Method for producing organopolysiloxane emulsion composition

Abstract

The present invention provides a method for producing an organopolysiloxane emulsion composition that has a low octamethyltetrasiloxane content, small particle size, and good long-term stability. [Solution] <Step (I)> (A) Organopolysiloxane represented by the following formula (1): 100 parts by mass HO(R 1 2SiO) n H (1)(B) Silane compound represented by the following formula (2): 0.01 to 10 parts by mass R 2 1st Round 1 (3-a) Si(OR 3 ) a (2) A method for producing an organopolysiloxane emulsion composition in which the amount of octamethylcyclotetrasiloxane is 3,000 ppm or less and the particle size of the emulsion is 1 μm or less, by emulsifying a mixture containing (C) surfactant: 1 to 8 parts by mass and (D-1) water: 1 to 10,000 parts by mass, and then emulsion polymerization is carried out at a temperature of less than 40°C in the presence of (E) an acid catalyst.

Description

[Technical Field]

[0001] The present invention relates to a method for producing an organopolysiloxane emulsion composition, and more specifically, to a method for producing an organopolysiloxane emulsion composition in which the content of octamethylcyclotetrasiloxane is suppressed. [Background technology]

[0002] Conventionally, emulsions obtained by emulsifying high-viscosity organopolysiloxanes have been used in a variety of applications, including cosmetics, personal care compositions, home care compositions, mold release agents, lubricants, coatings, fiber treatment agents, and resin modifiers. These applications require emulsions with small particle sizes and good temporal stability. However, when emulsifying using high-viscosity organopolysiloxanes as raw materials, the particle size of the emulsion particles is limited to a few micrometers, making it difficult to prepare smaller particles, and the resulting emulsion compositions often exhibit poor temporal stability. Therefore, various emulsion polymerization methods have been investigated to obtain emulsions with small particle sizes and good temporal stability.

[0003] For example, a method is known in which emulsion polymerization is carried out using a strong acid or strong base on an emulsified cyclic siloxane oligomer (Patent Documents 1 and 2). Using these methods, an emulsion of a high-viscosity polyorganosiloxane with an emulsion particle size of 300 nm or less can be obtained.

[0004] In recent years, there has been a growing demand for silicone emulsions with reduced octamethylcyclotetrasiloxane content. Methods described in Patent Documents 1 and 2 have shown that the resulting emulsions contain over 40,000 ppm of octamethylcyclotetrasiloxane, and methods to reduce this content are being investigated.

[0005] For example, the viscosity of organopolysiloxane at 25°C is 3,000 to 100,000 mm². 2 A method is known in which an organopolysiloxane with a molecular chain end sealed with a silanol group and containing octamethylcyclotetrasiloxane at a temperature of 1,000 ppm or less is emulsified at a temperature of less than 40°C in the presence of an acid catalyst, followed by emulsion polymerization (Patent Document 3). It is said that this method yields an emulsion in which the organopolysiloxane contains octamethyltetrasiloxane at a concentration of 3,000 ppm or less. However, in the above method, the viscosity of the polymerization monomer is 3,000 to 100,000 mm². 2 Due to its high viscosity of 1 / s, strong mechanical shear force is required to reduce the particle size of the emulsion composition made from this polymerization monomer, which may result in poor long-term stability of the resulting emulsion.

[0006] Furthermore, the viscosity at 25°C is 200-2,000 mm². 2 A method is known in which a mixture containing an organopolysiloxane in which the molecular terminal chains with a silanol group are sealed with a silanol group, a surfactant having an alkylnaphthalene skeleton, and water is emulsified, and then emulsion polymerization is carried out at a temperature of 40°C or lower in the presence of an acid catalyst (Patent Document 4). It is said that using this method, an emulsion can be obtained in which the viscosity of the resulting organopolysiloxane at 25°C is 300,000 mPa·s or more, the content of octamethyltetrasiloxane contained in the organopolysiloxane is 3,000 ppm or less, and the particle size of the resulting emulsion particles is 500 nm or less. However, this method has the disadvantage that it is difficult to incorporate reactive functional groups into the organopolysiloxane, and the range of applications of the emulsion is limited. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Special Publication No. 34-2041 [Patent Document 2] Special Publication No. 41-13995 [Patent Document 3] WO2013 / 153833 A1 [Patent Document 4] WO2017 / 038938 A1 [Summary of the Invention] [Problems to be Solved by the Invention]

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing an organopolysiloxane emulsion composition having a low content of octamethyltetrasiloxane, a small particle size, and good stability over time, which is contained in the organopolysiloxane emulsion composition. [Means for Solving the Problems]

[0009] In order to solve the above problems, in the present invention, A method for producing an organopolysiloxane emulsion composition, comprising: <Step (I)> (A) 100 parts by mass of an organopolysiloxane represented by the following general formula (1) and having an octamethylcyclotetrasiloxane content of 1,000 ppm or less: HO(R 1 2SiO) n [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​These are, independently of each other, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms bonded to the carbon atoms are replaced by an acryloxy group, a methacryloxy group, or a mercapto group, and R 3 (Each element is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a is 2 or 3.) (C) Surfactants: 1 to 8 parts by mass, (D-1) Water: 1 to 10,000 parts by mass, An emulsion composition is prepared by emulsifying a mixture containing the following: <Process (II)> The emulsion composition obtained in step (I) above is, if necessary, (D-2) Water: 0 to 10,000 parts by mass, The present invention provides a method for producing an organopolysiloxane emulsion composition, characterized by adding (E) an acid catalyst and then emulsion polymerization at a temperature of less than 40°C (however, if (C) a surfactant has catalytic activity, the addition of the acid catalyst can be omitted), wherein the amount of octamethylcyclotetrasiloxane contained in the resulting organopolysiloxane emulsion composition is 3,000 ppm or less, and the particle size of the resulting emulsion is 1 μm or less.

[0010] The present invention provides a method for producing an organopolysiloxane emulsion composition that has a low content of octamethyltetrasiloxane, small particle size, and good long-term stability.

[0011] Furthermore, it is preferable that the molecular weight of the organopolysiloxane in the organopolysiloxane emulsion composition used in the present invention at 25°C be 5,000 to 500,000.

[0012] In the present invention, it is preferable to use organopolysiloxanes with such molecular weights.

[0013] Furthermore, it is preferable to use a silane compound (B) in the present invention in which a=2 in the general formula (2).

[0014] The silane compound (B) used in the present invention is preferably of the type described above.

