JPH09208801A - Curable water-base resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable water-base resin compsn. which has a good storage stability and can be cured by the dehydration reaction between a prim- hydroxyl group and a carbonyl group by incorporating a prim-hydroxyl compd. and a high-molecular ketone compd. into a water-base medium. SOLUTION: This compsn. is prepd. by incorporating, into a water-base medium, 1-99wt.% prim-hydroxyl compd. pref. having at least two functionalities and 1-99wt.% high-molecular ketone compd. which has carbonyl groups each existing between two carbon atoms (provided at least one hydrogen atom is attached to at least one of the two carbon atoms). The compsn. can be cured by heating in the absence of a catalyst, though the presence of a dehydration catalyst in an amt. of 0.01-80wt.% of the sum of the compds. is desirable.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable aqueous resin composition which is cured by utilizing a dehydration reaction of a primary hydroxyl group and a ketone group, and further for a film forming material such as paint and ink,
The present invention relates to a curable aqueous resin composition that can be used for adhesives and the like.

[0002]

2. Description of the Related Art Conventionally, a curable aqueous resin composition is obtained by reacting emulsion particles having a hydroxyl group on the particle surface with acrylic acid chloride, and therefore it is very difficult to control the introduction amount of the acrylic group, Was also difficult. There was also a problem with storage stability. Further, there is a crosslinked gel (microgel) as a method for increasing the solvent resistance. Microgel can be synthesized by an emulsion polymerization method by synthesizing a compound having an active double bond such as an acrylic monomer by using vinyl monomers having two or more active double bonds such as divinylbenzene. Funke: Macro
mol. Chem. 76, 259 (1979). Further, JP-A-51-101952 discloses that a vinyl ether compound can be obtained from cyclohexanone and alcohol. However, in this case, since a solvent such as toluene was used, it was necessary to remove water generated as an azeotrope from the system by heating.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a curable aqueous resin composition having good storage stability, which is a copolymer obtained in an aqueous system and can be cured by utilizing the dehydration reaction of primary hydroxyl groups and ketone groups. It is provided.

[0004]

The present invention comprises a primary hydroxyl group-containing compound in an aqueous medium and two adjacent carbon atoms, provided that at least one carbon atom is bound to at least one hydrogen atom. The present invention relates to a curable aqueous resin composition containing a ketone group-containing polymer compound. Further, the present invention relates to the curable aqueous resin composition, wherein the primary hydroxyl group-containing compound is a divalent or higher valent primary hydroxyl group-containing compound compound, and further a dehydration catalyst is added.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula of the dehydration reaction by primary hydroxyl group and ketone group in the present invention is shown below.

[0006]

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The aqueous medium of the present invention means that the water-miscible solvent is 0.
It is a mixture of water and a water-miscible solvent containing 50% by weight. Preferred is a mixture of water and a water-miscible solvent containing 0 to 20% by weight of a water-miscible solvent. Examples of the water-miscible solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol and t-butanol, ketone type solvents such as acetone, methyl ethyl ketone and cyclohexanone, tetrahydrofuran and dioxane. Ether organic solvent, acetonitrile, dimethylformamide, diethylformamide, dimethylacetamide, diethylformamide, N
-Methylpyrrolidone, tetramethylurea, dimethylsulfoxide, hexamethylphosphortriamide, ethylene carbonate, aprotic organic solvents such as propylene carbonate, ethylene glycol dimethyl ether,
Ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether,
There are ethylene glycol organic solvents such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether and diethylene glycol, formic acid, acetic acid, propionic acid, pyridine and triethylamine.

In the present invention, examples of the primary hydroxyl group-containing compound include a primary hydroxyl group-containing polymer compound obtained by vinyl-polymerizing a hydroxyl group-containing vinyl monomer. Examples of the primary hydroxyl group-containing vinyl monomer used for producing these polymer compounds include acrylate-based monomers, acrylamide-based monomers, and polyolefin-based monomers.

