JPH083021B2 - Aqueous acrylic-polyester graft resin composition and aqueous coating agent or aqueous ink using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room temperature crosslinkable aqueous coating resin composition based on a condensation polymer containing a polyester segment and a graft copolymer based on a vinyl polymer. More specifically, it has excellent adhesion to plastic substrates such as polypropylene and polyester, and is water resistant, hot water resistant, and has excellent durability such as solvent resistance, and a room temperature crosslinking aqueous resin composition and an aqueous coating agent using the same. It relates to water-based ink.

[0002]

2. Description of the Related Art As the problems of global environmental pollution and global warming become more serious, there is an increasing trend in the field of coating agents / inks to replace conventional solvent type coating agents / inks with water-based ones. Under these circumstances, water-based paints with coating film properties (wear resistance, adhesion, weather resistance, heat resistance, water resistance, solvent resistance) and coating workability that are comparable to conventional solvent-type coating resins. Demand for coating resins is growing, but at the current technology level,
The technical level of water-based resin has not yet reached the level of replacing solvent-based paints.

As the polyester-based water-soluble coating resin, a linear aqueous high-molecular-weight polyester resin containing a sulfonic acid group has been proposed as an undercoat agent for imparting easy adhesion to a polyester film (US
P4476189). In order to improve the adhesiveness of the coating agent, a method of modifying with an acrylic resin or a method of grafting a hydrophilic polyester resin with the acrylic resin as a trunk polymer has been proposed (Japanese Patent Laid-Open No. 63-
46237, JP-A-63-34139). By modifying acrylic resin of water-based high molecular weight polyester resin, not only easy adhesion to polyester film but also easy adhesion to polypropylene film is exhibited, but it is not enough when considering application to fields such as laminating adhesives. It remains at a good level. In these polyester-acrylic composite coating resins based on the prior art, because of the ionic groups and / or hydrophilic groups introduced to impart water solubility or water dispersibility to the polyester resin, these Under the present circumstances, the water resistance and hot water resistance of the coating film from the above coating resin are inferior to the solvent type polyurethane resin.

As described above, polyester (PE
T) and polypropylene (OPP), which have different polarities and are closely adhered to each other, have water resistance,
It was extremely difficult to produce a polyester-based water-based coating resin that gives a coating film having hot water resistance, solvent resistance, heat resistance, abrasion resistance, etc., within the range of conventional techniques.

[0005]

Under the circumstances, the present inventors have excellent adhesion to both polyester and polypropylene materials, and have excellent water resistance, hot water resistance, solvent resistance, heat resistance, wear resistance, etc. The inventors have made earnest studies on a method of obtaining an aqueous resin that gives an excellent coating film.

[0006]

The present inventors have arrived at the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the above-mentioned object of the present invention is

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[Chemical 4] Of 5% to 70% by weight of a polyester segment-containing polymer containing a polymerizable unsaturated monomer having a ketone group and a polymerizable unsaturated monomer having a carboxyl group. A resin mainly composed of a graft copolymer obtained by graft-polymerizing an unsaturated monomer mixture, and a room temperature-curable aqueous resin composition obtained by dissolving or dispersing a polyfunctional hydrazide compound in an aqueous medium. Can be achieved. The resin composition of the present invention has coating film properties similar to those of conventional solvent-type coating resins and is used for water-based coating agents and water-based inks.

Hereinafter, the present invention will be described in detail. Corresponds to the trunk polymer of the graft copolymer contained in the aqueous resin composition of the present invention

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[Chemical 6] The polyester segment containing is produced, for example, by the following method. That is, it can be obtained by carrying out a polycondensation reaction between a mixture of various diol compounds and a mixture of various dicarboxylic acids containing terephthalic acid (and / or isophthalic acid).

Examples of the diol compound include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol, bisphenol A ethylene oxide adduct, dimethylolpropionic acid, polycaprolactone, polyethylene glycol, polytetramethylene glycol, bisphenol Examples thereof include ethylene oxide adducts of S.

