO = 50)
N / N by reacting 29.4 parts of monobutyl ether (/ 50% by weight) and 173.2 parts of isophorone diisocyanate.
A prepolymer solution having terminal isocyanate groups with a CO% of 1.5% was obtained. This prepolymer was then rapidly stirred with a homomixer while isophoronediamine and diethanolamine were added at 14.4 parts and 17.8 parts, respectively.
Of water solution containing 10 parts of solid content of 40 parts
%, A semi-transparent colloidal aqueous terminal polyurethane resin A having a hydroxyl group at a temperature of 25 ° C. of 200 cps was prepared. Further, with respect to 100 parts of the aqueous polyurethane resin having the terminal hydroxyl group, Coronate C306 which is an aqueous isocyanate is used.
10 parts of 2 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were blended immediately before using the adhesive to obtain the composition of the present invention. Table 1 shows the results of a hot water resistance test conducted on this adhesive composition.

Comparative Example 1 52.3 parts of polypropylene glycol having an OH value of 280,
In the same manner as in Example 2, 329.1 parts of polypropylene glycol having an OH value of 56 and neopentyl glycol 8.8.
Parts, dimethylolpropionic acid 35.2 parts, polyoxyethylene polyoxypropylene copolymer (molecular weight about 30
00, EO / PO = 50/50% by weight) (29.4 parts) and isophorone diisocyanate (173.3 parts) were reacted to obtain a prepolymer solution having a terminal isocyanate group. Then, this prepolymer was charged into an aqueous solution 1078 containing 54.7 parts of isophoronediamine while stirring at high speed with a homomixer to obtain an aqueous white terminal amine aqueous solution having a solid content of 40% and a viscosity of 80 cps at 25 ° C. Polyurethane resin B was prepared. Further, 100 parts of the aqueous polyurethane resin B having the terminal amine was mixed with 7 parts of Epicron EM85-75W (manufactured by Dainippon Ink and Chemicals, Inc.), which is an aqueous epoxy, to obtain an adhesive composition. The results of hot water resistance test carried out on this adhesive composition in the same manner as in Example 1 are shown in Table 1.

Example 2 Polyester 513.4 composed of ethylene glycol having an OH value of 56 / neopentyl glycol / 1.6 hexanediol / terephthalic acid / isophthalic acid / adipic acid
Part, neopentyl glycol 7.3 parts, dimethylolpropionic acid 33.8 parts, and isophorone diisocyanate 166.9 parts are reacted to obtain a prepolymer solution having a terminal isocyanate group with an NCO% of 2.6%. It was Then, this prepolymer was stirred at high speed with a homomixer while an aqueous solution part 970 containing 21.3 parts and 26.3 parts of isophoronediamine and diethanolamine, respectively.
It is put into a container and the solid content is 40% and the viscosity at 25 ° C is 200.
A cps translucent colloidal aqueous terminal polyurethane resin C having hydroxyl groups was prepared. Further, 15 parts of Coronate C3062 (manufactured by Nippon Polyurethane Industry Co., Ltd.), which is an aqueous isocyanate, was blended with 100 parts of the aqueous polyurethane resin C having terminal hydroxyl groups immediately before using the adhesive to obtain a composition of the present invention. Table 1 shows the results of a hot water resistance test conducted on this adhesive composition.

Comparative Example 2 To 100 parts of the aqueous polyurethane resin C containing a carboxyl group at the terminal hydroxyl group of Example 2, was added 10 parts of an aqueous epoxy resin, Epiclone EM85-75W (manufactured by Dainippon Ink and Chemicals, Inc.). To obtain an adhesive composition. The results of hot water resistance test carried out on this adhesive composition in the same manner as in Example 1 are shown in Table 1.

Example 3 Finetex ES6 was used as the aqueous polyester resin.
50 (manufactured by Dainippon Ink and Chemicals, Inc.) was selected, and 100 parts of this aqueous polyester resin was mixed with 10 parts of an aqueous isocyanate, Coronate C3062 (manufactured by Nippon Polyurethane Co., Ltd.) immediately before using the adhesive. To obtain the composition of the present invention. Table 2 shows the results of a hot water resistance test conducted on this adhesive composition.

Comparative Example 3 Finetex ES650 was selected as the water-based polyester resin in the same manner as in Example 1, and 100 parts of this water-based polyester resin was used as the water-based epoxy resin Epicron EM85-75W (Dainippon Ink and Chemicals, Inc. ) Made 1
An adhesive composition was obtained by blending 0 part. Table 2 shows the results of a hot water resistance test conducted on this adhesive composition in the same manner as in Example 3.

