JPH05179102A - Aqueous cross-linkable resin composition - Google Patents

Abstract

PURPOSE:To improve the water resistance, solvent resistance, adhesion and smoothness of a coating film of an aq. cross-linkable resin compsn. by mixing a specific carbonylated copolymer resin with an aq. dispersion of a resin and a hydrazine deriv. CONSTITUTION:At least 0.5wt.% carbonylated unsatd. monomer contg. at least one aldo or keto group and one polymerizable unsatd. double bond per molecule is copolymerized with at least 0.5wt.% ethylenically unsatd. carboxylic acid, 33-99wt.% unsatd. monomer copolymerizable with the foregoing monomers and having a water solubility at 20 deg.C of at most 8g/100ml of water, and 0-69wt.% other unsatd. monomer in a water-soluble or hydrophilic solvent, followed by the addition thereto of an alkali and/or an org. solvent to obtain a carbonylated copolymer resin having a rate of solubilization of at least 5wt.%. The obtained resin is mixed with an aq. dispersion of a resin and a hydrazine deriv. having at least two hydrazino groups per molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous crosslinkable resin composition, which is heated or irradiated with ultraviolet rays or radiation when a film is formed by evaporating water in order to easily cause a crosslinking reaction at room temperature. Coating materials such as wood, metal, paper, plastics, slate, etc., which can provide a film having excellent water resistance, solvent resistance and substrate adhesion, and gloss without requiring special means such as It can be advantageously used as an adhesive, a fiber processing agent, a pressure sensitive adhesive and the like.

[0002]

2. Description of the Related Art Conventionally, aqueous resin dispersions have been widely used as coating agents for coatings, adhesives, fiber processing agents, adhesives, etc., and unlike solvent-based ones, they are pollution-free and resource-saving. Since it is excellent in workability, it has been positively converted from the solvent type to the aqueous resin dispersion type.

However, in conventional aqueous resin dispersions, the polymer is present in the form of particles and the molecular weight is generally 5
Since it has a high molecular weight of 0,000 to 1,000,000, it is inferior in fluidity, and as a result, it has drawbacks such as insufficient penetration into a base material and the like, adhesion to the base material, and a smooth coating film cannot be obtained. It was

In order to improve these drawbacks, attempts have been made to make a so-called micro emulsion having a small particle size and to add a water-soluble resin. However, in order to reduce the particle size of the polymer, a large amount of emulsifier must be used, and if a large amount of emulsifier is used, the water resistance of the film will be reduced due to the effect of the emulsifier. Further, the addition of the water-soluble resin reduces the water resistance of the film, and is not suitable for practical use.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to provide an aqueous crosslinkable resin composition capable of providing a film excellent in water resistance, adhesion to a substrate, smoothness and gloss. ..

[0006]

Means for Solving the Problems As a result of various studies to solve the above problems, the present inventors have found that an aqueous resin dispersion contains an aqueous resin having a carbonyl group in its molecular chain, Moreover, the object could be achieved by adding a specific copolymer resin having a relatively low hydrophilicity and a hydrazine derivative having two or more hydrazino groups.

That is, the aqueous crosslinkable resin composition of the present invention contains (A) (a) at least one aldo group or keto group and one polymerizable unsaturated double bond in the molecule. Carbonyl group-containing unsaturated monomer 0.5% by weight or more, (b)
0.5% by weight or more of ethylenically unsaturated carboxylic acid, (c)
An unsaturated monomer copolymerizable with (a) a carbonyl group-containing unsaturated monomer and (b) an ethylenically unsaturated carboxylic acid, which has a solubility in water at 20 ° C. of 8
30 to 99% by weight of an unsaturated monomer which is not more than g / 100 ml water, and (d) 0 to 69% by weight of an unsaturated monomer other than each of the monomers (a) to (c). A carbonyl group-containing copolymer resin obtained by copolymerization of a monomer mixture consisting of (B) an aqueous resin dispersion, and (C) a hydrazine derivative having at least two hydrazino groups in the molecule, And the solubilization rate of the (A) carbonyl group-containing copolymer resin is 5% by weight or more by the addition of an alkali and / or an organic solvent. It is a composition characterized by being solution treated.

