JP2008150292A - Alpha-oxoamide group-containing compound, method for producing the same and polymer thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbonyl group-containing compound extremely high in storage stability, and to provide a polymer using the compound. <P>SOLUTION: The compound contains an (α-oxoamidoalkoxy)carbonylamino group represented by formula (I) (wherein Y a 1 to 6C straight chain alkylene or the 1 to 6C straight chain alkylene whose hydrogen atoms are partially or wholly substituted with one or more 1 to 6C substituents; R<SP>1</SP>is a 1 to 16C substituent; and R<SP>2</SP>is H or a 1 to 8C substituent) in the molecule, and the polymer is obtained by polymerizing the (meth)acryloyl group-having compound (I). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an α-oxoamide group-containing compound, and is useful as a raw material for plastics, paints, pressure-sensitive adhesives, adhesives, paper processing agents, inks, and the like.

  A compound introduced with a carbonyl group is combined with a resin or a crosslinking agent having a group that crosslinks the carbonyl group, as described in, for example, Patent Document 1, Non-Patent Document 1, and Non-Patent Document 2. It is possible to change the characteristics in various ways, which is industrially useful.

  As a typical method for introducing a carbonyl group into a compound, a method in which a polyol and t-butyl acetoacetate are mixed and heated to distill off t-butanol, or a method in which acetoacetoxyethyl methacrylate is copolymerized is known. . By these techniques, the carbonyl group is introduced into the compound in the form of an acetoacetoxy group. However, as described in Non-Patent Document 3, for example, a compound having an acetoacetoxy group decomposes over time in water by reverse Claisen condensation of acetoacetoxy group, that is, reverse reaction of Claisen condensation. Therefore, there is a problem that storage stability is poor. The reason why the acetoacetoxy group undergoes reverse reaction of Claisen condensation is that two carbonyl groups in the acetoacetoxy group have a β-ketoester type structure, that is, a β-diketo type structure, and one carbonyl group is an ester carbonyl group. It is thought that it is a group. That is, one method for preventing decomposition due to reverse Claisen condensation is to eliminate the β-diketo structure in the compound. For these reasons, a compound having a carbonyl group introduced in a form other than the β-diketo type has been demanded.

Japanese Patent Laid-Open No. 7-113063 Prog. Org. Coat. , 29, 175 (1996) Prog. Org. Coat. , 27, 73 (1996) J. et al. Coat. Technol. , 70 (881), 57 (1998)

  An object of the present invention is to provide a carbonyl group-containing compound having extremely excellent storage stability, and to provide a polymer using the compound.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific compound having a (α-oxoamidoalkoxy) carbonylamino group as a basic skeleton can solve the above problems, and It came to be completed.

  Since the compound of the present invention does not have a β-diketo type acetoacetoxy group, there is no fear of decomposition due to reverse Claisen condensation. This is because the compound has an α-oxoamide group instead of an acetoacetoxy group, but the α-oxoamide group has an α-diketo structure in which reverse Claisen condensation is impossible in principle. is there.

  Thus, the present invention provides the following formula (I) in the molecule:

[Wherein Y is a linear alkylene group having 1 to 6 carbon atoms, or a part or all of hydrogen of the alkylene group is substituted with a substituent having 1 to 6 carbon atoms, and R ¹ is carbon number. 1 to 16 substituents, R ² represents a hydrogen atom or a C 1-8 substituent. ]
And a compound having a (α-oxoamidoalkoxy) carbonylamino group represented by the formula:

The present invention also provides:
Following formula (II)

[Wherein, R ¹ represents a substituent having ¹ to 16 carbon atoms, and R ³ represents a hydrogen atom or a substituent having 1 to 18 carbon atoms. ]
And the following formula (III) obtained by reacting a compound represented by the formula: and at least one compound selected from the group consisting of alcohol, thiol, acetal and orthoester

[Wherein, X ¹ , X ² and X ³ are the same or different and are an oxygen atom or a sulfur atom, R ⁴ and R ⁵ are the same or different and each have a C 1-18 substituent, R ⁶ is A hydrogen atom or a substituent having 1 to 18 carbon atoms, and two or more substituents selected from R ⁴ , R ⁵ and R ⁶ are bonded to each other to form two substituents selected from X ¹ , X ² and X ³ A heterocycle having the above as a hetero atom may be formed, and R ¹ has the same meaning as described above. ]
A compound represented by the following formula (IV)

[Wherein Y is a linear alkylene group having 1 to 6 carbon atoms, or a part or all of hydrogen of the alkylene group is substituted with a substituent having 1 to 6 carbon atoms, and R ² is a hydrogen atom. Or a C1-C8 substituent is shown. ]
The following formula (V) obtained by reacting with the compound represented by

[Wherein the symbols are as defined above. ]
The compound represented by the following formula (VI) is obtained by reacting with an isocyanate group-containing compound.

[Wherein the symbols are as defined above. ]
And a compound having an (α-oxoamidoalkoxy) carbonylamino group, which is reacted with water in a dilute acid or in the presence of an acidic compound.

  The present invention also relates to a polymer having an (α-oxoamidoalkoxy) carbonylamino group.

  The carbonyl group-containing compound of the present invention has an (α-oxoamidoalkoxy) carbonylamino group as a basic skeleton, that is, has an α-diketo type structure, and has a β-diketo type acetoacetoxy group. Since there is no risk of decomposition due to reverse Claisen condensation because it does not have, it has excellent storage stability. In addition, among the carbonyl group-containing compounds, a compound having an (α-oxoamidoalkoxy) carbonylamino group and a (meth) acryloyloxy group may be obtained by polymerizing alone or with another vinyl monomer. A polymer having an (alkoxy) carbonylamino group can be synthesized, and this polymer is also excellent in storage stability.

  The carbonyl group-containing compound of the present invention can be used as a raw material for synthesizing a resin as described above, or as a base resin, a crosslinking agent, etc. By combining it with a crosslinking agent, it is possible to change its properties in various ways.

  Therefore, the carbonyl group-containing compound of the present invention is a plastic, paint, adhesive, adhesive, paper processing agent, ink, hair spray resin, cosmetic, hair dye, beauty nail material, photosensitive resin, polymer modification. It is extremely useful for applications such as a quality agent, an ion exchange resin, a carrier resin, and a drug sustained release resin.

  The compound containing an (α-oxoamidoalkoxy) carbonylamino group of the present invention is a compound containing an (α-oxoamidoalkoxy) carbonylamino group represented by the following formula (I).

In the formula, Y is a linear alkylene group having 1 to 6 carbon atoms, or a part or all of hydrogen of the alkylene group is substituted with a substituent having 1 to 6 carbon atoms, and R ¹ is ¹ carbon atom. to 16 substituents, ^{R 2} denotes a hydrogen atom or a substituent having 1 to 8 carbon atoms. When the number of carbon atoms in R ¹ is 17 or more, the time required for producing the compound of the present invention may increase significantly.

  The method for producing the compound containing the (α-oxoamidoalkoxy) carbonylamino group represented by the above formula (I) of the present invention is not particularly limited, but for example, the following production method is simple. It is preferable.

Process 1 : The following formula (II)

[Wherein, R ¹ represents a substituent having ¹ to 16 carbon atoms, and R ³ represents a hydrogen atom or a substituent having 1 to 18 carbon atoms. ]
Is reacted with at least one compound selected from the group consisting of alcohol, thiol, acetal and orthoester. The resulting compound is represented by the following formula (III).

[Wherein, X ¹ , X ² and X ³ are the same or different and are an oxygen atom or a sulfur atom, R ⁴ and R ⁵ are the same or different and each have a C 1-18 substituent, R ⁶ is A hydrogen atom or a substituent having 1 to 18 carbon atoms, and two or more substituents selected from R ⁴ , R ⁵ and R ⁶ are bonded to each other to form two substituents selected from X ¹ , X ² and X ³ A heterocycle having the above as a hetero atom may be formed, and R ¹ has the same meaning as described above. ]
Step 2 : The obtained compound represented by the above formula (III) is converted into the following formula (IV)

[Wherein Y is a linear alkylene group having 1 to 6 carbon atoms, or a part or all of hydrogen of the alkylene group is substituted with a substituent having 1 to 6 carbon atoms, and R ² is a hydrogen atom. Or a C1-C8 substituent is shown. ]
It is made to react with the compound represented by these. The resulting compound has the following formula (V)

[Wherein the symbols are as defined above. ]
It is represented by

Step 3 : By reacting the obtained compound represented by the above formula (V) with an isocyanate group-containing compound, the following formula (VI)

[Wherein the symbols are as defined above. ]
The compound containing the organic group represented by these is obtained.

