Amino-modified silicone emulsion composition, method for producing same, fiber treatment agent, and hair cosmetic

Abstract

An amino-modified silicone emulsion composition containing: (A) 100 parts by mass of an amino-modified silicone having a specific amino equivalent weight and an octamethylcyclotetrasiloxane content of 5000 ppm or less; (B) 0.5-20 parts by mass of an amino-modified silicone having a viscosity of 10-230 mPa * s at 25 DEG C and an amino equivalent weight of 500-3000 g / mol, and an octamethylcyclotetrasiloxane content of 5000 ppm or less; (C) 5 to 100 parts by mass of a nonionic surfactant; (D) 10-2000 parts by mass of water, which contains a small amount of octamethylcyclotetrasiloxane, has excellent storage and dilution stability, and imparts an excellent feeling of use such as sliding properties and tactile sensation when blended in a hair cosmetic.

Description

Technical Field

[0001] The present invention relates to an amino-modified organic silicon emulsion composition and a method for producing the same, a fiber treating agent and a hair cosmetic. Background Art

[0002] Amino-modified silicone can impart excellent softness and feel to fibers and is widely used as a fiber treatment agent. In recent years, amino-modified silicone has also been used in softeners and detergents for general consumers to improve the feel of clothes (Patent Document 1: Japanese Patent Publication No. 2008-150756). In addition, amino-modified silicone has excellent adhesion and softening effects on hair and is widely used in hair cosmetics (Patent Document 2: Japanese Patent Publication No. 5794637).

[0003] In recent years, the regulations on cyclic low molecular weight siloxanes (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane) have been strengthened in various countries, and the reduction of cyclic low molecular weight siloxanes in silicone products has become a problem. In particular, for products such as detergents, softeners, shampoos, conditioners and other hair cosmetics that flow into wastewater after use, the amount of cyclic low molecular weight siloxanes contained in the products may be restricted.

[0004] Amino-modified silicones are effective in hair cosmetics such as shampoos and conditioners, and fiber treatment agents such as detergents and softeners for washing. On the other hand, amino-modified silicones contain cyclic low-molecular-weight siloxanes that are by-produced during production. Fiber treatment agents and hair cosmetics containing amino-modified silicones may contain a large amount of cyclic low-molecular-weight siloxanes.

[0005] In order to reduce the amount of cyclic low-molecular-weight siloxane in these products, a method of performing a step of removing volatile components during the production of amino-modified silicone is used. By using amino-modified silicone in which the amount of cyclic low-molecular-weight siloxane is reduced in advance, the amount of cyclic low-molecular-weight siloxane contained in fiber treatment products and hair cosmetic products can be reduced. However, the emulsification property of amino-modified silicone from which the volatile components have been removed is reduced, and the stability when prepared as an emulsion may be greatly reduced. In addition, amino-modified silicone may produce cyclic low-molecular-weight siloxane as a by-product during storage.

[0006] In order to reduce the amount of cyclic low molecular weight contained in amino-modified silicone emulsion, the following research has been conducted so far. In Japanese Patent Publication No. 2013-532741 (Patent Document 3), a method for producing an emulsion using polydialkylsiloxane, aminofunctional organopolysiloxane, quaternary ammonium surfactant and water is proposed. In Patent Document 3, a quaternary ammonium surfactant must be added. If an emulsion containing a quaternary ammonium surfactant is added to a shampoo containing an anionic surfactant, the stability may be reduced.

[0007] In Japanese Patent Table 2015-500926 (Patent Document 4), a process of applying an emulsion of an aminofunctional organopolysiloxane, a quaternary ammonium surfactant, a nonionic surfactant and water to a fiber is proposed. Compared with the previous method, it is reported that octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in the emulsion are difficult to increase over time. However, a quaternary ammonium surfactant must be used. As in the case of Patent Document 3, if the emulsion of Patent Document 4 is used in a shampoo containing an anionic surfactant, the stability may be reduced.

[0008] In Japanese Patent Gazette No. 6258213 (Patent Document 5), a composition of an emulsion of an aminofunctional organopolysiloxane containing less than 0.1% by mass of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), a quaternary ammonium surfactant, a nonionic surfactant, and water is reported. However, since the quaternary ammonium surfactant must be added, similar to the cases of Patent Documents 3 and 4, if the emulsion of Patent Document 5 is added to a shampoo or the like containing an anionic surfactant, the stability may be reduced.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2008-150756

[0012] Patent Document 2: Japanese Patent No. 5794637

[0013] Patent Document 3: Japanese Patent Application No. 2013-532741

[0014] Patent Document 4: Japanese Patent Application No. 2015-500926

[0015] Patent Document 5: Japanese Patent No. 6258213 Summary of the invention

[0016] Problems to be solved by the invention

[0017] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide an amino-modified silicone emulsion composition which has a low content of octamethylcyclotetrasiloxane (D4), is excellent in storage and dilution stability, and further, can impart excellent feel in use such as slipperiness and touch by being blended into hair cosmetics and fiber treatment agents.

[0018] Means for solving problems

[0019] The present inventors have conducted intensive studies to achieve the above-mentioned object and have found that an amino-modified silicone emulsion composition containing two kinds of amino-modified silicones (A) and (B) having different viscosities, (C) a nonionic surfactant and (D) water has a low content of octamethylcyclotetrasiloxane and is excellent in storage and dilution stability. Furthermore, by adding the amino-modified silicone emulsion composition to a hair cosmetic or a fiber treatment agent, it can impart excellent feel during use such as slipperiness and touch, thereby completing the present invention.

[0020] Therefore, the present invention provides the following inventions.

[0021] 1. An amino-modified silicone emulsion composition, comprising:

[0022] (A) an amino-modified silicone represented by the following average composition formula (I), having a viscosity at 25° C. of 250 to 100,000 mPa·s, an amino equivalent of 1,000 to 25,000 g / mol, and an octamethylcyclotetrasiloxane content of 5,000 ppm or less: 100 parts by mass,

[0023] [Chemistry 1]

[0024]

[0025] [Where R 1 are independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 Independently of each other, the general formula (2)

[0026] -R 4 -(NH-R 5 ) p -NH2(2)

[0027] (R 4 and R 5 Each independently represents a divalent organic group having 1 to 6 carbon atoms, and p represents 0 or 1. 3 are independently selected from R 1 , R 2 , -OH, -OCH3 and -OC2H5, a, b, c, d and e are numbers satisfying the range of 2≤a≤10, 10≤b≤1300, 0≤c≤50, 0≤d≤5, 0≤e≤5, wherein when c=0, R3 For R 2 . ]

[0028] (B): amino-modified silicone represented by the following average composition formula (II), having a viscosity of 10 to 230 mPa·s at 25° C., an amino equivalent of 500 to 3000 g / mol, and an octamethylcyclotetrasiloxane content of 5000 ppm or less: 0.5 to 20 parts by mass,

[0029] [Chemistry 2]

[0030]

[0031] [Where R 1 are independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 Independently of each other, the general formula (2)

[0032] -R 4 -(NH-R 5 ) p -NH2 (2)

[0033] (R 4 and R 5 are independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1. 3 are independently selected from R 1 , R 2 , -OH, -OCH3 and -OC2H5, f and g are 5≤f≤200, 0≤g≤30, wherein when g=0, R 3 For R 2 . ]

[0034] (C) nonionic surfactant: 5 to 100 parts by weight,

[0035] (D) Water: 10 to 2000 parts by mass,

[0036] The average particle size of the emulsified particles is 400 nm or less.

[0037] 2. The amino-modified silicone emulsion composition according to 1, wherein the (C) nonionic surfactant does not contain polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0038] 3. The amino-modified silicone emulsion composition according to 1 or 2, wherein the content of decamethylcyclopentasiloxane in the components (A) and (B) is 5000 ppm or less.