Examples of the hydroxyl group-containing vinyl monomer include acrylic vinyl monomers and ethylene vinyl monomers. Examples of the acrylic vinyl monomer include ethylene glycol (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, tetraethylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, Polyethylene glycol (meth) acrylate, 4-hydroxybutyl acrylate, 3-
Hydroxypropyl acrylate, tetraethylene glycol acrylate, tetrapropylene glycol acrylate, N- (hydroxymethyl) acrylamide,
There are acrylic vinyl monomers having a hydroxyl group such as N- (hydroxyethyl) acrylamide and diacetone acrylamide. As an ethylene vinyl monomer,
For example, there are vinyl monomers containing a primary hydroxyl group such as allyl alcohol, 4-hydroxy-1-butene, 4-hydroxymethylstyrene, 4-hydroxyethylstyrene, 1,4-dihydroxy-2butene, but two or more kinds, It is also possible to mix and use them at an arbitrary ratio.

As the hydroxyl group-containing compound, it is possible to use a copolymer of 1 to 99% by weight of the hydroxyl group-containing vinyl monomer and 1 to 99% by weight of another monomer, preferably the hydroxyl group-containing vinyl monomer 1 to 70. It is a copolymer of 5% by weight and 5 to 90% by weight of another vinyl monomer. As the vinyl monomer having no hydroxyl group used for such copolymerization, styrene, methyl (meth) acrylate,
(Meth) acrylic acid, vinyl acetate, ethylene, propylene, vinyl chloride, acrylonitrile, vinylpyrrolidone, butadiene, isoprene vinylidene fluoride, vinylidene chloride, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, crotonic acid , Cinnamic acid,
There are p-vinylphenylsulfonic acid, p-vinylphenylphosphoric acid, p-vinylphenylboric acid, p-vinylphenylsilicic acid, p-vinylphenol, ethyl 2-phosphate (meth) acrylate and the like. These other vinyl monomers can also be mixed and used in an arbitrary ratio.

As the primary hydroxyl group-containing polymer compound, hydroxyl group-containing polyhydric alcohols and natural polymers can be used, but the amount used is relative to the ketone group-containing polymer.
It is 1 to 99% by weight, preferably 10 to 70% by weight. Examples of the hydroxyl group-containing polyhydric alcohols include polyethylene glycol, polypropylene oxide, polytetrahydrofuran, and polybutadiene diol. As the natural polymer, for example, cellulose,
There is chitin etc. Examples of the modified natural polymer include cellulose acetate, chitosan, hydroxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cyclic polysaccharides, modified cellulose and the like.

As the primary hydroxyl group-containing compound of the present invention, a monovalent or polyvalent low molecular weight hydroxyl group-containing compound can be used, but the amount used is 1 with respect to the ketone group-containing polymer.
˜99% by weight, preferably 1 to 70% by weight. As these monovalent hydroxyl group-containing low molecular weight compounds,
For example, methanol, ethanol, propanol, butanol, hexanol, octanol, tridecyl alcohol, isoamyl alcohol, trimethylolpropane, lauryl alcohol, nonyl alcohol, neopentyl alcohol, 4-hydroxy-2-butanone, 3-
Methyl-3-methoxybutanol, furyl alcohol,
Examples include tetrahydrofuryl alcohol, ethanolamine, hydroxyethylpiperazine and the like. Examples of the polyvalent primary hydroxyl group-containing compound include pentaerythritol,
Ethylene glycol, propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, butanediol, 1,3-butanediol, trimethylolethane, octanediol, diethylene glycol, triethylene glycol, allyl alcohol, 3-methyl −
1,5-pentanediol, N-methyl-N, N-diethanolamine, N, N-diethylethanolamine,
Tris- (2-hydroxyethyl) isocyanurate,
There are divalent to hexavalent alcohols such as hexamethylol melamine and hexaethylol melamine. These compounds can be used as a mixture of two or more kinds.

