Amino-modified silicone emulsion composition and fiber treatment agent

Abstract

An amino-modified silicone emulsion composition containing (A) 100 parts by mass of an amino-modified silicone represented by the following average compositional formula (I), having a viscosity at 25 DEG C of 10-50,000 mPa * s, and an amino equivalent of 500-25,000 g / mol; (B) 5 to 100 parts by mass of a nonionic surfactant; the amino-modified silicone emulsion composition has excellent stability when stored at a high temperature, is less susceptible to increase in octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) after a period of time, and is capable of suppressing yellowing of fibers.

Description

Technical Field

[0001] This invention relates to amino-modified organosilicon emulsion compositions and fiber treatment agents. Background Technology

[0002] To date, various silicone materials, such as dimethyl silicone, epoxy-modified silicone, and amino-modified silicone, are widely used as treatment agents to impart softness and smoothness to various fibers or fiber products. Among them, amino-modified silicone has an excellent effect on imparting softness to fibers and is used as a treatment agent in fiber processing, detergent, and softener.

[0003] When using amino-modified silicone as a fiber treatment agent, surfactants are generally used to emulsify and disperse the silicone in water, thus utilizing it as an emulsion composition (aqueous composition). In the case of amino-modified silicone emulsion compositions, not only the storage stability of the emulsion composition, but also the byproducts of cyclic low-molecular-weight siloxanes (such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane) during storage sometimes become problems. In recent years, regulations related to cyclic low-molecular-weight siloxanes (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylcyclohexasiloxane) have become stricter in various countries, making it a challenge to reduce the content of cyclic low-molecular-weight siloxanes in silicone products. In the case of amino-modified silicone emulsion compositions, even when the amount of cyclic low-molecular-weight siloxanes is small immediately after manufacturing, hydrolysis and equilibration reactions of the silicone sometimes occur due to the alkalinity of the amino group and the presence of water, resulting in the byproduct of cyclic low-molecular-weight siloxanes over time.

[0004] To address the aforementioned issues, the following research has been conducted to date. Patent Document 1: Japanese Patent Publication No. 2013-532741 discloses a method for manufacturing an emulsion using polydialkylsiloxane, an amino-functionalized organopolysiloxane, a quaternary ammonium surfactant, and water. Patent Document 2: Japanese Patent Publication No. 2015-500926 discloses a process for applying an emulsion using an amino-functionalized organopolysiloxane, a quaternary ammonium surfactant, a nonionic surfactant, and water to fibers, reporting that compared to existing methods, the levels of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in the emulsion do not easily increase over time. Patent Document 3: Japanese Patent No. 6258213 discloses a composition using an amino-functionalized organopolysiloxane with less than 0.1% by mass of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), a quaternary ammonium surfactant, a nonionic surfactant, and water in an emulsion.

[0005] In these prior art technologies, quaternary ammonium surfactants must be incorporated. If an emulsion containing a cationic surfactant is incorporated into a shampoo, softener, or similar product containing anionic surfactants, its stability may decrease. Furthermore, as shown in Patent Document 4: Japanese Patent Application Publication No. 2021-70746, an amino-modified silicone emulsion composition containing specific amounts of acetic acid or lactic acid does not readily increase in octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) over time.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Publication No. 2013-532741

[0009] Patent Document 2: Japanese Patent Publication No. 2015-500926

[0010] Patent Document 3: Japanese Patent No. 6258213

[0011] Patent Document 4: Japanese Patent Application Publication No. 2021-70746 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] Fiber products treated with amino-modified silicone emulsion compositions suffer from yellowing due to the degradation of amino groups. When using amino-modified silicone emulsion compositions, numerous issues arise, including storage stability, suppression of cyclic low-molecular-weight siloxane byproducts, and prevention of yellowing of fiber products, which are currently difficult to resolve simultaneously.

[0014] The present invention was made in view of the above-mentioned actual situation, and aims to provide an amino-modified organosilicon emulsion composition and fiber treatment agent with excellent stability during high-temperature storage, and which does not easily increase the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecylcyclohexasiloxane (D6) over time, thereby inhibiting yellowing of fibers.

[0015] Methods for solving problems

[0016] To achieve the above objectives, the inventors conducted in-depth research and discovered that an amino-modified organosilicon emulsion composition containing (A) an amino-modified organosilicon with a specific structure, (B) a nonionic surfactant, and (C) water exhibits better storage stability compared to existing products, with less accumulation of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) over time. Furthermore, fiber treatment agents using this amino-modified organosilicon emulsion composition can inhibit yellowing of fibers, thus completing this invention.

[0017] Therefore, the present invention provides the following amino-modified organosilicon emulsion composition.

[0018] 1. An amino-modified organosilicon emulsion composition, comprising:

[0019] (A) 100 parts by mass of amino-modified organosilicon with a viscosity of 10–50000 mPa·s at 25°C and an amino equivalent of 500–25000 g / mol, expressed by the following average composition formula (I).

[0020] [Chemistry 1]

[0021]

[0022] [In the formula, R] 1 Independently selected from unsubstituted or substituted monovalent hydrocarbon groups with 1 to 20 carbon atoms, -OH, -OCH3, and -OC2H5, R 2 R are groups represented independently by general formula (2). 3 Independently for R 1 or R 2 Let a, b, c, d, and e be numbers satisfying the following ranges: 2 ≤ a ≤ 10, 10 ≤ b ≤ 1300, 0 ≤ c ≤ 50, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, when c = 0, R... 3 At least one of them is R 2 .

[0023] -R 4 -(NR 6 -R 5 ) p -NR 6 twenty two)

[0024] (where R is in the formula) 4 and R 5 Each group consists of a divalent organic group with 1 to 6 carbon atoms, and p = 0 to 3. R 6 R is a hydrogen atom or a group represented by general formula (3) that are independent of each other. 6 More than 10 mol% of the components are groups represented by general formula (3).

[0025] -CH2-CHR 7 -COOR 8 (3)

[0026] (In the above formula (3), R) 7 R is a hydrogen atom or a methyl group. 8 It is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 30 carbon atoms.

[0027] (B) Nonionic surfactant: 5-100 parts by weight, and

[0028] (C) Water: 10 to 10,000 parts by weight.