[0039] 4. The amino-modified silicone emulsion composition according to any one of 1 to 3, wherein the content of dodecamethylcyclohexasiloxane in the components (A) and (B) is 5000 ppm or less.

[0040] 5. The amino-modified silicone emulsion composition according to any one of 1 to 4, wherein the content of a component that volatilizes when heated at 105° C. for 3 hours in the component (A) is 1.5% by mass or less.

[0041] 6. The amino-modified silicone emulsion composition according to any one of 1 to 4, wherein the content of a component that volatilizes when heated at 105° C. for 3 hours in the component (B) is 1.5% by mass or less.

[0042] 7. The amino-modified silicone emulsion composition according to any one of 1 to 6, which does not contain a cationic surfactant.

[0043] 8. The amino-modified silicone emulsion composition according to any one of 1 to 7, which does not contain an anionic surfactant.

[0044] 9. A fiber treatment agent comprising: the amino-modified silicone emulsion composition according to any one of 1 to 8.

[0045] 10. A hair cosmetic comprising: the amino-modified silicone emulsion composition according to any one of 1 to 8.

[0046] 11. The method for producing an amino-modified silicone emulsion composition according to any one of 1 to 8, comprising the step of mixing the components (A), (B), (C), and (D).

[0047] Effects of the Invention

[0048] According to the present invention, it has been found that octamethylcyclotetrasiloxane (D4) has a low content and is excellent in storage and dilution stability, and further, can impart excellent feel in use such as slipperiness and touch by blending it into hair cosmetics and fiber treatment agents, thereby completing the present invention. DETAILED DESCRIPTION

[0049] Hereinafter, the present invention will be described in detail.

[0050] [(A) ingredient]

[0051] The component (A) of the present invention is composed of the following average composition formula (I):

[0052] [Chemistry 3]

[0053]

[0054] [Where R 1are independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 Independently of each other, the general formula (2)

[0055] -R 4 -(NH-R 5 ) p -NH2(2)

[0056] (R 4 and R 5 are independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1. 3 are independently selected from R 1 , R 2 , -OH, -OCH3 and -OC2H5, a, b, c, d and e are numbers satisfying the range of 2≤a≤10, 10≤b≤1300, 0≤c≤50, 0≤d≤5, 0≤e≤5. Where c=0, R 3 For R 2 . ]

[0057] The amino-modified silicone has 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 can be used alone or two or more types can be used in combination.

[0058] R 1 Each of them is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, 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 groups, and phenyl groups are preferred, and methyl is more preferred.

[0059] R 2 Independently of each other, the general formula (2)

[0060] -R 4 -(NH-R 5 ) p -NH2(2)

[0061] (R 4 and R 5are independently divalent organic groups having 1 to 6 carbon atoms, and p is 0 or 1. ) as a group represented by. Examples of divalent organic groups having 1 to 6 carbon atoms include divalent hydrocarbon groups such as alkylene, alkenylene, and arylene. Examples of the group represented by 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 in terms of the ease of obtaining the raw materials.

[0062] R 3 are independently selected from R 1 , R 2 , -OH, -OCH3 and -OC2H5. The amino-modified silicone of the present invention (A) contains one or more amino-modified silicones as R 2 The group represented by the general formula (2) is appropriately selected from R 3 If the group represented by the general formula (2) is not contained, the amount of amino groups in the amino-modified silicone is too small, and the adhesion to fibers and hair is reduced. In the case of c=0, R 3 For R 2 , for example, in R 3 =R 2 , 0<d, c may be less than 1 or c=0. 1 , R 2 and R 3 The content of the total number of methyl groups is preferably 70% or more.

[0063] a is 2≤a≤10, preferably 2≤a≤5, and more preferably a = 2. If a exceeds 10, the viscosity of the amino-modified silicone decreases excessively, and the emulsification property decreases.

[0064] b is 10≤b≤1300, preferably 150≤b≤1000, more preferably 170≤b≤500, and further preferably 200≤b≤450. If b is less than 10, the viscosity of the amino-modified silicone is excessively low, and the effect of imparting slippage to fibers and hair is reduced. On the other hand, if b exceeds 1300, the viscosity of the amino-modified silicone is excessively high, and the emulsification property is reduced.

[0065] c is 0≤c≤50, preferably 1≤c≤30, more preferably 1≤c≤15, and further preferably 3≤c≤10. On the other hand, if c exceeds 50, the amount of amino groups in the amino-modified silicone is too high, and yellowing may occur when the fiber is treated.

[0066] d is 0≤d≤5, preferably d = 0. If d exceeds 5, the viscosity of the amino-modified silicone decreases excessively, and the emulsification property deteriorates.

[0067] e is 0≤e≤5, preferably e=0. If e exceeds 5, the viscosity of the amino-modified silicone decreases excessively, and the emulsification property deteriorates.

[0068] The viscosity of component (A) at 25°C is 250 to 100,000 mPa·s, preferably 280 to 50,000 mPa·s, more preferably 300 to 10,000 mPa·s, and further preferably 1,000 to 3,500 mPa·s. If the viscosity is less than the above lower limit, the effect of imparting slippage to fibers and hair becomes poor. In addition, if the above upper limit is exceeded, the emulsification becomes poor. It should be noted that 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.). It should be noted that the rotor, the number of revolutions and the rotation time are appropriately selected as follows according to the viscosity.

[0069] The viscosity in the present invention is determined by the following rotor and rotation speed depending on the viscosity of the object to be measured.

[0070] When the viscosity is 10 mPa·s or more and less than 100 mPa·s, the rotor No. 1 and the rotation speed are 30 rpm.

[0071] When the viscosity is 100 mPa·s or more and less than 500 mPa·s, the rotor No. 2 and the rotation speed are 30 rpm.

[0072] When the viscosity is 500 mPa·s or more and less than 3000 mPa·s, the rotor No. 3 and the rotation speed are 30 rpm.

[0073] When the viscosity is 3000 mPa·s or more and less than 15000 mPa·s, the rotor No. 4 and the rotation speed are 30 rpm.

[0074] When the pressure is 15000mPa·s or more and less than 40000mPa·s, the rotor is No.6 and the rotation speed is 20rpm.

[0075] When the viscosity is 40000 mPa·s or more, the rotor is No. 7 and the rotation speed is 20 rpm.

[0076] The amino equivalent of component (A) is 1000 to 25000 g / mol, preferably 1200 to 20000 g / mol, more preferably 1300 to 10000 g / mol, and further preferably 1400 to 4000 g / mol. If the amino equivalent is less than the above lower limit, there are too many amino groups, so yellowing may occur when the fiber is treated. On the other hand, if the amino equivalent exceeds the above upper limit, there are too few amino groups, so the hydrophilicity that should be given to the amino-modified silicone is insufficient, thereby deteriorating the emulsification. It should be noted that the amino equivalent in the present invention is the number of grams of the amino-modified silicone that can be neutralized with 1 mol of hydrochloric acid, which is theoretically the molecular weight / number of nitrogen atoms. The amino equivalent can be measured by neutralization titration, for example, by an automatic titrator manufactured by Hiranuma Sangyo Co., Ltd. More specifically, it can be measured by the following method. The amino equivalent was measured by dissolving the target amino-modified silicone in a solvent of toluene / IPA mixed at a mass ratio of 1 / 1 and titrating with hydrochloric acid using an automatic titrator to an end point of pH = 7. The amino equivalent was calculated as the molecular weight of silicone per 1 mol of amino groups and was calculated according to the following formula.

