Rubber-coated film-forming silicone emulsion composition and method for producing the same

Abstract

The present invention provides a rubber-coated film-forming silicone emulsion composition and a method for producing the same, the rubber-coated film-forming silicone emulsion composition comprising (A) to (C) below and comprising components in (D) to (F) below, and octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) in (A) are less than 0.1% by weight. (A) an organopolysiloxane represented by formula (1) and having a toluene solution viscosity at 15 mass% of 200 mPa-s or more and containing 3 or more alkoxyl groups or hydroxyl groups bonded to silicon atoms; (B) a surfactant having an alkyl naphthalene skeleton; (C) water; (D) colloidal silica; (E) a reaction product of an amino-containing organoalkoxysilane and an acid anhydride; (F) an epoxy-containing organoalkoxysilane and / or a partial hydrolyzate thereof. Thus, a rubber-coated film-forming silicone emulsion composition and a method for producing the same can be provided which can form a film by drying, and which have good stability, durability, and softness over time, and which have reduced D4, D5, and D6.

Description

Technical Field

[0001] This invention relates to a rubber-coating-forming silicone emulsion composition and its preparation method. The rubber-coating-forming silicone emulsion composition can be used as a water-repellent coating agent and a raw material for coating agents to form a rubber coating by room temperature drying or heat treatment. Background Technology

[0002] Emulsion compositions that form a rubber coating upon drying have traditionally been composed of various elements and used as binders for fiber treatment, coatings for rubber, coatings for building materials, coatings for paper and plastic films, or additives to these formulations for the purpose of imparting lubricity, water repellency, softness, and peelability. Coatings formed from high molecular weight polymers generally exhibit improved properties compared to films formed from low molecular weight polymers; therefore, high molecular weight polymers are preferred for the aforementioned applications.

[0003] One method for forming a rubber coating involves simultaneously reacting alkenylsilyl groups and hydrosilyl groups during drying to form a coating of organosilicon elastomer. Examples of proposed compositions include emulsion compositions consisting of vinyl-terminated diorganopolysiloxanes, organohydrosiloxanes, and platinum catalysts; or emulsion compositions consisting of diorganopolysiloxanes containing vinyl groups at the molecular chain ends or side chains, polysiloxanes having hydrogen atoms bonded to silicon atoms, colloidal silica, and platinum catalysts. However, with these compositions, if the hydrosilyl-containing siloxanes and platinum catalysts are coexisting beforehand, a reaction may occur over time, potentially producing hydrogen gas. Therefore, mixing the organosilicon emulsion and platinum catalyst before use is necessary, which is inconvenient.

[0004] Furthermore, a method for ring-opening polymerization of cyclic siloxane oligomers in an emulsified state using strong acids or bases is known. This method yields a highly polymerizable polymer with alkoxy groups at the ends of the molecular chains, which are reactive groups capable of condensation. However, this method requires a lengthy polymerization process, thus increasing manufacturing costs.

[0005] In addition, in recent years, efforts have been made to develop a product that suppresses the content of cyclic siloxane oligomers such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6). However, emulsion compositions obtained by ring-opening polymerization of cyclic siloxane oligomers still have the problem of containing large amounts of D4, D5, and D6 as byproducts during the emulsification polymerization process.

[0006] As a method for obtaining a polymer with suppressed D4 byproducts, Patent Document 1 discloses a method of addition polymerization in an emulsion system. According to this method, an organohydropolysiloxane having three or more hydrosilane groups per molecule can be added to a linear diorganohydropolysiloxane having hydrosilane groups only at both ends of the molecular chain in an emulsion system. Since it is an addition reaction, cyclic siloxane oligomers such as D4, D5, and D6 as byproducts are not generated. However, because the coating derived from this emulsion has silane-ethylene bonds, it still suffers from lower elongation (durability) compared to a coating composed only of siloxane bonds. Furthermore, Patent Document 2 discloses a method of polycondensation of linear organopolysiloxanes and branched organopolysiloxanes in an emulsion system. Because it is a condensation reaction, cyclic siloxane oligomers such as D4, D5 and D6 as byproducts will not be produced. However, high-polymerization-degree polymers cannot be obtained, and the problem of not being able to form a coating from the emulsion still exists.

[0007] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2021-107487 Patent Document 2: Japanese Patent Application Publication No. 2017-48342 Summary of the Invention

[0008] (a) Technical problems to be solved The present invention was made in view of the above circumstances, and its object is to provide a rubber coating forming silicone emulsion composition and its preparation method that can form a coating by drying, has good stability over time and provides a coating with good durability and softness, and reduces the amount of D4, D5 and D6 contained as impurities.

[0009] (II) Technical Solution To solve the above-mentioned technical problems, the present invention provides a rubber coating forming silicone emulsion composition, characterized in that it contains one or more of the following components (A) to (C) and components (D) to (F): 100 parts by mass of (A) organopolysiloxane, represented by the following average composition formula (1), having a toluene viscosity of 200 mPa·s or higher at 25°C at 15% by mass, and containing at least 3 alkoxy or hydroxyl groups (hydroxyl groups) bonded to silicon atoms in one molecule. [Chemical Formula 1] In the average composition formula (1), R 1 R is an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or a hydroxyl group with 1 to 20 carbon atoms.2 Each of the following groups consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. a, b, c, and d are numbers that satisfy the requirement that the organopolysiloxane has a solubility viscosity of 200 mPa·s or higher in 15% by mass toluene at 25°C, and a ≥ 3 and c + d ≥ 1. 0.1 to 30 parts by weight of surfactant (B), which is represented by the following general formula (2) and has an alkylnaphthalene skeleton, R 3 n -C10H (7-n) -SO3M -(2) In general formula (2), R 3 It is a straight-chain or branched alkyl group with 1 to 30 carbon atoms, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, or tertiary ammonium ion. n is an integer from 1 to 3; 1 to 10,000 parts by weight of (C) water; 0-40 parts by weight of (D) colloidal silica; 0-10 parts by weight of the reaction product of (E) amino-containing organoalkoxysilanes with acid anhydrides; 0-10 parts by weight of (F) epoxy-containing organoalkoxysilanes and / or their partial hydrolysates, Among them, the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) in component (A) are each less than 0.1% by weight.

[0010] If it is the above-mentioned rubber coating forming silicone emulsion composition, it is a low-impurity composition that can form a coating by drying, has good stability over time, and can provide a coating with good durability and flexibility.

[0011] In this invention, it is further preferred that the amount of the (D) colloidal silica used is 1 to 40 parts by weight.

[0012] If the colloidal silica (D) is used in this way, the strength (especially hardness and tensile strength) of the coating formed by the emulsion composition can be increased.

[0013] In this invention, it is further preferred that M in the general formula (2) is a sodium ion.

[0014] If the composition is a rubber-coated silicone emulsion containing a surfactant with an alkyl naphthalene skeleton, a suitable emulsifying effect can be obtained.

[0015] In this invention, it is further preferred that the average particle size of the emulsified particles in the silicone emulsion composition formed by the rubber coating is less than 500 nm.

[0016] If the average particle size is as described above, the polymerization rate increases, which can reduce the content of byproducts such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6).

[0017] In this invention, it is further preferred that the dried coating of the rubber-coated silicone emulsion composition, with a thickness of 1 mm, has an elongation at break of 300% or more as measured according to JIS K 6251, and a tensile strength of 0.05 MPa or more as measured according to JIS K 6251 with a thickness of 1 mm. There is no particular limitation on the upper limit of the above parameters, but from the perspective of durability and flexibility, an elongation at break of approximately 2000% and a tensile strength of approximately 5.0 MPa are desirable.

[0018] If the elongation at break and tensile strength are as described above, there is no need to worry that the coating will easily peel off from the substrate due to friction after the silicone emulsion composition formed by the rubber coating is used to treat various substrates.

[0019] Furthermore, the present invention also provides a method for preparing a rubber-coated silicone emulsion composition, which is a method for preparing the rubber-coated silicone emulsion composition, characterized in that it includes the following steps (I) to (III), and the water (C) is added in such a way that the total amount of (C-1), (C-2) and (C-3) is 1 to 10,000 parts by mass: Step (I) yields an O / W emulsion comprising an oil phase component, the surfactant (B), and water (C-1), wherein the oil phase component comprises a branched organopolysiloxane (A-1) represented by general formula (3), a mixture of (A-1) and a linear organopolysiloxane (A-2) represented by general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain, or a mixture of (A-2) and an alkoxysilane and / or its hydrolytic condensate (A-3) represented by general formula (5). (A-1) A branched organopolysiloxane represented by the following general formula (3), [Chemical Formula 2] In general formula (3), R 4 Each is an alkoxy group with 1 to 20 carbon atoms, R 5 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted 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 represented by the following general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain. [Chemical Formula 3] In general formula (4), R 6 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. v is a number satisfying 0 ≤ v ≤ 2000. (A-3) Alkoxysilanes and / or their hydrolytic condensates represented by the following general formula (5), R7 e Si(OR 8 ) 4-e -(5) In general formula (5), R 7 R consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. 8 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms, and e is 0 or 1; Step (II) involves further adding water (C-2) as needed to the emulsion composition obtained from step (I), then polymerizing component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3) in the oil phase of the emulsion at 0-40°C for 1-48 hours in the presence of an acid catalyst (G), followed by neutralization, thereby obtaining an emulsion of organopolysiloxane (A), which is a condensation reaction product obtained from component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3), wherein the addition of the acid catalyst can be omitted when the surfactant (B) has a catalytic effect; Step (III) involves adding at least one of the following to the emulsion of component (A) obtained from step (II): colloidal silica (D), the reaction product of an amino-containing organoalkoxysilane and anhydride (E), an epoxy-containing organoalkoxysilane, and / or its partial hydrolysate, and adding water (C-3) as needed.

[0020] If the above preparation method is used, a rubber-coated silicone emulsion composition can be formed that can form a coating by drying, has good stability over time, provides good durability and softness, and reduces the amount of D4, D5 and D6 contained as impurities.