Of the raw material unsaturated monomers for producing the (A) carbonyl group-containing copolymer resin used for preparing the aqueous crosslinkable resin composition of the present invention, (a) is in the molecule Examples of the carbonyl group-containing unsaturated monomer having at least one aldo group or keto group and one polymerizable unsaturated double bond include acrolein, diacetone acrylamide, formyl styrene, and 4 to 7 carbons. Vinyl alkyl ketone having atoms (eg vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), general formula

[0009]

[Chemical 1]

(In the formula, 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 1 to 1 carbon atoms. Acrylic (or methacryl) oxyalkylpropenal represented by 4 alkyl groups), diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-
Hydroxypropyl acrylate acetyl acetate,
Examples thereof include butanediol-1,4-acrylate acetyl acetate. Particularly preferred monomers thereof are diacetone acrylamide, acrolein and vinyl methyl ketone. Two or more kinds of these monomers may be used in combination.

(A) The carbonyl group-containing unsaturated monomer is
It is 0.5% by weight or more, preferably 5 to 30% by weight, based on the total monomer mixture. If the amount of the monomer is too small,
The content of aldehyde groups or keto groups in the copolymer resin is too small, the crosslink density due to the reaction with the (C) hydrazine derivative decreases, and the film has sufficient water resistance, solvent resistance, blocking resistance, etc. Will not be obtained. If the amount of the monomer is too large, the alkali resistance, weather resistance, etc. of the film tend to decrease.

The (b) ethylenically unsaturated carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid, but preferably a monoolefinic unsaturated carboxylic acid having 3 to 5 carbon atoms. Is. In particular, acrylic acid, methacrylic acid, and itaconic acid are preferable. The amount of ethylenically unsaturated carboxylic acid is 0.5% by weight or more, preferably 1.0 to 40% by weight, based on the total monomer mixture. If the amount of the monomer is too small, sufficient solubilization (solubilization) will occur when solubilizing treatment is performed by adding an alkali and / or organic solvent.
Therefore, it is impossible to obtain sufficient smoothness and adhesion of the film. On the other hand, when the amount of the monomer is too large, the hydrophilicity of the copolymer resin becomes too high and the water resistance of the film tends to decrease. In particular, in order to provide a film with high water resistance, it is desirable to reduce the amount of the monomer within the above range as much as possible.

The unsaturated monomer (c) is a monomer copolymerizable with the above-mentioned (a) carbonyl group-containing unsaturated monomer and (b) the ethylenically unsaturated carboxylic acid, 20
It is a monomer whose solubility in water at 8 ° C is 8 g / 100 ml water or less. As a specific example, for example, carbon number 1
Acrylic acid or methacrylic acid ester of saturated alkanol of 10 such as methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate; vinyl aromatic compound such as styrene; halogen such as vinyl chloride, vinylidene chloride Vinyl chloride; unsaturated hydrocarbons such as ethylene and butadiene; vinyl esters such as vinyl acetate and vinyl propionate; and acrylonitrile, methacrylonitrile, glycidyl methacrylate and the like. The amount of this unsaturated monomer is 30 to 99% by weight, preferably 55 to 94% by weight, based on the total amount of unsaturated monomers.

(D) Monomers other than the above-mentioned monomers (a) to (c) include unsaturated amides such as acrylamide and methacrylamide; hydroxyethyl acrylate, hydroxypropyl acrylate and the like. Examples thereof include hydroxyl group-containing monomers; vinyl sulfonic acids, styrene sulfonic acids, and sulfonated monomers such as salts thereof; and other N-methylol acrylamides.
The amount of the other unsaturated monomer (d) is 0 to 69% by weight, preferably 0 to 15% by weight, based on the total amount of unsaturated monomers.

The copolymerization for producing the (A) carbonyl group-containing copolymer resin using each of the monomer mixtures of the above (a) to (d) is carried out by solution polymerization or emulsion polymerization.

The solvent used in the solution polymerization is not particularly limited, but a water-soluble or hydrophilic solvent is preferable from the viewpoint of compatibility with the produced copolymer resin and water. Specific examples thereof include monoalcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and t-butyl alcohol; ethylene glycol and its derivatives such as ethylene. Glycol monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether; diethylene glycol and its derivatives, such as diethylene glycol monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether; Others 1,
Examples include 4-dioxane and water. One type of these solvents may be used, or two or more types may be appropriately used in combination. As the solvent, those having a boiling point of 200 ° C. or less are generally preferable from the viewpoint of distillation after the polymerization or drying speed.

