Siloxane composition

Abstract

Disclosed is a siloxane composition which contains:(A) 80-20 parts by mass of a polyorganosiloxane which is composed of units that include an R1 3SiO1 / 2 unit and an SiO4 / 2 unit (in the formula, R1 independently denotes a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group) such that the molar ratio (R1 3SiO1 / 2 unit) / (SiO4 / 2 unit) is 0.6-1.0, and which has one or more Si-OH groups and one or more monovalent hydrocarbon groups having 1 to 10 carbon atoms in each molecule; and (B) 20-80 parts by mass of a compound which has one or more (meth)acryloyl groups in each molecule. The total of the component (A) and the component (B) is 100 parts by mass. This siloxane composition has good water repellency and provides treated fabric with good texture even though this siloxane composition is non-fluorinated.

Description

Siloxane Composition

[0001] The present invention relates to a siloxane composition, a fiber treatment agent, a fiber product, and a method for producing the same, which are capable of imparting good water repellency.

[0002] Textile materials are commonly used in our daily lives as materials for clothing, and have a wide range of other applications, including outdoor goods and industrial materials. As industrial materials, they are also used as components for final products in the automobile and aviation industries, as agricultural insect repellent sheets, and medical equipment, and various types of textile products are used in all industries.

[0003] Textile products are required to have various properties depending on their intended use and application, such as flexibility, texture, appropriate repellency, water repellency, oil repellency, slipperiness, and antibacterial properties. Textile processing begins with the initial spinning stage and involves multiple steps to obtain the final fiber. The properties required for textile products are generally imparted to the finished fiber by chemically treating it. Various chemical treatment agents are used, including fluorine-based, silicone-based, hydrocarbon-based, acrylic-based, and urethane-based agents.

[0004] Fluorine-based materials are known to have particularly good properties when it comes to liquid repellency. In addition to good water repellency, there are currently very few treatments other than fluorine-based that offer sufficient oil repellency.

[0005] However, with the recent increase in environmental awareness, a policy of avoiding the use of fluorine-based compounds, which are persistent and have a high tendency to accumulate in the environment, is spreading across various industries, and the same is true for textile treatment. Therefore, research and development is underway to replace existing fluorine-based textile treatment agents with non-fluorine-based ones.

[0006] Among non-fluorine-based fiber treatment agents, for example, Patent Documents 1 and 2 specify those containing a fluorine-free (meth)acrylic polymer as the main component. Normally, water repellency is imparted by blending a fluorine-containing (meth)acrylic monomer to form a polymer, but studies are being conducted to impart water repellency by using a monomer having a long-chain hydrocarbon group, using a silicone compound in combination, or other such means.

[0007] JP 2020-7681 A JP 2020-122094 A

[0008] The problem with treatment agents containing a (meth)acrylic polymer as a main component, as described in Patent Documents 1 and 2, is feel. Polymers with high glass transition points or polymers containing long-chain hydrocarbon groups tend to have a hard texture and insufficient slipperiness, so there is a need for improved feel. The present invention aims to provide a siloxane composition, a fiber treatment agent, and a textile product and method for producing the same that are non-fluorinated but have good water repellency and a good feel on treated fabrics.

[0009] As a result of intensive research into achieving the above object, the present inventors have discovered that the above problem can be solved by combining a polyorganosiloxane having a specific structure with a compound having (meth)acryloyl, and have thus achieved the present invention.

