Solid water-soluble polysiloxane compound having amino acid-containing group, and method for producing same

Abstract

This solid water-soluble polysiloxane compound having an amino acid-containing group and represented by general formula (1) has a solid form, and therefore can be reduced in cost for storage and transportation, and can be easily re-dissolved to prepare a solution upon use. (In the formula, R1, R2, and R3 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms; R4 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms; a is 0 or 1; m is 0 or a positive number less than 3; n is 0 or 1; and n + m is 0 or a positive number less than 3.)

Description

Solid water-soluble polysiloxane compound having amino acid-containing groups and method for producing the same

[0001] The present invention relates to a solid, water-soluble polysiloxane compound having an amino acid-containing group and a method for producing the same.

[0002] Organosilicon compounds having a hydrolyzable silyl group and an organic group allow the silanol groups generated by hydrolysis of the hydrolyzable silyl group to form covalent bonds with hydroxyl groups on the surface of inorganic materials, and the organic groups then react with the organic materials, making it possible to bond organic and inorganic materials that are normally difficult to bond together. Among the above organosilicon compounds, aminosilane compounds having an amino group can enhance the adhesion of organic-inorganic composite materials because the amino group shows high reactivity with various organic and inorganic materials.

[0003] With regard to the above aminosilane compounds, from the viewpoints of user safety and environmental conservation, silane compounds have been proposed that do not generate volatile organic compounds (VOCs) such as methanol or ethanol during use. For example, as disclosed in Patent Document 1, an aminosilane compound having an amino group is hydrolyzed to produce an organopolysiloxane composition such as a 3-aminopropylsilanetriol polymer, and by removing the alcohol generated after hydrolysis, it is possible to reduce the amount of alcohol generated.

[0004] Furthermore, Patent Document 2 proposes that the use of an amino acid-modified silanol compound and a silanol-containing aqueous solution as a surface treatment agent can impart hydrophilicity and antifouling properties to various organic and inorganic materials.

[0005] US Patent Application Publication No. 2020 / 0068897 JP 2013-116872 A

[0006] However, in all of the patent documents, the solution is an aqueous solution, which makes it difficult to secure a storage space and also increases transportation costs. In addition, the aqueous solution also has problems with storage stability.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water-soluble polysiloxane compound having an amino acid-containing group, which is in a solid state and therefore reduces storage and transportation costs, and which can be easily redissolved and used as a solution, and a method for producing the same.

[0008] As a result of extensive research to achieve the above object, the present inventors have discovered that because a water-soluble polysiloxane compound having a specific amino acid-containing group is in a solid state, its storage volume can be reduced compared to when it is in a liquid state, thereby not only reducing storage and transportation costs but also providing high stability against heat, light, and oxygen. They have also discovered that the aqueous solution obtained after redissolving the compound is substantially identical to the aqueous solution before drying, and can therefore be used for a longer period of time, thereby completing the present invention.

[0009] That is, the present invention provides: 1. a solid water-soluble polysiloxane compound having an amino acid-containing group represented by the following general formula (1): (In the formula, R 1 , R 2 and R 3 each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms; R 4 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a is 0 or 1, m is 0 or a positive number less than 3, n is 0 or 1, and n+m is 0 or a positive number less than 3. 2. A compound represented by the following general formula (2): [In the formula, R 1 ~R 4 , a and n have the same meanings as above, R 5 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 6 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosilyl group represented by the following general formula (3): 7 R 8 R 9 (3) (wherein, R 7 , R 8 and R 9and each independently represent an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.) with water to carry out a hydrolysis reaction, followed by drying.

[0010] The water-soluble polysiloxane compound having an amino acid-containing group of the present invention is solid, which not only reduces storage and transportation costs compared to liquid forms, but also has high stability against heat, light, and oxygen. Furthermore, the aqueous solution obtained by redissolving the water-soluble polysiloxane compound of the present invention is substantially the same as the aqueous solution before drying, so it can be used for a longer period without any changes in physical properties.