The polymerization initiator for solution polymerization is preferably oil-soluble. Specific examples thereof include azo initiators such as azobisisobutyronitrile and azobisvaleronitrile; organic peroxide initiators such as benzoyl peroxide, lauroyl peroxide and t-butyl peroxide; and other peroxides. Inorganic peroxide type initiators such as hydrogen and ammonium persulfate can also be used. These initiators may be used alone or in combination of two or more as appropriate. Further, a reducing agent such as rongalite, L-ascorbic acid, or an organic amine may be used in combination with these initiators and used as a redox initiator.

The carbonyl group-containing copolymer resin (A) can also be produced by emulsion polymerization. In this emulsion polymerization, an emulsifier is used and polymerization is carried out with a water-soluble polymerization initiator. Alternatively, a method of carrying out polymerization by soap-free polymerization or the like is used. Examples of the emulsifier include various anionic, cationic and nonionic emulsifiers, and further polymeric emulsifiers. A particularly preferred emulsifier is a carbonyl group-containing polymer emulsifier described in JP-A-64-48801, which is a publication of a patent application relating to the invention of the present inventors (a part).

The polymerization initiator used in emulsion polymerization is preferably an inorganic peroxide such as potassium persulfate, ammonium persulfate or hydrogen peroxide. These inorganic peroxides include
You may use together with the reducing agent as mentioned above as a redox initiator.

Various methods can be used as the method of supplying the monomers in the emulsion polymerization. For example, the batch charging method,
Various methods such as a monomer addition method and an emulsion addition method can be used. Further, a seed polymerization method in which the composition of the monomer to be added is sequentially changed, or a power hood polymerization method or the like can also be used. When such a method is used, the center portion of the produced copolymer resin particles and the outside can be separated from each other. The copolymer composition can be varied to control the degree of solubilization.

A chain transfer agent is preferably used in the emulsion polymerization. This is because the copolymer resin obtained by emulsion polymerization generally has a high molecular weight, so that when it is solubilized in water by the addition of an alkali and / or an organic solvent, it is difficult to achieve sufficient solubilization, but chain transfer This is because the use of the agent can reduce the molecular weight of the produced copolymer resin and facilitate the solubilization. Examples of the chain transfer agent include various mercaptans, α
-Methylstyrene, alkyl halides, alcohols and the like. The amount used is 0.03 to 5% by weight based on all the monomers.

The (A) carbonyl group-containing copolymer resin prepared by the solution polymerization or emulsion polymerization described in detail above is
The addition of an alkali and / or an organic solvent solubilizes the copolymer resin to a solubilization rate of 5% by weight or more. The solubilization treatment (that is, addition of an alkali and / or an organic solvent) ) May be before the initiation of the copolymerization for producing the (A) carbonyl group-containing copolymer resin, or at the time of the copolymerization, or (A) the carbonyl group-containing copolymer resin. And (B) resin aqueous dispersion and /
Alternatively, it may be before the (C) hydrazine derivative is mixed, during the mixing, or even after the mixing. In any case, the "solubilization rate" described in the present specification means the solubilization rate measured by the following method.

That is, in any of the above cases, the same conditions as in the actual solubilization treatment can be applied without mixing the (B) resin aqueous dispersion and the (C) hydrazine derivative at all. The resin composition was prepared by solubilization, and the obtained resin composition was diluted with water to a nonvolatile content of 15% by weight, and the diluted solution was subjected to centrifugal acceleration of 1.
After centrifuging at 8 × 10 ⁵ g for 60 minutes, the non-volatile content in the obtained supernatant was measured to be w parts by weight, and the non-volatile content in the diluent used for centrifugation was measured to obtain W. It means the solubilization rate represented by the following formula in parts by weight. Solubilization rate = w / W x 100 (% by weight)

Therefore, for example, when the copolymerization is carried out by adding an alkali and / or an organic solvent to the polymerization system before or during the polymerization for producing the (A) carbonyl group-containing copolymer resin. And a polymerization product containing the produced copolymer resin obtained by the copolymerization is
When the solubilization rate is already 5% by weight or more as it is, the polymerization product is simply mixed with (B) the resin aqueous dispersion and (C) the hydrazine derivative (in other words, the solubilization treatment is repeated. The aqueous crosslinkable resin composition of the present invention can be obtained (without addition of an alkali and / or an organic solvent).

