Rubber film-forming silicone emulsion composition and method for producing same, film, fiber treatment agent, and water repellent agent

Abstract

The present invention is a rubber film-forming silicone emulsion composition characterized by containing components (A)-(E): (A) 100 parts by mass of a specific organopolysiloxane represented by average compositional formula (1); (B) 0.1-30 parts by mass of a surfactant; (C) 1-10,000 parts by mass of water; (D) 0-40 parts by mass of colloidal silica; and (E) 0.5-50 parts by mass of a specific organopolysiloxane represented by average compositional formula (2). Consequently, provided is a rubber film-forming silicone emulsion composition that can form a film through drying, has good stability over time, and gives a film having good durability, strength, and flexibility.

Description

Rubber film-forming silicone emulsion composition, method for producing the same, film, fiber treatment agent, and water repellent agent

[0001] The present invention relates to a rubber film-forming silicone emulsion composition, a method for producing the same, a film, a fiber treatment agent, and a water-repellent agent.

[0002] Emulsion compositions that form a rubber film upon drying have traditionally been available in various compositions and are used as binders for fiber processing, rubber coatings, building material coatings, paper and plastic film coatings, or as additives thereof, for the purpose of imparting slipperiness, water repellency, flexibility, and release properties. Films formed from high molecular weight polymers generally have improved properties compared to films formed from low molecular weight polymers, therefore high molecular weight polymers are preferred in the above applications.

[0003] One method for forming a rubber film involves simultaneously forming a silicone elastomer film during drying through an addition reaction between alkenylsilyl groups and hydrosilyl groups. Proposed compositions include emulsion compositions consisting of vinyl-bound diorganopolysiloxane, organohydrogenpolysiloxane, and a platinum catalyst; and emulsion compositions containing vinyl groups on the molecular chain ends or side chains, polysiloxane with hydrogen atoms bonded to silicon atoms, colloidal silica, and a platinum catalyst. However, these compositions have a drawback: if hydrosilyl-containing siloxane and the platinum catalyst are present together, the reaction progresses over time and generates hydrogen gas. Therefore, mixing the silicone emulsion and platinum catalyst must be done before use, resulting in poor usability.

[0004] Furthermore, a method for forming rubber films is known that uses organopolysiloxane obtained by ring-opening polymerization of cyclic siloxane oligomers in an emulsified state with a strong acid or strong base. A composition has been proposed consisting of organopolysiloxane obtained by ring-opening polymerization, colloidal silica, a reaction product of amino group-containing organoalkoxysilane and acid anhydride, and epoxy group-containing organoalkoxysilane. However, ring-opening polymerization requires a long polymerization process, resulting in high manufacturing costs. In addition, the reaction product of amino group-containing organoalkoxysilane and acid anhydride undergoes yellowing and pH changes over time, leading to problems with the emulsion composition changing over time.

[0005] In addition, in recent years there has been a growing demand for environmentally friendly products that suppress the content of cyclic siloxane oligomers such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6). However, emulsion compositions obtained by ring-opening polymerization of cyclic siloxane oligomers have the problem of containing large amounts of D4, D5, and D6, which are by-products in the emulsion polymerization process.

[0006] As a method for obtaining a polymer with suppressed by-product amount of D4, for example, Patent Document 1 describes a method by addition polymerization in an emulsion system. According to this method, an organohydrogenpolysiloxane having three or more hydrosilyl groups per molecule and a linear diorganohydrogenpolysiloxane having hydrosilyl groups only at both ends of the molecular chain are subjected to an addition reaction in an emulsion system. Since it is an addition reaction, there is no by-production of cyclic siloxane oligomers such as D4, D5, and D6, but the film derived from the resulting emulsion has silethylene bonds, so it has the problem of having lower elongation (durability) than a film consisting only of siloxane bonds. Patent Document 2 also describes a method of condensation polymerization of a linear organopolysiloxane and a branched organopolysiloxane in an emulsion system. Because it is a condensation reaction, there is little by-product formation of cyclic siloxane oligomers such as D4, D5, and D6. However, high-molecular-weight polymers have not been obtained, and there was a problem in that a film could not be formed from the above emulsion.

[0007] Japanese Patent Publication No. 2021-107487, Japanese Patent Publication No. 2017-48342

[0008] The present invention has been made in view of the above circumstances, and provides a rubber film-forming silicone emulsion composition that can form a film by drying, has good temporal stability, and provides a film with good durability, strength, and flexibility. Furthermore, the present invention aims to provide a rubber film-forming silicone emulsion composition in which the amounts of impurities D4, D5, and D6 are reduced, a method for producing the same, a film which is a dried product of the rubber film-forming silicone emulsion composition, and a fiber treatment agent and a water repellent containing the above film-forming silicone emulsion composition.

[0009] To solve the above problems, the present invention provides a rubber film-forming silicone emulsion composition characterized by containing the following components (A) to (E). (A) Organopolysiloxane represented by the following average composition formula (1), having a 15% by mass toluene solubility viscosity of 200 mPa·s or more at 25°C, and containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass, (In the formula, R １ R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. ２ (B) Surfactant: 0.1 to 30 parts by mass, (C) Water: 1 to 10,000 parts by mass, (D) Colloidal silica: 0 to 40 parts by mass, (E) Organopolysiloxane represented by the following average composition formula (2): 0.5 to 50 parts by mass. (In the formula, R ３Each of these is independently a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organic group having 2 to 12 carbon atoms having a radical polymerization functional group, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ４ R is a monovalent group which may contain a heteroatom represented by the following formula (3), ５ Each of the following independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; e, f, g, h, and i represent the molar ratio of each siloxane unit, and are numbers satisfying 0 ≤ e ≤ 1, 0 ≤ f < 1, 0 ≤ g ≤ 1, 0 < h ≤ 1, 0 ≤ i < 1, and e + f + g + h + i = 1; α represents the number of moles of hydroxyl and alkoxy groups bonded to 1 mole of silicon atoms, and is a number satisfying 0 < α < 4.) *-V-W (3) (In formula (3), * represents a bond with a silicon atom, V is a linear or branched divalent hydrocarbon group having 1 to 40 carbon atoms, which may contain heteroatoms, and W represents an amine or amine salt structure, an amide structure, an epoxy structure, an alcohol structure, a carboxylic acid anhydride structure, a carboxylic acid structure, or a carboxylate salt structure.)

[0010] Such a rubber-film-forming silicone emulsion composition can form a film upon drying, exhibits good temporal stability, and provides a rubber-film-forming silicone emulsion composition that yields a film with good durability and flexibility.

[0011] Furthermore, in the present invention, it is preferable that W in formula (3) is a carboxylic acid anhydride structure, a carboxylic acid structure, a carboxylate salt structure, or an epoxy structure.

[0012] A rubber-coating silicone emulsion composition containing such (E) organopolysiloxane can improve the strength (especially hardness and tensile strength) and adhesion to the substrate of the film formed from the emulsion composition.

[0013] Furthermore, it is preferable that the surfactant (B) includes an anionic surfactant.

[0014] Such surfactants can provide a suitable emulsifying effect.

[0015] Furthermore, it is preferable that the mass-average molecular weight (Mw) of the organopolysiloxane (E) is 500 to 100,000.

[0016] (E) organopolysiloxanes with such mass-average molecular weights offer good handling and excellent uniform dispersibility in the composition, resulting in improved strength (especially hardness and tensile strength) of the film formed from the emulsion composition.

[0017] Furthermore, in the present invention, it is preferable that the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the rubber film-forming silicone emulsion composition is less than 0.1% by weight.

[0018] With this content level, it becomes a low-impurity, rubber-film-forming silicone emulsion composition that minimizes the content of environmentally harmful substances.

[0019] Furthermore, it is preferable that the average particle size of the emulsion particles in the rubber film-forming silicone emulsion composition is 500 nm or less.

[0020] With such an average particle size, the polymerization rate can be increased, and the amount of by-products octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) can be reduced.

[0021] The rubber film-forming silicone emulsion composition described above is preferably such that the dried film has an elongation at break of 300% or more at a thickness of 1 mm as measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or more at a thickness of 1 mm as measured in accordance with JIS K 6251.

[0022] With such elongation at break and tensile strength, there is no risk of the rubber film-forming silicone emulsion composition easily detaching from the substrate due to friction after being applied to various substrates.

[0023] Furthermore, the present invention provides a film which is a dried product of the rubber film-forming silicone emulsion composition.

[0024] Such a coating offers good durability and flexibility, and furthermore, the amount of impurities D4, D5, and D6 is reduced.

[0025] Furthermore, the present invention provides a fiber treatment agent comprising the rubber film-forming silicone emulsion composition.

[0026] Such fiber treatment agents exhibit good stability over time, good durability and flexibility, and furthermore, the amounts of impurities D4, D5, and D6 are reduced.

[0027] Furthermore, the present invention provides a water-repellent agent comprising the rubber film-forming silicone emulsion composition.

[0028] Such a water-repellent agent would have good stability over time, good durability and flexibility, and furthermore, the amount of impurities D4, D5, and D6 would be reduced.

[0029] Furthermore, the present invention provides a method for producing a rubber film-forming silicone emulsion composition, comprising the following steps (i) to (iii), wherein the total amount of (C-1), (C-2), and (C-3) below is 1 to 10,000 parts by mass, and the addition of (C) water. (i) A step of obtaining an O / W type emulsion comprising an oil phase component containing (A-1) a branched organopolysiloxane represented by the following general formula (4), a mixture of (A-1) and the following (A-2), or a mixture of (A-2) and the following (A-3), (B) a surfactant, and (C-1) water, (A-1): branched organopolysiloxane represented by the following general formula (4) (In the formula, R ６ These are, independently of each other, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and R ７is, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. w, x, y, and z are positive numbers satisfying w≥3, x≥5, y + z≥1, and 10≤w + x + y + z≤1,000. ) (A-2): A linear organopolysiloxane having a hydroxyl group or an alkoxy group at both ends of the molecular chain, represented by the following general formula (5) (In the formula, R ８ is, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. v is a positive number satisfying 0≤v≤2,000. ) (A-3): An alkoxysilane represented by the following general formula (6) and / or its hydrolysis condensate R ９ ｊ Si(OR １０ ) ４－ｊ (6) (Here, R ９ is, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R １０ is, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. j is 0 or 1. ) (ii) After adding (C-2) water to the O / W type emulsion composition obtained in the step (i) as necessary, the component (A-1) in the oil phase component of the O / W type emulsion, or a mixture of the component (A-1) and the component (A-2), or a mixture of the component (A-2) and the component (A-3) is polymerized at 0 to 40°C for 1 to 48 hours in the presence of (F) an acid catalyst (however, when the surfactant (B) has a catalytic action, the addition of the acid catalyst can be omitted), and after polymerization, neutralization is carried out to obtain an emulsion of (A) an organopolysiloxane which is a condensation reaction product obtained from the component (A-1), or a mixture of the component (A-1) and the component (A-2), or a mixture of the component (A-2) and the component (A-3). (iii) A step of adding (E) an organopolysiloxane and, if necessary, (D) colloidal silica and / or (C-3) water to the emulsion of the component (A) obtained in the step (ii).

[0030] With this manufacturing method, a rubber film-forming silicone emulsion composition can be formed that can be dried to create a film, has good temporal stability, provides a film with good durability and flexibility, and further reduces the amount of impurities D4, D5, and D6.

[0031] Furthermore, in the method for producing the above-mentioned rubber film-forming silicone emulsion composition, it is preferable to use (A-2) a linear organopolysiloxane having a hydroxyl group or alkoxy group represented by the general formula (5) at both ends of the molecular chain, wherein the viscosity at 25°C is 200 mPa·s or more and less than 2000 mPa·s.

