Amino-modified silicone

Abstract

Provided is an amino-modified silicone that has excellent heat resistance, is difficult to color, is difficult to color even after heating the treated fabric when treating fibers, has excellent adsorptivity and durability to fibers, and has excellent adsorptivity to hair when treating hair. 【Solution means】The following formula (I) TIFF2026088563000020.tif29161 [In the formula, R 1 is a group selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, -OH, -OCH3 and -OC2H5, and R 2 is the formula (2) -R 4 -(NH-R 5 ) p -NH2(2) (In the formula, R 4 is a divalent organic group having 1 to 6 carbon atoms, R 5 is a divalent organic group having 3 carbon atoms, and p is 1 to 3.) is a group represented by the formula, and R 3 is a group selected from R 1 and R 2 . a is 2 ≦ a ≦ 10, b is 5 ≦ b ≦ 1,000, c is 0 ≦ c ≦ 50, d is 0 ≦ d ≦ 5, and e is 0 ≦ e ≦ 5.], and an amino-modified silicone containing one or more groups represented by the general formula (2) represented by R 2 is used.

Description

[Technical Field]

[0001] This invention relates to amino-modified silicones. More specifically, it relates to amino-modified silicones containing aminoalkyl groups that exhibit less yellowing even under high-temperature treatment, emulsion compositions containing the amino-modified silicone, fiber treatment agents, and hair cosmetics. [Background technology]

[0002] Conventionally, various silicone compounds such as dimethyl silicone, epoxy-modified silicone, and amino-modified silicone have been widely used as treatment agents to impart flexibility, smoothness, and other properties to various fibers or textile products. Among these, amino-modified silicones, which can impart particularly good flexibility to various fibers or textile products, are frequently used. In particular, fiber treatment agents mainly composed of amino-modified silicones having -C3H6NH2 groups, -C3H6NHC2H4NH2 groups, etc. as aminoalkyl groups are widely used because they exhibit excellent flexibility.

[0003] However, fibers treated with amino-modified silicones containing -C3H6NH2 groups or -C3H6NHC2H4NH2 groups suffer from degradation of the amino groups due to heat, drying, or heat and ultraviolet light over time. In particular, white or light-colored fibers or textile products have the disadvantage of changing to a yellowish color and losing flexibility.

[0004] To prevent the yellowing mentioned above, a conventional method has been used in which aminoalkyl groups are modified by reacting amino-modified silicone with organic acid anhydrides or chlorides, epoxy compounds, higher fatty acids, or carbonates.

[0005] However, for these materials, although an improved yellowing prevention effect is observed compared to unmodified amino-modified silicone, the effect is still insufficient, and there is a drawback in that they are inferior to the unmodified ones in terms of imparting flexibility and smoothness to fibers. Further, when modifying the aminoalkyl group by the above method, the hydrogen atom on the nitrogen atom (so-called active hydrogen) will react. The unmodified aminoalkyl group is excellent in adsorption and durability to fibers due to the presence of active hydrogen, but there is a problem that when the aminoalkyl group is modified and the active hydrogen is lost, the adsorption and durability to fibers will decrease. Furthermore, depending on the substituent that modifies the aminoalkyl group, there is a problem that the substituent itself yellows due to heat and the polysiloxane itself is colored.

[0006] Patent Document 1: International Publication No. 2020 / 235522 proposes a method of modifying by reacting an epoxy compound having an aminoalkyl group and an aromatic group. It is shown that by incorporating a highly heat-resistant aromatic group into the molecule, it is possible to suppress the coloring of amino-modified silicone. However, in the above invention, the yellowing of the cloth treated with amino-modified silicone is not described. Also, in order to impart hydrophilicity to amino-modified silicone, methods of modifying the aminoalkyl group with various compounds have been proposed (Patent Document 2: Japanese Patent Application Laid-Open No. 2014-084398, Patent Document 3: Japanese Patent Application Laid-Open No. 2021-088670), but the yellowing of the cloth treated with amino-modified silicone is not described for these inventions either.

[0007] In addition, amino-modified silicone is also excellent in adhesion to hair and softening effect, and is widely used in hair cosmetics such as shampoos and conditioners (Patent Document 4: Japanese Patent Application Laid-Open No. 2013-220991). When containing amino-modified silicone having -C3H6NH2 group and -C3H6NHC2H4NH2 group, there is a problem that the amino group deteriorates due to heat, ultraviolet rays, etc. over time, and the shampoo and conditioner turn yellow.

Prior Art Documents

Patent Documents

[0008] [Patent Document 1] International Publication No. 2020 / 235522 [Patent Document 2] Japanese Patent Publication No. 2014-084398 [Patent Document 3] Japanese Patent Publication No. 2021-088670 [Patent Document 4] Japanese Patent Publication No. 2013-220991 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] In view of the problems of the above-mentioned prior art, the present invention aims to provide an amino-modified silicone that has excellent heat resistance, is less prone to discoloration after heating, the treated fabric is less prone to discoloration after heating when used to treat fibers, has excellent adsorption and durability to fibers, and has excellent adsorption to hair when used to treat hair. [Means for solving the problem]

[0010] As a result of diligent research to achieve the above objectives, the inventors of the present invention have found that the following amino-modified silicone exhibits excellent heat resistance, is less prone to discoloration after heating, the treated fabric is less prone to discoloration after heating when used to treat fibers, has excellent adsorption and durability to fibers, and has excellent adsorption to hair when used to treat hair, thus leading to the present invention.

