Silicone emulsion composition for forming rubber film, and method for producing the same

Abstract

To provide a silicone emulsion composition and a method for producing the same, which are capable of forming a film by drying, the film having good stability, durability, and flexibility, and in which the amount of D4, D5, and D6 is reduced.SOLUTION: A silicone emulsion composition for forming a rubber film, comprises the following components (A) to (C) and any of the following components (D) to (F), wherein D4, D5, and D6 in component (A) are less than 0.1 wt.%: (A) an organopolysiloxane represented by formula (1), having a toluene dissolution viscosity of 200 mPa s or more, and containing an alkoxy group or a hydroxy group bonded to three or more silicon atoms in one molecule; (B) a surfactant represented by the general formula R3n-C10H(7-n)-SO3M and having an alkylnaphthalene skeleton; (C) water; (D) colloidal silica; (E) a reaction product of an amino group-containing organoalkoxysilane and an acid anhydride; and (F) an epoxy group-containing organoalkoxysilane and / or a partial hydrolysate thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a rubber film-forming silicone emulsion composition that forms a rubber film upon drying at room temperature or heat treatment and is useful as a water-repellent coating agent or a raw material for coating agents, and to a method for producing the same. [Background technology]

[0002] Emulsion compositions that form rubber films when dried have conventionally been made up of a variety of compositions, and are used as binders for fiber treatment, rubber coating agents, building material coating agents, paper and plastic film coating agents, etc., or as additives thereto, for the purpose of imparting slipperiness, water repellency, flexibility, and releasability. Films formed from high-molecular-weight polymers generally have improved properties compared to films formed from low-molecular-weight polymers, and therefore high-molecular-weight polymers are preferred for 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. Examples of such compositions include emulsion compositions comprising a terminally vinyl-blocked diorganopolysiloxane, an organohydrogenpolysiloxane, and a platinum catalyst, as well as emulsion compositions comprising a terminally or side-vinyl-containing diorganopolysiloxane, a polysiloxane containing silicon-bonded hydrogen atoms, colloidal silica, and a platinum catalyst. However, in these compositions, the coexistence of a hydrosilyl-containing siloxane and a platinum catalyst can cause a reaction to proceed over time or generate hydrogen gas, making it necessary to mix the silicone emulsion with the platinum catalyst before use, which is inconvenient.

[0004] In addition, cyclic siloxane oligomers can be emulsified and then subjected to ring-opening polymerization with a strong acid or strong base. A method of polymerizing a polymer having a condensable reactive group such as an alkoxy group at the molecular chain end is also known, and this method can produce a polymer with a high degree of polymerization. However, this method requires a long polymerization process, which increases the production cost.

[0005] Additionally, in recent years, there has been a growing demand for products with reduced contents 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-produced during the emulsion polymerization process.

[0006] Patent Document 1, for example, describes a method for obtaining a high molecular weight polymer with reduced by-production of D4 by addition polymerization in an emulsion system. According to this method, an organohydrogenpolysiloxane having three or more hydrosilyl groups per molecule is subjected to an addition reaction in an emulsion system with a linear diorganohydrogenpolysiloxane having hydrosilyl groups only at both ends of the molecular chain. Because this is an addition reaction, no cyclic siloxane oligomers such as D4, D5, or D6 are by-produced. However, the coating derived from this emulsion contains silethylene bonds, which results in lower elongation (durability) than a coating composed solely of siloxane bonds. Patent Document 2 also describes a method for condensation polymerization of a linear organopolysiloxane and a branched organopolysiloxane in an emulsion system. Because it is a condensation reaction, the by-production of cyclic siloxane oligomers such as D4, D5, and D6 is small, but polymers with a high degree of polymerization are not obtained, and there is a problem in that a film cannot be formed from the emulsion. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent Publication No. 2021-107487 [Patent Document 2] JP 2017-48342 A Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above circumstances, and its object is to provide a rubber film-forming silicone emulsion composition that can form a film upon drying, has good stability over time, gives a film that is durable and flexible, and has reduced amounts of the impurities D4, D5, and D6, as well as a method for producing the same. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention provides a rubber film-forming silicone emulsion composition that contains the following components (A) to (C) and also contains one or more of the following components (D) to (F): The rubber film-forming silicone emulsion composition is characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in component (A) is less than 0.1% by weight. (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula (1), which has a 15% by mass toluene solution viscosity at 25°C of 200 mPa·s or more and contains at least three alkoxy groups or hydroxy groups (hydroxyl groups) bonded to silicon atoms per molecule: [ka] (In the formula, R 1 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 hydroxy group, and R 2 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a, b, c, and d are numbers such that the viscosity of the organopolysiloxane in a 15% by mass toluene solution at 25°C is 200 mPa s or greater, and a ≥ 3 and c + d ≥ 1. (B) a surfactant having an alkylnaphthalene skeleton represented by the following general formula (2): 0.1 to 30 parts by mass R 3 n -C 10 H (7-n) -SO3M-(2) (In the formula, R 3 is a linear or branched alkyl group having 1 to 30 carbon atoms, and M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or a tertiary ammonium ion. n is an integer of 1 to 3. (C) Water: 1~10000 parts by mass (D) Colloidal silica: 0 to 40 parts by mass (E) Reaction product of amino group-containing organoalkoxysilane and acid anhydride: 0 to 10 parts by mass (F) Epoxy group-containing organoalkoxysilane and / or partial hydrolyzate thereof: 0 to 10 parts by mass

[0010] Such a rubber film-forming silicone emulsion composition is capable of forming a film upon drying, has good stability over time, and is a low-impurity composition capable of providing a film with good durability and flexibility.

[0011] Furthermore, in the present invention, the amount of (D) colloidal silica used is preferably 1 to 40 parts by mass.

[0012] When the (D) colloidal silica is used in this manner, the strength (particularly hardness and tensile strength) of the film formed from the emulsion composition can be improved.

[0013] Furthermore, in the present invention, M in the general formula (2) is preferably a sodium ion.

[0014] A rubber film-forming silicone emulsion composition containing a surfactant having such an alkylnaphthalene skeleton provides a favorable emulsification effect.

[0015] Furthermore, in the present invention, it is desirable that the average particle size of the emulsified particles in the rubber film-forming silicone emulsion composition be 500 nm or less.

[0016] Such an average particle size increases the polymerization rate and reduces the amounts of by-products octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6).

[0017] Furthermore, in the present invention, it is desirable that the rubber film-forming silicone emulsion composition be a composition that produces a dried film having an elongation at break of 300% or greater at a thickness of 1 mm, measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or greater at a thickness of 1 mm, measured in accordance with JIS K 6251.

[0018] With such elongation at break and tensile strength, when the rubber film-forming silicone emulsion composition is applied to various substrates, there is no risk of the coating easily coming off the substrate due to friction.

[0019] The present invention also provides a method for producing the rubber film-forming silicone emulsion composition, comprising the steps (I) to (III) below, wherein 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: (I) a step of obtaining an O / W emulsion containing an oil phase component comprising a branched organopolysiloxane (A-1) represented by the following general formula (3), a mixture of the (A-1) and a linear organopolysiloxane (A-2) having hydroxy groups or alkoxy groups at both molecular chain terminals represented by the following general formula (4), or a mixture of the (A-2) and an alkoxysilane represented by the following general formula (5) and / or a hydrolysis condensate thereof (A-3), the surfactant (B), and water (C-1); (A-1) A branched organopolysiloxane represented by the following general formula (3): [ka] (In the formula, R 4 are each independently an alkoxy group having 1 to 20 carbon atoms, and R 5 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. w, x, y, and z are numbers that satisfy w≧3, x≧5, y+z≧1, and 10≦w+x+y+z≦1000. (A-2) A linear organopolysiloxane having hydroxy or alkoxy groups at both molecular chain terminals, represented by the following general formula (4): [ka] (In the formula, R 6 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and v is a number satisfying the relationship 0≦v≦2000. (A-3) Alkoxysilane represented by the following formula (5) and / or its hydrolysis condensate R 7 e Si(OR 8 ) 4-e -(5) (where R 7 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 8 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 0 or 1. (II) A step of further adding water (C-2) to the emulsion composition obtained in step (I) as necessary, and then polymerizing the component (A-1), a mixture of the components (A-1) and (A-2), or a mixture of the components (A-2) and (A-3) in the oil phase components of the emulsion in the presence of an acid catalyst (G) (however, if the surfactant (B) has catalytic activity, the addition of the acid catalyst can be omitted) at 0 to 40°C for 1 to 48 hours, followed by neutralization after polymerization to obtain an emulsion of organopolysiloxane (A), which is a condensation reaction product obtained from the component (A-1), a mixture of the components (A-1) and (A-2), or a mixture of the components (A-2) and (A-3). (III) a step of adding at least one of the (D) colloidal silica, the (E) reaction product of an amino group-containing organoalkoxysilane with an acid anhydride, and the (F) epoxy group-containing organoalkoxysilane and / or a partial hydrolyzate thereof, and optionally water (C-3), to the emulsion of component (A) obtained in step (II).

[0020] This production method allows the formation of a rubber film-forming silicone emulsion composition that can form a film upon drying, has good stability over time, and provides a film that is durable and flexible, and further has reduced amounts of D4, D5, and D6 contained as impurities.