[0029] 2. The amino-modified organosilicon emulsion composition according to 1, further comprising (D) organic acid: 0.05 to 10 parts by weight.

[0030] 3. The amino-modified organosilicon emulsion composition according to 1 or 2, wherein, in formula (3), R 8 It is an unsubstituted or substituted monovalent hydrocarbon group with 6 to 20 carbon atoms.

[0031] 4. The amino-modified organosilicon emulsion composition according to any one of 1 to 3, wherein, in component (A), the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecylcyclohexasiloxane are each 3000 ppm or less.

[0032] 5. The amino-modified organosilicon emulsion composition according to any one of 1 to 4, wherein component (B) is a poly(oxyethylene) secondary alkyl ether with an ethylene oxide (EO) chain added to the hydroxyl group of a secondary alcohol.

[0033] 6. The amino-modified organosilicon emulsion composition according to any one of 1 to 5, wherein the combination of component (A) and component (B) is a combination in which a mixture of 90 parts by weight of component (A) and 10 parts by weight of component (B) does not gel when heated at 170°C for 1 hour.

[0034] 7. The amino-modified organosilicon emulsion composition according to any one of 1 to 6, wherein component (A) is an amino-modified organosilicon without alkoxy groups.

[0035] 8. The amino-modified organosilicon emulsion composition according to any one of 1 to 7, wherein the increase in the amount of each of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecylcyclohexasiloxane relative to the mass of component (A) when the amino-modified organosilicon emulsion composition is stored at 25°C for 6 months is less than 2000 ppm.

[0036] 9. A fiber treatment agent comprising an amino-modified organosilicon emulsion composition according to any one of 1 to 8.

[0037] The effects of the invention

[0038] The inventors discovered that, according to the present invention, an amino-modified silicone emulsion composition with excellent stability during high-temperature storage, and with minimal increase in the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) over time, thereby inhibiting yellowing of fibers, is obtained, thus completing the present invention. Detailed Implementation

[0039] The present invention will now be described in detail.

[0040] [(A) ingredient]

[0041] The (A) component of this invention is an amino-modified organosilicon represented by the following average composition formula (I).

[0042] [Chemistry 2]

[0043]

[0044] [In the formula, R] 1 Independently selected from unsubstituted or substituted monovalent hydrocarbon groups with 1 to 20 carbon atoms, -OH, -OCH3, and -OC2H5, R 2 These are groups that are independently represented by general formula (2).

[0045] -R 4 -(NR 6 -R 5 ) p -NR 6 twenty two)

[0046] (where R is in the formula) 4 and R 5 Each group consists of a divalent organic group with 1 to 6 carbon atoms, and p = 0 to 3. R 6 R is a hydrogen atom or a group represented by general formula (3) that are independent of each other. 6 More than 10 mol% of the components are groups represented by general formula (3).

[0047] -CH2-CHR 7 -COOR 8 (3)

[0048] (In the above formula (3), R) 7 R is a hydrogen atom or a methyl group. 8 (A monovalent hydrocarbon group consisting of 1 to 30 carbon atoms, either unsubstituted or substituted.)

[0049] R 3 Independently for R 1 or R 2 Let a, b, c, d, and e be numbers satisfying the following ranges: 2 ≤ a ≤ 10, 10 ≤ b ≤ 1300, 0 ≤ c ≤ 50, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, when c = 0, R... 3 At least one of them is R 2 . ]

[0050] (A) The viscosity of component at 25°C is 10-50000 mPa·s and the amino equivalent is 500-25000 g / mol. It can be used alone or in combination of two or more components.

[0051] R 1 The groups are independently selected from unsubstituted or substituted monovalent hydrocarbon groups, -OH, -OCH3, and -OC2H5, having 1 to 20 carbon atoms. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl; alkenyl groups such as vinyl, allyl, 5-hexenyl, and oleyl; and aryl groups such as phenyl, tolyl, and naphthyl. Among these, methyl, long-chain (6 to 20 carbon atoms) alkyl groups, and phenyl groups are examples. Methyl is preferred.

[0052] R 2 Each group is a group represented by the general formula (2) and they are independent of each other.

[0053] -R 4 -(NR 6 -R 5 ) p -NR 6 twenty two)

[0054] (where R is in the formula) 4 and R 5 Each group consists of a divalent organic group with 1 to 6 carbon atoms, and p = 0 to 3. R 6 R is a hydrogen atom or a group represented by general formula (3) that are independent of each other. 6 More than 10 mol% of the components are groups represented by general formula (3).

[0055] -CH2-CHR 7 -COOR 8 (3)

[0056] (In the above formula (3), R) 7 R is a hydrogen atom or a methyl group. 8 (A monovalent hydrocarbon group consisting of 1 to 30 carbon atoms, either unsubstituted or substituted.)

[0057] R 4 and R 5 These are divalent organic groups that are independent of each other and have 1 to 6 carbon atoms. Examples of divalent hydrocarbon groups include alkylene, alkenylene, and arylene.

[0058] R 6 R is a hydrogen atom or a group represented by general formula (3) that are independent of each other. 6 More than 10 mol% of the components are groups represented by general formula (3), preferably R. 6More than 20 mol% of the components are groups represented by general formula (3), more preferably R. 6 More than 30 mol% of the group is represented by the general formula (3)-. There is no particular upper limit, and it can be 100 mol%. By making R 6 More than 10 mol% of the group is represented by the general formula (3), which can suppress the increase of D4, D5 and D6 after a period of time and suppress the yellowing of the fiber.

[0059] R 8 The group is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 30 carbon atoms, preferably 6 to 20, and more preferably 8 to 18. Examples of unsubstituted or substituted monovalent hydrocarbon groups with 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and octadecyl, and aryl groups such as phenyl, tolyl, and naphthyl. These groups can have a straight-chain structure or a branched structure. Octyl, dodecyl, and octadecyl are preferred.

