Amino-modified silicone emulsion composition and fiber treatment agent
The amino-modified silicone emulsion composition with specific components addresses stability and flexibility issues, enhancing water absorption and emulsification for fabric treatment.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- SHIN ETSU CHEMICAL CO LTD
- Filing Date
- 2025-10-17
- Publication Date
- 2026-05-28
Smart Images
Figure JP2025036575_28052026_PF_FP_ABST
Abstract
Description
Amino-modified silicone emulsion composition and fiber treatment agent
[0001] The present invention relates to an amino-modified silicone emulsion composition and a fiber treatment agent.
[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] Also, the higher the silicone concentration in the emulsion, the more advantageous it is in terms of transportation costs and the like. However, it is difficult to create a high-concentration emulsion composition with excellent stability. In Patent Document 2, a high-concentration amino-modified silicone emulsion that can impart water absorption and flexibility to fibers has been proposed. However, there are cases where long-term stability, water absorption, and flexibility are insufficient. There is a need for an amino-modified silicone emulsion that is excellent in emulsion stability and can impart high flexibility and water absorption to fabrics.
[0006] Japanese Patent Application Laid-Open No. 2013-220991, Japanese Patent Application Laid-Open No. 2014-084398
[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 fabrics.
[0008] In order to solve the above problems, in the present invention, (A) the following average composition formula (1) [In the formula, R １ are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ２ are each independently a 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) is a polyoxyalkylene-containing organic group, 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. ) 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 group is selected from the above, 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, the (A) component contains at least one group represented by the above general formula (2) in one molecule, and R ５ Of these, 30% or more are polyoxyalkylene-containing organic groups represented by the general formula (3) above. 100 parts by mass of amino-modified silicone, represented by [ ], having a viscosity of 10 to 5,000 mPa·s at 25°C and an amino group equivalent of 500 to 5,000 g / mol, (B): the average composition formula (4) below [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) (wherein, R ４ and R ６ These are divalent organic groups with 1 to 6 carbon atoms, and f is a number from 0 to 2. ) These are groups 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 -OC４ 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. The present invention provides an amino-modified silicone emulsion composition comprising: (A) 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, expressed as (A) 5 to 80 parts by mass per 100 parts by mass of component (A); (C) a nonionic surfactant, 3 to 30 parts by mass per 100 parts by mass of component (A); (D) anionic surfactant, 0 to 10 parts by mass per 100 parts by mass of component (A); (E) an 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).
[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) [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 the general formula (2) -R ４ - (NR ５ -R ６ ) ｆ -NR ５ ２ (2) (wherein, 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 independent 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) is a polyoxyalkylene-containing organic group, 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. ) 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 is selected from, where a, b, and c are numbers satisfying 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, and 1 ≤ c ≤ 30, R ５ It is preferable that the amino-modified silicone is represented by "[ ] , 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] With such an average particle size, the stability of the emulsion is enhanced.
[0018] Further, the present invention provides a fiber treating agent containing the above amino-modified silicone emulsion composition.
[0019] The amino-modified silicone emulsion composition of the present invention can be particularly preferably used for a fiber treating agent.
[0020] The amino-modified silicone emulsion composition of the present invention is excellent in storage stability and can impart high flexibility and water absorbency to a cloth.
[0021] As described above, there has been a demand for the development of an amino-modified silicone emulsion composition that is excellent in stability and can impart high flexibility and water absorbency to a cloth.
[0022] As a result of intensive studies to achieve the above object, the present inventors have found that an amino-modified silicone emulsion composition containing the following components (A) to (F) is excellent in stability and can impart high flexibility and water absorbency to a cloth, and have found that it is suitable for a fiber treating agent, thus arriving at the present invention.
