Emulsion composition of film-forming organopolysiloxane and method for producing the same

Abstract

The present invention is an emulsion composition of a film-forming organopolysiloxane, the emulsion composition being characterized by comprising: 100 parts by mass of (A) an organopolysiloxane which is represented by average composition formula (1), has a viscosity of at least 300,000 mPa∙s at 25ºC, and contains alkoxy groups or hydroxy groups bonded to at least two silicon atoms in one molecule; 0.1-30 parts by mass of (B) a cationic surfactant; 30-3,000 parts by mass of (C) water; and 0.5-50 parts by mass of (D) colloidal silica. Consequently, provided is an emulsion composition of a film-forming organopolysiloxane having favorable film formability, excellent film strength and flexibility after curing, and favorable storage stability. (In the formula, R1 is a hydrogen atom or a C1-C20 monovalent organic group, and R2 is a C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkoxy group, or a hydroxy group.)

Description

[Technical Field]

[0001] The present invention relates to an emulsion composition of a film-forming organopolysiloxane, and a method for producing the composition. [Background technology]

[0002] Silicone emulsion compositions that form rubber coatings have been known for a long time in various compositions and are used in a variety of applications such as weatherstripping agents, coating agents, binders, and fiber treatment agents.

[0003] For example, a silicone emulsion composition comprising a hydroxylated diorganopolysiloxane, colloidal silica, and an organotin compound or organic amine compound (Patent Document 1), a silicone emulsion composition comprising a hydroxyl group-containing organopolysiloxane, a Si-H group-containing organopolysiloxane, colloidal silica, an amide group and a carboxyl group-containing silane, an epoxy group-containing silane, and a curing catalyst (Patent Document 2), a silicone emulsion composition comprising an alkenyl group-containing organopolysiloxane, a Si-H group-containing organopolysiloxane, colloidal silica, a reaction product of aminosilane and an acid anhydride, an epoxy silane, and an addition reaction catalyst (Patent Document 3), and a molecular end sealed with a hydroxyl group. Silicone emulsion compositions comprising a hydrogen siloxane, emulsifier, water, and curing catalyst (Patent Document 4), silicone emulsion compositions comprising a colloidal silica-silicone core shell, curing catalyst, emulsifier, and water (Patent Documents 5-7), silicone emulsion compositions comprising a hydroxyl group-containing organopolysiloxane, colloidal silica, silanes containing amide and carboxyl groups, epoxy group-containing silanes, curing catalysts, and photocatalytic oxides (Patent Document 8), and silicone emulsion compositions comprising a hydroxyl group-containing organopolysiloxane, colloidal silica, silanes containing amide and carboxyl groups, and epoxy group-containing silanes (Patent Document 9) have been proposed.

[0004] Furthermore, because organopolysiloxanes can impart flexibility and lubricity to various fibers or textile products, silicone emulsion compositions that form a rubber coating are also used as fiber treatment agents. A known method for producing such a rubber-coated silicone emulsion composition involves using cyclic siloxane oligomers or terminally silanol-blocked organopolysiloxanes as raw materials, emulsifying them, and then performing emulsion polymerization with a strong acid or strong base.

[0005] When using anionic surfactants, which have strong catalytic activity, polymerization reactions occur rapidly, and this has been the subject of much research and numerous proposed methods for a long time. However, emulsion polymerization emulsions using anionic surfactants have poor compatibility with cationic emulsions and chemicals, which are widely used, particularly in textile processing and hair cosmetics. When combined, their stability decreases, leading to problems such as limited usage and formulation conditions.

[0006] On the other hand, when using common cationic surfactants such as cetyltrimethylammonium chloride or trimethylammonium chloride from beef tallow as surfactants, the catalytic activity is weak, resulting in an extremely slow polymerization rate. Therefore, it is difficult to obtain a silicone emulsion with a high degree of polymerization sufficient to form a rubber film.

[0007] Patent Document 10 proposes that by emulsifying a terminally silanol-blocked organopolysiloxane with a highly hydrophobic trialkylmethyl-type cationic surfactant and an alkyltrimethyl-type cationic surfactant (including nonionic surfactants in some cases), and then adding an alkaline catalyst to carry out polymerization, an organopolysiloxane emulsion with a high degree of polymerization, capable of forming a film in a shorter time than conventional methods, can be obtained. However, it has been pointed out that the cured film of the above composition has the problem of being soft and having low strength. In addition, these emulsions have the problem of separating in less than three months. The organopolysiloxane in this emulsion has a high degree of polymerization, capable of forming a film. Therefore, once it separates, it is impossible to stably disperse it again no matter how high the shear stirring, making it difficult to use industrially, and further improvement of long-term stability was needed. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Unexamined Patent Publication No. 56-16553 [Patent Document 2] Japanese Patent Application Publication No. 8-85760 [Patent Document 3] Japanese Patent Application Publication No. 9-208826 [Patent Document 4] Japanese Patent Application Publication No. 9-208900 [Patent Document 5] Japanese Patent Application Publication No. 9-208901 [Patent Document 6] Japanese Patent Application Publication No. 9-208902 [Patent Document 7] Japanese Patent Application Publication No. 9-208903 [Patent Document 8] Japanese Patent Publication No. 2002-363494 [Patent Document 9] Japanese Patent Publication No. 2008-231276 [Patent Document 10] Japanese Patent Publication No. 2021-95455 [Overview of the project] [Problems that the invention aims to solve]

[0009] The present invention has been made in view of the problems of the prior art described above, and aims to provide an emulsion composition of a film-forming organopolysiloxane that has good film-forming properties, excellent strength and flexibility of the film after curing, and good storage stability of the emulsion. The present invention also aims to provide a method for producing the above film-forming organopolysiloxane emulsion composition. [Means for solving the problem]

[0010] To solve the above problems, the present invention provides an emulsion composition of a film-forming organopolysiloxane characterized by containing the following (A) to (D). (A) Organopolysiloxane represented by the following average composition formula (1), having a viscosity of 300,000 mPa·s or more at 25°C, and containing at least two alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass [ka] (In the formula, R 1 R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, either unsubstituted or substituted. 2 (where a 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, where a is an integer between 2 and 1,000, b is an integer between 10 and 10,000, c is an integer between 0 and 1,000, d is an integer between 0 and 1,000, and c+d is an integer between 0 and 2,000, and the viscosity of the organopolysiloxane at 25°C is 300,000 mPa·s or higher.) (B) Cationic surfactant: 0.1 to 30 parts by mass (C) Water: 30~3,000 parts by mass (D) Colloidal silica: 0.5 to 50 parts by mass

[0011] The emulsion composition of the film-forming organopolysiloxane of the present invention has good film-forming properties, is excellent in the strength and flexibility of the film after curing, and also has good storage stability of the emulsion.

[0012] In this case, it is preferable that the (B) cationic surfactant contains any one or both of the following (B-1) or (B-2). (B-1)Q 1 3(CH3)N + ·X - Cationic surfactant represented by: 0 to 30 parts by mass (B-2)Q 2 α (CH3) 4-α N + ·X - Cationic surfactant represented by: 0 to 30 parts by mass (Q 1 is the same or different monovalent organic group having 6 to 30 carbon atoms, Q<00000​​​​​​​​​​​​​​​​​ R 3 O(EO) p (PO) q H (In the formula, R 3 (where is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. p and q are independent integers between 0 and 100, where p + q > 0.)

[0017] Such component (E) has an appropriate balance of hydrophilicity and hydrophobicity in the surfactant, and is compatible with components (B-1) and (B-2), thereby increasing the stability of the emulsion. In addition, the properties of the nonionic surfactant itself make it easy to handle when manufacturing the emulsion.

[0018] In the present invention, it is preferable that the (D) colloidal silica has a particle surface treated with an oxide of a metal other than silicon.

[0019] In this (D) component, the surface of the surface-treated colloidal silica particles becomes positively charged over a wide pH range, generating an electrical repulsion between the surface-treated colloidal silica particles and the emulsion particles in the emulsion composition. This makes them less likely to coalesce and aggregate, thus allowing the emulsion to be dispersed more stably.

[0020] The emulsion composition of the present invention may further contain a salt comprising a basic substance consisting of either ammonia or an organic amine, or both, and an acidic substance.

[0021] Even when containing such salts, the emulsion composition of the present invention exhibits good film-forming properties, excellent strength and flexibility of the cured film, and good storage stability of the emulsion.

[0022] Furthermore, it is preferable that the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition is 1,000 ppm (by mass, the same applies hereinafter) or less for each. Furthermore, it is more preferable that the total content of each of the following in the emulsion composition is 1,000 ppm or less: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10).

[0023] Because the emulsion composition of the present invention contains a small amount of such low molecular weight cyclic siloxanes, it exhibits excellent properties of the cured film (such as elongation at break).

[0024] The average particle size of the emulsion contained in the emulsion composition is preferably 1 μm or less, and more preferably 500 nm or less.

[0025] In the emulsion composition of the present invention, the buoyancy acting on the particles is reduced in proportion to the volume of the particles, allowing for uniform dispersion within the emulsion. Aggregation and coalescence of particles are suppressed, and even after long-term storage, concentration separation or bilayer separation does not occur.

[0026] Furthermore, the emulsion composition of the present invention can have an antiviral activity value Mv of 2.0 or higher according to JIS L 1922.

[0027] The emulsion composition of the present invention can be applied to a target substance, such as a substrate to which antiviral properties are to be imparted, to form a coating containing a substance that exhibits antiviral performance.

[0028] Furthermore, the present invention relates to a method for producing an emulsion composition of the above-mentioned film-forming organopolysiloxane, comprising the following steps (I) to (III), wherein steps (II) and (III) are performed after step (I) in any order or simultaneously. The present invention provides a method for producing an emulsion composition of a film-forming organopolysiloxane, characterized by adding water (C) so that the total amount of (C-1), (C-2), and (C-3) below is 30 to 3,000 parts by mass. (I) A step of preparing an emulsion composition by emulsifying a mixture containing the following components (A-1), (A-2), (B), and (C-1), (A-1) Organopolysiloxanes with terminal alkoxy groups and terminal silanol groups that have a viscosity of 300,000 mPa·s or less at 25°C. (A-2) Alkoxysilane represented by the following formula (3) R 4 e Si(OR 5 ) 4-e (3) (Here, R 4 R is a hydrogen atom or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms, independently of each other. 5 Each of these is independently a hydrogen atom, or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms. e is either 0 or 1. The sum of (A-1) and (A-2) is 100 parts by mass, and the ratio of (A-2) to (A-1) is between 0 and 0.2. (B) Cationic surfactant: 0.1 to 30 parts by mass (C-1) Water: 30~3,000 parts by mass (II) Add (C-2) water to the obtained emulsion composition if necessary, and polymerize it in the presence of (F) a basic catalyst at 0 to 40°C for 1 to 150 hours, followed by neutralization. (III) Further adding (D) colloidal silica: 0.5 to 50 parts by mass, and (C-3) water as necessary.

[0029] This method for producing an emulsion composition of a film-forming organopolysiloxane according to the present invention allows for the efficient production of an emulsion composition that has good film-forming properties, excellent strength and flexibility of the film after curing, and good storage stability of the emulsion.

[0030] In this case, either ammonia or an organic amine, or both, can be used as the (F) basic catalyst.

[0031] Using such a catalyst, it is possible to significantly suppress the by-production of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) while satisfying the requirement that the viscosity of the organopolysiloxane in the emulsion composition of the film-forming organopolysiloxane at 25°C be 300,000 mPa·s or higher, and the content of each can be reduced to 1,000 ppm or less.

[0032] Furthermore, it is preferable to use either (B-1) or (B-2) or both of the following as the cationic surfactant (B). (B-1)Q 1 3(CH3)N + ·X - Cationic surfactants indicated by: 0-30 mass department (B-2)Q 2 α (CH3) 4-α N + ·X - Cationic surfactants indicated by: 0-30 mass department (Q 1 Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different. 2 (B-1) is a monovalent organic group having 6 to 30 carbon atoms, either identical or different; X is independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms; α is an integer of 1 or 2; however, the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

[0033] This method of producing emulsion compositions allows for the efficient production of compositions with better storage stability.

[0034] Furthermore, in any of steps (I) to (III) above, (E) nonionic surfactant may be added in an additional 0.1 to 30 parts by mass per 100 parts by mass of the total of (A-1) and (A-2).