[0021] Furthermore, in the present invention, the viscosity of the linear organopolysiloxane (A-2) represented by general formula (4) having hydroxy or alkoxy groups at both molecular chain terminals at 25°C is desirably 200 mPa·s or more and less than 2000 mPa·s. The viscosity of component (A-2) at 25°C can be measured, for example, using a rotational viscometer.

[0022] Such a viscosity makes it easy to prepare an emulsion.

[0023] The present invention also provides a film that is a dried product of the rubber film-forming silicone emulsion composition.

[0024] Such a coating has good durability and flexibility, and furthermore, the amounts of D4, D5, and D6 contained as impurities are reduced.

[0025] Furthermore, in the present invention, it is desirable that the coating have an elongation at break of 300% or more at a thickness of 1 mm, measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or more at a thickness of 1 mm, measured in accordance with JIS K 6251.

[0026] Such a coating will have good durability and flexibility.

[0027] The present invention also provides a fiber treatment agent that contains the rubber film-forming silicone emulsion composition described above.

[0028] Such a fiber treatment agent has good stability over time, good durability and flexibility, and further has reduced amounts of D4, D5, and D6 contained as impurities.

[0029] Furthermore, the present invention provides a water repellent agent characterized by containing the rubber film-forming silicone emulsion composition described above.

[0030] Such a water repellent agent has good stability over time, good durability and flexibility, and further has reduced amounts of D4, D5 and D6 contained as impurities. [Effects of the Invention]

[0031] As described above, the rubber film-forming silicone emulsion composition provided by the present invention can provide films with excellent durability and flexibility, and because the amounts of D4, D5, and D6 contained as impurities are reduced, there are no concerns about their impact on the environment. DETAILED DESCRIPTION OF THE INVENTION

[0032] As described above, there has been a need for the development of a rubber film-forming silicone emulsion composition that can form a film upon drying, has good stability over time, gives a film that is durable and flexible, and has reduced amounts of the impurities D4, D5, and D6, as well as a method for producing the same.

[0033]

[0006] As a result of extensive research conducted by the present inventors to achieve the above object, they have discovered that by condensation polymerizing a silicone emulsion containing a branched organopolysiloxane having alkoxy groups at its molecular terminals, or a mixture of a branched organopolysiloxane having alkoxy groups at its molecular terminals and a linear organopolysiloxane having hydroxy or alkoxy groups at both molecular terminals, or a mixture of a linear organopolysiloxane having hydroxy or alkoxy groups at both molecular terminals and an alkoxysilane in the presence of a polymerization catalyst, and then adding one or more of the following components: colloidal silica, or a reaction product of an amino-containing organoalkoxysilane and an acid anhydride, or an epoxy-containing organoalkoxysilane and / or a partial hydrolyzate thereof, it is possible to form a rubber film with excellent adhesion to substrates in a short period of time, and further to obtain a silicone emulsion composition with reduced amounts of D4, D5, and D6 contained as impurities, thereby completing the present invention.

[0034] That is, the present invention provides a rubber film-forming silicone emulsion composition that contains the following components (A) to (C) and also contains one or more of the following components (D) to (F): This relates to a rubber film-forming silicone emulsion composition characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in component (A) is less than 0.1% by weight. (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula (1), which has a 15% by mass toluene solution viscosity at 25°C of 200 mPa·s or more and contains at least three alkoxy groups or hydroxy groups bonded to silicon atoms per molecule: [ka] (In the formula, R 1 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 hydroxy group, and R 2 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a, b, c, and d are numbers such that the viscosity of the organopolysiloxane in a 15% by mass toluene solution at 25°C is 200 mPa s or greater, and a ≥ 3 and c + d ≥ 1. (B) a surfactant having an alkylnaphthalene skeleton represented by the following general formula (2): 0.1 to 30 parts by mass R 3 n -C 10 H (7-n) -SO3M-(2) (In the formula, R 3 is a linear or branched alkyl group having 1 to 30 carbon atoms, and M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or a tertiary ammonium ion. n is an integer of 1 to 3. (C) Water: 1~10000 parts by mass (D) Colloidal silica: 0 to 40 parts by mass (E) Reaction product of amino group-containing organoalkoxysilane and acid anhydride: 0 to 10 parts by mass (F) Epoxy group-containing organoalkoxysilane and / or partial hydrolyzate thereof: 0 to 10 parts by mass

[0035] The present invention will be described in more detail below, but the present invention is not limited thereto.

[0036] [(A) Organopolysiloxane] Component (A) is an organopolysiloxane that has a 15% by mass toluene solution viscosity of 200 mPa·s or greater at 25°C and contains at least three alkoxy or hydroxy groups bonded to silicon atoms per molecule, and is represented by the following average composition formula (1): [ka] (In the formula, R 1 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 hydroxy group, and R 2 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a, b, c, and d are numbers such that the viscosity of the organopolysiloxane in a 15% by mass toluene solution at 25°C is 200 mPa s or greater, and a ≥ 3 and c + d ≥ 1. The emulsion composition of the present invention contains 100 parts by mass of this component (A).

[0037] In the above formula (1), R 1 R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxy group, which may be linear, branched, or cyclic. Specific examples thereof include, in addition to a hydroxy group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, a tetradecyloxy group, or a group in which some or all of the hydrogen atoms bonded to these groups have been substituted with a halogen atom, an amino group, a cyano group, or the like. 1 Among these, methyl, hydroxy, methoxy and ethoxy groups are preferred, but the alkyl group is set so that one molecule contains at least three alkoxy or hydroxy groups bonded to silicon atoms.

[0038] R 2are each 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. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl; and aryl groups such as phenyl, tolyl, and naphthyl. 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 have been substituted with halogen atoms, amino groups, acryloxy groups, methacryloxy groups, epoxy groups, mercapto groups, carboxyl groups, hydroxyl groups, etc. Preferred are monovalent hydrocarbon groups having 1 to 6 carbon atoms, such as methyl groups, ethyl groups, propyl groups, butyl groups, and phenyl groups. 2 More preferably, 80% or more of the groups are methyl groups.

[0039] In composition formula (1), a, b, c, and d are numbers that satisfy the requirement that the organopolysiloxane have a 15% by weight toluene solution viscosity at 25°C of 200 mPa·s or greater, preferably 500 mPa·s or greater, and more preferably 1000 mPa·s or greater. The 15% by weight toluene solution viscosity at 25°C in the present invention is a value measured using a BH-type rotational viscometer at 25°C. A viscosity less than 200 mPa·s may result in a decrease in the strength of the silicone rubber coating. There is no particular upper limit, but to avoid impairing the elongation of the coating, it can be set to, for example, 20,000 mPa·s. In composition formula (1), a, b, c, and d satisfy the requirements a≧3 and c+d≧1, and b preferably has a ratio of 10 to 1000 relative to the sum of c+d.

[0040] Specific examples of the organopolysiloxane of component (A) in the present invention include, but are not limited to, the average compositional formula below: In the average compositional formula below, f, g, h, i, j, and k are each 1 or greater, and the viscosity of the polyorganosiloxane in a 15% by mass toluene solution at 25°C is a value that satisfies the requirement of 200 mPa s or greater. [ka]

[0041] Component (A) needs to be made into an emulsion. However, component (A) alone is usually a gel-like to rubber-like solid, and it is difficult to obtain a stable emulsion. Therefore, it is desirable to produce the emulsion by the emulsion polymerization method described below.

[0042] The content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the organopolysiloxane of component (A) is less than 0.1% by mass, preferably 0.08% by mass or less, and more preferably 0.05% by mass or less. There is no particular lower limit, and it may be 0% by mass. The amount of (A) can be 10 to 90 parts by mass, preferably 15 to 80 parts by mass, and more preferably 20 to 70 parts by mass, relative to 100 parts by mass of the total composition.

[0043] [(B) Surfactant] The component (B) is a surfactant represented by the following general formula (2) and has an alkylnaphthalene skeleton, and these can be used alone or in combination of two or more. R 3 n -C 10 H (7-n) -SO3M-(2) That is [ka] (In the formula, R 3is a linear or branched alkyl group having 1 to 30 carbon atoms, and M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or a tertiary ammonium ion. n is an integer of 1 to 3.

[0044] In general formula (2), R 3 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and is not particularly limited, but from the viewpoint of emulsifying effect, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, or an isopropyl group is preferred. From the viewpoint of emulsifying effect, M is preferably a sodium ion, a potassium ion, an ammonium ion, or a triethanolammonium ion, and a sodium ion is particularly preferred. When M is a hydrogen ion, component (B) has a catalytic action, and therefore the amount of acid catalyst (G) used, which will be described later, can be reduced.

[0045] Specific examples of surfactants having an alkylnaphthalene skeleton represented by general formula (2) include butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, tetradecylnaphthalenesulfonic acid, hexadecylnaphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, bisisopropylnaphthalene acid, trisisopropylnaphthalene acid, and salts thereof.

[0046] 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 it is less than 0.1 part by mass, a stable emulsion will not be obtained, and if it is more than 30 parts by mass, the resulting film will be brittle and lacking in elongation. Alternatively, the amount can be 0.05 to 20 parts by mass, preferably 1 to 10 parts by mass, and more preferably 1.5 to 5 parts by mass, per 100 parts by mass of the total composition.