[0010] Therefore, the present invention provides the following inventions: 1. (A) R 1 3SiO 1 / 2 Units and SiO 4 / 2 units, wherein R 1 each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. 1 3SiO 1 / 2 Unit) / (SiO 4 / 21. A siloxane composition comprising: 80 to 20 parts by mass of a polyorganosiloxane having one or more Si—OH groups and one or more monovalent hydrocarbon groups having 1 to 10 carbon atoms in one molecule, with a molar ratio of (a) to (b) of 0.6 to 1.0; and (B) 20 to 80 parts by mass of a compound having one or more (meth)acryloyl groups in one molecule, wherein the total of components (A) and (B) is 100 parts by mass. 2. The siloxane composition according to 1, further comprising: (C) a surfactant in an amount of 0.5 to 100 parts by mass per 100 parts by mass of components (A) and (B) combined; and (D) water in an amount of 25 to 2,000 parts by mass per 100 parts by mass of components (A) and (B) combined. 3. The siloxane composition according to 1 or 2, further comprising: (E) an organic solvent in an amount of 10 to 20,000 parts by mass per 100 parts by mass of components (A) and (B) combined. 4. 4. The siloxane composition according to any one of 1 to 3, wherein the amount of Si-OH groups contained in component (A) is 0.05 to 0.2 mol per 100 g. 5. The siloxane composition according to any one of 1 to 4, wherein component (B) is a compound having one or more (meth)acryloyl groups in one molecule. 6. A fiber treatment agent comprising the composition according to any one of 1 to 5. 7. A textile product in which fibers have been treated with the fiber treatment agent according to 6. 8. A method for producing the textile product according to 6, comprising the steps of immersing fibers in the fiber treatment agent and heat-treating the immersed fibers.

[0011] According to the present invention, it is possible to provide a siloxane composition, a fiber treatment agent, a fiber product, and a method for producing the same, which are non-fluorine-based but have good water repellency and give treated fabrics a good feel.

[0012] [Component (A)] The component (A) is (A)R 1 3SiO 1 / 2 Units and SiO 4 / 2 and a unit, 1 each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. 1 3SiO 1 / 2 Unit) / (SiO 4 / 2The polyorganosiloxane has a molar ratio of 0.6 to 1.0, and has one or more Si—OH groups and one or more monovalent hydrocarbon groups having 1 to 10 carbon atoms per molecule. These polyorganosiloxanes can be used alone or in combination of two or more.

[0013] R 1 are independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. Examples of monovalent hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, and butyl; and aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl. Examples of alkenyl groups having 2 to 10 carbon atoms include vinyl, allyl, butenyl, hexenyl, and octenyl. Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, and butoxy. Preferred monovalent hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, and butyl, with methyl being more preferred. Component (A) is a polyorganosiloxane having one or more Si—OH groups and one or more monovalent hydrocarbon groups having 1 to 10 carbon atoms per molecule, and R 1 is selected appropriately.

[0014] The component (A) is R 1 3SiO 1 / 2 Units and SiO 4 / 2 It is composed of units including units (R 1 3SiO 1 / 2 Unit) / (SiO 4 / 2 The molar ratio of the hydroxybenzoates (units) is 0.6 to 1.0, preferably 0.65 to 0.95, and more preferably 0.68 to 0.92. If the molar ratio is less than 0.6, the texture of the fibers may become hard when used as a fiber treatment agent, whereas if it exceeds 1.0, sufficient water repellency may not be obtained.

[0015] The component (A) is R 1 3SiO 1 / 2 Units and SiO 4 / 2 The present invention is not impaired by the R 1 SiO 3 / 2 Unit, R1 2SiO 2 / 2 If these are contained, the content of these units is preferably 10% or less, more preferably 5% or less, based on the total number of siloxane units.

[0016] The weight-average molecular weight (Mn) of component (A) is preferably 1,500 to 10,000, and more preferably 2,000 to 8,000. If the weight-average molecular weight (Mn) is 1,500 or more, the texture of the treated fiber will be better, and if it is 10,000 or less, more than sufficient water repellency will be obtained. Note that the number-average molecular weight (Mn) in the present invention is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard substance, and the measurement method is described in detail in the Examples.

[0017] The amount of Si-OH groups contained in component (A) is preferably 0.05 to 0.2 mol per 100 g, more preferably 0.06 to 0.15 mol, and even more preferably 0.07 to 0.12 mol. If the amount of Si-OH is 0.05 or more per 100 g, more sufficient water repellency will be obtained, and if it is 0.2 or less per 100 g, the texture of the treated fiber will be better.

[0018] [Component (B)] Component (B) is a compound having one or more (meth)acryloyl groups in one molecule, and can be used alone or in combination of two or more. This compound is a component that, when used as a fiber treatment agent, cures upon heat treatment to form a polymer network.