[0032] If component (A-2) has this viscosity, the emulsion can be easily prepared.

[0033] As described above, the rubber film-forming silicone emulsion composition provided by the present invention can provide a film with excellent temporal stability, durability, and flexibility. Furthermore, since the amounts of impurities D4, D5, and D6 are reduced, there is no concern about environmental impact.

[0034] As described above, there was a need for the development of a rubber-film-forming silicone emulsion composition and a method for producing the same, which can form a film by drying, has good temporal stability, provides a film with good durability and flexibility, and further reduces the amount of impurities D4, D5, and D6.

[0035] As a result of diligent research to achieve the above objective, the present inventors have found that a rubber film-forming silicone emulsion composition comprising (A) a specific organopolysiloxane containing at least three alkoxy or hydroxyl groups bonded to silicon atoms in one molecule, (B) a surfactant, (C) water, (D) colloidal silica, and (E) the specific organopolysiloxane can form a rubber film with excellent hardness and flexibility in a short time, and furthermore, can form a rubber film-forming silicone emulsion composition with excellent long-term stability and reduced amounts of impurities D4, D5, and D6, thus completing the present invention.

[0036] In other words, the present invention is a rubber film-forming silicone emulsion composition characterized by containing the following components (A) to (E): (A) Organopolysiloxane represented by the following average composition formula (1), having a 15% by mass toluene solubility viscosity of 200 mPa·s or more at 25°C, and containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass, (In the formula, R １ R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. ２ (B) Surfactant: 0.1 to 30 parts by mass, (C) Water: 1 to 10,000 parts by mass, (D) Colloidal silica: 0 to 40 parts by mass, (E) Organopolysiloxane represented by the following average composition formula (2): 0.5 to 50 parts by mass. (In the formula, R ３ Each of these is independently a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organic group having 2 to 12 carbon atoms having a radical polymerization functional group, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ４ R is a monovalent group which may contain a heteroatom represented by the following formula (3), ５Each of the following independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; e, f, g, h, and i represent the molar ratio of each siloxane unit, and are numbers satisfying 0 ≤ e ≤ 1, 0 ≤ f < 1, 0 ≤ g ≤ 1, 0 < h ≤ 1, 0 ≤ i < 1, and e + f + g + h + i = 1; α represents the number of moles of hydroxyl and alkoxy groups bonded to 1 mole of silicon atoms, and is a number satisfying 0 < α < 4.) *-V-W (3) (In formula (3), * represents a bond with a silicon atom, V is a linear or branched divalent hydrocarbon group having 1 to 40 carbon atoms, which may contain heteroatoms, and W represents an amine or amine salt structure, an amide structure, an epoxy structure, an alcohol structure, a carboxylic acid anhydride structure, a carboxylic acid structure, or a carboxylate salt structure.)

[0037] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0038] [(A) Organopolysiloxane] Component (A) of the present invention is an organopolysiloxane represented by the following average composition formula (1), having a 15% by mass toluene solubility viscosity of 200 mPa·s or more at 25°C, and containing at least three alkoxy or hydroxyl groups bonded to silicon atoms in one molecule. (In the formula, R １ R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. ２ (Each is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, where a, b, c, and d are the molar ratios of each siloxane unit, and are positive numbers satisfying a ≥ 3, c + d ≥ 1, and 10 ≤ b / (c + d) ≤ 5000.)

[0039] In the above average composition formula (1), R １ R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. ２These are, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, where a, b, c, and d are the molar ratios of each siloxane unit, and are positive numbers satisfying a≧3, c+d≧1, and 10≦b / (c+d)≦5000. In the emulsion composition of the present invention, this component (A) is contained in 100 parts by mass.

[0040] In the above average composition formula (1), R １ R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and may be linear, branched, or cyclic. Specifically, in addition to the hydroxyl group, examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; phenyl group, tolyl group, naphthyl group; methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group, or groups in which some or all of the hydrogen atoms bonded to these groups are substituted with halogen atoms, amino groups, cyano groups, etc. １ Among these, methyl, hydroxyl, methoxy, and ethoxy groups are preferred, but the molecule is set to contain at least three alkoxy or hydroxyl groups bonded to silicon atoms. There is no particular upper limit to the number of alkoxy or hydroxyl groups bonded to silicon atoms in one molecule, but for example, it can be 50 or less.

[0041] The above R ２Each is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. Specifically, examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups, cycloalkyl groups such as cyclopentyl and cyclohexyl groups, alkenyl groups such as vinyl groups, and aryl groups such as phenyl, tolyl, and naphthyl groups. Examples of substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms include those in which some of the hydrogen atoms in the monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified above are replaced with halogen atoms, amino groups, acryloxy groups, methacryloxy groups, epoxy groups, mercapto groups, carboxyl groups, hydroxyl groups, etc. Preferably, it is a monovalent hydrocarbon group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and total R ２ It is even more preferable if more than 80% of the group consists of methyl groups.

[0042] In the average empirical formula (1), a, b, c, and d are the molar ratios of each siloxane unit, and are positive numbers satisfying a≧3, c+d≧1, and 10≦b / (c+d)≦5000. In the empirical formula (1), a, b, c, and d are the molar ratios of each siloxane unit, with a representing the ratio of terminal structures (M units) of component (A), b representing the ratio of linear siloxane chain structures (D units) of component (A), and c and d representing the ratio of branched siloxane structures (T units and Q units) of component (A), and are positive numbers satisfying a≧3, c+d≧1, and 10≦b / (c+d)≦5000. Here, b / (c+d) represents the ratio of linear units (D units) to branched units (T units + Q units) of the organopolysiloxane, with a value of 50 ≤ b / (c+d) ≤ 2500 being preferred, a value of 100 ≤ b / (c+d) ≤ 2000 being more preferred, and a value of 150 ≤ b / (c+d) ≤ 1000 being particularly preferred. If the value falls outside the above range, it becomes impossible to obtain a film with excellent strength and flexibility from the rubber film-forming silicone emulsion composition.

[0043] Specific examples of the organopolysiloxane of component (A) in the present invention include, but are not limited to, the following. In the following average composition formula, R １ The group is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group; Me and Ph represent a methyl group and a phenyl group, respectively; k, l, m, n, o, and p are each 1 or greater; and the value satisfies the requirement that the 15% by mass toluene solubility viscosity of the polyorganosiloxane at 25°C is 200 mPa·s or greater. In the formula, the bond portion showing the branched structure of the organopolysiloxane represents a direct bond between a silicon atom and an oxygen atom.

[0044]

[0045] The above component (A) has a 15% by mass toluene dissolution viscosity at 25°C of 200 mPa·s or more, preferably a number of 500 mPa·s or more, and more preferably a number of 1000 mPa·s or more. In this invention, the 15% by mass toluene dissolution viscosity is the measured value obtained using a BH type rotational viscometer at 25°C. If it is less than 200 mPa·s, the strength of the silicone rubber film may decrease. There is no particular upper limit, but in order to not impair the elongation of the film, it can be set to, for example, 20000 mPa·s.

[0046] The above component (A) needs to be in the form of an emulsion, but component (A) alone is usually a gel-like to rubbery solid, and it is difficult to obtain a stable emulsion from it. Therefore, it is desirable to produce the emulsion by the emulsion polymerization method described later.

[0047] In the present invention, component (A) is 100 parts by mass, but it can be 10 to 90% by mass, preferably 15 to 80% by mass, and more preferably 20 to 70% by mass in the total composition.

[0048] [(B) Surfactant] As the surfactant component (B) of the present invention, known substances can be used, but anionic surfactants or nonionic surfactants are preferred, and these can be used alone or in combination of two or more. In particular, in order to obtain a suitable emulsifying effect, it is preferable to use an anionic surfactant, or an anionic surfactant and a nonionic surfactant.

[0049] Examples of the above-mentioned anionic surfactants include those listed below, which can be used individually or in combination of two or more as appropriate.

[0050] (I) Alkyl sulfate or its salt represented by the following general formula (7) R １１ OSO ３ M (7) (wherein, R １１M is a linear or branched alkyl group having 6 to 30 carbon atoms, preferably a linear or branched alkyl group having 6 to 12 carbon atoms. M is a hydrogen ion, an alkali metal ion such as potassium or sodium, an alkaline earth metal ion such as magnesium or calcium, an ammonium ion, or a tertiary ammonium ion such as triethanolammonium ion. When M is a hydrogen ion, it also acts as a polymerization catalyst in the emulsion polymerization method described later. From the viewpoint of emulsifying effect, sodium ions, potassium ions, ammonium ions, and triethanolammonium ions are preferred for M.

[0051] Specific examples of alkyl sulfates or their salts include hexyl sulfate, octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, octadecyl sulfate, eicosyl sulfate, or alkali metal salts such as lithium salts, sodium salts, and potassium salts of these, alkaline earth metal salts such as magnesium salts and calcium salts, triethanolammonium salt, ammonium salt, etc.

[0052] (II) Alkylbenzenesulfonic acid or its salt represented by the following general formula (8) R １１ -C ６ H ４ -SO ３ M (8) (wherein, R １１ , and M are defined in general formula (7). In the above general formula (8), R １１ (Is preferably a linear or branched alkyl group having 6 to 12 carbon atoms, and is preferably sodium ions, potassium ions, ammonium ions, or triethanolammonium ions from the viewpoint of emulsifying effect.)

[0053] Specific examples of alkylbenzenesulfonic acid or its salts include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, and their salts.

[0054] (III) Alkylnaphthalene sulfonic acid represented by the following general formula (9) or its salt R １１γ -C １０ H （７－γ） -SO ３ M (9) (wherein, R １１ And M is defined in general formula (7), and γ is an integer from 1 to 3. In the above general formula (9), R １１ (Is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and is preferably sodium ions, potassium ions, ammonium ions, or triethanolammonium ions from the viewpoint of emulsifying effect.)

[0055] Specific examples of alkylnaphthalene sulfonic acid or its salts include butylnaphthalene sulfonic acid, pentylnaphthalene sulfonic acid, decylnaphthalene sulfonic acid, dodecylnaphthalene sulfonic acid, tetradecylnaphthalene sulfonic acid, hexadecylnaphthalene sulfonic acid, isopropylnaphthalene sulfonic acid, bisisopropylnaphthalene acid, trisisopropylnaphthalene acid and its salts.

[0056] (IV) Higher fatty acids and their salts Specific examples of higher fatty acids and their salts include lauric acid, stearic acid, oleic acid, linolenic acid, etc., and alkali metal salts such as lithium salts, sodium salts, potassium salts, etc., alkaline earth metal salts such as magnesium salts, calcium salts, triethanolammonium salt, ammonium salt, etc.

[0057] (V) Polyoxyethylene alkyl ether sulfate and its salts represented by the following general formula (10) R １１ (EO) δ (PO) ε SO ３ M (10) (wherein, R １１ And M are defined as in general formula (7). EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be block-like or random. δ and ε are independently positive numbers between 0 and 100, preferably 1 ≤ δ + ε ≤ 50.

[0058] Specific examples of the above-mentioned polyoxyethylene alkyl ether sulfates and their salts include polyoxyethylene hexyl ether sulfate, polyoxyethylene octyl ether sulfate, polyoxyethylene decyl ether sulfate, polyoxyethylene dodecyl ether sulfate, polyoxyethylene tetradecyl ether sulfate, polyoxyethylene hexadecyl ether sulfate, polyoxyethylene octadecyl ether sulfate, polyoxyethylene eicosyl ether sulfate, and alkali metal salts such as lithium salts, sodium salts, and potassium salts thereof, alkaline earth metal salts such as magnesium salts and calcium salts, triethanolammonium salt, ammonium salt, and the like.

