JP2001040319A - Water-based adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-based adhesive capable of giving a flexible and durable bond by using a water-based emulsion containing as the resin component a self-emulsifiable copolymer containing an ethylenically unsaturated monomer. SOLUTION: The self-emulsifiable copolymer is produced by chemically combining an ethylenically unsaturated monomer with a mercapto-containing and hydrophilic-polar-group-containing urethane prepolymer through radical polymerization or by chemically combining an ethylenically unsaturated monomer with an organic polyisocyanate, a mercapto-containing, active-hydrogen- group-containing compound through urethane formation reaction and radical polymerization. This copolymer is emulsified in water. The ethylenically unsaturated monomer is desirably an ethylenically unsaturated monomer (mixture) containing at least a hydrophilic-polar-group-containing ethylenically unsaturated monomer or an ethylenically unsaturated monomer (mixture) containing at least a keto-containing or aldehydo-containing ethylenically unsaturated monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flexible and durable aqueous adhesive.

[0002]

2. Description of the Related Art Heretofore, adhesives based on organic solvents have often been used. However, in recent years, water-based adhesives have been developed due to safety and health problems such as explosion fires and pollution problems such as water pollution and air pollution.

[0003] Aqueous polyurethane emulsions and aqueous acrylic emulsions are known, and many of them are applied to aqueous adhesives. However, water-based polyurethane adhesives generally have good adhesion but poor heat resistance, and water-based acrylic adhesives have the opposite tendency to water-based polyurethane adhesives.

Therefore, various studies have been made to make use of the characteristics of urethane and the characteristics of acrylic. For example,
JP-A-4-252202 proposes an aqueous resin obtained by dispersing an acrylic monomer in a polyurethane emulsion and then polymerizing it, and describes that the aqueous resin can be applied to an adhesive. Also, Japanese Patent Application Laid-Open No. 10-1398
No. 39 discloses an aqueous polyurethane obtained by synthesizing a polyurethane resin using a hydroxy compound having a polymerizable unsaturated group, and then reacting a polymerizable unsaturated monomer with a polymerizable unsaturated group present in urethane. -A vinyl copolymer is proposed, and there is a description that the aqueous resin can be applied to an adhesive.

[0005]

However, in the method described in JP-A-4-252202, since the acrylic resin is produced in the polyurethane emulsion, the polyurethane resin and the acrylic resin are basically mixed. It is. Originally, the acrylic resin and the urethane resin have poor compatibility, so that the adhesive layer is likely to be non-uniform, which may lower the adhesive strength. In addition, Japanese Patent Application Laid-Open
According to the method described in JP-A-139839, a polyurethane-based resin having two or more ethylenically unsaturated double bonds in one molecule is produced without using a chain transfer agent at the time of resin production. When this occurs, gelation is likely to occur.

[0006] An object of the present invention is to provide a flexible and adhesive water-based adhesive.

[0007]

That is, the present invention provides the following (1) to (7). (1) A water-based emulsion comprising, as a resin component, a self-emulsifiable copolymer in which an ethylenically unsaturated monomer and a urethane prepolymer containing a mercapto group and a hydrophilic polar group are bonded by radical polymerization. adhesive.

(2) An ethylenically unsaturated monomer, an organic polyisocyanate, a compound containing a mercapto group and an active hydrogen group, and a compound containing a hydrophilic polar group and an active hydrogen group are combined by urethanation reaction and radical polymerization. An aqueous adhesive comprising an aqueous emulsion containing a self-emulsifiable copolymer as a resin component.

(3) The aqueous adhesive according to (1) or (2), wherein the ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least a hydrophilic polar group-containing ethylenically unsaturated monomer.

(4) The aqueous adhesive according to (1) or (2), wherein the ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least a keto group or aldehyde group-containing ethylenically unsaturated monomer.

(5) The urethane prepolymer containing a mercapto group and a hydrophilic polar group is a urethane prepolymer further containing an ethylenically unsaturated double bond in addition to the mercapto group and the hydrophilic polar group. , (3) or (4).

(6) The urethane prepolymer containing a mercapto group and a hydrophilic polar group is a urethane prepolymer containing a keto group or an aldehyde group in addition to the mercapto group and the hydrophilic polar group, or a mercapto group, a hydrophilic polar group and A urethane prepolymer containing a keto group or an aldehyde group in addition to the ethylenically unsaturated double bond,
The aqueous adhesive according to (1), (3) or (4).

(7) An aqueous adhesive comprising the aqueous adhesive according to (4), (5) or (6) and a polyfunctional hydrazide compound.

(8) An aqueous adhesive comprising the aqueous adhesive according to any one of (1) to (7) and an aqueous polyisocyanate-based curing agent.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the self-emulsifying copolymer of the present invention, a hydrophilic polar group is introduced into at least the urethane segment. This self-emulsifiable copolymer is obtained by using a mercapto group of a hydrophilic polar group-containing urethane prepolymer having a mercapto group or a mercapto group of a compound containing an active hydrogen group as a chain transfer agent. Has a structure in which an ethylenically unsaturated double bond is subjected to radical polymerization or urethanation reaction at the same time.

The components of the self-emulsifying copolymer of the present invention will be described. Examples of the ethylenically unsaturated monomer used in the present invention include a hydrophilic polar group-containing ethylenically unsaturated monomer, a keto group or aldehyde group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers. These can be used alone or as a mixture of any combination. Ethylenically unsaturated monomers (mixtures) containing at least an ethylenically unsaturated monomer containing a hydrophilic polar group, or ethylenically unsaturated monomers containing a keto group or an aldehyde group are used. An ethylenically unsaturated monomer (mixture) containing at least a saturated monomer is preferred, and in this case, an ethylenically unsaturated monomer (mixture) containing 50 to 95 mol% of other ethylenically unsaturated monomers is preferred. In the present invention, in order to impart self-emulsifiability to the obtained copolymer, a hydrophilic polar group is introduced into at least the urethane segment, but a hydrophilic polar group is introduced into both the acrylic segment and the urethane segment. It is preferable to do so, as it is possible to impart self-emulsifying properties to the copolymer with a smaller amount of introduction than to introduce only one of them.

Examples of the hydrophilic polar group-containing ethylenically unsaturated monomer include poly (oxyalkylene) ether glycol monoacrylate and poly (oxyalkylene)
Compounds having an ethylenically unsaturated double bond and an epoxy group such as ether glycol monomethacrylate, poly (oxyalkylene) ether glycol monoalkyl ether acrylate, poly (oxyalkylene) ether glycol monoalkyl ether methacrylate, glycidyl acrylate and glycidyl methacrylate. Oxyethylene group-containing ethylenically unsaturated monomers such as poly (oxyethylene) chain-containing ethylenically unsaturated monomers such as compounds to which alkylene oxide is added, compounds represented by the formula 1, etc., and acrylic acid, methacrylic acid, and maleic acid. Acid, maleic anhydride, maleic acid monoesters,
Carboxylic acid-containing ethylenically unsaturated monomers such as fumaric acid, fumaric acid monoesters, itaconic acid, itaconic acid monoesters, sulfonated styrene, sulfonated α-
Methylstyrene, acid-containing ethylenically unsaturated monomers such as sulfonic acid-containing ethylenically unsaturated monomers such as compounds represented by the following formulas 2 or 3, allylamine, N, N
-Dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, those obtained by adding an alkylene oxide thereto, primary compounds such as a compound represented by the formula 4 And base-containing ethylenically unsaturated monomers such as secondary and tertiary amino group-containing ethylenically unsaturated monomers.

[0018]

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[0019]

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[0020]

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[0021]

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Examples of the ethylenically unsaturated monomer containing a keto group or an aldehyde group include acrolein, diacetone acrylamide, diacetone methacrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, vinyl acetophenone, vinyl benzophenone, acrylic Oxypropenal, diacetone acrylate, acetonitrile acrylate,
2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, methacryloxypropenal, diacetone methacrylate, acetonitrile methacrylate, 2
-Hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-methacrylate acetyl acetate, and the like.

Other ethylenically unsaturated monomers include alkyl acrylate, cycloalkyl acrylate,
Acrylic esters such as phenyl acrylate, benzyl acrylate and glycidyl acrylate; alkyl methacrylates, cycloalkyl methacrylates; methacrylic esters such as phenyl methacrylate, benzyl methacrylate and glycidyl methacrylate; vinyl acetate; propionic acid Vinyl ester compounds such as vinyl; vinyl alkyl ethers such as vinyl methyl ether; vinyl ether compounds such as vinyl cyclohexyl ether, vinyl phenyl ether, vinyl benzyl ether and vinyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile , Ethylenically unsaturated double bond-containing aromatic compounds such as styrene, vinyltoluene and α-methylstyrene, and halogenated vinyls such as vinyl chloride and vinyl bromide. , Vinylidene halides such as vinylidene chloride and vinylidene bromide; maleic diesters such as dialkyl maleate; fumaric diesters such as dialkyl fumarate; itaconic diesters such as dimethyl itaconate; Dialkylacrylamides such as dimethylacrylamide, N-vinylpyrrolidone, heterocyclic vinyl compounds such as 2-vinylpyridine, etc.
2-hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, 2
-Hydroxyethyl acrylate ε-caprolactone adduct, 2-hydroxyethyl acrylate β-methyl-γ-valerolactone adduct, glycerol monoacrylate, hydroxyl group-containing acrylates such as glycerol diacrylate, 2-hydroxyethyl methacrylate, hydroxy Propyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, ε-caprolactone adduct of 2-hydroxyethyl methacrylate, β-methyl-γ-valerolactone adduct of 2-hydroxyethyl methacrylate, glycerol monomethacrylate, glycerol dimethacrylate, etc. Hydroxyl-containing methacrylates, allyl alcohol, glycerol monoallyl ether, Allyl compounds such as roll diallyl ether. Of these, preferred are 2-hydroxyethyl acrylate,
Active hydrogen group-containing ethylenically unsaturated monomers such as ε-caprolactone adduct of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and ε-caprolactone adduct of 2-hydroxyethyl methacrylate.

