JP2007277402A - Aqueous curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous curable composition which comprises a carbonyl group-containing vinylic polymer and a specific cross-linking agent reacting with the carbonyl group, can safely be produced from low toxic raw materials and is excellent in storage stability. <P>SOLUTION: This aqueous curable composition comprises (A) a glyoxylamide group-having vinylic polymer represented by the general formula (I) (R<SP>1</SP>is H or a 1 to 8C organic group), and (B) a primary amino group and/or a secondary amino group-having compound, and/or (C) a hydrazide group and/or semicarbazide group-having compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous curable composition containing a vinyl polymer having a carbonyl group.

  An aqueous curable composition comprising a vinyl polymer containing a carbonyl group and a crosslinking agent that reacts with carbonyl is useful because it often exhibits room temperature crosslinking.

  A vinyl polymer containing a carbonyl group is obtained by homopolymerizing, for example, a monomer having a carbonyl group and a (meth) acryloyloxy group or a (meth) acrylamide group, or by copolymerizing with another monomer. can get.

  Examples of such carbonyl group-containing vinyl polymers include N- (1,1-dimethyl-3-oxobutyl) acrylamide (common name: diacetone acrylamide), acetoacetoxyethyl methacrylate (also known as 2- (methacryloyloxy). Vinyl polymers obtained by homopolymerizing () ethyl acetoacetate) or the like or copolymerizing with other monomers are known.

  N- (1,1-dimethyl-3-oxobutyl) acrylamide is usually produced by reacting acrylonitrile, concentrated sulfuric acid and acetone (see Patent Document 1).

  However, since acrylonitrile is highly toxic and highly volatile at the time of production, it easily contaminates the air in the vicinity of the production facility, and uses a large amount of concentrated sulfuric acid that is highly oxidative and corrosive. There was a problem of accompanying. For this reason, the aqueous curable composition using the vinyl polymer containing the carbonyl group which can be manufactured without using acrylonitrile or concentrated sulfuric acid as a raw material was calculated | required.

  Acetoacetoxyethyl methacrylate can be produced from t-butyl acetoacetate and 2-hydroxyethyl methacrylate, and it is not necessary to use acrylonitrile or concentrated sulfuric acid as a raw material. Therefore, the production work of acetoacetoxyethyl methacrylate is less dangerous than the production work of N- (1,1-dimethyl-3-oxobutyl) acrylamide.

  A curable composition obtained by blending a polymer having a carbonyl group obtained by using acetoacetoxyethyl methacrylate as a monomer with a crosslinking agent that reacts with the carbonyl group is useful as a room temperature curable aqueous curable composition. It is known (see Non-Patent Document 1).

However, a polymer or copolymer of acetoacetoxyethyl methacrylate has a problem of poor storage stability in water due to degradation over time due to a reverse Claisen condensation reaction of an acetoacetoxy group in water (see Non-Patent Document 2). ). The reason why the acetoacetoxy group undergoes reverse reaction of Claisen condensation is that the two carbonyl groups in the acetoacetoxy group have a β-diketo structure, and one carbonyl group is the carbonyl group of the ester. It is thought that there is. Accordingly, there has been a demand for an aqueous curable composition utilizing a vinyl polymer containing a carbonyl group having no β-diketo structure that does not cause a reverse Claisen condensation reaction.
JP2000-159736 Prog. Org. Coat., 27, 73-78 (1996) J. Coat. Technol., 70 (881), 57-68 (1998)

  An object of the present invention is to provide a water-based curing containing a vinyl polymer containing a carbonyl group and a specific cross-linking agent that reacts with the carbonyl group, which can be produced safely using a less toxic raw material and has excellent storage stability. It is to provide a sex composition.

  Other objects and features of the present invention will become apparent from the following description.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using a vinyl polymer having a glyoxiramide group, and the present invention has been completed. .

  The present invention provides an aqueous curable composition containing a vinyl polymer having a glyoxyramide group and a specific crosslinking agent, as shown below.

  1. (A) General formula (I)

[Wherein, R ¹ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms. And a vinyl polymer having a glyoxyramide group represented by:
(B) a compound having a primary amino group and / or a secondary amino group, which may be partially or completely neutralized with a Bronsted acid, and / or
(C) The aqueous curable composition containing the compound which has a hydrazide group and / or a semicarbazide group.

2. The vinyl polymer (A) is
(1) General formula (II)

[Wherein, X ¹ , X ² and X ³ independently represent an oxygen atom or a sulfur atom. R ² , R ³ and R ⁴ independently represent a hydrogen atom or an organic group having 1 to 18 carbon atoms. ^Two or three organic groups selected from R ² , R ³ and R ⁴ may be bonded to each other to form a heterocyclic ring. The compound represented by the general formula (III)

[In formula, Y is a C1-C6 linear alkylene group which may have a C1-C6 organic group as a substituent. R ¹ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms. And a compound represented by the general formula (IV)

[Wherein, X ¹ , X ² , Y, R ¹ , R ² and R ³ are the same as described above. A step of obtaining a compound represented by the formula:
(2) A compound of the general formula (IV) is reacted with (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride to give a general formula (V)

[Wherein, X ¹ , X ² , Y, R ¹ , R ² and R ³ are the same as described above. R ⁵ represents a hydrogen atom or a methyl group. And (3) reacting the compound of general formula (V) with water in a dilute acid or in the presence of an acidic compound to give a compound of general formula (VI)

[Wherein, Y, R ¹ and R ⁵ are the same as described above. Through a step of obtaining a monomer having a glyoxyramide group and a (meth) acryloyloxy group represented by
Item 2. The aqueous curable composition according to Item 1, wherein the monomer is obtained by homopolymerization or copolymerization with another vinyl monomer.

  3. Item 2. The aqueous curable composition according to Item 1, comprising a vinyl polymer (A) obtained by homopolymerization or copolymerization in an organic solvent.

  4). Item 2. The aqueous curable composition according to Item 1, comprising a vinyl polymer (A) obtained by homopolymerization or copolymerization in water in an emulsified state.

  5. Item 2. The aqueous curable composition according to Item 1, wherein the vinyl polymer (A) further has at least one anionic group selected from the group consisting of a carboxylate group, a phosphate group and a sulfonate group.

  6). The aqueous solution according to item 1, wherein the vinyl polymer (A) further has at least one nonionic hydrophilic group selected from the group consisting of a polyoxyethylene group, a polyoxypropylene group and a polyoxyethylene polyoxypropylene group. Curable composition.

  7). The aqueous solution according to item 1, wherein the compound (B) is at least one compound selected from the group consisting of ammonia, (polyamino) alkanes, (polyamino) polyether compounds, poly (ethyleneimine), and poly (aminoalkene). Curable composition.

  8). Item 2. The aqueous composition according to Item 1, wherein the compound (B) is produced using a compound having two or more glycidyl groups in one molecule and an amine compound and / or a ketimine compound of an amine compound as a raw material. Curable composition.

  9. Item 1. The compound (B) and / or the compound (C) further has at least one nonionic hydrophilic group selected from the group consisting of a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene polyoxypropylene group. The water-based curable composition described in 1.

  10. Item 2. The aqueous curable composition according to Item 1, wherein the molar concentration of the glyoxiramide group in the vinyl polymer (A) is 0.02 to 6 mol / Kg.

  11. In the above item 1, wherein the total molar concentration of the primary amino group and secondary amino group which may be partially or completely neutralized with Bronsted acid in the compound (B) is 0.02 to 35 mol / Kg. The aqueous curable composition as described.

  12 Item 2. The aqueous curable composition according to Item 1, wherein the total molar concentration of the hydrazide group and the semicarbazide group in the compound (C) is 0.02 to 12 mol / Kg.

  13. Even if the blending ratio of the vinyl polymer (A) and the compound (B) is neutralized with a Bronsted acid in part or all of the glyoxiramide group in the vinyl polymer (A) and the compound (B). The sum of good primary amino groups and secondary amino groups is (number of moles of glyoxiramide groups) / (total of primary amino groups and secondary amino groups which may be partially or completely neutralized with Bronsted acid) Item 2. The aqueous curable composition according to Item 1, wherein the number of moles is from 0.1 to 10.

  14 The blending ratio of the vinyl polymer (A) and the compound (C) is such that the total of the glyoxiramide group in the vinyl polymer (A) and the hydrazide group and semicarbazide group in the compound (C) is (number of moles of glyoxiramide group). ) / (Total number of moles of hydrazide group and semicarbazide group) = 0.1-10, the aqueous curable composition according to item 1 above.

  15. The vinyl polymer (A) may further have a carboxyl group and / or a carboxylate group, and the total molar concentration of the carboxyl group and the carboxylate group in the vinyl polymer (A) is 0.02 to 0.02. Item 2. The aqueous curable composition according to Item 1, which is 2 mol / Kg.

  16. The vinyl polymer (A) may further have a carboxyl group and / or a carboxylate group, and (total number of moles of carboxyl group and carboxylate group in the vinyl polymer (A)) / (compound (B) A part or all of (B) may be neutralized with Bronsted acid, and the total number of moles of primary amino group and secondary amino group is 0.05 to 10. Aqueous curable composition.

  In the present specification, the number average molecular weight is a value obtained by converting the number average molecular weight measured by gel permeation chromatograph on the basis of the number average molecular weight of polystyrene.

  In the present specification, (meth) acrylate means acrylate and methacrylate, (meth) acrylamide means acrylamide and methacrylamide, and (meth) acryloyl means acryloyl and methacryloyl, respectively.

  In this specification, the vinyl polymer means a polymer obtained by homopolymerizing a polymerizable double bond-containing monomer with a polymerizable double bond-containing monomer having another structure.

  Hereinafter, a vinyl polymer having a glyoxyramide group represented by the general formula (I) is referred to as a vinyl polymer (A).

Vinyl polymer (A)
The vinyl polymer (A) of the present invention has the general formula (I)

[Wherein, R ¹ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms. ] A vinyl polymer having a glyoxyramide group represented by the formula:

  That is, the vinyl polymer (A) has an α-diketo type general formula (I) glyoxiramide group which does not have a risk of decomposition by reverse Claisen condensation instead of the β-diketo type acetoacetoxy group. Thus, it has excellent storage stability even in water.

  In addition, since the vinyl polymer (A) has the above glyoxiramide group, it crosslinks primary amino group, secondary amino group, primary ammonium group, secondary ammonium group, hydrazide group, semicarbazide group and the like. Sufficient reactivity with a compound having a functional group.

Accordingly, the vinyl polymer (A), and
(B) a compound having a primary amino group and / or a secondary amino group, which may be partially or completely neutralized with a Bronsted acid, and / or
(C) The aqueous composition containing the compound which has a hydrazide group and / or a semicarbazide group can be utilized as a useful curable composition.

  The number average molecular weight of the vinyl polymer (A) is not particularly limited, but is preferably in the range of about 1,000 to 1,000,000 for ease of production.

In the glyoxiramide group represented by the general formula (I), examples of the organic group having 1 to 8 carbon atoms represented by R ¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and isomers thereof. An alkyl group having a structure; alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, and butoxyethyl can be exemplified. When the number of carbon atoms in R ¹ is 9 or more, the time required for production increases and productivity may decrease.

Production method of vinyl polymer (A) The production method of the vinyl polymer (A) of the present invention is not particularly limited. As a method for producing the vinyl polymer (A), the following general formula (II)

[Wherein, X ¹ , X ² and X ³ independently represent an oxygen atom or a sulfur atom. R ² , R ³ and R ⁴ independently represent a hydrogen atom or an organic group having 1 to 18 carbon atoms. ^Two or three organic groups selected from R ² , R ³ and R ⁴ may be bonded to each other to form a heterocyclic ring. The production method using a compound represented by the above as a starting material is simple and preferable.

  As the compound represented by the general formula (II), commercially available compounds may be used, glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid hemiacetal, glyoxylic acid ester, glyoxylic acid ester hydrate, glyoxylic acid You may use what is manufactured by using 1 or more types chosen from the group of ester hemiacetal as a raw material. In the present invention, glyoxylic acid is represented by the following formula (VII), glyoxylic acid hydrate is represented by the following formula (VIII), glyoxylic acid hemiacetal is represented by the following formula (IX), glyoxylic acid ester is represented by the following formula (X), glyoxyl. The acid ester hydrate is represented by the following formula (XI), and the glyoxylate ester hemiacetal is represented by the following formula (XII). These may use a commercially available thing and may manufacture it by a well-known method.

[In each formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently represent an organic group having 1 to 18 carbon atoms. ].

Here, R < ⁶ >, R < ⁷ >, R <^8> , R < ⁹ > and R < ¹⁰ > are 1-18 organic groups which may contain an oxygen atom, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, etc. An alkoxyalkyl group such as methoxyethyl and butoxyethyl.

  In the following, one or more selected from the group of glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid hemiacetal, glyoxylic acid ester, glyoxylic acid ester hydrate, glyoxylic acid ester hemiacetal is used as a raw material and represented by the formula (II) A method for producing the compound is described.

  One or more compounds selected from the group consisting of glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid hemiacetal, glyoxylic acid ester, glyoxylic acid ester hydrate, and glyoxylic acid ester hemiacetal When these are produced as raw materials, these raw materials are reacted with at least one compound selected from the group consisting of the following alcohols, thiols, acetals and orthoesters.

  As alcohol, a C1-C18 hydroxyl-containing compound is preferable. Examples of the hydroxyl group-containing compound include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, Monools such as heptadecanol, octadecanol and isomers thereof; ether group-containing monools such as propylene glycol monomethyl ether, propylene glycol monopropyl ether and ethylene glycol monobutyl ether; ethylene glycol, propylene glycol, 1, 3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol Diols such as 2-ethyl-1,3-hexanediol; glycerin, trimethylolethane, trimethylolpropane, and the like triols such as trimethylol octane. These can be used individually by 1 type or in mixture of 2 or more types.

  As the thiol, a mercapto group-containing compound having 1 to 18 carbon atoms is preferable. Examples of the mercapto group-containing compound include methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, cyclohexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecane. Examples include monothiols such as thiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol and isomers thereof; and dithiols such as 1,2-ethanedithiol and 1,3-propanedithiol. These can be used individually by 1 type or in mixture of 2 or more types.