Step 4 : The obtained compound containing an organic group represented by the above formula (VI) is reacted with water in a dilute acid or in the presence of an acidic compound, thereby being represented by the formula (I) (α Compounds of the invention containing -oxoamidoalkoxy) carbonylamino groups can be obtained.

In the compound represented by formula (II) used in step 1 of the above production method, R ¹ is a substituent having ¹ to 16 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl and alkyl groups of their isomeric structures; examples thereof include organic groups containing 1 to 16 carbon atoms such as methoxymethyl and ethoxymethyl. Particularly preferred are industrially available methyl groups. When the carbon number of R ¹ is 17 or more, compatibility with other polymers tends to decrease when the compound is applied to the polymer. R ³ is a hydrogen atom or a substituent having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and their isomeric alkyl groups; organic groups containing oxygen atoms such as butoxyethyl, methoxypropyl, propoxypropyl, etc. are mentioned. Alternatively, a substituent having 1 to 8 carbon atoms is preferable, and a hydrogen atom or a substituent having 1 to 4 carbon atoms is more preferable. When the number of carbon atoms is 19 or more, the time for producing the compound represented by the formula (III) greatly increases and the productivity tends to decrease.

  The alcohol to be reacted with the compound represented by formula (II) in Step 1 is preferably a hydroxyl group-containing compound having 1 to 18 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol. , Nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol and monools of these isomers; propylene glycol monomethyl ether, propylene glycol monopropyl ether , Ether group-containing monools such as ethylene glycol monobutyl ether; ethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-1 Diols such as 3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-1,3-hexanediol; triols such as glycerin, trimethylolethane, trimethylolpropane, and trimethyloloctane And the like. These can be used alone or in combination.

  The thiol to be reacted with the compound represented by formula (II) in Step 1 is preferably a mercapto group-containing compound having 1 to 18 carbon atoms, such as methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, Cyclohexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanthiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol and monothiols of these isomers; Examples include dithiols such as 1,2-ethanedithiol and 1,3-propanedithiol. These can be used alone or in combination.

  As the acetal to be reacted with the compound represented by formula (II) in Step 1, a compound having a structure 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. The ketone used here is not particularly limited, but is preferably a ketone having 3 to 9 carbon atoms, and examples thereof include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, cyclohexanone, and isophorone. Examples of acetals include 2,2-dimethoxypropane, 2,2-diethoxypropane, 2,2-dibutoxypropane, 2,2-dimethoxybutane, 2,2-diethoxybutane, 2,2-dibutoxy Acyclic acetals such as butane, 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-di Xanthine, 2,2-dimethyl-4-methyl-1,3-dioxane, 2-ethyl-2-methyl-1,3-dioxane, 2-ethyl-2-methyl-4-methyl-1,3-dioxane, Examples thereof include cyclic acetals such as 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 particularly preferable because it is easily available industrially. These can be used alone or in combination.

  The orthoester to be reacted with the compound represented by the formula (II) in Step 1 is not particularly limited, but preferably has 4 to 14 carbon atoms because of its availability, for example, trimethyl orthoformate, ortho Examples include triethyl formate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triisopropyl orthoacetate, tributyl orthoacetate, and among these, trimethyl orthoformate and triethyl orthoformate are inexpensive. Trimethyl orthoacetate and triethyl orthoacetate are particularly preferred. These can be used alone or in combination.

  Although the total amount of the compound selected from the group consisting of alcohol, thiol, acetal and orthoester used in Step 1 is not particularly limited, it is preferably 1 to 10 moles relative to the compound represented by Formula (II). Equivalent, more preferably 1.05 to 5 molar equivalent.

  The reaction in Step 1 is usually performed for several tens of minutes to several tens of hours by mixing the compound represented by the formula (II) and at least one compound selected from the group consisting of alcohol, thiol, acetal and orthoester. Do it. This reaction may be performed in an atmosphere of an inert gas such as nitrogen in order to prevent coloring of the product. If necessary, heat, pressurize, add a small amount of acid catalyst, use a solvent, remove water, ketone, ester, alcohol, thiol, etc. generated in the system out of the system Then, the reaction may be promoted. The heating is usually preferably 30 to 200 ° C. However, if the temperature is too low, the reaction promoting effect is small, and if the temperature is too high, the product is likely to be colored.

  The acid catalyst is not particularly limited. For example, inorganic Bronsted 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 Acid 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 tricarboxylate Rate, 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 compound Antimony compounds, metal triflates, metal tetrafluoroborate salt, Lewis acids such as metal acetylacetonate salts; clay, activated clay, acid clay, silica, alumina, zeolites, and the like solid acid catalysts such as cation exchange resins. 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 Amberlyst 15JWET, Amberlyst 15DRY, Amberlyst 16WET, Amberlyst 31WET (manufactured by Rohm & Haas), RCP-160M, RCP-150H, RCP-170H, PK-216 (Above, manufactured by Mitsubishi Chemical Corporation), Dowex 50W (manufactured by Dow Chemical Co., Ltd.) 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, 0.01 to 10 with respect to the compound represented by formula (II). Mole% is preferable, and in the case of solid acid catalysts, 0.1 to 500% by weight is preferable with respect to the compound represented by the formula (II). Solid acid catalysts can be separated by filtration after the reaction.

  Moreover, a well-known organic solvent can be used as a solvent. The amount of the solvent to be used is not particularly limited, but if it is too much, the economical efficiency is lowered, so that it is preferably 10 times or less with respect to the weight of the compound represented by the formula (II). Removal of water, ketones, esters, alcohols, thiols, etc. generated in the system outside the system may be performed under pressure, normal pressure, or reduced pressure conditions by heating or blowing a gas such as air or nitrogen as necessary. Can be done.

In the reaction of Step 1, an antioxidant may be added to the system in order to prevent the formation of peroxide. Although it does not specifically limit as antioxidant, For example, Quinone type compounds, such as benzoquinone; Phenolic compounds, such as hydroquinone, hydroquinone monomethyl ether, and di-t-butylmethylphenol; Amines 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. When the antioxidant is added, the total amount of the compound represented by the formula (II) and the compound selected from the group consisting of alcohol, thiol, acetal and orthoester is not particularly limited, but preferably 10 In the compound represented by the formula (III) obtained by the reaction in Step 1, X ¹ , X ² , X ³ , R ⁴ , R ⁵ and R ⁶ are preferably from 10,000 to 10,000 ppm, particularly preferably from 100 to 5,000 ppm. Is subordinately determined by the type of alcohol, thiol, acetal and / or orthoester used in the reaction, and when using the above-mentioned type of alcohol, thiol, acetal and / or orthoester, X ¹ , X ² and ^{X 3} are each oxygen atom or a sulfur atom, respectively ^{R 4} and ^{R 5} substituents having 1 to 18 carbon atoms, ^{R 6} is An atom or a substituent having 1 to 18 carbon ^atoms, R 4, ^{R 5} and the two or more substituents selected from ^{R 6} are bonded to each other ^X 1, ^{X 2} and ^{X 3} of two or more selected May be formed as a heteroatom, and R ¹ is as defined above.

  Examples of the compound represented by the formula (III) include 2,2-dialkoxyalkanoic acid esters, 2-alkyl-2-alkoxycarbonyl-1,3-dioxolanes, 2-alkyl-2-alkoxycarbonyl-1 , 3-dioxanes, 2,2-di (alkylthio) alkanoic acid esters, 2,2-di (alkylthio) thioalkanoic acid esters, 2-alkyl-2-alkoxycarbonyl-1,3-dithiolanes, 2- Alkyl-2-alkoxycarbonyl-1,3-dithianes, 2-alkyl-2- (alkylthio) carbonyl-1,3-dithiolanes, 2-alkyl-2- (alkylthio) carbonyl-1,3-dithianes, etc. Is mentioned.