[0059] (VI) Polyoxyethylene alkylphenyl ether sulfate represented by the following general formula (11) and its salts R １１ -C ６ H ４ -O (EO) δ - (PO) ε -SO ３ M (11) (wherein, R １１ And M are defined as in general formula (7), and EO, PO, δ, and ε are defined as in general formula (10) above.

[0060] Specific examples of the above-mentioned polyoxyethylene alkylphenyl ether sulfate and its salts include polyoxyethylene hexylphenyl ether sulfate, polyoxyethylene octylphenyl ether sulfate, polyoxyethylene decylphenyl ether sulfate, polyoxyethylene dodecylphenyl ether sulfate, polyoxyethylene tetradecylphenyl ether sulfate, polyoxyethylene hexadecylphenyl ether sulfate, and alkali metal salts such as lithium salts, sodium salts, and potassium salts thereof, alkaline earth metal salts such as magnesium salts and calcium salts, triethanolammonium salt, ammonium salt, and the like.

[0061] Examples of the above nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, etc., and one or more can be used individually or selected as appropriate. Among these, those represented by the following general formula (12) are preferred. R １２ O-(EO) δ’ (PO) ε’ R １３ (12) (wherein, R １２ R is a linear or branched alkyl group having 8 to 30 carbon atoms. １３ δ' represents a hydrocarbon group having 1 to 10 carbon atoms, which may contain a hydrogen atom or a heteroatom; EO represents an ethylene oxide group; and PO represents a propylene oxide group. Their arrangement may be block-like or random. δ' and ε' are independently positive numbers between 0 and 100, provided that δ' + ε' > 0.

[0062] In particular, in the above general formula (12), R １２ The alkyl group is preferably a linear or branched alkyl group having 8 to 13 carbon atoms, and δ' and ε' are preferably 0 to 25 independently, with 0 < δ' + ε' ≤ 50.

[0063] Specific examples of the above general formula (12) include polyoxyethylene octyl ether, polyoxyethylene polyoxypropylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene polyoxypropylene tridecyl ether, and polyoxyethylene cetyl ether. It is also possible to use reactive surfactants having functional groups. These surfactants can be used individually or in combination of two or more. The alkyl group can be linear or branched.

[0064] The amount of component (B) used is 0.1 to 30 parts by mass, preferably 1.5 to 7 parts by mass, and more preferably 2 to 6 parts by mass, per 100 parts by mass of component (A). If the amount is less than 0.1 parts by mass, a stable emulsion cannot be obtained, and if it is more than 30 parts by mass, the resulting film will be brittle and lack elongation. The total amount of component (B) can be 0.05 to 20% by mass, preferably 1 to 10% by mass, and more preferably 1.5 to 5% by mass. Furthermore, in order to obtain a strong film, it is preferable that 30% or more by mass of the total amount of component (B) is an anionic surfactant.

[0065] [(C) Water] Component (C) of the present invention is water, which is a dispersion medium for the organopolysiloxane of component (A) above, the colloidal silica of component (D) above, and the organopolysiloxane of component (E) above.

[0066] The amount of component (C) is 1 to 10,000 parts by mass, preferably 60 to 500 parts by mass, per 100 parts by mass of component (A). If the amount is greater than 10,000 parts by mass, the concentration of the film-forming component will be low, making it uneconomical, and if it is less than 1 part by mass, the viscosity of the aqueous silicone dispersion will be high, making it difficult to manufacture and handle. Furthermore, the total composition can contain 5 to 95% by mass, preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.

[0067] [(D) Colloidal Silica] The colloidal silica, which is component (D) of the present invention, is added as a film reinforcing agent and crosslinks with component (A), thereby greatly improving the strength (especially hardness and tensile strength) of the film formed from the emulsion composition. The colloidal silica may have its particle surface treated with a metal oxide, and it is preferable to incorporate it as a so-called silica sol (aqueous dispersion of colloidal silica) dispersed in water. The pH is not particularly limited, but a range of 4 to 10 is preferred for safety in use. The concentration of colloidal silica in the aqueous dispersion is not particularly limited, and for example, it may be 10 to 60% by mass. Commercially available colloidal silica can also be used, and there are no restrictions on the type, but for example, it may be stabilized with sodium, ammonium, or aluminum with a particle size of 5 to 50 nm. Specifically, examples include Snowtex (manufactured by Nissan Chemical Corporation), Rudox (manufactured by Grace Co., Ltd.), Silicadol (manufactured by Nippon Chemical Corporation), and Cataloid (manufactured by JGC Catalysts & Chemicals Corporation).

[0068] The amount of component (D) is 0 to 40 parts by mass per 100 parts by mass of component (A), and the inclusion of component (D) is necessary to maintain the strength and durability of the silicone film. Preferably, the amount of component (D) is 5 to 30 parts by mass, more preferably 10 to 20 parts by mass. It can also be 0 to 30% by mass, preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass in the total composition.

[0069] [(E) Organopolysiloxane] The organopolysiloxane, which is component (E) of the present invention, is added as a film reinforcing agent and substrate adhesion agent, and can greatly improve the strength (especially hardness and tensile strength) of the film formed from the emulsion composition, and also improves adhesion to the substrate. Component (E) is preferably water-dispersible from the viewpoint of dispersibility. Water dispersibility means, for example, that when the organopolysiloxane is mixed with water, shaken, and left to stand at 25°C for 24 hours, no clear separation or insolubilization is observed. Examples of water dispersion forms include transparent dissolution, suspension, emulsion, and self-emulsification, and these forms may be used for formulation.

[0070] The organopolysiloxane of component (E) above is represented by the following average composition formula (2). (In the formula, R ３ Each of these is independently a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organic group having 2 to 12 carbon atoms having a radical polymerization functional group, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ４ R is a monovalent group which may contain a heteroatom represented by the following formula (3), ５ Each of the following independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; e, f, g, h, and i represent the molar ratio of each siloxane unit, and are numbers satisfying 0 ≤ e ≤ 1, 0 ≤ f < 1, 0 ≤ g ≤ 1, 0 < h ≤ 1, 0 ≤ i < 1, and e + f + g + h + i = 1; α represents the number of moles of hydroxyl and alkoxy groups bonded to 1 mole of silicon atoms, and is a number satisfying 0 < α < 4.) *-V-W (3) (In formula (3), * represents a bond with a silicon atom, V is a linear or branched divalent hydrocarbon group having 1 to 40 carbon atoms, which may contain heteroatoms, and W represents an amine or amine salt structure, an amide structure, an epoxy structure, an alcohol structure, a carboxylic acid anhydride structure, a carboxylic acid structure, or a carboxylate salt structure.)

[0071] The above R ３ Examples of the above-mentioned monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group, but alkyl groups having 1 to 3 carbon atoms are preferred, and methyl group and ethyl group are particularly preferred.

[0072] Examples of organic groups having 2 to 12 carbon atoms and possessing the above-mentioned radical polymerizable functional group include vinyl groups, 3-acryloyloxypropyl groups, and 3-methacryloyloxypropyl groups.

[0073] Examples of the above aryl groups having 6 to 18 carbon atoms include unsubstituted aryl groups such as phenyl and naphthyl groups, alkylaryl groups such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl groups, but phenyl groups are preferred. Examples of aralkyl groups having 7 to 20 carbon atoms include benzyl and phenylethyl groups.

[0074] Furthermore, the alkyl groups, organic groups, aryl groups, and aralkyl groups mentioned above may have some or all of their hydrogen atoms substituted with halogen atoms (fluorine, chlorine, bromine, or iodine atoms). Specific examples include chloromethyl, chloropropyl, bromoethyl, trifluoropropyl, chlorophenyl, and bromophenyl groups.

[0075] In the above average composition formula (2), R ４ V is a monovalent group which may contain a heteroatom represented by formula (3) above. In formula (3) above, the divalent hydrocarbon group of V having 1 to 40 carbon atoms may include ether bonds, amide bonds, urethane bonds, urea bonds, sulfide bonds, etc. Preferably it is an alkylene group or (poly)oxyalkylene group having 1 to 10 carbon atoms, more preferably methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, octamethylene groups, and even more preferably an ethylene group or trimethylene group.

[0076] In formula (3) above, the amine or amine salt structure of W can be specifically listed below, but is not limited to these structures. -NH ２ -NH ３ ＋ X － - NHC ２ H ４ NH ２ - NHC ２ H ４ NH ３ ＋ X －(In the above structure, X represents the residue of the acid used in forming the amine salt.)

[0077] In the above formula (3), specific examples of the amide structure of W include, but are not limited to, the following structures. -NHCO-NH ２ -NHCO-C Ｙ H （２Ｙ＋１） (In the above structure, Y represents the chain length of the carboxylic acid used in forming the amide, and typically 1 ≤ Y ≤ 30.)

[0078] In the above formula (3), specific examples of the epoxy structure of W include, but are not limited to, the following structures.

[0079] In the above formula (3), the alcohol structure of W is the structure formed by ring-opening of the above epoxy structure. Specific examples include, but are not limited to, the following structures. -CH ２ CH(OH)-CH ２ R １４ -O-CH ２ CH(OH)-CH ２ R １４ (In the above structure, R １４ represents the residue of an amine, alcohol, or acid that reacts with the epoxy group)

[0080] In the above formula (3), examples of the carboxylic acid anhydride structure of W include succinic anhydride structure, maleic anhydride structure, phthalic anhydride structure, cyclopentanedicarboxylic anhydride structure, cyclohexanedicarboxylic anhydride structure, norbornanedicarboxylic anhydride structure, norbornenedicarboxylic anhydride structure, etc.

[0081] In the above formula (3), examples of the carboxylic acid structure of W include carboxyl group, succinic acid structure, maleic acid structure, phthalic acid structure, cyclopentanedicarboxylic acid structure, cyclohexanedicarboxylic acid structure, norbornanedicarboxylic acid structure, norbornenedicarboxylic acid structure, etc. formed by ring-opening of the above carboxylic acid anhydride structure.

[0082] In formula (3) above, the carboxylate salt structure of W can be a salt of a carboxyl group contained in the carboxylic acid structure and a basic compound. The basic compound is not particularly limited and can be alkali metal hydroxides, alkaline earth metal hydroxides, amine compounds, etc.

[0083] The above R ４ Among these, alcohol structures, epoxy group structures, carboxylic acid anhydride structures, carboxylic acid structures, and carboxylate salt structures are preferred from the viewpoint of substrate adhesion, and carboxylic acid anhydride structures, carboxylic acid structures, carboxylate salt structures, or epoxy structures are particularly preferred. When a carboxylic acid anhydride structure, carboxylic acid structure, or carboxylate salt structure is present, it also acts to some extent as a catalyst for crosslinking and curing the components of the composition of the present invention by a condensation reaction.

[0084] In the above average composition formula (2), R ５ Each of these is independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, with a hydrogen atom, a methyl group, or an ethyl group being preferred.

[0085] In the above average composition formula (2), e, f, g, h, and i represent the molar ratios of each siloxane unit, and are numbers that satisfy 0 ≤ e ≤ 1, 0 ≤ f < 1, 0 ≤ g ≤ 1, 0 < h ≤ 1, 0 ≤ i < 1, and e + f + g + h + i = 1, respectively.

[0086] e is a number satisfying 0 ≤ e ≤ 1, but from the viewpoint of the strength of the film obtained from this composition, a number satisfying 0 ≤ e ≤ 0.5 is preferred, and a number satisfying 0 ≤ e ≤ 0.2 is more preferred.