[0011] The aqueous solution containing the N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer after atmospheric distillation obtained in Example 1-1 1 1 is a diagram showing the H-NMR spectrum of the aqueous solution containing the N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer after atmospheric distillation obtained in Example 1-2. 1 1 is a diagram showing the H-NMR spectrum of the aqueous solution containing the N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer after atmospheric distillation obtained in Example 1-3. 1 1 is a diagram showing the H-NMR spectrum of the aqueous solution containing the N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer after atmospheric distillation obtained in Example 1-4. 1 1 is a diagram showing the H-NMR spectrum of the aqueous solution containing the N-carboxymethyl-3-aminopropylsilanetriol polymer after atmospheric distillation obtained in Example 1-5. 1 1 is a diagram showing the H-NMR spectrum of an aqueous solution obtained by redissolving the solid N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer after the accelerated test obtained in Example 2-1 in water. 11 is a diagram showing the H-NMR spectrum of an aqueous solution obtained by redissolving the solid N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer after the accelerated test obtained in Example 2-2 in water. 1 1 is a diagram showing the H-NMR spectrum of an aqueous solution obtained by redissolving the solid N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer after the accelerated test obtained in Example 2-3 in water. 1 1 is a diagram showing the H-NMR spectrum of an aqueous solution obtained by redissolving the solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer obtained in Example 2-4 after the accelerated test in water. 1 1 is a diagram showing the H-NMR spectrum of an aqueous solution obtained by redissolving the solid N-carboxymethyl-3-aminopropylsilanetriol polymer after the accelerated test obtained in Example 2-5 in water. 1 FIG. 1 shows a H-NMR spectrum.

[0012] The present invention will be described in detail below. The solid water-soluble polysiloxane compound having an amino acid-containing group of the present invention is represented by the following general formula (1) (hereinafter referred to as "compound (1)").

[0013]

[0014] In the above general formula (1), R 1 , R 2 and R 3 each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

[0015] R 1 , R 2 and R 3Examples of the monovalent hydrocarbon group include linear, branched, or cyclic alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, 1-propenyl, and 2-propenyl (allyl) groups; aryl groups such as phenyl, tolyl, and naphthyl groups; and aralkyl groups such as phenylmethyl and 2-phenylethyl groups. Among these, R 1 , R 2 and R 3 As the alkyl group, a hydrogen atom, a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an alkenyl group, an aryl group, or an aralkyl group is preferable, and from the viewpoint of easy availability of raw materials in particular, a hydrogen atom or an unsubstituted linear alkyl group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom, a methyl group, or an ethyl group is even more preferable.

[0016] Some or all of the hydrogen atoms in each of the hydrocarbon groups may be substituted with other substituents, and specific examples of such substituents include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, (iso)propoxy, and phenoxy; halogen atoms such as fluorine, chlorine, bromine, and iodine; cyano, amino, acyl, alkoxycarbonyl groups having 1 to 5 carbon atoms, carboxy, alkylsilyl groups having 1 to 5 carbon atoms, and alkoxysilyl groups having 1 to 5 carbon atoms, and these can also be used in combination. There are no particular limitations on the substitution positions of these substituents, and there are no particular limitations on the number of substituents.

[0017] In the above general formula (1), R 4 R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. 4 The monovalent hydrocarbon group of R 1 , R 2 and R 3Examples of the monovalent hydrocarbon groups include the same groups as those exemplified above.

[0018] In the above general formula (1), a is 0 or 1, preferably 1. m is a positive number of 0 or less than 3, preferably 0 or less than 2, and more preferably 0 or 1 or less. n is 0 or 1, preferably 0. However, n+m is a positive number of 0 or less than 3, preferably 0 or less than 2, and more preferably 0 or 1 or less.

