JPH04180910A - Aqueous solution or dispersion of crosslinking resin composition - Google Patents

Abstract

PURPOSE:To obtain the title solution or dispersion which can give a film improved in smoothness and adhesion by dissolving or dispersing a composition containing a specified crosslinking resin and a crosslinking agent in water. CONSTITUTION:10-90wt.% water-insoluble macromonomer (A) of a number- average molecular weight of 300-100000, obtained by introducing a polymerizable double bond into one end of a molecular chain of a polymer obtained by polymerizing an ethylenically unsaturated monomer, is copolymerized with 0.5-50wt.% water-soluble polymerizable unsaturated monomer (B) copolymerizable with component A, 1-50wt.% polymerizable unsaturated monomer (C) having an aldo group or a keto group and being copolymerizable with components A and B and 0-88.5wt.% ethylenically unsaturated monomer (D) other than components A-C and copolymerizable therewith at 50-200 deg.C for 1-10hr. The obtained product is optionally neutralized or quaternized to obtain a water-soluble or water-dispersible copolymer resin. This resin and a crosslinking agent (e.g. oxalic dihydrazide) are dissolved or dispersed in water.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an aqueous solution of a crosslinkable resin composition that can be crosslinked even at room temperature, and a water-soluble or particulate water-dispersible copolymer used in this aqueous solution. Regarding coalesced resin.

(Prior Art and its Problems) Conventionally, organic solvent type resin compositions have been used in many fields such as paints and adhesives. However, this one
There is a problem in that a large amount of organic solvent is volatilized when used, and in recent years, there has been a shift from organic solvent type to aqueous type due to the need to make them non-polluting and non-hazardous.

The aqueous type is broadly divided into an aqueous emulsion type obtained by emulsion polymerization and a water-soluble type. In the case of an aqueous emulsion type, when used, a film is formed through the fusion of emulsion particles, so there are problems with adhesion to the material and smoothness of the film surface. In particular, this problem becomes more pronounced when membrane formation is carried out by crosslinking reaction in order to improve membrane performance. On the other hand, in the case of a water-soluble type, it tends to have a very high viscosity, and there are significant restrictions on its use.

Although it is possible to lower the viscosity by blending a large amount of organic solvent, the intended purpose of making it water-based, such as making it non-polluting and non-hazardous, cannot be achieved.

(Means for Solving the Problems) The present inventor has conducted extensive research in order to obtain an aqueous resin composition free from the above-mentioned problems, starting from a water-soluble type.

As a result, a composition that combines a specific crosslinked resin with a water-soluble polymer in the main chain and a hydrophobic polymer in the side chain and a crosslinking agent is water-soluble or water-dispersible in the form of fine particles, and has sufficient crosslinkability. The aqueous liquid of this product has a low viscosity and is sufficiently practical, and the film obtained from this aqueous liquid has a smooth surface and good adhesion to the material. This discovery led to the completion of the present invention.

That is, the present invention provides [I] A) 10 to 90% by weight of a water-insoluble macromer in which a polymerizable double bond is introduced at one end of a polymer chain obtained by polymerizing an ethylenically unsaturated monomer.
, B) 0.5 to 50% by weight of a water-soluble polymerizable unsaturated monomer copolymerizable with the macromer A), C) the macromer A)
and D) a polymerizable unsaturated monomer copolymerizable with the monomer B) and having an aldo or keto group, and D) copolymerizable with the macromer A), the monomers B) and C). , a polymerizable unsaturated mixture containing 0 to 88.5% by weight of ethylenically unsaturated monomers other than A), B) and C) is copolymerized, and if necessary, neutralized or converted into a quaternary salt. The present invention provides an aqueous solution of a crosslinkable resin composition, which contains as main components a water-soluble or particulate water-dispersible copolymer resin obtained by the above method, and [II] a crosslinking agent.

The present invention further relates to [I] a water-soluble or particulate water-dispersible copolymer resin used in the above-mentioned aqueous liquid.

Each of the components A) to D) used in preparing the water-soluble or particulate water-dispersible copolymer resin [I] in the present invention will be explained below.

A) = ll-soluble macromer A water-insoluble macromer (hereinafter abbreviated as "macromer A") is a copolymer resin (grafted product) with [I] acid component that becomes a water-insoluble side chain. and the number average molecular weight is 300 to 100,000, preferably 500 to 5.
0,000, more preferably 1,000 to 20,000, and a substantially water-insoluble oligomer or polymer having a polymerizable carbon-carbon double bond at one end of the polymer chain of a monomer having a polymerizable carbon-carbon double bond. It is. When the molecular weight of Macromer A is less than 300, the effect of reducing the viscosity due to grafting in the resulting aqueous [I] acid component liquid is small; on the other hand, when the molecular weight exceeds 100,000, the viscosity is high and the [I] acid component polymerization operation becomes difficult. Become.