The ketone group-containing vinyl monomer of the present invention is
By using this, a structure in which a ketone group having two adjacent carbon atoms (but at least one hydrogen atom is bonded to at least one carbon atom) is introduced into a side chain, and an ester group or Compounds having only a carboxyl group are excluded, but it is also possible to use an ester group or a carboxyl group-containing compound in the molecule. Examples of the ketone group-containing vinyl monomer include 4- (meth) acryloyl-2-butanone and 3- (meth) acryloyl-2-butanone.
(Meth) acryloyl-2-butanone, 2- (meth) acryloyl-3-methyl-2-butanone, 5- (meth)
(Meth) acryloylalkylketone compounds such as acryloyl-2-pentanone, 4- (meth) acryloyl-4-methyl-2-pentanone, diethyl methacryloyldiacetylmethaneacryloylmalonate, acryloylacetylacetone, vinyl methyl ketone, vinyl ethyl ketone, Vinyl alkyl ketone compounds such as vinyl isobutyl ketone, hydroxymethyl vinyl ketone, t-butyl vinyl ketone neopentyl vinyl ketone, α-chlorovinyl methyl ketone, mesityl oxide, acetoacetoxyethyl (meth) acrylate or diacetone acrylamide, benzalacetone And the like.

As the ketone group-containing polymer compound, a copolymer of 1 to 99% by weight of a vinyl monomer containing a ketone group and 1 to 99% by weight of another vinyl monomer can be used. The preferred amount is 1 to 7 of vinyl monomer containing a ketone group.
It is a copolymer of 0% by weight and 5 to 90% by weight of another vinyl monomer. Examples of such a vinyl monomer containing no ketone group include styrene, methyl (meth) acrylate, (meth) acrylic acid, ethylene, propylene, acetylene, vinyl chloride, vinyl acetate, vinylpyrrolidone,
Vinylcarbazole, acrylonitrile, butadiene,
Propylene, isoprene, vinyl pyridine, butyl vinyl ether, vinylidene fluoride, vinylidene chloride, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride,
Citraconic acid, crotonic acid, cinnamic acid, p-vinylphenylsulfonic acid, p-vinylphenylphosphoric acid, p-vinylphenylboric acid, p-vinylphenylsilicic acid, p-vinylphenol, ethyl 2-phosphate (meta ) There are acrylates and the like, and two or more kinds of other vinyl monomers can be mixed and used at an arbitrary ratio.

In the curable aqueous resin composition used in the present invention, the amount of the primary hydroxyl group-containing compound and the ketone group-containing polymer compound used is 1 to 99% by weight of the primary hydroxyl group-containing compound and the ketone-containing polymer compound 1 to 99. It is a mixed resin composition with wt%. Compounds containing primary hydroxyl group 5 to 70 are preferred.
It is a mixed resin composition of 5 wt% and 5 to 70 wt% of a ketone group-containing polymer compound.

Examples of the copolymerization method in the present invention include water-based suspension polymerization, emulsion polymerization, dispersion polymerization and other water-based polymerization methods which are general radical polymerization methods or resox polymerization methods. Further, in order to obtain the curable aqueous resin composition of the present invention, a method of polymerizing in an organic solvent or dissolving a copolymer in an organic solvent and then dispersing in a water system to remove the organic solvent can be used.

The curing reaction of the curable aqueous resin composition of the present invention proceeds by heat treatment even without a catalyst, but it is preferable to use a dehydration catalyst together. The dehydration catalyst used is from 0.01% by weight to 80% by weight, preferably 0.0% by weight, based on the amount of resin.
Add from 1% to 10% by weight. As the dehydration catalyst, there are an acid catalyst, a basic catalyst, an inorganic salt catalyst, a photoinitiating catalyst and the like. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, bromic acid, iodic acid, fluoric acid, sulfuric acid, phosphoric acid, boric acid and boron fluoride, acetic acid, propionic acid, benzoic acid, trifluoroacetic acid, p-toluenesulfonic acid and the like. There are acidic organic compounds such as organic acids and phenol. Further, polymer compounds having groups such as carboxyl group, sulfonyl group, phosphoric acid group and the like such as polyacrylic acid and polystyrene sulfonic acid can also be used.

Examples of the base catalyst include amine compounds such as pyridine, pyrrolidine, piperidine and triethylamine, metal hydroxide compounds such as sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide, sodium methoxide, In addition to metal alcoholates such as potassium methoxide, lithium ethylate and potassium t-butoxide, sodium carbonate, potassium carbonate, Grineer's reagent, metal chelate compound and the like can be used. Examples of the inorganic salt include sulfate, phosphate, borate, and hydrochloride. As the organic salt, for example, a salt obtained by a neutralization reaction between a carboxyl group such as acetate and an alkaline compound can be used. It is also possible to use a dehydrating agent such as molecular sieve or anhydrous calcium chloride, and it is also possible to use it together with other catalysts.

