JP2656711B2 - Aqueous crosslinkable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a film which easily undergoes a crosslinking reaction at room temperature and, after crosslinking, has excellent water resistance, water whitening resistance, blocking resistance, heat resistance, solvent resistance, adhesiveness and hardness. Paint varnish, external clear varnish, stone-like finish binder, top coat, OP varnish, etc. The present invention relates to an aqueous crosslinkable resin composition that can be advantageously used as a printing ink, an adhesive, a fiber processing agent, and the like.

[0002]

2. Description of the Related Art Aqueous crosslinkable resin compositions comprising an aqueous dispersion of a carbonyl group-containing copolymer resin and a hydrazine derivative having at least two hydrazino groups in the molecule are known (for example, Japanese Patent Application Laid-Open (JP-A) No. 2002-122,089). JP-A-57-3850, JP-A-64-48801 and the like.

[0003] Such an aqueous crosslinkable resin composition can be easily crosslinked at room temperature to form a film having excellent physical properties. However, since the surface drying rate after application of the resin composition is too high, it is necessary to apply a seam. There is a problem that unevenness and shrinkage cracks easily occur in the dried coating film. In order to improve these drawbacks, attempts have been made to use a large amount of an emulsifier, or to add a wetting agent or a water-soluble resin. However, in any case, the water resistance of the film is reduced, and the film is not practically used.

On the other hand, in order to improve water resistance, there are a method of further adding an epoxy group-containing compound and a method of using an epoxy group-containing monomer as a monomer constituting an aqueous resin dispersion. In this case, although the water resistance of the film is improved, gelation is likely to occur due to the use of an epoxy group, so that it is usually necessary to use two liquids, and there is a problem that the handling becomes complicated.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to improve the above-mentioned disadvantages of the conventional aqueous dispersion of a carbonyl group-containing copolymer resin containing a hydrazine derivative. After cross-linking, give a film with excellent water resistance, water whitening resistance, blocking resistance, heat resistance, solvent resistance, adhesion and hardness after cross-linking, and the surface drying property of the film can be adjusted appropriately and good An object of the present invention is to provide an aqueous crosslinkable resin composition which has workability and is easy to handle without gelation.

[0006]

Means for Solving the Problems The inventors of the present invention have made various studies to solve the above-mentioned problems, and as a result, the following objects have been attained by adopting the following constitution.
That is, the aqueous crosslinkable resin composition of the present invention comprises (A)
Carbonyl group-containing resin aqueous dispersion comprising resin particles having at least two layers containing a carbonyl group in the outermost layer, (B) a hydrazine derivative having at least two hydrazino groups in the molecule, and (C) an epoxy group Is an aqueous crosslinkable resin composition comprising an epoxy group-containing compound containing at least two in the molecule, wherein 5% by weight or more of the outermost layer of the resin particles of the aqueous carbonyl group-containing resin dispersion is solubilized. And 4 to 50% by weight of the whole particles are solubilized.

The resin of the aqueous carbonyl group-containing resin aqueous dispersion (A) in the present invention has at least a two-layer structure, as long as it contains a carbonyl group in its outermost layer. (A) a carbonyl group-containing monomer containing at least one ald or keto group and one polymerizable unsaturated double bond in the molecule, (b) an ethylenically unsaturated monomer, Saturated carboxylic acid, (c) 20
A monomer having a solubility in water at 8 ° C. of 8 g / 100 ml or less, and an appropriate combination of (d) other unsaturated monomers can improve the physical properties by solubilization and balance the physical properties such as water resistance. It is preferable in terms of keeping.

The above-mentioned monomer (a) for preparing the aqueous resin dispersion (A) includes, for example, acrolein, diacetone acrylamide, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl Methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), general formula

[0009]

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(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, and R ⁴ is an alkyl group having 1 to 3 carbon atoms. Acryl (or methacryl) oxyalkyl propenal, diacetone acrylate, acetonyl acrylate, diacetone methacrylate,
Hydroxypropyl acrylate acetyl acetate,
Butanediol-1,4-acrylate acetyl acetate and the like. Particularly preferred monomers are diacetone acrylamide, acrolein and vinyl methyl ketone. These monomers may be used in combination of two or more kinds.