In the present invention, "macromer" refers to Macrom.

It is an abbreviation for 1ecular monomer, and in macromer A, a known method can be used to introduce a polymerizable unsaturated group at the terminal. For example, ① a method in which allyl chloride, methacrylic acid chloride, etc. are allowed to act on a living polymer anion. , a method in which epichlorohydrin is applied to a living polymer anion to introduce a glycidyl group to the polymer end, and this is reacted with an unsaturated carbodiic acid such as (meth)acrylic acid; A method in which a hydroxyl group is reacted with an unsaturated monomer containing one or more isocyanate groups such as incyanatoethyl methacrylate, or a method in which a carboxyl group is introduced at the end of a living polymer and this carboxyl group is reacted with an unsaturated monomer containing an epoxy group such as glycidyl methacrylate. , ■Mercaptan chain transfer agent having a carboxyl group,
For example, mercaptoacetic acid, 2-mercaptopropionic acid,
A radically polymerizable monomer is polymerized in the presence of 3-mercaptopropionic acid, etc., or a carboxyl group-containing polymerization initiator, such as azobiscyanovaleric acid, azobiscyanopropionic acid, etc., to obtain an oligomer or polymer having a terminal carboxyl group. A method in which a terminal carboxyl group is reacted with a compound having an epoxy group such as glycidyl methacrylate, glycidyl acrylate, or allyl glycidyl ether and a polymerizable unsaturated group; (2) a mercaptan chain transfer agent having a hydroxyl group, such as 2-mercaptoethanol; A radically polymerizable monomer is polymerized in the presence of a hydroxyl group to obtain an oligomer or polymer having a terminal hydroxyl group, and this terminal hydroxyl group is isocyanated with a diisocyanate compound. A method of reacting a compound having a saturated group, or a method of reacting an oligomer or polymer having a terminal hydroxyl group with a monoisocyanate having a polymerizable unsaturated group such as isocyanatoethyl methacrylate, and ■ a mercaptan having an amino group. A radically polymerizable monomer is polymerized in the presence of a chain transfer agent such as 2-aminoethanethiol to obtain an oligomer or polymer having a terminal amino group, and this product is injected with an epoxy group and polymerizable unsaturation in the same manner as in ① above. A method of reacting a compound having a group with a group can be used.

Among the above methods for producing macromers, method (2) is particularly preferred because it is a radical polymerization method that is advantageous for industrial production and the reaction is easy. In method (2), a tertiary amine or a quaternary ammonium salt can be used as a reaction catalyst for reacting an oligomer or polymer having a terminal carboxyl group with glycidyl methacrylate or the like.

In order to prevent coloring of the macromonomer, it is preferable to use a quaternary ammonium salt such as tetrabutylammonium bromide.

The structural units of macromer A in the present invention are known ethylenically unsaturated monomers, and are not particularly limited. Typical examples include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, and isopropyl acrylate. , butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate,
C8 to C2 of (meth)acrylic acid such as octyl methacrylate, lauryl methacrylate, and stearyl methacrylate
Alkyl or cycloalkyl ester of 4; C8-□8 alkoxy of (meth)acrylic acid such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc. Alkyl ester; (meth) of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.
02-8 hydroxyalkyl esters of acrylic acid: acrylic or methacrylamide such as acrylamide, methacrylamide, dimethylacrylamide; styrene;
Aromatic unsaturated monomers such as vinyltoluene, α-methylstyrene, N-vinylpyrrolidone, and vinylpyridine; Olefins such as ethylene, propylene, butylene, and pentene; Diene compounds such as butadiene, Raysophon, and chlorobrene; Propionic acid Examples include vinyl, vinyl acetate, acrylonitrile, methacrylate trile, vinyl bivalate, and Beoba monomer (product of Shell Chemical Co., Ltd.), which are used as appropriate depending on desired performance.

Macromer A in the present invention can be obtained by reacting the ethylenically unsaturated monomers described above by the methods described in (1) to (4) above. In the radical polymerization methods (1) to (2), when a mercaptan chain transfer agent is used, a polymerization initiator can be used together with the mercaptan chain transfer agent to polymerize the ethylenically unsaturated monomer.

The glass transition point (Tg) of macromer A is important from the viewpoint of storage stability in a mixed system of [Il copolymer resin and [rl] crosslinking agent. When Tg is low, [1] The polymer chains of the resin move freely, so the solid content must be kept low to maintain stability. On the other hand, when Tg is high, [I] The polymer chains of the resin move freely. Since the hydrophilic main chain is also fixed by aggregation between side chains, stability can be maintained even at a considerably high solids content.Therefore, the glass transition point to the macromer is preferably -10°C or higher, more preferably is 5
℃ or higher, more preferably 20℃ or higher.