[0047] In the present invention, by using a surfactant containing a surfactant having an alkylnaphthalene skeleton represented by general formula (2) as component (B), the emulsion particles obtained in step (I) described below can be easily reduced in size, the polymerization rate can be increased, and the amounts of the by-products octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) can be significantly reduced.

[0048] The rubber film-forming silicone emulsion composition of the present invention may optionally contain a surfactant in addition to component (B). When using other surfactants, anionic or nonionic surfactants are preferred, with anionic surfactants being particularly preferred. These can be used alone or in combination of two or more. When other surfactants are added, they are preferably added so that the total amount of component (B) and other surfactants is 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A). Furthermore, to suppress the amount of by-products D4 to D6, it is preferable that component (B) account for 30 parts by mass or more per 100 parts by mass of the total amount of surfactants.

[0049] Examples of anionic surfactants include alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkanesulfonates, N-acyltaurate salts, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinate salts, fatty acid salts, polyoxyethylene alkyl ether carboxylate salts, N-acylamino acid salts, monoalkyl phosphate salts, dialkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate salts, and the like. These surfactants can be used singly or in combination of two or more, as appropriate.

[0050] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes, and polyoxyethylene polyoxypropylene-modified organopolysiloxanes. These can be used alone or in combination of two or more, as appropriate.

[0051] [(C)Water] Water, component (C), is the dispersion medium for organopolysiloxane, component (A), colloidal silica, component (D), the reaction product of amino-containing organoalkoxysilane and acid anhydride, component (E), and epoxy-containing organoalkoxysilane and / or its partial hydrolyzate, component (F).

[0052] The amount of component (C) blended is 1 to 10,000 parts by weight, preferably 60 to 500 parts by weight, per 100 parts by weight of component (A). More than 10,000 parts by weight results in a low concentration of film-forming components, making it uneconomical. Less than 1 part by weight increases the viscosity of the aqueous silicone dispersion, making it difficult to manufacture and handle. The amount can be 5 to 95 parts by weight, preferably 10 to 90 parts by weight, and more preferably 20 to 90 parts by weight, per 100 parts by weight of the total composition.

[0053] [(D) Colloidal silica] The colloidal silica (component (D)) is added as a film reinforcing agent and can significantly improve the strength (particularly hardness and tensile strength) of the film formed from the emulsion composition. The colloidal silica particle surface may be treated with a metal oxide, and it is preferably formulated as a silica sol (aqueous colloidal silica dispersion) 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 also not particularly limited, and may be, for example, 10 to 60% by mass. Commercially available colloidal silica can be used without any restrictions on type, but examples include those with a particle size of 5 to 50 nm stabilized with sodium, ammonium, or aluminum. Specific examples include Snowtex (manufactured by Nissan Chemical Industries, Ltd.), Ludox (manufactured by Grace Chemicals Co., Ltd.), Silicadol (manufactured by Nippon Chemical Industry Co., Ltd.), and Cataloid (manufactured by JGC Catalysts and Chemicals Co., Ltd.).

[0054] The blending amount of component (D) is 0 to 40 parts by mass per 100 parts by mass of component (A). If it is more than 40 parts by mass, the silicone coating may become hard and brittle, and the durability of the water repellency may decrease. The blending amount of component (D) is preferably 1 to 40 parts by mass, even more preferably 5 to 30 parts by mass, and even more preferably 10 to 20 parts by mass. Furthermore, per 100 parts by mass of the total composition, it can be 0 to 30 parts by mass, preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass.

[0055] [(E) Reaction product of amino group-containing organoalkoxysilane and acid anhydride] The reaction product of component (E), an amino-containing organoalkoxysilane and acid anhydride, is a product of the reaction of an amino-containing alkoxysilane with a dicarboxylic acid anhydride. It is a component that improves adhesion between the silicone coating and the substrate, and also functions slightly as a catalyst for crosslinking and curing the components of the composition of the present invention through a condensation reaction. Component (E) is preferably formulated as a solution diluted with a reaction solvent, as described below. The solution concentration of component (E) is not particularly limited, and may be, for example, approximately 10 to 80% by mass. The amino-containing alkoxysilane used as the raw material is represented by the following general formula (6), and specific examples include the following: X(R 9 )3Si -(6) (In the formula, R 9 is an 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 at least one of them is an alkoxy group.

[0056] In formula (6), X is the formula -R 10 (NHR 10 ) e NHR 11 (wherein R 10 are the same or different divalent hydrocarbon groups having 1 to 6 carbon atoms, R 11 is R 9 or a hydrogen atom, and e is an integer of 0 to 6). Specific examples of X include N-2-(aminoethyl)-3-aminopropyl, 3-aminopropyl, and N-phenyl-3-aminopropyl, and among these, N-2-(aminoethyl)-3-aminopropyl and 3-aminopropyl are preferred.

[0057] In formula (6), R 9 is an 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, R 1 and the like, but at least one of them is an alkoxy group. 9 Among these, a methyl group, a methoxy group, and an ethoxy group are preferred.

[0058] Specific examples of the amino group-containing alkoxysilane of the present invention include, but are not limited to, the following: (C2H5O)3SiC3H6NH2, (C2H5O)2(CH3)SiC3H6NH2, (CH3O)3SiC3H6NH2, (CH3O)2(CH3)SiC3H6NH2, (CH3O)3SiC3H6NHC2H4NH2, (CH3O)2(CH3)SiC3H6NHC2H4NH2

[0059] Examples of dicarboxylic acid anhydrides to be reacted with the amino group-containing alkoxysilane include maleic anhydride, phthalic anhydride, succinic anhydride, methylsuccinic anhydride, glutaric anhydride, itaconic anhydride, etc. Among these, maleic anhydride is preferred.

[0060] The reaction between the amino group-containing organoalkoxysilane and the acid anhydride is preferably carried out in a ratio of the amino group to the acid anhydride (molar ratio) of 0.5 to 2, preferably 0.55 to 1.8, and more preferably 0.6 to 1.5. The reaction can be easily carried out by mixing the components in a hydrophilic organic solvent at room temperature or under heating, if necessary. Examples of hydrophilic organic solvents include alcohols such as methanol, ethanol, isopropanol, and butanol; ketones such as acetone and methyl ethyl ketone; acetonitrile; and tetrahydrofuran. The reaction temperature is preferably 0 to 100°C, particularly 5 to 80°C, and the reaction time is usually 0.5 to 40 hours, particularly 1 to 24 hours.

[0061] The amount of component (E) blended is 0 to 10 parts by mass, preferably 2 to 7 parts by mass, and more preferably 2.5 to 6 parts by mass, per 100 parts by mass of component (A). If it is more than 10 parts by mass, the stability of the emulsion composition decreases and it becomes impossible to store for a long period of time. Furthermore, the amount can be 0 to 5 parts by mass, preferably 0.1 to 4 parts by mass, and more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the total composition.

[0062] [(F) Epoxy group-containing organoalkoxysilane and / or partial hydrolyzate thereof] Component (F), an epoxy-containing organoalkoxysilane and / or its partial hydrolyzate, is a component that improves adhesion between the silicone coating and the substrate. Specific examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethoxymethylsilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyldimethoxymethylsilane.

[0063] The amount of component (F) blended is 0 to 10 parts by mass per 100 parts by mass of component (A). If it is more than 10 parts by mass, the coating will be hard and brittle, and the durability of water repellency will decrease. It is preferably 0 to 7 parts by mass, more preferably 0 to 6 parts by mass, and when blended, it is preferably 1 part by mass or more to effectively exert its effects. It can also be 0 to 5 parts by mass, preferably 0.1 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass per 100 parts by mass of the total composition.

[0064] The rubber film-forming silicone emulsion composition of the present invention may contain a catalyst for accelerating the condensation reaction, 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 added may be 0.001 to 1 part by mass per 100 parts by mass of component (A).

[0065] The rubber film-forming silicone emulsion composition of the present invention may also contain inorganic powders, pigments, dyes, thickeners, preservatives, antibacterial agents, deodorants, rust inhibitors, antioxidants, antifoaming agents, antistatic agents, UV absorbers, antifreeze agents, water-soluble resins, organic resin emulsions, and the like.

[0066] The emulsion composition of the present invention has almost no change in the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) after storage at 25°C for 6 months from the time of production, and each content is less than 0.1% by mass. Preferably, each content is less than 0.09% by mass, more preferably less than 0.08% by mass. There is no lower limit for each content, but it can be set to, for example, 0.005% by mass.

[0067] The emulsion composition of the present invention has film-forming properties. There are no particular limitations on the method for producing the film, but by removing water from the emulsion composition, the organopolysiloxane in the emulsion composition aggregates to form a uniform film. There are no particular limitations on the method for removing water, but for example, water may be removed in a short time at 100°C or higher, or water may be removed gradually at 25°C.

[0068] For example, the coating is formed by weighing out the emulsion composition so that the nonvolatile content is 8.0 g and placing it on a 15 cm x 10 cm PP (polypropylene) tray, drying it at 25°C for 48 hours, and then drying it further for 1 hour at 105°C. The hardness, tensile strength, and elongation of the coating prepared as above are measured in accordance with JIS K6249 to evaluate the physical properties of the coating.

