Silicone-based zwitterionic compounds

Abstract

This invention provides a silicon-based zwitterionic compound that exhibits excellent surface tension reduction capabilities. [Solution] A silicone-based zwitterionic compound represented by the following formula (1). JPEG2026121133000025.jpg26169 (In the formula, R1 represents an unsubstituted alkyl group having 1 to 4 carbon atoms. R2 to R4 are the same or different and represent an unsubstituted alkylene group having 1 to 10 carbon atoms. n is 1 to 40.)

Description

[Technical Field]

[0001] This invention relates to silicone-based zwitterionic compounds. [Background technology]

[0002] Fluorine-based surfactants have a high ability to reduce surface tension and, when mixed with coating compositions, are additives that achieve excellent penetration, wettability, leveling properties, and surface functionality. Numerous fluorine-based surfactants have been proposed for this purpose.

[0003] However, in recent years, fluorine regulations have become stricter, and the non-fluorinated use of materials is being considered. An example of a non-fluorinated surfactant is the technology described in Patent Document 1. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 62-243698 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the surfactant described in Patent Document 1 has inferior surface tension reduction ability compared to fluorine-based surfactants, and therefore lacks the performance to serve as a substitute material for fluorine-based surfactants. The object of this invention is to provide a silicone-based zwitterionic compound that exhibits excellent surface tension reduction ability. [Means for solving the problem]

[0006] In order to solve the above problems, the inventors of this invention conducted extensive research and found that a silicone-based zwitterionic compound having a specific structure exhibits excellent surface tension reduction ability.

[0007] The present invention has been completed based on these findings and includes the inventions in the broad aspects shown below. [Item 1] A silicone-based zwitterionic compound represented by the following formula (1). [Chemical formula] (In the formula, R1 represents an unsubstituted alkyl group having 1 to 4 carbon atoms. R2 to R4 are the same or different and represent an unsubstituted alkylene group having 1 to 10 carbon atoms. n is 1 to 40.) [Item 2] The silicone-based zwitterionic compound according to Item 1, wherein the weight average molecular weight of the zwitterionic compound is 300 to 3000. [Item 3] The silicone-based zwitterionic compound according to Item 1 or 2, wherein the surface tension of a 0.1 mass% aqueous solution of the zwitterionic compound is 25 mN / m or less. [Item 4] A composition containing the silicone-based zwitterionic compound according to any one of Items 1 to 3. [Item 5] A surfactant containing the silicone-based zwitterionic compound according to any one of Items 1 to 3. [Item 6] A paint containing the silicone-based zwitterionic compound according to any one of Items 1 to 3. [Item 7] A leveling agent containing the silicone-based zwitterionic compound according to any one of Items 1 to 3. [Item 8] A method for producing the silicone-based zwitterionic compound according to any one of Items 1 to 3, including a step of aminating a compound represented by the following formula (2). [Chemical formula] (In the formula, R1 represents an unsubstituted alkyl group having 1 to 4 carbon atoms. R2 and R3 are the same or different and represent an unsubstituted alkyl group having 1 to 10 carbon atoms. n is 1 to 40. X represents a leaving group.) [Effects of the Invention]

[0008] According to the present invention, a silicone-based zwitterionic compound showing excellent surface tension reducing ability can be provided.

Embodiments for Carrying Out the Invention

[0009] The silicone-based zwitterionic compound according to the present invention is represented by the following formula (1).

Chemical formula

[0010] In formula (1), R1 represents an unsubstituted alkyl group having 1 to 4 carbon atoms. Examples of the unsubstituted alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and isobutyl group. Among these, an ethyl group, n-propyl group, and n-butyl group are preferable, and it is particularly preferable that R1 is an n-butyl group.

[0011] In formula (1), R2 to R4 are the same or different and each represents an unsubstituted alkylene group having 1 to 10 carbon atoms. It is preferable that R2 to R4 are the same or different and each is an unsubstituted alkylene group having 1 to 8 carbon atoms, and more preferably an unsubstituted alkylene group having 1 to 6 carbon atoms. It is preferable that R2 is an unsubstituted alkylene group having 1 to 8 carbon atoms, more preferably an unsubstituted alkylene group having 1 to 6 carbon atoms, and even more preferably an unsubstituted alkylene group having 1 to 4 carbon atoms. It is preferable that R3 is an unsubstituted alkylene group having 1 to 8 carbon atoms, more preferably an unsubstituted alkylene group having 1 to 6 carbon atoms, and even more preferably an unsubstituted alkylene group having 1 to 4 carbon atoms. It is preferable that R4 is an unsubstituted alkylene group having 1 to 8 carbon atoms, more preferably an unsubstituted alkylene group having 1 to 6 carbon atoms, and even more preferably an unsubstituted alkylene group having 1 to 4 carbon atoms.