[0087] f is a number satisfying 0 ≤ f < 1, but from the viewpoint of the strength of the film obtained from this composition, a number satisfying 0 ≤ f ≤ 0.5 is preferred, and a number satisfying 0 ≤ f ≤ 0.2 is more preferred.

[0088] g is a number satisfying 0 ≤ g ≤ 1, but from the viewpoint of the adhesion of the film obtained from this composition to the substrate, a number satisfying 0 ≤ g ≤ 0.95 is preferred, and a number satisfying 0 ≤ g ≤ 0.85 is more preferred.

[0089] h is a number satisfying 0 < h ≤ 1, but from the viewpoint of the strength of the film obtained from this composition and the adhesion to the substrate, a number satisfying 0.01 ≤ h ≤ 0.95 is preferred, and a number satisfying 0.03 ≤ h ≤ 0.9 is more preferred.

[0090] i is a number satisfying 0 ≤ i < 1, but from the viewpoint of the flexibility of the film obtained from this composition, a number satisfying 0 ≤ i < 0.5 is preferred, and a number satisfying 0 ≤ i ≤ 0.2 is more preferred.

[0091] α represents the number of moles of hydroxyl groups and alkoxy groups bonded to one mole of silicon atoms, and is a number satisfying 0 < α < 4. However, from the viewpoint of the stability of the organopolysiloxane, a number satisfying 0 < α ≤ 2.5 is preferred, and a number satisfying 0.1 < α ≤ 2.0 is more preferred.

[0092] The following are examples of specific structures representing component (E) of the present invention, but are not limited to these. In the following formula, R ５ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; e', f', g', h', i', α' are numbers that satisfy e, f, g, h, i, α in the average composition formula (2); β is a number from 0 to 20; X is an acid residue used in amine salt formation; Y represents the chain length of the carboxylic acid used in amide formation, where 1 ≤ Y ≤ 30; and Z is a base residue used in carboxylate salt formation.

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] The weight-average molecular weight (Mw) of the organopolysiloxane of component (E) above is preferably 500 to 100,000, more preferably 500 to 20,000, and particularly preferably 500 to 10,000, from the viewpoint of handling and uniform dispersibility. Note that the weight-average molecular weight in this invention is the value on a polystyrene basis in gel permeation chromatography (GPC).

[0099] The amount of component (E) is 0.5 to 50 parts by mass per 100 parts by mass of component (A). If the amount is greater than 50 parts by mass, the silicone film may become hard and brittle, potentially reducing the durability of the film. If the amount is less than 0.5 parts by mass, the durability and strength of the resulting film may be reduced. The amount of component (E) is preferably 0.75 to 45 parts by mass, more preferably 1 to 30 parts by mass. Furthermore, it can be 0.05 to 45% by mass, preferably 0.5 to 40% by mass, and even more preferably 1 to 35% by mass in the total composition.

[0100] [Other Additives] The rubber film-forming silicone emulsion composition of the present invention may contain catalysts to promote condensation reactions, such as sodium compounds, aluminum compounds, potassium compounds, calcium compounds, vanadium compounds, iron compounds, cobalt compounds, nickel compounds, zinc compounds, zirconium compounds, tin compounds, and barium compounds. The amount of these catalysts can be 0.001 to 1 part by mass per 100 parts by mass of component (A). Preferably, the total amount of these catalysts in the composition is 0.0005 to 0.5% by mass.

[0101] The rubber film-forming silicone emulsion composition of the present invention may contain inorganic powders, pigments, dyes, thickeners, preservatives, antibacterial agents, deodorants, rust inhibitors, antioxidants, defoamers, antistatic agents, ultraviolet absorbers, antifreeze agents, water-soluble resins, organic resin emulsions, etc., in a range appropriate to the purpose of the present invention. Preferably, the above components make up 0 to 10% by mass of the total composition.

[0102] The emulsion composition of the present invention preferably contains less than 0.1% by mass of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), more preferably less than 0.09% by mass, and particularly preferably less than 0.08% by mass. There is no lower limit to the content of each, but for example, it can be 0.005% by mass. The emulsion composition of the present invention can suppress changes in the content of D4, D5, and D6 from immediately after manufacture to after storage at 40°C for 3 months.

[0103] The emulsion composition of the present invention has film-forming properties. There are no particular restrictions on the method of forming the film, but by removing water from the emulsion composition, the organopolysiloxane in the emulsion composition aggregates and forms a uniform film. There are no particular restrictions on the method of removing water, but for example, the water may be removed quickly at 100°C or above, or it may be removed gradually at 25°C.

[0104] For example, a film can be formed by weighing an emulsion composition into a 15 cm x 10 cm PP (polypropylene) tray so that the non-volatile content is 8.0 g, drying it at 25°C for 48 hours, and then drying it further at 105°C for 1 hour. The physical properties of the film prepared as described above can be evaluated by measuring its hardness, tensile strength, and elongation in accordance with JIS K 6249.

[0105] The rubber film-forming silicone emulsion composition described above is preferably such that the dried film has an elongation at break of 300% or more at a thickness of 1 mm as measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or more at a thickness of 1 mm as measured in accordance with JIS K 6251.

[0106] With such elongation at break and tensile strength, there is no risk of the rubber film-forming silicone emulsion composition easily detaching from the substrate due to friction after being applied to various substrates.

[0107] [Method for Producing Rubber Film-Forming Silicone Emulsion Composition] The method for producing a rubber film-forming silicone emulsion composition of the present invention includes the following steps (i) to (iii), and is a method for producing a rubber film-forming silicone emulsion composition by adding the following (C) water so that the total amount of the following (C-1), (C-2) and (C-3) is 1 to 10,000 parts by mass. (i) Step of obtaining an O / W type emulsion containing an oil phase component containing (A-1) a branched organopolysiloxane represented by the following general formula (4), a mixture of (A-1) and the following (A-2), or a mixture of (A-2) and the following (A-3), (B) a surfactant, and (C-1) water, (A-1): Branched organopolysiloxane represented by the following general formula (4) (In the formula, R ６ are each independently an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group, and R ７ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. w, x, y, z are positive numbers satisfying w≧3, x≧5, y + z≧1, and 10≦w + x + y + z≦1,000.) (A-2): Linear organopolysiloxane having a hydroxyl group or an alkoxy group at both ends of the molecular chain represented by the following general formula (5) (In the formula, R ８ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. v is a positive number satisfying 0≦v≦2,000.) (A-3): Alkoxysilane represented by the following general formula (6) and / or its hydrolysis condensate R ９ ｊ Si(OR １０ ) ４－ｊ (6) (Here, R ９ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R １０(i) (i) (ii) After adding (C-2) water as necessary to the O / W type emulsion composition obtained in step (i) above, polymerize the (A-1) component, a mixture of (A-1) and (A-2) components, or a mixture of (A-2) and (A-3) components in the oil phase component of the O / W type emulsion at 0 to 40°C for 1 to 48 hours in the presence of (F) acid catalyst (however, if (B) surfactant has catalytic activity, the addition of the acid catalyst can be omitted), and neutralize after polymerization to obtain an emulsion of (A) organopolysiloxane, which is a condensation product obtained from the (A-1) component, a mixture of (A-1) and (A-2) components, or a mixture of (A-2) and (A-3) components. (iii) A step of adding (E) organopolysiloxane and, if necessary, (D) colloidal silica and / or (C-3) water to the emulsion of component (A) obtained in step (iii).

[0108] [(A-1) Branched organopolysiloxane] Component (A-1) is a branched organopolysiloxane represented by the above general formula (4), and has a 15% by mass toluene solubility viscosity of 200 mPa·s or more at 25°C. It is a raw material for organopolysiloxane component (A) that contains at least three alkoxy groups or hydroxyl groups bonded to silicon atoms in one molecule.

[0109] In the above general formula (4), R ６ These are, independently of each other, alkoxy groups or hydroxyl groups having 1 to 20 carbon atoms. The alkoxy groups having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, examples include methoxy, ethoxy, propanoxy, butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, and 2-ethylhexyloxy groups. Methoxy, ethoxy, propanoxy, butoxy, and pentyloxy groups are preferred, and methoxy, ethoxy, and propanoxy groups are more preferred.

[0110] The above R ７These are, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically R ２ The same example is given, R ５ It is industrially and property-wise desirable that more than 80% of the group consists of methyl groups.

[0111] In equation (4) above, w, x, y, and z are positive numbers satisfying w≧3, x≧5, y+z≧1, and 10≦w+x+y+z≦1000. Preferably, 3≦w≦50, 10≦x≦900, 1≦y≦20, 0≦z≦10, and 10≦w+x+y+z≦800.

[0112] The following are some examples of specific structures representing the above-mentioned (A-1) component, but are not limited to these. In the formula, Me, Et, and Ph represent a methyl group, an ethyl group, and a phenyl group, respectively, and the branched bonding portion of the organopolysiloxane represents a direct bond between a silicon atom and an oxygen atom. Also, q, r, s, t, and u are each 1 or greater and are numbers that satisfy the ranges of w, x, y, and z in formula (4).

[0113]

[0114]

[0115]

[0116] As component (A-1), a product can be used in which the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained therein is 0.1% by mass or less. Preferably, each is less than 0.07% by mass, more preferably less than 0.06% by mass. There is no lower limit to the content of each, but for example, it can be 0.001% by mass.

[0117] In the method for producing the emulsion composition of the present invention, by using raw materials with a low content of such low molecular weight cyclic siloxanes, an emulsion composition with a low content of low molecular weight cyclic siloxanes can be efficiently produced.

[0118] [(A-2) Linear organopolysiloxane having hydroxyl or alkoxy groups at both ends of the molecular chain] Component (A-2) is a linear organopolysiloxane represented by general formula (5) having hydroxyl or alkoxy groups at both ends of the molecular chain, and serves as a raw material for component (A) of the present invention, which is an organopolysiloxane component containing alkoxy or hydroxyl groups bonded to at least three silicon atoms in one molecule. (In the formula, R ８ (Each is an independent hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted. v is a positive number satisfying 0 ≤ v ≤ 2000.)

[0119] In the above general formula (5), R ８ These are, independently of each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically R ２ The same example is given, R ８ It is industrially and property-wise desirable that more than 50% of it be methyl groups. The R at the end of the molecular chain of the general formula (5) above. ８ From the viewpoint of reactivity, it is preferable that it be a hydrogen atom.

[0120] In the general formula (5) above, v can typically take values ​​from 1 to 2000. Preferably, 10 ≤ v ≤ 1500, and particularly preferably 20 ≤ v ≤ 1000.

[0121] The viscosity of component (A-2) above is measured using a BH-type rotational viscometer at 25°C, preferably between 200 mPa·s and less than 2000 mPa·s, more preferably between 300 mPa·s and less than 1800 mPa·s, and particularly preferably between 500 and less than 1600 mPa·s. A viscosity of 200 mPa·s or higher is preferable as it facilitates the preparation of the emulsion described later.

[0122] Specific examples of the above (A-2) component include, but are not limited to, the average empirical formula shown below. In the general formula below, q', q'+r', and q'+r'+s' can typically take values ​​between 1 and 2,000.