[0023] That is, the present invention provides: (A) The following average compositional formula (1) [In the formula, R １ are each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ２ are each independently a group represented by the 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 group represented by the general formula (3) -CH ２ -CH(OH)CH ２ O-(C ２ H ４ O) ｇ -(C ３ H ６ O) ｈ-Z (3) is a polyoxyalkylene-containing organic group, 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. ) 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 group is selected from the above, 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, the (A) component contains at least one group represented by the above general formula (2) in one molecule, and R ５ Of these, 30% or more are polyoxyalkylene-containing organic groups represented by the general formula (3) above. 100 parts by mass of amino-modified silicone, represented by [ ], having a viscosity of 10 to 5,000 mPa·s at 25°C and an amino group equivalent of 500 to 5,000 g / mol, (B): the average composition formula (4) below [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) (wherein, R ４ and R ６ These are divalent organic groups with 1 to 6 carbon atoms, and f is a number from 0 to 2. ) These are groups 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 -OC４ 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. The amino-modified silicone emulsion composition contains: (A) 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, expressed as (A) 5 to 80 parts by mass per 100 parts by mass of component (A); (C) a nonionic surfactant, 3 to 30 parts by mass per 100 parts by mass of component (A); (D) anionic surfactant, 0 to 10 parts by mass per 100 parts by mass of component (A); (E) an 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).
[0024] The present invention will be described in detail below, but the present invention is not limited to these descriptions.
[0025] [Component (A)] Component (A) is the following average composition formula (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 the general formula (2) -R ４ - (NR ５ -R ６ ) ｆ -NR ５ ２ (2) (wherein, 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 independent 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) is a polyoxyalkylene-containing organic group, 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. ) 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 group is selected from the above, 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, the (A) component contains at least one group represented by the above general formula (2) in one molecule, and R ５ More than 30% of these are polyoxyalkylene-containing organic groups represented by the general formula (3) above. It is an amino-modified silicone having a viscosity of 10 to 5,000 mPa·s at 25°C and an amino group equivalent of 500 to 5,000 g / mol.
[0026] 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.
[0027] R ２ These are independent of each other, and the general formula (2) -R ４ - (NR ５ -R ６ ) ｆ -NR５ ２ (2) (wherein, 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 independent 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 is a polyoxyalkylene-containing organic group represented by (3), 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 unit and oxypropylene unit may form a block polymer or a random polymer.) The group is represented by ). Note that component (A) contains at least one group represented by general formula (2) in one molecule.
[0028] R ４ , R ６ These are independently divalent organic groups having 1 to 6 carbon atoms. Examples of divalent organic groups having 1 to 6 carbon atoms include divalent hydrocarbon groups such as alkylene groups, alkenylene groups, and arylene groups. Among the divalent hydrocarbon groups, alkylene groups such as methylene groups, ethylene groups, propylene groups, and butylene groups are preferred, with ethylene groups and propylene groups being particularly preferred.
[0029] f is between 0 and 2, preferably 1. f can be, for example, an integer.
[0030] R ５ These are independent 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) is a polyoxyalkylene-containing organic group, and 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, -OCH ３ , -OC ２ H ５、 -OC ３ H ７ and -OC ４ H ９ It is a base selected from R １ , -OH, -OCH ３ , -OC ２ H ５ It is preferable.
[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] The value of b is 5 ≤ b ≤ 300, preferably 5 ≤ b ≤ 100, more preferably 10 ≤ b ≤ 50, and even more preferably 15 ≤ b ≤ 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, the amount of amino groups in the amino-modified silicone is too high, which may cause yellowing when the fiber is treated.
[0037] d is 0 ≤ d ≤ 5, and d = 0 is preferred. 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] (A) The amino group equivalent of component 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 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-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 amount (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). [In the formula, R １These 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 the general formula (2) -R ４ - (NR ５ -R ６ ) ｆ -NR ５ ２ (2) (wherein, 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 independent 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) is a polyoxyalkylene-containing organic group, 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. ) 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 is selected from, where a, b, and c are numbers satisfying 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, and 1 ≤ c ≤ 30, R ５ More than 30% of these 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, R １ or -OH, -OCH ３, -OC ２ H ５、 -OC ３ H ７ and -OC ４ H ９ It is a base selected from R １ or -OH, -OCH ３ , -OC ２ H ５ The base selected from among them is particularly preferable.