[0021] In this invention, it is further preferred that the (A-2) is a linear organopolysiloxane represented by general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain, and that its viscosity at 25°C is 200 mPa·s or more and less than 2000 mPa·s. Furthermore, the viscosity of component (A-2) at 25°C can be measured, for example, using a rotational viscometer.

[0022] If the viscosity is as described above, it is easy to make an emulsion.

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

[0024] If the coating is as described above, it becomes a coating with good durability and flexibility, and reduces the amount of D4, D5 and D6 contained as impurities.

[0025] In this invention, it is further preferred that the coating, with a thickness of 1 mm, has an elongation at break of 300% or more as measured according to JIS K 6251, and a tensile strength of 0.05 MPa or more as measured according to JIS K 6251, with a thickness of 1 mm. There are no particular upper limits to these parameters, but from the perspective of durability and flexibility, an elongation at break of approximately 2000% and a tensile strength of approximately 5.0 MPa are desirable.

[0026] If the coating is as described above, it becomes a coating with good durability and flexibility.

[0027] Furthermore, the present invention provides a fiber treatment agent, characterized in that it comprises the rubber-coating forming silicone emulsion composition.

[0028] If the fiber treatment agent is as described above, it exhibits good stability, durability, and softness over time, and reduces the amount of D4, D5, and D6 contained as impurities.

[0029] Furthermore, the present invention provides a water repellent, characterized in that it comprises the rubber-coated forming silicone emulsion composition.

[0030] If the water repellent is as described above, it exhibits good stability, durability, and softness over time, and reduces the amount of D4, D5, and D6 contained as impurities.

[0031] (III) Beneficial Effects As described above, if the rubber coating provided by the present invention is formed into an organosilicon emulsion composition, a coating with good durability and flexibility can be provided. Furthermore, the amount of D4, D5, and D6 contained as impurities can be reduced, thus eliminating concerns about environmental impact. Detailed Implementation

[0032] As described above, the aim is to develop a rubber-coated silicone emulsion composition and its preparation method that can form a coating through drying, exhibit good stability over time, provide good durability and flexibility, and reduce the amount of D4, D5 and D6 contained as impurities.

[0033] To achieve the above-mentioned objectives, the inventors of this application conducted in-depth research and discovered that by polycondensing an organosilicon emulsion comprising a branched organopolysiloxane with alkoxy groups at the molecular ends, or a mixture of a branched organopolysiloxane with alkoxy groups at the molecular ends and a linear organopolysiloxane with hydroxyl or alkoxy groups at both ends of the molecular chain, or a mixture of a linear organopolysiloxane with hydroxyl or alkoxy groups at both ends of the molecular chain and an alkoxysilane, in the presence of a polymerization catalyst, and by adding one or more of the following components: colloidal silica, or the reaction product of an amino-containing organoalkoxysilane and an anhydride, or an epoxy-containing organoalkoxysilane and / or its partial hydrolysate, an organosilicon emulsion composition that can form a rubber coating with excellent substrate adhesion in a short time and reduces the amount of D4, D5, and D6 contained as impurities can be obtained, thereby completing the present invention.

[0034] That is, the present invention relates to a rubber coating forming silicone emulsion composition, characterized in that it comprises one or more of the following components (A) to (C) and components (D) to (F): 100 parts by mass of (A) organopolysiloxane, represented by the following average composition formula (1), having a toluene viscosity of 200 mPa·s or higher at 25°C at 15% by mass, and containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule. [Chemical Formula 4] In the average composition formula (1), R 1 R is an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or a hydroxyl group with 1 to 20 carbon atoms. 2 Each of the following groups consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. a, b, c, and d are numbers that satisfy the requirement that the organopolysiloxane has a solubility viscosity of 200 mPa·s or higher in 15% by mass toluene at 25°C, and a ≥ 3 and c + d ≥ 1. 0.1 to 30 parts by weight of surfactant (B), which is represented by the following general formula (2) and has an alkylnaphthalene skeleton, R 3 n -C 10 H (7-n) -SO3M -(2) In general formula (2), R 3 It is a straight-chain or branched alkyl group with 1 to 30 carbon atoms, M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion or tertiary ammonium ion, and n is an integer from 1 to 3. 1 to 10,000 parts by weight of (C) water; 0-40 parts by weight of (D) colloidal silica; 0-10 parts by weight of the reaction product of (E) amino-containing organoalkoxysilanes with acid anhydrides; 0-10 parts by weight of (F) epoxy-containing organoalkoxysilanes and / or their partial hydrolysates, Among them, the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) in component (A) are each less than 0.1% by weight.

[0035] The present invention will now be described in more detail, but the invention is not limited to these descriptions.

[0036] [(A) Organopolysiloxane] (A) is an organopolysiloxane that has a viscosity of more than 200 mPa·s when dissolved in 15% toluene at 25°C, and contains at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule, and is represented by the following average composition formula (1).

[0037] [Chemical Formula 5] In the average composition formula (1), R 1 R is an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or a hydroxyl group with 1 to 20 carbon atoms. 2 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. a, b, c, and d are numbers that satisfy the requirement that the organopolysiloxane has a solubility viscosity of 200 mPa·s or higher at 25°C in 15% by mass of toluene. Furthermore, a ≥ 3 and c + d ≥ 1.

[0038] The emulsion composition of the present invention may contain 100 parts by weight of component (A).

[0039] In the above average composition formula (1), R 1It can be an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or a hydroxyl group, which can be straight-chain, branched, or cyclic. Specifically, in addition to hydroxyl, examples include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl; phenyl, tolyl, naphthyl; methoxy, ethoxy, propoxy, butoxy, hexoxy, heptoxy, octyloxy, decoxy, tetradecoxy; or a group in which some or all of the hydrogen atoms bonded to these groups are replaced by halogen atoms, amino groups, cyano groups, etc. As R 1 The preferred compounds are methyl, hydroxy, methoxy, and ethoxy, but are specified as having at least three alkoxy or hydroxyl groups bonded to silicon atoms in one molecule.

[0040] R 2 These are monovalent hydrocarbon groups, each consisting independently of a hydrogen atom or of 1 to 20 carbon atoms, either substituted or unsubstituted. Examples of unsubstituted monovalent hydrocarbon groups with 1 to 20 carbon atoms include: alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, and aralkyl groups with 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. As a monovalent hydrocarbon group with 1 to 20 substituted carbon atoms, examples can be given of groups formed by substituting some hydrogen atoms of the monovalent hydrocarbon groups with 1 to 20 carbon atoms mentioned above with halogen atoms, amino groups, acryloyloxy groups, methacryloyloxy groups, epoxy groups, mercapto groups, carboxyl groups, hydroxyl groups, etc. Preferably, monovalent hydrocarbon groups with 1 to 6 carbon atoms are used, such as methyl, ethyl, propyl, butyl, and phenyl groups. Further preferred are all R groups. 2 More than 80% of it is methyl.

[0041] In the average composition formula (1), a, b, c, and d are numbers that satisfy the requirement that the 15% mass toluene dissolution viscosity of the organopolysiloxane at 25°C is 200 mPa·s or more, preferably 500 mPa·s or more, and more preferably 1000 mPa·s or more. Furthermore, the 15% mass toluene dissolution viscosity at 25°C in this invention refers to the measured value when measured using a BH type rotational viscometer at 25°C. If it is less than 200 mPa·s, the strength of the silicone rubber coating may decrease. There is no specific upper limit, but to avoid impairing the elongation of the coating, it can be set to, for example, 20000 mPa·s. In composition formula (1), a, b, c, and d are preferably: a ≥ 3, c + d ≥ 1, and the ratio of b to the total of c + d is preferably 10 to 1000.

[0042] Specific examples of organopolysiloxanes as component (A) in this invention include the following average composition formulas, but are not limited thereto. In the following average composition formulas, f, g, h, i, j, and k are each 1 or more, and are values ​​that satisfy the requirement that the polyorganosiloxane has a 15% by mass toluene solubility viscosity of 200 mPa·s or more at 25°C.

[0043] [Chemical Formula 6] (A) Components need to be made into emulsions. When (A) Components are alone, they usually appear as gel-like to rubber-like solids, making it difficult to obtain stable emulsions. Therefore, it is desirable to manufacture emulsions by the emulsification polymerization method described later.

[0044] (A) The content of each of the organopolysiloxanes, namely octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6), is less than 0.1% by mass, preferably less than 0.08% by mass, and more preferably less than 0.05% by mass. The lower limit is not particularly limited and can be 0% by mass.

[0045] Relative to 100 parts by weight of the total composition, (A) can be set to 10 to 90 parts by weight, preferably 15 to 80 parts by weight, and more preferably 20 to 70 parts by weight.

[0046] [(B) Surfactant] (B) The component is a surfactant represented by the following general formula (2) and having an alkylnaphthalene skeleton, which can be used alone or in combination with two or more.

[0047] R 3 n -C 10 H (7-n) -SO3M -(2) That is: [Chemical Formula 7] In general formula (2), R 3 It is a straight-chain or branched alkyl group with 1 to 30 carbon atoms, M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion or tertiary ammonium ion, and n is an integer from 1 to 3.

[0048] In general formula (2), R 3 The preferred alkyl group is a straight-chain or branched alkyl group with 1 to 20 carbon atoms, and there is no particular limitation. However, for the purpose of emulsification, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and isopropyl are preferred. For the purpose of emulsification, M is preferably a sodium ion, potassium ion, ammonium ion, or triethanolamine ion, and sodium ion is particularly preferred. When M is a hydrogen ion, component (B) has a catalytic effect, thus reducing the amount of acid catalyst (G) described later.

[0049] Specific examples of surfactants represented by general formula (2) and having an alkylnaphthalene skeleton include: butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, tetradecylnaphthalenesulfonic acid, hexadecylnaphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, diisopropylnaphthalene, triisopropylnaphthalene and their salts.