[0035] With this method for producing emulsion compositions, the emulsifying ability of component (E) is enhanced, making emulsification easier and enabling the efficient production of compositions with dramatically improved emulsion stability.

[0036] A nonionic surfactant represented by the following formula can be used as component (E). R 3 O(EO) p (PO) q H (In the formula, R 3 (where is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. p and q are independent integers between 0 and 100, where p + q > 0.)

[0037] Such components (E) have properties that make them easy to handle when manufacturing emulsions.

[0038] Furthermore, it is preferable to use colloidal silica as component (D), in which the particle surface is treated with an oxide of a metal other than silicon.

[0039] When such a (D) component is used, an electrical repulsion is generated between the surface-treated colloidal silica particles and the emulsion particles in the emulsion composition, making them less likely to coalesce and aggregate, thus enabling the efficient production of a more stable emulsion composition.

[0040] Furthermore, it is preferable to use a component (A-1) in which the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained therein is 1,000 ppm or less.

[0041] In the method for producing the emulsion composition of the present invention, by using raw materials with a low content of such low molecular weight cyclic siloxanes, an emulsion composition with a low content of low molecular weight cyclic siloxanes can be efficiently produced.

[0042] In the method for producing the emulsion composition of the present invention, the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition can be set to 1,000 ppm or less, and the total content of each of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10) contained in the emulsion composition can also be set to 1,000 ppm or less.

[0043] The present invention provides a method for producing emulsion compositions that contain a low amount of such low molecular weight cyclic siloxanes, and this method makes it possible to efficiently produce such emulsion compositions. [Effects of the Invention]

[0044] The present invention provides an emulsion composition of a film-forming organopolysiloxane (hereinafter also referred to as the emulsion composition) that has good film-forming properties, excellent strength and flexibility of the cured film, and good storage stability of the emulsion, as well as a film. Furthermore, by treating various fibers or textile products with this composition, flexibility and lubricity can be imparted. Moreover, a textile treatment agent containing the emulsion composition of the present invention as an active ingredient has excellent wash durability and can maintain flexibility and lubricity even after washing. [Modes for carrying out the invention]

[0045] As a result of diligent research to achieve the above objective, the present inventors have found that an emulsion composition of a film-forming organopolysiloxane containing specific amounts of (A) a specific organopolysiloxane with a viscosity of 300,000 mPa·s or more at 25°C, (B) a cationic surfactant, (C) water, and (D) colloidal silica has good film-forming properties, excellent strength and flexibility of the film after curing, and good storage stability of the emulsion, leading to the present invention.

[0046] In other words, the present invention is an emulsion composition of a film-forming organopolysiloxane characterized by containing the following (A) to (D). (A) Organopolysiloxane represented by the following average composition formula (1), having a viscosity of 300,000 mPa·s or more at 25°C, and containing at least two alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass [ka] (In the formula, R 1 R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, either unsubstituted or substituted. 2(where a 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, where a is an integer between 2 and 1,000, b is an integer between 10 and 10,000, c is an integer between 0 and 1,000, d is an integer between 0 and 1,000, and c+d is an integer between 0 and 2,000, and the viscosity of the organopolysiloxane at 25°C is 300,000 mPa·s or higher.) (B) Cationic surfactant: 0.1 to 30 parts by mass (C) Water: 30~3,000 parts by mass (D) Colloidal silica: 0.5 to 50 parts by mass

[0047] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0048] [Emulsion composition of film-forming organopolysiloxane] The emulsion composition of the film-forming organopolysiloxane of the present invention is (A) Organopolysiloxane represented by the following average composition formula (1), having a viscosity of 300,000 mPa·s or more at 25°C, and containing at least two alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass [ka] (In the formula, R 1 R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, either unsubstituted or substituted. 2 (where a 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, where a is an integer between 2 and 1,000, b is an integer between 10 and 10,000, c is an integer between 0 and 1,000, d is an integer between 0 and 1,000, and c+d is an integer between 0 and 2,000, and the viscosity of the organopolysiloxane at 25°C is 300,000 mPa·s or higher.) (B) Cationic surfactant: 0.1 to 30 parts by mass (C) Water: 30~3,000 parts by mass (D) Colloidal silica: 0.5 to 50 parts by mass It contains the following. If necessary, it may also contain components other than those listed in (A) to (D). Each component is described below.

[0049] [(A) component] (A) An organopolysiloxane represented by the following average composition formula (1), having a viscosity of 300,000 mPa·s or more at 25°C, and containing at least two alkoxy or hydroxyl groups bonded to silicon atoms in one molecule. In the emulsion composition of the present invention, this component (A) is contained in 100 parts by mass. [ka] (In the formula, R 1 R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, either unsubstituted or substituted. 2 (where a 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, where a is an integer between 2 and 1,000, b is an integer between 10 and 10,000, c is an integer between 0 and 1,000, d is an integer between 0 and 1,000, and c+d is an integer between 0 and 2,000, and the viscosity of the organopolysiloxane at 25°C is 300,000 mPa·s or higher.)

[0050] In equation (1) above, R 1R is a monovalent organic group having 1 to 20 carbon atoms, which is a hydrogen atom or an unsubstituted or substituted carbon atom, and may be linear, branched, or cyclic. Specifically, examples 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 phenyl, tolyl, and naphthyl; alkenyl groups such as vinyl and allyl; or in which some of the hydrogen atoms in these organic group structures are substituted with halogen atoms or polar group-containing organic groups such as amino, acryloxy, methacryloxy, epoxy, and mercapto. 1 It is industrially and property-wise desirable that more than 80% of the group consists of methyl groups.

[0051] R 2 The group is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and may be linear, branched, or cyclic. Specifically, in addition to the hydroxyl group, examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; phenyl group, tolyl group, naphthyl group; methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group, or groups in which some or all of the hydrogen atoms bonded to these groups are substituted with halogen atoms, amino groups, cyano groups, etc. 2 Among these, methyl groups, hydroxyl groups, methoxy groups, and ethoxy groups are preferred, but the molecule is configured to contain at least two alkoxy or hydroxyl groups bonded to silicon atoms.

[0052] a, b, c, and d are integers that satisfy the viscosity of the organopolysiloxane at 25°C to be 300,000 mPa·s or more.

[0053] a is an integer between 2 and 1,000, preferably between 2 and 500, and more preferably between 2 and 100. If a is greater than 1,000, the flexibility of the silicone rubber coating may be reduced. b is an integer between 10 and 10,000, preferably between 50 and 7,000, and more preferably between 100 and 5,000. If b is less than 10, the flexibility of the silicone rubber coating may be poor or no coating may be formed at all, and if it is greater than 10,000, the tear strength and tensile strength of the coating may decrease. c is an integer between 0 and 1,000, preferably between 0 and 200, and more preferably between 0 and 100. If c is greater than 1,000, the flexibility of the silicone rubber coating may be reduced, and the tear strength and tensile strength of the coating may decrease. d is an integer between 0 and 1,000, preferably between 0 and 200, and more preferably between 0 and 100. If d is greater than 1,000, the flexibility of the silicone rubber coating may decrease, and the tear strength and tensile strength of the coating may also decrease. Furthermore, c+d is an integer between 0 and 2,000, preferably between 0 and 400, and more preferably between 0 and 200.

[0054] The organopolysiloxane of component (A) has a viscosity of 300,000 mPa·s or more at 25°C, preferably 400,000 mPa·s or more, more preferably 500,000 mPa·s or more, more preferably 1,000,000 mPa·s or more, and most preferably is so viscous that it cannot be measured by the viscosity measurement method described later.

[0055] In this invention, viscosity (absolute viscosity) refers to the measured value obtained using a BM-type rotational viscometer (TVB-10M) at 25°C. The viscosity of any substance whose viscosity cannot be measured even with the M4 rotor (maximum measurement limit viscosity of 2,000,000 mPa·s), which is the highest viscosity rotor available for the BM-type rotational viscometer, or any substance that gets tangled in the rotor of the BM-type rotational viscometer and cannot be measured, or any substance that does not dissolve in toluene and therefore cannot be measured, is all 300,000 mPa·s or higher.

[0056] Specific examples of the organopolysiloxane of component (A) in the present invention include, but are not limited to, the following average composition formula. In the following average composition formula, a, b, b1, b2, b3, c, c1, c2, c3, and d are values ​​that satisfy the viscosity of the polyorganosiloxane at 25°C to be 300,000 mPa·s or more, and a, b, c, and d are the same as above. b1, b2, and b3 are integers in the range where their sum is b, i.e., 10 to 10,000, and c1, c2, and c3 can be integers in the range where their sum is c, i.e., 0 to 1,000.

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [(B) Component] Component (B) is a cationic surfactant, and is contained in an amount of 0.1 to 30 parts by mass, preferably 0.2 to 25 parts by mass, of component (B) per 100 parts by mass of component (A). department It is contained, more preferably in amounts of 0.5 to 20 parts by mass. If the amount of component (B) is less than 0.1 parts by mass or more than 30 parts by mass, the emulsion may become unstable, or it may become difficult to increase the degree of polymerization by de-alcoholization polymerization or dehydration polymerization of the alkoxy groups or hydroxyl groups contained in the organopolysiloxane.

[0061] Furthermore, component (B) preferably contains either or both of the following components (B-1) or (B-2). (B-1)Q 1 3(CH3)N + ·X- Cationic surfactants shown (B-2)Q 2 α (CH3) 4-α N + ·X - Cationic surfactants shown (Q 1 Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different. 2 (where X is a monovalent organic group with 6 to 30 carbon atoms, either identical or different; X is a halogen atom or a monovalent carboxyl group with 1 to 6 carbon atoms, and α is an integer of 1 or 2.)

[0062] These cationic surfactants, components (B-1) and (B-2), are intended to emulsify and disperse organopolysiloxanes in water. However, in addition to their function as emulsifiers, the inventors of the present invention have considered the following mechanisms of action for components (B-1) and (B-2).

[0063] In the method for producing an organopolysiloxane emulsion composition of the present invention, when an OH catalyst (alkaline catalyst) is added after emulsifying and dispersing the organopolysiloxane in water, the OH that is generated in the aqueous phase - It is believed that the exchange of counterions between the cationic surfactants, which are components (B-1) and (B-2), allows the cationic surfactants themselves to act as catalysts, and as a result, the organopolysiloxane of component (A) can be polymerized to a higher degree more efficiently.

[0064] (B-1) The cationic surfactant, as described above, Q 1 3(CH3)N + ·X - It is a cationic surfactant represented by Q 1 Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different, preferably a monovalent organic group having 7 to 20 carbon atoms, and more preferably a monovalent organic group having 8 to 18 carbon atoms. 1If the number of carbon atoms is 6 or more, the hydrophilicity of the surfactant is appropriate, and the frequency of contact with the organopolysiloxane of component (A) becomes sufficient, allowing the organopolysiloxane to be polymerized to a high degree, and this polymerization does not take long. Also, Q 1 If the number of carbon atoms is 30 or less, it has sufficient emulsifying power as a surfactant, and a stable emulsion can be obtained.

[0065] Q 1 Specific examples include alkyl groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosanyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl; and alkenyl groups such as oleyl. Among these, octyl, dodecyl, hexadecyl, and octadecyl are preferred.

[0066] Also, X - This is a halogen ion or a monovalent carboxyl ion having 1 to 6 carbon atoms, specifically Cl - , Br - , I - Halogen ions such as HClO - CH3COO - C2H5COO - Examples of carboxyl ions include Cl - , Br - , HCOO - CH3COO - It is preferable.

[0067] Specific examples of component (B-1) include, but are not limited to, trihexylmethylammonium chloride, triheptylmethylammonium chloride, trioctylmethylammonium chloride, trinonylmethylammonium chloride, tridecylmethylammonium chloride, trilaurylmethylammonium chloride, trioctylmethylammonium acetate, and trilaurylmethylammonium acetate.

[0068] The amount of cationic surfactant component (B-1) used can be 0 to 30 parts by mass per 100 parts by mass of component (A), preferably 0.2 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass. Using 0 to 30 parts by mass results in good emulsion stability.

