JPH083020B2 - Aqueous acrylic-polyester graft resin composition and coating agent or 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 resin composition based on a condensation polymer containing a polyester segment and a graft copolymer based on a vinyl polymer. More specifically, a room temperature crosslinkable aqueous resin composition having excellent adhesion to plastic substrates such as polypropylene and polyester, and excellent durability such as water resistance, hot water resistance and solvent resistance, and a coating agent or an aqueous solution using the same It is about 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
P4,476,189). Further, 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 using the acrylic resin as a trunk polymer has been proposed (Japanese Patent Laid-Open Publication No. 6-58242).
3-46237, 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 must be significantly 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 has been extremely difficult to produce a polyester-based water-based 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 objects of the present invention include SO ₃ M groups (M is an alkali metal or alkaline earth metal) and / or
Or a COOX group (X is H, or NHR ₁ R ₂ R ₃ group, R ₁ , R ₂ , and R ₃ are H, an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, A graft copolymer having a polymer having a polyester segment as a main component having an aralkyl group or a nucleus-substituted aralkyl group, which represents the same or different substituents as a main component, and a polymerizable unsaturated monomer as a graft chain component. Polymer, polyfunctional hydrazide compound, water-miscible organic solvent, and a room temperature-curable aqueous resin composition comprising water, wherein the graft chain component is a polymerizable unsaturated monomer containing a ketone group or an aldehyde group. This can be achieved by an aqueous resin composition characterized by being a polymer composed of a polymerizable unsaturated monomer group as an essential component. 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. The polyester polymer having SO ₃ M groups and / or COOX groups corresponding to the trunk polymer in the aqueous resin composition of the present invention is produced, for example, by the following method. That is, S
The polyester polymer having an O ₃ M group undergoes a polycondensation reaction between various diol compounds and various dicarboxylic acid compounds, and when a copolymerized polyester resin is produced, an SO ₃ M group (M Is a diol compound containing an alkali metal or an alkaline earth metal) or (and)
Obtained by using a dicarboxylic acid compound.

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.

Examples of diol compounds containing SO ₃ M groups include the following compounds.

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Examples of dicarboxylic acid compounds containing SO ₃ M groups include the following compounds.

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[Chemical 4]

The copolymerized polyester resin of the present invention is produced by a known technique for producing 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, pentanediol and dimethyl terephthalate, dimethyl isophthalate,
The transesterification reaction is carried out with the sodium salt of 5-sulfoisophthalic acid dimethyl ester, and then polycondensation is carried out under reduced pressure, whereby the copolyester resin containing SO ₃ M groups of the present invention can be obtained. When carrying out this transesterification reaction, it is preferable to use the diol in a molar ratio of 1.0 times or more, preferably 1.1 times or more, of the diester.

To carry out this transesterification reaction, manganese acetate, zinc acetate, calcium acetate, which are usually used,
A catalyst such as tetra-n-butyl titanate may be used. The transesterification reaction is generally 150 to 250 at atmospheric pressure.
It is carried out at a temperature of ° C. It is suitable that the transesterification reaction is usually continued to a reaction rate of 50 to 90%.
After completion of the transesterification reaction, in order to deactivate the transesterification catalyst, usually phosphoric acid, trimethyl phosphate or sulfuric acid, p-
Toluenesulfonic acid or the like is added.

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.

Typical examples of the SO ₃ M group-containing copolyester resin used in the present invention include the following types. (1) Ethylene glycol (EG), terephthalic acid (TP
A) and sodium 5-sulfoisophthalate (SSIA)
Copolyester consisting of (TPA / SSIA molar ratio = 85/15) (2) Ethylene glycol, neopentyl glycol (N
PG), terephthalic acid, isophthalic acid (IPA) and 5-
Copolyester consisting of sodium sulfoisophthalate (EG / NPG molar ratio = 50/50, TPA / IP
A / SSIA molar ratio = 47/47/16) (3) Ethylene glycol, neopentyl glycol, terephthalic acid, isophthalic acid, sebacic acid (SA) and 5-
Copolyester consisting of sodium sulfoisophthalate (EG / NPG = 50/50 (molar ratio), TPA /
IPA / SA / SSIA = 40/40/5/15 (molar ratio)) (4) 1,4-butanediol (BG), terephthalic acid,
Copolyester consisting of isophthalic acid and 5-sulfoisophthalic acid (TPA / IPA / SSIA = 47/47
/ 16 (molar ratio))