  According to this production method, the compound represented by the formula (III) 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. Moreover, the purity can be further increased by performing distillation purification, extraction operation or washing with water as necessary.

  When an acid catalyst is used in the reaction of step 1, before or after concentration, distillation purification, extraction operation or washing of the solution containing the compound represented by formula (III), a part or all of the acid catalyst used is It 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, acidic clay, activated clay, alumina, silica, zeolite, ion exchange resin, and basic inorganic compound.

  In step 2, the compound represented by the formula (III) may be reacted with the compound represented by the formula (IV) after increasing the purity, or the solution containing the compound represented by the formula (III) may be completely removed. The compound may be reacted with the compound represented by the formula (IV) without purification. In the latter case, this solution may be appropriately concentrated, extracted, washed and / or filtered as necessary. In the latter case, when an acid catalyst is used in step 1, all or part of the acid catalyst is neutralized with a base in advance before mixing with the compound represented by formula (IV). Alternatively, it may be adsorbed and removed by an adsorbent.

In the compound represented by the formula (IV), R ² is a hydrogen atom or a substituent having 1 to 8 carbon atoms, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and isomers thereof. Alkyl groups having a structure; examples thereof include an organic group having 1 to 8 carbon atoms including an oxygen atom, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable because of easy availability. When the number of carbon atoms is 9 or more, the time for producing the compound represented by formula (V) may increase and productivity may decrease.

  Y is a linear alkylene group having 1 to 6 carbon atoms, or a part or all of hydrogen of the alkylene group substituted with a substituent having 1 to 6 carbon atoms. When the number of carbon atoms of each substituent when substituted is 7 or more, the time for producing the compound represented by the formula (V) may be significantly increased and productivity may be lowered. Examples of the compound represented by the formula (IV) 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-amino-2-propanol derivatives such as 1- (isopropylamino) -2-propanol, 1- (butylamino) -2-propanol, 1- (t-butylamino) -2-propanol; -1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 2-amino-1 2-amino-1-alkanol derivatives such as pentanol and 2-amino-1-hexanol; 1-amino-2-butanol, 1- (methylamino) -2-butanol, 1- (ethylamino) -2- 1-aminobutanol derivatives such as butanol, 1- (isopropylamino) -2-butanol, 1- (butylamino) -2-butanol, 1- (t-butylamino) -2-butanol; 3-amino-1 Ω-amino-1-alkanol derivatives such as -propanol, 4-amino-1-butanol, 6-amino-1-hexanol and the like. Among these, 2-aminoethanol derivatives in which Y is an ethylene group are preferable for shortening the time for producing the compound represented by the formula (V).

  The amount of the compound represented by the formula (IV) to act on the compound represented by the formula (III) is not particularly limited, but is preferably 1 to 3 mol relative to the compound represented by the formula (III). The equivalent, more preferably 1.05 to 1.5 molar equivalent.

  The reaction of the compound represented by the formula (III) and the compound represented by the formula (IV) is performed by mixing them and usually taking several tens of minutes to several tens of hours. This reaction may be performed in an inert gas atmosphere to prevent the product from being colored. At this time, if necessary, the reaction can be promoted by heating, pressurizing, adding a catalyst, using a solvent, or removing alcohol generated in the system out of the system. it can. The heating is usually preferably about 30 to 230 ° 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.

  As the catalyst, both an acid catalyst and a base catalyst can be used, but it is more preferable to use a base catalyst. The base catalyst is not particularly limited. For example, metal hydroxides, metal alkoxides, metal oxides, ammonia, amines, metal carboxylates, metal phenoxides, basic organic onium salts, hydroxide ions or carboxylate ions. An anion exchange resin containing The addition amount of the base catalyst is not particularly limited, but when using a metal hydroxide, metal alkoxide, metal oxide, ammonia, amine, metal carboxylate, metal phenoxide, basic organic onium salt, etc. 0.01-10 mol% is preferable with respect to the compound represented by (III), and 0.1-500 weight% is preferable when using an anion exchange resin. The anion exchange resin can be separated by filtration after the reaction.

  Moreover, although a well-known organic solvent can be used for a solvent, a solvent with comparatively high polarity is more preferable. The amount of the solvent to be used is not particularly limited, but if it is too much, the economy is lowered, and therefore it is preferably 10 times or less with respect to the weight of the compound represented by the formula (III). Removal of the alcohol produced in the system to the outside of the system can be performed under normal pressure or reduced pressure conditions 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 2, an antioxidant may be added to the 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. When an antioxidant is added, it is not particularly limited with respect to the total amount of the compound represented by the formula (III) and the compound represented by the formula (IV), but is preferably 10 to 10,000 ppm, particularly preferably Is 100 to 5,000 ppm.

The compound represented by the formula (V) is obtained by reacting the compound represented by the formula (III) with the compound represented by the formula (IV). X ¹ , X ² , R ¹ , R ² , R ⁴ and R ⁵ in the formula (V) depend on the structure of the compound represented by the formula (III) and the compound represented by the formula (IV) used in the reaction. Dependently determined. Examples of the compound represented by the formula (V) include N- (2-hydroxyalkyl) -2,2-dialkoxyalkanoic acid amide, N-alkyl-N- (2-hydroxyalkyl) -2,2-di Alkoxyalkanoic acid amides, 2-alkyl-2- (2-hydroxyalkyl) aminocarbonyl-1,3-dioxolanes, 2-alkyl-2- (N-alkyl-N- (2-hydroxyalkyl) amino) carbonyl- 1,3-dioxolanes, 2-alkyl-2- (2-hydroxyalkyl) aminocarbonyl-1,3-dioxanes, 2-alkyl-2- (N-alkyl-N- (2-hydroxyalkyl) amino) Carbonyl-1,3-dioxanes, N- (3-hydroxyalkyl) -2,2-dialkoxyalkanoic acid amides, N-alkyl-N- ( 3-hydroxyalkyl) -2,2-dialkoxyalkanoic acid amide, 2-alkyl-2- (3-hydroxyalkyl) aminocarbonyl-1,3-dioxolanes, 2-alkyl-2- (N-alkyl-N) -(3-hydroxyalkyl) amino) carbonyl-1,3-dioxolanes, 2-alkyl-2- (3-hydroxyalkyl) aminocarbonyl-1,3-dioxanes, 2-alkyl-2- (N-alkyl) -N- (3-hydroxyalkyl) amino) carbonyl-1,3-dioxanes, N- (4-hydroxyalkyl) -2,2-dialkoxyalkanoic acid amide, N-alkyl-N- (4-hydroxyalkyl) ) -2,2-dialkoxyalkanoic acid amide, 2-alkyl-2- (4-hydroxyalkyl) aminocarbonyl-1 3-dioxolanes, 2-alkyl-2- (N-alkyl-N- (4-hydroxyalkyl) amino) carbonyl-1,3-dioxolanes, 2-alkyl-2- (4-hydroxyalkyl) aminocarbonyl- 1,3-dioxanes, 2-alkyl-2- (N-alkyl-N- (4-hydroxyalkyl) amino) carbonyl-1,3-dioxanes, N- (5-hydroxyalkyl) -2,2- Dialkoxyalkanoic acid amides, N-alkyl-N- (5-hydroxyalkyl) -2,2-dialkoxyalkanoic acid amides, 2-alkyl-2- (5-hydroxyalkyl) aminocarbonyl-1,3-dioxolanes 2-alkyl-2- (N-alkyl-N- (5-hydroxyalkyl) amino) carbonyl-1,3-dioxolanes 2-alkyl-2- (5-hydroxyalkyl) aminocarbonyl-1,3-dioxanes, 2-alkyl-2- (N-alkyl-N- (5-hydroxyalkyl) amino) carbonyl-1,3-dioxane N- (6-hydroxyalkyl) -2,2-dialkoxyalkanoic acid amide, N-alkyl-N- (6-hydroxyalkyl) -2,2-dialkoxyalkanoic acid amide, 2-alkyl-2- (6-hydroxyalkyl) aminocarbonyl-1,3-dioxolanes, 2-alkyl-2- (N-alkyl-N- (6-hydroxyalkyl) amino) carbonyl-1,3-dioxolanes, 2-alkyl- 2- (6-hydroxyalkyl) aminocarbonyl-1,3-dioxanes, 2-alkyl-2- (N-alkyl-N- (6- Hydroxyalkyl) amino) carbonyl-1,3-dioxanes, N- (2-hydroxyalkyl) -2,2-di (alkylthio) alkanoic acid amides, N-alkyl-N- (2-hydroxyalkyl) -2 , 2-Di (alkylthio) alkanoic acid amides, 2-alkyl-2- (2-hydroxyalkyl) aminocarbonyl-1,3-dithiolanes, 2-alkyl-2- (N-alkyl-N- (2- Hydroxyalkyl) amino) carbonyl-1,3-dithiolanes, 2-alkyl-2- (2-hydroxyalkyl) aminocarbonyl-1,3-dithianes, 2-alkyl-2- (N-alkyl-N- ( 2-hydroxyalkyl) amino) carbonyl-1,3-dithianes, N- (3-hydroxyalkyl) -2,2-di (alkylthio) Lucanamides, N-alkyl-N- (3-hydroxyalkyl) -2,2-di (alkylthio) alkanoic acid amides, 2-alkyl-2- (3-hydroxyalkyl) aminocarbonyl-1,3- Dithiolanes, 2-alkyl-2- (N-alkyl-N- (3-hydroxyalkyl) amino) carbonyl-1,3-dithiolanes, 2-alkyl-2- (3-hydroxyalkyl) aminocarbonyl-1, Examples include 3-dithianes, 2-alkyl-2- (N-alkyl-N- (3-hydroxyalkyl) amino) carbonyl-1,3-dithianes, and the like.