The alkali used for the solubilization treatment is an inorganic water-soluble alkali such as sodium hydroxide or potassium hydroxide; or an inorganic salt which shows alkalinity when dissolved in water, such as sodium hydrogen carbonate or pyrophosphate. Sodium and the like; other examples include aqueous ammonia and organic amines. Addition of alkali is as described above.
It is not always necessary after the formation of the copolymer, and in some cases (A) an alkali is added to the (b) ethylenically unsaturated carboxylic acid before the copolymerization for forming the carbonyl group-containing copolymer resin. Copolymerization may be performed after neutralization. Further, the addition of the alkali in the case of solution polymerization, may be in the presence of the solvent used for the copolymerization, or by adding the alkali to the copolymer resin after distilling the solvent as an aqueous solution and partially Alternatively, it may be completely solubilized in water. The amount of alkali used may be an amount that completely neutralizes the carboxyl groups in the copolymer resin or an amount that partially neutralizes the carboxyl groups.

The organic solvent used for the solubilization treatment may be supplementarily added when it cannot be sufficiently solubilized in water only by adding an alkali, or may be solubilized by adding only an organic solvent. Further, in the case of producing the (A) carbonyl group-containing copolymer resin by solution polymerization, when the organic solvent used as the polymerization solvent can directly serve as the organic solvent for solubilization, In particular, it may not be necessary to newly add an organic solvent, and in some cases, an organic solvent different from the organic solvent used as the polymerization solvent may be added. Examples of the organic solvent used include the same ones as described above as the solvent used for the solution polymerization. Particularly preferred organic solvents include texanol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and their acetates, bezyl alcohol, butyl carbitol acetate, 2,2,4-trimethyl-1,3-pentanediol and the like. ..

Next, the (B) resin aqueous dispersion used in the present invention is an aqueous emulsion of a synthetic resin obtained by synthesis or a wide variety of natural resins, and a synthetic resin obtained by emulsion polymerization. Emulsion is preferred.

As is generally known, the synthetic resin aqueous dispersion obtained by emulsion polymerization uses an emulsifier, a reactive emulsifier or a protective colloid as a dispersant, and a water-soluble initiator as an unsaturated monomer. Is obtained by (co) polymerizing in water. Examples of the unsaturated monomer include acrylic acid, methacrylic acid, various esters thereof, vinyl aromatic compounds such as styrene, vinyl halides,
Acrylonitrile, methacrylonitrile, saturated carboxylic acid vinyl ester, conjugated dienes, ethylene, unsaturated hydrocarbons such as propylene, using an appropriate combination according to the purpose, usually copolymer resin aqueous dispersion What was made into is used suitably.

In addition to the resin aqueous dispersion obtained by emulsion polymerization, there are, for example, polyurethane resin emulsion, alkyd resin emulsion, bisphenol type epoxy resin emulsion, and the like. It can be used as an aqueous resin dispersion.

Particularly preferred (B) resin aqueous dispersion is 0.5 to 20 of the above-mentioned (a) carbonyl group-containing unsaturated monomer.
% By weight; 0 to (b) ethylenically unsaturated carboxylic acid
10% by weight; at least one selected from an alkyl ester of acrylic acid or methacrylic acid having 1 to 10 carbon atoms, acrylonitrile, methacrylonitrile, vinyl aromatic compound, vinyl halide, vinyl ester of saturated carboxylic acid, ethylene and butadiene. Unsaturated monomer 5
5 to 99% by weight; and other monomers other than the above 0 to 15
It is an aqueous dispersion of a copolymer resin obtained by emulsion polymerization of a monomer mixture of wt%.

The carbonyl group-containing unsaturated monomer (a) used in this case is the (a) carbonyl group-containing unsaturated monomer used in the production of the above-mentioned (A) carbonyl group-containing copolymer resin. Since it is the same as the monomer, the aqueous crosslinkable resin composition of the present invention using the above-mentioned particularly preferable aqueous resin dispersion containing the unsaturated monomer as a constituent component contains (C) a hydrazine derivative. As a mediator, (A) a carbonyl group-containing copolymer resin is mutually complicated, (B) a copolymer resin constituting an aqueous resin dispersion, and both resins (A) and (B) are complicated. Since the crosslinks can be formed, the physical properties of the crosslinked film are further improved.

