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

Abstract

To provide a water-soluble polysiloxane compound having an amino acid-containing group, which has a solid form, thereby enabling reduction in cost for storage and transportation and allowing easy re-dissolution for use as a solution.SOLUTION: Provided is a solid water-soluble polysiloxane compound having an amino acid-containing group represented by the following general formula (1). (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.)SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] An organosilicon compound having a hydrolyzable silyl group and an organic group enables bonding between an organic material and an inorganic material that are normally difficult to bond because the silanol group generated by hydrolysis of the hydrolyzable silyl group forms a covalent bond with the hydroxyl group on the surface of the inorganic material, and further the organic group reacts with the organic material. Among the above organosilicon compounds, an aminosilane compound having an amino group can enhance the adhesion of an organic-inorganic composite material because the amino group exhibits high reactivity with various organic and inorganic materials.

[0003] Regarding the above aminosilane compound, from the viewpoints of user safety and environmental protection, a silane compound that does not generate volatile organic components (VOCs) such as methanol and ethanol during use has been proposed. For example, as in Patent Document 1, an aminosilane compound having an amino group generates an organopolysiloxane composition such as 3-aminopropylsilanetriol polymer by hydrolysis, and by removing the alcohol generated after hydrolysis, it is possible to reduce the amount of alcohol generated.

[0004] Further, in Patent Document 2, it has been proposed that by using an amino acid-modified silanol compound and a silanol-containing aqueous solution as a surface treatment agent, hydrophilicity and antifouling properties can be imparted to various organic and inorganic materials.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] However, in the case of any of the patent documents, since it is an aqueous solution, the volume is large, it is difficult to secure a storage place, and transportation costs are also incurred. In addition, in the case of an aqueous solution, there is also a problem with storage stability.

[0007] The present invention has been made in view of the above circumstances, and provides a water-soluble polysiloxane compound having an amino acid-containing group that can reduce costs during storage and transportation because it is in a solid state, and can be easily redissolved and used as a solution, and a method for producing the same.

MEANS FOR SOLVING THE PROBLEMS

[0008] As a result of intensive studies to achieve the above object, the present inventors have found that a water-soluble polysiloxane compound having a predetermined amino acid-containing group is in a solid state, so that the storage volume can be reduced compared to the liquid state. As a result, not only can the costs during storage and transportation be reduced, but also the stability against heat, light or oxygen is high. In addition, since the aqueous solution obtained after redissolving it is substantially the same as the aqueous solution before drying, it has been found that it can be used for a longer period of time, and the present invention has been completed.

[0009] That is, the present invention is 1. A solid water-soluble polysiloxane compound having an amino acid-containing group represented by the following general formula (1),

CHEMICAL FORMULA

Chemical formula

Advantages of the Invention

[0010] Since the water-soluble polysiloxane compound having an amino acid-containing group of the present invention is in a solid state, not only can the costs during storage and transportation be reduced compared to the liquid state, but also it has high stability against heat, light, or oxygen. In addition, since 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, it can be used over a longer period without accompanying changes in physical properties.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Mode for Carrying Out the Invention

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

[0013]

Chemical formula

[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, more preferably 1 to 5 carbon atoms.

[0015] R 1 , R 2 and R 3 Examples of the monovalent hydrocarbon group include linear, branched or cyclic alkyl groups, alkenyl groups, aryl groups, aralkyl groups and the like. Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl, cyclohexyl groups; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl) groups; aryl groups such as phenyl, tolyl, naphthyl groups; aralkyl groups such as phenylmethyl, 2-phenylethyl groups and the like. Among these, R 1 、R 2 and R 3 are preferably a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 5 carbon atoms. Particularly from the viewpoint of easy availability of raw materials, 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] Note that part or all of the hydrogen atoms of each of the above hydrocarbon groups may be substituted with other substituents. Specific examples of such substituents include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, (iso)propoxy and phenoxy groups; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group, amino group, acyl group, alkoxycarbonyl groups having 1 to 5 carbon atoms, carboxy group, alkylsilyl groups having 1 to 5 carbon atoms, alkoxysilyl groups having 1 to 5 carbon atoms, etc. These can also be used in combination. The substitution positions of these substituents are not particularly limited, nor is the number of substituents limited.