  The compound represented by the formula (V) obtained by the reaction in Step 2 is often obtained in the form of a solution according to this production method. 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 a base catalyst is used in Step 2, before the solution containing the compound represented by formula (V) is concentrated, distilled, purified, recrystallized, extracted, or washed, a part or all of the used base catalyst is removed. It 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.

  In step 3, the compound represented by the formula (V) may be reacted with an isocyanate group-containing compound after increasing its purity, or the solution containing the compound represented by the formula (V) may be completely purified without purification. You may make it react with a group containing compound. In the latter case, this solution may be concentrated, separated, washed and / or filtered as necessary. In the latter case, and when a catalyst is used when the compound represented by the formula (III) and the compound represented by the formula (IV) are reacted, they are mixed with the isocyanate group-containing compound. Before, a part or all of the used catalyst may be neutralized or removed by adsorption with an adsorbent.

The organic group represented by the formula (VI) is a carbamate-derived group obtained by reacting the compound represented by the formula (V) with an isocyanate group-containing compound. X ¹ , X ² , R ¹ , R ² , R ⁴ and R ⁵ in the formula (VI) are dependently determined by the structure of the compound represented by the formula (V) used in the reaction. Examples of the organic group represented by the formula (VI) include (2,2-dialkoxyalkanoic acid amide) alkoxycarbonylamino group, (N-alkyl-2,2-dialkoxyalkanoic acid amide) alkoxycarbonylamino group. , (2-alkyl-2- (1,3-dioxolane) carboxamide) alkoxycarbonylamino group, (N-alkyl-2-alkyl-2- (1,3-dioxolane) carboxamide) alkoxycarbonylamino group, Alkyl-2- (1,3-dioxane) carboxamido) alkoxycarbonylamino group, (N-alkyl-2-alkyl-2- (1,3-dioxane) carboxamido) alkoxycarbonylamino group, (2,2-di ( Alkylthio) alkanoic acid amide) alkoxycarbonylamino group, (N-al) -2,2-di (alkylthio) alkanoic acid amide) alkoxycarbonylamino group, (2-alkyl-2- (1,3-dithiolane) carboxamido) alkoxycarbonylamino group, (N-alkyl-2-alkyl-2) -(1,3-dithiolane) carboxamido) alkoxycarbonylamino group, (2-alkyl-2- (1,3-dithiane) carboxamido) alkoxycarbonylamino group, (N-alkyl-2-alkyl-2- (1, 3-dithian) carboxamide) alkoxycarbonylamino group and the like.

  The isocyanate group-containing compound to be reacted with the compound represented by the formula (V) is a compound having one or more isocyanate groups in the molecule, and is a monofunctional isocyanate compound or a polyfunctional isocyanate compound. Specifically, 1-isocyanate hexane, 1-isocyanate dodecane, cyclohexyl isocyanate, phenyl isocyanate, (meth) acryloyl isocyanate, (2-isocyanatoethyl) (meth) acryloyl isocyanate, m-isopropenyl-α, α'-dimethyl Compounds having both hydroxyl groups and (meth) acryloyloxy groups such as benzyl isocyanate (TMI) and 2-hydroxyethyl (meth) acrylate and 1-isocyanate-3,5,5-trimethyl-3- (isocyanatomethyl) cyclohexane ( Monoisocyanates having 4 to 50 carbon atoms such as adducts of diisocyanate compounds such as IPDI); diphenylmethane-4,4′-diisocyanate (MDI), 1,5-naphthalene diisocyanate, tolylene diene Sosocyanate (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- (isocyanatomethyl) cyclohexane (IPDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), m -Diisocyanates having 4 to 25 carbon atoms such as tetramethylxylylene diisocyanate (TMXDI), diisocyanate norbornane, di (isocyanatemethyl) norbornane; 2-isocyanatoethyl) -2,6-diisocyanate Triisocyanates having 6 to 30 carbon atoms such as nate caproate (LTI); urethane structure-containing polyisocyanate, biuret structure-containing polyisocyanate, isocyanurate structure-containing polyisocyanate, polyfunctional hydroxyl group-containing compound-modified polyisocyanate, allophanate structure-containing polyisocyanate Polyisocyanates such as isocyanate and uretdione structure-containing polyisocyanate having a number average molecular weight of 300 to 1,000,000 and an average isocyanate functional group number of 2 to 5,000 in one molecule; The number average molecular weight obtained by homopolymerizing the group-containing vinyl monomer or copolymerizing with another vinyl monomer is 1,000 to 1,000,000, and the average isocyanate group in one molecule Polyisocyanates having a number of groups of 2 to 5,000; a number average molecular weight derived from one or more selected from the above-mentioned monoisocyanates, diisocyanates, triisocyanates and polyisocyanates is 300 to 1, Polyisocyanates having an average number of isocyanate functional groups in one molecule of 3 to 5,000; one or more selected from the above-mentioned monoisocyanates, diisocyanates, triisocyanates and polyisocyanates; The number average molecular weight derived from a polyfunctional hydroxyl group-containing compound, one or more selected from a hydroxyl group-containing compound and water is 300 to 1,000,000, and the average number of isocyanate functional groups in one molecule is Examples thereof include polyisocyanates having 2 to 5,000.

  In the present invention, the number average molecular weight is a value measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

  The polyfunctional hydroxyl group-containing compound mentioned above is a polyol having a number average molecular weight of 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, hydroxypivalin Acid-neo pliers Glycol ester, dimethylolpropanoic acid, dimethylolbutanoic acid, trimethylolethane, trimethylolpropane, trimethylolbutane, glycerin, pentaerythritol, a compound having two or more hydroxyl groups in one molecule and ethylene oxide, propylene oxide, tetrahydrofuran, A ring-opening adduct of lactone and / or cyclocarbonate, a reaction product of a compound having both an amino group and a hydroxyl group in the molecule and an epoxy group-containing compound, a compound having both an amino group and a hydroxyl group in the molecule, Examples include reaction products with polyisocyanates, hydroxyl group-containing polyester resins, hydroxyl group-containing polyurethane resins, hydroxyl group-containing polycarbonate resins, hydroxyl group-containing vinyl copolymers, and epoxy resins. The resin can be synthesized by a known method.

  The monofunctional hydroxyl group-containing compound is a monool having a number average molecular weight of 32 to 5,000 and one hydroxyl group in one molecule. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexane Alkanols such as hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol; propylene glycol monomethyl ether, propylene glycol monopropyl ether , Ether group-containing monools such as ethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, etc. It is.

  Examples of the isocyanate group-containing vinyl monomer include (meth) acryloyl isocyanate, (2-isocyanatoethyl) (meth) acryloyl isocyanate, m-isopropenyl-α, α'-dimethylbenzyl isocyanate (TMI), hydroxyl group-containing vinyl Examples include adducts of monomers and the above diisocyanates.

  Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, addition products of these hydroxyl group-containing vinyl monomers and lactones, and the like. .

As said other vinyl-type monomer, a well-known thing can be used, Although it does not specifically limit, For example,
(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, C1-C30 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid such as isobornyl (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): Adducts of hydroxyalkyl esters of acrylic acid or methacrylic acid and ε-caprolactone, such as Plaxel FM-3 (manufactured by Daicel Chemical Industries, “Placcel” is a trade name).
(6): Polyalkylene glycol mono (meth) acrylates, 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. An 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): Olefin 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 and propenyl esters of fatty acids having 1 to 20 carbon atoms such as vinyl acetate, vinyl propionate, vinyl caprate, Veova monomer (made by Shell Chemical Co., Ltd., vinyl ester of branched higher fatty acid), isopropenyl acetate, etc. 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, benzyl vinyl ether, and the like.
(13): acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, etc. Carboxyl group-containing unsaturated monomer.
(14): Hydrolyzable alkoxysilyl group-containing unsaturated monomers such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, 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; Nitrogen-containing unsaturated monomers such as 1-vinyl-2-pyrrolidone, 4-vinylpyridine and (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): A polymerizable amine such as allylamine.
(22): Acid anhydride monomers such as maleic anhydride and itaconic anhydride.
And so on.

  In the present invention, (meth) acrylate means acrylate and methacrylate.

  In step 3, the compound represented by the formula (V) and the isocyanate group-containing compound are usually mixed and then reacted at room temperature or under heating conditions. The amount of the isocyanate group-containing compound used is not particularly limited with respect to the compound represented by the formula (V), but the amount of the isocyanate group is 1 to 3 molar equivalents, more preferably 1 to 2 molar equivalents. It is preferable to do this. The heating is usually preferably about 40 to 190 ° C., but if the temperature is too low, the progress of the reaction is slow, and if the temperature is too high, side reactions tend to occur.

  A known organic solvent can be used as the solvent. In this case, the solvent is preferably an aprotic solvent, and particularly preferably an ester, ether, N-alkylamide, ketone or the like. 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 5 times or less with respect to the weight of the compound represented by the formula (V).

  A catalyst may be used to promote the reaction. 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 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 zirconium tetraalkoxide and zirconium tetrahalide; Zinc compounds such as zinc dicarboxylate and zinc halide; Aluminum compounds; Lead compounds; Bismuth compounds; Antimony compounds; Metal acetyl Acetonate compounds; solid acid catalysts such as clay, acidic clay, activated clay, silica, alumina, zeolite, and cation exchange resin are particularly preferred from the viewpoint of reaction rate. The amount of the catalyst to be added is not particularly limited, but is preferably 0.01 to 10 mol% for the catalyst other than the solid acid catalyst with respect to the compound represented by the formula (V), and is preferably about 0.1% for the solid acid catalyst. 1 to 500% by weight is preferred.

  When a catalyst is used in the production of the compound having an organic group represented by formula (VI) in Step 3, part or all of the catalyst used after the production may be neutralized or adsorbed with an adsorbent. It may be removed. 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.

  In Step 4, the reaction between the compound having an organic group represented by the formula (VI) and water can be carried out 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. There is no particular need to increase the acid concentration of these dilute acids, such as 0.01-15% hydrochloric acid, 0.01-20% hydrobromic acid, 0.01-20% dilute nitric acid, 0.01-20% sulfuric acid, etc. Diluted acid is sufficient, and from the viewpoint of safety and ease of handling, 0.05-7% hydrochloric acid, 0.05-10% hydrobromic acid, 0.05-10% dilute nitric acid, 0. More preferred is 05 to 10% sulfuric acid. The amount of the diluted acid to be used is not particularly limited, but is 0.01 to 10 times, more preferably 0.1 to 5 times the weight of the compound having an organic group represented by the formula (VI). If the amount of dilute acid exceeds 10 times, production efficiency decreases.

  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 and trifluoroacetic acid Carboxylic acids such as monochloroacetic 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, cation exchange resin, etc. . 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 among them, an ion exchange resin having a sulfonic acid group or a phosphoric acid group is preferable. Examples of commercially available cation exchange resins include Amberlyst 15JWET, Amberlyst 15DRY, Amberlyst 16WET, Amberlyst 31WET (manufactured by Rohm & Haas), RCP-160M, RCP-150H, RCP-170H, PK-216 (Above, manufactured by Mitsubishi Chemical Corporation), Dowex 50W (manufactured by Dow Chemical Co., Ltd.) 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 about 0.01 to the compound having an organic group represented by formula (VI) 100 mol% is preferable, and in the case of solid acid catalysts, 0.1 to 500 wt% is preferable with respect to the compound having an organic group represented by the formula (VI). In this case, the amount of water coexisting with the acidic compound is not particularly limited, but is 0.0001 to 10 times, more preferably 0.001 times the weight of the compound having an organic group represented by the formula (VI). 001 to 5 times. If the amount of water exceeds 10 times, production efficiency falls. Solid acid catalysts can be separated by filtration after the reaction.

  When the compound having the organic group represented by the formula (VI) and water are allowed to react with the acidic compound, the compound having the organic group represented by the formula (VI) and the acidic compound are mixed in advance, Water may be added later, or the compound having the organic group represented by the formula (VI) and water may be mixed in advance, and the acidic compound may be added later.

  The reaction of the compound having an organic group represented by the formula (VI) in Step 4 with water may be performed in a dilute acid or in the presence of an acidic compound, or may be heated to increase the reaction rate. It may be good or pressurized. 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 it is too high, 10-100 degreeC is especially preferable.

  In this reaction, there may be no solvent other than water, but an organic solvent can be used if necessary. As the organic solvent, known alcohols, ester derivatives, amide derivatives, ether derivatives, hydrocarbon solvents, 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, so that it is preferably 10 times or less with respect to the weight of the compound having an organic group represented by the formula (VI). This reaction may be performed in an atmosphere of an inert gas such as nitrogen in order to prevent coloring of the product.

  The reaction in step 4 can also be performed in a two-phase system. When this reaction is carried out in a two-phase system, an onium salt or the like may be added to increase the reaction rate.

  By reacting a compound having an organic group represented by formula (VI) with water in a dilute acid or in the presence of an acidic compound, the compound has an (α-oxoamidoalkoxy) carbonylamino group represented by formula (I) A compound can be obtained.

  In the production of the compound having an (α-oxoamidoalkoxy) carbonylamino group represented by the formula (I) in Step 4, a part or all of the diluted acid or acidic compound used may be neutralized or adsorbed. It may be removed by adsorption with an agent. 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.

  In addition, water remaining in the system after the reaction, by-product alcohol and thiol can be distilled off under normal pressure or reduced pressure, and at normal temperature or under heating. Further, the solvent used in the reaction may be distilled off during or after the reaction.