Specific examples of the dicarboxylic acid compound include:
Terephthalic acid, isophthalic acid, orthophthalic acid, 2,6
-Naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid,
Glutaric acid, adipic acid, suberic acid, azelaic acid,
Examples thereof include sebacic acid, dodecanedioic acid, dimer acid, maleic anhydride and the like. Hydroxypivalic acid having both a hydroxyl group and a carboxyl group in the molecule, p-hydroxybenzoic acid and the like can also be used in the production of the polyester polymer of the present invention.

The copolymerized polyester resin of the present invention is produced by a known production technique of a saturated polyester resin having a high molecular weight, that is, a DMT method (transesterification method) or a direct polymerization method using a known transesterification catalyst and a polymerization catalyst. can do. More specifically, in the case of the DMT method, diol components such as ethylene glycol, neopentyl glycol, butanediol and pentanediol, and sodium salts of dimethyl terephthalate, dimethyl isophthalate and dimethyl 5-sulfoisophthalate are used. The transesterification reaction is carried out at 1, then polycondensation is carried out under reduced pressure to obtain the copolyester resin containing SO ₃ M groups of the present invention.

When carrying out this transesterification reaction,
The molar ratio of diol to diester is 1.0 times or more,
It is preferable to use 1.1 times or more. To carry out this transesterification reaction, a commonly used catalyst such as manganese acetate, zinc acetate or calcium acetate tetra-n-butyl titanate may be used. The transesterification reaction is generally carried out at a temperature of 150 to 250 ° C under normal pressure. The transesterification reaction usually has a reaction rate of 50 to 90%.
It is appropriate to continue to the range of. After the completion of the transesterification reaction, phosphoric acid, trimethyl phosphate, sulfuric acid, p-toluenesulfonic acid, etc. are usually added to deactivate the transesterification catalyst.

After deactivating the transesterification catalyst, the catalyst is added to the reaction mixture and the polycondensation reaction is carried out under reduced pressure to obtain the copolyester resin of the present invention. Examples of commonly used catalysts include antimony trioxide, germanium dioxide, tetra-n-butyl titanate and the like. The polycondensation reaction is usually performed at 220 to 280 ° C. under a high vacuum of 0.5 Torr or less.

As the polymer containing a polyester segment used in the present invention, a copolyester resin having a hydroxyl group at the terminal synthesized by the above method may be used as it is, but this copolyester resin is suitable. A polymer (urethane-modified polyester) which has been chain-extended by reacting with a diisocyanate compound may be used. The use of this urethane-modified polyester is preferable in that a coating film having excellent transparency can be obtained from the coating resin composition of the present invention.

Typical examples of the polymer containing a polyester segment include the types shown below. (1) Copolyester (EG / N) consisting of ethylene glycol (EG), neopentyl glycol (NPG), terephthalic acid (TPA) and isophthalic acid (IPA)
PG = 50/50 (molar ratio), TPA / IPA = 50 /
50 (molar ratio), OH value = 5 to 50 mg-KOH / g) (2) Ethylene glycol, neopentyl glycol,
Copolyester consisting of terephthalic acid, isophthalic acid and sebacic acid (SA) (EG / NPG = 50/50)
(Molar ratio), TPA / IPA / SA = 45/45/10
(Molar ratio), OH value = 5 to 50 mg-KOH / g)

(3) Copolyester consisting of ethylene glycol, bisphenol A ethylene oxide adduct (Bis-AEO), terephthalic acid and isophthalic acid (EG / Bis-AEO = 75/25 (molar ratio), TP
A / IPA = 50/50 (molar ratio), OH value = 5-50
mg-KOH / g) (4) ethylene glycol, neopentyl glycol,
Copolyester consisting of terephthalic acid and sebacic acid (EG / NPG = 60/40 (molar ratio), terephthalic acid / sebacic acid = 70/30 (molar ratio), OH value = 5-5
0 mg-KOH / g)

(5) Copolyester consisting of butanediol, terephthalic acid, isophthalic acid and sebacic acid (TPA / IPA / SA = 33/33/34 (molar ratio), OH value = 5 to 50 mg-KOH / g) (6) ethylene glycol, neopentyl glycol,
Copolyester oligomer composed of terephthalic acid and isophthalic acid (EG / NPG = 50/50 (molar ratio),
TPA / IPA = 50/50 (molar ratio), OH value = 15
~ 50 mg-KOH / g) to a diisocyanate compound (4,4'-methylenebisdiisocyanate, 2,4-
Urethane-modified polyester polyol obtained by reacting tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. under the condition that the equivalent relationship of the terminal groups is OH / NCO> 1.