[0011] Accordingly, the present invention provides the following invention. 1. The following average empirical formula (I) [ka] [In the formula, R 1 These are groups independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, -OH, -OCH3, and -OC2H5. R 2 These are independently, general formula (2) -R4 -(NH-R 5 ) p -NH2(2) (In the formula, R 4 is a divalent organic group having 1 to 6 carbon atoms, R 5 is a divalent organic group having 3 carbon atoms, and p is 1 to 3.) is a group represented by R 3 are, independently of each other, groups selected from R 1 and R 2 . a is 2 ≤ a ≤ 10, b is 5 ≤ b ≤ 1,000, c is 0 ≤ c ≤ 50, d is 0 ≤ d ≤ 5, and e is 0 ≤ e ≤ 5.) represented by, and contains one or more groups represented by the general formula (2) where R 2 is an amino-modified silicone having a viscosity at 25°C of 10 to 50,000 mPa·s and an amino group equivalent of 500 to 20,000 g / mol 2. The amino-modified silicone according to item 1, wherein the group represented by formula (2) is a group selected from the following (2-1) to (2-5) -CH2-CH2-CH2-NH-CH2-CH(CH3)-NH2(2-1) -CH2-CH2-CH2-NH-CH(CH3)-CH2-NH2(2-2) -CH2-CH2-CH2-NH-CH2-CH2-CH2-NH2(2-3) -CH2-CH2-CH2-(NH-CH2-CH2-CH2)2-NH2(2-4) -CH2-CH(CH3)-CH2-NH-CH2-CH(CH3)-NH2(2-5) 3. The amino-modified silicone according to item 1, wherein R 5 is a divalent organic group having 1 to 6 carbon atoms with a branched structure 4. The amino-modified silicone according to item 1, which contains one or more alkoxy groups in the molecule 5. (A) 100 parts by mass of the amino-modified silicone according to item 1, (B) 5 to 100 parts by mass of a nonionic surfactant, and (C) 10 to 10,000 parts by mass of water An amino-modified silicone emulsion composition containing [a specific substance]. A fiber treatment agent comprising an amino-modified silicone as described in any of 6.1 to 6.4, or an amino-modified silicone emulsion composition as described in 5. A hair cosmetic comprising an amino-modified silicone as described in any of sections 7.1 to 4, or an amino-modified silicone emulsion composition as described in section 5. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide an amino-modified silicone that has excellent heat resistance, is less prone to discoloration after heating, the treated fabric is less prone to discoloration after heating when used to treat fibers, has excellent adsorption and durability to fibers, and when used to treat hair, has excellent adsorption to hair. [Modes for carrying out the invention]

[0013] The present invention will be described in detail below. The amino-modified silicone of the present invention will be referred to as component (A). [(A) component] The (A) amino-modified silicone of the present invention has the following average composition formula (I) [ka] [In the formula, R 1 These are groups independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, -OH, -OCH3, and -OC2H5. R 2 These are independently, general formula (2) -R 4 -(NH-R 5 ) p -NH2(2) (In the formula, R 4 R is a divalent organic group having 1 to 6 carbon atoms. 5 (It is a divalent organic group with 3 carbon atoms, and p is 1 to 3.) It is a base represented by, R 3 They are independent of each other, R 1 and R 2 It is a base selected from among them. For , the conditions are 2≦a≦10, for b, 5≦b≦1,000, for c, 0≦c≦50, for d, 0≦d≦5, and for e, 0≦e≦5. It is represented as R 2 This is an amino-modified silicone containing one or more groups represented by the general formula (2), having a viscosity of 10 to 50,000 mPa·s at 25°C, and an amino group equivalent of 500 to 20,000 g / mol.

[0014] R 1 These groups are independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, -OH, -OCH3, and -OC2H5. Examples of unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl groups; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl groups; and aryl groups such as phenyl, tolyl, and naphthyl groups. Among these, methyl, -OCH3, and -OC2H5, long-chain (6 to 20 carbon atoms) alkyl groups, and phenyl groups are preferred, with methyl groups being more preferred.

[0015] R 2 These are independently, general formula (2) -R 4 -(NH-R 5 ) p -NH2(2) (In the formula, R 4 R is a divalent organic group having 1 to 6 carbon atoms. 5 (It is a divalent organic group with 3 carbon atoms, and p is 1 to 3.) It is a group represented by R. 4 R is a divalent organic group having 1 to 6 carbon atoms. 5 R is a divalent organic group having 3 carbon atoms, and divalent organic groups having 1 to 6 carbon atoms include divalent hydrocarbon groups such as alkylene groups, alkenylene groups, and arylene groups. 4 and R 5 Each of these elements may be the same or different within a single compound.

[0016] R 5 This is a divalent organic group with 3 carbon atoms, and can have either a linear or branched structure. For example, the group represented by formula (2) includes the following: -CH2-CH2-CH2-NH-CH2-CH(CH3)-NH2(2-1) -CH2-CH2-CH2-NH-CH(CH3)-CH2-NH2(2-2) -CH2-CH2-CH2-NH-CH2-CH2-CH2-NH2(2-3) -CH2-CH2-CH2-(NH-CH2-CH2-CH2)2-NH2(2-4) -CH2-CH(CH3)-CH2-NH-CH2-CH(CH3)-NH2(2-5)

[0017] R 5 It is preferably a divalent organic group having 1 to 6 carbon atoms and having a branched structure, the group represented by (2-1), (2-2), and (2-5) above is preferred, the group represented by (2-1) and (2-5) is more preferred, and having a branched structure is even more preferred from the viewpoint of suppressing discoloration after heating.

[0018] R 3 They are independent of each other, R 1 and R 2 It is a base selected from. In the formula, R 2 It contains one or more groups represented by the general formula (2), and R 3 Furthermore, a, b, c, d, and e are selected as appropriate to achieve this.

[0019] (A) Amino-modified silicones are preferably made to contain alkoxy groups such as -OCH3 and -OC2H5, as this improves their adsorption and durability to fibers.

[0020] The value of 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 becomes too low, and its emulsifying properties decrease.

[0021] b satisfies 5 ≤ b ≤ 1,000, preferably 10 ≤ b ≤ 800, and more preferably 20 ≤ b ≤ 500. If b is less than 5, the viscosity of the amino-modified silicone becomes too low, and the effect of imparting slipperiness to the fiber decreases. On the other hand, if b exceeds 1,000, the viscosity of the amino-modified silicone becomes too high, and the emulsifiability decreases.

