Emulsion composition of film-forming organopolysiloxane and production method therefor

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

Film-forming organopolysiloxane emulsion composition and method for producing same

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

[0002] Silicone emulsion compositions for forming rubber coatings have been known in a variety of compositions and are used in a variety of applications, including weatherstrips, coatings, binders, and fiber treatments.

[0003] For example, there are disclosed a silicone emulsion composition comprising a hydroxylated diorganopolysiloxane, colloidal silica, and an organic tin compound or an organic amine compound (Patent Document 1), a silicone emulsion composition comprising a hydroxy group-containing organopolysiloxane, a Si—H group-containing organopolysiloxane, colloidal silica, an amide group- and 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 an aminosilane and an acid anhydride, an epoxysilane, and an addition reaction catalyst (Patent Document 3), and a silicone emulsion composition comprising a silicone having molecular ends blocked with hydroxyl groups. Proposed silicone emulsion compositions include a silicone emulsion composition comprising a hydrogen siloxane, an emulsifier, water, and a curing catalyst (Patent Document 4); a silicone emulsion composition comprising a colloidal silica-silicone core-shell material, a curing catalyst, an emulsifier, and water (Patent Documents 5 to 7); a silicone emulsion composition comprising a hydroxy group-containing organopolysiloxane, colloidal silica, an amide group- and carboxyl group-containing silane, an epoxy group-containing silane, a curing catalyst, and a photocatalytic oxide (Patent Document 8); and a silicone emulsion composition comprising a hydroxy group-containing organopolysiloxane, colloidal silica, an amide group- and carboxyl group-containing silane, and an epoxy group-containing silane (Patent Document 9).

[0004] Furthermore, because organopolysiloxanes can impart flexibility and lubricity to various fibers or textile products, silicone emulsion compositions that form rubber coatings are also used as fiber treatment agents. A known method for producing such silicone emulsion compositions that form rubber coatings involves emulsion polymerization using a strong acid or strong base in an emulsified state using a cyclic siloxane oligomer or a silanol-terminated organopolysiloxane as a raw material.

[0005] When an anionic surfactant with strong catalytic activity is used as the surfactant, the polymerization reaction occurs quickly, and therefore research has been conducted for a long time, and many methods have been proposed. However, emulsion polymerization emulsions using anionic surfactants are incompatible with cationic emulsions and chemicals, which are widely used in fiber treatment and hair cosmetics, among others, and when they are blended, stability decreases, which causes problems such as limitations on the conditions of use and blending.

[0006] On the other hand, when common cationic surfactants such as cetyltrimethylammonium chloride or tallow trimethylammonium chloride are used as surfactants, the polymerization rate is extremely slow due to their weak catalytic action, making it difficult to obtain a silicone emulsion with a high enough degree of polymerization to form a rubber coating.

[0007] Patent Document 10 proposes that an organopolysiloxane emulsion having such a high degree of polymerization that a film can be formed in a shorter time than conventional methods can be obtained by emulsifying a terminally silanol-blocked organopolysiloxane using a highly hydrophobic trialkylmethyl-type cationic surfactant in combination with an alkyltrimethyl-type cationic surfactant (possibly including a nonionic surfactant), followed by polymerization by adding an alkali catalyst. However, the cured film of the composition has been found to be soft and weak. Furthermore, these emulsions have the problem of separating within three months. The organopolysiloxane in this emulsion has such a high degree of polymerization that it can form a film. Therefore, once separated, it is impossible to redisperse it stably, even with high shear stirring, making it difficult to use industrially. Further improvements in long-term stability are needed.

[0008] JP 56-16553 A JP 8-85760 JP 9-208826 JP 9-208900 JP 9-208901 JP 9-208901 9-208902 publication JP 9-208903 publication JP 2002-363494 publication JP 2008-231276 publication JP 2021-95455 publication

[0009] The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object the provision of an emulsion composition of a film-forming organopolysiloxane that has good film-forming properties, produces a film that is excellent in strength and flexibility after curing, and has good emulsion storage stability, as well as a method for producing the film-forming organopolysiloxane emulsion composition.

[0010] In order to solve the above problems, the present invention provides a film-forming organopolysiloxane emulsion composition characterized by containing the following (A) to (D): (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula (1), which has a viscosity at 25°C of 300,000 mPa·s or more and contains at least two alkoxy or hydroxy groups bonded to silicon atoms per molecule: (In the formula, R １ are each independently a hydrogen atom or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, and R ２ represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group; a represents an integer from 2 to 1,000, b represents an integer from 10 to 10,000, c represents an integer from 0 to 1,000, d represents an integer from 0 to 1,000, and c+d represents an integer from 0 to 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: 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, and the film after curing has excellent strength and flexibility, and the emulsion also has good storage stability.

[0012] In this case, it is preferable that the cationic surfactant (B) contains either or both of the following (B-1) and (B-2): (B-1) Q １ ３ (CH ３ ) N ＋ ・X － (B-2)Q: 0 to 30 parts by mass ２ α (CH ３ ) ４－α N ＋ ・X － Cationic surfactant represented by the formula: 0 to 30 parts by mass (Q １ are the same or different monovalent organic groups having 6 to 30 carbon atoms, Q ２ are the same or different monovalent organic groups having 6 to 30 carbon atoms, X are each 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.

[0013] Such an emulsion composition has better storage stability.

[0014] The emulsion composition of the present invention preferably further contains (E) a nonionic surfactant in an amount of 0.1 to 30 parts by mass per 100 parts by mass of component (A).

[0015] Such an emulsion composition can be emulsified more easily by complementing the emulsifying ability of component (E), and the stability of the emulsion can be dramatically improved.

[0016] In this case, the nonionic surfactant (E) is preferably one represented by the following formula: ３ O (EO) ｐ (PO) ｑ H (wherein, R ３ represents 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, and the arrangement thereof may be block or random. p and q are each independently an integer of 0 to 100, provided that p+q>0.

[0017] Component (E) has an appropriate balance of hydrophilicity and hydrophobicity, is compatible with components (B-1) and (B-2), and enhances emulsion stability. Furthermore, the properties of the nonionic surfactant itself make it easy to handle during emulsion production.

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

[0019] The component (D) causes the surfaces of the surface-treated colloidal silica particles to be positively charged over a wide pH range, generating an electric repulsive force between the surface-treated colloidal silica particles and the emulsion particles in the emulsion composition, making them less likely to coalesce or aggregate, thereby enabling the emulsion to be dispersed more stably.

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

[0021] Even when the emulsion composition of the present invention contains such salts, it has good film-forming properties, and the strength and flexibility of the film after curing are excellent, and the storage stability of the emulsion is also good.

[0022] Preferably, the emulsion composition contains octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in an amount of 1,000 ppm or less (mass equivalent, the same applies hereinafter). More preferably, the emulsion composition contains hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10) in a total amount of 1,000 ppm or less.

[0023] The emulsion composition of the present invention has a low content of such low molecular weight cyclic siloxanes, and therefore has excellent coating properties (such as elongation at break) after curing.

[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 applied to the particles is reduced in proportion to the particle volume, allowing the particles to be uniformly dispersed in the emulsion, suppressing aggregation or coalescence of the particles, and preventing separation into light and dark layers or separation into two layers even after long-term storage.

[0026] The emulsion composition of the present invention may have an antiviral activity value Mv according to JIS L 1922 of 2.0 or more.

[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 properties.

[0028] The present invention also provides a method for producing an emulsion composition of the above-mentioned film-forming organopolysiloxane, comprising the following steps (I) to (III), in which steps (II) and (III) are carried out in any order or simultaneously after step (I), and (C) water (C) is added so that the total amount of the following components (C-1), (C-2), and (C-3) 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) an organopolysiloxane blocked with terminal alkoxy groups and / or terminal silanol groups, having a viscosity at 25°C of 300,000 mPa·s or less, (A-2) an alkoxysilane R represented by the following formula (3): ４ ｅ Si(OR ５ ) ４－ｅ (3) (where R ４ are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and R ５ are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. e is 0 or 1.) The total of (A-1) and (A-2) is 100 parts by mass, and the ratio of (A-2) to (A-1) is 0 to 0.2. (B) Cationic surfactant: 0.1 to 30 parts by mass (C-1) Water: 30 to 3,000 parts by mass (II) If necessary, further adding water (C-2) to the obtained emulsion composition, and (F) polymerizing in the presence of a basic catalyst at 0 to 40°C for 1 to 150 hours, and further neutralizing, (III) Further adding 0.5 to 50 parts by mass of colloidal silica (D) and, if necessary, further adding water (C-3).

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

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

[0031] The use of such a catalyst makes it possible to significantly suppress the by-production of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), while still ensuring that the viscosity of the organopolysiloxane in the emulsion composition of the film-forming organopolysiloxane at 25°C is 300,000 mPa·s or more, and to keep the content of each of these compounds to 1,000 ppm or less.

[0032] As the cationic surfactant (B), it is preferable to use either or both of the following (B-1) and (B-2): (B-1) Q １ ３ (CH ３ ) N ＋ ・X － Cationic surfactant represented by the formula (B-2): 0 to 30 parts by mass ２ α (CH ３ ) ４－α N ＋ ・X － Cationic surfactant represented by the formula (Q １ are the same or different monovalent organic groups having 6 to 30 carbon atoms, Q ２ are the same or different monovalent organic groups having 6 to 30 carbon atoms, each 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.

[0033] Such a method for producing an emulsion composition makes it possible to efficiently produce an emulsion composition with better storage stability.

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

[0035] Such a method for producing an emulsion composition can efficiently produce a composition that can be emulsified more easily due to the function of supplementing the emulsifying ability of the component (E) and has dramatically improved emulsion stability.

[0036] The component (E) may be a nonionic surfactant represented by the following formula: ３ O (EO) ｐ (PO) ｑ H (wherein, R ３ represents 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, and the arrangement thereof may be block or random. p and q are each independently an integer of 0 to 100, provided that p+q>0.