[0069] Furthermore, the cationic surfactant of component (B-2) is, as described above, Q 2 α (CH3) 4-α N + ·X - The cationic surfactant shown can improve the stability of emulsions. Here, Q 2 Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different, preferably a monovalent organic group having 12 to 28 carbon atoms, and more preferably a monovalent organic group having 18 to 26 carbon atoms. 2 If the number of carbon atoms is 6 or more, the emulsion will have good stability. Q 2 If the number of carbon atoms is 30 or less, Q 1 Similar to the case above, it has sufficient emulsifying power as a surfactant, and a stable emulsion can be obtained. Q 2 X - The above Q 1 X - This is the same as α being an integer of 1 or 2.

[0070] (B-2)Specific examples of components include hexyltrimethylammonium chloride, phenyltrimethylammonium chloride, heptyltrimethylammonium chloride, benzyltrimethylammonium chloride, octyltrimethylammonium chloride, nonyltrimethylammonium chloride, decyltrimethylammonium chloride, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, stearyltrimethylammonium chloride, eicosyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexyltrimethylammonium acetate, phenyltrimethylammonium acetate, heptyltrimethylammonium acetate, benzyltrimethylammonium acetate, octyltrimethylammonium acetate, nonyltrimethylammonium acetate, decyltrimethylammonium acetate, lauryltrimethylammonium acetate, myristyltrimethylammonium acetate, hexadecyltrimethylammonium Cetate, stearyltrimethylammonium acetate, eicosyltrimethylammonium acetate, behenyltrimethylammonium acetate, dihexyldimethylammonium chloride, diphenyldimethylammonium chloride, hexylphenyldimethylammonium chloride, heptylphenyldimethylammonium chloride, octylphenyldimethylammonium chloride, nonylphenyldimethylammonium chloride, decylphenyldimethylammonium chloride, laurylphenyldimethylammonium chloride, myristylphenyldimethylammonium chloride, hexadecylphenyldimethylammonium chloride, stearylphenyldimethylammonium chloride, eicosylphenyldimethylammonium chloride, behenyldimethylammonium chloride, diheptyldimethylammonium chloride, dibenzyldimethylammonium chloride, dioctyldimethylammonium chloride, dinonyldimethylammonium chloride, didecyldimethylammonium chloride, dilauryldimethylammonium chloride,Examples include, but are not limited to, dimyristyldimethylammonium chloride, dihexadecyldimethylammonium chloride, distearyldimethylammonium acetate, diicosyldimethylammonium acetate, dibehenyldimethylammonium acetate, dihexyldimethylammonium acetate, diphenyldimethylammonium acetate, diheptyldimethylammonium acetate, dibenzyldimethylammonium acetate, dioctyldimethylammonium acetate, dinonyldimethylammonium acetate, didecyldimethylammonium acetate, dilauryldimethylammonium acetate, dimyristyldimethylammonium acetate, dihexadecyldimethylammonium acetate, distearyldimethylammonium acetate, diicosyldimethylammonium acetate, dibehenyldimethylammonium acetate, etc.

[0071] The amount of cationic surfactant component (B-2) used can be 0 to 30 parts by mass per 100 parts by mass of component (A), preferably 0.2 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass. If the amount is 30 parts by mass or less, the stability of the emulsion will be good.

[0072] As described above, in the emulsion composition of the present invention, component (B-1) is contained in a quantity of 0 to 30 parts by mass and component (B-2) in a quantity of 0 to 30 parts by mass per 100 parts by mass of component (A), but the total amount of component (B-1) and component (B-2) is in the range of 0.1 to 30 parts by mass. If the total amount is within this range, the stability of the emulsion will be good.

[0073] (Component (B-1)) has higher hydrophobicity than (component (B-2)). Therefore, it has a high contact frequency with the organopolysiloxane of (component (A)), and while an effect of accelerating the polymerization rate can be expected, it has high hydrophobicity and inferior emulsifying ability compared to (component (B-2)). Therefore, when only (B-1) is used, depending on conditions such as the composition of the emulsion, particle size, viscosity, pH, etc., it is necessary to further enhance the stability of the emulsion over time. Thus, by using (component (B-2)) which has a higher emulsifying ability in combination with (component (B-1)), the stability of the emulsion can be enhanced while accelerating the polymerization rate.

[0074] As described above, it is also possible to use only (component (B-1)), but by using (component (B-1)) and (component (B-2)) in combination, the stability of the emulsion can be enhanced while accelerating the polymerization rate. The cationic surfactant which is (B-1) is Q 1 3(CH3)N + ·X - and is represented by, and the cationic surfactant of (B-2) is Q 2 α (CH3) 4-α N + ·X - and is a cationic surfactant represented by. (B-1) has three substituents Q of quaternary ammonium 1 and (B-2) is characterized by one or two substituents Q of quaternary ammonium 2 . The monovalent organic group Q 1 , Q 2 has higher hydrophobicity as the number of carbon atoms increases, and due to its bulkiness, the steric hindrance becomes larger. By selecting Q 1 , Q 2 , these effects can be adjusted to achieve a preferable polymerization rate and the stability of the emulsion. In the combination of (component (B-1)) and (component (B-2)), the total number of carbon atoms of the substituents of each quaternary ammonium is not particularly limited, but from the viewpoint of obtaining a suitable emulsion, the total number of carbon atoms of the substituents of the quaternary ammonium of (B-1) (the total number of carbon atoms in three Q 1 and one methyl group) is N (B-1) and the total number of carbon atoms of the substituents of the quaternary ammonium of (B-2) (one or two Q 2(and the total number of carbon atoms in the remaining methyl group) N (B-2) As N (B-1) and N (B-2) The difference between N and N is preferably between 0 and 35, the lower limit may be any integer from 0 to 4, and the upper limit may be any integer from 30 to 34. (B-1) and N (B-2) By setting the difference to an appropriate value, a suitable emulsion can be obtained. Also, Q 1 The number of carbon atoms and Q 2 There are no particular restrictions on the combination of carbon numbers, but from the viewpoint of obtaining a suitable emulsion, Q 1 The number of carbon atoms and Q 2 The difference in the number of carbon atoms is preferably between 0 and 15, the lower limit may be any integer from 0 to 4, and the upper limit may be any integer from 10 to 14. Q 1 The number of carbon atoms and Q 2 By setting the difference in the number of carbon atoms to an appropriate value, the hydrophilicity of the surfactant, the frequency of contact between component (A) and the organopolysiloxane, and the emulsifying power can be appropriately adjusted. This allows for a high degree of polymerization of the organopolysiloxane through condensation polymerization and a suitable polymerization rate, thus enabling the acquisition of a stable and suitable emulsion.

[0075] [(C) component] The emulsion composition of the present invention contains water as component (C) in an amount of 30 to 3,000 parts by mass, preferably 40 to 2,400 parts by mass, per 100 parts by mass of component (A). Too little water will prevent the formation of an oil-in-water emulsion, while too much water will be uneconomical.

[0076] [(D) component] Component (D) is colloidal silica, and is present in an amount of 0.5 to 50 parts by mass of component (D) per 100 parts by mass of component (A).

[0077] Component (D), colloidal silica, acts as a coating reinforcer. Even in applications where the strength of the coating (especially hardness and tensile strength) is weak and durability is required, and emulsion compositions cannot be used, the strength (especially hardness and tensile strength) of the coating formed from the emulsion composition can be dramatically improved by using colloidal silica.

[0078] In the present invention, colloidal silica is preferably hydrophilic and can be used as an aqueous dispersion. There are no restrictions on the type of colloidal silica as long as it can be mixed with the emulsion composition; commercially available colloidal silica may be used.

[0079] In particular, using colloidal silica whose particle surface is treated with an oxide of a metal other than silicon can significantly improve the stability of the emulsion. Preferred metal oxides other than silicon include substances with an isoelectric point of 5 or higher, such as aluminum oxide, titanium oxide, iron oxide, zinc oxide, and magnesium oxide. By using such colloidal silica, the surface of the colloidal silica particles becomes positively charged over a wide pH range, generating an electrical repulsion between it and the emulsion particles in the emulsion composition, making them less likely to coalesce and aggregate, thus allowing for more stable dispersion. The isoelectric point can be measured, for example, in accordance with JIS R1638:1999. Furthermore, by using such colloidal silica, when removing water to form a film, electrical repulsion occurs between the emulsion particles and between the colloidal silica particles in the emulsion composition, making them less likely to coalesce and aggregate, thus allowing for a more uniform (more dispersed) film to be obtained. This dramatically improves the strength (especially hardness and tensile strength) of the film formed from the emulsion composition.

[0080] Specific examples of colloidal silica include Snowtex C, Snowtex XL, Snowtex 30L, Snowtex YL, Snowtex O, Snowtex OL, Snowtex OYL, Snowtex NXS, Snowtex NS, Snowtex N, Snowtex N-40, Snowtex AK, Snowtex AK-L, and Snowtex AK-YL (manufactured by Nissan Chemical Industries, Ltd.). Among the above, Snowtex AK, Snowtex AK-L, and Snowtex AK-YL, which have their colloidal silica surfaces treated with alumina, are particularly preferred, but this is not limited to these. The average particle size of colloidal silica is not particularly limited, but the above average particle size of colloidal silica can be used.

[0081] An example of a similar composition containing silica / organopolysiloxane / water is the Pickering emulsion composition. Pickering emulsions refer to emulsions stabilized by the adsorption (orientation) of solid particles at the liquid / liquid interface. They have attracted attention in recent years because emulsion compositions can be manufactured without emulsifiers. Commonly used solid microparticles in Pickering emulsion compositions include hydrophobic silica, hydrophobic cellulose, silicone resin powder, hollow hemispherical silicone particles, polyamide resin, talc, and hydrophobic pigments. Regarding silica in particular, hydrophobic silica is generally used, which is modified by reacting the hydroxyl groups on the hydrophilic silica surface with trifunctional silanes, thereby hydrophobicizing the surface with hydrocarbons. On the other hand, colloidal silica, which is preferably used in the present invention, is an aqueous dispersion of hydrophilic silica microparticles having many silanol groups (Si-OH) on its surface, and preferably its surface is coated with a metal oxide excluding silicon. Therefore, the Pickering emulsion composition and the emulsion composition of the present invention are compositionally different. Furthermore, in this invention, colloidal silica is not adsorbed (oriented) at the liquid / liquid (organopolysiloxane / water) interface, but is stably dispersed in the aqueous phase (continuous phase) while undergoing charge repulsion. Therefore, in terms of dispersion mechanism, it differs from Pickering emulsion compositions.

[0082] [(E) component] Component (E) is a nonionic surfactant, and 0.1 to 30 parts by mass of component (E) can be contained in proportion to 100 parts by mass of component (A).

[0083] The nonionic surfactant component (E) complements the emulsifying ability that is lacking in components (B-1) and (B-2) alone, thereby enabling easy emulsification and dramatically improving the stability of the emulsion.

[0084] The nonionic surfactant component (E) preferably has the following structure. R 3 O(EO) p (PO) q H (In the formula, R 3 (where is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. p and q are independent integers between 0 and 100, where p + q > 0.)

[0085] (E) The nonionic surfactant, as described above, 3 O(EO) p (PO) q It is preferably a nonionic surfactant represented by H, and R 3 This is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably a linear or branched alkyl group having 12 to 22 carbon atoms, and more preferably a linear or branched alkyl group having 13 to 18 carbon atoms.

[0086] R 3If the number of carbon atoms is 8 or more, the hydrophilicity of the surfactant is appropriate, and it has good compatibility with components (B-1) and (B-2), so there is no risk of concentration separation or bilayer separation even after 2 months. Also, R 3 If the number of carbon atoms is 30 or less, the hydrophobicity is not too high and sufficient emulsification is possible. Also, R 3 Since the number of carbon atoms is 30 or less, there is no need to increase the degree of polymerization of the ethylene oxide group (p in the formula) to increase hydrophilicity. For this reason, the degree of polymerization of the ethylene oxide group can be low, and the properties of the nonionic surfactant itself become easy to handle when manufacturing emulsions.

[0087] R 3 Specific examples include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl. Among these, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl are preferred, and tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl are more preferred.

[0088] EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be block-like or random. p and q are independent integers from 0 to 100, preferably from 2 to 80, and more preferably from 4 to 60. However, p + q > 0. Note that as the degree of polymerization of PO (q in the formula) increases, the hydrophobicity increases and the emulsifying properties of nonionic surfactants tend to decrease; therefore, it is preferable that p > q.