[0015] Furthermore, it is preferable to use a surfactant containing an anionic surfactant as the (C) surfactant used in the present invention.

[0016] It is preferable that the surfactant (C) used in the present invention contains such a surfactant.

[0017] In the present invention, it is preferable to use a surfactant (C) that includes an anionic surfactant having an alkylnaphthalene skeleton of the following general formula (5) as the surfactant (C). R 5 m -C 10 H (7-m) -SO3M (5) (In the formula, R 5 R is a linear or branched alkyl group having 1 to 30 carbon atoms, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, or tertiary ammonium ion. m is an integer from 1 to 3. Note that -SO3M in the formula is bonded to the 1st or 2nd position of the naphthalene ring. 5 The bonding position is one of the following: position 3, 4, 5, 6, 7, or 8.

[0018] In the present invention, it is preferable to use an anionic surfactant as the (C) surfactant. [Effects of the Invention]

[0019] As described above, the method for producing the organopolysiloxane emulsion composition of the present invention makes it possible to obtain an organopolysiloxane emulsion composition that has a low content of octamethyltetrasiloxane, small particle size, and good stability over time. Furthermore, since reactive functional groups can be introduced into the obtained organopolysiloxane emulsion composition, a wider range of applications can be obtained by reacting with or polymerizing it with other compounds in subsequent processes. [Modes for carrying out the invention]

[0020] As mentioned above, there has been a need to develop a method for producing organopolysiloxane emulsion compositions with a low content of octamethyltetrasiloxane.

[0021] As a result of diligent research to achieve the above objective, the present inventors have discovered that by using an organopolysiloxane having a specific structure with an octamethylcyclotetrasiloxane content of 1,000 ppm or less and a silane compound having a specific structure as monomer components for emulsion polymerization, and then emulsifying with a surfactant and polymerizing, it is possible to provide a method for producing an organopolysiloxane emulsion composition that has a low octamethyltetrasiloxane content, small particle size, and good stability over time, thus completing the present invention.

[0022] In other words, the present invention is A method for producing an organopolysiloxane emulsion composition, <Process (I)> (A) Organopolysiloxane represented by the following general formula (1), having an octamethylcyclotetrasiloxane content of 1,000 ppm or less: 100 parts by mass, HO(R 1 2SiO) n H (1) (In the formula, R 1These are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and n is the viscosity of organopolysiloxane (A) at 25°C, which is 40 mm². 2 / s or more, 2,000mm 2 This is a number less than / s. (B) Silane compound selected from the structure represented by the following general formula (2): 0.01 to 10 parts by mass, R 2 1st Round 1 (3-a) Si(OR 3 ) a (2) (In the formula, R 1 R in the general formula (1) above is 1 It is synonymous with R 2 These are, independently of each other, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms bonded to the carbon atoms are replaced by an acryloxy group, a methacryloxy group, or a mercapto group, and R 3 (Each element is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a is 2 or 3.) (C) Surfactants: 1 to 8 parts by mass, (D-1) Water: 1 to 10,000 parts by mass, An emulsion composition is prepared by emulsifying a mixture containing the following: <Process (II)> The emulsion composition obtained in step (I) above is, if necessary, (D-2) Water: 0 to 10,000 parts by mass, This method for producing an organopolysiloxane emulsion composition is characterized by adding (E) an acid catalyst and then emulsion polymerization at a temperature of less than 40°C (however, if (C) a surfactant has catalytic activity, the addition of the acid catalyst can be omitted), wherein the amount of octamethylcyclotetrasiloxane contained in the resulting organopolysiloxane emulsion composition is 3,000 ppm or less, and the particle size of the resulting emulsion is 1 μm or less.

[0023] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0024] [Organopolysiloxane emulsion composition] The raw materials used in the manufacturing method of the present invention will be described below.

[0025] <(A) Organopolysiloxane> The organopolysiloxane of component (A) used in the present invention is an organopolysiloxane represented by the following general formula (1), wherein the content of octamethyltetrasiloxane is 1,000 ppm or less. HO(R 1 2SiO) n H (1) (In the formula, R 1 These are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and n is the viscosity of organopolysiloxane (A) at 25°C, which is 40 mm². 2 / s or more, 2,000mm 2 This is a number less than / s.

[0026] The above R 1These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms. Examples of unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. Specifically, examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, and hexenyl; and aryl groups such as phenyl, tolyl, and naphthyl. Examples of substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms include those in which some of the hydrogen atoms in the monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified above are replaced with halogen atoms, amino groups, acryloxy groups, methacryloxy groups, epoxy groups, mercapto groups, carboxyl groups, hydroxyl groups, etc. Preferably, the monovalent hydrocarbon group has 1 to 6 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, or phenyl group. Total R 1 It is even more preferable if more than 80% of the group consists of methyl groups.

[0027] The above n represents the viscosity of the organopolysiloxane at 25°C, which is 40 mmHg. 2 / s or more, 2,000mm 2 This is a number less than / s, and is between 60 and 1,800 mm. 2 A number that results in / s is preferable, and is between 100 and 1,600 mm. 2 A more preferable number is 300 to 1,500 mm, where / s is the case. 2 A number that results in / s is particularly preferable. 2 If the viscosity is less than / s, it becomes necessary to increase the emulsion polymerization time to achieve the desired viscosity of the organopolysiloxane contained in the target organopolysiloxane emulsion composition, or the amount of octamethyltetrasiloxane produced as a by-product during emulsion polymerization increases. On the other hand, if the viscosity is 2,000 mm2 If the value is greater than / s, it becomes difficult to reduce the particle size of the desired emulsion.

[0028] The content of octamethyltetrasiloxane in the organopolysiloxane of component (A) above is 1,000 ppm (by mass, the same applies hereinafter) or less, and is particularly preferably 500 ppm or less. The lower limit is not particularly limited and may be 0 ppm.

[0029] <(B) Silane compounds> The component (B) used in the present invention is a silane compound selected from the structure represented by the following general formula (2), and these can be used individually or in combination of two or more. R 2 1st Round 1 (3-a) Si(OR 3 ) a (2) (In the formula, R 1 R in the general formula (1) above is 1 It is synonymous with R 2 These are, independently of each other, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms bonded to the carbon atoms are replaced by an acryloxy group, a methacryloxy group, or a mercapto group, and R 3 (Each element is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a is 2 or 3.)

[0030] In the above general formula (2), R 1 This is as stated above.