[0037] The properties of such component (E) make it easy to handle when producing an emulsion.

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

[0039] When such a component (D) is used, an electrical repulsive force is generated between the surface-treated colloidal silica particles and the emulsion particles in the emulsion composition, making them less likely to coalesce or aggregate, and therefore a more stable emulsion composition can be produced efficiently.

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

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

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

[0043] According to the method for producing an emulsion composition of the present invention, an emulsion composition with a low content of such low molecular weight cyclic siloxanes can be produced efficiently.

[0044] The film-forming organopolysiloxane emulsion composition (hereinafter also referred to as emulsion composition) of the present invention can provide a film-forming organopolysiloxane emulsion composition and a film that have good film-forming properties, excellent film strength and flexibility after curing, and good emulsion storage stability. Furthermore, by applying the composition to various fibers or textile products, it is possible to impart flexibility and lubricity. Furthermore, a fiber 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.

[0045]

[0006] As a result of extensive research conducted by the present inventors in order to achieve the above-mentioned object, they discovered that an emulsion composition of a film-forming organopolysiloxane containing specific amounts of (A) a specific organopolysiloxane having a viscosity of 300,000 mPa·s or more at 25°C, (B) a cationic surfactant, (C) water, and (D) colloidal silica exhibits good film-forming properties, produces a film that is excellent in strength and flexibility after curing, and has good emulsion storage stability, which led to the completion of the present invention.

[0046] That is, the present invention provides a film-forming organopolysiloxane emulsion composition characterized by containing the following (A) to (D): (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula (1), which has a viscosity at 25°C of 300,000 mPa·s or more and contains at least two alkoxy or hydroxy groups bonded to silicon atoms in each molecule: (In the formula, R １ are each independently a hydrogen atom or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, and R ２ represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group; a represents an integer from 2 to 1,000, b represents an integer from 10 to 10,000, c represents an integer from 0 to 1,000, d represents an integer from 0 to 1,000, and c+d represents an integer from 0 to 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: 0.5 to 50 parts by mass.

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

[0048] [Film-Forming Organopolysiloxane Emulsion Composition] The film-forming organopolysiloxane emulsion composition of the present invention comprises: (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula (1), which has a viscosity at 25°C of 300,000 mPa·s or more and contains at least two alkoxy groups or hydroxy groups bonded to silicon atoms in each molecule: (In the formula, R １ are each independently a hydrogen atom or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, and R ２ represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy or hydroxy group having 1 to 20 carbon atoms; a is an integer from 2 to 1,000, b is an integer from 10 to 10,000, c is an integer from 0 to 1,000, d is an integer from 0 to 1,000, and c + d are integers satisfying the condition of 0 to 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; and (D) Colloidal silica: 0.5 to 50 parts by mass. If necessary, components other than components (A) to (D) may also be contained. Each component is described below.

[0049] [Component (A)] (A) is an organopolysiloxane represented by the following average composition formula (1), which has a viscosity at 25°C of 300,000 mPa s or more and contains at least two alkoxy groups or hydroxy groups bonded to silicon atoms per molecule. The emulsion composition of the present invention contains 100 parts by mass of this component (A). (In the formula, R １ are each independently a hydrogen atom or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, and R ２represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group; a represents an integer from 2 to 1,000, b represents an integer from 10 to 10,000, c represents an integer from 0 to 1,000, d represents an integer from 0 to 1,000, and c+d is an integer that satisfies the range of 0 to 2,000, and the viscosity of the organopolysiloxane at 25°C is 300,000 mPa·s or greater.

[0050] In the above formula (1), R １ are each independently a hydrogen atom or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, which may be linear, branched, or cyclic. Specific 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; and alkenyl groups such as vinyl and allyl. These organic group structures may also include those in which some of the hydrogen atoms have been substituted with halogen atoms or organic groups containing polar groups such as amino, acryloxy, methacryloxy, epoxy, and mercapto. １ It is desirable from the viewpoint of industrial and property points of view that 80% or more of the groups are methyl groups.

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

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

[0053] a is an integer from 2 to 1,000, preferably an integer from 2 to 500, and more preferably an integer from 2 to 100. If a is greater than 1,000, the flexibility of the silicone rubber coating may be poor. b is an integer from 10 to 10,000, preferably an integer from 50 to 7,000, and more preferably an integer from 100 to 5,000. If b is less than 10, the flexibility of the silicone rubber coating may be poor or the coating may not form. If b is greater than 10,000, the tear strength and tensile strength of the coating may be reduced. c is an integer from 0 to 1,000, preferably an integer from 0 to 200, and more preferably an integer from 0 to 100. If c is greater than 1,000, the flexibility of the silicone rubber coating may be poor or the tear strength and tensile strength of the coating may be reduced. 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 be poor, and the tear strength and tensile strength of the coating may be reduced. 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 at 25°C of 300,000 mPa·s or more, 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 a viscosity so high that it cannot be measured by the viscosity measurement method described below.

[0055] The viscosity (absolute viscosity) in the present invention is a measured value measured using a BM type rotational viscometer (TVB-10M) at 25° C. The viscosity of all of the samples whose viscosity cannot be measured even using the M4 rotor (maximum measurable viscosity: 2,000,000 mPa s), which is the rotor capable of measuring the highest viscosity among BM type rotational viscometers, samples that cannot be measured because they wrap around the rotor of the BM type rotational viscometer, and samples that cannot be measured because they do not dissolve in toluene, is 300,000 mPa s or more.

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

[0057]

[0058]

[0059]

[0060] [Component (B)] 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, and more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (A). If the amount of component (B) is less than 0.1 part by mass or more than 30 parts by mass, the emulsion may become unstable, and it may become difficult to achieve a high degree of polymerization through dealcoholization condensation polymerization or dehydration condensation polymerization between alkoxy groups or hydroxy groups contained in the organopolysiloxane.

[0061] Furthermore, the component (B) preferably contains either or both of the following component (B-1) or component (B-2): (B-1)Q １ ３ (CH ３ ) N ＋ ・X－ A cationic surfactant represented by (B-2)Q ２ α (CH ３ ) ４－α N ＋ ・X － A cationic surfactant (Q １ are the same or different monovalent organic groups having 6 to 30 carbon atoms, Q ２ are the same or different monovalent organic groups having 6 to 30 carbon atoms, X are each independently a halogen atom or a monovalent carboxyl group having 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 used to emulsify and disperse the organopolysiloxane in water. The present inventors believe that the mechanisms of action of components (B-1) and (B-2) may be the following, in addition to their function as emulsifiers.

[0063] In the method for producing an organopolysiloxane emulsion composition of the present invention, after the organopolysiloxane is emulsified and dispersed in water, a basic catalyst (alkali catalyst) is added to the aqueous phase to produce OH groups. － It is believed that the exchange of counter ions between the cationic surfactants (B-1) and (B-2) and the cationic surfactant itself acts as a catalyst, thereby more efficiently achieving a high degree of polymerization for the organopolysiloxane (A).

[0064] The cationic surfactant (B-1) is, as described above, １ ３ (CH ３ ) N ＋ ・X － Q is a cationic surfactant represented by １ are the same or different monovalent organic groups having 6 to 30 carbon atoms, preferably 7 to 20 carbon atoms, and more preferably 8 to 18 carbon atoms. １When Q has 6 or more carbon atoms, the surfactant has adequate hydrophilicity, and the frequency of contact with the organopolysiloxane of component (A) is sufficient, allowing the organopolysiloxane to be highly polymerized, and the time required to achieve this high polymerization is short. １ If the number of carbon atoms is 30 or less, the emulsifying power as a surfactant is sufficient, and a stable emulsion can be obtained.

[0065] Q １ Specific examples of the alkyl group 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, etc. Among these, octyl, dodecyl, hexadecyl, and octadecyl are preferred.

[0066] Also, X － is a halogen ion or a monovalent carboxyl ion having 1 to 6 carbon atoms, specifically Cl － ,Br － , I － Halogen ions such as HCOO － , C.H. ３ COO － , C ２ H ５ COO － Among them, Cl － ,Br － , HCOO － , C.H. ３ COO － is preferred.

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

[0068] The amount of cationic surfactant used as component (B-1) is 0 to 30 parts by mass, preferably 0.2 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (A). An amount of 0 to 30 parts by mass improves emulsion stability.

[0069] Furthermore, the cationic surfactant of component (B-2) has, as described above, Q ２ α (CH ３ ) ４－α N ＋ ・X － It is a cationic surfactant represented by the formula Q and can improve the stability of emulsions. ２ are the same or different monovalent organic groups having 6 to 30 carbon atoms, preferably 12 to 28 carbon atoms, and more preferably 18 to 26 carbon atoms. ２ If the number of carbon atoms in the group is 6 or more, the emulsion stability will be good. ２ If the number of carbon atoms in １ As in the case of (1), the surfactant has sufficient emulsifying power, and a stable emulsion can be obtained. ２ X － is the above Q １ X － where α is an integer of 1 or 2.