[0077] Amino equivalent (g / mol) = {[sample amount (g)] × 1000)} / {[hydrochloric acid equivalent concentration (N)] × [hydrochloric acid titration (mL)] × [hydrochloric acid titer (F)]}

[0078] The content of octamethylcyclotetrasiloxane in component (A) is 5000ppm (mass) or less, preferably 3000ppm or less, and more preferably 1000ppm or less. The content of decamethylcyclopentasiloxane is preferably 5000ppm or less. More preferably 3000ppm or less, and further preferably 1000ppm or less. The content of dodecamethylcyclohexasiloxane is preferably 5000ppm or less, more preferably 3000ppm or less, and further preferably 1000ppm or less. It should be noted that there is no lower limit on the content of octamethyltetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and for example, it can be set to 10ppm each.

[0079] The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (A) can be measured 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 in the acetone solution by vibration, the acetone solution of the supernatant is measured by gas chromatography.

[0080] (A) Amino-modified silicone can be easily obtained by a known synthesis method. For example, as described in the examples of International Publication No. 2021 / 1320571, it is obtained by subjecting a compound selected from cyclic siloxanes such as octamethylcyclotetrasiloxane, 3-aminopropyldiethoxymethylsilane or N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane or its hydrolyzate, and hexamethyldisiloxane as other raw materials to a balancing reaction in the presence of a catalyst such as an alkali metal hydroxide or tetramethylammonium hydroxide.

[0081] The amount of the component (A) that is volatilized under heating at 105°C for 3 hours is preferably 1.5% by mass or less, more preferably 1.2% by mass or less, and further preferably 1.0% by mass or less. It is believed that the amount of the component that is volatilized under heating at 105°C for 3 hours is mainly composed of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Therefore, by making the amount of the component that is volatilized under heating at 105°C for 3 hours less than the above value, the cyclic low molecular weight siloxane contained in the obtained amino-modified silicone emulsion can be reduced. The so-called component that is volatilized under heating at 105°C for 3 hours is, for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and a low molecular weight organic polysiloxane having an amino group. The so-called low molecular weight refers to an organic siloxane with a degree of polymerization of 8 or less, especially a degree of polymerization of 7 or less, and a straight chain, branched, or cyclic shape. There is no lower limit to the content of the volatile components, but the lower the content, the better.

[0082] The amount of components that volatilize under heating at 105°C for 3 hours can be determined using an air-supplied constant-temperature thermostat. Specifically, 2.0 g of amino-modified silicone (hereinafter referred to as the sample) is weighed into a 50 ml beaker, and the beaker is allowed to stand in an air-supplied constant-temperature thermostat set at 105°C for 3 hours. After 3 hours, the beaker is taken out, cooled in a dryer, weighed, and the mass reduction of the sample is measured. Based on the mass of the sample before heating and storage, the mass ratio of the components that volatilize under heating is calculated as a percentage. If the amino-modified silicone is placed in an air-supplied constant-temperature thermostat, volatile low-molecular compounds having a boiling point exceeding 105°C, for example, volatile low-molecular compounds having a boiling point of 200°C, also volatilize.

[0083] When synthesizing component (A), octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane are by-produced according to the manufacturing method. In order to make the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane less than 5000 ppm, it is preferred to implement a step of removing the volatile components of the obtained component (A). The octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (A) can be removed by a known method. For example, by spraying nitrogen gas to component (A) and performing reduced pressure distillation under the conditions of 80 to 200°C, 5 to 40 hours, and 5 to 30 mmHg, the octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (A) can be reduced to less than 5000 ppm in component (A).

[0084] [(B) ingredient]

[0085] Component (B) is represented by the following average composition formula (II):

[0086] [Chemistry 4]

[0087]

[0088] [Where R 1 are independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 Independently of each other, the general formula (2)

[0089] -R 4 -(NH-R 5 ) p -NH2(2)

[0090] (R 4 and R 5 are independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1. 3 are independently selected from R 1 , R 2 , -OH, -OCH3 and -OC2H5, f and g are 5≤f≤200, 0≤g≤30. In the case of g=0, R 3 For R 2 . ]

[0091] The amino-modified silicone has a viscosity of 10 to 230 mPa·s at 25° C., an amino equivalent of 500 to 3000 g / mol, and an octamethylcyclotetrasiloxane content of 5000 ppm or less. One type can be used alone or two or more types can be used in combination.

[0092] R 1Each of them is independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, 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 groups, and phenyl groups are preferred, and methyl is more preferred.

[0093] R 2 Independently of each other, the general formula (2)

[0094] -R 4 -(NH-R 5 ) p -NH2(2)

[0095] (R 4 and R 5 are independently divalent organic groups having 1 to 6 carbon atoms, and p is 0 or 1. ) as a group represented by. Examples of divalent organic groups having 1 to 6 carbon atoms include divalent hydrocarbon groups such as alkylene, alkenylene, and arylene. Examples of the group represented by 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 in terms of the ease of obtaining the raw materials.

[0096] R 3 are independently selected from R 1 , R 2 , -OH, -OCH3 and -OC2H5. The amino-modified silicone (B) of the present invention contains one or more amino-modified silicones as R 2 The group represented by the general formula (2) is appropriately selected from R 3 If the group represented by the general formula (2) is not contained, the amount of amino groups in the amino-modified silicone is too small, and the adhesion to fibers and hair is reduced. In the case of g=0, R 3 For R 2 . f is 5≤f≤200, preferably 10≤f≤100, more preferably 20≤f≤80, and particularly preferably 30≤f≤50. If f is less than 5, the viscosity of the amino-modified silicone is excessively reduced, and the effect of imparting slippage to fibers and hair is reduced. On the other hand, if f exceeds 200, the effect of improving the emulsification of component (B) is reduced. g is 0≤g≤30, preferably 1 to 10.

[0097] The viscosity of the 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 further preferably 35 to 80 mPa·s. If the viscosity is less than the above lower limit, the effect of imparting slippage to fibers and hair is reduced. If the viscosity exceeds the above upper limit, the effect of improving the emulsification of the component (B) is reduced.

[0098] The amino equivalent of component (B) is 500 to 3000 g / mol, preferably 600 to 2500 g / mol, more preferably 750 to 2200 g / mol, and particularly preferably 1000 to 2000 g / mol. If the amino equivalent is less than the above lower limit, there are too many amino groups, so yellowing may occur when the fiber is treated. On the other hand, if the amino equivalent exceeds the above upper limit, there are too few amino groups, so the effect of improving the emulsification of component (B) is reduced.

[0099] The content of octamethylcyclotetrasiloxane in component (B) is 5000ppm or less, preferably 3000ppm or less, and more preferably 1000ppm or less. The content of decamethylcyclopentasiloxane is preferably 5000ppm or less. More preferably 3000ppm or less, and further preferably 1000ppm or less. The content of dodecamethylcyclohexasiloxane is preferably 5000ppm or less, more preferably 3000ppm or less, and further preferably 1000ppm or less. It should be noted that there is no lower limit on the content of octamethyltetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and for example, it can be set to 10ppm each.

[0100] The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (B) can be measured by gas chromatography. Specifically, 0.1 g of the sample is added to 10 mL of acetone and shaken for about 2 hours. After the cyclic low molecular weight siloxane is extracted in the acetone solution by vibration, the acetone solution of the supernatant is measured by gas chromatography.

[0101] The amount of the component volatilizing under heating at 105°C for 3 hours present in the component (B) is preferably 1.5% by mass or less, more preferably 1.2% by mass or less, and further preferably 1.0% by mass or less. It is believed that the amount of the component volatilizing under heating at 105°C for 3 hours is mainly composed of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Therefore, by making the amount of the component volatilizing under heating at 105°C for 3 hours less than the above value, the cyclic low molecular weight siloxane contained in the obtained amino-modified silicone emulsion can be reduced. The so-called component volatilizing under heating at 105°C for 3 hours is, for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and a low molecular weight organic polysiloxane having an amino group. The so-called low molecular weight refers to an organic siloxane having a degree of polymerization of 8 or less, especially a degree of polymerization of 7 or less, and a straight chain, branched, or cyclic shape. There is no lower limit to the content of the volatile component, but a smaller value is more preferable. The amount of the component volatilized by heating at 105° C. for 3 hours is measured in the same manner as above.