[0050] The amount of component (B) relative to 100 parts by weight of component (A) can be 0.1 to 30 parts by weight, preferably 1.5 to 7 parts by weight, and more preferably 2 to 6 parts by weight. If less than 0.1 parts by weight, a stable emulsion cannot be obtained; if more than 30 parts by weight, the resulting film becomes non-stretchable and brittle. Furthermore, the amount relative to 100 parts by weight of the total composition can be 0.05 to 20 parts by weight, preferably 1 to 10 parts by weight, and more preferably 1.5 to 5 parts by weight.

[0051] In this invention, by using a surfactant comprising a surfactant represented by general formula (2) and having an alkylnaphthalene skeleton as component (B), it is possible to easily reduce the particle size of the emulsion particles obtained by the later-described step (I), increase the polymerization rate, and significantly reduce the amount of byproducts octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6).

[0052] The silicone emulsion composition for forming a rubber coating of the present invention may optionally contain surfactants other than component (B). When using other surfactants, anionic or nonionic surfactants are preferred, with anionic surfactants being particularly preferred. These other surfactants can be used alone or in combination of two or more. When other surfactants are added arbitrarily, they are preferably added in a manner where the total amount of component (B) and other surfactants is 0.1 to 30 parts by mass relative to 100 parts by mass of component (A), more preferably in a manner where the total amount of component (B) and other surfactants is 0.5 to 15 parts by mass, and even more preferably in a manner where the total amount of component (B) and other surfactants is 1 to 10 parts by mass. Furthermore, in order to suppress the amount of byproducts D4 to D6, component (B) is preferably 30 parts by mass or more relative to 100 parts by mass of surfactants.

[0053] Examples of anionic surfactants include: sodium dodecyl sulfate and other alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, alkylbenzene sulfonates, polyoxyethylene alkylphenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkane sulfonates, N-acyl taurate, dialkyl sulfosuccinate, monoalkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinate, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, and polyoxyethylene alkyl ether phosphate salts. These anionic surfactants can be used individually or in combination with one or more of these types.

[0054] 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 sorbitan fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglycerol 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 nonionic surfactants can be used individually or in combination with one or more of these surfactants.

[0055] [(C) Water] (C) The water component is: (A) the organopolysiloxane, (D) the colloidal silica, (E) the reaction product of the amino-containing organoalkoxysilane with acid anhydride, and (F) the dispersion medium of the epoxy-containing organoalkoxysilane and / or its partial hydrolysate.

[0056] The amount of component (C) is 1 to 10,000 parts by mass relative to 100 parts by mass of component (A), preferably 60 to 500 parts by mass. If it is more than 10,000 parts by mass, the concentration of the film-forming component is low, which is uneconomical. If it is less than 1 part by mass, the viscosity of the aqueous silicone dispersion will be high, making it difficult to manufacture or handle. Furthermore, relative to 100 parts by mass of the total composition, it can be set to 5 to 95 parts by mass, preferably 10 to 90 parts by mass, and more preferably 20 to 90 parts by mass.

[0057] [(D) Colloidal silica] (D) The colloidal silica is added as a coating reinforcing agent, which can significantly improve the strength (especially hardness and tensile strength) of the coating formed by the emulsion composition. The surface of the colloidal silica particles may be treated with metal oxides, preferably in the form of silica sol (aqueous dispersion of colloidal silica) dispersed in water. The pH is not particularly limited, but for safety during use, a range of 4 to 10 is preferred. The concentration of colloidal silica in the aqueous dispersion is not particularly limited, for example, 10 to 60% by mass is acceptable. Commercially available colloidal silica can also be used, and there is no limitation on the type. For example, it can be colloidal silica with a particle size of 5 to 50 nm that has been stabilized with sodium, ammonium, and aluminum. Specific examples include Snowtex (manufactured by Nissan Chemical Corporation), Ludox (manufactured by Grace Corporation), Silicadol (manufactured by Nippon Chemical Industrial Co., Ltd.), and Cataloid (manufactured by JGC Catalysts & Chemicals Ltd.).

[0058] The amount of component (D) incorporated relative to 100 parts by weight of component (A) is 0 to 40 parts by weight. When it exceeds 40 parts by weight, the silicone coating becomes hard and brittle, and the durability of the water repellency may decrease. The amount of component (D) incorporated is preferably 1 to 40 parts by weight, more preferably 5 to 30 parts by weight, and even more preferably 10 to 20 parts by weight. Furthermore, relative to 100 parts by weight of the entire composition, it can be set to 0 to 30 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight.

[0059] [(E) Reaction products of amino-containing organoalkoxysilanes with acid anhydrides] The reaction product of the amino-containing organoalkoxysilane and acid anhydride in component (E) is a substance formed by reacting the amino-containing organoalkoxysilane with dicarboxylic acid anhydride. It is a component used to improve the adhesion between the silicone coating and the substrate, and also acts as a catalyst to crosslink and cure the components of the composition of the present invention through a condensation reaction. Component (E) is preferably incorporated in the form of a solution diluted with the reaction solvent described later. The concentration of the solution of component (E) is not particularly limited, for example, about 10 to 80% by mass. The amino-containing alkoxysilane used as a raw material is represented by the following general formula (6), and the following compounds are specifically listed.

[0060] X(R 9 )3Si -(6) In general formula (6), R 9 It 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.

[0061] In general formula (6), X is derived from formula -R 10 (NHR 10 ) e NHR 11 (where R is in the formula) 10 R is a divalent hydrocarbon group of the same or different types, with 1 to 6 carbon atoms. 11 For R 9 X represents an amino group (or a hydrogen atom, where e is an integer from 0 to 6). Specifically, X can be exemplified by N-2-(aminoethyl)-3-aminopropyl, 3-aminopropyl, N-phenyl-3-aminopropyl, etc., among which N-2-(aminoethyl)-3-aminopropyl and 3-aminopropyl are preferred.

[0062] In general formula (6), R 9 It can be 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 can be any of straight-chain, branched, or cyclic, as specifically listed with R in general formula (1). 1 The same groups are required, but at least one of them must be an alkoxy group. As R 9 Methyl, methoxy, and ethoxy compounds are particularly preferred.

[0063] Specific examples of amino-containing alkoxysilanes in this invention include the following compounds, but are not limited thereto.

[0064] (C2H5O)3SiC3H6NH2、 (C2H5O)2(CH3)SiC3H6NH2、 (CH3O)3SiC3H6NH2、 (CH3O)2(CH3)SiC3H6NH2、 (CH3O)3SiC3H6NHC2H4NH2、 (CH3O)2(CH3)SiC3H6NHC2H4NH2 Examples of dicarboxylic anhydrides that can be used to react with the aforementioned amino-containing alkoxysilanes include maleic anhydride, phthalic anhydride, succinic anhydride, methylsuccinic anhydride, glutaric anhydride, and itaconic anhydride. Among these, maleic anhydride is preferred.

[0065] In the reaction of an amino-containing organoalkoxysilane with an anhydride, the mixing ratio of the two is preferably 0.5 to 2 (molar ratio of amino to anhydride), and more preferably 0.55 to 1.8, and more preferably 0.6 to 1.5. Furthermore, this can be easily carried out by mixing in a hydrophilic organic solvent as needed at room temperature or under heating. Examples of such hydrophilic organic solvents include: alcohols such as methanol, ethanol, isopropanol, and butanol; ketones such as acetone and methyl ethyl ketone; and acetonitrile and tetrahydrofuran. Additionally, the reaction temperature is 0 to 100°C, particularly preferably 5 to 80°C, and the reaction time is typically 0.5 to 40 hours, especially 1 to 24 hours.

[0066] The amount of component (E) relative to 100 parts by weight of component (A) is 0 to 10 parts by weight, preferably 2 to 7 parts by weight, and more preferably 2.5 to 6 parts by weight. A dosage exceeding 10 parts by weight will lead to a decrease in the stability of the emulsion composition, making long-term storage impossible. Furthermore, relative to 100 parts by weight of the total composition, it can be set to 0 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 0.5 to 3 parts by weight.

[0067] [(F) Epoxy-containing organoalkoxysilanes and / or their partial hydrolysates] (F) Components containing epoxy-containing organoalkoxysilanes and / or their partial hydrolysates are used to improve the adhesion between the silicone coating and the substrate. Specific examples include: γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropyldimethoxymethylsilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyldimethoxymethylsilane, etc.

[0068] The amount of component (F) incorporated is 0 to 10 parts by mass relative to 100 parts by mass of component (A). Incorporation of more than 10 parts by mass will cause the coating to harden and become brittle, and will also reduce the durability of the water-repellent properties. Preferably, it is 0 to 7 parts by mass, more preferably 0 to 6 parts by mass, and when incorporated, it is preferably 1 part by mass or more to ensure its effective performance. Furthermore, relative to 100 parts by mass of the entire composition, it can be set to 0 to 5 parts by mass, preferably 0.1 to 4 parts by mass, and more preferably 0.5 to 3 parts by mass.

[0069] The rubber-coated silicone emulsion composition of the present invention may contain a catalyst for promoting the condensation reaction of 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 incorporated relative to 100 parts by mass of component (A) can be set to 0.001 to 1 part by mass.

[0070] The rubber-coated silicone emulsion composition of the present invention may contain inorganic powders, pigments, dyes, thickeners, preservatives, bactericides, deodorizers, rust inhibitors, antioxidants, defoamers, antistatic agents, ultraviolet absorbers, antifreeze agents, water-soluble resins, organic resin emulsions, etc.

[0071] The emulsion composition of the present invention, after being stored at 25°C for 6 months, contains substantially no change in the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) compared to immediately after manufacture, and each content is less than 0.1% by mass. Preferably, each is less than 0.09% by mass, more preferably less than 0.08% by mass. Furthermore, there are no limitations on the lower limit of each content, for example, it can be set to 0.005% by mass.