[0012] <( Examples of unsubstituted alkylene groups having 1 to 10 carbon atoms include linear alkylene groups having 1 to 10 carbon atoms (methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, etc.) and branched alkylene groups having 3 to 10 carbon atoms (1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylpropylene group, 1-hexylpropylene group, 1-hexylbutylene group, 1-octylethylene group, etc.). In particular, R2 is preferably a trimethylene group, R3 is preferably an ethylene group, and R4 is preferably a methylene group.

[0013] In formula (1), n ​​is between 1 and 40. Preferably, n is between 1 and 35, more preferably between 2 and 35, even more preferably between 3 and 30, and most preferably between 4 and 25. When n is within the above range, the ability to reduce surface tension is excellent. Furthermore, if n exceeds 40, there is a risk that the solubility in solvents (especially water solubility) will decrease.

[0014] The weight-average molecular weight of the silicone-based zwitterionic compound represented by formula (1) is preferably 300 to 3000, more preferably 350 to 2700, and even more preferably 400 to 2500.

[0015] Specific examples of silicone-based zwitterionic compounds represented by formula (1) include, but are not limited to, the following.

[0016] [ka] (In the formula, n is between 1 and 40.)

[0017] The method for producing the silicone-based zwitterionic compound represented by formula (1) of the present invention is not particularly limited, but for example, it can be produced by a method that includes a step of aminating the compound represented by the following formula (2). [ka] (In the formula, R1 represents an unsubstituted alkyl group having 1 to 4 carbon atoms. R2 and R3 are the same or different and represent an unsubstituted alkyl group having 1 to 10 carbon atoms. n is between 1 and 40. X represents a leaving group.)

[0018] In equation (2), R1, R2, R3, and n are as defined above.

[0019] In formula (2), X represents a leaving group. A leaving group is a group that is eliminated during the reaction and is not particularly limited, but examples include iodine, bromine, chlorine, methylsulfonyloxy group (-OSO2CH3), p-toluenesulfonyloxy group (-OSO2C6H5CH3), trifluoromethylsulfonyloxy group (-OSO2CF3), etc., with methylsulfonyloxy group (-OSO2CH3) being preferred.

[0020] The compound represented by formula (2) can be synthesized, for example, from the compound represented by formula (3) below using known synthesis methods. Furthermore, the compound represented by formula (3) below is available commercially, such as FM-0411P (manufactured by JNC Corporation). [ka] (In the formula, R1, R2, R3, and n are as defined above.)

[0021] The amination reaction of the compound represented by equation (2) can be represented, for example, by the following reaction equation. [ka] (In the formula, R1, R2, R3, and n are as defined above.)

[0022] In the above reaction, the amount of dimethylamine used is preferably 1 to 5 moles, and more preferably 2 to 5 moles, per mole of the compound represented by formula (2).

[0023] The reaction temperature in the above reaction is typically between 0°C and 100°C, or the boiling point of the solvent.

[0024] The reaction time is typically 1 to 48 hours, preferably 1 to 20 hours.

[0025] The reaction solvent is not particularly limited as long as it allows the reaction to proceed favorably, but examples include toluene, xylene, acetonitrile, dimethylformamide, water, or a mixture thereof. The amount of solvent used is usually 10 parts by mass or less, preferably 0.2 to 5 parts by mass, per 1 part by mass of the compound represented by formula (2).

[0026] If necessary, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium.

[0027] After the reaction is complete, the compound represented by formula (4) can be obtained by removing impurities (e.g., unreacted raw materials) by washing with an organic solvent or by concentrating the reaction solution. If necessary, further purification may be performed using known methods.

