TW202423395A - Amino-modified silicone emulsion composition, method for manufacturing same, fiber treatment agent, and hair cosmetic - Google Patents

Abstract

An amino-modified polysiloxane emulsion composition having a low content of octamethylcyclotetrasiloxane and excellent storage and dilution stability, and imparting excellent use feeling such as smoothness and touch by being formulated in hair cosmetics, comprising (A) 100 parts by mass of amino-modified polysiloxane with a specific amino equivalent and an octamethylcyclotetrasiloxane content of 5,000 ppm or less (B) 0.5 to 20 parts by mass of amino-modified polysiloxane with a viscosity of 10 to 230 mPa·s at 25°C, an amino equivalent of 500 to 3,000 g/mol, and an octamethylcyclotetrasiloxane content of 5,000 ppm or less (C) Non-ionic surfactant: 5~100 parts by mass (D) Water: 10~2,000 parts by mass.

Description

Amine-modified polysilicone emulsion composition and its manufacturing method, fiber treatment agent and hair cosmetic

The present invention relates to an amino-modified polysilicone emulsion composition and a preparation method thereof, a fiber treating agent and a hair cosmetic.

Amino-modified silicone can give excellent softness and texture to fibers, and has been widely used as a fiber treatment agent. In recent years, based on the purpose of improving the texture of clothing, amino-modified silicone has been used in softeners and detergents for general consumers (Patent Document 1: Japanese Patent Publication No. 2008-150756). In addition, amino-modified silicone has excellent adhesion and softening effects on hair, and is also widely used in hair cosmetics (Patent Document 2: Japanese Patent Publication No. 5794637).

In recent years, the regulations of various countries on cyclic low molecular weight siloxanes (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane) have been continuously strengthened, and reducing the cyclic low molecular weight siloxanes in silicone products has become an issue. In particular, there are restrictions on the amount of cyclic low molecular weight siloxanes contained in products such as detergents, softeners, and hair cosmetics such as shampoos and conditioners that flow into wastewater after use.

Amino-modified polysiloxanes are effective in hair cosmetics such as shampoos and conditioners, and fiber treatment agents such as washing detergents and softeners. However, amino-modified polysiloxanes contain cyclic low-molecular-weight siloxanes as a by-product during production. Fiber treatment agents and hair cosmetics containing amino-modified polysiloxanes sometimes contain a large amount of cyclic low-molecular-weight siloxanes.

In order to reduce the cyclic low molecular weight silicone in these products, a method of removing volatile components is used in the production of amino-modified polysiloxane. By using amino-modified polysiloxane that has previously reduced the cyclic low molecular weight silicone, the cyclic low molecular weight silicone contained in fiber treatment agent products and hair cosmetic products can be reduced, but the amino-modified polysiloxane with volatile components removed will have reduced emulsification and greatly reduce the stability when made into an emulsion. In addition, amino-modified polysiloxane will produce cyclic low molecular weight silicone as a by-product during storage.

In order to reduce the amount of cyclic low molecular weight contained in amino-modified polysilicone emulsion, the following review has been conducted so far. In Japanese Patent Publication No. 2013-532741 (Patent Document 3), a method for producing an emulsion using polydialkylsiloxane, amino-functional organic polysiloxane, quaternary ammonium surfactant and water is proposed. In Patent Document 3, quaternary ammonium surfactant must be prepared, but when the emulsion containing quaternary ammonium surfactant is prepared in shampoo containing anionic surfactant, there is a risk of reduced stability.

In the Japanese Patent Publication No. 2015-500926 (Patent Document 4), it is proposed to apply an emulsion of amino-functional organic polysiloxane, quaternary ammonium surfactant, non-ionic surfactant and water to fibers. It is reported that compared with the previous method, octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in the emulsion are less likely to increase over time. However, the quaternary ammonium surfactant must be prepared. As in the case of Patent Document 3, the emulsion of Patent Document 4 may have reduced stability when prepared in shampoo containing anionic surfactants.

In Japanese Patent Gazette No. 6258213 (Patent Document 5), an emulsion composition is reported, which is composed of an amino-functional organic polysiloxane with an amount of less than 0.1% by mass of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), a quaternary ammonium surfactant, a nonionic surfactant, and water. However, the quaternary ammonium surfactant must be prepared, and similar to the cases of Patent Documents 3 and 4, the emulsion of Patent Document 5 may have reduced stability when prepared in shampoo or the like prepared with an anionic surfactant. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2008-150756 [Patent Document 2] Japanese Patent Publication No. 5794637 [Patent Document 3] Japanese Patent Publication No. 2013-532741 [Patent Document 4] Japanese Patent Publication No. 2015-500926 [Patent Document 5] Japanese Patent Publication No. 6258213

[Problems to be solved by the invention]

The present invention was completed in view of the above situation, and its purpose is to provide an amino-modified polysilicone emulsion composition with a low content of octamethylcyclotetrasiloxane (D4), excellent storage and dilution stability, and to impart excellent smoothness, touch and other use feelings by being formulated into hair cosmetics or fiber treatment agents. [Means for solving the problem]

As a result of active research to achieve the above-mentioned purpose, the inventors have found that an amino-modified polysiloxane emulsion composition containing two amino-modified polysiloxanes (A) and (B) of different viscosities, (C) a non-ionic surfactant and (D) water has a low content of octamethylcyclotetrasiloxane and excellent storage and dilution stability. Furthermore, by being formulated into hair cosmetics or fiber treatment agents, the composition can be given excellent use feeling such as smoothness and touch, thereby completing the present invention.

Therefore, the present invention provides the following inventions. 1. An amino-modified polysilicone emulsion composition, wherein the average particle size of the emulsified particles is 400 nm or less, and contains (A) an amino-modified polysilicone represented by the following average composition formula (I), an amino-modified polysilicone having an amino equivalent of 1,000 to 25,000 g/mol and a viscosity of 250 to 100,000 mPa·s at 25°C, and an octamethylcyclotetrasiloxane content of 5,000 ppm or less: 100 parts by weight [wherein, R ¹ is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is independently a group represented by the general formula (2), -R ⁴ -(NH-R ⁵ ) _p -NH ₂ (2) (R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1), R ³ is independently a group selected from R ¹ , R ² , -OH, -OCH ₃ and -OC ₂ H ₅ , a, b, c, d and e are numbers satisfying the range of 2≦a≦10, 10≦b≦1,300, 0≦c≦50, 0≦d≦5, 0≦e≦5, but when c=0, R ³ is R ² ], (B): Amino-modified polysiloxane represented by the following average composition formula (II), with a viscosity of 10-230 mPa·s at 25°C, an amino equivalent of 500-3,000 g/mol, and an octamethylcyclotetrasiloxane content of 5,000 ppm or less: 0.5-20 parts by weight [wherein, R ¹ is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is independently a group represented by the general formula (2), -R ⁴ -(NH-R ⁵ ) _p -NH ₂ (2) (R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1), R ³ is independently a group selected from R ¹ , R ² , -OH, -OCH ₃ and -OC ₂ H ₅ , f and g are 5≦f≦200, 0≦g≦30, but when g=0, R ³ is R ² ], (C) nonionic surfactant: 5~100 parts by mass (D) water: 10~2,000 parts by mass. 2. The amino-modified polysiloxane emulsion composition of 1, wherein the nonionic surfactant (C) does not contain polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether. 3. The amino-modified polysiloxane emulsion composition of 1 or 2, wherein the content of decamethylcyclopentasiloxane in the components (A) and (B) is 5,000 ppm or less. 4. The amino-modified polysiloxane emulsion composition of any one of 1 to 3, wherein the content of dodecamethylcyclohexasiloxane in the components (A) and (B) is 5,000 ppm or less. 5. The amino-modified polysiloxane emulsion composition of any one of 1 to 4, wherein the content of the component (A) that is volatile when heated at 105°C for 3 hours is 1.5% by mass or less. 6. An amino-modified polysilicone emulsion composition as described in any one of 1 to 4, wherein the content of the component (B) that is volatile upon heating at 105°C for 3 hours is 1.5% by mass or less. 7. An amino-modified polysilicone emulsion composition as described in any one of 1 to 6, which does not contain a cationic surfactant. 8. An amino-modified polysilicone emulsion composition as described in any one of 1 to 7, which does not contain an anionic surfactant. 9. A fiber treatment agent comprising an amino-modified polysilicone emulsion composition as described in any one of 1 to 8. 10. A hair cosmetic comprising an amino-modified polysilicone emulsion composition as described in any one of 1 to 8. 11. A method for producing an amino-modified polysilicone emulsion composition as described in any one of 1 to 8, comprising the step of mixing the above-mentioned components (A), (B), (C) and (D). [Effect of the invention]

