JPH078936B2 - Aqueous resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aqueous resin composition having good storage stability.
More specifically, the present invention relates to a one-part room temperature cross-linkable aqueous resin composition that causes a crosslinking reaction at room temperature due to evaporation of water to form a film that is excellent in water resistance and oil resistance, and that is smooth and elastic.

[Conventional technology]

Acrylic and vinyl-based water-based resin compositions conventionally used for adhesives, paints, paper processing agents, fiber processing agents, etc. are roughly classified into water-based resin dispersions and water-soluble resins. Many are used. Although these compositions are sometimes used as they are, they have been made into a crosslinkable composition to crosslink functional groups after film formation to improve water resistance, oil resistance, heat resistance and the like. However, this method is a so-called two-pack type composition in which a urea resin, a melamine resin and a modified product thereof, and an isocyanate compound are blended with an aqueous resin composition immediately before use, so that the method is bound by the pot life. Workability was poor. On the other hand, there are also one-part crosslinkable aqueous resin compositions, which contain a polymerizable monomer having a functional group such as N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide and acrylamide. It is used as a polymerization component, and is a heat-crosslinking aqueous resin composition that requires heat treatment in all, and these not only require heat energy, but also have a problem of formalin generation in the process of cross-linking reaction. there were.

Recently, however, a room temperature crosslinkable one-part aqueous resin dispersion has been developed, for example, German Patent Application Publication No. 149570.
6, JP-A-54-110248, JP-A-54-144432, JP-A-57-3850
No. 59-131682 and No. 62-95374, these are poor in freeze-thaw stability during storage at low temperature, which is the fate of the aqueous resin dispersion, and a film formed from the presence of particles. There was difficulty in smoothness.

[Problems to be Solved by the Invention]

Aqueous resin dispersions are generally easy to handle because they are low-cost, low-toxic and non-flammable, and require almost all the measures for working environment and handling of dangerous substances found in general organic solvent type compositions. It is widely used because it does not. However, the aqueous resin dispersion has two major fatal drawbacks. One of them is poor storage stability at low temperature due to low freeze-thaw stability, and second is a coating film that is considered to be due to the particle size and distribution of the applied aqueous resin dispersion and viscous behavior. Is low in smoothness.
It is said that the best way to solve these problems is to use an aqueous resin, but in order to make the conventional aqueous resin a cross-linking type,
As in the case of the aqueous resin dispersion, it was necessary to blend a urea resin, a melamine resin and its modified product, a crosslinking agent such as an isocyanate compound, and a curing catalyst each time it was used. In this way, it is troublesome and inefficient to mix the crosslinking agent and the curing catalyst each time it is used, and since the compound is restricted by the pot life, it must be used within a certain time. It is inconvenient and uneconomical. Also N-methylol (meta)
A conventional one-part heat-crosslinking aqueous resin using a polymerizable monomer having a functional group such as acrylamide, N-butoxymethyl (meth) acrylamide, and acrylamide as a copolymerization component has a thermal energy necessary for the crosslinking reaction and Not only is it expensive to manufacture, maintain, and manage the equipment, but it cannot be applied to coated materials that cannot be heat-treated, so there are drawbacks such as limited application areas. There was a problem with formalin that occurs in the course of the reaction.

In view of such circumstances, it is an object of the present invention to provide a one-part type aqueous resin composition having a room temperature crosslinkability and having a specific composition.

[Means and Actions for Solving the Problems]

As a result of intensive studies conducted by the present inventors, an aqueous resin composition obtained by making a copolymer containing a specific carboxylic acid group and a carbonyl group into an aqueous solution and adding a hydrazine compound thereto can achieve the above object. Therefore, the present invention has been completed.

That is, the present invention comprises 2 to 50 parts by weight of the unsaturated carboxylic acid (A), at least 1 selected from a ketone group or an aldehyde group.
A monomer comprising 1 to 30 parts by weight of the carbonyl group-containing unsaturated compound (B) and 20 to 97 parts by weight of the monomer (C) copolymerizable therewith in a polar solvent (D). , An aqueous polymer [I] obtained by neutralizing the copolymer obtained by solution polymerization using an oil-soluble polymerization initiator (E) with an aqueous alkaline solution (F) to make it aqueous, and at least 2 The present invention relates to an aqueous resin composition containing a hydrazine compound [II] having a hydrazino group and having excellent storage stability.