[0028] By reacting the compound represented by formula (4) with an alkylcarboxylic acid compound, a silicone-based zwitterionic compound represented by formula (1) can be obtained. This reaction can be represented, for example, by the following reaction equation. [ka] (In the formula, R1, R2, R3, R4, and n are as defined above. X1 represents a leaving group. M represents a hydrogen atom, alkali metal, amine base, or ammonium base.)

[0029] In formula (5), X1 represents a leaving group. A leaving group is a group that is eliminated during the reaction and is not particularly limited, but examples include iodine, bromine, chlorine, methylsulfonyloxy group (-OSO2CH3), p-toluenesulfonyloxy group (-OSO2C6H5CH3), trifluoromethylsulfonyloxy group (-OSO2CF3), etc., with bromine or chlorine being preferred.

[0030] In formula (5), M represents a hydrogen atom, an alkali metal, an amine base, or an ammonium base. Examples of alkali metals include lithium, sodium, and potassium. Examples of amine bases include trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, and pyridine.

[0031] The alkylcarboxylic acid compound represented by formula (5) is preferably a haloalkylcarboxylate salt. Examples of haloalkylcarboxylate salts include, but are not limited to, sodium chloroacetate, sodium 3-chloropropionate, sodium 4-chlorobutyrate, sodium 5-chlorovalerate, sodium bromoacetate, sodium 3-bromopropionate, sodium 4-bromobutyrate, and sodium 5-bromovalerate.

[0032] In the above reaction, the total amount of alkylcarboxylic acid compound represented by formula (5) used is preferably 1 to 10 moles, and more preferably 1 to 5 moles, per mole of the compound represented by formula (4).

[0033] The above reaction is carried out in the presence of a base. Examples of bases include organic bases such as triethylamine, tributylamine, pyridine, 4-dimethylaminopyridine, diazabicyclononene, and diazabicycloundecene; inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; and organolithium compounds such as methyllithium and butyllithium.

[0034] The reaction temperature in the above reaction is typically between 0°C and 100°C, or the boiling point of the solvent.

[0035] The reaction time is typically 1 to 48 hours, preferably 1 to 20 hours.

[0036] Examples of reaction solvents include water, methanol, ethanol, isopropanol, tetrahydrofuran, diethyl ether, ethyl acetate, acetonitrile, acetone, and methyl ethyl ketone. When using a solvent, the amount of solvent used is usually 10 parts by mass or less, preferably 0.5 to 5 parts by mass, per 1 part by mass of the compound represented by formula (4). Two or more solvents may be mixed and used as needed.

[0037] If necessary, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium.

[0038] After the reaction is complete, the silicon-based zwitterionic compound represented by formula (1) can be obtained by removing impurities (e.g., unreacted raw materials) by washing with an organic solvent and concentrating the reaction solution. If necessary, further purification may be performed using known methods.

[0039] The silicone-based zwitterionic compound represented by formula (1) can be used as a surfactant on its own. It can also be used as a composition (surfactant composition) containing water and / or an organic solvent. The composition may contain one of the silicone-based zwitterionic compounds represented by formula (1) alone, or two or more in combination. Examples of organic solvents that can be used include hexylene glycol, ethanol, methanol, isopropyl alcohol, ethylene glycol, N-methylpyrrolidone, N,N-dimethylformamide, propylene glycol monomethyl ether acetate, methyl ethyl ketone, ethyl acetate, n-butyl acetate, etc. It is preferable to use water or a mixed solvent of water and an organic solvent as the water and / or organic solvent.

[0040] The content of the silicone-based zwitterionic compound represented by formula (1) in the above surfactant composition is not particularly limited as long as it exhibits surfactant properties, but for example, it is about 0.01 to 90% by mass, preferably about 0.1 to 60 parts by mass, and more preferably about 0.5 to 50 parts by mass, per 100 parts by mass of the total amount of the surfactant composition.

[0041] The above surfactant composition may appropriately contain rust inhibitors, catalysts, antibacterial agents, flame retardants, defoaming agents, thickeners, viscosity modifiers, ultraviolet absorbers, preservatives, antifreeze agents, wetting agents, pH adjusters, stabilizers, light-resistant stabilizers, weather-resistant stabilizers, neutralizing agents, matting agents, drying accelerators, foaming agents, non-stick agents, degradation inhibitors, etc., within limits that do not hinder the objectives of the present invention. These may be used individually or in combination of two or more. Each of these additives can be used, for example, in an amount ranging from 0.01 to 10 parts by mass per 100 parts by mass of the total amount of the surfactant composition.