[0070] Specific examples of the component (B-2) include hexyltrimethylammonium chloride, phenyltrimethylammonium chloride, heptyltrimethylammonium chloride, benzyltrimethylammonium chloride, octyltrimethylammonium chloride, nonyltrimethylammonium chloride, decyltrimethylammonium chloride, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, stearyltrimethylammonium chloride, icosyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexyltrimethylammonium acetate, phenyltrimethylammonium acetate, heptyltrimethylammonium acetate, benzyltrimethylammonium acetate, octyltrimethylammonium acetate, nonyltrimethylammonium acetate, decyltrimethylammonium acetate, lauryltrimethylammonium acetate, myristyltrimethylammonium acetate, and hexadecyltrimethylammonium acetate. Acetate, stearyl trimethylammonium acetate, icosyl trimethylammonium acetate, behenyl trimethylammonium acetate, dihexyl dimethyl ammonium chloride, diphenyl dimethyl ammonium chloride, hexyl phenyl dimethyl ammonium chloride, heptyl phenyl dimethyl ammonium chloride, octyl phenyl dimethyl ammonium chloride, nonyl phenyl dimethyl ammonium chloride, decyl phenyl dimethyl ammonium chloride, lauryl phenyl dimethyl ammonium chloride, myristyl phenyl dimethyl ammonium chloride, hexadecyl phenyl dimethyl ammonium chloride, stearyl phenyl dimethyl ammonium chloride, icosyl phenyl dimethyl ammonium chloride, behenyl dimethyl ammonium chloride, diheptyl dimethyl ammonium chloride, dibenzyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, dinonyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dilauryl dimethyl ammonium chloride,Examples of the ammonium hydroxide include, but are not limited to, dimyristyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, distearyl dimethyl ammonium acetate, diicosyl dimethyl ammonium acetate, dibehenyl dimethyl ammonium acetate, dihexyl dimethyl ammonium acetate, diphenyl dimethyl ammonium acetate, diheptyl dimethyl ammonium acetate, dibenzyl dimethyl ammonium acetate, dioctyl dimethyl ammonium acetate, dinonyl dimethyl ammonium acetate, didecyl dimethyl ammonium acetate, dilauryl dimethyl ammonium acetate, dimyristyl dimethyl ammonium acetate, dihexadecyl dimethyl ammonium acetate, distearyl dimethyl ammonium acetate, diicosyl dimethyl ammonium acetate, and dibehenyl dimethyl ammonium acetate.

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

[0072] As described above, the emulsion composition of the present invention contains 0 to 30 parts by mass of component (B-1) and 0 to 30 parts by mass of component (B-2) per 100 parts by mass of component (A), and the total amount of components (B-1) and (B-2) is within 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] Because component (B-1) is more hydrophobic than component (B-2), it comes into contact with the organopolysiloxane of component (A) more frequently, which is expected to have the effect of accelerating the polymerization rate. However, because of its high hydrophobicity, it has inferior emulsifying ability to component (B-2). Therefore, when using only (B-1), it is necessary to further improve the emulsion's stability over time, depending on the emulsion's composition, particle size, viscosity, pH, and other conditions. Therefore, by using component (B-2), which has a higher emulsifying ability than component (B-1), in combination, it is possible to increase the emulsion's stability while maintaining a high polymerization rate.

[0074] As mentioned above, it is possible to use only the component (B-1), but by using the components (B-1) and (B-2) in combination, it is possible to increase the stability of the emulsion while maintaining an increased polymerization rate. The cationic surfactant (B-1) is １ ３ (CH ３ ) N ＋ ・X － The cationic surfactant (B-2) is represented by Q ２ α (CH ３ ) ４－α N ＋ ・X － (B-1) is a cationic surfactant represented by the formula: １ Thus, (B-2) is one or two substituents Q of the quaternary ammonium. ２ The monovalent organic group Q １ , Q ２ The more carbon atoms in a molecule, the more hydrophobic it becomes, and the greater the steric hindrance due to its bulkiness. １ , Q ２ By selecting the above, it is possible to adjust these effects and achieve a favorable polymerization rate and emulsion stability. In the combination of component (B-1) and component (B-2), the total number of carbon atoms in the substituents of each quaternary ammonium is not particularly limited. However, from the viewpoint of obtaining a favorable emulsion, it is preferable to select the total number of carbon atoms (three Q １ and the total number of carbon atoms in one methyl group) （Ｂ－１）The total number of carbon atoms of the quaternary ammonium group in (B-2) (one or two Q ２ and the total number of carbon atoms in the remaining methyl groups) （Ｂ－２） As N （Ｂ－１） and N （Ｂ－２） The difference between N and N is preferably 0 to 35, with the lower limit being any integer between 0 and 4, and the upper limit being any integer between 30 and 34. （Ｂ－１） and N （Ｂ－２） By adjusting the difference between Q and Q to an appropriate value, a suitable emulsion can be obtained. １ The number of carbon atoms and Q ２ There are no particular limitations on the combination of carbon numbers of Q. However, from the viewpoint of obtaining a suitable emulsion, １ The number of carbon atoms and Q ２ The difference in the number of carbon atoms between Q and Q is preferably 0 to 15, with the lower limit being any integer between 0 and 4, and the upper limit being any integer between 10 and 14. １ The number of carbon atoms and Q ２ By adjusting the difference in the number of carbon atoms between the groups to an appropriate value, the hydrophilicity of the surfactant, the frequency of contact with the organopolysiloxane of component (A), and the emulsifying power can be adjusted to appropriate values, and the organopolysiloxane can be polymerized to a high degree by condensation polymerization, thereby making the polymerization rate favorable, thereby enabling the production of a stable and favorable emulsion.

[0075] [Component (C)] The emulsion composition of the present invention contains 30 to 3,000 parts by mass, and preferably 40 to 2,400 parts by mass, of water as component (C) per 100 parts by mass of component (A). If the amount of water is too small, an oil-in-water emulsion will not be obtained, and if the amount of water is too large, it is uneconomical.

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

[0077] The colloidal silica of component (D) acts as a coating reinforcing agent. Even in cases where the strength (especially hardness and tensile strength) of the coating is weak and the emulsion composition cannot be used in applications where durability is required, the use of colloidal silica can dramatically improve the strength (especially hardness and tensile strength) of the coating formed from the emulsion composition.

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

[0079] In particular, the use of colloidal silica whose particle surface has been treated with an oxide of a metal other than silicon can significantly improve emulsion stability. As the oxide of a metal other than silicon, a substance with an isoelectric point of 5 or higher, such as aluminum oxide, titanium oxide, iron oxide, zinc oxide, or magnesium oxide, is preferred. By using such colloidal silica, the colloidal silica particle surface becomes positively charged over a wide pH range, generating an electric repulsive force between the colloidal silica and the emulsion particles in the emulsion composition, making them less likely to coalesce or aggregate, thereby enabling more stable dispersion. The isoelectric point may be measured, for example, in accordance with JIS R1638:1999. Furthermore, by using such colloidal silica, when removing water to form a coating, an electric repulsive force is generated between the emulsion particles and the colloidal silica in the emulsion composition, making them less likely to coalesce or aggregate, resulting in a more uniform (more dispersed) coating, which can dramatically improve the strength (particularly hardness and tensile strength) of the coating 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.), and among the above, Snowtex AK, Snowtex AK-L, and Snowtex AK-YL, in which the surface of colloidal silica is treated with alumina, are particularly preferred, but are not limited to these. The average particle size of the colloidal silica is not particularly limited, and the average particle size of the above-mentioned colloidal silica can be used.

[0081] An example of a similar composition containing silica / organopolysiloxane / water is a Pickering emulsion composition. A Pickering emulsion is an emulsion stabilized by the adsorption (orientation) of solid particles at the liquid / liquid interface. This emulsion composition has attracted attention in recent years because it can be produced without emulsifiers. The solid particles typically used in Pickering emulsion compositions include hydrophobic silica, hydrophobic cellulose, silicone resin powder, hollow hemispherical silicone particles, polyamide resin, talc, and hydrophobic pigments. Regarding silica, hydrophobic silica is commonly used, in which the hydroxyl groups on the surface of the hydrophilic silica are reacted with a trifunctional silane or the like to modify the surface with a hydrocarbon or the like to make it hydrophobic. Meanwhile, the colloidal silica preferably used in the present invention is an aqueous dispersion of hydrophilic silica particles having many silanol groups (Si—OH) on the surface, preferably coated with a metal oxide other than silicon. Therefore, Pickering emulsion compositions and the emulsion composition of the present invention are compositionally different. Furthermore, in the present invention, the colloidal silica is not adsorbed (oriented) at the liquid / liquid (organopolysiloxane / water) interface, but is stably dispersed in the aqueous phase (continuous phase) while experiencing charge repulsion, and therefore the dispersion mechanism is also different from that of Pickering emulsion compositions.

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

[0083] The nonionic surfactant, component (E), acts to compensate for the emulsifying ability that is insufficient when components (B-1) and (B-2) are used alone, thereby facilitating emulsification and dramatically improving emulsion stability.

[0084] The nonionic surfactant of component (E) preferably has the following structure: ３ O (EO) ｐ (PO) ｑ H (wherein, R ３represents 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, and the arrangement thereof may be block or random. p and q are each independently an integer of 0 to 100, provided that p+q>0.

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

[0086] R ３ If the number of carbon atoms in R is 8 or more, the surfactant has appropriate hydrophilicity, has good compatibility with the components (B-1) and (B-2), and is free from the risk of separation into a light and dark layer or two layers even after two months. ３ If the number of carbon atoms in R is 30 or less, the hydrophobicity is not too high and sufficient emulsification can be achieved. ３ Since the number of carbon atoms in the nonionic surfactant 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. Therefore, the degree of polymerization of the ethylene oxide group may be low, and the properties of the nonionic surfactant itself are easy to handle when producing an emulsion.

[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, heptadecyl, octacosyl, nonacosyl, triacontyl, etc. 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, and their arrangement may be block or random. p and q are each independently an integer of 0 to 100, preferably an integer of 2 to 80, and more preferably an integer of 4 to 60, provided that p+q>0. Note that as the degree of polymerization of PO (q in the formula) increases, hydrophobicity increases and the emulsifiability of the nonionic surfactant tends to decrease, so 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, for purposes such as supplementing emulsion stability, it is not problematic to add cationic surfactants other than components (B-1) and (B-2), such as quaternary ammonium salts and alkylamine acetates, or amphoteric surfactants such as alkyl betaines and alkyl imidazolines. In the present invention, in addition to cationic surfactants, nonionic or amphoteric surfactants such as those described above can also be added, but anionic surfactants with strong catalytic activity do not necessarily need to be added. Since the present invention can obtain an emulsion polymerization emulsion without adding an anionic surfactant, the emulsion composition of the present invention can be used with cationic emulsions and chemicals used in fiber treatment applications and hair cosmetics, and is useful in that it is stable and does not require limitations on use and formulation conditions. This is a feature of the present invention not found in conventional emulsion polymerization emulsions using anionic surfactants.