[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]
[0047] [Component (B)] Component (B) is the following average composition formula (4) [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) (wherein, R ４ and R ６ These are divalent organic groups with 1 to 6 carbon atoms, and f is a number from 0 to 2. ) These are groups 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 ９The group is selected from the above, where 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. However, the above component (B) contains at least one group represented by the above general formula (5) in one molecule. It is an amino-modified silicone represented by ], 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.
[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 -NH ２ (5) (Caution ４ and R ６ The groups are independently divalent organic groups having 1 to 6 carbon atoms, and f is a number from 0 to 2.) 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、 -OC ２ H ５、 -OC ３ H ７ and -OC ４ H ９ It is a base selected from R １ or -OH, -OCH ３、 -OC ２ H ５、 -OC ３ H ７ More preferably, 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 fibers are 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]
[0065] [Component (C)] 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 values are 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 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] [Component (D)] 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, alkanesulfonate, 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] [Component (E)] 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, preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts by mass, per 100 parts by mass of component (A).
[0079] [Component (F)] 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. Preferably, it is 80 nm or less, and more preferably 60 nm or less. If the average particle size is 100 nm or less, the stability of the emulsion is increased and separation during long-term storage can be suppressed. 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 (F) a portion of 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 emulsified, it is stirred for 15 to 180 minutes with 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 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 achieved, 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. It is possible to use colloid mills (IKA, PUC, Nippon Seiki Seisakusho, Iwaki), high-sheer mixers (Silverson, Primix), homomixers (Primix), homodispers (Primix), adihomomickers (Primix), combimix (Primix), a tri-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, MC5 (Leo Lab), etc.
[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] Specific examples of silicone components other than components (A) and (B) include 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 fiber treatment agent such as a fabric softener or laundry detergent. For example, the amino-modified silicone emulsion composition can be blended into a fiber treatment agent at a concentration of 0.1 to 20% by mass, preferably 0.5 to 10% by mass. If the blending amount is above the lower limit, there is little risk of deterioration of texture. On the other hand, if the blending amount is below the upper limit, there is little risk of yellowing during storage.
[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 (nanoPartica SZ-100V2, manufactured by HORIBA Corporation) after diluting the emulsion approximately 50 times with water.
[0092] pH: This value was measured at 25°C using a pH meter (LAQUA, manufactured by HORIBA).
[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) Viscosity: 680 mPa・s, amino group equivalent: 2900 g / mol
[0097] (A-2) Amino-modified silicone Amino-modified silicone represented by the following formula (A-2) Viscosity: 270 mPa・s, amino group equivalent: 3000 g / mol
[0098] (B) Amino-modified silicone
[0099] (B-1) Amino-modified silicone Amino-modified silicone represented by the following formula (B-1) Viscosity: 650 mPa・s, amino group equivalent: 1920 g / mol
[0100] (B-2) Amino-modified silicones represented by the following formula (B-2) Viscosity: 1250 mPa・s, amino group equivalent: 1700 g / mol
[0101] (C) Nonionic surfactants (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 surfactant (D-1) Emal 20C (product name): Manufactured by Kao Chemical Co., Ltd., aqueous solution of sodium polyoxyethylene lauryl ether sulfate (active ingredient: 25%, water: 75%)
[0103] (E) Organic acids (E-1) Acetic acid (E-2) Lactic acid
[0104] [Example 1] 100.00 parts by mass of amino-modified silicone represented by formula (A-1) above, 50.00 parts by mass of amino-modified silicone represented by formula (B-1) above, 16.00 parts by mass of (C-1) Emulgen 1108, 4.00 parts by mass of (D-1) Emal 20C, 2.45 parts by mass of (E-2) lactic acid, and 40.35 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-1).
