JP3521927B2 - Aqueous print laminate adhesive composition and print lamination method - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides an excellent adhesive strength, water resistance, and adhesive strength after adhesion of a film and paper or printing paper.
The present invention relates to a water-based print laminating adhesive composition exhibiting heat resistance and a very excellent appearance, and a print laminating method using the same. Print laminating refers to the protection of the printing surface or the paper surface such as paper containers, publications, cards, posters, packaging materials, and other printed products such as paper products, water resistance,
This is a processing method in which a flexible base material such as a plastic film or a metal foil is laminated on the surface for the purpose of imparting oil resistance, glossing, beautification and the like.

Therefore, when the present print laminating method is used, it is possible to realize a very excellent gloss and appearance equal to or higher than those of the organic solvent type after print laminating various films and papers including printing paper. In addition, it is possible to suppress the discoloration of the ink of the printed matter and the yellowing of the coated paper.

[0003]

2. Description of the Related Art As an adhesive for print lamination for bonding various films and printing paper, from the viewpoint of satisfying both the glossy appearance of the processed product and the required quality such as adhesiveness, water resistance and oil resistance. There is a need for a liquid curable adhesive, and conventionally, a two-liquid curable organic solvent adhesive such as an ethylene-vinyl acetate polymer or an acrylic resin has been used. In recent years, there has been a strong demand for the adhesive to be a non-organic solvent, such as improving the working environment, strengthening the Fire Service Law, and restricting the release of VOCs into the atmosphere. However, the water-based adhesive has poor water resistance because it contains a large amount of hydrophilic groups in the resin, and the curing system used for the water-based adhesive tends to cause discoloration of the printing ink and yellowing of the coated paper. In addition, since it takes a long time to cure, it is inferior in ruled lineability, and the performance required in the conventional organic solvent-based adhesive cannot be satisfied. Further, when a high molecular weight aqueous resin is used, the discoloration of the printing ink and the yellowing of the coated paper can be reduced to some extent, but the problem that the finished appearance of the printed laminate is remarkably deteriorated occurs. The current situation.

[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 performance of water-based adhesives composed of water-soluble or water-dispersible resins by using carboxylic acid and metal ion system, but discoloration of printing ink, yellowing of coated paper, ruled line, and The current situation is that we have not yet obtained sufficient results from the aspect of the appearance of the printed laminated product.

[0005]

SUMMARY OF THE INVENTION In view of such a situation, the present inventors have shown a very excellent appearance of a processed product, and do not cause discoloration of printing ink or yellowing of coated paper. As a result of repeated research to develop an aqueous print laminating adhesive composition exhibiting excellent adhesive strength, water resistance and oil resistance and a print laminating method using the same, an aqueous dispersion having a functional group capable of reacting with an isocyanate group Of the water-dispersible polyisocyanate compound and a water-based print laminate adhesive composition containing the water-dispersible polyisocyanate compound, and a print laminating method using the same were found to achieve the above objects, and the present invention was completed. It is a thing.

That is, the present invention comprises an aqueous laminate adhesive composition comprising a water-dispersible polyurethane resin having a functional group capable of reacting with an isocyanate group and a water-dispersible polyisocyanate compound, and the use thereof. It is a laminating method performed by

The polyisocyanate compound used for producing the water-dispersible polyurethane resin having a functional group capable of reacting with the isocyanate group of the present invention is, 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′-dicyclohexylmethane diisocyanate and the like can be mentioned. .

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 functional group capable of reacting with the isocyanate group of the water-dispersible polyurethane resin of the present invention includes hydroxyl group, phenolic hydroxyl group, carboxyl group and its salt, amino group, sulfonic acid group and its salt, and mercapto group. However, from the viewpoint of odor and 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, a method of introducing a terminal hydroxyl group obtained by reacting an excess amount of polyol and polyisocyanate, a polyurethane resin having a terminal isocyanate group obtained by reacting an excess amount of polyisocyanate and 2-aminoethanol, 2,2 ′ There is a method of reacting amino alcohols such as dihydroxydiethylamine and aminophenols such as 0, m, p-aminophenol and the like to introduce a hydroxyl group.

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 a polycarboxylic acid, trimellitic anhydride, and a polycarboxylic anhydride having one carboxyl group.