[0091] [Other Components] The emulsion composition of the present invention may further contain a salt composed of a basic substance composed of either or both of ammonia and an organic amine and an acidic substance. The emulsion composition of the present invention desirably contains a salt composed of a basic substance composed of ammonia or an organic amine and a strong acidic substance or a weak acidic substance. This salt composed of a basic substance composed of ammonia or an organic amine and a strong acidic substance or a weak acidic substance is a salt produced by neutralizing a basic catalyst (alkali catalyst) used for polymerization when producing the emulsion composition of the present invention, as described below.

[0092] By using ammonia and / or an organic amine as a catalyst, it is possible to significantly suppress the by-production of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), and to keep the respective contents to 1,000 ppm or less, while still ensuring that the viscosity of the organopolysiloxane in the organopolysiloxane emulsion composition of the present invention is 300,000 mPa s or more at 25°C.

[0093] Therefore, in the present invention, when a strong or weak acid is added as a neutralizing agent to terminate polymerization, a basic substance consisting of ammonia or an organic amine and a salt consisting of a strong or weak acid are generated in the emulsion composition. Even when the emulsion composition of the present invention contains the above salt, it has good film-forming properties, excellent strength and flexibility of the cured film, and good emulsion storage stability. However, to improve the stability of the emulsion composition, a low content of the above salt is preferable. 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] In order to prevent separation of the emulsion composition, it is preferable that the emulsion composition does not contain a large amount of a component that generally has the effect of reducing emulsion stability, such as alcohol, etc. 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, the cationic surfactants of components (B-1) and (B-2) are sometimes sold in a form diluted with a solvent (particularly alcohol) such as ethanol or IPA, but the concentration of the solvent (particularly alcohol) is preferably 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 (particularly alcohol) is greater than 20% by mass, the stability of the emulsion may decrease, making it more likely to separate over time. The alcohol refers to an aliphatic alcohol having 1 to 20 carbon atoms. The numerical ranges shown above are merely examples and are not limited thereto. The ranges may be set taking into consideration the stability of the emulsion composition, including other components.

[0096]

[0023] Furthermore, although there is no particular limitation on the particle size of the emulsion composition of the present invention, from the viewpoint of emulsion stability, the average particle size of the emulsion composition is preferably 1 μm or less, more preferably 500 nm or less. If the average particle size is 1 μm or less, the buoyancy applied to the particles in the emulsion corresponding to the particle volume becomes small, allowing the particles to be uniformly dispersed in the emulsion, suppressing aggregation and coalescence between particles, and preventing concentration separation or separation into two layers even after long-term storage. In this specification, the average particle size refers to the particle size at 50% of the integrated value in the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer.

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

[0098] In the method for producing an emulsion composition described below, a cyclic siloxane oligomer such as octamethylcyclotetrasiloxane is used as the low-molecular-weight siloxane to be subjected to emulsion polymerization, because it is easily available and easy to emulsify and undergo ring-opening polymerization.However, the ring-opening polymerization of a cyclic siloxane oligomer is an equilibration reaction, and the emulsion obtained after emulsion polymerization usually contains cyclic siloxane oligomers, such as octamethylcyclotetrasiloxane, remaining in the polysiloxane.Therefore, the oligomers may volatilize from the emulsion during storage or use, impairing the physical stability of the emulsion system.In addition, when such an emulsion is used in large quantities as a hair cosmetic for hair treatment, especially when a heated blow-drying treatment is involved, the volatilized oligomers may pollute the surrounding environment or cause contact failure in electrical equipment. Furthermore, when such emulsions are used in skin cosmetics, the low-molecular-weight cyclic siloxane oligomers contained therein can impair the feel due to their volatility. Therefore, there is a need to reduce the amount of such cyclic siloxane oligomers in emulsions. In particular, among cyclic siloxanes, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are easily produced in equilibration reactions. These stable and volatile compounds are also required to be reduced in 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. The product contains unreacted cyclic siloxane oligomers, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. To avoid the aforementioned problems caused by the cyclic siloxane oligomers remaining after emulsion polymerization, it is preferable to reduce the content of cyclic siloxane oligomers in the raw materials.The cyclic siloxane oligomer content of component (A) can be controlled in this manner, for example, by distilling off the cyclic siloxane oligomer present in the polymer obtained by ring-opening polymerization under reduced pressure.

[0099] As described above, in recent years, there has been a demand for products with reduced contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like, and therefore it is preferable that the content of cyclic siloxanes in the emulsion composition be within the above range.

[0100] In the emulsion composition of the present invention, the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are almost unchanged after storage for 6 months at 25°C compared to immediately after production. Emulsion compositions in which the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are each less than 1,000 ppm immediately after production still have the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) of 1,000 ppm or less even after storage for 6 months at 25°C.

[0101] The emulsion composition of the present invention has film-forming properties. There are no particular limitations on the method for producing the film, but by removing water from the emulsion composition, the organopolysiloxane in the emulsion composition aggregates to form a uniform film. There are no particular limitations on the method for removing water, but for example, water may be removed in a short time at 100°C or higher, or water may be removed gradually at 25°C.

[0102] For example, the coating is formed by weighing out the emulsion composition so that the nonvolatile content is 8.0 g and placing it on a 15 cm x 10 cm PP (polypropylene) tray, drying it at 25° C. for 48 hours, and then further drying it at 105° C. for 1 hour. The hardness, tensile strength, and elongation of the coating prepared as above are measured in accordance with JIS K6249 to evaluate the physical properties of the coating.

[0103] [Method for Producing Emulsion Composition] Next, the method for producing the emulsion composition of the present invention is carried out by the following steps: Namely, the method for producing the emulsion composition of the film-forming organopolysiloxane comprises the following steps (I) to (III), in which, after step (I), steps (II) and (III) are carried out in any order or simultaneously, and (C) water is added so that the total amount of the following (C-1), (C-2), and (C-3) 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) an organopolysiloxane blocked with terminal alkoxy groups and / or terminal silanol groups, having a viscosity of 300,000 mPa·s or less at 25°C; (A-2) an alkoxysilane R represented by the following formula (3): ４ ｅ Si(OR ５ ) ４－ｅ (3) (where R ４ are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and R ５ are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. e is 0 or 1.) The total of (A-1) and (A-2) is 100 parts by mass, and the ratio of (A-2) to (A-1) is 0 to 0.2. (B) Cationic surfactant: 0.1 to 30 parts by mass (C-1) Water: 30 to 3,000 parts by mass (II) If necessary, further adding water (C-2) to the obtained emulsion composition, and (F) polymerizing in the presence of a basic catalyst at 0 to 40°C for 1 to 150 hours, and further neutralizing, (III) Further adding 0.5 to 50 parts by mass of colloidal silica (D) and, if necessary, further adding water (C-3).

[0104] The steps (II) and (III) may be carried out in any order after the step (I), and may also be carried out simultaneously.

[0105] [Component (A-1)] First, (A-1) an organopolysiloxane blocked with terminal alkoxy groups and / or terminal silanol groups, having a viscosity at 25°C of 300,000 mPa·s or less, serves as the raw material for the organopolysiloxane of component (A). The viscosity of the organopolysiloxane blocked with terminal alkoxy groups and / or terminal silanol groups 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, resulting in a highly stable emulsion. Note that the organopolysiloxane may have a branched structure as long as the viscosity at 25°C is 300,000 mPa·s or less. Even when the terminal group is an alkoxy group such as a methoxy group or an ethoxy group, it can be hydrolyzed in the emulsion composition to form a silanol group, and therefore organopolysiloxanes capped with alkoxy groups can also be polymerized in the same way.

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

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

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

[0109] Here, R ４ are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. 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; and alkenyl groups such as vinyl and allyl. These organic group structures may also include those in which some of the hydrogen atoms have been substituted with halogen atoms or organic groups containing polar groups such as amino, acryloxy, methacryloxy, epoxy, and mercapto. ４ It is desirable from the viewpoint of industrial and property standpoint that 80% or more of R be methyl groups. ５ are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. ５ The monovalent organic group having 1 to 20 carbon atoms is the same as the above R ４ and a methyl group, an ethyl group, a propyl group, or a butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[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 resulting coating will have sufficient strength and durability.

[0111] Specific examples of the component (A-2) 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 of suitable silanes include methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatopropyltriethoxysilane, but are not limited thereto.

[0112] [Components (B), (D), and (E)] In the method of producing an emulsion composition of a film-forming organopolysiloxane of the present invention, either or both of the following (B-1) and (B-2) can be used as the cationic surfactant (B): (B-1)Q １ ３ (CH ３ ) N ＋ ・X － Cationic surfactant represented by the formula (B-2): 0 to 30 parts by mass ２ α (CH ３ ) ４－α N ＋ ・X － Cationic surfactant represented by the formula (Q １ are the same or different monovalent organic groups having 6 to 30 carbon atoms, Q ２ is a monovalent organic group having 6 to 30 carbon atoms, X are each 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.) In addition, in any of steps (I) to (III), a nonionic surfactant (E) can be 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). Furthermore, a nonionic surfactant represented by the following formula can also be used as component (E). R ３ O (EO) ｐ (PO) ｑ H (wherein, R ３ represents 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, and these groups may be arranged in a block or random manner. p and q are each independently an integer of 0 to 100, with the proviso that p+q>0.) Furthermore, colloidal silica whose particle surface has been 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 those described above.

[0114] [Component (C-1), Component (C-2), Component (C-3)] Component (C-1), Component (C-2), and Component (C-3) refer to the water used in step (I) and, if necessary, step (II) and step (III). The total amount of component (C-1), component (C-2), and component (C-3) used is the amount of water used in component (C).

[0115] In step (I), the amount of water used as 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 particles.