[0017] In the above general formula (1), R 4 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. As the monovalent hydrocarbon group of R 4 , groups similar to the monovalent hydrocarbon groups exemplified by R 1 , R 2 and R 3 are included.

[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 a positive number of 0 or less than 2, more preferably a positive number of 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 a positive number of 0 or less than 2, more preferably a positive number of 0 or 1 or less.

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

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

[0021] Since the above compound (1) is solid at 25°C, not only can the costs during storage and transportation be reduced compared to the liquid state, but also its stability against heat, light, and oxygen is high. Furthermore, since the aqueous solution obtained after redissolving the above compound (1) is substantially the same as the aqueous solution before drying, it can be used over a longer period without accompanying changes in physical properties.

[0022] The solvent is not particularly limited when the above compound (1) is redissolved in a solvent for use, and examples include water; hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, octane, isooctane, benzene, toluene, xylene, mesitylene, tetralin; alcohol solvents such as methanol, ethanol, isopropanol, tert-butanol; ether solvents such as diethyl ether, tetrahydrofuran, dioxane; ester solvents such as ethyl acetate, butyl acetate; aprotic polar solvents such as acetonitrile; chlorinated hydrocarbon solvents such as dichloromethane, 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, the method for producing a water-soluble polysiloxane compound having a solid amino acid-containing group of the present invention will be described. The above 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 it under normal pressure or reduced pressure as necessary.

[0024]

Chemical formula

[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, more preferably 1 to 5 carbon atoms. As the monovalent hydrocarbon group of R 5 , groups similar to the monovalent hydrocarbon groups exemplified by R 1 , R 2 and R 3 can be mentioned.

[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, 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] As the monovalent hydrocarbon group of R 6 , groups similar to the monovalent hydrocarbon groups exemplified by R 1 , R 2 and R 3 can be mentioned. In the above general formula (3), R 7 , R 8 and R 9Each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. R 7 , R 8 and R 9 Examples of the monovalent hydrocarbon group of 1 , R 2 and R 3 include the same groups as the monovalent hydrocarbon groups exemplified by

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

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

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

[0031] Specific examples of the above 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, 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-(triethylsiloxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(triethylsiloxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(triisopropylsiloxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(triisopropylsiloxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(1-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, 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-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-aminopropyltrimethoxysilane, 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, N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropylmethyldimethoxysilane, etc.

[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, N-(2-triisopropylsiloxycarbonyl)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, N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropyltrimethoxysilane.

[0033] Examples of the mixing method of compound (2) and water include, for example, a method of adding compound (2) to water or a method of adding water to compound (2). From the viewpoints of the progress of the hydrolysis reaction and the energy load during drying, the water used in the above mixing is preferably 1.5 to 10,000 moles, more preferably 1.5 to 1,000 moles, and even more preferably 1.5 to 100 moles per 1 mole of the above compound (2).

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

[0035] During mixing, a solvent other than water can also be used as needed. Examples of the solvents 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 can be used alone or in combination of two or more.

[0036] From the reaction solution obtained as described above, the generated alcohol, water, and solvent can be removed by drying to obtain the solid compound (1). The drying method is not particularly limited, and examples include freeze drying, zeodration, fluidized bed drying, tray drying, vacuum evaporation, and spray drying. Vacuum evaporation and spray drying are preferred. Drying can be performed using these methods alone or in combination of two or more. Moreover, the pressure and temperature at that time are not particularly limited, but under normal pressure or reduced pressure, preferably 0 to 200 °C, more preferably 50 to 200 °C.