Examples of the radical polymerization initiator used for radical polymerization of the ethylenically unsaturated monomer include, for example,
2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, azobiscyanovaleric acid, 1,1 '
-Azobis- (cyclohexane-1-carbonitrile), 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-
Azo compounds such as 2,4-dimethylvaleronitrile),
1,1-bis (t-butylperoxy) -3,3,5-
Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) ) Cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide,
Diisopropylbenzene hydroperoxide, p-
Menthol hydroperoxide, t-hexyl peroxide, 1,1,3,3-tetramethylbutyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, di-t-butyl peroxide, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxide, toluylbenzoyl peroxide, diisopropylperoxydicarbonate, di-n-propyl Peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-methoxybutylperoxydi Boneto, di-2-ethylhexyl peroxydicarbonate, di (3-methyl-3-
Methoxybutyl) peroxydicarbonate, α, α '
Bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,
3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t −
Hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-bis (2-ethylhexylperoxy) hexane, 1,1,3,3-
Tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy- 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxylaurate, t-
Butylperoxy-3,5,5-trimethylhexanate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl- 2,5-bis (benzoylperoxy) hexane, 2,5-dimethyl-2,
5-bis (m-toluoylperoxy) hexane, t-
Organic peroxides such as butyl peroxy acetate, t-hexyl peroxy benzoate, t-butyl peroxy-m-toluoyl benzoate, t-butyl peroxy benzoate, bis (t-butyl peroxy) isophthalate, and the like. .

The urethane prepolymer containing a mercapto group and a hydrophilic polar group used in the present invention includes, for example, an organic polyisocyanate, a compound containing a mercapto group and an active hydrogen group, and a compound containing a hydrophilic polar group and an active hydrogen group. Reaction product of a compound having an active hydrogen group, if desired. The active hydrogen group is a group having a reactivity with an isocyanate group equal to or higher than a mercapto group, that is, a hydroxyl group, an amino group, an imino group, a mercapto group, or the like.

The organic polyisocyanate includes
4,4'-diphenylmethane diisocyanate, 2,
4'-diphenylmethane diisocyanate, 2,2'-
Diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate,
2-nitrodiphenyl-4,4'-diisocyanate,
2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,
4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-
Phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate,
Aromatic diisocyanates such as 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, lysine diisocyanate, o-xylene diisocyanate, m −
Aliphatic diisocyanates such as xylene diisocyanate, p-xylene diisocyanate, tetramethyl xylene diisocyanate, etc., isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethyl xylene diisocyanate, etc. Is mentioned.
Further, modified adducts of these organic diisocyanates,
So-called modified polyisocyanates such as buret modified products, isocyanurate modified products, uretonimine modified products, uretdione modified products, carbodiimide modified products and the like can also be used. Further, such as polyphenylene polymethylene polyisocyanate, crude toluene diisocyanate, etc.
A polyisocyanate which is a so-called polymeric body can also be used. These organic polyisocyanates can be used alone or in combination of two or more. Among these organic polyisocyanates, when considering weather resistance and the like, aliphatic and alicyclic polyisocyanates are preferable, and hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are most preferred. preferable.

Examples of the compound containing a mercapto group and an active hydrogen group to be reacted with the organic polyisocyanate include polythiol, hydroxythiol, aminothiol and the like.

Examples of polythiols include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-
Hexanedithiol, 1,2,3-propanetrithiol, tetrakis (mercaptomethyl) methane, 1,1-
Cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 3,6-dioxaoctane-1,8-dimercaptan , 2-methylcyclohexane-2,3-dithiol,
Bicyclo [2,2,1] hepta-exo-cis-2,
3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1
-Propanol (2-mercaptoacetate), 2, 3
-Dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl Methyl ether, 2,2-bis (mercaptomethyl) -1,
3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane Tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1- (1′-mercaptomethylthio) -2,3-dimercaptopropane, 1- (2'-mercaptoethylthio) -2,3-dimercaptopropane, 1- (3'-mercaptopropylthio) -2,3-
Dimercaptopropane, 1- (4'-mercaptobutylthio) -2,3-dimercaptopropane, 1- (5'-
Mercaptopentylthio) -2,3-dimercaptopropane, 1- (6′-mercaptohexylthio) -2,3
-Dimercaptopropane, 1,2-bis (1'-mercaptomethylthio) -3-mercaptopropane, 1,2-
Bis (2'-mercaptoethylthio) -3-mercaptopropane, 1,2-bis (3'-mercaptopropylthio) -3-mercaptopropane, 1,2-bis (4'-
Mercaptobutylthio) -3-mercaptopropane,
1,2-bis (5'-mercaptopentylthio) -3-
Mercaptopropane, 1,2-bis (6'-mercaptohexylthio) -3-mercaptopropane, 1,2,3
-Tris (1'-mercaptomethylthio) propane,
1,2,3-tris (2'-mercaptoethylthio) propane, 1,2,3-tris (3'-mercaptopropylthio) propane, 1,2,3-tris (4'-mercaptobutylthio) propane , 1,2,3-tris (5 '
Aliphatic polythiols such as -mercaptopentylthio) propane, 1,2,3-tris (6'-mercaptohexylthio) propane, 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,
4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethyl) Oxy) benzene, 1,3-bis (mercaptomethyloxy) benzene, 1,4-bis (mercaptomethyloxy) benzene, 1,2-bis (mercaptoethyloxy) benzene, 1,3-bis (mercaptoethyloxy) Benzene, 1,4-bis (mercaptoethyloxy) benzene, 1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,3 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1, 2,3-tris (mercaptomethyloxy) benzene, 1,2,4-tris (mercaptomethyloxy) benzene, 1,3,5-tris (mercaptomethyloxy) benzene, 1,2,3-tris (mercaptoethyl) Oxy) benzene, 1,2,4-tris (mercaptoethyloxy) benzene, 1,3,5-tris (mercaptoethyl Carboxymethyl) benzene, 1,2,
3,4-tetramercaptobenzene, 1,2,3,5-
Tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,2 4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4
-Tetrakis (mercaptoethyl) benzene, 1,2,2
3,5-tetrakis (mercaptoethyl) benzene,
1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyloxy) benzene, 1,2,2 4,5-tetrakis (mercaptomethyloxy) benzene, 1,2,3
4-tetrakis (mercaptoethyloxy) benzene,
1,2,3,5-tetrakis (mercaptoethyloxy) benzene, 1,2,4,5-tetrakis (mercaptoethyloxy) benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 4,
4'-dimercaptodibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,
6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol,
9,10-anthracenedimethanethiol, 1,3-di (4'-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol Aromatic polythiols such as 2,4-di (4'-mercaptophenyl) pentane, and 2,5-dichlorobenzene-1,3-
Dithiol, 1,3-di (4'-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-
Halogen-substituted aromatic polythiols such as chlorine-substituted products such as 1,2-dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene, and bromine-substituted products, and 2-methyl Amino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6
-Dithiol-sym-triazine, 2-amino-4,
6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-
Triazine, 2-phenoxy-4,6-dithiol-s
ym-triazine, 2-thiobenzeneoxy-4,6-
Polythiols containing a heterocyclic ring such as dithiol-sym-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine; furthermore, 1,2-bis (mercaptomethylthio) benzene and 1,3-bis ( Mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio)
Benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercapto Ethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 2,3,5-
Tetrakis (mercaptomethylthio) benzene, 1,
2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4 , 5-tetrakis (mercaptoethylthio) benzene, bis (4-mercaptophenyl) sulfide or the like, or an aromatic polythiol containing a sulfur atom in addition to a mercapto group such as an alkylated product thereof, bis (mercaptomethyl) sulfide, bis (Mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1,2-
Bis (mercaptomethylthio) ethane, 1,2- (2-
Mercaptoethylthio) ethane, 1,2- (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3 -Mercaptopropylthio) propane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3
-Tris (mercaptomethylthio) propane, 1,2,2
3-tris (2-mercaptoethylthio) propane,
1,2,3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl)
Methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane,
Bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc., or esters of thioglycolic acid or mercaptopropionic acid, hydroxymethylsulfide-bis (2-mercaptoacetate), hydroxymethylsulfide -Bis (3-mercaptopropionate), hydroxyethyl sulfide-
Bis (2-mercaptoacetate), hydroxyethyl sulfide-bis (3-mercaptopropionate),
Hydroxypropyl sulfide-bis (2-mercaptoacetate), hydroxypropyl sulfide-bis (3-mercaptopropionate), hydroxymethyldisulfide-bis (2-mercaptoacetate), hydroxymethyldisulfide-bis (3-mercaptopropionate) ), Hydroxyethyl disulfide-bis (2-mercaptoacetate), hydroxyethyl disulfide-bis (3-mercaptopropionate), hydroxypropyl disulfide-bis (2-mercaptoacetate), hydroxypropyl disulfide-bis (3-mercaptoprotate) Pionate), 2-mercaptoethyl ether-bis (2-mercaptoacetate), 2
-Mercaptoethyl ether-bis (3-mercaptopropionate), 1,4-dithiane-2,5-diol-bis (2-mercaptoacetate), 1,4-dithiane-2,5-diol-bis (3 -Mercaptopropionate), thioglycolic acid-bis (2-mercaptoethyl ester), thiodipropionic acid-bis (2-mercaptoethyl ester), 4,4-thiodibutylic acid-bis (2-mercaptoethyl ester), Dithiodiglycolic acid-bis (2-mercaptoethyl ester), dithiodipropionic acid-bis (2-mercaptoethyl ester), 4,4-dithiodibutylic acid-bis (2-mercaptoethyl ester), thiodiglycolic acid- Screw (2,
3-dimercaptopropyl ester), thiodipropionic acid-bis (2,3-dimercaptopropyl ester), dithioglycolic acid-bis (2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3
Aliphatic dithiols containing a sulfur atom in addition to a mercapto group such as -dimercaptopropyl ester);
Thiophenedithiol, 2,5-bis (mercaptomethyl) tetrahydrothiophene, bis (mercaptomethyl) -1,3-dithiolane, 2,5-dimercapto-
1,3,4-thiadiazole, 2,5-dimercapto-
1,4-dithiane, 2,5-dimercaptomethyl-1,
Examples thereof include a heterocyclic compound containing a sulfur atom in addition to a mercapto group such as 4-dithiane.

