JP2000204223A - One-component crosslinking resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-component crosslinking resin compsn. excellent in workability and also in water resistance, water resistant adhesion, and solvent resistance. SOLUTION: This compsn. is prepared by compounding a water soluble hydrazine compd. (D) to a polymer emulsion obtd. by emulsion polymerization of an unsaturated monomer contg. a carbonyl group (B) having at least one carbonyl group selected from among aldo group or keto group and a double bond capable of polymerization in a molecule and an ethylenic unsaturated monomer other than (B)(C) with an acryl amide modified polyvinyl alcohol (A) as a dispersant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention is excellent in workability,
The present invention also relates to a one-component crosslinkable resin composition having excellent water resistance, water resistance, and solvent resistance.

[0002]

2. Description of the Related Art Emulsions prepared by using polyvinyl alcohol (hereinafter abbreviated as PVA) as a dispersant (protective colloid agent) have been used for a long time in many applications including adhesives and paints. However, since PVA itself is water-soluble, the film obtained from the emulsion easily swells in water.
Since A is eluted, there is a problem that its water resistance is insufficient.

[0003] For this reason, various methods have been tried so far to increase the water resistance of a film obtained from an emulsion containing PVA as a dispersant. For example, an adhesive in which a crosslinking agent is blended with an emulsion containing PVA as a dispersant is known, and although the water resistance is improved to some extent, there is a problem that gelation is apt to occur due to the coexistence of the crosslinking agent, resulting in poor workability. In order to solve these drawbacks, attempts have been made to use modified PVA instead of PVA. For example, JP-A-8-113687 discloses that a synthetic resin emulsion containing acetoacetylated polyvinyl alcohol is soluble in water. One-component crosslinkable synthetic resin emulsions comprising an organic amine and a water-soluble hydrazine derivative are disclosed. JP-A-10-130455 discloses a water-soluble hydrazine compound, a water-soluble hydrazine compound, and a water-based emulsion containing a diacetone acrylamide-modified PVA as an emulsifying / dispersing agent and a polymer of an ethylenically unsaturated monomer as a dispersoid. An emulsion composition comprising an amine or ammonia is disclosed.

[0004]

However, in the above-mentioned disclosed technology, satisfactory performance cannot be obtained with respect to high-order water resistance that can respond to recent market requirements.
Water resistance and solvent resistance are insufficient, and there is still a problem in practicality.

[0005]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies to solve the above problems, as a result of using acrylamide-modified PVA (A) as a dispersant, at least one carbonyl group selected from an ald group or a keto group and one polymerizable diamine in a molecule. A water-soluble hydrazine compound (A) is added to a polymer emulsion obtained by emulsion polymerization of a carbonyl group-containing unsaturated monomer (B) having a heavy bond and an ethylenically unsaturated monomer (C) other than (B). The one-part crosslinkable resin composition containing D) was found to be excellent in workability and excellent in water resistance, water resistance and solvent resistance, and completed the present invention.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Acrylamide-modified P used as a dispersant in the present invention
VA (A) can be produced by a known method such as saponifying a polymer obtained by copolymerizing a fatty acid vinyl ester and an acrylamide monomer.

The fatty acid vinyl esters used in the above copolymerization include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and the like, with vinyl acetate being industrially preferred.

Acrylamide monomers include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-phenylacrylamide,
N′-dimethylacrylamide, N, N′-diethylacrylamide, N, N′-dipropylacrylamide,
N, N'-di-butylacrylamide, N, N'-diphenylacrylamide, N-methyloylacrylamide, methacrylamide, N-methylmethacrylamide,
N-ethyl methacrylamide, N-propyl methacrylamide, N-butyl methacrylamide, N-phenyl methacrylamide, N, N'-dimethyl methacrylamide, N, N'-diethyl methacrylamide, N, N'-
Dipropyl methacrylamide, N, N'-di-butyl methacrylamide, N, N'-diphenyl methacrylamide, N-methylol methacrylamide, diacetone acrylamide and the like are preferable, and diacetone acrylamide is preferable.