The monomer (a) is an essential component for preparing the present resin aqueous dispersion (A), and the amount of the monomer (a) used is preferably 0.5% of all the monomers constituting the resin particles. weight%
As described above, the content is more preferably 2 to 30% by weight. If the amount of the monomer (a) is too small, the crosslinking reaction with the hydrazine derivative is not sufficiently performed, and improvement in water resistance cannot be expected. If the amount of the monomer (a) is too large, the physical properties corresponding to the amount are used. Not only is there no improvement in the film, but the film obtained from the composition becomes brittle and not practical.

The monomer (a) may be contained in either the inner or outer layer of the resin particles of the aqueous resin dispersion of the present invention. However, the outermost layer is indispensable. Is preferred from the viewpoint of the water resistance of the film.
In the outermost layer, 0.5% of all monomers constituting the outermost layer
% By weight or more, and particularly preferably 2 to 20% by weight. In the inner layer, 0.5% by weight or more of all monomers constituting the inner layer is preferable, and 1 to 15% by weight is particularly preferable.

The monomer (b) for preparing the resin aqueous dispersion (A) may be a monocarboxylic acid or a polyvalent carboxylic acid, but preferably has 3 to 5 carboxylic acids. Mono- or diolefinically unsaturated carboxylic acids having carbon atoms. Particularly, acrylic acid, methacrylic acid and itaconic acid are preferred. The amount of the monomer (b) used is 0.5% by weight or more, preferably 2 to 40% by weight, of the total monomers constituting the outermost layer in the outermost layer. Is preferably less than 4% by weight of all monomers constituting

If the amount of the same monomer in the outermost layer is too small, sufficient solubilization (water-solubilization) cannot be achieved when the solubilization treatment is performed by adding an alkali and / or organic solvent. Cannot obtain sufficient smoothness, adhesion, gloss and water whitening resistance. On the other hand, if the amount of the monomer is too large, the water resistance of the film is reduced, and the adhesion to the coated object is reduced. On the other hand, if the amount of the same monomer in all the monomers constituting the inner layer except the outermost layer is too large, there is a problem that the water resistance is lowered, which is not preferable.

The monomer (c) for preparing the resin aqueous dispersion (A) is a monomer copolymerizable with the monomers (a) and (b), 8 solubility in
g / 100 ml water or less. Specific examples thereof include acrylic acid or methacrylic acid esters of saturated alkanols having 1 to 10 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-
Ethylhexyl acrylate; vinyl aromatic compounds such as styrene; vinyl halides such as vinyl chloride and vinylidene chloride; unsaturated hydrocarbons such as ethylene and butadiene; vinyl esters such as vinyl acetate and vinyl propionate; other acrylonitrile, methacrylonitrile;
Glycidyl methacrylate and the like can be mentioned.

The amount of the monomer (c) used in the outermost layer is 30 to 99% by weight, preferably 55 to 94% by weight of the total monomers constituting the outermost layer. Is preferably 80 to 99.5% by weight of all monomers constituting the inner layer. If the amount of the same monomer in the outermost layer is too small, the water resistance is reduced or the film becomes brittle, and if the amount of the same monomer is too large, the water resistance is reduced and the substrate adhesion is reduced. . If the amount of the same monomer in all the monomers constituting the inner layer except the outermost layer is too small, the water resistance is lowered or the film becomes brittle.

The monomer (d) for preparing the resin aqueous dispersion (A) is a monomer other than the monomers (a) to (c) described above. Unsaturated amides such as acrylamide and methacrylamide; hydroxyl-containing monomers such as hydroxyethyl acrylate and hydroxypropyl acrylate; sulfonated monomers such as vinylsulfonic acid, styrenesulfonic acid and salts thereof; and other N-methylolacrylamide And so on.
(D) The amount of the other unsaturated monomer is from 0 to 69% by weight, preferably from 0 to 15% by weight of the total amount of the unsaturated monomers constituting the resin particles.
% By weight.

The monomer (d) is not an essential component in both the outermost layer and the inner layer. If the amount of the monomer (d) is too large, the hydrophilicity of the obtained resin particles becomes too high. The water resistance of the resulting coating decreases. A method for producing an aqueous resin dispersion (A) of resin particles having at least a two-layer structure using each of the monomer mixtures described above includes:
The monomer mixture constituting the inner layer is previously polymerized in water to form an emulsion state, and then the monomer mixture constituting the outermost layer is added and emulsion-polymerized.

For the emulsion polymerization of the monomer mixture constituting each layer, a method of performing polymerization with a water-soluble polymerization initiator using an emulsifier, a method of performing polymerization by soap-free polymerization, and the like are used. Examples of the emulsifier include various anionic, cationic, and nonionic emulsifiers, and further, a polymer emulsifier. 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 according to the present invention (partly).