Examples of hydroxythiols include 2-mercapto-1-hydroxyethane, 2-mercapto-1-hydroxypropane, 1-mercapto-2-hydroxypropane, 3-mercapto-1-hydroxypropane,
Monomercaptomonool compounds such as mercapto-1-hydroxybutane, 3-mercapto-1-hydroxybutane, 4-mercapto-1-hydroxybutane, thioglycerol, 2,3-dihydroxy-1-mercaptobutane, 2,3 -Dihydroxy-1-mercaptopentane, 3,4-dihydroxy-1-mercaptobutane,
3,4-dihydroxy-1-mercaptopentane, 3,
Monomercaptodiol compounds such as 4-dihydroxy-1-mercaptohexane, 2-hydroxy-1,3-dimercaptopropane, 1-hydroxy-2,3-dimercaptopropane, 2-hydroxy-1,3-di Mercaptobutane, 1-hydroxy-2,3-dimercaptobutane, 2-hydroxy-1,3-dimercaptopentane,
2-hydroxy-1,3-dimercaptohexane, 3-
And dimercaptomonool compounds such as hydroxy-1,4-dimercaptobutane, 3-hydroxy-1,4-dimercaptopentane and 3-hydroxy-1,4-dimercaptohexane.

Examples of the aminothiol include β-mercaptoethylamine, β-mercaptopropylamine, γ-mercaptopropylamine, 2-aminothiophenol,
3-aminothiophenol, 4-aminothiophenol and the like can be mentioned.

These compounds containing a mercapto group and an active hydrogen group may be used alone or in combination of two or more. Preferred compounds used in the present invention containing a mercapto group and an active hydrogen group are hydroxythiol and aminothiol. Particularly preferred compounds are 2-mercapto-1-hydroxyethane, thioglycerol, β-mercapto Ethylamine.

Examples of the compound containing an active hydrogen group (other than a mercapto group) to be reacted with an organic polyisocyanate include those which are called long-chain polyols in the polyurethane industry and those which are called chain extenders. In the present invention, the urethane prepolymer containing a mercapto group and a hydrophilic polar group preferably contains 50 to 90% by mass of a long-chain polyol.

Examples of the long-chain polyol include polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, animal and plant polyols, and copolyols thereof.
These long-chain polyols may be used alone or in combination of two or more.

Examples of the polyester polyol include known succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, and naphthalenedicarboxylic acid. , One or more polycarboxylic acids such as trimellitic acid, acid esters, or acid anhydrides, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-
Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8- Octanediol, 1,9-nonanediol, diethylene glycol,
Dipropylene glycol, 1,4-cyclohexanedimethanol, or ethylene oxide or propylene oxide adduct of bisphenol A, low molecular weight polyols such as trimethylolpropane, glycerin, pentaerythritol, hexamethylenediamine, xylylenediamine, isophoronediamine, etc. And a polyester polyol or polyester amide polyol obtained by a dehydration condensation reaction with at least one of low molecular weight polyamines, low molecular weight amino alcohols such as monoethanolamine and diethanolamine. Lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular polyols, low molecular polyamines and low molecular amino alcohols as initiators are also included.

Examples of the polycarbonate polyol include those obtained by a dealcoholation reaction, a dephenolization reaction or the like of a low molecular weight polyol used in the synthesis of the above-mentioned polyester polyol and diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate or the like. Can be

Examples of the polyether polyol include polyethylene glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, or the like using the low-molecular polyol, low-molecular polyamine, or low-molecular amino alcohol used in the polyester polyol described above as an initiator. Examples thereof include polypropylene glycol, polytetramethylene ether glycol, and the like, and polyether polyols obtained by copolymerizing them, and further, polyester ether polyols using the above-described polyester polyols and polycarbonate polyols as initiators.

Examples of polyolefin polyols include hydroxyl-containing polybutadiene, hydrogenated hydroxyl-containing polybutadiene, hydroxyl-containing polyisoprene, hydrogenated hydroxyl-containing polyisoprene, hydroxyl-containing chlorinated polypropylene, and hydroxyl-containing chlorinated polyethylene.

The animal and plant polyols include castor oil polyols and silk fibroin.

In addition, as long as it has two or more active hydrogen groups, in addition to the dimer acid polyol and the hydrogenated dimer acid polyol, an epoxy resin, a polyamide resin,
Resins such as polyester resin, acrylic resin, rosin resin, urea resin, melamine resin, phenol resin, coumarone resin, and polyvinyl alcohol can also be suitably used as the long-chain polyol.

The number average molecular weight of these long-chain polyols is preferably from 500 to 10,000, particularly preferably from 1,000 to 5,000. In the present invention, considering the adhesion as an aqueous ink, durability and the like, polyester polyol,
It is more preferable that the long-chain polyol contains 50 to 100% by mass of either a polycarbonate polyol or a dimer acid-based polyol.

The chain extender is a compound containing two or more active hydrogen groups in a molecule having a number average molecular weight of less than 500,
Specifically, the above-mentioned low-molecular polyol, low-molecular polyamine, low-molecular amino alcohol and the like can be mentioned.

In the aqueous adhesive of the present invention, when a compound containing an active hydrogen group which reacts with an organic polyisocyanate and an ethylenically unsaturated double bond is used in the production of a self-emulsifying copolymer, the molecular weight can be reduced. It is preferable because control becomes easy. In this case, the acrylic oligomer and urethane have a grafted structure, and the acrylic segment and the urethane segment form a self-emulsifiable copolymer linked by a group generated by radical polymerization of an ethylenically unsaturated double bond. Will be included. Examples of the compound containing an active hydrogen group and an ethylenically unsaturated double bond include ethylenically unsaturated monomers containing an active hydrogen group among the other ethylenically unsaturated monomers described above. Of these, preferred are 2-hydroxyethyl acrylate, ε-caprolactone adduct of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and ε-caprolactone adduct of 2-hydroxyethyl methacrylate.

The hydrophilic polar group of the compound containing an active hydrogen group and a hydrophilic polar group to be reacted with the organic polyisocyanate may be a hydrophilic nonionic group, a hydrophilic anionic group, a hydrophilic cationic group, or a hydrophilic amphoteric group. Group. The hydrophilic nonionic group is a portion of a repeating unit of an oxyethylene group introduced into a main chain or a side chain of the resin. Hydrophilic anionic group, carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid,
It is composed of an acid such as phosphinic acid, thiosulfonic acid and the like, and a basic neutralizer described later. The acid component is directly linked to the self-emulsifying copolymer, but the neutralizing agent is not directly linked to the copolymer. The hydrophilic cationic group comprises a base such as a tertiary amino group and an acidic neutralizing agent described later. The base component is directly linked to the self-emulsifying copolymer, but the neutralizing agent is not directly linked to the copolymer.