As the above-mentioned copolymerization method of the fatty acid vinyl ester and the acrylamide monomer, various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, which are conventionally known, are possible. Is preferably industrially used as a solvent.

As a method for saponifying a copolymer obtained by copolymerizing a fatty acid vinyl ester and an acrylamide monomer, conventionally known alkali saponification or acid saponification can be applied. An alkali saponification method in which an alkali hydroxide is added to a combined methanol solution or a mixed solution of methanol and water, methyl acetate, benzene or the like is industrially preferable.

The acrylamide-modified PVA (A) used as a dispersant in the present invention can be copolymerized with a fatty acid vinyl ester or acrylamide-based monomer, for example, crotonic acid, so long as the effects of the present invention are not impaired. Unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid and esters, salts, anhydrides, nitriles, maleic acid, itaconic acid, unsaturated dicarboxylic acids such as fumaric acid and salts thereof, monomethyl maleate, monomethyl itaconate, etc. Unsaturated dibasic acid monoalkyl esters of 2 to 2 carbon atoms
30, α-olefins, alkyl vinyl ethers,
It may be copolymerized with vinylpyrrolidone and the like. In addition, the obtained acrylamide-modified PVA may be post-modified by a reaction such as acetalization, urethanization, etherification, grafting, or phosphoric esterification within a range not to impair the effects of the present invention.

Acrylamide-modified P used in the present invention
The content (degree of modification) of the acrylamide group of VA (A) is preferably in the range of 0.1 to 15 mol%, more preferably 0.5 to 15 mol%.
10 mol%. Acrylamide group content of 0.1
If the amount is less than 15 mol%, the water resistance tends to be insufficient. If the content exceeds 15 mol%, not only the effect of the water resistance becomes saturated, but also the pot life decreases and the workability decreases. This is not preferred because of problems.

The degree of polymerization and the degree of saponification of the acrylamide-modified PVA (A) are not particularly limited, but the degree of polymerization is preferably 300 to 3000, more preferably 500 to 25.
00. The saponification degree is preferably 85 mol% or more, and more preferably 90 to 99 mol%. If the degree of polymerization is less than 300, the water resistance tends to be insufficient. If the degree of polymerization exceeds 3000 or the degree of saponification is less than 85 mol%, the dispersibility of the obtained emulsion is poor, and aggregation and precipitation tend to occur. There is not preferred.

The carbonyl group-containing monomer (B) of the present invention
Is a carbonyl group-containing unsaturated monomer having at least one carbonyl group selected from ald groups or keto groups and one polymerizable double bond in the molecule, and is preferably a monoolefinically unsaturated alkoxide. Compound or monoolefinically unsaturated keto compound. Of course, an ester bond as a carbonyl group together with a polymerizable double bond

Examples of the carbonyl group-containing monomer (B) include, for example, acrolein, diacetone acrylamide, formylstyrene, and vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, Vinyl butyl ketone), acrylic (or methacryl) oxyalkyl propanal represented by the following general formula (1), diacetone acrylate,
2-hydroxypropyl acrylate acetyl acetate, butanediol-1, 4-acrylate acetyl acetate and the like can be mentioned. Particularly preferred monomers are diacetone acrylamide, acrolein, and vinyl methyl ketone.

[0016]

Embedded image (Wherein 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, R ⁴ is 1 to 4 These carbonyl group-containing monomers (B) may be used alone or
Two or more kinds may be contained.

Examples of the ethylenically unsaturated monomer (C) other than the above (B) of the present invention include halogenated olefins such as vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride; vinyl formate; Vinyl esters such as vinyl, vinyl propionate, vinyl versatate, and vinyl pivalate; acrylic esters such as acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; and methyl methacrylate Methacrylates such as ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and quaternized products thereof. Examples thereof include acrylamide-based monomers such as acrylamide, methacrylamide, N-methylolacrylamide, and N-dimethylacrylamide, and diene-based polymers such as N-vinylpyrrolidone, butadiene, isoprene, and chloroprene. Vinyl, vinyl versatate, methyl methacrylate, and butyl acrylate. These are used alone or in combination of two or more.