According to the present invention, it is found that octamethylcyclotetrasiloxane (D4) has a low content and excellent storage and dilution stability. Furthermore, by being formulated into hair cosmetics or fiber treatment agents, it can impart excellent use feelings such as smoothness and touch, thereby completing the present invention.

The present invention is described in detail below. [Component (A)] The component (A) of the present invention is represented by the following average composition formula (I), and is an amino-modified polysiloxane having a viscosity of 250 to 100,000 mPa·s at 25°C, an amino equivalent of 1,000 to 25,000 g/mol, and an octamethylcyclotetrasiloxane content of 5,000 ppm or less. One type may be used alone or two or more types may be used in combination. [In the formula, R ¹ is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is independently a group represented by the general formula (2), -R ⁴ -(NH-R ⁵ ) _p -NH ₂ (2) (R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1), R ³ is independently a group selected from R ¹ , R ² , -OH, -OCH ₃ and -OC ₂ H ₅ , and a, b, c, d and e are numbers satisfying the range of 2≦a≦10, 10≦b≦1,300, 0≦c≦50, 0≦d≦5, and 0≦e≦5, but when c=0, R ³ is R ² ].

R ¹ is independently a non-substituted monovalent alkyl group having 1 to 20 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl; and aryl groups such as phenyl, tolyl, and naphthyl. Among them, methyl, long-chain (6 to 20 carbon atoms) alkyl, and phenyl are preferred, and methyl is more preferred.

R ² is independently a group represented by the general formula (2). -R ⁴ -(NH-R ⁵ -) _p NH ₂ (2) (R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1) Examples of the divalent organic group having 1 to 6 carbon atoms include divalent alkylene groups, alkenylene groups, and arylene groups. Examples of the group represented by the general formula (2) include 2-aminoethyl, 3-aminopropyl, 6-aminohexyl, N-(2-aminoethyl)-3-aminopropyl, N-(3-aminopropyl)-3-aminopropyl, and N-(2-aminoethyl)-6-aminohexyl. Among them, 3-aminopropyl or N-(2-aminoethyl)-3-aminopropyl is preferred from the viewpoint of easy availability of raw materials.

R ³ is independently selected from R ¹ , R ² , -OH, -OCH ₃ and -C ₂ H _5. The amino-modified polysilicone (A) of the present invention is a group represented by the general formula (2) containing one or more R ² , and R ³ and a, b, c, d and e are appropriately selected as described above. When the group represented by the general formula (2) is not contained, the amount of amino groups in the amino-modified polysilicone is too small, so that the adhesion to fibers or hair is reduced. When c=0, R ³ is R ² , for example, R ³ =R ² , when 0＜d, c may be less than 1 or c=0. In addition, the content of methyl groups relative to the total number of R ¹ , R ² and R ³ is preferably 70% or more.

a is 2≦a≦10, preferably 2≦a≦5, and more preferably a = 2. When a exceeds 10, the viscosity of the amino-modified polysilicone becomes too low, thereby reducing the emulsification property.

b is 10≦b≦1,300, preferably 150≦b≦1,000, more preferably 170≦b≦500, and even more preferably 200≦b≦450. When b is less than 10, the viscosity of the amino-modified polysilicone becomes too low, and the effect of imparting smoothness to fibers and hair is reduced. On the other hand, when b exceeds 1,300, the viscosity of the amino-modified polysilicone becomes too high, and the emulsification property is reduced.

c is 0≦c≦50, preferably 1≦c≦30, more preferably 1≦c≦15, and even more preferably 3≦c≦10. On the other hand, when c exceeds 50, the amount of amine groups in the amino-modified polysilicone is too high, which may cause the fiber to turn yellow during treatment.

d is 0≦d≦5, preferably d=0. When d exceeds 5, the viscosity of the amino-modified polysilicone becomes too low and the emulsification property becomes poor.

e is 0≦e≦5, preferably e=0. When e exceeds 5, the viscosity of the amino-modified polysilicone becomes too low and the emulsification property becomes poor.

The viscosity of component (A) at 25°C is 250~100,000 mPa·s, preferably 280~50,000 mPa·s, more preferably 300~10,000 mPa·s, and even more preferably 1,000~3,500 mPa·s. When the viscosity does not reach the above lower limit, the effect of imparting smoothness to fibers or hair is reduced. And when it exceeds the above upper limit, the emulsification property deteriorates. In the present invention, the viscosity is a value measured by a BM type viscometer or a BH type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.). In addition, according to the viscosity, the rotor, the number of rotations and the rotation time are appropriately selected as follows.

The viscosity of the present invention is determined by setting the rotor and the number of rotations as follows based on the viscosity of the object being measured. When the viscosity is 10mPa·s or more but less than 100mPa·s, use rotor No. 1 and rotate at 30rpm. When the viscosity is 100mPa·s or more but less than 500mPa·s, use rotor No. 2 and rotate at 30rpm. When the viscosity is 500mPa·s or more but less than 3,000mPa·s, use rotor No. 3 and rotate at 30rpm. When the viscosity is 3,000mPa·s or more but less than 15,000mPa·s, use rotor No. 4 and rotate at 30rpm. When the viscosity is 15,000mPa·s or more but less than 40,000mPa·s, use rotor No. 6 and rotate at 20rpm. When the viscosity is 40,000mPa·s or more, use rotor No. 7 and rotate at 20rpm.