(7) Ethylene glycol, neopentyl glycol, copolyester oligomer composed of terephthalic acid and isophthalic acid (EG / NPG = 50/50)
(Molar ratio), TPA / IPA = 50/50 (molar ratio),
OH value = 15 to 50 mg-KOH / g), acid value obtained by reacting dimethylolpropionic acid and isophorone diisocyanate under the condition of terminal group concentration ratio (OH / NCO = 1.5 to 2.0) 10-40 mg-KOH / g urethane-modified polyester polyol (8) ethylene glycol, neopentyl glycol,
Copolyester oligomer composed of terephthalic acid and isophthalic acid (EG / NPG = 50/50 (molar ratio),
TPA / IPA = 50/50 (molar ratio), OH value = 15
˜50 mg-KOH / g), glycerin monoallyl ether (Daicel Chemical Industries, Ltd.), and isophorone diisocyanate at the terminal group concentration ratio (OH / NCO = 1.5 to 2.0).
A urethane-modified polyester polyol having a double bond on the pendant obtained by reacting under the conditions of.

Polymers containing polyester segments of the present invention may contain modest levels of ionizable functional groups such as carboxyl groups, and by using a backbone polymer containing such ionic groups, The dispersion stability of the aqueous coating resin composition obtained by the invention is improved, and it effectively contributes to the reduction of the particle size of emulsion particles. A preferable carboxyl group content is 1 to 100 mg-KOH / g, more preferably 5 to 40 mg-KOH / g as an acid value based on the dry weight of the polymer having a polyester segment.

The polymer containing the polyester segment in the present invention has, as an essential component,

[Chemical 7]

Embedded image Is contained in an amount of 5% by weight or more and 70% by weight or less. When the content of the terephthaloyl residue and / or the isophthaloyl residue is less than 5% by weight, the solvent resistance, water resistance, heat resistance, abrasion resistance and mechanical strength of the coating film obtained from the aqueous resin of the present invention However, the impact resistance is insufficient, which is not preferable. When the content of the terephthaloyl residue and / or the isophthaloyl residue exceeds 70%, the solubility of the polymer having the polyester segment of the present invention in an organic solvent becomes poor, so that the graft polymerization of the vinyl monomer can be performed. It is difficult to produce an aqueous resin having stable dispersibility, which is not preferable. With respect to the molecular weight of the polymer containing the polyester segment in the present invention, Mw (weight average molecular weight) = 3,000 or more, Mw = 100,000 or less in terms of polystyrene by gel permeation chromatography,
More preferably, Mw = 5,000 or more, Mw = 50,0
It is preferably 00 or less. When Mw is less than 3,000, the toughness and abrasion resistance of the coating film obtained from the aqueous resin composition of the present invention are insufficient, which is not preferable. Mw
= 100,000 is not preferable because the polymerization stability during graft polymerization and the dispersion stability of the obtained aqueous resin composition are deteriorated.

Examples of the polymerizable unsaturated monomer used for grafting to the polymer containing the polyester segment of the present invention include methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, Methacrylic acid esters such as cyclohexyl methacrylate, nonyl methacrylate, lauryl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acrylate such as octyl acrylate Acid esters, styrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene,
Aromatic vinyl monomers such as chloromethylstyrene and vinyltoluene, unsaturated nitriles such as acrylonitrile and methacrylonitrile, conjugated diolefins such as butadiene and isoprene, divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diethylene Polyfunctional vinyl monomers such as methacrylate, allyl methacrylate, diallyl phthalate, trimethylolpropane triacrylate, glycerin diallyl ether, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate,
Amide-based monomers such as acrylamide, methacrylamide, n-methylol methacrylamide, hydroxy group-containing monomers such as β-hydroxyethyl acrylate and β-hydroxyethyl methacrylate, amino group such as dimethylaminoethyl acrylate and diethylaminoethyl acrylate Polymers, glycidyl methacrylate, glycidyl group-containing monomers such as glycidyl methacrylate,
Vinyl monomers such as vinyl acetate, vinyl chloride and vinylidene chloride may be mentioned.