  As the acetal, a compound obtained by dehydration condensation of a hydroxyl group-containing compound having 1 to 18 carbon atoms and a ketone under acid catalyst conditions is suitable. Although it does not specifically limit as a ketone used here, A C3-C9 ketone is preferable. Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, cyclohexanone, and isophorone. Specific examples of the acetal include 2,2-dimethoxypropane, 2,2-diethoxypropane, 2,2-dibutoxypropane, 2,2-dimethoxybutane, 2,2-diethoxybutane, 2,2- Acyclic acetals such as dibutoxybutane, 2,2-dimethoxy-4-methylpentane, 2,2-diethoxy-4-methylpentane, 2,2-dibutoxy-4-methylpentane; 2,2-dimethyl-1 , 3-dioxolane, 2,2-dimethyl-4-methyl-1,3-dioxolane, 2-ethyl-2-methyl-1,3-dioxolane, 2-ethyl-2-methyl-4-methyl-1,3 -Dioxolane, 2-isobutyl-2-methyl-1,3-dioxolane, 2-isobutyl-2-methyl-4-methyl-1,3-dioxolane, 2,2-dimethyl-1 3-dioxane, 2,2-dimethyl-4-methyl-1,3-dioxane, 2-ethyl-2-methyl-1,3-dioxane, 2-ethyl-2-methyl-4-methyl-1,3- Examples thereof include cyclic acetals such as dioxane, 2-isobutyl-2-methyl-1,3-dioxane, and 2-isobutyl-2-methyl-4-methyl-1,3-dioxane. Among these, 2,2-dimethoxypropane, 2,2-dimethoxybutane, 2,2-diethoxypropane, 2,2-diethoxybutane, 2,2-dimethyl-1,3-dioxolane and 2,2- Dimethyl-4-methyl-1,3-dioxolane is preferred because it is easily available industrially. These acetals can be used individually by 1 type or in mixture of 2 or more types.

  The orthoester is not particularly limited, but an orthoester having 4 to 14 carbon atoms is preferable from the viewpoint of availability. Examples of such orthoesters include trimethyl orthoformate, triethyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triisopropyl orthoacetate, tributyl orthoacetate and the like. More preferred are trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate and triethyl orthoacetate. These can be used individually by 1 type or in mixture of 2 or more types.

  Glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid hemiacetal, glyoxylic acid ester, glyoxylic acid ester hydrate, glyoxylic acid ester hemiacetal selected from the group consisting of alcohols, thiols, acetals and orthoesters The amount of the compound selected from the group consisting of is not particularly limited, but glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid hemiacetal, glyoxylic acid ester, glyoxylic acid ester hydrate, glyoxylic acid ester hemiacetal group About 1 to 10 mol is preferable, and about 1.05 to 5 mol is more preferable with respect to 1 mol in total of one or more selected.

  The reaction is usually carried out for about 10 minutes to 30 hours. This reaction may be performed in an inert gas atmosphere such as nitrogen in order to prevent the product from being colored. If necessary, heating, pressurization, a small amount of an acid catalyst, or a solvent may be used. Further, water, ketone, ester, alcohol, thiol and the like generated in the reaction system may be removed from the system to promote the reaction. The heating is usually preferably about 30 to 200 ° C, but if the temperature is too low, the reaction promoting effect is small, and if the temperature is too high, the product tends to be colored.

  The acid catalyst is not particularly limited, and examples thereof include inorganic Bronsted acids such as dilute sulfuric acid, dilute hydrochloric acid, and phosphoric acid; organic sulfonic acids such as paratoluenesulfonic acid and methanesulfonic acid; monoalkyl phosphoric acid, dialkyl phosphoric acid, and the like. Phosphate esters; carboxylic acids such as formic acid, trifluoroacetic acid, oxalic acid; trimethylsilyl halide, boron trifluoride complex, titanium tetraalkoxide, titanium tetrahalide, dialkyltin oxide, dialkyltin dicarboxylate, monoalkyltin tri Carboxylate, tin dicarboxylate, tin tetrachloride, zirconium tetraalkoxide, zirconium tetrahalide, zinc salt, chromium salt, manganese salt, iron salt, copper salt, cerium salt, scandium salt, yttrium salt, lanthanoid salt, lead compound , Bismuth Lewis acids such as compounds, antimony compounds, metal triflates, metal tetrafluoroborate salts, metal acetylacetonate salts; solid acid catalysts such as clay, activated clay, acid clay, silica, alumina, zeolite, cation exchange resin, etc. Can be mentioned.

  As the cation exchange resin, an ion exchange resin having a functional group such as a sulfonic acid group, a phosphoric acid group, or a carboxyl group is preferable, and an ion exchange resin having a sulfonic acid group or a phosphoric acid group is particularly preferable. Examples of commercially available cation exchange resins include “Amberlist 15JWET”, “Amberlist 15DRY”, “Amberlist 16WET”, “Amberlist 31WET” (above, Rohm & Haas, trade name), “RCP-160M”. ”,“ RCP-150H ”,“ RCP-170H ”,“ PK-216 ”(trade name, manufactured by Mitsubishi Chemical Corporation),“ Dowex 50W ”(trade name, manufactured by Dow Chemical Company), and the like.

  The addition amount of the acid catalyst is not particularly limited, but in the case of inorganic acids, organic sulfonic acids, phosphate esters, carboxylic acids and Lewis acids, it is 0 with respect to 1 mol of the compound represented by the general formula (II). About 0.01 to 10 mol is preferable. In the case of solid acid catalysts, about 0.1 to 500 parts by weight is preferable with respect to 100 parts by weight of the compound represented by the general formula (II). Solid acid catalysts can be separated by filtration after the reaction.

  A known organic solvent can be used as the reaction solvent. The amount of the solvent to be used is not particularly limited, but if it is too much, the economical efficiency is lowered, and therefore it is preferably about 10 times or less the weight of the compound represented by the general formula (II).

  Removal of water, ketones, esters, alcohols, thiols, etc. generated in the reaction system outside of the system is performed under pressure, normal pressure, or reduced pressure, if necessary, by heating or using a gas such as air or nitrogen. It can be done by blowing.

  In order to prevent the formation of peroxides, an antioxidant may be added to the system. Although it does not specifically limit as antioxidant, For example, quinone type compounds, such as benzoquinone; Phenol type compounds, such as hydroquinone, hydroquinone monomethyl ether, and di-t-butylmethylphenol; Amine compounds, such as a phenylenediamine type compound and phenothiazine One or more selected from N-oxyl compounds, nitroso compounds, nitrogen oxides and the like can be used. In the case of adding an antioxidant, the total amount of the compound represented by the general formula (II) and the compound selected from the group consisting of alcohol, thiol, acetal and orthoester is not particularly limited. About 10,000 ppm is preferable, and about 100 to 5,000 ppm is more preferable.

The compound represented by the general formula (II) is one or more selected from the group of glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid hemiacetal, glyoxylic acid ester, glyoxylic acid ester hydrate, glyoxylic acid ester hemiacetal X ¹ , X ² , X ³ , R ² , R ³ and R ⁴ are subordinately determined depending on the type of alcohol, thiol, acetal or orthoester used in the reaction. In the case where the alcohol, thiol, acetal or orthoester of the above kind is used, X ¹ , X ² and X ³ are each an oxygen atom or a sulfur atom, and R ² , R ³ and R ⁴ are 1 to 18 hydrogen atoms or carbon atoms each is an organic ^group, two or three selected from R 2, ^{R 3} and ^{R 4} Machine group may form a heterocyclic ring containing two or three heteroatoms bonded to selected from X ^1, X ² and X ³ together. Examples of such a heterocyclic ring include cyclic acetal, cyclic thioacetal, and cyclic orthoester.

  Examples of the compound represented by the general formula (II) include 2,2-dialkoxyacetic acid ester, 2-alkoxycarbonyl-1,3-dioxolane, 2-alkoxycarbonyl-1,3-dioxane, 2,2-dioxane. (Alkylthio) acetic acid ester, 2,2-di (alkylthio) thioacetic acid ester, 2-alkoxycarbonyl-1,3-dithiolane, 2-alkoxycarbonyl-1,3-dithiane, 2- (alkylthio) carbonyl-1,3 -Dithiolane, 2- (alkylthio) carbonyl-1,3-dithiane and the like.

  The compound represented by the general formula (II) is often obtained in the form of a solution. By concentrating this solution, a highly pure compound can be obtained. Moreover, the purity can be further increased by performing distillation purification, extraction operation or washing with water as necessary.

  When an acid catalyst was used in the production of the compound represented by the general formula (II), the solution containing the compound represented by the general formula (II) was used before concentration, distillation purification, extraction operation or washing. Part or all of the acid catalyst may be neutralized with a base, or adsorbed and removed with an adsorbent. Although it does not specifically limit as this base, For example, a metal hydroxide, a metal oxide, an alkoxide, ammonia, an amine, a metal carboxylate etc. are mentioned. The adsorbent is not particularly limited, and examples thereof include clay, acid clay, activated clay, alumina, silica, zeolite, ion exchange resin, and basic inorganic compound.

  The compound represented by the general formula (II) is one or more selected from the group of glyoxylic acid, glyoxylic acid hydrate, glyoxylic acid hemiacetal, glyoxylic acid ester, glyoxylic acid ester hydrate, glyoxylic acid ester hemiacetal You may manufacture by a well-known method, without using as a raw material.

  For example, the vinyl polymer (A) is obtained by homopolymerizing a vinyl monomer having a glyoxyramide group obtained through the following steps 1 to 3 using a compound represented by the general formula (II) as a starting material, or other It is obtained by copolymerizing with a vinyl monomer.

Process 1
In step 1, the compound represented by the general formula (II) is converted into the general formula (III).

[In formula, Y is a C1-C6 linear alkylene group which may have a C1-C6 organic group as a substituent. R ¹ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms. And a compound represented by the general formula (IV)

[Wherein, X ¹ , X ² , Y, R ¹ , R ² and R ³ are the same as described above. ] The process of obtaining the compound represented by this.

  In step 1, the compound of the general formula (II) may be purified and then reacted with the compound of the general formula (III), or the solution containing the compound of the general formula (II) may be purified without purification. ). When purifying, operations such as concentration, extraction, washing, and filtration can be performed. When an acid catalyst is used in step 1, all or part of the acid catalyst may be neutralized with a base in advance before mixing with the compound of the general formula (III). Alternatively, it may be adsorbed and removed with an adsorbent.

In the compound represented by the general formula (III), R ¹ is a hydrogen atom; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and alkyl groups having an isomeric structure thereof; It is preferably an organic group having 1 to 8 or the like, but is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms because of easy availability. When R ¹ is an organic group having 9 or more carbon atoms, the time for producing the compound represented by the general formula (IV) may increase and productivity may decrease.

  In the compound represented by the general formula (III), when the substituent of the linear alkylene group having 1 to 6 carbon atoms represented by Y is an organic group having 7 or more carbon atoms, the general formula (IV ) May significantly increase the time for producing the compound represented by and may decrease the productivity.

  Specific examples of the compound of the general formula (III) include 2-aminoethanol, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (isopropylamino) ethanol, 2- (butylamino) ethanol, 2-aminoethanol derivatives such as 2- (t-butylamino) ethanol; 1-amino-2-propanol, 1- (methylamino) -2-propanol, 1- (ethylamino) -2-propanol, 1- ( 1-amino-2-propanol derivatives such as isopropylamino) -2-propanol, 1- (butylamino) -2-propanol, 1- (t-butylamino) -2-propanol; 2-amino-1-propanol; 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 2-amino-1-pentano 2-amino-1-alkanol derivatives such as 2-amino-1-hexanol; 1-amino-2-butanol, 1- (methylamino) -2-butanol, 1- (ethylamino) -2-butanol, 1-aminobutanol derivatives such as 1- (isopropylamino) -2-butanol, 1- (butylamino) -2-butanol, 1- (t-butylamino) -2-butanol; 3-amino-1-propanol; And ω-amino-1-alkanol derivatives such as 4-amino-1-butanol and 6-amino-1-hexanol. Among these, 2-aminoethanol derivatives in which Y is an ethylene group are preferable from the viewpoint that the time for producing the compound represented by the general formula (IV) can be shortened.

  The amount of the compound represented by the general formula (III) to be reacted with the compound represented by the general formula (II) is not particularly limited, but is 1 to 3 mol per 1 mol of the compound of the general formula (II). The degree is preferable, and about 1.05 to 1.5 mol is more preferable.

  The reaction of the compound of the general formula (II) and the compound of the general formula (III) is performed by mixing these and usually taking about 10 minutes to 30 hours. This reaction may be performed in an inert gas atmosphere to prevent the product from being colored. Moreover, in order to accelerate | stimulate reaction, a heating, pressurization, catalyst addition, use of a solvent, removal of the produced | generated alcohol, etc. can be performed as needed.

  The reaction temperature is usually preferably about 30 to 230 ° C. However, if the temperature is too low, the effect of promoting the reaction is small, and if the temperature is too high, the product tends to be colored.

  As the catalyst, either an acid catalyst or a base catalyst can be used, but it is more preferable to use a base catalyst. Although it does not specifically limit as a base catalyst, For example, a metal hydroxide, a metal alkoxide, a metal oxide, ammonia, an amine, a metal carboxylate, a metal phenoxide, a basic organic onium salt, a hydroxide ion or a carboxylate ion is contained. Examples include anion exchange resins. The addition amount of the base catalyst is not particularly limited, but when a metal hydroxide, metal alkoxide, metal oxide, ammonia, amine, metal carboxylate, metal phenoxide, basic organic onium salt, or the like is used, a general formula ( The amount is preferably about 0.01 to 10 mol with respect to 1 mol of the compound represented by II). When an anion exchange resin is used, the amount is 0.1 to 500 with respect to 100 parts by weight of the compound represented by the general formula (II). About parts by weight are preferred. The anion exchange resin can be separated by filtration after the reaction.

  A known organic solvent can be used as the reaction solvent, but it is preferable to use a solvent having a relatively high polarity. The amount of the solvent to be used is not particularly limited, but if it is too much, the economical efficiency is lowered, and therefore it is preferably about 10 times or less with respect to the weight of the compound represented by the general formula (II). Removal of the alcohol produced in the reaction system to the outside of the system can be performed under normal pressure or reduced pressure by heating or blowing a gas such as air or nitrogen as necessary. In the case of blowing gas, an inert gas is preferable in order to prevent coloring of the product, and nitrogen is preferable from an economical viewpoint.

  In the reaction of step 1, an antioxidant may be added to the reaction system in order to prevent the formation of peroxide. Although it does not specifically limit as antioxidant, For example, 1 or more types of the said antioxidant can be used. In the case of adding an antioxidant, the total amount of the compound represented by the general formula (II) and the compound represented by the general formula (III) is not particularly limited, but is preferably about 10 to 10,000 ppm. 100 to 5,000 ppm is more preferable.

The compound represented by the general formula (IV) is obtained by reacting the compound of the general formula (II) with the compound of the general formula (III). X ¹ , X ² , R ¹ , R ² and R ³ in the general formula (IV) are subordinately determined by the structures of the compound of the general formula (II) and the compound of the general formula (III) used in the reaction. Is.