[0031] The above R 2These are, independently of each other, alkenyl groups having 2 to 6 carbon atoms, or in which some of the hydrogen atoms bonded to the carbon atoms are substituted with acryloxy, methacryloxy, or mercapto groups. Specific examples of alkenyl groups having 2 to 6 carbon atoms include vinyl, allyl, and hexenyl groups. Examples of groups in which some of the hydrogen atoms bonded to the carbon atoms are substituted with acryloxy, methacryloxy, or mercapto groups include 3-acryloxypropyl, 3-methacryloxypropyl, and 3-mercaptopropyl groups.

[0032] The above R 3 Each of these is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, and hexyl groups.

[0033] The above 'a' represents 2 or 3. By introducing reactive functional groups into the organopolysiloxane emulsion composition obtained in this invention, a wider range of applications can be achieved by reacting with or polymerizing it with other compounds in subsequent processes.

[0034] Furthermore, in the present invention, it is preferable to use a silane compound (B) in which a=2 in the general formula (2).

[0035] The above silane compounds specifically include vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltripropoxysilane, 3-(meth)acryloxypropyltriisopropoxysilane, and 3-(meth)acryloxypropyl Examples include (meth)acryloxysilanes such as ropiltributoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropylmethyldipropoxysilane, 3-(meth)acryloxypropylmethyldiisopropoxysilane, and 3-(meth)acryloxypropylmethyldibutoxysilane; and mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Preferably, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and more preferably 3-(meth)acryloxypropylmethyldimethoxysilane and 3-(meth)acryloxypropylmethyldiethoxysilane can be used.

[0036] In addition to the silane compound shown in the general formula (2) above, other silane compounds can also be used in combination.

[0037] The amount of component (B) used is 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of component (A). If the amount is less than 0.01 parts by mass, the proportion of reactive functional groups is too low, which will adversely affect the application in subsequent processes. For example, the reactivity when reacting or polymerizing with compounds such as acrylic monomers in subsequent processes may be poor, or the amount of acrylic component in the resulting silicone acrylic graft polymer may be low, resulting in deterioration of properties such as a decrease in the transparency and strength of the film. If the amount exceeds 10 parts by mass, the proportion of reactive functional groups is too high, which will adversely affect the application in subsequent processes. For example, the amount of acrylic component in the silicone acrylic graft polymer obtained by reacting or polymerizing with compounds such as acrylic monomers in subsequent processes may be high, resulting in deterioration of properties such as a decrease in the sliding properties of the film.

[0038] <(C) Surfactants> The surfactant of component (C) used in the present invention is not particularly limited as long as it can emulsify and disperse components (A) and (B) in water, but anionic surfactants or nonionic surfactants are preferred, and these can be used individually or in combination of two or more. In particular, anionic surfactants alone or a combination of anionic surfactants and nonionic surfactants is preferred.

[0039] Examples of the above-mentioned anionic surfactants include alkyl sulfate, alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, or salts thereof. However, from the viewpoint of the stability of the emulsion composition, the performance as an acid catalyst in emulsion polymerization, and availability, alkyl sulfate and its salts, alkylbenzene sulfonic acid and its salts are preferred.

[0040] Specific examples of the alkyl sulfates and their salts mentioned above include compounds represented by the following general formula (3). R 4 OSO3M (3) (In the formula, R 4 (where M is a linear or branched alkyl group having 6 to 30 carbon atoms, and M is a hydrogen ion, an alkali metal ion such as potassium or sodium, an alkaline earth metal ion such as magnesium or calcium, an ammonium ion, or a tertiary ammonium ion such as triethanolammonium.)

[0041] In the above general formula (3), R 4 The alkyl group is preferably a linear or branched alkyl group having 6 to 12 carbon atoms, and M is preferably a sodium ion, potassium ion, ammonium ion, or triethanolammonium ion from the viewpoint of emulsifying effect.

[0042] Specific examples of alkyl sulfates and their salts represented by the general formula (3) above include hexyl sulfate, octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, octadecyl sulfate, eicosyl sulfate, or alkali metal salts such as lithium salts, sodium salts, potassium salts, alkaline earth metal salts such as magnesium salts, calcium salts, triethanolammonium salt, ammonium salt, etc.

[0043] Specific examples of alkylbenzene sulfonic acid and its salts include compounds represented by the following general formula (4). R 4 -C6H4-SO3M (4) (In the formula, R 4 As defined in general formula (3), is a linear or branched alkyl group having 6 to 30 carbon atoms, and M is as defined in general formula (3), such as a hydrogen ion, an alkali metal ion such as potassium or sodium, an alkaline earth metal ion such as magnesium or calcium, an ammonium ion, or a tertiary ammonium ion such as triethanolammonium.

[0044] In the above general formula (4), R 4The alkyl group is preferably a linear or branched alkyl group having 6 to 12 carbon atoms, and M is preferably a sodium ion, potassium ion, ammonium ion, or triethanolammonium ion due to its emulsifying effect.

[0045] Specific examples of alkylbenzenesulfonic acid and its salts represented by the above general formula (4) include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, or alkali metal salts such as lithium salts, sodium salts, potassium salts, alkaline earth metal salts such as magnesium salts, calcium salts, triethanolammonium salt, ammonium salt, etc. As component (C) above, these anionic surfactants can be used alone or in combination of two or more.

[0046] Specific examples of the alkylnaphthalene sulfonic acid and its salts include compounds represented by the following general formula (5). In the present invention, it is preferable to use an anionic surfactant having the alkylnaphthalene skeleton of the following general formula (5). [ka] (In the formula, R 5 R is a linear or branched alkyl group having 1 to 30 carbon atoms, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, or tertiary ammonium ion. m is an integer from 1 to 3. Note that -SO3M in the formula is bonded to the 1st or 2nd position of the naphthalene ring. 5 The bonding position is one of the following: position 3, 4, 5, 6, 7, or 8.

[0047] In the above general formula (5), R 5is a linear or branched alkyl group having 1 to 30 carbon atoms, M is a hydrogen ion; an alkali metal ion such as potassium or sodium; an alkaline earth metal ion such as magnesium or calcium; or a tertiary ammonium ion such as ammonium ion or triethanolammonium. m is an integer from 1 to 3. Note that -SO3M is bonded to the 1st or 2nd position of the naphthalene ring. Also, R 5 The bonding position is one of the following: position 3, 4, 5, 6, 7, or 8.