The aqueous resin composition according to the present invention has the above-mentioned aqueous resin dispersion (particle size = 0.1 μm) in which the crosslinking reaction is mainly concentrated at the dispersion particle interface.
Unlike m-order), it is a water-based resin of aqueous solution or ultrafine particle dispersion (particle size: 0.01 μm order), and the coating made from these undergoes a cross-linking reaction almost uniformly, so the coating has toughness. In addition, the coating film has excellent smoothness and has the water resistance and oil resistance found in general crosslinked aqueous dispersions. Furthermore, formalin is not generated during the crosslinking reaction process. The aqueous resin also has extremely good freeze-thaw stability during winter storage, which is found in general aqueous resin dispersions.

In the water-based resin composition of the present invention, the reaction between the carbonyl group contained in the water-based resin and the hydrazine compound hardly progresses in the presence of water, but as water vaporizes to form a film, the crosslinking reaction rapidly. Has the effect of progressing to. That is, the aqueous resin composition of the present invention is stable because the crosslinking reaction is extremely suppressed during storage due to the presence of water,
When the water-based resin composition is applied to a coated body and the water content disappears, the crosslinking reaction rapidly proceeds at room temperature, so that heat treatment is not required and the film is excellent in water resistance, oil resistance and heat resistance. It becomes a one-pack type aqueous resin composition having room temperature crosslinkability and is extremely useful as an adhesive, a paint, a paper processing agent, a fiber processing agent and the like.

The unsaturated carboxylic acid (A) used in the production of the aqueous polymer [I] is necessary for making the produced copolymer water-soluble or ultrafine particles, and the amount used is the monomer composition of the copolymer and It is used in the range of 2 to 50 parts by weight, although it varies greatly depending on the molecular weight and distribution, and / or the type of (A) and the state of distribution in the copolymer, but it is preferably 3 to 20 parts by weight. . Examples of unsaturated carboxylic acids that can be used are (meth)
Acrylic acid, maleic acid, fumaric acid and itaconic acid can be mentioned, and these can be used alone or in combination, but (meth) acrylic acid is particularly preferable. The water-solubility of the polymer depends largely on the monomer composition, as described above, and includes hydrophilic monomers such as (meth) acrylamide and N-methyl (meth).
(Meth) acrylamide derivatives such as acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethyl-2-aminoethyl (meth) acrylamide, and N-methylol (meth) acrylamide: p-vinyl sulfonic acid, 2 -Unsaturated sulfonic acid such as acrylamido-2-methylpropanesulfonic acid or its sodium or ammonium salt: 2-hydroxyethyl (meth) acrylate, hydroxyl group-containing acrylate such as 2-hydroxypropyl (meth) acrylate When used as a polymerizable monomer, the amount of unsaturated carboxylic acid used can be reduced. However, the storage stability of the aqueous resin composition obtained by copolymerizing a large amount of hydrophilic monomers is reduced.

The carbonyl group of the carbonyl group-containing unsaturated compound (B) used in the production of [I] is a ketone (C═O) or an aldehyde (—CHO), and does not include a carboxyl group or a carbonyl group contained in amide. The compound is not particularly limited as long as it is copolymerizable with the monomer (C), and the amount of the compound is 1 to 30% based on the copolymer, and it can be used alone or in combination. Specifically, acrolein, formyl styrene, general formula (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or 1
Is an alkyl group having ₃ to 3 carbon atoms, R ₃ is an alkyl group having 1 to 3 carbon atoms, and R ₄ is an alkyl group having 1 to 4 carbon atoms) (meta) ) Acroyloxyalkylpropanal, (meth)
Compounds containing active aldehyde groups such as acrylamidopivalinaldehyde and acrylamidomethylanisaldehyde: diacetone acrylamide, vinyl alkyl ketones having 4 to 7 carbon atoms such as vinyl methyl ketone, diacetone (meth) acrylate, acetonyl acrylate, 2-hydroxy Active ketone-containing compounds such as propyl acrylate-acetyl acetate and butanediol acrylate-acetyl acetate are used, among which acrolein and diacetone acrylamide are particularly preferable.