The copolyester resin used in the present invention is produced by a polycondensation reaction using a bifunctional monomer glycol and a dicarboxylic acid as raw materials, but does not involve the formation of a gel during the polycondensation reaction. within,
Trifunctional or higher functional monomers such as trimethylolpropane, trimellitic acid and butanetetracarboxylic acid may be used in combination. In the present invention, the copolyester having SO ₃ M group which is preferably used is ethylene glycol,
It is a copolymer containing neopentyl glycol, terephthalic acid, isophthalic acid and sodium 5-sulfoisophthalate as main components.

COOX (X is H or NHR ₁ R ₂ R ₃
R ₁ , R ₂ , and R ₃ are the same or different substituents selected from H, an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a nuclear-substituted aralkyl group. A polyester polymer having a group) represents a polycarboxylic acid having 3 or more functional groups in place of the SO ₃ M group-containing dicarboxylic acid used in the production of the above-mentioned SO ₃ M group-containing polyester polymer. It can be produced by using an acid.

A specific example of the method will be described below. Polyester by polycondensation reaction of diol components such as ethylene glycol, neopentyl glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol and dicarboxylic acid components such as terephthalic acid, isophthalic acid, adipic acid and sebacic acid When producing a polymer, it can be produced by allowing a polyvalent carboxylic acid having three or more carboxyl groups in one molecule to coexist, such as trimellitic acid and butanetetracarboxylic acid. As another method, a polyester polymer having an OH end group is reacted with a compound having an acid anhydride group such as succinic anhydride, trimellitic acid, pyromellitic anhydride, phthalic anhydride, and maleic anhydride. After converting a part or all of the OH end groups into carboxyl groups, the free carboxyl groups are neutralized with amines. As another method, a dihydric alcohol compound having a carboxyl group in the molecule such as a polyester resin having hydroxyl groups at both ends and dimethylolpropionic acid is reacted with a diisocyanate compound to have a polyester segment and a pendant carboxyl group. After obtaining the polymer, a method of neutralizing a free carboxyl group in the polymer with amines can be mentioned.

SO₃Have both M group and COOX group
The polymer containing the polyester segment has the above-mentioned S
O₃Method for producing polyester containing M groups and COOX
Can be obtained in combination with a method for producing a polyester containing a group.
However, the other method is to use SO in the molecule.₃M group
OH-terminated polyester polymer containing and SO in the molecule ₃
Both OH-terminated polyester polymers containing M groups are
Reacts with a cyanate compound to form S in a single polymer chain.
O₃Polyester cell that has both M group and COOX
And a method of producing a polymer having a pigment.

As the polymer having a polyester segment containing SO ₃ M group and / or COOX group used in the present invention, the copolyester resin synthesized by the above method is used. A polymer (urethane-modified polyester) obtained by reacting a resin with an appropriate diisocyanate compound in the presence of a polyether polyol or other polyester polyol may be used.

The SO ₃ M groups and / or CO of the present invention
Regarding the content of the ionic functional group in the polymer containing the polyester segment having an OX group, when expressed by the value of the acid value in the free acid state, the acid value is 1 to 30.
0 mg-KOH / g, more preferably 30 to 200 mg
It is preferably in the range of -KOH / g. If the acid value is less than 1, the dispersibility of the aqueous resin of the present invention is poor, which is not preferable. When the acid value exceeds 300 mg, the water resistance of the coating film made of the water-based resin of the present invention is poor, which is not preferable.

