Amino-modified silicone emulsion composition and fiber treatment agent

Abstract

We provide an amino-modified silicone emulsion that offers excellent stability and can impart high flexibility and water absorption to fabrics. [Solution] (A) Equation (1) TIFF2026089973000025.tif22157 Amino-modified silicone, (B): Formula (4) TIFF2026089973000026.tif21153 An amino-modified silicone emulsion composition comprising (C) an amino-modified silicone, (D) an anionic surfactant, (E) an organic acid, and (F) water.

Description

[Technical Field]

[0001] The present invention relates to an amino-modified silicone emulsion composition and a fiber treatment agent. [Background technology]

[0002] Amino-modified silicones can impart excellent flexibility and texture to fibers and are widely used as fiber treatment agents. In recent years, amino-modified silicones have also been used in fabric softeners and detergents for general consumers to improve the texture of clothing. Furthermore, amino-modified silicones have excellent adhesion to hair and softening effects, and are widely used in cosmetics such as hair care products (Patent Document 1).

[0003] In textile processing and cosmetic applications, amino-modified silicones are often emulsified and dispersed in water using surfactants, etc., and used as oil-in-water emulsions. Emulsions are inherently unstable compositions because they combine immiscible components such as oil and water into a homogeneous phase using surfactants, etc., and various methods for improving their stability are being investigated. Generally, the smaller the particle size of an emulsion, the more stable it is. Emulsions with a particle size of 100 nm or less and a transparent appearance are called microemulsions, and are useful in applications where shear stability during dilution is required. Many microemulsions and methods for producing them have been proposed to date.

[0004] Furthermore, fibers treated with silicone-based treatment agents generally exhibit water repellency. Even fibers that are inherently absorbent become hydrophobic after silicone treatment, which has the drawback of almost completely eliminating their sweat-absorbing properties when used in clothing, for example. To address this, research has been conducted to impart both flexibility and water absorption to fibers. For example, water absorption can be improved by incorporating amino groups and polyoxyalkylene groups into the same silicone molecule. However, incorporating polyoxyalkylene groups has the drawback of significantly reducing flexibility and smoothness. To improve these drawbacks, a technique has been proposed to modify aminoalkyl groups by reacting amino-modified silicone with a polyoxyalkylene glycidyl ether compound.

[0005] Furthermore, while a higher silicone concentration in the emulsion offers advantages in terms of transportation costs, it is difficult to produce a high-concentration emulsion composition with excellent stability. Patent Document 2 proposes a high-concentration amino-modified silicone emulsion that can impart water absorption and flexibility to fibers, but it may lack long-term stability, water absorption, and flexibility. Therefore, there is a need for an amino-modified silicone emulsion that is highly stable and can impart high flexibility and water absorption to fabric. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2013-220991 [Patent Document 2] Japanese Patent Publication No. 2014-084398 [Overview of the project] [Problems that the invention aims to solve]

[0007] In view of the problems of the above prior art, an object of the present invention is to provide an amino-modified silicone emulsion composition that is excellent in stability and can impart high flexibility and water absorption to a fabric.

Means for Solving the Problems

[0008] In order to solve the above problems, in the present invention, (A) The following average composition formula (1)

Chemical formula

[0009] Such a material would result in an amino-modified silicone emulsion that offers excellent stability and can impart high flexibility and water absorption to fabrics.

[0010] Furthermore, the above-mentioned component (A) is the following average composition formula (6) [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 These are independent of each other, and general formula (2) -R 4 -(NR 5 -R 6 ) f -NR 5 2(2) (In the formula, R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is 0 to 2. 5 These are, independently of each other, hydrogen atoms or general formula (3) -CH2-CH(OH)CH2O-(C2H4O) g -(C3H6O) h -Z (3) The polyoxyalkylene-containing organic group is represented by , where Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene units and oxypropylene units may form block polymers or random polymers. It is a group represented by R 9 They are independent of each other, R 1 Alternatively, -OH, -OCH3, -OC2H 5、The base is selected from -OC3H7 and -OC4H9, where a, b, and c are numbers satisfying 2≦a≦10, 5≦b≦300, and 1≦c≦30, R 5 Of these, more than 30% are polyoxyalkylene-containing organic groups represented by the general formula (3) above. Preferably, the amino-modified silicone is expressed as such, has a viscosity of 10 to 1,500 mPa·s at 25°C, and an amino group equivalent of 500 to 5,000 g / mol.

[0011] In the present invention, such materials can be suitably used as component (A).

[0012] Furthermore, the R of component (A) 5 Preferably, 75% or more of these are polyoxyalkylene-containing organic groups represented by the general formula (3) above.

[0013] With such a design, the effects of the present invention can be more fully realized.

[0014] Furthermore, the R of component (B) 8 However, all R 1 It is preferable that the group is represented by [the symbol shown].

[0015] With such a design, the effects of the present invention can be more fully realized.

[0016] Furthermore, the amino-modified silicone emulsion composition of the present invention preferably has an average particle size of 100 nm or less.

[0017] Such an average particle size increases the stability of the emulsion.

[0018] Furthermore, the present invention provides a fiber treatment agent that contains the above-mentioned amino-modified silicone emulsion composition.

[0019] The amino-modified silicone emulsion composition of the present invention can be used particularly suitably as a fiber treatment agent. [Effects of the Invention]

[0020] The amino-modified silicone emulsion composition of the present invention has excellent storage stability and can impart high flexibility and water absorption to fabrics. [Modes for carrying out the invention]

[0021] As described above, there was a need to develop an amino-modified silicone emulsion composition that is highly stable and can impart high flexibility and water absorption to fabrics.

[0022] As a result of diligent research to achieve the above objective, the present inventors have found that an amino-modified silicone emulsion composition containing the following components (A) to (F) is highly stable and can impart high flexibility and water absorption to fabrics, and is suitable as a fiber treatment agent, thus leading to the present invention.