[0022] c satisfies 0 ≤ c ≤ 50, preferably 0 ≤ c ≤ 30, and more preferably 0 ≤ c ≤ 15. It is also possible that 0 < c. If c exceeds 50, the amount of amino groups in the amino-modified silicone is too large, and there is a risk of yellowing when treating the fiber.

[0023] d satisfies 0 ≤ d ≤ 5, and d = 0 is preferred. If d exceeds 5, the viscosity of the amino-modified silicone becomes too low, and the emulsifiability deteriorates.

[0024] e satisfies 0 ≤ e ≤ 5, and e = 0 is preferred. If e exceeds 5, the viscosity of the amino-modified silicone becomes too low, and the emulsifiability deteriorates.

[0025] (A) The viscosity of the amino-modified silicone at 25°C is 10 to 50,000 mPa·s, preferably 50 to 30,000 mPa·s, more preferably 100 to 5,000 mPa·s, and even more preferably 160 to 3,000 mPa·s. If the viscosity is less than the above lower limit, the effect of imparting slipperiness to the fiber deteriorates. If it exceeds the above upper limit, the emulsifiability 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.). The rotor, rotation speed, and rotation time are appropriately selected as follows according to the viscosity.

[0026] In the present invention, the viscosity is set as follows for the rotor and rotation speed according to the viscosity of the measurement object. When the viscosity is 10 mPa·s or more and less than 100 mPa·s, rotor No. 1, rotation speed 30 rpm, When the viscosity is 100 mPa·s or more and less than 500 mPa·s, rotor No. 2, rotation speed 30 rpm, For viscosity between 500 mPa·s and 3,000 mPa·s, use rotor No. 3 and rotation speed of 30 rpm. For viscosity between 3,000 mPa·s and 15,000 mPa·s, use rotor No. 4 and a rotation speed of 30 rpm. For viscosity between 15,000 mPa·s and less than 40,000 mPa·s, use rotor No. 6 and a rotation speed of 20 rpm. For viscosity of 40,000 mPa·s or higher, use rotor No. 7 and a rotation speed of 20 rpm.

[0027] (A) The amino group equivalent of the amino-modified silicone is 500 to 20,000 g / mol, preferably 600 to 10,000 g / mol, more preferably 750 to 3,000 g / mol, and even more preferably 800 to 2,500 g / mol. Setting the amino group equivalent above the above limit can further suppress yellowing when the fiber is treated. On the other hand, setting the amino group equivalent below the above upper limit allows for more sufficient hydrophilicity to be provided as the amino-modified silicone, and further improves emulsification. In this invention, the amino group equivalent is the number of grams of the amino-modified silicone that can be neutralized with 1 mole of hydrochloric acid, and theoretically, it is molecular weight / number of nitrogen atoms. The amino group 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 group equivalent is measured by dissolving the target amino-modified silicone in a solvent mixture of toluene and IPA in a mass ratio of 1:1, and then titrating with hydrochloric acid using an automatic titrator to the endpoint of pH=7. The amino group equivalent is calculated as the molecular weight of silicone per mole of amino groups, and is calculated using the following formula. Amino group equivalent (g / mol) = {[Sample volume (g)] × 1,000} / {[Hydrochloric acid normality (N)] × [Hydrochloric acid titration volume (mL)] × [Hydrochloric acid titer (F)]}

[0028] (A) Examples of amino-modified silicones include the following:

[0029] [ka]

[0030] [ka] (In the formula, b and c are the same as above. Unspecified terminals are -CH3.)

[0031] [Manufacturing method] (A) Amino-modified silicones can be obtained by adapting known synthesis methods. For example, they can be obtained by equilibrating a cyclic siloxane such as octamethylcyclotetrasiloxane with an aminoalkyl group-containing alkoxysilane such as (N-(3-aminopropyl)-3-aminopropyl)trimethoxymethylsilane, or its hydrolysate, and a compound selected from other raw materials such as hexamethyldisiloxane, in the presence of a catalyst such as an alkali metal hydroxide or tetramethylammonium hydroxide. Furthermore, it can be obtained by demethanol reaction of terminally hydroxyl-blocked dimethylpolysiloxane and an aminoalkyl group-containing alkoxysilane such as (N-(3-aminopropyl)-3-aminopropyl)trimethoxymethylsilane, either without a catalyst or in the presence of a catalyst such as an alkali metal hydroxide.

[0032] [Amino-modified silicone emulsion composition] The amino-modified silicone emulsion composition of the present invention is (A) Amino-modified silicone: 100 parts by mass, (B) Nonionic surfactant: 5 to 100 parts by mass, and (C) Water: 10~10,000 parts by mass This is an amino-modified silicone emulsion composition containing [a specific substance].

[0033] (A) Amino-modified silicone can also be incorporated into the emulsion composition. (A) Component can be used alone or in combination of two or more. (A) The amount of component is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass, in the composition.

[0034] [(B) Component] Component (B) is a nonionic surfactant, which can be used alone or in appropriate combinations of two or more. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes, and polyoxyethylene polyoxypropylene-modified organopolysiloxanes. Among these, polyoxyalkylene alkyl ethers are preferred, and polyoxyethylene alkyl ethers and polyoxyethylene propylene alkyl ethers are more preferred. In particular, from the viewpoint of suppressing yellowing when used as a fiber treatment agent, poly(oxyethylene) secondary alkyl ethers, which are obtained by adding an EO chain to the hydroxyl group of a linear secondary alcohol, are preferred.

[0035] (B) As for the surfactant component, from the viewpoint of environmental impact, it is preferable that it does not contain polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0036] From the viewpoint of emulsion stability, the HLB value of the nonionic surfactant (or the total HLB value of the mixture if multiple surfactants are used) 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. Note that the HLB value is calculated using the Griffin method. When using two or more nonionic surfactants, the HLB value is calculated using the following formula. N = N1 × W1 + N2 × W2 N: HLB value when using two types of surfactants with different HLB values N1, N2: HLB of each surfactant W1, W2: Weight fraction of each surfactant (W1 + W2 = 1)

[0037] The amount of component (B) is 5 to 100 parts by mass per 100 parts by mass of component (A), 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. If the amount of component (B) is below the lower limit, the stability of the emulsion will be poor, and if it exceeds the upper limit, the effect of imparting slipperiness to the fibers will be poor.