[0069] [Method for producing rubber film-forming silicone emulsion composition] Next, the method for producing the rubber film-forming silicone emulsion composition of the present invention is carried out in the following steps: A method for producing a rubber film-forming silicone emulsion composition, comprising the steps (I) to (III) below, and adding water (C) so that the total amount of (C-1), (C-2), and (C-3) below is 1 to 10,000 parts by mass. (I) A step of obtaining an O / W emulsion containing an oil phase component comprising a branched organopolysiloxane (A-1) represented by the following general formula (3), a mixture of the (A-1) and a linear organopolysiloxane (A-2) having hydroxy or alkoxy groups at both molecular chain terminals represented by the following general formula (4), or a mixture of the (A-2) and an alkoxysilane represented by the following general formula (5) and / or its hydrolysis condensate (A-3), the surfactant (B), and water (C-1). (A-1) A branched organopolysiloxane represented by the following general formula (3): [ka] (In the formula, R 4 are each independently an alkoxy group having 1 to 20 carbon atoms, and R 5 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. w, x, y, and z are numbers that satisfy w≧3, x≧5, y+z≧1, and 10≦w+x+y+z≦1000. (A-2) A linear organopolysiloxane having hydroxy or alkoxy groups at both molecular chain terminals, represented by the following general formula (4): [ka] (In the formula, R 6 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and v is a number satisfying the relationship 0≦v≦2000. (A-3) Alkoxysilane represented by the following formula (5) and / or its hydrolysis condensate R 7 e Si(OR 8 ) 4-e -(5) (where R 7are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 8 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 0 or 1. (II) A step of further adding water (C-2) to the emulsion composition obtained in step (I) as necessary, and then polymerizing the component (A-1), a mixture of the components (A-1) and (A-2), or a mixture of the components (A-2) and (A-3) in the oil phase components of the emulsion in the presence of an acid catalyst (G) (however, if the surfactant (B) has catalytic activity, the addition of the acid catalyst can be omitted) at 0 to 40°C for 1 to 48 hours, followed by neutralization after polymerization to obtain an emulsion of organopolysiloxane (A), which is a condensation reaction product obtained from the component (A-1), a mixture of the components (A-1) and (A-2), or a mixture of the components (A-2) and (A-3). (III) A step of adding at least one of the (D) colloidal silica, the (E) reaction product of an amino group-containing organoalkoxysilane and an acid anhydride, and the (F) epoxy group-containing organoalkoxysilane and / or a partial hydrolyzate thereof, and optionally water (C-3), to the emulsion of component (A) obtained in step (II).

[0070] [(A-1) Branched organopolysiloxane] Component (A-1) is a branched organopolysiloxane represented by the general formula (3) above, which has a 15% by mass toluene solution viscosity of 200 mPa s or greater at 25°C and serves as a raw material for organopolysiloxane (A), which contains at least three alkoxy or hydroxy groups bonded to silicon atoms per molecule.

[0071] R in general formula (3) 4are each independently an alkoxy group having 1 to 20 carbon atoms, and the alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specific examples include a methoxy group, an ethoxy group, a propanoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, and a 2-ethylhexyloxy group. A methoxy group, an ethoxy group, a propanoxy group, a butoxy group, and a pentyloxy group are preferred, and a methoxy group, an ethoxy group, and a propanoxy group are more preferred.

[0072] R 5 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically R 2 The same examples are given as above, but R 5 It is desirable from an industrial and property standpoint that 80% or more of the groups be methyl groups.

[0073] In formula (3), w, x, y, and z are numbers that satisfy w≧3, x≧5, y+z≧1, and 10≦w+x+y+z≦1000. Preferably, w, x, y, and z satisfy 3≦w≦50, 10≦x≦900, 1≦y≦20, and 0≦z≦10, respectively.

[0074] Specific structures of component (A-1) of the present invention include, but are not limited to, those shown below, where Me, Et, and Ph represent methyl, ethyl, and phenyl groups, respectively. [ka] (In the formula, e, f, g, h, i, and j are each 1 or more, and are numbers that satisfy the ranges of w, x, y, and z in the formula (3).)

[0075] The component (A-1) may contain octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in an amount of 0.1% by mass or less. Preferably, each amount is less than 0.07% by mass, more preferably less than 0.06% by mass. There is no lower limit to the amount of each component, but it can be set to, for example, 0.001% by mass.

[0076] In the method for producing an 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. Each content is preferably less than 0.09% by mass, more preferably less than 0.08% by mass. There is no lower limit for each content, but it can be, for example, 0.005% by mass.

[0077] [(A-2) Linear organopolysiloxane having hydroxy or alkoxy groups at both molecular chain terminals] Component (A-2) is a linear organopolysiloxane represented by general formula (4) having hydroxy or alkoxy groups at both molecular chain terminals, and is the raw material for organopolysiloxane (A), which contains at least three alkoxy or hydroxy groups bonded to silicon atoms per molecule. [ka] (In the formula, R 6 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and v is a number satisfying the relationship 0≦v≦2000.

[0078] In formula (4), R 6 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and specifically, R 2 The same examples are given as above, but R 6 It is desirable from an industrial and property standpoint that 50% or more of the R at the molecular chain terminal in formula (4) be methyl groups. 6is preferably a hydrogen atom from the viewpoint of reactivity.

[0079] In formula (4), v can typically take a value of 0 to 2000. Preferably, 10≦v≦1500, and particularly preferably, 20≦v≦1000.

[0080] There are no particular restrictions on the viscosity of component (A-2), but it is preferably 200 mPa·s or more but less than 2000 mPa·s, more preferably 300 mPa·s or more but less than 1800 mPa·s, and particularly preferably 500 to less than 1600 mPa·s, as measured at 25°C using a BH-type rotational viscometer. If the viscosity is less than 200 mPa·s, it may be difficult to prepare the emulsion described below.

[0081] Specific examples of the component (A-2) include, but are not limited to, the average composition formula shown below: In the general formula shown below, p, q+r, and q+r+s can typically take values ​​of 1 to 2000. [ka]

[0082] Component (A-2) undergoes a condensation reaction with component (A-1) or component (A-3) to produce an organopolysiloxane (A) having a 15% by mass toluene solution viscosity at 25°C of 200 mPa·s or greater and containing at least three alkoxy or hydroxy groups bonded to silicon atoms per molecule. When used in combination with component (A-1), the amount of component (A-2) used is preferably 0.1 to 99.9 parts by mass, and more preferably 1 to 99 parts by mass, per 100 parts by mass of components (A-1) and (A-2) combined. 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 most preferably 95 to 99.9 parts by mass, per 100 parts by mass of components (A-2) and (A-3) combined. When the amount of component (A-2) is within the above range, the resulting film will have sufficient strength and flexibility.

[0083] [(A-3) Alkoxysilane represented by the following formula (5) and / or its hydrolysis condensate] Component (A-3) is an alkoxysilane represented by formula (5) below and / or a hydrolysis condensate thereof, which serves as a raw material for organopolysiloxane component (A), which has a 15% by mass toluene solution viscosity of 200 mPa s or greater at 25°C and contains at least three alkoxy groups or hydroxy groups bonded to silicon atoms per molecule. R 7 e Si(OR 8 ) 4-e -(5) (where R 7 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 8 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 0 or 1.

[0084] In formula (5), R 7 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group 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, and organic groups in which some of the hydrogen atoms in the organic group structure have been substituted with halogen atoms or organic groups containing polar groups such as amino, acryloxy, methacryloxy, epoxy, and mercapto. 7 It is desirable from an industrial and property standpoint that 80% or more of the groups be methyl groups.

[0085] R 8 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 8 The monovalent organic group having 1 to 20 carbon atoms is the above-mentioned R 7and a methyl group, an ethyl group, a propyl group, or a butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0086] Specific examples of the component (A-3) 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, and 3- Examples of the silane 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-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatopropyltriethoxysilane.

[0087] Component (A-3) undergoes a condensation reaction with component (A-2) to produce component (A), an organopolysiloxane having a 15% by mass toluene solution viscosity of 200 mPa·s or greater at 25°C and containing at least three alkoxy or hydroxy groups bonded to silicon atoms per 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 components (A-2) and (A-3) combined. When the amount of component (A-2) is within the above range, the resulting coating has good flexibility.

[0088] [(C-1), (C-2), (C-3) water] Components (C-1), (C-2), and (C-3) refer to the water used in step (I) and, if necessary, steps (II) and (III). The total amount of water used in component (C) is the sum of the amounts of components (C-1), (C-2), and (C-3). These components are added so that the total amount is 1 to 10,000 parts by mass.

[0089] [(G) Acid catalyst] Component (G) is an acid catalyst and serves as a reaction catalyst for component (A-1), a mixture of components (A-1) and (A-2), or a mixture of components (A-2) and (A-3). When component (B) has catalytic activity, component (G) may not be necessary. When component (G) is used, it can be used alone or in combination with two or more types. Component (G) may be formulated as an aqueous solution.