The mixing ratio of the (A) carbonyl group-containing copolymer resin and the (B) resin aqueous dispersion in the present invention may be arbitrary, but it is a solid content weight ratio of (A) / (B). Preferably 0.01-4.0, more preferably 0.1-1.
It is 0. If the proportion of the (A) carbonyl group-containing copolymer resin is too low, the effect of improving the adhesion, smoothness and gloss of the coating to the substrate cannot be sufficiently obtained, and if the proportion is too high, the water resistance of the coating is high. Sex decreases. In the latter case, the cause of the decrease in the water resistance of the coating film is the direct influence of the increase in the proportion of the (A) carbonyl group-containing copolymer resin, which is relatively poor in water resistance, and the (A) carbonyl group. The increase in the content of the copolymer resin contained (B) makes it impossible to effectively prevent the infiltration of water into the inside of the film by the resin aqueous dispersion, thereby facilitating the cleavage reaction of the cross-linking bond with water. It is presumed that the synergistic effects will act synergistically.

The method of blending the (A) carbonyl group-containing copolymer resin and the (B) resin aqueous dispersion is not particularly limited. For example, to an organic solvent solution containing a (A) carbonyl group-containing copolymer resin obtained by solution polymerization, an alkali solution is added, the solvent is distilled off, and then a (B) resin aqueous dispersion is added. Alternatively, the solvent may be added without being distilled off. When the (A) carbonyl group-containing copolymer resin is obtained by emulsion polymerization, an alkali and / or organic solvent is added to the (A) carbonyl group-containing copolymer resin aqueous dispersion to solubilize it. After that, the (B) resin aqueous dispersion may be added. Alternatively, the (A) carbonyl group-containing copolymer resin and the (B) resin aqueous dispersion may be mixed and then the alkali and / or organic solvent may be added.

The hydrazine having at least two hydrazino groups in the molecule (C) used in the present invention is, for example, a dicarboxylic acid dihydrazide having 2 to 10 carbon atoms, particularly 4 to 6 carbon atoms (for example, dihydrazide). Oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide), an aliphatic having 2 to 4 carbon atoms Hydrazine (eg ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-
Dihydrazine etc.)

In addition, the general formula

[0036]

[Chemical 2]

[In the formula, X is a hydrogen atom or a carboxyl group, Y is a hydrogen atom or a methyl group, A is each unit of acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester or maleic anhydride. , B is a unit of a monomer copolymerizable with acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester or maleic anhydride. Further, k, m and n are numbers satisfying the following formulas: 2 mol% ≦ k ≦ 100 mol% 0 mol% ≦ (m + n) ≦ 98 mol% (k + m + n) = 100 mol%. ] The polymer represented by the above can also be used as the hydrazine derivative. Such polymers are described in detail, for example, in JP-A-55-6535.

The mixing ratio of the (C) hydrazine derivative is
The ratio of (A) the carbonyl group-containing copolymer resin and (B) and the carbonyl group contained in the aqueous resin dispersion (C) and hydrazino group, (> C = O) / - preferably with (NHNH ₂₎ molar ratio Is 0.2 to 5.0, more preferably 0.3 to 2.
It is a ratio of 0. If the proportion of the hydrazine derivative (C) is too small, the cross-linking between the resins will be insufficient and the water resistance will decrease. Further, if the proportion is too large, not only the effect of improving the water resistance commensurate with it cannot be obtained, but also the coating becomes opaque and easily becomes brittle.

The aqueous crosslinkable resin composition of the present invention includes pigments, mica powder, barite, which are generally known to be added to paints, pressure sensitive adhesives, fiber processing agents, adhesives and the like.
Pigments such as titanium oxide; potassium, sodium or ammonium salts of condensed phosphoric acid such as hexametaphosphoric acid; sodium or ammonium salts of polyacrylic acid, conventional anionic or nonionic surfactants;
Thickeners such as methyl cellulose, ethyl cellulose, propyl cellulose, carboxymethyl cellulose, polyvinyl alcohol and the like; various additives such as dispersants, tackifiers, flame retardants and the like can be added.

[0040]

EXAMPLES Hereinafter, copolymer resin preparation examples, resin aqueous dispersion preparation examples, examples and comparative examples will be described in detail. The "parts" and "%" described in these examples are on a weight basis.

