Film-forming organopolysiloxane emulsion composition and method for producing same

Abstract

The present invention provides an emulsion composition of a film-forming organopolysiloxane, which is characterized by comprising: (A) an organopolysiloxane that is represented by the following average compositional formula (1) and has a viscosity of 300,000 mPas or more at 25 DEG C and that contains at least two alkoxy groups or hydroxyl groups bonded to a silicon atom in one molecule, and (B) an organopolysiloxane that has a viscosity of 1,000,000 mPas or more at 25 DEG C and that has a viscosity of 1,000,000 mPas or more at 25 DEG C and that has a viscosity of 1,000,000 mPas or more at 25 DEG C and that has a viscosity of 1,000,000 mPas or more at 25 DEG C; the content of (A) organopolysiloxane is 100 parts by mass; (B) 0.1 to 30 parts by mass of a cationic surfactant; (C) 30 to 3,000 parts by mass of water; and (D) 0.5 to 50 parts by mass of colloidal silicon dioxide. As a result, provided is a film-forming organopolysiloxane emulsion composition having good film-forming properties, excellent film strength and flexibility after curing, and good storage stability. (In the formula, R1 is a hydrogen atom or a monovalent organic group with the carbon atom number of 1-20, and R2 is an alkyl group with the carbon atom number of 1-20, an aryl group with the carbon atom number of 6-20, an alkoxy group with the carbon atom number of 1-20 or a hydroxyl group. > # imgabs0 #

Description

Technical Field

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

[0002] Silicone emulsion compositions for forming rubber films have been known in the past in various compositions and have been used in various applications such as sealants (weather strips), coating agents, adhesives, and fiber treatment agents.

[0003] For example, there are proposed silicone emulsion compositions composed of hydroxylated diorganopolysiloxane, colloidal silica, and an organic tin compound or an organic amine compound (Patent Document 1); silicone emulsion compositions composed of hydroxyl-containing organopolysiloxane, Si-H-containing organopolysiloxane, colloidal silica, amide- and carboxyl-containing silane, epoxy-containing silane, and a curing catalyst (Patent Document 2); silicone emulsion compositions composed of alkenyl-containing organopolysiloxane, Si-H-containing organopolysiloxane, colloidal silica, a reaction product of aminosilane and acid anhydride, epoxysilane, and an addition reaction catalyst (Patent Document 3); silicone emulsion compositions composed of a hydroxyl-containing organopolysiloxane, colloidal silica, a reaction product of an aminosilane and an acid anhydride, an epoxysilane, and an addition reaction catalyst (Patent Document 4); and silicone emulsion compositions composed of a hydroxyl-containing organopolysiloxane, colloidal silica, and an epoxy-containing silane. The present invention discloses an organosilicon emulsion composition comprising a hydrogen siloxane with a terminal end capped with a hydrogen siloxane, an emulsifier, water and a curing catalyst (Patent Document 4); an organosilicon emulsion composition comprising a colloidal silica-organosilicon core-shell, a curing catalyst, an emulsifier and water (Patent Documents 5-7); an organosilicon emulsion composition comprising a hydroxyl-containing organopolysiloxane, colloidal silica, an amide- and carboxyl-containing silane, an epoxy-containing silane, a curing catalyst and a photocatalytic oxide (Patent Document 8); an organosilicon emulsion composition comprising a hydroxyl-containing organopolysiloxane, colloidal silica, an amide- and carboxyl-containing silane, an epoxy-containing silane (Patent Document 9), etc.

[0004] Furthermore, since organopolysiloxane can impart flexibility and lubricity to various fibers or fiber products, a type of organopolysiloxane emulsion composition that forms a rubber coating is used as a fiber treating agent.

[0005] As a method for producing such a rubber film-forming silicone emulsion composition, there is known a method of emulsifying a cyclic siloxane oligomer or an organopolysiloxane terminally blocked with a silanol group as a raw material and then performing emulsion polymerization using a strong acid or a strong base.

[0006] When anionic surfactants with strong catalytic effects are used as surfactants, polymerization reactions occur rapidly, and therefore research has been conducted since ancient times and various methods have been proposed. However, emulsion polymerization emulsions using anionic surfactants are not compatible with cationic emulsions or chemicals used in large quantities for fiber treatment applications, hair cosmetic applications, etc., and there are problems such as reduced stability when blended, and limited use conditions and blending conditions.