B: Hexagonal monomer A water-soluble polymerizable unsaturated monomer (hereinafter abbreviated as "monomer BJ") can be copolymerized with macromer A, and can be made to have strong hydrophilic properties by itself or by neutralization or quaternary salt formation. The monomer may be any of anionic, cationic, and nonionic monomers.

Monomer B is a monomer that forms the main chain in [I] the resin, makes the main chain hydrophilic, and makes the [I] resin water-soluble or particulate water-dispersible (hereinafter referred to as "water-soluble or particulate water-dispersible"). "water-soluble" is sometimes abbreviated as "water-soluble." If the hydrophilicity of monomer B is insufficient,
It cannot exhibit the characteristics of a grafted product and has a high viscosity.

Typical examples of monomer B include, for anionic systems, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, and styrene sulfonic acid. acid sodium, etc.; cationic types include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylamide and dimethylaminopropylmethacrylamide, and glycidyl (meth)
Adducts of acrylate and amines, etc.: Examples of nonionic types include (meth)acrylates having a polyoxyethylene chain.

Among the monomers B, anionic and cationic monomers function as water-soluble monomer units by being neutralized or converted into quaternary salts before or after polymerization.

The polymerizable unsaturated monomer having an aldo group or a keto group (hereinafter abbreviated as "monomer C") is contained in a small amount in one molecule (one aldehyde group or keto group and one macromer A).
, is a monomer having one carbon-carbon double bond that can be radically copolymerized with monomer B. In particular, these are monoethylenically unsaturated aldehyde compounds and keto compounds which are free-radically polymerizable. Typical specific examples include acrolein, diaseptone acrylamide, diacetone methacrylamide, formylstyrene, acrylamide pivalaldehyde, methacrylamide bivalaldehyde, 3-acrylamidomethyl-anisaldehyde, diacetone acrylate, and acetonyl acrylate. , diacetone methacrylate, 2-hydroxypropyl acrylate acetylacetate, butanediol acrylate acetylacetate, vinyl alkyl ketone, and the like. Among the above-mentioned compounds, keto compounds, especially diaseptone acrylamide, are preferred.

The aldo group or keto group in the monomer C acts as a crosslinking functional group that reacts with a crosslinking agent.

D) Composition: Other ethylene monomers Other ethylenically unsaturated monomers (hereinafter abbreviated as "monomer D") can be copolymerized with macromer A, monomer B, and monomer C, and the macromer A , Monomer B and Monomer C can be used without particular limitation as long as they are ethylenically unsaturated monomers.

Representative examples of monomer D include the ethylenically unsaturated monomers exemplified as the structural units of macromer A above.

By copolymerizing the macromer A, monomers B, C and D, the water-soluble copolymer resin [I] of the present invention can be obtained. These macromers in copolymer production,
The blending ratio of monomers is as follows. (The sum of macromer A, monomers B, C and D is 100% by weight.) Macromer A: 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 35 to 70% by weight, Monomer B: 0 .5-50% by weight, preferably 2-30%
% by weight, more preferably 2-10% by weight, Monomer C: 1-50% by weight, preferably 5-30% by weight, even more preferably 8-25% by weight, Monomer D: 0-88.5% by weight, preferably is 0-7
3% by weight, more preferably from 0 to 55% by weight. If the proportion of macromer A is less than 10% by weight, the viscosity of the resin aqueous liquid of the resulting copolymer resin, especially in a system with a small amount of organic solvent, may decrease. Viscosity increases. On the other hand, if the copolymer resin obtained when the proportion of macromer A exceeds 90% by weight is water-based, it will not become water-soluble and will become an emulsion with a larger particle size, so the membrane obtained from this emulsion will have a surface There is a problem that the surface becomes rough and the surface is not smooth.

If the proportion of monomer B is less than 0.5% by weight, the hydrophilicity of the main chain of the obtained copolymer resin will be insufficient, and the characteristics as a graft polymer will not be exhibited, resulting in high viscosity. On the other hand, if the proportion of monomer B exceeds 50% by weight, there is a problem that the cured film from the resulting resin composition is too hydrophilic and has poor water resistance.

If the proportion of monomer C is less than 1% by weight, the crosslinking reaction between the resulting copolymer and the crosslinking agent will not be sufficient, so the mechanical properties, chemical resistance, water resistance, etc. of the resulting cured product will tend to deteriorate. . On the other hand, monomers A, monomers B, C, and if necessary, monomer D are blended in a predetermined ratio and copolymerized, and if necessary, by neutralization or quaternary salting, [I] water-soluble A copolymer resin is obtained. Although various methods other than emulsion polymerization can be used as the copolymerization method, a method in which the above-mentioned copolymerization components are radically polymerized in an organic medium is common.