Specifically, compounds containing a hydrophilic nonionic group and an active hydrogen group include poly (oxyalkylene) ether polyols having one or more active hydrogen groups.
Poly (oxyalkylene) having at least one active hydrogen group
Fatty acid ester polyols and the like. The poly (oxyalkylene) ether polyol having one or more active hydrogen groups can be obtained by addition-polymerizing an alkylene oxide using a compound having one or more active hydrogen groups as an initiator. The initiator includes methanol, ethanol,
Propanol, n-butanol, cyclohexanol,
Phenol, ethylene glycol, propylene glycol, aniline, trimethylolpropane, glycerin,
Pentaerythritol and the like. Of these, the molecular weight is smaller, such as ethylene glycol,
Bifunctional ones are preferred. Examples of the alkylene oxide include ethylene oxide and propylene oxide. Note that a compound having an epoxy group such as styrene oxide, epichlorohydrin, or butyl glycidyl ether may be used as a part of the alkylene oxide. In addition, examples of the fatty acid used for producing the poly (oxyalkylene) fatty acid ester polyol having one or more active hydrogen groups include acetic acid, propionic acid, and butyric acid. The polyether chains present in the above-mentioned raw materials are preferably those having 3 to 300, especially 5 to 200, and having 50 mol% or more, particularly 60 mol% or more of oxyethylene groups.

Compounds containing a hydrophilic anionic group-forming group and an active hydrogen group include α-hydroxypropionic acid, hydroxysuccinic acid, dihydroxysuccinic acid, ε
-Hydroxypropane-1,2,3-tricarboxylic acid,
Hydroxyacetic acid, α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, ricinoleic acid, ricinostearol acid, salicylic acid, mandelic acid, etc., oleic acid, ricinoleic acid, hydroxy hydroxylated unsaturated fatty acids such as linoleic acid Fatty acids, glutamine, asparagine, lysine, diaminopropionic acid, ornithine,
Diamine-type amino acids such as diaminobenzoic acid and diaminobenzenesulfonic acid; monoamine-type amino acids such as glycine, alanine, glutamic acid, taurine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, and sulfamic acid; or 2,2-dimethylolpropion acid,
A carboxylic acid-containing polyol such as 2,2-dimethylolbutyric acid or 2,2-dimethylolvaleric acid, a chelate type such as a 1: 1 (molar ratio) adduct of iminodiacetic acid and glycidol, and 5-sulfoisophthalic acid skeleton were introduced. Polyester polyol, polycaprolactone using water or a carboxyl group-containing alcohol as an initiator, an ester exchange product between an active hydrogen group-containing polyester and a carboxyl group-containing alcohol, an ester exchange product between an active hydrogen group-containing polycarbonate and a carboxyl group-containing alcohol, and the like. No. Further, the above-mentioned long-chain polyols and low-molecular-weight glycols, trimethylolpropane, low-molecular-weight polyols and polyamines such as glycerin, and a half-ester mixture containing a carboxyl group obtained by reacting with a polycarboxylic acid anhydride, Half amide mixtures can also be used. In particular, when a polyol is added to a dianhydride such as pyromellitic anhydride, two carboxylic acids are generated, so that a hydrophilic anionic group can be introduced into the molecular chain of the polyester polyol. As a basic neutralizing agent for forming a hydrophilic anionic group, ethylamine,
Trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine,
Organic amines such as N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, N, N-dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, pyridine and the like And alkali metals such as lithium, potassium and sodium; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and ammonia. Preferred among these are organic amines and ammonia, and particularly preferred are ethylamine, trimethylamine, triethylamine, N, N-dimethylethanolamine, and ammonia. The compound containing a hydrophilic anionic group-forming group and an active hydrogen group and the basic neutralizer may be used alone or in combination of two or more.

Compounds containing a hydrophilic cationic group-forming group and an active hydrogen group include N, N-dimethylethanolamine, N, N-diethylethanolamine,
N-dipropylethanolamine, N, N-diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine,
N, N-dimethylpropanolamine, N-methyl-N
-Ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine,
N, N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N-methyl-bis (3-aminopropyl) amine, N-methyl-
Bis (2-aminopropyl) amine and the like can be mentioned. Further, ammonia and primary amines such as methylamine, and secondary amines such as dimethylamine with alkylene oxide added thereto can also be used. Examples of the acidic neutralizing agent for forming a hydrophilic cationic group include hydrochloric acid,
Inorganic and organic acids such as acetic acid, propionic acid, lactic acid, cyanoacetic acid, phosphoric acid and sulfuric acid. Examples of the quaternizing agent include dimethyl sulfate, benzyl chloride, bromoacetamide, chloroacetamide, and alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide. Other compounds containing a hydrophilic cationic group and an active hydrogen group include cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts. In addition, these compounds containing a hydrophilic cationic group-forming group and an active hydrogen group and an acidic neutralizer may be used alone or in combination of two or more.

Examples of the compound containing a hydrophilic amphoteric group and an active hydrogen group include a compound containing an amphoteric group such as a sulfobetaine group formed by a reaction between a tertiary amino group-containing polyol and sultone. .

The amount of the hydrophilic polar group introduced into the self-emulsifying copolymer of the present invention is as follows. In the case where a hydrophilic nonionic group is introduced, the content of the hydrophilic nonionic group (preferably, ethylene oxide unit) is 0.1 to 40% by mass, particularly 0%, based on the entire self-emulsifying copolymer. 0.5 to 30% by mass is preferred. When the content of the nonionic hydrophilic polar group is out of this range, the heat resistance and water resistance of the adhesive layer tend to deteriorate. In the case of introducing a hydrophilic anionic group, a hydrophilic cationic group or a hydrophilic amphoteric group, 0.1 to 1.2 mmol based on the entire self-emulsifying copolymer.
/ G, particularly preferably 0.3 to 1.0 mmol / g. When the content of the ionic hydrophilic polar group is out of this range, the adhesion to the substrate and the stability of the water-based adhesive tend to deteriorate.

The hydrophilic polar group preferred in the present invention is a hydrophilic anionic group in consideration of the water resistance and the like of the adhesive layer.
More preferably, weak acids with 3 ≦ pKa <7 and 7 <pKa
A hydrophilic anionic group consisting of a weak base of ≦ 12 (provided that pKa = −log ₁₀ Ka and Ka is an acidity constant in a dilute aqueous solution at 25 ° C.), particularly preferably carboxylic acid-ammonia Or a hydrophilic anionic group that is a carboxylic acid-organic tertiary amine. The reason is as follows. That is, the hydrophilic anionic group is composed of an acid directly bonded to the resin and a free (free) base neutralizer. In a weak anionic group of a weak acid and a weak base, the affinity between the acid and the base is weak and the molecular weight of the neutralizing agent is small, so that the neutralizing agent is easily scattered when the adhesive layer is formed. As a result, the hydrophilicity of the resin in which the neutralizing agent has scattered is lower than before the scattering. As a result, it is considered that the water resistance of the adhesive layer is improved. From the above, in the present invention, it is preferable to use at least one of carboxylic acid-containing ethylenically unsaturated monomers and carboxylic acid group-containing polyol, and more specifically, acrylic acid, methacrylic acid,
It is preferable to use at least one or more of dimethylolpropionic acid and dimethylolbutanoic acid.

The number average molecular weight of the self-emulsifying copolymer in the aqueous adhesive of the present invention is from 5,000 to 100,000.
Is preferred, and 10,000 to 80,000 is more preferred. When the number average molecular weight is less than 5,000, the adhesive strength becomes insufficient. If it exceeds 100,000, the workability in the production of an aqueous emulsion becomes poor. The number average molecular weight in the present invention is a value measured by gel permeation chromatography using a refractive index detector in terms of polystyrene. The average particle size of the copolymer in the aqueous adhesive of the present invention is preferably from 1 to 1,000 nm, particularly preferably from 3 to 900 nm. In addition, the average particle diameter in the present invention is a value obtained by analyzing a value measured by a dynamic light scattering method by a cumulant method.

The self-emulsifying copolymer in the aqueous adhesive of the present invention preferably has a keto group or an aldehyde group. This is achieved by adding a polyfunctional hydrazide compound to an aqueous emulsion of a self-emulsifying copolymer.
This is because liquid room temperature curability can be imparted.

Examples of those used for introducing a keto group into the acrylic segment include the aforementioned ethylenically unsaturated monomers containing a keto group or an aldehyde group. As those used to introduce a keto group into the urethane segment, hydroxymethyl ethyl ketone,
Hydroxyethyl methyl ketone, bis (hydroxymethyl) ketone, hydroxymethyl-2-hydroxyethylketone, bis (2-hydroxyethyl) ketone, aminomethylethylketone, bis (aminomethyl) ketone, aminomethyl-2-aminoethylketone, bis (2-aminoethyl) ketone and the like.

In the present invention, it is preferable to introduce a keto group or an aldehyde group into at least the acrylic segment.
Considering the availability of raw materials, it is more preferable to introduce a keto group or an aldehyde group only in the acrylic segment. Further, in consideration of the toxicity of the raw material of the obtained resin, a compound into which a keto group is introduced is preferable.