In the curable aqueous resin composition of the present invention, a vinyl bond is formed by the curing reaction, and therefore the curing reaction can be promoted by adding a vinyl bond crosslinking reaction catalyst. As such a reaction catalyst, a cationic polymerization initiator and a radical polymerization initiator can be used. Examples of the cationic polymerization initiator include sulfuric acid, phosphoric acid, trifluoroacetic acid, and examples of the Lewis acid include aluminum chloride, titanium tetrachloride, tin tetrachloride, iodine, boron trifluoride and the like. Examples of the radical polymerization initiator include cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, dibenzoyl peroxide, hydrogen peroxide, and azobisisooxide. Butyronitrile,
Ammonium persulfate, potassium persulfate, sodium persulfate, metal peroxides, hyponitrites, metal chelate compounds and the like can be used alone or in combination.
Further, a cationic polymerization initiator and a radical polymerization initiator can be used in combination. In addition, in the curable aqueous resin composition of the present invention, it is preferable to use a cationic polymerization initiator in combination with a radical polymerization initiator in terms of storage stability. Further, as a dehydration catalyst for the curable aqueous resin composition of the present invention, any substance that releases a Lewis acid or an inorganic or organic acid by ultraviolet rays or visible light can be used.

The photoinitiating catalyst may be any one which releases a Lewis acid or an inorganic or organic acid upon irradiation with light, and can be divided into an ultraviolet initiating catalyst and a visible light initiating catalyst. As an ultraviolet initiation catalyst, there is a combination of an onium salt, a (thia) pyrylium salt and an ultraviolet sensitizer. Examples of onium salts and (thia) pyrylium salts include halogens with onium compounds or (thia) pyrylium compounds, BF ₄ , PF ₆ , AsF ₆ , ClO ₄ , and SbF.
₆ , CF ₃ SO ₃ , CH ₃ SO ₃ , CH ₃ C ₆ H ₄ SO
A salt such as ₃ can be used. Specific examples of onium salts include British Patent 1388492 and JP-A-53-13.
3428, described tris (trichloromethyl) -2,
2,4,6-Substituted triazine compounds such as 4,6-triazine, JP-A-1-54440, European Patent 109
851, Europe 126712, and Journal of Imaging Science, Vol. 30, p. 170 (1986), iron arene complexes, diphenyliodonium hexafluorophosphate, diaryl such as di (p-tolyl) iodonium hexafluoroantimonate. Iodonium salt derivatives, triphenylsulfonium hexafluorophosphate, diphenylphenacylsulfonium hexafluoroantimonate and other sulfonium salt derivatives, tetraphenyloxosulfonium hexafluorophosphate and other oxosulfonium salt derivatives, dimethylphenacylsulfonium (n-butyl) triphenyl Examples thereof include sulfonium organic boron complexes such as borate.

Examples of the pyrylium salt of the (thia) pyrylium salt include 2,4,6-triphenylpyrylium, 2,
4,6-tris (4-methoxyphenyl) pyrylium,
Any derivative of pyrylium salt such as 2,4,6-trimethylphenylpyrylium may be used. As the thiapyrylium salt, 2,4,6-triphenylthiapyrylium, 2,
It is not limited to specific examples as long as it is a thiapyrylium salt derivative such as 4,6-tris (4-methoxyphenyl) thiapyrylium and 2,4,6-methylphenylthiapyrylium. Pyrylium, a chlorine derivative of thiapyrylium, a bromine derivative, In addition to iodine derivatives, fluorine derivatives, fluoroborate derivatives, perchlorate derivatives, fluoroantimonate derivatives, fluorophosphonate derivatives, fluoroarsenate derivatives, “Chemish Berichte (Cheich
m. Ber. ) ”, Pp. 2309-2320 (195
9), or "Journal of Organic Chemistry (J. Org. Chem.) No. 36".
The compounds described in Vol. 600, page 602 (1971) can be exemplified. Further, an onium salt and a (thia) pyrylium salt can be mixed and used at an arbitrary ratio. As the ultraviolet sensitizer, it is preferable to use an onium salt or a pyrylium salt when it is not decomposed by ultraviolet irradiation.