[0060] R 3 Independently for R 1 or R 2 Let a, b, c, d, and e be numbers satisfying the following ranges: 2 ≤ a ≤ 10, 10 ≤ b ≤ 1300, 0 ≤ c ≤ 50, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, when c = 0, R... 3 At least one of them is R 2 Choose R appropriately. 3 and a, b, c, d, and e such that the (A) amino-modified organosilicon of the present invention comprises more than one R 2 That is, the group represented by general formula (2). In the case of c = 0, R 3 At least one of them is R 2 The molecule contains more than one R 2 That is, the group represented by general formula (2). If the group represented by general formula (2) is not present, the amount of amino in the amino-modified organosilicon is too small, which reduces the adhesion to the fiber.

[0061] (A) The component is preferably free of alkoxy groups. If alkoxy groups are included, hydrolysis may occur in the emulsion composition, potentially reducing the emulsion's storage stability and increasing the byproduct yield of cyclic low-molecular-weight siloxanes. Furthermore, methyl groups are preferred relative to R. 1 R 2 and R 3 The total number of items contained in the product was more than 70 mol%.

[0062] 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 organosilicon will decrease excessively, and its emulsifying properties will decrease.

[0063] The value of b is 10 ≤ b ≤ 1300, preferably 50 ≤ b ≤ 1000, and more preferably 100 ≤ b ≤ 500. If b is less than 10, the viscosity of the amino-modified silicone decreases excessively, reducing its effect on imparting lubricity to the fibers. On the other hand, if b exceeds 1300, the viscosity of the amino-modified silicone increases excessively, reducing its emulsifying properties.

[0064] The value of c is 0 ≤ c ≤ 50, preferably 1 ≤ c ≤ 30, more preferably 1 ≤ c ≤ 15, and even more preferably 3 ≤ c ≤ 10. If c exceeds 50, the amount of amino groups in the amino-modified organosilicon is excessive, which may cause yellowing during fiber treatment.

[0065] The viscosity d should be 0 ≤ d ≤ 5, with d = 0 being preferred. If d exceeds 5, the viscosity of the amino-modified organosilicon will decrease excessively, resulting in poor emulsification.

[0066] The value of e is 0 ≤ e ≤ 5, with e = 0 being preferred. If e exceeds 5, the viscosity of the amino-modified organosilicon will decrease excessively, resulting in poor emulsification.

[0067] (A) The viscosity of component A at 25°C is 10–50,000 mPa·s, preferably 50–30,000 mPa·s, more preferably 300–5,000 mPa·s, and even more preferably 500–3,000 mPa·s. If the viscosity is below the lower limit mentioned above, the effect of imparting sliding properties to the fibers deteriorates. On the other hand, if the viscosity exceeds the upper limit mentioned above, the emulsifying properties deteriorate. It should be noted that in this invention, the viscosity is a value measured using a BM-type viscometer or a BH-type viscometer (e.g., manufactured by Tokyo Keiki Co., Ltd.). It should be noted that, depending on the viscosity, the rotor, rotation speed, and rotation time are appropriately selected as described below.

[0068] The viscosity in this invention is determined based on the viscosity of the object being measured, and the rotor and rotation speed are as described below.

[0069] For a viscosity of 10 mPa·s or higher but less than 100 mPa·s, rotor No. 1, speed 30 rpm,

[0070] For a viscosity of 100 mPa·s or higher but less than 500 mPa·s, rotor No. 2, rotation speed 30 rpm,

[0071] When the viscosity is above 500 mPa·s but below 3000 mPa·s, rotor No. 3, speed 30 rpm,

[0072] When the viscosity is above 3000 mPa·s but below 15000 mPa·s, rotor No. 4, speed 30 rpm,

[0073] For a viscosity of 15000 mPa·s or higher but less than 40000 mPa·s, rotor No. 6, speed 20 rpm,

[0074] With a viscosity of 40000 mPa·s or higher, rotor No. 7, speed 20 rpm

[0075] (A) The amino equivalent of the component is 500 to 25000 g / mol, preferably 1000 to 10000 g / mol, and more preferably 1500 to 5000 g / mol. By setting the amino equivalent to the above range, the hydrophilicity that should be given to the amino-modified organosilicon can be imparted, and the possibility of yellowing can be reduced more likely when treating fibers.

[0076] The amino equivalent in this invention refers to the number of grams of amino-modified organosilicon that can be neutralized with 1 mole of hydrochloric acid; theoretically, it is the molecular weight divided by the number of nitrogen atoms. The amino equivalent can be determined using a neutralization titration method, for example, an automatic titration apparatus manufactured by Hiranuma Sangyo Co., Ltd. More specifically, it can be determined using the following method: The amino-modified organosilicon, which is the target for neutralization, is dissolved in a solvent in which toluene and IPA are mixed at a mass ratio of 1:1. The solution is titrated with hydrochloric acid using an automatic titrator until the endpoint of pH = 7, and the amino equivalent is determined. The amino equivalent is calculated as the molecular weight of organosilicon per mole of amino group using the following formula.

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

[0078] (A) In the composition, the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylcyclohexasiloxane is preferably 3000 ppm or less, more preferably 2000 ppm or less, and even more preferably 1000 ppm or less. Furthermore, there is no lower limit on the content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylcyclohexasiloxane; for example, it can be set to 10 ppm each.

[0079] In this invention, the cyclic low-molecular-weight siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6)) in (A) amino-modified organosilicon and amino-modified organosilicon emulsion compositions are analyzed by gas chromatography. Specifically, a small amount of amino-modified organosilicon or an amino-modified organosilicon emulsion is added to an organic solvent (e.g., acetone, hexane) that can dissolve the cyclic low-molecular-weight siloxanes, and the mixture is shaken for approximately 30 minutes to 2 hours. After the cyclic low-molecular-weight siloxanes are extracted in the organic solvent by shaking, the organic solvent containing the cyclic low-molecular-weight siloxanes is determined by gas chromatography (e.g., Agilent 7890B). Specifically, 0.1 g of the sample is added to 10 mL of acetone and the mixture is shaken for 2 hours. After the cyclic low-molecular-weight siloxanes are extracted in the acetone solution by shaking, the acetone solution of the supernatant is determined by gas chromatography.

[0080] As a component (A), amino-modified organosilicones, specifically, for example, the following amino-modified organosilicones can be listed. It should be noted that the bonding sequence of siloxanes is not subject to the following restrictions (the same applies below).