[0023] In other words, the present invention is (A) The following average composition formula (1) [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 These are independent of each other, and general formula (2) -R 4 -(NR 5 -R 6 ) f -NR 5 2(2) (In the formula, R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is 0 to 2. 5 These are, independently of each other, hydrogen atoms or general formula (3) -CH2-CH(OH)CH2O-(C2H4O) g -(C3H6O) h -Z (3) The polyoxyalkylene-containing organic group is represented by , where Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene units and oxypropylene units may form block polymers or random polymers. It is a group represented by R 3 They are independent of each other, R 1 and R 2 A group selected from the following options, or -OH, -OCH3, -OC2H 5、 The base is selected from -OC3H7 and -OC4H9, where a, b, c, d, and e are numbers satisfying the ranges 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, 0 ≤ c ≤ 30, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, component (A) contains at least one group represented by the general formula (2) in one molecule, R 5 Of these, more than 30% are polyoxyalkylene-containing organic groups represented by the general formula (3) above. Amino-modified silicone: 100 parts by mass, expressed as such, with a viscosity of 10-5,000 mPa·s at 25°C and an amino group equivalent of 500-5,000 g / mol. (B): The following average empirical formula (4) [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 7 These are independent of each other, and the general formula (5) -R 4 -(NH-R 6 ) f -NH2(5) (In the formula, R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is a number between 0 and 2. It is a group represented by R 8 They are independent of each other, R 1 and R 7 A group selected from the following options, or -OH, -OCH3, -OC2H 5、-OC3H7 and -OC4H9 are selected groups, where i, j, k, l, and m are numbers satisfying the ranges 2 ≤ i ≤ 10, 100 ≤ j ≤ 1,000, 0 ≤ k ≤ 30, 0 ≤ l ≤ 5, and 0 ≤ m ≤ 5. However, component (B) contains at least one group represented by the general formula (5) in one molecule. Amino-modified silicone, expressed as such, with a viscosity of 100 to 50,000 mPa·s at 25°C and an amino group equivalent of 500 to 10,000 g / mol: 5 to 80 parts by mass per 100 parts by mass of component (A), (C) Nonionic surfactant: 3 to 30 parts by mass per 100 parts by mass of component (A) above, (D) Anionic surfactant: 0 to 10 parts by mass per 100 parts by mass of component (A) above, (E) Organic acid: 0.05 to 10 parts by mass per 100 parts by mass of component (A), and (F) Water: 8 to 400 parts by mass per 100 parts by mass of component (A) This is an amino-modified silicone emulsion composition containing [the specified substance].

[0024] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0025] [(A) component] (A) The component is given by the following average composition formula (1) [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 These are independent of each other, and general formula (2) -R 4 -(NR 5 -R 6 ) f -NR 5 2(2) (In the formula, R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is 0 to 2. 5 These are, independently of each other, hydrogen atoms or general formula (3) -CH2-CH(OH)CH2O-(C2H4O) g -(C3H6O) h -Z (3) It is a polyoxyalkylene-containing organic group represented by, and Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene unit and the oxypropylene unit may form a block polymer or a random polymer.) It is a group represented by, R 3 are independently of each other, a group selected from the options of R 1 and R 2 or a group selected from -OH, -OCH3, -OC2H 5、 -OC3H7 and -OC4H9, and a, b, c, d and e are numbers satisfying the ranges of 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, 0 ≤ c ≤ 30, 0 ≤ d ≤ 5, 0 ≤ e ≤ 5.) However, the component (A) contains at least one group represented by the general formula (2) in one molecule, and 30% or more of R 5 is a polyoxyalkylene-containing organic group represented by the general formula (3).] It is an amino-modified silicone represented by, having a viscosity at 25°C of 10 to 5,000 mPa·s and an amino group equivalent of 500 to 5,000 g / mol.)

[0026] R 1 are independently of each other unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms. For example, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, tetradecyl group, octadecyl group, etc.; alkenyl groups such as vinyl group, allyl group, 5-hexenyl group, oleyl group, etc.; aryl groups such as phenyl group, tolyl group, naphthyl group, etc. Among them, methyl group, long-chain (6 to 20 carbon atoms) alkyl group, phenyl group are preferred, and methyl group is more preferred.)

[0027] R 2 are independently of each other the general formula (2) -R4 -(NR 5 -R 6 ) f -NR 5 2(2) (wherein, R 4 and R 6 are each independently a divalent organic group having 1 to 6 carbon atoms, and f is 0 to 2. R 5 are each independently a hydrogen atom or a group represented by the general formula (3) -CH2-CH(OH)CH2O-(C2H4O) g -(C3H6O) h -Z (3) is a polyoxyalkylene-containing organic group represented by, and Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene units and oxypropylene units may form a block polymer or a random polymer.) is a group represented by. The component (A) contains at least one group represented by the general formula (2) in one molecule.)

[0028] R 4 , R 6 are each independently a divalent organic group having 1 to 6 carbon atoms. Examples of the divalent organic group having 1 to 6 carbon atoms include divalent hydrocarbon groups such as an alkylene group, an alkenylene group, and an arylene group. As the divalent hydrocarbon group, alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group are preferable, and an ethylene group and a propylene group are particularly preferable.)

[0029] f is 0 to 2, preferably 1. f can be, for example, an integer.)

[0030] R 5 are each independently a hydrogen atom or a group represented by the general formula (3) -CH2-CH(OH)CH2O-(C2H4O) g -(C3H6O) h -Z (3) is a polyoxyalkylene-containing organic group represented by, R 5More than 30% of these are polyoxyalkylene-containing organic groups represented by general formula (3). In general formula (3), g is a number from 2 to 30, more preferably 3 to 15, and particularly preferably 4 to 10. If g is smaller than the lower limit, the effect of imparting water absorption to the fibers will be insufficient, and if it is larger than the upper limit, the effect of imparting flexibility will be insufficient, which is undesirable. h is a number from 0 to 20, preferably 0 to 10, and even more preferably 0 to 5. If h is larger than the upper limit, the water absorption of the fibers will be insufficient. The polyoxyethylene units and polyoxypropylene units may be one polymer or two copolymers, and may be block polymers or random polymers.

[0031] In the polyoxyalkylene-containing organic group described above, Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or an acyl group. Examples of such monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl and tolyl groups; alkenyl groups such as vinyl and allyl groups; and halogenated alkyl groups and halogenated alkenyl groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms such as chlorine and fluorine. In particular, Z is preferably a hydrogen atom; an alkyl group such as a methyl group, ethyl group, propyl group, and butyl group; or an acyl group such as an acetyl group and benzoyl group. Methyl, butyl, and acetyl groups are especially preferred.