In the method of radical polymerization in an organic medium, known polymerization initiators that can be used in solution polymerization, such as azo type and peroxide type, can be used as the polymerization initiator for radical polymerization. It is desirable to keep the amount of organic medium used during polymerization as small as possible, but if a large amount is used to facilitate the polymerization operation due to the viscosity during polymerization, etc. It is desirable that it can be easily removed from the system during the process, and preferably has a boiling point of 150°C or lower, more preferably 130°C or lower. The type of organic solvent used is not particularly limited, but from the viewpoint of toxicity, odor, and ease of removal, toluene, xylene, ethylbenzene, methanol, ethanol, propatool, butanol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like are preferred. As for the copolymerization conditions, the temperature and time commonly used in solution polymerization can be applied, and the temperature and time generally used are 50°C.
It takes about 1 to 10 hours at ~200°C.

The copolymer obtained by copolymerization is made water-soluble as it is or by neutralization or quaternary salting to obtain [I] water-soluble copolymer resin. That is, if monomer B, which is a component of the copolymer, is nonionic or has been neutralized or quaternary salted, it can be water-soluble as it is,
When monomer B has an anionic group such as a carboxyl group or a sulfonic acid group that becomes an anion upon neutralization,
By neutralizing with ammonia, amines, alkali metals, etc., or when monomer B has a cationic group such as an amino group that becomes a cation upon neutralization, organic acids such as acetic acid, propionic acid, lactic acid, acrylic acid, etc. It can be made water-soluble by neutralizing it with an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid.

In the water-soluble copolymer resin of the present invention, the side chain is formed of water-insoluble macromer A, and the main chain is water-soluble and formed of monomers B, C, and D. In water, the macromer side It exists with many chains inside and many main chains outside. The monomer C component, which serves as a crosslinking point, exists in the external hydrophilic main chain, which is advantageous in terms of crosslinkability with the crosslinking agent, and since crosslinking is carried out in the main chain, which is the main chain. Water resistance is effectively improved by crosslinking. However, a crosslinkable monomer component can also be used as a constituent component of macromer A in addition to the main chain.

In the present invention, the above [I] water-soluble copolymer and [II]
] A crosslinking agent is used in combination with a crosslinking agent to provide an aqueous solution of a crosslinkable resin composition containing this composition as a main component. Compounds or resins having two or more can be used.

As the crosslinking agent, a polyhydrazide compound is preferable. Polyhydrazide compounds have hydrazide groups in one molecule.
It has two or more O (-C-NH-NH2), specifically, saturated aliphatic carboxylic acid dihydrazide having 2 to 18 carbon atoms, such as oxalic acid dihydrazide, malonic acid dihydrazide, koha(acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide etc.; dihydrazide of monoolefinically unsaturated dicarboxylic acids such as maleic acid dihydrazide, fumaric acid dihydrazide and itaconic acid dihydrazide; polyhydrazide of carbonic acid such as carbonic acid dihydrazide and general formula where X means a number of 1 to 5, preferably 1 to 3): bissemicarbazide, especially a compound represented by the general formula (wherein the group -R- is a linear or branched carbon atom of 2 to 7 or a carbocyclic residue with 6 to 8 carbon atoms, e.g. aliphatic,
Alicyclic or aromatic bis-semicarbazides; polyhydrazides of aromatic polycarboxylic acids, such as dihydrazide of phthalic acid, terephthalic acid or isophthalic acid, and dihydrazide, trihydrazide or tetrahydrazide of pyromellitic acid; at least 2 in one molecule pieces, often 20
Polyhydrazides of polyacrylic acid having ~100 hydrazide groups; trihydrazides such as nitrilotriacetic acid trihydrazide or tetrahydrazides such as ethylenediaminetetraacetic acid tetrahydrazide.

If the above-mentioned polyhydrazide compound has too strong hydrophobicity, water dispersion will be difficult and a uniform crosslinked coating film will not be obtained.
It is preferable to use a compound with a value of about 0 or less). Suitable representative examples include dihydrazide compounds of C4-1□ dicarboxylic acids, such as succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, ceotic acid dihydrazide, and the like.

In the present invention, the crosslinking reaction between an aldo group or a keto group and a hydrazide group occurs according to the following formula.

The amount of the crosslinking agent added is generally preferably around the equivalent amount. For example, in the case of a polyhydrazide compound, [I] The number of hydrazide groups is hydrazide based on the total number of aldo groups and keto groups in the water-soluble copolymer resin. When a polyhydrazide compound is used with the ratio of number of groups/total number of aldo groups and keto groups being preferably 1/10 to 10/l, more preferably 1/1, crosslinking is possible at room temperature, but crosslinking is performed by heating. You can also do that.