Specific examples of the UV sensitizer include benzoin ether compounds such as benzyl, benzoin and benzyl dialkyl ketal derivatives, and acetophenone compounds such as 2-hydroxy-2-methylpropiophenone and pt-butyltrichloro. Acetophenone, p-
Dimethylaminoacetophenone, benzophenone-based benzophenone, 4-chlorobenzophenone, o-
Methyl benzoin benzoate, 4-4'-dialkylaminobenzophenone derivative, thioxaton-based thioxatone, 2-chlorothioxaton, 2-alkylthioxaton derivative, and other 2-alkylanthraquinone derivatives, but not limited thereto. It is not necessary that the onium salt be decomposed by UV irradiation, and two or more kinds of these UV sensitizers can be mixed and used.

As the visible light initiating catalyst, there is a combination of the above-mentioned onium salt, (thia) pyrrinium salt and a visible light sensitizer. As the visible light sensitizer, unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzal and camphorquinone, benzyne derivatives, fluorene derivatives, naphthoquinone derivatives, Anthraquinone derivative, xanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, merocyanine derivative, oxonol derivative, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium Derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazy Porphyrazine derivatives, phthalocyanine derivatives, tetra-aza porphyrazine derivatives, tetra quinoxalinium Lilo porphyrazine derivatives, naphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, Tetoraferin derivatives, annulene derivatives,
Examples include spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, and organic ruthenium complexes.
Others More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), edited by Chuzaburo Ikemori, "Special". Functional materials "(1986, CMC), but the dyes and sensitizers are not limited to these, and other dyes and sensitizers that absorb light in the visible light range. Can be mentioned. Two or more kinds of these may be used in an arbitrary ratio if necessary.

When a copolymer is obtained by the emulsion polymerization method in the present curable aqueous resin composition, the particle size can be controlled by using a surfactant. As the surfactant, there are cation type, nonion type and anion type, and the amount used is 0.01% by weight to 10% by weight, preferably 0.01% by weight to 5% by weight relative to the amount of the resin.
Add% by weight. Specifically, as the cationic surfactant, an alkylpyrinium chloride derivative, cetyltrimethylammonium bromide, and as the anionic surfactant, sodium dodecyl sulfate, sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, nonionic surfactant. Activators include, but are not limited to, polyethylene glycol monolaurate, sorbitan monolaurate, etc. Other than those described in Shintaro Kunizawa, "Emulsion Latex Handbook" (Taisei Publishing Co., 1982). The above-mentioned surfactants are listed, and other compounds can be used as long as they have an action as a surfactant. Other than this, it is also possible to use a reactive macromer derivative which is effective as a surfactant. Specifically, there is a polyethylene glycol derivative of methyl (meth) acrylate, and the amount used is from 0.1% by weight to 20% by weight of the resin amount.
% By weight is preferred. The macromer is not limited to this, and any macromer can be used as long as it has an effect as a surfactant.

The curable aqueous resin composition of the present invention contains polymerizable vinyl monomers, polymers containing active double bonds, epoxy compounds which undergo ring-opening polymerization with a cationic catalyst, epoxy modified polymers, caprolactam, caprolactone. It is also possible to use cyclic monomers such as The curable aqueous resin composition of the present invention includes a pigment, a dye,
Resins, plasticizers, inorganic salts, and reactive monomers can be added.

[0026]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (Production Example 1) Synthesis of Aqueous Copolymer A A 500 ml four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was charged with diacetone acrylamide 20.0 g N-vinylpyrrolidone (NVP) 80. 0.0 g Potassium persulfate 0.5 g Distilled water 150.0 g was charged and well stirred while flowing nitrogen gas, and the temperature inside the flask was raised to 70 ° C. in a water bath. 4 reaction as it is
Continued for hours.

Synthesis of Aqueous Copolymer B Into a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser, methyl vinyl ketone 20.0 g N-vinylpyrrolidone (NVP) 80.0 g Charge 0.5 g of potassium persulfate and 150.0 g of distilled water, stir well while flowing nitrogen gas, and raise the temperature inside the flask to 70 ° C. in a water bath. 4 reaction as it is
Continued for hours.