[0089] Specific examples of component (E) include, but are not limited to, polyoxyethylene(4) lauryl ether, polyoxyethylene(9) lauryl ether, polyoxyethylene(23) lauryl ether, polyoxyethylene(5) tridecyl ether, polyoxyethylene(10) tridecyl ether, polyoxyethylene(6) cetyl ether, polyoxyethylene(7) cetyl ether, polyoxyethylene(6) stearyl ether, polyoxyethylene(7) stearyl ether, polyoxyethylene(20) stearyl ether, polyoxyethylene(50) stearyl ether, and polyoxyethylene(60) stearyl ether.

[0090] Furthermore, there is no problem in adding cationic surfactants other than components (B-1) and (B-2), such as quaternary ammonium salts and alkylamine acetates, or amphoteric surfactants such as alkyl betaine and alkylimidazoline, for purposes such as supplementing the stability of the emulsion. In this invention, in addition to cationic surfactants, nonionic or amphoteric surfactants as described above may be added, but anionic surfactants with strong catalytic activity do not need to be added. In this invention, an emulsion polymerization emulsion can be obtained without adding anionic surfactants, so the emulsion composition of this invention can be used together with cationic emulsions and agents used in textile processing applications and hair cosmetics applications, and has the advantage of good stability and not being limited in terms of usage conditions or formulation conditions. This is a feature of this invention that is not seen in conventional emulsion polymerization emulsions using anionic surfactants.

[0091] [Other ingredients] The emulsion composition of the present invention may further contain a salt comprising a basic substance consisting of either ammonia or an organic amine, or both, and an acidic substance. The emulsion composition of the present invention preferably contains a basic substance consisting of ammonia and an organic amine, and a salt consisting of a strongly acidic substance and a weakly acidic substance. This basic substance consisting of ammonia and an organic amine, and the salt consisting of a strongly acidic substance and a weakly acidic substance is a salt produced by neutralizing the basic catalyst (alkaline catalyst) used for polymerization when producing the emulsion composition of the present invention, as described later.

[0092] By using ammonia and / or organic amines as catalysts, it is possible to significantly suppress the by-product formation of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) while satisfying the requirement that the viscosity of the organopolysiloxane in the organopolysiloxane emulsion composition of the present invention be 300,000 mPa·s or more at 25°C, and the content of each can be reduced to 1,000 ppm or less.

[0093] Therefore, in the present invention, when a strongly acidic or weakly acidic acid is added as a neutralizing agent to stop polymerization, a basic substance consisting of ammonia or an organic amine and a salt consisting of a strongly acidic or a weakly acidic substance are formed in the emulsion composition. The emulsion composition of the present invention, even when containing the above-mentioned salt, exhibits good film-forming properties, excellent strength and flexibility of the cured film, and good storage stability of the emulsion. However, to further improve the stability of the emulsion composition, it is preferable to have a lower salt content. The salt concentration in the emulsion composition is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0094] Furthermore, in order to suppress the separation of the emulsion composition, it is preferable that the emulsion composition does not contain large amounts of components that generally have the effect of reducing the stability of the emulsion, such as alcohol. The alcohol concentration in the emulsion composition is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0095] Furthermore, while the cationic surfactants of components (B-1) and (B-2) are sometimes sold diluted in a solvent (especially alcohol) such as ethanol or IPA, it is preferable that the concentration of the solvent (especially alcohol) be 20% by mass or less, more preferably 13% by mass or less, and even more preferably 7% by mass or less. If the concentration of the solvent (especially alcohol) is higher than 20% by mass, the stability of the emulsion may decrease, making separation more likely over time. The above-mentioned alcohol refers to aliphatic alcohols having 1 to 20 carbon atoms. Note that the numerical ranges shown above are merely examples and are not limited to these; the range should be set considering the stability of the emulsion composition, including other components.

[0096] Furthermore, there are no particular restrictions on the particle size of the emulsion composition of the present invention, but from the viewpoint of emulsion stability, the average particle size of the emulsion composition is preferably 1 μm or less, and more preferably 500 nm or less. If the average particle size is 1 μm or less, the buoyancy acting on the particles in the emulsion is small in proportion to the volume of the particles, allowing for uniform dispersion in the emulsion, suppressing aggregation and coalescence between particles, and preventing concentration separation or bilayer separation even after long-term storage. In this specification, the average particle size refers to the particle size at 50% of the cumulative value in the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer.

[0097] The emulsion composition of the film-forming organopolysiloxane of the present invention may contain octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in an emulsion composition of 1,000 ppm or less, for each component. Furthermore, the total content of each of the following in the emulsion composition may be 1,000 ppm or less: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10).

[0098] In the method for producing emulsion compositions described later, cyclic siloxane oligomers such as octamethylcyclotetrasiloxane are used as low molecular weight siloxanes for emulsion polymerization because they are readily available and undergo emulsification and ring-opening polymerization easily. However, ring-opening polymerization of cyclic siloxane oligomers is an equilibration reaction, and the emulsion after emulsion polymerization usually contains residual cyclic siloxane oligomers, such as octamethylcyclotetrasiloxane, in the polysiloxane. Therefore, during storage or use, the oligomer may volatilize from the emulsion, impairing the physical stability of the emulsion system. Furthermore, if such an emulsion is used in large quantities, for example, as a hair cosmetic for hair treatment, especially when heat blow-drying is involved, the volatilized oligomer may contaminate the surrounding environment or cause contact failure in electrical equipment. Moreover, if such an emulsion is used in skin cosmetics, the low molecular weight cyclic siloxane oligomer contained therein may impair the feel due to its volatile properties. Therefore, it has become necessary to suppress the amount of cyclic siloxane oligomer in the emulsion. In particular, among cyclic siloxanes, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are easily produced in equilibrium reactions, are stable compounds, and are volatile, so it has become necessary to suppress their content. Such silanol-terminated polydiorganosiloxanes can be synthesized, for example, by hydrolysis and polycondensation of dimethyldichlorosilane, or by ring-opening polymerization of the corresponding cyclic siloxane oligomer in the presence of an acidic catalyst such as sulfuric acid, or an alkaline catalyst such as potassium hydroxide or potassium silanolate. Unreacted cyclic siloxane oligomers, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, may be present in the product. However, to avoid the aforementioned problems caused by residual cyclic siloxane oligomers after emulsion polymerization, it is preferable to suppress the content of cyclic siloxane oligomers in the starting materials. Controlling the cyclic siloxane oligomer of component (A) can be achieved, for example, by distilling off the existing cyclic siloxane oligomers from the polymer obtained by ring-opening polymerization under reduced pressure.

[0099] Thus, in recent years, there has been a growing demand for products with reduced content of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Therefore, it is preferable to keep the cyclic siloxane content in the emulsion composition within the above range.

[0100] The emulsion compositions of the present invention maintain virtually unchanged content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) after storage at 25°C for 6 months compared to immediately after production. Furthermore, emulsion compositions in which the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) is less than 1,000 ppm immediately after production maintain a content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) of 1,000 ppm or less after storage at 25°C for 6 months.

[0101] The emulsion composition of the present invention has film-forming properties. There are no particular restrictions on the method of forming the film, but by removing water from the emulsion composition, the organopolysiloxane in the emulsion composition aggregates and forms a uniform film. There are no particular restrictions on the method of removing water, but for example, the water may be removed quickly at 100°C or above, or it may be removed gradually at 25°C.

[0102] For example, the coating is formed by weighing the emulsion composition into a 15cm x 10cm PP (polypropylene) tray so that the non-volatile content is 8.0g, drying it at 25°C for 48 hours, and then drying it further at 105°C for 1 hour. The properties of the coating prepared as described above are evaluated by measuring its hardness, tensile strength, and elongation in accordance with JIS K6249.

[0103] [Method for producing emulsion composition] Next, the method for producing the emulsion composition of the present invention is carried out in the following steps. That is, A method for producing an emulsion composition of the above-mentioned film-forming organopolysiloxane, comprising the following steps (I) to (III), wherein steps (II) and (III) are performed after step (I) in any order or simultaneously. A method for producing an emulsion composition of a film-forming organopolysiloxane, characterized by adding water (C) such that the total amount of (C-1), (C-2), and (C-3) below is 30 to 3,000 parts by mass. (I) A step of preparing an emulsion composition by emulsifying a mixture containing the following components (A-1), (A-2), (B), and (C-1), (A-1) Organopolysiloxanes with terminal alkoxy groups and terminal silanol groups that have a viscosity of 300,000 mPa·s or less at 25°C. (A-2) Alkoxysilane represented by the following formula (3) R 4 e Si(OR 5 ) 4-e (3) (Here, R 4 R is a hydrogen atom or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms, independently of each other. 5 Each of these is independently a hydrogen atom, or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms. e is either 0 or 1. The sum of (A-1) and (A-2) is 100 parts by mass, and the ratio of (A-2) to (A-1) is between 0 and 0.2. (B) Cationic surfactant: 0.1 to 30 parts by mass (C-1) Water: 30~3,000 parts by mass (II) Add (C-2) water to the obtained emulsion composition if necessary, and polymerize it in the presence of (F) a basic catalyst at 0 to 40°C for 1 to 150 hours, followed by neutralization. (III) Further adding (D) colloidal silica: 0.5 to 50 parts by mass, and (C-3) water as necessary.

[0104] Furthermore, steps (II) and (III) can be performed in any order after step (I), and may also be performed simultaneously.

[0105] [(A-1) component] First, (A-1) a terminal alkoxy group, or a terminal silanol group-blocked organopolysiloxane, having a viscosity of 300,000 mPa·s or less at 25°C is a raw material for the organopolysiloxane which is component (A). The viscosity of the terminal alkoxy group, or a terminal silanol group-blocked organopolysiloxane, at 25°C is preferably 150,000 mPa·s or less, more preferably 50,000 mPa·s or less. If the viscosity at 25°C is 300,000 mPa·s or less, the emulsion particle size will be small and the emulsion will be highly stable. It should be noted that if the viscosity at 25°C is 300,000 mPa·s or less, it may have a branched structure. Even if the terminal is an alkoxy group such as a methoxy group or an ethoxy group, it can be hydrolyzed in the emulsion composition to become a silanol group, so polymerization is similarly possible with terminal alkoxy group-blocked organopolysiloxanes.

[0106] As component (A-1), a product can be used in which the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained therein is 1,000 ppm or less. In the method for producing the emulsion composition of the present invention, by using raw materials with a low content of such low molecular weight cyclic siloxanes, an emulsion composition with a low content of low molecular weight cyclic siloxanes can be efficiently produced.

[0107] (A-1) Specific examples of components include, but are not limited to, the average composition formula shown below. In the average composition formula below, g, h+i, and h+i+j are values ​​that satisfy the viscosity of the terminal alkoxy group and / or terminal silanol group-blocked organopolysiloxane at 25°C to be less than 300,000 mPa·s. In addition, g, h+i, and h+i+j in the general formula below can typically take values ​​between 1 and 2000. [ka]

[0108] [(A-2) component] The organoalkoxysilane, which is component (A-2), is a raw material for the organopolysiloxane, which is component (A), and is the organoalkoxysilane represented by the following formula (3). R 4 e Si(OR 5 ) 4-e (3) (Here, R 4 R is a hydrogen atom or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms, independently of each other. 5 Each of these is independently a hydrogen atom, or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms. e is either 0 or 1.

[0109] Here, R 4 R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, either substituted or unsubstituted. Examples of monovalent organic groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, and naphthyl; alkenyl groups such as vinyl and allyl; or in which some of the hydrogen atoms in these organic group structures are substituted with halogen atoms or polar group-containing organic groups such as amino, acryloxy, methacryloxy, epoxy, and mercapto. 4 It is industrially and property-wise desirable that more than 80% of the components consist of methyl groups. 5 These are, independently of each other, a hydrogen atom, or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms. 5 As a monovalent organic group with 1 to 20 carbon atoms, see the above R 4 It is the same as, and methyl, ethyl, propyl, and butyl groups are preferred, with methyl and ethyl groups being even more preferred.

[0110] The amount of component (A-2) used is 0 to 20 parts by mass, preferably 0 to 15 parts by mass, more preferably 0 to 10 parts by mass, and particularly preferably 0 to 5 parts by mass, per 100 parts by mass of the total of components (A-1) and (A-2). If the amount of component (A-2) is within the above range, the coating will have sufficient strength and durability.