[0090] Examples of the component (G) include the following components. [(G-1) Alkyl sulfuric acid represented by the following general formula (7), alkylbenzenesulfonic acid represented by the following general formula (8)] R 12 OSO3H-(7) (In the formula, R 12 is a straight-chain or branched alkyl group having 6 to 30 carbon atoms. R 12 -C6H4-SO3H -(8) (In the formula, R12 is a linear or branched alkyl group having 6 to 30 carbon atoms as defined in general formula (7). In general formulas (7) and (8), R 12 is preferably a linear or branched alkyl group having 6 to 12 carbon atoms.

[0091] Specific examples of the alkyl sulfate represented by the general formula (7) include hexyl sulfate, octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, octadecyl sulfate, and icosyl sulfate.

[0092] Specific examples of alkylbenzenesulfonic acids represented by the general formula (8) include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, and hexadecylbenzenesulfonic acid.

[0093] [(G-2)Higher fatty acid] Specific examples include lauric acid, stearic acid, oleic acid, and linolenic acid.

[0094] [(G-3) Polyoxyethylene alkyl ether sulfate represented by the following general formula (9)] R 12 O(EO) t (PO) u SO3H -(9) (In the formula, R 12 is a linear or branched alkyl group having 6 to 30 carbon atoms as defined in general formula (7). EO represents an ethylene oxide group, and PO represents a propylene oxide group, and their arrangement may be block or random. t and u are independently integers of 0 to 100, with the proviso that t+u>0, particularly 50≧t+u≧1.

[0095] Specific examples of the polyoxyethylene alkyl ether sulfate represented by general formula (9) 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 eicosyl ether sulfate.

[0096] [(G-4) Polyoxyethylene alkylphenyl ether sulfate represented by the following general formula (10)] R 12 -C6H4-O(EO) t (PO) u SO3H -(10) (In the formula, R 12 is a linear or branched alkyl group having 6 to 30 carbon atoms as defined in general formula (7). EO, PO, t, and u are as defined in general formula (9), where EO represents an ethylene oxide group and PO represents a propylene oxide group, and their arrangement may be block or random. t and u are independently integers of 0 to 100, with the proviso that t+u>0, particularly 50≧t+u≧1.

[0097] Specific examples of the polyoxyethylene alkyl phenyl ether sulfate represented by general formula (10) include polyoxyethylene hexyl phenyl ether sulfate, polyoxyethylene octyl phenyl ether sulfate, polyoxyethylene decyl phenyl ether sulfate, polyoxyethylene dodecyl phenyl ether sulfate, polyoxyethylene tetradecyl phenyl ether sulfate, and polyoxyethylene hexadecyl phenyl ether sulfate.

[0098] [(G-5) Bronsted acid] Examples of Bronsted acids 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, acidic zeolites, acid-activated filler earth, and acid-activated carbon black.

[0099] The amount of component (G) used (however, if the surfactant in component (B) is an acid and has catalytic properties, it is included in component (B)) should be at least 0.1 part by mass, and preferably 0.2 part by mass or more, per 100 parts by mass of component (A). If the amount is less than 0.1 part by mass, the polymerization rate will be extremely slow. There is no particular upper limit, but an amount of 50 parts by mass or less is preferred from the standpoint of the stability over time of the resulting rubber film-forming silicone emulsion composition.

[0100] The manufacturing method of the present invention will be described below.

[0101] <Process (I)> An emulsion composition is prepared by emulsifying an oil phase component containing a branched organopolysiloxane (A-1) represented by general formula (3), or a mixture of (A-1) and a linear organopolysiloxane (A-2) having hydroxy or alkoxy groups at both molecular chain terminals represented by general formula (4), or a mixture of (A-2) and an alkoxysilane represented by general formula (5) and / or its hydrolysis condensate (A-3), with a surfactant (B) and a mixture of water (C-1). The emulsification can be carried out using an emulsifier such as a Homodisper, Homomixer, colloid mill, line mixer, universal mixer, ultramixer, planetary mixer, combimix, or high-pressure homogenizer. An emulsifier that uses shear force to reduce the emulsion particle size, such as a Homodisper, Homomixer, or colloid mill, is preferred, and a Homodisper is more preferred.

[0102] In step (I), the amount of water used as component (C-1) is 1 to 10,000 parts by mass per 100 parts by mass of component (A), and varies depending on the type of emulsifier used to reduce the particle size of the emulsion particles.

[0103] For example, when a high-pressure homogenizer that uses high pressure to reduce the particle size of emulsion particles (an emulsifier that pressurizes a treatment liquid to high or ultra-high pressure and passes it through a slit to generate shear force, or an emulsifier that causes pressurized treatment liquids to collide obliquely with each other at ultra-high speed to form fine particles) is used, the amount of component (C-1) used is preferably 1 to 10,000 parts by mass, more preferably 4 to 6,000 parts by mass, and even more preferably 6 to 4,000 parts by mass per 100 parts by mass of component (A).

[0104] Furthermore, when using emulsifiers that use shear force to reduce the emulsion particle size, such as a homodisper (an emulsifier that generates shear force by rotating a circular disk with sawtooth teeth on the periphery at high speed), a homomixer (an emulsifier that generates shear force by rotating a rotor installed inside at high speed with a stator attached to the periphery), or a colloid mill (an emulsifier that feeds each component into the gap between a rapidly rotating disk and a fixed disk to generate shear force and emulsify), the amount of component (C-1) used is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, and even more preferably 4 to 6 parts by mass, per 100 parts by mass of component (A). Adding more than 10 parts by mass here can make it difficult to obtain an emulsion composition with emulsion particles of a small size, such as 500 nm or less, while adding less than 1 part by mass can make it difficult to obtain an O / W emulsion.

[0105] In this step, the emulsification temperature is preferably 1 to 80°C. If component (B) has catalytic activity, the cyclization reaction also proceeds at the same time, so emulsification is preferably carried out at a temperature below 40°C. If emulsification is carried out at a temperature above 40°C, there is a risk of excessive production of octamethylcyclotetrasiloxane (D4). Therefore, the temperature is preferably below 30°C, and more preferably below 25°C.

[0106] <Process (II)> The emulsion obtained in step (I) is diluted with water (C-2) as needed, and emulsion polymerization is carried out at a temperature of 0 to 40°C, with the addition of component (G) as needed, to obtain an emulsion composition of component (A).

[0107] When component (C-2) is added, it can then be further emulsified and dispersed using an emulsifying machine such as a high-pressure homogenizer.

[0108] When emulsion polymerization of the emulsion composition is performed, it is recommended that the polymerization step be performed at a temperature of 0 to 40°C for 48 hours or less. If polymerization is performed at a temperature higher than 40°C, there is a risk of excessive production of D4. Therefore, a temperature of 25°C or less is preferred, and 15°C or less is more preferred. Furthermore, if the polymerization time exceeds 48 hours, there is a risk of excessive production of D4 as a by-product, so the polymerization time is preferably 1 to 40 hours, and more preferably 5 to 30 hours.

[0109] Polymerization is carried out until the organopolysiloxane of component (A) has a 15% by mass toluene solution viscosity of 200 mPa s or greater at 25°C. Here, the 15% by mass toluene solution 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, adding toluene so that the organopolysiloxane becomes 15% by mass, dissolving the organopolysiloxane, and then measuring the solution using a rotational viscometer or the like.

[0110] After the polymerization is completed, the resulting emulsion composition is usually neutralized with a basic substance, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, or an amine compound such as triethanolamine or triethylamine.

[0111] At this time, preservatives, antifungal agents, etc. may be added to enhance the shelf life of the emulsion composition.

[0112] <Process (III)> The emulsion of component (A) obtained in step (II) is diluted with water (C-3) as necessary, and components (D), (E), and (F) are added. Note that if the colloidal silica of component (D) is in the form of an aqueous dispersion, the water in the aqueous colloidal silica solution is also included in component (C-3).

[0113] To maintain emulsion stability, it is preferable to add premixed components (D), (E), and (F) to the emulsion of component (A) under stirring. If components (E) and (F) are not added, component (D) can be added to the emulsion of component (A) under stirring.

[0114] The average particle size of the emulsion particles in the emulsion composition obtained by the production method of the present invention is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 350 nm or less. There is no particular lower limit, but it is about 30 nm or more. The average particle size of the emulsion particles is the median diameter value measured by laser diffraction / scattering light.

[0115] The organopolysiloxane emulsion composition of the present invention is capable of forming a rubber film after drying and can be used by treating or impregnating the surface of various substrates such as fiber, paper, metal, wood, rubber, plastic, glass, etc. The method of application to the substrate can be any of the various conventional coating methods, such as dipping, spraying, roll coating, bar coating, and brush coating.

[0116] The silicone emulsion composition obtained by the above method has component (A) dispersed therein and can be easily diluted with water. The silicone emulsion composition of the present invention forms a rubber film upon drying. The rubber film may be sticky, but is not gel-like. The drying temperature is appropriately selected from 1 to 250°C, and a film can be formed even at room temperature (normal temperature), such as 25°C. The drying time is preferably from a few seconds to one week. Because high-temperature treatment can damage various substrates, it is most preferable to dry at normal temperature.

[0117] The elongation and tensile strength of the films 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 applying the rubber film-forming silicone emulsion composition to various substrates, the film may easily fall off from the substrate due to friction.