[0081] [Chemistry 3]

[0082]

[0083] [Chemistry 4]

[0084]

[0085] [Chemistry 5]

[0086]

[0087] [Chemistry 6]

[0088]

[0089] [Chemistry 7]

[0090]

[0091] [Chemistry 8]

[0092]

[0093] [Chemistry 9]

[0094]

[0095] [Chemistry 10]

[0096]

[0097] (In the formula, b and c are the same as above. R) 6In addition to the groups mentioned above, it may contain less than 90 mol% hydrogen atoms. (The wavy line indicates the bonding site.)

[0098] (A) The amino-modified organosilicon of component (A) can be obtained, for example, by reacting an amino-modified organosilicon represented by formulas (a-1) to (a-5) with a (meth)acrylate compound represented by general formula (AE).

[0099] [Chemistry 11]

[0100]

[0101] The reaction of the amino-modified organosilicon represented by formulas (a-1) to (a-5) above with the (meth)acrylate represented by (AE) above can be carried out according to existing known methods without particular limitation. For example, the reaction can be carried out in the absence of solvent or in the presence of lower alcohols such as isopropanol, toluene, xylene, etc., at 50 to 120°C, preferably 70 to 100°C, for 1 to 10 hours, preferably 2 to 5 hours.

[0102] [(B) Component]

[0103] (B) The component is a nonionic surfactant, which can be used alone or in appropriate combinations of two or more. Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene tridecyl ether, 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, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene hardened castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene modified organopolysiloxanes, and polyoxyethylene polyoxypropylene modified organopolysiloxanes. Among these, polyoxyethylene alkyl ethers are preferred, and polyoxyethylene alkyl ethers and polyoxyethylene oxypropylene alkyl ethers are more preferred. In particular, from the viewpoint of inhibiting yellowing when used as a fiber treatment agent, poly(oxyethylene) secondary alkyl ethers with ethylene oxide (EO) chains added to the hydroxyl groups of secondary alcohols are preferred.

[0104] From an environmental impact perspective, the surfactant used as component (B) is preferably free of polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0105] From the viewpoint of emulsion stability, the HLB value of the nonionic surfactant (the overall HLB value of the mixture when 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. Furthermore, the HLB value is calculated using the Griffin method. When using two or more nonionic surfactants, the HLB value is calculated using the following formula.

[0106] N = N1 × W1 + N2 × W2

[0107] N: HLB values ​​when using two surfactants with different HLB values

[0108] N1, N2: HLB values ​​of each surfactant

[0109] W1, W2: Weight fraction of each surfactant (W1 + W2 = 1)

[0110] In the compositions of the present invention, cationic surfactants and anionic surfactants can be used in addition to the nonionic surfactant of component (B).

[0111] Examples of anionic surfactants include alkyl sulfate salts such as sodium dodecyl sulfate, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, alkylbenzene sulfonates, polyoxyethylene alkylphenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkane sulfonates, N-acyl taurate, dialkyl sulfosuccinate, monoalkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinate, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, and polyoxyethylene alkyl ether phosphate salts.

[0112] Examples of cationic surfactants include quaternary ammonium salts such as alkyl trimethylammonium salt, dialkyl dimethylammonium salt, polyoxyethylene alkyl dimethylammonium salt, dipolyoxyethylene alkyl methylammonium salt, trimeroxyethylene alkylammonium salt, and alkyl benzyl dimethylammonium salt, as well as alkylpyridinium salts, monoalkylamine salts, and monoalkylamide amine salts.

[0113] The content of component (B) relative to 100 parts by mass of component (A) is 5 to 100 parts by mass, preferably 2 to 80 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 4 to 60 parts by mass. If the content of component (B) is less than the lower limit mentioned above, the stability of the emulsion deteriorates; if it exceeds the upper limit mentioned above, the effect of imparting lubricity to the fibers deteriorates.

[0114] The preferred combination of component (A) and component (B) is a mixture of 90 parts by mass of component (A) and 10 parts by mass of component (B) that does not gel when heated at 170°C for 1 hour. The gelation in this invention is evaluated using the following method: 1.5 g of a mixture of 90 parts by mass of amino-modified silicone (component A) and 10 parts by mass of nonionic surfactant (component B) is weighed onto a 60 mm diameter aluminum dish and stretched on the dish until homogeneous. The mixture is then left to stand for 1 hour in a blower-controlled thermostat set at 170°C. After natural cooling, the dish is tilted at 60° to check for the presence or absence of fluidity of the composition. The absence of fluidity is considered gelation.

[0115] [(C) Component]

[0116] (C) is water, and all types of water, such as ion-exchanged water and purified water, can be used. The content of component (C) relative to 100 parts by mass of component (A) is 10 to 10,000 parts by mass, preferably 50 to 2,000 parts by mass, and more preferably 70 to 1,000 parts by mass.

[0117] The amino-modified silicone emulsion composition of the present invention preferably has an average particle size of 500 nm or less, more preferably 400 nm or less, even more preferably 350 nm or less, and particularly preferably 300 nm or less. By making the average particle size 500 nm or less, the stability of the emulsion is further improved. There is no limitation on the lower limit of the average particle size; for example, it can be set to 50 nm. To make the particle size within this range, the content of component (B), the shear force during emulsion preparation, and the temperature can be adjusted. It should be noted that the average particle size in the present invention is the particle size at 50% of the cumulative volume value in the particle size distribution determined by laser diffraction and scattering. As a measuring device, for example, the LA960 (manufactured by HORIBA Co., Ltd.) can be cited. In the present invention, the average particle size is the value measured using the LA960 (manufactured by HORIBA Co., Ltd.), representing the particle size at 50% of the cumulative value in the particle size distribution.

[0118] [(D) Organic acids]

[0119] From the perspective of the preservation stability of the emulsion, it is preferable to incorporate (D) organic acids into the amino-modified organosilicon emulsion composition of the present invention, allowing for the use of one or more acids individually or in appropriate combinations. Specifically, examples include monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aromatic carboxylic acids, and acidic amino acids. More specifically, examples include monocarboxylic acids such as acetic acid, propionic acid, and octanoic 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.