  Examples of the compound represented by the general formula (IV) include N- (2-hydroxyalkyl) -2,2-dialkoxyacetamide, N-alkyl-N- (2-hydroxyalkyl) -2,2- Dialkoxyacetamide, 2- (2-hydroxyalkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (2-hydroxyalkyl) amino) carbonyl-1,3-dioxolane, 2- (2-hydroxyalkyl) aminocarbonyl-1,3-dioxane, 2- (N-alkyl-N- (2-hydroxyalkyl) amino) carbonyl-1,3-dioxane, N- (3-hydroxyalkyl) -2 , 2-dialkoxyacetamide, N-alkyl-N- (3-hydroxyalkyl) -2,2-dialkoxyacetamide, 2- (3-hydroxy Alkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (3-hydroxyalkyl) amino) carbonyl-1,3-dioxolane, 2- (3-hydroxyalkyl) aminocarbonyl-1,3 -Dioxane, 2- (N-alkyl-N- (3-hydroxyalkyl) amino) carbonyl-1,3-dioxane, N- (4-hydroxyalkyl) -2,2-dialkoxyacetamide, N-alkyl -N- (4-hydroxyalkyl) -2,2-dialkoxyacetamide, 2- (4-hydroxyalkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (4-hydroxy) Alkyl) amino) carbonyl-1,3-dioxolane, 2- (4-hydroxyalkyl) aminocarbonyl-1,3-dioxy Sun, 2- (N-alkyl-N- (4-hydroxyalkyl) amino) carbonyl-1,3-dioxane, N- (5-hydroxyalkyl) -2,2-dialkoxyacetamide, N-alkyl- N- (5-hydroxyalkyl) -2,2-dialkoxyacetamide, 2- (5-hydroxyalkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (5-hydroxyalkyl) ) Amino) carbonyl-1,3-dioxolane, 2- (5-hydroxyalkyl) aminocarbonyl-1,3-dioxane, 2- (N-alkyl-N- (5-hydroxyalkyl) amino) carbonyl-1,3 -Dioxane, N- (6-hydroxyalkyl) -2,2-dialkoxyacetamide, N-alkyl-N- (6-hydroxyalkyl) 2,2-dialkoxyacetamide, 2- (6-hydroxyalkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (6-hydroxyalkyl) amino) carbonyl-1,3- Dioxolane, 2- (6-hydroxyalkyl) aminocarbonyl-1,3-dioxane, 2- (N-alkyl-N- (6-hydroxyalkyl) amino) carbonyl-1,3-dioxane, N- (2-hydroxy) Alkyl) -2,2-di (alkylthio) acetamide, N-alkyl-N- (2-hydroxyalkyl) -2,2-di (alkylthio) acetamide, 2- (2-hydroxyalkyl) aminocarbonyl-1,3 -Dithiolane, 2- (N-alkyl-N- (2-hydroxyalkyl) amino) carbonyl-1,3-dithiolane, -(2-hydroxyalkyl) aminocarbonyl-1,3-dithiane, 2- (N-alkyl-N- (2-hydroxyalkyl) amino) carbonyl-1,3-dithiane, N- (3-hydroxyalkyl)- 2,2-di (alkylthio) alkanoic acid amide, N-alkyl-N- (3-hydroxyalkyl) -2,2-di (alkylthio) acetamide, 2- (3-hydroxyalkyl) aminocarbonyl-1,3- Dithiolane, 2- (N-alkyl-N- (3-hydroxyalkyl) amino) carbonyl-1,3-dithiolane, 2- (3-hydroxyalkyl) aminocarbonyl-1,3-dithiane, 2- (N-alkyl) -N- (3-hydroxyalkyl) amino) carbonyl-1,3-dithiane and the like.

  The compound represented by the general formula (IV) obtained by the reaction in Step 1 is often obtained in the form of a solution. By concentrating this solution, a highly pure compound can be obtained. If necessary, a compound with higher purity can be obtained by distillation purification, recrystallization, extraction operation, washing with water, and the like.

  When a base catalyst is used in Step 1, a part or all of the used base catalyst is used before concentration, distillation purification, recrystallization, extraction operation or washing of the solution containing the compound represented by the general formula (IV). May be neutralized with an acid, or adsorbed and removed with an adsorbent. Although it does not specifically limit as acid, For example, inorganic Bronsted acids, such as dilute sulfuric acid, dilute hydrochloric acid, and phosphoric acid; Organic sulfonic acids, such as para-toluenesulfonic acid and methanesulfonic acid; Phosphoric acids, such as monoalkyl phosphoric acid and dialkyl phosphoric acid Examples include esters; carboxylic acids such as formic acid, trifluoroacetic acid, and oxalic acid; metal-containing compounds exhibiting Lewis acidity; solid acid catalysts such as clay, silica, zeolite, and cation exchange resin. The adsorbent is not particularly limited, and examples thereof include acidic clay, activated clay, alumina, silica, zeolite, a basic inorganic compound, and an ion exchange resin.

Process 2
In step 2, the compound represented by general formula (IV) obtained in step 1 is converted into (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride. By reaction, the following general formula (V)

[Wherein, X ¹ , X ² , Y, R ¹ , R ² and R ³ are the same as described above. R ⁵ represents a hydrogen atom or a methyl group. ] The process of obtaining the compound represented by this.

  In step 2, the compound represented by the general formula (IV) is purified and then reacted with (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride. (Meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic halide or (meth) acrylic anhydride without purification of a solution containing the compound represented by the general formula (IV). You may make it react. In the case of purification, operations such as concentration, liquid separation, washing, and filtration can be performed. In addition, when a catalyst is used to react the compound of general formula (II) with the compound of general formula (III), (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic acid Before mixing with halide or (meth) acrylic anhydride, a part or all of the catalyst used may be neutralized or adsorbed and removed with an adsorbent.

The compound represented by the general formula (V) is an ester form of the compound of the general formula (IV) and (meth) acrylic acid. X ¹ , X ² , R ¹ , R ² , R ³ and R ⁵ in the general formula (V) are the compounds of the general formula (IV) and (meth) acrylic acid ester, (meth) acrylic acid, It is dependently determined by the structure of (meth) acrylic acid halide or (meth) acrylic anhydride.

  Examples of the compound represented by the general formula (V) include N- (2-((meth) acryloyloxy) alkyl) -2,2-dialkoxyacetamide, N-alkyl-N- (2-(( (Meth) acryloyloxy) alkyl) -2,2-dialkoxyacetamide, 2- (2-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (2-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxolane, 2- (2-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dioxane, 2- (N- Alkyl-N- (2-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxane, N- (3-((meth) acryloyloxy) a Alkyl) -2,2-dialkoxyacetamide, N-alkyl-N- (3-((meth) acryloyloxy) alkyl) -2,2-dialkoxyacetamide, 2- (3-((meta ) Acryloyloxy) alkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (3-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxolane, 2- (3 -((Meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dioxane, 2- (N-alkyl-N- (3-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxane, N- (4-((meth) acryloyloxy) alkyl) -2,2-dialkoxyacetamide, N-alkyl-N- (4-((meth) acrylo Ruoxy) alkyl) -2,2-dialkoxyacetamide, 2- (4-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (4- ((Meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxolane, 2- (4-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dioxane, 2- (N-alkyl-N -(4-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxane, N- (5-((meth) acryloyloxy) alkyl) -2,2-dialkoxyacetamide, N- Alkyl-N- (5-((meth) acryloyloxy) alkyl) -2,2-dialkoxyacetamide, 2- (5-((meth) acrylo) Ruoxy) alkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (5-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxolane, 2- (5- ( (Meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dioxane, 2- (N-alkyl-N- (5-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxane, N- (6-((Meth) acryloyloxy) alkyl) -2,2-dialkoxyacetamide, N-alkyl-N- (6-((meth) acryloyloxy) alkyl) -2,2-dialkoxyaceta , 2- (6-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dioxolane, 2- (N-alkyl-N- (6-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxolane, 2- (6-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dioxane, 2- (N- Alkyl-N- (6-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dioxane, N- (2-((meth) acryloyloxy) alkyl) -2,2-di (alkylthio) acetamide N-alkyl-N- (2-((meth) acryloyloxy) alkyl) -2,2-di (alkylthio) acetamide, 2- (2-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3 -Dithiolane, 2- (N-alkyl-N- (2-((meth) acryloyloxy) alkyl) amino) carbonyl-1,3- Thiolane, 2- (2-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dithiane, 2- (N-alkyl-N- (2-((meth) acryloyloxy) alkyl) amino) carbonyl- 1,3-dithiane, N- (3-((meth) acryloyloxy) alkyl) -2,2-di (alkylthio) acetamide, N-alkyl-N- (3-((meth) acryloyloxy) alkyl)- 2,2-di (alkylthio) acetamide, 2- (3-((meth) acryloyloxy) alkyl) aminocarbonyl-1,3-dithiolane, 2- (N-alkyl-N- (3-((meth) acryloyl) Oxy) alkyl) amino) carbonyl-1,3-dithiolane, 2- (3-((meth) acryloyloxy) alkyl) aminocarbonyl- , 3-dithiane, 2-(N-alkyl--N- (3 - ((meth) acryloyloxy) alkyl) amino) carbonyl-1,3-dithiane and the like.

  The reaction between the compound of general formula (IV) and (meth) acrylic acid ester is carried out by transesterification. As the (meth) acrylic acid ester used in this reaction, a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms is preferable, and methyl (meth) acrylate and ethyl (meth) acrylate are preferred because the reaction rate is high. A relatively low boiling point (meth) acrylic acid ester having a C 1-4 alkyl group such as butyl (meth) acrylate is more preferred. When the alkyl group has 19 or more carbon atoms, the reaction rate tends to decrease.

  The transesterification reaction is usually performed by heating under normal pressure, under pressure or under reduced pressure. The amount of the (meth) acrylic acid ester to be used is not particularly limited with respect to 1 mol of the compound represented by the general formula (IV), but is preferably about 1 to 10 mol, and more preferably about 1 to 5 mol. The heating is usually preferably about 60 to 180 ° C. However, if the temperature is too low, the progress of the reaction is slow, and if the temperature is too high, the product is easily polymerized. Further, the reaction may be promoted by adding a catalyst, using a solvent, or removing alcohol generated in the system from the system.

  As the catalyst, at least one catalyst selected from the group consisting of a Bronsted acid catalyst, a base catalyst, and a Lewis acid catalyst can be used, and a Lewis acid catalyst is preferable from the viewpoint of high catalyst performance. Examples of the Lewis acid catalyst used here are not particularly limited, but titanium compounds such as titanium tetraalkoxide and titanium tetrahalide; dialkyltin oxide, dialkyltin dicarboxylate, monoalkyltin tricarboxylate, tin dicarboxylate Zinc compounds such as zinc tetracarboxylate and zinc halides; zinc compounds such as zinc dicarboxylate and zinc halides; lead compounds; bismuth compounds; antimony compounds; clays; Examples thereof include solid acid catalysts such as acid clay, activated clay, silica, alumina, zeolite, and cation exchange resin.

  Among the above catalysts, in particular, the use of a tin compound as a catalyst can increase the purity of the compound represented by the general formula (V). Therefore, it is preferable to use a tin compound as the catalyst. Specific examples of the tin compound include dialkyltin oxides such as dioctyltin oxide and dibutyltin oxide; dialkyltin dicarboxylates such as dioctyltin diacetate, dioctyltin dilaurate, dibutyltin diacetate and dibutyltin dilaurate; monooctyltin Monoalkyltin tricarboxylates such as triacetate, monooctyltin trilaurate, monobutyltin triacetate, monobutyltin trilaurate; monoalkyltin oxides such as monooctyltin oxide and monobutyltin oxide; tin dicarboxylates such as tin diacetate and tin dilaurate An organic distanoxane such as a tetraalkyl distanoxane derivative. Among these, dialkyltin oxide and organic distanoxane are more preferable. Furthermore, dialkyl tin oxides such as dioctyl tin oxide are particularly preferred from the viewpoint of inexpensiveness.

  The addition amount of the catalyst is not particularly limited, but for the catalyst other than the solid acid catalyst, about 0.01 to 10 mol is preferable with respect to 1 mol of the compound represented by the general formula (IV). Is preferably about 0.1 to 500 parts by weight per 100 parts by weight of the compound represented by formula (IV).

  In the reaction of Step 2, the reaction can be promoted by using a solvent or removing alcohol generated in the reaction system out of the system. In this case, a known organic solvent can be used as the solvent to be used, and the amount of the solvent used is not particularly limited, but if it is too much, the economic efficiency is lowered, so that it is 5 times the weight of the compound represented by the general formula (IV). The following degree is preferable. Removal of the alcohol generated in the reaction system to the outside of the system can be performed under normal pressure, reduced pressure, or increased pressure.

  The reaction between the compound represented by the general formula (IV) and (meth) acrylic acid is carried out by dehydration condensation exchange. The dehydration condensation reaction is usually performed by heating. The heating is usually preferably about 60 to 230 ° C. However, if the temperature is too low, the reaction proceeds slowly, and if the temperature is too high, the product is easily polymerized. The amount of (meth) acrylic acid to be used is not particularly limited with respect to 1 mol of the compound represented by the general formula (IV), but is about 1 to 10 mol, more preferably about 1 to 5 mol. Further, the reaction may be promoted by adding a catalyst, using a solvent, or removing water generated in the reaction system to the outside of the system.

  The catalyst is preferably a Bronsted acid catalyst and / or a Lewis acid catalyst. The Bronsted acid used here is not particularly limited, but inorganic acids such as dilute sulfuric acid, dilute hydrochloric acid and phosphoric acid; organic sulfonic acids such as paratoluenesulfonic acid and methanesulfonic acid; monoalkyl phosphoric acid, dialkyl phosphoric acid and the like These phosphate esters are more preferred from the viewpoint of high reaction rate. The Lewis acid used here is not particularly limited, but tin compounds such as dialkyltin oxide, dialkyltin dicarboxylate, monoalkyltin tricarboxylate, tin dicarboxylate, and tin tetrachloride; zirconium tetraalkoxide, Zirconium compounds such as zirconium tetrahalides; zinc compounds such as zinc dicarboxylate and zinc halides; lead compounds; bismuth compounds; antimony compounds; clays, activated clays, acid clays, silicas, aluminas, zeolites, cation exchange resins, etc. Solid acid catalysts and the like are more preferable from the viewpoint of high reaction rate. The amount of the catalyst added is not particularly limited, but for a catalyst other than the solid acid catalyst, about 0.01 to 10 mol is preferable with respect to 1 mol of the compound represented by the general formula (IV). About 0.1-500 weight part is preferable with respect to 100 weight part of compounds represented by general formula (IV). As the solvent, a known aprotic organic solvent can be used. The amount of the solvent to be used is not particularly limited, but if it is too much, the economical efficiency is lowered, and therefore it is preferably about 5 times or less with respect to the weight of the compound represented by the general formula (IV). Removal of water generated in the reaction system to the outside of the system can be performed under normal pressure, reduced pressure, or increased pressure.

  The reaction between the compound represented by the general formula (IV) and the (meth) acrylic acid halide is usually carried out in the presence of a base. The base is for neutralizing the acid to be generated, and is not particularly limited, and examples thereof include triethylamine, pyridine, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like. The amount of (meth) acrylic acid halide used is preferably about 1 to 2 moles per mole of the compound represented by formula (V), and the amount of base used is based on 1 mole of (meth) acrylic acid halide. About 1 to 2 mol is preferable. The reaction is usually carried out at about -70 to 80 ° C. However, if the temperature is too low, the progress of the reaction is slow, and if the temperature is too high, a by-product is likely to be formed. In this reaction, an organic solvent or water can be used as a solvent. When water is used, it often becomes a two-phase system, so an onium salt or the like may be added to sufficiently stir and increase the reaction rate. The amount of the solvent to be used is not particularly limited, but if it is too much, the economical efficiency is lowered.