Examples

[0037] Hereinafter, the present invention will be specifically described with reference to 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 normal pressure to obtain 68.8 g of an aqueous solution containing N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer. The 1 1H-NMR spectrum of the obtained aqueous solution is shown in Chart in Figure 1. Thereafter, 25.5 g of the obtained aqueous solution was dried at 90 °C under 0.2 kPa to remove low-boiling components, and 14.5 g of white solid N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer was obtained.

[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 normal pressure to obtain 25.6 g of an aqueous solution containing N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer. The 1 1H-NMR spectrum of the obtained aqueous solution is shown in Chart in Figure 2. Thereafter, the obtained aqueous solution was dried at 90 °C under 0.2 kPa to remove low-boiling components, and 11.6 g of white solid N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer was obtained.

[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 at atmospheric pressure to obtain 32.8 g of an aqueous solution containing N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilane triol polymer. The 1 1H-NMR spectrum is shown in Chart in Figure 3. Thereafter, the resulting aqueous solution was dried at 0.2 kPa and 90 °C to remove low-boiling components, and 14.7 g of white solid N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilane triol polymer was obtained.

[0041] [Example 1-4] Synthesis of N-(2-carboxy)ethyl-3-aminopropylmethylsilane diol 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 at atmospheric pressure to obtain 21.7 g of an aqueous solution containing N-(2-carboxy)ethyl-3-aminopropylmethylsilane diol polymer. The 1 1H-NMR spectrum is shown in Chart in Figure 4. Thereafter, the resulting aqueous solution was dried at 0.2 kPa and 90 °C to remove low-boiling components, and 9.1 g of white solid N-(2-carboxy)ethyl-3-aminopropylmethylsilane diol polymer was obtained.

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

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

[0044] [Example 2-2] The solid N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilane triol polymer obtained in Example 1-2 was subjected to an accelerated test (heated at 60 °C for 2 weeks), and its appearance was confirmed. As a result, the solid N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilane triol polymer remained white, unchanged from before the accelerated test. Further, when 1.0 g of the solid N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer after the above acceleration test was dissolved in 2.5 g of water, a colorless and transparent aqueous solution was obtained. The 1 1H-NMR spectrum of the obtained aqueous solution is shown in a chart in FIG. 7. From FIGS. 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 acceleration test in water was substantially the same as the aqueous solution before drying in Example 1-2.

[0045] [Example 2-3] The solid N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer obtained in Example 1-3 was subjected to an acceleration test (heating at 60° C. for 2 weeks), and its appearance was confirmed. As a result, the solid N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer remained white, unchanged from before the acceleration test. Further, when 1.0 g of the solid N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer after the above acceleration test was dissolved in 2.5 g of water, a colorless and transparent aqueous solution was obtained. The 1 1H-NMR spectrum of the obtained aqueous solution is shown in a chart in FIG. 8. From FIGS. 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 acceleration test in water was substantially the same as 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 acceleration test (heating at 60° C. for 2 weeks), and its appearance was confirmed. As a result, the solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer remained white, unchanged from before the acceleration test. Further, when 1.0 g of the solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer after the above acceleration test was dissolved in 2.5 g of water, a colorless and transparent aqueous solution was obtained. The 1 1H-NMR spectrum of the obtained aqueous solution is shown in Chart in Fig. 9. From Fig. 4 and Fig. 9, it was found that the aqueous solution obtained by redissolving the solid N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer after the acceleration test in water was substantially the same as the aqueous solution before drying in Examples 1-4.

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

[0048] [Comparative Example 1] To 15.0 g of the aqueous solution after atmospheric distillation obtained in Example 1-1 above, water was added 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, and 27.3 g of a transparent aqueous solution was obtained. When the obtained aqueous solution was subjected to an acceleration 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). 【Chemical 1】 (wherein, 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, 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) 【Chemical 2】 [wherein, R 1 to 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) (wherein 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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