[0120] When compounding, the content of component (D) relative to 100 parts by mass of component (A) 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.

[0121] When the amino-modified silicone emulsion composition is stored at 25°C for 6 months, the increase in the amount of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) relative to the mass of component (A) is preferably less than 2000 ppm, more preferably less than 1500 ppm, and even more preferably less than 1000 ppm. By making the increase in the amount of each of (D4) to (D6) less than 3000, the mixing amount of the amino-modified silicone emulsion composition of the present invention can be unrestricted and the design range becomes wider when it is compounded in articles intended for use as fiber treatment agents, softeners, etc., which are drained after use.

[0122] The pH of the composition of the present invention at 25°C is preferably 3.5 to 7.5, more preferably 3.7 to 7.0, and even more preferably 4.0 to 6.5. Furthermore, in the present invention, pH is the value measured by a pH meter (e.g., LAQUA manufactured by HORIBA Corporation) at 25°C.

[0123] [Manufacturing Method]

[0124] The compositions of the present invention can be prepared, for example, by mixing component (C) with components (A) and (B) and emulsifying and dispersing them using conventional methods. Water-in-oil (O / W) emulsions are preferred. Furthermore, by further diluting the emulsion with water, it can be used for the applications described later. There are no particular limitations on the amount of water used for dilution, and it can be adjusted appropriately according to the intended use.

[0125] A detailed example of the emulsification formulation is described below. For example, in a mixing apparatus: COMBI MIX (PRIMIX Co., Ltd.), amino-modified organosilicon (component A), nonionic surfactant, organic acid (component D), and a portion of water (component C) were mixed, and emulsification was performed using a homogeneous mixer (using a rotor rotating within a stator) at 500–5000 rpm or a DISPER mixer (using toothed blades rotating) at 500–5000 rpm and 5–50 rpm. After complete emulsification, the mixture was stirred for 15–180 minutes using a DISPER mixer at 500–5000 rpm and 5–50 rpm until the specified particle size was achieved. Then, the remaining water (component C) was added, and the mixture was diluted using a homogeneous mixer at 2000–3000 rpm to prepare the amino-modified organosilicon emulsion composition of the present invention.

[0126] There is no particular specification for the emulsification temperature, but 0–80°C is preferred, and 10–60°C is more preferred. Emulsification is easier at temperatures between 10 and 60°C, and the resulting emulsion tends to be more stable. If the amino-modified silicone emulsion composition is heated at 70–80°C for 1–30 hours, the particle size may sometimes decrease or the viscosity may decrease. Therefore, in the manufacture of the amino-modified silicone emulsion composition, a heating step of 70–80°C can be introduced depending on the target particle size and viscosity. During emulsification, the pressure can be not only atmospheric pressure but also reduced pressure or increased pressure. When emulsifying under reduced pressure or increased pressure, air bubbles are less likely to be incorporated, and emulsification can be effective. The pressure used for reduced pressure is preferably higher than the vapor pressure of the raw material to prevent the raw material from evaporating. Furthermore, there is no particular specification for the emulsification time; it can be set to the time required to achieve the target particle size. Generally, 30–360 minutes is preferred.

[0127] There are no particular limitations on the type of emulsifier used during emulsification, as long as it can agitate the raw materials and the emulsion composition. Suitable equipment includes colloid mills with a stirring section consisting of a rotor and stator (IKA Corporation, PUC Corporation, Nippon Seiki Co., Ltd., Eway Corporation), High Shear Mixers (Silverson Corporation, PRIMIX Corporation), Homo Disper (PRIMIX Corporation), AgiHomomixer (PRIMIX Corporation), Combimix (PRIMIX Corporation), a three-shaft dispersion mixer combining a homogeneous mixer, Homo Disper, and Anchor Mixer, and twin-screw mixers with co-rotating or counter-rotating screws such as HAAKE Mini LabII (Thermo Scientific), MC15, and MC5 (Rheolab Ltd.).

[0128] In the amino-modified silicone emulsion composition of the present invention, according to the purpose of the invention, water-soluble polymers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, polyvinylpyrrolidone, alginate, xanthan gum, and acrylic polymers can be mixed in as protective colloids or thickeners. Furthermore, antibacterial agents or preservatives such as oxazoline compounds and aromatic carboxylates, fragrances, antioxidants, rust inhibitors, dyes, fillers, curing catalysts, organic powders, and inorganic powders can be mixed in. The amounts of these components are selected from their respective preferred amounts.

[0129] [Fiber treatment agent]

[0130] The amino-modified silicone emulsion composition of the present invention is also extremely useful for fiber treatment agents such as softeners and detergents, and can be used to formulate fiber treatment agents containing the amino-modified silicone emulsion composition. The amount of the amino-modified silicone emulsion composition in the fiber treatment agent, based on solids, is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass. If the content is too low, the desired hand feel may not be adequately achieved; on the other hand, if the content is too high, yellowing may occur during storage of the fiber treatment agent. The fiber treatment agent can also be used after appropriate dilution.

[0131] Example

[0132] The following examples and comparative examples illustrate the invention in detail, but the invention is not limited to the examples described below. It should be noted that when the name of the compound product is stated, the content refers to the content of the compound product. The various determination methods are shown below.

[0133] [Average particle size of emulsion particles]

[0134] The emulsion composition was diluted with water by about 10 times and the particle size was measured using a laser diffraction particle size analyzer (HORIBA Co., Ltd. LA960) to obtain the particle size at 50% of the volume cumulative value.

[0135] [pH]

[0136] The pH of the emulsion composition was determined at 25°C using a pH meter (LAQUA manufactured by HORIBA Corporation).

[0137] [Viscosity]

[0138] The viscosity was measured using a BM-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 25°C.

[0139] [Amino equivalent]

[0140] The determination was performed using an automated titration apparatus (manufactured by Hiranuma Sangyo Co., Ltd.). The amino-modified organosilicon, to be neutralized, was dissolved in a solvent containing a 1 / 1 mass mixture of toluene and IPA. The solution was titrated with hydrochloric acid using an automated titrator until the endpoint of pH 7, and the amino equivalent was determined. The amino equivalent was calculated as the molecular weight of organosilicon per mole of amino group using the following formula.