[0032] (A) Component R 5It is preferable that 30% or more of these are polyoxyalkylene-containing organic groups represented by general formula (3), 75% or more are polyoxyalkylene-containing organic groups represented by general formula (3), more preferably 90% or more are polyoxyalkylene-containing organic groups represented by general formula (3), and particularly preferably 95% or more are polyoxyalkylene-containing organic groups represented by general formula (3). There is no upper limit to the above, but it can be, for example, 100%.

[0033] R 3 They are independent of each other, R 1 and R 2 A group selected from the following options, or -OH, -OCH3, -OC2H 5、 A group selected from -OC3H7 and -OC4H9, R 1 -OH, -OCH3, and -OC2H5 are preferred.

[0034] 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.

[0035] b is between 5 and 300, preferably 5 and 100, more preferably 10 and 50, and even more preferably 15 and 35. If b is less than 5, the viscosity of the amino-modified silicone becomes too low, reducing its effect in imparting flexibility to the fibers. On the other hand, if b exceeds 300, the effect in imparting water absorption decreases.

[0036] c is 0 ≤ c ≤ 30, preferably 1 ≤ c ≤ 10, and more preferably 1 ≤ c ≤ 5. If c exceeds 30, there is too much amino group in the amino-modified silicone, which may cause yellowing when the fiber is treated.

[0037] d is 0 ≤ d ≤ 5, and d = 0 is preferable. If d exceeds 5, the viscosity of the amino-modified silicone becomes too low, resulting in poor emulsification.

[0038] e is 0 ≤ e ≤ 5, and e = 0 is preferable. If e exceeds 5, the viscosity of the amino-modified silicone becomes too low, resulting in poor emulsification.

[0039] The viscosity of component (A) at 25°C is 10 to 5,000 mPa·s, preferably 50 to 1,500 mPa·s, more preferably 100 to 800 mPa·s, and even more preferably 150 to 500 mPa·s. If the viscosity is below the lower limit, the effect of imparting flexibility to the fibers will be poor. If it exceeds the upper limit, the emulsifying properties will be poor. In this invention, the viscosity is the value measured using a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.). The rotor, rotation speed, and rotation time are appropriately selected according to the viscosity.

[0040] The amino group equivalent of component (A) is 500 to 5,000 g / mol, preferably 1,500 to 4,500 g / mol, and more preferably 2,000 to 3,500 g / mol. If the amino group equivalent is below the lower limit, there are too many amino groups, which may cause yellowing when applied to fibers. On the other hand, if the amino group equivalent exceeds the upper limit, there are too few amino groups, resulting in insufficient hydrophilicity as an amino-modified silicone, which leads to poor emulsification.

[0041] In this invention, the amino group equivalent is the number of grams of the target 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 target amino-modified silicone is dissolved in a solvent of toluene / IPA mixed in a mass ratio of 1 / 1, and the amino group equivalent is measured by 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 by 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)]}

[0042] Component (A) is more preferably represented by the following general formula (6). [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 These are independent of each other, and general formula (2) -R 4 -(NR 5 -R 6 ) f -NR 5 2(2) (In the formula, R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is 0 to 2. 5 These are, independently of each other, hydrogen atoms or general formula (3) -CH2-CH(OH)CH2O-(C2H4O) g -(C3H6O) h -Z (3) The polyoxyalkylene-containing organic group is represented by , where Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene units and oxypropylene units may form block polymers or random polymers. It is a group represented by R 9 They are independent of each other, R 1 Alternatively, -OH, -OCH3, -OC2H 5、 The base is selected from -OC3H7 and -OC4H9, where a, b, and c are numbers satisfying 2≦a≦10, 5≦b≦300, and 1≦c≦30, R 5 Of these, more than 30% are polyoxyalkylene-containing organic groups represented by the general formula (3) above.

[0043] R 1 , R 2 , R 4 , R 5 , R 6 Details of a, b, c, f, g, h, and Z are as described above, and R 9 They are independent of each other, R1 Alternatively, -OH, -OCH3, -OC2H 5、 A group selected from -OC3H7 and -OC4H9, R 1 Alternatively, a group selected from -OH, -OCH3, and -OC2H5 is particularly preferred.

[0044] Note that the variable (R) in the above general formulas (1) and (6) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 9 The definitions of a, b, c, d, e, f, g, h, Z, etc. apply only in the above general formulas (1) and (6).

[0045] (A) Specific examples of components include the following. Note that the order of siloxane bonding is not limited to the following.

[0046] [ka]

[0047] [(B) Component] (B) Component is the following average composition formula (4) [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 7 These are independent of each other, and the general formula (5) -R 4 -(NH-R 6 ) f -NH2(5) (In the formula, R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is a number between 0 and 2. It is a group represented by R 8 They are independent of each other, R 1 and R 7 A group selected from the following options, or -OH, -OCH3, -OC2H5、 -OC3H7 and -OC4H9 are selected groups, where i, j, k, l, and m are numbers satisfying the ranges 2 ≤ i ≤ 10, 100 ≤ j ≤ 1,000, 0 ≤ k ≤ 30, 0 ≤ l ≤ 5, and 0 ≤ m ≤ 5. However, component (B) contains at least one group represented by the general formula (5) in one molecule. It is an amino-modified silicone expressed as such, with a viscosity of 100-50,000 mPa·s at 25°C and an amino group equivalent of 500-10,000 g / mol.

[0048] R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms. Examples 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, long-chain (6 to 20 carbon atoms) alkyl groups, and phenyl groups are preferred, with methyl groups being more preferred.

[0049] R 7 These are independent of each other, and the general formula (5) -R 4 -(NH-R 6 -) f -NH2(5) (R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is a number between 0 and 2. The group is represented by . Examples of divalent organic groups having 1 to 6 carbon atoms include divalent hydrocarbon groups such as alkylene groups, alkenylene groups, and arylene groups. Examples of groups represented by general formula (5) include 2-aminoethyl group, 3-aminopropyl group, 6-aminohexyl group, N-(2-aminoethyl)-3-aminopropyl group, N-(3-aminopropyl)-3-aminopropyl group, and N-(2-aminoethyl)-6-aminohexyl group. Among these, the 3-aminopropyl group or the N-(2-aminoethyl)-3-aminopropyl group is preferred from the standpoint of ease of obtaining raw materials. However, component (B) contains at least one group represented by general formula (5) in one molecule.