[0007] On the other hand, when a common cationic surfactant such as cetyltrimethylammonium chloride and tallow trimethylammonium chloride is used as a surfactant, the catalytic effect is weak and the polymerization rate is extremely slow, making it difficult to obtain a silicone emulsion with a high degree of polymerization to form a rubber film.

[0008] Patent document 10 proposes that an organopolysiloxane end-capped with a trialkylmethyl type cationic surfactant and an alkyltrimethyl type cationic surfactant (including a nonionic surfactant according to the circumstances) with extremely high hydrophobicity be used simultaneously for emulsification, and then an alkali catalyst is added for polymerization, thereby obtaining an organopolysiloxane emulsion with a high degree of polymerization that can form a film in a shorter time than before. However, the cured film of the above-mentioned composition is pointed out to have a problem of soft hardness and low strength of the film. In addition, these emulsions have the problem of separation in less than 3 months. The organopolysiloxane in the emulsion has a high degree of polymerization that forms a film. Therefore, once separated, no matter how high the shear stirring is, it is impossible to stably disperse it again, so it is difficult to use in industry, and it is necessary to further improve long-term stability.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 56-16553

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 8-85760

[0013] Patent Document 3: Japanese Patent Application Laid-Open No. 9-208826

[0014] Patent Document 4: Japanese Patent Application Laid-Open No. 9-208900

[0015] Patent Document 5: Japanese Patent Application Laid-Open No. 9-208901

[0016] Patent Document 6: Japanese Patent Application Laid-Open No. 9-208902

[0017] Patent Document 7: Japanese Patent Application Laid-Open No. 9-208903

[0018] Patent Document 8: Japanese Patent Application Publication No. 2002-363494

[0019] Patent Document 9: Japanese Patent Application Publication No. 2008-231276

[0020] Patent Document 10: Japanese Patent Application Publication No. 2021-95455 Summary of the invention

[0021] 1. Technical issues to be resolved

[0022] The present invention is made in view of the technical problems to be solved in the above-mentioned prior art, and its purpose is to provide an emulsion composition of a film-forming organopolysiloxane, which has good film-forming properties, excellent strength and flexibility of the film after curing, and good storage stability of the emulsion. In addition, the present invention also aims to provide a method for producing the emulsion composition of the film-forming organopolysiloxane.

[0023] (II) Technical solution

[0024] In order to solve the above-mentioned technical problems, the present invention provides an emulsion composition of a film-forming organopolysiloxane, characterized in that it contains the following (A) to (D).

[0025] (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 hydroxyl groups bonded to silicon atoms in one molecule, wherein the organopolysiloxane (A) is 100 parts by mass;

[0026] [Chemical formula 1]

[0027]

[0028] In formula (1), R 1 are independently a hydrogen atom, or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, 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, wherein 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 of 0 to 2,000, and these are values ​​satisfying that the viscosity of the organopolysiloxane at 25° C. is 300,000 mPa·s or more;

[0029] (B) a cationic surfactant, which is 0.1 to 30 parts by weight;

[0030] (C) water, 30 to 3,000 parts by mass;

[0031] (D) Colloidal silica, in an amount of 0.5 to 50 parts by mass.

[0032] The emulsion composition of the film-forming organopolysiloxane of the present invention has good film-forming properties, is excellent in strength and flexibility of the film after curing, and also has good storage stability of the emulsion.

[0033] In this case, it is preferred that the cationic surfactant (B) comprises any one or both of the following (B-1) or (B-2),

[0034] (B-1)Q 1 3(CH3)N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0035] (B-2)Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0036] Q 1 is a monovalent organic group having 6 to 30 carbon atoms of the same or different types, Q 2 are monovalent organic groups having 6 to 30 carbon atoms of the same or different types, X are independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, and α is an integer of 1 or 2; wherein the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

[0037] With such an emulsion composition, the storage stability of the emulsion is further improved.

[0038] Preferably, the emulsion composition of the present invention further contains 0.1 to 30 parts by mass of (E) a nonionic surfactant based on 100 parts by mass of the (A) component.