[0048] In the above general formula (5), R 5 The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and from the viewpoint of emulsification, M is preferably a sodium ion, potassium ion, ammonium ion, or triethanolammonium ion.

[0049] Specific examples of alkylnaphthalenesulfonic acid and its salts represented by the general formula (5) above include butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, tetradecylnaphthalenesulfonic acid, hexadecylnaphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, bisisopropylnaphthalenesulfonic acid, trisisopropylnaphthalenesulfonic acid and their salts.

[0050] Examples of the nonionic surfactants mentioned above include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers and polyoxyethylene oxypropylene alkyl ethers; sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene fatty acid esters. However, from the viewpoint of the stability and safety of the emulsion composition, polyoxyalkylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters are particularly preferred.

[0051] Specific examples of these include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene oxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene oxypropylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate.

[0052] The amount of component (C) used is 1 to 8 parts by mass, preferably 2 to 7 parts by mass, and more preferably 3 to 6 parts by mass, per 100 parts by mass of component (A). If the amount added is less than 1 part by mass, the stability of the emulsion composition will be poor, and if the amount added exceeds 8 parts by mass, the properties of the film formed from the emulsion composition will be poor. Note that the above amounts represent the amount of the active ingredient of the surfactant, and if used as an aqueous solution of the surfactant, the value excludes water.

[0053] <(D)Water> The water component (D) used in this invention consists of (D-1) used in step (I) and (D-2) used in step (II) as needed. In step (I), the amount of water component (D-1) used is 1 to 10,000 parts by mass per 100 parts by mass of (A), and varies depending on the type of emulsifier used to reduce the particle size of the emulsion.

[0054] For example, when using a high-pressure homogenizer (an emulsifier that pressurizes the processing liquid to high pressure or ultra-high pressure and obtains shear force by passing it through a slit, or an emulsifier that atomizes by causing pressurized processing liquids to collide obliquely at ultra-high speed) to reduce the particle size of emulsion particles by processing at high pressure, the amount of component (D-1) used is preferably 1 to 10,000 parts by mass, more preferably 4 to 6,000 parts by mass, and even more preferably 6 to 4,000 parts by mass, per 100 parts by mass of component (A).

[0055] Furthermore, when using emulsifiers such as homodispers (emulsifiers that obtain shear force by rapidly rotating a circular disc with saw-toothed teeth on its outer circumference), homomixers (emulsifiers that obtain shear force by rapidly rotating a rotor installed inside with a stator installed on the outer circumference), and colloid mills (emulsifiers that obtain shear force by feeding each component into the gap between a rapidly rotating disc and a fixed disc) to reduce the particle size of emulsion particles using shear force, the amount of component (D-1) used is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, and even more preferably 4 to 6 parts by mass, per 100 parts by mass of component (A). Within this range of usage, an emulsion composition with excellent stability and a small particle size of 1 μm or less can be obtained.

[0056] In step (II) above, water of component (D-2) may or may not be added, and it is preferable that it be 10,000 parts by mass or less (0 to 10,000 parts by mass) per 100 parts by mass of (A). If component (D-2) is added, it is more preferable that it be 0.1 to 1,000 parts by mass. In addition, it is generally preferable to add water of component (D-2) when using emulsifiers such as homodispersers, homomixers and colloid mills.

[0057] <(E) Acid catalyst> The component (E) used in this invention is an acid catalyst, and if component (C) has catalytic activity (for example, if an acid is used as component (C)), the addition of component (E) can be omitted. Furthermore, when component (E) is used, it can be used alone or in combination of two or more types.

[0058] (E) The following components (E-1) to (E-5) are examples of components (E-1) to (E-5).

[0059] (E-1) Alkyl sulfuric acid represented by the following general formula (6), or alkylbenzene sulfonic acid represented by the following general formula (7). R 7 OSO3H (6) (In the formula, R 7 (A linear or branched alkyl group has 6 to 30 carbon atoms.) R 5 -C6H4-SO3H (7) (In the formula, R 5 (As defined in the general formula (5) above, it is a linear or branched alkyl group having 1 to 30 carbon atoms.)

[0060] In the above general formulas (6) and (7), R 5 and R 7 It is preferable that the alkyl group is a linear or branched alkyl group having 6 to 12 carbon atoms.

[0061] Specific examples of alkyl sulfates represented by the above general formula (6) include hexyl sulfate, octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, octadecyl sulfate, and eicosyl sulfate.

[0062] Specific examples of alkylbenzenesulfonic acid represented by the above general formula (7) include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, and hexadecylbenzenesulfonic acid.

[0063] (E-2) Higher fatty acids Specific examples include lauric acid, stearic acid, oleic acid, and linolenic acid.

[0064] (E-3) Polyoxyethylene alkyl ether sulfate represented by the following general formula (8) R 5 O(EO) s (PO)t SO3H (8) (In the formula, R 5 As defined in the general formula (5) above, is a linear or branched alkyl group having 1 to 30 carbon atoms. EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. s and t are each independent integers from 0 to 100, where s+t>0, and especially 1≦s+t≦50.

[0065] Specific examples of polyoxyethylene alkyl ether sulfate represented by the above general formula (8) include polyoxyethylene hexyl ether sulfate, polyoxyethylene octyl ether sulfate, polyoxyethylene decyl ether sulfate, polyoxyethylene dodecyl ether sulfate, polyoxyethylene tetradecyl ether sulfate, polyoxyethylene hexadecyl ether sulfate, polyoxyethylene octadecyl ether sulfate, and polyoxyethylene eicosyl ether sulfate.

[0066] (E-4) Polyoxyethylene alkylphenyl ether sulfate represented by the following general formula (9) R 5 -C6H4-O(EO) s (PO) t SO3H (9) (In the formula, R 5 As defined in the general formula (5) above, is a linear or branched alkyl group having 1 to 30 carbon atoms. EO, PO, s, and t are defined in the general formula (8) above, with EO representing an ethylene oxide group and PO representing a propylene oxide group, and their arrangement may be blocky or random. s and t are each independent integers from 0 to 100, where s+t>0, and especially 1≦s+t≦50.

[0067] Specific examples of polyoxyethylene alkylphenyl ether sulfate represented by the above general formula (9) include polyoxyethylene hexylphenyl ether sulfate, polyoxyethylene octylphenyl ether sulfate, polyoxyethylene decylphenyl ether sulfate, polyoxyethylene dodecylphenyl ether sulfate, polyoxyethylene tetradecylphenyl ether sulfate, and polyoxyethylene hexadecylphenyl ether sulfate.