The amino equivalent of component (A) is 1,000~25,000 g/mol, preferably 1,200~20,000 g/mol, more preferably 1,300~10,000 g/mol, and even more preferably 1,400~4,000 g/mol. When the amino equivalent does not reach the aforementioned lower limit, there is a possibility of yellowing of the fiber during treatment due to excessive amino groups. On the other hand, when the amino equivalent exceeds the aforementioned upper limit, there are too few amino groups, and the hydrophilicity that should be given to the amino-modified polysilicone is insufficient, thereby deteriorating the emulsification. In addition, the amino equivalent of the present invention is the number of grams of amino-modified polysilicone that can be neutralized by 1 mol of hydrochloric acid, which is theoretically molecular weight/number of nitrogen atoms. Amine equivalent can be measured by neutralization titration, such as the automatic titration device manufactured by Hiranuma Sangyo Co., Ltd. More specifically, it can be measured by the following method. The target amino-modified siloxane is dissolved in a solvent of toluene/IPA mixed at a mass ratio of 1/1, and the amine equivalent is measured by titrating with hydrochloric acid to an end point of pH=7 using an automatic titrator. The amine equivalent is calculated as the molecular weight of polysilicone per 1 mol of amine group and is calculated by the following formula. Amine equivalent (g/mol) = {[sample amount (g)] × 1,000)} / {[hydrochloric acid equivalent concentration (N)] × [hydrochloric acid titration amount (mL)] × [hydrochloric acid valency (F)]}

The content of octamethylcyclotetrasiloxane in component (A) is 5,000 ppm (mass) or less, preferably 3,000 ppm or less, and more preferably 1,000 ppm or less. The content of decamethylcyclopentasiloxane is preferably 5,000 ppm or less. More preferably, it is 3,000 ppm or less, and even more preferably, it is 1,000 ppm or less. The content of dodecamethylcyclohexasiloxane is preferably 5,000 ppm or less, more preferably, it is 3,000 ppm or less, and even more preferably, it is 1,000 ppm or less. The lower limits of the contents of octamethyltetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are not limited, but can be, for example, 10 ppm each.

The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (A) can be determined by gas chromatography. Specifically, 0.1 g of the sample to be measured is added to 10 mL of acetone and shaken for about 2 hours. After the cyclic low molecular weight siloxane is extracted into the acetone solution by shaking, the acetone solution of the supernatant is measured by gas chromatography.

(A) Amino-modified polysiloxane can be easily obtained by a known synthesis method. For example, as described in the example of International Publication No. 2021/1320571, a cyclic siloxane such as octamethylcyclotetrasiloxane is subjected to a balancing reaction with 3-aminopropyldiethoxymethylsilane or N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane or its hydrolyzate, and a compound selected from hexamethyldisiloxane as other raw materials in the presence of a catalyst such as an alkali metal hydroxide or tetramethylammonium hydroxide.

The amount of the component (A) that is present in the component (A) and that is volatile when heated at 105°C/3 hours is preferably 1.5 mass % or less, more preferably 1.2 mass % or less, and even more preferably 1.0 mass % or less. The amount of the component that is volatile when heated at 105°C/3 hours is considered to be mainly composed of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane. Therefore, by setting the amount of the component that is volatile when heated at 105°C/3 hours to less than the above value, the cyclic low molecular weight siloxane contained in the obtained amino-modified polysiloxane emulsion can be reduced. The components that are volatile when heated at 105°C for 3 hours are, for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and low molecular weight organic polysiloxanes with amino groups. The low molecular weight refers to organic polysiloxanes with a degree of polymerization of 8 or less, especially a degree of polymerization of 7 or less, and are linear, branched or cyclic. There is no lower limit on the content of the above volatile components, and the less the better.

The determination of the amount of components that are volatile when heated at 105°C/3 hours can be performed using a constant temperature thermostat with air supply. Specifically, 2.0g of amino-modified polysilicone (hereinafter referred to as sample) is weighed into a 50ml beaker, and the beaker is placed in a constant temperature thermostat with air supply set at 105°C for 3 hours. After 3 hours, the beaker is taken out, cooled in a desiccator and weighed to determine the amount of mass loss of the sample. Based on the mass of the sample before heating and storage, the mass ratio of the component that is volatile upon heating is calculated as 100%. When the amino-modified polysilicone is placed in a constant temperature thermostat with air supply, volatile low molecular weight compounds with a boiling point exceeding 105°C, for example, volatile low molecular weight compounds with a boiling point of 200°C, also volatilize.

When synthesizing component (A), octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane are by-produced due to the manufacturing method. However, in order to make the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane below 5,000 ppm, it is preferred to carry out a step of removing volatile components of the obtained component (A). Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (A) can be removed by a known method. For example, by blowing nitrogen into component (A) and performing reduced pressure distillation at 80-200°C, 5-40 hours, and 5-30 mmHg, the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in component (A) can be reduced to 5,000 ppm or less.

[Component (B)] Component (B) is represented by the following average composition formula (II), and is an amino-modified polysiloxane having a viscosity of 10 to 230 mPa·s at 25°C, an amino equivalent of 500 to 3,000 g/mol, and an octamethylcyclotetrasiloxane content of 5,000 ppm or less. One type may be used alone or two or more types may be used in combination. [wherein, R ¹ is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is independently a group represented by the general formula (2), -R ⁴ -(NH-R ⁵ ) _p -NH ₂ (2) (R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1), R ³ is independently a group selected from R ¹ , R ² , -OH, -OCH ₃ and -OC ₂ H ₅ , and f and g are 5≦f≦200, 0≦g≦30, but when g=0, R ³ is R ² ].

R ¹ is independently a non-substituted monovalent alkyl group having 1 to 20 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl; and aryl groups such as phenyl, tolyl, and naphthyl. Among them, methyl, long-chain (6 to 20 carbon atoms) alkyl, and phenyl are preferred, and methyl is more preferred.

R ² is independently a group represented by the general formula (2). -R ⁴ -(NH-R ⁵ -) _p NH ₂ (2) (R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1) Examples of the divalent organic group having 1 to 6 carbon atoms include divalent alkylene groups, alkenylene groups, and arylene groups. Examples of the group represented by the general formula (2) include 2-aminoethyl, 3-aminopropyl, 6-aminohexyl, N-(2-aminoethyl)-3-aminopropyl, N-(3-aminopropyl)-3-aminopropyl, and N-(2-aminoethyl)-6-aminohexyl. Among them, 3-aminopropyl or N-(2-aminoethyl)-3-aminopropyl is preferred from the viewpoint of easy availability of raw materials.

R ³ is independently selected from R ¹ , R ² , -OH, -OCH ₃ and -C ₂ H _5. The amino-modified polysilicone (B) of the present invention is a polysilicone containing one or more groups represented by the general formula (2) of R ² , and R ³ , f and g are appropriately selected as described above. When the polysilicone does not contain a group represented by the general formula (2), the amount of amino groups in the amino-modified polysilicone is too small, and the adhesion to fibers or hair is reduced. When g=0, R ³ is R ² , and f is 5≦f≦200, preferably 10≦f≦100, more preferably 20≦f≦80, and particularly preferably 30≦f≦50. When f is less than 5, the viscosity of the amino-modified silicone becomes too low, and the effect of imparting smoothness to fibers and hair is reduced. On the other hand, when f exceeds 200, the effect of improving the emulsification of component (B) is reduced. g is 0≦g≦30, preferably 1-10.

The viscosity of component (B) at 25°C is 10 to 230 mPa·s, preferably 20 to 200 mPa·s, more preferably 30 to 180 mPa·s, and even more preferably 35 to 80 mPa·s. When the viscosity is less than the above lower limit, the effect of imparting smoothness to fibers or hair becomes poor. When the viscosity exceeds the above upper limit, the effect of improving the emulsification of component (B) decreases.

The amine equivalent of component (B) is 500-3,000 g/mol, preferably 600-2,500 g/mol, more preferably 750-2,200 g/mol, and particularly preferably 1,000-2,000 g/mol. When the amine equivalent is less than the lower limit, there is a possibility that the fiber will turn yellow when treated due to excessive amine groups. On the other hand, when the amine equivalent exceeds the upper limit, there is too little amine group, which reduces the effect of improving the emulsification of component (B).