[0116] For example, when an emulsifier such as a high-pressure homogenizer that uses pressure to reduce the size of emulsion particles is used, the amount of component (C-1) used is not particularly limited and may be 30 to 3,000 parts by mass per 100 parts by mass of component (A). However, when an emulsifier such as a Homodisper (an emulsifier consisting of a circular disk with sawtooth teeth on the outer periphery), a Homomixer (an emulsifier consisting of a rotor and a stator), or a colloid mill (an emulsifier that feeds each component into the gap between a rapidly rotating disk and a fixed disk to emulsify) that uses shearing force to reduce the size of emulsion particles is used, 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 emulsion particle size using shear force, adding 200 parts by mass or less of component (C-1) will allow the shear force to work efficiently, reducing the emulsion particle size and improving the stability of the emulsion composition. On the other hand, adding 1 part by mass or more will make it easier to obtain an O / W 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 (i.e., water as component (C)) is preferably 30 to 3,000 parts by mass relative to 100 parts by mass of component (A). When component (C-2) is added, the amount of component (C-2) used may be adjusted appropriately so as to achieve a concentration and viscosity appropriate for the intended use. Note that it is usually preferable to add water as component (C-2) when using an emulsifier such as a homodisper, homomixer, or colloid mill.

[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 (i.e., water for component (C)) is preferably 30 to 3,000 parts by mass per 100 parts by mass of component (A). When component (C-3) is added, the amount of component (C-3) used can be appropriately adjusted so as to achieve a concentration and viscosity appropriate for the intended use. Note that when the colloidal silica for component (D) is an aqueous dispersion, the water in the colloidal silica aqueous dispersion is also included in component (C-3).

[0120] [Component (F)] In the method for producing a film-forming organopolysiloxane emulsion composition of the present invention, water (C-2) is further added to the emulsion composition obtained in step (II), if necessary, and polymerization is carried out in the presence of a basic catalyst (F) at 0 to 40°C for 1 to 150 hours, followed by neutralization. In this case, either ammonia or an organic amine, or both, can be used as the basic catalyst (F). Examples of the basic catalyst (alkali catalyst) of component (F) include alkali metal hydroxides and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, as well as 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 of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the emulsion composition to 1,000 ppm or less, the alkali catalyst is preferably ammonia or triethanolamine, and more preferably ammonia.

[0122] Many emulsion polymerizations using common cationic surfactants, such as cetyltrimethylammonium chloride and tallow trimethylammonium chloride, have been reported. However, because these cationic emulsifiers have weak catalytic activity, it is common to use a strong base, such as an alkali metal hydroxide or alkaline earth metal hydroxide, as a catalyst to compensate for this, as described above. However, in the present invention, the use of component (B-1) significantly improves catalytic activity, making the use of a strong base unnecessary; polymerization can proceed sufficiently using only a weak base, such as ammonia or an organic amine. Therefore, in order to promote polymerization and to minimize the by-production of cyclic siloxanes (such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6)), it is preferable to use ammonia (aqueous ammonia) or an organic amine as the alkaline catalyst, and it is more preferable to use ammonia (aqueous ammonia).

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

[0124] The amount of alkali 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 as component (B-1) and the cationic surfactant as component (B-2).

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

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

[0127] However, the amount of alkali catalyst used is not limited to the above and may be outside the above range if necessary. Furthermore, when the content of cyclic siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), etc.) is not particularly limited depending on the intended use, the alkali catalyst used may be the alkali metal hydroxide or alkaline earth metal hydroxide described above.

[0128] Furthermore, when adding the alkali catalyst to the emulsion composition, the alkali catalyst may be diluted with water before use. In this case, the amount of water used for dilution is not particularly limited, 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). In this case, the concentration of the alkali catalyst becomes appropriate, and the emulsion composition becomes stable and easy to handle.

[0129] A uniform emulsion composition is prepared using an emulsifier such as a homogenizer, homodisper, homomixer, colloid mill, or line mixer from the silanol-terminated organopolysiloxane (component (A-1)), the organoalkoxysilane (component (A-2)), the cationic surfactant (component (B)), and water (component (C-1)). Water (component (C-2)) is optionally added to the resulting emulsion composition, followed by polymerization at 0 to 40°C for 1 to 150 hours in the presence of an alkali catalyst (component (F)), followed by neutralization. Then, colloidal silica (component (D)) and, if necessary, water (C-3) are added.

[0130] The polymerization temperature is 0 to 40° C., preferably 5 to 30° C. If the polymerization temperature is 0° C. or higher, the 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 by-product cyclic siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), etc.) is suppressed to 1,000 ppm or less.

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

[0132] After a predetermined polymerization time, the polymerization reaction can be stopped by neutralization. Neutralization here 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, and hydrochloric acid, formic acid, and acetic acid are preferred. Note that neutralization can also be carried out using an ion exchange resin instead of using an acidic compound.

[0133] The emulsion compositions of the highly polymerized organopolysiloxane of the present invention obtained by the above method are suitable for use as fiber treatment agents, release agents, water repellents, cosmetic raw materials, etc., and can be used to impart excellent softness, slip properties, water repellency, volume, etc. to various fibers, leather, paper, hair, etc. 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 highly polymerized organopolysiloxane of the present invention may contain various thickeners, pigments, dyes, penetrating agents, antistatic agents, antifoaming agents, flame retardants, antibacterial agents, preservatives, water repellents, crosslinking agents, adhesion improvers, as well as other silicone oils, silicone resins, silica, acrylic resins, urethane resins, and the like, as appropriate.

[0135] The emulsion composition of the highly polymerized organopolysiloxane of the present invention is capable of forming a coating after drying and can be used by treating or impregnating the surface of various substrates such as fibers, paper, metal, wood, rubber, plastic, glass, etc. The coating method for the substrate can be any of the various conventional coating methods, such as dipping, spraying, roll coating, bar coating, and brush coating.

[0136] The emulsion composition of the high polymerization degree organopolysiloxane of the present invention may have an antiviral activity value Mv of 2.0 or more according to JIS L 1922 and thus exhibit antiviral performance. This antiviral performance is believed to be exhibited by the cationic surfactant in the emulsion composition. Furthermore, since the emulsion composition of the high polymerization degree organopolysiloxane of the present invention has the ability to form a film, when the emulsion composition is applied to a target substance, such as a substrate, to which antiviral properties are to be imparted to form a film, the film contains a substance that exhibits antiviral performance, and therefore has excellent durability and can be expected to exhibit long-term antiviral performance.

[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, "%" means "% by mass" unless otherwise specified.

[0138] [Examples 1 to 25, Comparative Examples 1 to 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 per 100 parts by mass of component (A).

[0139] Example 1 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ion-exchanged water (component (C-1)) and 45.0 g of ion-exchanged water (component (C-2)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous potassium hydroxide solution prepared by previously diluting 1.4 g of 85% potassium hydroxide (component (F-1)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 1.4 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion of colloidal silica (component (D-1)) containing 30% active ingredient (Snowtex AK-YL: Nissan Chemical Industries, Ltd.; containing component (C-3); the same applies hereinafter) was added and uniformly dispersed using a homomixer, yielding emulsion A. Emulsion A had a non-volatile content of 39.3% after drying at 105°C for 3 hours.

[0140] Example 2 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of colloidal silica (manufactured by Nissan Chemical Industries, Ltd.) and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. After that, an aqueous ammonia solution prepared by previously diluting 1.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 1.4 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL: manufactured by Nissan Chemical Industries, Ltd.) containing 30% active ingredient of colloidal silica (component (D-1)) was added and uniformly dispersed using a homomixer, yielding Emulsion B. Emulsion B had a non-volatile content of 40.0% after drying at 105°C for 3 hours.

[0141] Example 3 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous triethanolamine solution prepared by diluting 3.2 g of triethanolamine (component (F-3)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours. The polymerization was then terminated by neutralization with 1.4 g of acetic acid. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL: Nissan Chemical Industries, Ltd.) containing 30% active ingredient of colloidal silica (component (D-1)) was added and uniformly dispersed using a homomixer, yielding Emulsion C. Emulsion C had a non-volatile content of 40.2% after drying at 105°C for 3 hours.

[0142] Example 4 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of behenyltrimethylammonium chloride (an active ingredient of component (B-2-1)) in ethanol (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 9.0 g of an 80% ethanol preparation (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion D. Emulsion D had a nonvolatile content of 40.4% after drying at 105°C for 3 hours.

[0143] Example 5 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.) containing 80% of the active ingredient of behenyltrimethylammonium chloride (component (B-2-1)) (active ingredient: 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene lauryl ether (component (E-1)) (Emulgen 109P, manufactured by Kao Corporation), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours. The polymerization was then terminated by neutralization with 2.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion E. Emulsion E had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0144] Example 6 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion F. Emulsion F had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0145] Example 7 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-2)) having a viscosity of 50,000 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion G. Emulsion G had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0146] Example 8 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-3)) having a viscosity of 200,000 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain Emulsion H. Emulsion H had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0147] Example 9 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 30.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion I. Emulsion I had a nonvolatile content of 43.4% after drying at 105°C for 3 hours.

[0148] Example 10 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 100.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion J. Emulsion J had a nonvolatile content of 40.0% after drying at 105°C for 3 hours.

[0149] Example 11 A mixture of 298.5 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 1.5 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion K. Emulsion K had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0150] Example 12 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.) containing 9.0 g of an 80% active ingredient of behenyltrimethylammonium chloride (component (B-2-1)) (active ingredient: 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 90.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 285.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain Emulsion L. Emulsion L had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0151] Example 13 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.) containing 80% of the active ingredient of behenyltrimethylammonium chloride (component (B-2-1)) (active ingredient: 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene stearyl ether (component (E-3)) (Emulgen 350, manufactured by Kao Corporation), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain Emulsion M. Emulsion M had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0152] Example 14 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 30.0 g of 30% behenyltrimethylammonium chloride (component (B-2-1)) in ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 30.0 g of a 80% ethanol preparation of the active ingredient, behenyltrimethylammonium chloride (component (B-2-1)) (active ingredient Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 0.4 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 0.4 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% active ingredient of colloidal silica (component (D-1)) was added, and the mixture was uniformly dispersed using a homomixer to obtain Emulsion N. Emulsion N had a nonvolatile content of 41.1% after drying at 105°C for 3 hours.