The polymerization initiator used in the emulsion polymerization is preferably an inorganic peroxide such as potassium persulfate, ammonium persulfate and hydrogen peroxide. These inorganic peroxides include:
A redox initiator may be used in combination with a reducing agent. Various methods can be used as a method for supplying the monomer in the emulsion polymerization. For example, various methods such as a batch charging method, a monomer addition method, and an emulsion addition method can be used. In addition, a seed polymerization method in which the composition of the monomer to be added is sequentially changed, a power feed polymerization method, or the like can also be used.When such a method is used, the central part of the produced copolymer resin particles and the outside can be used. The degree of solubilization can be adjusted by changing the copolymer composition.

In the emulsion polymerization, it is preferable to use a chain transfer agent. This is because the copolymer resin obtained by emulsion polymerization is generally of high molecular weight, so that it is difficult to sufficiently solubilize it when water is solubilized by adding an alkali and / or organic solvent. If a transfer agent is used, the molecular weight of the produced copolymer resin can be reduced, and the above-mentioned solubilization becomes easy.

Therefore, it is effective to add the outermost layer component at the time of polymerization. The amount of the chain transfer agent used is 0.01 to 100 parts by weight based on the total amount of monomers in the layer.
~ 3 parts by weight are preferred. The chain transfer agent used is
Any chain transfer agent commonly used for the polymerization and copolymerization of vinyl monomers and the like may be used. Specific examples thereof include, for example, methyl mercaptan, t-butyl mercaptan, decyl mercaptan, benzyl mercaptan, lauryl mercaptan, stearyl mercaptan,
Mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid; alcohols such as methanol, n-propanol, isopropanol, t-butanol, benzyl alcohol, allyl alcohol; hydrocarbons such as ethylbenzene and cumene And halogenated hydrocarbons such as chloroethane, chloroform, carbon tetrachloride and carbon tetrabromide.

The outermost layer of the resin particles of the aqueous resin dispersion (A) prepared by the emulsion polymerization described in detail above has a resin solubilization rate of 5% by weight or more, preferably 5% by weight or more, by the addition of an alkali and / or an organic solvent. Is solubilized so as to be 15% by weight or more, and 4 to 50% by weight, preferably 5 to 35% by weight of the whole particles is solubilized.

When the resin particles have a three-layer structure or more, the outermost layer is called an outermost layer, and the other inner two or more layers are called an inner layer. The solubilization rate of the inner layer is 5%.
% By weight or more and the solubilization rate of the whole particles is 4 to 50% by weight
And less than 30% by weight, preferably 0.3 to 25%
It is desirable that the content be% by weight.

If the solubilization ratio of the whole particles is too small, the adhesion and gloss of the coating film obtained from the present composition to the substrate will be lowered, and if the solubilization ratio of the whole particles is too large, the coating obtained will be too large. The water resistance of the film decreases. The solubilization treatment (that is, the addition of an alkali and / or an organic solvent) may be performed before the start of polymerization for producing the aqueous resin dispersion,
It may be during the polymerization. In any case, the “solubilization rate” described in the present specification refers to the solubilization rate measured by the following method.

Except that no hydrazine derivative or the like is added, a solubilization treatment is performed under exactly the same conditions as the actual solubilization treatment to prepare a resin aqueous dispersion, and the obtained resin aqueous dispersion has a nonvolatile content of 15% by weight. % After dilution with water
The diluted solution was centrifuged at a centrifugal acceleration of 1.8 × 10 ⁵ g for 60 minutes, and the amount of nonvolatile components in the obtained supernatant was measured.
When the amount of non-volatile components in the above-mentioned diluent used for centrifugation is measured and the amount is expressed as W parts by weight, the solubilization ratio is represented by the following formula.

Solubilization ratio = w / W × 100 (% by weight) Therefore, for example, an alkali and / or organic solvent is added to a polymerization system before or during polymerization for producing an aqueous resin dispersion to copolymerize. If the polymerization product containing the produced copolymer resin obtained by the polymerization has already reached a solubilization ratio of 5% by weight or more as it is, It is not necessary to add an alkali and / or organic solvent for the treatment.
The solubilization ratio of each layer of the outermost layer or the inner layer excluding the outermost layer component is determined by the same conditions as those for preparing the resin particles of the aqueous resin dispersion (A) used in the present invention. Only the mixture is polymerized and determined by the method detailed above.