[0105] [Example 2] 100.00 parts by mass of amino-modified silicone represented by formula (A-1) above, 36.37 parts by mass of amino-modified silicone represented by formula (B-1) above, 14.54 parts by mass of (C-2) Emulgen 109P, 3.60 parts by mass of (D-1) Emal 20C, 0.61 parts by mass of (E-2) lactic acid, and 36.47 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-2).
[0106] [Example 3] 100.00 parts by mass of amino-modified silicone represented by formula (A-1) above, 11.12 parts by mass of amino-modified silicone represented by formula (B-1) above, 11.85 parts by mass of (C-2) Emulgen 109P, 2.96 parts by mass of (D-1) Emal 20C, 0.50 parts by mass of (E-2) lactic acid, and 29.70 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-3).
[0107] [Example 4] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 23.08 parts by mass of amino-modified silicone represented by formula (B-1) above, 12.31 parts by mass of (C-2) Emulgen 109P, 3.08 parts by mass of (D-1) Emal 20C, 0.51 parts by mass of (E-2) lactic acid, and 30.83 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-4).
[0108] [Example 5] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 33.33 parts by mass of amino-modified silicone represented by formula (B-1) above, 13.34 parts by mass of (C-2) Emulgen 109P, 3.32 parts by mass of (D-1) Emal 20C, 0.55 parts by mass of (E-2) lactic acid, and 33.41 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-5).
[0109] [Example 6] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 14.29 parts by mass of amino-modified silicone represented by formula (B-1) above, 11.43 parts by mass of (C-2) Emulgen 109P, 2.84 parts by mass of (D-1) Emal 20C, 0.47 parts by mass of (E-2) lactic acid, and 28.64 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-6).
[0110] [Example 7] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 23.08 parts by mass of amino-modified silicone represented by formula (B-2) above, 12.31 parts by mass of (C-2) Emulgen 109P, 3.08 parts by mass of (D-1) Emal 20C, 0.51 parts by mass of (E-2) lactic acid, and 30.83 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain an amino-modified silicone emulsion composition (I-7).
[0111] [Example 8] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 33.33 parts by mass of amino-modified silicone represented by formula (B-2) above, 13.34 parts by mass of (C-2) Emulgen 109P, 3.32 parts by mass of (D-1) Emal 20C, 0.55 parts by mass of (E-2) lactic acid, and 33.41 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-8).
[0112] [Example 9] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 33.33 parts by mass of amino-modified silicone represented by formula (B-2) above, 13.34 parts by mass of (C-2) Emulgen 109P, 0.55 parts by mass of (E-2) Lactic acid, and 33.41 parts by mass of (F) Ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (I-9).
[0113] [Example 10] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 33.33 parts by mass of amino-modified silicone represented by formula (B-2) above, 13.34 parts by mass of (C-2) Emulgen 109P, 3.32 parts by mass of (D-1) Emal 20C, 0.40 parts by mass of (E-1) Acetic acid, and 33.41 parts by mass of (F) Ion-exchanged water were mixed using a homomixer and emulsified to obtain an amino-modified silicone emulsion composition (I-10).
[0114] [Comparative Example 1] 100.00 parts by mass of the amino-modified silicone represented by the above formula (A-1), 6.67 parts by mass of (C-1) Emulgen 1108, 3.00 parts by mass of (D-1) Emal 20C, and 1.44 parts by mass of (E-1) Acetic acid were mixed using a homomixer and emulsified to obtain an amino-modified silicone emulsion composition (II-1).
[0115] [Comparative Example 2] 100.00 parts by mass of amino-modified silicone represented by formula (A-1) above, 6.67 parts by mass of (C-1) Emulgen 1108, 1.44 parts by mass of (E-1) Acetic acid, and 3.00 parts by mass of (F) Ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-2).
[0116] [Comparative Example 3] 100.00 parts by mass of amino-modified silicone represented by formula (A-1) above, 6.66 parts by mass of (C-1) Emulgen 1108, 4.52 parts by mass of (D-1) Emal 20C, 3.25 parts by mass of (E-2) lactic acid, and 0.43 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-3).