The content of octamethylcyclotetrasiloxane in the component (B) is 5,000 ppm or less, preferably 3,000 ppm or less, and more preferably 1,000 ppm or less. The content of decamethylcyclopentasiloxane is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and even more preferably 1,000 ppm or less. The content of dodecamethylcyclohexasiloxane is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and even more preferably 1,000 ppm or less. The lower limits of the contents of octamethyltetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are not limited, but can be, for example, 10 ppm each.

The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in the component (B) can be determined by gas chromatography. Specifically, 0.1 g of the sample to be measured is added to 10 mL of acetone and shaken for about 2 hours. After the cyclic low molecular weight siloxane is extracted into the acetone solution by shaking, the acetone solution of the supernatant is measured by gas chromatography.

The amount of the component (B) that is volatile when heated at 105°C/3 hours is preferably 1.5 mass % or less, more preferably 1.2 mass % or less, and even more preferably 1.0 mass % or less. The amount of the component that is volatile when heated at 105°C/3 hours is considered to be mainly composed of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Therefore, by setting the amount of the component that is volatile when heated at 105°C/3 hours to less than the above value, the cyclic low molecular weight siloxane contained in the obtained amino-modified polysiloxane emulsion can be reduced. The components that are volatile when heated at 105°C for 3 hours are, for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and low molecular weight organic polysiloxanes with amino groups. The low molecular weight is a linear, branched or cyclic organic polysiloxane with a degree of polymerization of 8 or less, especially a degree of polymerization of 7 or less. There is no lower limit on the content of the above volatile components, and the less the better. The determination of the amount of the components that are volatile when heated at 105°C for 3 hours is the same as above.

(B) Amino-modified polysiloxane can be easily obtained by a known synthesis method, similar to component (A). For example, it can be obtained by allowing a cyclic siloxane such as octamethylcyclotetrasiloxane to react with 3-aminopropyldiethoxymethylsilane or N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane or its hydrolyzate, and a compound selected from hexamethyldisiloxane as other raw materials in the presence of a catalyst such as an alkali metal hydroxide or tetramethylammonium hydroxide.

When synthesizing component (B), octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane are by-produced due to the manufacturing method. However, in order to reduce the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane to 5,000 ppm or less, it is preferred to perform a step of removing volatile components of the obtained component (B). Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (B) can be removed by a known method. For example, by blowing nitrogen into component (B) and removing it under reduced pressure at 80-200°C, 5-40 hours, and 0.5-30 mmHg or less, the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in component (B) can be set to 5,000 ppm or less.

Component (B) is an amino-modified polysilicone different from component (A). The effects of component (B) are considered to be as follows. The amino polysilicone of component (A) is obtained by removing cyclic low molecular weight siloxane, but at this time, low molecular weight components containing hydrophilic amine groups are also removed. Low molecular weight components containing amine groups are considered to play the role of emulsification enhancers, but the stability of the resulting emulsion becomes lower because the emulsification of the removed component (A) is low. The inventors of the present invention believe that amino polysilicone with a specific viscosity and amine equivalent like component (B) has the function of improving emulsification. In the amino-modified polysilicone emulsion composition of the present invention, it is considered that by using component (B) in addition to component (A), the emulsification property is not reduced even when the cyclic low molecular weight siloxane is removed, thereby improving the stability of the obtained emulsion.

The content of component (B) is 0.5 to 20 parts by mass relative to 100 parts by mass of component (A). Preferably, it is 1 to 15 parts by mass, more preferably, it is 2 to 10 parts by mass, and even more preferably, it is 2.5 to 5.0 parts by mass relative to 100 parts by mass of component (A).

[Component (C)] Component (C) is a nonionic surfactant, which may be used alone or in combination of two or more. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyglycerol fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene hardened castor oil fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene modified organic polysiloxane, polyoxyethylene polyoxypropylene modified organic polysiloxane, etc. Among them, polyoxyethylene alkyl ether is preferred, and polyoxyethylene alkyl ether and polyoxyethylene propylene alkyl ether are more preferred.

From the viewpoint of environmental load, the surfactant as component (C) preferably does not contain polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

From the perspective of emulsion stability, non-ionic surfactants (when using multiple types, the HLB value of the entire mixture) are preferably in the range of HLB values of 10.0~18.0, more preferably HLB values of 11.0~17.0, and even more preferably 12.0~16.0. HLB is a value calculated by the Griffin method. The HLB value is calculated by the following formula. N=N1×W1+N2×W2 N: HLB value when using two surfactants with different HLB values: N N1, N2: HLB of each surfactant W1, W2: Weight fraction of each surfactant (W1+W2=1)

In the composition of the present invention, in addition to the nonionic surfactant of component (C), a cationic surfactant or anionic surfactant may be used.

Examples of anionic surfactants include alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylbenzene sulfonates, polyoxyethylene alkylphenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkane sulfonates, N-acyl taurates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, monoalkyl phosphates, dialkyl phosphates, polyoxyethylene alkyl ether phosphates, and the like.

Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dimeroxyethylenealkylmethylammonium salts, trimeroxyethylenealkylammonium salts, and alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamideamine salts.

Since the use of cationic surfactants or anionic surfactants will reduce the stability when mixed with ionic agents such as shampoo, the composition of the present invention preferably does not contain cationic surfactants or anionic surfactants.

The content of component (C) is 5 to 100 parts by mass, preferably 2 to 80 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 4 to 60 parts by mass, relative to 100 parts by mass of component (A). Particularly preferably, it is 15 to 35 parts by mass relative to 100 parts by mass of component (A). If the content of component (C) is less than the above lower limit, the stability will be deteriorated, and if it exceeds the above upper limit, the effect of imparting smoothness to fibers and hair will be deteriorated.

[(D) component] (D) component is water, and any water such as ion exchange water and purified water can be used. The content of (D) component is 10 to 2,000 parts by mass, preferably 50 to 1,000 parts by mass, relative to 100 parts by mass of (A) component.

The average particle size of the emulsified particles of the amino-modified silicone emulsion composition of the present invention is 400 nm or less, preferably 350 nm or less, and even more preferably 300 nm or less. When the average particle size is greater than 400 nm, the stability of the emulsion is low, and separation may occur immediately. The lower limit of the average particle size is not limited, but may be, for example, 80 nm. In order to keep the particle size within this range, it is only necessary to adjust the content of component (C), the shear force during the preparation of the emulsion, and the temperature. The average particle size of the present invention is the particle size at 50% of the volume cumulative value in the particle size distribution obtained by the laser diffraction/scattering method. An example of a measuring device is LA960 (manufactured by HORIBA). In the present invention, the average particle size is a value measured using LA960 (manufactured by HORIBA Corporation), and represents a particle size at which the cumulative value is 50% in the particle size distribution.

[Manufacturing method] The amino-modified polysilicone emulsion composition of the present invention only needs to have a step of mixing components (A) to (D), and can be prepared, for example, by the following method. Component (D) can be mixed with component (A), component (B) and component (C), and emulsified and dispersed in a conventional manner. Among them, an oil-in-water (O/W type) emulsion is preferred. Moreover, water can be further added to the emulsion for dilution and can be used for the purposes described below. The amount of water used for dilution is not particularly limited, and can be appropriately adjusted according to the purpose.