Further, the aqueous adhesive of the present invention uses an aqueous emulsion comprising a self-emulsifiable copolymer having a keto group or an aldehyde group and a polyfunctional hydrazide compound. As described above, this water-based emulsion has a one-part liquid curing property at room temperature.
Unlike the two-pack type, there is no cause of measurement error between the main agent and the curing agent, and heat energy at the time of bonding is not necessary except for scattering water, so that productivity is excellent.

The polyfunctional hydrazide compound in the present invention is a compound having two or more hydrazide groups in one molecule, and specifically, 4,4'-bisbenzenedihydrazide, 2,6-pyridinedihydrazide , 1,4-cyclohexanedihydrazide, dihydrazide compounds such as N, N'-hexamethylenebissemicarbazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, Azelaic dihydrazide, sebacic dihydrazide, dodecane dihydrazide, hexadecane dihydrazide, maleic dihydrazide, fumaric dihydrazide,
Itaconic dihydrazide, terephthalic dihydrazide,
Isophthalic dihydrazide, phthalic dihydrazide,
Dicarboxylic acid dihydrazides, such as 2,6-naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, etc., citric acid trihydrazide, 1,2,4-benzenetrihydrazide, nitrilotriacetic acid Tricarboxylic acid trihydrazides such as trihydrazide, cyclohexanetricarboxylic acid trihydrazide, trimellitic acid trihydrazide, etc .; tetracarboxylic acids such as ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide and pyromellitic acid tetrahydrazide Acid tetrahydrazides, carbonic dihydrazides represented by formula 5, carbohydrazide, thiocarbodihydrazide, formula 6
And an acid hydrazide-based polymer having a group represented by the formula (7).

[0056]

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[0057]

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Preferred among these polyfunctional hydrazide compounds are those having a solubility in water at 25 ° C. of 3% or more, and particularly preferred are carbohydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, and the like. Adipic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, and citric acid trihydrazide.

The amount of the polyfunctional hydrazide compound to be added is 0.1 to the keto group or aldehyde group of the self-emulsifying copolymer.
1-2 equivalents, especially 0.3-1.5 equivalents, are preferred. When the addition amount of the polyfunctional hydrazide compound is less than 0.1 equivalent, the crosslink density is too low, and the adhesive strength becomes insufficient. If the amount exceeds 2 equivalents, the amount of the free hydrazide compound increases, so that the adhesive strength tends to be adversely affected.

Next, a method for producing the water-based emulsion of the self-emulsifying copolymer used in the present invention will be described. The method for producing an aqueous emulsion of a self-emulsifying copolymer of the present invention comprises a combination of the following three steps. First step (urethane-forming step): a step of reacting an isocyanate group with an active hydrogen group. Second step (radical copolymerization step): a step of radically polymerizing an ethylenically unsaturated monomer using a mercapto group as a chain transfer agent. Third step (emulsification step): a step of emulsifying the obtained copolymer in water.

The first step is a step for obtaining a urethane prepolymer containing a mercapto group and a hydrophilic polar group. In the first step, for example, the aforementioned organic polyisocyanate, a compound containing a mercapto group and an active hydrogen group, a compound containing a hydrophilic polar group and an active hydrogen group, and a compound containing an active hydrogen group as desired Are sequentially (a) or simultaneously (b). At this time, the final equivalent ratio of all isocyanate groups to all active hydrogen groups is determined by the factors such as the target number average molecular weight, the average number of functional groups of the organic polyisocyanate and the average number of functional groups of the active hydrogen group-containing compound. A condition is calculated that does not satisfy the condition. The compounding ratio is described in J. P. Flo
ry, Khun et al. follow the theory of gelation theoretically calculated, but in fact, by reacting at a compounding ratio that takes into account the reactivity ratio of the reactive groups contained in the components, it is possible to produce without gelation it can.

(A) When reacting sequentially, for example,
An organic polyisocyanate, a compound containing an active hydrogen group other than a hydrophilic polar group and a mercapto group, and optionally a compound containing an active hydrogen group are reacted under an isocyanate group excess condition to synthesize an isocyanate group-terminated prepolymer. Next, a urethane prepolymer containing a mercapto group and a hydrophilic polar group is obtained by, for example, reacting a compound containing a mercapto group and an active hydrogen group under an excess of active hydrogen groups including the mercapto group. (B) When reacting simultaneously, for example, an organic polyisocyanate, a compound containing an active hydrogen group other than a hydrophilic polar group and a mercapto group, a compound containing a mercapto group and an active hydrogen group, and optionally an active hydrogen group A urethane prepolymer containing a mercapto group and a hydrophilic polar group can be obtained by, for example, reacting the compound contained under an excess of active hydrogen groups including a mercapto group. In any case, the isocyanate group reacts preferentially with a hydroxyl group, an amino group, an imino group, etc., which are more reactive than the mercapto group,
Finally, a urethane prepolymer containing a mercapto group and a hydrophilic polar group free of isocyanate groups is obtained. In addition, (b) the method of reacting simultaneously
This is preferable because the number of manufacturing steps is reduced.

The urethanization reaction may be carried out in a molten state, a bulk state, or, if necessary, a solvent commonly used in the polyurethane industry, for example, an aromatic hydrocarbon solvent such as toluene, xylene or ethylbenzene, or an ester such as methyl acetate or ethyl acetate. Solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; glycol ether ester solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ether solvents such as tetrahydrofuran and dioxane; methanol and ethanol , Alcoholic solvents such as isopropanol, dimethylformamide, dimethylacetamide, N
One or more polar solvents such as -methylpyrrolidone can be used in combination. Further, at the time of the urethanization reaction, a urethanization catalyst can be used if necessary. Specific examples include organic metal compounds such as dibutyltin dilaurate and dioctyltin dilaurate; organic amines such as triethylenediamine and triethylamine; and salts thereof. The reaction temperature at this time is 30 to
120 ° C, more preferably 50-100 ° C. The reaction device is not particularly limited as long as the reaction can be performed uniformly, and for example, a reaction vessel equipped with a stirring device, a kneader,
A mixing and kneading apparatus such as a single-screw or multi-screw extrusion reactor can be used. Considering the second step and the third step, the reaction apparatus is preferably a reaction vessel equipped with a stirrer.

The raw materials in the second step include, for example, (1)
Urethane prepolymer containing mercapto group and hydrophilic polar group obtained in the first step, ethylenically unsaturated monomer, radical polymerization initiator, or (2) organic polyisocyanate, hydrophilic polar group and activity (other than mercapto group) A compound containing a hydrogen group, a compound containing a mercapto group and an active hydrogen group, and optionally (another) a compound containing an active hydrogen group, an ethylenically unsaturated monomer, and a radical polymerization initiator. That is, the method (1) is a method in which the second step proceeds after the first step, and the method (2) is a method in which the first step and the second step are simultaneously performed. In the second step,
It is preferable to use the above-mentioned organic solvent because of easy removal of reaction heat and easy stirring. In the present invention, the method (1) is preferred.

The specific method of charging each raw material in the second step is not particularly limited, and all raw materials may be charged at once or may be divided and charged. Further, they may be charged in batches or may be charged continuously. A preferable charging method is a method in which the reaction system is charged later by at least dropping a radical polymerization initiator.

In the method (1), a urethane prepolymer containing a mercapto group and a hydrophilic polar group can be obtained.
The number average molecular weight of this urethane prepolymer is 1,000.
It is preferably from 50,000 to 50,000, particularly preferably from 3,000 to 40,000. If the number average molecular weight is too small, the urethanization reaction is insufficient, so that it tends to lack flexibility. On the other hand, when the number average molecular weight exceeds 50,000, the second step and the third step tend to be difficult because the viscosity is too large.

The content of the mercapto group before the radical copolymerization is 0.01 to 1.0 mmol in terms of solid content.
/ G, particularly preferably 0.03 to 0.5 mmol / g. Mercapto group content is 0.01 mmol / g
If it is less than the desired value, the desired self-emulsifying copolymer is difficult to obtain. The mercapto group content is 1.0 mmol / g
When the number is more than 1, chain transfer occurs more than necessary, and the molecular weight of the copolymer becomes difficult to elongate. The use of a compound containing an active hydrogen group and an ethylenically unsaturated double bond in the reaction system is preferred because the molecular weight of the obtained self-emulsifying copolymer is easily controlled. The amount of the compound introduced is preferably 80 mol% or less, more preferably 5 to 75 mol%, and more preferably 10 to 70 mol%, based on the mercapto group.
Is most preferred.

The amount of the polymerization initiator charged in the radical copolymerization is 0.1 to 0.1 times the total number of moles of the double bond existing before the reaction.
10 mol%, especially 0.5 to 8 mol%, is preferred. When the charged amount of the radical polymerization initiator is too small, the copolymerization is difficult to proceed well, and it is difficult to obtain a target copolymer. When the amount of the radical polymerization initiator charged is too large, the molecular weight of the obtained copolymer is too small, and the strength and durability tend to be insufficient.

The reaction temperature during the radical copolymerization is from 30 to 1
20 ° C, especially 50-100 ° C, is preferred.