The copolymerizable monomer (C) used in the production of [I] is not particularly limited as long as it is copolymerizable with the above-mentioned unsaturated carboxylic acid (A) and carbonyl group-containing unsaturated compound (B). The amount used is 20 to 97 parts by weight. Specifically 1 to
(Meth) acrylic acid ester having 8 carbon atoms, for example methyl (meth) acrylate, ethyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl: vinyl of alkane monocarboxylic acid having 1 to 12 carbon atoms Esters such as vinyl acetate, vinyl propionate, vinyl-n-butyrate, vinyl versatate: unsaturated amides or imides such as (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N-methylol (meth) acrylamide, alkoxymethyl (meth) acrylamide such as N-butoxymethyl (meth) acrylamide, maleic acid imide, maleic acid diamide: vinyl aromatic monomer such as styrene, p -
Methyl styrene etc. are mentioned. In general, any monomer can be used as a monomer of the present invention as long as it has a radically polymerizable monomer, and vinyl chloride, vinylidene chloride, vinylidene fluoride and other halogen-containing vinyl compounds: ethylene, 1, Mono- or di-olefins such as 3-butadiene: α-β olefinically unsaturated acids such as esters of maleic acid and fumaric acid: other (meth) acrylonitrile, and the like. These monomers can be used alone or in combination depending on the application.

The polar solvent (D) used in the production of [I] is a water-soluble or hydrophilic solvent, specifically, a monoalcohol having 1 to 4 carbon elements such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n- Butyl alcohol, isobutyl alcohol and t-bityl alcohol:
Ethylene glycol and its derivatives such as ethylene glycol monomethyl ether, monomethyl ether acetate, monoethyl ether, diethyl ether, monoethyl ether acetate, monoisopropyl ether, monobutyl ether, diethyl ether, monoethyl ether acetate, monoisopropyl ether, monobutyl ether acetate Diethylene glycol and its derivatives such as diethylene glycol monomethyl ether, monoethyl ether, monoethyl ether acetate, mono-n-butyl ether, mono-t-butyl ether, dimethyl ether, methyl ethyl ether, diethyl ether monoacetate: triethylene glycol and its derivatives such as Monomethyl ether of triethylene glycol, mono Ethyl ether: Propylene glycol and its derivatives such as propylene glycol monomethyl ether, monoethyl ether, mono-n-butyl ether, mono-t-butyl ether, methyl ether acetate: Dipropylene glycol and its derivatives such as dipropylene glycol monomethyl ether, mono Ethyl ether: tripropylene glycol and its derivatives such as tripropylene glycol monomethyl ether: glycerin and its derivatives such as glycerin monoacetate: trimethylene glycol and its derivatives such as 1-butoxy-ethoxypropanol, 3,3-dimethyl-3-methoxy Propanol, 3-methoxybutylacetate: butanediol and its derivatives such as 3-methoxybutanol, 3-methyl-3-methoxybutanol , 3-methyl-3-methoxybutyl acetate, 3-methyl-1,3-butanediol: acetylene glycol derivatives for example 2,4,
7,9-Tetramethyl-5-decyne-4,7-diol and its ethylene oxide adduct, 2,6-dimethyl-4-octyne-
3,6-diol: Other dioxane, 1,5-pentanediol, hexylene glycol, trimethylolpropane,
Examples include 1,2,6-hexanetriol and low molecular weight polyethylene glycols, but monoalkyl ethers of ethylene glycol or propylene glycol are generally preferred. In addition, these solvents can be used alone or in combination.