[0038] In addition to the nonionic surfactant of component (B), cationic surfactants and anionic surfactants may be used in the composition of the present invention, to the extent that they do not impair the effects of the present invention.

[0039] Examples of anionic surfactants include alkyl sulfate esters such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, alkylbenzene sulfonate, polyoxyethylene alkylphenyl ether sulfonate, alkyl diphenyl ether disulfonate, alkane sulfonate, N-acyl taurate, dialkyl sulfosuccinate, monoalkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinate, fatty acid salts, polyoxyethylene alkyl ether carboxylate, N-acyl amino acid salt, monoalkyl phosphate salt, dialkyl phosphate salt, and polyoxyethylene alkyl ether phosphate salt.

[0040] Cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, and alkylbenzyldimethylammonium salts, as well as alkylpyridinium salts, monoalkylamine salts, and monoalkylamidoamine salts.

[0041] (B) When surfactants other than component are added, the amount is preferably 1 to 80 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 4 to 60 parts by mass, per 100 parts by mass of component (A).

[0042] [(C) component] Component (C) is water, and all types of water can be used, such as deionized water and purified water. The amount of component (C) is 10 to 10,000 parts by mass per 100 parts by mass of component (A), preferably 50 to 2,000 parts by mass, and more preferably 70 to 1,000 parts by mass.

[0043] The amino-modified silicone emulsion composition of the present invention preferably has an average particle size of 500 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less. It is very preferably 300 nm or less. If the average particle size is greater than 500 nm, the emulsion stability is low, and separation may occur quickly. There is no lower limit to the average particle size, but it can be, for example, 50 nm. To achieve this particle size range, the amount of component (B), the shear force during emulsion preparation, and the temperature can be adjusted.

[0044] In this invention, the average particle size is the particle size at 50% of the cumulative volume in the particle size distribution determined by laser diffraction and scattering. An example of a measuring device is the LA960 (manufactured by HORIBA). In this invention, the average particle size is a value measured using the LA960 (manufactured by HORIBA) and represents the particle size at 50% of the cumulative volume in the particle size distribution.

[0045] The composition of the present invention preferably has a pH of 3.5 to 7.5 at 25°C, more preferably 3.7 to 7.0, and even more preferably 4.0 to 6.5. In this invention, the pH is the value obtained by measuring the emulsion at 25°C using a pH meter (LAQUA, manufactured by HORIBA).

[0046] The composition of the present invention may contain an acid to adjust the pH. When an acid is used, an organic acid is preferred. The acid can be used alone or in combination of two or more as appropriate. Specifically, examples include monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aromatic carboxylic acids, and acidic amino acids. More specifically, examples include monocarboxylic acids such as acetic acid, propionic acid, and caprylic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, and fumaric acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; aromatic carboxylic acids selected from benzoic acid, salicylic acid, and phthalic acid; and acidic amino acids such as glutamic acid and aspartic acid. When an acid is added, 0.05 to 10 parts by mass is preferred, and 0.1 to 5 parts by mass is more preferred, per 100 parts by mass of component (A).

[0047] [Manufacturing method] The composition of the present invention can be prepared, for example, by the following method: Component (C) can be mixed with components (A) and (B), and then emulsified and dispersed according to conventional methods. Among these, an oil-in-water (O / W) emulsion is preferred. The emulsion can also be further diluted with water and used for the applications described later. The amount of water used for dilution is not particularly limited and can be adjusted as appropriate depending on the application.

[0048] An example of the details of the emulsification formulation is as follows: For example, in a mixing device: Combimix (Primix Corporation), (A) amino-modified silicone, (B) nonionic surfactant, and (C) a portion of the water component are combined and emulsified using a homomixer (a stirrer that uses the rotation of a rotor in a stator) at 500-5,000 rpm or a disper (a stirrer that uses the rotation of toothed blades) at 500-5,000 rpm and an anchor at 5-50 rpm. After the entire mixture is emulsified, it is stirred for 15-180 minutes using a disper at 500-5,000 rpm and an anchor at 5-50 rpm until the desired particle size is achieved. Then, the remaining (C) water component is added and diluted with a homomixer at 2,000-3,000 rpm to prepare the amino-modified silicone emulsion of the present invention.

[0049] There are no specific requirements for the emulsification temperature, but it is preferably 0 to 80°C, more preferably 10 to 60°C. At temperatures of 10 to 60°C, emulsification is easier, and the resulting emulsion tends to be more stable. Heating amino-modified silicone emulsion at 70 to 80°C for 1 to 30 hours may reduce the particle size or decrease the viscosity; therefore, a heating step at 70 to 80°C may be included in the production of amino-modified silicone emulsion depending on the desired particle size and viscosity. During emulsification, the pressure may be atmospheric pressure, reduced pressure, or increased pressure. When emulsifying under reduced pressure or increased pressure, foam is less likely to be incorporated, and emulsification may be more effective. When using reduced pressure, it is preferable that the pressure be higher than the vapor pressure of the raw materials to prevent volatilization of the raw materials. There are no specific requirements for the emulsification time; it should be the time until the desired particle size is reached, but it is generally preferable to use a time of 30 to 360 minutes.

[0050] There are no particular restrictions on the emulsifier used for emulsification, as long as it can stir the raw materials and the emulsified composition. Colloid mills (IKA, PUC, Nippon Seiki Seisakusho, Iwaki), high-sheer mixers (Silverson, Primix), homodispers (Primix), ad-homomixers (Primix), which have a stirring section consisting of a rotor and a stator, as well as Combimix (Primix), a three-screw dispersion kneader that combines a homomixer, homodisperser, and anchor mixer, and twin-screw mixers with co-direction or anomalous direction screws such as HAAKE Mini Lab II (Thermo Scientific), MC15, and MC5 (Leo Lab) can be used.