[0019] Specific examples of the compound (1) include N-carboxymethyl-3-aminopropyl silanetriol polymer, N-carboxymethyl-3-aminopropyl methyl silanediol polymer, N-(1-carboxy)ethyl-3-aminopropyl silanetriol polymer, N-(1-carboxy)ethyl-3-aminopropyl methyl silanediol polymer, N-(1-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer, N-(1-carboxy-1-methyl)ethyl-3-aminopropyl methyl silanediol polymer, N-(2-carboxy)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy)ethyl-3-aminopropyl methyl silanediol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropyl methyl silanediol polymer, N-(2-carboxy-2-methyl)ethyl N-(2-carboxy-1-phenyl)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy-2-methyl)ethyl-3-aminopropyl methyl silanediol polymer, N-(2-carboxy-1-phenyl)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy-1-phenyl)ethyl-3-aminopropyl methyl silanediol polymer, N-(2-carboxy-2-phenyl)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy-2-phenyl)ethyl-3-aminopropyl methyl silanediol polymer, N-(1,2-dicarboxy)ethyl-3-aminopropyl silanetriol polymer, N-(1,2-dicarboxy)ethyl-3-aminopropyl methyl silanediol polymer, N-(2,3-dicarboxy)propyl-3-aminopropyl methyl silanediol polymer, and the like.

[0020] Among these, aminopropyl silanetriol polymers having one carboxy group, such as N-carboxymethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy)ethyl-3-aminopropylmethyl silanediol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer, and N-(2-carboxy-2-methyl)ethyl-3-aminopropyl silanetriol polymer, are particularly preferred; and aminopropyl silanetriol polymers having two carboxy groups, such as N-(1,2-dicarboxy)ethyl-3-aminopropyl silanetriol polymer and N-(2,3-dicarboxy)propyl-3-aminopropyl silanetriol polymer, are preferred.

[0021] Since the compound (1) is solid at 25° C., it can reduce storage and transportation costs compared to a liquid form, and is also highly stable against heat, light, and oxygen. Furthermore, the aqueous solution obtained after redissolving the compound (1) is substantially the same as the aqueous solution before drying, and therefore can be used for a longer period without any change in physical properties.

[0022] When compound (1) is redissolved in a solvent for use, the solvent is not particularly limited, and examples thereof include water; hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, octane, isooctane, benzene, toluene, xylene, mesitylene, and tetralin; alcohol solvents such as methanol, ethanol, isopropanol, and tert-butanol; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. Among these, water, alcohol solvents, and aprotic polar solvents are preferred, water and alcohol solvents are more preferred, and water is even more preferred. These solvents may be used alone or in combination of two or more.

[0023] Next, a method for producing the solid water-soluble polysiloxane compound having an amino acid-containing group of the present invention will be described. Compound (1) is usually obtained by mixing a silane compound having an amino acid ester-containing group represented by the following general formula (2) (hereinafter referred to as "compound (2)") with water to carry out a hydrolysis reaction, and then drying the mixture under normal pressure or reduced pressure as necessary.

[0024] (In the formula, R 1 ~R 4 , a and n have the same meanings as above.)

[0025] In the above general formula (2), R 5 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. 5 The monovalent hydrocarbon group of R 1 , R 2 and R 3 Examples of the monovalent hydrocarbon groups include the same groups as those exemplified above.

[0026] In the above general formula (2), R 6 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, or a triorganosilyl group represented by the following general formula (3): —SiR 7 R 8 R 9 (3)

[0027] R 6 The monovalent hydrocarbon group of R 1 , R 2 and R 3 In the above general formula (3), R 7 , R 8 and R 9 R each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. 7 , R 8 and R 9 The monovalent hydrocarbon group of R 1 , R2 and R 3 Examples of the monovalent hydrocarbon groups include the same groups as those exemplified above.

[0028] Among these, R 7 , R 8 and R 9 As the alkyl group, an unsubstituted linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; an alkenyl group; or an aryl group is preferable, and from the viewpoint of easy availability of raw materials in particular, an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms; or an alkenyl group is more preferable, and a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group is even more preferable.