[0050] f is between 0 and 2, preferably 1. f can be, for example, an integer.

[0051] R 8 They are independent of each other, R 1 and R 7 A group selected from the following options, or -OH, -OCH 3、 -OC2H 5、 A group selected from -OC3H7 and -OC4H9, R 1 or -OH, -OCH 3、 -OC2H 5、 -OC3H7 is more preferred, R 1 This is particularly preferable. Also, R 8 However, all R 1 It is particularly preferable that the group is represented by [the formula shown].

[0052] i, j, k, l, and m are numbers that satisfy the ranges 2 ≤ i ≤ 10, 100 ≤ j ≤ 1,000, 0 ≤ k ≤ 30, 0 ≤ l ≤ 5, and 0 ≤ m ≤ 5.

[0053] i is 2 ≤ i ≤ 10, preferably 2 ≤ i ≤ 5, and more preferably i = 2. If i exceeds 10, the viscosity of the amino-modified silicone becomes too low, and its emulsifying properties decrease.

[0054] The value of j is 100 ≤ j ≤ 1,000, preferably 150 ≤ j ≤ 800, more preferably 170 ≤ j ≤ 500, and even more preferably 180 ≤ j ≤ 350. If j is less than 100, the viscosity of the amino-modified silicone becomes too low, reducing its effect in imparting flexibility to the fibers. On the other hand, if j exceeds 1,000, the viscosity of the amino-modified silicone becomes too high, reducing its emulsifying properties.

[0055] k is 0 ≤ k ≤ 30, preferably 1 ≤ k ≤ 20, more preferably 1 ≤ k ≤ 15, and even more preferably 3 ≤ k ≤ 10. On the other hand, if k exceeds 30, the amount of amino groups in the amino-modified silicone is too high, which may cause yellowing when the fiber is treated.

[0056] l is 0 ≤ l ≤ 5, and l = 0 is preferable. If l exceeds 5, the viscosity of the amino-modified silicone becomes too low, resulting in poor emulsification.

[0057] m is 0 ≤ m ≤ 5, and m = 0 is preferable. If m exceeds 5, the viscosity of the amino-modified silicone becomes too low, resulting in poor emulsification.

[0058] Note that the variable (R) in the general formula (4) above 1 , R 4 , R 6 , R 7 , R 8 The definitions of f, i, j, k, l, m, etc. apply only in the above general formula (4).

[0059] The viscosity of component (B) at 25°C is 100 to 50,000 mPa·s, preferably 150 to 10,000 mPa·s, more preferably 300 to 5,000 mPa·s, and even more preferably 500 to 3,500 mPa·s. If the viscosity is below the lower limit, the effect of imparting slipperiness to fibers and hair will be poor. If it exceeds the upper limit, the emulsifying properties will be poor.

[0060] The amino group equivalent of component (B) is 500 to 10,000 g / mol, preferably 1,000 to 7,000 g / mol, and more preferably 1,200 to 3,000 g / mol. If the amino group equivalent is below the lower limit, there are too many amino groups, which may cause yellowing when applied to fibers. On the other hand, if the amino group equivalent exceeds the upper limit, there are too few amino groups, resulting in insufficient hydrophilicity as an amino-modified silicone, which leads to poor emulsification.

[0061] The content of component (B) is 5 to 80 parts by mass per 100 parts by mass of component (A), preferably 10 to 60 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 35 parts by mass.

[0062] In this invention, the mixing ratio of component (A) and component (B) is considered to contribute significantly to improving the stability of the emulsion composition. To prepare a stable emulsion composition, it is necessary to form a strong interface between the aqueous phase and the oil phase to prevent the two phases from mixing. Component (A) has hydrophilic groups such as polyoxyalkylene groups within its molecule and exhibits both lipophilic and hydrophilic properties. Therefore, it is difficult to form a stable emulsion with component (A) alone or when the proportion of component (A) is extremely high. In contrast, it is considered that the stability of the emulsion can be improved by using a component with low hydrophilicity, such as component (B), in combination. Furthermore, if the amount of component (B) is too high, the proportion of hydrophilic components decreases, which reduces the water absorption effect on fibers, and is undesirable.

[0063] (B) Specific examples of components include the following. Note that the order of siloxane bonding is not limited to the following.

[0064] [ka]

[0065] [(C) component] Component (C) is a nonionic surfactant. It can be used alone or in appropriate combinations of two or more components.

[0066] 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.

[0067] Among these, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters are preferred, and polyoxyethylene alkyl ethers and polyoxyethylene propylene alkyl ethers are particularly preferred.

[0068] (C) As for the nonionic surfactant component, from the viewpoint of environmental impact, it is preferable that it does not contain polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0069] From the viewpoint of emulsion stability, the HLB value of the nonionic surfactant (or the entire 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 surfactants with different HLB values, the HLB value is calculated using the following formula.

[0070] N = N1 × W1 + N2 × W2 N: HLB value when using two types of surfactants with different HLB values: N N1, N2: HLB of each surfactant W1, W2: Weight fraction of each surfactant (W1 + W2 = 1)

[0071] The content of component (C) is 3 to 30 parts by mass, preferably 5 to 25 parts by mass, and more preferably 10 to 20 parts by mass, per 100 parts by mass of component (A).

[0072] [(D) component] Component (D) is an anionic surfactant.

[0073] 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.

[0074] Among these, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, alkylbenzene sulfonate, monoalkyl phosphate, dialkyl phosphate, and polyoxyethylene alkyl ether phosphate are preferred, and polyoxyethylene alkyl ether sulfate and polyoxyethylene alkyl ether phosphate are particularly preferred.

[0075] The content of component (D) is 0 to 10 parts by mass per 100 parts by mass of component (A), preferably 0.2 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass.

[0076] [(E) component] Component (E) is an organic acid, which can be used alone or in appropriate combinations of two or more. The composition of the present invention contains an organic acid, which allows a quaternary salt to be formed during emulsification by some of the amino groups of components (A) and (B) and the organic acid (E), thereby forming a microemulsion.