In the present invention, in order to obtain the aqueous liquid of the crosslinkable resin composition, [I] the water-soluble copolymer resin may be dissolved or dispersed in water, and then [II] the crosslinking agent may be mixed in the aqueous liquid. Alternatively, the two may be mixed and then dissolved or dispersed in water.

In the aqueous solution of the crosslinkable resin composition of the present invention, when the water-soluble copolymer resin [I] has a crosslinkable functional group other than an aldo group or a keto group, a crosslinking agent that reacts with the crosslinkable functional group is used in combination. can do. For example, when the water-soluble copolymer resin [I] has a hydroxyl group, a melamine resin, a blocked isocyanate compound, etc. can be used in combination with [I]
When the resin has a carboxyl group, an epoxy resin or the like can be used in combination.

(Actions and Effects of the Invention) The water-soluble copolymer resin in the aqueous liquid of the composition of the present invention is a graft polymer composed of a hydrophobic side chain composed of a water-insoluble macromer and a hydrophilic main chain. In water, it exists in a water-soluble state with the macromer side chain located inside and the main chain located outside, and has a large viscosity-lowering effect.

In addition, since the monomer C component that serves as a crosslinking point exists in the hydrophilic main chain located externally, crosslinking with the crosslinking agent takes place in the hydrophilic part of the main chain, so crosslinking can improve water resistance. done effectively. In addition, when a polyhydrazide compound is used as a crosslinking agent, the crosslinking reaction between the aldo group or keto group in the water-soluble copolymer resin and the polyhydrazide compound as the crosslinking agent occurs even at room temperature, so room temperature crosslinking occurs. Can be made into a mold.

In addition, [I] water-soluble copolymers are not obtained by emulsion polymerization (the copolymers can move molecules freely to some extent, and even when they have a particle shape, the fusion of the particles and the material It has excellent wettability.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Note that "parts" and "%" below are based on weight.

Production example 1 174 g of n-butanol in a 4-bottle flask with a capacity of 212
were mixed, heated and maintained at 110°C.

The following mixture was added dropwise into this over 2 hours.

n-Butyl methacrylate 134g Acrylic acid 19g Diacetone acrylamide 63g Toluene solution of macromonomer AA-6 (Note-1) with solid content 45% 3
15g2.2'-Azobisisobutyronitrile 6g (
Note-1) Macromonomer AA-6: Toagosei Chemical Industry (
Co., Ltd., a macromer having a polymerizable double bond at the end of a polymethyl methacrylate chain, number average molecular weight of 6000° After completion of dropwise addition, it was aged for 30 minutes, and then 3 g of azobisisobutyronitrile was gradually added over 30 minutes. After further aging for 1 hour, 165 g of organic solvent was recovered by heating to 130"C.
After cooling to 0° C., adding 26 g of triethylamine and mixing for 20 minutes, 532 g of deionized water was added dropwise and mixed uniformly.

After distilling off the solvent from the resulting mixed solution at 50° C. under reduced pressure, 100 g of water was added to obtain copolymer resin aqueous liquid A. Aqueous liquid A had a solid content of 34.9%, a pH of 8.13, a viscosity of 4 Boise (B-type viscometer, 12 rpm), and a residual organic solvent content of 3% n-butanol. Further, the peak molecular weight of the resin (according to gel permeation chromatography rGPC) was about 23,000.

Production Example 2 174 g of n-butanol was blended into a 4-bottle flask with a capacity of 2 flooded, and heated and maintained at 115°C.

The following mixture was added dropwise into this over 2 hours.

Methyl methacrylate 134g Acrylic acid 19g Diaseptone acrylamide 63g Macromonomer AB-6
(Note-2) 143g2.2'-Azobisisobutyronitrile 6g (Note-2) Macromonomer AB-6:
Manufactured by Toagosei Kagaku Kogyo Co., Ltd., a macromer having a polymerizable double bond at the end of a poly n-butyl acrylate chain, number average molecular weight of 6000° After completion of the dropwise addition, it was aged for 30 minutes, and then 3 g of azobisisobutyronitrile was added. was gradually added over 30 minutes, aged at 120°C for another 2 hours, cooled to 80°C, added 26g of triethylamine and mixed, and then added 53g of deionized water.
2 g was added dropwise and mixed uniformly. 50% of the obtained mixture
Copolymer resin aqueous liquid B was obtained by distilling off the solvent under reduced pressure at °C.
I got it. Aqueous liquid B has a solid content of 40.1%, pH 7.53,
The viscosity is 130 boise (B type viscometer, 12 rpm),
The residual organic solvent content was 10% n-butanol.

In addition, the peak molecular weight of the resin (according to GPC) is approximately 230
It was 00.