Copolymer Resin Preparation Example 1 Temperature controller, anchor type stirrer, reflux condenser, supply container,
After the inside of the reaction vessel equipped with a thermometer and a nitrogen introducing tube was replaced with nitrogen, 130 parts of ethylene glycol monobutyl ether was charged.

Separately, the following composition was prepared as a feed. Feed material Ethylene glycol monobutyl ether 110 parts Methacrylic acid 5 parts Diacetone acrylamide 20 parts 2-Hydroxyethyl acrylate 5 parts Methyl methacrylate 70 parts Benzoyl peroxide 3 parts

Then, while maintaining the inside of the reaction vessel at 80 ° C., the above-mentioned feed was continuously fed thereto in small portions over 3 hours. After the end of the supply, the same temperature was maintained for 2 hours to complete the polymerization.

This solution was concentrated by distillation until the nonvolatile content became 60%, and then 23 g of a 10% sodium hydroxide aqueous solution was added to obtain an ethylene glycol monobutyl ether solution of a carbonyl group-containing copolymer resin having a nonvolatile content of 54%. Obtained.

Copolymer Resin Preparation Example 2 Into the same reaction vessel as used in Preparation Example 1 above, the following materials were charged. 50 parts of water 35% aqueous solution of sulfuric acid half ester sodium salt of p-nonylphenol with 20 mol of ethylene oxide (referred to as "anionic emulsifier A") 2 parts P-nonylphenol with 25 mol of ethylene oxide ("nonionic emulsifier B") 2% of a 20% aqueous solution of

Separately, the following mixture was prepared as the feed I. Feed I Water 50 parts 35% aqueous solution of the above anionic emulsifier A 4 parts 20% aqueous solution of the above nonionic emulsifier B 5 parts Methyl methacrylate 40 parts Butyl acrylate 38 parts Diacetone acrylamide 15 parts Acrylic acid 7 parts 0.4 part of t-dodecyl mercaptan

Separately, an aqueous solution prepared by dissolving 0.6 part of potassium persulfate in 20 parts of water was prepared as the feed II.

After purging the inside of the reaction vessel with nitrogen gas, 10% of the feed I was added to the charge, and the mixture was heated to 90 ° C. Then, 10% of the feed II was injected into the reaction vessel and then the remaining feeds I and II were fed uniformly in parallel in small portions over 3.5 hours. After the end of the supply, the temperature was kept at 90 ° C. for 1.5 hours to complete the emulsion polymerization.

A 100% aqueous solution of sodium hydroxide was added to 100 parts of the resin aqueous dispersion obtained as described above, and the pH was adjusted to pH 10.
To 8.5, and then 5 parts of benzyl alcohol was added, and the mixture was diluted with water so that the nonvolatile content was 25%.

Copolymer Resin Preparation Example 3 Isopropanol 1 was placed in the same reaction vessel as in Preparation Example 1 above.
Charge 30 parts and change the feed to the following feed,
Otherwise, the polymerization was carried out in the same manner as in Example 1.

Feeds Isopropanol 110 parts Acrylic acid 4 parts Diacetone acrylamide 10 parts Ethyl acrylate 86 parts Azobisisobutyronitrile 1 part

After the completion of the polymerization reaction, 22 parts of a 10% aqueous sodium hydroxide solution and 300 parts of water were added to neutralize the carboxyl groups in the copolymer to make it aqueous. Then, 320 parts of a mixture of isopropanol and water was distilled off from the obtained aqueous resin composition using a rotary evaporator to completely remove the carbonyl group-containing copolymer resin having a nonvolatile content of 28% and PH 8.5 into water. A dissolved solution was obtained.

Copolymer Resin Preparation Example 4 Polymerization was carried out in the same manner as in Preparation Example 3 except that the supply was changed as follows, and post-treatment was carried out in the same manner to prepare a copolymer containing no carbonyl group. A polymer resin was obtained.

Feeds Isopropanol 110 parts Acrylic acid 10 parts Ethyl acrylate 20 parts Methyl methacrylate 57 parts 2-Hydroxyethyl acrylate 13 parts

Copolymer Resin Preparation Example 5 An aqueous dispersion of a carbonyl group-containing copolymer resin was obtained in the same manner as in Preparation Example 2 except that the feed I was changed as follows.