[0141] Amino equivalent (g / mol) = {[sample amount (g)] × 1000} / {[hydrochloric acid equivalent concentration (N)] × [hydrochloric acid titration volume (mL)] × [hydrochloric acid titer (F)]}

[0142] [Amounts of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6)]

[0143] Add 0.1 g of the sample to 10 mL of acetone and shake for approximately 2 hours. After extraction of the cyclic low-molecular-weight siloxane into the acetone solution by shaking, the acetone content of the supernatant is determined using gas chromatography (Agilent 7890B). The gas chromatograph uses a DB-5MS column (Agilent Technologies), and the column temperature is 300 °C. Tetradecane is used as the internal standard.

[0144] [Gelation test of (A) component and (B) after mixing and heating]

[0145] Weigh 1.5 g of a mixture of 90 parts by mass of amino-modified organosilicon (A) and 10 parts by mass of nonionic surfactant (B) onto an aluminum dish with a diameter of 60 mm. Let it stand for 1 hour in a blower-controlled thermostat set at 170 °C. After 1 hour, remove the dish and allow it to cool naturally. Tilt the dish at 60° and check the fluidity of the composition. Mark the fluidity as "○" (no gelation) and the lack of fluidity as "×" (gelation).

[0146] The components used in the examples and comparative examples are described below.

[0147] (A-1) Amino-modified organosilicon

[0148] Amino-modified organosilicon represented by the following average formula

[0149] [Chemistry 12]

[0150]

[0151] R 2 :-C3H6NR 6 C2H4NR 6 2,

[0152] R 6 :-H (70 mol%), -CH2-CH2-COOC8H 17 (R 6 Viscosity (30 mol%): 960 mPa·s, Amino equivalent: 1660 g / mol

[0153] The amount of octamethylcyclotetrasiloxane in component (A-1) is 100 ppm.

[0154] (A-1) Amount of decamethylcyclopentasiloxane in component: 200 ppm

[0155] (A-1) Dodecylcyclohexasiloxane content: 300 ppm (A-2) Amino-modified organosilicon

[0156] Amino-modified organosilicon represented by the following average formula

[0157] [Chemistry 13]

[0158]

[0159] R 2 :-C3H6NR 6 C2H4NR 6 2,

[0160] R 6 : -H (70 mol%), -CH2-CH2-COOC 12 H 25 (R 6 Viscosity (30 mol%): 1190 mPa·s, Amino equivalent: 1810 g / mol

[0161] The amount of octamethylcyclotetrasiloxane in component (A-2) is 120 ppm.

[0162] The amount of decamethylcyclopentasiloxane in component (A-2) is 230 ppm.

[0163] (A-2) Dodecylcyclohexasiloxane content: 330 ppm (A-3) Amino-modified organosilicon

[0164] Amino-modified organosilicon represented by the following average formula

[0165] [Chemistry 14]

[0166]

[0167] R 2 :-C3H6NR 6 C2H4NR 6 2,

[0168] R 6 :H (50 mol%), -CH2-CH2-COOC 12 H 25 (R 6 Viscosity (50 mol%): 1330 mPa·s, Amino equivalent: 2240 g / mol

[0169] The amount of octamethylcyclotetrasiloxane in component (A-3) is 100 ppm.

[0170] (A-3) Amount of decamethylcyclopentasiloxane in component: 250 ppm

[0171] (A-3) Dodecylcyclohexasiloxane content: 300 ppm (A-4) Amino-modified organosilicon

[0172] Amino-modified organosilicon represented by the following average formula

[0173] [Chemistry 15]

[0174]

[0175] R 2 :-C3H6NR 6 C2H4NR 6 2,

[0176] R 6 -CH2-CH2-COOC 12 H 25 (100 mol%)

[0177] Viscosity: 2370 mPa·s, Amine equivalent: 2750 g / mol

[0178] The amount of octamethylcyclotetrasiloxane in component (A-4) is 100 ppm.

[0179] The amount of decamethylcyclopentasiloxane in component (A-4) is 220 ppm.

[0180] (A-4) Dodecylcyclohexasiloxane content: 290 ppm (A-5) Amino-modified organosilicon

[0181] Amino-modified organosilicon represented by the following average formula

[0182] [Chemistry 16]

[0183]

[0184] R 2 :-C3H6NR 6 C2H4NR 6 2,

[0185] R 6 : -H (90 mol%), -CH2-CH2-COOC 12 H 25 (R 6 Viscosity (10 mol%): 430 mPa·s, Amino equivalent: 7410 g / mol

[0186] The amount of octamethylcyclotetrasiloxane in component (A-5) is 160 ppm.

[0187] The amount of decamethylcyclopentasiloxane in component (A-5) is 300 ppm.

[0188] (A-5) Dodecylcyclohexasiloxane content: 320 ppm (A-6) Amino-modified organosilicon

[0189] Amino-modified organosilicon represented by the following average formula

[0190] [Chemistry 17]

[0191]

[0192] R 2 :-C3H6NR 6 2,

[0193] R 6 : -H (50 mol%), -CH2-CH2-COOC 12 H 25 (R 6 Viscosity (50 mol%): 50 mPa·s, Amino equivalent: 1420 g / mol

[0194] The amount of octamethylcyclotetrasiloxane in component (A-6) is 230 ppm.

[0195] The amount of decamethylcyclopentasiloxane in component (A-6) is 310 ppm.

[0196] (A-6) Dodecylcyclohexasiloxane content: 420 ppm (A-7) Amino-modified organosilicon (comparative)

[0197] [Chemistry 18]

[0198]

[0199] R 2 :-C3H6NHC2H4NH2,

[0200] Viscosity: 800 mPa·s, Amine equivalent: 1500 g / mol

[0201] The amount of octamethylcyclotetrasiloxane in component (A-7) is 310 ppm.

[0202] The amount of decamethylcyclopentasiloxane in component (A-7) is 360 ppm.