[0117] [Comparative Example 4] 100.00 parts by mass of amino-modified silicone represented by the above formula (A-1), 6.66 parts by mass of (C-2) Emulgen 109P, 4.48 parts by mass of (D-1) Emal 20C, 1.09 parts by mass of (E-2) lactic acid, and 22.39 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-4).
[0118] [Comparative Example 5] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 23.07 parts by mass of amino-modified silicone represented by formula (B-1) above, 12.31 parts by mass of (C-2) Emulgen 109P, 3.08 parts by mass of (D-1) Emal 20C, 0.51 parts by mass of (E-2) lactic acid, and 5.44 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-5).
[0119] [Comparative Example 6] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 100.00 parts by mass of amino-modified silicone represented by formula (B-2) above, 26.66 parts by mass of (C-2) Emulgen 109P, 6.64 parts by mass of (D-1) Emal 20C, 1.11 parts by mass of (E-2) lactic acid, and 66.84 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified to obtain amino-modified silicone emulsion composition (II-6).
[0120] [Comparative Example 7] 100.00 parts by mass of amino-modified silicone represented by formula (A-2) above, 3.90 parts by mass of amino-modified silicone represented by formula (B-2) above, 10.39 parts by mass of (C-2) Emulgen 109P, 2.60 parts by mass of (D-1) Emal 20C, 0.43 parts by mass of (E-2) lactic acid, and 26.03 parts by mass of (F) ion-exchanged water were mixed using a homomixer and emulsified 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 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 at a 100% wringing rate, and dried at 150°C for 2 minutes to prepare a treated cloth for flexibility evaluation. After that, one drop (25 μL) of tap water was added to this treated cloth using a dropper, and the time (seconds) until the water droplet was completely absorbed into the cloth was measured.
[0123] [Flexibility 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. Three panelists touched this treated cloth and evaluated its flexibility compared to the untreated cloth using the following scoring system. The results are shown below based on the total scores of the three panelists and the sum of their scores.
[0124] <Evaluation Criteria> 3 points: The texture is very good compared to untreated fabric. 2 points: The texture is good compared to untreated fabric. 1 point: The texture is the same as untreated fabric. 0 points: The texture is bad compared to untreated fabric.
[0125] <Judgment> ◎: 7 points or more in total ○: 5 to 6 points in total △: 3 to 4 points in total ×: 2 points or less in total
[0126] [Room Temperature Stability Evaluation] Each emulsion obtained in the examples and comparative examples was stored at 25°C for 3 months. After storage, the emulsions were visually inspected. ○ indicated that no separation had occurred, △ indicated that layer separation was observed but returned to homogeneity after stirring, and × indicated that gel precipitation had occurred.
[0127] [High-Temperature Stability Evaluation] Each emulsion obtained in the examples and comparative examples was stored at 50°C for one month. After storage, the emulsions were visually inspected. ○ indicated that no separation had occurred, △ indicated that layer separation was observed but returned to homogeneity after stirring, and × indicated that gel precipitation had occurred.
[0128]
[0129]
[0130]
[0131]
[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, in which component (B) was not used in combination, Comparative Example 5, in which the amount of (F) water was small, and Comparative Examples 6 to 7, in which component (B) was used in combination but in excessive or insufficient amounts, showed poor stability at room temperature and high temperatures.
[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 following average empirical formula (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 the general formula (2) -R ４ - (NR ５ -R ６ ) ｆ -NR５ ２ (2) (wherein, 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 independent 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) is a polyoxyalkylene-containing organic group, 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. ) 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 group is selected from the above, 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, the (A) component contains at least one group represented by the above general formula (2) in one molecule, and R ５ Of these, 30% or more are polyoxyalkylene-containing organic groups represented by the general formula (3) above. 100 parts by mass of amino-modified silicone, represented by [ ], having a viscosity of 10 to 5,000 mPa·s at 25°C and an amino group equivalent of 500 to 5,000 g / mol, (B): the average composition formula (4) below [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) (wherein, R ４ and R ６ These are divalent organic groups with 1 to 6 carbon atoms, and f is a number from 0 to 2. ) These are groups 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 emulsion composition characterized by containing: (A) an amino-modified silicone expressed as ], 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, in an amount of 5 to 80 parts by mass per 100 parts by mass of component (A); (C) a nonionic surfactant, in an amount of 3 to 30 parts by mass per 100 parts by mass of component (A); (D) anionic surfactant, in an amount of 0 to 10 parts by mass per 100 parts by mass of component (A); (E) an organic acid, in an amount of 0.05 to 10 parts by mass per 100 parts by mass of component (A); and (F) water, in an amount of 8 to 400 parts by mass per 100 parts by mass of component (A).