The molecular weight of the polymer having a polyester segment corresponding to the trunk polymer in the present invention is Mw (weight average molecular weight) = 3,000 or more in terms of polystyrene by gel permeation chromatography, Mw.
= 100,000 or less, more preferably Mw = 5,000
It is desirable that 0 or more and Mw = 50,000 or less. When Mw is less than 3,000, the toughness and abrasion resistance of the coating film from the aqueous resin composition of the present invention are insufficient, which is not preferable. When Mw exceeds 100,000, the polymerization stability at the time of graft polymerization and the dispersion stability of the obtained aqueous resin composition are deteriorated, which is not preferable.

Examples of the polymerizable unsaturated monomer used for grafting onto the copolyester containing SO ₃ M groups of the present invention include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 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 Aromatic vinyl monomers such as acid esters, styrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, chloromethylstyrene and vinyltoluene, unsaturated nitriles such as acrylonitrile and methacrylonitrile, butadiene and isoprene. Conjugated diolefins such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate, diphthalic acid Polyfunctional vinyl monomers such as vinyl chloride, trimethylolpropane triacrylate, glycerin diallyl ether, polyethylene glycol dimethacrylate, and polyethylene glycol diacrylate, amide monomers such as acrylamide, methacrylamide, and n-methylol methacrylamide, β-hydroxy Ethyl acrylate, hydroxy group-containing monomers such as β-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, amino group-containing polymers such as diethylaminoethyl acrylate, glycidyl methacrylate, glycidyl group-containing monomers such as glycidyl methacrylate, acetic acid Vinyl monomers such as vinyl, vinyl chloride and vinylidene chloride may be mentioned.

In order to obtain an aqueous coating resin having good coating film physical properties, from the above vinyl 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.

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

Embedded image (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) ) Becomes an insufficient level, and when the amount of the ketone group-containing vinyl monomer used exceeds the above range, the storage stability of the room temperature curable aqueous resin composition of the present invention becomes poor, and also in terms of cost. It will be a disadvantage.

The graft copolymer of the present invention is the S of the present invention.
A copolymerized polyester resin containing O ₃ M groups and / or COOX groups is dissolved or dispersed in a medium containing water as a main component, and a radically polymerizable unsaturated monomer is added to this solution or dispersion. It is obtained by carrying out polymerization. As a graft copolymerization initiator, a known radical polymerization initiator can be used, and specific examples thereof include 2,2′-azobisisobutyronitrile,
t-butyl hydroperoxide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2 ′
-Azobis- (2-amidinopropane) dihydrochloride, 2,
2'-azobis- (2,4-dimethylvaleronitrile), 4,4'-azobis-4-cyanovaleric acid, potassium persulfate, ammonium persulfate and the like can be mentioned. These 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.

SO ₃ M groups and / or C in the present invention
It is desirable that the weight of the polymer (A) having a polyester segment containing an OOX group and the total weight (B) of the vinyl monomers have the following relationship. 0.1 ≦ B / (A + B) ≦ 0.9 When B / (A + B) is less than 0.1, solvent resistance and water resistance of the coating film from the vinyl / polyester composite aqueous resin obtained by graft polymerization Is not preferable because it is insufficient. When B / (A + B) exceeds 0.9, it is difficult to obtain an aqueous resin having stable dispersibility, 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, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, terephthalic acid dihydrazide, terehydrazide, terephthalic acid Oxybisbenzenesulfonyl hydrazide, trimesic acid trihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (VDH), enocosane diacid dihydrazide, 7,11-octadecadiene-1,18-dicarbo Hydrazides, polyacrylic acid hydrazides, acrylamide-acrylic acid hydrazide copolymers.

Among these, adipic acid dihydrazide (ADH), isophthalic acid dihydrazide and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (VDH) were preferably used. The equivalent of carbonyl group contained in the graft copolymer of the present invention is 0.
01 to 2.0 equivalents, preferably 0.5 to 1.5 equivalents of hydrazide groups are used. 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.