[0042] The silicone-based zwitterionic compound represented by formula (1) has excellent surface tension-reducing ability and is useful as a substitute material for fluorine-based surfactants. The silicone-based zwitterionic compound represented by formula (1) preferably has a surface tension of 25 mN / m or less, and more preferably 20 mN / m or less, when prepared as a 0.1% by mass aqueous solution. Furthermore, the silicone-based zwitterionic compound represented by formula (1) preferably has a surface tension of 30 mN / m or less, more preferably 25 mN / m or less, and particularly preferably 20 mN / m or less, when prepared as a 0.01% by mass aqueous solution. In this specification, surface tension is measured by the Wilhelmy method (liquid temperature 20°C) as described in the examples. Thus, since the silicone-based zwitterionic compound represented by formula (1) has excellent surface tension-reducing ability even at low concentrations, it is preferable that the amount added can be reduced when using this compound as an additive.

[0043] The silicone-based zwitterionic compound represented by formula (1) of the present invention, and the surfactant containing the same (fluorine-based surfactant composition), have excellent surface tension-reducing capabilities as described above, and can therefore be suitably used as additives, leveling agents, etc., in various materials using aqueous solvents or organic solvents, such as paints and coating materials.

[0044] When using the silicone-based zwitterionic compound of the present invention as an additive for paints, coating materials, etc., it is preferable to include 0.005 to 10 parts by mass, and more preferably 0.01 to 1 part by mass, of the silicone-based zwitterionic compound per 100 parts by mass of the paint composition. If the amount added is within the above range, the surface tension can be sufficiently reduced, and the desired leveling properties can be obtained.

[0045] Furthermore, when using a silicone-based zwitterionic compound represented by formula (1) as a leveling agent, the content of the compound is not particularly limited as long as it exhibits the performance of a leveling agent. For example, it is about 0.1 to 60 parts by mass, preferably about 0.5 to 50 parts by mass, per 100 parts by mass of the total amount of the leveling agent composition. [Examples]

[0046] The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

[0047] ( 1 H-NMR analysis conditions) Equipment: JEOL Ltd. JNM-ECZ400S Frequency: 400MHz Deuterated solvent: Deuterated methanol Reference peak: Tetramethylsilane was set to 0.00 ppm.

[0048] (Materials used) • Terminally hydroxy-modified siloxane [ka] (In the formula, R1 is an n-butyl group, R2 is an n-propylene group, and R3 is an ethylene group.) Compound A: n=4, molecular weight 510. Compound B: n=approximately 10, weight-average molecular weight 1150, manufactured by JNC Corporation as FM-0411P. Compound C: n=approximately 20, weight average molecular weight 2000. Compound D: n=approximately 64, weight-average molecular weight 5000, manufactured by JNC Corporation, FM-0421.

[0049] (Synthesis Example 1) Preparation of Zwitterionic Compound 1 (Mesyl group protection of hydroxy-modified siloxanes at one end) [ka] (In the formula, n=4.) Compound A (30 g, 0.059 mol), methanesulfonyl chloride (8.1 g, 0.071 mol), and ethyl acetate (30 g) were added to a 200 mL beaker and stirred under cooling conditions (0-10°C). After stirring for 30 minutes, triethylamine (7.1 g, 0.071 mol) diluted with ethyl acetate (6.0 g) was added in small amounts. After addition, the mixture was stirred at room temperature for 5 hours. Stirring was stopped, and the reaction mixture was filtered (No. 5A). The filtrate was washed with water, and the solvent was removed using a rotary evaporator. 30.6 g of the mesylated product (yield: 88.4%, pale yellow transparent liquid) was recovered. 1 The H-NMR results are as follows: 1 H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 3.0ppm(3H,s), 3.4ppm(2H,t), 3.7ppm(2H,t), 4.3ppm(2H,t)