[0136] [2] The above component (A) is the following average composition formula (6) [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 the general formula (2) -R ４ - (NR ５ -R ６ ) ｆ -NR ５ ２ (2) (wherein, 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 independent 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) is a polyoxyalkylene-containing organic group, 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. ) 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 is selected from, where a, b, and c are numbers satisfying 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, and 1 ≤ c ≤ 30, R ５ More than 30% of these are polyoxyalkylene-containing organic groups represented by the general formula (3). The amino-modified silicone emulsion composition according to [1] above is characterized by being an amino-modified silicone 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 these 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 [1] to [3] above, wherein the group is represented by [1].
[0139] [5]: The amino-modified silicone emulsion composition according to any one 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) [wherein, R １ are each independently a non-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ２ are each independently a group represented by the general formula (2) -R ４ -(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 polyoxyalkylene-containing organic group represented by the general formula (3) -CH ２ -CH(OH)CH ２ O-(C ２ H ４ O) ｇ -(C ３ H ６ O) ｈ -Z (3), where Z is a hydrogen atom, a substituted or non-substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an acyl group. g is a number from 2 to 30, and h is a number from 0 to 20. The oxyethylene units and oxypropylene units may form a block polymer or a random polymer.).), and R ３ are each independently a group selected from the options of R １ and R ２ , or a group selected from -OH, -OCH ３ , -OC ２ H ５、 -OC ３ H ７ and -OC ４ H ９ ４ selected from. a, b, c, d, and e are numbers satisfying the ranges of 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, 0 ≤ c ≤ 30, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, the component (A) contains at least one group represented by the general formula (2) in one molecule, and R ５ Of these, 30% or more are polyoxyalkylene-containing organic groups represented by the general formula (3) above. 100 parts by mass of amino-modified silicone, represented by [ ], having a viscosity of 10 to 5,000 mPa·s at 25°C and an amino group equivalent of 500 to 5,000 g / mol, (B): the average composition formula (4) below [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) (wherein, R ４ and R ６ These are divalent organic groups with 1 to 6 carbon atoms, and f is a number from 0 to 2. ) These are groups 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 emulsion composition characterized by containing: (A) an amino-modified silicone expressed as ], 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, in an amount of 5 to 80 parts by mass per 100 parts by mass of component (A); (C) a nonionic surfactant, in an amount of 3 to 30 parts by mass per 100 parts by mass of component (A); (D) anionic surfactant, in an amount of 0 to 10 parts by mass per 100 parts by mass of component (A); (E) an organic acid, in an amount of 0.05 to 10 parts by mass per 100 parts by mass of component (A); and (F) water, in an amount of 8 to 400 parts by mass per 100 parts by mass of component (A).
2. The above component (A) is the following average composition formula (6) [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 the general formula (2) -R ４ - (NR ５ -R ６ ) ｆ -NR ５ ２ (2) (wherein, 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 independent 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) is a polyoxyalkylene-containing organic group, 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. ) 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 is selected from, where a, b, and c are numbers satisfying 2 ≤ a ≤ 10, 5 ≤ b ≤ 300, and 1 ≤ c ≤ 30, R ５ More than 30% of these are polyoxyalkylene-containing organic groups represented by the general formula (3). The amino-modified silicone emulsion composition according to claim 1 is characterized in that it is an amino-modified silicone 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. 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. 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.