[0051] The amino-modified silicone emulsion of the present invention may contain water-soluble polymers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, polyvinylpyrrolidone, alginates, xanthan gum, and acrylic acid polymers as protective colloidal agents or thickeners, depending on the purpose of the present invention. Furthermore, antibacterial or preservative agents such as oxazoline compounds and aromatic carboxylates, fragrances, antioxidants, rust inhibitors, dyes, fillers, curing catalysts, organic powders, inorganic powders, etc., may be added. The above components are preferably present in an amount of 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, in the amino-modified silicone emulsion.

[0052] [Fiber treatment agent] Furthermore, the amino-modified silicone and amino-silicone emulsion of the present invention are also useful as textile treatment agents such as fabric softeners and laundry detergents. The amount of amino-modified silicone is preferably 0.005 to 10% by mass, and more preferably 0.1 to 5% by mass, in the textile treatment agent.

[0053] The amount of amino-modified silicone emulsion is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass, in the fiber treatment agent. Using an amount greater than the above will further improve the texture. If the amount is below the above upper limit, there is little risk of yellowing during storage. It can also be diluted with water before use.

[0054] The fiber treatment agent of the present invention is not particularly limited in terms of the fibers or textile products that can be treated with it. It is effective on all natural fibers such as cotton, silk, linen, wool, angora, and mohair, as well as synthetic fibers such as polyester, polyethylene, polypropylene, nylon, acrylic, and spandex, and blended fibers combining these. Furthermore, there are no restrictions on their form or shape. Not only are raw material forms such as staples, filaments, tows, and yarns, but also various processed forms such as woven fabrics, knitted fabrics, stuffings, and nonwoven fabrics can be treated with the fiber treatment agent of the present invention.

[0055] The amino-modified silicone and amino-silicone emulsion of the present invention can suppress yellowing during fiber processing compared to the conventional technology. Yellowing during fiber processing is caused by the b of the treated fabric. * The values ​​can be compared and evaluated by measuring them with a colorimeter, etc. In the present invention, b * The value is L * a * b * b in the color system * This is a value, and it is adopted in JIS Z 8781-4. * A smaller value indicates higher whiteness and lower yellowing. (Image of treated surface b) * The lower the value and the closer it is to the untreated (blank) value, the lower the yellowing and the more desirable it is. * An example of a measurement method is the following test method: A cotton broadcloth is impregnated in a toluene solution containing 1% by mass of amino-modified silicone for 10 seconds, squeezed with a roller, dried at 100°C for 2 minutes, and then heat-treated at 200°C for 3 minutes to obtain the treated cloth. The b of each treated cloth is measured using a colorimeter (SE7700, manufactured by Nippon Denshoku Industries Ltd.). * Measure the value. At this time, compare it with the b value (blank) of the fabric that has only undergone heat treatment. * Preferably, the increase in b is 0.40 or less. * The increase is more preferably 0.30 or less, and particularly preferably 0.20 or less. * There is no lower limit to the increase in , but it can be set to, for example, 0.01.

[0056] [Hair Cosmetics] The amino-modified silicone and amino-silicone emulsion of the present invention are useful in hair cosmetics such as shampoos and conditioners. The amount of amino-modified silicone is preferably 0.005 to 10% by mass, and more preferably 0.1 to 5% by mass, in the hair cosmetic.

[0057] The amount of amino-modified silicone emulsion is preferably 0.1 to 20% by mass in the hair cosmetic, and more preferably 0.5 to 10% by mass. If the amount is above the lower limit, a sufficient conditioning effect on the hair is obtained, and if it is below the upper limit, there is no stickiness and a pleasant feel. The hair cosmetic can further contain known ingredients, such as cationic surfactants, polyhydric alcohols, and hair active ingredients. [Examples]

[0058] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified in the following examples, the "%" in composition refers to mass %.

[0059] [Measurement method] Viscosity was measured using a BM-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a temperature of 25°C.

[0060] Amino group equivalent: Measured using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.). The amino-modified silicone in question was dissolved in a solvent of toluene / IPA mixed in a mass ratio of 1:1, and the amino group equivalent was measured by titrating with hydrochloric acid using an automatic titrator until the endpoint of pH=7. The amino group equivalent is calculated as the molecular weight of silicone per mole of amino groups, and is calculated using the following formula. Amino group equivalent (g / mol) = {[Sample volume (g)] × 1,000} / {[Hydrochloric acid normality (N)] × [Hydrochloric acid titration volume (mL)] × [Hydrochloric acid titer (F)]}

[0061] Average particle size: This is the particle size at 50% volume integration, measured using a laser diffraction particle size analyzer (HORIBA LA960) after diluting the emulsion composition approximately 10 times with water.

[0062] pH: The pH of the emulsion composition was measured at 25°C using a pH meter (LAQUA, HORIBA).

[0063] [Synthesis Example 1] 258.9 g of α,ω-dihydroxydimethylsiloxane represented by the average structural formula (X-1) below and 41.1 g of alkoxysilane represented by the formula (Y-1) below were charged into a 500 mL glass flask equipped with an ester adapter, a condenser, and a thermometer, and the reaction was carried out at 120 °C for 3 hours under nitrogen bubbling. Distillation of methanol was observed in the ester adapter due to the demethanol reaction. After the reaction was complete, the obtained product was analyzed. 29 Si-NMR and 1 Structural identification was performed by 1H-NMR. As a result, an amino-modified silicone represented by the following formula (A-1) was obtained. The viscosity of the obtained compound was 150 mPa·s, and the amine equivalent was 840 g / mol.

[0064] [ka]

[0065] [Synthesis Example 2] In a 500 mL glass flask equipped with an ester adapter, a condenser, and a thermometer, 258.9 g of α,ω-dihydroxydimethylsiloxane represented by the average structural formula (X-1) and 41.1 g of alkoxysilane represented by the formula (Y-2) were charged and reacted at 120 °C for 3 hours under nitrogen bubbling. Distillation of methanol was observed in the ester adapter due to the demethanol reaction. After the reaction was complete, the obtained product was analyzed. 29 Si-NMR and 1Structural identification was performed using 1H-NMR. As a result, it was found that an amino-modified silicone represented by the following formula (A-2) was obtained. The viscosity of the obtained compound was 165 mPa·s, and the amine equivalent was 850 g / mol.