As a method for producing a polymer emulsion using the above (A) to (C), the above (B) and (C) are added to the aqueous solution or dispersion of (A) at once or continuously. Emulsion polymerization, or a method in which a mixture obtained by emulsifying (B) and (C) with an aqueous solution or dispersion of (A) is continuously added (dropped) to water to carry out emulsion polymerization. Alternatively, a method of adding (A) to the reaction system of (B) and (C) may be used.

The mixing ratio of (B) and (C) is as follows:
(B) / (C) = 0.5 / 99.5 to 40/60 (weight ratio) is preferable, and the ratio is more preferably 2/98 to 30/70.
If the compounding ratio is less than 0.5 / 99.5, it will be described later (D)
The crosslinking reaction with is slow, and the water resistance of the resulting coating film becomes insufficient. If it exceeds 40/60, the resulting coating film and adhesive layer become too hard, which is not preferred. Also,
The amount of (A) used is usually 1 to 30 parts by weight based on 100 parts by weight of the total of (B) and (C). When the amount is less than 1 part by weight, the polymerization stability is poor, the number of blocks and coarse particles increases, and when the amount exceeds 30 parts by weight, the water resistance of the obtained coating film may be deteriorated.

As the polymerization initiator used in the production of the polymer (emulsion), a known polymerization initiator usually used for emulsion polymerization can be used. For example, hydrogen peroxide, potassium persulfate, sodium persulfate,
And persulfates such as ammonium persulfate. Also,
Redox initiators include (a) hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide,
At least one selected from the group consisting of persulfate, t-butyl persulfate and t-butyl perbenzoate, (b) Fe ²⁺ , C
Among metal ions capable of undergoing electron transfer, such as r ²⁺ , V ²⁺ , Co ²⁺ , Ti ³⁺ , Cu ²⁺ , and (c) reducing substances such as Rongalite, 1-ascorbic acid, I)
And (b) or (a), (b) and (c).

As the water-soluble hydrazine compound (D) used in the present invention, various compounds can be used, such as hydrazine, hydrazine hydrate, hydrate or salt of hydrazine, phenylhydrazine, methylhydrazine, and the like.
Aromatic or aliphatic hydrazines such as ethylhydrazine, n-propylhydrazine, n-butylhydrazine, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, and salts thereof. Benzoic acid hydrazide, formic acid hydrazide, acetate hydrazide, propionic acid hydrazide, n-butyric acid hydrazide, isobutyric acid hydrazide, n-valeric acid hydrazide, monocarboxylic acid hydrazide such as pivalic acid hydrazide, oxalic acid dihydrazide, and malonone. Dicarboxylic acid dihydrazide, carbonic acid dihydrazide, etc. Such as a polymer compound having a hydrazino group, such as hydrazine and N- amino polyacrylamide. These hydrazine compounds may be used alone or in combination.

Among them, N- having a number average degree of polymerization of 30 or more,
Aminopolyacrylamide is more preferred since it has a particularly high effect of imparting water resistance to the resin, and has a low adverse effect on the human body because it is a polymer. This N-aminopolyacrylamide can be produced by reacting hydrazine hydrate with polyacrylamide. Even if all of the amide groups of polyacrylamide have reacted with hydrazine, unreacted amide groups remain. Is also good. That is, the N-aminopolyacrylamide used in the present invention is represented by the following general formula (2).

[0023]

Embedded image

In the above general formula, n = 0.1 to
It is desirable that 100 mol% and m = 0 to 99.9 mol%. That is, the content of the hydrazino group in the N-aminopolyacrylamide in this case is 0.1 mol%.
Or more, more preferably 1 mol%.
That is all.

The amount of the water-soluble hydrazine compound (D) used in the present invention can be variously varied, but is usually 0.1 to 100 parts by weight of the acrylamide-modified PVA (A). 1 to 50 parts by weight, preferably 0.5 to 3 parts by weight
0 parts by weight are used. When the amount of the water-soluble hydrazine compound (D) is less than 0.1 part by weight, the effect of water resistance is low, and when it exceeds 50 parts by weight, the effect of water resistance is not only saturated, Unreacted water-soluble hydrazine compound (D) may elute into water, which is not preferable.