Examples of the alkali used for the solubilization treatment include inorganic water-soluble alkalis such as sodium hydroxide and potassium hydroxide; or inorganic salts which show alkalinity when dissolved in water, such as sodium hydrogen carbonate and pyrophosphate. Sodium and the like; and other examples include aqueous ammonia and organic amines. As described above, the addition of the alkali
It is not always necessary to perform the polymerization after the polymerization of the aqueous resin dispersion, and in some cases, the copolymerization may be performed after adding an alkali to the monomer before polymerization to neutralize the monomer. The amount of the alkali used may be an amount that completely neutralizes the carboxyl group in the copolymer resin, or may be an amount that partially neutralizes the carboxyl group.

The organic solvent used in the solubilization treatment may be supplementarily added when water cannot be sufficiently solubilized by adding only an alkali, or may be solubilized by adding only an organic solvent. The organic solvent to be used is not particularly limited, but texanol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and their acetates, benzyl alcohol, butyl carbitol acetate, 2,2,4-trimethyl-1,3,3
-Pentanediol and the like.

The composition of the present invention is prepared by adding at least two hydrazine derivatives having at least two hydrazino groups and at least two epoxy groups to the aqueous resin dispersion (A) prepared as described above. An epoxy group-containing compound is added. The hydrazine having at least two hydrazino groups in the molecule includes, for example, 2
Dicarboxylic acid dihydrazides having from 10 to 10, especially from 4 to 6 carbon atoms (eg oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, maleic dihydrazide, fumaric dihydrazide, Itaconic dihydrazide), aliphatic water-soluble dihydrazines having 2 to 4 carbon atoms (e.g. ethylene-
1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, etc.).

Further, the general formula:

[0032]

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(Wherein 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, acrylate, methacrylate or maleic anhydride. , B are units of a monomer copolymerizable with acrylamide, methacrylamide, acrylate, methacrylate or maleic anhydride, and k, m and n are 2 mol% ≦ k ≦ A polymer represented by the following formula: 100 mol% 0 mol% ≦ (m + n) ≦ 98 mol% (k + m + n) = 100 mol%) can also be used as the hydrazine derivative. Such a polymer is described in detail, for example, in JP-A-55-6535.

Examples of the epoxy group-containing compound having at least two epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and propylene. Examples thereof include polyglycidyl ethers of polyhydric alcohols such as diglycidyl ether and polypropylene glycol diglycidyl ether, glycidyl ether alicyclic epoxy resins of bisphenol A, nitrogen-containing epoxy resins, polybutadiene-type epoxy resins, and urethane-modified epoxy resins.

The aqueous crosslinkable resin composition of the present invention comprises (A) the carbonyl group-containing resin aqueous dispersion described above, (B) a hydrazine derivative and (C) an epoxy group-containing compound. Component (C) is used in an amount of 0.1 to 100 parts by weight, preferably 0.3 to 60 parts by weight, based on 100 parts by weight of the solid content of the component). When the proportion of the component (C) is too small, the properties of the coating film obtained are not sufficiently improved,
If the amount is too large, it becomes sticky or gels and the handleability decreases.

The component (B) has a ratio of an ald group, a keto group and an epoxy group to a hydrazino group contained in the composition.
The molar ratio is 0.2 to 8 mol, preferably 0.5 to 4 mol. If the proportion of the hydrazine derivative is too small,
Improvement of water resistance cannot be expected because the cross-linking between the resins is not sufficiently performed, and even if the ratio is too large, not only the water resistance improvement effect corresponding to that is not obtained, but also the film It becomes opaque and brittle, and the crosslinking effect is reduced.

In the present invention, various synthetic resin emulsions and synthetic rubber latex, modifiers such as various tackifiers, extenders such as inorganic fillers, thickeners or viscosity regulators, defoamers and the like are added as required. I can do it.

[0038]

The present invention will be described in detail below with reference to examples and comparative examples. "Parts" and "%" described in these examples are based on weight. Example 1 Temperature controller, squirrel-type stirrer, reflux condenser, supply container,
After the inside of a reaction vessel equipped with a thermometer and a nitrogen inlet tube was purged with nitrogen, the following composition was charged therein.

Water 35 parts 35% aqueous solution of sulfuric acid half ester sodium salt of ethylene oxide 20 mol added p-nonylphenol (referred to as “anionic emulsifier A”) 1.8 parts ethylene oxide 25 mol added p-nonylphenol (“nonionic The following mixtures were prepared as feeds I, II and III separately from 2 parts of a 20% aqueous solution of "emulsifier B").