An example of the details of the emulsification formula is as follows. Mix (A) amino-modified polysilicone, (B) amino-modified polysilicone, (C) nonionic surfactant, and (D) a portion of water in Combi Mix (Primix), and emulsify with a homomixer (a stirrer that rotates with a rotor in a rotating stator) at 2,000 rpm or with a disperser (a stirrer that rotates with toothed blades) at 2,000 rpm and an anchor at 20 rpm. After the whole is emulsified, stir with a disperser at 2,000 rpm and an anchor at 30 rpm for 15 to 180 minutes until it becomes a specific particle size, add the remaining component (D) water and dilute with a homogenizer at 2,000 to 3,000 rpm to prepare the amino-modified polysilicone emulsion composition of the present invention.

The temperature during emulsification is not particularly specified, but preferably 0~80℃, more preferably 10~60℃. Emulsification is easy at a temperature of 10℃~60℃, and the emulsion produced tends to be more stable. When the amino-modified polysilicone emulsion composition is heated at 70~80℃ for 1~30 hours, the particle size decreases or the viscosity decreases. Therefore, when manufacturing the amino-modified polysilicone emulsion composition, a heating step at 70~80℃ can also be added according to the target particle size or viscosity. During emulsification, the pressure can be not only normal pressure, but also reduced pressure or increased pressure. When emulsification is carried out under reduced pressure or increased pressure, bubbles are not easily mixed in, and emulsification can be effectively achieved. The pressure during decompression is preferably higher than the vapor pressure of the raw material so that the raw material does not volatilize. Also, the emulsification time is not particularly specified, as long as it is set to a time that can achieve the target particle size, but it is generally preferably 30 to 360 minutes.

The emulsifier used during emulsification is not particularly limited as long as it can stir the raw materials or the emulsified composition. Examples of the emulsifier include a colloid mill (IKA, PUC, Nippon Seiki, IWAKI) having a stirring section consisting of a rotor and a stator, a high shear mixer (Silverson, Primix), a homomixer (Primix), a homodisperser (Primix), an AGI homomixer (Primix), a three-axis dispersion kneading machine that combines a homomixer, a homodisperser, and an anchor mixer (Combi Mix) (Primix), a two-axis mixer with screws in the same or different directions, such as HAAKE Mini Lab II (Thermo Technology), or MC15, MC5 (Leo Lab), etc.

In addition to the above-mentioned components (A) to (D), the amino-modified polysilicone emulsion composition of the present invention can be mixed with various optional components as needed within the scope that does not impair the purpose of the present invention. Examples of such optional components include polysilicone components other than components (A) and (B), additives, etc.

Specific examples of the polysilicone component other than components (A) and (B) include silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, and alkyl-modified silicone oil. When the polysilicone component other than components (A) and (B) is added, the amount thereof is preferably 5 to 10 parts by weight relative to 100 parts by weight of component (A).

As additives, inorganic acids or organic acids can be formulated, for example, to improve the emulsion stability. Specific examples of inorganic acids or organic acids include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid, lactic acid, citric acid, etc. The amount of inorganic acid or organic acid added can be set arbitrarily, but it is preferably an amount that adjusts the pH of the emulsion composition of the present invention to 3-7. Examples of other additives include protective colloid agents, thickeners, antifreeze agents, preservatives, antirust agents, antioxidants, fragrances, ultraviolet absorbers, antibacterial agents, hardening catalysts, organic powders, inorganic powders, dyes, pigments, fillers, etc. When the above additives are formulated, the amount thereof is not particularly limited as long as it does not impair the purpose of the present invention. For example, the amount thereof in the amino-modified polysilicone emulsion composition may be 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less.

[Fiber treatment agent] In addition, the amino-modified polysilicone emulsion composition of the present invention can also be used in fiber treatment agents such as softeners or detergents. For example, the amino-modified polysilicone emulsion composition can be mixed in the fiber treatment agent at 0.1-20 mass%, preferably 0.5-10 mass%. If the content is above the lower limit, the risk of quality degradation is reduced. On the other hand, if the content is below the upper limit, the risk of yellowing during storage is reduced. It can also be diluted with water when used. Furthermore, there is no particular restriction on the fibers or fiber products that can be treated with the fiber treatment agent of the present invention. It is effective for natural fibers such as cotton, silk, linen, wool, angora wool, mohair, etc., synthetic fibers such as polyester, polyethylene, polypropylene, nylon, acrylic, spandex, etc., and blended fibers formed by combining these fibers. Moreover, its form and shape are not limited to raw material shapes such as short fibers, filaments, tows, yarns, etc., and various processed forms such as fabrics, knitwear, stuffing, non-woven fabrics, etc. can also be treated by the fiber treatment agent of the present invention.

[Hair cosmetics] The amino-modified polysilicone emulsion composition of the present invention can be used in hair cosmetics such as shampoo or conditioner. As for the content, for example, the amino-modified polysilicone emulsion composition is preferably in an amount of 0.1 to 20% by mass in the hair cosmetic, and more preferably 0.5 to 10% by mass. If the content is above the lower limit, a sufficient hair care effect can be obtained for the hair, and if it is below the upper limit, there is no sticky feeling and it is a better touch. The hair cosmetic can further be formulated with known ingredients, such as cationic surfactants, polyols, hair active ingredients, etc. [Example]

The following examples and comparative examples are shown to specifically illustrate the present invention, but the present invention is not limited to the following examples. When the content is recorded in the name of the prepared product, it is the content of the prepared product. The measurement methods are as follows.

Average particle size: The emulsion composition was diluted about 10 times with water and measured using a laser diffraction particle size analyzer (LA960 manufactured by HORIBA). The average particle size is the particle size at which the cumulative volume value is 50%.

pH: The emulsion composition was measured at 25°C using a pH meter (LAQUA manufactured by HORIBA).

Viscosity: measured at 25°C using a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.).

Amine equivalent: measured by an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.). The target amino-modified siloxane is dissolved in a solvent of toluene/IPA mixed at a mass ratio of 1/1, and the amine equivalent is measured by titrating with hydrochloric acid to an end point of pH=7 using an automatic titrator. The amine equivalent is calculated as the molecular weight of polysilicone per 1 mol of amino group and is calculated by the following formula. Amine equivalent (g/mol) = {[sample amount (g)] × 1,000)}/{[hydrochloric acid equivalent concentration (N)] × [hydrochloric acid titration amount (mL)] × [hydrochloric acid valency (F)]}

The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane was measured as follows. 0.1 g of the sample was added to 10 mL of acetone and shaken for about 2 hours. After the cyclic low molecular weight siloxane was extracted into the acetone solution by shaking, the acetone solution of the supernatant was measured by a gas chromatograph (Agilent 7890B (manufactured by Agilent Technologies)). The column of the gas chromatograph was DB-5MS (manufactured by Agilent Technologies), the temperature inside the column during measurement was 300°C, and tetradecane was used as the internal standard substance.

Volatile component content when heated at 105℃/3 hours: Weigh 2.0g of amino-modified polysilicone in a 50mL beaker, and place the beaker in a constant temperature thermostat set at 105℃ for 3 hours. Take out the beaker after 3 hours, cool it in a desiccator and weigh it to determine the mass loss of the sample. The constant temperature thermostat is made by YAMATO Science Co., Ltd. (DN-610H). The air volume during heating is ^12.3m3 /min. The volume of the thermostat is 223L, the internal dimensions are 620×600×600mm, and there are two exhaust ports with an inner diameter of 30mm on the back. The 50 mL beaker used was a 50 mL beaker manufactured by Shibata Scientific Co., Ltd. (HARIO) (product code 010020-5051A, main body outer diameter 46 mm, height 61 mm).