Further, by neutralizing these carboxyl groups to form a salt, the polyurethane can be made water-dispersible. Examples of the neutralizing agent include non-volatile bases such as sodium hydroxide and potassium hydroxide; tertiary amines such as trimethylamine and triethylamine; and volatile bases such as ammonia. Although it can be neutralized later, ammonia is particularly preferable from the viewpoint of water resistance, residual odor and the like.

In order to produce the water-dispersible polyurethane resin of the present invention, it is preferable to use polyoxyalkylene monoalkyl ether. The polyoxyalkylene monoalkyl ether that can be used has a molecular weight of 300 to
10,000 polyethylene glycol monoalkyl ether (wherein the alkyl group has 1 to 4 carbon atoms), or an alkyl alcohol having 1 to 4 carbon atoms as an initiator,
Ethylene oxide as an essential component, propylene oxide, butylene oxide, styrene oxide,
Polyoxyalkylene monoalkyl having a molecular weight of 300 to 10,000, which is obtained by block or random copolymerization with at least one kind of monomers such as epichlorohydrin, tetrahydrofuran and cyclohexylene, and which contains at least 30% by weight of ethylene oxide repeating units. An example is ether. Among them, polyoxyalkylene monoalkyl ether copolymerized with ethylene oxide, particularly polyoxyalkylene monoalkyl ether copolymerized with ethylene oxide having a molecular weight of 500 to 5,000 is preferable.

In the present invention, the hydrophilic monofunctional polyether containing ethylene oxide is localized not at the main chain of the polyurethane but at the terminal end thereof, thereby improving the appearance of the printed laminate. To enable that.

The polyoxyalkylene monoalkyl ether used in the water-dispersible polyurethane resin of the present invention is
Water-dispersible polyurethane resin solid content 10 finally obtained
It is preferable to contain an amount corresponding to 3 to 30% by weight per 0 parts by weight, and if it is 3% or less, an excellent appearance cannot be obtained, and if it is 30% or more, discoloration of the printing ink occurs.

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 water-dispersible polyisocyanate compound of the present invention is a water-dispersible polyisocyanate compound obtained by reacting a hydrophilic group-containing compound as a water-dispersibility-imparting agent with polyisocyanate. The hydrophilic-containing compound is preferably a compound obtained by reacting a polyoxyalkylene monoalkyl ether, a polyol having at least two or more hydroxyl groups in the molecule, and an organic isocyanate. Furthermore, as the polyols, fatty acid esters are preferable.

The polyisocyanate compound used to obtain the water-dispersible polyisocyanate compound of the present invention includes, 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 '
-Polyisocyanate compounds such as dimethyl-4,4'-dicyclohexylmethane diisocyanate, or their isocyanurate-type or buret-type 3
Substantially hydrophobic polyisocyanates such as a functional polyisocyanate or a prepolymer having a terminal isocyanate group obtained by a reaction with a bifunctional or higher functional polyol compound can be mentioned.

As the polyoxyalkylene monoalkyl ether, the alkyl group is preferably methyl, ethyl, and butyl, and the alkylene oxide is preferably ethylene oxide, and further propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexyl oxide. Examples thereof include those obtained by block or random copolymerization with at least one kind of monomers such as siren.

As the polyol, any polyol that can be used in producing a water-dispersible polyurethane resin can be used, but fatty acid esters are particularly preferable, and any one can be used as long as it contains two or more hydroxyl groups. The fatty acid ester of can also be used. Examples of the fatty acid ester include caproic acid, ethylcaproic acid, caprylic acid, capric acid, lauric acid, oleic acid, or linoleic acid monoglyceride or mono- or disorbate, or ricinoleic acid mono-, di-, or triglyceride. .

As the organic isocyanate for obtaining the hydrophilic group-containing 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'-dicyclohexylmethane diisocyanate and the like can be mentioned.

An emulsifier may be used in the water-dispersible polyisocyanate compound of the present invention. As the emulsifier, for example, 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, etc. Alkylphenyl condensate ether type, sorbitan derivative type such as polyoxyethylene sorbitol tetraoleate, alkylamine type such as polyoxyethylene lauryl amino ether, monool type such as polyoxyalkylene alkyl ether, alkanol such as lauric acid diethanolamide Nonionic emulsifiers such as amide type; fatty acid salts such as sodium oleate, alkyl sulfate salts, alkylbenzene sulfonates, alkylsulfosuccinates, sodium Tarensurufon salts, polyoxyethylene alkyl sulfates, alkane sulfonates sodium salt,
Examples thereof include anionic emulsifiers such as sodium salt of alkyldiphenyl ether sulfonate and phosphoric acid ester.