[0068] (E-5) Brønsted acid Examples include hydrochloric acid, hydrobromic acid, sulfuric acid, chlorosulfonic acid, phosphoric acid, orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, boric acid, nitric acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic 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, succinic acid, cations, acidic zeolite, acid-activated filler earth, and acid-activated carbon black.

[0069] The amount of component (E) used (however, if the surfactant of component (C) is an anionic surfactant and M in the above general formula (3), (4), or (5) is a hydrogen atom, and has catalytic activity and is included in the acid catalyst of component (E), then the total amount includes the amount of this component (C) used) is preferably at least 0.1 parts by mass, more preferably 0.3 parts by mass, and even more preferably 0.5 parts by mass, per 100 parts by mass of component (A). 0.1 parts by mass or more is preferable as it does not risk slowing down the polymerization rate. There is no particular upper limit, but 125 parts by mass or less is preferred.

[0070] [Method for producing organopolysiloxane emulsion composition] The method for producing the organopolysiloxane emulsion composition of the present invention will be described below.

[0071] <Process (I)> In step (I) of the present invention, an emulsion composition is prepared by emulsifying a mixture containing components (A), (B), (C), and (D-1). For emulsification here, an emulsifier such as a homodisper, homomixer, colloid mill, line mixer, universal mixer, ultramixer, planetary mixer, combimix, or high-pressure homogenizer can be used, but preferably an emulsifier that reduces the particle size of emulsion particles using shear force, such as a homodisper, homomixer, or colloid mill, is used, more preferably a homodisper.

[0072] In this step, the emulsification temperature is preferably 1 to 80°C. If component (C) has catalytic activity, the cyclization reaction of component (A), which is a side reaction, proceeds simultaneously, so it is preferable to carry out emulsification at a temperature below 40°C. Carrying out emulsification at a temperature below 40°C is preferable because it eliminates the risk of excessive formation of octamethylcyclotetrasiloxane. For this reason, it is more preferable to have a temperature below 30°C, and even more preferable to have a temperature below 25°C.

[0073] In step (I) above, the mixture is mixed under high shear force until the particle size of the emulsion composition is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. The smaller the particle size of the emulsion composition obtained in step (I), the higher the polymerization rate in step (II), leading to a reduction in polymerization time and suppression of octamethylcyclotetrasiloxane formation. Furthermore, if the particle size of the emulsion composition obtained in step (I) is 500 nm or less, the particle size of the final emulsion composition obtained through the next step will also be 500 nm or less. In this invention, the particle size of the emulsion composition is the median diameter value measured by a laser diffraction / scattering particle size distribution analyzer LA-950 (manufactured by Horiba, Ltd.).

[0074] <Process (II)> In step (II) of the present invention, component (D-2) is optionally added to the emulsion composition obtained in step (I) and dispersed, and then emulsion polymerization is carried out at a temperature of less than 40°C in the presence of an acid catalyst (E) (however, if the surfactant (C) has catalytic activity, the addition of the acid catalyst may be omitted). Polymerization is carried out until the molecular weight of the organopolysiloxane at 25°C is 5,000 or more.

[0075] Furthermore, if component (D-2) is added to the emulsion composition obtained in step (I) above, it can be further emulsified and dispersed using an emulsifier such as a high-pressure homogenizer, if necessary.

[0076] When the above emulsion composition is subjected to emulsion polymerization, the polymerization step is preferably carried out at a temperature below 40°C for 48 hours or less. Polymerization at a temperature higher than 40°C may result in excessive formation of octamethylcyclotetrasiloxane. Therefore, the temperature is preferably below 30°C, more preferably below 25°C, and particularly preferably below 15°C. Furthermore, if the polymerization time is within 48 hours, there is no risk of excessive formation of octamethylcyclotetrasiloxane, which is preferable. Therefore, 1 to 40 hours is preferred, and 5 to 30 hours is more preferred.

[0077] The molecular weight (M) of the organopolysiloxane produced by emulsion polymerization in step (II) above is preferably 5,000 to 500,000, more preferably 8,000 to 450,000, even more preferably 10,000 to 400,000, and most preferably 100,000 to 300,000 at 25°C. Having this molecular weight results in good curability and slipperiness when used as a coating agent. Furthermore, when graft copolymerized with acrylic monomers or the like in a subsequent step, a coating agent with the excellent slipperiness characteristic of silicone is obtained.

[0078] Here, the molecular weight (M) of the polyorganosiloxane can be calculated from the specific viscosity ηsp (25°C) of a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml. ηsp = (η / η0) - 1 (η0: Viscosity of toluene, η: Viscosity of toluene solution of organopolysiloxane with a concentration of 1 g / 100 ml) ηsp = [η] + 0.3[η] 2 [η] = 2.15×10 -4 M 0.65 (References: Nakamuta, Nippon Kagaku, 77 858

[1956] , Doklady Akad. Nauk. U.S.S.R. 89 65

[1953] )

[0079] <Neutralization step> The production method of the present invention can include a neutralization step of neutralizing the obtained organopolysiloxane emulsion composition with a basic substance after the above polymerization is completed. Examples of the basic substance include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine, triethylamine, etc.

[0080] The content of octamethylcyclotetrasiloxane contained in the organopolysiloxane in the organopolysiloxane emulsion composition obtained in the present invention is 3,000 ppm or less, preferably 2,000 ppm or less, and more preferably 1,000 ppm or less. The lower limit is not particularly limited and may be 0 ppm.

[0081] The content of decamethylcyclopentasiloxane contained in the organopolysiloxane in the organopolysiloxane emulsion composition obtained in the present invention is preferably 3,000 ppm or less, more preferably 2,000 ppm or less, and particularly preferably 1,000 ppm or less. The lower limit is not particularly limited and may be 0 ppm.

[0082] The content of dodecamethylcyclohexasiloxane contained in the organopolysiloxane in the organopolysiloxane emulsion composition obtained in the present invention is preferably 3,000 ppm or less, more preferably 2,000 ppm or less, and particularly preferably 1,000 ppm or less. The lower limit is not particularly limited and may be 0 ppm.

[0083] <Other ingredients> In addition to the components (A) to (E) above, various additives can be incorporated into the organopolysiloxane emulsion composition of the present invention.

[0084] For example, depending on the purpose, thickeners, antifreezes, preservatives, rust inhibitors, antioxidants, UV absorbers, solvents, etc., can be added.