[0102] The amino-modified silicone (B) can be easily obtained by a known synthesis method, similar to the component (A). For example, it can be obtained by subjecting a compound selected from cyclic siloxanes such as octamethylcyclotetrasiloxane, 3-aminopropyldiethoxymethylsilane or N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane or its hydrolyzate, and hexamethyldisiloxane as another raw material to an equilibrium reaction in the presence of a catalyst such as an alkali metal hydroxide or tetramethylammonium hydroxide.

[0103] When synthesizing component (B), octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane are produced as by-products according to the manufacturing method. In order to make the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane less than 5000ppm, it is preferred to implement a step of removing the volatile components of the obtained component (B). The octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (B) can be removed by a known method. For example, by spraying nitrogen gas to component (B) and performing reduced pressure distillation at 80 to 200°C, 5 to 40 hours, and 0.5 to 30 mmHg, the octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (B) can be less than 5000ppm in component (B).

[0104] Component (B) is an amino-modified silicone different from component (A). The effect of component (B) is considered to be as follows. The amino silicone of component (A) has removed the cyclic low-molecular siloxane, but at this time, the hydrophilic low-molecular component containing amino groups is also removed. It is believed that the low-molecular component containing amino groups functions as an emulsification enhancer, and the emulsification is low with only the component (A) removed, and the stability of the obtained emulsion is reduced. The inventors believe that amino silicone with a specific viscosity and amino equivalent such as component (B) has the function of improving emulsification. It is believed that: with respect to the amino-modified silicone emulsion composition of the present invention, by using component (B) in addition to component (A), the emulsification is not reduced even in a state where the cyclic low-molecular siloxane is removed, and the stability of the obtained emulsion is improved.

[0105] The content of the component (B) is 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass, and even more preferably 2.5 to 5.0 parts by mass, based on 100 parts by mass of the component (A).

[0106] [(C) ingredient]

[0107] (C) component is a nonionic surfactant, which can be used alone or in combination of two or more. As the nonionic surfactant, for example, 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 organopolysiloxane, polyoxyethylene polyoxypropylene modified organopolysiloxane, etc. can be listed. Among them, polyoxyethylene alkyl ether is preferred, and polyoxyethylene alkyl ether and polyoxyethylene propylene alkyl ether are more preferred.

[0108] The surfactant as the component (C) preferably does not contain polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether from the viewpoint of environmental load.

[0109] From the perspective of the stability of the emulsion, the HLB value of the nonionic surfactant (when using multiple types, the HLB value of the entire mixture) is preferably in the range of 10.0 to 18.0, more preferably 11.0 to 17.0, and even more preferably 12.0 to 16.0. It should be noted that HLB is a value calculated using the Griffin method. The HLB value is calculated by the following formula.

[0110] N=N1×W1+N2×W2

[0111] N: HLB value when using two surfactants with different HLB values: N

[0112] N1, N2: HLB of each surfactant

[0113] W1, W2: weight fraction of each surfactant (W1+W2=1)

[0114] In the composition of the present invention, a cationic surfactant or an anionic surfactant may be used in addition to the nonionic surfactant of the component (C).

[0115] Examples of the anionic surfactant include alkyl sulfate ester salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate ester salts, polyoxyethylene alkylphenyl ether sulfate ester salts, alkylbenzene sulfonates, polyoxyethylene alkylphenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkane sulfonates, N-acyltaurates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acylamino acid salts, monoalkyl phosphate ester salts, dialkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, and the like.

[0116] Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylene alkyldimethylammonium salts, dimeroxyethylene alkylmethylammonium salts, trimeroxyethylene alkylammonium salts, and alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamideamine salts.

[0117] If a cationic surfactant or anionic surfactant is used, the stability will be reduced when mixed with ionic drugs such as shampoo. Therefore, it is preferred that the composition of the present invention does not contain a cationic surfactant or anionic surfactant.

[0118] The content of the 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 further preferably 4 to 60 parts by mass, relative to 100 parts by mass of the component (A). It is particularly preferably 15 to 35 parts by mass relative to 100 parts by mass of the component (A). If the content of the component (C) is less than the above lower limit, the stability is deteriorated, and if it exceeds the above upper limit, the effect of imparting slippage to the fiber or hair is deteriorated.

[0119] [(D) ingredient]

[0120] The component (D) is water, and any water such as ion exchange water and purified water can be used. The content of the component (D) is 10 to 2000 parts by mass, preferably 50 to 1000 parts by mass, based on 100 parts by mass of the component (A).

[0121] 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 more preferably 300 nm or less. If the average particle size is larger than 400 nm, the stability of the emulsion is low, and separation sometimes occurs immediately. There is no restriction on the lower limit of the average particle size, and it can be set to 80 nm, for example. In order to make the particle size within this range, the content of component (C), the shear force during the preparation of the emulsion, and the temperature can be adjusted. It should be noted that the average particle size in the present invention is the particle size at the volume cumulative value of 50% in the particle size distribution obtained by the laser diffraction and scattering method. As a measuring device, for example, LA960 (manufactured by HORIBA Corporation) can be cited. In the present invention, the average particle size is a value measured using LA960 (manufactured by HORIBA Corporation), which represents the particle size at the cumulative value of 50% in the particle size distribution.

[0122] [Manufacturing method]

[0123] As for the amino-modified silicone emulsion composition of the present invention, it is sufficient as long as there is a process for mixing components (A) to (D). For example, it can be prepared by the following method. Component (D) can be mixed with component (A), component (B) and component (C), and emulsified and dispersed according to a conventional method to prepare it. Among them, oil-in-water droplet (O / W type) emulsion is preferred. In addition, water is further added to the emulsion for dilution, and it can be used for the purposes described below. There is no particular restriction on the amount of water used for dilution, and it can be appropriately adjusted according to the purpose.

[0124] An example of a detailed emulsification formula is as follows. In Compimix (Plain Mic Co., Ltd.), (A) component amino-modified silicone, (B) component amino-modified silicone, (C) nonionic surfactant, and (D) a portion of water are mixed and emulsified using a homomixer (a stirrer that utilizes the rotation of the rotor in the stator) at 2000 rpm or a DISPER (a stirrer that utilizes the rotation of toothed blades) at 2000 rpm and an ANCHOR at 20 rpm. After all emulsification is completed, stir for 15 to 180 minutes at a DISPER of 2000 rpm and an ANCHOR of 30 rpm until the particle size reaches a predetermined value, then add the remaining water of component (D), and dilute with a homomixer at 2000 to 3000 rpm to prepare the amino-modified silicone emulsion composition of the present invention.

[0125] The temperature during emulsification is not particularly specified, but is preferably 0 to 80°C, and more preferably 10 to 60°C. Emulsification is easy at a temperature of 10 to 60°C, and the produced emulsion tends to be more stable. If the amino-modified silicone emulsion composition is heated at 70 to 80°C for 1 to 30 hours, the particle size may become smaller or the viscosity may decrease. Therefore, in the production of the amino-modified silicone emulsion composition, a heating step of 70 to 80°C may be introduced according to the target particle size and viscosity. During emulsification, the pressure may be not only normal pressure, but also reduced pressure or pressurized pressure. When emulsification is performed under reduced pressure or pressurized pressure, bubbles are sometimes not easily mixed in, and emulsification can be effectively performed. As for the pressure during reduced pressure, it is preferably higher than the vapor pressure of the raw material so that the raw material does not volatilize. In addition, the emulsification time is not particularly specified, as long as it is set to the time to achieve the target particle size, and generally, it is preferably 30 to 360 minutes.