[0123] The above-mentioned component (A-2) can be condensed with the above-mentioned component (A-1) or component (A-3) to obtain component (A) of the present invention, which is an organopolysiloxane component having a 15% by mass toluene solubility viscosity of 200 mPa·s or more at 25°C and containing at least three alkoxy or hydroxyl groups bonded to silicon atoms in one molecule. When used in combination with (A-1), the amount of component (A-2) used is preferably 0.1 to 99.9 parts by mass, and particularly preferably 1 to 99 parts by mass, per 100 parts by mass of the total of components (A-1) and (A-2). When used in combination with component (A-3), the amount is preferably 80 to 99.9 parts by mass, more preferably 90 to 99.9 parts by mass, and particularly preferably 95 to 99.9 parts by mass, per 100 parts by mass of the total of components (A-2) and (A-3). If the amount of component (A-2) is within the above range, the resulting film will have sufficient strength and flexibility.

[0124] [(A-3) Alkoxysilane and / or hydrolysis condensate represented by the following formula (6)] Component (A-3) is an alkoxysilane and / or hydrolysis condensate represented by the following formula (6), which is component (A) of the present invention, has a 15% by mass toluene dissolution viscosity at 25°C of 200 mPa·s or more, and is a raw material for organopolysiloxane components containing at least three alkoxy or hydroxyl groups bonded to silicon atoms in one molecule. R ９ ｊ Si ( OR １０ ) ４－ｊ (6) (Here, R ９ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, independently of each other. １０ Each of these is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted. (j is 0 or 1.)

[0125] In the above formula (6), R ９R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, and cycloheptyl, aryl groups such as vinyl, alkenyl, phenyl, tolyl, and naphthyl, or in which some of the hydrogen atoms in the structure of these organic groups are substituted with halogen atoms or organic groups containing polar groups such as amino, acryloxy, methacryloxy, epoxy, and mercapto. Here, R ９ It is industrially and property-wise desirable that more than 80% of the group consists of methyl groups.

[0126] The above R １０ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted. １０ The monovalent organic group having 1 to 20 carbon atoms is the one described above, R ９ It is the same as, and methyl, ethyl, propyl, and butyl groups are preferred, with methyl and ethyl groups being more preferred.

[0127] Specific examples of the above (A-3) component include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 Examples include, but are not limited to, methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatetopropyltriethoxysilane.

[0128] The above-mentioned component (A-3) undergoes a condensation reaction with component (A-2) to obtain component (A) of the present invention, which is an organopolysiloxane component having a 15% by mass toluene solubility viscosity of 200 mPa·s or more at 25°C and containing at least three alkoxy or hydroxyl groups bonded to silicon atoms in one molecule. The amount of component (A-3) used is preferably 0.10 to 20 parts by mass, more preferably 0.10 to 10 parts by mass, and particularly preferably 0.10 to 5 parts by mass, per 100 parts by mass of the total of components (A-2) and (A-3). When the amount of component (A-2) is within the above range, the flexibility of the resulting film is good.

[0129] [(C-1), (C-2), and (C-3) Water] Components (C-1), (C-2), and (C-3) are the water used in process (i) and, if necessary, in processes (ii) and (iii), respectively. The sum of the amounts used for components (C-1), (C-2), and (C-3) is the amount of water used for component (C). These are added so that the total is between 1 and 10,000 parts by mass.

[0130] [(F) Acid Catalyst] Component (F) is an acid catalyst and is a reaction catalyst for component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3). If component (B) has catalytic activity, component (F) may not be necessary. When component (F) is used, it can be used alone or in appropriate combinations of two or more types. Component (F) may also be formulated as an aqueous solution.

[0131] The following are examples of the above-mentioned (F) component.

[0132] [(F-1) Alkyl sulfuric acid represented by the following general formula (13), alkylbenzene sulfonic acid represented by the following general formula (14), or alkylnaphthalene sulfonic acid represented by the following general formula (15)] R １５ OSO ３ H (13) (wherein, R １５ (A is a linear or branched alkyl group having 6 to 30 carbon atoms.) １５ -C ６ H ４-SO ３ H (14) (wherein, R １５ R is a linear or branched alkyl group having 6 to 30 carbon atoms, as defined in general formula (13). １５ γ´ -C １０ H （７－γ´） -SO ３ H (15) (wherein, R １５ As defined in general formula (13), γ' is a linear or branched alkyl group having 6 to 30 carbon atoms, and γ' is an integer from 1 to 3.

[0133] In the above general formulas (13), (14), and (15), R １５ A linear or branched alkyl group having 3 to 12 carbon atoms is preferred.

[0134] Specific examples of alkyl sulfates represented by the general formula (13) above include hexyl sulfate, octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, octadecyl sulfate, and eicosyl sulfate.

[0135] Specific examples of alkylbenzenesulfonic acids represented by the above general formula (14) include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, and hexadecylbenzenesulfonic acid.

[0136] Specific examples of alkylnaphthalenesulfonic acid represented by the above general formula (15) include butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, tetradecylnaphthalenesulfonic acid, hexadecylnaphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, bisisopropylnaphthalene acid, trisisopropylnaphthalene acid, and the like.

[0137] [(F-2) Higher fatty acids] Specific examples include lauric acid, stearic acid, oleic acid, and linolenic acid.

[0138] [(F-3) Polyoxyethylene alkyl ether sulfate represented by the following general formula (16)] R １５ O (EO) ζ (PO) η SO ３ H (16) (wherein, R １５ ζ is a linear or branched alkyl group having 6 to 30 carbon atoms, as defined in general formula (13). EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. ζ and η are independent integers from 0 to 100, where ζ + η > 0, and especially 1 ≤ ζ + η ≤ 50.

[0139] Specific examples of polyoxyethylene alkyl ether sulfate represented by the above general formula (16) include polyoxyethylene hexyl ether sulfate, polyoxyethylene octyl ether sulfate, polyoxyethylene decyl ether sulfate, polyoxyethylene dodecyl ether sulfate, polyoxyethylene tetradecyl ether sulfate, polyoxyethylene hexadecyl ether sulfate, polyoxyethylene octadecyl ether sulfate, and polyoxyethylene icosyl ether sulfate.

[0140] [(F-4) Polyoxyethylene alkylphenyl ether sulfate represented by the following general formula (17)] R １５ -C ６ H ４ -O (EO) ζ (PO) η SO ３ H (17) (wherein, R １５ ζ is a linear or branched alkyl group having 6 to 30 carbon atoms, as defined in general formula (13). EO, PO, ζ, and η are as defined in general formula (16), where EO represents an ethylene oxide group and PO represents a propylene oxide group, and their arrangement may be blocky or random. ζ and η are independent integers from 0 to 100, where ζ + η > 0, and especially 1 ≤ ζ + η ≤ 50.

[0141] Examples of polyoxyethylene alkylphenyl ether sulfate represented by the above general formula (17) include polyoxyethylene hexylphenyl ether sulfate, polyoxyethylene octylphenyl ether sulfate, polyoxyethylene decylphenyl ether sulfate, polyoxyethylene dodecylphenyl ether sulfate, polyoxyethylene tetradecylphenyl ether sulfate, and polyoxyethylene hexadecylphenyl ether sulfate.

[0142] When using the above components (F-1), (F-2), (F-3), and (F-4), they also exhibit surfactant properties, as described above.

[0143] [(F-5) Brønsted Acids] Examples of Brønsted acids in (F-5) include hydrochloric acid, hydrobromic acid, sulfuric acid, chlorosulfonic acid, phosphoric acid, orthophosphoric acid, metaphosphoric acid, and polyphosphoric acid, boric acid, nitric acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, carboxylic acid, chloroacetic acid, trichloroacetic acid, acetic acid, acrylic acid, benzoic acid, trifluoroacetic acid, citric acid, crotonic acid, formic acid, fumaric acid, maleic acid, malonic acid, tannic acid, itaconic acid, lactic acid, tartaric acid, oxalic acid, phthalic acid, and succinic acid, cation exchange resins, acid zeolites, acid-activated filler earth, and acid-activated carbon black.

[0144] The amount of component (F) used (however, if the surfactant of component (B) is an acid and has catalytic activity, the addition of the acid catalyst can be omitted) is preferably at least 0.1 parts by mass, and more preferably 0.2 parts by mass or more, per 100 parts by mass of component (A). An appropriate polymerization rate can be achieved with 0.1 parts by mass or more. There is no particular upper limit, but it is preferable that it be 10 parts by mass or less from the viewpoint of the long-term stability of the resulting rubber film-forming silicone emulsion composition.

[0145] The method for producing the rubber film-forming silicone emulsion composition of the present invention will be described below.

[0146] <Step (i)> This step involves emulsifying an oil phase component containing a branched organopolysiloxane represented by the following general formula (4), a mixture of (A-1) and (A-2), or a mixture of (A-2) and (A-3), with a mixture containing (B) a surfactant and (C-1) water to obtain an O / W type emulsion. Emulsification here can be performed using an emulsifier such as a homodisper, homomixer, colloid mill, line mixer, universal mixer, ultramixer, planetary mixer, combimix, or high-pressure homogenizer. Preferably, an emulsifier such as a homodisper, homomixer, or colloid mill is used to reduce the particle size of the emulsion using shear force, and more preferably a homodisper.

[0147] The amount of water used for component (C) above is 1 to 10,000 parts by mass per 100 parts by mass of component (A), and in step (i) above, the amount of water used for component (C)1 varies depending on the type of emulsifier used to reduce the particle size of the emulsion particles.

[0148] For example, when using a high-pressure homogenizer (an emulsifier that pressurizes the processing liquid to high pressure or ultra-high pressure and obtains shear force by passing it through a slit, or an emulsifier that atomizes pressurized processing liquids by causing them to collide obliquely at ultra-high speed) to reduce the particle size of emulsion particles using high pressure, the amount of component (C-1) used is preferably 1 to 10,000 parts by mass, more preferably 2 to 6,000 parts by mass, and even more preferably 3 to 4,000 parts by mass, per 100 parts by mass of component (A).

[0149] Furthermore, when using emulsifiers such as homodispers (emulsifiers that obtain shear force by rapidly rotating a circular disc with saw-toothed teeth on its outer circumference), homomixers (emulsifiers that generate shear force by rapidly rotating a rotor installed inside with a stator installed on the outer circumference), and colloid mills (emulsifiers that emulsify by feeding each component into the gap between a rapidly rotating disc and a fixed disc to generate shear force), the amount of component (C-1) used is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of component (A). If the amount is 20 parts by mass or less, a small-particle emulsion with excellent stability can be obtained, and if it is 1 part by mass or more, the formation of an O / W type emulsion becomes easy.

[0150] In this step, the emulsification temperature is preferably 1 to 80°C. If component (B) has catalytic activity, the cyclization reaction will also proceed simultaneously, so it is preferable to carry out emulsification at a temperature of less than 40°C, more preferably less than 30°C, and especially more preferably less than 25°C.

[0151] <Step (ii)> The O / W type emulsion obtained in step (i) is diluted with (C-2) water as needed, and emulsion polymerization is carried out at a temperature of 0 to 40°C, with component (F) added as needed, to obtain an emulsion composition of component (A).

[0152] When component (C-2) is added, it can be further emulsified and dispersed using an emulsifier such as a high-pressure homogenizer. When adding component (C-2), it is preferably 0.1 to 9000 parts by mass, more preferably 0.1 to 5000 parts by mass, and even more preferably 1 to 1000 parts by mass, per 100 parts by mass of component (A).

[0153] When emulsion polymerization is performed on the above O / W type emulsion composition, it is recommended that the polymerization process be carried out at a temperature of 0 to 40°C for no more than 48 hours. To suppress the formation of D4, a temperature of 25°C or lower is preferable, and 15°C or lower is more preferable. Furthermore, the polymerization time is preferably 1 to 40 hours, and more preferably 5 to 30 hours.