  The reaction between the compound represented by the general formula (IV) and (meth) acrylic anhydride is carried out by alcoholysis of the acid anhydride. The amount of (meth) acrylic anhydride to be used is not particularly limited with respect to 1 mol of the compound represented by the general formula (IV), but is preferably about 1 to 5 mol, more preferably about 1 to 3 mol. . In this reaction, a catalyst may be used to promote the reaction. As the catalyst, any of a Bronsted acid catalyst, a base catalyst, and a Lewis acid catalyst may be used. The Bronsted acid is not particularly limited. For example, inorganic acids such as dilute sulfuric acid, dilute hydrochloric acid and phosphoric acid; organic sulfonic acids such as paratoluenesulfonic acid and methanesulfonic acid; phosphorus such as monoalkyl phosphoric acid and dialkyl phosphoric acid Examples include acid esters. Examples of the base catalyst include triethylamine, pyridine, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like. Examples of the Lewis acid catalyst include titanium compounds such as titanium tetraalkoxide and titanium tetrahalide; tin compounds such as dialkyltin oxide, dialkyltin dicarboxylate, monoalkyltin tricarboxylate, tin dicarboxylate, and tin tetrachloride; Zirconium compounds such as zirconium tetraalkoxide and zirconium tetrahalide; zinc compounds such as zinc dicarboxylate and zinc halide; lead compounds; bismuth compounds; antimony compounds; clay, acid clay, activated clay, silica, alumina, zeolite, cation And solid acid catalysts such as exchange resins. The amount of the catalyst added is not particularly limited, but for the catalyst other than the solid acid catalyst, about 0.01 to 10 mol is preferable with respect to 1 mol of the compound represented by the general formula (IV). Is preferably about 0.1 to 500 parts by weight per 100 parts by weight of the compound represented by formula (IV). As the solvent, an aprotic organic solvent can be used. The amount of the solvent to be used is not particularly limited, but if it is too much, the economical efficiency is lowered.

  In the reaction of the compound represented by the general formula (IV) with (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride, polymerization of the product is carried out. In order to prevent this, it is preferable to blow a gas containing oxygen into the reaction system or to add a polymerization inhibitor into the system.

  The polymerization inhibitor is not particularly limited. For example, quinone compounds such as benzoquinone; phenol compounds such as hydroquinone, hydroquinone monomethyl ether and di-t-butylmethylphenol; amine compounds such as phenylenediamine compounds and phenothiazines. One or more selected from N-oxyl compounds, nitroso compounds, nitrogen oxides and the like can be used. When adding a polymerization inhibitor, the compound represented by the general formula (IV) and (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride Although it does not specifically limit with respect to a total amount, Preferably it is 10-10,000 ppm, Most preferably, it is 100-5,000 ppm.

  The compound represented by the general formula (V) is often obtained in the form of a solution. By concentrating this solution, a highly pure compound can be obtained. Moreover, a compound with higher purity can be obtained by performing distillation purification, recrystallization, extraction operation or washing with water as necessary.

  When the solution containing the compound represented by the general formula (V) is concentrated, purified by distillation or recrystallized, in order to prevent polymerization of the product, a gas containing oxygen is blown into the system, It is preferable to add a polymerization inhibitor.

  When a catalyst is used in the production of the compound represented by the general formula (V), before concentration, distillation purification, recrystallization, extraction operation or washing of the solution containing the compound represented by the general formula (V), Part or all of the used catalyst may be neutralized or adsorbed and removed with an adsorbent. The adsorbent is not particularly limited, and examples thereof include acidic clay, activated clay, alumina, silica, zeolite, ion exchange resin, acidic inorganic compound, and basic inorganic compound.

Process 3
In step 3, the compound represented by general formula (V) obtained in step 2 is reacted with water in the presence of a dilute acid or in the presence of an acidic compound to form the following general formula (VI):

[Wherein, Y, R ¹ and R ⁵ are the same as described above. ] Is a step of obtaining a monomer having a glyoxyramide group and a (meth) acryloyloxy group.

  In step 3, the compound represented by the general formula (V) may be purified and then reacted with water in a dilute acid or in the presence of an acidic compound and water, or represented by the general formula (V). The solution containing the compound may be reacted with water in a dilute acid or in the presence of an acidic compound and water without purification. When purifying, operations such as concentration, extraction, washing, and filtration can be performed. In addition, when a catalyst is used in the reaction in Step 2, a part or all of the used catalyst is neutralized with an acid before reacting with water in a dilute acid or in the presence of an acidic compound and water. Alternatively, it may be adsorbed and removed by an adsorbent.

  The reaction of the compound represented by the general formula (V) with water can be performed in a dilute acid or in the presence of an acidic compound and water.

  Examples of the diluted acid include diluted hydrochloric acid, diluted hydrobromic acid, diluted nitric acid, diluted sulfuric acid and the like. It is not necessary to increase the acid concentration of these dilute acids. As the dilute acid, 0.001 to 15 wt% hydrochloric acid, 0.001 to 20 wt% hydrobromic acid, 0.001 to 20 wt% dilute nitric acid, 0.001 to 20 wt% sulfuric acid and the like are preferable. Further, from the viewpoint of safety and ease of handling, 0.01 to 7% by weight hydrochloric acid, 0.01 to 10% by weight hydrobromic acid, 0.01 to 10% by weight dilute nitric acid, 0.01 to 10% by weight Sulfuric acid and the like are more preferable. The amount of the diluted acid used is not particularly limited, but is preferably about 0.01 to 10 times, more preferably about 0.1 to 5 times the weight of the compound represented by the general formula (V). . If the amount of dilute acid exceeds about 10 times, production efficiency decreases.

  Examples of acidic compounds include phosphoric acid compounds such as phosphoric acid, monoalkyl phosphoric acid, and dialkyl phosphoric acid; organic sulfonic acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, and methanesulfonic acid; oxalic acid, trifluoroacetic acid, and monochloro. Examples thereof include carboxylic acids such as acetic acid, formic acid, and acetic acid; metal triflates, metal tetrafluoroborate, Lewis acids; solid acid catalysts such as clay, acidic clay, activated clay, silica, alumina, zeolite, and cation exchange resin. As the cation exchange resin, an ion exchange resin having a functional group such as a sulfonic acid group, a phosphoric acid group, or a carboxyl group is preferable, and an ion exchange resin having a sulfonic acid group or a phosphoric acid group is more preferable. Examples of commercially available cation exchange resins include “Amberlist 15JWET”, “Amberlist 15DRY”, “Amberlist 16WET”, “Amberlist 31WET” (above, Rohm & Haas, trade name), “RCP-160M”. ”,“ RCP-150H ”,“ RCP-170H ”,“ PK-216 ”(trade name, manufactured by Mitsubishi Chemical Corporation),“ Dowex 50W ”(trade name, manufactured by Dow Chemical Company), and the like. The addition amount of the acidic compound is not particularly limited, but in the case of phosphoric acid compounds, organic sulfonic acids, carboxylic acids, and Lewis acids, 0.01 to 100 with respect to 1 mol of the compound represented by the general formula (V). About a molar amount is preferable, and in the case of solid acid catalysts, about 0.1 to 500 parts by weight is preferable with respect to 100 parts by weight of the compound represented by formula (V). In this case, the amount of water coexisting with the acidic compound is not particularly limited, but is preferably about 0.01 to 10 times the weight of the compound represented by the general formula (V), About 5 times the amount is more preferable. If the amount of water exceeds about 10 times, the production efficiency falls. Solid acid catalysts can be separated by filtration after the reaction. When the compound represented by the general formula (V) and water are reacted in the presence of an acidic compound, the compound represented by the general formula (V) and the acidic compound are mixed first, and water is added later. Alternatively, the compound represented by the general formula (V) and water may be mixed first, and the acidic compound may be added later.

  The reaction of the compound represented by the general formula (V) with water may be carried out in order to increase the reaction rate or under pressure, even when it is carried out either in a dilute acid or in the presence of an acidic compound. good. Although reaction temperature is not specifically limited, Usually, it is from 0 degreeC to the temperature which recirculate | refluxs. Since reaction rate will be slow when too low, and it may color when too high, about 10-100 degreeC is especially preferable. In this reaction, there may be no solvent other than water, but an organic solvent can be used in combination as necessary. As the organic solvent, alcohols, ester derivatives, amide derivatives, ether derivatives, hydrocarbons, halogenated hydrocarbons and the like can be used. The amount of the solvent to be used is not particularly limited, but if it is too much, the economical efficiency is lowered.

  This reaction can also be carried out in a two-phase system. In the case of reacting this reaction in a two-phase system, an onium salt or the like may be added to increase the reaction rate. Removal of the alcohol produced in the system to the outside of the system can be performed under normal pressure, reduced pressure, or increased pressure by heating or blowing a gas such as air or nitrogen as necessary. This reaction may be performed in an atmosphere of an inert gas such as nitrogen in order to prevent coloring of the product.

  When the compound represented by the general formula (V) is reacted with water in a dilute acid or in the presence of an acidic compound, in order to prevent polymerization of the product, a gas containing oxygen is blown into the system or polymerized in the system. It is preferable to add an inhibitor. Although it does not specifically limit as a polymerization inhibitor, For example, 1 or more types chosen from the said polymerization inhibitor etc. can be used. When a polymerization inhibitor is added, it is not particularly limited with respect to the weight of the compound represented by the general formula (V), but is preferably about 10 to 10,000 ppm, particularly preferably about 100 to 5,000 ppm. .

  The monomer represented by the general formula (VI) can be obtained by reacting the compound represented by the general formula (V) with water in a dilute acid or in the presence of an acidic compound. In this case, it is often obtained in the form of a solution. If necessary, a monomer with higher purity can be obtained by repeating concentration, distillation purification, recrystallization, extraction operation or washing with water.

  When the monomer represented by the general formula (VI) is concentrated, purified by distillation or recrystallized, in order to prevent polymerization of the product, a gas containing oxygen is blown into the system, or the aforementioned polymerization is prohibited in the system. It is preferable to add an agent.

  In the production of the monomer represented by the general formula (VI), before the solution containing the compound is concentrated, distilled, purified, recrystallized, extracted, or washed, a part or all of the used dilute acid or acidic compound is added. They may be summed or removed by adsorption with an adsorbent. The adsorbent is not particularly limited, and examples thereof include acidic clay, activated clay, alumina, silica, zeolite, ion exchange resin, acidic inorganic compound, and basic inorganic compound.

  Examples of the monomer represented by the general formula (VI) thus obtained include N- (2-((meth) acryloyloxy) alkyl) glyoxiramide, N-alkyl-N- (2-((meta And) acryloyloxy) alkyl) glyoxiramide.

  Specific examples of the compound of the general formula (VI) include N- (2-((meth) acryloyloxy) ethyl) glyoxiramide, N- (1,1-dimethyl-2-((meth) acryloyloxy) ethyl) glyoxiramide N- (1-methyl-2-((meth) acryloyloxy) ethyl) glyoxiramide, N- (1-ethyl-2-((meth) acryloyloxy) ethyl) glyoxiramide, N- (3-((meth) Acryloyloxy) propyl) glyoxiramide, N- (4-((meth) acryloyloxy) butyl) glyoxiramide, N- (5-((meth) acryloyloxy) pentyl) glyoxiramide, N- (6-((meth) acryloyloxy) ) Hexyl) glyoxiramide, N- (2-methyl-2-((meth) acryloyloxy) Til) glyoxiramide, N- (2-((meth) acryloyloxy) ethyl) -N-methyl-glyoxiramide, N- (1,1-dimethyl-2-((meth) acryloyloxy) ethyl) -N-methyl- Glyoxiramide, N- (1-methyl-2-((meth) acryloyloxy) ethyl) -N-methyl-glyoxiramide, N- (1-ethyl-2-((meth) acryloyloxy) ethyl) -N-methyl- Glyoxiramide, N- (3-((meth) acryloyloxy) propyl) -N-methyl-glyoxiramide, N- (4-((meth) acryloyloxy) butyl) -N-methyl-glyoxiramide, N- (5- ( (Meth) acryloyloxy) pentyl) -N-methyl-glyoxiramide, N- (6-((meth) acryloyloxy) Cis) hexyl) -N-methyl-glyoxiramide, N- (2-methyl-2-((meth) acryloyloxy) ethyl) -N-methyl-glyoxiramide, N- (2-((meth) acryloyloxy) ethyl) -N-ethyl-glyoxiramide, N- (1,1-dimethyl-2-((meth) acryloyloxy) ethyl) -N-ethyl-glyoxiramide, N- (1-methyl-2-((meth) acryloyloxy) Ethyl) -N-ethyl-glyoxiramide, N- (1-ethyl-2-((meth) acryloyloxy) ethyl) -N-ethyl-glyoxiramide, N- (3-((meth) acryloyloxy) propyl) -N -Ethyl-glyoxiramide, N- (4-((meth) acryloyloxy) butyl) -N-ethyl-glyoxiramide, N- 5-((meth) acryloyloxy) pentyl) -N-ethyl-glyoxiramide, N- (6-((meth) acryloyloxy) hexyl) -N-ethyl-glyoxiramide, N- (2-methyl-2-(( (Meth) acryloyloxy) ethyl) -N-ethyl-glyoxiramide, N- (2-((meth) acryloyloxy) ethyl) -N-isopropyl-glyoxiramide, N- (1,1-dimethyl-2-((meth)) (Acryloyloxy) ethyl) -N-isopropyl-glyoxiramide, N- (1-methyl-2-((meth) acryloyloxy) ethyl) -N-isopropyl-glyoxiramide, N- (1-ethyl-2-((meth)) Acryloyloxy) ethyl) -N-isopropyl-glyoxiramide, N- (3-((meth) acrylo) Ruoxy) propyl) -N-isopropyl-glyoxiramide, N- (4-((meth) acryloyloxy) butyl) -N-isopropyl-glyoxiramide, N- (5-((meth) acryloyloxy) pentyl) -N-isopropyl -Glyoxiramide, N- (6-((meth) acryloyloxy) hexyl) -N-isopropyl-glyoxiramide, N- (2-methyl-2-((meth) acryloyloxy) ethyl) -N-isopropyl-glyoxiramide, N -(2-((meth) acryloyloxy) ethyl) -N-butyl-glyoxiramide, N- (1,1-dimethyl-2-((meth) acryloyloxy) ethyl) -N-butyl-glyoxiramide, N- ( 1-methyl-2-((meth) acryloyloxy) ethyl) -N-buty Ru-glyoxiramide, N- (1-ethyl-2-((meth) acryloyloxy) ethyl) -N-butyl-glyoxiramide, N- (3-((meth) acryloyloxy) propyl) -N-butyl-glyoxiramide, N- (4-(((meth) acryloyloxy) butyl) -N-butyl-glyoxiramide, N- (5-((meth) acryloyloxy) pentyl) -N-butyl-glyoxiramide, N- (6-((meta ) Acryloyloxy) hexyl) -N-butyl-glyoxiramide, N- (2-methyl-2-((meth) acryloyloxy) ethyl) -N-butyl-glyoxiramide, N- (2-((meth) acryloyloxy) Ethyl) -Nt-butyl-glyoxiramide, N- (1,1-dimethyl-2-((meth) acryloyl) Xyl) ethyl) -Nt-butyl-glyoxiramide, N- (1-methyl-2-((meth) acryloyloxy) ethyl) -Nt-butyl-glyoxiramide, N- (1-ethyl-2- ( (Meth) acryloyloxy) ethyl) -Nt-butyl-glyoxiramide, N- (3-((meth) acryloyloxy) propyl) -Nt-butyl-glyoxiramide, N- (4-((meth) acryloyl) Oxy) butyl) -Nt-butyl-glyoxiramide, N- (5-((meth) acryloyloxy) pentyl) -Nt-butyl-glyoxiramide, N- (6-((meth) acryloyloxy) hexyl) -Nt-butyl-glyoxiramide, N- (2-methyl-2-((meth) acryloyloxy) ethyl) -Nt-butyl-g Okishiramido and the like.