Commercially available water-dispersible polyisocyanate compounds include CR manufactured by Dainippon Ink and Chemicals, Inc.
-60N, Nippon Polyurethane Co. Coronate C306
2, C3053, dismodule DA manufactured by Sumitomo Bayer Urethane Co., Ltd., and the like.

When the mixed solution of the water-dispersible polyurethane resin having a functional group capable of reacting with an isocyanate group and the water-dispersible polyisocyanate compound of the present invention is used as an aqueous adhesive, another aqueous resin such as, for example, Vinyl acetate-based, ethylene vinyl acetate-based, acrylic styrene-based emulsions; styrene-butadiene-based, acrylonitrile-butadiene-based, acrylic-butadiene-based, polychloroprene-based, vinylpyridine-based, butyl rubber-based, natural rubber latex, etc .; polyethylene-based , An ionomer such as a polyolefin-based ionomer; and an epoxy-based water dispersion or the like can be blended at an arbitrary ratio and used.

When the mixed solution of the water-dispersible polyurethane resin having a functional group capable of reacting with an isocyanate group and the water-dispersible polyisocyanate compound of the present invention is used as an aqueous adhesive, in addition to the above-mentioned components, known components are known. Are fillers, softeners, anti-aging agents, stabilizers, adhesion promoters, leveling agents, defoamers, plasticizers, inorganic fillers, tackifying resins,
Fibers, colorants such as pigments, 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 or the like is preferably used. A rosin derivative or the like is preferably used as the tackifying resin.

The water-dispersible polyurethane resin having a functional group capable of reacting with these isocyanate groups and the water-dispersible polyisocyanate compound are blended before use. The solvent of the water-dispersible polyurethane resin is water, but a slight amount of an organic solvent may be added and used in order to improve the emulsion properties. The water-dispersible polyisocyanate compound may have a resin solid content of 100%, or may be used by diluting with an organic solvent in order to improve mixing efficiency at the time of compounding with the water-dispersible polyurethane resin.

The compounding ratio of the water-dispersible polyurethane resin and the water-dispersible polyisocyanate compound is such that the water-dispersible polyisocyanate compound is equivalent to 100 equivalents of the functional groups capable of reacting with the isocyanate groups contained in the water-dispersible polyurethane resin. The isocyanate group equivalent of can be used in an amount corresponding to an equivalent of 30 to 500, preferably 50
~ 300.

The aqueous adhesive of the present invention, which comprises a mixture of a water-dispersible polyurethane resin having a functional group capable of reacting with an isocyanate group and a water-dispersible polyisocyanate compound, reacts with the isocyanate group in the water-dispersible polyurethane resin. A reaction catalyst can be used to accelerate the reaction between the functional groups capable of reacting with the isocyanate in the water-dispersible polyisocyanate resin. For example, triethanolamine,
Triethylenediamine, tetramethylbutanediamine,
1,8-diaza-bicyclo (5,4,0) undecene-
7. Phenol salt, 1,8-diaza-bicyclo (5,5
4,0) undecene-7.octylate, 1,8-diaza-bicyclo (5,4,0) undecene-7.oleate, butyltin oxide, tin octate, 1,4-diaza (2,2) , 2) Bicyclooctane and the like.

In the print laminating method of the present invention, for example, a water-based adhesive composition comprising a water-dispersible polyurethane resin having a functional group capable of reacting with an isocyanate group and a water-dispersible polyisocyanate compound is applied to form a coating film. Thickness is 0.1-1000 μm and coating amount is 0.1-1000
Apply to a flexible substrate so that g / m ² -dry, and
Drying with a dryer at 0 to 180 ° C., water or water containing an organic solvent is evaporated, and the adhesive coated surface of the flexible substrate, paper,
Synthetic paper or various base materials such as paper and printed matter such as synthetic paper at a temperature of 40 to 180 ° C. and a pressure of 30 to 300 kg /
It is a method of performing thermocompression bonding with a thermocompression bonding roll having a cm ² .