Production Example 3 174 g of propylene glycol monomethyl ether was blended into a four-bottle flask with a capacity of 2 g, and the mixture was heated and maintained at 115°C. The following mixture was added dropwise into this over 2 hours.

Styrene 124g Acrylic acid 29g Diaseptone acrylamide 63g Macromonomer AB-61
43g 2.2'-Azobisisobutyronitrile After dropping 6g, it was aged for 30 minutes, then 3g of azobisisobutyronitrile was gradually added over 30 minutes, and further 120
After aging at ℃ for 1 hour, it was heated to 135 ℃ and 71 g of organic solvent was recovered. Then, the reaction mixture in the flask was heated to 80°C.
After cooling and adding and mixing 40g of triethylamine,
632 g of deionized water was added dropwise and mixed uniformly. The solvent of the obtained mixture was distilled off under reduced pressure at 50°C to obtain a copolymer resin aqueous liquid C. Aqueous liquid C has a solid content of 32.5%, p
H8,45, viscosity 151 boise (B type viscometer, 12 r
pm), and the residual organic solvent content was 7% propylene glycol monomethyl ether. The peak molecular weight (according to GPC) of the resin was about 26,000.

Production Example 4 Production example except that the mixture to be dropped has the following composition, the amount of organic solvent recovered before neutralization is 75.5 g, the amount of triethylamine blended is 26 g, and the amount of deionized water to be dropped is 532 g. A copolymer resin aqueous liquid was obtained in the same manner as in 3.

Methyl methacrylate 67gn-butyl acrylate 33g acrylic acid
19g Dia7ton Acrylamide 63g Macromonomer AB-6179g 2.2'-Azobisisobutyronitrile 5g The aqueous liquid has a solid content of 40.3%, pH 7.74, and a viscosity of 104 Boise (B-type viscometer, 12 rpm). The residual organic solvent content was 7% propylene glycol monomethyl ether. The peak molecular weight of the resin (according to GPC) is approximately 1
It was 7000.

Production Example 5 The amount of propylene glycol monomethyl ether added to the flask was 100 g, the mixture to be added dropwise was a mixture with the following composition, and the amount of organic solvent recovered before neutralization was 130 g.
A copolymer resin aqueous liquid E was obtained in the same manner as in Production Example 3, except that the amount of triethylamine compounded was 26 g and the amount of deionized water added was 532 g.

n-Butyl acrylate 100g Acrylic acid 19g Diaseptone acrylamide 63g Macromonomer AA-6
179 g 2.2'-Azobisisobutyronitrile 5 g Propylene glycol monomethyl ether 50 g Aqueous liquid E has a solid content of 41.4%, a pH of 188, a viscosity of 8 boids (B-type viscometer, 12 rpm), and a residual organic solvent content. is 9% propylene glycol monomethyl ether
Met. The peak molecular weight (according to GPC) of the resin was about 14,000.

Production example 6 Capacity 2! 100 g of propylene glycol monomethyl ether was added to a four-bottle flask and heated to and maintained at 115°C. The following mixture was added dropwise into this over 2 hours.

Isobutyl methacrylate 98g Acrylic acid 19g Diaseptone acrylamide 63g Macromonomer AA-61
79g 2.2'-azobisisobutyronitrile 5g propylene glycol monomethyl ether 50g After completion of dropwise addition, ripen for 30 minutes, then gradually add 3g of azobisisobutyronitrile over 30 minutes, and further at 120°C for 1 hour. After aging, it was heated to 135° C. and 144 g of organic solvent was recovered. Next, 108 g of isobutanol was added while cooling the reactant in the flask, and 8
When the temperature reached 0° C., 26 g of triethylamine was added and mixed, and then 632 g of deionized water was added dropwise and mixed uniformly.

The resulting mixed solution was subjected to solvent distillation at 50° C. under reduced pressure to obtain copolymer resin aqueous solution F. Aqueous liquid F has a solid content of 42.
6%, pH 7.88, viscosity 28 boise (B type viscometer, 1
2 rpm), and the residual organic solvent content was 5% propylene glycol monomethyl ether. The peak molecular weight of the resin (according to GPC) was about 24,000.

Production Example 7 174 g of propylene glycol monomethyl ether was blended into a four-bottle flask with a capacity of 2°C, and the mixture was heated and maintained at 115°C. The following mixture was added dropwise into this over 2 hours.