[0153] Example 15 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 1.5 g of behenyltrimethylammonium chloride (an active ingredient of component (B-2-1)) in ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 1.5 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 7.4 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours. The polymerization was then terminated by neutralization with 8.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion O. Emulsion O had a nonvolatile content of 44.3% after drying at 105°C for 3 hours.

[0154] Example 16 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol-based behenyl trimethylammonium chloride (component (B-2-1)), an active ingredient of which is 80% (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper, and 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 11.1 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 12.9 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% active ingredient of colloidal silica (component (D-1)) was added, and the mixture was uniformly dispersed using a homomixer to obtain Emulsion P. After drying at 105°C for 3 hours, Emulsion P had a nonvolatile content of 42.6%.

[0155] Example 17 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.) containing 80% of the active ingredient behenyltrimethylammonium chloride (component (B-2-1)) (active ingredient: 9.0 g), polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.) and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 22.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 25.8 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% active ingredient of colloidal silica (component (D-1)) was added, and the mixture was uniformly dispersed using a homomixer to obtain Emulsion Q. After drying at 105°C for 3 hours, Emulsion Q had a nonvolatile content of 43.2%.

[0156] Example 18 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol solution containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 180.0 g of an aqueous dispersion (Snowtex C, manufactured by Nissan Chemical Industries, Ltd.) containing 20% ​​of the active ingredient of colloidal silica (component (D-2)) was added and dispersed uniformly using a homomixer to obtain Emulsion R. Emulsion R had a nonvolatile content of 39.4% after drying at 105°C for 3 hours.

[0157] Example 19 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of behenyltrimethylammonium chloride (an active ingredient of component (B-2-1)) in ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then raised to 30°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion S. Emulsion S had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0158] Example 20 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol solution containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.) containing 9.0 g of an 80% active ingredient of behenyltrimethylammonium chloride (component (B-2-1)) (active ingredient: 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 2 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion T. Emulsion T had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0159] Example 21 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol (manufactured by Lion Specialty Chemicals Co., Ltd.) containing 80% of the active ingredient behenyltrimethylammonium chloride (component (B-2-1)) (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was then added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 144 hours, after which the polymerization was terminated by neutralization with 2.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% active ingredient of colloidal silica (component (D-1)) was added, and the mixture was uniformly dispersed using a homomixer to obtain Emulsion U. After drying at 105°C for 3 hours, Emulsion U had a nonvolatile content of 42.0%.

[0160] Example 22 300.0 g of an organopolysiloxane (component (A-1-4)) having a viscosity of 1,500 mPa s at 25°C and having branched units (in the general formula (1), R １ = methyl group, R ２ = methoxy group, a = 3, b = 450, c = 1, d = 0), trioctylmethylammonium chloride (component (B-1-1)) active ingredient 95% ethanol product (TOMAC: Linyi Connect Chemical Technology) Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion V. Emulsion V had a nonvolatile content of 42.0% after drying at 105°C for 3 hours.

[0161] Example 23 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol solution containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of 98% stearyltrimethylammonium chloride (component (B-2-2)) (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper, and 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion W. Emulsion W had a nonvolatile content of 41.3% after drying at 105°C for 3 hours.

[0162] Example 24 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) by heating 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) containing 95% active ingredient, and 98 g of methyl cyclopentasiloxane (D6) containing 98% active ingredient were mixed in advance. An emulsion was prepared by uniformly emulsifying and dispersing 8.0 g of 10% stearyltrimethylammonium chloride (component (B-2-2)) (manufactured by Tokyo Chemical Industry Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper, and 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)). Thereafter, the liquid temperature was lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain Emulsion X. Emulsion X had a nonvolatile content of 40.3% after drying at 105°C for 3 hours.

[0163] Example 25 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating 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) containing 95% active ingredient, and 10 g of behenyltrimethylammonium chloride ( An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of an 80% ethanol preparation of the active ingredient (component (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper, and 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)). Thereafter, the liquid temperature was lowered to 15°C, and polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 2.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion Y. Emulsion Y had a nonvolatile content of 41.1% after drying at 105°C for 3 hours.

[0164] Comparative Example 1 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C, in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm each (detection limit) by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), 1.0 g of polyoxyethylene terephthalate (component (A-2-2)), and 1.0 g of methyl cyclopentasiloxane (component (A-2-3)). An emulsion was prepared by uniformly emulsifying and dispersing 24.0 g of methyltridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.) and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours. The polymerization was then terminated by neutralization with 2.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% active ingredient of colloidal silica (component (D-1)) was added and uniformly dispersed using a homomixer, yielding emulsion CA. Emulsion CA had a nonvolatile content of 41.1% after drying at 105°C for 3 hours.

[0165] Comparative Example 2 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.) containing 9.0 g of an 80% active ingredient of behenyltrimethylammonium chloride (component (B-2-1)) (active ingredient: 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 2 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 84.0 g of ion-exchanged water (component (C-3)) was added and dispersed uniformly using a homomixer to obtain emulsion CB. Emulsion CB had a nonvolatile content of 39.6% after drying at 105°C for 3 hours.

[0166] Comparative Example 3 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. Co., Ltd.), 9.0 g of an ethanol preparation of 80% behenyltrimethylammonium chloride (active ingredient (B-2-1)) (Lipocard 22-80: manufactured by Lion Specialty Chemicals Co.), 24.0 g of polyoxyethylene tridecyl ether ((E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water ((C-1)) were uniformly emulsified and dispersed using a homomixer and a disper to prepare an emulsion. 330.0 g of ion-exchanged water ((C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of an aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution ((F-2)) with 60.0 g of ion-exchanged water ((C-2)). The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours, followed by neutralization with 2.6 g of acetic acid to terminate the polymerization. Next, 84.0 g of ion-exchanged water (component (C-3)) was added and dispersed uniformly using a homomixer to obtain emulsion CC. Emulsion CC had a nonvolatile content of 39.6% after drying at 105°C for 3 hours.

[0167] Comparative Example 4 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C, in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm each (detection limit) by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), 1.0 g of polyoxyethylene terephthalate (component (A-2-2)), and 1.0 g of methyl cyclopentasiloxane (component (A-2-3)). An emulsion was prepared by uniformly emulsifying and dispersing 24.0 g of methyltridecyl ether (component (E-2)) (Newcol 1310: manufactured by Nippon Nyukazai Co., Ltd.) and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper. 330.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. An aqueous ammonia solution prepared by previously diluting 2.2 g of a 30% aqueous ammonia solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was then added. The liquid temperature was then lowered to 15°C, and polymerization was carried out for 24 hours. The polymerization was then terminated by neutralization with 2.6 g of acetic acid. Next, 84.0 g of ion-exchanged water (component (C-3)) was added and uniformly dispersed using a homomixer, yielding Emulsion CD. Emulsion CD had a non-volatile content of 38.6% after drying at 105°C for 3 hours.

[0168] Comparative Example 5 A mixture of 294.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of triethoxyphenylsilane (component (A-2-1)), and an ethanol-based mixture containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) was used. An attempt was made to prepare an emulsion by uniformly emulsifying and dispersing 120.0 g of ethanol (manufactured by Nippon Paper Industries Co., Ltd.) and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper, but separation occurred immediately and a uniform emulsion could not be obtained, so the emulsion was not evaluated.

[0169] Comparative Example 6 300.0 g of a dimethylpolysiloxane (component (A-3)) capped at both ends with trimethylsilyl groups and having a viscosity of 1,500 mPa·s at 25°C, in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm (detection limit) each by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, and an ethanol solution containing 95% of the active ingredient trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: Linyi Connect Chemical Technology) An emulsion was prepared by uniformly emulsifying and dispersing 9.0 g of ethanol (Lipocard 22-80, manufactured by Lion Specialty Chemicals Co., Ltd.) containing 80% active ingredient behenyltrimethylammonium chloride (component (B-2-1)), 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disper, and 390.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% active ingredient colloidal silica (component (D-1)) was added and uniformly dispersed using a homomixer, yielding 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 a dimethylpolysiloxane (component (A-3)) end-blocked with trimethylsilyl groups and having a viscosity of 1,500 mPa·s at 25°C, in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm each (detection limit) by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 24.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), and 45.0 g of ion-exchanged water (component (C-1)), using a homomixer and a disper, and 390.0 g of ion-exchanged water (component (C-2)) was further added to this emulsion, and the mixture was uniformly dispersed using a homomixer. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and dispersed uniformly using a homomixer to obtain emulsion CF. After drying at 105°C for 3 hours, emulsion CF had a non-volatile content of 41.0%.

[0171] Comparative Example 8 300.0 g of a silanol-endblocked organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa s at 25°C and in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) had been reduced to less than 10 ppm each (detection limit) by heating and mixing at 150°C under a reduced pressure of 10 mmHg or less, 6.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310, manufactured by Nippon Nyukazai Co., Ltd.), 10.5 parts of the anionic surfactant sodium dodecylbenzenesulfonate, and 18.0 g of ion-exchanged water (component (C-1)) were emulsified using a Homodisper. 254.7 g of ion-exchanged water (component (C-2)) was further added to this emulsion and uniformly dispersed using a homomixer, followed by the addition of 3.6 g of concentrated hydrochloric acid as an acid catalyst. The liquid temperature was then lowered to 10°C, and polymerization was carried out for 22 hours, after which the polymerization was terminated by neutralization with 7.2 g of triethanolamine. Next, 120.0 g of an aqueous dispersion (Snowtex AK-YL: manufactured by Nissan Chemical Industries, Ltd.) containing 30% active ingredient of colloidal silica (component (D-1)) was added, and an attempt was made to uniformly disperse the mixture using a homomixer; however, separation occurred 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 to 25 and Comparative Examples 1 to 4, 6, and 7 were measured using the evaluation methods described below, and the results are shown in Tables 1 to 3. Each emulsion composition obtained was weighed into a 15 cm x 10 cm PP (polypropylene) tray so that the nonvolatile content was 8.0 g, and dried at 25°C for 48 hours to volatilize the water. Examples 1 to 25 and Comparative Example 3 formed rubber-like coatings, while Comparative Examples 1, 2, and 4 were fluid liquids. The "Extraction Viscosity (mPa s)" column in Tables 1 to 3 shows the extraction viscosity for emulsions whose viscosity could be measured using the method described below, and the properties of the coating for those whose viscosity could not be measured.