[0111] (A-2)Specific examples of components include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Examples include, but are not limited to, methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatetopropyltriethoxysilane.

[0112] [(B) component, (D) component, (E) component] The method for producing the film-forming organopolysiloxane emulsion composition of the present invention can be used by using either (B-1) or (B-2) or both of the following as the (B) cationic surfactant. (B-1)Q 1 3(CH3)N + ·X - Cationic surfactants indicated by: 0-30 mass department (B-2)Q 2 α (CH3) 4-α N + ·X - Cationic surfactants indicated by: 0-30 mass department (Q 1 Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different. 2 (B-1) is a monovalent organic group having 6 to 30 carbon atoms, X is independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, and α is an integer of 1 or 2, provided that the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass. Furthermore, in any of steps (I) to (III) above, (E) nonionic surfactant may be added in an additional 0.1 to 30 parts by mass per 100 parts by mass of the total of (A-1) and (A-2). Furthermore, a nonionic surfactant represented by the following formula can also be used as component (E). R 3 O(EO) p (PO) q H (In the formula, R 3 (where is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. p and q are independent integers between 0 and 100, where p + q > 0.) Furthermore, colloidal silica, in which the particle surface is treated with an oxide of a metal other than silicon, can also be used as component (D).

[0113] The components (B), (D), and (E) used in the method for producing the emulsion composition of the present invention are the same as described above.

[0114] [(C-1) component, (C-2) component, (C-3 component)] Components (C-1), (C-2), and (C-3) refer to the water used in process (I) and, if necessary, in processes (II) and (III). The sum of the amounts used for components (C-1), (C-2), and (C-3) is the amount of water used for component (C).

[0115] In process (I), the amount of water used for component (C-1) is 30 to 3,000 parts by mass per 100 parts by mass of component (A), and varies depending on the type of emulsifier used to reduce the particle size of the emulsion.

[0116] For example, emulsifiers such as high-pressure homogenizers that use pressure to reduce the particle size of emulsion particles. When using the above, the amount of component (C-1) used is not particularly limited to 30 to 3,000 parts by mass per 100 parts by mass of component (A). However, when using an emulsifier such as a homodisper (an emulsifier consisting of a circular disc with sawtooth teeth on its outer circumference) that reduces the particle size of emulsion particles using shear force, a homomixer (an emulsifier consisting of a rotor and a stator), or a colloid mill (an emulsifier that emulsifies by feeding each component into the gap between a high-speed rotating disc and a fixed disc), the amount of component (C-1) used is preferably 1 to 200 parts by mass, more preferably 2 to 100 parts by mass, and even more preferably 5 to 50 parts by mass per 100 parts by mass of component (A).

[0117] When using an emulsifier that reduces the particle size of emulsion particles using shear force, adding component (C-1) in amounts of 200 parts by mass or less allows the shear force to work efficiently, reducing the particle size of the emulsion particles and improving the stability of the emulsion composition. Furthermore, if the amount is 1 part by mass or more, it is likely to form an O / W type emulsion.

[0118] In step (II), component (C-2) may or may not be added, but the total amount of components (C-1), (C-2), and (C-3) used (which is water in component (C)) is preferably 30 to 3,000 parts by mass per 100 parts by mass of component (A). When adding component (C-2), the amount of component (C-2) used should be adjusted appropriately to achieve a concentration and viscosity suitable for the intended use. It is generally preferable to add water (component (C-2)) when using emulsifiers such as homodispersers, homomixers, and colloid mills.

[0119] In step (III), component (C-3) may or may not be added, but the total amount of components (C-1), (C-2), and (C-3) used (which is water in component (C)) is preferably 30 to 3,000 parts by mass per 100 parts by mass of component (A). When adding component (C-3), the amount of component (C-3) used should be adjusted as appropriate to achieve the appropriate concentration and viscosity for the intended use. Furthermore, if the colloidal silica component (D) is an aqueous dispersion, the water in the colloidal silica aqueous dispersion should also be included in component (C-3).

[0120] [(F) component] In the method for producing the film-forming organopolysiloxane emulsion composition of the present invention, water (C-2) is added to the emulsion composition obtained in step (II) if necessary, polymerization is carried out at 0 to 40°C for 1 to 150 hours in the presence of a basic catalyst (F), and then neutralization is performed. In this case, either ammonia or an organic amine, or both, can be used as the (F) basic catalyst. Component (F), the basic catalyst (alkaline catalyst), includes alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, as well as alkaline earth metal hydroxides, ammonia, and organic amines. Examples of organic amines include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and alkylamines such as monomethylamine, diethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine.

[0121] In order to keep the content of each cyclic siloxane such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the emulsion composition below 1,000 ppm, the alkaline catalyst is preferably ammonia and / or triethanolamine, and more preferably ammonia.

[0122] Numerous emulsion polymerizations using common cationic surfactants such as cetyltrimethylammonium chloride and trimethylammonium chloride from beef tallow have been reported. However, because these cationic emulsifiers have weak catalytic activity, it is common to use strong bases such as alkali metal hydroxides or alkaline earth metal hydroxides as catalysts to compensate for this. However, in the present invention, the catalytic activity can be greatly improved by using component (B-1), so there is no need to use strong bases, and polymerization can proceed sufficiently even with just ammonia, which is a weak base, and organic amines. Therefore, in order to promote polymerization and produce almost no by-products of cyclic siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), etc.), it is preferable to use ammonia (ammonia water), and organic amines as alkaline catalysts, and it is more preferable to use ammonia (ammonia water).

[0123] In the method for producing the film-forming organopolysiloxane emulsion composition of the present invention, it is preferable that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition be 1,000 ppm or less, and it is also preferable that the total content of each of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10) contained in the emulsion composition be 1,000 ppm or less.

[0124] The amount of alkaline catalyst used is preferably 0.1 to 10 equivalents, and more preferably 0.2 to 5 equivalents, relative to the total molar amount of the cationic surfactant component (B-1) and the cationic surfactant component (B-2).

[0125] By using 0.1 equivalents or more relative to the total molar amount of the cationic surfactant component (B-1) and the cationic surfactant component (B-2), an emulsion composition containing a high degree of polymerization organopolysiloxane can be obtained in a short time.

[0126] Furthermore, if the amount used is 10 equivalents or less relative to the total molar amount of the cationic surfactant component (B-1) and the cationic surfactant component (B-2), the stability of the emulsion composition is good, and the amount of by-products of cyclic siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), etc.) is kept below 1,000 ppm.

[0127] However, the amount of alkaline catalyst used is not limited to the above and may be outside the above range if necessary. Also, if there are no particular restrictions on the content of cyclic siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), etc.) in the application, the alkali metal hydroxides or alkaline earth metal hydroxides mentioned above may be used as the alkaline catalyst.

[0128] Furthermore, when adding an alkaline catalyst to the emulsion composition, the alkaline catalyst may be diluted with water beforehand. In this case, there is no particular limit to the amount of water used for dilution, as long as it is in the range of 30 to 3,000 parts by mass of component (C) per 100 parts by mass of component (A). Doing so ensures that the concentration of the alkaline catalyst is appropriate, stabilizing the emulsion composition and making it easier to handle.

[0129] A homogeneous emulsion composition is prepared using an emulsifier such as a homogenizer, homodisper, homomixer, colloid mill, or line mixer. After adding water (C-2) to the obtained emulsion composition as needed, polymerization is carried out at 0-40°C for 1-150 hours in the presence of an alkaline catalyst (F), followed by neutralization. Then, colloidal silica (D) and water (C-3) are added as needed.

[0130] Furthermore, the polymerization temperature is 0 to 40°C, preferably 5 to 30°C. If the polymerization temperature is 0°C or higher, polymerization proceeds quickly and is practical, and the emulsion does not freeze and has good stability. If the polymerization temperature is 40°C or lower, the emulsion has good stability, and the amount of cyclic siloxanes produced as by-products (such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6)) is kept below 1,000 ppm.

[0131] Furthermore, the polymerization time is 1 to 150 hours, preferably 1 to 120 hours. Polymerization is sufficient if it is 1 hour or more, and industrially sufficient if it is 150 hours or less.

[0132] The polymerization reaction can be stopped by neutralization after a predetermined polymerization time. Neutralization can be carried out by adding an acidic compound. Examples of acidic compounds (neutralizing agents) include hydrochloric acid, formic acid, acetic acid, propionic acid, and lactic acid, with hydrochloric acid, formic acid, and acetic acid being preferred. Alternatively, neutralization can be performed using an ion exchange resin instead of an acidic compound.

[0133] The emulsion composition of the high degree of polymerization organopolysiloxane of the present invention obtained by the above method is suitably used as a fiber treatment agent, mold release agent, water repellent, cosmetic raw material, etc., and can impart excellent flexibility, slipperiness, water repellency, volume, etc., to various fibers, leather, paper, hair, etc., when treated with this composition. Examples of fibers include, but are not limited to, natural fibers such as cotton, linen, silk, and wool, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene, vinylon, polyvinyl chloride, and spandex, and semi-synthetic fibers such as acetate.

[0134] The emulsion composition of the high degree of polymerization organopolysiloxane of the present invention may be appropriately blended with various thickeners, pigments, dyes, penetrating agents, antistatic agents, defoaming agents, flame retardants, antibacterial agents, preservatives, water repellents, crosslinking agents, adhesion enhancers, and other silicone oils, silicone resins, silica, acrylic resins, urethane resins, etc.

[0135] The emulsion composition of high-molecular-weight organopolysiloxane of the present invention can form a film after drying and can be used by treating or impregnating the surface of various substrates such as fibers, paper, metal, wood, rubber, plastic, and glass. Various conventional coating methods such as dipping, spraying, roll coating, bar coating, and brush coating can be used to apply the composition to the substrate.

[0136] Furthermore, the emulsion composition of the high degree of polymerization organopolysiloxane of the present invention may have antiviral properties, with an antiviral activity value Mv of 2.0 or higher according to JIS L 1922. This antiviral performance is thought to be exhibited by the cationic surfactant in the emulsion composition. In addition, since the emulsion composition of the high degree of polymerization organopolysiloxane of the present invention has film-forming ability, applying the emulsion composition to a target substance such as a substrate to which antiviral properties are to be imparted and forming a film results in a film containing a substance that exhibits antiviral properties, thus providing excellent durability and the expectation of long-term antiviral performance. [Examples]

[0137] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, unless otherwise specified, "%" refers to "mass%".

[0138] [Examples 1-25, Comparative Examples 1-8] Emulsions A to Y of Examples 1 to 25 and emulsions CA to CF of Comparative Examples 1 to 4, 6, and 7 were prepared as follows. Note that emulsions could not be obtained in Comparative Examples 5 and 8. Tables 1 to 3 show the amount (parts by mass) of each component relative to 100 parts by mass of component (A).

[0139] [Example 1] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.) and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous potassium hydroxide solution, in which 1.4g of 85% potassium hydroxide (component (F-1)) was diluted with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 1.4g of acetic acid. Next, 120.0g of an aqueous dispersion of colloidal silica (component (D-1)) containing 30% active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation: contains component (C-3). The same applies hereinafter) was added and uniformly dispersed using a homomixer to obtain emulsion A. Emulsion A had a non-volatile content of 39.3% after drying at 105°C for 3 hours.

[0140] [Example 2] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.) and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by 1.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 1.4g of acetic acid. Next, 120.0g of an aqueous dispersion of 30% colloidal silica (component (D-1)) active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion B. Emulsion B had a non-volatile content of 40.0% after drying at 105°C for 3 hours.

[0141] [Example 3] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.) and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous triethanolamine solution, prepared by diluting 3.2g of triethanolamine (component (F-3)) with 60.0g of ion-exchanged water (component (C-2)), was added. Subsequently, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, after which polymerization was stopped by neutralization with 1.4g of acetic acid. Next, 120.0g of an aqueous dispersion of colloidal silica (component (D-1)) with 30% active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion C. Emulsion C had a non-volatile content of 40.2% after drying at 105°C for 3 hours.

[0142] [Example 4] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion D. Emulsion D had a non-volatile content of 40.4% after drying at 105°C for 3 hours.