In order to obtain an aqueous coating resin having good coating film physical properties, among the above vinyl-based monomers,
Acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,
It is preferable to select a monomer mixture containing ethyl methacrylate, butyl methacrylate, hexyl methacrylate, glycidyl methacrylate, or another methacrylic acid ester, or styrene as a main component.

Specific examples of the polymerizable unsaturated monomer having a carboxyl group used in the present invention include methacrylic acid, acrylic acid, itaconic acid, crotonic acid, β-methacryloxyethyl acid succinate and β. -Methacryloxyethyl acid maleate, β-methacryloxyethyl acid hexahydrate phthalate, β-methacryloxyethyl acid phthalate and the like can be mentioned, but not particularly limited thereto. The carboxyl group introduced into the graft chain of the graft copolymer of the present invention,
It exhibits the action of being converted to a carbochelate group by neutralization with an amine and contributing to the formation of a stable dispersion.

Examples of vinyl monomers having an aldehyde group or a ketone group include acrolein, diacetone acrylamide, hydroxymethylated diacetone acrylamide, p-formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc. formula

[Chemical 9] (Here, R ¹ is H or CH ₃ , R ² is H or an alkyl group having 1 to ³ carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, and R ⁴ is an alkyl group having 1 to ⁴ carbon atoms. Acrylic (or methacryl) oxypropenal represented by group), diacetone acrylate, acetonitrile acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, and the like.

Particularly preferred monomers thereof include diacetone acrylamide, acrolein and vinyl methyl ketone. Two or more kinds of these monomers having a ketone group may be contained in the graft chain. In the present invention, the amount of the ketone group-containing vinyl monomer used is 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the total dry weight of the graft polymer. When the amount of the ketone group-containing vinyl monomer used falls below the above range, the physical properties of the coating film formed by the reaction of the graft polymer and the polyfunctional hydrazide compound (adhesiveness, water resistance, hot water resistance, solvent resistance) ) Is at an insufficient level. When the amount of the ketone group-containing vinyl monomer used exceeds the above range, the storage stability of the room temperature curable aqueous coating resin composition of the present invention becomes poor, which is also disadvantageous in terms of cost.

To produce the graft copolymer of the present invention, the polymer having the polyester segment of the present invention is dissolved or dispersed in an organic solvent, and a radical polymerizable monomer mixture is added. However, it is more preferable to introduce a double bond as a graft chain introduction site into the terminal or side chain of the polyester segment-containing polymer of the present invention, and then to add the double bond. It is preferable to polymerize a mixture of radically polymerizable monomers in the presence of a polymer to obtain a graft copolymer.

The following method is mentioned as a typical method for producing the polymer having the double bond introduced therein. (1) When a polyester is produced, a compound containing a double bond such as maleic anhydride is used as a dicarboxylic acid component, and a compound containing a double bond such as glycerin monoallyl ether is used as a diol component together with a saturated bifunctional compound, A polyester containing double bonds is produced. (2) The double bond is introduced at the end of the polymer by reacting the OH end group of the polymer having a polyester segment with methacroyl isocyanate.

(3) The double bond is introduced into the terminal of the polymer by reacting the COOH end group of the polymer having the polyester segment with glycidyl methacrylate. To introduce a carboxyl group at the end of a polymer having a polyester segment, when producing a polyester polymer by polycondensation reaction of a diol component and a dicarboxylic acid component, trimellitic acid, butanetetracarboxylic acid, etc. It can be produced by adding the above polyvalent carboxylic acid having a carboxyl group. As another method, a polyester polymer having an OH end group is succinic anhydride, trimellitic acid, pyromellitic dianhydride,
Examples thereof include a method of reacting with a compound having an acid anhydride group such as phthalic anhydride or maleic anhydride to convert a part of the OH end group into a carboxyl end group.