[0203] (A-7) Dodecylcyclohexasiloxane content: 400 ppm (A-8) Amino-modified organosilicon (comparative)

[0204] [Chemistry 19]

[0205]

[0206] R 2 :-C3H6NR 6 C2H4NR 6 2,

[0207] R 6: -H (95 mol%), -CH2-CH2-COOC 12 H 25 (R 6 (5 moles of)

[0208] Viscosity: 840 mPa·s, Amine equivalent: 1590 g / mol

[0209] The amount of octamethylcyclotetrasiloxane in component (A-8) is 130 ppm.

[0210] The amount of decamethylcyclopentasiloxane in component (A-8) is 280 ppm.

[0211] The amount of dodecylcyclohexasiloxane in component (A-8) is 390 ppm.

[0212] (A-9) Amino-modified organosilicon (comparative product)

[0213] Amino-modified organosilicon represented by the following average formula

[0214] [Chemistry 20]

[0215]

[0216] R 2 :-C3H6NH2,

[0217] Viscosity: 52 mPa·s, Amine equivalent: 1420 g / mol

[0218] The amount of octamethylcyclotetrasiloxane in component (A-9) is 150 ppm.

[0219] The amount of decamethylcyclopentasiloxane in component (A-9) is 240 ppm.

[0220] The amount of dodecylcyclohexasiloxane in component (A-9) is 320 ppm.

[0221] (B) Nonionic surfactants

[0222] (B-1) Poly(oxyethylene) secondary alkyl ether [Softanol 90 (trade name): Nippon Shokubai Co., Ltd., HLB value = 13.3]

[0223] (B-2): Polyoxyethylene tridecyl ether [NEWCOL 1310 (trade name): manufactured by Nippon Emulsifier Co., Ltd., HLB value = 13.7]

[0224] (D) Organic acids

[0225] (D-1)acetic acid

[0226] [Example 1]

[0227] The following ingredients were mixed using a homogeneous mixer: (A) amino-modified organosilicon A-1: ​​100 parts by mass, (B-1) Softanol 90: 20 parts by mass, (C) deionized water: 190 parts by mass, and (D-1) acetic acid: 2 parts by mass. The mixture was then emulsified and dispersed to obtain an amino-modified organosilicon emulsion composition (I-1). The average particle size of the emulsion particles in (I-1) was 340 nm, and the pH was 4.7.

[0228] [Example 2]

[0229] The following ingredients were mixed using a homogeneous mixer: (A) amino-modified organosilicon A-2: 100 parts by mass, (B-1) Softanol 90: 20 parts by mass, (C) deionized water: 190 parts by mass, and (D-1) acetic acid: 2 parts by mass. The mixture was then emulsified and dispersed to obtain an amino-modified organosilicon emulsion composition (I-2). The average particle size of the emulsion particles in (I-2) was 340 nm, and the pH was 4.7.

[0230] [Example 3]

[0231] The following ingredients were mixed using a homogeneous mixer: (A) amino-modified organosilicon A-3: 100 parts by mass, (B-1) Softanol 90: 20 parts by mass, (C) deionized water: 190 parts by mass, and (D-1) acetic acid: 2 parts by mass. The mixture was then emulsified and dispersed to obtain an amino-modified organosilicon emulsion composition (I-3). The average particle size of the emulsion particles in (I-3) was 290 nm, and the pH was 4.5.

[0232] [Example 4]

[0233] The following ingredients were mixed using a homogeneous mixer: (A) amino-modified organosilicon A-4: 100 parts by mass, (B-1) Softanol 90: 20 parts by mass, (C) deionized water: 190 parts by mass, and (D-1) acetic acid: 2 parts by mass. The mixture was then emulsified and dispersed to obtain an amino-modified organosilicon emulsion composition (I-4). The average particle size of the emulsion particles in (I-4) was 290 nm, and the pH was 4.4.

[0234] [Example 5]

[0235] The amino-modified organosilicon A-5 (100 parts by weight), Softanol 90 (20 parts by weight), ion-exchanged water (190 parts by weight), and acetic acid (0.5 parts by weight) were mixed using a homogeneous mixer and emulsified to obtain an amino-modified organosilicon emulsion composition (I-5). The average particle size of the emulsion particles in (I-5) was 350 nm, and the pH was 4.6.

[0236] [Example 6]

[0237] The following ingredients were mixed using a homogeneous mixer and then emulsified and dispersed to obtain an amino-modified organosilicon emulsion composition (I-6): 100 parts by weight of (A) amino-modified organosilicon A-6, 20 parts by weight of (B-1) Softanol 90, 190 parts by weight of (C) ion-exchanged water, and 2 parts by weight of (D-1) acetic acid. The average particle size of the emulsion particles in (I-6) was 350 nm, and the pH was 5.0.

[0238] [Example 7]

[0239] The following ingredients were mixed using a homogeneous mixer: (A) amino-modified organosilicon A-3: 100 parts by mass, (B-2) NEWCOL 1310: 20 parts by mass, (C) ion-exchanged water: 190 parts by mass, and (D-1) acetic acid: 2 parts by mass. The mixture was then emulsified and dispersed to obtain an amino-modified organosilicon emulsion composition (I-7). The average particle size of the emulsion particles in (I-7) was 320 nm, and the pH was 4.6.

[0240] [Example 8]

[0241] The following ingredients were mixed using a homogeneous mixer and then emulsified and dispersed to obtain an amino-modified organosilicon emulsion composition (I-8): 100 parts by mass of (A) amino-modified organosilicon A-2, 20 parts by mass of (B-2) NEWCOL 1310, 190 parts by mass of (C) ion-exchanged water, and 2 parts by mass of (D-1) acetic acid. The average particle size of the emulsion particles in (I-8) was 330 nm, and the pH was 4.7.

[0242] [Comparative Example 1]

[0243] The following ingredients were mixed using a homogeneous mixer and emulsified to obtain an amino-modified organosilicon emulsion composition (II-1): 100 parts by weight of (A) amino-modified organosilicon A-7 (comparative standard), 20 parts by weight of (B-1) NEWCOL 1310, 190 parts by weight of (C) ion-exchanged water, and 2 parts by weight of (D-1) acetic acid. The average particle size of the emulsion particles in (II-1) was 380 nm, and the pH was 4.9.