[0143] [Example 5] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals), 24.0g of polyoxyethylene lauryl ether (component (E-1)) (Emulgen 109P: manufactured by Kao Corporation), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion E. Emulsion E had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0144] [Example 6] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion F. Emulsion F had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0145] [Example 7] This ethanol product (TOMAC: Linyi Connect Chemical Technology) contains 294.0 g of a double-ended organopolysiloxane (component (A-1-2)) with a viscosity of 50,000 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and 95% of the active ingredients of trioctylmethylammonium chloride (component (B-1-1)), which has been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce the levels of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) to less than 10 ppm each (detection limit), and has a viscosity of 50,000 mPa·s at 25°C. An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion G. Emulsion G had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0146] [Example 8] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-3) with a viscosity of 200,000 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1) as active ingredients. The cyclic siloxanes, such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), were previously heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion H. Emulsion H had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0147] [Example 9] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 30.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion I. Emulsion I had a non-volatile content of 43.4% after drying at 105°C for 3 hours.

[0148] [Example 10] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 100.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion J. Emulsion J had a non-volatile content of 40.0% after drying at 105°C for 3 hours.

[0149] [Example 11] This ethanol product (TOMAC: Linyi Connect Chemical Technology) contains 298.5g of a double-ended silanol-blocked organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25°C, 1.5g of triethoxyphenylsilane (component (A-2-1)), and 95% of the active ingredients of trioctylmethylammonium chloride (component (B-1-1)), which has been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) to less than 10 ppm each (detection limit), and has a viscosity of 1,500 mPa·s at 25°C. An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion K. Emulsion K had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0150] [Example 12] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 90.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. An emulsion was then prepared by adding 285.0g of ion-exchanged water (component (C-2)) to this emulsion and uniformly dispersing it using a homomixer. After that, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. Subsequently, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion L. Emulsion L had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0151] [Example 13] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals), 24.0g of polyoxyethylene stearyl ether (component (E-3)) (Emulgen 350: manufactured by Kao Corporation), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion M. Emulsion M had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0152] [Example 14] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 30.0g of (manufactured by Co., Ltd.), 30.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 0.4g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 0.4g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion N. Emulsion N had a non-volatile content of 41.1% after drying at 105°C for 3 hours.

[0153] [Example 15] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 1.5g of (manufactured by Co., Ltd.), 1.5g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 7.4g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 8.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion O. Emulsion O had a non-volatile content of 44.3% after drying at 105°C for 3 hours.

[0154] [Example 16] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. An emulsion was then prepared by adding 330.0g of ion-exchanged water (component (C-2)) to this emulsion and dispersing it uniformly using a homomixer. After that, an aqueous ammonia solution, which had been pre-diluted by diluting 11.1g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. Subsequently, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 12.9g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion P. Emulsion P had a non-volatile content of 42.6% after drying at 105°C for 3 hours.

[0155] [Example 17] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 22.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 25.8g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion Q. Emulsion Q had a non-volatile content of 43.2% after drying at 105°C for 3 hours.

[0156] [Example 18] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 180.0 g of an aqueous dispersion of colloidal silica (component D-2) containing 20% ​​of the active ingredient (Snowtex C: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion R. Emulsion R had a non-volatile content of 39.4% after drying at 105°C for 3 hours.

[0157] [Example 19] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was raised to 30°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion S. Emulsion S had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0158] [Example 20] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 2 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion T. Emulsion T had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0159] [Example 21] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 144 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion U. Emulsion U had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0160] [Example 22] The cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm each (detection limit) by preheating and mixing at 150°C under reduced pressure of 10 mmHg or less. The viscosity at 25°C is 1,500 mPa·s, and it contains 300.0 g of organopolysiloxane (components (A-1-4)) with branched units (in general formula (1), R 1 =methyl group, R 2 = Methoxy group, a=3, b=450, c=1, d=0), 95% ethanol product with trioctylmethylammonium chloride ((B-1-1) component) as the active ingredient (TOMAC: Linyi Connect Chemical Technology) An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion V. Emulsion V had a non-volatile content of 42.0% after drying at 105°C for 3 hours.

[0161] [Example 23] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 8.0g of stearyltrimethylammonium chloride (component B-2-2) (manufactured by Tokyo Chemical Industry Co., Ltd.) with 98% active ingredient, 24.0g of polyoxyethylene tridecyl ether (component E-2) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component C-1) using a homomixer and disperser. An emulsion was then prepared by adding 330.0g of ion-exchanged water (component C-2) to this emulsion and dispersing it uniformly using a homomixer. After that, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component F-2) with 60.0g of ion-exchanged water (component C-2), was added. Subsequently, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion W. Emulsion W had a non-volatile content of 41.3% after drying at 105°C for 3 hours.

[0162] [Example 24] The following ingredients were used: 294.0 g of a double-ended organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25°C, in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm each (detection limit) by preheating and mixing at 150°C under reduced pressure of 10 mmHg or less; 6.0 g of triethoxyphenylsilane (component (A-2-1)); 9.0 g of trioctadecylmethylammonium chloride (component (B-1-2)) (manufactured by AstaTech) with an active ingredient content of 95%; and 98% active ingredient. An emulsion was prepared by uniformly emulsifying and dispersing 8.0g of % stearyltrimethylammonium chloride (component B-2-2) (manufactured by Tokyo Chemical Industry Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component E-2) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component C-1) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component C-2) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by 2.2g of 30% aqueous ammonia solution (component F-2) with 60.0g of ion-exchanged water (component C-2), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion X. Emulsion X had a non-volatile content of 40.3% after drying at 105°C for 3 hours.

[0163] [Example 25] In advance, by heating and mixing under reduced pressure of 10 mmHg or less at 150 °C, cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are reduced to less than 10 ppm (detection limit) each. 294.0 g of both-terminal silanol group-blocked organopolysiloxane ((A-1-1) component) with a viscosity of 1,500 mPa·s at 25 °C, 6.0 g of triethoxyphenylsilane ((A-2-1) component), 9.0 g of trioctadecylmethylammonium chloride ((B-1-2) component) with an active ingredient of 95% (manufactured by AstaTech), 9.0 g of an ethanol product of behenyltrimethylammonium chloride ((B-2-1) component) with an active ingredient of 80% (Lipcard 22-80: manufactured by Lion Specialty Chemicals), 24.0 g of polyoxyethylene tridecyl ether ((E-2) component) (Newcol 1310: manufactured by Nippon Emulsion Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1) component) are uniformly emulsified and dispersed using a homomixer and a disperser to prepare an emulsion. Then, 330.0 g of ion-exchanged water ((C-2) component) is further added to this emulsion and uniformly dispersed using a homomixer. After that, an aqueous ammonia solution prepared by diluting 2.2 g of a 30% aqueous ammonia solution ((F-2) component) with 60.0 g of ion-exchanged water ((C-2) component) is added. Then, the liquid temperature is lowered to 15 °C, polymerization is carried out for 24 hours, and the polymerization is stopped by neutralizing with 2.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica ((D-1) component) with an active ingredient of 30% (Snowtex AK-YL: manufactured by Nissan Chemical Industries, Ltd.) is added and uniformly dispersed using a homomixer to obtain Emulsion Y. The non-volatile content of Emulsion Y after drying at 105 °C for 3 hours was 41.1%.

[0164] [Comparative Example 1] The following are the components of a polyoxyethylene polysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C: 294.0 g of a bipolar polysiloxane (component A-1-1) with cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) having been previously heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce each to less than 10 ppm (detection limit), 6.0 g of triethoxyphenylsilane (component A-2-1), and polyoxyethylene An emulsion was prepared by uniformly emulsifying and dispersing 24.0 g of tridecyl ether (component E-2) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.) and 45.0 g of deionized water (component C-1) using a homomixer and disperser. To this emulsion, 330.0 g of deionized water (component C-2) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by 2.2 g of 30% aqueous ammonia solution (component F-2) with 60.0 g of deionized water (component C-2), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and the polymerization was stopped by neutralization with 2.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) with 30% active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion CA. Emulsion CA had a non-volatile content of 41.1% after drying at 105°C for 3 hours.

[0165] [Comparative Example 2] Previously, by heating and mixing under reduced pressure of 10 mmHg or less at 150°C, cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecylmethylcyclohexasiloxane (D6) were each reduced to less than 10 ppm (detection limit). 294.0 g of both-terminal silanol group-blocked organopolysiloxane ((A-1-1) component) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane ((A-2-1) component), 9.0 g of an ethanol product with 95% active ingredient of trioctylmethylammonium chloride ((B-1-1) component) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd), 9.0 g of an ethanol product with 80% active ingredient of behenyltrimethylammonium chloride ((B-2-1) component) (Lipcard 22-80: manufactured by Lion Specialty Chemicals), 24.0 g of polyoxyethylene tridecyl ether ((E-2) component) (Newcol 1310: manufactured by Nippon Emulsion Co., Ltd), and 45.0 g of ion-exchanged water ((C-1) component) were uniformly emulsified and dispersed using a homomixer and a disperser to prepare an emulsion. Then, 330.0 g of ion-exchanged water ((C-2) component) was further added to this emulsion and uniformly dispersed using a homomixer. After that, an aqueous ammonia solution obtained by diluting 2.2 g of a 30% aqueous ammonia solution ((F-2) component) with 60.0 g of ion-exchanged water ((C-2) component) was added. Then, the liquid temperature was lowered to 15°C, polymerization was carried out for 2 hours, and the polymerization was stopped by neutralizing with 2.6 g of acetic acid. Next, 84.0 g of ion-exchanged water ((C-3) component) was added and uniformly dispersed using a homomixer to obtain emulsion CB. The non-volatile content of emulsion CB after drying at 105°C for 3 hours was 39.6%.

[0166] [Comparative Example 3] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of ethanol containing 80% behenyltrimethylammonium chloride (component (B-2-1)) as the active ingredient (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. To this emulsion, 330.0g of ion-exchanged water (component (C-2)) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by diluting 2.2g of 30% aqueous ammonia solution (component (F-2)) with 60.0g of ion-exchanged water (component (C-2)), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6g of acetic acid. Next, 84.0 g of deionized water (component C-3) was added and uniformly dispersed using a homomixer to obtain emulsion CC. After drying emulsion CC at 105°C for 3 hours, the non-volatile content was 39.6%.

[0167] [Comparative Example 4] The following are the components of a polyoxyethylene polysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C: 294.0 g of a bipolar polysiloxane (component A-1-1) with cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) having been previously heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce each to less than 10 ppm (detection limit), 6.0 g of triethoxyphenylsilane (component A-2-1), and polyoxyethylene An emulsion was prepared by uniformly emulsifying and dispersing 24.0 g of tridecyl ether (component E-2) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.) and 45.0 g of deionized water (component C-1) using a homomixer and disperser. To this emulsion, 330.0 g of deionized water (component C-2) was added and uniformly dispersed using a homomixer. Then, an aqueous ammonia solution, which had been pre-diluted by 2.2 g of 30% aqueous ammonia solution (component F-2) with 60.0 g of deionized water (component C-2), was added. After that, the liquid temperature was lowered to 15°C and polymerization was carried out for 24 hours, and polymerization was stopped by neutralization with 2.6 g of acetic acid. Next, 84.0 g of deionized water (component C-3) was added and uniformly dispersed using a homomixer to obtain emulsion CD. Emulsion CD had a non-volatile content of 38.6% after drying at 105°C for 3 hours.

[0168] [Comparative Example 5] This product contains 294.0 g of a double-ended organopolysiloxane (component A-1-1) with a viscosity of 1,500 mPa·s at 25°C, 6.0 g of triethoxyphenylsilane (component A-2-1), and 95% trioctylmethylammonium chloride (component B-1-1), all of which are active ingredients of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), which have been pre-heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). We attempted to prepare an emulsion by uniformly emulsifying and dispersing 120.0g of (manufactured by Co., Ltd.) and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. However, the emulsion separated immediately, and we were unable to obtain a uniform emulsion, so we did not evaluate the emulsion.