[0154] The polymerization described above is carried out until the organopolysiloxane of component (A) has a 15% by mass toluene soluble viscosity of 200 mPa·s or more at 25°C. Here, the 15% by mass toluene soluble viscosity can be measured, for example, by adding the polymerized emulsion composition to a polar solvent such as alcohol while stirring to break down the emulsion and extract the organopolysiloxane, drying this organopolysiloxane at 105°C for 3 hours or more, and then adding toluene so that the organopolysiloxane is 15% by mass and dissolving it, and measuring the viscosity using a rotational viscometer or the like.

[0155] After the polymerization described above is complete, it is preferable to neutralize the resulting emulsion composition with a basic substance. Examples of basic substances include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, triethanolamine, triethylamine, and other amine compounds. The pH after neutralization is preferably 6.5 to 8.5, and more preferably 6.7 to 7.5. If the pH is within the above range, the polymerization of organopolysiloxane will not progress due to changes over time, and the stability over time will not deteriorate. The amount of basic substance added is preferably 0.1 to 5 moles of basic substance relative to the number of moles of acid catalyst (F) component, and more preferably 0.3 to 3 moles.

[0156] At this time, preservatives, fungicides, etc., can be added to improve the shelf life of the O / W type emulsion composition. Preferably, the above components are added to the O / W type emulsion composition in an amount of 0.001 to 0.1% by mass.

[0157] <Step (iii)> The emulsion composition of component (A) obtained in step (ii) is diluted with water (C-3) as needed, and components (D) and (E) are added. If the colloidal silica of component (D) is an aqueous dispersion and the organopolysiloxane of component (E) is an aqueous dispersion, the water in the colloidal silica aqueous solution and the organopolysiloxane aqueous dispersion are also included in component (C-3). When adding component (C-3), it is preferably 0.1 to 1000 parts by mass, more preferably 0.5 to 5000 parts by mass, and even more preferably 1 to 1000 parts by mass, per 100 parts by mass of component (A).

[0158] The addition of components (D) and (E) may be done by adding pre-mixed components (D) and (E) to the emulsion of component (A) under stirring, or by adding components (D) and (E) to the emulsion of component (A) under stirring.

[0159] The average particle size of the emulsion particles obtained by the method for producing a rubber-coating silicone emulsion of the present invention is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 350 nm or less. The lower limit is not particularly limited, but is approximately 30 nm or more. The average particle size of the emulsion particles is the median diameter value determined by laser diffraction and scattered light.

[0160] The pH of the emulsion composition obtained by the rubber film-forming silicone emulsion production method of the present invention is preferably 6.0 to 9.0, and more preferably 6.5 to 9.0. When the pH is within the above range, the stability over time is good, and the by-product formation of D4, D5, and D6 over time can be suppressed.

[0161] <Film Formation> The rubber film-forming silicone emulsion composition of the present invention can form a rubber film after drying and can be used by treating or impregnating the surface of various substrates such as fibers, paper, metal, wood, rubber, plastic, and glass. Various conventional coating methods such as dipping, spraying, roll coating, bar coating, and brush coating can be used as application methods to the substrate.

[0162] The rubber-film-forming silicone emulsion composition obtained by the above method has component (A) dispersed and can be easily diluted with water. The rubber-film-forming silicone emulsion composition of the present invention can form a film when dried. The film may be sticky, but it is not gel-like. The drying temperature can be appropriately selected from 1 to 250°C, and a film can be formed even at room temperature (ambient temperature) such as 25°C. The drying time is preferably a few seconds to one week. Since high-temperature treatment may damage various substrates, drying at room temperature is most preferable.

[0163] The elongation and tensile strength of the film obtained from the rubber film-forming silicone emulsion of the present invention are as follows. If the elongation or tensile strength is too low, for example, after treating various substrates with the rubber film-forming silicone emulsion composition, the film may easily detach from the substrate due to friction.

[0164] A film made from the dried rubber film-forming silicone emulsion composition of the present invention can have a thickness of 1 mm and an elongation at break of 300% or more, as measured in accordance with JIS K 6251, and a tensile strength at break of 0.05 MPa or more, as measured in accordance with JIS K 6251.

[0165] The method for producing the above-mentioned film is not particularly limited. For example, it can be obtained by pouring a rubber film-forming silicone emulsion composition in an amount that will have a thickness of approximately 1 mm after drying into a polypropylene resin tray and drying it at 25°C for 48 hours.

[0166] The above coating preferably has an elongation at break of 300% or more, and more preferably 500% or more, when measured in accordance with JIS K 6251 for a dumbbell-shaped test piece No. 3. There is no particular upper limit to the above elongation at break, but it can be, for example, 2000% or less. The tensile strength of the coating at break (test method specified in JIS K 6251) is preferably 0.05 MPa or more, and more preferably 0.10 MPa or more. There is no particular upper limit to the above tensile strength at break, but it can be, for example, 5.0 MPa or less.

[0167] <Fiber Treatment Agent> The present invention also provides a fiber treatment agent containing the rubber film-forming silicone emulsion composition. Such a fiber treatment agent has good stability over time, good durability and flexibility, and furthermore, the amount of D4, D5, and D6 contained as impurities is reduced.

[0168] <Water-repellent agent> Furthermore, the present invention provides a water-repellent agent comprising the rubber film-forming silicone emulsion composition. Such a water-repellent agent has good stability over time, good durability and flexibility, and furthermore, the amounts of D4, D5, and D6 contained as impurities are reduced.

[0169] 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. Also, "parts" means parts by mass. The viscosity, with units of mP·s, is the value measured using a BH viscometer at 25°C.

[0170] [Manufacturing Example 1] (D-1) Colloidal silica (manufactured by Nissan Chemical Corporation: Snowtex C, active ingredient 20%) 23 parts are stirred with a paddle, and (E-1) organopolysiloxane having an epoxy structure represented by the following average composition formula (18) (in the above average composition formula (2), e=0, f=0.1, g=0, h=0.9, i=0, α=2.1 (α １ = 1.7, α ２ (=0.4), Mw=600, (partially containing epoxy groups with open rings as described in formula (19) below) 0.9 parts were gradually added and dispersed to obtain a mixture of components (D) and (E) (mixture I).

[0171] [Manufacturing Example 2] 23 parts of colloidal silica (D-1) manufactured by Nissan Chemical Corporation: Snowtex C, 20% active ingredient) were stirred with a paddle, and 3 parts of an aqueous dispersion of (E-2) organopolysiloxane having a sodium salt structure of pentenoic acid, represented by the following average composition formula (20) (in the above average composition formula (2), e=0.19, f=0, g=0.78, h=0.03, i=0, α=0.2, Mw=2500, 30% active ingredient) were gradually added and dispersed to obtain a mixture of components (D) and (E) (Mixed Solution II).

[0172] [Example 1] 50 parts of (A-1-1) branched organopolysiloxane (in general formula (21) below, w=3, x=400, y=1, z=0), represented by the following general formula (21), were emulsified by homodisperser with 3.02 parts of (B-1) Neoperex G-65 (manufactured by Kao Corporation: 65% aqueous solution of alkylbenzene sulfonate), 0.21 parts of (B-2) Emulgen 104P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), 0.62 parts of (B-3) Emulgen 123P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), and 1.15 parts of (C-1) water (the water in component (B) also acts as component (C-1)). 40.77 parts of (C-2) water were added to the obtained emulsion and diluted and dispersed by homomixer. Next, 3.48 parts of (F-1) 20% dodecylbenzenesulfonic acid aqueous solution were added, and emulsion polymerization was carried out at 10°C for 16 hours. Then, 0.70 parts of 20% sodium carbonate aqueous solution were added to the obtained emulsion, and the emulsion of component (A) was obtained by dilution and dispersion with a homomixer. The 15% toluene dissolution viscosity of component (A) in the obtained emulsion at 25°C was 1,000 mPa·s. 23.9 parts of a pre-prepared mixture I was added to 74.2 parts of this emulsion and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 1 and 5 below.

[0173] [Example 2] To 74.2 parts of the emulsion of component (A) obtained in Example 1, 26 parts of the previously prepared mixed solution II were added and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 1 and 5 below.

[0174] [Example 3] An emulsion of component (A) was obtained in the same manner as in Example 1, except that the raw materials for component (A) of Example 1 were changed to 44.79 parts of (A-1-1) branched organopolysiloxane represented by the general formula (21) (wherein w=4, x=400, y=1, z=0) and 5.21 parts of (A-2-1) organopolysiloxane having a viscosity of 700 mPa·s and silanol groups at the molecular chain ends, represented by the general formula (22) below (wherein v'≒200). The 15% by mass toluene dissolution viscosity of component (A) in the obtained emulsion at 25°C was 4800 mPa·s. 23.9 parts of a pre-prepared mixed solution I was added to 74.2 parts of this emulsion and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 1 and 5 below.

[0175] [Example 4] To 74.2 parts of the emulsion of component (A) obtained in Example 3, 26 parts of the previously prepared mixed solution II were added and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 1 and 5 below.

[0176] [Example 5] 49.64 parts of (A-2-1) organopolysiloxane having silanol groups at the end of the molecular chain with a viscosity of 700 mPa·s, 0.36 parts of (A-3-1) triethoxyphenylsilane, 3.02 parts of (B-1) Neoperex G-65 (manufactured by Kao Corporation: 65% aqueous solution of alkylbenzene sulfonate sodium), 0.21 parts of (B-2) Emulgen 104P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), 0.62 parts of (B-3) Emulgen 123P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), and 1.15 parts of (C-1) water were emulsified by homodisperser (the water in component (B) also acts as component (C-1)). 40.77 parts of (C-2) water were added to the obtained emulsion and diluted and dispersed by homomixer. Next, 3.48 parts of (F-1) 20% dodecylbenzenesulfonic acid aqueous solution were added, and emulsion polymerization was carried out at 10°C for 24 hours. Then, 1.41 parts of 10% sodium carbonate aqueous solution were added to the obtained emulsion, and the emulsion of component (A) was obtained by dilution and dispersion with a homomixer. The 15% toluene dissolution viscosity of component (A) in the obtained emulsion at 25°C was 200 mPa·s. 23.9 parts of a pre-prepared mixture I was added to 74.2 parts of this emulsion and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 2 and 6 below.

[0177] [Example 6] To 74.2 parts of the emulsion of component (A) obtained in Example 5, 26 parts of the previously prepared mixed solution II were added and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 2 and 6 below.

[0178] [Example 7] 20.55 parts of (A-1-1) branched organopolysiloxane represented by the general formula (21) (wherein w=4, x=400, y=1, z=0 in the general formula (21)) and 29.45 parts of (A-2-1) organopolysiloxane having a viscosity of 700 mPa·s and silanol groups at the end of the molecular chain, represented by the general formula (22), and (B-1) Neoperex G-65 (manufactured by Kao Corporation: alkylbenzyl 3.02 parts of a 65% aqueous solution of sodium sulfonate, 0.21 parts of (B-2) Emulgen 104P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), 0.62 parts of (B-3) Emulgen 123P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), and 1.15 parts of (C-1) water were emulsified by homodisperser (the water in component (B) also acts as component (C-1)). 40.77 parts of (C-2) water were added to the obtained emulsion and diluted and dispersed using a homomixer. Next, 3.48 parts of (F-1) 20% aqueous solution of dodecylbenzenesulfonic acid were added, and emulsion polymerization was carried out at 10°C for 16 hours. After that, 0.70 parts of 20% aqueous solution of sodium carbonate were added to the obtained emulsion and diluted and dispersed using a homomixer to obtain the emulsion of component (A). The viscosity of component (A) in the obtained emulsion at 25°C with 15% by mass of toluene was 1500 mPa·s. 74.2 parts of this emulsion were mixed with 26 parts of a pre-prepared mixture II and dispersed by paddle stirring to obtain a rubber-film-forming silicone emulsion composition. The results are shown in Tables 2 and 6 below.