The total weight of the ethylenically unsaturated monomers,
The ratio of the urethane raw material to the charged weight is 5/95 to 95.
/ 5, particularly preferably 10/90 to 90/10. When the amount of the ethylenically unsaturated monomer is larger than this ratio, the adhesiveness of the water-based adhesive to the polar base material tends to decrease.
If the amount is small, the resolubility of the water-based adhesive tends to be poor.

When the first step and the second step are completed, the third step
Proceed to process. The emulsification method is not particularly limited, and is performed by a conventionally known method. When an acid or a tertiary amine is present in the system, it is preferable to charge the neutralizing agent or the quaternizing agent before charging the water or simultaneously with the water. After the emulsification with water, if an organic solvent is present in the system, it is preferable to remove the solvent. The content of the residual solvent in the aqueous emulsion of the present invention is preferably less than 5%. The removed organic solvent can be recovered and used in the second step.

The water-based adhesive of the present invention may contain, if necessary, a pigment, a water-based emulsion of the self-emulsifying copolymer.
Other resin emulsions, suspensions, dispersions, aqueous solutions such as dyes, polyurethanes, acrylic resins, polyesters, polyolefins, polyamides, rubbers,
Water for solid content and viscosity adjustment, organic solvents such as isopropanol and N-methylpyrrolidone for surface tension adjustment, preservatives, antifungal agents, antibacterial agents, antiblocking agents,
Dispersion stabilizer, thixotropic agent, antioxidant, ultraviolet absorber, antifoaming agent, thickener, film forming aid, surfactant, filler, catalyst,
It is obtained by blending a lubricant, an antistatic agent, a plasticizer, a leveling agent, an anti-gelling agent, a light stabilizer, an antistatic agent and the like, and using a ball mill, a sand grind mill or the like.

In the case of an aqueous adhesive in which a keto group or an aldehyde group is present in the self-emulsifying copolymer and a polyfunctional hydrazide compound is blended in an aqueous emulsion, water is scattered after bonding, so that the adhesive is cured at room temperature. A practically usable adhesive layer is formed. Further, when a water-based polyisocyanate-based curing agent is added immediately before the application of the adhesive to give the adhesive layer a crosslinked structure, the adhesive strength is further improved. In this case, (generate)
Heating may be performed to promote the reaction between the isocyanate group and the active hydrogen group. This water-based polyisocyanate-based curing agent is a water-based polyisocyanate in which an isocyanate group may be blocked, so that the blocking agent does not come off during curing and the adhesiveness is not reduced.
Aqueous polyisocyanates in which isocyanate groups are not blocked are preferred, and self-emulsifying polyisocyanates in which isocyanate groups are not blocked are more preferred. Specific examples of the curing agent include Aquanate 100 and 200 manufactured by Nippon Polyurethane Industry. When an aqueous polyisocyanate-based curing agent is used, the compounding amount thereof is (generated) isocyanate groups / active hydrogen groups = 10
/ 1 to 1/10 (molar ratio).

The water-based adhesive of the present invention can be used for plastic materials such as vinyl chloride, polystyrene and polyethylene, paper,
It is useful for bonding the same or different materials to be adhered, such as various cellulosic materials such as cloth and wood, inorganic materials such as concrete, slate and calcium silicate, and metal materials such as aluminum foil and copper foil.

The aqueous adhesive of the present invention can be applied by a known method, for example, using an apparatus or equipment such as a roll coater, knife coater, bar coater, spray, or brush.

The amount of the aqueous adhesive applied is 1 to 10
g / m ² is preferred. If the coating amount is too small, the adhesive strength becomes insufficient, and if it is too large, it takes time to give an impression,
Productivity tends to decrease.

The applied water-based adhesive is preferably dried before bonding, except when bonding a porous substance such as paper. Drying may be performed under any condition of normal temperature or heating, but in any case, drying is preferably performed until water evaporates and a uniform adhesive layer is formed.

The bonding is usually performed by applying pressure, but at this time, using a nip roll, a press or the like.
At this time, heating may be performed or room temperature may be performed. However, it is preferable to perform pressure bonding while heating, since adhesive force is easily developed in a short time. In this case, the preferable crimping condition is 5
0.1 to 2 MPa at 0 to 150 ° C.

The water-based adhesive obtained by the present invention includes structural members such as ceilings, outer walls and indoor walls, decorative boards, laminated films, various panels, label seals, and the like.
Automotive interiors, furniture and the like.

[0081]

The aqueous adhesive of the present invention uses an aqueous emulsion of a self-emulsifiable copolymer by a radical reaction of a mercapto group. , The adhesion is good. In addition, when compared with a conventional acrylic-urethane copolymer,
Since the possibility of gelation is low, stable production can be achieved.

[0082]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Unless otherwise specified, “%” in Synthesis Examples, Examples and Comparative Examples
Means “% by mass”.

[Synthesis of Urethane Prepolymer] Synthesis Example 1 400 g of polyol A and 14.9 g of DMBA were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen sealed tube, and a cooler.
HEMA 9.1 g, MHE 10.1 g, MEK 5
6 g was charged and dissolved at 50 ° C. Next, after adding 67.3 g of HDI and 0.05 g of DBTDL, 75
The reaction was carried out at 0 ° C until the peak of the isocyanate group disappeared by infrared absorption analysis. Then, MEK 195g, I
251 g of PA was charged, and a urethane prepolymer solution PA containing a mercapto group and a hydrophilic polar group having a solid content of 50.0% PA
-1 was obtained. The number average molecular weight of this PA-1 was 5,000.
0, no keto group was contained, the mercapto group content was 0.26 mmol / g, and the carboxylic acid content was 0.20 mmol / g in terms of solid content.

Synthesis Examples 2 to 4 and 6 to 7 In the same manner as in Synthesis Example 1, P
A-2 to 4, 6 to 7 were synthesized. The results are shown in Tables 1 and 2.

Synthesis Example 5 In the same reactor as in Synthesis Example 1, 400 g of polyol E was added.
13.4 g of DMPA and 212 g of MEK were charged, and 50
Dissolved at ° C. Then, 88.9 g of IPDI and D
After charging 0.15 g of BTDL, the mixture was reacted at 75 ° C. for 4 hours to obtain an isocyanate group-terminated prepolymer solution. Then, MEA 15.4g, MEK 42g, I
An amine solution consisting of 254 g of PA was charged and a solid content of 4% was obtained.
A 9.8% mercapto group- and carboxyl group-containing urethane prepolymer solution PA-5 was obtained. PA-5 had a number average molecular weight of 5,000, no keto group, and a solid content of 0.39 mmol / g mercapto group and 0.19 mmol / g carboxylic acid.

[0086]

[Table 1]

[0087]

[Table 2]

In Synthesis Examples 1 to 7 and Tables 1 and 2, polyol A: polycaprolactone diol using ethylene glycol as an initiator (number average molecular weight: 2,000) Polyol B: ethylene glycol / neopentyl glycol = 8/2 ( Polyester diol (number average molecular weight: 2,000) obtained from a mixed glycol having a molar ratio of 5) and a mixed dicarboxylic acid having an adipic acid / isophthalic acid ratio of 5/5 (molar ratio). Polyol C: dimer acid and 1,6-hexanediol Dimer acid diol (number average molecular weight 2,
000) Polyol D: Polyester diol obtained from 3-methyl-1,5-pentanediol and adipic acid (number-average molecular weight 2,000) Polyol E: 1,6-hexanediol / neopentyl glycol = 8/2 (mol) Polyesterdiol (number average molecular weight: 2,000) obtained from a mixed glycol having the following ratios) and adipic acid: DMBA: dimethylolbutanoic acid DMPA: dimethylolpropionic acid MHE: 2-mercapto-1-hydroxyethane TGL: thioglycerol MEA: β - mercaptoethylamine HMK: bis (hydroxymethyl) ketone HEMA: 2-hydroxyethyl methacrylate EtOH: ethanol HDI: hexamethylene diisocyanate H ₆ -XDI: hydrogenated xylylene diisocyanate H _12- MDI: hydrogenated diphenylmethane diisocyanate IPDI: isophorone diisocyanate DBTDL: dibutyltin dilaurate MEK: methyl ethyl ketone IPA: isopropanol

[Synthesis of Self-Emulsifying Acrylic-Urethane Copolymer] Synthesis Example 8 PA-1 was added to a dropping tank of a reactor (tank) equipped with a stirrer, thermometer, nitrogen seal tube, cooler, and dropping tank. 30.0
g, MMA 3.3 g, BA 25.0 g, St 3.0.
8 g, 0.5 g of AA, 2.5 g of DAAA, AIBN
1.0 g, MEK 25 g, IPA 25 g,
Mix evenly. On the other hand, PA-1 was charged with 30.
0 g, MMA 3.2 g, BA 25.0 g, St 3.7 g, AA 0.5 g, DAAA 2.5 g, ME
10 g of K and 10 g of IPA were charged and uniformly mixed.
Next, the reaction tank was heated to 75 ° C., and the mixture in the dropping tank was dropped over 5 hours. Thereafter, the reaction was further performed at the same temperature for 7 hours. Thereafter, 2.0 g of TEA was charged and neutralized sufficiently, and hydrazide water consisting of 149 g of distilled water and 2.6 g of ADH was charged and emulsified. Then 60
MEK and IPA present in the system were removed at 1 ° C. × 13.3 kPa to obtain a self-emulsifiable acrylic-urethane copolymer aqueous emulsion EA-1 having a solid content of 40.1%.
I got EA-1 has a viscosity of 80 mPa · s (25 ° C.)
The number average molecular weight of the acrylic-urethane copolymer is 350,000.
The average particle size is 180 nm, the keto group content is 0.29 mmol / g in terms of solid content, and the carboxylate content is 0.1.
20 mmol / g.