[0066] [ka]

[0067] [Synthesis Example 3] In a 500 mL glass flask equipped with an ester adapter, a condenser, and a thermometer, 252.6 g of α,ω-dihydroxydimethylsiloxane represented by the average structural formula (X-1) and 47.4 g of alkoxysilane represented by the formula (Y-3) were charged and reacted at 120 °C for 3 hours under nitrogen bubbling. Distillation of methanol was observed in the ester adapter due to the demethanol reaction. After the reaction was complete, the obtained product was analyzed. 29 Si-NMR and 1 Structural identification was performed using 1H-NMR. As a result, it was found that an amino-modified silicone represented by the following formula (A-2) was obtained. The viscosity of the obtained compound was 190 mPa·s, and the amine equivalent was 610 g / mol.

[0068] [ka]

[0069] [Synthesis Example 4] In a 500 mL glass flask equipped with an ester adapter, a condenser, and a thermometer, 258.9 g of α,ω-dihydroxydimethylsiloxane represented by the average structural formula (X-1) and 41.1 g of alkoxysilane represented by the formula (Y-4) were charged and reacted at 120 °C for 3 hours under nitrogen bubbling. Distillation of methanol was observed in the ester adapter due to the demethanol reaction. After the reaction was complete, the obtained product was examined. 29 Si-NMR and 1Structural identification was performed using 1H-NMR. As a result, it was found that an amino-modified silicone represented by the following formula (A-4) was obtained. The viscosity of the obtained compound was 175 mPa·s, and the amine equivalent was 860 g / mol.

[0070] [ka]

[0071] [Synthesis Example 5] In a separable flask equipped with a thermometer, stirrer, reflux condenser, and nitrogen gas inlet tube, 91.10 parts by mass of octamethylcyclotetrasiloxane, 4.40 parts by mass of a hydrolysate of aminosilane represented by formula (Y-5), 4.70 parts by mass of dimethyl silicone represented by formula (Q-1), and 0.07 parts by mass of potassium silicate were heated at 150°C for 4 hours to perform 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 vacuum strip was performed for 10 hours under conditions of 140°C and 15 mmHg or less to remove low-boiling fractions and obtain an oily compound (A-5). Regarding the obtained product, 29 Si-NMR and 1 Structural identification was performed using 1H-NMR. As a result, it was found that an amino-modified silicone represented by the following formula (A-5) was obtained. The viscosity of the obtained compound was 1,300 mPa·s, and the amine equivalent was 1,700 g / mol.

[0072] [ka]

[0073] [Synthesis Example 6] In a separable flask equipped with a thermometer, stirrer, reflux condenser, and nitrogen gas inlet tube, 91.10 parts by mass of octamethylcyclotetrasiloxane, 4.42 parts by mass of a hydrolysate of aminosilane represented by formula (Y-6), 4.70 parts by mass of dimethyl silicone represented by formula (Q-1), and 0.07 parts by mass of potassium silicate were heated at 150°C for 4 hours to perform 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 vacuum strip was performed for 10 hours under conditions of 140°C and 15 mmHg or less to remove low-boiling fractions and obtain an oily compound (A-5). Regarding the obtained product, 29 Si-NMR and 1 Structural identification was performed using 1H-NMR. As a result, it was found that an amino-modified silicone represented by the following formula (A-6) was obtained. The viscosity of the obtained compound was 1,280 mPa·s, and the amine equivalent was 1,720 g / mol.

[0074] [ka]

[0075] [Comparative Synthesis Example 1] In a 500 mL glass flask equipped with an ester adapter, a condenser, and a thermometer, 261.0 g of α,ω-dihydroxydimethylsiloxane represented by the average structural formula (X-1) and 39.0 g of alkoxysilane represented by the formula (Y-7) were charged, and the reaction was carried out at 120 °C for 3 hours under nitrogen bubbling. Distillation of methanol was observed in the ester adapter due to the demethanol reaction. After the reaction was complete, the obtained product was analyzed. 29 Si-NMR and 1 Structural identification was performed using 1H-NMR. As a result, it was found that an amino-modified silicone represented by the following formula (A-7) was obtained. The viscosity of the obtained compound was 145 mPa·s, and the amine equivalent was 830 g / mol.

[0076] [ka]

[0077] [Comparative Synthesis Example 2] In a 500 mL glass flask equipped with an ester adapter, condenser, and thermometer, 205.3 g of α,ω-dihydroxydimethylsiloxane represented by the average structural formula (X-1) and 32.6 g of alkoxysilane represented by the formula (Y-1) were charged, and the reaction was carried out at 120 °C for 3 hours under nitrogen bubbling. Distillation of methanol was observed in the ester adapter due to the demethanol reaction. After the reaction was complete, 62.1 g of phenylglycidyl ether represented by the formula (Z-1) and 15.0 g of isopropyl alcohol were charged, and the reaction was carried out at 80 °C for 4 hours under a nitrogen gas atmosphere. After the reaction was complete, the isopropyl alcohol was removed under reduced pressure of 10 mmHg at 110 °C for 2 hours. Regarding the obtained product, 29 Si-NMR and 1 Structural identification was performed using 1H-NMR. As a result, it was found that an amino-modified silicone represented by the following formula (A-8) was obtained. The viscosity of the obtained compound was 350 mPa·s, and the amine equivalent was 1,870 g / mol.

[0078] [ka] (In the formula, wavy lines indicate connections.)

[0079] [Examples 1-6, Comparative Examples 1-2] As Examples 1-6 and Comparative Examples 1-2, the amino-modified silicones (A-1)-(A-8) obtained in the above synthesis examples were subjected to the evaluation tests described below. The results are shown in Table 1.