Isobutyl methacrylate 98g Acrylic acid 19g Diaseptone acrylamide 63g Toluene solution of macromonomer AW-63 (Note-3) with solid content 50%
354g2.2'-Azobisisobutyronitrile 5
g (Note-3) Macromonomer AW-6S: Manufactured by Toagosei Kagaku Kogyo Co., Ltd., macromer having a polymerizable double bond at the end of a polyisobutyl methacrylate chain, number average molecular weight of 6000° After completion of dropwise addition, aging for 30 minutes Then, 3 g of azobisisobutyronitrile was gradually added over 30 minutes, and the mixture was further aged at 120°C for 1 hour, and then heated to 130°C to recover 199['] of organic solvent. Next, 108 g of isopropanol was added while cooling the reactant in the flask, and when the temperature reached 80° C., 26 g of triethylamine was added and mixed, and then 632 g of deionized water was added dropwise and mixed uniformly. The solvent of the obtained mixture was distilled off under reduced pressure at 50° C. to obtain a copolymer resin aqueous liquid G. Aqueous liquid G had a solid content of 36.4%, a pH of 8.17, a viscosity of 3.5 Bois (B-type viscometer, 12 rpm), and a residual organic solvent content of 5% propylene glycol monomethyl ether. The peak molecular weight of the resin (according to GPC) is approximately 24,000.
Met.

Production Example 8 Propylene glycol monomethyl ether loog was blended into a four-loof flask with a capacity of 212, and heated to 115°C.
held. The following mixture was added dropwise into this over 2 hours.

Isobutyl methacrylate 96gN, N-
Dimethylaminopropylacrylamide 21g Diaseptone acrylamide 63g Macromonomer A
A-6179g 2.2'-Azobisisobutyronitrile 5g Propylene glycol monomethyl ether 50g After the addition was completed, the mixture was aged for 30 minutes, then 3g of azobisisobutyronitrile was gradually added over 30 minutes, and further heated at 120°C. After aging for 1 hour, it was heated to 135° C. and 142 g of organic solvent was recovered. Next, 108 g of isopropanol was added while cooling the reactant in the flask.
When the temperature reached 80° C., 9 g of acetic acid was added and mixed, and then 532 g of deionized water was added dropwise and mixed uniformly. The solvent of the obtained mixture was distilled off under reduced pressure at 50°C to obtain a copolymer resin aqueous liquid H. Aqueous liquid H has a solid content of 39.7% and a pH of 5.
, 39, viscosity 127 voices (B type viscometer, 12 rpm)
The residual organic solvent content was 9% propylene glycol monomethyl ether. The peak molecular weight of the resin (as determined by GPC) was approximately 14,000.

Production Example 9 The amount of propylene glycol monomethyl ether blended into the flask is 174 g, the mixture to be added dropwise is a mixture with the following composition, the amount of organic solvent recovered before neutralization is 61 g, and the amount of acetic acid blended is 8 g. Except for this, the same procedure as in Production Example 8 was carried out to obtain a copolymer resin aqueous liquid (2).

Methyl methacrylate 67g N-Butyl acrylate 31g N,N-dimethylaminopropylacrylamide 19g Diaseptone acrylamide 63g Macromonomer A
B-6179g 2.2'-azobisisobutyronitrile 5g aqueous liquid■
has a solid content of 42.4%, a pH of 5.59, and a viscosity of 70 boids (
B type viscometer, 12 rpm), and the residual organic solvent content was 7% propylene glycol monomethyl ether. In addition, the peak molecular weight of the resin (according to GPC) is 1
It was 4000.

Production Example 10 The amount of propylene glycol monomethyl ether added to the flask was 100 g, the mixture to be added dropwise was a mixture with the following composition, and the organic solvent before neutralization was recovered by heating to 140 ° C. The amount recovered was 97 g. Copolymer resin aqueous liquid J was obtained in the same manner as in Production Example 7, except that the amount of triethylamine to be blended was 14 g and the amount of deionized water to be blended was 532 g.

Styrene 74g Acrylic acid Logdia 7ton Acrylamide 36g 70% solids solution of Macro-Natsuma-AHM-6 (Note-4) in toluene
343g2.2'-Azobisisobutyronitrile 2
g (Note-4) Macromonomer AHM-6: Manufactured by Toagosei Kagaku Kogyo Co., Ltd., macromer having a polymerizable double bond at the end of a poly 2-ethylhexyl methacrylate chain, average molecular weight approximately 60
00゜Aqueous liquid J has a solid content of 47.8%, a pH of 8.27, and a viscosity of 11.
5 voids (B-type viscometer 12 rpm), and the residual organic solvent content is 3% of propylene glycol monomethyl ether.
%Met. Also, the peak molecular weight of the resin (by GPC)
was approximately 38,000.

Production example 11 (for comparison) Capacity 2! 250 g of propylene glycol monomethyl ether was added to a four-bottle flask, and the mixture was heated and maintained at 115°C. The following mixture was added dropwise into this over 2 hours.