(4) A compound having a double bond and a hydroxy group in the molecule such as β-hydroxyethyl methacrylate after introducing an NCO end group by reacting a polyester polymer having an OH end group with a diisocyanate compound. It is also possible to introduce a double bond at the end of the polymer by reacting with. (5) When a radical-polymerizable monomer mixture is polymerized in the coexistence of a polyester polymer having an OH end group, a radical-polymerizable monomer that can participate in a reaction with an OH end group such as methacryloyl isocyanate. I
Both the process of introducing a double bond at the terminal of the polymer and the process of graft polymerization may be simultaneously performed in situ.

Radical polymerization is preferred as the method for polymerizing the vinyl-based monomer, and the initiator for radical polymerization is
2,2'-azobisisobutyronitrile, t-butyl hydroperoxide, 1,1'-azobis- (cyclohexane-1-carbonitrile), 2,2'-azobis- (2-amidinopropane) dihydrochloric acid Salt, 2,2'-azobis- (2,4-dimethylvaleronitrile), potassium persulfate, 2,2'-azobis- (2-amidinopropane) dihydrochloride, 4,4'-azobis-4-cyano Examples include valerian calculus and ammonium persulfate, which are preferably used in the range of 0.1 to 5 wt% with respect to the vinyl monomer. In carrying out the present invention, a stable aqueous resin can be obtained without using a surfactant which is used when carrying out a usual emulsion polymerization. However, a surfactant or a self-emulsifying vinyl monomer may be used in combination if necessary.

Regarding the ratio of the polymer containing the polyester segment corresponding to the trunk polymer component and the graft chain of the vinyl monomer in the present invention, the total weight (B) of the vinyl monomers includes the polyester segment. 0.1 ≦ B / (A + B) ≦ with respect to the total weight (A) of the polymer
It should be in the range of 0.9. B / (A + B) is 0.1
If it is less than the above range, the dispersion stability of the aqueous resin composition obtained by the graft polymerization is deteriorated, which is not preferable. Further, in this case, the adhesion of the coating film obtained from the aqueous resin of the present invention to OPP deteriorates, which is not preferable. B / (A + B) is 0.
When it exceeds 9, the water resistance and solvent resistance of the coating film obtained from the water-based resin of the present invention deteriorate, which is not preferable.

Examples of the polyfunctional hydrazide compound used as the crosslinking agent in the present invention include 2 to 30 in the molecule.
The following polyhydric carboxylic acid polyhydrazides containing 1 carbon atom are mentioned. Oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide (ADH), sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide,
Fumaric acid dihydrazide, itaconic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide,
4,4'-oxybisbenzenesulfonyl hydrazide,
Trimesic acid trihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (V
DH), enocosanic diacid dihydrazide, 7,11-octadecadiene-1,18-dicarbohydrazide, polyacrylic acid hydrazide, acrylamide-acrylic acid hydrazide copolymer.

Among these, adipic acid dihydrazide,
Isophthalic acid dihydrazide and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin were preferably used. 0.01 to 2.0 equivalents, preferably 0.5 to 1.5 equivalents of hydrazide groups are used per equivalent of carbonyl group contained in the graft copolymer of the present invention.
The hydrazine group contained in these polyfunctional hydrazide compounds reacts with the carbonyl group of the graft copolymer when the water of the aqueous dispersion of the present invention evaporates by drying, and forms a network structure film.

The water-miscible organic solvent used in the present invention has a wettability to a substrate such as plastic when forming a coating film from a paint or ink using the coating resin composition of the present invention. And is effective in improving the volatility of the solvent. Specific examples thereof include alcohol solvents such as methanol, n-propyl alcohol, i-propyl alcohol, ethyl alcohol, industrial ethyl alcohol, ethylene glycol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl. Examples include ketones, ketone-based solvents such as cyclohexanone, and ether-based solvents such as tetrahydrofuran, dioxane, dimethoxyethane, and the like, but are not limited to these exemplified ones.
Any one can be used as long as it can be uniformly mixed with 1 part by weight or more added to 100 parts by weight of water. Of these, preferred are isopropyl alcohol, ethyl alcohol, and industrial ethyl alcohol.