[0080] [Heat resistance of amino-modified silicone] 100g of each amino-modified silicone obtained in the synthesis example and comparative synthesis example was placed in a glass bottle and heated at 150°C for 5 hours. After heating, the amino-modified silicone was visually inspected for discoloration, and those that were not discolored were marked with "○" and those that were discolored were marked with "×".

[0081] [Yellowing of treated fabric] Each amino-modified silicone obtained in the synthesis example and comparative synthesis example was diluted with toluene so that component (A) was 1% by mass, and a treatment solution was prepared. Cotton broadcloth was impregnated in this treatment solution for 10 seconds, squeezed with a roller, and then dried at 100°C for 2 minutes. After that, heat treatment was performed at 200°C for 3 minutes to obtain the treated cloth. The b* values ​​of each treated fabric were measured using a colorimeter (SE7700, manufactured by Nippon Denshoku Industries Co., Ltd.). * A smaller value indicates higher whiteness and lower yellowing, resulting in a better outcome. The b value (blank) of a cloth subjected to heat treatment only, without impregnation with the treatment solution, was 0.54. In this invention, a value of 0.95 or less is considered acceptable, 0.90 or less is preferred, 0.85 or less is more preferred, and 0.70 or less is particularly preferred.

[0082] [Table 1]

[0083] [Table 2]

[0084] As is clear from the table above, the amino-modified silicone of the present invention exhibits minimal discoloration during heating, excellent heat resistance, and furthermore, minimal yellowing when applied to fabric.

[0085] [Evaluation of emulsion compositions] The amino-modified silicones obtained in the above synthesis and comparative synthesis examples were used to prepare and evaluate silicone emulsion compositions as follows. The following surfactants were used as component (B). Unless otherwise specified, the tests were conducted at room temperature.

[0086] (B) Nonionic surfactants (B-1) Poly(oxyethylene) secondary alkyl ether [Softanol 90 (product name): manufactured by Nippon Shokubai, HLB value = 13.3] (B-2) Polyoxyethylene tridecyl ether [Newcol 1310 (product name): Manufactured by Nippon Emulsifier Co., Ltd., HLB value = 13.7] The following quantities refer to the amount of each ingredient.

[0087] [Example 7] (A-1) Amino-modified silicone represented by the above formula (A-1): 100 parts by mass (B-1) Poly(oxyethylene) secondary alkyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-1). The average particle size of (I-1) was 280 nm, and the pH was 4.7.

[0088] [Example 8] (A-2) Amino-modified silicone represented by the above formula (A-2): 100 parts by mass (B-1) Poly(oxyethylene) secondary alkyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain amino-modified silicone emulsion composition (I-2). The average particle size of (I-2) was 250 nm, and the pH was 4.5.

[0089] [Example 9] (A-3) Amino-modified silicone represented by the above formula (A-3): 100 parts by mass (B-1) Poly(oxyethylene) secondary alkyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-3). The average particle size of (I-3) was 310 nm, and the pH was 5.1.

[0090] [Example 10] (A-4) Amino-modified silicone represented by the above formula (A-4): 100 parts by mass (B-1) Poly(oxyethylene) secondary alkyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-4). The average particle size of (I-4) was 230 nm, and the pH was 4.5.

[0091] [Example 11] (A-5) Amino-modified silicone represented by the above formula (A-5): 100 parts by mass (B-1) Poly(oxyethylene) secondary alkyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 1 part by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-5). The average particle size of (I-5) was 310 nm, and the pH was 4.6.

[0092] [Example 12] (A-6) Amino-modified silicone represented by the above formula (A-6): 100 parts by mass (B-1) Poly(oxyethylene) secondary alkyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 1 part by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-6). The average particle size of (I-6) was 320 nm, and the pH was 4.6.

[0093] [Example 13] (A-1) Amino-modified silicone represented by the above formula (A-1): 100 parts by mass (B-2) Polyoxyethylene tridecyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-7). The average particle size of (I-7) was 300 nm, and the pH was 4.7.

[0094] [Example 14] (A-2) Amino-modified silicone represented by the above formula (A-2): 100 parts by mass (B-2) Polyoxyethylene tridecyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-8). The average particle size of (I-8) was 280 nm, and the pH was 4.5.

[0095] [Example 15] (A-4) Amino-modified silicone represented by the above formula (A-4): 100 parts by mass (B-2) Polyoxyethylene tridecyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-8). The average particle size of (I-8) was 270 nm, and the pH was 4.4.

[0096] [Comparative Example 3] (A-7) Amino-modified silicone represented by the above formula (A-7) Comparative Example 1: 100 parts by mass (B-1) Poly(oxyethylene) secondary alkyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (II-1). The average particle size of (II-1) was 310 nm, and the pH was 5.2.

[0097] [Comparative Example 4] (A-8) Amino-modified silicone represented by the above formula (A-8) in Comparative Example 2: 100 parts by mass (B-1) Poly(oxyethylene) secondary alkyl ether: 20 parts by mass (C) Ion-exchanged water: 190 parts by mass (Optional component) Acetic acid: 2 parts by mass These were mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (II-2). The average particle size of (II-2) was 350 nm, and the pH was 4.3.

[0098] The obtained silicone emulsion compositions were evaluated for [flexibility], "yellowing during fiber processing," and "wash durability" using the following methods. The results are shown in the table.