Feed I Water 50 parts 35% aqueous solution of the above anionic emulsifier A 2 parts 20% aqueous solution of the above nonionic emulsifier B 5 parts Acrylic acid 0.3 parts Diacetone acrylamide 15 parts Methyl methacrylate 49. 7 parts Butyl acrylate 35 parts

Table 1 shows the polymerization method, the monomer composition, the polymerization solvent, the chain transfer agent present in the polymerization system, and the nonvolatile content of the produced resin composition in the above-mentioned copolymer resin preparation examples 1 to 5. It was as shown.

[0058]

[Table 1]

Copolymer Resin Preparation Examples 6 to 10 The compositions of the monomer and chain transfer agent were changed as shown in Table 2, and in the case of Preparation Example 9, the same method as in Preparation Example 3 was used. In the case of Preparation Examples 6 to 8 and 10, carbonyl group-containing copolymer resin aqueous dispersions were prepared in the same manner as in Preparation Example 2 above. The nonvolatile content of each obtained resin composition was as shown in Table 2.

[0060]

[Table 2]

Resin Aqueous Dispersion Preparation Example a In a reaction vessel similar to that used in Preparation Example 1 above, the following were charged.

Water 200 parts 35% aqueous solution of anionic emulsifier A 5 parts 20% aqueous solution of nonionic emulsifier B 20 parts

Separately, the following mixture was prepared as a feed I. Feed I Water 200 parts 35% aqueous solution of the above anionic emulsifier A 25 parts Acrylic acid 10 parts Diacetone acrylamide 23 parts Butyl acrylate 198 parts Styrene 235 parts

Separately, as a feed II, a solution of 2.5 parts of potassium persulfate in 85 parts of water was prepared.

After purging the reaction vessel with nitrogen gas, 10% of feed I was added to the charge and the mixture was heated to 85.degree. Then 10% of Feed II was injected into the reaction vessel,
In addition, the remaining feeds I and II were fed into the reaction vessel in parallel in small portions over 3 to 3.5 hours. After the end of the supply, the temperature was raised to 90 ° C. and the temperature was kept for another 1.5 hours to carry out emulsion polymerization. The resulting resin aqueous dispersion has a nonvolatile content of 47% and a minimum film forming temperature of 24 ° C.
Met.

Aqueous Resin Liquid Dispersion Preparation Examples b to e The monomer composition of the feed I in the above Preparation Example a was changed to the monomer composition shown in Table 3, and the emulsification was performed in the same manner as in Preparation Example a. Polymerization and neutralization were carried out in the same manner to obtain a copolymer resin aqueous dispersion.

Table 3 shows the monomer compositions, the non-volatile components and the minimum film-forming temperature of the resin dispersions produced in the above resin aqueous dispersion preparation examples a to e.

[0068]

[Table 3]

Example 1 30 parts of ethylene glycol monobutyl ether solution having a nonvolatile content of 54% obtained in Preparation Example 1 of copolymer resin, aqueous dispersion of copolymer resin 1 obtained in Preparation Example a of resin aqueous solution 1
15 parts, and a 20% aqueous solution of adipic dihydrazide 1
5 parts were mixed.

With respect to the dry film of the obtained aqueous resin composition, the water resistance, solvent resistance, substrate adhesion and smoothness of the film were tested by the following test methods, and the evaluation results are shown in Table 4. there were.

Water resistance test of film: 20 ° C. so that the film thickness after drying the aqueous resin composition on a glass plate becomes 500 μm.
And dried for 1 week to form a film. This film is 5 cm x 5 c
Punching test pieces were made in m square. This test piece was immersed in water at 20 ° C. for 24 hours, then taken out and the water absorption rate (%) of the film
Was measured.

Solvent resistance test of film: A test piece prepared under the same conditions as in the water resistance test was immersed in toluene at 20 ° C. for 24 hours.
After soaking for a period of time, it was taken out and the edge expansion coefficient (%) of the film was measured.

Substrate adhesion test: An aqueous resin composition was coated on each of the substrates shown in Tables 4 to 7 so that the dry coating film thickness was 20 μm, and dried at 20 ° C. for 1 week. A test piece was prepared. The test piece was subjected to a peeling test using an adhesive tape (Cellotape, a registered trademark of Nichiban Co., Ltd.) and evaluated according to the following criteria. A: Not separated at all B: Partly separated C: Separated at a considerable part

Film smoothness test: Drying of the aqueous resin composition on a glass plate, and the smoothness of the crosslinked coating film were visually examined and evaluated according to the following criteria. A: extremely smoothness B: slightly inferior smoothness C: poorly smoothness

Examples 2 to 10 Comparative Examples 1 to 7 In Example 4, the types and amounts of the copolymer resin, the resin aqueous dispersion and the hydrazine derivative were changed as shown in Table 4, and other than Example 1 An aqueous resin composition was prepared in the same manner, and its physical properties were tested in the same manner.