As the flexible substrate used in the present invention,
For example, PVC, PET, biaxially stretched PP, unstretched PP,
Various plastic films such as PE, nylon, polyvinyl alcohol, vinylidene chloride coated OPP, polystyrene, EVOH, polycarbonate and cellophane, various metal vapor deposition films, metal foils and the like can be used. The water-based adhesive coating method can be widely used if it is known. Examples thereof include roll coating, gravure coating, knife coating, reverse coating and kiss coating. As a dryer, if it is known, it can be widely used. For example, a hot air drier, an infrared irradiation type drier, a microwave irradiation type drier, or a drying device in which at least two or more of them are used in combination can be used. As the paper or the synthetic paper, if it is publicly known, it can be widely used. For example, imitation paper, fine paper, art paper, graft paper, pure white roll paper,
Parchment paper, waterproof paper, glassine paper, cardboard paper, etc. can be mentioned.

A print laminated product obtained by carrying out print lamination using an aqueous print laminate adhesive composition comprising a water-dispersible polyurethane resin having a functional group capable of reacting with an isocyanate group of the present invention and a water-dispersible polyisocyanate compound. Made it possible to develop a color appearance of the printing ink and a yellowing of the coated paper, and to produce an appearance as good as or better than that of a print laminated product using a conventional organic solvent-based adhesive.

[0036]

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 Polypropylene glycol 104.5 having an OH value of 280
Parts, polypropylene glycol 228.0 with an OH value of 56
Parts, dimethylolpropionic acid 15.5 parts, polyoxyethylene polyoxypropylene copolymer (molecular weight about 30
00, EO / PO = 50/50% by weight) 52.2 parts of monobutyl ether and Coronate T-80 (mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) 12
1.8 parts of NCO was reacted to obtain a prepolymer solution having a terminal isocyanate group of 3.22%. Then, this prepolymer was put into an aqueous solution containing 42.0 parts of diethanolamine while stirring at high speed with a homomixer, and 7.9 parts of 25% aqueous ammonia was added after the addition to give a solid content of 40% at 25 ° C. Of a semi-transparent colloidal water-dispersible polyurethane resin (A-) having a viscosity of 300 cps
1) was prepared.

Next, 554.0 parts of polyoxyethylene monomethyl ether having an OH value of 81 and Coronate T-8 were used.
0 (manufactured by Nippon Polyurethane Industry Co., Ltd.) was mixed with 140 parts and reacted at 50 ° C. for 5 hours to obtain a prepolymer having a terminal isocyanate. Then, 100.0 parts of oleic acid monoglyceride having an OH value of 220 and 1 part of the above prepolymer
70 parts were mixed and reacted at 60 ° C. for 3 hours to prepare a water dispersibility imparting agent. 10 parts of this water dispersibility-imparting agent and 100 parts of Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.) were mixed and held at 60 ° C. for 5 hours to give an isocyanate content of 19%, a viscosity of 3500 cps, and a viscous appearance. A water-dispersible isocyanate (I-1) as a transparent liquid was obtained. The isocyanate-containing resin has a solid content of 100%, but has a property of being easily dispersed in water.

This water-dispersible polyurethane resin (A-1)
Table 2 shows the results of the evaluation of the aqueous adhesive composition obtained by mixing the water-dispersible isocyanate (I-1) with the water-dispersible isocyanate (I-1) as shown in Table 1.

Comparative Example 1 37.2 parts of polypropylene glycol having an OH value of 280,
469.2 parts of polypropylene glycol having an OH value of 56,
Dimethylolpropionic acid 21.5 parts, polyoxyethylene polyoxypropylene copolymer (molecular weight about 300
0, EO / PO = 50/50% by weight) 72.2 parts of monobutyl ether and 121.8 parts of Coronate T-80 (manufactured by Nippon Polyurethane Industry Co., Ltd.) are reacted to produce a terminal isocyanate having an NCO% of 2.33%. A prepolymer solution containing a pendant group was obtained. Then, this prepolymer was put into an aqueous solution containing 51.1 parts of isophorone diamine (manufactured by Daicel Hüls) while stirring at high speed with a homomixer,
After adding 7.9 parts of 25% aqueous ammonia, solid content 35
%, A semi-transparent colloidal water-dispersible polyurethane resin having terminal amine groups (A-2) having a viscosity of 300 cps at 25 ° C. was prepared.

This water-dispersible polyurethane resin (A-2)
And a water-dispersible epoxy, Epicuron EM85-75
Table 2 shows the results obtained by performing print lamination on an aqueous adhesive composition prepared by blending W (manufactured by Dainippon Ink and Chemicals, Inc.) as shown in Table 1 and performing evaluation.