[0118] A coating made from the dried rubber film-forming silicone emulsion composition of the present invention can have an elongation at break of 300% or more at a thickness of 1 mm, measured in accordance with JIS K 6251, and a tensile strength at break of 0.05 MPa or more, also measured in accordance with JIS K 6251.

[0119] There are no particular restrictions on the method for producing the film. For example, the film can be obtained by pouring an amount of rubber film-forming silicone emulsion composition into a polypropylene resin tray so that the thickness after drying will be approximately 1 mm, and then drying at 25°C for 48 hours.

[0120] The coating preferably has an elongation at break of 300% or more, more preferably 500% or more, of a dumbbell-shaped No. 3 test piece measured in accordance with JIS K 6251. The coating preferably has a tensile strength at break (test method specified in JIS K 6251) of 0.05 MPa or more, more preferably 0.10 MPa or more.

[0121] <Textile treatment agent> The present invention also provides a fiber treatment agent containing the rubber film-forming silicone emulsion composition described above, which exhibits good stability over time, durability, and flexibility, and also contains reduced amounts of D4, D5, and D6 as impurities.

[0122] <Water repellent> The present invention also provides a water repellent containing the rubber film-forming silicone emulsion composition, which exhibits good stability over time, durability, and flexibility, and also contains reduced amounts of D4, D5, and D6 as impurities.

[0123] This specification includes the following inventions. [Example]

[0124] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Furthermore, "parts" means parts by mass. The viscosity, expressed in mPa·s, is a value measured at 25°C using a BH-type rotational viscometer.

[0125] [Manufacturing Example 1] After dissolving 15.4 parts of maleic anhydride in 50 parts of ethanol, 34.6 parts of 3-aminopropyltriethoxysilane was added dropwise at room temperature over 1 hour, and the reaction was continued for a further 24 hours under reflux of ethanol at 80°C, yielding a pale yellow, transparent solution (E-1) containing 50% of component (E).

[0126] [Manufacturing Example 2] While paddle stirring 23 parts of colloidal silica (D-1) (Nissan Chemical Industries: Snowtex C, active ingredient 20%), 1.9 parts of (E-1) was gradually added and dispersed, and then 0.9 parts of 3-glycidoxypropyltriethoxysilane (F-1) was gradually added and dispersed to obtain a mixed solution of components (D), (E), and (F). (Mixed Solution I)

[0127] [Manufacturing Example 3] While paddle stirring 1.9 parts of (E-1), 0.9 parts of (F-1) 3-glycidoxypropyltriethoxysilane was gradually added and dispersed to obtain a mixed solution of components (E) and (F). (Mixed Solution II)

[0128] [Example 1] 50 parts of (A-1-1) branched organopolysiloxane (in general formula (10) below, w = 3, x = 400, y = 1, z = 0) represented by the following general formula (10) was emulsified with 3.04 parts of (B-1) Pelex NBL (Kao Corporation: 35% aqueous solution of sodium alkylnaphthalenesulfonate), 0.90 parts of (B-2) Newcol 291PG (Nippon Nyukazai Co., Ltd.: 70% aqueous solution of dioctyl sulfosuccinate), and 1.15 parts of (B-3) Emal 270J (Kao Corporation: 70% aqueous solution of sodium polyoxyethylene lauryl ether sulfate) using a homodisper (the water in component B becomes component (C-1)). 40.02 parts of (C-2) water was added to the resulting emulsion, and the mixture was diluted and dispersed using a homomixer. Next, 3.48 parts of a 20% aqueous solution of dodecylbenzenesulfonic acid (G-1) was added, followed by emulsion polymerization at 15°C for 13 hours. 1.41 parts of a 10% aqueous solution of sodium carbonate was then added to the resulting emulsion, and the mixture was diluted and dispersed using a homomixer to obtain an emulsion of component (A). The structure of the resulting component (A) is shown in average composition formula (11) below (in average composition formula (11), a = 3, b = 400, c = 1, d = 0). 25.8 parts of previously prepared mixed liquid I was added to 74.2 parts of this emulsion, and the mixture was dispersed using paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Table 1. [ka] [ka]

[0129] [Example 2] A rubber film-forming silicone emulsion composition was obtained by adding 23 parts of (D) colloidal silica (Nissan Chemical Industries, Ltd.: active ingredient 20%) to 74.2 parts of the emulsion of component (A) obtained in Example 1 and dispersing using a paddle stirrer. The results are shown in Table 1.

[0130] [Example 3] A rubber film-forming silicone emulsion composition was obtained by adding 2.8 parts of the previously prepared mixed liquid II to 74.2 parts of the emulsion of component (A) obtained in Example 1 and dispersing the mixture using a paddle stirrer. The results are shown in Table 1.

[0131] [Example 4] A rubber film-forming silicone emulsion composition was obtained in the same manner as in Example 1, except that the polymerization was carried out at 5°C for 48 hours. The results are shown in Table 2.

[0132] [Example 5] A rubber film-forming silicone emulsion composition was obtained in the same manner as in Example 1, except that the raw material for component (A) in Example 1 was changed to branched organopolysiloxane (A-1-2) represented by the above general formula (10) (in general formula (10) above, w=4, x=400, y=0, z=1). The structure of the obtained component (A) is as shown in the above average composition formula (11) (in average composition formula (11), a=4, b=400, c=0, d=1). The results are shown in Table 2.

[0133] [Example 6] A rubber film-forming silicone emulsion composition was obtained in the same manner as in Example 1, except that the raw material for component (A) in Example 1 was changed to branched organopolysiloxane (A-1-3) represented by the above general formula (10) (in the above general formula (10), w=4, x=700, y=2, z=0). The structure of the obtained component (A) is as shown in the above average composition formula (11) (in the average composition formula (11), a=4, b=700, c=2, d=0). The results are shown in Table 2.

[0134] [Example 7] A rubber film-forming silicone emulsion composition was obtained in the same manner as in Example 1, except that the raw materials for component (A) in Example 1 were changed to 20.55 parts of (A-1-1) a branched organopolysiloxane represented by the general formula (10) above (in general formula (10) above, w=3, x=400, y=1, z=0) and 29.45 parts of (A-2) an organopolysiloxane having a viscosity of 700 mPa s and containing silanol groups at the molecular chain ends. The structure of the resulting component (A) was as shown in the average composition formula (11) above (in average composition formula (11), a=3, b=900, c=1, d=0). The results are shown in Table 3.

[0135] [Example 8] A rubber film-forming silicone emulsion composition was obtained in the same manner as in Example 1, except that the raw materials for component (A) in Example 1 were changed to 33.66 parts of (A-1-1) a branched organopolysiloxane represented by general formula (10) above (in general formula (10) above, w=3, x=400, y=1, z=0) and 16.34 parts of (A-2) an organopolysiloxane having a viscosity of 700 mPa s and containing silanol groups at the molecular chain ends. The structure of the resulting component (A) was as shown in average formula (11) above (in average formula (11) a=3, b=600, c=1, d=0). The results are shown in Table 3.

[0136] [Example 9] An emulsion composition was prepared in the same manner as in Example 1, except that the raw materials for component (A) in Example 1 were changed to 44.79 parts of (A-1-1) a branched organopolysiloxane represented by the general formula (10) above (in general formula (10) above, w = 3, x = 400, y = 1, z = 0) and 5.21 parts of (A-2) an organopolysiloxane having a viscosity of 700 mPa s and silanol groups at the molecular chain terminals. The structure of the resulting component (A) is as shown in the average composition formula (11) above (in average composition formula (11), a = 3, b = 450, c = 1, d = 0). The results are shown in Table 3.

[0137] [Example 10] 49.82 parts of (A-2) organopolysiloxane with a viscosity of 700 mPa·s and silanol groups at the molecular chain ends, 0.18 parts of (A-3) triethoxyphenylsilane, 3.04 parts of (B-1) Pelex NBL (Kao Corporation: 35% aqueous solution of sodium alkylnaphthalenesulfonate), 0.90 parts of (B-2) Newcol 291PG (Nippon Nyukazai Co., Ltd.: 70% aqueous solution of dioctyl sulfosuccinate), and 1.15 parts of (B-3) Emal 270J (Kao Corporation: 70% aqueous solution of sodium polyoxyethylene lauryl ether sulfate) were emulsified using a homodisper (the water in component B becomes component (C-1)). 40.02 parts of (C-2) water were added to the resulting emulsion, and the mixture was diluted and dispersed using a homomixer. Next, 3.48 parts of 20% aqueous dodecylbenzenesulfonic acid (G-1) was added, followed by emulsion polymerization at 15°C for 22 hours. 1.41 parts of a 10% aqueous sodium carbonate solution was then added to the resulting emulsion, and the mixture was diluted and dispersed using a homomixer to obtain an emulsion of component (A). The structure of the resulting component (A) is shown in the average composition formula (11) above (in average composition formula (11), a = 3, b = 900, c = 1, d = 0). 25.8 parts of the previously prepared mixed liquid I was added to 74.2 parts of this emulsion, and the mixture was dispersed using paddle stirring to obtain a rubber film-forming silicone emulsion composition. The results are shown in Table 4.