[0077] Specifically, examples include monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aromatic carboxylic acids, and acidic amino acids. More specifically, examples include monocarboxylic acids such as formic acid, 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. As organic acids in the present invention, carboxylic acids having 1 to 8 carbon atoms are preferred. Among these, formic acid, acetic acid, lactic acid, and citric acid are more preferred.

[0078] The content of component (E) is 0.05 to 10 parts by mass per 100 parts by mass of component (A), preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts by mass.

[0079] [(F) component] Component (F) is water, and all types of water can be used, such as deionized water and purified water. The content of component (F) is 8 to 400 parts by mass per 100 parts by mass of component (A), preferably 10 to 200 parts by mass, and particularly preferably 20 to 100 parts by mass.

[0080] The amino-modified silicone emulsion composition of the present invention preferably has an average particle size of 100 nm or less. 80 nm or less is preferred, and 60 nm or less is even more preferred. An average particle size of 100 nm or less enhances the stability of the emulsion and suppresses separation during long-term storage. There is no lower limit to the average particle size, but it can be, for example, 10 nm. In this invention, the average particle size is the particle size at 50% of the cumulative value in the particle size distribution determined by dynamic light scattering. An example of a measuring device is the nanoPartica SZ-100V2 (manufactured by HORIBA). In this invention, the average particle size is a value measured using the nanoPartica SZ-100V2 (manufactured by HORIBA) and represents the particle size at 50% of the cumulative value in the particle size distribution.

[0081] [Manufacturing method] The amino-modified silicone emulsion composition of the present invention can be prepared, for example, by the following method.

[0082] The product can be prepared by mixing component (F) with components (A), (B), (C), (D), and (E), and emulsifying and dispersing them in accordance with 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.

[0083] An example of the emulsification formulation details is as follows: Combimix (Primix Corporation) is mixed with (A) amino-modified silicone, (B) amino-modified silicone, (C) nonionic surfactant, (D) anionic surfactant, (E) organic acid, and a portion of (F) water. The mixture is then emulsified using a homomixer (a stirrer that uses the rotation of a rotor in a stator) at 2,000 rpm or a disper (a stirrer that uses the rotation of toothed blades) at 2,000 rpm and an anchor at 20 rpm. After the mixture is completely emulsified, it is stirred for 15 to 180 minutes at a disper at 2,000 rpm and an anchor at 30 rpm until the desired particle size is achieved. Then, the remaining (F) water is added and the mixture is diluted with a homomixer at 2,000 to 3,000 rpm to prepare the amino-modified silicone emulsion of the present invention.

[0084] There are no specific requirements for the emulsification temperature, but it is preferably 0 to 80°C, more preferably 10 to 60°C. Emulsification is easier at temperatures between 10°C and 60°C, and the resulting emulsion tends to be more stable. Heating an 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 emulsions 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, which can lead to more effective emulsification. 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.

[0085] 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-shear mixers (Silverson, Primix), homomixers (Primix), homodispers (Primix), ad-homomixers (Primix), combimix (Primix), which are three-screw dispersion kneaders that combine 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.

[0086] The amino-modified silicone emulsion composition of the present invention may contain various optional components in appropriate amounts, in addition to the above components (A) to (F). Examples of such optional components include silicone components other than components (A) and (B), additives, etc.

[0087] Examples of silicone components other than components (A) and (B) include, for example, silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil. When silicone components other than components (A) and (B) are included, the amount is preferably 1 to 10 parts by mass per 100 parts by mass of component (A).

[0088] Examples of additives include inorganic acids, protective colloids, thickeners, antifreezes, preservatives, rust inhibitors, antioxidants, fragrances, UV absorbers, antibacterial agents, curing catalysts, organic powders, inorganic powders, dyes, and fillers. The amount of additives is preferably 0.01 to 5% by mass relative to the composition.

[0089] [Fiber treatment agent] Furthermore, the amino-modified silicone emulsion composition of the present invention is also useful as a textile treatment agent such as a fabric softener or laundry detergent. For example, the amino-modified silicone emulsion composition can be incorporated into a textile treatment agent at a concentration of 0.1 to 20% by mass, preferably 0.5 to 10% by mass. If the amount incorporated is above the lower limit, there is little risk of deterioration in texture. On the other hand, if the amount incorporated is below the upper limit, there is little risk of yellowing during storage. [Examples]

[0090] 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. Note that, if a product name is specified, the amounts indicated refer to the amounts in that product.

[0091] Average particle size: This value was measured using a dynamic light scattering particle size analyzer (HORIBA nanoPartica SZ-100V2) after diluting the emulsion approximately 50 times with water.

[0092] pH: This value was measured at 25°C using a pH meter (HORIBA LAQUA).

[0093] Viscosity: The value was measured using a BM-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a temperature of 25°C.

[0094] Amino group equivalent: This value was measured using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.).

[0095] (A) Amino-modified silicone

[0096] (A-1) Amino-modified silicone Amino-modified silicone represented by the following formula (A-1) [ka] Viscosity: 680mPa·s, amino group equivalent: 2900g / mol

[0097] (A-2) Amino-modified silicone Amino-modified silicone represented by the following formula (A-2) [ka] Viscosity: 270mPa·s, amino group equivalent: 3000g / mol

[0098] (B) Amino-modified silicone

[0099] (B-1) Amino-modified silicone Amino-modified silicone represented by the following formula (B-1) [ka] Viscosity: 650mPa·s, amino group equivalent: 1920g / mol

[0100] (B-2) Amino-modified silicone Amino-modified silicone represented by the following formula (B-2) [ka] Viscosity: 1250mPa·s, amino group equivalent: 1700g / mol

[0101] (C) Nonionic surfactant (C-1) Emulgen 1108 (product name): Manufactured by Kao Chemical Co., Ltd., polyoxyethylene alkyl ether, HLB value 13.5 (C-2) Emulgen 109P (product name): Manufactured by Kao Chemical Co., Ltd., polyoxyethylene lauryl ether, HLB value = 13.6

[0102] (D) Anionic surfactants (D-1) Emal 20C (product name): Manufactured by Kao Chemical Co., Ltd., sodium polyoxyethylene lauryl ether sulfate aqueous solution (active ingredient: 25%, water: 75%)

[0103] (E)Organic acid (E-1) Acetic Acid (E-2) Lactic Acid

[0104] [Example 1] Amino-modified silicone represented by the above formula (A-1): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-1): 50.00 parts by mass, (C-1) Emulgen 1108: 16.00 parts by mass, (D-1) Emar 20C: 4.00 parts by mass, (E-2) Lactic acid: 2.45 parts by mass and, (F) Ion-exchanged water: 40.35 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-1).