  Examples of the compound having an (α-oxoamidoalkoxy) carbonylamino group represented by the formula (I) thus obtained include (2-pylvamidoethoxy) carbonylamino group, (2- (N -Methyl-pylvamide) ethoxy) carbonylamino group, (2- (N-ethyl-pylvamide) ethoxy) carbonylamino group, (2- (N-propyl-pylvamide) ethoxy) carbonylamino group, (2- (N-isopropyl) -Pyruvamide) ethoxy) carbonylamino group, (2- (N-butyl-pylvamide) ethoxy) carbonylamino group, (2- (N-isobutyl-pylvamide) ethoxy) carbonylamino group, (2- (N-sec-butyl) -Pyruvamide) ethoxy) carbonylamino group, (2- (Nt-butyl-pyruvamide) ethoxy) carba Bonylamino group, (2-pyruvamidepropoxy) carbonylamino group, (2-methyl-2- (pyrubamido) propoxy) carbonylamino group, (2-pyruvamidebutoxy) carbonylamino group, (3-pyruvamidepropoxy) ) Carbonylamino group, (4-pyruvamidebutoxy) carbonylamino group, (5-pyruvamidepentoxy) carbonylamino group, (6-pyruvamidehexoxy) carbonylamino group, (1-methyl-2- (Pyruvamide) propoxy) carbonylamino group, (1-ethyl-2- (pylvamide) propoxy) carbonylamino group, (1-methyl-2- (pylvamide) ethoxy) carbonylamino group, (1-methyl-2- (N -Methyl-pylvamide) ethoxy) carbonylamino group, (1-methyl-2- (N-ethyl-pyr) (Mido) ethoxy) carbonylamino group, (1-methyl-2- (N-propyl-pylvamide) ethoxy) carbonylamino group, (1-methyl-2- (N-isopropyl-pylvamide) ethoxy) carbonylamino group, (1 -Methyl-2- (N-butyl-pylvamide) ethoxy) carbonylamino group, (1-methyl-2- (N-isobutyl-pylvamide) ethoxy) carbonylamino group, (1-methyl-2- (N-sec- (Butyl-pylvamide) ethoxy) carbonylamino group, (1-methyl-2- (Nt-butyl-pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (pylvamide) ethoxy) carbonylamino group, (1 -Ethyl-2- (N-methyl-pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (N-ethyl) Til-pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (N-propyl-pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (N-isopropyl-pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (N-butyl-pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (N-isobutyl-pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (N- sec-butyl-pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (Nt-butyl-pylvamide) ethoxy) carbonylamino group, (3- (N-methyl-pylvamide) propoxy) carbonylamino group, (3- (N-ethyl-pylvamide) propoxy) carbonylamino group, (3- (N-propyl- Rubamide) propoxy) carbonylamino group, (3- (N-isopropyl-pylvamide) propoxy) carbonylamino group, (3- (N-butyl-pylvamide) propoxy) carbonylamino group, (3- (N-isobutyl-pylvamide) Examples thereof include compounds having a propoxy) carbonylamino group, (3- (N-sec-butyl-pyruvamide) propoxy) carbonylamino group, (3- (Nt-butyl-pylvamide) propoxy) carbonylamino group, and the like.

Among these, (2-pylvamide ethoxy) carbonylamino group, (2- (N-methyl-pylvamide) ethoxy) carbonylamino group, (2- (N-ethyl-pylvamide) ethoxy) carbonylamino group, (2 -(N-propyl-pylvamide) ethoxy) carbonylamino group, (2- (N-isopropyl-pylvamide) ethoxy) carbonylamino group, (2- (N-butyl-pylvamide) ethoxy) carbonylamino group, (2- ( N-isobutyl-pylvamide) ethoxy) carbonylamino group, (2- (N-sec-butyl-pylvamide) ethoxy) carbonylamino group, (2- (Nt-butyl-pylvamide) ethoxy) carbonylamino group, (2 -Methyl-2- (pyruvamide) propoxy) carbonylamino group, (3-pyruvamide pro Compounds having a (xy) carbonylamino group, (1-methyl-2- (pylvamide) ethoxy) carbonylamino group, (1-ethyl-2- (pylvamide) ethoxy) carbonylamino group, etc. are readily available as raw materials. In addition, (2-pylvamidoethoxy) carbonylamino group, (2- (N-methyl), wherein R ¹ is a methyl group, R ² is a hydrogen atom or a methyl group, and Y is an ethylene group A compound having a -pyruvamide) ethoxy) carbonylamino group or the like is particularly preferable because the raw material is inexpensive.

  When a compound having both an isocyanate group and a (meth) acryloyloxy group is used as the isocyanate group-containing compound to be reacted with the compound represented by the formula (V), an (α-oxoamidoalkoxy) carbonylamino group in Step 4 is used. And a compound having both (meth) acryloyloxy groups.

  Further, as the isocyanate group-containing compound to be reacted with the compound represented by the formula (V), a compound having two or more isocyanate groups is used, and after the reaction with the compound represented by the formula (V), the remaining In the same manner, by reacting a hydroxyl group-containing vinyl monomer with the isocyanate group of (2) or reacting a compound having two or more isocyanate groups with the compound represented by formula (V) and the hydroxyl group-containing vinyl monomer at the same time ( A compound having both an [alpha] -oxoamidoalkoxy) carbonylamino group and a (meth) acryloyloxy group is obtained.

  The addition reaction can be performed at room temperature or under heating conditions. The amount of the polyfunctional isocyanate compound to be used is not particularly limited with respect to the total amount of the hydroxyl group derived from the hydroxyl group derived from the hydroxyl group-containing vinyl monomer and the compound represented by the above (V), although the amount of the isocyanate group is 0.5. It is preferable to make it to be -1.5 equivalent, preferably 0.8-1.2 equivalent.

  The heating is usually preferably about 40 to 150 ° C. However, if the temperature is too low, the progress of the reaction is slow, and if the temperature is too high, the polymerization reaction tends to occur.

  In order to prevent the polymerization from proceeding during the addition reaction, a polymerization inhibitor may be added to the system, or oxygen or air may be blown into the system. Examples of the polymerization inhibitor include quinone compounds such as benzoquinone; phenol compounds such as hydroquinone, hydroquinone monomethyl ether, and di-t-butylmethylphenol; amine compounds such as phenylenediamine compounds and phenothiazine; N-oxyl compounds; One or more selected from nitroso compounds, nitrogen oxides and the like can be used. The addition amount in the case of adding a polymerization inhibitor is not particularly limited with respect to the total amount of the hydroxyl group-containing vinyl monomer and the aforementioned diisocyanates, but is preferably 10 to 10,000 ppm, particularly preferably 100 to 5,000 ppm. It is.

  A known organic solvent can be used as the solvent. In this case, the solvent is preferably an aprotic solvent, and particularly preferably an ester, ether, N-alkylamide, ketone or the like. The amount of the solvent to be used is not particularly limited, but if it is too much, the economic efficiency is lowered, so that it is preferably 5 times or less based on the total weight of the hydroxyl group-containing vinyl monomer and the aforementioned diisocyanates.

  A catalyst may be used to promote the reaction. 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 catalyst performance. The Lewis acid catalyst used here is not particularly limited, and examples thereof include titanium compounds such as titanium tetraalkoxide and titanium tetrahalide; dialkyltin oxide, dialkyltin dicarboxylate, monoalkyltin tricarboxylate, and tin dicarboxylate. Zinc compounds such as zirconium tetraalkoxide and zirconium tetrahalide; Zinc compounds such as zinc dicarboxylate and zinc halide; Aluminum compounds; Lead compounds; Bismuth compounds; Antimony compounds; Metal acetyl Acetonate compounds; solid acid catalysts such as clay, acidic clay, activated clay, silica, alumina, zeolite, and cation exchange resin are particularly preferred from the viewpoint of reaction rate. The addition amount of the catalyst is not particularly limited, but is preferably 0.01 to 10 mol% for the catalyst other than the solid acid catalyst with respect to the hydroxyl group-containing vinyl monomer, and 0.1 to 500 weight for the solid acid catalyst. % Is preferred.

  When a catalyst is used in the addition reaction, part or all of the catalyst used after production 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.

  A compound having both the (α-oxoamidoalkoxy) carbonylamino group and the (meth) acryloyloxy group is polymerized alone or copolymerized with another vinyl monomer to give (α-oxoamidoalkoxy) A polymer having a carbonylamino group can be synthesized.

  The polymer is a compound having both an organic group represented by the formula (VI) and a (meth) acryloyloxy group, and this compound is polymerized alone or copolymerized with another vinyl monomer. The polymer having the organic group represented by the formula (VI) is synthesized first, and then reacted with water in a dilute acid or in the presence of an acidic compound to produce (α- Polymers containing oxoamidoalkoxy) carbonylamino groups can also be synthesized. Water remaining in the system after reaction and by-product alcohol and thiol can be distilled off under normal pressure or reduced pressure, and at normal temperature or under heating. Further, the solvent used in the reaction may be distilled off during or after the reaction.

  As a polymerization method for obtaining a polymer, a known method can be used. For example, radical polymerization, coordination polymerization, group transfer polymerization (functional group transfer polymerization), ATRP polymerization (atom transfer polymerization), chain transfer polymerization, etc. The method 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. The number average molecular weight of the vinyl polymer obtained by polymerization is not particularly limited, but is preferably about 1,000 to 1,000,000.

  The present invention will be specifically described below with reference to examples, but these examples are merely illustrative and do not limit the present invention, and may be changed within the scope of the present invention. .