[0085] The organopolysiloxane emulsion composition obtained in the present invention can be applied to the surface of a substrate such as fibers, metals, ceramic inorganic materials, glass, wood, paper products, plastics, cement, concrete, or mortar, and cured at room temperature or by heating to form a cured film (protective film). Furthermore, because it has reactive functional groups, for example, by graft copolymerization with acrylic monomers in a subsequent process, a silicone acrylic graft copolymer resin emulsion can be obtained in which the cured film is transparent and has sliding and water-repellent properties. [Examples]

[0086] The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these. In the following examples, parts represent parts by mass, and % represents mass percent.

[0087] [Example 1] Viscosity is 700 mm 2 / s is an organopolysiloxane (A-1) having a silanol group at the end of the molecular chain (in general formula (1), R 192.09 parts of (methyl group, octamethylcyclotetrasiloxane content 50 ppm or less) and 0.09 parts of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxysilane) were mixed, and 2.0 parts of Perex NBL (manufactured by Kao Corporation, 35% aqueous solution of alkylnaphthalene sulfonate sodium), 1.18 parts of Newcol 291-PG (manufactured by Nippon Emulsifier Co., Ltd., 70% propylene glycol solution of dialkyl succinate sulfonate sodium), and 1.51 parts of Emal 270J (manufactured by Kao Corporation, 70% aqueous solution of polyoxyethylene alkyl ether sulfate sodium) were dissolved in ion-exchanged water. The mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. To this emulsion, 2.6 parts of Neoperex GS-P (manufactured by Kao Corporation, alkylbenzene sulfonic acid), diluted with deionized water, were added, and emulsion polymerization was carried out at 10°C for 20-25 hours. Subsequently, 0.46 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.07 parts of the preservative ACTICIDE LA2011 (manufactured by So Japan Co., Ltd., aqueous solution of methylisothiazolinone, chloromethylisothiazolinone, and bronopol) were added to obtain the emulsion composition. The solid content was 53.6%, the octamethylcyclotetrasiloxane content was 800 ppm, the viscosity of the organopolysiloxane emulsion composition was 105 mPa·s, the average particle size was 0.28 μm, and the molecular weight (M) was 300,000.

[0088] [Example 2] Viscosity is 700 mm 294.29 parts of organopolysiloxane (A-1) having a silanol group at the end of the / s molecular chain and 0.09 parts of KBM-502 (same as above) were mixed, and 1.02 parts of Perex NBL (same as above), 0.6 parts of Newcol 291-PG (same as above), and 0.77 parts of Emal 270J (same as above) were dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 2.67 parts of Neoperex GS-P (same as above), diluted with deionized water, were added to this emulsion, and emulsion polymerization was carried out at 10°C for 20-25 hours. After that, 0.48 parts of sodium carbonate dissolved in deionized water were added to the resulting emulsion to neutralize it, and finally 0.08 parts of the preservative ACTICIDE LA2011 (same as above) were added to obtain the emulsion composition. The solid content was 53.1%, the octamethylcyclotetrasiloxane content was 860 ppm, the viscosity of the organopolysiloxane emulsion composition was 285 mPa·s, the average particle size was 0.68 μm, and the molecular weight (M) was 300,000.

[0089] [Example 3] Viscosity is 700 mm 2 92.09 parts of organopolysiloxane (A-1) having a silanol group at the end of the / s molecular chain and 0.09 parts of KBM-502 (same as above) were mixed, and 2.0 parts of cinolin 100 (Shin Nippon Rika Co., Ltd., sodium alkyl sulfate), 1.18 parts of Newcol 291-PG (same as above), and 1.51 parts of Emal 270J (same as above) were dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 2.6 parts of Neoperex GS-P (same as above), diluted with deionized water, were added to this emulsion, and emulsion polymerization was carried out at 10°C for 20-25 hours. After that, 0.46 parts of sodium carbonate dissolved in deionized water were added to the resulting emulsion to neutralize it, and finally 0.07 parts of the preservative ACTICIDE LA2011 (same as above) were added to obtain the emulsion composition. The solid content was 53.8%, the octamethylcyclotetrasiloxane content was 2,240 ppm, the viscosity of the organopolysiloxane emulsion composition was 1,420 mPa·s, the average particle size was 0.32 μm, and the molecular weight (M) was 300,000.

[0090] [Example 4] Viscosity is 700 mm 2 91.98 parts of organopolysiloxane (A-1) having a silanol group at the end of the molecular chain of / s, 0.09 parts of KBM-502 (same as above), and 0.12 parts of KF-96L-0.65cs (Hexamethyldisiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed, and 2.0 parts of Perex NBL (same as above), 1.18 parts of Newcol 291-PG (same as above), and 1.51 parts of Emal 270J (same as above) were dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. 2.6 parts of Neoperex GS-P (same as above), diluted with deionized water, were added to this emulsion, and emulsion polymerization was carried out at 10°C for 20-25 hours. Subsequently, 0.46 parts of sodium carbonate dissolved in deionized water were added to the obtained emulsion to neutralize it, and finally, 0.07 parts of the preservative ACTICIDE LA2011 (same as above) were added to obtain the emulsion composition. The solid content was 52.9%, the octamethylcyclotetrasiloxane content was 1,180 ppm, the viscosity of the organopolysiloxane emulsion composition was 92 mPa·s, the average particle size was 0.22 μm, and the molecular weight (M) was 170,000.

[0091] [Comparative Example 1] A mixture of 17.5 parts KBM-502 (same as above) and 0.007 parts BHT (dibutylhydroxytoluene) was mixed with 5.61 parts of 0.1N hydrochloric acid water, and the mixture was stirred at 60°C for 3 hours to induce a hydrolysis-condensation reaction. After separating and removing the aqueous phase by liquid-liquid separatory, 14.03 parts toluene and 6.0 parts deionized water were added, and the mixture was washed with water to separate and remove residual hydrochloric acid and by-product methanol. The toluene was then removed by reduced pressure distillation at 90°C to obtain the KBM-502 condensation product. 0.08 parts of the obtained KBM-502 condensation product was mixed with 97.29 parts DMC (dimethylcyclosiloxane), and 1.36 parts NIKKOL SLS (sodium lauryl sulfate, manufactured by Nikko Chemicals Co., Ltd.) was dissolved in deionized water. This mixture was emulsified using a homomixer and homodisper, and then treated with a high-pressure homogenizer. To this emulsion, 0.97 parts of Neoperex GS-P (same as above), diluted with deionized water, were added and emulsion polymerization was carried out at 55°C for 20-25 hours, followed by further emulsion polymerization at 10-20°C for 20-25 hours. Subsequently, 0.3 parts of sodium carbonate dissolved in deionized water were added to the resulting emulsion to neutralize it and obtain an emulsion composition. The solid content was 45.0%, the octamethylcyclotetrasiloxane content was 24,000 ppm, the viscosity of the organopolysiloxane emulsion composition was 80 mPa·s, the average particle size was 0.30 μm, and the molecular weight (M) was 250,000.