[0105] [Example 2] Amino-modified silicone represented by the above formula (A-1): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-1): 36.37 parts by mass, (C-2) Emulgen 109P: 14.54 parts by mass, (D-1) Emar 20C: 3.60 parts by mass, (E-2) Lactic acid: 0.61 parts by mass and, (F) Ion-exchanged water: 36.47 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-2).

[0106] [Example 3] Amino-modified silicone represented by the above formula (A-1): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-1): 11.12 parts by mass, (C-2) Emulgen 109P: 11.85 parts by mass, (D-1) Emar 20C: 2.96 parts by mass, (E-2) Lactic acid: 0.50 parts by mass and (F) Ion-exchanged water: 29.70 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-3).

[0107] [Example 4] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-1): 23.08 parts by mass, (C-2) Emulgen 109P: 12.31 parts by mass, (D-1) Emar 20C: 3.08 parts by mass, (E-2) Lactic acid: 0.51 parts by mass and, (F) Ion-exchanged water: 30.83 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-4).

[0108] [Example 5] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-1): 33.33 parts by mass, (C-2) Emulgen 109P: 13.34 parts by mass, (D-1) Emar 20C: 3.32 parts by mass, (E-2) Lactic acid: 0.55 parts by mass and (F) Ion-exchanged water: 33.41 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-5).

[0109] [Example 6] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-1): 14.29 parts by mass, (C-2) Emulgen 109P: 11.43 parts by mass, (D-1) Emar 20C: 2.84 parts by mass, (E-2) Lactic acid: 0.47 parts by mass and, (F) Ion-exchanged water: 28.64 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-6).

[0110] [Example 7] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-2): 23.08 parts by mass, (C-2) Emulgen 109P: 12.31 parts by mass, (D-1) Emar 20C: 3.08 parts by mass, (E-2) Lactic acid: 0.51 parts by mass and, (F) Ion-exchanged water: 30.83 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-7).

[0111] [Example 8] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-2): 33.33 parts by mass, (C-2) Emulgen 109P: 13.34 parts by mass, (D-1) Emar 20C: 3.32 parts by mass, (E-2) Lactic acid: 0.55 parts by mass and, (F) Ion-exchanged water: 33.41 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-8).

[0112] [Example 9] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-2): 33.33 parts by mass, (C-2) Emulgen 109P: 13.34 parts by mass, (E-2) Lactic acid: 0.55 parts by mass and, (F) Ion-exchanged water: 33.41 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-9).

[0113] [Example 10] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-2): 33.33 parts by mass, (C-2) Emulgen 109P: 13.34 parts by mass, (D-1) Emar 20C: 3.32 parts by mass, (E-1) Acetic acid: 0.40 parts by mass and (F) Ion-exchanged water: 33.41 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (I-10).

[0114] [Comparative Example 1] Amino-modified silicone represented by the above formula (A-1): 100.00 parts by mass, (C-1) Emulgen 1108: 6.67 parts by mass, (D-1) Emar 20C: 3.00 parts by mass, (E-1) Acetic acid: 1.44 parts by mass, The mixture was mixed and emulsified using a homomixer to obtain amino-modified silicone emulsion composition (II-1).

[0115] [Comparative Example 2] Amino-modified silicone represented by the above formula (A-1): 100.00 parts by mass, (C-1) Emulgen 1108: 6.67 parts by mass, (E-1) Acetic acid: 1.44 parts by mass, (F) Ion-exchanged water: 3.00 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (II-2).

[0116] [Comparative Example 3] Amino-modified silicone represented by the above formula (A-1): 100.00 parts by mass, (C-1) Emulgen 1108: 6.66 parts by mass, (D-1) Emar 20C: 4.52 parts by mass, (E-2) Lactic acid: 3.25 parts by mass and, (F) Ion-exchanged water: 0.43 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (II-3).

[0117] [Comparative Example 4] Amino-modified silicone represented by the above formula (A-1): 100.00 parts by mass, (C-2) Emulgen 109P: 6.66 parts by mass, (D-1) Emar 20C: 4.48 parts by mass, (E-2) Lactic acid: 1.09 parts by mass and, (F) Ion-exchanged water: 22.39 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (II-4).

[0118] [Comparative Example 5] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-1): 23.07 parts by mass, (C-2) Emulgen 109P: 12.31 parts by mass, (D-1) Emar 20C: 3.08 parts by mass, (E-2) Lactic acid: 0.51 parts by mass and, (F) Ion-exchanged water: 5.44 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (II-5).

[0119] [Comparative Example 6] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-2): 100.00 parts by mass, (C-2) Emulgen 109P: 26.66 parts by mass, (D-1) Emar 20C: 6.64 parts by mass, (E-2) Lactic acid: 1.11 parts by mass and, (F) Ion-exchanged water: 66.84 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (II-6).

[0120] [Comparative Example 7] Amino-modified silicone represented by the above formula (A-2): 100.00 parts by mass, Amino-modified silicone represented by the above formula (B-2): 3.90 parts by mass, (C-2) Emulgen 109P: 10.39 parts by mass, (D-1) Emar 20C: 2.60 parts by mass, (E-2) Lactic acid: 0.43 parts by mass and, (F) Ion-exchanged water: 26.03 parts by mass The mixture was mixed and emulsified using a homomixer to obtain an amino-modified silicone emulsion composition (II-7).

[0121] The obtained silicone emulsion compositions were evaluated for "water absorption," "flexibility," "room temperature stability," and "high temperature stability" using the following method. The formulation, pH, average particle size, viscosity, and evaluation results for each emulsion composition are shown in Tables 1 to 4. In the tables, the amount of component (D) is the amount of the active ingredient (sodium polyoxyethylene lauryl ether sulfate only), not the amount used in the product. In the tables, the amount of water (F) is the total amount of water added as deionized water and the water contained in component (D).