[0032]

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. Adhesiveness The aqueous resin composition of the present invention is used as a coating agent for a corona-treated biaxially oriented polyethylene terephthalate film or (Toray Industries, Ltd. “Lumirror” P60, 12μ) corona-treated biaxially oriented polypropylene film (Toray Industries, Inc.).
"Trefan" 2545, 20μ) with a bar coater No.
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. After the cellotape peeling test,
From the area ratio of the remaining portion of the coating film, ○ (100% remaining),
A three-level judgment of Δ (70% or more remaining) and × (50% or more peeling) was made.

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. B: The coating film is slightly whitened. There are slight wrinkles on the coating. ×: The coating film becomes white. Large wrinkles occur on the coating film.
The coating film falls off from the base film.

3. Solvent resistance The coated article 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. ○ …… More than 20 times. △ …… 5 to 20 times. ×: less than 5 times.

Example 1 207.5 g of water, 0.5 g of 28% ammonia water, Vylonal MD1250 (Toyobo Co., Ltd.) were 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. 175 g of a water-dispersed saturated copolyester resin manufactured by Co., Ltd. and 0.3 g of sodium thiosulfate were charged, and the temperature was raised while continuing stirring.
After the internal temperature reached 80 ° C, ethyl acrylate (EA) 6
7.5 g, butyl acrylate (BA) 12 g, glycidyl methacrylate (GMA) 10.5 g, diacetone acrylamide (DAAM) 7.5 g, Perex OTP
(Sodium dialkylsulfosuccinate; Kao Corporation)
3 g) and a mixed aqueous solution of 2 g of ammonium persulfate and 25 g of distilled water were added dropwise in parallel over 2 hours. 30 minutes after the completion of dropping 1.5 g of ammonium persulfate
A mixed aqueous solution of 25 g of water and water was added dropwise over 2 hours. 8
After continuing stirring at 0 ° C. for another hour, the mixture was cooled to room temperature to obtain an aqueous dispersion A of polyester-acrylic graft copolymer. The solid content of this aqueous dispersion was 30%, the viscosity was 0.1 poise, and the pH was 7.2.

Example 2 Under the same polymerization conditions as in Example 1, Vylonal MD
The amounts of -1250, ethyl acrylate, and butyl acrylate charged were changed as shown in Table 1 to obtain aqueous dispersions B and C of polyester-acrylic graft copolymer.

Example 3 In the same flask as in the previous example, water 207.5, 281 ammonia water 0.5 g Polyester WR-961 (Nippon Gosei Co., Ltd. product, water-solubilized with ammonium carboxylate) 175
g, 0.3 g of sodium thiosulfate were charged and the temperature was raised. Inner temperature is 7
After reaching 5 ° C, 67.5 g of ethyl acrylate (EA),
Butyl acrylate (BA) 12g, styrene (ST) 7
g, glycidyl methacrylate (GMA) 0.5 g, diacetone acrylamide (DAAM) 7.5 g, Perex OTP (Kao anion surface-active agent) 3 g, and a mixed aqueous solution of ammonium persulfate 2 g and water 25 g for 2 hours. Parallel dripping is performed. 30 minutes after the end of the dropping, 2 g of a mixed aqueous solution of 1.5 g of ammonium persulfate and 25 g of water was added.
Drip over time. After heat-curing for another hour, a 30% viscosity 0.1 ps, pH 7.0 emulsion solution (D) was obtained.

Example 4 For each 100 g of aqueous dispersion A, B, C, D prepared by the method described in Examples 1 and 2, 1.4
g of dihydrazide compound, VDH (manufactured by Ajinomoto Co., Inc.) was added to prepare a room temperature curable aqueous resin. These were applied as coating agents to PET films and OPP films, and the adhesion, hot water resistance and alcohol resistance were evaluated, and the results shown in Table 2 were obtained.

Comparative Example 1 Bayronal MD-1250 was prepared by using PET film and OPP.
It was applied to a film and evaluated for adhesion, hot water resistance and alcohol resistance, and the results shown in Table 2 were obtained.