[0138] [Comparative Example 1] 1.95 parts of (A-1-4) a branched organopolysiloxane represented by the general formula (10) above (in general formula (10) above, w = 3, x = 30, y = 1, z = 0) and 48.05 parts of (A-2) an organopolysiloxane having a viscosity of 700 mPa s and silanol groups at the molecular chain ends were emulsified with 3.04 parts of (B-1) Pelex NBL (manufactured by Kao Corporation: a 35% aqueous solution of sodium alkylnaphthalenesulfonate), 0.90 parts of (B-2) Newcol 291PG (manufactured by Nippon Nyukazai Co., Ltd.: a 70% aqueous solution of dioctyl sulfosuccinate), and 1.15 parts of (B-3) Emal 270J (manufactured by Kao Corporation: a 70% aqueous solution of sodium polyoxyethylene lauryl ether sulfate) using a Homodisper (the water in component B becomes component (C-1)). To the resulting emulsion, 40.02 parts of water (C-2) was added, and the mixture was diluted and dispersed using a homomixer. Next, 3.48 parts of a 20% aqueous solution of dodecylbenzenesulfonic acid (G-1) was added, followed by emulsion polymerization at 15°C for 13 hours. 1.41 parts of a 10% aqueous solution of sodium carbonate was then added to the resulting emulsion, and the mixture was diluted and dispersed using a homomixer to obtain an emulsion composition of component (A). The structure of the resulting component (A) was as shown in the average composition formula (11) above (in average composition formula (11), a = 3, b = 900, c = 1, d = 0). The results are shown in Table 4.

[0139] Comparative Example 2 28.88 parts of an alkenyl group-containing organopolysiloxane represented by the following general formula (12), 12.40 parts of a linear diorganohydrogenpolysiloxane represented by the following general formula (13) having hydrosilyl groups only at both molecular chain terminals, and 8.72 parts of an organohydrogenpolysiloxane represented by the following general formula (14) having four hydrosilyl groups per molecule were emulsified with 3.04 parts of (B-1) Pelex NBL (manufactured by Kao Corporation: 35% aqueous solution of sodium alkylnaphthalenesulfonate), 0.90 parts of (B-2) Newcol 291PG (manufactured by Nippon Nyukazai Co., Ltd.: 70% solution of dioctyl sulfosuccinate), and 1.15 parts of (B-3) Emal 270J (manufactured by Kao Corporation: 70% aqueous solution of sodium polyoxyethylene lauryl ether sulfate) using a Homodisper. The resulting emulsion was diluted and dispersed using a homomixer. This emulsion was transferred to a glass flask equipped with an anchor-type impeller stirrer and adjusted to 20-25°C. A mixed solution of 0.02 parts of an 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 with stirring and stirred for 12 hours to obtain an emulsion of a silethylene bond-containing organopolysiloxane. 23 parts of (D) colloidal silica (Nissan Chemical Industries, Ltd.: active ingredient 20%) was added to 74.2 parts of this emulsion and dispersed using a paddle stirrer to obtain a rubber film-forming silicone emulsion composition. The results are shown in Table 4. [ka] [ka] [ka]

[0140] Comparative Example 3 A rubber film-forming silicone emulsion composition was obtained by adding 25.8 parts of the previously prepared mixed liquid I to 74.2 parts of the emulsion of silethylene bond-containing organopolysiloxane obtained in Comparative Example 2 and dispersing the mixture using a paddle stirrer. The results are shown in Table 5.

[0141] Comparative Example 4 A mixture of 50 parts octamethylcyclotetrasiloxane and 0.18 parts triethoxyphenylsilane was added with an aqueous solution of (B-4) sodium dodecylbenzenesulfonate diluted with 4.5 parts water and an aqueous solution of (B-5) dodecylbenzenesulfonic acid diluted with 4.5 parts water, and the mixture was emulsified using a homomixer. 39.82 parts of water was then added, and the mixture was diluted and dispersed using a homomixer. A high-pressure emulsifier was then used to obtain an emulsion, which was then stirred at 50°C for 40 hours and then at 15°C for 12 hours. The resulting emulsion was neutralized by adding 1.0 parts of a 10% aqueous solution of sodium carbonate, and then an aqueous solution of (B-6) sodium lauryl sulfate diluted with 1.5 parts of water was added and dissolved by stirring to obtain an emulsion of component (A) (surfactant (B-5) was the acid catalyst). The structure of the resulting component (A) is as shown in the average compositional formula (11) above (in average compositional formula (11), a = 3, b = 900, c = 1, d = 0). 25.8 parts of previously prepared mixed liquid I was added to 74.2 parts of this emulsion and dispersed using paddle stirring, yielding a rubber film-forming silicone emulsion composition. The results are shown in Table 5.

[0142] The physical properties and characteristics of each of the rubber film-forming silicone emulsions described above were measured or evaluated according to the methods described below.

[0143] [Emulsion stability] 100g of silicone emulsion composition was placed in a 100ml glass bottle and left to stand at 40°C for one month, after which the appearance was observed. If the emulsion formed a uniform single phase with no separation observed, it was rated as having good stability and indicated by a "◯", whereas if separation into two phases was observed it was rated as having poor stability and indicated by an "X".

[0144] [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.).

[0145] [Viscosity in 15% toluene solution] To 20 g of the emulsion composition prior to the addition of components (D) to (F), 40 g of isopropyl alcohol (IPA) was added to break the emulsion and extract the organopolysiloxane. The extracted organopolysiloxane was washed twice with 40 g of IPA, and the IPA was then 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, and the viscosity of a 15% toluene solution was measured at 25°C using a BH-type rotational viscometer.

[0146] [Cyclic siloxane content in emulsion] 0.1 g of each emulsion composition was extracted (shaken for 3 hours) with 10 mL of acetone containing 20 ppm (by mass) of tetradecane as an internal standard, followed by centrifugation. The upper layer (acetone layer) was collected and analyzed by gas chromatography to quantify the D4, D5, and D6 contents.

[0147] [Film properties] 20 g of each emulsion composition was poured into a disposable polypropylene tray (150 mm x 105 mm x 10 mm) and dried at 25°C for 48 hours to produce a film approximately 1 mm thick. The hardness, tensile strength (MPa·s), and elongation at break (%) of the resulting film were measured in accordance with JIS K6249. Hardness was measured using a Type A durometer tester and an Asker C tester, which is measured in accordance with the Society of Rubber Industry, Japan Standards (SRIS).

[0148] [Film-forming properties] The state of the film obtained above was evaluated based on the following evaluation criteria. ◯: A uniform film is formed and is strong enough to be peeled off from the disposable tray. △: A uniform film is formed, but it cannot be peeled off from the disposable tray. ×: No uniform film was formed.

[0149] [Table 1]

[0150] [Table 2]

[0151] [Table 3]

[0152] [Table 4]

[0153] [Table 5]

[0154] The manufacturing method of the present invention (Examples 1-10) allows the production of rubber film-forming silicone emulsion compositions that exhibit excellent stability over time, provide durable, flexible films, and contain reduced amounts of the impurities D4, D5, and D6. On the other hand, the absence of additives in the emulsion of component (A) results in unsatisfactory film-forming ability and film properties (Comparative Example 1). Furthermore, the viscosity of emulsions prepared by addition polymerization in an emulsifying system (Comparative Examples 2 and 3) in 15% toluene was difficult to measure because the extract was insoluble in toluene. Although the tensile strength was comparable to or better than that of the films obtained from the emulsions of the present invention, the film elongation was low and durability was poor. Comparative Example 4 obtained a polymer by ring-opening polymerization of a cyclic siloxane oligomer using an acid catalyst. However, the polymerization time was long and the cyclic siloxane content was high. In contrast, Examples 5-9 shortened the polymerization time and reduced the cyclic siloxane content, resulting in films comparable to those of Comparative Example 4.

[0155] The composition of the present invention provides a coating film excellent in hardness, tensile strength and elongation, and is therefore useful as a fiber treatment agent, water repellent, coating agent and binder to be applied to various substrates.