  Moreover, as a monomer represented by general formula (VI), the compound whose Y is an ethylene group which may have a C1-C6 organic group as a substituent, Y is C1-C1 as a substituent. The compound etc. which are the linear propylene groups which may have 6 organic groups are preferable.

  As the monomer represented by the general formula (VI), a compound in which Y is an ethylene group or a linear propylene group is more preferable from the viewpoint of easy availability of raw materials. Specific examples of such compounds include N- (2-((meth) acryloyloxy) ethyl) glyoxiramide, N- (1,1-dimethyl-2-((meth) acryloyloxy) ethyl) glyoxiramide, N- (1-ethyl-2-((meth) acryloyloxy) ethyl) glyoxiramide, N- (3-((meth) acryloyloxy) propyl) glyoxiramide, N- (2-(((meth) acryloyloxy) ethyl) -N -Methyl-glyoxiramide, N- (2-((meth) acryloyloxy) ethyl) -N-ethyl-glyoxiramide, N- (2-((meth) acryloyloxy) ethyl) -N-isopropyl-glyoxiramide, N- ( 2-((meth) acryloyloxy) ethyl) -N-butyl-glyoxiramide, N- (2- (Meth) acryloyloxy) ethyl) -N-t-butyl - Guriokishiramido the like, and the like.

As the monomer represented by the general formula (VI), Y is an ethylene group, R ¹ is a alkyl group, especially a methyl group having 1 to 4 carbon hydrogen or C, R ⁵ is a hydrogen atom or a methyl group Is preferable because the raw material is inexpensive. Specific examples of such compounds include N- (2-((meth) acryloyloxy) ethyl) glyoxiramide, N- (2-((meth) acryloyloxy) ethyl) -N-methyl-glyoxiramide, and the like. .

Production of vinyl polymer (A) The vinyl polymer (A) can be produced, for example, by the method shown in the following (i) or (ii).

  (I) The monomer represented by the general formula (VI) is polymerized alone or copolymerized with another vinyl monomer.

  (Ii) After the compound represented by the general formula (V) is polymerized alone or copolymerized with another vinyl monomer, the obtained polymer is used in a dilute acid or in the presence of an acidic compound. And react with water. The reaction conditions with water in this case can be the same as in the case of producing the monomer represented by the general formula (VI) by reacting the compound represented by the general formula (V) with water.

  The monomer represented by the general formula (VI) and the compound represented by the general formula (V) may be used for polymerization in a solution state having a relatively low purity, or after the purity is increased. It may be used for polymerization.

  As other vinyl-based monomers mentioned above, known ones can be used and are not particularly limited. For example, the following (1) to (22) are mentioned.

  (1) Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl C1-C30 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid such as (meth) acrylate.

  (2) C2-C18 alkoxyalkyl ester of acrylic acid or methacrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate and the like.

  (3) Vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and p-chlorostyrene.

  (4) C2-C8 hydroxyalkyl ester of acrylic acid or methacrylic acid, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

  (5) An adduct of a hydroxyalkyl ester of acrylic acid or methacrylic acid and ε-caprolactone, for example, “Placcel FM-3” (trade name, manufactured by Daicel Chemical Industries).

  (6) Poly (alkylene glycol) mono (meth) acrylates, polypropylene glycol mono (meth) acrylates, polyethylene glycol polypropylene glycol mono (meth) acrylates and other polyalkylene glycol mono (meth) acrylates; methyl Alkyl polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylate, methyl polyoxypropylene (meth) acrylate, methyl polyoxyethylene polyoxypropylene (meth) acrylate; and hydroxyalkyl vinyl ethers.

  (7) Glycidyl (meth) acrylate, diglycidyl fumarate, allyl glycidyl ether, ε-caprolactone-modified glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc. Epoxy group-containing unsaturated monomer.

  (8) Perfluoroalkyl esters of acrylic acid or methacrylic acid such as perfluorobutylethyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate.

  (9) Olefins such as ethylene, propylene, butylene and pentene.

  (10) Diene compounds such as butadiene, isoprene and chloroprene.

  (11) Fluoroolefins such as trifluoroethylene, tetrafluoroethylene, and vinylidene fluoride.

  (12) Vinyl esters of fatty acids having 1 to 20 carbon atoms such as vinyl acetate, vinyl propionate, vinyl caprate, “veova monomer” (trade name, Shell Chemical Co., vinyl ester of branched higher fatty acid), isopropenyl acetate, etc. Or vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, and benzyl vinyl ether.

  (13) Carboxyl such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 5-carboxypentyl (meth) acrylate Group-containing unsaturated monomer.

  (14) Hydrolyzable alkoxysilyl group-containing unsaturated monomers such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and 2-styrylethyltrimethoxysilane.

  (15) Nitrogen-containing alkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and Nt-butylaminoethyl (meth) acrylate.

  (16) Acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Polymerizable amides such as N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, diacetone acrylamide; 2-vinylpyridine, 1 -Nitrogen-containing unsaturated monomers such as vinyl-2-pyrrolidone, 4-vinylpyridine, (meth) acryloylmorpholine.

  (17) Sulfonic acid monomers such as vinyl sulfonic acid, methallyl sulfonic acid, sulfoethyl (meth) acrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and salts thereof.

  (18) An esterified product of a hydroxyl group-containing unsaturated monomer such as 2- (meth) acryloyloxyethyl acid phosphate and a phosphoric acid compound.

  (19) A phosphoric acid-containing unsaturated monomer such as a product obtained by adding a phosphoric acid compound to an epoxy group such as glycidyl (meth) acrylate.

  (20) Polymerizable nitriles such as acrylonitrile and methacrylonitrile.

  (21) Polymerizable amines such as allylamine.

  (22) Acid anhydride monomers such as maleic anhydride and itaconic anhydride.

  As the polymerization method, known methods can be used. For example, radical polymerization, coordination polymerization, group transfer polymerization (functional group transfer polymerization), ATRP polymerization (atom transfer polymerization), chain transfer polymerization, and the like can be used. .

  Moreover, a well-known thing can be used as a form of superposition | polymerization, for example, uniform polymerization in a solution, batch polymerization, emulsion polymerization, dispersion polymerization, suspension polymerization etc. can be used.

  In particular, the polymerization or copolymerization of the monomer compound of the general formula (VI) is preferably performed in an organic solvent or in an emulsified state in water.

  For example, the monomer compound of the general formula (VI) and other vinyl monomers may be copolymerized in an organic solvent using a polymerization initiator.

  Examples of the organic solvent used in the solution polymerization method include aromatic solvents such as toluene, xylene, and “Swazole 1000” (trade name, high-boiling petroleum solvent) manufactured by Cosmo Oil; ethyl acetate, propyl Ester solvents such as pionate, butyl propionate, ethoxyethyl propionate, 3-methoxybutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone Solvents; Alcohol solvents such as ethylene glycol monobutyl ether, propylene glycol monopropyl ether and butanol; Ether solvents such as tetrahydrofuran and dipropylene glycol dimethyl ether; N Methyl-2-pyrrolidinone, N, and the like amide solvents such as N- dimethylacetamide. These organic solvents can be used alone or in combination of two or more.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, di-t-amyl peroxide, t-butyl peroctoate, 2,2 Well-known radical polymerization initiators, such as' -azobis (2-methylbutyronitrile), can be mentioned. The amount of the polymerization initiator used is preferably about 0.01 to 30% by weight, more preferably about 0.1 to 20% by weight, based on the weight of the monomer to be polymerized.

  As polymerization conditions, the reaction temperature is usually room temperature to about 200 ° C., and the reaction time is about 2 to 10 hours.

  Further, for example, the monomer compound of the general formula (VI) and other vinyl monomers are copolymerized in an emulsion state in water using a polymerization initiator in the presence of a dispersion stabilizer such as a surfactant. Also good.

  Examples of the dispersion stabilizer include an anionic emulsifier, a nonionic emulsifier, and an amphoteric ion emulsifier. Specifically, examples of the anionic emulsifier include fatty acids, alkyl sulfate esters, alkylbenzene sulfonates, and alkyl phosphates. Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amines, alkyl alkanolamides, and the like. . Examples of the zwitterionic emulsifier include alkylbedine. The concentration of the emulsifier is in the range of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the weight of the monomer to be polymerized.

  Examples of the polymerization initiator include radical polymerization initiators such as ammonium persulfate and 4,4′-azobis (4-cyanobutanoic acid). The amount of the polymerization initiator is based on the weight of the monomer to be polymerized. , About 0.01 to 10% by weight, preferably about 0.1 to 5% by weight.

  As polymerization conditions, the reaction temperature is usually about 60 to 90 ° C. and the reaction time is about 5 to 10 hours.

  The vinyl polymer (A) thus obtained has the following general formula (I)

[Wherein, R ¹ is the same as above], and is a vinyl polymer having a glyoxiramide group. Since this glyoxiramide group is cured by reacting with a crosslinking agent that reacts with a carbonyl group, the polymer is useful as a base resin for various curable compositions.

  The number average molecular weight of the vinyl polymer (A) is not particularly limited, but is preferably in the range of about 1,000 to 1,000,000 for ease of production.

  In addition to the glyoxiramide group, the vinyl polymer (A) having at least one anionic group selected from a carboxylate group, a phosphate group and a sulfonate group can be suitably used for an aqueous curable composition. Such a polymer having an anionic group can be prepared, for example, by the following method (1) or (2).

  (1) A monomer represented by the general formula (VI) is combined with other vinyl monomers including one or more monomers selected from a carboxyl group-containing vinyl monomer, a phosphate group-containing vinyl monomer, and a sulfonic acid group-containing monomer. After polymerization, some or all of the carboxyl group, phosphoric acid group and sulfonic acid group are obtained by neutralization with a basic compound.

  (2) Others including a monomer represented by the general formula (VI) and one or more anionic group-containing vinyl monomers selected from a carboxylate group-containing vinyl monomer, a phosphate group-containing vinyl monomer, and a sulfonate group-containing vinyl monomer It is obtained by copolymerizing with a vinyl monomer.

  Examples of the carboxyl group-containing vinyl monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 5-carboxyl. Examples thereof include carboxyl group-containing unsaturated monomers such as pentyl (meth) acrylate.

  As a carboxylate group containing vinyl monomer, the salt of the said carboxyl group containing vinyl monomer can be mention | raise | lifted, for example.

  Examples of the phosphoric acid group-containing vinyl monomer include esterified products of a hydroxyl group-containing unsaturated monomer such as 2- (meth) acryloyloxyethyl acid phosphate and a phosphoric acid compound.

  Examples of the phosphate group-containing vinyl monomer include salts of the above-mentioned phosphate group-containing vinyl monomers.

  Examples of the sulfonic acid group-containing vinyl monomer include sulfonic acid monomers such as vinyl sulfonic acid, methallyl sulfonic acid, sulfoethyl (meth) acrylate, styrene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid. .

  Examples of the sulfonate group-containing vinyl monomer include salts of the sulfonic acid group-containing vinyl monomer.

  In addition to the glyoxyramide group, the polymer of the present invention further has at least one nonionic hydrophilic group selected from the group consisting of a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene polyoxypropylene group. Those can also be suitably used in the aqueous curable composition. Such a polymer having a nonionic hydrophilic group can be prepared, for example, by the following method.

  A monomer represented by the general formula (VI), a monoalkyl polyoxyethylene group-containing vinyl monomer, a monoalkyl polyoxypropylene group-containing vinyl monomer, a monoalkyl polyoxyethylene polyoxypropylene group-containing vinyl monomer, hydroxy (polyoxyethylene) ) Other vinyl series containing at least one nonionic hydrophilic group-containing vinyl monomer selected from a group-containing vinyl monomer, a hydroxy (polyoxypropylene) group-containing vinyl monomer and a hydroxy (polyoxyethylene polyoxypropylene) group-containing vinyl monomer It can be obtained by copolymerization with a monomer.

Aqueous curable composition The aqueous curable composition of the present invention comprises (A) the following general formula (I):

[Wherein, R ¹ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms. And a vinyl polymer having a glyoxyramide group represented by:
(B) a compound having a primary amino group and / or a secondary amino group, which may be partially or completely neutralized with a Bronsted acid, and / or
(C) a compound having a hydrazide group and / or a semicarbazide group,
Is obtained by mixing.

Compound (B)
The compound (B) is a compound having a primary amino group and / or a secondary amino group, which may be partially or completely neutralized with a Bronsted acid. Moreover, the compound (B) may have a tertiary amino group and / or a quaternary ammonium group. A primary to tertiary amino group, when neutralized with a Bronsted acid, becomes a primary to tertiary ammonium group. Among these groups, the primary-secondary amino group and primary-secondary ammonium group are (N-alkyl-N- (2-acylacyl) amino) alkyloxycarbonylamino groups possessed by the vinyl polymer (A). By performing the crosslinking reaction at room temperature or under heating, the excellent curability of the composition of the present invention is exhibited.

  Here, the primary ammonium group is represented by the following formula (XIII), the secondary ammonium group is represented by the following formula (XIV), the tertiary ammonium group is represented by the following formula (XV), and the quaternary ammonium group is represented by the following formula (XVI). , Respectively. In the formulas (XIII) to (XVI), X represents an acid residue of Bronsted acid.

  The compound (B) preferably has a number average molecular weight of about 17 to 1,000,000, and includes a low molecular weight compound or a resinous high molecular weight compound. If the number average molecular weight of the compound (B) exceeds about 1,000,000, the compatibility with the vinyl polymer (A) may be lowered.

  Bronsted acids used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic sulfonic acids such as paratoluenesulfonic acid and methanesulfonic acid; and organic low molecules such as formic acid, succinic acid, acetic acid, propionic acid, and butyric acid Carboxylic acid; and oxyacids such as oxyacetic acid and lactic acid.

  The compound containing two or more primary amino groups and / or secondary amino groups in one molecule is not particularly limited. For example, ammonia, (polyamino) alkane, (polyamino) polyether, poly (ethyleneimine) ), Poly (aminoalkene) and the like.