Feed I Water 35 parts 35% aqueous solution of anionic emulsifier A above 3.7 parts 20% aqueous solution of nonionic emulsifier B above 3.5 parts Styrene 37.5 parts Butyl acrylate 37.1 parts Diacetone acrylamide 4.0 parts Acrylic acid 0.4 parts Feed II water 8 parts 35% aqueous solution of the above anionic emulsifier A 0.8 parts 20% aqueous solution of the above nonionic emulsifier B 1.05 parts Styrene 1 5.5 parts Methyl methacrylate 3.6 parts Butyl acrylate 13.9 parts Diacetone acrylamide 1.0 part Acrylic acid 1.0 part T-dodecyl mercaptan 0.2 parts Feed III water 12 parts Potassium persulfate 0.5 Department

In a reaction vessel, 10% of the feed I was added, and 8
Heated to 5 ° C., then injected 10% of Feed III into the reaction vessel. After a 10 minute hold, Feed I was added over 3 hours and at intervals of 1 hour Feed II was added over 1 hour. Feed III is feed from the start of feed I addition
It was continuously and uniformly supplied until the addition of II was completed. After the addition, the temperature was maintained at 90 ° C. for another 1.5 hours, and then the emulsion polymerization was terminated to obtain an aqueous resin dispersion having a nonvolatile content of about 50%. Aqueous ammonia was added to the obtained dispersion to adjust the pH to 9.3,
6 parts of benzyl alcohol as an organic solvent and 25.7 parts of a 20% solution of adipic dihydrazide therein,
2.6 parts of ethylene glycol glycidyl ether was added, and water was further added so that the viscosity became 5,000 to 8,000 cps, to obtain an aqueous crosslinkable resin composition. In addition,
The solubilization rate of the outer layer component was 95%, and the solubilization rate of the whole particles was 11.3%.

Examples 2 to 6 and Comparative Examples 1 to 6 Except that the monomer composition, alkali, solvent, hydrazine derivative and type and amount of the epoxy group-containing compound were changed as shown in Tables 1 and 2, An aqueous resin composition was prepared in the same manner as in Example 1. The amounts of water and each emulsifier in the feed were distributed to the inner layer and the outer layer according to the weight of the monomer mixture.

[0043]

[Table 1]

[0044]

[Table 2]

* 1 ADH: 20% aqueous solution of adipic dihydrazide [Evaluation of physical properties] The aqueous resin compositions obtained in the respective Examples and Comparative Examples were evaluated by the following methods.

Appearance of coating film: 20 ° C., 60% RH
In a constant temperature chamber with a doctor knife on a glass plate
The film was applied so as to have a thickness of 00 μm, dried for 5 days in a place free from wind, and the film was visually and finger-touched to determine whether there was any abnormality. Specular, colorless and transparent, with no extract on the surface were regarded as normal, others were regarded as abnormal, in which case the state was described.

Water Whitening Resistance: A sample similar to the above-mentioned sample for measuring the appearance was prepared, immersed in a constant temperature water bath at 20 ° C. and 40 ° C. at an inclination of 70 ° upward and immersed for 7 days to change the whitening state of the film to a color tone. Was evaluated. The evaluation level is colorless → light blue → blue-white → white and white.

Toluene swelling ratio: poured onto a glass plate covered with Teflon so that the film thickness after drying becomes about 500 μm,
Dry at 0 ° C. for 7 days. On the 5th day, the film was peeled off from Teflon and dried upside down. This film was punched into a 5 cm × 5 cm square to obtain a test piece. The test piece was immersed in toluene at 20 ° C., taken out after immersion for 24 hours, and the length of the side was measured with a vernier caliper. Toluene swelling ratio (%) = {(after immersion-before immersion) dimension} ÷ dimension before immersion｝ × 100

Water absorption: A test piece similar to the above-mentioned sample for measuring the swelling ratio of toluene was prepared, immersed in a constant temperature water bath at 20 ° C. for 2 days, the water content on the surface was immediately removed, and the water was weighed precisely. The rate was determined.

The results are shown in Tables 3 and 4. Further, 0.5 part of an antifoaming agent (trade name manufactured by San Nopco Co., Ltd.) is added to 100 parts by weight of the solid content of the aqueous crosslinking resin composition of the present invention.
Foamaster AP), 320 parts of porcelain sand (100m
esh) and cold water 80 parts (trade name, manufactured by Dowa Mining Co., Ltd.
KD 50mesh) was added to prepare a paint, which was also evaluated by the following method. The results are also shown in Tables 3 and 4.
It was shown to.