[0179] [Example 8] 44.79 parts of (A-1-2) branched organopolysiloxane (in general formula (23) below, w=4, x=400, y=0, z=1) represented by the following general formula (23), and 5.21 parts of (A-2-1) organopolysiloxane having a viscosity of 700 mPa·s and silanol groups at the end of the molecular chain, represented by the above general formula (22), and (B-1) Neoperex G-65 (manufactured by Kao Corporation: alkylbenzyl 3.02 parts of a 65% aqueous solution of sodium sulfonate, 0.21 parts of (B-2) Emulgen 104P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), 0.62 parts of (B-3) Emulgen 123P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), and 1.15 parts of (C-1) water were emulsified by homodisperser (the water in component (B) also acts as component (C-1)). 40.77 parts of (C-2) water were added to the obtained emulsion and diluted and dispersed using a homomixer. Next, 3.48 parts of (F-1) 20% aqueous solution of dodecylbenzenesulfonic acid were added, and emulsion polymerization was carried out at 10°C for 16 hours. After that, 0.70 parts of 20% aqueous solution of sodium carbonate were added to the obtained emulsion and diluted and dispersed using a homomixer to obtain the emulsion of component (A). The viscosity of component (A) in the obtained emulsion at 25°C with 15% by mass of toluene was 2000 mPa·s. 74.2 parts of this emulsion were mixed with 26 parts of a pre-prepared mixture II and dispersed by paddle stirring to obtain a rubber-film-forming silicone emulsion composition. The results are shown in Tables 2 and 6 below.

[0180]

[0181] [Comparative Example 1] 44.79 parts of (A-1-1) branched organopolysiloxane represented by the general formula (21) (in the general formula (21), w=3, x=400, y=1, z=0) and 5.21 parts of (A-2-1) organopolysiloxane represented by the formula (22) having a viscosity of 700 mPa·s and silanol groups at the end of the molecular chain, and (B-1) Neoperex G-65 (manufactured by Kao Corporation: alkylbenzene) 3.02 parts of a 65% aqueous solution of sodium sulfonate, 0.21 parts of (B-2) Emulgen 104P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), 0.62 parts of (B-3) Emulgen 123P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), and 1.15 parts of (C-1) water were emulsified by homodisperser (the water in component (B) also acts as component (C-1)). 40.77 parts of (C-2) water were added to the obtained emulsion and diluted and dispersed using a homomixer. Next, 3.48 parts of (F-1) 20% aqueous solution of dodecylbenzenesulfonic acid were added, and emulsion polymerization was carried out at 10°C for 16 hours. After that, 0.70 parts of 20% aqueous solution of sodium carbonate were added to the obtained emulsion and diluted and dispersed using a homomixer to obtain the emulsion of component (A). The viscosity of component (A) in the obtained emulsion at 25°C, when dissolved in 15% by mass of toluene, was 4800 mPa·s. The results are shown in Tables 3 and 7 below.

[0182] [Comparative Example 2] 28.88 parts of an alkenyl group-containing organopolysiloxane represented by the following general formula (24), 12.40 parts of a linear diorganohydrogenpolysiloxane having hydrosilyl groups only at both ends of the molecular chain, represented by the following general formula (25), and 8.72 parts of an organohydrogenpolysiloxane having four hydrosilyl groups per molecule, represented by the following general formula (26), were emulsified by homodisperser with (B-1) Neoperex G-65 (manufactured by Kao Corporation: 65% aqueous solution of alkylbenzene sulfonate), (B-2) Emulgen 104P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), (B-3) Emulgen 123P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), and (C-1) water, 1.15 parts. 44.96 parts of water were added to the obtained emulsion and diluted and dispersed using a homomixer. This emulsion was transferred to a glass flask equipped with an anchor-shaped stirring device, and after being heated to 20-25°C, a mixed solution of 0.02 parts of isododecane solution of a platinum-vinyl group-containing disiloxane complex (platinum content 0.5%) and 0.02 parts of polyoxyethylene lauryl ether (ethylene oxide addition moles = 9 moles) was added under stirring, and the mixture was stirred at the same temperature for 12 hours to obtain an emulsion of silethylene bond-containing organopolysiloxane. 23 parts of (D) colloidal silica (manufactured by Nissan Chemical Corporation: active ingredient 20%) were added to 74.2 parts of this emulsion and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 3 and 7 below.

[0183]

[0184] [Comparative Example 3] A rubber film-forming silicone emulsion composition was obtained by adding 26 parts of a pre-prepared mixture II to 74.2 parts of the silethylene bond-containing organopolysiloxane emulsion obtained in Comparative Example 2 and dispersing it by paddle stirring. The results are shown in Tables 3 and 7 below.

[0185] [Comparative Example 4] A mixture of 50 parts octamethylcyclotetrasiloxane and 0.18 parts triethoxyphenylsilane was mixed with an aqueous solution of 0.50 parts (B-4) sodium dodecylbenzenesulfonate diluted with 4.5 parts of water and an aqueous solution of 0.50 parts (B-5) dodecylbenzenesulfonic acid diluted with 4.5 parts of water, and the mixture was emulsified using a homomixer. Then, 39.82 parts of water was added and the mixture was diluted and dispersed using a homomixer, and an emulsion was obtained by high-pressure treatment once at a processing pressure of 100 MPa using a high-pressure emulsifier. The obtained emulsion was stirred at 50°C for 40 hours and at 15°C for 12 hours, neutralized by adding 1.0 part of a 10% sodium carbonate aqueous solution, and then an aqueous solution of 0.50 parts (B-6) sodium lauryl sulfate diluted with 1.5 parts of water was added and stirred to dissolve and obtain an emulsion of component (A) (surfactant (B-5) is an acid catalyst). The viscosity of component (A) in the obtained emulsion at 25°C with 15% by mass of toluene was 1200 mPa·s. To 74.2 parts of this emulsion, 23 parts of colloidal silica (D) manufactured by Nissan Chemical Corporation: Snowtex C, 20% active ingredient), 1.9 parts of a reaction product of maleic anhydride and 3-aminopropyltriethoxysilane (maleic anhydride:3-aminopropyltriethoxysilane = 1:1 (molar ratio)), and 25.8 parts of a mixture of 0.9 parts of 3-glycidoxypropyltriethoxysilane (mixture III) were added and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 4 and 8 below.

[0186] [Comparative Example 5] 44.79 parts of (A-1-1) branched organopolysiloxane (in general formula (21), w=3, x=400, y=1, z=0) represented by the general formula (21), and 5.21 parts of (A-2-1) organopolysiloxane having a viscosity of 700 mPa·s and silanol groups at the end of the molecular chain, and (B-1) Neoperex G-65 (manufactured by Kao Corporation: sodium alkylbenzenesulfonate) 3.02 parts of a 65% aqueous solution of (B-2) Emulgen 104P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), 0.21 parts of (B-3) Emulgen 123P (manufactured by Kao Corporation: polyoxyethylene lauryl ether), and 1.15 parts of (C-1) water were emulsified by homodisperser (the water in component (B) also acts as component (C-1)). 40.77 parts of (C-2) water were added to the obtained emulsion and diluted and dispersed using a homomixer. Next, 3.48 parts of a 20% aqueous solution of (F-1) dodecylbenzenesulfonic acid were added, and emulsion polymerization was carried out at 10°C for 16 hours. After that, 0.70 parts of a 20% aqueous solution of sodium carbonate were added to the obtained emulsion and diluted and dispersed using a homomixer to obtain the emulsion of component (A). The viscosity of component (A) in the obtained emulsion at 25°C with 15% by mass of toluene was 4800 mPa·s. 25.8 parts of the mixed solution III described in Comparative Example 4 were added to 74.2 parts of this emulsion and dispersed by paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Tables 4 and 8 below.

[0187] The physical properties and characteristics of each of the above-mentioned rubber-film-forming silicone emulsions were measured or evaluated according to the methods described below.

[0188] [Emulsion pH] The pH of each emulsion was measured using a pH meter at 25°C.

[0189] [Cyclic Siloxane Content in Emulsions] 0.1 g of each emulsion composition was extracted with 10 mL of acetone containing 20 ppm (by mass) of tetradecane as an internal standard (shaking for 3 hours), then centrifuged, and the upper layer (acetone layer) was collected and the D4, D5, and D6 content was quantified by gas chromatography analysis.

[0190] [Emulsion Stability] 100g of the silicone emulsion composition was placed in a 100ml glass bottle and left at 40°C for 3 months, after which the appearance was observed. If the emulsion formed a uniform single phase with no separation and no change in color, it was evaluated as having good stability and was indicated with a "○". If separation into two phases was observed or a change in color was observed, it was evaluated as having poor stability and was indicated with a "×". In addition, the pH and cyclic siloxane content of each emulsion composition were measured using the method described above after being left at 40°C for 2 months.

[0191] [Average particle size of emulsion] The median diameter of each emulsion was measured using a laser diffraction / scattering particle size distribution analyzer LA-960 (Horiba, Ltd.).

[0192] [15% Toluene Dissolution Viscosity] Organopolysiloxane was extracted by disintegrating the emulsion by adding 40 g of isopropyl alcohol (IPA) to 20 g of the emulsion composition before adding components (D) to (F). The extracted organopolysiloxane was washed twice with 40 g of IPA, and the IPA was completely dried at 105°C. After drying, 7.5 g of organopolysiloxane and 42.5 g of toluene were placed in a 50 ml glass bottle and shaken for 24 hours. The 15% toluene dissolution viscosity was measured at 25°C using a BH-type rotational viscometer.

[0193] [Physical Properties of the Film] 20 g of each emulsion composition was poured into a disposable polypropylene resin tray (150 mm x 105 mm x 10 mm) and dried at 25°C for 48 hours to produce a film with a thickness of approximately 1 mm. The tensile strength (MPa·s), elongation at break (%), and hardness of the obtained film were measured. Tensile strength and elongation at break were measured in accordance with JIS K 6249. Hardness was measured using the rubber hardness tester of the Asker C tester, which is measured in accordance with the Japan Rubber Association Standard (SRIS).

[0194] [Film Formation] The state of the film obtained above was evaluated based on the following evaluation criteria. ○: Forms a uniform film and has sufficient strength to be peeled off the disposable tray. △: Forms a uniform film, but cannot be peeled off the disposable tray. ×: Does not form a uniform film.

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203] According to the manufacturing method of the present invention (Examples 1 to 8), a rubber film-forming silicone emulsion composition can be obtained that provides a film with good stability over time, good durability and flexibility, and has reduced amounts of impurities D4, D5, and D6.

[0204] On the other hand, in Comparative Example 1, where the emulsion of component (A) does not use additives (components (D) and (E)), it can be seen that the film-forming ability and film properties are not satisfactory (Examples 3, 4, and Comparative Example 1). Furthermore, the 15% toluene solubility of the emulsions prepared by addition polymerization in an emulsion system (Comparative Examples 2 and 3) was difficult to measure because the extract did not dissolve in toluene. In addition, in Comparative Example 2, where component (A) of the present invention is different, although the tensile strength is equivalent to or better than that of the film obtained from the emulsion composition of the present invention, it can be seen that the durability is inferior due to the low elongation of the film.