[0126] The emulsifier used for emulsification is not particularly limited as long as it can stir the raw materials and the emulsified composition. A colloid mill having a stirring portion consisting of a rotor and a stator (IKA, PUC, Nippon Seiki Seisaku-sho, Iwaki Co., Ltd.), a high shear mixer (Silverson, Plurimics), a homomixer (Plurimics), a homodisperser (Plurimics), an Adihomicser (Plurimics), a Compimix (Plurimics) which is a three-shaft dispersion kneading machine combining a homomixer, a homodisperser and an anchor mixer, HAAKE MiniLabII (Thermo Scientific) which is a twin-screw mixer having screws in the same direction or in opposite directions, MC15, MC5 (Leo Labs), etc. can be used.

[0127] The amino-modified silicone emulsion composition of the present invention may contain, in addition to the above-mentioned components (A) to (D), various optional components in appropriate amounts as long as they do not impair the purpose of the present invention. Such optional components include silicone components other than components (A) and (B), additives, and the like.

[0128] As the organosilicon component other than components (A) and (B), specifically, for example, silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, and alkyl-modified silicone oil can be cited. When an organosilicon component other than components (A) and (B) is added, the amount thereof is preferably 5 to 10 parts by mass relative to 100 parts by mass of component (A).

[0129] As an additive, for example, an inorganic acid or an organic acid can be added 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 the inorganic acid or organic acid added can be set arbitrarily, and is preferably an amount that adjusts the pH of the emulsion composition of the present invention to 3 to 7. As other additives, protective colloids, thickeners, antifreeze agents, preservatives, rust inhibitors, antioxidants, fragrances, ultraviolet absorbers, antibacterial agents, curing catalysts, organic powders, inorganic powders, dyes, pigments, fillers, etc. can be listed. When the above-mentioned additives are added, the amount is not particularly limited as long as it is within the range that does not damage the purpose of the present invention. For example, it can also be set to 10% by mass or less in the amino-modified silicone emulsion composition, preferably 5% by mass or less, and more preferably 3% by mass or less.

[0130] [Fiber treatment agent]

[0131] In addition, the amino-modified silicone emulsion composition of the present invention is also useful in fiber treatment agents such as softeners and detergents. For example, the amino-modified silicone emulsion composition can be mixed with 0.1 to 20% by mass, preferably 0.5 to 10% by mass, in the fiber treatment agent. As long as the content is above the above lower limit, the possibility of reduced feel is small. On the other hand, as long as the content is below the above upper limit, the possibility of yellowing during storage is small. In addition, it can also be diluted with water when used. In addition, there is no particular limitation on the fibers or fiber products that can be treated with the fiber treatment agent of the present invention. It is also effective for natural fibers such as cotton, silk, linen, wool, angora, mohair, polyester, polyethylene, polypropylene, nylon, acrylic, spandex, and blended fibers of their combination. In addition, there is no limitation on the form and shape thereof, and the fiber treating agent of the present invention can treat products in various forms, including woven fabrics, knitted fabrics, stuffed cotton, nonwoven fabrics, etc., and is not limited to raw material forms such as staple fibers, filaments, tows, and yarns.

[0132] [Hair cosmetics]

[0133] The amino-modified silicone emulsion composition of the present invention can be used in hair cosmetics such as shampoo and conditioner. As for the content, for example, the amino-modified silicone emulsion composition is preferably used 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 not less than the above lower limit, a sufficient conditioning effect on the hair can be obtained, and if it is not more than the above upper limit, the hair will not be sticky and will have a preferred touch. In the hair cosmetic, known ingredients can be further blended, for example, cationic surfactants, polyols, hair effective ingredients, etc. can be listed.

[0134] Example

[0135] The present invention is specifically described below with examples and comparative examples, but the present invention is not limited to the following examples. It should be noted that when the content is recorded with the name of the compounding product, it is the content of the compounding product. The following are the various measurement methods.

[0136] Average particle size: The particle size at the cumulative volume value of 50% is measured by diluting the emulsion composition about 10 times with water using a laser diffraction particle size measuring device (LA960 manufactured by HORIBA Corporation).

[0137] pH: The emulsion composition was measured at 25°C using a pH meter (LAQUA manufactured by HORIBA Corporation).

[0138] Viscosity: measured at 25°C using a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

[0139] Amino equivalent: measured by an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.). The amino-modified silicone of interest was dissolved in a solvent of toluene / IPA mixed at a mass ratio of 1 / 1, and titrated with hydrochloric acid using an automatic titrator until the pH reached 7, thereby measuring the amino equivalent. The amino equivalent was calculated as the molecular weight of the silicone per 1 mol of amino groups, and was calculated according to the following formula.

[0140] Amino equivalent (g / mol) = {[sample amount (g)] × 1000)} / {[hydrochloric acid equivalent (N)] × [hydrochloric acid titration (mL)] × [hydrochloric acid titer (F)]}

[0141] The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane was determined 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 in the acetone solution by vibration, the acetone solution of the supernatant was measured by gas chromatography (Agilent 7890B (manufactured by Agilent Technologies)). The column of the gas chromatograph was DB-5MS (manufactured by Agilent Technologies), the temperature in the column during the measurement was 300°C, and tetradecane was used as the internal standard substance.

[0142] Content of components volatile under heating at 105°C for 3 hours: 2.0 g of amino-modified silicone was weighed into a 50 mL beaker, and the beaker was placed in a constant temperature thermostat set at 105°C for 3 hours. After 3 hours, the beaker was taken out, cooled in a desiccator, and weighed to measure the mass reduction of the sample. The constant temperature thermostat used was manufactured by Yamato Scientific Co., Ltd. (DN-610H), and the air volume during heating was 12.3 m 3 / min, the thermostat has an internal volume of 223 L, an inner dimension of 620×600×600 mm, and two exhaust ports with an inner diameter of 30 mm on the back. A 50 mL beaker manufactured by Shibata Scientific Co., Ltd. (HARIO) (product code 010020-5051A, body outer diameter 46 mm, height 61 mm) was used.

[0143] (A) Amino-modified silicone

[0144] (A-1) Amino-modified silicone

[0145] The amino-modified silicone represented by the following average formula (I)

[0146] [Chemistry 5]

[0147]

[0148] R 1 :-CH3,R 2 :-C3H6NHC2H4NH2,R 3 : -CH3, a=2, b=200, c=1, d=0, e=0, viscosity: 400mPa·s, amino equivalent: 7000g / mol

[0149] Amount of octamethylcyclotetrasiloxane in component (A-1): less than 100 ppm (below the detection limit)

[0150] Amount of decamethylcyclopentasiloxane in component (A-1): 200 ppm

[0151] (A-1) Dodecamethylcyclohexasiloxane content: 300 ppm

[0152] Content of the component (A-1) that volatilizes when heated at 105°C for 3 hours: 0.6% by mass

[0153] (A-1) Manufacturing method

[0154] In a separable flask equipped with a thermometer, a stirrer, a reflux condenser, 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 dimethylorganosilicon 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. Then, 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.

[0155] Then, vacuum stripping was performed for 10 hours under the conditions of 140° C. and 15 mmHg or less to remove the low boiling point fraction, thereby obtaining an oily compound (A-1).

[0156] [Chemistry 6]

[0157]

[0158] (A-2) Amino-modified silicone

[0159] The amino-modified silicone represented by the above average formula (I)

[0160] R 1 :-CH3,R 2 :-C3H6NHC2H4NH2,R 3 : -CH3, a=2, b=280, c=6, d=0, e=0, viscosity: 1300 mPa·s, amino equivalent: 1700 g / mol

[0161] (A-2) Octamethylcyclotetrasiloxane content: less than 100 ppm

[0162] Amount of decamethylcyclopentasiloxane in component (A-2): 200 ppm

[0163] (A-2) Amount of dodecamethylcyclohexasiloxane in component: 200 ppm

[0164] Content of the component (A-2) that volatilizes when heated at 105°C for 3 hours: 0.4% by mass

[0165] (A-2) Manufacturing method

[0166] In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, 91.10 parts by mass of octamethylcyclotetrasiloxane, 4.40 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 4.40 parts by mass of dimethylorganosilicon represented by the above 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. Then, 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.