(A) Amino-modified polysiloxane (A-1) Amino-modified polysiloxane is an amino-modified siloxane represented by the following average formula (I): R ¹ ：-CH ₃ ，R ² ：-C ₃ H ₆ NHC ₂ H ₄ NH ₂ ，R ³ ：-CH ₃ ，a=2，b=200，c=1，d=0，e=0，Viscosity：400mPa·s，Amine equivalent：7,000g/molAmount of octamethylcyclotetrasiloxane in component (A-1): less than 100ppm (below the detection limit)Amount of decamethylcyclopentasiloxane in component (A-1): 200ppmAmount of dodecamethylcyclohexasiloxane in component (A-1): 300ppmContent of components volatile when heated at 105℃/3h in component (A-1): 0.6% by mass

(A-1) Production method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 90.01 parts by mass of octamethylcyclotetrasiloxane, 1.08 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 8.81 parts by mass of dimethylpolysiloxane represented by the following formula (III), and 0.07 parts by mass of potassium silicate were heated at 150°C for 4 hours to carry out an equilibrium reaction. Subsequently, 0.03 parts by mass of epichlorohydrin was added, and the mixture was heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a reduced pressure belt was applied at 140°C and 15 mmHg or less for 10 hours to remove the low-boiling distillate, thereby obtaining an oily compound (A-1).

(A-2) Amino-modified polysiloxane Amino-modified polysiloxane represented by the above average formula (I): R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -CH ₃ , a=2, b=280, c=6, d=0, e=0, viscosity: 1,300 mPa·s, amine equivalent: 1,700 g/mol Amount of octamethylcyclotetrasiloxane in component (A-2): less than 100 ppm Amount of decamethylcyclopentasiloxane in component (A-2): 200 ppm Amount of dodecamethylcyclohexasiloxane in component (A-2): 200 ppm Content of components volatile when heated at 105°C/3 hours in component (A-2): 0.4 mass%

(A-2) Production method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 91.10 parts by mass of octamethylcyclotetrasiloxane, 4.40 parts by mass of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane hydrolyzate, 4.40 parts by mass of dimethylpolysiloxane represented by the above formula (III), and 0.07 parts by mass of potassium silicate are heated at 150°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin is added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a reduced pressure zone was applied at 140°C and below 15 mmHg for 10 hours to remove the low-boiling distillate and obtain an oily compound (A-2).

(A-3) Amino-modified polysiloxane Amino-modified polysiloxane represented by the above average formula (I): R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NH ₂ , R ³ : -CH ₃ , a=2, b=410, c=8, d=0, e=0, viscosity: 2,700 mPa·s, amine equivalent: 3,900 g/mol Amount of octamethylcyclotetrasiloxane in component (A-3): 100 ppm Amount of decamethylcyclopentasiloxane in component (A-3): 300 ppm Amount of dodecamethylcyclohexasiloxane in component (A-3): 400 ppm Content of components volatile when heated at 105°C/3 hours in component (A-3): 0.6 mass%

(A-3) Production method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 93.32 parts by mass of octamethylcyclotetrasiloxane, 3.21 parts by mass of 3-aminopropylmethyldiethoxysilane hydrolyzate, 3.37 parts by mass of dimethylpolysiloxane represented by the above formula (III), and 0.07 parts by mass of potassium silicate are heated at 150°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin is added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a decompression zone was applied at 140°C and below 15 mmHg for 10 hours to remove the low-boiling distillate and obtain an oily compound (A-3).

(A-4) Amino-modified polysiloxane (comparative product) Amino-modified polysiloxane represented by the above average formula (I): R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -CH ₃ , a=2, b=200, c=1, d=0, e=0, viscosity: 300 mPa·s, amine equivalent: 7,200 g/mol Amount of octamethylcyclotetrasiloxane in component (A-4): 73,000 ppm Amount of decamethylcyclopentasiloxane in component (A-4): 45,000 ppm Amount of dodecamethylcyclohexasiloxane in component (A-4): 15,900 ppm (A-4) Volatile component content when heated at 105℃/3 hours: 14.2 mass%

(A-4) Preparation method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 90.01 parts by mass of octamethylcyclotetrasiloxane, 1.08 parts by mass of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane hydrolyzate, 8.81 parts by mass of dimethylpolysiloxane represented by the following formula (III), and 0.07 parts by mass of potassium silicate are heated at 150°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin is added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a decompression belt is not applied, and an oily compound (A-4) is obtained in the state of a residual low-boiling distillate.

(A-5) Amino-modified polysiloxane (comparative product) Amino-modified polysiloxane represented by the above average formula (I): R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NH ₂ , R ³ : -CH ₃ , a=2, b=900, c=2, d=0, e=0, viscosity: 25,000 mPa·s, amine equivalent: 32,000 g/mol Amount of octamethylcyclotetrasiloxane in component (A-5): 250 ppm Amount of decamethylcyclopentasiloxane in component (A-5): 400 ppm Amount of dodecamethylcyclohexasiloxane in component (A-5): 480 ppm Content of components volatile when heated at 105°C/3 hours in component (A-5): 0.8 mass%

(A-5) Production method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 98.10 parts by mass of octamethylcyclotetrasiloxane, 0.34 parts by mass of 3-aminopropylmethyldimethoxysilane hydrolyzate, 1.46 parts by mass of dimethylpolysiloxane represented by the above formula (III), and 0.07 parts by mass of potassium silicate are heated at 150°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin is added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a decompression zone was applied at 140°C and below 15 mmHg for 10 hours to remove the low-boiling distillate and obtain an oily compound (A-5).

(B) Amino-modified polysilicone (B-1) Amino-modified polysilicone R ¹ ：-CH ₃ ，R ² ：-C ₃ H ₆ NHC ₂ H ₄ NH ₂ ，R ³ ：-CH ₃ ，f=37，g=1.1，Viscosity：55mPa·s，Amine equivalent：1,250g/mol (B-1) Octamethylcyclotetrasiloxane content：less than 100ppm (B-1) Decamethylcyclopentasiloxane content：less than 100ppm (B-1) Dodecamethylcyclohexasiloxane content：300ppm (B-1) Volatile component content when heated at 105℃/3h：0.2wt%

(B-1) Production method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 59.51 parts by mass of octamethylcyclotetrasiloxane, 5.78 parts by mass of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane hydrolyzate, 34.61 parts by mass of dimethylpolysiloxane represented by the above formula (III), and 0.07 parts by mass of potassium silicate are heated at 150°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin is added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a reduced pressure zone was applied at 140°C and below 15 mmHg for 10 hours to remove the low-boiling distillate and obtain an oily compound (B-1).

(B-2) Amino-modified polysiloxane Amino-modified polysiloxane represented by the above average formula (II): R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -CH ₃ , f=67, g=1.2, viscosity: 140 mPa·s, amine equivalent: 2,000 g/mol Amount of octamethylcyclotetrasiloxane in component (B-2): 200 ppm Amount of decamethylcyclopentasiloxane in component (B-2): 300 ppm Amount of dodecamethylcyclohexasiloxane in component (B-2): 300 ppm Content of components volatile when heated at 105°C/3 hours in component (B-2): 0.3% by weight

(B-2) Production method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 77.62 parts by mass of octamethylcyclotetrasiloxane, 3.58 parts by mass of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane hydrolyzate, 18.70 parts by mass of dimethylpolysiloxane represented by the above formula (III), and 0.07 parts by mass of potassium silicate are heated at 150°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin is added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a decompression zone was applied for 10 hours at 140°C and below 15 mmHg to remove the low-boiling distillate and obtain an oily compound (B-2).