[0072] The emulsion composition of the present invention has film-forming properties. The method of film formation is not particularly limited; by removing water from the emulsion composition, the organopolysiloxanes in the emulsion composition will coagulate to form a uniform film. The method of water removal is not particularly limited; for example, water can be removed at temperatures above 100°C for a short time, or water can be removed slowly at 25°C.

[0073] For example, a coating can be formed as follows: An emulsion composition with a non-volatile component content of 8.0 g is measured in a 15 cm × 10 cm PP (polypropylene) tray, dried at 25°C for 48 hours, and then further dried at 105°C for 1 hour. The hardness, tensile strength, and elongation of the coating prepared above are measured according to JIS K 6251 to evaluate the coating's physical properties.

[0074] [Preparation method of silicone emulsion composition formed by rubber coating] Next, the method for preparing the rubber-coated silicone emulsion composition of the present invention is carried out through the following steps.

[0075] That is, a method for preparing a rubber-coating-forming silicone emulsion composition, characterized in that it includes the following steps (I) to (III), and the water (C) is added in such a way that the total amount of (C-1), (C-2) and (C-3) is 1 to 10,000 parts by mass: Step (I) yields an O / W emulsion comprising an oil phase component, the surfactant (B), and water (C-1), wherein the oil phase component comprises a branched organopolysiloxane (A-1) represented by general formula (3), a mixture of (A-1) and a linear organopolysiloxane (A-2) represented by general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain, or a mixture of (A-2) and an alkoxysilane and / or its hydrolytic condensate (A-3) represented by general formula (5). (A-1) A branched organopolysiloxane represented by the following general formula (3), [Chemical Formula 8] In general formula (3), R 4 Each is an alkoxy group with 1 to 20 carbon atoms, R 5 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted 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 represented by the following general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain. [Chemical Formula 9] In general formula (4), R 6 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. v is a number satisfying 0 ≤ v ≤ 2000. (A-3) Alkoxysilanes and / or their hydrolytic condensates represented by the following general formula (5), R 7 e Si(OR 8 ) 4-e -(5) In equation (5), R 7 R consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. 8Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms, and e is 0 or 1; Step (II) involves further adding water (C-2) to the emulsion composition obtained from step (I) as needed, then polymerizing component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3) in the oil phase of the emulsion at 0-40°C for 1-48 hours in the presence of an acid catalyst (G), followed by neutralization, thereby obtaining an emulsion of organopolysiloxane (A), which is a condensation reaction product obtained from component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3), wherein the addition of the acid catalyst can be omitted when the surfactant (B) has a catalytic effect; Step (III) involves adding at least one of the following to the emulsion of component (A) obtained from step (II): colloidal silica (D), the reaction product of an amino-containing organoalkoxysilane and anhydride (E), and an epoxy-containing organoalkoxysilane and / or its partial hydrolysate (F), and adding water (C-3) as needed.

[0076] [(A-1) Branched organopolysiloxane] (A-1) is a branched organopolysiloxane represented by the above general formula (3), and is a raw material of organopolysiloxane (A) with a viscosity of 200 mPa·s or more at 15% by mass of toluene at 25°C and containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule.

[0077] In general formula (3), R 4 Each alkoxy group is independently composed of 1 to 20 carbon atoms. As an alkoxy group with 1 to 20 carbon atoms, it can be any of straight-chain, branched, or cyclic. Specific examples include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octoxy, decoxy, dodecyloxy, 2-ethylhexoxy, etc., with methoxy, ethoxy, propoxy, butoxy, and pentoxy being preferred, and methoxy, ethoxy, and propoxy being more preferred.

[0078] R 5 Each group consists of a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, as exemplified by R. 2 The same functional groups, but in terms of industrial applicability and properties, it is desirable for more than 80% of the R groups to be present. 5 It is a methyl group.

[0079] In general 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. The preferred values ​​are: 3≤w≤50, 10≤x≤900, 1≤y≤20, and 0≤z≤10.

[0080] Examples of compounds representing the specific structures of components (A-1) of the present invention include those shown below, but are not limited thereto. Furthermore, Me, Et, and Ph in the following general formulas represent methyl, ethyl, and phenyl, respectively.

[0081] [Chemical Formula 10] In equation (10), e, f, g, h, i, and j are all greater than or equal to 1, and are numbers that satisfy the range of w, x, y, and z in the general equation (3).

[0082] As the component (A-1), compounds containing octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) in an amount of 0.1% by mass or less can be used. Preferably, each is less than 0.07% by mass, more preferably less than 0.06% by mass. Furthermore, there are no lower limits for each content; for example, it can be set to 0.001% by mass.

[0083] In the method for preparing the emulsion composition of the present invention, by using the above-mentioned raw materials with a low content of low molecular weight cyclic siloxanes, an emulsion composition with a low content of low molecular weight cyclic siloxanes can be efficiently manufactured. Preferably, the content is less than 0.09% by mass, more preferably less than 0.08% by mass. In addition, there is no limitation on the lower limit of each content, for example, it can be set to 0.005% by mass.

[0084] [(A-2) Straight-chain organopolysiloxanes with hydroxyl or alkoxy groups at both ends of the molecular chain] (A-2) is a linear organopolysiloxane represented by general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain, and is a raw material of organopolysiloxane (A) containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule.

[0085] [Chemical Formula 11] In general formula (4), R 6 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. v is a number that satisfies 0 ≤ v ≤ 2000.

[0086] In general formula (4), R 6Each group consists of a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, as exemplified by R. 2 The same functional groups, but in terms of industrial applicability and properties, it is desirable to have more than 50% R 6 It is a methyl group. In terms of reactivity, the R at the end of the molecular chain in general formula (4) 6 Hydrogen atoms are preferred.

[0087] In general formula (4), v can usually be a value of 0 to 2000. Preferably, 10 ≤ v ≤ 1500, and particularly preferably 20 ≤ v ≤ 1000.

[0088] The viscosity of component (A-2) is not particularly limited, but its measured value at 25°C using a BH type rotational viscometer is preferably 200 mPa·s or more and less than 2000 mPa·s, more preferably 300 mPa·s or more and less than 1800 mPa·s, and particularly preferably 500 mPa·s or more and less than 1600 mPa·s. If the viscosity is less than 200 mPa·s, the preparation of the emulsion described later may become difficult.

[0089] As specific examples of component (A-2), the following average composition formulas can be listed, but are not limited to. In the following general formulas, p, q+r, and q+r+s can generally take values ​​from 1 to 2000 as mentioned above.

[0090] [Chemical Formula 12] Component (A-2) undergoes a condensation reaction with component (A-1) or (A-3) to obtain an organopolysiloxane (A) component that has a toluene solubility viscosity of 200 mPa·s or higher at 25°C and contains at least three alkoxy or hydroxyl groups bonded to silicon atoms per molecule. As for the amount of component (A-2), when used simultaneously with component (A-1), it is preferably 0.1 to 99.9 parts by mass, particularly preferably 1 to 99 parts by mass, relative to a total of 100 parts by mass of components (A-1) and (A-2). When used simultaneously with component (A-3), it is preferably 80 to 99.9 parts by mass, more preferably 90 to 99.9 parts by mass, particularly preferably 95 to 99.9 parts by mass, relative to a total of 100 parts by mass of components (A-2) and (A-3). As long as the amount of component (A-2) is within the above range, sufficient strength and flexibility are achieved after coating.

[0091] [(A-3) Alkoxysilanes and / or their hydrolytic condensates represented by the following general formula (5)] (A-3) is an alkoxysilane and / or its hydrolytic condensate represented by the following general formula (5), and is a raw material of an organopolysiloxane (A) component with a viscosity of 200 mPa·s or more at 15% by mass of toluene at 25°C and containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule.

[0092] R 7 e Si(OR 8 ) 4-e -(5) In equation (5), R 7 R consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. 8 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. e is 0 or 1.

[0093] In general formula (5), R 7 These are monovalent hydrocarbon groups with 1 to 20 carbon atoms, each consisting independently of a hydrogen atom or either substituted or unsubstituted carbon atoms. Examples of monovalent hydrocarbon groups with 1 to 20 carbon atoms include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as vinyl, alkenyl, phenyl, tolyl, and naphthyl; or groups formed by replacing some hydrogen atoms in these organic groups with halogen atoms or polar organic groups such as amino, acryloyloxy, methacryloyloxy, epoxy, and mercapto groups. In terms of industrial applicability and properties, it is desirable that 80% or more of the R... 7 It is a methyl group.

[0094] R 8 Each group consists of a hydrogen atom or a substituted or unsubstituted carbon atom, and is a monovalent hydrocarbon group having 1 to 20 carbon atoms. As R 8 Monovalent organic groups with 1 to 20 carbon atoms, which are related to the above R 7 The same group is preferred, with methyl, ethyl, propyl, and butyl being more preferred, and methyl and ethyl being more preferred.

[0095] Specific examples of components (A-3) include, but are not limited to, the following compounds: methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-ethoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyl 3-Methoxypropyltrimethoxysilane, 3-Methoxypropylmethyldiethoxysilane, 3-Methoxypropyltriethoxysilane, 3-Acryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-Triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-Ureapropyltriethoxysilane, 3-Mercaptopropylmethyldimethoxysilane, 3-Mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanate-propyltriethoxysilane, etc.

[0096] Component (A-3) undergoes a condensation reaction with component (A-2) to obtain an organopolysiloxane (A) component that has a toluene solubility viscosity of 200 mPa·s or higher at 25°C and contains at least three alkoxy or hydroxyl groups bonded to silicon atoms per molecule. The amount of component (A-3) 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, relative to a total of 100 parts by mass of components (A-2) and (A-3). As long as the amount of component (A-2) is within the above range, the obtained coating exhibits good flexibility.

[0097] [(C-1), (C-2), (C-3) Water] Components (C-1), (C-2), and (C-3) are the total amount of water used in process (I) and, depending on the water required for process (II) and process (III). Component (C) is added in quantities ranging from 1 to 10,000 parts by mass.