[0029] Specific examples of the triorganosilyl group represented by the general formula (3) include trimethylsilyl, ethyldimethylsilyl, diethylmethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, hexyldimethylsilyl, octyldimethylsilyl, decyldimethylsilyl, octadecyldimethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, triphenylsilyl, and tert-butyldiphenylsilyl groups.

[0030] Among these, from the viewpoint of easy availability of raw materials, a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a triisopropylsilyl group, and a tert-butyldiphenylsilyl group are more preferred, and a trimethylsilyl group and a triisopropylsilyl group are even more preferred.

[0031] Specific examples of the compound (2) include N-(methoxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropyltriethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropylmethyldiethoxysilane, N-(ethoxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(ethoxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, and N-(ethoxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane. N-(ethoxycarbonyl)methyl-3-aminopropyltriethoxysilane, N-(ethoxycarbonyl)methyl-3-aminopropylmethyldiethoxysilane, N-(trimethylsiloxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(trimethylsiloxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(trimethylsiloxycarbonyl)methyl-3-aminopropyltriethoxysilane, N-(trimethylsiloxycarbonyl)methyl-3-aminopropylmethyldiethoxysilane, N-(triethyl N-(1-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N -(1-methoxycarbonyl-1-methyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methoxycarbonyl-1-methyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropyltriethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropylmethyldiethoxysilane,N-(2-ethoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropyltriethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropylmethyldiethoxysilane, N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropyltriethoxysilane, N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropylmethyldiethoxysilane, N-(2-triethylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-triethylsiloxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-triisopropylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-triisopropylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane N-(2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl-2-phenyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl-2-phenyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(1-methyl-2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane propyltrimethoxysilane, N-(1-methyl-2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(1-phenyl-2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-phenyl-2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-[1,2-bis(methoxycarbonyl)]ethyl-3-aminopropyltrimethoxysilane, N-[1,2-bis(methoxycarbonyl)]ethyl-3-aminopropylmethyldimethoxysilane,Examples include N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropyltrimethoxysilane and N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropylmethyldimethoxysilane.

[0032] Among these, particularly preferred are N-(methoxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropyltriethoxysilane, N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, and N-(2-triisopropylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane. N-(2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methyl-2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-phenyl-2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-[1,2-bis(methoxycarbonyl)]ethyl-3-aminopropyltrimethoxysilane, and N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropyltrimethoxysilane are preferred.

[0033] Examples of methods for mixing compound (2) with water include adding compound (2) to water, adding water to compound (2), etc. The amount of water used in the mixing is preferably 1.5 to 10,000 mol, more preferably 1.5 to 1,000 mol, and even more preferably 1.5 to 100 mol per mol of compound (2), from the viewpoints of the progress of the hydrolysis reaction and the energy load during drying.

[0034] The temperature and pressure during the mixing are not particularly limited, but are preferably 0 to 120°C, more preferably 10 to 60°C, under normal pressure. The reaction time is also not particularly limited, but is preferably 1 to 40 hours, more preferably 1 to 20 hours. Furthermore, a catalyst is not particularly required, but an acid such as hydrochloric acid, sulfuric acid, or acetic acid; or a base such as sodium hydroxide, potassium hydroxide, or sodium carbonate may be added.

[0035] During mixing, a solvent other than water can also be used if necessary. Examples of the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, octane, isooctane, benzene, toluene, xylene, mesitylene, and tetralin; alcohol solvents such as methanol, ethanol, isopropanol, and tert-butanol; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

[0036] The produced alcohol, water, and solvent can be removed from the reaction solution obtained as described above by drying to obtain solid compound (1). The drying method is not particularly limited, but examples include freeze drying, zeodration, fluidized bed drying, tray drying, vacuum evaporation, and spray drying, with vacuum evaporation and spray drying being preferred. These methods may be used alone or in combination of two or more. The pressure and temperature during drying are not particularly limited, but are preferably normal pressure or reduced pressure, and are preferably 0 to 200°C, more preferably 50 to 200°C.