The one-part crosslinked resin composition of the present invention thus obtained is preferably further added with a water-soluble organic amine or ammonia in order to further prevent the storage stability and the aggregation and precipitation of the emulsion. Various organic amines can be used, for example, monoethanolamine, aminoethylethanolamine, monoisopropanolamine, N- (2-hydroxypropyl) ethylenediamine, 2-amino-1-butanol, -Amino-2-methyl-1-propanol, 3-
Amino-1-propanol, 2-amino-2-methyl-
1,3-propanediol, 2-amino-2-ethyl-
Primary alkanolamines such as 1,3-propanediol and tris (hydroxyethyl) -aminomethane, secondary alkanolamines such as diethanolamine, methylethanolamine, butylmethanolamine, N-acetylethanolamine and diisopropylamine; Ethanolamine, methyldiethanolamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, tertiary alkanolamines such as triisopropanolamine, methylamine, ethylamine, n-propylamine, isopropylamine, allylamine, n-butylamine, isobutylamine, t-
Examples include primary alkylamines such as butylamine and cyclohexylamine, secondary alkylamines such as dimethylamine, diethylamine and diisopropylamine, and tertiary alkylamines such as trimethylamine. The effect is not changed by using ammonia. These water-soluble organic amines and ammonia can be used alone or in combination of two or more.

The amount of the water-soluble organic amine or ammonia to be added can be various and can be selected according to the purpose of use, but is preferably at least equimolar to the water-soluble hydrazine compound (D). When the amount is less than equimolar to the water-soluble hydrazine compound (D), the pot life is improved as compared with the case where no water-soluble organic amine or ammonia is added, but the effect is small.

The resin compositions obtained from the above (A) to (D) are very stable, have a long pot life, do not cause coagulation and sedimentation of the emulsion, and can carry out a crosslinking reaction and a coating film formation during drying. Although it becomes a liquid cross-linking type resin composition, such a one-part cross-linking type resin composition may optionally include other derivatives such as starch, methylcellulose, cellulose derivatives such as carboxymethylcellulose, polyacrylic acid derivatives, and gelatin. Inorganic fillers such as natural polymers, synthetic polymers, clay, kaolin, talc, silica, calcium carbonate,
A plasticizer such as glycerin and sorbitol, a surfactant, an antifoaming agent, a chelating agent and the like can be blended within a range that does not impair the effects of the present invention.

The one-component crosslinkable resin composition of the present invention is characterized in that, when the crosslinker is mixed with the emulsion, the presence of the acrylamide-modified PVA (A) causes the presence of the carbonyl group-containing unsaturated monomer (B) and the water-soluble hydrazine. Although the reaction with the compound (D) is suppressed, the reaction proceeds in the process of drying after being applied to a coating film or the like. At that time, the crosslinking proceeds even when the coating is dried at room temperature or when dried by heating, so that the purpose of the coating film such as water resistance can be achieved.

The one-part crosslinkable resin composition of the present invention is excellent
Water resistance, water resistance adhesion, solvent resistance, blocking resistance,
Non-woven binder, wood adhesive,
Useful for paper adhesives, cloth adhesives, PVC floor tile adhesives, paper processing agents, mortar admixtures, and paints.