[0244] [Comparative Example 2]

[0245] The amino-modified organosilicon A-8 (comparative standard): 100 parts by mass, (B-1) Softanol 90: 20 parts by mass, (C) deionized water: 190 parts by mass, and (D-1) acetic acid: 2 parts by mass were mixed using a homogeneous mixer and emulsified to obtain an amino-modified organosilicon emulsion composition (II-2). The average particle size of the emulsion particles in (II-2) was 340 nm, and the pH was 4.9.

[0246] [Comparative Example 3]

[0247] The amino-modified organosilicon A-9 (comparative standard): 100 parts by weight, (B-1) Softanol 90: 20 parts by weight, (C) deionized water: 190 parts by weight, and (D-1) acetic acid: 0.5 parts by weight were mixed using a homogeneous mixer and emulsified to obtain an amino-modified organosilicon emulsion composition (II-3). The average particle size of (II-3) was 370 nm, and the pH was 5.6.

[0248] The resulting silicone emulsion compositions were tested for "storage stability of the emulsion" and "yellowing during fiber treatment" using the methods described below. The evaluation results are recorded in the table.

[0249] [Storage stability of emulsions]

[0250] 100g of each emulsion composition obtained in the examples and comparative examples was placed in a glass bottle and left to stand at 40°C for one month. The non-volatile components in the upper and lower layers were then measured (105°C, 3 hours). The storage stability (presence or absence of separation) of the emulsion was evaluated by dividing the non-volatile component value of the upper layer by the non-volatile component value of the lower layer. A value closer to 1 indicates less separation and higher stability; a value further away from 1 indicates greater separation and lower stability.

[0251] Yellowing during fiber treatment

[0252] For each emulsion composition obtained in the Examples and Comparative Examples, deionized water was added to dilute it so that component (A) became 1% by mass, thus preparing a treatment solution. A wide-width cotton fabric was immersed in this treatment solution for 10 seconds, pressed with rollers, and dried at 100°C for 2 minutes. Then, a heat treatment was performed at 200°C for 2 minutes to produce a treated fabric. The b-value of each treated fabric was measured using a colorimeter (SE7700, manufactured by Nippon Denshoku Kogyo Co., Ltd.). A smaller b-value indicates higher whiteness and lower yellowing, which is a good result. Furthermore, the b-value (blank) of the fabric that was not immersed in the treatment solution but only subjected to heat treatment was 0.54.

[0253] [Increased amounts of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6)]

[0254] After storing the samples at 25°C for 6 months, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylcyclohexasiloxane were determined using the method described above. The increase in mass after storage relative to the mass before storage was calculated using the mass of component (A).

[0255] [Table 1]

[0256]

[0257] [Table 2]

[0258]

[0259] [Table 3]

[0260]

[0261] The results above demonstrate that the amino-modified organosilicon emulsion composition of the present invention exhibits excellent storage stability and can also suppress the increase of cyclic low-molecular-weight siloxanes over time. Furthermore, it also exhibits low yellowing during fiber treatment.

[0262] Industrial availability

[0263] The amino-modified organosilicon emulsion composition of the present invention exhibits excellent storage stability and can also suppress the increase of cyclic low-molecular-weight siloxanes over time. Furthermore, it also exhibits low yellowing during fiber treatment.

Claims

1. An amino-modified organosilicon emulsion composition, comprising: (A) 100 parts by mass of amino-modified organosilicon with a viscosity of 10–50000 mPa·s at 25°C and an amino equivalent of 500–25000 g / mol, expressed by the following average composition formula (I). [Chemistry 1] In the formula, R 1 Independently selected from unsubstituted or substituted monovalent hydrocarbon groups with 1 to 20 carbon atoms, -OH, -OCH3, and -OC2H5, R 2 R are groups represented independently by general formula (2). 3 R is independent of each other. 1 or R 2 a, b, c, d, and e are numbers satisfying the following ranges: 2 ≤ a ≤ 10, 10 ≤ b ≤ 1300, 0 ≤ c ≤ 50, 0 ≤ d ≤ 5, and 0 ≤ e ≤ 5. However, when c = 0, R... 3 At least one of them is R 2 , -R 4 -(NO 6 -R 5 ) p -NR 6 2(2) In the formula, R 4 and R 5 Independently, they are divalent organic groups with 1 to 6 carbon atoms, p = 0 to 3, R 6 R is a hydrogen atom or a group represented by general formula (3) that are independent of each other. 6 More than 10 mol% of the components are groups represented by general formula (3). -CH2-CHR 7 -COOR 8 (3) In equation (3) above, R 7 R is a hydrogen atom or a methyl group. 8 It is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 30 carbon atoms. (B) Nonionic surfactant: 5-100 parts by weight, and (C) Water: 10 to 10,000 parts by weight.

2. The amino-modified organosilicon emulsion composition according to claim 1, further comprising (D) organic acid: 0.05 to 10 parts by weight.

3. The amino-modified organosilicon emulsion composition according to claim 1, wherein, in formula (3), R 8 It is an unsubstituted or substituted monovalent hydrocarbon group with 6 to 20 carbon atoms.

4. The amino-modified organosilicon emulsion composition according to claim 1, wherein, in component (A), the contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecylcyclohexasiloxane are each less than 3000 ppm.

5. The amino-modified silicone emulsion composition according to claim 1, wherein component (B) is a poly(oxyethylene) secondary alkyl ether in which an ethylene oxide (EO) chain is formed by the addition of hydroxyl groups to a secondary alcohol.

6. The amino-modified organosilicon emulsion composition according to claim 1, wherein the combination of component (A) and component (B) is a combination in which 90 parts by weight of component (A) and 10 parts by weight of component (B) are mixed and heated at 170°C for 1 hour without gelling.

7. The amino-modified organosilicon emulsion composition according to claim 1, wherein component (A) is an amino-modified organosilicon without alkoxy groups.

8. The amino-modified organosilicon emulsion composition according to claim 1, wherein the increase in the amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecylcyclohexasiloxane of the amino-modified organosilicon emulsion composition relative to the mass of component (A) is less than 2000 ppm.

9. A fiber treatment agent comprising the amino-modified organosilicon emulsion composition according to any one of claims 1 to 8.

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