[0050] (Amination of mesylated terminally modified siloxane) [ka] (In the formula, n=4.) The above mesylated product (20 g, 0.034 mol), tetrabutylammonium bromide (2.8 g, 0.0087 mol), 50% aqueous solution of dimethylamine (16 g, 0.18 mol), and toluene (10 g) were added to a 100 mL round-bottom flask and stirred at 80°C for 6 hours. Stirring was stopped and the reaction mixture was separated into layers. The lower layer was separated and extracted with ethyl acetate. The upper layer and extract were washed with water, and the solvent was removed using a rotary evaporator. 17.8 g of the aminate (yield: 97.5%, pale yellow transparent liquid) was recovered. 1 The H-NMR results are as follows: 1H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 2.2ppm(6H,s), 2.5ppm(2H,t), 3.3ppm(2H,t), 3.5ppm(2H,t)

[0051] (Quaternary ignition of amination-modified terminal siloxanes) [ka] (In the formula, n=4.) The above amination product (5.0 g, 9.3 mmol), water (10 g), IPA (10 g), and sodium chloroacetate (2.9 g, 25 mmol) were added to a 50 mL round-bottom flask and stirred, then heated under reflux for 1 hour. A 20 wt% aqueous solution of sodium hydroxide (1.9 g, 9.3 mmol) was added dropwise, and the mixture was heated under reflux for 13 hours. Potassium carbonate was added to the reaction mixture and stirred to separate the reaction mixture into layers. After separating the upper layer containing the target product, the solvent was removed using a rotary evaporator, and 5.19 g of zwitterionic compound 1 (yield: 94.0%, white viscous solid) was recovered. 1 The H-NMR results are as follows: 1 H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 3.3ppm(6H,s), 3.4ppm(4H,m), 3.7-4.0ppm(4H,m)

[0052] (Synthesis Example 2) Preparation of Zwitterionic Compound 2 (Mesyl group protection of hydroxy-modified siloxanes at one end) [ka] (In the formula, n=approximately 10.) Compound B (1200 g, 1.04 mol), methanesulfonyl chloride (143 g, 1.25 mol) and ethyl acetate (1200 g) were added to a 5 L plastic container and stirred under cooling conditions (0 - 10 °C). After stirring for 30 minutes, triethylamine (126 g, 1.25 mol) diluted with ethyl acetate (240 g) was added little by little. After the addition, the mixture was stirred at room temperature for 5 hours. Stirring was stopped and the reaction solution was filtered (No. 5A). The filtrate was washed with water and the solvent was distilled off using a rotary evaporator. 1210 g (yield: 94.5%, pale yellow transparent liquid) of the mesylated product was recovered. The 1 1H-NMR is as follows. 1 1H-NMR (CDCl3) δ (ppm): 0.5 ppm (4H, m), 0.9 ppm (3H, t), 1.3 ppm (4H, m), 1.6 ppm (2H, m), 3.0 ppm (3H, s), 3.4 ppm (2H, t), 3.7 ppm (2H, t), 4.3 ppm (2H, t)

[0053] (Amination of the mesylated one-terminal modified siloxane)

Chemical formula

[0054] (Quaternary ignition of amination-modified terminal siloxanes) [ka] (In the formula, n=approximately 10.) The above amination product (5.00 g, 4.25 mmol), water (5.00 g), IPA (5.00 g), and sodium chloroacetate (0.990 g, 8.50 mmol) were added to a 50 mL round-bottom flask and stirred, then heated under reflux for 1 hour. A 20 wt% aqueous solution of sodium hydroxide (0.850 g, 4.25 mmol) was added dropwise, and the mixture was heated under reflux for 13 hours. Potassium carbonate was added to the reaction mixture and stirred to separate the reaction mixture into layers. After separating the upper layer containing the target product, the solvent was removed using a rotary evaporator, and 4.52 g of zwitterionic compound 2 (yield: 86.1%, white viscous solid) was recovered. 1 The H-NMR results are as follows: 1 H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 3.3ppm(6H,s), 3.4ppm(4H,m), 3.7-4.0ppm(4H,m)

[0055] (Synthesis Example 3) Preparation of Zwitterionic Compound 3 (Mesyl group protection of hydroxy-modified siloxanes at one end) [ka] (In the formula, n=approximately 20.) Compound C (20 g, 10 mmol), methanesulfonyl chloride (1.4 g, 12 mmol), and ethyl acetate (20 g) were added to a 100 mL beaker and stirred under cooling conditions (0-10°C). After stirring for 30 minutes, triethylamine (1.2 g, 12 mmol), diluted with ethyl acetate (4.0 g), was added in small amounts. After addition, the mixture was stirred at room temperature for 5 hours. Stirring was stopped, and the reaction mixture was filtered (No. 5A). The filtrate was washed with water, and the solvent was removed using a rotary evaporator. 19.7 g of the mesylated product (yield: 94.8%, pale yellow transparent liquid) was recovered. 1 The H-NMR results are as follows: 1 H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 3.0ppm(3H,s), 3.4ppm(2H,t), 3.7ppm(2H,t), 4.3ppm(2H,t)