[0037] EXAMPLES The present invention will be specifically explained below by showing examples and comparative examples, but the present invention is not limited to the following examples.

[0038] Example 1-1 Synthesis of N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer 79.7 g of water was charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 53.1 g (0.2 mol) of N-(2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure to obtain 68.8 g of an aqueous solution containing N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer. 1 The H-NMR spectrum is shown in the chart of Figure 1. Thereafter, 25.5 g of the obtained aqueous solution was dried at 0.2 kPa and 90°C to remove low boiling components, yielding 14.5 g of a white solid N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer.

[0039] Example 1-2 Synthesis of N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer 40.0 g of water was charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 20.0 g (0.072 mol) of N-(2-methoxycarbonyl-1-methyl)ethyl-3-aminopropyltrimethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure to obtain 25.6 g of an aqueous solution containing N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer. 1 The H-NMR spectrum is shown in the chart of Figure 2. The obtained aqueous solution was then dried at 0.2 kPa and 90°C to remove low boiling components, yielding 11.6 g of a white solid N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer.

[0040] Example 1-3 Synthesis of N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer 40.0 g of water was charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 20.0 g (0.072 mol) of N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyltrimethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure to obtain 32.8 g of an aqueous solution containing N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer. 1 The H-NMR spectrum is shown in the chart of Figure 3. The obtained aqueous solution was then dried at 0.2 kPa and 90°C to remove low boiling components, yielding 14.7 g of a white solid N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer.

[0041] Example 1-4 Synthesis of N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer 25.0 g of water was charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 14.6 g (0.05 mol) of N-(2-ethoxycarbonyl)ethyl-3-aminopropylmethyldiethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure to obtain 21.7 g of an aqueous solution containing N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer. 1 The H-NMR spectrum is shown in the chart of Figure 4. The resulting aqueous solution was then dried at 0.2 kPa and 90°C to remove low boiling components, yielding 9.1 g of a white solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer.

[0042] [Example 1-5] Synthesis of N-carboxymethyl-3-aminopropylsilanetriol polymer 35.1 g of water and 0.20 g of acetic acid were charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 20.0 g (0.065 mol) of N-ethoxycarbonylmethyl-3-aminopropyltriethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure to obtain 24.3 g of an aqueous solution containing N-carboxymethyl-3-aminopropylsilanetriol polymer.1 The H-NMR spectrum is shown in the chart of Figure 5. The obtained aqueous solution was then dried at 0.2 kPa and 90°C to remove low boiling components, yielding 11.4 g of a white solid N-carboxymethyl-3-aminopropylsilanetriol polymer.

[0043] [Example 2-1] The solid N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer obtained in Example 1-1 was subjected to an accelerated test (heated at 60°C for 2 weeks) and its appearance was confirmed. The solid N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer was white, unchanged from before the accelerated test. Furthermore, when 1.0 g of the solid N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer after the accelerated test was dissolved in 2.5 g of water, a colorless and transparent aqueous solution was obtained. The obtained aqueous solution 1 The H-NMR spectrum is shown in the chart of Figure 6. From Figures 1 and 6, it was found that the aqueous solution obtained by redissolving the solid N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer after the accelerated test in water was substantially identical to the aqueous solution before drying in Example 1-1.

[0044] [Example 2-2] The solid N-(2-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer obtained in Example 1-2 was subjected to an accelerated test (heated at 60°C for 2 weeks) and its appearance was confirmed. The solid N-(2-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer was white, unchanged from before the accelerated test. Furthermore, when 1.0 g of the solid N-(2-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer after the accelerated test was dissolved in 2.5 g of water, a colorless and transparent aqueous solution was obtained. The resulting aqueous solution 1 The H-NMR spectrum is shown in the chart of Figure 7. From Figures 2 and 7, it was found that the aqueous solution obtained by redissolving the solid N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer after the accelerated test in water was substantially identical to the aqueous solution before drying in Example 1-2.