[0122] [Water absorption evaluation] Deionized water was added to each emulsion obtained in the examples and comparative examples and stirred to prepare a test solution by diluting it so that the total of components (A) and (B) was 2% by mass. A polyester / cotton broadcloth (65% / 35%) was immersed in this test solution for 10 seconds, then squeezed using a roll at a 100% wringing rate, and dried at 150°C for 2 minutes to prepare a treated cloth for flexibility evaluation. Next, one drop (25 μL) of tap water was added to the treated cloth using a dropper, and the time (in seconds) until the water droplet was completely absorbed by the cloth was measured.

[0123] [Flexibility Assessment] Ion-exchanged water was added to each of the emulsions obtained in the examples and comparative examples, and the mixture was stirred and diluted to prepare a test solution such that the total of component (A) and component (B) was 2% by mass. A polyester / cotton broadcloth (65% / 35%) was immersed in this test solution for 10 seconds, then squeezed using a roll under the condition of a squeezing ratio of 100%, and dried at 150°C for 2 minutes to produce a treated cloth for flexibility evaluation. Three panelists felt the touch of this treated cloth and evaluated the flexibility based on the following scores compared with the untreated cloth. The results are shown according to the following evaluation criteria based on the total score of the three panelists.

[0124] <Evaluation Criteria> 3 points: The touch feeling is very good compared with the untreated cloth. 2 points: The touch feeling is good compared with the untreated cloth. 1 point: The touch feeling is equivalent to that of the untreated cloth. 0 point: The touch feeling is poor compared with the untreated cloth.

[0125] <Judgment> ◎: Total 7 points or more ○: Total 5 - 6 points △: Total 3 - 4 points ×: Total 2 points or less

[0126] [Room Temperature Stability Evaluation] Regarding each of the emulsions obtained in the examples and comparative examples, they were stored in a static state at 25°C for 3 months. After storage, the emulsions were visually inspected. Those that were not separated were marked as ○, those in which layer separation was confirmed but returned to uniformity by stirring were marked as △, and those in which gel precipitation was confirmed were marked as ×.

[0127] [High Temperature Stability Evaluation] Regarding each of the emulsions obtained in the examples and comparative examples, they were stored in a static state at 50°C for 1 month. After storage, the emulsions were visually inspected. Those that were not separated were marked as ○, those in which layer separation was confirmed but returned to uniformity by stirring were marked as △, and those in which gel precipitation was confirmed were marked as ×.

[0128]

Table 1

[0129] [Table 2]

[0130] [Table 3]

[0131] [Table 4]

[0132] As is clear from the above results, the amino-modified silicone emulsion compositions of the present invention in Examples 1 to 10 exhibited good stability and excellent water absorption and flexibility-imparting effects. On the other hand, Comparative Examples 1 to 4, which did not use component (B), Comparative Example 5, which had a small amount of (F) water, and Comparative Examples 6 to 7, which used component (B) but in excessive or insufficient amounts, showed poor stability at room temperature and high temperatures. [Industrial applicability]

[0133] The amino-modified silicone emulsion composition of the present invention has good stability, excellent water absorption and flexibility-imparting effects, and is suitable as a fiber treatment agent.

[0134] This specification includes the following inventions:

[0135] [1]: (A) The average empirical formula (1) below [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 These are independent of each other, and general formula (2) -R 4 -(NR 5 -R 6 ) f -NR5 2(2) (wherein R 4 and R 6 are each independently a divalent organic group having 1 to 6 carbon atoms, and f is 0 to 2. R 5 are each independently a hydrogen atom or a group represented by the general formula (3) -CH2-CH(OH)CH2O-(C2H4O) g -(C3H6O) h -Z (3) is a polyoxyalkylene-containing organic group represented by, Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene units and oxypropylene units may form a block polymer or a random polymer.) is a group represented by, and R 3 are each independently a group selected from the options of R 1 and R 2 , or a group selected from -OH, -OCH3, -OC2H 5、 -OC3H7 and -OC4H9, and a, b, c, d and e are numbers satisfying the ranges of 2≦a≦10, 5≦b≦300, 0≦c≦30, 0≦d≦5, 0≦e≦5.) However, the component (A) contains at least one group represented by the general formula (2) in one molecule, and 30% or more of R 5 is a polyoxyalkylene-containing organic group represented by the general formula (3).) represented by, having a viscosity at 25°C of 10 to 5,000 mPa·s and an amino group equivalent of 500 to 5,000 g / mol: 100 parts by mass, (B): The following average composition formula (4) [Chemical formula] [wherein R 1 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 7 are each independently a group represented by the general formula (5) -R 4 -(NH-R 6 ) f -NH2(5) (In the formula, R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is a number between 0 and 2. It is a group represented by R 8 They are independent of each other, R 1 and R 7 A group selected from the following options, or -OH, -OCH3, -OC2H 5、 -OC3H7 and -OC4H9 are selected groups, where i, j, k, l, and m are numbers satisfying the ranges 2 ≤ i ≤ 10, 100 ≤ j ≤ 1,000, 0 ≤ k ≤ 30, 0 ≤ l ≤ 5, and 0 ≤ m ≤ 5. However, component (B) contains at least one group represented by the general formula (5) in one molecule. Amino-modified silicone, expressed as such, with a viscosity of 100 to 50,000 mPa·s at 25°C and an amino group equivalent of 500 to 10,000 g / mol: 5 to 80 parts by mass per 100 parts by mass of component (A), (C) Nonionic surfactant: 3 to 30 parts by mass per 100 parts by mass of component (A) above, (D) Anionic surfactant: 0 to 10 parts by mass per 100 parts by mass of component (A) above, (E) Organic acid: 0.05 to 10 parts by mass per 100 parts by mass of component (A), and (F) Water: 8 to 400 parts by mass per 100 parts by mass of component (A) An amino-modified silicone emulsion composition characterized by containing [a specific substance].