[0034]

EXAMPLES The present invention will now be described in more detail with reference to examples. The physical properties in the examples were evaluated as follows. 1. Adhesion The aqueous coating resin composition of the present invention was treated with corona 2
A bar coater No. was formed on an axially stretched polyethylene terephthalate film or (Toray Industries, Inc. “Lumirror” P60, 12μ) corona-treated biaxially oriented polypropylene film (Toray Industries, Inc. “Trefan” 2545, 20μ). 5 was applied, and after being dried constantly for 24 hours, a cellotape peeling test was performed. The coating conditions were set so that the coating thickness after drying was in the range of 2 to 5 µ. From the area ratio of the remaining portion of the coating film after the cellotape peel test, ○ (100% remaining), △ (70
% Or more) and x (peeling of 50% or more) were judged in three stages.

2. Hot water resistance The coated product prepared by the above method was immersed in boiling water for 10 minutes and taken out, and the following three grades were judged from the change in appearance. ◯: No big difference from the state before the boiling water test Δ: The coating film is slightly whitened. There are slight wrinkles on the coating. X: The coating film is whitened. Large wrinkles occur on the coating film. The coating film falls off from the base film.

3. Solvent resistance The coated product prepared by the method of paragraph 1 was rubbed with absorbent cotton impregnated with ethyl alcohol, and the number of strokes until the base film was exposed was judged in three steps. O: Over 20 times. Δ: 5 to 20 times. ×: less than 5 times.

Example 1 A 1-liter 4-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a nitrogen blowing tube and a stirrer was charged with 160 g of methyl ethyl ketone and then stirred to obtain a saturated copolyester resin Elitel 3200 ( Unitika Co., Ltd., high molecular weight polymer with a molecular weight of 15,000)
22.5 g chips were added. After raising the internal temperature to 80 ° C., which took 30 minutes, stirring was continued for 1 hour to dissolve the polymer chips. From the dropping funnel, use styrene (S
T) 29.6 g, methyl methacrylate (MMA) 24
g, C _{12 to} C ₁₃ long-chain alkyl methacrylate (SL) 2
2.5 g, 2-ethylhexyl acrylate (2EH
A) 20 g, butyl acrylate (BA) 20 g, diacetone acrylamide (DAAM) 7.5 g, acrylic acid (AA) 3.9 g and azobisisobutyronitrile 1.5
The mixture of g was added dropwise over 1.5 hours. After continuing stirring at 80 ° C. for another 1.5 hours, 160 g of isopropyl alcohol was gradually added dropwise to form a non-aqueous dispersion. After 5.9 g of 28% ammonia water was added dropwise for neutralization, 713 g of water was added dropwise for dilution. Subsequently, the internal temperature was raised to 90 ° C., and the low boiling point solvent was distilled off to 275.5.
g. The solid content of the aqueous dispersion thus obtained is 2
The viscosity was 0.9%, the viscosity was 0.07 poise, and the pH was 7.3.

Example 2 60 g of methyl ethyl ketone was placed in the same reaction vessel as in Example 1.
, Saturated copolyester resin Elitel 33
22.5 g of a powder of 20 (manufactured by Unitika Ltd., oligomer having a molecular weight of 1800) was added, and the internal temperature was raised to 80 ° C. to dissolve. Styrene (ST) 2 from the dropping funnel
9.6 g, methyl methacrylate (MMA) 24 g, C ₁₂
-C ₁₃ alkyl methacrylate (SL) 22.5 g, butyl acrylate (BA) 20 g, diacetone acrylamide (DAAM) 7.5 g, acrylic acid (AA) 3.9
g, and a mixture of 1.5 g of azobisisobutyronitrile were added dropwise over 1.5 hours. After continuing stirring at 80 ° C. for another 1.5 hours, 60 g of isopropyl alcohol was gradually added dropwise to form a non-aqueous dispersion. After neutralizing by dropwise addition of 5.9 g of 28% aqueous ammonia, 603 g of water
Was added dropwise to dilute. Subsequently, the internal temperature was raised to 90 ° C. while blowing nitrogen, and the low boiling point solvent was distilled off. The solid content of the aqueous dispersion thus obtained was 29.35.
%, The viscosity was 0.1 poise, and the pH was 7.0.