(B-3) Amino-modified polysiloxane Amino-modified polysiloxane represented by the above average composition formula (II): R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -OCH ₃ , f=30, g=1, viscosity: 50 mPa·s, amine equivalent: 1,170 g/mol Amount of octamethylcyclotetrasiloxane in component (B-3): 300 ppm Amount of decamethylcyclopentasiloxane in component (B-3): 300 ppm Amount of dodecamethylcyclohexasiloxane in component (B-3): 500 ppm Content of components volatile when heated at 105°C/3 hours in component (B-3): 0.4 mass%

(B-3) Production method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 91.61 parts by mass of octamethylcyclotetrasiloxane, 8.29 parts by mass of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and 0.07 parts by mass of potassium silicate were heated at 120°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin was added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a reduced pressure belt was applied at 130°C and 15 mmHg or less for 10 hours to remove the low-boiling distillate, and an oily compound (B-3) was obtained.

(B-4) Amino-modified polysiloxane (comparative product) R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -CH ₃ , f=300, g=1, viscosity: 1,600 mPa·s, amine equivalent: 10,000 g/mol Amount of octamethylcyclotetrasiloxane in (B-4) component: 100 ppm Amount of decamethylcyclopentasiloxane in (B-4) component: 200 ppm Amount of dodecamethylcyclohexasiloxane in (B-4) component: 400 ppm Amount of components volatile when heated at 105°C/3 hours in (B-4) component: 0.3 mass%

(B-4) Production method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 94.66 parts by mass of octamethylcyclotetrasiloxane, 0.73 parts by mass of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane hydrolyzate, 4.51 parts by mass of dimethylpolysiloxane represented by the above formula (III), and 0.07 parts by mass of potassium silicate are heated at 150°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin is added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, a decompression zone was applied at 150°C and below 15 mmHg for 10 hours to remove the low-boiling distillate and obtain an oily compound (B-4).

(B-5) Amino-modified polysiloxane (comparative product) Amino-modified polysiloxane represented by the above average formula (II): R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -CH ₃ , f=37, g=1.1, viscosity: 40 mPa·s, amine equivalent: 1,500 g/mol Amount of octamethylcyclotetrasiloxane in component (B-5): 28,500 ppm Amount of decamethylcyclopentasiloxane in component (B-5): 21,400 ppm Amount of dodecamethylcyclohexasiloxane in component (B-5): 7,700 ppm Content of components volatile when heated at 105°C/3 hours in component (B-5): 8.3 mass%

(B-5) Preparation method In a separable flask equipped with a thermometer, a stirrer, a reflux cooler and a nitrogen inlet tube, 59.51 parts by mass of octamethylcyclotetrasiloxane, 5.78 parts by mass of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane hydrolyzate, 34.61 parts by mass of dimethylpolysiloxane represented by the above formula (III), and 0.07 parts by mass of potassium silicate are heated at 150°C for 4 hours to carry out an equilibrium reaction. Thereafter, 0.03 parts by mass of epichlorohydrin is added and heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, the oily compound (B-5) is obtained in the state of residual low-boiling distillate without applying a decompression belt.

(C) Non-ionic surfactants (C-1) Newcol 1310 (trade name): manufactured by Nippon Emulsifier Co., Ltd., polyoxyethylene tridecyl ether, HLB value = 13.7 (C-2) Emulgen 104P (trade name): manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value = 9.6 (C-3) Emulgen 123P (trade name): manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value = 16.9

[Example 1] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 10 parts by mass of amino-modified polysilicone B-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-1) having a non-volatile content of 39.4% by mass at 105°C/3 hours. The average particle size of (I-1) was 230 nm and the pH was 5.8.

[Example 2] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 5 parts by mass of amino-modified polysilicone B-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-2) having a non-volatile content of 38.8% by mass at 105°C/3 hours. The average particle size of (I-2) was 240 nm and the pH was 5.6.

[Example 3] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 2.5 parts by mass of amino-modified polysilicone B-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-3) having a non-volatile content of 38.5% by mass at 105°C/3 hours. The average particle size of (I-3) was 280 nm and the pH was 5.6.

[Example 4] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 10 parts by mass of amino-modified polysilicone B-1, (C-2) 6 parts by mass of Emulgen 104P, (C-3) 24 parts by mass of Emulgen 123P, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-4) having a non-volatile content of 39.7% by mass at 105°C/3 hours. The average particle size of (I-4) was 220 nm and the pH was 5.8.

[Example 5] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 5 parts by mass of amino-modified polysilicone B-2, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-5) having a non-volatile content of 38.5% by mass at 105°C/3 hours. The average particle size of (I-5) was 240 nm and the pH was 5.8.

[Example 6] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 5 parts by mass of amino-modified polysilicone B-3, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-6) having a non-volatile content of 38.9% by mass at 105°C/3 hours. The average particle size of (I-6) was 270 nm and the pH was 5.5.

[Example 7] (A) 100 parts by mass of amino-modified polysilicone A-2, (B) 5 parts by mass of amino-modified polysilicone B-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-7) having a non-volatile content of 39.6% by mass at 105°C/3 hours. The average particle size of (I-7) was 220 nm and the pH was 5.6.

[Example 8] (A) 100 parts by mass of amino-modified polysilicone A-2, (B) 2.5 parts by mass of amino-modified polysilicone B-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-8) having a non-volatile content of 39.4% by mass at 105°C/3 hours. The average particle size of (I-8) was 210 nm and the pH was 5.6.

[Example 9] (A) 100 parts by mass of amino-modified polysilicone A-2, (B) 5 parts by mass of amino-modified polysilicone B-2, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-9) having a non-volatile content of 39.7% by mass at 105°C/3 hours. The average particle size of (I-9) was 240 nm and the pH was 5.5.

[Example 10] (A) 100 parts by mass of amino-modified polysilicone A-2, (B) 5 parts by mass of amino-modified polysilicone B-1, (C-2) 6 parts by mass of Emulgen 104P, (C-3) 24 parts by mass of Emulgen 123P, (D) 220 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-10) having a non-volatile content of 39.2% by mass at 105°C/3 hours. The average particle size of (I-10) was 210 nm and the pH was 5.3.

[Example 11] (A) 100 parts by mass of amino-modified polysilicone A-3, (B) 5 parts by mass of amino-modified polysilicone B-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 1.23 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-11) having a non-volatile content of 38.9% by mass at 105°C/3 hours. The average particle size of (I-11) was 260 nm and the pH was 5.6.

[Example 12] (A) 100 parts by mass of amino-modified polysilicone A-2, (B) 2.5 parts by mass of amino-modified polysilicone B-1, (C-1) 15 parts by mass of Newcol 1310, (D) 235 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (I-12) having a non-volatile content of 39.4% by mass at 105°C/3 hours. The average particle size of (I-12) was 230 nm and the pH was 5.9.

[Comparative Example 1] (A) 100 parts by mass of amino-modified polysilicone A-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (II-1) having a non-volatile content of 36.9% by mass at 105°C/3 hours. The average particle size of (II-1) was 25,300 nm and the pH was 5.3.

[Comparative Example 2] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 5 parts by mass of amino-modified polysilicone B-4, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (II-2) having a non-volatile content of 37.9% by mass at 105°C/3 hours. The average particle size of (II-2) was 11,800 nm and the pH was 5.4.