[0136] [2]: The above component (A) is the average composition formula (6) [ka] [In the formula, R 1 These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 These are independent of each other, and general formula (2) -R 4 -(NR 5 -R 6 ) f -NR 5 2(2) (In the formula, R 4 and R 6 These are independently divalent organic groups with 1 to 6 carbon atoms, and f is 0 to 2. 5 These are, independently of each other, hydrogen atoms or general formula (3) -CH2-CH(OH)CH2O-(C2H4O) g -(C3H6O) h -Z (3) The polyoxyalkylene-containing organic group is represented by , where Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene units and oxypropylene units may form block polymers or random polymers. It is a group represented by R 9 They are independent of each other, R 1 Alternatively, -OH, -OCH3, -OC2H 5、 The base is selected from -OC3H7 and -OC4H9, where a, b, and c are numbers satisfying 2≦a≦10, 5≦b≦300, and 1≦c≦30, R 5 Of these, more than 30% are polyoxyalkylene-containing organic groups represented by the general formula (3) above. The amino-modified silicone emulsion composition according to [1] above, characterized in that it is an amino-modified silicone expressed as such, having a viscosity of 10 to 1,500 mPa·s at 25°C and an amino group equivalent of 500 to 5,000 g / mol.

[0137] [3]: R of component (A) 5 The amino-modified silicone emulsion composition according to [1] or [2] above, characterized in that 75% or more of the members are polyoxyalkylene-containing organic groups represented by the general formula (3).

[0138] [4]: R of component (B) 8 However, all R 1 An amino-modified silicone emulsion composition according to any one of the above [1] to [3], wherein the group is represented by [1].

[0139] [5]: The amino-modified silicone emulsion composition according to any of [1] to [4] above, characterized in that the average particle size is 100 nm or less.

[0140] [6]: A fiber treatment agent characterized by comprising the amino-modified silicone emulsion composition described in any of [1] to [5] above.

[0141] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. (A) The following average composition formula (1) 【Chemistry 1】 [In the formula, R １ These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R ２ These are independent of each other, and general formula (2) -R ４ -(NR) ５ -R ６ ) ｆ -NR ５ ２ (2) (In the formula, R ４ and R ６ are each independently a divalent organic group having 1 to 6 carbon atoms, and f is 0 to 2. R ５ are each independently a hydrogen atom or a general formula (3) -CH ２ -CH(OH)CH ２ O-(C ２ H ４ O) ｇ -(C ３ H ６ O) ｈ -Z (3) The polyoxyalkylene-containing organic group is represented by , where Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene units and oxypropylene units may form block polymers or random polymers. It is a group represented by R ３ They are independent of each other, R １ and R ２ A group selected from the following options, or -OH, -OCH ３ , -OC ２ H ５、 -OC ３ H ７ and -OC ４ H ９ The base is selected from the following, where a, b, c, d, and e are numbers satisfying the ranges 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, 0 ≤ c ≤ 30, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, component (A) contains at least one group represented by the general formula (2) in one molecule, R ５ More than 30% of these are polyoxyalkylene-containing organic groups represented by the general formula (3) above. Amino-modified silicone, expressed as such, with a viscosity of 10 to 5,000 mPa·s at 25°C and an amino group equivalent of 500 to 5,000 g / mol: 100 parts by mass, (B): The following average empirical formula (4) 【Chemistry 2】 [In the formula, R １ These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R ７ These are independent of each other, and the general formula (5) -R ４ -(NH-R ６ ) ｆ -NH ２ (5) (In the formula, R ４ and R ６ These are independently divalent organic groups with 1 to 6 carbon atoms, and f is a number between 0 and 2. It is a group represented by R ８ They are independent of each other, R １ and R ７ A group selected from the following options, or -OH, -OCH ３ , -OC ２ H ５、 -OC ３ H ７ and -OC ４ H ９ The group is selected from the above, where i, j, k, l, and m are numbers satisfying the ranges 2 ≤ i ≤ 10, 100 ≤ j ≤ 1,000, 0 ≤ k ≤ 30, 0 ≤ l ≤ 5, and 0 ≤ m ≤ 5. However, the above (B) component contains at least one group represented by the above general formula (5) in one molecule. An amino-modified silicone having a viscosity of 100 to 50,000 mPa·s at 25°C and an amino group equivalent of 500 to 10,000 g / mol: 5 to 80 parts by mass per 100 parts by mass of component (A), (C) Nonionic surfactant: 3 to 30 parts by mass per 100 parts by mass of component (A) above, (D) Anionic surfactant: 0 to 10 parts by mass per 100 parts by mass of component (A), (E) Organic acid: 0.05 to 10 parts by mass per 100 parts by mass of component (A), and (F) Water: 8 to 400 parts by mass per 100 parts by mass of component (A) An amino-modified silicone emulsion composition characterized by containing [a specific substance].

2. The above component (A) is the following average composition formula (6) 【Transformation 3】 [In the formula, R １ These are, independently of each other, unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R ２ These are independent of each other, and general formula (2) -R ４ -(NR) ５ -R ６ ) ｆ -NR ５ ２ (2) (In the formula, R ４ and R ６ These are independently divalent organic groups having 1 to 6 carbon atoms, and f is 0 to 2. ５ These are, independently of each other, hydrogen atoms or general formula (3) -CH ２ -CH(OH)CH ２ O-(C ２ H ４ O) ｇ -(C ３ H ６ O) ｈ -Z (3) The polyoxyalkylene-containing organic group is represented by , where Z is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, h is a number from 0 to 20, and the oxyethylene units and oxypropylene units may form block polymers or random polymers. It is a group represented by R ９ They are independent of each other, R １ or -OH, -OCH ３ , -OC ２ H ５、 -OC ３ H ７ and -OC ４ H ９ A base chosen from R, where a, b, and c are numbers satisfying 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, and 1 ≤ c ≤ 30. ５ More than 30% of these are polyoxyalkylene-containing organic groups represented by the general formula (3) above. The amino-modified silicone emulsion composition according to claim 1, characterized in that it is an amino-modified silicone expressed as such, having a viscosity of 10 to 1,500 mPa·s at 25°C and an amino group equivalent of 500 to 5,000 g / mol.

3. The R of component (A) ５ The amino-modified silicone emulsion composition according to claim 1, characterized in that 75% or more of the organic groups are polyoxyalkylene-containing organic groups represented by the general formula (3).

4. The R of component (B) ８ However, all R １ The amino-modified silicone emulsion composition according to claim 1, wherein the group is represented by .

5. The amino-modified silicone emulsion composition according to claim 1, characterized in that the average particle size is 100 nm or less.

6. A fiber treatment agent characterized by comprising the amino-modified silicone emulsion composition according to any one of claims 1 to 5.

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