The oil-soluble polymerization initiator (E) used in the production of [I] may be a peroxide-based and / or azo-based radical polymerization initiator, specifically, a peroxide-based polymerization initiator such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide. Ketone peroxides such as: diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide:
Hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, cumene hydroperoxide and t-butyl hydrate peroxide: Dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide: Examples include peroxyketals such as butyl-4,4-di (t-butylperoxy) pentoate and ethyl-3,3-di (t-acylperoxy) butyrate: alkylperesters: percarbonates. In the azo system, for example, 2,2'-azibisisobutyronitrile, 1,1'-azibis (cyclohexane) -1-carbonitrile) and other azonitriles: 2,2'-azobis (2-amidinopropane) dihydrochloride , 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and other azoamidines. It should be noted that these polymerization initiators may be combined with a reducing agent such as an organic amine to form a redox system.

Examples of the alkaline solution (F) used in the production of [I] include ammonia, caustic soda, an aqueous solution of caustic potash, and organic amines such as triethanolamine. When water resistance is desired, ammonia water is particularly preferable. . The amount used is preferably 1 to 1.2 equivalents with respect to the carboxyl group of the unsaturated carboxylic acid to be copolymerized, but it is also conceivable that the aqueous solution may be modified by blending a third component other than the present invention. Is not limited.

The amount of the hydrazine compound [II] having at least two hydrazino groups to be incorporated in [I] is 0.2 to 1,5 mol, preferably 1 to 1 mol of carbonyl group contained in the copolymer.
It is 0.3 to 0.5 mol. The compound is specifically an aliphatic dicarboxylic acid hydrazide such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide and sebacic acid dihydrazide: carbonic acid dihydrazide and the general formula An alicyclic or aromatic bissemicarbazide represented by the formula (wherein R is, for example, o-, m-, p-phenylene, toluylene, cyclohexylidene and methylcyclohexylidene): a polyhydrazide of an aromatic polycarboxylic acid such as phthalate Examples thereof include acid dihydrazide, (tere) isophthalic acid dihydrazide, and pyromellitic acid di-, tri- and tetrahydrazides. Further, polyacrylic acid polyhydrazide, nitriloacetic acid trihydrazide, ethylenediaminetetraacetic acid tetrahydrazide and the like can be mentioned, but succinic acid dihydrazide and adipic acid dihydrazide which are dihydrazides of aliphatic dicarboxylic acid are particularly preferable.

The aqueous resin composition may optionally contain trace amounts of iron, cobalt, nickel, copper, zinc and manganese hydrochlorides, sulfates or acetates.

Further, when it is used as a paint, it is a commonly used extender pigment such as calcium carbonate, clay, talc, perlite and / or titanium oxide: sodium hexametaphosphate, ammonium salt, anionic and / or nonionic emulsifier. Pigment dispersant such as: carboxymethyl cellulose, methyl cellulose, ethyl cellulose, a third component such as a thickener such as PVA may be blended. It is also possible to incorporate a wide variety of synthetic and / or natural resin latices.

〔Example〕

Examples will be shown below, but the amounts used are parts by weight or% by weight unless otherwise specified.

Example 1 84 parts of ethylene glycol monomethyl ether as a solvent component is charged into a 1-capacity flask equipped with a stirrer, a heat exchanger, a thermometer, a dropping funnel and an initiator charging port. Next, 141.5 parts of butyl acrylate as a monomer component and acrylic acid (8
32.3 parts of 0% aqueous solution) and 3.7 parts of diacetone acrylamide were uniformly mixed and dissolved, 25% of which was charged into a flask, and the remaining 75% was used for dropping. While stirring, increase the internal temperature to 70 ℃,
Add 0.24 parts benzoyl peroxide dissolved in 10 parts isopropyl alcohol. Then, the internal temperature was adjusted to 90 ° C., the reaction was carried out for 30 minutes, and then the previously prepared monomer for dropping was evenly dropped and polymerized for 1 hour. 20 minutes after the completion of dropping, 0.24 parts of benzoyl peroxide dissolved in 6 parts of isopropyl alcohol was added again in order to increase the polymerization rate, followed by aging for 2 hours. After that, the internal temperature was cooled to 50 ° C or lower, and ammonia water (NH ₃ 25
%) 27 parts was diluted with 27 parts of water and gradually added dropwise to make a uniform state, and then 523 parts of water was added to obtain an aqueous polymer. Then, 19 parts of a 10% aqueous solution of adipic dihydrazide was added to obtain an aqueous resin composition.