[0019] Examples of component (B) include butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, glycerin monoacrylate, 3-acryloylpropyltrimethoxysilane, 3-acryloylpropylmethyldimethoxysilane, 3-acryloylpropyldimethylmethoxysilane, 1,4-butanediol diacrylate, 1,6-hexanediol acrylate, 1,9- Examples of suitable components include nonanediol diacrylate, 1,10-decanediol diacrylate, glycerin diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, glycerin triacrylate, ethoxylated glycerin triacrylate, tris-(2-acryloxyethyl)isocyanurate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexacrylate, and acryloyl group-containing organopolysiloxane. Component (B) is preferably a compound containing one or two (meth)acryloyl groups per molecule. The presence of one or two (meth)acryloyl groups per molecule results in a softer texture of fibers when used as a fiber treatment agent. Furthermore, those that are less likely to volatilize so that the active ingredient remains on the fiber even during heat treatment at high temperatures are preferred, and lauryl acrylate, cetyl acrylate, stearyl acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, etc. are preferred.

[0020] The amount of component (A) is 80 to 20 parts by mass, and the amount of component (A) is 20 to 80 parts by mass, with the total amount of component (A) and component (B) being 100 parts by mass. That is, the amount of component (A) and component (B) is, in terms of mass ratio, (A) / (B) = 20 / 80 to 80 / 20, preferably (A) / (B) = 25 / 75 to 75 / 25, and more preferably (A) / (B) = 30 / 70 to 70 / 30. Sufficient water repellency cannot be obtained outside the range of (A) / (B) = 20 / 80 to 80 / 20.

[0021] Using component (A) or component (B) alone as a fiber treatment agent does not impart water repellency. However, blending both components together can impart water repellency to the object being treated. While the mechanism behind this is unclear, it is believed that component (B) polymerizes upon heat treatment to form a network, and component (A) is then fixed within this network, thereby imparting water repellency. Furthermore, the monovalent hydrocarbon groups of component (A) with 1 to 10 carbon atoms appear on the surface, imparting a suitable degree of slipperiness.

[0022] In addition to the above components (A) and (B), the composition of the present invention may contain the following optional components. [Component (C)] Component (C) is a surfactant. Examples include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. These may be used alone or in appropriate combinations of two or more.

[0023] 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, polyoxyethylene sorbit 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.

[0024] Examples of anionic surfactants include alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkanesulfonates, N-acyltaurate salts, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylate salts, N-acylamino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, and the like.

[0025] Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamidoamine salts.

[0026] Examples of the amphoteric surfactant include alkyldimethylamine oxide, alkyldimethylcarboxybetaine, alkylamidopropyldimethylcarboxybetaine, alkylhydroxysulfobetaine, and alkylcarboxymethylhydroxyethylimidazolinium betaine.

[0027] As component (C), nonionic surfactants and anionic surfactants are preferred, with nonionic surfactants being particularly preferred. There are no particular restrictions on the HLB, but a preferred range is 9 to 17. The HLB is measured according to the Griffin method.

[0028] When component (C) is blended, the amount is preferably 0.5 to 100 parts by mass, more preferably 1.0 to 50 parts by mass, and even more preferably 2.0 to 25 parts by mass, per 100 parts by mass of the total of components (A) and (B). By using an amount of 0.5 parts by mass or more, emulsification becomes easier, and by using an amount of 100 parts by mass or less, the functions of components (A) and (B) are more effectively exhibited.

[0029] [Component (D)] Component (D) is water. When component (D) is blended, the amount is preferably 25 to 2,000 parts by mass, more preferably 30 to 1,800 parts by mass, and even more preferably 40 to 1,500 parts by mass, per 100 parts by mass of the total of components (A) and (B). By using an amount of 25 parts by mass or more, emulsification becomes easier, and by using an amount of 2,000 parts by mass or less, the storage stability of the composition is improved.