[0205] Furthermore, in Comparative Example 4, a polymer obtained by ring-opening polymerization of a cyclic siloxane oligomer with an acid catalyst was used as component (A) of the present invention, and in Comparative Example 5, the same emulsion composition of component (A) as in Examples 3 and 4 was used, and a rubber film-forming silicone emulsion composition was obtained by adding component (D), the reaction product of an amino group-containing organoalkoxysilane and an acid anhydride, and an epoxy group-containing organoalkoxysilane (mixture III). In Comparative Example 4, the polymerization time was long, it contained a large amount of cyclic siloxane, and yellowing over time and significant by-production of cyclic siloxane were observed. On the other hand, in Examples 1 to 8, it can be seen that good films were formed while suppressing the polymerization time, the reduction in cyclic siloxane content, and changes over time. In Comparative Example 5, yellowing over time and by-production of cyclic siloxane were observed, whereas in Examples 1 to 8, good films were formed while suppressing changes over time.

[0206] The composition of the present invention provides a film with excellent hardness, tensile strength, and elongation, making it useful as a fiber treatment agent, water repellent, coating agent, and binder agent for coating various substrates.

[0207] This specification includes the following aspects: [1]: A rubber film-forming silicone emulsion composition characterized by comprising the following components (A) to (E): (A) Organopolysiloxane represented by the following average composition formula (1), having a 15% by mass toluene solubility viscosity of 200 mPa·s or more at 25°C, and containing at least three alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass, (In the formula, R １ R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. ２(B) Surfactant: 0.1 to 30 parts by mass, (C) Water: 1 to 10,000 parts by mass, (D) Colloidal silica: 0 to 40 parts by mass, (E) Organopolysiloxane represented by the following average composition formula (2): 0.5 to 50 parts by mass. (In the formula, R ３ Each of these is independently a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organic group having 2 to 12 carbon atoms having a radical polymerization functional group, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ４ R is a monovalent group which may contain a heteroatom represented by the following formula (3), ５Each of the following independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; e, f, g, h, and i represent the molar ratio of each siloxane unit, and are numbers satisfying 0 ≤ e ≤ 1, 0 ≤ f < 1, 0 ≤ g ≤ 1, 0 < h ≤ 1, 0 ≤ i < 1, and e + f + g + h + i = 1; and α represents the number of moles of hydroxyl and alkoxy groups bonded to 1 mole of silicon atoms, and is a number satisfying 0 < α < 4. ) *-V-W (3) (In formula (3), * represents a bond with a silicon atom, V is a linear or branched divalent hydrocarbon group having 1 to 40 carbon atoms, which may contain a heteroatom, and W represents an amine or amine salt structure, an amide structure, an epoxy structure, an alcohol structure, a carboxylic acid anhydride structure, a carboxylic acid structure, or a carboxylic acid salt structure.) [2]: The rubber film-forming silicone emulsion composition according to [1], characterized in that in formula (3), W is a carboxylic acid anhydride structure, a carboxylic acid structure, a carboxylic acid salt structure, or an epoxy structure. [3]: The rubber film-forming silicone emulsion composition according to [1] or [2], characterized in that the (B) surfactant includes an anionic surfactant. [4]: ​​The rubber film-forming silicone emulsion composition according to any one of [1] to [3], characterized in that the mass average molecular weight (Mw) of the (E) organopolysiloxane is 500 to 100,000. [5]: The rubber film-forming silicone emulsion composition according to any one of [1] to [4], characterized in that the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the rubber film-forming silicone emulsion composition is less than 0.1% by weight. [6]: The rubber film-forming silicone emulsion composition according to any one of [1] to [5], characterized in that the average particle size of the emulsion particles in the rubber film-forming silicone emulsion composition is 500 nm or less.[7]: A rubber film-forming silicone emulsion composition according to any one of [1] to [6], wherein the dried film has an elongation at break of 300% or more at a thickness of 1 mm as measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or more at a thickness of 1 mm as measured in accordance with JIS K 6251. [8]: A film characterized by being a dried product of the rubber film-forming silicone emulsion composition according to any one of [1] to [7]. [9]: A fiber treatment agent characterized by containing the rubber film-forming silicone emulsion composition according to any one of [1] to [7].

[10] : A water repellent characterized by containing the rubber film-forming silicone emulsion composition according to any one of [1] to [7].

[11] : A method for producing a rubber film-forming silicone emulsion composition, comprising the steps of (i) to (iii) below, and characterized in that water (C) is added so that the total amount of (C-1), (C-2), and (C-3) below is 1 to 10,000 parts by mass, as described in any one of [1] to [7]. (i) A step of obtaining an O / W type emulsion comprising an oil phase component including (A-1) a branched organopolysiloxane represented by the following general formula (4), a mixture of (A-1) and (A-2) below, or a mixture of (A-2) and (A-3) below, (B) a surfactant, and (C-1) water, (A-1): A branched organopolysiloxane represented by the following general formula (4). (In the formula, R ６ These are, independently of each other, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and R ７ (A-2): A linear organopolysiloxane having hydroxyl groups or alkoxy groups at both ends of the molecular chain, represented by the following general formula (5). (In the formula, R ８R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, independently of each other. v is a positive number satisfying 0 ≤ v ≤ 2,000.) (A-3): Alkoxysilane and / or hydrolysis condensates represented by the following general formula (6) R ９ ｊ Si ( OR １０ ) ４－ｊ (6) (Here, R ９ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, independently of each other. １０ (i) (i) (ii) After adding (C-2) water as necessary to the O / W type emulsion composition obtained in step (i) above, polymerize the (A-1) component, a mixture of (A-1) and (A-2) components, or a mixture of (A-2) and (A-3) components in the oil phase component of the O / W type emulsion at 0 to 40°C for 1 to 48 hours in the presence of (F) acid catalyst (however, if (B) surfactant has catalytic activity, the addition of the acid catalyst can be omitted), and neutralize after polymerization to obtain an emulsion of (A) organopolysiloxane, which is a condensation product obtained from the (A-1) component, a mixture of (A-1) and (A-2) components, or a mixture of (A-2) and (A-3) components. (iii) A step of adding (E) organopolysiloxane and, if necessary, (D) colloidal silica and / or (C-3) water to the emulsion of component (A) obtained in step (ii).

[12] : A method for producing a rubber film-forming silicone emulsion composition according to

[11] , characterized in that (A-2) a linear organopolysiloxane represented by the general formula (5) having hydroxyl groups or alkoxy groups at both ends of the molecular chain, has a viscosity of 200 mPa·s or more and less than 2000 mPa·s at 25°C.

[0208] 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 rubber film-forming silicone emulsion composition characterized by containing the following components (A) to (E): (A) Organopolysiloxane represented by the following average composition formula (1), having a 15% by mass toluene solubility of 200 mPa·s or more at 25°C, and containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass, (In the formula, R １ R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. ２ (B) Surfactant: 0.1 to 30 parts by mass, (C) Water: 1 to 10,000 parts by mass, (D) Colloidal silica: 0 to 40 parts by mass, (E) Organopolysiloxane represented by the following average composition formula (2): 0.5 to 50 parts by mass. (In the formula, R ３ Each of these is independently a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organic group having 2 to 12 carbon atoms having a radical polymerization functional group, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R ４ R is a monovalent group which may contain a heteroatom represented by the following formula (3), ５ Each of the following independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; e, f, g, h, and i represent the molar ratio of each siloxane unit, and are numbers satisfying 0 ≤ e ≤ 1, 0 ≤ f < 1, 0 ≤ g ≤ 1, 0 < h ≤ 1, 0 ≤ i < 1, and e + f + g + h + i = 1; α represents the number of moles of hydroxyl and alkoxy groups bonded to 1 mole of silicon atoms, and is a number satisfying 0 < α < 4.) *-V-W (3) (In formula (3), * represents a bond with a silicon atom, V is a linear or branched divalent hydrocarbon group having 1 to 40 carbon atoms, which may contain heteroatoms, and W represents an amine or amine salt structure, an amide structure, an epoxy structure, an alcohol structure, a carboxylic acid anhydride structure, a carboxylic acid structure, or a carboxylate salt structure.) 2. The rubber film-forming silicone emulsion composition according to claim 1, characterized in that W in formula (3) is a carboxylic acid anhydride structure, a carboxylic acid structure, a carboxylate salt structure, or an epoxy structure.

3. The rubber film-forming silicone emulsion composition according to claim 1, characterized in that the (B) surfactant includes an anionic surfactant.

4. The rubber film-forming silicone emulsion composition according to claim 1, characterized in that the mass-average molecular weight (Mw) of the (E) organopolysiloxane is 500 to 100,000.

5. The rubber film-forming silicone emulsion composition according to claim 1, characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the rubber film-forming silicone emulsion composition is less than 0.1% by weight.

6. The rubber film-forming silicone emulsion composition according to claim 1, characterized in that the average particle size of the emulsion particles in the rubber film-forming silicone emulsion composition is 500 nm or less.

7. A rubber film-forming silicone emulsion composition according to any one of claims 1 to 6, wherein the dried film has an elongation at break of 300% or more at a thickness of 1 mm as measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or more at a thickness of 1 mm as measured in accordance with JIS K 6251.

8. A film characterized by being a dried product of the rubber film-forming silicone emulsion composition according to any one of claims 1 to 6.

9. A fiber treatment agent characterized by comprising the rubber film-forming silicone emulsion composition described in any one of claims 1 to 6.

10. A water repellent characterized by comprising the rubber film-forming silicone emulsion composition described in any one of claims 1 to 6.

11. A method for producing a rubber film-forming silicone emulsion composition, comprising the following steps (i) to (iii), and adding the following (C) water so that the total amount of the following (C-1), (C-2) and (C-3) is 1 to 10,000 parts by mass. The method for producing a rubber film-forming silicone emulsion composition according to any one of claims 1 to 6, characterized in that. (i) An oil phase component containing (A-1) a branched organopolysiloxane represented by the following general formula (4), a mixture of (A-1) and the following (A-2), or a mixture of (A-2) and the following (A-3), (B) a surfactant, and (C-1) water, to obtain an O / W type emulsion. (A-1): A branched organopolysiloxane represented by the following general formula (4) (In the formula, R ６ are each independently an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group, and R ７ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. w, x, y, z are positive numbers satisfying w≧3, x≧5, y + z≧1, and 10≦w + x + y + z≦1,000.) (A-2): A linear organopolysiloxane having a hydroxyl group or an alkoxy group at both ends of the molecular chain, represented by the following general formula (5) (In the formula, R ８ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. v is a positive number satisfying 0≦v≦2,000.) (A-3): Any one or both of an alkoxysilane represented by the following general formula (6) and its hydrolysis condensate R ９ ｊ Si(OR １０ ) ４－ｊ (6) (Here, R ９ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R １０ (i) (i) (ii) After adding (C-2) water as necessary to the O / W type emulsion composition obtained in step (i) above, polymerize the (A-1) component, a mixture of (A-1) and (A-2) components, or a mixture of (A-2) and (A-3) components in the oil phase component of the O / W type emulsion at 0 to 40°C for 1 to 48 hours in the presence of (F) acid catalyst (however, if (B) surfactant has catalytic activity, the addition of the acid catalyst can be omitted), and neutralize after polymerization to obtain an emulsion of (A) organopolysiloxane, which is a condensation product obtained from the (A-1) component, a mixture of (A-1) and (A-2) components, or a mixture of (A-2) and (A-3) components. (iii) A step of adding (E) organopolysiloxane and, if necessary, either (D) colloidal silica and (C-3) water, or both, to the emulsion of component (A) obtained in step (iii).

12. (A-2) A method for producing a rubber film-forming silicone emulsion composition according to 11, characterized in that a linear organopolysiloxane represented by the general formula (5) having hydroxyl groups or alkoxy groups at both ends of the molecular chain is used, and has a viscosity of 200 mPa·s or more and less than 2000 mPa·s at 25°C.

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