Example 2 137.8 parts of butyl acrylate and acrylic acid (8
An aqueous resin composition was obtained in the same manner as in Example 1 except that 32.3 parts of 0% aqueous solution) and 7.4 parts of diacetone acrylamide were used.

However, the amount of 10% aqueous solution of adipic dihydrazide added is 38
It was a department.

Example 3 A flask similar to that in Example 1 was charged with 117.6 parts of ethylene glycol monomethyl ether as a solvent component. Next, butyl acrylate 101.6 parts as a monomer component, methyl methacrylate 114.1 parts, diacetone acrylamide 10.4 parts,
22.4 parts of methacrylic acid was uniformly dissolved, 25% of the solution was charged into a flask, and 0.32 part of benzoyl peroxide was uniformly dissolved in the remaining 75% to be used for dropping. The internal temperature was raised to 90 ° C with stirring, 0.13 parts of benzoyl peroxide dissolved in 14 parts of ethylene glycol monomethyl ether was added, and after reacting for 30 minutes, the monomer for dropping was uniformly added dropwise over 1.5 hours for polymerization. did.
20 minutes after the completion of dropping, 0.11 part of benzoyl peroxide dissolved in 14 parts of ethylene glycol monomethyl ether was added again in order to increase the polymerization rate, followed by aging for 2 hours. The reaction during this period was performed at the boiling point of the raw material. After that, the internal temperature is cooled to 50 ° C or lower, 20 parts of ammonia water (NH ₃ 25%) is diluted with 20 parts of water, and gradually added dropwise to make a uniform state.
The polymer was hydrated by adding 7 parts.

Thereafter, 53.5 parts of a 10% aqueous solution of adipic dihydrazide was added to obtain an aqueous resin composition.

Example 4 0.16 benzoyl peroxide added for dropwise addition of monomer components
Parts, except that the amount of benzoyl peroxide added to the flask for starting the reaction was 0.064 parts, the same procedure as in Example 3 was carried out.

Example 5 0.08 benzoyl peroxide added for dropwise addition of monomer components
Parts, except that 0.032 parts of benzoyl peroxide added to the flask to start the reaction was used, and the same procedure as in Example 3 was carried out.

Example 6 A flask similar to that in Example 1 is charged with 28 parts of ethylene glycol monomethyl ether as a solvent component. Next, 154.1 parts of butyl acrylate as a monomer component (I) and 0.08 part of benzoyl peroxide are dissolved in 7.4 parts of diacetone acrylamide, and 16 parts of methacrylic acid as a monomer component (II) is separately prepared. The internal temperature was raised to 110 ° C. with stirring, and the monomer component (I) was uniformly added dropwise over 1.5 hours and (II) over 2 hours to polymerize. Completion of addition of monomer component (II) 20
After 8 minutes, 0.08 part of benzoyl peroxide dissolved in 10 parts of ethylene glycol monomethyl ether was added to increase the polymerization rate, and the mixture was aged for 2 hours. The reaction during this period was performed at the boiling point of the raw material. After that, cool the internal temperature to below 50 ℃,
Dilute 14.3 parts of ammonia water (NH ₃ 25%) with 14.3 parts of water,
After gradually dropping to a uniform state, 66 parts of ethylene glycol monomethyl ether and 577 parts of water were added to make the polymer aqueous. Then 10% of adipic dihydrazide
38 parts of the aqueous solution was added to obtain an aqueous resin composition.