[0099] [Flexibility of the treated fabric] Each emulsion obtained in the Examples and Comparative Examples was diluted with deionized water to prepare a test solution so that component (A) was 2% by mass. A polyester / cotton broadcloth (65% / 35%, manufactured by Tanigashira Shoten Co., Ltd.) was immersed in this test solution for 10 seconds, then squeezed using a roller, and heated at 150°C for 2 minutes to prepare a treated cloth for flexibility evaluation. Three panelists touched the treated cloth and evaluated its flexibility compared to the untreated cloth using the following scoring system. The results are presented based on the total scores of the three panelists, according to the following evaluation criteria. <Rating> 3 points: It feels much better to the touch compared to untreated fabric. Points 2: It feels better to the touch compared to untreated fabric. 1 point: The feel is equivalent to untreated fabric. 0 points: The texture is worse compared to untreated fabric. <Evaluation Criteria> ◎: Total score of 7 points or more ○: Total 5-6 points △: Total 3-4 points ×: 2 points or less in total

[0100] [Yellowing of treated fabric] Each emulsion obtained in the Examples and Comparative Examples was diluted with deionized water so that component (A) was 1% by mass to prepare the treatment solution. Cotton broadcloth was impregnated in this treatment solution for 10 seconds, squeezed with a roller, and then dried at 100°C for 2 minutes. After that, heat treatment was performed at 200°C for 2 minutes to prepare the treated cloth. The b value of each treated cloth was measured using a colorimeter (SE7700, manufactured by Nippon Denshoku Industries Ltd.). A smaller b value indicates higher whiteness and lower yellowing, and a better result. The b value (blank) of the cloth that was subjected to heat treatment only without impregnation in the treatment solution was 0.54.

[0101] [Washing durability] Deionized water was added to each emulsion composition obtained in the Examples and Comparative Examples, and the test solution was prepared by diluting it so that component (A) was 2% by mass. Polyester / cotton broadcloth (65% / 35%, manufactured by Tanigashira Shoten Co., Ltd.) was immersed in the test solution for 10 seconds, then squeezed using a roller, and dried at 150°C for 2 minutes. After that, the treated cloth was washed once in a washing machine according to the method in accordance with JIS L0217 103. The amount of silicone remaining on the fiber surface after one wash was measured using an X-ray fluorescence analyzer (manufactured by Rigaku Co., Ltd.). The remaining rate (%) was calculated by comparing it with the case where no washing was performed.

[0102] [Hair Conditioning Evaluation] Manufacturing of hair conditioner for evaluation A hair conditioner for evaluation was manufactured according to the composition shown in the table below.

[0103] [Table 3] *1: KF-96H-100000cs (Shin-Etsu Chemical Co., Ltd.)

[0104] Five panelists conducted a usability test. After washing their hair with a commercially available shampoo, they applied each of the hair treatments described above to their hair, rinsed it, and then dried it. The ease of combing, smoothness, and moisturizing effect during rinsing were evaluated using the following criteria. The usability and conditioning effect were judged based on the following criteria.

[0105] <Evaluation Criteria> 5 points: very good 4 points: Good 3 points: Average 2 points: Slightly poor 1 point: Defective

[0106] <Judgment> ◎: Average score 4.5 or higher ○: Average score between 3.5 and 4.5 △: Average score between 2.5 and 3.5 ×: Average score less than 2.5

[0107] [Hair conditioner yellowing] 50g of the hair conditioner listed in the table above was placed in a glass bottle and stored at 50°C for 12 weeks. The appearance after storage was visually observed. Products that showed no change in color compared to before storage were marked with "○", and those that showed yellowing after storage were marked with "×".

[0108] [Table 4]

[0109] [Table 5]

[0110] [Table 6]

[0111] As is clear from the results above, the amino-modified silicone emulsion of the present invention exhibited low yellowing during fiber treatment. Furthermore, it also showed excellent washing durability. In addition, it was able to suppress yellowing when conditioner was added. [Industrial applicability]

[0112] The amino-modified silicone of the present invention exhibits minimal discoloration upon heating, excellent heat resistance, and minimal yellowing when applied to fabric. Furthermore, it boasts excellent wash durability, making it useful as a textile treatment agent. It also receives high marks as a conditioner, suppressing yellowing when incorporated into conditioners, and is therefore useful as a hair cosmetic.

Claims

1. The average empirical formula (I) below 【Chemistry 1】 [In the formula, R 1 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, -OH, -OCH 3 and -OC 2 H 5 It is a base selected from, R 2 These are independently, general formula (2) -R 4 -(NH-R 5 ) p -NH 2 (2) (In the formula, R 4 R is a divalent organic group having 1 to 6 carbon atoms. 5 (It is a divalent organic group with 3 carbon atoms, and p is 1 to 3.) It is a base represented by, R 3 They are independent of each other, R 1 and R 2 It is a base selected from among them. [where a is 2 ≤ a ≤ 10, b is 5 ≤ ​​b ≤ 1,000, c is 0 ≤ c ≤ 50, d is 0 ≤ d ≤ 5, and e is 0 ≤ e ≤ 5.] It is represented as R 2 An amino-modified silicone containing one or more groups represented by the general formula (2), having a viscosity of 10 to 50,000 mPa·s at 25°C, and an amino group equivalent of 500 to 20,000 g / mol.

2. The amino-modified silicone according to claim 1, wherein the group represented by formula (2) is selected from the following (2-1) to (2-5). -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH(CH 3 )-NH 2 (2-1) -CH 2 -CH 2 -CH 2 -NH-CH(CH) 3 )-CH 2 -NH 2 (2-2) -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -CH 2 -NH 2 (2-3) -CH 2 -CH 2 -CH 2 -(NH-CH 2 -CH 2 -CH 2 ) 2 -NH 2 (2-4) -CH 2 -CH(CH 3 )-CH 2 -NH-CH 2 -CH(CH 3 )-NH 2 (2-5)

3. R 5 The amino-modified silicone according to claim 1, wherein is a divalent organic group having 1 to 6 carbon atoms and having a branched structure.

4. The amino-modified silicone according to claim 1, comprising one or more alkoxy groups in the molecule.

5. (A) Amino-modified silicone according to claim 1: 100 parts by mass, (B) Nonionic surfactant: 5 to 100 parts by mass, and (C) Water: 10 to 10,000 parts by mass An amino-modified silicone emulsion composition containing [a specific substance].

6. A fiber treatment agent comprising an amino-modified silicone according to any one of claims 1 to 4, or an amino-modified silicone emulsion composition according to claim 5.

7. A hair cosmetic comprising an amino-modified silicone according to any one of claims 1 to 4, or an amino-modified silicone emulsion composition according to claim 5.

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