  Specifically, for example, poly (C2-C20) such as ethylenediamine, N, N'-dimethylethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine and the like. Methylenediamine or polymethylenediamine having an organic substituent at the N-position of this polymethylenediamine; ethylene glycol bis (2-aminoethyl) ether, diethylene glycol bis (2-aminoethyl) ether, tripropylene glycol (2-aminoethyl) ) Diamines containing an oxyalkylene group such as ether or a polyoxyalkylene group; alicyclic diamines having about 3 to 10 carbon atoms such as 1,2-cyclohexyldiamine and 1,4-cyclohexyldiamine; -Xylylenediamine, m-xylylenediamine, p-xylylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 1,4-naphthylenediamine, 4,4 ' -Aromatic diamines having about 6 to 20 carbon atoms such as diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone; polyethylene polyamines such as diethylenetriamine, N-ethyldiethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. A polyamine having about 4 to 20 carbon atoms, or a polyamine having an organic substituent at the N-position of the polyamine; an aliphatic triamine having about 3 to 20 carbon atoms such as 1,2,3-triaminopropane; , 3-aminobenzene, etc. 6 to 6 carbon atoms A structure obtained by converting two or more hydroxyl groups of a compound obtained by reacting an alkylene oxide such as ethylene oxide and / or propylene oxide with a polyol such as trimethylolpropane or pentaerythritol into an aromatic group. And polyamines containing polyoxyalkylene groups; polyamines obtained by further reacting the diamine, triamine or polyamine with an alkylene oxide such as ethylene oxide and / or propylene oxide.

  Moreover, a cationic resin can also be used as a compound (B). Although it does not specifically limit as a cationic resin, For example, resin which is the reaction material of the resin derived from an epoxy group containing compound or an epoxy group containing compound, and primary and / or secondary organic amine or its derivative; Copolymers of amino group-containing polymerizable unsaturated compounds and vinyl monomers; amino group-containing polymerizable unsaturated compounds, copolymers of amide group-containing polymerizable unsaturated compounds and vinyl monomers; polyamide resins; Cationic resins exhibiting water dispersibility when an acid compound is added; resins obtained by reacting an epoxy group-containing compound or a resin derived from an epoxy group-containing compound with a cationizing agent; polycarboxylic acid and polyamine Resins obtained by protonation of polycondensates with acid; polyisocyanate compounds and polyisocyanates of polyols and mono- or polyamines Resins protonated pressurized product with acid; polycarboxylic acid resins and resins obtained by protonation with acid adducts of an alkylene imine, and the like.

  The cationic resin may be modified with a vinyl copolymer, polybutadiene, unsaturated group-containing alkyd resin, polyester, polyurethane, polycarbonate, polyol, polyamine, polycarboxylic acid, ε-caprolactone, and derivatives thereof. . Further, the polyisocyanate may be further reacted during the modification.

  As the resin derived from the epoxy group-containing compound or the epoxy group-containing compound, those produced using an active hydrogen-containing compound and epichlorohydrin as raw materials are preferable. Examples of the active hydrogen-containing compound include polyphenol compounds, polyether polyols, polyester polyols, polyamidoamines, and polycarboxylic acids. The number average molecular weight of the epoxy group-containing compound or the resin derived from the epoxy group-containing compound is preferably about 200 or more, more preferably about 400 to 4,000, and particularly preferably about 800 to 2,000.

  Examples of the polyphenol compound that is an active hydrogen-containing compound include 2,2-bis (4-hydroxyphenyl) propane, 4,4-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis. (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxy-tert-butyl-phenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) ) Methane, tetra-1,1,2,2- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenylsulfone, phenol novolak, cresol novolak and the like.

  Examples of the cationic resin include the following resins (i) to (iii).

  (i) A cationic resin which is an adduct of an epoxy group-containing compound or a resin derived from an epoxy group-containing compound and a monoamine or polyamine described in, for example, US Pat. No. 3,984,299.

  (ii) Secondary monoamines and polyamines having a primary amino group ketiminated and a resin derived from an epoxy group-containing compound or an epoxy group-containing compound, for example, as described in US Pat. No. 4,017,438 And a cationic resin that is an adduct.

  (iii) For example, obtained by etherification of an epoxy group-containing compound or a resin derived from an epoxy group-containing compound and a hydroxy compound having a ketiminated primary amino group described in JP-A-59-43013 Cationic resin that is a reaction product.

  As the cationic resin which is the compound (B), those produced using a compound having two or more glycidyl groups in one molecule and an amine compound as a raw material are preferable. This amine compound may be ketiminized.

  Examples of the compound having two or more glycidyl groups in one molecule include bisphenol A such as “Epicoat 828”, “Epicoat 1001”, and “Epicoat 1002” (all trade names manufactured by Japan Epoxy Resins Co., Ltd.). Terminal diglycidyl ether type aromatic ring-containing resins derived from bisphenol F such as “Epicoat 806”, “Epicoat 4004P”, and “Epicoat 4007P” (all trade names manufactured by Japan Epoxy Resins Co., Ltd.) Diglycidyl ether type aromatic ring-containing resins; ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether And terminal polyglycidyl ether type aliphatic resins such as polypropylene glycol diglycidyl ether.

  Examples of the amine compound include monoamine, diamine, triamine, and polyamine. Examples of monoamines include aminoalkanes having 4 to 18 carbon atoms such as butylamine, dibutylamine, 2-ethylhexylamine, octylamine, dodecylamine, stearylamine; ethanolamine, 2- (N-methylamino) ethanol, ( And oxygen atom-containing monoamino compounds such as 2-hydroxyethoxy) ethylamine and 2-amino-2-methyl-1-propanol. As the diamine, triamine, and polyamine, those described above can be used.

  Examples of the ketimine compound of the above amine compound include a compound obtained by reacting a primary amino group of diethylenetriamine with a ketone such as methyl isobutyl ketone and ketimine, and obtained by reacting the amino group of 2-aminoethanol with a ketone. And amine derivatives in which a part or all of the amino groups are ketiminated. When a ketimine compound of an amine compound is reacted with a compound having two or more glycidyl groups in one molecule and / or an amine compound, water is then added, and if necessary, Bronsted acids such as acetic acid and formic acid. Can be added to hydrolyze the ketimine moiety and regenerate the amino group.

  The compound (B) may have a cationic group such as a sulfonium group or a phosphonium group.

  The compound (B) having a cationic group is prepared, for example, according to a conventional method by adding a tertiary amine salt, a secondary sulfide salt, or a tertiary phosphine to the epoxy group of the cationic resin having the epoxy group. It can be synthesized by reacting a salt.

  Tertiary amine salts include tertiary amines such as triethylamine, triethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, N, N-diethylethanolamine, N-ethyldiethanolamine, hydrochloric acid, sulfuric acid, Inorganic acids such as phosphoric acid; organic sulfonic acids such as paratoluenesulfonic acid and methanesulfonic acid; organic low-molecular carboxylic acids such as oxalic acid, acetic acid, formic acid and propionic acid; and mixtures with oxyacids such as oxyacetic acid and lactic acid. I can give you.

  Examples of the secondary sulfide salt include mixtures of sulfides such as diethyl sulfide, diphenyl sulfide, tetramethylene sulfide, thiodiethanol and the like and acids as described above.

  Examples of the tertiary phosphine salt include a mixture of a phosphine such as triethylphosphine, phenyldimethylphosphine, diphenylmethylphosphine, triphenylphosphine and the like acid.

  Further, the compound (B) may have a nonionic hydrophilic group. The nonionic hydrophilic group is not particularly limited, and examples thereof include a polyoxyethylene group, a polyoxypropylene group, a polyoxyethylene polyoxypropylene group, a poly (N-vinylpyrrolidone) group, a poly (vinylformamide) group, and a poly ( Acrylamide) group, poly (N-alkylacrylamide) group, poly (N, N-dialkylacrylamide) group and the like. Among these, from the viewpoint of easy introduction, a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene polyoxypropylene group are preferable.

  Examples of techniques for introducing polyoxyethylene groups include polyoxyethylene derivatives having hydroxyl groups such as polyethylene glycol and polyethylene glycol monoalkyl ether; polyoxypropylene derivatives having hydroxyl groups such as polypropylene glycol and polypropylene glycol monoalkyl ether A resin derived from a polyalkylene glycol compound and an epoxy group-containing compound and / or an epoxy group-containing compound selected from polyoxyethylene polyoxypropylene derivatives having a hydroxyl group such as polyethylene polypropylene glycol and polyethylene polypropylene glycol monoalkyl ether; And a polyisocyanate, or the polyalkylene glycol compound, A thione resin and a polyisocyanate may be reacted, or a resin derived from the polyalkylene glycol compound, an epoxy group-containing compound and / or an epoxy group-containing compound, the cationic resin and a polyisocyanate may be reacted. . In the production of these compounds (B), after introducing a nonionic hydrophilic group, an amine compound such as monoamine, diamine, triamine, or polyamine or a ketimine compound of amine may be reacted.

Compound (C)
The compound (C) is a compound having a hydrazide group and / or a semicarbazide group. The compound (C) preferably has an average of two or more hydrazide groups and / or semicarbazide groups in one molecule, and includes low molecular weight compounds to resinous high molecular weight compounds. The number average molecular weight is not particularly limited, but is preferably about 90 to 1,000,000, and more preferably about 150 to 100,000.

  Examples of the compound (C) include hydrazides such as carbonic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, poly (N-aminoacrylamide); and hydrazides and epoxy group-containing compounds. Addition reaction product; addition reaction product of hydrazide and polyisocyanate; semicarbazide obtained by addition reaction of polyisocyanate and hydrazine; semicarbazide obtained by addition reaction of polyisocyanate, hydrazine and epoxy group-containing compound, etc. Is mentioned. Addition reaction of hydrazide and epoxy group-containing compound, addition reaction of hydrazide and polyisocyanate, addition reaction of polyisocyanate and hydrazine, addition reaction of polyisocyanate, hydrazine and epoxy group-containing compound are not particularly limited, It can be performed under known conditions.

  The polyisocyanate is not particularly limited, and a bifunctional or higher polyisocyanate can be used. For example, the following can be used.

  (I) Diphenylmethane-4,4′-diisocyanate (MDI), 1,5-naphthalene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methyl-1,5-diisocyanate Pentane (MPDI), 1,6-diisocyanate hexane (HDI), 2,2,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), lysine diisocyanate, 1-isocyanate-3,5,5-trimethyl-3 -(Isocyanatemethyl) cyclohexane (IPDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), m-tetramethylxylylene diisocyanate (TMXDI), diisocyanate norbornane, di (isocyanate) Diisocyanates having 4 to 25 carbon atoms such as tomethyl) norbornane.

  (ii) Triisocyanates having 6 to 30 carbon atoms such as 2-isocyanatoethyl-2,6-diisocyanate caproate (LTI).

  (iii) polyisocyanates such as isocyanurate structure-containing polyisocyanate, allophanate structure-containing polyisocyanate, biuret structure-containing polyisocyanate, uretdione structure-containing polyisocyanate, urethane structure-containing polyisocyanate, polyfunctional hydroxyl group-containing compound-modified polyisocyanate, Polyisocyanates having a number average molecular weight of about 300 to 1,000,000 and an average number of isocyanate functional groups in one molecule of about 2 to 5,000.

  (iv) The number average molecular weight obtained by homopolymerizing an isocyanate group-containing vinyl monomer or copolymerizing with another vinyl monomer is about 1,000 to 1,000,000, Polyisocyanates having an average isocyanate functional group number of about 2 to 5,000.

  (v) one or more selected from monoisocyanates, diisocyanates, triisocyanates and polyisocyanates of (i) to (iv) above, a polyfunctional hydroxyl group-containing compound, a monofunctional hydroxyl group-containing compound and water. Polyisocyanates having a number average molecular weight of about 300 to 1,000,000 obtained by reacting with one or more kinds, and an average number of isocyanate functional groups in one molecule of about 2 to 5,000.

  The polyfunctional hydroxyl group-containing compounds mentioned in the above (iii) and (v) are polyols having a number average molecular weight of about 60 to 100,000 and having two or more hydroxyl groups in one molecule. Specific examples include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butanediol, polytetramethylene glycol, methylpropanediol, pentanediol, methylpentanediol, hexanediol, neopentylglycol, 2-butyl-2-ethyl. -1,3-propanediol, 2,2′-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 2-ethyl-1,3-hexanediol, 2,2 , 4-trimethyl-1,3-pentanediol, hydroxypivalic acid-neopentylglycol ester, dimethylolpropanoic acid, dimethylolbutanoic acid and other diols; trimethylolethane, trimethylolpropaline , Trimethylol butane, glycerin, pentaerythritol and other polyols having a triol or higher; ring-opening adducts of a compound having two or more hydroxyl groups in one molecule with ethylene oxide, propylene oxide, tetrahydrofuran, lactone, cyclocarbonate, etc .; one molecule Reaction product of compound having both amino group and hydroxyl group and epoxy group-containing compound; reaction product of compound having both amino group and hydroxyl group in one molecule and polyisocyanate; hydroxyl group-containing polyester resin; hydroxyl group A polyurethane resin containing; a hydroxyl group-containing polycarbonate resin; a hydroxyl group-containing vinyl copolymer; an epoxy resin. These resins can be synthesized by a known method.

  The monofunctional hydroxyl group-containing compound mentioned in the above (v) is a monool having a number average molecular weight of about 32 to 5,000 and one hydroxyl group in one molecule. Specific examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol. Alkanols such as octadecanol; ether group-containing monools such as propylene glycol monomethyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, and polyethylene glycol monoethyl ether.

  Examples of the isocyanate group-containing vinyl monomer mentioned in (iv) above include (meth) acryloyl isocyanate, (2-isocyanatoethyl) (meth) acryloyl isocyanate, m-isopropenyl-α, α′-dimethylbenzyl isocyanate ( TMI), adducts of a hydroxyl group-containing vinyl monomer and the diisocyanates. Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, and addition products of these hydroxyl group-containing vinyl monomers and lactones. It is done.

  As other vinyl monomers mentioned in the above (iv), known monomers can be used and are not particularly limited.

  Further, the compound (C) may have a nonionic hydrophilic group. The nonionic hydrophilic group is not particularly limited, and examples thereof include a polyoxyethylene group, a polyoxypropylene group, a polyoxyethylene polyoxypropylene group, a poly (N-vinylpyrrolidone) group, a poly (vinylformamide) group, and a poly ( Acrylamide) group, poly (N-alkylacrylamide) group, poly (N, N-dialkylacrylamide) group and the like. Among these, from the viewpoint of easy introduction, a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene polyoxypropylene group are preferable.

  As a method for introducing a polyoxyethylene group, for example, polyethylene glycol or a compound having two or more hydroxyl groups in one molecule as a polyfunctional hydroxyl group-containing compound mentioned in the above (iii) and (v) and ring opening of ethylene oxide Use of an adduct or the like, or use of ethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether or the like as the monofunctional hydroxyl group-containing compound mentioned in (v).

Preparation and Application of Aqueous Curable Composition The aqueous curable composition of the present invention can be obtained by mixing the vinyl polymer (A) and the compound (B) and / or the compound (C). This mixing can be performed by a conventional mixing method, for example, an operation such as stirring and shaking. In mixing, water and / or an organic solvent may be added and mixed. Although the temperature at the time of mixing is not specifically limited, It is preferable to carry out at room temperature vicinity from a viewpoint of the ease of water-based curable composition manufacture.