In each of Examples other than Example 4 and each Comparative Example, the kinds and amounts of the copolymer resin, the resin aqueous dispersion and the hydrazine derivative were changed as shown in Tables 4 to 7,
In addition, an aqueous resin composition was prepared in the same manner as in Example 1 except that ethylene glycol monobutyl ether was mixed in the respective amounts, and the physical properties of the film were tested in the same manner.

Tables 4 to 7 show the composition ratios (parts) of the aqueous resin compositions obtained in these Examples and Comparative Examples, and the test results of the physical properties of the film.

[0078]

[Table 4]

[0079]

[Table 5]

[0080]

[Table 6]

[0081]

[Table 7]

Note to Tables 4 to 7: * 1 ... Adipic acid dihydrazide * 2 ... Addition amount of ethylene glycol monobutyl ether corresponds to 5% with respect to the amount of (B) resin aqueous dispersion. Is.

As is clear from Tables 4 to 7, the resin compositions of the Examples have higher water resistance than the resin compositions of the Comparative Examples.
Excellent in terms of solvent resistance, substrate adhesion and smoothness.

[0084]

Industrial Applicability The resin composition of the present invention can be easily dried and crosslinked and cured at room temperature to give a film excellent in water resistance, solvent resistance, adhesion to a substrate and smoothness. ..

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshinori Kato 1000 Kawajiri-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Verde Diesie Co., Ltd. (72) Inventor Takeshi Kurita 1000, Kawajiri-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Verditsie Co., Ltd. Within

Claims (3)

[Claims] 1. A carbonyl group-containing unsaturated monomer containing at least one aldo group or keto group and one polymerizable unsaturated double bond in the molecule (A) (a). weight%
Above, (b) 0.5 wt% of ethylenically unsaturated carboxylic acid
As described above, (c) the unsaturated monomer containing a carbonyl group-containing unsaturated monomer and (b) the unsaturated monomer copolymerizable with the ethylenically unsaturated carboxylic acid, 30-99% by weight of an unsaturated monomer having a solubility of 8 g / 100 ml or less in water, and (d) an unsaturated monomer 0-69 other than each of the monomers (a) to (c). Carbonyl group-containing copolymer resin obtained by copolymerization of monomer mixture consisting of 1 wt%, (B) resin aqueous dispersion, and (C) hydrazine derivative having at least two hydrazino groups in the molecule And the solubilization rate of the (A) carbonyl group-containing copolymer resin becomes 5% by weight or more by the addition of an alkali and / or an organic solvent. Characterized by being solubilized in The aqueous crosslinkable resin composition. 2. The (B) aqueous resin dispersion contains a carbonyl group-containing unsaturated monomer containing at least one aldo group or keto group and one polymerizable unsaturated double bond in the molecule. 0.5 to 20% by weight, ethylenically unsaturated carboxylic acid 0
10% by weight, an alkyl ester of acrylic acid or methacrylic acid having 1 to 10 carbon atoms, a vinyl aromatic compound,
Vinyl halide, vinyl ester of saturated carboxylic acid,
55 to 99.5% by weight of at least one unsaturated monomer selected from the group consisting of acrylonitrile, methacrylonitrile, ethylene, and butadiene, and unsaturated monomers other than the above-mentioned monomers The aqueous crosslinkable resin composition according to claim 1, which is a resin dispersion obtained by copolymerizing a monomer mixture of 0 to 15% by weight. 3. An (A) carbonyl group-containing copolymer resin and (B) an aldo group or keto group in an aqueous resin dispersion,
(C) The ratio of the hydrazine derivative to the hydrazino group is (>
C = O) / (- NHNH 2) are in a molar ratio 0.2 to 5.0, and (A) the ratio of the carbonyl-containing copolymer resin (B) aqueous resin dispersion, (A) The weight ratio of the resin / (B) resin is 0.01 to 4.0.
The aqueous crosslinkable resin composition according to item 1.