[0173] [Viscosity of Extracted Organopolysiloxane] 300 g of each emulsion composition was added to 2 L of IPA with stirring to break down the emulsion and extract the organopolysiloxane. This organopolysiloxane was dried at 105° C. for 3 hours and then measured using a BM-type rotational viscometer (TVB-10M) at 25° C. Note that the viscosities of the organopolysiloxanes that could not be measured even using the M4 rotor (maximum measurable viscosity of 2,000,000 mPa s), which is the rotor capable of measuring the highest viscosity among BM-type rotational viscometers, those that could not be measured because they wrapped around the rotor of the BM-type rotational viscometer, and those that could not be measured because they did not dissolve in toluene, were all viscosities of 300,000 mPa s or higher.

[0174] [Average Particle Size of Emulsion] This is the particle size at 50% 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] [Content of Cyclic Siloxanes] 0.1 g of each emulsion composition was extracted (shaken for 3 hours) with 10 mL of acetone containing 20 ppm (by mass) of tetradecane as an internal standard, and then left to stand overnight. The acetone layer was then collected and analyzed by gas chromatography (Agilent 7890B (manufactured by Agilent Technologies)) to quantify the amount of cyclic siloxanes (hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10)) (mass converted value).

[0176] [Film Formability] Each emulsion composition was weighed out onto a 15 cm x 10 cm PP (polypropylene) tray so that the nonvolatile content was 8.0 g, dried at 25°C for 48 hours, and then further dried at 105°C for 1 hour, and whether a film was formed was evaluated. A: A uniform film was formed, and it was strong enough to be easily peeled off from the disposable tray. B: A uniform film was formed, but it could not be peeled off from the disposable tray, or the film was deformed when peeled off. C: A uniform film was not formed.

[0177] [Evaluation of Physical Properties of Coating] The hardness (type C durometer hardness), tensile strength and elongation at break of the coating prepared above were measured in accordance with JIS K 6249. The evaluation results are 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 and stored in a thermostatic chamber at 25°C. After 3 months, 6 months, and 12 months, the appearance was visually observed and the non-volatile content of the upper and lower layers was measured, and the storage stability was evaluated based on the following evaluation criteria. <Evaluation criteria> A: No separation of the upper and lower layers was observed. B: Slight separation of the upper and lower layers was observed. C: Complete separation into two layers.

[0179] [Storage stability of emulsion (40°C)] 100 g of each emulsion composition was placed in a glass bottle and stored in a thermostatic chamber at 40°C for 30 days. After that, the appearance was visually observed and the non-volatile contents of the upper and lower layers were measured, and the storage stability was evaluated based on the following evaluation criteria. <Evaluation criteria> A: No separation of the upper and lower layers was observed. B: Slight separation of the upper and lower layers was observed. C: Complete separation into two layers.

[0180]

[0181]

[0182]

[0183] In the "Extraction viscosity (mPa s)" column in Tables 1 to 3, "rubber-like" indicates that the viscosity could not be measured by the above method, the coating was rubber-like in nature, and the viscosity at 25°C was 300,000 mPa s or more.

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

[0185] In contrast, as shown in Table 3, in Comparative Examples 1 and 4, in which no cationic surfactant was used, the extracted organopolysiloxane had a low viscosity and a low molecular weight, resulting in poor film-forming properties. In Comparative Examples 2 and 3, in which a cationic surfactant was used but colloidal silica was not used, the extracted organopolysiloxane had a high viscosity, but in Comparative Example 2, the viscosity at 25°C was less than 300,000 mPa·s, making it impossible to form a uniform film. In Comparative Example 3, although the viscosity was sufficient, the hardness and tensile strength of the film were insufficient. In Comparative Example 5, in which an excessive amount of component (B) was blended, the emulsion became unstable, and a uniform emulsion could not be obtained. In Comparative Examples 6 and 7, in which a low-viscosity dimethylpolysiloxane capped with trimethylsilyl groups at both ends, which is not capable of polymerization (condensation polymerization by dehydration or dealcoholization), was used instead of component (A) of the present invention, no film with sufficient physical properties was obtained, even when silica was used alone or in combination with a nonionic surfactant. In Comparative Example 8, in which an anionic surfactant with a strong catalytic activity was used instead of a cationic surfactant, high-viscosity anionic emulsion polymerization proceeded at a lower temperature (10°C), but the addition of colloidal silica made the emulsion unstable, and a uniform emulsion could not be obtained. Thus, the emulsion compositions obtained with the formulations of Comparative Examples 1 to 8 either did not produce a uniform emulsion, did not form a coating, or formed a coating, but the coating strength was weak.

[0186] Furthermore, in emulsion A of Example 1, which was prepared using potassium hydroxide as the (F) basic catalyst, the content of cyclic siloxanes D4 to D6 exceeded 5,000 ppm by mass, but the physical properties (hardness, tensile strength, and elongation at break) and storage stability of the resulting coating were good. Thus, even with the emulsion composition of the present invention, the physical properties and storage stability of the resulting coating are good, even if low-molecular-weight cyclic siloxanes remain, and the step of removing the low-molecular-weight cyclic siloxanes can be omitted, thereby reducing production costs. In contrast, in emulsion B of Example 2, which was prepared using ammonia as the (F) basic catalyst, the content of cyclic siloxanes D4 to D6 was significantly reduced to less than 200 ppm by mass, and the physical properties and storage stability of the resulting coating were good. This shows that the method for producing an emulsion composition of the present invention not only makes it possible to reduce the content of each of the cyclic siloxanes D4 to D6 in the resulting emulsion composition to 1,000 ppm or less, but also makes it easy to reduce the total content of the cyclic siloxanes D3 to D10 in the emulsion composition to 1,000 ppm or less by using, as the emulsion raw material component (A-1), a low-molecular-weight cyclic polysiloxane that has been previously reduced in terminal alkoxy groups and / or a terminal silanol group-blocked organopolysiloxane in combination with an appropriate basic catalyst. Therefore, the emulsion composition and method for producing the same of the present invention have great industrial utility.

[0187] [Antiviral Performance Test of Treated Fabrics] Test solutions were prepared by adding ion-exchanged water to emulsion compositions F and Z and diluting to a solids content of 1%. A standard cotton fabric for antiviral performance testing was immersed in the test solution for 10 seconds, then squeezed using a roll at a squeezing rate of 100%, and dried at 150°C for 2 minutes to prepare each test fabric. Each test fabric was subjected to an antiviral performance test using the following test method. The specifications and standards are shown in Table 4, and the results are shown in Table 5. [Test method] JIS L 1922:2016 Method for measuring virus infectivity: Plaque assay [Test virus] Influenza virus Influenza A virus (H3N2): ATCC VR-1679

[0188]

[0189] From the above table, it was confirmed that Emulsion F has antiviral properties.

[0190] [Industrial Applicability] The film-forming organopolysiloxane emulsion composition of the present invention has good film-forming properties, and can provide a film-forming silicone emulsion composition and a film that have excellent film strength after curing and good emulsion storage stability. Furthermore, since the film-forming organopolysiloxane emulsion composition of the present invention can have an extremely low cyclic siloxane content, there is little concern about the cyclic siloxane volatilizing and contaminating the inside of the equipment when a substrate or the like is subjected to heat treatment, or about the product itself being contaminated by cyclic siloxane or silicon dioxide powder derived from cyclic siloxane, making it industrially useful and highly versatile, and therefore it can be widely applied not only to fiber treatment agents, but also to release agents, water repellents, cosmetics, hair cosmetics, etc.

[0191] This specification encompasses the following aspects: [1]: A film-forming organopolysiloxane emulsion composition comprising the following (A) to (D): (A) 100 parts by mass of an organopolysiloxane represented by the following average composition formula (1), having a viscosity at 25°C of 300,000 mPa·s or more and containing at least two alkoxy groups or hydroxy groups bonded to silicon atoms per molecule: (In the formula, R １ are each independently a hydrogen atom or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, and R ２(B) Cationic surfactant: 0.1 to 30 parts by mass (C) Water: 30 to 3,000 parts by mass (D) Colloidal silica: 0.5 to 50 parts by mass [2]: The film-forming organopolysiloxane emulsion composition of [1], wherein the (B) cationic surfactant contains either or both of the following (B-1) and (B-2): (B-1) Q １ ３ (CH ３ ) N ＋ ・X － (B-2)Q: 0 to 30 parts by mass ２ α (CH ３ ) ４－α N ＋ ・X － Cationic surfactant represented by the formula: 0 to 30 parts by mass (Q １ are the same or different monovalent organic groups having 6 to 30 carbon atoms, Q ２ is a monovalent organic group having 6 to 30 carbon atoms, each 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.) [3]: An emulsion composition of a film-forming organopolysiloxane according to [1] or [2], further comprising 0.1 to 30 parts by mass of a nonionic surfactant (E) per 100 parts by mass of component (A). [4]: ​​An emulsion composition of a film-forming organopolysiloxane according to [3], characterized in that the nonionic surfactant (E) is represented by the following formula: R ３ O (EO) ｐ (PO) ｑ H (wherein, R ３represents 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, and the arrangement thereof may be block or random. p and q are each independently an integer of 0 to 100, with the proviso that p+q>0.) [5]: An emulsion composition of a film-forming organopolysiloxane according to any one of [1] to [4], wherein the colloidal silica (D) has a particle surface treated with an oxide of a metal other than silicon. [6]: An emulsion composition of a film-forming organopolysiloxane according to any one of [1] to [5], further comprising a salt formed from an acidic substance and a basic substance formed from either or both of ammonia and an organic amine. [7]: The film-forming organopolysiloxane emulsion composition according to any one of [1] to [6], wherein the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition are each 1,000 ppm or less. [8]: The emulsion composition of any one of [1] to [7], wherein the total content of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10) contained in the emulsion composition is 1,000 ppm or less. [9]: The emulsion composition of any one of [1] to [8], wherein the average particle size of the emulsion contained in the emulsion composition is 1 μm or less.