Example 3 50 g of methyl ethyl ketone was placed in the same reaction vessel as in Example 1.
Saturated copolyester resin Elitel 332
0 (manufactured by Unitika Ltd.) 22.5 g of powder was added to 80
The internal temperature is raised to ℃ to dissolve. Methyl ethyl ketone 10 g from a dropping funnel while circulating nitrogen in the reaction vessel.
Methacryloyl isocyanate (MAI) 1.35g
Is added dropwise over 10 minutes to introduce a double bond into the polyester component. After aging for 20 minutes, from a dropping funnel, 29.6 g of styrene (ST), 24 g of methyl methacrylate (MMA), 22.5 g of C _{12 to} C ₁₃ alkyl methacrylate (SL), butyl acrylate (BA).
40 g, diacetone acrylamide (DAAM) 7.5
g, methacrylic acid (MAA) 3.9 g, and azobisisobutyronitrile 1.5 g were added dropwise over 1.5 hours. Thereafter, the same procedure as in Example 3 was performed. The solid content of the obtained aqueous dispersion is 29.5%, the viscosity is 0.3 poise,
The pH was 7.3.

Example 4 Methyl ethyl ketone was added to a reaction vessel similar to that in Example 120.
g Saturated Copolyester Resin Elitel 332
0 (manufactured by Unitika Ltd.) 45 g of powder is added and the internal temperature is raised to 80 ° C. to dissolve. While passing nitrogen gas through the reaction vessel, methyl ethyl ketone 10 was added from the dropping funnel.
A solution of 2.7 g of methacryloyl isocyanate in 1 g was added dropwise over 10 minutes, and 2 parts was added to the polyester component.
Introduce a heavy bond. After aging for 20 minutes, 29.6 g of styrene (ST) and methyl methacrylate (M
MA) 16.5g, C ₁₂ ~C ₁₃ alkyl methacrylate (SL) 22.5 g, butyl acrylate (BA) 25
g, diacetone acrylamide (DAAM) 7.5 g,
A mixture of 3.9 g of acrylic acid (AA) and 1.5 g of azobisisobutyronitrile was added dropwise over 1.5 hours. Thereafter, the same procedure as in Example 3 was performed. The solid content of the obtained aqueous dispersion is 29.8%, the viscosity is 0.5 poise, and the pH is 7.
It was 5.

Example 5 An equivalent amount of the hydrazide compound VDH (manufactured by Ajinomoto Co., Inc.) was added to 100 gr of each of the aqueous dispersions AB CD prepared by the method described in Examples 1, 2, 3, and 4.
Was added to prepare a room temperature curable aqueous coating resin. While seeing the solution stability and gloss of these water-based coating resins, they were applied to PET film and OPP film at the same time, and the adhesion, hot water resistance and alcohol resistance were evaluated.
The results shown in are obtained.

Comparative Examples 1 and 2 A 30% solution of Byron 3200 and 3320 (toluene / methyl ethyl ketone = 4/1 mixed solvent was used as a solvent) was applied to a PET film and an OPP film to obtain adhesion, hot water resistance and alcohol resistance. Was evaluated and the results shown in Table 2 were obtained.

Comparative Example 3 To the aqueous dispersion C of the polyester-acrylic graft copolymer, the dihydrazide compound VDH was not added, and P was added as it was.
It was applied to an ET film and an OPP film and evaluated for adhesion, hot water resistance and alcohol resistance, and the results shown in Table 2 were obtained.