Isobutyl methacrylate 98g Acrylic acid 19g Guiacetone acrylamide 63g Methyl methacrylate
179g 2.2'-Azobisisobutyronitrile After dropping 7g, it was aged for 30 minutes, then 3g of azobisisobutyronitrile was gradually added over 30 minutes, and further aged at 120°C for 1 hour, 135
133g of organic solvent was recovered by heating to 10°C.Then, while cooling the reactant in the flask, 10g of isopropanol was added.
When the temperature reached 80° C., 26 g of triethylamine was added and mixed, and then 532 g of deionized water was added dropwise and mixed uniformly. The solvent of the obtained mixture was distilled off under reduced pressure at 50°C, but the solvent was hardly able to be distilled off due to the high viscosity. The aqueous liquid finally obtained had a solid content of 31.6%, but had no fluidity and could not be used.

Production Example 12 (for comparison) 242 g of deionized water in a 4-bottle flask with a capacity of 212,
Ammonium persulfate 0.7g and Hinyekol 707
3F (manufactured by Nippon Nyukazai Co., Ltd., anionic surfactant,
2.0 g of active ingredient (30%) was blended and heated and maintained at 80°C. Add 4 pre-emulsions of the following mixture into this.
dripped over time.

Deionized water 352g Nucor 707 SF 65'g Ammonium persulfate 1.3g Methyl methacrylate 372μm-Butyl acrylate
161g61g Guiacetone Acrylamide 134g Acrylic Acid
After dropping 3 g, the mixture was aged for 30 minutes, then a solution of 0.7 g of ammonium persulfate dissolved in 7 g of deionized water was gradually added over 30 minutes, and further aged for 2 hours to obtain a copolymer emulsion liquid. Ta. The obtained emulsion liquid had a solid content of 50.3%, a pH of 2.03, and an emulsion particle size of 111 μm.

Furthermore, when 0.8 g of adipic acid dihydrazide was uniformly mixed with 50 g of this emulsion, and this was coated with a 250 μm doctor blade and dried at room temperature, the surface was not smooth and cracks appeared on the coated surface. Furthermore, when a similarly coated piece was dried at 80°C for 10 minutes, the surface did not become smooth.

Examples 1 to 1O For each of the copolymer resin aqueous liquids A to J obtained in Production Examples 1 to 1O, 0. Adipic acid dihydrazide in an amount equivalent to g equivalent and water were added to obtain an aqueous solution of a crosslinkable resin composition having a solid content of 33%. This aqueous liquid was tested for storage stability and film performance after painting. The test results are shown in Table 1.

The test was conducted according to the test method below.

Method 2: Storage stability: The paint was stored indoors at 20°C, and the state of the paint was examined after 1 and 3.7 days. Those in which no abnormalities such as thickening were observed were marked as ○.

It was painted on a curable glass plate with a 250 μm doctor blade and left to stand in a 20"C room, and after 1.3.7 days, the paint film was subjected to a pencil scratch test. Evaluation was performed based on membrane tearing.

It was coated on a solvent-resistant zinc diphosphate-treated steel plate using a #65 bar coater and dried at 20'C for 7 days. Xylene was placed in spots on the coated film, and after drying at room temperature, the appearance was observed. A sample in which no trace of the coating film was dissolved was rated as ○.

The coating film was coated with a #65 bar coater on a steel plate treated with adhesive zinc diphosphate and dried at 20"C for 7 days.
This was done by the base grain tape method specified in K5400 8.5°2. However, the gap between the cuts was set to l■. Evaluation was made based on the number of squares that remained without peeling out of 100 squares.

Claims (4)

[Claims] (1) A) 10 to 90% by weight of a water-insoluble macromer obtained by polymerizing an ethylenically unsaturated monomer and introducing a polymerizable double bond at one end of the polymer chain; 0.5 to 50% by weight of a polymerizable water-soluble polymerizable unsaturated monomer; C) a polymerizable unsaturated monomer 1 that is copolymerizable with the macromer A) and the monomer B) and has an aldo group or a keto group; ~50% by weight and D) 0 to 88.5% by weight of ethylenically unsaturated monomers other than A), B) and C) copolymerizable with the macromer A), the monomers B) and C) A water-soluble or particulate water-dispersible copolymer resin obtained by copolymerizing a polymerizable unsaturated mixture of and, if necessary, neutralizing or converting it into a quaternary salt. (2) An aqueous liquid of a crosslinkable resin composition, which contains the water-soluble or particulate water-dispersible copolymer resin according to claim 1 and a crosslinking agent as main components. (3) The aqueous solution of the crosslinkable resin composition according to claim 2, wherein the crosslinking agent is a polyhydrazide compound. (4) The aqueous solution of the crosslinkable resin composition according to claim 3, wherein the amount of organic solvent is 10% by weight or less.