[0031]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “%” and “part” mean on a weight basis unless otherwise specified. Production Example 1 (Production of acrylamide-modified PVA) In a flask equipped with a stirrer, a thermometer, and a dropping funnel reflux condenser, 670 parts of vinyl acetate, 15 parts of diacetone acrylamide, and 180 parts of methanol were charged and nitrogen in the system was charged. After the replacement, the internal temperature was raised to 60 ° C. A solution prepared by dissolving 1 part of 2,2-azobisisobutyronitrile in 40 parts of methanol was added to the system, and polymerization was started. Five hours after the start of the polymerization, a solution prepared by dissolving 40 parts of diacetone acrylamide in 40 parts of methanol was dropped at a constant rate to carry out the polymerization, and after 7 hours, dinitrobenzene was added as a polymerization inhibitor to terminate the polymerization. did. The polymerization yield was 75%. The remaining vinyl acetate was distilled off while adding methanol vapor to the obtained reaction mixture to obtain a 50% methanol solution of a vinyl acetate polymer containing diacetone acrylamide as a copolymerization component. To 500 parts of this mixture, 50 parts of methanol and 10 parts of a 5% methanol solution of sodium hydroxide were added and mixed well.
The saponification reaction was performed at 0 ° C. The obtained gel is pulverized, thoroughly washed with methanol, and then dried to obtain diacetone acrylamide-modified PVA (denaturation degree: 6.3 mol%, polymerization degree: 2000, saponification degree of vinyl acetate component: 98.4 mol%). ) Got.

Production Examples 2 and 3 By changing the charge composition as shown in Table 1, acrylamide-modified PVA as shown in Table 2 was obtained in the same manner as in Production Example 1.

(Production of one-component cross-linkable resin composition) 500 parts of ion-exchanged water was prepared in a glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet. Acetone acrylamide modified PVA resin (A)
39 parts were charged and completely dissolved at 95 ° C. This is 70
° C, 0.5 parts of ammonium persulfate was added,
While stirring under a nitrogen atmosphere, 55 parts of diacetone acrylamide (B) and 460 parts of vinyl acetate (C) were continuously added over 2 hours, the temperature was raised to 80 ° C., and an aging reaction was further performed for 2 hours. The emulsion polymerization was completed to obtain a polymer emulsion.

This polymer emulsion (solid concentration 51
%) Was added to 100 parts of a 10% aqueous solution of monoethanolamine, mixed well to adjust the pH to 7, and then N-aminopolyacrylamide (D) [manufactured by Otsuka Chemical Co., Ltd .;
0, a 10% aqueous solution of hydrazino group modification degree 10.0 mol%] was added and mixed again to produce a one-part crosslinked resin composition, and the following evaluation was performed.

Pot Life The one-part crosslinkable resin composition was left at 30 ° C. and evaluated as follows. ◎ −−− No change in viscosity even after 3 months ○ −−− Slightly thickened after 3 months △ −−− Significantly thickened after 3 months × −−− Gelled after 3 months

The water-resistant one-component cross-linkable resin composition is cast on a slide glass (under which newsprint printed in 8-point type is placed), and heated at 30 ° C.
The film was dried in a 65% RH atmosphere for 4 hours to prepare a film having a thickness of 200 μm. One drop of pure water was dropped on the film, and the time until the hiragana of the printed characters became unreadable due to the whitening of the film was measured.

Adhesiveness The adhesive strength of the one-part crosslinkable resin composition was evaluated by the following method according to a normal test for compressive rupture adhesive strength and a water resistance test (JIS-K6862). 25mm x 35mm, 10mm thick rod material is 25mm x
It is applied to a 35 mm adhesive surface at 100 g / m ² , bonded together and compressed with a load of 5 kgf / cm ² for 5 minutes at 20 ° C.
Dry at 65 RH% for 48 hours. In the normal test (normal adhesive strength), the adhesive strength was measured as it was, and in the water resistance test (water resistant adhesive strength), after immersion in water at 30 ° C. for 3 hours, the adhesive strength was measured in a wet state.

A film prepared in the same manner as in the solvent resistance was coated with Magic (registered trademark).
A line was drawn with the ink and wiped off with ethyl acetate, and the state of the film was evaluated as follows. ○ −−− No magic ink lines remain on the coating film. △ −−− The line of the magic ink is thinly left on the coating film. × −−− Magic ink lines remain dark on the coating film.

Example 2 A one-part crosslinked resin composition was prepared and evaluated in the same manner as in Example 1, except that the component (A) was changed to that prepared in Production Example 2. .