[0169] [Comparative Example 6] This product contains 300.0 g of dimethylpolysiloxane (component A-3) with a viscosity of 1,500 mPa·s at 25°C and 95% active ingredients of trioctylmethylammonium chloride (component B-1-1), and trioctylmethylammonium chloride (component B-1-1). The cyclic siloxanes, such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), were previously heated and mixed at 150°C under reduced pressure of 10 mmHg or less to reduce their concentration to less than 10 ppm (detection limit). The ethanol product (TOMAC: Linyi Connect Chemical Technology) contains 95% active ingredients. An emulsion was prepared by uniformly emulsifying and dispersing 9.0g of (manufactured by Co., Ltd.), 9.0g of an ethanol product containing 80% behenyltrimethylammonium chloride (component (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals), 24.0g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), and 45.0g of ion-exchanged water (component (C-1)) using a homomixer and disperser. An emulsion was then prepared by adding 390.0g of ion-exchanged water (component (C-2)) to this emulsion and dispersing it uniformly using a homomixer. Next, 120.0g of an aqueous dispersion of colloidal silica (component (D-1)) containing 30% active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and dispersed uniformly using a homomixer to obtain emulsion CE. Emulsion CE had a non-volatile content of 41.9% after drying at 105°C for 3 hours.

[0170] [Comparative Example 7] An emulsion was prepared by uniformly emulsifying and dispersing 300.0 g of dimethylpolysiloxane (component (A-3)), which has a viscosity of 1,500 mPa·s at 25°C and whose cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm each (detection limit) by heating and mixing at 150°C under reduced pressure of 10 mmHg or less, 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.) and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and disperser. An additional 390.0 g of ion-exchanged water (component (C-2)) was added to this emulsion and uniformly dispersed using a homomixer. Next, 120.0 g of an aqueous dispersion of colloidal silica (component D-1) containing 30% of the active ingredient (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) was added and uniformly dispersed using a homomixer to obtain emulsion CF. Emulsion CF had a non-volatile content of 41.0% after drying at 105°C for 3 hours.

[0171] [Comparative Example 8] 300.0 g of a double-ended organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25°C, in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm each (detection limit) by heating and mixing at 150°C under reduced pressure of 10 mmHg or less, 6.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Emulsifier Co., Ltd.), 10.5 parts of sodium dodecylbenzenesulfonate, an anionic surfactant, and 18.0 g of ion-exchanged water (component (C-1)) were emulsified by homodispersion. To this emulsion, 254.7g of deionized water (component C-2) was added and uniformly dispersed using a homomixer. Then, 3.6g of concentrated hydrochloric acid, an acid catalyst, was added. After that, the liquid temperature was lowered to 10°C and polymerization was carried out for 22 hours, and the polymerization was stopped by neutralization with 7.2g of triethanolamine. Next, an attempt was made to uniformly disperse 120.0g of a 30% aqueous dispersion of colloidal silica (component D-1) (Snowtex AK-YL: manufactured by Nissan Chemical Corporation) using a homomixer, but it separated immediately, and a uniform emulsion could not be obtained, so the emulsion was not evaluated.

[0172] [Evaluation of emulsions] The physical properties and characteristics of each emulsion obtained in Examples 1-25 and Comparative Examples 1-4, 6, and 7 were measured using the evaluation method described below, and the results are shown in Tables 1-3. Each of the obtained emulsion compositions was weighed into a 15cm x 10cm PP (polypropylene) tray so that the non-volatile content was 8.0g, and dried at 25°C for 48 hours to allow the water to evaporate. Examples 1-25 and Comparative Example 3 formed a rubbery film, while Comparative Examples 1, 2, and 4 were fluid liquids. In the "Extracted Viscosity (mPa·s)" column of Tables 1-3, the extracted viscosity is shown for emulsions whose viscosity could be measured using the method described below, and the properties of the film are shown for those whose viscosity could not be measured.

[0173] [Viscosity of extracted organopolysiloxane] Each emulsion composition (300g) was added to 2L of IPA while stirring to break down the emulsion and extract the organopolysiloxane. This organopolysiloxane was dried at 105°C for 3 hours and then measured at 25°C using a BM-type rotational viscometer (TVB-10M). It should be noted that any samples whose viscosity could not be measured even with the M4 rotor (maximum measurement limit 2,000,000 mPa·s), the highest viscosity rotor available for the BM-type rotational viscometer, or those that became entangled in the rotor and could not be measured, or those that did not dissolve in toluene and therefore could not be measured, all had a viscosity of 300,000 mPa·s or higher.

[0174] [Average particle size of emulsion] This represents the particle size at 50% of the cumulative value in the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer (Partica LA-960, manufactured by Horiba, Ltd.).

[0175] [Cyclic siloxane content] 0.1 g of each emulsion composition was extracted with 10 mL of acetone containing 20 ppm (by mass) of tetradecane as an internal standard (shaking for 3 hours), and after being left overnight, the acetone layer was collected and analyzed by gas chromatography (Agilent 7890B (Agilent Technologies)) to quantify the cyclic siloxanes (hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10)) (by mass).

[0176] [Film forming property] Each emulsion composition was weighed into a 15 cm × 10 cm PP (polypropylene) tray so that the non-volatile content was 8.0 g, dried at 25°C for 48 hours, and then further dried at 105°C for 1 hour to evaluate whether a film was formed. A: Forms a uniform film and has sufficient strength to be easily peeled from the disposable tray. B: Forms a uniform film, but cannot be peeled from the disposable tray or the film is deformed during peeling. C: Does not form a uniform film.

[0177] [Evaluation of film physical properties] For the film prepared above, the hardness (Type C durometer hardness), tensile strength, and elongation at break were measured according to JIS K6249. The evaluation results are also shown in Tables 1 to 3.

[0178] [Storage stability of emulsion (25°C)] 100 g of each emulsion composition was placed in a glass bottle, stored statically in a constant temperature bath at 25°C, and after 3 months, 6 months, and after 12 months, the appearance was visually observed and the non-volatile content of the upper and lower layers was measured to evaluate the storage stability based on the following evaluation criteria. <Evaluation criteria> A: No shade separation is observed between the upper and lower layers. B: Slight shade separation is confirmed between the upper and lower layers. C: Completely separated into two layers.

[0179] [Storage stability of emulsion (40°C)] 100 g of each emulsion composition was placed in a glass bottle, stored statically in a constant temperature bath at 40°C for 30 days, and after that, the appearance was visually observed and the non-volatile content of the upper and lower layers was measured to evaluate the storage stability based on the following evaluation criteria. <Evaluation criteria> A: No shade separation is observed between the upper and lower layers. B: Slight shade separation is confirmed between the upper and lower layers. C: Completely separated into two layers.

[0180] [Table 1]

[0181] [Table 2]

[0182] [Table 3]

[0183] In the "Extracted Viscosity (mPa·s)" column in Tables 1-3, "rubbery" indicates that the viscosity could not be measured using the method described above, the film has a rubbery texture, and the viscosity at 25°C is 300,000 mPa·s or higher.

[0184] As shown in Tables 1 and 2, the emulsion compositions of the film-forming organopolysiloxane (high-molecular-weight organopolysiloxane) of the present invention in Examples 1 to 25 have strong film-forming ability and also exhibit excellent storage stability.

[0185] In contrast, as shown in Table 3, in Comparative Examples 1 and 4, where cationic surfactants were not used, the extracted organopolysiloxane had low viscosity and low molecular weight, resulting in poor film-forming properties. In Comparative Examples 2 and 3, where cationic surfactants were used but colloidal silica was not, the viscosity of the extracted organopolysiloxane increased. However, in Comparative Example 2, the viscosity at 25°C was less than 300,000 mPa·s, and a uniform film could not be formed. In Comparative Example 3, although the viscosity was sufficient, the hardness and tensile strength of the film were insufficient. In Comparative Example 5, where component (B) was added in excess, the emulsion became unstable, and a uniform emulsion could not be obtained. In Comparative Examples 6 and 7, where low-viscosity dimethylpolysiloxane with trimethylsilyl groups at both ends that cannot be polymerized (condensation polymerization by dehydration or de-alcoholization) was used instead of component (A) of the present invention, although silica was included, a film with sufficient physical properties could not be obtained, whether using cationic surfactants alone or in combination with nonionic surfactants. In Comparative Example 8, where a more catalytic anionic surfactant was used instead of a cationic surfactant, high-viscosity anionic emulsion polymerization proceeded at a lower temperature (10°C). However, the addition of colloidal silica made the emulsion unstable, and a uniform emulsion could not be obtained. Thus, the emulsion compositions obtained with the compositions of Comparative Examples 1 to 8 either failed to produce a uniform emulsion, failed to form a film, or, if a film was formed, had weak film strength.

[0186] Furthermore, (F) Emulsion A of Example 1, prepared using potassium hydroxide as a basic catalyst, had a content of cyclic siloxanes D4-D6 exceeding 5000 ppm by mass, but the resulting film exhibited good physical properties (hardness, tensile strength, and elongation at break) and storage stability. Thus, even if low molecular weight cyclic siloxanes remain in the emulsion composition of the present invention, the resulting film exhibits good physical properties and storage stability, and the step of removing low molecular weight cyclic siloxanes can be omitted, thereby reducing manufacturing costs. In contrast, emulsion B of Example 2, prepared using ammonia as a basic catalyst (F), showed a significantly reduced content of cyclic siloxanes D4-D6 to less than 200 ppm by mass, and the physical properties and storage stability of the resulting film were good. From this, it can be seen that, according to the method for producing the emulsion composition of the present invention, by using a terminal alkoxy group, or a terminal silanol group-blocked organopolysiloxane, with a reduced low molecular weight cyclic polysiloxane as component (A-1) of the emulsion raw material in combination with an appropriate basic catalyst, it is possible not only to reduce the content of each cyclic siloxane D4-D6 in the resulting emulsion composition to 1,000 ppm or less, but also to easily reduce the total content of each cyclic siloxane D3-D10 in the emulsion composition to 1,000 ppm or less. Therefore, the emulsion composition and method for producing the same of the present invention have high industrial value.

[0187] [Antiviral performance test of treated fabric] Test solutions were prepared by adding deionized water to emulsion compositions F and Z and diluting them to a solid content of 1%. Standard cotton cloths for antiviral performance testing were immersed in the test solution for 10 seconds, then squeezed using a roller at 100% wringing ratio, and dried at 150°C for 2 minutes to produce each test cloth. Each test cloth was subjected to antiviral performance testing according to the test method described below. The standards and criteria are shown in Table 4, and the results are shown in Table 5. [Test Method] JIS L 1922:2016 Method for measuring viral infectivity titer: Plaque assay [Test Virus] Influenza A virus (H3N2):ATCC VR-1679

[0188] [Table 4]

[0189] [Table 5] From the table above, it was confirmed that emulsion F possesses antiviral properties.

[0190] [Industrial applicability] The film-forming organopolysiloxane emulsion composition of the present invention provides a film-forming silicone emulsion composition and a film that exhibits good film-forming properties, excellent film strength after curing, and good storage stability of the emulsion. Furthermore, since the film-forming organopolysiloxane emulsion composition of the present invention can contain extremely low levels of cyclic siloxane, there is little concern about cyclic siloxane volatilizing and contaminating equipment when the substrate is subjected to heat treatment, etc., or about contamination of the product itself by cyclic siloxane or silicon dioxide powder derived from cyclic siloxane. Therefore, it is industrially useful and highly versatile, and can be widely applied not only as a fiber treatment agent but also as a mold release agent, water repellent, cosmetic, hair cosmetic, etc.