Comparative Example 4 (Preparation of Acrylic Emulsion Polymer) 60 g of methyl ethyl ketone was placed in a 1 liter 4-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a nitrogen blowing tube and a stirrer, and heated to 80 ° C. Warmed.
While circulating nitrogen in the reaction vessel, 39 g of styrene (ST) and methyl methacrylate (MMA) were added from a dropping funnel.
31.5 g, C _{12 to} C ₁₃ long-chain alkyl methacrylate (SL) 22.5 g, butyl acrylate (BA) 3
A mixture of 7.5 g, methacrylic acid (MAA) 19.5 g, and azobisisobutyronitrile 1.5 g was added dropwise over 1.5 hours. After continuing stirring at 80 ° C for 3 hours, add 200 g of isopropyl alcohol and add 28%.
Ammonia water (14 g) was added dropwise for neutralization and then H ₂ O 90
NV 30.1% viscosity 0.2 ps pH 7.5
To obtain an acrylic water-insoluble resin.

Comparative Example 5 Instead of the Elitel 3320 used in Example 2, polybutylene adipate (produced by Asahi Denka Co., Ltd., molecular weight 1,000) was used, and other reaction conditions and operating conditions were changed. Without, an aqueous dispersion E was obtained. The solid content of the aqueous dispersion E was 29.2%, the viscosity was 0.09 poise, and the pH was 7.0. For 100 g of aqueous dispersion E,
A room temperature-curable aqueous coating resin was prepared by adding 1.4 g of a hydrazide compound. Evaluating the solution stability of this aqueous coating resin, the gloss of the coating film, the adhesion to PET and OPP films, the hot water resistance and the alcohol resistance,
The results shown in Table 2 were obtained.

[0046]

[Table 1]

[0047]

[Table 2]

Example 6 100 g of the aqueous dispersion (A) obtained by the method of Example 5 was added to the hydrazide compound VDH (manufactured by Ajinomoto Co., Inc.).
0.9 g was added and dissolved uniformly to prepare an aqueous coating resin composition. 163 g of titanium oxide R-830 (manufactured by Ishihara Sangyo Co., Ltd.), 100 g of the aqueous coating resin composition (E), 18 g of isopropyl alcohol, and 15 g of ion-exchanged water were added to the mill base, and the mixture was rotated with a batch type sand grinder. After dispersion for 45 minutes under the condition of several 1600 rpm, 45 parts by weight of the aqueous coating resin composition E, 7 parts by weight of isopropyl alcohol and 5 parts by weight of deionized water were added to 100 parts by weight of the mill base to red down. After filtering the white ink thus obtained through a stainless steel mesh of 400 mesh,
Biaxially oriented polypropylene film (manufactured by Toray Industries, Inc., “Trefan” 2445 20μ) using a monochromatic printing type gravure printing suitability tester (manufactured by Kumagai Riki Kogyo Co., Ltd.)
Thickness) and biaxially oriented polyester film (Toray Industries, Inc.)
, "Lumirror" P60, 12 μm thickness).
The printing conditions are printing speed 60m / min, printing pressure 20k.
It was g / cm. When the adhesiveness of the ink was examined by a cellophane tape peeling test, no peeling of the ink was observed in both types of films.

[0049]

As is clear from the examples and comparative examples, the aqueous coating resin composition and the ink composition of the present invention have excellent adhesion to both polyester and polypropylene substrates having significantly different surface polarities. It can be seen that the water resistance and solvent resistance of the coating film obtained from the product are comparable to those of conventional solvent-based paints. Therefore, the composition of the present invention can be widely used in the fields of plastic molded products, water-based paints for films, and water-based inks, and also contributes to preservation of the global environment.

Claims (4)

[Claims] Claims: Embedded image To a polymer containing a polyester segment containing 5% by weight or more and 70% by weight or less, a polymerizable unsaturated monomer having a ketone group or an aldehyde group and a polymerizable unsaturated monomer having a carboxyl group are included. An aqueous resin composition obtained by dissolving or dispersing, in a water medium, a resin mainly composed of a graft copolymer obtained by graft-polymerizing a polymerizable unsaturated monomer mixture and a polyfunctional hydrazide compound. 2. The aqueous resin composition according to claim 1, wherein the polymerizable unsaturated monomer containing a ketone group is diacetone acrylamide. 3. An aqueous coating agent comprising the resin composition according to claim 1 or 2. 4. A water-based ink comprising the resin composition according to claim 1.