Comparative Example 2 The aqueous dispersion resistance A of the polyester-acrylic graft copolymer was added as it was without adding the dihydrazide compound VDH.
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 3 (Preparation of Acrylic Emulsion Polymer) A reflux condenser, a thermometer, a dropping funnel, a nitrogen blowing tube and a stirrer were provided. A 1 liter 4-necked flask was charged with 300 g of water and 4.5 g of Rebenol WX (sodium polyoxyethylene alkyl ether sulfate; manufactured by Kao Corporation), stirring was started with a stirrer, and the temperature was gradually raised. After the internal temperature reached 80 ° C., ethyl acrylate 67.
A mixture of 5 g, 12 g of butyl acrylate, 52 g of styrene, 7.5 g of diacetone acrylamide, 10.5 g of glycidyl methacrylate and an aqueous solution of 2 g of ammonium persulfate and 25 g of distilled water was added dropwise in parallel over 2 hours. After the dropping was completed, an aqueous solution containing 1.5 g of ammonium persulfate and 25 g of distilled water was added dropwise over 2 hours. After the dropping was completed, stirring was continued at 80 ° C. for 1 hour.
After cooling the reaction mixture to room temperature, 1.0 g of 28% aqueous ammonia was added to obtain an emulsion polymer. The solid content of this emulsion polymer is 30%, the viscosity is 0.5 poise, and the pH is 7.0.
Met. This emulsion polymer was treated with P in the same manner as in Example 2.
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.

[0041]

[Table 1]

[0042]

Example 5 100 g of the aqueous dispersion (A) obtained by the method of Example 1 was added to the hydrazide compound VDH (manufactured by Ajinomoto Co., Inc.).
1.4 g was added and dissolved uniformly to prepare an aqueous coating resin composition (E). 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 dispersing 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. The white ink thus obtained was filtered through a stainless steel mesh of 400 mesh, and then a biaxially stretched polypropylene film was used using a monochromatic printing type gravure printing suitability tester (Kumagaya Riki Kogyo Co., Ltd.). (Toray Industries, Inc. "Trefan" 2445 20μ thick)
Printing was performed on a biaxially stretched polyester film (“Lumirror” P60, 12 μm thick manufactured by Toray Industries, Inc.). Printing conditions are printing speed 60m / min, printing pressure 20kg / cm
Met. 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.

[0044]

As is apparent from the above Examples and Comparative Examples, the water-based resin composition, water-based coating agent and ink composition of the present invention have excellent adhesion to both polyester and polypropylene substrates having remarkably different surface polarities. It is also clear that the water resistance and solvent resistance of the coating film obtained from this composition are comparable to those of conventional solvent type paints. Therefore, the composition of the present invention can be widely used in the fields of plastic molded products, water-based coating agents for films, and water-based inks, and also contributes to preservation of the global environment.

Claims (5)

[Claims] 1. SO₃M group (M is an alkali metal or
Lucari earth metal) and / or COOX group (X is H,
Or NHR₁R₂R₃And R is₁, R ₂, R₃Is
H, an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group,
Reel group, substituted aryl group, aralkyl group or nuclear substitution
Representing the same or different substituents selected from aralkyl groups
Based on a polyester segment having
The polymer is the backbone polymer component and the polymerizable unsaturated monomer is
Graft copolymer, polyfunctional hydrazide as soft chain component
Compounds, organic solvents that are miscible with water, and water
In the room temperature curable aqueous resin composition, the graft chain component
Is unsaturated containing a ketone or aldehyde group
Consist of a group of polymerizable unsaturated monomers containing monomer as an essential component
An aqueous resin composition, which is a polymer as described above. 2. The aqueous resin composition according to claim 1, wherein the polyester segment contains an aromatic ring. 3. The aqueous resin composition according to claim 1, wherein the polymerizable unsaturated monomer containing a ketone group is diacetone acrylamide. 4. An aqueous coating agent comprising the resin composition according to claim 1, 2 or 3. 5. A water-based ink comprising the resin composition according to claim 1, 2 or 3.