[0030] [Component (E)] Component (E) is an organic solvent and can be used alone or in combination of two or more. Component (E) makes components (A) and (B) compatible. Components (A) and (B) are basically compatible, but in some cases, a low-viscosity treatment liquid is required in processes such as fiber treatment, and in such cases, component (E) is effective. Examples of the component (E) include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin, hydrocarbon solvents such as industrial gasoline, petroleum benzine, and solvent naphtha, ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonylacetone, and cyclohexanone, ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate, and diethyl ether. Examples of suitable solvents include ether solvents such as ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; solvents having an ester and an ether moiety, such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate; siloxane solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane; and mixed solvents thereof. Among these, toluene, xylene, heptane, octane, isododecane, ethyl acetate, butyl acetate, and the like are preferred because they are versatile and can easily dissolve component (A) and component (B).

[0031] When component (E) is added, the amount is preferably 10 to 20,000 parts by mass, and more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the total of components (A) and (B).

[0032] [Others] In addition to the aforementioned components (A) to (E), the siloxane composition of the present invention may contain optional components as long as the effects of the present invention are not impaired. Examples of siloxane components other than component (A) include silicone oil, silicone oligomer, silane compound, silicone resin, compounds other than (B) having three or more (meth)acryloyl groups per molecule, and other organic compounds. In addition, additives to improve adhesion to the target substrate, fillers to increase coating strength, antioxidants to improve stability, and other fiber additives such as antistatic agents, slip agents, leveling agents, pigments, dyes, phosphorescent agents, foaming agents, plasticizers, anti-wrinkle agents, flame retardants, antistatic agents, and heat-resistant agents, as well as antioxidants, UV absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, deodorizers, and antibacterial agents may also be added. When these other components are added, the amount is preferably 10% by mass or less of the siloxane composition.

[0033] The siloxane composition of the present invention can be a non-fluorine-based composition because it does not contain fluorine or a component containing fluorine, and yet has good water repellency and provides a good feel to the treated fabric.

[0034] [Uses] The siloxane composition of the present invention is used by treating the surface of various substrates such as fibers, paper, metal, wood, rubber, plastic, and glass. The substrate can be treated by any of the various conventional coating methods, such as dipping, spraying, roll coating, bar coating, and brush coating. The amount of treatment is appropriately selected depending on the substrate and the intended use, and can be, for example, 0.1 to 200 g / m 2 is preferred, and 1 to 100 g / m 2 is more preferred.

[0035] The siloxane composition of the present invention is effective for treating all types of fibers, including natural fibers such as cotton, silk, linen, wool, angora, and mohair, as well as synthetic fibers such as polyester, nylon, acrylic, urethane, and spandex, and textile products made from these fibers. There are no limitations on the form or shape of the fibers, and the present invention is applicable to treating not only raw materials such as staple, filament, tow, and yarn, but also various processed forms such as woven fabrics, knitted fabrics, wadding, nonwoven fabrics, paper, sheets, and films.

[0036] Substrates other than fibers that can be used with the siloxane composition of the present invention include inorganic porous materials such as concrete, lightweight concrete, lightweight aerated concrete (ALC), mortar, various cement boards, gypsum boards, calcium silicate boards, bricks, roofing tiles, tiles, stone, etc. The siloxane composition of the present invention can also be used for walls primarily made of diatomaceous earth, clay, plaster, etc., and organic porous materials such as paper, wood, leather, etc.

[0037] [Water Repellent Composition] The siloxane composition of the present invention has the above-mentioned effects and is therefore suitable as a water repellent composition.

[0038] [Fiber Treatment Agent] The siloxane composition of the present invention is useful as an active ingredient in a fiber treatment agent because the treated fiber surface has excellent water repellency. This composition may be used as a fiber treatment agent directly, or may be appropriately incorporated into a fiber treatment agent. The total amount of components (A) and (B) of the present invention in the fiber treatment agent may be appropriately selected, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, of the treatment agent.

[0039] [Textile Products] The present invention provides textile products in which fibers are treated with a fiber treatment agent. Examples of methods for producing textile products include a step of immersing fibers in the fiber treatment agent and a step of heat-treating the immersed fibers. The immersion step is not particularly limited, and the temperature and time are appropriately selected. The treatment amount is not particularly limited, but is preferably 0.1 to 200 g / m 2 Preferably, 1 to 100 g / m 2In the step of heat-treating the immersed fiber, the heating temperature is preferably 130 to 200°C, more preferably 140 to 180°C, and the heating time is preferably 30 seconds to 30 minutes, more preferably 1 to 20 minutes. For example, by heating the treated article, an article with a more water-repellent treatment can be obtained.