[0056] (Amination of mesylated terminally modified siloxane) [ka] (In the formula, n=approximately 20.) The above mesylated product (10 g, 4.8 mmol), tetrabutylammonium bromide (0.31 g, 0.96 mmol), 50% aqueous solution of dimethylamine (1.7 g, 19 mmol), and toluene (10 g) were added to a 100 mL beaker and stirred at 80°C for 6 hours. Stirring was stopped and the reaction mixture was separated into layers. The lower layer was separated and extracted with ethyl acetate. The upper layer and extract were washed with water, and the solvent was removed using a rotary evaporator. 9.54 g of the aminate (yield: 97.8%, pale yellow transparent liquid) was recovered. 1 The H-NMR results are as follows: 1H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 2.2ppm(6H,s), 2.5ppm(2H,t), 3.3ppm(2H,t), 3.5ppm(2H,t)

[0057] (Quaternary ignition of amination-modified terminal siloxanes) [ka] (In the formula, n=approximately 20.) The above amination product (5.0 g, 2.5 mmol), water (10 g), IPA (10 g), and sodium chloroacetate (0.58 g, 5.0 mmol) were added to a 50 mL round-bottom flask and stirred, then heated under reflux for 1 hour. A 20 wt% aqueous solution of sodium hydroxide (0.50 g, 2.5 mmol) was added dropwise, and the mixture was heated under reflux for 13 hours. Potassium carbonate was added to the reaction mixture and stirred to separate the reaction mixture into layers. After separating the upper layer containing the target product, the solvent was removed using a rotary evaporator, and 4.51 g of zwitterionic compound 3 (yield: 87.8%, white viscous solid) was recovered. 1 The H-NMR results are as follows: 1 H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 3.3ppm(6H,s), 3.4ppm(4H,m), 3.7-4.0ppm(4H,m)

[0058] (Comparative synthesis example 1) Preparation of zwitterionic compound 4 (Mesyl group protection of hydroxy-modified siloxanes at one end) [ka] (In the formula, n=approximately 64.) Compound D (10 g, 2.0 mmol), methanesulfonyl chloride (0.27 g, 2.4 mmol), and ethyl acetate (10 g) were added to a 100 mL beaker and stirred under cooling conditions (0-10°C). After stirring for 30 minutes, triethylamine (0.24 g, 2.4 mmol) diluted with ethyl acetate (2.0 g) was added in small amounts. After addition, the mixture was stirred at room temperature for 5 hours. Stirring was stopped, and the reaction mixture was filtered (No. 5A). The filtrate was washed with water, and the solvent was removed using a rotary evaporator. 9.75 g of the mesylated product (yield: 96.0%, pale yellow transparent liquid) was recovered. 1 The H-NMR results are as follows: 1 H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 3.0ppm(3H,s), 3.4ppm(2H,t), 3.7ppm(2H,t), 4.3ppm(2H,t)

[0059] (Amination of mesylated terminally modified siloxane) [ka] (In the formula, n=approximately 64.) The above mesylated product (5.0 g, 0.98 mmol), tetrabutylammonium bromide (0.063 g, 0.20 mmol), dimethylamine 50% aqueous solution (0.36 g, 3.9 mmol), and toluene (5.0 g) were added to a 100 mL round-bottom flask and stirred at 80°C for 6 hours. Stirring was stopped and the reaction mixture was separated into layers. The lower layer was separated and extracted with ethyl acetate. The upper layer and extract were washed with water, and the solvent was removed using a rotary evaporator. 4.19 g of the aminate (yield: 84.4%, pale yellow transparent liquid) was recovered. 1 The H-NMR results are as follows: 1H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 2.2ppm(6H,s), 2.5ppm(2H,t), 3.3ppm(2H,t), 3.5ppm(2H,t)