Example 3 A one-part crosslinkable resin composition was prepared and evaluated in the same manner as in Example 1 except that the component (A) was changed to that prepared in Production Example 3. .

Example 4 A one-part crosslinked resin composition was prepared and evaluated in the same manner as in Example 1, except that the addition of 2 parts of an aqueous monoethanolamine solution was omitted.

Example 5 A one-part crosslinked resin composition was prepared and evaluated in the same manner as in Example 1, except that 2 parts of ammonia was added instead of 2 parts of the monoethanolamine aqueous solution. .

Comparative Example 1 In Example 1, PVA (degree of polymerization: 2) was used as the component (A).
000, a saponification degree of 99.0 mol%), and a one-part crosslinked resin composition was prepared and evaluated in the same manner as in Example 1.

Comparative Example 2 A one-part crosslinked resin composition was prepared in the same manner as in Example 1 except that the addition of the component (B) was omitted.
It was evaluated similarly.

Comparative Example 3 A one-part crosslinked resin composition was prepared in the same manner as in Example 1 except that the addition of the component (C) was omitted.
It was evaluated similarly.

Comparative Example 4 A one-part crosslinked resin composition was prepared in the same manner as in Example 1 except that the addition of the component (D) was omitted.
It was evaluated similarly. Table 3 shows the evaluation results of the examples and the comparative examples.

[0047]

[Table 1] Preparation composition Vinyl acetate methanol acryl amide monomer production example 1 670 parts 260 parts * diacetone acryl amide 55 parts * (180 + 40 + 40) (15 + 40) Production example 2 670 parts 260 parts * acryl amide 50 Part * (180 + 40 + 40) (10 + 40) Production Example 3 670 parts 260 parts * Methacrylamide 50 parts * (180 + 40 + 40) (10 + 40) * The total amount is shown.

[0048]

Table 2 Degree of saponification Degree of polymerization Degree of modification (mol%) (mol%) Preparation Example 1 98.4 2000 6.3 Preparation Example 2 98.7 1400 5.0 Preparation Example 3 98.0 1000 4.5

[0049]

[Table 3]   Hot life Water resistance Normal adhesive strength Water resistant adhesive strength Solvent resistance(Time) (kgf / cm ² ) (kgf / cm ² ) Example 1 ◎ 8 hours or more 85.0 83.0 ○ 〃 2 ◎ 8 hours or more 83.0 80.5 ○ ３ 3 ◎ 8 hours or more 80.0 78.0 ○ ４ 4 ○ 8 hours or more 84.5 81.0 ○〃 5 ○ 8 hours or more 83.5 79.7 ○ Comparative Example 1 × 40 minutes 77.5 38.0 △ 〃 2 △ 30 minutes 70.0 27.6 × ３ 3 ◎ 5 minutes 68.0 8.8 ×〃 4 ◎ 2 minutes 70.5 7.3 ×

[0050]

According to the present invention, acrylamide-modified PVA (A) is used as a dispersant, and a carbonyl group-containing unsaturated compound having at least one carbonyl group selected from ald groups or keto groups and one polymerizable double bond in the molecule. A one-component liquid obtained by mixing a water-soluble hydrazine compound (D) with a polymer emulsion obtained by emulsion polymerization of a monomer (B) and an ethylenically unsaturated monomer (C) other than the above (B). The cross-linked resin composition has excellent workability and excellent water resistance, water resistance, and solvent resistance, so it has a nonwoven fabric binder, wood adhesive, paper adhesive, cloth adhesive, PVC floor tile adhesive, and paper processing. It is very useful as an agent, mortar admixture, and paint.

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Claims (1)

[Claims] An acrylamide-modified polyvinyl alcohol (A) is used as a dispersant, and a carbonyl group having at least one aldo group or keto group in the molecule and one carbonyl group having one polymerizable double bond is used. A water-soluble hydrazine compound (D) is blended in a polymer emulsion obtained by emulsion polymerization of a saturated monomer (B) and an ethylenically unsaturated monomer (C) other than the above (B). A one-component cross-linkable resin composition characterized by the following.