[0098] (G) acid catalyst Component (G) is an acid catalyst and is a reaction catalyst for component (A-1), or a mixture of components (A-1) and (A-2), or a mixture of components (A-2) and (A-3). Component (G) is sometimes unnecessary when component (B) has catalytic activity. When using component (G), one type can be used alone or in appropriate combinations of two or more types. Component (G) can be incorporated in the form of an aqueous solution.

[0099] The following compounds can be listed as components (G).

[0100] [(G-1) Alkyl sulfuric acid represented by the following general formula (7), alkyl benzene sulfonic acid represented by the following general formula (8)] R 12 OSO3H -(7) In general formula (7), R 12 It is a straight-chain or branched alkyl group with 6 to 30 carbon atoms.

[0101] R 12 -C6H4-SO3H -(8) In general formula (8), R 12 As defined in general formula (7), it is a straight-chain or branched alkyl group having 6 to 30 carbon atoms.

[0102] In general formulas (7) and (8), R 12 Preferably, it is a straight-chain or branched alkyl group with 6 to 12 carbon atoms.

[0103] Specific examples of alkyl sulfuric acid represented by general formula (7) include: hexyl sulfuric acid, octyl sulfuric acid, decyl sulfuric acid, dodecyl sulfuric acid, tetradecyl sulfuric acid, hexadecyl sulfuric acid, octadecyl sulfuric acid, eicosyl sulfuric acid, etc.

[0104] Specific examples of alkylbenzene sulfonic acids represented by general formula (8) include: hexylbenzene sulfonic acid, octylbenzene sulfonic acid, decylbenzene sulfonic acid, dodecylbenzene sulfonic acid, tetradecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, etc.

[0105] [(G-2) higher fatty acids] Specific examples include lauric acid, stearic acid, oleic acid, and linolenic acid.

[0106] [(G-3) Polyoxyethylene alkyl ether sulfuric acid represented by the following general formula (9)] R 12 O(EO) t (PO) u SO3H -(9) In general formula (9), R 12As defined in general formula (7), it is a straight-chain or branched alkyl group with 6 to 30 carbon atoms. EO represents vinyl oxide, and PO represents propylene oxide. These groups can be arranged in a block or random configuration. t and u are independent integers from 0 to 100, but t+u>0, especially 50≥t+u≥1.

[0107] As specific examples of polyoxyethylene alkyl ether sulfuric acid represented by general formula (9), examples include: polyoxyethylene hexyl ether sulfuric acid, polyoxyethylene octyl ether sulfuric acid, polyoxyethylene decyl ether sulfuric acid, polyoxyethylene dodecyl ether sulfuric acid, polyoxyethylene tetradecyl ether sulfuric acid, polyoxyethylene hexadecyl ether sulfuric acid, polyoxyethylene octadecyl ether sulfuric acid, polyoxyethylene eicosyl ether sulfuric acid, etc.

[0108] [(G-4) Polyoxyethylene alkylphenyl ether sulfuric acid represented by the following general formula (10)] R 12 -C6H4-O(EO) t (PO) u SO3H -(10) In general formula (10), R 12 As defined in general formula (7), it is a straight-chain or branched alkyl group with 6 to 30 carbon atoms. EO, PO, t, and u are defined as in general formula (9), where EO represents vinyl oxide and PO represents propylene oxide. These groups can be arranged in a block or random configuration. t and u are independent integers from 0 to 100, but t+u>0, and in particular 50≥t+u≥1.

[0109] As specific examples of polyoxyethylene alkylphenyl ether sulfuric acid represented by general formula (10), examples include: polyoxyethylene hexylphenyl ether sulfuric acid, polyoxyethylene octylphenyl ether sulfuric acid, polyoxyethylene decylphenyl ether sulfuric acid, polyoxyethylene dodecylphenyl ether sulfuric acid, polyoxyethylene tetradecylphenyl ether sulfuric acid, polyoxyethylene hexadecylphenyl ether sulfuric acid, etc.

[0110] [(G-5) Brønsted acid] Examples of Brønsted 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 clay and acid-activated carbon black, etc.

[0111] The amount of component (G) (wherein, if the surfactant of component (B) is an acid and has a catalytic effect, it is included in component (B)) is at least 0.1 parts by mass, preferably 0.2 parts by mass or more, relative to 100 parts by mass of component (A). If it is less than 0.1 parts by mass, the polymerization rate will become extremely slow. In addition, there is no particular upper limit, but in terms of the long-term stability of the obtained rubber film-forming silicone resin composition, it is preferably 50 parts by mass or less.

[0112] The preparation method of the present invention will be described below.

[0113] <Process (I)> An emulsion composition is prepared by emulsifying a mixture comprising an oil phase component, a surfactant (B), and water (C-1). The oil phase component comprises a branched organopolysiloxane (A-1) represented by general formula (3), or a mixture of (A-1) and a linear organopolysiloxane (A-2) represented by general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain, or a mixture of (A-2) and an alkoxysilane represented by general formula (5) and / or its hydrolytic condensate (A-3). The emulsification here can be performed using emulsifiers such as homogenizers, homogenizers, colloid mills, inline mixers, general-purpose mixers, super mixers, planetary mixers, combination mixers, and high-pressure homogenizers. Emulsifiers that reduce the particle size of the emulsion particles by using shear force, such as homogenizers, homogenizers, and colloid mills, are preferred, and homogenizers are more preferably homogenizers.

[0114] In process (I), the amount of water used in component (C-1) is 1 to 10,000 parts by mass relative to 100 parts by mass of component (A), and will vary depending on the type of emulsifier used to reduce the particle size of the emulsion particles.

[0115] For example, when using a high-pressure homogenizer that reduces the particle size of emulsion particles by utilizing high pressure (an emulsifier that pressurizes the treatment liquid to high or ultra-high pressure and causes it to pass through a slit to obtain shear force, or an emulsifier that produces microparticles by obliquely colliding the pressurized treatment liquid with each other at ultra-high speed), the amount of component (C-1) is preferably 1 to 10,000 parts by mass relative to 100 parts by mass of component (A), more preferably 4 to 6,000 parts by mass, and even more preferably 6 to 4,000 parts by mass.

[0116] Furthermore, when using homogenizers (emulsifiers that generate shear force by rotating a circular disc with serrated edges on the outer periphery at high speed), homogenizers (emulsifiers that generate shear force by placing the test sample on the outer periphery and rotating a motor inside at high speed), colloid mills (emulsifiers that generate shear force by loading each component into the gap between a high-speed rotating disc and a fixed disc), the amount of component (C-1) is preferably 1 to 10 parts by mass relative to 100 parts by mass of component (A), more preferably 2 to 8 parts by mass, and even more preferably 4 to 6 parts by mass. Here, if more than 10 parts by mass are added, it may be difficult to obtain an emulsion composition with a particle size of 500 nm or less; if less than 1 part by mass, it may become difficult to obtain an O / W type emulsion.

[0117] In this process, the emulsification temperature is preferably 1~80°C. Furthermore, when component (B) has a catalytic effect, a cyclization reaction also occurs simultaneously; therefore, emulsification is preferably carried out at a temperature below 40°C. If emulsification is carried out at a temperature above 40°C, the formation of octamethylcyclotetrasiloxane (D4) may increase. Therefore, a temperature below 30°C is preferred, and particularly preferably below 25°C.

[0118] <Process (II)> The emulsion obtained in step (I) is diluted with water (C-2) as required, and emulsified and polymerized at a temperature of 0 to 40°C, according to the addition of component (G) as required, thereby obtaining an emulsion composition of component (A).

[0119] When the (C-2) component is added, it can be further emulsified and dispersed using an emulsifier such as a high-pressure homogenizer.

[0120] When emulsifying the emulsion composition, the polymerization process is recommended to be carried out at a temperature of 0 to 40°C and within 48 hours. If polymerization is carried out at a temperature higher than 40°C, the formation of D4 may increase. Therefore, it is preferable to polymerize at 25°C or lower, more preferably at 15°C or lower. Furthermore, if the polymerization time exceeds 48 hours, the amount of D4 as a byproduct may increase; therefore, it is preferable to polymerize at 1 to 40 hours, more preferably at 5 to 30 hours.

[0121] The polymerization is carried out until the organopolysiloxane of component (A) has a toluene dissolution viscosity of 200 mPa·s or higher at 25°C at 15% by mass. Here, the toluene dissolution viscosity at 15% by mass is obtained, for example, by adding toluene while stirring the polymerized emulsion composition in a polar solvent such as an alcohol, thereby disrupting the emulsion and extracting the organopolysiloxane. After drying the organopolysiloxane at 105°C for more than 3 hours, the substance obtained by adding toluene at 15% by mass of organopolysiloxane is measured using a rotational viscometer or the like.

[0122] After polymerization, the resulting emulsion composition is usually neutralized using an alkaline substance. Examples of alkaline substances include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, triethanolamine, triethylamine, and other amine compounds.

[0123] To improve the preservation performance of the emulsion composition, preservatives, antifungal agents, etc., can be added.

[0124] <Process (III)> For the emulsion of component (A) obtained from process (II), dilute it with water (C-3) as needed, and add components (D), (E), and (F). In addition, when the colloidal silica of component (D) is an aqueous dispersion, the water in the colloidal silica aqueous solution is also included in component (C-3).

[0125] To maintain emulsion stability, it is preferable to add pre-mixed components (D), (E), and (F) to the emulsion of component (A) under stirring, in order to add components (D), (E), and (F) in this case. If components (E) and (F) are not added, simply add component (D) to the emulsion of component (A) under stirring.

[0126] The average particle size of the emulsion particles in the emulsion composition obtained by the preparation method of the present invention is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 350 nm or less. The lower limit is not particularly limited, but is approximately 30 nm or more. Furthermore, the average particle size of the emulsion particles is the median particle size obtained using laser diffraction scattering light.