[0191] This specification includes the following embodiments: [1]: An emulsion composition of a film-forming organopolysiloxane characterized by containing the following (A) to (D). (A) Organopolysiloxane represented by the following average composition formula (1), having a viscosity of 300,000 mPa·s or more at 25°C, and containing at least two alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass [ka] (In the formula, R 1 R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, either unsubstituted or substituted. 2(where a 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, where a is an integer between 2 and 1,000, b is an integer between 10 and 10,000, c is an integer between 0 and 1,000, d is an integer between 0 and 1,000, and c+d is an integer between 0 and 2,000, and the viscosity of the organopolysiloxane at 25°C is 300,000 mPa·s or higher.) (B) Cationic surfactant: 0.1 to 30 parts by mass (C) Water: 30~3,000 parts by mass (D) Colloidal silica: 0.5 to 50 parts by mass [2]: An emulsion composition of a film-forming organopolysiloxane according to [1], characterized in that the (B) cationic surfactant contains either or both of the following (B-1) or (B-2). (B-1)Q 1 3(CH3)N + ·X - Cationic surfactants indicated by: 0-30 parts by mass (B-2)Q 2 α (CH3) 4-α N + ·X - Cationic surfactants indicated by: 0-30 parts by mass (Q 1 Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different. 2 (B-1) is a monovalent organic group having 6 to 30 carbon atoms, (X) is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, and (α) is an integer of 1 or 2. However, the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass. [3]: An emulsion composition of a film-forming organopolysiloxane according to [1] or [2], further characterized by containing (E) a nonionic surfactant in an amount of 0.1 to 30 parts by mass per 100 parts by mass of component (A). [4]: An emulsion composition of the film-forming organopolysiloxane according to [3], characterized in that the (E) nonionic surfactant is represented by the following formula. R 3 O(EO) p (PO) q H (In the formula, R 3 (where is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. p and q are independent integers between 0 and 100, where p + q > 0.) [5]: An emulsion composition of any one of the film-forming organopolysiloxanes from [1] to [4], characterized in that the (D) colloidal silica has a particle surface treated with an oxide of a metal other than silicon. [6]: An emulsion composition of any one of the film-forming organopolysiloxanes from [1] to [5], further comprising a salt comprising a basic substance consisting of either ammonia or an organic amine or both, and an acidic substance. [7]: An emulsion composition of any one of the film-forming organopolysiloxanes [1] to [6], characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition is 1,000 ppm or less. [8]: An emulsion composition of any one of the film-forming organopolysiloxanes [1] to [7], characterized in that the total content of each of the following contained in the emulsion composition is 1,000 ppm or less: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10). [9]: An emulsion composition of any one of [1] to [8] of a film-forming organopolysiloxane, characterized in that the average particle size of the emulsion contained in the emulsion composition is 1 μm or less.

[10] : An emulsion composition of a film-forming organopolysiloxane according to [9], characterized in that the average particle size of the emulsion contained in the emulsion composition is 500 nm or less.

[11] : An emulsion composition of any one of the film-forming organopolysiloxanes [1] to

[10] , characterized in that the antiviral activity value Mv in JIS L 1922 is 2.0 or higher.

[12] : A method for producing an emulsion composition of the film-forming organopolysiloxane of [1], comprising the following steps (I) to (III), wherein after step (I), steps (II) and (III) are performed in any order or simultaneously. A method for producing an emulsion composition of a film-forming organopolysiloxane, characterized by adding water (C) such that the total amount of (C-1), (C-2), and (C-3) below is 30 to 3,000 parts by mass. (I) A step of preparing an emulsion composition by emulsifying a mixture containing the following components (A-1), (A-2), (B), and (C-1), (A-1) Organopolysiloxanes with terminal alkoxy groups and terminal silanol groups that have a viscosity of 300,000 mPa·s or less at 25°C. (A-2) Alkoxysilane represented by the following formula (3) R 4 e Si(OR 5 ) 4-e (3) (Here, R 4 R is a hydrogen atom or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms, independently of each other. 5 Each of these is independently a hydrogen atom, or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms. e is either 0 or 1. The sum of (A-1) and (A-2) is 100 parts by mass, and the ratio of (A-2) to (A-1) is between 0 and 0.2. (B) Cationic surfactant: 0.1 to 30 parts by mass (C-1) Water: 30~3,000 parts by mass (II) Add (C-2) water to the obtained emulsion composition if necessary, and polymerize it in the presence of (F) a basic catalyst at 0 to 40°C for 1 to 150 hours, followed by neutralization. (III) Further adding (D) colloidal silica: 0.5 to 50 parts by mass, and (C-3) water as necessary.

[13] : A method for producing the film-forming organopolysiloxane emulsion composition of

[12] , characterized by using either ammonia or an organic amine or both as the (F) basic catalyst.

[14] : A method for producing the film-forming organopolysiloxane emulsion composition of

[12] or

[13] , characterized in that either (B-1) or (B-2) or both of the following are used as the (B) cationic surfactant. (B-1)Q 1 3(CH3)N + ·X - Cationic surfactants indicated by: 0-30 mass department (B-2)Q 2 α (CH3) 4-α N + ·X - Cationic surfactants indicated by: 0-30 mass department (Q 1 Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different. 2 (B-1) is a monovalent organic group having 6 to 30 carbon atoms, X is independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, and α is an integer of 1 or 2, provided that the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

[15] : A method for producing an emulsion composition of any one of the film-forming organopolysiloxanes from

[12] to

[14] , characterized in that in any of the steps (I) to (III) above, (E) a nonionic surfactant is further added in an amount of 0.1 to 30 parts by mass of the total of (A-1) and (A-2).

[16] : A method for producing the film-forming organopolysiloxane emulsion composition of

[15] , characterized in that the (E) component is a nonionic surfactant represented by the following formula. R 3 O(EO) p (PO) q H (In the formula, R 3 (where is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. p and q are independent integers between 0 and 100, where p + q > 0.)

[17] : A method for producing an emulsion composition of any one of the film-forming organopolysiloxanes from

[12] to

[16] , characterized in that the (D) component is colloidal silica whose particle surface is treated with an oxide of a metal other than silicon.

[18] : A method for producing an emulsion composition of any one of the film-forming organopolysiloxanes from

[12] to

[17] , characterized in that the (A-1) component is one in which the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained therein is 1,000 ppm or less.

[19] : A method for producing an emulsion composition of any one of the film-forming organopolysiloxanes

[12] to

[18] , characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition is 1,000 ppm or less.

[20] : A method for producing an emulsion composition of any one of the film-forming organopolysiloxanes from

[12] to

[19] , characterized in that the total amount of each of the following contained in the emulsion composition is 1,000 ppm or less: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10).

[0192] 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. An emulsion composition of a film-forming organopolysiloxane characterized by containing the following (A) to (D). (A) Organopolysiloxane represented by the following average composition formula (1), having a viscosity of 300,000 mPa·s or more at 25°C, and containing at least two alkoxy or hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass 【Chemistry 1】 (In the formula, R １ R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, either unsubstituted or substituted. ２ (where a 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, a is an integer between 2 and 1,000, b is an integer between 10 and 10,000, c is an integer between 0 and 1,000, d is an integer between 0 and 1,000, c + d is an integer between 0 and 2,000, and the viscosity of the organopolysiloxane at 25°C is 300,000 mPa·s or more.) (B) Cationic surfactant: 0.1 to 30 parts by mass (C) Water: 30 to 3,000 parts by mass (D) Colloidal silica whose particle surface is treated with an oxide of a metal other than silicon: 0.5 to 50 parts by mass

2. The emulsion composition of a film-forming organopolysiloxane according to claim 1, characterized in that the (B) cationic surfactant contains either or both of the following (B-1) or (B-2). (B-1)Q １ ３ (CH ３ )N ＋ ・X － Cationic surfactants indicated by: 0 to 30 parts by mass (B-2)Q ２ α (CH ３ ) ４－α N ＋ ・X － Cationic surfactants indicated by: 0 to 30 parts by mass (Q １ Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different. ２ (B-1) is a monovalent organic group having 6 to 30 carbon atoms, X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, and α is an integer of 1 or 2. However, the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.)

3. The emulsion composition of a film-forming organopolysiloxane according to claim 1, further characterized in that it contains (E) a nonionic surfactant in an amount of 0.1 to 30 parts by mass per 100 parts by mass of component (A).

4. The emulsion composition of a film-forming organopolysiloxane according to claim 3, characterized in that the (E) nonionic surfactant is represented by the following formula. 2 ３ 9(59) ｐ (0) ｑ 8 (In the formula, R ３ (where is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. p and q are independent integers between 0 and 100, provided that p + q > 0.)

5. The emulsion composition of a film-forming organopolysiloxane according to claim 1, further characterized in that it contains a salt comprising a basic substance consisting of either ammonia or an organic amine, or both, and an acidic substance.

6. The emulsion composition of a film-forming organopolysiloxane according to claim 1, characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition is 1,000 ppm or less.

7. The emulsion composition of a film-forming organopolysiloxane according to claim 1, characterized in that the total content of each of the following contained in the emulsion composition is 1,000 ppm or less: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10).

8. The emulsion composition of a film-forming organopolysiloxane according to claim 1, characterized in that the average particle size of the emulsion contained in the emulsion composition is 1 μm or less.

9. The emulsion composition of a film-forming organopolysiloxane according to claim 8, characterized in that the average particle size of the emulsion contained in the emulsion composition is 500 nm or less.

10. An emulsion composition of a film-forming organopolysiloxane according to any one of claims 1 to 9, characterized in that the antiviral activity value Mv in JIS L 1922 is 2.0 or higher.

11. A method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 1, comprising the following steps (I) to (III), wherein after step (I), steps (II) and (III) are performed in any order or simultaneously. A method for producing an emulsion composition of a film-forming organopolysiloxane, characterized by adding water (C) such that the total amount of (C-1), (C-2), and (C-3) below is 30 to 3,000 parts by mass. (I) A step of preparing an emulsion composition by emulsifying a mixture containing the following components (A-1), (A-2), (B), and (C-1), (A-1) Organopolysiloxanes with terminal alkoxy groups and terminal silanol groups that have a viscosity of 300,000 mPa·s or less at 25°C. (A-2) Alkoxysilane represented by the following formula (3) R ４ ｅ Si(OR ５ ) ４－ｅ (3) (Here, R ４ These are, independently of each other, a hydrogen atom, or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms, and R ５ Each of these is independently a hydrogen atom, or a monovalent organic group having 1 to 20 substituted or unsubstituted carbon atoms. e is either 0 or 1. The sum of (A-1) and (A-2) is 100 parts by mass, and the ratio of (A-2) to (A-1) is between 0 and 0.

2. (B) Cationic surfactant: 0.1 to 30 parts by mass (C-1) Water: 30 to 3,000 parts by mass (II) Add (C-2) water to the obtained emulsion composition if necessary, and polymerize it in the presence of (F) a basic catalyst at 0 to 40°C for 1 to 150 hours, followed by neutralization. (III) Further, (D) colloidal silica whose particle surface is treated with an oxide of a metal other than silicon: 0.5 to 50 parts by mass, and (C-3) water as necessary.

12. A method for producing a film-forming organopolysiloxane emulsion composition according to claim 11, characterized in that ammonia or an organic amine or both are used as the (F) basic catalyst.

13. A method for producing an emulsion composition of a film-forming organopolysiloxane according to 11, characterized in that either (B-1) or (B-2) or both of the following are used as the cationic surfactant (B). (B-1) Q １ ３ (CH ３ ) N ＋ ・X － Cationic surfactants indicated by: 0 to 30 parts by mass (B-2) Q ２ α (CH ３ ) ４－α N ＋ ・X － Cationic surfactants indicated by: 0 to 30 parts by mass (Q １ Q is a monovalent organic group having 6 to 30 carbon atoms, either identical or different. ２ (B-1) is a monovalent organic group having 6 to 30 carbon atoms, X is independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, and α is an integer of 1 or 2, provided that the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.)

14. A method for producing an emulsion composition of a film-forming organopolysiloxane according to 11, characterized in that in any of the steps (I) to (III) above, (E) a nonionic surfactant is further added in an amount of 0.1 to 30 parts by mass per 100 parts by mass of the total of (A-1) and (A-2).

15. A method for producing a film-forming organopolysiloxane emulsion composition according to claim 14, characterized in that a nonionic surfactant represented by the following formula is used as the (E) component. 2 ３ 9(59) ｐ (0) ｑ 8 (In the formula, R ３ (where is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, and PO represents a propylene oxide group; their arrangement may be blocky or random. p and q are independent integers between 0 and 100, provided that p + q > 0.)

16. A method for producing a film-forming organopolysiloxane emulsion composition according to claim 11, characterized in that colloidal silica, whose particle surface is treated with a metal oxide other than silicon, is used as the (D) component.

17. A method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 11, characterized in that the (A-1) component used is one in which the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained therein is 1,000 ppm or less.

18. A method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 11, characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition is 1,000 ppm or less.

19. A method for producing an emulsion composition of a film-forming organopolysiloxane according to any one of claims 11 to 18, characterized in that the total content of each of the following contained in the emulsion composition is 1,000 ppm or less: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10).

Images