[0040] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0041] [Weight Average Molecular Weight (Mw)] In the examples, the weight average molecular weight (Mw) is a value obtained by GPC (gel permeation chromatography) analysis using polystyrene as a standard substance under the following conditions. (Measurement conditions) GPC measurement device: HLC-8320 (manufactured by Tosoh Corporation) Detector: differential refractive index detector (RI) Measurement solvent: toluene Flow rate: 0.35 mL / min GPC columns: (passed in the following order) TSKgel Guardcolumn SuperHZ-L (4.6 mm I.D. × 2 cm × 1) TSKgel SuperHZ4000 (4.6 mm I.D. × 15 cm × 1) TSKgel SuperHZ3000 (4.6 mm I.D. × 15 cm × 1) TSKgel SuperHZ2000 (4.6 mm I.D. × 15 cm × 2) (all manufactured by Tosoh Corporation) Measurement temperature: 40°C Sample injection amount: 10 μL (toluene solution with a silicone concentration of 0.5% by mass)

[0042] [Example 1] (A-1) MeSiO as component (A) 1 / 2 Units and SiO 4 / 2 Polysiloxane (MeSiO) consisting of units and having hydroxyl groups bonded to silicon atoms 1 / 2 Unit) / SiO 4 / 2A solution was obtained by mixing 70 parts by mass of a copolymer of (a)-1,2-dimethyl-2-propanol (a copolymer of (a)-1,2-dimethyl-2-propanol (a)-1,2-dimethyl-2-propanol (a)-1,2-dimethyl-2-propanol (a)-1,2-dimethyl-2-propanol (a)-1,2-dimethyl-2-propanol (b)-1,2-dimethyl-2-propanol (c)-1,2-dimethyl-2-propanol (d)-1,2-dimethyl-2-propanol (d)-1,2-dimethyl-2-propanol (e)-1,2-dimethyl-2-propanol (e)-1,2-dimethyl-2-propanol (e)-1,2-dimethyl-2-propanol (e)-1,2-dimethyl-2-propanol (f ...

[0043] Examples 2 to 5 Compositions were obtained in the same manner as in Example 1, except that the amounts of components (A-1) and (B-1) were as shown in the table.

[0044] [Example 6] (A-2) MeSiO instead of (A-1) 1 / 2 Units and SiO 4 / 2 Polysiloxane (MeSiO) consisting of units and having hydroxyl groups bonded to silicon atoms 1 / 2 Unit) / SiO 4 / 2 A composition was obtained in the same manner as in Example 2, except that the unit (molar ratio) was 0.80, the weight average molecular weight was 4,400, and the Si—OH content was 0.10 mol / 100 g.

[0045] [Example 7] (A-3) MeSiO instead of (A-1) 1 / 2 Units and SiO 4 / 2 Polysiloxane (MeSiO) consisting of units and having hydroxyl groups bonded to silicon atoms 1 / 2 Unit) / SiO 4 / 2 A composition was obtained in the same manner as in Example 2, except that the unit (molar ratio) was 0.76, the weight average molecular weight was 5,200, and the Si—OH content was 0.06 mol / 100 g.

[0046] Example 8 A composition was obtained in the same manner as in Example 2, except that (B-1) was replaced with (B-2) 1,10-decanediol diacrylate.

[0047] Example 9 A composition was obtained in the same manner as in Example 2, except that (B-1) was replaced with (B-3) lauryl acrylate.

[0048] Example 10 A composition was obtained in the same manner as in Example 2, except that (B-1) was replaced with (B-4) cetyl acrylate.

[0049] Example 11 A composition was obtained in the same manner as in Example 2, except that (C-3) polyoxyethylene lauryl ether (HLB=9.7) and (C-4) polyoxyethylene alkyl ether (HLB=18.1) were used in place of (C-1) and (C-2) in the amounts shown in the table.