[0156] The present specification includes the following aspects. [1] A rubber film-forming silicone emulsion composition comprising the following components (A) to (C) and at least one of the following components (D) to (F): A rubber film-forming silicone emulsion composition, characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in component (A) is less than 0.1% by weight. (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula (1), which has a 15% by mass toluene solution viscosity at 25°C of 200 mPa·s or more and contains at least three alkoxy groups or hydroxy groups bonded to silicon atoms per molecule: [ka] (In the formula, R 1 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 hydroxy group, and R 2 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a, b, c, and d are numbers such that the viscosity of the organopolysiloxane in a 15% by mass toluene solution at 25°C is 200 mPa s or greater, and a ≥ 3 and c + d ≥ 1. (B) a surfactant having an alkylnaphthalene skeleton represented by the following general formula (2): 0.1 to 30 parts by mass R 3 n -C 10 H (7-n) -SO3M (2) (In the formula, R 3is a linear or branched alkyl group having 1 to 30 carbon atoms, and M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or a tertiary ammonium ion. n is an integer of 1 to 3. (C) Water: 1~10000 parts by mass (D) Colloidal silica: 0 to 40 parts by mass (E) Reaction product of amino group-containing organoalkoxysilane and acid anhydride: 0 to 10 parts by mass (F) Epoxy group-containing organoalkoxysilane and / or partial hydrolyzate thereof: 0 to 10 parts by mass [2] The rubber film-forming silicone emulsion composition according to [1], wherein the amount of (D) colloidal silica used is 1 to 40 parts by mass. [3] The rubber film-forming silicone emulsion composition according to [1] or [2], wherein M in the general formula (2) is a sodium ion. [4] The rubber film-forming silicone emulsion composition according to any one of [1] to [3], wherein the average particle size of the emulsified particles in the rubber film-forming silicone emulsion composition is 500 nm or less. [5] The rubber film-forming silicone emulsion composition according to any one of [1] to [4], wherein the dried film has an elongation at break of 300% or more at a thickness of 1 mm, measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or more at a thickness of 1 mm, measured in accordance with JIS K 6251. [6] A method for producing a rubber film-forming silicone emulsion composition according to any one of [1] to [5], comprising the following steps (I) to (III), characterized in that (C) water is added so that the total amount of (C-1), (C-2), and (C-3) below is 1 to 10,000 parts by mass: (I) a step of obtaining an O / W emulsion containing an oil phase component comprising a branched organopolysiloxane (A-1) represented by the following general formula (3), a mixture of the (A-1) and a linear organopolysiloxane (A-2) having hydroxy groups or alkoxy groups at both molecular chain terminals represented by the following general formula (4), or a mixture of the (A-2) and an alkoxysilane represented by the following general formula (5) and / or its hydrolysis condensate (A-3), a surfactant (B), and water (C-1); (A-1) A branched organopolysiloxane represented by the following general formula (3): [ka] (In the formula, R 4 are each independently an alkoxy group having 1 to 20 carbon atoms, and R 5 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. w, x, y, and z are numbers that satisfy w≧3, x≧5, y+z≧1, and 10≦w+x+y+z≦1000. (A-2) A linear organopolysiloxane having hydroxy or alkoxy groups at both molecular chain terminals, represented by the following general formula (4): [ka] (In the formula, R 6 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and v is a number satisfying the relationship 0≦v≦2000. (A-3) Alkoxysilane represented by the following formula (5) and / or its hydrolysis condensate R 7 e Si(OR 8 ) 4-e (5) (where R 7 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 8 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 0 or 1. (II) A step of adding water (C-2) to the emulsion composition obtained in step (I) as necessary, and then polymerizing the component (A-1), a mixture of the components (A-1) and (A-2), or a mixture of the components (A-2) and (A-3) in the oil phase of the emulsion at 0 to 40°C for 1 to 48 hours in the presence of an acid catalyst (G) (however, when the surfactant (B) has catalytic activity, the addition of the acid catalyst can be omitted), followed by neutralization after polymerization to obtain an emulsion of organopolysiloxane (A), which is a condensation reaction product obtained from the component (A-1), a mixture of the components (A-1) and (A-2), or a mixture of the components (A-2) and (A-3). (III) A step of adding at least one of the (D) colloidal silica, the (E) reaction product of an amino group-containing organoalkoxysilane and an acid anhydride, and the (F) epoxy group-containing organoalkoxysilane and / or a partial hydrolyzate thereof, and optionally water (C-3), to the emulsion of component (A) obtained in step (II). [7] A method for producing a rubber film-forming silicone emulsion composition according to [6], characterized in that the viscosity at 25°C of the linear organopolysiloxane (A-2) represented by general formula (4) and having hydroxy or alkoxy groups at both molecular chain terminals is 200 mPa·s or more but less than 2000 mPa·s. [8] A film which is a dried product of the rubber film-forming silicone emulsion composition described in any one of [1] to [5]. [9] The coating according to [8], characterized in that it has an elongation at break of 300% or more at a thickness of 1 mm measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or more at a thickness of 1 mm measured in accordance with JIS K 6251.

[10] A fiber treatment agent comprising the rubber film-forming silicone emulsion composition according to any one of [1] to [5].

[11] A water repellent agent comprising the rubber film-forming silicone emulsion composition according to any one of [1] to [5].

[0157] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A rubber film-forming silicone emulsion composition comprising the following components (A) to (C) and at least one of the following components (D) to (F): A rubber film-forming silicone emulsion composition, characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in component (A) is less than 0.1% by weight. (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula (1), which has a 15% by mass toluene solution viscosity at 25°C of 200 mPa·s or more and contains at least three alkoxy groups or hydroxy groups bonded to silicon atoms in each molecule: 【Chemical 1】 (In the formula, R １ 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 hydroxy group; R ２ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and a, b, c, and d are numbers such that the viscosity of the organopolysiloxane in a 15% by mass toluene solution at 25°C is 200 mPa s or greater, and a ≥ 3 and c + d ≥ 1. (B) a surfactant represented by the following general formula (2) and having an alkylnaphthalene skeleton: 0.1 to 30 parts by mass R ３ ｎ -C １０ H （７－ｎ） -SO ３ M (2) (In the formula, R ３ is a linear or branched alkyl group having 1 to 30 carbon atoms, M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or a tertiary ammonium ion, and n is an integer of 1 to 3. (C) Water: 1 to 10,000 parts by mass (D) Colloidal silica: 0 to 40 parts by mass (E) Reaction product of amino group-containing organoalkoxysilane and acid anhydride: 0 to 10 parts by mass (F) Epoxy group-containing organoalkoxysilane and / or partial hydrolyzate thereof: 0 to 10 parts by mass

2. 2. The rubber film-forming silicone emulsion composition according to claim 1, wherein the amount of (D) colloidal silica used is 1 to 40 parts by mass.

3. 2. The rubber film-forming silicone emulsion composition according to claim 1, wherein M in general formula (2) is a sodium ion.

4. 2. The rubber film-forming silicone emulsion composition according to claim 1, wherein the average particle size of the emulsified particles in said rubber film-forming silicone emulsion composition is 500 nm or less.

5. 2. The rubber film-forming silicone emulsion composition according to claim 1, wherein the dried film produced has an elongation at break of 300% or greater at a thickness of 1 mm, as measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or greater at a thickness of 1 mm, as measured in accordance with JIS K 6251.

6. A method for producing the rubber film-forming silicone emulsion composition according to any one of claims 1 to 5, comprising the steps (I) to (III) below, wherein 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: (I) a step of obtaining an O / W emulsion containing an oil phase component comprising a branched organopolysiloxane (A-1) represented by the following general formula (3), a mixture of the (A-1) and a linear organopolysiloxane (A-2) represented by the following general formula (4) having hydroxy groups or alkoxy groups at both molecular chain terminals, or a mixture of the (A-2) and an alkoxysilane represented by the following general formula (5) and / or a hydrolysis condensate thereof (A-3), the surfactant (B), and water (C-1); (A-1) A branched organopolysiloxane represented by the following general formula (3): 【Chemistry 2】 (In the formula, R ４ are each independently an alkoxy group having 1 to 20 carbon atoms, and R ５ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms; and w, x, y, and z are numbers that satisfy w≧3, x≧5, y+z≧1, and 10≦w+x+y+z≦1000. (A-2) A linear organopolysiloxane having hydroxy or alkoxy groups at both molecular chain terminals, represented by the following general formula (4): 【Chemistry 3】 (In the formula, R ６ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and v is a number satisfying the relationship 0≦v≦2000. (A-3) Alkoxysilane represented by the following formula (5) and / or its hydrolysis condensate: R ７ ｅ Si(OR ８ ) ４－ｅ (5) (where R ７ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ８ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms; and e is 0 or 1. (II) A step of further adding water (C-2) to the emulsion composition obtained in step (I) as necessary, and then polymerizing the component (A-1), a mixture of the components (A-1) and (A-2), or a mixture of the components (A-2) and (A-3) in the oil phase component of the emulsion at 0 to 40°C for 1 to 48 hours in the presence of an acid catalyst (G) (however, when the surfactant (B) has a catalytic effect, the addition of the acid catalyst can be omitted), followed by neutralization after polymerization to obtain an emulsion of organopolysiloxane (A), which is a condensation reaction product obtained from the component (A-1), a mixture of the components (A-1) and (A-2), or a mixture of the components (A-2) and (A-3). (III) A step of adding at least one of the (D) colloidal silica, the (E) reaction product of an amino group-containing organoalkoxysilane and an acid anhydride, and the (F) epoxy group-containing organoalkoxysilane and / or a partial hydrolyzate thereof, and optionally water (C-3), to the emulsion of component (A) obtained in step (II).

7. The method for producing a rubber film-forming silicone emulsion composition according to claim 6, wherein the viscosity at 25°C of the linear organopolysiloxane (A-2) represented by general formula (4) and having hydroxy or alkoxy groups at both molecular chain terminals is at least 200 mPa s but less than 2,000 mPa s.

8. A film which is a dried product of the rubber film-forming silicone emulsion composition according to any one of claims 1 to 5.

9. 9. The coating of claim 8, wherein the coating has an elongation at break of 300% or more at a thickness of 1 mm, measured in accordance with JIS K 6251, and a tensile strength of 0.05 MPa or more at a thickness of 1 mm, measured in accordance with JIS K 6251.

10. A fiber treatment agent comprising the rubber film-forming silicone emulsion composition according to any one of claims 1 to 5.

11. A water repellent agent comprising the rubber film-forming silicone emulsion composition according to any one of claims 1 to 5.

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