[0127] The organopolysiloxane emulsion composition of the present invention can form a rubber coating after drying and can be used to treat or impregnate the surfaces of various substrates such as fibers, paper, metals, wood, rubber, plastics, and glass. As a method of coating the substrate, various conventionally known coating methods such as dipping, spraying, roller coating, bar coating, and brush coating are possible.

[0128] For the silicone emulsion composition obtained by the above method, component (A) is dispersed and can be easily diluted with water. The silicone emulsion composition of the present invention forms a rubber coating by drying. The rubber coating may be viscous, but not gel-like. The drying temperature can be appropriately selected from 1 to 250°C, and the coating can also be formed at room temperature (room temperature), such as 25°C. The drying time is preferably from a few seconds to one week. Sometimes high-temperature treatment may damage various substrates, so drying is most preferably carried out at room temperature.

[0129] The elongation and tensile strength of the silicone emulsion obtained by forming the silicone emulsion with the rubber coating of the present invention are shown below. If the elongation or tensile strength is too low, for example, after treating various substrates with the silicone emulsion composition formed by the rubber coating, the coating may easily detach from the substrate due to friction.

[0130] The coating formed by the dried product of the silicone emulsion composition formed by the rubber coating of the present invention has an elongation at break of 300% or more as measured according to JIS K 6251 with a thickness of 1 mm, and a tensile strength of 0.05 MPa or more as measured according to JIS K 6251 with a thickness of 1 mm.

[0131] The manufacturing method of the above-mentioned coating is not particularly limited. For example, it can be obtained by flowing a rubber coating forming an organosilicon emulsion composition, with a dried thickness of about 1 mm, into a polypropylene resin tray and drying it at 25°C for 48 hours.

[0132] The above-mentioned coating preferably has an elongation at break of 300% or more, more preferably 500% or more, based on the dumbbell-shaped No. 3 test piece as determined by JIS K 6251. The tensile strength at break of the coating (tested by the method specified in JIS K 6251) is preferably 0.05 MPa or more, more preferably 0.10 MPa or more.

[0133] <Fiber Treatment Agent> Furthermore, the present invention provides a fiber treatment agent characterized by comprising the aforementioned rubber-coating forming silicone emulsion composition. The fiber treatment agent described above exhibits good stability over time, good durability and softness, and reduces the amount of D4, D5, and D6 contained as impurities.

[0134] <Water Repellent> Furthermore, the present invention provides a water repellent, characterized in that it comprises the aforementioned rubber-coating forming silicone emulsion composition. If it is the above-mentioned water repellent, it is a water repellent with good stability over time, good durability and flexibility, and a reduced amount of D4, D5, and D6 contained as impurities.

[0135] This specification includes the following inventions.

[0136] Example The following examples and comparative examples are shown, and the present invention is specifically described; however, the present invention is not limited to the examples described below. Furthermore, "parts" refers to parts by mass. Additionally, the viscosity in mPa·s is a value measured at 25°C using a BH type rotational viscometer.

[0137] [Manufacturing Example 1] 15.4 parts of maleic anhydride were dissolved in 50 parts of ethanol, and 34.6 parts of 3-aminopropyltriethoxysilane were added dropwise over 1 hour at room temperature. The reaction was then carried out at 80°C under reflux of ethanol for 24 hours to obtain a solution (E-1) containing 50% of the pale yellow transparent (E) component.

[0138] [Manufacturing Example 2] While stirring 23 parts of (D-1) colloidal silica (manufactured by Nissan Chemical Corporation, SNOW TEX C active ingredient 20%) with a stirring paddle, 1.9 parts of (E-1) were slowly added and dispersed. Then, 0.9 parts of (F-1) 3-epoxypropoxypropyltriethoxysilane were slowly added and dispersed to obtain a mixture of components (D), (E), and (F) (mixture I).

[0139] [Manufacturing Example 3] While stirring 1.9 parts of (E-1) with a stirrer, slowly add 0.9 parts of (F-1)3-epoxypropoxypropyltriethoxysilane and disperse it to obtain a mixture of components (E) and (F) (mixture II).

[0140] [Example 1] In 50 parts of a branched organopolysiloxane (A-1-1) represented by the following general formula (10) (where w=3, x=400, y=1, z=0), 3.04 parts of (B-1) Pelex NBL (manufactured by Kao Corporation: 35% aqueous solution of sodium alkylnaphthalene sulfonate), 0.90 parts of (B-2) NEWCOL 291PG (manufactured by Nippon Nyukazai Co., Ltd.: 70% aqueous solution of dioctyl sulfosuccinate), and 1.15 parts of (B-3) EMAL 270J (manufactured by Kao Corporation: 70% aqueous solution of sodium polyoxyethylene dodecyl ether sulfate) were emulsified using a homogenizer (the water in component B is component (C-1)). 40.02 parts of (C-2) water were added to the obtained emulsion, and the emulsion was diluted and dispersed using a homogenizer. Next, 3.48 parts of (G-1) 20% dodecylbenzenesulfonic acid aqueous solution were added, and emulsification polymerization was carried out at 15°C for 13 hours. Afterwards, 1.41 parts of 10% sodium carbonate aqueous solution were added to the obtained emulsion, and it was diluted and dispersed using a homogenizer to obtain the emulsion of component (A). The structure of the obtained component (A) is shown in the following average composition formula (11) (in the average composition formula (11), a=3, b=400, c=1, d=0). 25.8 parts of pre-prepared mixture I were added to 74.2 parts of this emulsion and dispersed by stirring with a paddle to obtain a rubber-coated silicone emulsion composition. The results are shown in Table 1.

[0141] [Chemical Formula 13] [Chemical Formula 14] [Example 2] 23 parts of colloidal silica (manufactured by Nissan Chemical Corporation, 20% active ingredient) were added to 74.2 parts of the emulsion of component (A) obtained in Example 1 and dispersed by stirring with a paddle to obtain a rubber-coating-forming silicone emulsion composition. The results are shown in Table 1.

[0142] [Example 3] 2.8 parts of pre-prepared mixture II were added to 74.2 parts of the emulsion of component (A) obtained in Example 1 and dispersed by stirring with a paddle to obtain a rubber-coating-forming silicone emulsion composition. The results are shown in Table 1.

[0143] [Example 4] The polymerization conditions in Example 1 were set to 5°C for 48 hours, otherwise, a rubber-coated silicone emulsion composition was obtained in the same manner as in Example 1. The results are shown in Table 2.

[0144] [Example 5] The raw material of component (A) in Example 1 was changed to a branched organopolysiloxane (A-1-2) represented by the general formula (10) (where w=4, x=400, y=0, z=1), except that a rubber-coating forming silicone emulsion composition was obtained in the same manner as in Example 1. The structure of the obtained component (A) is shown in the average composition formula (11) (where a=4, b=400, c=0, d=1). The results are shown in Table 2.

[0145] [Example 6] The raw material of component (A) in Example 1 was changed to a branched organopolysiloxane (A-1-3) represented by the general formula (10) (where w=4, x=700, y=2, z=0), and a rubber-coating forming silicone emulsion composition was obtained in the same manner as in Example 1. The structure of the obtained component (A) is shown in the average composition formula (11) (where a=4, b=700, c=2, d=0). The results are shown in Table 2.

[0146] [Example 7] The raw materials of component (A) in Example 1 were changed to 20.55 parts of a branched organopolysiloxane (A-1-1) represented by the general formula (10) (w=3, x=400, y=1, z=0 in the general formula (10)) and 29.45 parts of an organopolysiloxane (A-2) with a viscosity of 700 mPa·s and silanol groups at the ends of the molecular chain. Otherwise, a rubber-coating forming silicone emulsion composition was obtained in the same manner as in Example 1. The structure of the obtained component (A) is shown in the average composition formula (11) (a=3, b=900, c=1, d=0 in the average composition formula (11)). The results are shown in Table 3.

[0147] [Example 8] The raw materials of component (A) in Example 1 were changed to 33.66 parts of a branched organopolysiloxane (A-1-1) represented by the general formula (10) (w=3, x=400, y=1, z=0 in the general formula (10)) and 16.34 parts of an organopolysiloxane (A-2) with a viscosity of 700 mPa·s and silanol groups at the ends of the molecular chain. Otherwise, a rubber-coating forming silicone emulsion composition was obtained in the same manner as in Example 1. The structure of the obtained component (A) is shown in the average composition formula (11) (a=3, b=600, c=1, d=0 in the average composition formula (11)). The results are shown in Table 3.

[0148] [Example 9] The raw materials of component (A) in Example 1 were changed to 44.79 parts of a branched organopolysiloxane (A-1-1) represented by the general formula (10) (where w=3, x=400, y=1, z=0 in the general formula (10)) and 5.21 parts of an organopolysiloxane (A-2) with a viscosity of 700 mPa·s and silanol groups at the ends of the molecular chain. Otherwise, the emulsion composition was obtained in the same manner as in Example 1. The structure of the obtained component (A) is shown in the average composition formula (11) (where a=3, b=450, c=1, d=0 in the average composition formula (11)). The results are shown in Table 3.

[0149] [Example 10] In a mixture of 49.82 parts of (A-2) an organopolysiloxane with silanol groups at the molecular chain ends (viscosity 700 mPa·s) and 0.18 parts of (A-3) triethoxyphenylsilane, 3.04 parts of (B-1) Pelex NBL (manufactured by Kao Corporation: 35% aqueous solution of sodium alkylnaphthalene sulfonate), 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) EMAL270J (manufactured by Kao Corporation: 70% aqueous solution of sodium polyoxyethylene dodecyl ether sulfate) were emulsified using a homogenizer (the water in component B is 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 homogenizer. Next, 3.48 parts of (G-1) 20% dodecylbenzenesulfonic acid aqueous solution were added, and emulsification polymerization was carried out at 15°C for 22 hours. Afterwards, 1.41 parts of 10% sodium carbonate aqueous solution were added to the obtained emulsion, and it was diluted and dispersed using a homogenizer to obtain the emulsion of component (A). The structure of the obtained component (A) is shown in the average composition formula (11) (in the average composition formula (11), a=3, b=900, c=1, d=0). 25.8 parts of pre-prepared mixture I were added to 74.2 parts of this emulsion and dispersed by stirring with a paddle to obtain a rubber-coated silicone emulsion composition. The results are shown in Table 4.