[0092] [Comparative Example 2] 100.0 parts of organopolysiloxane (A-1) with a viscosity of 700 mm² / s and silanol groups at the end of the molecular chain were added to 5.0 parts of Perex NBL (same as above) and 6.0 parts of deionized water, and emulsified by homodisperser. 85.4 parts of deionized water were added to the resulting first emulsion and diluted and dispersed by homomixer. Next, 1.2 parts of concentrated hydrochloric acid was added, and emulsion polymerization was carried out at 10°C for 22 hours. Subsequently, 2.4 parts of triethanolamine were added to the resulting emulsion and diluted and dispersed by homomixer to obtain an emulsion composition. The solid content was 53.3%, the octamethylcyclotetrasiloxane content was 700 ppm, the viscosity of the organopolysiloxane emulsion composition was 380 mPa·s, the average particle size was 0.15 μm, and the molecular weight (M) was 190,000.

[0093] <Method for measuring solid content> Approximately 1 g of the resin emulsion (sample) obtained in Examples 1-4 and Comparative Examples 1 and 2 was accurately weighed onto an aluminum foil dish, placed in a drying oven maintained at approximately 105°C, heated for 1 hour, then removed from the drying oven and allowed to cool in a desiccator. The weight of the dried sample was measured, and the evaporation residue was calculated using the following formula. R: Evaporation residue (%) W: Mass of the aluminum foil dish containing the sample before drying (g) L: Mass of the aluminum foil tray (g) T: Mass of the aluminum foil dish containing the dried sample (g) Aluminum foil tray dimensions: 70φ × 12h (mm)

[0094] <Octamethylcyclotetrasiloxane (D4) content in emulsion> 0.1 g of organopolysiloxane emulsion composition was extracted with 10 mL of acetone containing 20 ppm (by mass) of tetradecane as an internal standard (shaking for 3 hours). After standing overnight, the acetone layer was collected and octamethylcyclotetrasiloxane was quantified by gas chromatography analysis.

[0095] <Viscosity Measurement> The viscosity of the emulsion was measured using a BM-type viscometer with rotor No. 2, at 25°C and 6 rpm.

[0096] <Average particle size> This is the particle size (median diameter) at 50% of the cumulative value in the volume-based particle size distribution measured using the LA-950 laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd.).

[0097] <Molecular weight measurement method> The molecular weight (M) was determined from the specific viscosity of a toluene solution of organopolysiloxane at a concentration of 1 g / 100 mL.

[0098] Specifically, 20 g of the emulsion was mixed with 20 g of IPA (isopropyl alcohol), and after the emulsion was destroyed, the IPA was discarded, and the remaining rubbery organopolysiloxane was dried at 105 °C for 3 hours. Toluene was added thereto to obtain a toluene solution of organopolysiloxane with a concentration of 1 g / 100 mL, and the measurement was carried out at 25 °C using an Ubbelohde viscometer. The molecular weight (M) was determined by substituting the measured viscosity into the following formula. ηsp = (η / η0) - 1 (η0: Viscosity of toluene, η: Viscosity of the toluene solution of organopolysiloxane with a concentration of 1 g / 100 mL) ηsp = [η] + 0.3[η] 2 [η] = 2.15×10 -4 M 0.65 (References: Nakata, Nippon Kasei Kagaku Kaishi, 77, 858

[1956] , Doklady Akad. Nauk. U.S.S.R., 89, 65

[1953] )

[0099] The compounding amounts and evaluation results of the respective components of Examples 1 to 4, Comparative Examples 1 and 2 are shown in Tables 1 and 2, respectively.

[0100]

Table 1

[0101]

Table 2

[0102] <Copolymerization with methyl methacrylate> Using the organopolysiloxane emulsion compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 2, copolymerization with methyl methacrylate was carried out according to the following formulation, and evaluation was carried out.

[0103] [Examples 1 to 4, Comparative Example 2] 59.0 parts of the obtained organopolysiloxane emulsion composition was placed in a reaction vessel and diluted with 20.8 parts of deionized water. After adjusting the temperature to 30°C, 13.4 parts of methyl methacrylate were added dropwise over 3 to 5 hours, using ferrous sulfate as an initiator, along with peroxides and activators, to carry out polymerization by redox reaction.

[0104] [Comparative Example 1] 69.2 parts of the obtained organopolysiloxane emulsion composition were placed in a reaction vessel and diluted with 10.0 parts of deionized water. After adjusting the temperature to 30°C, 13.4 parts of methyl methacrylate were added dropwise over 3 to 5 hours, using ferrous sulfate as an initiator, along with peroxide and activator, to carry out polymerization by redox reaction.

[0105] <Fabrication of individual membranes> Using a bar coater No. 10 or No. 12, a PET film (manufactured by Toray Industries, Inc., part number: Lumirror #125-S10) was coated to a film thickness of 10 μm after drying, and individual films were prepared by drying in a 105°C dryer for 5 minutes.

[0106] <Measuring the water contact angle> After bringing 0.2 μL of deionized water droplets into contact with each film, the contact angle of the droplets was measured 10 seconds later using an automatic contact angle measuring device DMO-601 (manufactured by Kyowa Interfacial Chemical Co., Ltd.).

[0107] <Measurement of static and dynamic friction coefficients> Using a HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.), a 200g stainless steel metal indenter was brought into perpendicular contact with the coating films of each of the above examples and comparative examples, and the frictional force was measured when it was moved at 3 cm / min. From the frictional force, the static friction coefficient and the kinetic friction coefficient were calculated.

[0108] <Tucked feel> The surface of the PET film, which had a single layer formed on it, was evaluated by touching it with a finger. ○: No tackiness, good glide. ×: It has a tacky feel, and you feel resistance on your fingers; it doesn't slide well.

[0109] [Table 3] All raw materials used are listed in parts by mass.

[0110] [Table 4] All raw materials used are listed in parts by mass.