[0167] Then, vacuum stripping was performed for 10 hours under the conditions of 140° C. and 15 mmHg or less to remove the low boiling point fraction, thereby obtaining an oily compound (A-2).

[0168] (A-3) Amino-modified silicone

[0169] The amino-modified silicone represented by the above average formula (I)

[0170] R 1 :-CH3,R 2 :-C3H6NH2,R 3 : -CH3, a=2, b=410, c=8, d=0, e=0, viscosity: 2700 mPa·s, amino equivalent: 3900 g / mol

[0171] Amount of octamethylcyclotetrasiloxane in component (A-3): 100 ppm

[0172] Amount of decamethylcyclopentasiloxane in component (A-3): 300 ppm

[0173] Amount of dodecamethylcyclohexasiloxane in component (A-3): 400 ppm

[0174] Content of the component (A-3) that volatizes when heated at 105°C for 3 hours: 0.6% by mass

[0175] (A-3) Manufacturing method

[0176] In a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen inlet tube, 93.32 parts by mass of octamethylcyclotetrasiloxane, 3.21 parts by mass of a hydrolyzate of 3-aminopropylmethyldiethoxysilane, 3.37 parts by mass of dimethylorganosilicon represented by the above 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. Then, 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.

[0177] Then, vacuum stripping was performed for 10 hours under the conditions of 140° C. and 15 mmHg or less to remove the low boiling point fraction, thereby obtaining an oily compound (A-3).

[0178] (A-4) Amino-modified silicone (comparative product)

[0179] The amino-modified silicone represented by the above average formula (I)

[0180] R 1 :-CH3,R 2 :-C3H6NHC2H4NH2,R 3 : -CH3, a=2, b=200, c=1, d=0, e=0, viscosity: 300 mPa·s, amino equivalent: 7200 g / mol

[0181] Amount of octamethylcyclotetrasiloxane in component (A-4): 73000 ppm

[0182] Amount of decamethylcyclopentasiloxane in component (A-4): 45000 ppm

[0183] Amount of dodecamethylcyclohexasiloxane in component (A-4): 15900 ppm

[0184] Content of the component (A-4) that volatilizes when heated at 105°C for 3 hours: 14.2% by mass

[0185] (A-4) Manufacturing method

[0186] In a separable flask equipped with a thermometer, a stirrer, a reflux condenser 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 dimethylorganosilicon represented by the above 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. Then, 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.

[0187] Then, the reduced pressure stripping was not performed, and an oily compound (A-4) was obtained with a low boiling point fraction remaining.

[0188] (A-5) Amino-modified silicone (comparative product)

[0189] The amino-modified silicone represented by the above average formula (I)

[0190] R 1 :-CH3,R 2 :-C3H6NH2,R 3 : -CH3, a=2, b=900, c=2, d=0, e=0, viscosity: 25000 mPa·s, amino equivalent: 32000 g / mol

[0191] Amount of octamethylcyclotetrasiloxane in component (A-5): 250 ppm

[0192] Amount of decamethylcyclopentasiloxane in component (A-5): 400 ppm

[0193] Amount of dodecamethylcyclohexasiloxane in component (A-5): 480 ppm

[0194] Content of the component (A-5) that volatilizes when heated at 105°C for 3 hours: 0.8% by mass

[0195] (A-5) Manufacturing method

[0196] In a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen inlet tube, 98.10 parts by mass of octamethylcyclotetrasiloxane, 0.34 parts by mass of a hydrolyzate of 3-aminopropylmethyldimethoxysilane, 1.46 parts by mass of dimethylorganosilicon represented by the above 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. Then, 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. Then, under the conditions of 140° C. and 15 mmHg or less, a reduced pressure stripping was carried out for 10 hours to remove a low boiling point fraction, thereby obtaining an oily compound (A-5).

[0197] (B) Amino-modified silicone

[0198] (B-1) Amino-modified silicone

[0199] [Chemistry 7]

[0200]

[0201] R 1 :-CH3,R 2 :-C3H6NHC2H4NH2,R 3 : -CH3, f=37, g=1.1, viscosity: 55mPa·s, amino equivalent: 1250g / mol

[0202] (B-1) Octamethylcyclotetrasiloxane content: less than 100 ppm

[0203] (B-1) Amount of decamethylcyclopentasiloxane in component: less than 100 ppm

[0204] (B-1) Dodecamethylcyclohexasiloxane content: 300 ppm

[0205] Content of the component (B-1) that volatilizes when heated at 105°C for 3 hours: 0.2% by mass

[0206] (B-1) Manufacturing method

[0207] In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, 59.51 parts by mass of octamethylcyclotetrasiloxane, 5.78 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 34.61 parts by mass of dimethylorganosilicon represented by the above 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. Then, 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.

[0208] Then, vacuum stripping was carried out for 10 hours under the conditions of 140°C and 15 mmHg or less to remove the low boiling point fraction, thereby obtaining an oily compound (B-1).

[0209] (B-2) Amino-modified silicone

[0210] The amino-modified silicone represented by the above average formula (II)

[0211] R 1 :-CH3,R 2 :-C3H6NHC2H4NH2,R 3 :-CH3, f=67, g=1.2, viscosity: 140mPa·s, amino equivalent: 2000g / mol

[0212] Amount of octamethylcyclotetrasiloxane in component (B-2): 200 ppm

[0213] Amount of decamethylcyclopentasiloxane in component (B-2): 300 ppm

[0214] (B-2) Dodecamethylcyclohexasiloxane content: 300 ppm

[0215] Content of the component (B-2) that volatizes when heated at 105°C for 3 hours: 0.3% by mass

[0216] (B-2) Manufacturing method

[0217] In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, 77.62 parts by mass of octamethylcyclotetrasiloxane, 3.58 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 18.70 parts by mass of dimethylorganosilicon represented by the above 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. Then, 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.

[0218] Then, vacuum stripping was performed for 10 hours under the conditions of 140°C and 15 mmHg or less to remove the low boiling point fraction, thereby obtaining an oily compound (B-2).

[0219] (B-3) Amino-modified silicone

[0220] The amino-modified silicone represented by the above average composition formula (II)

[0221] R 1 :-CH3,R 2 :-C3H6NHC2H4NH2,R 3:-OCH3, f=30, g=1, viscosity: 50mPa·s, amino equivalent: 1170g / mol

[0222] Amount of octamethylcyclotetrasiloxane in component (B-3): 300 ppm

[0223] Amount of decamethylcyclopentasiloxane in component (B-3): 300 ppm

[0224] (B-3) Dodecamethylcyclohexasiloxane content: 500 ppm

[0225] Content of the component (B-3) that volatilizes when heated at 105°C for 3 hours: 0.4% by mass

[0226] (B-3) Manufacturing method

[0227] In a separable flask equipped with a thermometer, a stirrer, a reflux condenser, 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. Then, 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.

[0228] Then, vacuum stripping was performed for 10 hours under the conditions of 130° C. and 15 mmHg or less to remove the low boiling point fraction, thereby obtaining an oily compound (B-3).