[0150] [Comparative Example 1] In 1.95 parts of branched organopolysiloxane (A-1-4) represented by the general formula (10) (w=3, x=30, y=1, z=0 in the general formula (10)) and 48.05 parts of organopolysiloxane (A-2) with a viscosity of 700 mPa·s and silanol groups at the molecular chain ends, 3.04 parts of (B-1) Pelex NBL (manufactured by Kao Corporation: 35% aqueous solution of sodium alkyl naphthalene sulfonate), 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 dodecyl ether sulfate) were emulsified using a homogenizer (the water in component B is component (C-1)). 40.02 parts of (C-2) water were added to the obtained emulsion, and the emulsion was diluted and dispersed using a homogenizer. Then, 3.48 parts of a 20% dodecylbenzenesulfonic acid aqueous solution (G-1) were added, and emulsification polymerization was carried out at 15°C for 13 hours. Afterwards, 1.41 parts of a 10% sodium carbonate aqueous solution were added to the obtained emulsion, and the emulsion was diluted and dispersed using a homogenizer to obtain the emulsion composition of component (A). The structure of the obtained component (A) is shown in the average composition formula (11) (in the average composition formula (11), a=3, b=900, c=1, d=0). The results are shown in Table 4.

[0151] [Comparative Example 2] In 28.88 parts of an alkenyl organopolysiloxane represented by general formula (12), 12.40 parts of a linear diorganohydrogen polysiloxane represented by general formula (13) having hydroxyl groups only at both ends of the molecular chain, and 8.72 parts of an organohydrogen polysiloxane represented by general formula (14) having 4 hydroxyl groups per molecule, 3.04 parts of (B-1) PelexNBL (manufactured by Kao Corporation: 35% aqueous solution of sodium alkylnaphthalene sulfonate), 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) EMAL270J (manufactured by Kao Corporation: 70% aqueous solution of sodium polyoxyethylene dodecyl ether sulfate) were emulsified using a homogenizer. 43.25 parts of water were added to the obtained emulsion, and the emulsion was diluted and dispersed using a homogenizer. The emulsion was transferred to a glass flask equipped with an anchor-type stirring device. After adjusting the temperature to 20–25 °C, a mixture of 0.02 parts of a platinum-vinyldisiloxane complex solution (0.5% platinum content) and 0.02 parts of polyoxyethylene dodecyl ether (ethylene oxide addition molar number = 9 mol) was added under stirring. The mixture was stirred at the same temperature for 12 hours to obtain an organopolysiloxane emulsion containing ethylene silane bonds. 23 parts of (D) colloidal silica (manufactured by Nissan Chemical Corporation, 20% active ingredient) were added to 74.2 parts of this emulsion and dispersed using a stirring paddle to obtain a rubber-coating-forming organosilicon emulsion composition. The results are shown in Table 4.

[0152] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] [Comparative Example 3] 25.8 parts of a pre-prepared mixture I were added to 74.2 parts of an emulsion of a silicone-containing ethylene-bonded organopolysiloxane obtained from Comparative Example 2, and the mixture was stirred and dispersed using a stirrer to obtain a rubber-coating-forming organosilicon emulsion composition. The results are shown in Table 5.

[0153] [Comparative Example 4] To a mixture of 50 parts octamethylcyclotetrasiloxane and 0.18 parts triethoxyphenylsilane, an aqueous solution of sodium dodecylbenzenesulfonate (B-4) diluted with 4.5 parts water and an aqueous solution of sodium dodecylbenzenesulfonic acid (B-5) diluted with 4.5 parts water were added, and the mixture was emulsified using a homogenizer. Then, 39.82 parts water were added, and the mixture was diluted and dispersed using a homogenizer. The emulsion was then subjected to a high-pressure treatment at 100 MPa using a high-pressure emulsifier to obtain an emulsion. The obtained emulsion was stirred at 50°C for 40 hours and then at 15°C for 12 hours. 1.0 part of a 10% sodium carbonate aqueous solution was added for neutralization. Further, an aqueous solution of sodium dodecyl sulfate (B-6) diluted with 1.5 parts water was added, and the mixture was stirred to dissolve, thus obtaining the emulsion of component (A) (surfactant (B-5) is an acid catalyst). The structure of the obtained component (A) is shown in the average composition formula (11) (in the average composition formula (11), a=3, b=900, c=1, d=0). 25.8 parts of a pre-prepared mixture I were added to 74.2 parts of this emulsion and dispersed by stirring with a paddle to obtain a rubber-coating-forming silicone emulsion composition. The results are shown in Table 5.

[0154] The physical properties and characteristics of the above-mentioned rubber-coated silicone emulsion compositions were determined and evaluated according to the methods shown below.

[0155] [Emulsion stability] Pour 100g of the silicone emulsion composition into a 100ml glass bottle and observe its appearance after one month at 40°C. Emulsions that form a uniform single phase without separation are considered to have good stability and are marked "0". Emulsions that separate into two phases are considered to have poor stability and are marked "×".

[0156] [Average particle size of the emulsion] The median particle size of each emulsion was determined using a laser diffraction scattering particle size distribution analyzer LA-960 (manufactured by Horiba, Ltd.).

[0157] [15% Toluene Dissolution Viscosity] 40g of isopropanol (IPA) was added to 20g of the emulsion composition before the addition of components (D) to (F), thereby disrupting the emulsion to extract organopolysiloxanes. The extracted organopolysiloxanes were washed twice with 40g of IPA, and the IPA was completely dried at 105°C. After drying, 7.5g of organopolysiloxanes and 42.5g of toluene were poured into a 50mL glass bottle and shaken for 24 hours. The viscosity of the solution in 15% toluene was measured using a BH type rotational viscometer at 25°C.

[0158] [Cyclic siloxane content in emulsions] 0.1 g of each emulsion composition was extracted with 10 mL of acetone containing 20 ppm (mass) tetradecane as an internal standard (vibrated for 3 hours), followed by centrifugation. The upper layer (acetone layer) was collected and the contents of D4, D5, and D6 were quantified by gas chromatography analysis.

[0159] [Physical properties of the coating] 20g of each emulsion composition was poured into a disposable polypropylene resin tray (150mm×105mm×10mm) and dried at 25°C for 48 hours to form a film with a thickness of approximately 1mm. The hardness, tensile strength (MPa·s), and elongation at break (%) of the obtained film were determined according to JIS K 6251. Furthermore, regarding hardness, the rubber hardness was determined using a Type A hardness tester and an Asker C testing machine according to the Japan Rubber Industry Association Standard Specification (SRIS).

[0160] [Coating Formation] The condition of the coating obtained above is evaluated based on the following evaluation criteria.

[0161] 〇: Forms a uniform coating and has the strength to peel off from a single tray.

[0162] △: Forms a uniform coating, but cannot be peeled off from a disposable tray.

[0163] ×: The coating was not uniform.

[0164] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] According to the preparation method of the present invention (Examples 1-10), a rubber-coated silicone emulsion composition with good stability over time, good durability and flexibility can be obtained, and the amount of D4, D5 and D6 contained as impurities is reduced. On the other hand, if the additive is not used in the emulsion of component (A), the coating forming ability and coating properties cannot be satisfied (Comparative Example 1). In addition, the emulsions (Comparative Examples 2 and 3) prepared by addition polymerization in the emulsion system have a 15% toluene dissolution viscosity, and the extract cannot be dissolved in toluene, making it difficult to measure the viscosity. However, compared with the coating obtained by the emulsion of the present invention, the tensile strength is of the same to good level, but the durability is poor due to the low elongation of the coating. In Comparative Example 4, a high molecular weight polymer was obtained by ring-opening polymerization of cyclic siloxane oligomers using an acid catalyst. However, the polymerization time was long and a large amount of cyclic siloxanes were contained. However, Examples 5-9 shortened the polymerization time and reduced the cyclic siloxane content, and a coating of the same degree as that of Comparative Example 4 was formed.

[0165] The compositions of the present invention can provide coatings with excellent hardness, tensile hardness, and elongation, and therefore can be used as fiber treatment agents, water repellents, coating agents, and adhesives for coating various substrates.

[0166] This specification contains the following specifications.

[0167] [1] A rubber-coating forming silicone emulsion composition, characterized in that it comprises the following components (A) to (C) and one or more of the following components (D) to (F): 100 parts by mass of (A) organopolysiloxane, represented by the following average composition formula (1), having a toluene viscosity of 200 mPa·s or higher at 25°C at 15% by mass, and containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule. [Chemical Formula 18] In the average composition formula (1), R 1 R is an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or a hydroxyl group with 1 to 20 carbon atoms. 2 Each of the following groups consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. a, b, c, and d are numbers that satisfy the requirement that the organopolysiloxane has a solubility viscosity of 200 mPa·s or higher in 15% by mass toluene at 25°C, and a ≥ 3 and c + d ≥ 1. 0.1 to 30 parts by weight of surfactant (B), which is represented by the following general formula (2) and has an alkylnaphthalene skeleton, R 3 n-C 10 H (7-n) -SO3M -(2) In general formula (2), R 3 It is a straight-chain or branched alkyl group with 1 to 30 carbon atoms, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, or tertiary ammonium ion. n is an integer from 1 to 3; 1 to 10,000 parts by weight of (C) water; 0-40 parts by weight of (D) colloidal silica; 0-10 parts by weight of the reaction product of (E) amino-containing organoalkoxysilanes with acid anhydrides; 0-10 parts by weight of (F) epoxy-containing organoalkoxysilanes and / or their partial hydrolysates, Among them, the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) in component (A) are each less than 0.1% by weight.