Example 2 Polypropylene glycol having an OH value of 280 145.5
Parts, OH number 56 polypropylene glycol 57.8
Parts, dimethylolpropionic acid 12.5 parts, polyoxyethylene polyoxypropylene copolymer (molecular weight about 30
00, EO / PO = 50/50% by weight) monobutyl ether 84.3 parts and Coronate T-80 (manufactured by Nippon Polyurethane Industry Co., Ltd.) 121.8 parts are reacted to obtain NCO%.
A prepolymer solution having 3.98% of terminal isocyanate groups was obtained. Next, this prepolymer was put into an aqueous solution containing 17.1 and 21.0 parts of isophoronediamine and diethanolamine, respectively, while stirring at high speed with a homomixer, and 25% aqueous ammonia was added to 7.9.
Parts after addition, solid content 40%, viscosity at 25 ° C 400c
A semi-transparent colloidal water-dispersible polyurethane resin (B-1) having terminal hydroxyl groups of ps was prepared.

This water-dispersible polyurethane resin (B-1)
And the water-dispersible isocyanate (I-1) described in Example 1
Table 2 shows the results obtained by performing print lamination on the water-based adhesive composition obtained by blending and with each other as shown in Table 1.

Example 3 Water-dispersible polyurethane resin (A-1) described in Example 1
And water-dispersible isocyanate Coronate 3062
Table 2 shows the results of evaluation of the water-based adhesive composition obtained by blending with (Japan Polyurethane Industry Co., Ltd.) as shown in Table 1 and performing print lamination.

Evaluation method Appearance: Appearance 2 days after lamination Film adhesion: Adhesion of adhesive to film after adhering film and printed material for 2 days at room temperature Ink adhesion: Adhesion of film and printed material Adhesiveness of adhesive to printing ink after standing at room temperature for 2 days Water resistance: After bending the laminated product, temperature 50
Observation of floating after accelerating for 2 days at 80 ° C and 80% humidity Oil resistance: Folded observation line after accelerating the laminated product after folding it and sandwiching it with paper soaked in light oil for 2 days Properties: Immediately after pressing the ruled line on the laminated product, 2
Observation of film floating after day Ink discoloration: Laminated product was heated at a temperature of 50 ° C and a humidity of 8
Observation of ink discoloration after accelerated at 0% for 7 days Paper yellowing: Laminated with plain coated paper, temperature 50
Observe yellowing after accelerated for 7 days at ℃ and 80% humidity

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

The print laminated product obtained according to the present invention does not cause discoloration of printing ink or yellowing of coated paper, and exhibits excellent adhesive strength, ruled line property, water resistance and oil resistance. In the past, it was difficult to make the appearance of the processed product equal to that of the organic solvent-based adhesive with the water-based adhesive, but the present invention makes the appearance of the processed product very excellent while being water-based. Made it possible.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-49-339 (JP, A) JP-A-2-16181 (JP, A) JP-A 61-291613 (JP, A) JP-A 64-- 69619 (JP, A) JP 57-170972 (JP, A) JP 4-323292 (JP, A) JP 7-293987 (JP, A) JP 6-80948 (JP, A) JP-A-5-202162 (JP, A) JP-A-59-159871 (JP, A) JP-A-1-284579 (JP, A) JP-A-3-277680 (JP, A) JP-A-60-141711 (JP, A) JP 62-270613 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 175/00-201/10 C08G 18/87-18/87 C08L 75 / 00-75/08

Claims (3)

(57) [Claims] 1. A water-based print laminate adhesive composition containing a water-dispersible polyurethane resin having at least two functional groups capable of reacting with an isocyanate group, and a water-dispersible polyisocyanate compound, wherein
Polyurethane resin is added to 100 parts by weight of solid content
3 to 30 oxyalkylene monoalkyl ether residues
Water-dispersible polyisocyanates as described above having a weight percentage of
However, with polyoxyalkylene monoalkyl ether,
Polyol containing at least two hydroxyl groups in the molecule
Of poly (isocyanate)
Addition of compound to polyisocyanate as water dispersibility imparting agent
Water-dispersible polyisocyanate compound described above . 2. The water-based print laminate adhesive composition according to claim 1 is applied to a flexible substrate to form an adhesive layer, and the adhesive layer is dried, and then the adhesive-formed surface and paper or printing. A print laminating method comprising thermocompression bonding with paper. 3. The aqueous print laminating adhesive composition according to claim 1 is applied to paper or printing paper to form an adhesive layer, and the adhesive layer is dried, and then the adhesive forming surface and the paper or printing. A print laminating method comprising thermocompression bonding with paper.