[0050] Example 12 A composition was obtained in the same manner as in Example 2, except that (C-5) polyoxyethylene lauryl ether (HLB=13.6) was used in place of (C-1) and (C-2) in the amounts shown in the table.

[0051] [Example 13] (A-1) MeSiO as component (A) 1 / 2 Units and SiO 4 / 2 Polysiloxane (MeSiO) consisting of units and having hydroxyl groups bonded to silicon atoms 1 / 2 Units / SiO 4 / 2 (B) 1,9-nonanediol diacrylate (B-1), component (B), and component (E) toluene (E-1) were mixed at room temperature in the amounts shown in the table to obtain a uniform composition.

[0052] Example 14 A composition was obtained in the same manner as in Example 13, except that (E-2) a hydrocarbon solvent, IP Solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.), was used instead of (E-1) as the component (E).

[0053] Comparative Example 1: (A-1) MeSiO as component (A) 1 / 2 Units and SiO 4 / 2 Polysiloxane (MeSiO) consisting of units and having hydroxyl groups bonded to silicon atoms 1 / 2 Units / SiO 4 / 2A solution ((A-1) concentration 80% by mass) containing (Z) ethylene glycol monobutyl ether acetate as a solvent (unit (molar ratio) = 0.85, weight average molecular weight 4,000, Si—OH content 0.08 mol / 100 g) was prepared, and to this solution were added (C-1) polyoxyethylene lauryl ether (HLB = 9.5) and (C-2) polyoxyethylene lauryl ether (HLB = 16.8) as component (C), and water as component (D), and the mixture was mixed using a homomixer, followed by further mixing using a homodisper to obtain a composition with improved dispersibility. The amounts used were as shown in the table.

[0054] Comparative Example 2 A composition was obtained in the same manner as in Example 1, except that the amounts of components (A-1) and (B-1) were as shown in the table.

[0055] Comparative Example 3 A composition was obtained in the same manner as in Example 1, except that the amounts of components (A-1) and (B-1) were as shown in the table.

[0056] [Comparative Example 4] The composition described in Example 1 of Patent Document 1 (JP 2020-7681 A) was prepared. (X1) A glass reaction vessel was charged with 80 g of styrene, 0.4 g of alkylbenzyldimethylammonium chloride (Sanisol C manufactured by Kao Corporation) as a disinfectant, 2.45 g of polyoxyethylene oleyl ether (equivalent to 9 mol of EO) as a surfactant, 2.45 g of polyoxyethylene oleyl ether (equivalent to 13 mol of EO), and 200 g of ion-exchanged water, and the resulting mixture was stirred at 60 ° C. to obtain a mixed solution. The mixed solution was treated at 40 MPa using a high-pressure homogenizer at 40 ° C. to obtain an emulsion. This emulsion was transferred to a glass reaction vessel, and 0.3 g of azobis(isobutylamidine) dihydrochloride was added at room temperature. The mixture was then polymerized at 70 ° C. for 15 hours under a nitrogen atmosphere. Ion-exchanged water was added to this solution to adjust the component concentration to 20% by mass. This aqueous polymer solution was designated X1. (X2) Pursuant to the method described in JP 2017-218713 A, 98 g of stearyl acrylate, 2 g of 2-hydroxyethyl methacrylate, 1 g of stearyl trimethylammonium chloride surfactant, 6 g of polyoxyethylene lauryl ether (equivalent to 7 mol of EO), 2 g of polyoxyethylene lauryl ether (equivalent to 21 mol of EO), 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol, and 224.7 g of ion-exchanged water were placed in a glass reaction vessel and stirred at 50 ° C. to obtain a mixed solution. The mixed solution was treated at 40 MPa using a high-pressure homogenizer at 40 ° C. to obtain an emulsion. This emulsion was transferred to a glass reaction vessel, and 0.3 g of azobis(isobutylamidine) dihydrochloride was added at room temperature. The mixture was then polymerized at 60 ° C. for 10 hours under a nitrogen atmosphere. Ion-exchanged water was added to this solution to adjust the component concentration to 30% by mass. This aqueous polymer solution is designated X2. (X3) In Patent Document 1, Meikanate, a blocked isocyanate-based crosslinking agent, is used as the crosslinking agent, but Duranate WL72-100 (manufactured by Asahi Kasei) was used as an alternative crosslinking agent. The amounts were X1: 2.25 parts by mass, X2: 7.50 parts by mass, and X3: 1.0 part by mass.