  From the viewpoint of sufficient curability of the composition of the present invention and water resistance of a cured product such as a coating film thereof, the molar concentration of the glyoxiramide group represented by the general formula (I) in the vinyl polymer (A) is: The amount is preferably about 0.02 to 6 mol / Kg, and more preferably about 0.05 to 3 mol / Kg. From the same viewpoint, the total molar concentration of the primary amino group and the secondary amino group, which may be partially or completely neutralized with Bronsted acid, is 0.02 to 35 mol / It is preferably about Kg, more preferably about 0.05 to 25 mol / Kg, and the total molar concentration of hydrazide group and semicarbazide group in compound (C) is 0.02 to 12 mol / kg. It is preferably about Kg, more preferably about 0.05 to 12 mol / Kg.

  The blending ratio of the vinyl polymer (A) and the compound (B) is such that the glyoxiramide group in the vinyl polymer (A) and a part or all of the compound (B) are neutralized with Bronsted acid. The sum of good primary amino groups and secondary amino groups is (number of moles of glyoxiramide groups) / (total of primary amino groups and secondary amino groups which may be partially or completely neutralized with Bronsted acid) The number of moles) is preferably about 0.1 to 10, and more preferably about 0.2 to 5. When the ratio is less than 0.1 and exceeds 10, the curability of the composition is often lowered, which is not preferable.

  The blending ratio of the vinyl polymer (A) and the compound (C) is such that the total of the glyoxiramide group in the vinyl polymer (A) and the hydrazide group and semicarbazide group in the compound (C) is (glyoxiramide group The number of moles) / (total number of moles of hydrazide group and semicarbazide group) is preferably about 0.1 to 10, and more preferably about 0.2 to 5. When the ratio is less than 0.1 and exceeds 10, the curability of the composition is often lowered, which is not preferable.

  In order to increase the viscosity stability at the time of storage of this aqueous curable composition, it is preferable that the vinyl polymer (A) has a carboxyl group and / or a carboxylate group. It is more preferable to have about 0.02 to 2 mol / Kg.

  Moreover, when mix | blending a compound (B), from the same viewpoint, (the total number of moles of the carboxyl group and carboxylate group in a vinyl polymer (A)) / (part or all in a compound (B)) Is more preferably a total number of moles of primary amino groups and secondary amino groups that may be neutralized with Bronsted acid)) = 0.05-10.

  The aqueous curable composition of the present invention can be used as a one-pack type or a two-pack type, and in any case, exhibits excellent curability at room temperature or under heating. The aqueous curable composition may gradually thicken over time depending on the type and combination of the vinyl polymer (A) and the compound (B) and / or the compound (C). When compound (B) is blended, in order to suppress thickening, it is preferable to neutralize part or all of the primary to tertiary amino groups in compound (B) with Bronsted acid. By this neutralization, the effective storage period in the one-pack type can be extended, and the pot life (pot life) in the two-pack type can be extended.

  In the composition of the present invention, the compound (B) often has a tertiary amino group in addition to the primary amino group and / or the secondary amino group, and in this case, it is neutralized with a Bronsted acid. The ratio between the total number of moles of the first to third grade amino groups and the total number of moles of the first to third grade ammonium groups generated by neutralizing the amino groups with Bronsted acid is (the first to third grade amino groups). The total number of moles of groups) / (total number of moles of primary to tertiary ammonium groups) = 0 to 6.0 is preferable from the viewpoint of excellent stability of the composition.

  The aqueous curable composition of the present invention includes, for example, a film forming aid, a surfactant, a dispersant, an emulsifier, a surface conditioner, an antiseptic, an antibacterial agent, an antifoaming agent, a color pigment, Various additives such as extender pigments, fillers, thickeners, plasticizers, rust inhibitors and organic solvents may be blended. Examples of the organic solvent in this case include alcohols such as ethanol and ethylene glycol; ethers such as tetrahydrofuran, dipropylene glycol dimethyl ether and propylene glycol monomethyl ether; esters such as ethyl acetate and butyl acetate; methyl isobutyl ketone and methyl ethyl ketone. Ketones such as; amides such as N-methyl-2-pyrrolidinone and N, N-dimethylacetamide; aliphatic, alicyclic or aromatic hydrocarbons such as hexane, cyclohexane, toluene and xylene. it can.

  The aqueous curable composition of the present invention may be neutralized with a glyoxyramide group in the vinyl polymer (A) and a Bronsted acid in the compound (B) by evaporation of the aqueous medium at the time of coating film formation. Since the dehydration condensation reaction with a good primary or secondary amino group, or a hydrazide group or semicarbazide group in the compound (C) proceeds smoothly, the crosslinking efficiency is high. Therefore, the crosslinking reaction proceeds even at room temperature, and a cured product such as a crosslinked coating film having good heat resistance, solvent resistance, and water resistance can be obtained. Moreover, the aqueous curable aqueous composition of the present invention can be crosslinked by heating, if necessary.

  The aqueous curable composition of the present invention includes an aqueous paint, an aqueous adhesive, an aqueous adhesive, an aqueous paper processing agent, an aqueous ink, an aqueous hair spray composition, an aqueous cosmetic, an aqueous hair dye, and an aqueous nail polish. , Aqueous photosensitive resin compositions, aqueous polymer modifiers, aqueous ion exchange resin compositions, aqueous carrier resin compositions, aqueous drug sustained release resin compositions, molded article materials, and the like.

  The coating method in the case of using the aqueous curable composition of the present invention as an aqueous coating can be applied by a conventionally known method, for example, air spray, airless spray, brush coating, etc. Is preferably about 1 to 100 μm, more preferably about 5 to 60 μm, based on the cured coating film. In air spray and airless spray, electrostatic application may be performed as necessary.

  In addition, the aqueous curable composition of the present invention can be applied to a substrate having a conductive metal surface by electrodeposition coating. Specific examples of the substrate to be coated include an automobile body and an electric product.

  In this case, when the composition of the present invention is a cationic composition, it is carried out by a known method in which the object to be coated is used as a cathode and a separate anode is provided for electrodeposition. Moreover, when this invention composition is an anionic composition, it can carry out by making the electrode reverse with the case of a cationic composition.

  More specifically, for example, in the case of a cationic composition, the coating object is a cathode and the carbon plate is an anode, the bath temperature is about 20 to 35 ° C., the voltage is about 100 to 400 V, the current density is about 0.01 to 5 A, Electrodeposition can be applied in an energization time of about 1 to 10 minutes. In general, the coating film thickness is preferably about 10 to 40 μm and more preferably about 15 to 30 μm when heat-cured.

  According to the present invention, the following remarkable effects can be obtained.

  The vinyl polymer (A) having a glyoxyramide group of the general formula (I) has a carbonyl group having an α-diketo structure and does not have a carbonyl group having a β-diketo structure. There is no fear of decomposition, it has excellent storage stability, and it is not necessary to use highly toxic and low boiling point acrylonitrile or highly oxidative and highly corrosive concentrated sulfuric acid as a raw material for production, and it is possible to safely carry out production work. The aqueous curable composition of the present invention obtained by the combination with the compound (B) and / or the compound (C) is excellent in reactivity with the compound (B) and / or the compound (C) which is a crosslinking agent. Excellent room temperature curability.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. However, these examples do not limit the scope of the present invention, and may be changed without departing from the scope of the present invention.

  In each example, the heating residue (%), the curability of the composition, and the viscosity stability during storage were determined by the following methods.

Residual heating (%) : A sample of the solution or dispersion was placed on a tin plate, heated and dried in a drying oven at 125 ° C. for 3 hours, the weight of the residue was weighed, and calculated according to the following formula.

Residual heating (%) = (C / D) × 100
However, C represents the weight of the residue, and D represents the weight of the sample of the solution or dispersion.

Curability of the composition : The aqueous curable composition is coated on a glass plate with an applicator so that the cured film thickness is about 40 μm, and left in a thermostatic chamber at 20 ° C. for 7 days to obtain a coating film. Next, the obtained coating film was immersed in propylene glycol monomethyl ether for 24 hours, and then dried at 130 ° C. for 1 hour, and evaluated by propylene glycol monomethyl ether insoluble fraction (wt%).

a: Insoluble fraction (wt%) ≧ 80
b: Insoluble fraction (wt%) <80.

Viscosity stability at the time of storage : After measuring the viscosity at 20 ° C. of the aqueous curable composition, each was stored in a temperature-controlled room at 20 ° C. or 30 ° C. for 1 week under sealed conditions, and then the viscosity at 20 ° C. was measured again. The viscosity before storage was compared. The viscosity stability at the time of storage was evaluated using a viscosity change rate R (%) represented by the following formula. It shows that viscosity stability is so good that R is small. The viscosity (Pa · s) was measured using a “Bismetron viscometer” (manufactured by Shibaura System Co., Ltd.).

Viscosity change rate R (%) = | (viscosity after storage / viscosity before storage) -1 | × 100
However, | (viscosity after storage / viscosity before storage) -1 | indicates the absolute value of ((viscosity after storage / viscosity before storage) -1).

(Evaluation criteria) aa: R ≦ 25
a: 25 <R ≦ 50
b: 50 <R.

Production Example 1
Manufacture of monomer containing glyoxiramide group (1) Preparation of N- (2-hydroxyethyl) -N-methyl-2,2-dimethoxyacetamide Methyl 2,2-dimethoxyacetate in a 2 L flask under nitrogen atmosphere 1,005 g (7.5 mol) and 619 g (8.25 mol, 1.1 eq) of N-methyl-ethanolamine were mixed, and further 14.5 g (0.075 of 28% methanol solution of sodium methoxide). Mol, 1 mol%) was added and stirred. A mild fever was seen. Thereafter, the temperature was raised to 70 ° C., and the methanol produced was decompressed and distilled, and kept at 70 ° C. for 20 hours. Then, it concentrated by the evaporator and the produced | generated methanol was removed. After that, it was distilled to obtain 1,010 g of light yellow transparent liquid N- (2-hydroxyethyl) -N-methyl-2,2-dimethoxyacetamide (about 5.7 mol, yield 76%). .

(2) Production of N- (2- (methacryloyloxy) ethyl) -N-methyl-2,2-dimethoxyacetamide N- (2) obtained in (2) above was added to a 1000 ml flask equipped with a rectifying column. 2-hydroxyethyl) -N-methyl-2,2-dimethoxyacetamide 177 g (1 mol), methyl methacrylate 500 g (5 mol, 5 equivalents) and the following formula (XVII)

And 0.34 g of an N-oxyl compound represented by the formula, 0.34 g of hydroquinone monomethyl ether and 3.4 g of dioctyltin oxide were added and stirred. The temperature was raised to 105 ° C. while blowing air. Thereafter, methanol generated over time was distilled off over 12 hours while maintaining 105 ° C., and the pressure was reduced to 25 mmHg.

  Thereafter, 0.1 g of the N-oxyl compound represented by the formula (XVII), 0.1 g of hydroquinone monomethyl ether and 0.1 g of di-t-butylmethylphenol were added, followed by distillation while blowing air to obtain a pale yellow transparent As a result, 220 g of liquid N- (2- (methacryloyloxy) ethyl) -N-methyl-2,2-dimethoxyacetamide was obtained (yield 90%).

(4) Production of N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide N- (2- (methacryloyloxy) ethyl) -N-methyl-2,2- obtained in (3) above 220 g of dimethoxyacetamide and 664 g of water were mixed and stirred. N- (2- (methacryloyloxy) ethyl) -N-methyl as a raw material was added to a tower packed with 300 g of “Amberlyst 15JWET” (trade name, a strongly acidic cation exchange resin manufactured by Rohm & Haas). The mixture was circulated at 20-30 ° C. with appropriate stirring until the 2,2,2-dimethoxyacetamide almost disappeared. Thereafter, filtration was performed to obtain about 880 g of a solution containing about 20% of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide.

Production Example 2
Production of vinyl polymer (A-1) In a 300 ml flask purged with nitrogen, 28 g of deionized water and “New Coal N-707SN” (trade name, manufactured by Nippon Emulsifier Co., Ltd .; polyoxyethylene phenyl ether sulfate system) 0.08 g of emulsifier was added and heated to 85 ° C. with stirring. To this, 30 g of a 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Production Example 1, 38.9 g of methyl methacrylate, 14 g of styrene, 23.5 g of butyl acrylate, 2 -A mixture of 14.6 g of ethylhexyl acrylate, 30.6 g of deionized water, 6.6 g of "Newcol N-707SN" and 0.3 g of sodium persulfate as a polymerization initiator was added over 4 hours using a syringe. Thereafter, a mixture of 5.2 g of deionized water and 0.1 g of sodium persulfate was similarly added over 30 minutes. Thereafter, after aging for 2 hours and cooling to room temperature, a dispersion of a polymer (A-1) having a glyoxiramide group was obtained. The heating residue of this dispersion was about 52%. The molar concentration of the glyoxiramide group in this polymer was about 0.3 mol / Kg, and its number average molecular weight was about 400,000.

  In order to examine the storage stability of the dispersion obtained above, a decomposition acceleration test was conducted in which a part of the dispersion was held at 80 ° C. for 20 hours. When the solids obtained by drying a part of each dispersion before and after the test were analyzed by proton nuclear magnetic resonance spectroscopy, the spectra were almost the same. Was found to hardly progress. That is, it was confirmed that this vinyl copolymer (A-1) is excellent in storage stability.

Production Example 3
Production of vinyl polymer (A-2) In a 300 ml flask purged with nitrogen, 28 g of deionized water and “New Coal N-707SN” (trade name, manufactured by Nippon Emulsifier Co., Ltd .; polyoxyethylene phenyl ether sulfate system) 0.08 g of emulsifier was added and heated to 85 ° C. with stirring. To this, 30 g of a 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Production Example 1, 37.9 g of methyl methacrylate, 14 g of styrene, 23.5 g of butyl acrylate, 2 -A mixture of 14.6 g of ethylhexyl acrylate, 1 g of acrylic acid, 30.6 g of deionized water, 6.6 g of "Newcol N-707SN" and 0.3 g of sodium persulfate as a polymerization initiator was used for 4 hours using a syringe. Added. Thereafter, a mixture of 5.2 g of deionized water and 0.1 g of sodium persulfate was similarly added over 30 minutes. Thereafter, after aging for 2 hours and cooling to room temperature, a dispersion of a polymer (A-2) having a glyoxiramide group was obtained. The heating residue of this dispersion was about 52%. The molar concentration of glyoxiramide groups in this polymer was about 0.3 mol / Kg, the molar concentration of carboxyl groups was about 0.14 mol / Kg, and the number average molecular weight was about 400,000.

  A decomposition acceleration test was conducted in which a part of the dispersion was held at 80 ° C. for 20 hours. When the solids obtained by drying a part of each dispersion before and after the test were analyzed by proton nuclear magnetic resonance spectroscopy, the spectra were almost the same. Was found to hardly progress. That is, it was confirmed that this vinyl copolymer (A-2) is excellent in storage stability.