  The purity (%) of the product, the heating residue (%), and the polymerization rate (%) of the monomer were determined by the following methods.

Product purity (%) : calculated from the peak area of gas chromatography by the following formula.
Purity (%) = (A / B) × 100
However, A represents the peak area of the target product, and B represents the total area of all peaks.

Heat residue of solution (%) : 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 by 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.

Monomer polymerization rate (%) : calculated by the following formula.
Polymerization rate (%) = heat residue (%) / ((total weight of monomer + weight of radical generator) / (weight of solvent + total weight of monomer + weight of radical generator))
The abbreviations used in the examples mean the following.
m: multiplet s: singlet b: broad
Production Example 1 of Compound Having (α-Oxoamidoalkoxy) carbonylamino Group
(1) Production of methyl 2,2-dimethoxypropionate 841 g (8.25 mol) of methyl pyruvate, 1,060 g of trimethyl orthoformate (10 mol, 1.2 mol equivalent), methanol in a 5 L flask under nitrogen conditions 1,060 g and paratoluenesulfonic acid monohydrate 7.84 g (0.041 mol, 0.5 mol%) were added and stirred. A mild fever was observed. Then, it hold | maintained at the temperature of 55-58 degreeC for 10 hours. Thereafter, about 8 g of 28% methanol solution of sodium methoxide was added for neutralization. Then, it concentrated by the evaporator and removed most of excess trimethyl orthoformate, methanol, and the produced | generated methyl formate. Thereafter, distillation was performed to obtain 1,110 g (7.5 mol, yield 91%, purity 98%) of methyl 2,2-dimethoxypropionate as a colorless transparent liquid (boiling point: 80 ° C./40 mmHg). The above reaction can be represented by the following formula:

When the obtained liquid was analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR analysis (CDCl ₃ )), δ: 3.82 (3H, s), 3.29 (6H, s) and 1.53 A peak was observed at (3H, s). Further, when analysis by infrared spectroscopy (IR analysis) was performed, ν: 3632, 2999, 2953, 2837, 1749, 1455, 1437, 1373, 1293, 1216, 1192, 1144, 1046, 976, 892, 801, Absorption was observed at 761 and 676 cm ⁻¹ .

(2) Production of N- (2-hydroxyethyl) -N-methyl-2,2-dimethoxypropionic acid amide In a 2 L flask under nitrogen conditions, methyl 2,2-dimethoxypropionate obtained in (1) above 1,110 g (7.5 mol) and 619 g (8.25 mol, 1.1 equivalents) of N-methyl-ethanolamine were mixed, and 14.5 g (0.075 of a 28% methanol solution of sodium methoxide was added thereto. 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, about 5 g of acetic acid was added for neutralization. Then, it concentrated by the evaporator and the produced | generated methanol was removed. After that, distillation was performed to obtain 1,146 g (6.0 mol, yield 80%) of N- (2-hydroxyethyl) -N-methyl-2,2-dimethoxypropionic acid amide as a light yellow transparent liquid ( Boiling point: 135 ° C./2 mmHg, purity 96%).

  The above reaction can be represented by the following formula:

When the obtained liquid was analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR analysis (CDCl ₃ )), δ: 3.58-3.84 (4H, m), 2.99-3.32 ( 9H, m), 2.50-2.99 (1H, b) and 1.54-1.56 (3H, m). Further, when analysis by infrared spectroscopy (IR analysis) was performed, ν: 3445, 2945, 2837, 1634, 1498, 1456, 1437, 1404, 1375, 1226, 1149, 1106, 1041, 892, 747 and 655 cm ^−. Absorption was observed in ¹ .

(3) Production of compound having organic group represented by formula (VI) In a 500 ml flask, N- (2-hydroxyethyl) -N-methyl-2,2-dimethoxypropionic acid obtained in (2) above 90.7 g of amide (0.475 mol) and Duranate TPA-100 (manufactured by Asahi Kasei Chemicals Corporation: isocyanurate group-containing polyisocyanate, NCO content 23.1% by weight) 90.9 g (NCO content 0.50 mol) ) And 22.7 g of tetrahydrofuran were mixed and stirred. Further, 0.152 g of dibutyltin dilaurate was added and stirred, and kept at 70 ° C. for 18 hours. Thereafter, 22.7 g of propylene glycol monomethyl ether was added and stirred well, and further maintained at 70 ° C. for 20 hours, corresponding to the organic group represented by the formula (VI) (2- (N-methyl-2,2-dimethoxy). A solution of a compound having a propionic acid amido) ethoxy) carbonylamino group (solid content about 81%) was obtained. In order to analyze this compound, a part of the solution was dried under reduced pressure, and the obtained solid content was analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR analysis (CDCl ₃ )). The following peaks corresponding to N-methyl-2,2-dimethoxypropionic acid amide) ethoxy) carbonylamino group were confirmed. δ: 4.90-5.22 (1H, b), 4.17-4.33 (2H, m), 3.57-3.92 (2H, m), 3.27 (6H, s), 2.99-3.27 (3H, m), 1.50-1.51 (3H, m).

(4) Preparation of compound having organic group represented by formula (I) (2- (N-methyl-2,2-dimethoxypropionic acid amide) ethoxy) carbonyl obtained in (3) above in a 300 ml flask 180 g of a compound having an amino group (solid content: about 81%), 100 g of propylene glycol monomethyl ether, 70 g of water and 0.576 g of paratoluenesulfonic acid monohydrate were added, and the mixture was stirred at 90 ° C. for 4 hours. 0.153 g of triethylamine was added to partially neutralize the solution (solid content) of a compound having (2- (N-methyl-pylvamide) ethoxy) carbonylamino group corresponding to the organic group represented by the formula (I) About 37%). In order to analyze this compound, a part of the solution was dried under reduced pressure, and the obtained solid content was analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR analysis (CDCl ₃ )). The following peaks corresponding to the N-methyl-pylvamide) ethoxy) carbonylamino group were confirmed. δ: 4.80-5.15 (1H, b), 4.14-4.34 (2H, m), 3.55-3.75 (2H, m), 3.02-3.06 (3H) , M), 2.42 (3H, s).

  Next, 100 g of a solution of the compound having a 2- (N-methyl-pyruvamide) ethoxy) carbonylamino group (including about 37 g of solid, about 18 g of water and about 45 g of other organic solvent) is added to 19 g of water. Were mixed so that the solids content and water content were approximately the same, and a heat load of 48 hours was applied at 80 ° C. as an accelerated hydrolysis test. Thereafter, a part of the solution was dried under reduced pressure, and the obtained solid content was analyzed by nuclear magnetic resonance spectroscopy, and the amount of disappearance due to the heat load of (2- (N-methyl-pylvamide) ethoxy) carbonylamino group was determined. When calibrated, the disappearance was less than 3%. That is, it was confirmed that the compound having a (2- (N-methyl-pyruvamide) ethoxy) carbonylamino group is excellent in storage stability.

Comparative Example 1
To a 1 L flask, 134 g (1 mol) of trimethylolpropane, 474 g (3 mol) of t-butyl acetoacetate and 0.391 g of dibutyltin oxide were added, the temperature was raised to 120 ° C., the reaction was continued, and distillation was continued while reducing the pressure. The coming t-butyl alcohol was removed to obtain 386 g of a compound having an acetoacetoxy group. When this compound was analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR analysis (CDCl ₃ )), the following peaks corresponding to the acetoacetoxy group were confirmed. δ: 3.50 (2H, s), 2.27 (3H, s). Most acetoacetoxy groups existed as keto types.

  Next, 37 g of the obtained compound having an acetoacetoxy group, 37 g of water and 45 g of propylene glycol monomethyl ether were mixed so that the solids content and water content were almost the same, and the accelerated hydrolysis test was conducted at 80 ° C. A 48 hour heat load was applied. Thereafter, a part of the solution was dried under reduced pressure, and the obtained solid content was analyzed by nuclear magnetic resonance spectroscopy. When the amount of disappearance due to the heat load of the acetoacetoxy group was calibrated, the amount of disappearance was about 17%. It was. That is, the storage stability of the compound having an acetoacetoxy group was poor.