[0168] [2] The rubber-coated forming silicone emulsion composition according to [1] is characterized in that the amount of the (D) colloidal silica is 1 to 40 parts by weight.

[0169] [3] The rubber-coated silicone emulsion composition according to [1] or [2] is characterized in that M in the general formula (2) is a sodium ion.

[0170] [4] The rubber-coated silicone emulsion composition according to any one of [1] to [3] is characterized in that the average particle size of the emulsified particles in the rubber-coated silicone emulsion composition is less than 500 nm.

[0171] [5] The rubber-coated silicone emulsion composition according to any one of [1] to [4] is characterized in that the dried coating of the rubber-coated silicone emulsion composition has an elongation at break of 300% or more as measured according to JIS K 6251 with a thickness of 1 mm, and a tensile strength of 0.05 MPa or more as measured according to JIS K 6251 with a thickness of 1 mm.

[0172] [6] A method for preparing a rubber-coated silicone emulsion composition, which is a method for preparing a rubber-coated silicone emulsion composition as described in any one of [1] to [5], characterized in that it includes the following steps (I) to (III), and the water (C) is added in such a way that the total amount of (C-1), (C-2) and (C-3) is 1 to 10,000 parts by mass: Step (I) yields an O / W emulsion comprising an oil phase component, a surfactant (B), and water (C-1), wherein the oil phase component comprises a branched organopolysiloxane (A-1) represented by general formula (3), a mixture of said (A-1) and a linear organopolysiloxane (A-2) represented by general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain, or a mixture of said (A-2) and an alkoxysilane and / or its hydrolytic condensate (A-3) represented by general formula (5). (A-1) A branched organopolysiloxane represented by the following general formula (3), [Chemical Formula 19] In general formula (3), R 4 Each is an alkoxy group with 1 to 20 carbon atoms, R 5 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. w, x, y, and z are numbers satisfying w ≥ 3, x ≥ 5, y + z ≥ 1, and 10 ≤ w + x + y + z ≤ 1000. (A-2) A linear organopolysiloxane represented by the following general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain. [Chemical Formula 20] In general formula (4), R 6 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. v is a number satisfying 0 ≤ v ≤ 2000. (A-3) Alkoxysilanes and / or their hydrolytic condensates represented by the following general formula (5), R 7 e Si(OR 8 ) 4-e -(5) In general formula (5), R 7 R consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. 8 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. e is 0 or 1. Step (II) involves further adding water (C-2) as needed to the emulsion composition obtained from step (I), then polymerizing component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3) in the oil phase of the emulsion at 0-40°C for 1-48 hours in the presence of an acid catalyst (G), followed by neutralization, thereby obtaining an emulsion of organopolysiloxane (A), which is a condensation reaction product obtained from component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3), wherein the addition of the acid catalyst can be omitted when the surfactant (B) has a catalytic effect; Step (III) involves adding at least one of the following to the emulsion of component (A) obtained from step (II): colloidal silica (D), the reaction product of an amino-containing organoalkoxysilane and anhydride (E), an epoxy-containing organoalkoxysilane, and / or its partial hydrolysate, and adding water (C-3) as needed.

[0173] [7] The method for preparing the rubber coating forming organosilicon emulsion composition according to [6] is characterized in that the (A-2) is a linear organopolysiloxane with hydroxyl or alkoxy groups at both ends of the molecular chain represented by general formula (4), and the viscosity at 25°C is above 200 mPa·s and less than 2000 mPa·s.

[0174] [8] A coating, characterized in that it is the dried product of any one of the rubber coating forming silicone emulsion compositions described in any one of [1] to [5].

[0175] [9] The coating according to [8] is characterized in that the elongation at break, as measured by JIS K 6251, is 300% or more with a thickness of 1 mm, and the tensile strength, as measured by JIS K 6251, is 0.05 MPa or more with a thickness of 1 mm.

[0176]

[10] A fiber treatment agent, characterized in that it comprises a rubber-coating forming silicone emulsion composition as described in any one of [1] to [5].

[0177]

[11] A water repellent, characterized in that it comprises a rubber-coated silicone emulsion composition as described in any one of [1] to [5].

[0178] Furthermore, this invention is not limited to the above-described embodiments. The above embodiments are merely examples, and any technical solution having a substantially identical structure and achieving the same technical effect as the technical concept described in the claims of this invention is included within the technical scope of this invention.

Claims

1. A rubber-coating-forming silicone emulsion composition, characterized in that, The ingredient contains one or more of the following components (A) to (C) and components (D) to (F): 100 parts by mass of (A) organopolysiloxane, represented by the following average composition formula (1), having a toluene viscosity of 200 mPa·s or higher at 25°C at 15% by mass, and containing at least 3 alkoxy or hydroxyl groups bonded to silicon atoms in one molecule. [Chemical Formula 1] In the average composition formula (1), R 1 R is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group having 1 to 20 carbon atoms. 2 Each of the following groups consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. a, b, c, and d are numbers that satisfy the requirement that the organopolysiloxane has a solubility viscosity of 200 mPa·s or higher in 15% by mass toluene at 25°C, and a ≥ 3 and c + d ≥ 1. 0.1 to 30 parts by weight of surfactant (B), which is represented by the following general formula (2) and has an alkylnaphthalene skeleton, R 3 n -C 10 H (7-n) -SO3M (2) In general formula (2), R 3 It is a straight-chain or branched alkyl group with 1 to 30 carbon atoms, M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion or tertiary ammonium ion, and n is an integer from 1 to 3. 1 to 10,000 parts by weight of (C) water; 0-40 parts by weight of (D) colloidal silica; 0-10 parts by weight of the reaction product of (E) amino-containing organoalkoxysilanes with acid anhydrides; 0-10 parts by weight of (F) epoxy-containing organoalkoxysilanes and / or their partial hydrolysates, Among them, the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylcyclohexasiloxane (D6) in component (A) are each less than 0.1% by weight.

2. The rubber-coating-forming silicone emulsion composition according to claim 1, characterized in that, The amount of colloidal silica (D) used is 1 to 40 parts by mass.

3. The rubber-coating-forming silicone emulsion composition according to claim 1, characterized in that, In the general formula (2), M represents sodium ion.

4. The rubber-coating-forming silicone emulsion composition according to claim 1, characterized in that, The average particle size of the emulsified particles in the silicone emulsion composition formed by the rubber coating is less than 500 nm.

5. The rubber-coating-forming silicone emulsion composition according to claim 1, characterized in that, The dried film of this rubber-coated silicone emulsion composition has an elongation at break of 300% or more as measured according to JIS K 6251 with a thickness of 1 mm, and a tensile strength of 0.05 MPa or more as measured according to JIS K 6251 with a thickness of 1 mm.

6. A method for preparing a rubber-coated film-forming silicone emulsion composition, which is the method for preparing the rubber-coated film-forming silicone emulsion composition according to any one of claims 1 to 5, characterized in that it comprises the following steps (I) to (III), and the water (C) is added in such a manner that the total amount of (C-1), (C-2) and (C-3) is 1 to 10,000 parts by mass: Step (I) yields an O / W emulsion comprising an oil phase component, the surfactant (B), and water (C-1), wherein the oil phase component comprises a branched organopolysiloxane (A-1) represented by general formula (3), a mixture of (A-1) and a linear organopolysiloxane (A-2) represented by general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain, or a mixture of (A-2) and an alkoxysilane and / or its hydrolytic condensate (A-3) represented by general formula (5). (A-1) A branched organopolysiloxane represented by the following general formula (3), [Chemical Formula 2] In general formula (3), R 4 Each is an alkoxy group with 1 to 20 carbon atoms, R 5 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted 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 represented by the following general formula (4) having hydroxyl or alkoxy groups at both ends of the molecular chain. [Chemical Formula 3] In general formula (4), R 6 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms, and v is a number that satisfies 0 ≤ v ≤ 2000. (A-3) Alkoxysilanes and / or their hydrolytic condensates represented by the following general formula (5), R 7 e Si(OR 8 ) 4-e (5) In general formula (5), R 7 R consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms. 8 Each group consists of 1 to 20 monovalent hydrocarbon groups, which are either hydrogen atoms or substituted or unsubstituted carbon atoms, and e is 0 or 1; Step (II) involves further adding water (C-2) as needed to the emulsion composition obtained from step (I), then polymerizing component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3) in the oil phase of the emulsion at 0–40°C for 1–48 hours in the presence of an acid catalyst (G), followed by neutralization, thereby obtaining an emulsion of organopolysiloxane (A), which is a condensation reaction product obtained from component (A-1), a mixture of component (A-1) and component (A-2), or a mixture of component (A-2) and component (A-3), wherein… When the surfactant (B) has catalytic activity, the addition of the acid catalyst can be omitted; Step (III) involves adding at least one of the following to the emulsion of component (A) obtained from step (II): colloidal silica (D), the reaction product of an amino-containing organoalkoxysilane and anhydride (E), an epoxy-containing organoalkoxysilane, and / or its partial hydrolysate, and adding water (C-3) as needed.

7. The method for preparing the rubber-coated silicone emulsion composition according to claim 6, characterized in that, The (A-2) is a linear organopolysiloxane represented by general formula (4) with hydroxyl or alkoxy groups at both ends of the molecular chain, and has a viscosity of more than 200 mPa·s and less than 2000 mPa·s at 25°C.

8. A coating, characterized in that, It is the dried product of the rubber-coated silicone emulsion composition according to any one of claims 1 to 5.

9. The coating according to claim 8, characterized in that, The elongation at break, measured according to JIS K 6251, is 300% or more with a thickness of 1 mm, and the tensile strength, measured according to JIS K 6251, is 0.05 MPa or more with a thickness of 1 mm.

10. A fiber treatment agent, characterized in that, The composition comprising any one of claims 1 to 5.

11. A water-repellent agent, characterized in that, The composition comprising any one of claims 1 to 5.

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