Example 7 A flask similar to that in Example 1 was charged with 117.6 parts of propylene glycol monomethyl ether as a solvent component. Next, as a monomer component, ethyl acrylate 142.2 parts, methyl methacrylate 73.5 parts, diacetone acrylamide 10.4 parts,
Methacrylic acid (22.4 parts) was uniformly dissolved, 30% of which was charged into a flask, and the remaining 75% of 2,2'-azobisisobutyronitrile (0.22 parts) was uniformly dissolved and used for dropping. The internal temperature was raised to 90 ° C under stirring, 0.09 parts of 2,2'-azobisisobutyronitrile dissolved in 14 parts of propylene glycol monomethyl ether was added, and the reaction was carried out for 30 minutes. .
Polymerization was carried out by dropping evenly over 2 hours. 20 minutes after the completion of dropping, in order to increase the polymerization rate, 0.08 part of 2,2'-azobisisobutyronitrile dissolved in 14 parts of propylene glycol monomethyl ether was added again and aged for 2 hours. In addition,
The reaction during this period was carried out at the boiling point of the raw material. Then, cool the internal temperature to 50 ° C or below, and then use ammonia water (NH ₃ 25%) 2
After 0 part was diluted with 20 parts of water and gradually added dropwise to a uniform state, 807 parts of water was added to make the polymer aqueous. afterwards,
An aqueous resin composition was obtained by adding 53.5 parts of a 10% aqueous solution of adipic acid dihydrazide.

Example 8 The polymer was hydrophilized in the same manner as in Example 7. Then, 45.6 parts of a 10% aqueous solution of succinic acid dihydrazide was added to obtain an aqueous resin composition.

Example 9 A flask similar to that in Example 1 was charged with 117.6 parts of propylene glycol monomethyl ether as a solvent component. Next, as monomer components, 145.6 parts of ethyl acrylate, 73.6 parts of methyl methacrylate, 3.5 parts of acrolein, and 22.
Four parts were uniformly mixed, 30% of which was charged into a flask, and the remaining 0.2% of 70% 2,2'-azobisisobutyronitrile was uniformly dissolved and used for dropping. The internal temperature was raised to 90 ° C. with stirring, 0.09 parts of 2,2′-azobisisobutyronitrile dissolved in 14 parts of propylene glycol monomethyl ether was added, and after reacting for 30 minutes, 1.2 parts of the monomer for dropping was added. Polymerization was carried out by dropping evenly over time. After 20 minutes from the end of dropping, propylene glycol monomethyl ether was added again to increase the polymerization rate.
2,2'-azobisisobutyronitrile dissolved in 14 parts 0.0
8 parts was added and aged for 2 hours. The reaction during this period was performed at the boiling point of the raw material. After that, the internal temperature was cooled to 50 ° C or lower, 20 parts of ammonia water (NH ₃ 25%) was diluted with 20 parts of water and gradually added dropwise to a uniform state, and then 807 parts of water was added to polymerize the polymer. It became aqueous. Then, 45.6 parts of a 10% aqueous solution of succinic acid dihydrazide was added to obtain an aqueous resin composition.

Comparative Example 1 The aqueous polymer of Example 1 which did not contain a dihydrazide compound was used.

Comparative Example 2 The aqueous polymer of Example 2 which did not contain a dihydrazide compound was used.

Comparative Example 3 10% of adipic dihydrazide was added to the aqueous polymer of Example 1.
An aqueous resin composition was prepared by adding 5.7 parts of the aqueous solution.

Comparative Example 4 143.8 parts of butyl acrylate and acrylic acid (8
(0% aqueous solution) 32.3 parts, and diacetone acrylamide 1.4 parts were carried out in the same manner as in Example 1. However, the amount of 10% aqueous solution of adipic dihydrazide added was 9.8 parts.

Comparative Example 5 A flask similar to that of Example 1 was charged with 107 parts of acrylamide (40% aqueous solution), 7.5 parts of diacetone acrylamide, 1 part of isopropyl alcohol, and 382 parts of water, and the temperature was raised to 75 ° C. with stirring, and ammonium persulfate (10 parts) was added. % Aqueous solution), the mixture was reacted for 1.5 hours while maintaining the internal temperature at about 80 ° C., and then 1 part of ammonium persulfate (10% aqueous solution) was added again to increase the polymerization rate, and the mixture was aged for 1 hour. After cooling, use ammonia water
The pH was adjusted to about 9.5. Thereafter, 38.6 parts of a 10% aqueous solution of adipic dihydrazide was added to obtain an aqueous resin composition.