Production Example 4
Production of vinyl polymer (A-3) In a 300 ml flask purged with nitrogen, 32 g of deionized water and “New Coal N-707SN” (trade name, manufactured by Nippon Emulsifier Co., Ltd .; polyoxyethylene phenyl ether sulfate system) 0.08 g of emulsifier was added and heated to 85 ° C. with stirring. To this, 30 g of a 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Production Example 1, 36.4 g of methyl methacrylate, 14 g of styrene, 23.5 g of butyl acrylate, 2 -A mixture of 14.6 g of ethylhexyl acrylate, 2.5 g of acrylic acid, 30.6 g of deionized water, 6.6 g of "Newcol N-707SN" and 0.3 g of sodium persulfate as a polymerization initiator was added to the mixture using a syringe. Added over time. Thereafter, a mixture of 5.2 g of deionized water and 0.1 g of sodium persulfate was similarly added over 30 minutes. Thereafter, after aging for 2 hours and cooling to room temperature, a dispersion of a polymer (A-3) having a glyoxiramide group was obtained. The heating residue of this dispersion was about 52%. The molar concentration of glyoxiramide groups in this polymer was about 0.3 mol / Kg, the molar concentration of carboxyl groups was about 0.35 mol / Kg, and the number average molecular weight was about 400,000.

Production Example 5
Production of vinyl polymer (A-4) In a 300 ml flask purged with nitrogen, 28 g of deionized water and “New Coal N-707SN” (trade name, manufactured by Nippon Emulsifier Co., Ltd .; polyoxyethylene phenyl ether sulfate system) 0.08 g of emulsifier was added and heated to 85 ° C. with stirring. To this, 30 g of a 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Production Example 1, 37.9 g of methyl methacrylate, 14 g of styrene, 23.5 g of butyl acrylate, 2 -A mixture of 14.6 g of ethylhexyl acrylate, 1 g of acrylic acid, 30.6 g of deionized water, 6.6 g of "Newcol N-707SN" and 0.3 g of sodium persulfate as a polymerization initiator was used for 4 hours using a syringe. Added. Thereafter, a mixture of 5.2 g of deionized water and 0.1 g of sodium persulfate was similarly added over 30 minutes. Thereafter, after aging for 2 hours, 0.03 g of triethylamine was added to neutralize and cooled to room temperature, whereby a dispersion of a polymer (A-4) having a glyoxiramide group was obtained. The heating residue of this dispersion was about 52%. The molar concentration of glyoxiramide groups in this polymer is about 0.3 mol / Kg, the total molar concentration of carboxyl groups and carboxylate groups is about 0.14 mol / Kg, and its number average molecular weight is about 400,000 Met.

Production Example 6
Production of vinyl polymer (A-5) In a 300 ml flask purged with nitrogen, 32 g of deionized water and “New Coal N-707SN” (trade name, manufactured by Nippon Emulsifier Co., Ltd .; polyoxyethylene phenyl ether sulfate system) 0.08 g of emulsifier was added and heated to 85 ° C. with stirring. To this, 30 g of a 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Preparation Example 1, 38.9 g of methyl methacrylate, 14 g of styrene, 23 g of butyl acrylate, 2-ethylhexyl 14.6 g of acrylate, “Light Ester P-1M” (trade name, manufactured by Kyoeisha Chemical Co., Ltd., main component 2-hydroxyethyl methacrylate and phosphoric acid ester, amount of acid that can be titrated with potassium hydroxide about 8 .6 mol / Kg) 0.5 g, deionized water 30.6 g, “New Coal N-707SN” 6.6 g and polymerization initiator sodium persulfate 0.3 g over 4 hours using a syringe. added. Thereafter, a mixture of 5.2 g of deionized water and 0.1 g of sodium persulfate was similarly added over 30 minutes. Then, after aging for 2 hours, 0.03 g of triethylamine was added to neutralize and cooled to room temperature, whereby a dispersion of a polymer (A-5) having a phosphate group and a glyoxiramide group was obtained. The heating residue of this dispersion was about 52%. The molar concentration of the glyoxiramide group in this polymer was about 0.3 mol / Kg, and its number average molecular weight was about 400,000.

Production Example 7
Production of vinyl polymer (A-6) In a 300 ml flask purged with nitrogen, 32 g of deionized water and “New Coal N-707SN” (trade name, manufactured by Nippon Emulsifier Co., Ltd .; polyoxyethylene phenyl ether sulfate system) 0.08 g of emulsifier was added and heated to 85 ° C. with stirring. To this, 30 g of a 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Preparation Example 1, 38.9 g of methyl methacrylate, 14 g of styrene, 23 g of butyl acrylate, 2-ethylhexyl A mixture of 14.6 g of acrylate, 0.5 g of 2-acrylamido-2-methylsulfonic acid, 30.6 g of deionized water, 6.6 g of “Newcol N-707SN” and 0.3 g of sodium persulfate as a polymerization initiator. It was added over 4 hours using a syringe. Thereafter, a mixture of 5.2 g of deionized water and 0.1 g of sodium persulfate was similarly added over 30 minutes. Thereafter, after aging for 2 hours, 0.03 g of triethylamine was added for neutralization, and the mixture was cooled to room temperature. As a result, a dispersion of a polymer (A-6) having a sulfonate group and a glyoxiramide group was obtained. The heating residue of this dispersion was about 52%. The molar concentration of the glyoxiramide group in this polymer was about 0.3 mol / Kg, and its number average molecular weight was about 400,000.

Production Example 8
Production of vinyl polymer (A-7) In a 300 ml flask purged with nitrogen, 32 g of deionized water and “New Coal N-707SN” (produced by Nippon Emulsifier Co., Ltd .; polyoxyethylene phenyl ether sulfate ester emulsifier) 0.08 g was added and heated to 85 ° C. with stirring. To this, 30 g of an approximately 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Production Example 1, 36.4 g of methyl methacrylate, 14 g of styrene, 23 g of butyl acrylate, 2-ethylhexyl 14.6 g of acrylate, 2.5 g of acrylic acid, 0.5 g of “Blenmer PME-100” (trade name, manufactured by NOF Corporation, methoxypolyethylene glycol monomethacrylate), 30.6 g of deionized water, “New Coal N-707SN” 6 A mixture of 0.6 g and 0.3 g of polymerization initiator sodium persulfate was added using a syringe over 4 hours. Thereafter, a mixture of 5.2 g of deionized water and 0.1 g of sodium persulfate was similarly added over 30 minutes. Thereafter, after aging for 2 hours and cooling to room temperature, a dispersion of a polymer (A-7) having a carboxyl group and a polyoxyethylene group and having a glyoxyramide group was obtained. The heating residue of this dispersion was about 51%. The molar concentration of glyoxiramide groups in this polymer was about 0.3 mol / Kg, the molar concentration of carboxyl groups was about 0.35 mol / Kg, and the number average molecular weight was about 400,000.

Reference example 1
Production of polymer having acetoacetoxy group (E-1) Acetoacetoxyethyl instead of 30 g of about 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Production Example 1 A polymer (E-1) dispersion having an acetoacetoxy group was obtained in the same manner as in Production Example 2, except that 9 g of methacrylate (manufactured by Eastman) and 21 g of deionized water were used. The heating residue of this dispersion was about 50%. The number average molecular weight of this polymer was about 400,000.
In order to examine the storage stability of the dispersion obtained above, a decomposition acceleration test was performed in which the dispersion was held at 80 ° C. for 20 hours. For each of the dispersions before and after the test, a solid content obtained by partially drying under reduced pressure was analyzed by proton nuclear magnetic resonance spectroscopy. The amount of acetoacetoxy groups after the test was higher than that before the test. It decreased by about 25%. Therefore, since the acetoacetoxy group was decomposed by the accelerated test, it was confirmed that this polymer was inferior in storage stability.

Reference example 2
Production of polymer (F-1) having 1,1-dimethyl-3-oxobutyl group (for comparison)
Instead of 30 g of an approximately 20% solution of crude N- (2- (methacryloyloxy) ethyl) -N-methyl-glyoxiramide obtained in Preparation Example 1, 9 g of N- (1,1-dimethyl-3-oxobutyl) acrylamide and A polymer (F-1) dispersion having a 1,1-dimethyl-3-oxobutyl group was obtained in the same manner as in Production Example 2, except that 21 g of ionic water was used. The heating residue of this dispersion was about 52%. The concentration of 1,1-dimethyl-3-oxobutyl group in this polymer was about 0.38 mol / Kg.

  In order to examine the storage stability of the dispersion obtained above, a decomposition acceleration test was performed in which the dispersion was held at 80 ° C. for 20 hours. For each of the dispersions before and after the test, the solid content obtained by partially drying under reduced pressure was analyzed by proton nuclear magnetic resonance spectroscopy. The spectrum of the dispersion after the test was the same as before the test. Met.

Preparation of aqueous curable composition Each component was mixed by the mixing | blending shown in following Table 1, and the aqueous curable composition of Examples 1-11 and Comparative Examples 1-2 was prepared by stirring with a disper.

  In Table 1, the film forming aid is 2,2,4-trimethyl-1,3-pentanediol mono (2-methylpropanoate).

  The compounding quantity of Table 1 is a weight part. (A), (B), (C), the compounding quantity of each component of (F) is a weight part of solid content conversion.

  “Ratio 1” is (number of moles of glyoxiramide group) / (total number of moles of primary amino group and secondary amino group which may be partially or completely neutralized with Bronsted acid). , “Ratio 2” means (total number of moles of carboxyl groups and carboxylate groups in vinyl polymer (A)) / (part or all of compound (B) is Bronsted acid and primary amino group and 2 The “ratio 3” is (number of moles of glyoxiramide group) / (total number of moles of hydrazide group and semicarbazide group). However, the “ratio 1 *” in Comparative Examples 1 and 2 is (number of moles of 1,1-dimethyl-3-oxobutyl group) / (1 part amino which may be partially or completely neutralized with Bronsted acid) Group and the total number of moles of secondary amino group).

Evaluation of aqueous curable composition About each aqueous curable composition obtained in Examples 1-11 and Comparative Examples 1-2, the sclerosis | hardenability of the composition and the viscosity stability at the time of storage were evaluated. The results are shown in Table 2.

Claims (16)

(A) General formula (I)

[Wherein, R ¹ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms. And a vinyl polymer having a glyoxyramide group represented by:
(B) a compound having a primary amino group and / or a secondary amino group, which may be partially or completely neutralized with a Bronsted acid, and / or
(C) The aqueous curable composition containing the compound which has a hydrazide group and / or a semicarbazide group. The vinyl polymer (A) is
(1) General formula (II)

[Wherein, X ¹ , X ² and X ³ independently represent an oxygen atom or a sulfur atom. R ² , R ³ and R ⁴ independently represent a hydrogen atom or an organic group having 1 to 18 carbon atoms. ^Two or three organic groups selected from R ² , R ³ and R ⁴ may be bonded to each other to form a heterocyclic ring. The compound represented by the general formula (III)

[In formula, Y is a C1-C6 linear alkylene group which may have a C1-C6 organic group as a substituent. R ¹ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms. And a compound represented by the general formula (IV)

[Wherein, X ¹ , X ² , Y, R ¹ , R ² and R ³ are the same as described above. A step of obtaining a compound represented by the formula:
(2) A compound of the general formula (IV) is reacted with (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride to give a general formula (V)

[Wherein, X ¹ , X ² , Y, R ¹ , R ² and R ³ are the same as described above. R ⁵ represents a hydrogen atom or a methyl group. And (3) reacting the compound of general formula (V) with water in a dilute acid or in the presence of an acidic compound to give a compound of general formula (VI)

[Wherein, Y, R ¹ and R ⁵ are the same as described above. Through a step of obtaining a monomer having a glyoxyramide group and a (meth) acryloyloxy group represented by
2. The aqueous curable composition according to claim 1, wherein the monomer is obtained by homopolymerization or copolymerization with another vinyl monomer.   The aqueous curable composition according to claim 1, comprising a vinyl polymer (A) obtained by homopolymerization or copolymerization in an organic solvent.   The aqueous curable composition according to claim 1, comprising a vinyl polymer (A) obtained by homopolymerization or copolymerization in water in an emulsified state.   The aqueous curable composition according to claim 1, wherein the vinyl polymer (A) further has at least one anionic group selected from the group consisting of a carboxylate group, a phosphate group and a sulfonate group.   The aqueous polymer according to claim 1, wherein the vinyl polymer (A) further has at least one nonionic hydrophilic group selected from the group consisting of a polyoxyethylene group, a polyoxypropylene group and a polyoxyethylene polyoxypropylene group. Curable composition.   The aqueous solution according to claim 1, wherein the compound (B) is at least one compound selected from the group consisting of ammonia, (polyamino) alkanes, (polyamino) polyether compounds, poly (ethyleneimine), and poly (aminoalkene). Curable composition.   2. The aqueous solution according to claim 1, wherein the compound (B) is produced using a compound having two or more glycidyl groups in one molecule and an amine compound and / or a ketimine compound of an amine compound as a raw material. Curable composition.   The compound (B) and / or the compound (C) further has at least one nonionic hydrophilic group selected from the group consisting of a polyoxyethylene group, a polyoxypropylene group and a polyoxyethylene polyoxypropylene group. The water-based curable composition described in 1.   The aqueous curable composition according to claim 1, wherein the molar concentration of the glyoxyramide group in the vinyl polymer (A) is 0.02 to 6 mol / Kg.   The total molar concentration of the primary amino group and secondary amino group which may be partially or completely neutralized with Bronsted acid in the compound (B) is 0.02 to 35 mol / Kg. The aqueous curable composition as described.   The aqueous curable composition according to claim 1, wherein the total molar concentration of the hydrazide group and the semicarbazide group in the compound (C) is 0.02 to 12 mol / Kg.   Even if the blending ratio of the vinyl polymer (A) and the compound (B) is neutralized with a Bronsted acid in part or all of the glyoxiramide group in the vinyl polymer (A) and the compound (B). The sum of good primary amino groups and secondary amino groups is (number of moles of glyoxiramide groups) / (total of primary amino groups and secondary amino groups which may be partially or completely neutralized with Bronsted acid) The aqueous curable composition according to claim 1, wherein the number of moles is from 0.1 to 10.   The blending ratio of the vinyl polymer (A) and the compound (C) is such that the sum of the glyoxiramide group in the vinyl polymer (A) and the hydrazide group and semicarbazide group in the compound (C) is the number of moles of glyoxiramide group. The aqueous curable composition according to claim 1, wherein the ratio is such that the total number of moles of hydrazide group and semicarbazide group is 0.1 to 10.   The vinyl polymer (A) may further have a carboxyl group and / or a carboxylate group, and the total molar concentration of the carboxyl group and the carboxylate group in the vinyl polymer (A) is 0.02 to 0.02. The aqueous curable composition according to claim 1, which is 2 mol / Kg. The vinyl polymer (A) may further have a carboxyl group and / or a carboxylate group, and (total number of moles of carboxyl group and carboxylate group in the vinyl polymer (A)) / (compound The total number of moles of primary amino group and secondary amino group, which may be partially or completely neutralized with Bronsted acid in (B), is 0.05 to 10. Aqueous curable composition.