Example 2
A 300 ml flask was charged with 78 g of 2-isocyanatoethyl methacrylate, 0.17 g of 2,6-di-t-butyl-4-methylphenol and 0.03 g of dibutyltin dilaurate, and stirred at 110 ° C. while blowing air. Then, 96 g of (N- (2-hydroxyethyl) -N-methyl-2,2-dimethoxypropionic acid amide obtained in (2) of Example 1 was added dropwise and maintained at the same temperature for 10 hours. 174 g of ((2- (N-methyl-2,2-dimethoxypropionic acid amide) ethoxy) carbonylamino) ethyl methacrylate was obtained, and 174 g of tetrahydrofuran, 40 g of water and 0.34 g of paratoluenesulfonic acid monohydrate were obtained. And stirred at 80 ° C. for 5 hours, and then 0.1 g of triethylamine was added and partially added. Further, the solvent and water are volatilized and concentrated to have (2- (N-methyl-pylvamide) ethoxy) carbonylamino group and methacryloyloxy group corresponding to the organic group represented by the formula (I). About 150 g of the compound 2-((2- (N-methyl-pyruvamide) ethoxy) carbonylamino) ethyl methacrylate was obtained (purity 97%), which was analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR analysis). (CDCl ₃₎₎ where, (2- (N- methyl - Pirubamido) ethoxy) .Deruta was confirmed following peaks corresponding to carbonyl amino group and a methacryloyloxy group: 6.11 (1H, m), 5.60 (1H, m), 4.78-5.18 (1H, b), 4.12-4.36 (2H, m), 3.54-3.77 (2H, m), 3.00-3 .04 (3 , M), 2.41 (3H, s), 1.95 (3H, s).

  Next, 10 g of the obtained 2-((2- (N-methyl-pyruvamide) ethoxy) carbonylamino) ethyl methacrylate, 10 g of tetrahydrofuran and 5 g of water were mixed, and 80 g as an accelerated hydrolysis test was performed while air was blown into the mixture. A heat load of 24 hours was applied at 0C. Thereafter, a part of the solution was dried under reduced pressure, and the obtained solid content was analyzed by nuclear magnetic resonance spectroscopy, and the amount of disappearance due to the heat load of (2- (N-methyl-pylvamide) ethoxy) carbonylamino group was determined. When calibrated, the disappearance was as small as about 5%. That is, it was confirmed that 2-((2- (N-methyl-pyruvamide) ethoxy) carbonylamino) ethyl methacrylate is excellent in storage stability.

Example 3
A 200 ml flask purged with nitrogen was charged with 30 g of ethylene glycol monobutyl ether as a solvent and heated to 100 ° C. with stirring. While maintaining the same temperature, 10 g of 2-((2- (N-methyl-pylvamide) ethoxy) carbonylamino) ethyl methacrylate obtained in Example 2, 10 g of methyl methacrylate, 2 g of 2-hydroxyethyl acrylate, A mixture of 8 g of 2-ethylhexyl acrylate, 5 g of 2-ethylhexyl methacrylate, 5 g of styrene and 1.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) which is a radical generator is taken for 4 hours using a syringe pump. added. Thereafter, while maintaining the same temperature, a mixture of 30 g of ethylene glycol monobutyl ether and 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added in the same manner over 1 hour. Then, after aging at the same temperature for 1 hour, when cooled to room temperature, a viscous liquid was obtained. Since the heating residue of this liquid was 40.5% and the polymerization rate was calculated to be about 98%, the co-polymerization of 2-((2- (N-methyl-pylvamide) ethoxy) carbonylamino) ethyl methacrylate It was confirmed that the coalescence could be produced. In order to analyze this copolymer, a part of the solution was dried under reduced pressure, and the obtained solid content was analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR analysis (CDCl ₃ )). The following peaks corresponding to-(N-methyl-pylvamide) ethoxy) carbonylamino group were confirmed. δ: 4.80-5.15 (1H, b), 4.14-4.34 (2H, m), 3.55-3.75 (2H, m), 3.02-3.06 (3H) , M), 2.42 (3H, s).

Next, 5 g of water was further mixed with 50 g of the copolymer solution having (2- (N-methyl-pyruvamide) ethoxy) carbonylamino group (including about 20 g of a solid content and about 30 g of an organic solvent, respectively). As an accelerated hydrolysis test, a heat load of 48 hours was applied at 80 ° C. Thereafter, a part of the solution was dried under reduced pressure, and the obtained solid content was analyzed by nuclear magnetic resonance spectroscopy, and the amount of disappearance due to the heat load of (2- (N-methyl-pylvamide) ethoxy) carbonylamino group was determined. When calibrated, the disappearance was less than 3%. That is, it was confirmed that the compound having a (2- (N-methyl-pyruvamide) ethoxy) carbonylamino group is excellent in storage stability.

Claims (10)

In the molecule, the following formula (I)

[Wherein Y is a linear alkylene group having 1 to 6 carbon atoms, or a part or all of hydrogen of the alkylene group is substituted with a substituent having 1 to 6 carbon atoms, and R ¹ is carbon number. 1 to 16 substituents, R ² represents a hydrogen atom or a C 1-8 substituent. ]
A compound having an (α-oxoamidoalkoxy) carbonylamino group represented by:   The compound according to claim 1, wherein Y is an ethylene group or a part or all of hydrogen of the ethylene group is substituted with a substituent having 1 to 6 carbon atoms.   The compound according to claim 1, wherein Y is a propylene group or a part or all of hydrogen of the propylene group is substituted with a substituent having 1 to 6 carbon atoms. The compound according to claim 1 or 2, wherein Y is an ethylene group, R ¹ is a methyl group, and R ² is a hydrogen atom. The compound according to claim 1 or 2, wherein Y is an ethylene group, R ¹ is a methyl group, and R ² is an alkyl group having 1 to 4 carbon atoms. The compound according to claim 1 or 2, wherein Y is an ethylene group, R ¹ is a methyl group, and R ² is a methyl group.   Furthermore, the compound of Claims 1-6 which has a (meth) acryloyloxy group in a molecule | numerator. Following formula (II)

[Wherein, R ¹ represents a substituent having ¹ to 16 carbon atoms, and R ³ represents a hydrogen atom or a substituent having 1 to 18 carbon atoms. ]
And the following formula (III) obtained by reacting a compound represented by the formula: and at least one compound selected from the group consisting of alcohol, thiol, acetal and orthoester

[Wherein, X ¹ , X ² and X ³ are the same or different and are an oxygen atom or a sulfur atom, R ⁴ and R ⁵ are the same or different and each have a C 1-18 substituent, R ⁶ is A hydrogen atom or a substituent having 1 to 18 carbon atoms, and two or more substituents selected from R ⁴ , R ⁵ and R ⁶ are bonded to each other to form two substituents selected from X ¹ , X ² and X ³ A heterocycle having the above as a hetero atom may be formed, and R ¹ has the same meaning as described above. ]
A compound represented by the following formula (IV)

[Wherein Y is a linear alkylene group having 1 to 6 carbon atoms, or a part or all of hydrogen of the alkylene group is substituted with a substituent having 1 to 6 carbon atoms, and R ² is a hydrogen atom. Or a C1-C8 substituent is shown. ]
The following formula (V) obtained by reacting with the compound represented by

[Wherein the symbols are as defined above. ]
The compound represented by the following formula (VI) is obtained by reacting with an isocyanate group-containing compound.

[Wherein the symbols are as defined above. ]
The method for producing a compound according to any one of claims 1 to 7, wherein a compound having an organic group represented by formula (I) is reacted with water in a dilute acid or in the presence of an acidic compound.   (Α-oxoamidoalkoxy) carbonylamino group and a (meth) acryloyloxy group are obtained by homopolymerizing or copolymerizing with a vinyl monomer other than the compound. Polymers having an [alpha] -oxoamidoalkoxy) carbonylamino group. Following formula (VI)

[Wherein the symbols are as defined above. ]
A polymer obtained by homopolymerizing a compound having an organic group and a (meth) acryloyloxy group represented by formula (I) or copolymerizing with a vinyl monomer other than the compound is mixed with water in a dilute acid or in the presence of an acidic compound. A polymer having an (α-oxoamidoalkoxy) carbonylamino group, which is obtained by reaction.