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

[11] : The emulsion composition of a film-forming organopolysiloxane according to any one of [1] to

[10] , characterized in that it has an antiviral activity value Mv of 2.0 or more according to JIS L 1922.

[12] : A method for producing an emulsion composition of a film-forming organopolysiloxane according to [1], comprising the following steps (I) to (III), in which, after step (I), steps (II) and (III) are carried out in any order or simultaneously, and the (C) water is added so that the total amount of the following (C-1), (C-2), and (C-3) 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) an organopolysiloxane blocked with terminal alkoxy groups and / or terminal silanol groups, having a viscosity of 300,000 mPa·s or less at 25°C; and (A-2) an alkoxysilane R represented by the following formula (3): ４ ｅ Si(OR ５ ) ４－ｅ (3) (where R ４ are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and R ５are each independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. e is 0 or 1.) The total of (A-1) and (A-2) is 100 parts by mass, and the ratio of (A-2) to (A-1) is 0 to 0.2. (B) Cationic surfactant: 0.1 to 30 parts by mass; (C-1) Water: 30 to 3,000 parts by mass; (II) optionally adding water (C-2) to the resulting emulsion composition, and polymerizing the resulting emulsion composition at 0 to 40°C for 1 to 150 hours in the presence of a basic catalyst (F), followed by neutralization; (III) optionally adding colloidal silica (D): 0.5 to 50 parts by mass; and optionally adding water (C-3).

[13] : A method for producing an emulsion composition of a film-forming organopolysiloxane according to

[12] , characterized in that either or both of ammonia and an organic amine are used as the basic catalyst (F).

[14] : A method for producing an emulsion composition of a film-forming organopolysiloxane according to

[12] or

[13] , characterized in that either or both of the following (B-1) or (B-2) are used as the (B) cationic surfactant: (B-1)Q １ ３ (CH ３ ) N ＋ ・X － Cationic surfactant represented by the formula (B-2): 0 to 30 parts by mass ２ α (CH ３ ) ４－α N ＋ ・X － Cationic surfactant represented by the formula (Q １ are the same or different monovalent organic groups having 6 to 30 carbon atoms, Q ２is a monovalent organic group having 6 to 30 carbon atoms, X are each independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, and α is an integer of 1 or 2, with the proviso 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 a film-forming organopolysiloxane according to any one of

[12] to

[14] , characterized in that in any of steps (I) to (III), 0.1 to 30 parts by mass of a nonionic surfactant (E) is further added per 100 parts by mass of the total of (A-1) and (A-2).

[16] : A method for producing an emulsion composition of a film-forming organopolysiloxane according to

[15] , characterized in that a nonionic surfactant represented by the following formula is used as component (E): ３ O (EO) ｐ (PO) ｑ H (wherein, R ３represents 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, and the arrangement thereof may be block or random. p and q are each independently an integer of 0 to 100, with the proviso that p+q>0.)

[17] : A method for producing a film-forming organopolysiloxane emulsion composition according to any one of

[12] to

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

[18] : A method for producing a film-forming organopolysiloxane emulsion composition according to any one of

[12] to

[17] , characterized in that component (A-1) is a colloidal silica whose particle surface is treated with an oxide of a metal other than silicon.

[19] : A method for producing a film-forming organopolysiloxane emulsion composition according to any one of

[12] to

[17] , characterized in that component (A-1) contains octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in an amount of 1,000 ppm or less.

[19] : The method for producing an emulsion composition of a film-forming organopolysiloxane according to any one of

[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] : The method for producing an emulsion composition of a film-forming organopolysiloxane according to any one of

[12] to

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

[0192] The present invention is not limited to the above-described embodiments, which are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that provides similar effects is included within the technical scope of the present invention.

Claims

1. An emulsion composition of a film-forming organopolysiloxane, characterized by comprising the following components (A) to (D). (A) An organopolysiloxane represented by the following average composition formula (1), having a viscosity at 25°C of 300,000 mPa·s or more and containing at least two alkoxy groups or hydroxy groups bonded to silicon atoms in one molecule: 100 parts by mass 【Chemical 1】 (In the formula, R １ is independently of each other a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may be unsubstituted or substituted, and R ２ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a hydroxy group, a is an integer of 2 to 1,000, b is an integer of 10 to 10,000, c is an integer of 0 to 1,000, d is an integer of 0 to 1,000, and c + d is an integer satisfying 0 to 2,000, and the viscosity of the organopolysiloxane at 25°C is a value satisfying 300,000 mPa·s or more.) (B) A cationic surfactant: 0.1 to 30 parts by mass (C) Water: 30 to 3,000 parts by mass (D) Colloidal silica: 0.5 to 50 parts by mass

2. The emulsion composition of a film-forming organopolysiloxane according to Claim 1, wherein the component (B) cationic surfactant contains any one or both of the following (B-1) and (B-2). (B - 1)Q １ ３ (CH ３ )N ＋ ·X － The cationic surfactant represented by: 0 to 30 parts by mass (B - 2)Q ２ α (CH ３ ) ４－α N ＋ ·X － The cationic surfactant represented by: 0 to 30 parts by mass (Q １ is a monovalent organic group having 6 to 30 carbon atoms, which may be the same or different, Q ２ 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. 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 containing (E) a nonionic surfactant in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the component (A).

4. The emulsion composition of a film-forming organopolysiloxane according to Claim 3, wherein the component (E) nonionic surfactant is represented by the following formula. R ３ O(EO) ｐ (PO) ｑ H (In the formula, R ３ represents 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, and their arrangements may be block-like or random. p and q are each independently an integer of 0 to 100, provided that p + q > 0.)

5. The emulsion composition of a film-forming organopolysiloxane according to Claim 1, wherein the component (D) colloidal silica has a particle surface treated with an oxide of a metal other than silicon.

6. The emulsion composition of a film-forming organopolysiloxane according to Claim 1, further containing a salt composed of a basic substance consisting of any one or both of ammonia and organic amine and an acidic substance.

7. The emulsion composition of a film-forming organopolysiloxane according to Claim 1, wherein the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition are each 1,000 ppm or less.

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

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

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

11. The emulsion composition of the film-forming organopolysiloxane according to any one of claims 1 to 10, wherein the antiviral activity value Mv in JIS L 1922 is 2.0 or more.

12. A method for producing the emulsion composition of the film-forming organopolysiloxane according to claim 1, comprising the following steps (I) to (III), and after the step (I), the steps (II) and (III) are carried out in an arbitrary order or simultaneously. A method for producing the emulsion composition of the film-forming organopolysiloxane, characterized in that the water (C) is added so that the total amount of the following (C-1), (C-2), and (C-3) is 30 to 3,000 parts by mass. (I) A step of emulsifying a mixture containing the following components (A-1), (A-2), (B), and (C-1) to prepare an emulsion composition. (A-1) A terminal alkoxy group having a viscosity of 300,000 mPa·s or less at 25°C, or and a terminal silanol group-blocked organopolysiloxane (A-2) An alkoxysilane represented by the following formula (3) R ４ ｅ Si(OR ５ ) ４－ｅ (3) (Here, R ４ are, independently of one another, a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and R ５ are, independently of one another, a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. e is 0 or 1.) The total of (A-1) and (A-2) is 100 parts by mass, and the ratio of (A-2) to (A-1) is 0 to 0.

2. (B) Cationic surfactant: 0.1 to 30 parts by mass (C-1) Water: 30 to 3,000 parts by mass (II) Optionally add further (C-2) water to the obtained emulsion composition, and carry out polymerization at 0 to 40 ° C for 1 to 150 hours in the presence of (F) a basic catalyst, and further carry out neutralization. (III) Further add (D) colloidal silica: 0.5 to 50 parts by mass, and optionally add further (C-3) water. (Claim 13) The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein any one or both of ammonia or an organic amine are used as the (F) basic catalyst. (Claim 14) The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein any one or both of the following (B-1) or (B-2) are used as the (B) cationic surfactant. (B-1)Q １ ３ (CH ３ )N ＋ ·X － The cationic surfactant represented by: 0 to 30 parts by mass (B - 2)Q ２ α (CH ３ ) ４－α N ＋ ·X － The cationic surfactant represented by: 0 to 30 parts by mass (Q １ is a monovalent organic group having 6 to 30 carbon atoms, which may be the same or different, and Q ２ 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, 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.) (Claim 15) The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein in any one of the steps (I) to (III), further (E) a nonionic surfactant is added in an amount of 0.1 to 30 parts by mass based on a total of 100 parts by mass of (A-1) and (A-2). (Claim 16) The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 15, wherein a nonionic surfactant represented by the following formula is used as the (E) component. R ３ O(EO) ｐ (PO) ｑ H (In the formula, R ３ is a linear or branched alkyl group having 8 to 30 carbon atoms, EO represents an ethylene oxide group, PO represents a propylene oxide group, and their sequences may be block-like or random. p and q are each independently an integer of 0 to 100, provided that p + q > 0.) (Claim 17) The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein colloidal silica whose particle surface is treated with an oxide of a metal other than silicon is used as the (D) component. (Claim 18) The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained therein are each 1,000 ppm or less. (Claim 19) The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition are each 1,000 ppm or less. (Claim 20) The method for producing an emulsion composition of a film-forming organopolysiloxane according to any one of claims 12 to 19, characterized in that the total content of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosamethylcyclodecasiloxane (D10) contained in the emulsion composition is 1,000 ppm or less.

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