[0057] The compositions obtained above were evaluated as follows. The results are also shown in the table. [Preparation of Treated Fabric] The compositions obtained above were diluted to 1% by mass with water in the case of a water-containing composition, or with the same solvent in the case of a solvent-containing composition, to prepare a treatment solution. Polyester fabric and nylon fabric were immersed in the treatment solution, squeezed using a mangle, and heated at 150°C for 3 minutes to prepare treated fabrics. The pickup rate for polyester fabric was 100 to 110%, and the pickup rate for nylon fabric was 40 to 50%. The pickup rate is calculated by the following formula: Pickup rate (%) = (mass of base fabric after immersion in treatment bath and wringing - mass of base fabric before treatment) / (mass of base fabric before treatment) x 100

[0058] [Water repellency evaluation method] In accordance with the spray method of IS L 1092, a test was conducted in which a certain amount of shower-like water droplets were continuously sprayed on the treated fabric, and the results were visually evaluated according to the following grades. The higher the number, the better the result. 5: No adhesion and wetness on the surface 4: Slight adhesion and wetness on the surface 3: Partial wetness on the surface 2: Wetness on the surface 1: Wetness on the entire surface

[0059] [Method for evaluating feel] The feel of the treated fabrics described above when touched with the fingers was scored. Five panelists touched the fabric and judged it according to the following criteria, and the average of the scores was used as the score. A higher number indicates a better result. 5: Feel and smoothness similar to that of untreated fabric 4: Slightly harder than untreated fabric, but similar smoothness 3: Slightly harder than untreated fabric, and slightly less smooth 2: Harder than untreated fabric, and slightly less smooth 1: Harder than untreated fabric, and less smooth

[0060]

[0061]

[0062] In all cases, Examples 1 to 14 exhibited good water repellency and feel. As in Comparative Examples 1 to 3, compositions outside the scope of the present invention did not provide sufficient water repellency, and the use of component (A) alone directly resulted in hardness, resulting in a poor feel. Water repellency was achieved by the presence of components (A) and (B) in a certain ratio. Comparative Example 4, which was based on Patent Document 1, had polyester fabric: water repellency of 5, feel of 2.2; nylon fabric: water repellency of 5, feel of 2.6. The results showed that the water repellency was sufficient, but the feel was inferior to that of the present invention.

Claims

1. (A)R 1 3SiO 1 / 2 Units and SiO 4 / 2 units, wherein R 1 each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. 1 3SiO 1 / 2 Unit) / (SiO 4 / 2 a polyorganosiloxane having one or more Si—OH groups and one or more monovalent hydrocarbon groups having 1 to 10 carbon atoms in one molecule, in a molar ratio of 0.6 to 1.0; and (B) a compound having one or more (meth)acryloyl groups in one molecule, in which the total amount of components (A) and (B) is 100 parts by mass.

2. The siloxane composition according to claim 1, further comprising: (C) a surfactant: 0.5 to 100 parts by weight per 100 parts by weight of the combined total of components (A) and (B); and (D) water: 25 to 2,000 parts by weight per 100 parts by weight of the combined total of components (A) and (B).

3. The siloxane composition according to claim 1, further comprising (E) an organic solvent in an amount of 10 to 20,000 parts by weight per 100 parts by weight of the total of components (A) and (B).

4. The siloxane composition according to claim 1, wherein the amount of Si-OH groups contained in component (A) is 0.05 to 0.2 mol per 100 g.

5. The siloxane composition according to claim 1, wherein component (B) is a compound having one or more (meth)acryloyl groups in one molecule.

6. A fiber treatment agent comprising the composition according to any one of claims 1 to 5.

7. A textile product in which fibers are treated with the fiber treatment agent according to claim 6.

8. A method for producing a textile product according to claim 6, comprising the steps of immersing fibers in the fiber treatment agent and heat treating the immersed fibers.

Images