[0229] (B-4) Amino-modified silicone (comparative product)

[0230] R 1 :-CH3,R 2 :-C3H6NHC2H4NH2,R 3 :-CH3, f=300, g=1, viscosity: 1600mPa·s, amino equivalent: 10000g / mol

[0231] Amount of octamethylcyclotetrasiloxane in component (B-4): 100 ppm

[0232] Amount of decamethylcyclopentasiloxane in component (B-4): 200 ppm

[0233] (B-4) Dodecamethylcyclohexasiloxane content: 400 ppm

[0234] Content of the component (B-4) that volatilizes when heated at 105°C for 3 hours: 0.3% by mass

[0235] (B-4) Manufacturing method

[0236] In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet tube, 94.66 parts by mass of octamethylcyclotetrasiloxane, 0.73 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 4.51 parts by mass of dimethylorganosilicon represented by the above 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. Then, 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.

[0237] Then, vacuum stripping was performed for 10 hours at 150° C. and 15 mmHg or less to remove the low boiling point fraction, thereby obtaining an oily compound (B-4).

[0238] (B-5) Amino-modified silicone (comparative product)

[0239] The amino-modified silicone represented by the above average formula (II)

[0240] R 1 :-CH3,R 2 :-C3H6NHC2H4NH2,R 3 :-CH3, f=37, g=1.1, viscosity: 40mPa·s, amino equivalent: 1500g / mol

[0241] Amount of octamethylcyclotetrasiloxane in component (B-5): 28500 ppm

[0242] Amount of decamethylcyclopentasiloxane in component (B-5): 21400 ppm

[0243] (B-5) Dodecamethylcyclohexasiloxane content: 7700 ppm

[0244] Content of the component (B-5) that volatizes when heated at 105°C for 3 hours: 8.3% by mass

[0245] (B-5) Manufacturing method

[0246] In a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen inlet tube, 59.51 parts by mass of octamethylcyclotetrasiloxane, 5.78 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 34.61 parts by mass of dimethylorganosilicon represented by the above 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. Then, 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. Then, no vacuum stripping was carried out, and an oily compound (B-5) was obtained in a state where a low boiling point fraction remained.

[0247] (C) Nonionic surfactant

[0248] (C-1) Niucol 1310 (trade name): manufactured by Nippon Emulsifier Co., Ltd., polyoxyethylene tridecyl ether, HLB value = 13.7

[0249] (C-2) Emalgen 104P (trade name): manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value = 9.6

[0250] (C-3) Emalgen 123P (trade name): manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value = 16.9

[0251] [Example 1]

[0252] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 10 parts by mass of amino-modified silicone B-1, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-1) having a nonvolatile content of 39.4% by mass at 105° C. for 3 hours. The average particle size of (I-1) was 230 nm and the pH was 5.8.

[0253] [Example 2]

[0254] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 5 parts by mass of amino-modified silicone B-1, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-2) having a nonvolatile content of 38.8% by mass at 105° C. for 3 hours. The average particle size of (I-2) was 240 nm and the pH was 5.6.

[0255] [Example 3]

[0256] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 2.5 parts by mass of amino-modified silicone B-1, (C-1) 30 parts by mass of Nicoll 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-3) having a nonvolatile content of 38.5% by mass at 105° C. for 3 hours. The average particle size of (I-3) was 280 nm and the pH was 5.6.

[0257] [Example 4]

[0258] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 10 parts by mass of amino-modified silicone B-1, (C-2) 6 parts by mass of Emalgen 104P, (C-3) 24 parts by mass of Emalgen 123P, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-4) having a nonvolatile content of 39.7% by mass at 105° C. for 3 hours. The average particle size of (I-4) was 220 nm and the pH was 5.8.

[0259] [Example 5]

[0260] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 5 parts by mass of amino-modified silicone B-2, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion exchange water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-5) having a nonvolatile content of 38.5% by mass at 105° C. for 3 hours. The average particle size of (I-5) was 240 nm and the pH was 5.8.

[0261] [Example 6]

[0262] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 5 parts by mass of amino-modified silicone B-3, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-6) having a nonvolatile content of 38.9% by mass at 105° C. for 3 hours. The average particle size of (I-6) was 270 nm and the pH was 5.5.

[0263] [Example 7]

[0264] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-2, (B) 5 parts by mass of amino-modified silicone B-1, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-7) having a nonvolatile content of 39.6% by mass at 105° C. for 3 hours. The average particle size of (I-7) was 220 nm and the pH was 5.6.

[0265] [Example 8]

[0266] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-2, (B) 2.5 parts by mass of amino-modified silicone B-1, (C-1) 30 parts by mass of Nicoll 1310, (D) 220 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-8) having a nonvolatile content of 39.4% by mass at 105° C. for 3 hours. The average particle size of (I-8) was 210 nm and the pH was 5.6.

[0267] [Example 9]

[0268] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-2, (B) 5 parts by mass of amino-modified silicone B-2, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-9) having a nonvolatile content of 39.7% by mass at 105° C. for 3 hours. The average particle size of (I-9) was 240 nm and the pH was 5.5.

[0269] [Example 10]

[0270] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-2, (B) 5 parts by mass of amino-modified silicone B-1, (C-2) 6 parts by mass of Emalgen 104P, (C-3) 24 parts by mass of Emalgen 123P, (D) 220 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-10) having a nonvolatile content of 39.2% by mass at 105° C. for 3 hours. The average particle size of (I-10) was 210 nm and the pH was 5.3.

[0271] [Example 11]

[0272] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-3, (B) 5 parts by mass of amino-modified silicone B-1, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion-exchanged water, and 1.23 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-11) having a nonvolatile content of 38.9% by mass at 105° C. for 3 hours. The average particle size of (I-11) was 260 nm and the pH was 5.6.

[0273] [Example 12]

[0274] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-2, (B) 2.5 parts by mass of amino-modified silicone B-1, (C-1) Nicoll 1310, (D) 235 parts by mass of ion-exchanged water, and 2.82 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (I-8) having a nonvolatile content of 39.4% by mass at 105° C. for 3 hours. The average particle size of (I-12) was 230 nm and the pH was 5.9.

[0275] [Comparative Example 1]

[0276] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (C-1) 30 parts by mass of Nicoll 1310, (D) 220 parts by mass of ion exchange water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (II-1) having a nonvolatile content of 36.9% by mass at 105° C. for 3 hours. The average particle size of (II-1) was 25300 nm and the pH was 5.3.

[0277] [Comparative Example 2]

[0278] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 5 parts by mass of amino-modified silicone B-4, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (II-2) having a nonvolatile content of 37.9% by mass at 105° C. for 3 hours. The average particle size of (II-2) was 11800 nm and the pH was 5.4.

[0279] [Comparative Example 3]

[0280] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 5 parts by mass of amino-modified silicone B-5, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (II-3) having a nonvolatile content of 38.0% by mass at 105° C. for 3 hours. The average particle size of (II-3) was 220 nm and the pH was 5.7.

[0281] [Comparative Example 4]

[0282] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 0.1 parts by mass of amino-modified silicone B-1, (C-1) 30 parts by mass of Nicoll 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (II-4) having a nonvolatile content of 38.0% by mass at 105° C. for 3 hours. The average particle size of (II-4) was 1050 nm and the pH was 5.4.

[0283] [Comparative Example 5]

[0284] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-1, (B) 50 parts by mass of amino-modified silicone B-1, (II1) 30 parts by mass of Nicoll 1310, (D) 220 parts by mass of ion-exchanged water, and 0.69 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (II-5) having a nonvolatile content of 45.0% by mass at 105° C. for 3 hours. The average particle size of (II-5) was 200 nm and the pH was 6.2.

[0285] [Comparative Example 6]

[0286] Using a homomixer, (A) 100 parts by mass of amino-modified silicone A-5, (C-1) Nicoll 1310: 30 parts by mass, (D) 220 parts by mass of ion exchange water, and 0.15 parts by mass of acetic acid were mixed and emulsified to obtain an amino-modified silicone emulsion composition (II-6) having a nonvolatile content of 36.3% by mass at 105° C. for 3 hours. The average particle size of (II-6) was 380 nm and the pH was 5.6.