Comparative Example 6 Styrene 464 parts, 2-ethylhexyl acrylate 482 parts,
Aqueous resin dispersion of Showa High Polymer Co., Ltd. product obtained by emulsion polymerization of 10 parts of 2-hydroxyethyl methacrylate and 44 parts of acrylamide (40%) using nonionic and anionic emulsifiers was used.

Table 1 shows the main components, non-volatile components, pH, hydrazine compound blending amount, storage stability and low temperature stability of the aqueous resin compositions or aqueous polymers in the above Examples and Comparative Examples, and the smoothness and tensile strength of the film. Table 2 shows the relationship between the water resistance, toluene resistance, and water resistance.

Measurement Method 1. Storage Stability The aqueous resin composition or the aqueous polymer (hereinafter simply referred to as the aqueous resin) was allowed to stand at 20 ° C., and the presence or absence of an increase in viscosity was examined.

◎ No change for more than 30 days ○ Some increase in viscosity after 30 days △ Some increase in viscosity after 30 days × Gelation after 30 days 2. Low temperature stability The state of the aqueous solution was examined after 3 cycles of 16 hours (freezing) at 20 ° C and 8 hours (thawing) at 20 ° C.

◎ No abnormalities ○ Somewhat slightly increased viscosity △ Somewhat significantly increased viscosity × Loss of fluidity and gelation 3. Smoothness of film On the glass plate laminated with the aqueous resin of polyethylene film Inject so that the film thickness is about 0.35 mm, 20 ℃,
After drying at 65% RH for 1 week, a film was obtained.

◎ Very smooth ○ Good fairly smooth △ Very poor × Very bad 4. Tensile strength of the coating Cut the coating into 10 × 30 mm to form a tactile test piece with the chuck spacing at the center. It was set to 10 mm. Shimadzu Autograph AG for measurement
-A type was used and the crosshead speed was 100 mm / min.

5. Toluene resistance The dry film was measured to be about 25 mm square after being immersed in toluene for 24 hours. The elution and swelling ratios were calculated by the following formula.

Elution (%) = (Wo−Wd) / Wo × 100 Swelling (%) = (Ws−Wd) / Wd × 100 [Effects of the Invention] The aqueous resin obtained by the present invention has a one-pack type room temperature crosslinkability, and therefore has storage stability at ordinary temperatures and low temperatures not found in general aqueous resin dispersions, and the aqueous resin The obtained film is very smooth and has good transparency. Further, since the cross-linking of the film is formed by a carbonyl group and a hydrazino group, it is rich in oil resistance and water resistance and has toughness without the problem of formalin generation. Therefore, the water-based resin has a wide range of applications such as adhesives, paints, paper processing agents and fiber processing agents, and is particularly useful in fields where oil resistance, water resistance and coating film smoothness are required.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C09D 157/10 PDG C09J 157/10 JAX D21H 19/20

Claims (2)

[Claims] 1. 2 to 50 parts by weight of unsaturated carboxylic acid (A),
1 to 30 parts by weight of at least one carbonyl group-containing unsaturated compound (B) selected from a ketone group or an aldehyde group and 20 to 97 parts by weight of a monomer (C) copolymerizable therewith. A copolymer obtained by solution polymerization of a monomer in a polar solvent (D) using an oil-soluble polymerization initiator (E) is neutralized with an aqueous alkaline solution (F) to be water-based, and thus an aqueous polymer An aqueous resin composition having excellent storage stability, which is obtained by blending the compound [I] with a hydrazine compound [II] having at least two hydrazino groups. 2. The hydrazine compound [II] is added to the carbonyl group-containing unsaturated compound (B) in an amount of 0.2 to 1 per mol of the carbonyl group.
The aqueous resin composition according to claim 1, which is mixed with 1.5 mol.