[0051]

[Table 3]

[0052]

[Table 4]

[Evaluation of paint] Roller coating property: 100 g / m ² (wet) of a solvent-based sealer (Kikusui Chemical Industry Co., Ltd., trade name: Kikusui Primer BS) was previously applied to a 300 × 450 mm flexible plate.
And dried, a panel was prepared, and a coating compounded with a striping roller for an exterior material was applied at 1.5 kg / m ² . After further drying for 5 minutes, the same roller was applied again for 1/3 surface coating, and the stripes were aligned and applied. ○, ○-△, when the coating material is excessively wrapped around the roller, or the irregular pattern of the pattern at the seam
The judgment was made in three stages of Δ.

Drying time on touch: 2
The surface wetting disappearance time (minutes) was determined by finger touch every minute.

Appearance of coated surface: The coated plate was dried at 20 ° C. for 7 days, and the appearance was evaluated by finger touch and visual observation. Samples having no occurrence of slimming, drying shrinkage cracks and the like were regarded as normal, others were regarded as abnormal, and abnormal ones were described as states.

Hot water whitening resistance: A solvent-based sealer (Kikusui Chemical Industry Co., Ltd., trade name: Kikusui Primer BS) was previously applied to a 70 × 150 mm flexible plate at 100 g / m ^2.
Prepare a material coated so as to be (wet), attach a frame with a thickness of 2 mm to the plate, apply the blended paint with a spatula, and apply evenly to a thickness of 2 mm (wet) with a spatula. At 5
The test piece was dried for a day. On the fourth day of drying, the back and side surfaces are sealed with wax, and placed in a 40 ° C. constant temperature water bath.
After soaking for a day, the whitening state was evaluated. The evaluation criteria were the same as the water whitening resistance in the physical property evaluation.

Hot water softening resistance: A test piece similar to the sample used for the above hot water whitening resistance measurement was prepared, immersed in a constant temperature water bath at 40 ° C. for 7 days, scratched with nails, and evaluated. "○" The nail does not stand. "○ ~ △" Claws enter but do not collapse easily. "△" is brittle

Blocking resistance: A test piece similar to the test piece used for the above hot water whitening resistance measurement was prepared and placed in a 50 ° C. thermostat. The graft paper was sandwiched between the test pieces with a weight of 40 mmφ × 500 g and pressed for 24 hours. After the treatment, the weight was removed, and the sample was allowed to stand at 20 ° C. for 3 hours. "○" ... peels off almost without sound. "○-△"… More than half of them are attached, but no force is needed to peel them off and the sound is low. "△"… The sound is loud and sticks to the entire surface and requires much power to peel off.

[0059]

The aqueous crosslinkable resin composition of the present invention easily undergoes a cross-linking reaction at room temperature.
Gives a film with excellent blocking resistance, heat resistance, solvent resistance, adhesiveness and hardness, moderately controls the surface dryness of the film, has good workability, and is easy to handle without gelation It is.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C09J 163/00 JFP C09J 163/00 JFP (72) Inventor Takeshi Awata 1000 Kawajiri-cho, Yokkaichi, Mie Prefecture (72) Inventor: Ryutaro Hayashi 1000, Kawajiri-cho, Yokkaichi, Mie Prefecture, Japan Mitsubishi Electric Petrochemical Birdishe Co., Ltd. (56) References JP-A-57-3850 (JP, A) JP-A-64- 48801 (JP, A) JP-A-5-98071 (JP, A)

Claims (2)

(57) [Claims] (A) a carbonyl group-containing resin aqueous dispersion comprising resin particles having at least two layers containing a carbonyl group in the outermost layer, and (B) having at least two hydrazino groups in the molecule. An aqueous crosslinkable resin composition comprising a hydrazine derivative and (C) an epoxy group-containing compound containing at least two epoxy groups in a molecule, wherein the outermost layer of the resin particles of the aqueous carbonyl group-containing resin dispersion is 5%.
% By weight or more and 4 to 50% of the whole particles.
An aqueous crosslinkable resin composition characterized in that its weight% is solubilized. 2. The aqueous crosslinkable resin composition according to claim 1, wherein the solubilization ratio of the inner layer excluding the outermost layer of the resin particles of the aqueous carbonyl group-containing resin dispersion is less than 30% by weight.