Synthesis of Aqueous Copolymer C In a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser, methyl vinyl ketone 10.0 g Methyl methacrylate (MMA) 60.0 g polyvinyl Alcohol 2.0 g Sodium dodecyl sulphate 0.5 g Potassium persulfate 0.5 g Distilled water 250.0 g are charged and well stirred while flowing nitrogen gas, and the temperature inside the flask is raised to 70 ° C. in a water bath. 4 reaction as it is
Continued for hours. A milky white dispersion was obtained. The particle size of the dispersion was 500-2300 nm. Even when left at room temperature for 1 month, no agglutination reaction occurred and the particle size did not change.

Synthesis of Aqueous Copolymer D 4-hydroxybutyl acrylate 15.0 g N-vinylpyrrolidone (NVP) 85 in a 500 ml four-neck round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser. 0.0 g Potassium persulfate 0.8 g Distilled water 100.0 g was charged, and the mixture was well stirred while flowing nitrogen gas, and the temperature inside the flask was raised to 70 ° C. in a water bath. 4 reaction as it is
Continued for hours.

Synthesis of aqueous copolymer E 2-hydroxyethyl acrylate 15.0 g N-vinylpyrrolidone (NVP) 85 was placed in a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser. 0.0 g Potassium persulfate 0.8 g Distilled water 100.0 g was charged, and the mixture was well stirred while flowing nitrogen gas, and the temperature inside the flask was raised to 70 ° C. in a water bath. 4 reaction as it is
Continued for hours.

Synthesis of Aqueous Copolymer F In a 500 ml four-necked round bottom flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and condenser, 4-hydroxybutyl acrylate 10.0 g Methyl methacrylate (MMA) 60. 0 g Polyvinyl alcohol 2.0 g Sorbitan monolaurate 0.5 g Potassium persulfate 0.5 g Distilled water 250.0 g are charged, well stirred while flowing nitrogen gas, and the temperature inside the flask is raised to 70 ° C. in a water bath. . 4 reaction as it is
Continued for hours. A milky white dispersion was obtained. The particle size of the dispersion was 500-2500 nm. Even when left at room temperature for 1 month, no agglutination reaction occurred and the particle size did not change.

Example 1 Synthesis of Curable Aqueous Resin Composition Curable aqueous composition was synthesized using Samples A to F Sample A 14.0 g Sample D 14.0 g p-toluene sulfonic acid 0.4 g The curable aqueous resin composition was applied to a glass plate using a 1 mil applicator and air dried at room temperature using a dryer. The obtained substrate is placed in an oven at 150 ° C for 30
Heat treatment was performed for minutes. The obtained film was insoluble in MEK (methyl ethyl ketone) and water. In addition, Table 1 shows execution results of combining the synthesized polymers of Samples A to F.

Table 1 ─────────────────────────────────── Examples Examples Catalyst Catalyst Temperature (℃) Time (Min) Cured state ─────────────────────────────────── 1 AD P-TSA 120 30 ○ 2 A D ↑ 100 30 ○ 3 B D ↑ 120 30 ○ 4 C F ↑ 120 30 ○ 5 A E ↑ 120 30 ○ 6 B D ↑ 100 30 ○ 7 B E ↑ 120 30 ○ 8 D ー CDO ↑ 150 90 ○ 9 A-PT ↑ 150 90 90 ○ 10 AD ↑ + BPO 150 30 ○ 11 A D cupric sulfate 150 30 30 ○ 12 A D ferric sulfate 150 30 ○ 13 A D BF 100 20 ○ 14 AD no 150 30 X 15 AD ↑ 25 6000 X ──────────────── ────────────────────

Cured state; ◯: insoluble in water However, in Example 4, insoluble in MEK and DMF X: soluble in water p-TSA; p-toluenesulfonic acid CDO; 1,4-cyclohexanedione PT; pentaerythritol BF; Boron trifluoride ethyl ether complex BPO; Benzoyl peroxide (5% added to the amount of resin) Composition ratio: Samples are mixed 1: 1 by weight, catalytic amount; 5% added to the amount of resin

Example 2 Synthesis of UV Curable Resin Composition Samples A to F were used to synthesize a UV curable composition. Sample A 14.0 g Sample D 14.0 g Diphenyliodonium hexafluorophosphate (DIP) 0.4 g Benzophenone (BP) 0.4 g The above curable composition was applied to a glass substrate using a 1 mil applicator and dried at room temperature. And air dried. 80W / c with ozoneless type UV irradiation device
m (1 light), UV irradiation under the conditions of 5 m / min and post-treatment at 100 ° C for 30 minutes after irradiation, the film is water, M
It was insoluble in EK (methyl ethyl ketone) and DMF (dimethylformamide). In addition, synthesized sample A
Table 2 shows the results of an ultraviolet curing experiment conducted in the same manner as in Example 2 in which various combinations of polymers of to F were combined.