Synthesis Example 9 1.0 g of AIBN, 25 g of MEK, IPA
Was charged and uniformly mixed. On the other hand, in the reaction tank,
PA-1 60.0 g, MMA 6.5 g, BA 5
0.0 g, St 7.5 g, AA 1.0 g, DAAA
5.0 g, MEK 10 g, IPA 10 g,
Mix evenly. Next, the reaction tank was heated to 75 ° C., and the mixture in the dropping tank was dropped over 5 hours. Thereafter, the reaction was further performed at the same temperature for 7 hours. After that, TEA is increased to 2.0
g, neutralize it sufficiently, and then add 149 g of distilled water.
Emulsified. Then, at 60 ° C. × 13.3 kPa, MEK and IPA present in the system were removed to obtain an aqueous emulsion EA-2 of a self-emulsifiable acrylic-urethane copolymer having a solid content of 40.0%. Was. The viscosity of EA-2 is 7
0 mPa · s (25 ° C.), the number average molecular weight of the acrylic-urethane copolymer is 35,000, and the average particle size is 160 n.
m, the keto group content is 0.29 mmol /
g, carboxylate content was 0.20 mmol / g.

Synthesis Example 10 In a reactor (tank) equipped with the same dropping tank as in Synthesis Example 8, 26.9 g of MMA, 18.1 g of BA, and DA were added.
5.0 g of AA, 1.0 g of BPO, 25 g of MEK,
25 g of IPA was charged and uniformly mixed. On the other hand, 100.0 g of PA-2 was charged into the reaction vessel, heated to 75 ° C., and the mixture in the dropping vessel was dropped over 5 hours. Thereafter, the reaction was further performed at the same temperature for 7 hours. Thereafter, 0.9 g of TEA was charged and neutralized sufficiently, and hydrazide water consisting of 150 g of distilled water and 3.1 g of GDH was charged and emulsified. Thereafter, at 60 ° C. × 13.3 kPa, MEK and IPA present in the system were removed, and the solid content was 4%.
0.3% of a self-emulsifiable acryl-urethane copolymer aqueous emulsion EA-3 was obtained. The viscosity of EA-3 is 19
0 mPa · s (25 ° C.), the number average molecular weight of the acrylic-urethane copolymer is 32,000, and the average particle size is 140 n.
m, the keto group content is 0.38 mmol /
g and carboxylate content were 0.09 mmol / g.

Synthesis Example 11 4.2 g of MMA, 1.4 g of BA, and CHMA were placed in a dropping tank of a reactor (tank) equipped with the same dropping tank as in Synthesis Example 8.
8.5 g, DAAA 1.0 g, BPO 0.8 g,
15 g of MEK and 15 g of IPA were charged and uniformly mixed. On the other hand, 140.0 g of PA-3, MM
4.1 g of A, 1.3 g of BA, 8.5 g of CHMA,
1.0 g of DAAA was charged and uniformly mixed. Then
The mixture was heated to 75 ° C., and the mixture in the dropping tank was dropped over 5 hours. Thereafter, the reaction was further performed at the same temperature for 7 hours. Thereafter, 3.2 g of TEA was charged and neutralized sufficiently, and then hydrazide water consisting of 150 g of distilled water and 2.9 g of ADH was charged and emulsified. Then, 60 ° C x 13.3 kP
In a, MEK and IPA existing in the system were removed to obtain a self-emulsifiable acryl-urethane copolymer aqueous emulsion EA-4 having a solid content of 39.9%. EA-4
Has a viscosity of 250 mPa · s (25 ° C.), a number average molecular weight of the acryl-urethane copolymer is 30,000, an average particle diameter is 100 nm, and a keto group content is 0.33 m in terms of solid content.
mol / g, carboxylate content is 0.32 mmol /
g.

Synthesis Example 12 Using the raw materials shown in Table 3, an ethylenically unsaturated monomer, an initiator, a solvent and a urethane prepolymer were charged into a dropping tank, and reacted in the same manner as in Synthesis Example 10 to obtain a solid. A water-based emulsion EA-5 of a self-emulsifiable acrylic-urethane copolymer having a content of 30.2% was obtained. The viscosity of EA-5 is 4
0 mPa · s (25 ° C.), the number average molecular weight of the acrylic-urethane copolymer is 28,000, the average particle size is 50 nm,
In terms of solid content, the keto group content was 0.15 mmol / g, and the carboxylate content was 0.46 mmol / g.

Synthesis Example 13 Using the raw materials shown in Table 3, an initiator, a solvent and a urethane prepolymer, an ethylenically unsaturated monomer and a solvent were charged into a dropping tank and reacted in the same manner as in Synthesis Example 9. ,
An aqueous emulsion EA-6 of a self-emulsifiable acryl-urethane copolymer having a solid content of 40.2% was obtained. The viscosity of EA-6 is 20 mPa · s (25 ° C.), the number average molecular weight of the acrylic-urethane copolymer is 45,000, and the average particle size is 20.
0 nm, the keto group content is 0.59 mmol in terms of solid content.
/ G, carboxylate content was 0.30 mmol / g.

Synthesis Example 14 In a reactor (tank) equipped with the same dropping tank as in Synthesis Example 8, 25.9 g of MMA, 18.1 g of BA, and AA
1.0 g, DAAA 5.0 g, AIBN 1.0
g, 25 g of MEK and 25 g of IPA were uniformly mixed. On the other hand, the reaction tank was charged with 37.3% of polyol F.
g, 1.4 g of DMBA, 1.0 g of MHE, 1.7 g of HMK, 0.8 g of HEMA, and 25 g of MEK, and dissolved at 50 ° C. Then, 7.8 g of HDI
After charging, the mixed solution in the dropping tank was dropped at 75 ° C. over 5 hours. Thereafter, the reaction was further performed at the same temperature for 7 hours. Thereafter, an amine solution consisting of 25 g of IPA and 1.7 g of DMEA was charged and sufficiently neutralized.
Hydrazide water consisting of 1 g and 3.0 g of ADH was charged and emulsified. Thereafter, at 60 ° C. × 13.3 kPa, MEK and IPA present in the system were removed,
An aqueous emulsion EA-7 of a self-emulsifiable acrylic-urethane copolymer having a solid content of 39.8% was obtained. The viscosity of EA-7 is 200 mPa · s (25 ° C.), the number average molecular weight of the acrylic-urethane copolymer is 33,000, and the average particle size is 1
10 nm, the keto group content in terms of solid content is 0.34 mmol
l / g and the carboxylate content was 0.19 mmol / g.

Synthesis Examples 15 to 17 Using the raw materials shown in Table 4, an ethylenically unsaturated monomer, an initiator, a solvent and a urethane prepolymer were charged into a dropping tank and reacted in the same manner as in Synthesis Example 10. Water-based emulsion E of self-emulsifying acrylic-urethane copolymer
A-8, EB-1, and 2 were synthesized. The solid content of EA-8 is 29.9%, the viscosity is 30 mPa · s (25 ° C.), the number average molecular weight of the acrylic-urethane copolymer is 34,000,
The average particle size was 40 nm, the keto group was not contained in terms of solid content, and the carboxylate content was 0.69 mmol / g. EB-1 gelled when a urethane prepolymer and an ethylenically unsaturated monomer were radically copolymerized, so that the subsequent steps were omitted. The solid content of EB-2 is 4
0.1%, viscosity 1,200 mPa · s (25 ° C.), average particle size of acryl-urethane copolymer 200 nm, keto group content 0.29 mmol / g in terms of solid content, carboxylate content Was 0.20 mmol / g. In addition, when the number average molecular weight of EB-2 was measured, two molecular weight distributions were measured. Therefore, the number average molecular weight of each distribution was described. This is presumably because the urethane prepolymer hardly undergoes chain transfer because there is no mercapto group in the reaction system, and thus the acrylic resin and the polyurethane resin are in a state close to a mere blend.