[0045] [Example 2-3] The solid N-(2-carboxy-2-methyl)ethyl-3-aminopropyl silanetriol polymer obtained in Example 1-3 was subjected to an accelerated test (heated at 60°C for 2 weeks) and its appearance was confirmed. The solid N-(2-carboxy-2-methyl)ethyl-3-aminopropyl silanetriol polymer was white, unchanged from before the accelerated test. Furthermore, when 1.0 g of the solid N-(2-carboxy-2-methyl)ethyl-3-aminopropyl silanetriol polymer after the accelerated test was dissolved in 2.5 g of water, a colorless and transparent aqueous solution was obtained. The resulting aqueous solution 1 The H-NMR spectrum is shown in the chart of Figure 8. From Figures 3 and 8, it was found that the aqueous solution obtained by redissolving the solid N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer after the accelerated test in water was substantially identical to the aqueous solution before drying in Example 1-3.

[0046] [Example 2-4] The solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer obtained in Example 1-4 was subjected to an accelerated test (heated at 60°C for 2 weeks) and its appearance was confirmed. The solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer was white, unchanged from before the accelerated test. Furthermore, when 1.0 g of the solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer after the accelerated test was dissolved in 2.5 g of water, a colorless and transparent aqueous solution was obtained. The resulting aqueous solution 1 The H-NMR spectrum is shown in the chart of Figure 9. From Figures 4 and 9, it was found that the aqueous solution obtained by redissolving the solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer after the accelerated test in water was substantially identical to the aqueous solution before drying in Example 1-4.

[0047] [Example 2-5] The solid N-carboxymethyl-3-aminopropylsilanetriol polymer obtained in Example 1-5 was subjected to an accelerated test (heated at 60°C for 2 weeks) and its appearance was confirmed. The solid N-carboxymethyl-3-aminopropylsilanetriol polymer was white, unchanged from before the accelerated test. Furthermore, when 1.0 g of the solid N-carboxymethyl-3-aminopropylsilanetriol polymer after the accelerated test was dissolved in 2.5 g of water, a colorless and transparent aqueous solution was obtained. 1 The H-NMR spectrum is shown in the chart of Figure 10. From Figures 5 and 10, it was found that the aqueous solution obtained by redissolving the solid N-carboxymethyl-3-aminopropylsilanetriol polymer after the accelerated test in water was substantially the same as the aqueous solution before drying in Example 1-5.

[0048] Comparative Example 1: Water was added to 15.0 g of the aqueous solution after atmospheric distillation obtained in Example 1-1 to adjust the concentration so that the concentration of the N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer was the same as that of the aqueous solution in Example 2-1, thereby obtaining 27.3 g of a transparent aqueous solution. When the obtained aqueous solution was subjected to an accelerated test in the same manner as in Example 2-1, the aqueous solution turned yellow.

Claims

1. A water-soluble polysiloxane compound having a solid amino acid-containing group represented by the following general formula (1). (In the formula, R 1 , R 2 and R 3 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a is 0 or 1, m is a positive number less than 0 or 3, n is 0 or 1, and n + m is a positive number less than 0 or 3.) 2. The following general formula (2) [In the formula, R 1 ~R 4 , a and n represent the same meanings as described above, and R 5 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 6 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosilyl group represented by the following general formula (3). -SiR 7 R 8 R 9 (3) (In the formula, R 7 , R 8 and R 9 each independently represent an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)] A method for producing a water-soluble polysiloxane compound having a solid amino acid-containing group according to claim 1, which is obtained by mixing a silane compound having an amino acid ester-containing group represented by the formula with water, performing a hydrolysis reaction, and then drying.

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