Table 2 ─────────────────────────────────── Examples Examples Photopolymerization initiator Irradiation count Post-treatment time Cured state (times) (min) ──────────────────────────────────── 1 A D DIP + BP 1 30 ○ 2 AD ↑ 1 30 ○ 3 BD ↑ 2 30 ○ 4 C F ↑ 2 30 ○ 5 5 A E ↑ 1 30 ○ 6 B D ↑ 2 30 ○ 7 B E ↑ 1 30 ○ 8 A-PT + ↑ 4 150 ○ 9 A DDIP + TO + BPO1 30 ○ 10 A D DIP + TO 1 30 ○ 11 A D None 1 30 X ────────────────────────── ────────

Cured state: Good: insoluble in water X: soluble in water, but insoluble in MEK in Example 4 PT; pentaerythritol BPO; benzoyl peroxide (addition of 5% based on the amount of resin) TO: thioxanthone (resin 5% added to the amount) Composition ratio: Samples are mixed 1: 1 by weight, catalyst amount; 5% added to the resin amount

Example 3 Synthesis of Visible Light Curable Resin Composition Samples A to F were used to synthesize a visible light curable composition. Sample A 14.0 g Sample D 14.0 g Diphenyliodonium hexafluorophosphate (DIP) 0.4 g Di (diethylamino) ketocoumarin (dye) (KC) 0.4 g The above curable composition was applied to a glass substrate using a 1 mil applicator. And was air dried at room temperature using a dryer. The film was insoluble in water, MEK, and DMF after irradiation with visible light at an exposure dose of 300 mJ / cm 2 with a spot of 1 mm in diameter using a wavelength of 488 nm with an argon laser and post-treatment at 100 ° C. for 30 minutes after irradiation. . Other,
Table 3 shows the results of a photo-curing experiment by irradiation with visible light of 488 nm in the same manner as in Example 3 with various combinations of the synthesized polymers of Samples A to F.

Table 3 ────────────────────────────────── Examples Examples Photopolymerization initiator After irradiation Treatment time Cured state (mJ) (min) ─────────────────────────────────── 1 AD DIP + KC 300 30 ○ 2 AD ↑ 300 10 ○ 3 BD ↑ 300 30 ○ 4 C F ↑ 250 30 ○ 5 A E ↑ 250 30 ○ 6 BD ↑ 350 30 ○ 7 B E ↑ 250 30 ○ 8 C A ↑ 300 30 ○ 9 A-PT + ↑ 600 150 ○ 10 A DDIP + KC + BPO200 30 ○ 11 A D None 600 600 300 X 12 A D ↑ 950 600 X X ───────────────────── ─────────────

Cured state: ◯: Insoluble in water X: Soluble in water However, in Example 4, insoluble in MEK and DMF PT: Pentaerythritol BPO; Benzoyl peroxide (5% added to the amount of resin) Composition ratio: Sample Are mixed in a weight ratio of 1: 1; catalyst amount; 5% added to resin amount

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 33/00 LJH C08L 33/00 LJH C09D 133/00 PFY C09D 133/00 PFY 157/00 PDC 157 / 00 PDC

Claims (3)

[Claims] 1. A primary hydroxyl group-containing compound and two adjacent carbon atoms (provided that at least one carbon atom is bound to at least one hydrogen atom) in an aqueous medium.
A curable aqueous resin composition containing a ketone group-containing polymer compound having: 2. The curable aqueous resin composition according to claim 1, wherein the primary hydroxyl group-containing compound is a divalent or higher valent hydroxyl group-containing compound. 3. The curable aqueous resin composition according to claim 1, which further comprises a dehydration catalyst.