Example 4 As an aqueous polyacrylic resin, Acronal 80DN was used.
(Manufactured by Mitsubishi Yuka Birdish Co., Ltd.), 100 parts of this aqueous polyacrylic resin was mixed with 10 parts of an aqueous isocyanate, Coronate C3062 (manufactured by Nippon Polyurethane Co., Ltd.) immediately before using the adhesive. To obtain the composition of the present invention. Table 2 shows the results of a hot water resistance test conducted on this adhesive composition.

Comparative Example 4 As a water-based polyacrylic resin, Acronal 80DN was used.
(Okaka Birdish Co., Ltd.) was selected, and 100 parts of this water-based polyacrylic resin was mixed with 10 parts of Epicuron EM85-75W (manufactured by Dainippon Ink and Chemicals, Inc.) which is an aqueous epoxy. An adhesive composition was obtained. Table 2 shows the results of a hot water resistance test conducted on this adhesive composition in the same manner as in Example 3.

Laminate Sample Manufacturing Method The above adhesive was coated with 12 μm thick PET by gravure coating of a dry laminator having a dryer.
Film (Lumirror manufactured by Toray Industries, Inc.) or 15 μm thick
A nylon film (Emblem manufactured by Unitika Ltd.) was coated with a coating amount of 3 g / m ² -dry, dried with a drier,
In the case of the boil test, a 60 μm thick LLDPE film (Tocello TUX-HC manufactured by Tokyo Cellophane Paper Co., Ltd.),
In the case of the retort test, a CPP film with a thickness of 70 μm (Toray Synthetic Film Co., Ltd. Trefan NO-ZK6
2) and 60 ° C./2 kg / cm ² nip conditions, respectively, and laminates were subjected to aging at 40 ° C. for 3 days. In the case of an aluminum foil structure, an adhesive is applied on a 15 μm nylon film with a coating amount of 3 g / m ² -dry, dried and laminated with an aluminum foil, and then the aluminum surface is coated with the above adhesive amount. , 70 μm CPP film, and aged to obtain a laminated sample.

Hot water resistance test method Boil test: The above laminated sample was heat-sealed into bags, and then a mixture of edible oil and water (water / edible oil =
Appearance of the specimen after boiling and high temperature sterilization at 98 ° C for 1 hour, using the specimen filled with 10/1).

Retort test: The above laminated sample was heat-sealed into bags, and then filled with a mixture of edible oil and water (water / edible oil = 10/1) as a test sample at 120 ° C. for 30 minutes. Appearance of specimen after high temperature sterilization.

[0044]

[Table 1]

[0045]

[Table 2]

Evaluation ○: No appearance delamination
×: Appearance delamination included * 1 Water-based isocyanate manufactured by Nippon Polyurethane Co., Ltd. * 2 Water-based epoxy manufactured by Dainippon Ink and Chemicals, Inc.

[0047]

EFFECT OF THE INVENTION A laminate produced by the present laminating method using the water-based laminating adhesive composition of the present invention exhibits excellent water resistance and hot water resistance, which has hitherto been impossible with water-based adhesives. It is possible to produce a packaging material that does not peel off the film even in the high temperature sterilization process of the packaging container that is performed with filled food, and that also has excellent long-term storage stability and hygiene of the food. did.

Claims (4)

[Claims] 1. An aqueous laminating adhesive composition comprising a water-soluble or water-dispersible resin (A) having a functional group capable of reacting with an isocyanate group and a water-dispersible polyisocyanate compound (B). 2. The aqueous laminate adhesive composition according to claim 1, wherein the water-dispersible polyisocyanate compound (B) is a polyisocyanate compound dispersed in water with an emulsifier. 3. The aqueous laminating adhesive composition according to claim 1, wherein the water-dispersible polyisocyanate compound (B) is a self-emulsifiable polyisocyanate compound obtained by copolymerizing a hydrophilic group-containing compound. 4. A water-soluble or water-dispersible resin (A) having a flexible base material having a functional group capable of reacting with an isocyanate group.
And an aqueous laminating adhesive composition comprising a water-dispersible polyisocyanate compound (B) to form an adhesive layer and drying the adhesive layer, and then the adhesive coated surface and at least one other surface A laminating method comprising laminating a flexible base material.