[0111] From the results in Tables 1 to 4 above, all organopolysiloxane emulsion compositions of Examples 1 to 4 had an octamethyltetrasiloxane content of 3,000 ppm or less, an average particle size of 1 μm or less, and the molecular weight of the organopolysiloxane in the organopolysiloxane emulsion composition at 25°C was between 5,000 and 500,000.

[0112] On the other hand, Comparative Example 1, in which component (A) and polymerization temperature differ from the present invention, had a high content of octamethyltetrasiloxane at 24,000 ppm, and Comparative Example 2, in which component (B) differed, lacked reactive functional groups. As a result, a graft copolymer with methyl methacrylate could not be obtained in the evaluation samples listed in Table 4 above, resulting in an ununiform film and poor tackiness.

[0113] This specification includes the following embodiments. [1]: A method for producing an organopolysiloxane emulsion composition, <Process (I)> (A) Organopolysiloxane represented by the following general formula (1), having an octamethylcyclotetrasiloxane content of 1,000 ppm or less: 100 parts by mass, HO(R 1 2SiO) n H (1) (In the formula, R 1 These are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and n is the viscosity of organopolysiloxane (A) at 25°C, which is 40 mm². 2 / s or more, 2,000mm 2This is a number less than / s. (B) Silane compound selected from the structure represented by the following general formula (2): 0.01 to 10 parts by mass, R 2 1st Round 1 (3-a) Si(OR 3 ) a (2) (In the formula, R 1 R in the general formula (1) above is 1 It is synonymous with R 2 These are, independently of each other, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms bonded to the carbon atoms are replaced by an acryloxy group, a methacryloxy group, or a mercapto group, and R 3 (Each element is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a is 2 or 3.) (C) Surfactants: 1 to 8 parts by mass, (D-1) Water: 1 to 10,000 parts by mass, An emulsion composition is prepared by emulsifying a mixture containing the following: <Process (II)> The emulsion composition obtained in step (I) above is, if necessary, (D-2) Water: 0 to 10,000 parts by mass, A method for producing an organopolysiloxane emulsion composition, characterized by adding (E) an acid catalyst and then emulsion polymerization at a temperature of less than 40°C (however, if (C) a surfactant has catalytic activity, the addition of the acid catalyst may be omitted), wherein the amount of octamethylcyclotetrasiloxane contained in the resulting organopolysiloxane emulsion composition is 3,000 ppm or less, and the particle size of the resulting emulsion is 1 μm or less. [2]: A method for producing the organopolysiloxane emulsion composition according to [1], characterized in that the molecular weight of the organopolysiloxane in the organopolysiloxane emulsion composition at 25°C is 5,000 to 500,000. [3]: A method for producing an organopolysiloxane emulsion composition according to [1] or [2], characterized in that the (B) silane compound is one in which a=2 in the general formula (2). [4]: A method for producing an organopolysiloxane emulsion composition according to any one of [1] to [3], characterized in that the (C) surfactant includes an anionic surfactant. [5]: A method for producing an organopolysiloxane emulsion composition according to any one of [1] to [4], characterized in that the (C) surfactant includes an anionic surfactant having an alkylnaphthalene skeleton of the following general formula (5). R 5 m -C 10 H (7-m) -SO3M (5) (In the formula, R 5 R is a linear or branched alkyl group having 1 to 30 carbon atoms, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, or tertiary ammonium ion. m is an integer from 1 to 3. Note that -SO3M in the formula is bonded to the 1st or 2nd position of the naphthalene ring. 5 The bonding position is one of the following: position 3, 4, 5, 6, 7, or 8.

[0114] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. A method for producing an organopolysiloxane emulsion composition, <Step (I)> (A) Organopolysiloxane represented by the following general formula (1) and having an octamethylcyclotetrasiloxane content of 1,000 ppm or less: 100 parts by mass, HO(R １ ２ SiO) ｎ H (1) (In the formula, R １ These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, where n is the viscosity of organopolysiloxane (A) at 25°C, which is 40 mm². ２ / s or more, 2,000mm ２ (A number less than / s.) (B) Silane compound selected from the structure represented by the following general formula (2): 0.01 to 10 parts by mass, R ２ １ R １ （３－ａ） Si(OR ３ ) ａ (2) (In the formula, R １ R in the general formula (1) above is １ It is synonymous with R ２ R is an alkyl group having 1 to 6 carbon atoms, which is an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms bonded to the carbon atoms are replaced by an acryloxy group, a methacryloxy group, or a mercapto group, and R ３ (Each element is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a is 2 or 3.) (C) Surfactant: 1 to 8 parts by mass, (D-1) Water: 1 to 10,000 parts by mass, An emulsion composition is prepared by emulsifying a mixture containing the following: <Step (II)> The emulsion composition obtained in step (I) above is, if necessary, (D-2) Water: 0 to 10,000 parts by mass, A method for producing an organopolysiloxane emulsion composition, characterized by adding (E) an acid catalyst and then emulsion polymerization at a temperature of less than 40°C (however, if (C) a surfactant has catalytic activity, the addition of the acid catalyst may be omitted), wherein the amount of octamethylcyclotetrasiloxane contained in the resulting organopolysiloxane emulsion composition is 3,000 ppm or less, and the particle size of the resulting emulsion is 1 μm or less.

2. A method for producing the organopolysiloxane emulsion composition according to claim 1, characterized in that the molecular weight of the organopolysiloxane in the organopolysiloxane emulsion composition at 25°C is 5,000 to 500,000.

3. A method for producing an organopolysiloxane emulsion composition according to claim 1 or 2, characterized in that the (B) silane compound is one in which a = 2 in the general formula (2).

4. A method for producing an organopolysiloxane emulsion composition according to claim 1 or 2, characterized in that the (C) surfactant includes an anionic surfactant.

5. A method for producing an organopolysiloxane emulsion composition according to claim 4, characterized in that the (C) surfactant includes an anionic surfactant having an alkylnaphthalene skeleton of the following general formula (5). R ５ ｍ -C １０ H （７－ｍ） -SO ３ M (5) (In the formula, R ５ is a linear or branched alkyl group having 1 to 30 carbon atoms, M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, or tertiary ammonium ion, and m is an integer from 1 to 3. Note that -SO in the formula ３ M is bonded to the 1st or 2nd position of the naphthalene ring. Also, R ５ The bonding position is one of the following: position 3, 4, 5, 6, 7, or 8.

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