[0287] The obtained silicone emulsion composition was subjected to “storage stability evaluation”, “dilution stability evaluation”, “hair conditioning evaluation” and “fiber treatment agent evaluation” by the following methods. The results are collectively shown in the table.

[0288] [Storage stability evaluation]

[0289] Each emulsion composition obtained in Examples and Comparative Examples was stored at 25° C. for 1 month. The emulsion composition after storage was visually observed, and a case where no separation was observed was marked as ○, and a case where layer separation was observed was marked as ×.

[0290] [Dilution stability evaluation]

[0291] A solution prepared by diluting the silicone emulsion composition 100 times (by mass) with tap water was placed in a glass beaker and visually checked for the presence or absence of separation when stored at 25° C. for 20 hours. The “dilution stability” was evaluated based on the following indexes.

[0292] ○: No precipitates

[0293] △: Very little precipitate

[0294] ×: There is precipitate

[0295] [Hair Conditioning Evaluation]

[0296] Production of hair conditioner for evaluation

[0297] The silicone emulsion composition prepared in Examples or Comparative Examples was mixed with a hair conditioner having a composition shown in the following table to prepare a hair conditioner for evaluation.

[0298] [Table 1]

[0299] Ingredient Name quality% Dimethylbehenylamine 2.0 Behenyltrimethylammonium chloride 0.3 Stearyl Alcohol 4.5 Behenyl alcohol 1.5 Isononyl Isononanoate 0.5 Highly polymerized dimethyl polysiloxane※1 1.0 Glycolic acid 0.5 Malic Acid 0.1 Dipropylene glycol 3.0 Behenyl alcohol 0.3 Arginine 0.2 Panthenyl ethyl ether (Panthenyl ethyl ether) 0.1 Hydrolyzed conchiolin acid 0.05 Ginseng root extract 0.05 Soybean Extract 0.05 Eucalyptus Extract 0.05 Rice Germ Oil 0.05 Refined water 84.25 Each emulsion composition of the examples or comparative examples 1.50 total 100.0

[0300] [Hair conditioning effect]

[0301] The hair conditioning effect was evaluated by 5 evaluation panelists. After washing with commercially available shampoo, each of the above-obtained conditioners was applied to the hair, rinsed, and then dried. The smoothness and moist feeling as felt by fingers during rinsing were evaluated. The three items were comprehensively judged and the hair conditioning effect was evaluated according to the following evaluation criteria. The results were judged based on the average value of the evaluation panelists using the following judgment criteria.

[0302] <Evaluation Criteria>

[0303] 5 points: Very good

[0304] 4 points: Good

[0305] 3 points: Average

[0306] 2 points: Slightly poor

[0307] 1 point: Poor

[0308] <Judgment Criteria>

[0309] ◎: Average score 4.5 or above

[0310] ○: Average score is 3.5 or higher and less than 4.5

[0311] △: Average score is 2.5 or higher and less than 3.5

[0312] ×: Average score is less than 2.5

[0313] [Evaluation of fiber treatment agents]

[0314] Ion exchange water was added to each silicone emulsion composition obtained in the examples and comparative examples, stirred, and diluted in such a way that the total of component (A) and component (B) became 2 mass % to prepare a test solution. After immersing polyester / broad-width cotton cloth (65% / 35%) in the test solution for 10 seconds, it was squeezed with a roller under the condition of a squeezing rate of 100%, and dried at 150°C for 2 minutes to prepare a treated cloth for softness evaluation. The treated cloth was touched by hand by 3 evaluation panel members, and the softness was evaluated by comparing it with the untreated cloth according to the following evaluation criteria. The results were judged based on the total score of the 3 evaluation panel members using the following judgment criteria.

[0315] <Evaluation Criteria>

[0316] 3 points: The touch is very good compared to the untreated cloth.

[0317] 2 points: Compared with untreated cloth, the touch is good.

[0318] 1 point: The touch is the same as that of the untreated cloth. 0 point: The touch is worse than that of the untreated cloth.

[0319] <Judgment Criteria>

[0320] ◎: Total 7 points or more

[0321] ○: Total 5-6 points

[0322] △: 3 to 4 points in total

[0323] ×: Total score less than 2

[0324] [Table 2]

[0325]

[0326] [Table 3]

[0327]

[0328] [Table 4]

[0329]

[0330] The above results show that the amino-modified silicone emulsion composition of the present invention has good stability and can impart excellent properties by using it as a hair cosmetic or a fiber treatment agent.

[0331] Industrial Applicability

[0332] The amino-modified silicone emulsion composition of the present invention has a low content of cyclic low-molecular-weight siloxane and good stability, and is suitable for fiber treatment agents and hair cosmetics.

Claims

1. An amino-modified organosilicon emulsion composition, comprising the following ingredients: (A) an amino-modified silicone represented by the following average composition formula (I), having a viscosity at 25° C. of 250 to 100,000 mPa·s, an amino equivalent of 1,000 to 25,000 g / mol, and an octamethylcyclotetrasiloxane content of 5,000 ppm or less: 100 parts by mass, In the formula, R 1 are independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 are independently a group represented by the general formula (2), R 3 are independently selected from R 1 , R 2 , -OH, -OCH3 and -OC2H5, a, b, c, d and e are numbers satisfying the range of 2≤a≤10, 10≤b≤1300, 0≤c≤50, 0≤d≤5, 0≤e≤5, wherein, When c=0, R 3 For R 2 , -R 4 -(NH-R 5 ) p -NH2(2) R 4 and R 5 are each independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, (B): amino-modified silicone represented by the following average composition formula (II), having a viscosity of 10 to 230 mPa·s at 25° C., an amino equivalent of 500 to 3000 g / mol, and an octamethylcyclotetrasiloxane content of 5000 ppm or less: 0.5 to 20 parts by mass, In the formula, R 1 are independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 are independently a group represented by the general formula (2), R 3 are independently selected from R 1 , R 2 , -OH, -OCH3 and -OC2H5, f and g are 5≤f≤200, 0≤g≤30, wherein when g=0, R 3 For R 2 , -R 4 -(NH-R 5 ) p -NH2(2) R 4 and R 5 are independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, (C) nonionic surfactant: 5 to 100 parts by weight, (D) Water: 10 to 2000 parts by mass, The average particle size of the emulsified particles is 400 nm or less.

2. The amino-modified silicone emulsion composition according to claim 1, wherein (C) The nonionic surfactant does not contain polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

3. The amino-modified silicone emulsion composition according to claim 1, wherein The content of decamethylcyclopentasiloxane in the components (A) and (B) is 5000 ppm or less.

4. The amino-modified silicone emulsion composition according to claim 1, wherein The content of dodecamethylcyclohexasiloxane in the components (A) and (B) is 5000 ppm or less.

5. The amino-modified silicone emulsion composition according to claim 1, wherein The content of a component that volatilizes when heated at 105° C. for 3 hours in the component (A) is 1.5% by mass or less.

6. The amino-modified silicone emulsion composition according to claim 1, wherein The content of a component that volatilizes when heated at 105° C. for 3 hours in the component (B) is 1.5% by mass or less.

7. The amino-modified silicone emulsion composition according to claim 1, wherein: Contains no cationic surfactants.

8. The amino-modified silicone emulsion composition according to claim 1, wherein Contains no anionic surfactants. 9 . A fiber treating agent comprising: the amino-modified silicone emulsion composition according to claim 1 .

10. A hair cosmetic comprising: the amino-modified silicone emulsion composition according to any one of claims 1 to 8. 11 . The method for producing the amino-modified silicone emulsion composition according to claim 1 , comprising the step of mixing the components (A), (B), (C), and (D).

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