[0060] (Quaternary ignition of amination-modified terminal siloxanes) [ka] (In the formula, n=approximately 64.) The above amination product (4.0 g, 0.80 mmol), water (8.0 g), IPA (16 g), and sodium chloroacetate (0.19 g, 1.6 mmol) were added to a 50 mL round-bottom flask and stirred, then heated under reflux for 1 hour. A 20 wt% aqueous solution of sodium hydroxide (0.16 g, 0.80 mmol) was added dropwise, and the mixture was heated under reflux for 20 hours. Potassium carbonate was added to the reaction mixture and stirred to separate the reaction mixture into layers. After separating the upper layer containing the target product, the solvent was removed using a rotary evaporator, and 3.25 g of zwitterionic compound 1 (yield: 80.3%, white oily liquid) was recovered. 1 The H-NMR results are as follows: 1 H-NMR(CDCl3)δ(ppm): 0.5ppm(4H,m), 0.9ppm(3H,t), 1.3ppm(4H,m), 1.6ppm(2H,m), 3.3ppm(6H,s), 3.4ppm(4H,m), 3.7-4.0ppm(4H,m)

[0061] (Example 1) Using the zwitterionic compound 1 synthesized in Synthesis Example 1, a 1 wt% solution of water / ethanol (w / w=1 / 1) was prepared. The prepared solution was then further diluted with water to prepare solutions with concentrations of zwitterionic compound 1 of 0.01% by mass, 0.05% by mass, and 0.1% by mass in terms of solid content. The surface tension at each concentration was then measured. The results are shown in Table 1.

[0062] (Surface tension measurement) Equipment: Surface tension meter DY-300 (manufactured by Kyowa Interface Science Co., Ltd.) Condition: Wilhelmy platinum plating method Liquid temperature: 20℃ Evaluation Criteria ◎: 25mN / m or less. ○: Greater than 25 mN / m and less than or equal to 30 mN / m. △: Greater than 30 mN / m and less than or equal to 40 mN / m. ×: Greater than 40 mN / m

[0063] (Examples 2-3, Comparative Examples 1, 2) Except for using the compounds listed in Table 1, the surface tension was evaluated in the same manner as in Example 1. The results are shown in Table 1. In Comparative Example 1, it was not possible to prepare a 1 wt% solution of water / ethanol (w / w=1 / 1), making it difficult to measure the surface tension. In Comparative Example 2, the polyoxyethylene alkyl allyl ether used was Neugen ET-165 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0064] [Table 1]

[0065] The results from Examples 1-3 clearly demonstrate that the compounds of the present invention possess excellent surface tension reduction capabilities. Good results were also obtained compared to the hydrocarbon-based surfactant compound of Comparative Example 2.

[0066] In Comparative Example 1, the high molecular weight of zwitterionic compound 4 resulted in low solubility, making it difficult to prepare a 1 wt% solution in water / ethanol (w / w=1 / 1).

Claims

1. A silicone-based zwitterionic compound represented by the following formula (1). 【Chemistry 1】 (In the formula, R １ R represents an unsubstituted alkyl group having 1 to 4 carbon atoms. ２ ~R ４ (These are identical or different, representing an unsubstituted alkylene group having 1 to 10 carbon atoms. n is 1 to 40.)

2. The silicone-based zwitterionic compound according to claim 1, wherein the weight-average molecular weight of the zwitterionic compound is 300 to 3000.

3. The silicone-based zwitterionic compound according to claim 1, wherein the surface tension of a 0.1% by mass aqueous solution of the zwitterionic compound is 25 mN / m or less.

4. A composition comprising the silicone-based zwitterionic compound described in claim 1.

5. A surfactant comprising the silicone-based zwitterionic compound described in claim 1.

6. A paint comprising the silicone-based zwitterionic compound described in claim 1.

7. A leveling agent comprising the silicone-based zwitterionic compound described in claim 1.

8. A method for producing a silicone-based zwitterionic compound according to claim 1, comprising the step of aminating a compound represented by the following formula (2). 【Chemistry 2】 (In the formula, R １ R represents an unsubstituted alkyl group having 1 to 4 carbon atoms. ２ and R ３ (These are the same or different unsubstituted alkyl groups having 1 to 10 carbon atoms. n is between 1 and 40. X represents a leaving group.)

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