[Comparative Example 3] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 5 parts by mass of amino-modified polysilicone B-5, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (II-3) having a non-volatile matter content of 38.0% by mass at 105°C/3 hours. The average particle size of (II-3) was 220 nm and the pH was 5.7.

[Comparative Example 4] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 0.1 parts by mass of amino-modified polysilicone B-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (II-4) having a non-volatile matter content of 38.0% by mass at 105°C/3 hours. The average particle size of (II-4) was 1,050 nm and the pH was 5.4.

[Comparative Example 5] (A) 100 parts by mass of amino-modified polysilicone A-1, (B) 50 parts by mass of amino-modified polysilicone B-1, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (II-5) having a non-volatile matter content of 45.0% by mass at 105°C/3 hours. The average particle size of (II-5) was 200 nm and the pH was 6.2.

[Comparative Example 6] (A) 100 parts by mass of amino-modified polysilicone A-5, (C-1) 30 parts by mass of Newcol 1310, (D) 220 parts by mass of ion-exchanged water, and 0.15 parts by mass of acetic acid were mixed and emulsified using a homogenizer to obtain an amino-modified polysilicone emulsion composition (II-6) having a non-volatile content of 36.3% by mass at 105°C/3 hours. The average particle size of (II-6) was 380 nm and the pH was 5.6.

The obtained silicone emulsion composition was subjected to "storage stability evaluation", "dilution stability evaluation", "hair care evaluation" and "fiber treatment agent evaluation" by the following methods. The results are shown in the table.

[Storage stability evaluation] Each emulsion composition obtained in the embodiment/comparative example was stored at 25°C for 1 month. The emulsion composition after storage was visually confirmed, and those without separation were marked as ○, and those with layer separation were marked as ×.

[Dilution stability evaluation] The polysilicone emulsion composition was diluted with tap water to 100 times (mass) and the solution was placed in a glass beaker. Visually check whether there was separation when stored at 25°C for 20 hours. The "dilution stability" was evaluated based on the following indicators. ○: No precipitate △: Slight precipitate ×: Precipitate

[Hair Care Evaluation] Preparation of Hair Conditioner for Evaluation The polysilicone emulsion composition prepared in the Example or Comparative Example was mixed with the hair conditioner of the composition shown in the table below to prepare the hair conditioner for evaluation.

[Hair Care Effect] Five panelists evaluated the effect of hair care. After washing hair with a commercially available shampoo, apply each hair conditioner obtained above to the hair, rinse, and then dry the hair. The finger combing, smoothness, and moisturizing feeling during rinsing were evaluated. The three items were comprehensively judged and the hair care effect was evaluated according to the following evaluation criteria. The result was judged based on the average of the panel members and the following judgment criteria. <Evaluation criteria> 5 points: Very good 4 points: Good 3 points: Average 2 points: Slightly poor 1 point: Poor <Judgment criteria> ◎: Average score of 4.5 or more ○: Average score of 3.5 or more but less than 4.5 △: Average score of 2.5 or more but less than 3.5 ×: Average score less than 2.5

[Evaluation of fiber treatment agent] Ion-exchanged water was added to each of the polysilicone emulsion compositions obtained in the examples and comparative examples and stirred to prepare a test solution in such a way that the total of component (A) and component (B) was diluted to 2% by mass. After a polyester/cotton wide cloth (65%/35%) was immersed in the test solution for 10 seconds, it was extruded with a roller at a 100% extrusion rate and dried at 150°C for 2 minutes to prepare a treated cloth for softness evaluation. Three panelists touched the treated cloth and compared it with the untreated cloth, and the softness was evaluated according to the following evaluation criteria. Based on the total score of the three panelists, the results were evaluated according to the following judgment criteria. <Evaluation Criteria> 3 points: Compared with untreated fabric, the touch is very good. 2 points: Compared with untreated fabric, the touch is good. 1 point: The touch is the same as untreated fabric. 0 points: Compared with untreated fabric, the touch is poor. <Judgment Criteria> ◎: Total 7 points or more ○: Total 5~6 points △: Total 3~4 points ×: Total 2 points or less

It can be clearly understood from the above results that the amino-modified polysilicone emulsion composition of the present invention has good stability and can be given excellent properties by being used as a hair cosmetic or fiber treatment agent. [Industrial Applicability]

The amino-modified polysiloxane emulsion composition of the present invention has a low content of cyclic low molecular weight silicone and good stability. Furthermore, it is suitable for fiber treatment agents and hair cosmetics.

Claims (11)

An amino-modified polysilicone emulsion composition, wherein the average particle size of the emulsified particles is 400 nm or less, and contains (A) an amino-modified polysilicone represented by the following average composition formula (I), an amino-modified polysilicone having an amino equivalent of 1,000 to 25,000 g/mol and a viscosity of 250 to 100,000 mPa·s at 25° C., and an octamethylcyclotetrasiloxane content of 5,000 ppm or less: 100 parts by weight [wherein, R ¹ is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is independently a group represented by the general formula (2), -R ⁴ -(NH-R ⁵ ) _p -NH ₂ (2) (R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1), R ³ is independently a group selected from R ¹ , R ² , -OH, -OCH ₃ and -OC ₂ H ₅ , a, b, c, d and e are numbers satisfying the range of 2≦a≦10, 10≦b≦1,300, 0≦c≦50, 0≦d≦5, 0≦e≦5, but when c=0, R ³ is R ² ], (B): Amino-modified polysiloxane represented by the following average composition formula (II), with a viscosity of 10-230 mPa·s at 25°C, an amino equivalent of 500-3,000 g/mol, and an octamethylcyclotetrasiloxane content of 5,000 ppm or less: 0.5-20 parts by weight [wherein, R ¹ is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is independently a group represented by the general formula (2), -R ⁴ -(NH-R ⁵ ) _p -NH ₂ (2) (R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1), R ³ is independently a group selected from R ¹ , R ² , -OH, -OCH ₃ and -OC ₂ H ₅ , f and g are 5≦f≦200, 0≦g≦30, but when g=0, R ³ is R ² ], (C) nonionic surfactant: 5~100 parts by mass (D) water: 10~2,000 parts by mass. The amino-modified silicone emulsion composition of claim 1, wherein the non-ionic surfactant (C) does not contain polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether. The amino-modified polysiloxane emulsion composition of claim 1, wherein the content of decamethylcyclopentasiloxane in components (A) and (B) is less than 5,000 ppm. The amino-modified polysiloxane emulsion composition of claim 1, wherein the content of dodecamethylcyclohexasiloxane in components (A) and (B) is less than 5,000 ppm. The amino-modified polysilicone emulsion composition of claim 1, wherein the content of the component (A) that evaporates when heated at 105° C. for 3 hours is less than 1.5% by mass. The amino-modified polysilicone emulsion composition of claim 1, wherein the content of the component (B) that is volatile when heated at 105° C. for 3 hours is less than 1.5% by mass. The amino-modified polysilicone emulsion composition of claim 1 does not contain a cationic surfactant. The amino-modified polysilicone emulsion composition of claim 1 does not contain anionic surfactant. A fiber treating agent comprising the amino-modified polysilicone emulsion composition of any one of claims 1 to 8. A hair cosmetic comprising the amino-modified polysilicone emulsion composition of any one of claims 1 to 8. A method for producing an amino-modified polysilicone emulsion composition as claimed in any one of claims 1 to 8, comprising the step of mixing the above-mentioned components (A), (B), (C) and (D).