[Synthesis of Self-Emulsifying Acrylic Polymer] Synthesis Example 18 1.0 g of AIBN, 40 g of MEK, IPA were placed in a dropping tank of a reactor (tank) equipped with a dropping tank similar to that of Synthesis Example 8.
Was charged and uniformly mixed. On the other hand, in the reaction tank,
56.0 g of MMA, 34.6 g of BA, 4.4 of AA
g, 5.0 g DAAA, 10 g MEK, 1 IPA
0 g was charged and mixed uniformly. Next, the reaction tank was heated to 75 ° C.
, And the mixture in the dropping tank was dropped over 5 hours. Thereafter, the reaction was further performed at the same temperature for 7 hours. afterwards,
After 6.2 g of TEA was charged and neutralized sufficiently, 2 parts of distilled water was added.
Hydrazide water consisting of 28 g and 2.6 g of ADH was charged and emulsified. Thereafter, at 60 ° C. × 13.3 kPa, MEK and IPA present in the system were removed,
An aqueous emulsion EB-3 of a self-emulsifying acrylic polymer having a solid content of 30.0% was obtained. EB-3 has a viscosity of 80 mP
a · s (25 ° C.), number average molecular weight of acrylic polymer is 4
The average particle diameter was 3,000, the keto group content was 0.29 mmol / g, and the carboxylate content was 0.61 mmol / g in terms of solid content.

[Synthesis of Self-Emulsifying Polyurethane] Synthesis Example 19 400 g of polyol F was placed in the same reactor as in Synthesis Example 1.
44.6 g of DMBA, 18.0 g of HMK, and 52 g of MEK were charged and dissolved at 50 ° C. Next, HDI
After charging 106.0 g and 0.05 g of DBTDL,
The reaction was performed at 75 ° C. for 4 hours. Then, EtOH was added to 2.
After charging 8 g to eliminate residual isocyanate groups,
183 g of EK, 235 g of IPA, 5.3 g of TEA
Was neutralized sufficiently, and hydrazide water composed of 228 g of distilled water and 1.5 g of ADH was charged and emulsified. Then, 60 ° C x 13.3 kP
In a, MEK and IPA present in the system were removed to obtain a self-emulsifiable acryl-urethane copolymer aqueous emulsion EB-4 having a solid content of 30.2%. EB-4
Has a viscosity of 4,000 mPa · s (25 ° C.), a number average molecular weight of the polyurethane of 30,000 and an average particle size of 30 n.
m, the keto group content is 0.18 mmol /
g, carboxylate content was 0.53 mmol / g.

[0099]

[Table 3]

[0100]

[Table 4]

In Tables 3 and 4, MMA: methyl methacrylate BA: n-butyl acrylate AA: acrylate EHA: 2-ethylhexyl acrylate AN: acrylonitrile St: styrene CHMA: cyclohexyl methacrylate HEMA: 2-hydroxyethyl methacrylate DAAA: Diacetone acrylamide AIBN: 2,2'-azobisisobutyronitrile BPO: benzoyl peroxide ADH: adipic dihydrazide GDH: glutaric dihydrazide Polyol F: polycarbonate diol obtained from 1,6-hexanediol and diethyl carbonate (P
CD) and transesterification product of polycaprolactone diol (PCL) with ethylene glycol as initiator (PC
D / PCL = 8/2) (number average molecular weight 2,000) DMBA: dimethylolbutanoic acid MHE: 2-mercapto-1-hydroxyethane HMK: bis (hydroxymethyl) ketone EtOH: ethanol HDI: hexamethylene diisocyanate DBTDL: Dibutyltin dilaurate TEA: Triethylamine DMEA: N, N-dimethylethanolamine MEK: Methyl ethyl ketone IPA: Isopropanol

[Preparation of Adhesive-1] Example 1 Water was added to 100 g of aqueous emulsion EA-1 for 60 g.
(g) to prepare a (water-based) adhesive.

Examples 2 to 8 and Comparative Examples 1 to 4 The water-based emulsions EA-2 to 8 and EB-2 to 4 were used in place of the water-based emulsion EA-1, and the (water-based) adhesive was formulated as shown in Table 5. Was prepared.

[Adhesion Test-1] The prepared (water-based) adhesive was used as a bar coater No. In 6, the coating amount is 2 g / dry
As will become m ^2, and was applied to both sides by the combination of corona treated PET film / aluminum foil. The adhesive was applied to the adherend, and after taking an open time of 80 ° C. × 5 seconds, it was immediately bonded at 100 ° C. × 0.3 MPa. After bonding, it was allowed to stand at 50 ° C. × 24 hours. . Then 15
It was cut to a width of mm, and a T-type peel test was performed at a tensile speed of 50 mm / min and a measurement atmosphere of 25 ° C. × 50% RH. Table 5 shows the results of the adhesion test (adhesion strength (1)).

[0105]

[Table 5]

[Preparation of Adhesive-2] Example 9 Aquanate 100 (self-emulsifying polyisocyanate manufactured by Nippon Polyurethane Industry, isocyanate content = 17.0%) based on 100 g of aqueous emulsion EA-1
4.0 g, 17.6 g of isopropanol and 60 g of water were added to prepare an (aqueous) adhesive.

Examples 10 to 16 and Comparative Examples 5 to 8 Using the aqueous emulsions EA-2 to 8 and EB-2 to 4 in place of the aqueous emulsion EA-1, (aqueous) Was prepared.

[Adhesion Test-2] Prepared (Aqueous) Adhesive
Was applied in a dry amount of 2 g / m as in the adhesion test-1. ²
 Corona-treated PET film / Aluminum
Foil, corona treated CPP film / aluminum foil combination
And applied on both sides. Apply adhesive to adherend, 80 ℃
After taking 5 seconds of open time, immediately 100 ℃ x
Laminated at 0.3MPa, 50 ℃ × 24 after lamination
It was left still under the condition of time. Then cut to 15mm width
And tensile speed: 50 mm / min, measuring atmosphere: 25 ° C. × 5
A T-type peel test was performed at 0% RH. Also, bonding
Bent the test piece 100 times and observe the condition of the adhesive surface.
Was. Table 6 shows the results of the adhesion test (adhesion strength (2)).

[Adhesion Test-3] A prepared (water-based) adhesive was coated on a stainless steel plate (SUS304: width 25 mm, length 1).
25mm, thickness 2mm) and dry on canvas 4
g / m ² , apply an open time of 80 ° C. × 3 minutes, immediately bond at 80 ° C. × 1 MPa × 5 minutes, and after bonding, stir at 25 ° C. × 24 hours. Was placed. Thereafter, a 90 ° C. peel test was performed at a tensile speed of 50 mm / min and a measurement atmosphere of 25 ° C. × 50% RH.
Table 6 shows the results of the adhesion test (adhesion strength (3)).

[0110]

[Table 6]

Examples 1 to 16, Comparative Examples 1 to 8, Tables 5 and 6
In AL: Aluminum foil PET: Corona-treated polyethylene terephthalate CPP: Unstretched corona-treated polypropylene Adhesive strength measurement unit: N / cm Flexibility: ○ → No abnormality × → Destruction of adhesive layer, etc.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ichiro Higashikubo 3-5-37 Tsunashimahigashi, Kohoku-ku, Yokohama, Kanagawa Prefecture (72) Inventor Akira Kanno 3-5-37, Tsunashimahigashi, Kohoku-ku, Yokohama, Kanagawa Prefecture (72) Inventor Toshiaki Sasahara 3-34-27 Hongo, Seya-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Kazuya Sugimoto 4-1-10 Sakurada, Washinomiya-cho, Kita-Katsushika-gun, Saitama F-term (reference) 4J040 DL151 EF231 EF281 EF351 EF351 GA06 GA24 HC15 JA03 KA16

Claims (8)

[Claims] 1. An aqueous emulsion containing, as a resin component, a self-emulsifying copolymer in which an ethylenically unsaturated monomer and a urethane prepolymer containing a mercapto group and a hydrophilic polar group are bonded by radical polymerization. Water-based adhesive. 2. A self-bonded product comprising an ethylenically unsaturated monomer, an organic polyisocyanate, a compound containing a mercapto group and an active hydrogen group, and a compound containing a hydrophilic polar group and an active hydrogen group by a urethanation reaction and radical polymerization. An aqueous adhesive comprising an aqueous emulsion containing an emulsifying copolymer as a resin component. 3. The aqueous adhesive according to claim 1, wherein the ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least a hydrophilic polar group-containing ethylenically unsaturated monomer. 4. The aqueous adhesive according to claim 1, wherein the ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least a keto group or aldehyde group-containing ethylenically unsaturated monomer. 5. The urethane prepolymer containing a mercapto group and a hydrophilic polar group is a urethane prepolymer further containing an ethylenically unsaturated double bond in addition to the mercapto group and the hydrophilic polar group. Or the aqueous adhesive according to 4. 6. The urethane prepolymer containing a mercapto group and a hydrophilic polar group, a urethane prepolymer containing a keto group or an aldehyde group in addition to the mercapto group and the hydrophilic polar group, or a mercapto group, a hydrophilic polar group and ethylene The aqueous adhesive according to claim 1, 3 or 4, which is a urethane prepolymer containing a keto group or an aldehyde group in addition to the unsaturated double bond. 7. An aqueous adhesive comprising the aqueous adhesive according to claim 4, 5 and 6, and a polyfunctional hydrazide compound. 8. An aqueous adhesive comprising the aqueous adhesive according to any one of claims 1 to 7 and an aqueous polyisocyanate-based curing agent.