[0039] Such an emulsion composition can be emulsified more easily due to the supplementary emulsification ability of the component (E), and the stability of the emulsion can be dramatically improved.

[0040] In this case, it is preferred that the (E) nonionic surfactant is a compound represented by the following formula:

[0041] R 3 O(EO) p (PO) q H

[0042] In the formula, R 3 It is a straight-chain or branched alkyl group having 8 to 30 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random; p and q are independently integers of 0 to 100, wherein p+q>0.

[0043] Such component (E) has a more appropriate balance between the hydrophilicity and hydrophobicity of the surfactant, and has good compatibility with components (B-1) and (B-2), thereby improving the stability of the emulsion. In addition, the property state of the nonionic surfactant itself is also easy to handle when manufacturing the emulsion.

[0044] In the present invention, it is preferred that the particle surface of the colloidal silica (D) is treated with an oxide of a metal other than silicon.

[0045] Since the surface of the surface-treated colloidal silica particles of the component (D) is positively charged in a wide pH range, electrical repulsion occurs between the surface-treated colloidal silica particles and the emulsion particles in the emulsion composition, and the particles are less likely to be integrated and aggregated, thereby making it possible to disperse the emulsion more stably.

[0046] The emulsion composition of the present invention may further contain a salt composed of a basic substance and an acidic substance, wherein the basic substance is composed of either or both of ammonia and an organic amine.

[0047] Even if the emulsion composition of the present invention contains such a salt, it has good film-forming properties, the strength and flexibility of the film after curing are excellent, and the storage stability of the emulsion is also good.

[0048] Furthermore, it is preferred that the content of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition is 1,000 ppm or less (in terms of mass, the same shall apply hereinafter).

[0049] Furthermore, it is more preferred that the total content of each of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9) and eicosylcyclodecasiloxane (D10) contained in the emulsion composition is 1,000 ppm or less.

[0050] Since the emulsion composition of the present invention has a small content of such a low-molecular-weight cyclic siloxane, the properties of the coating film after curing (such as elongation during cutting) are excellent.

[0051] The average particle size of the emulsion contained in the emulsion composition is preferably 1 μm or less, more preferably 500 nm or less.

[0052] The emulsion composition of the present invention has a smaller buoyancy force on the particles relative to the volume of the particles, so that the particles can be evenly dispersed in the emulsion, and the aggregation and integration of the particles can be suppressed. Even if stored for a long time, the particles will not separate into light and dark or separate into two layers.

[0053] Furthermore, the antiviral activity value Mv of the emulsion composition of the present invention in accordance with JIS L 1922 can be 2.0 or more.

[0054] 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, thereby forming a coating film containing a substance that exhibits antiviral properties.

[0055] The present invention also provides a method for producing an emulsion composition of a film-forming organopolysiloxane, which is a method for producing the above-mentioned emulsion composition of a film-forming organopolysiloxane, comprising the following steps (I) to (III), wherein after step (I), steps (II) and (III) are performed in any order or simultaneously,

[0056] Furthermore, the water (C) is added so that the total amount of the following (C-1), (C-2) and (C-3) becomes 30 to 3,000 parts by mass.

[0057] (I) a step of emulsifying a mixture containing the following components (A-1), (A-2), (B) and (C-1) to prepare an emulsion composition,

[0058] (A-1) an organopolysiloxane having a viscosity of 300,000 mPa·s or less at 25° C. and terminally blocked with an alkoxy group or / and terminally blocked with a silanol group;

[0059] (A-2) an alkoxysilane represented by the following formula (3),

[0060] R 4 e Si(OR 5 ) 4-e (3)

[0061] In formula (3), R 4 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, R 5 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms; e is 0 or 1,

[0062] In addition, the total amount 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;

[0063] (B) a cationic surfactant, which is 0.1 to 30 parts by weight;

[0064] (C-1) water, 30 to 3,000 parts by mass;

[0065] (II) further adding (C-2) water to the obtained emulsion composition as needed, polymerizing at 0 to 40° C. for 1 to 150 hours in the presence of (F) a basic catalyst, and further neutralizing the mixture.

[0066] (III) A step of further adding 0.5 to 50 parts by mass of (D) colloidal silica and, if necessary, further adding (C-3) water.

[0067] According to such a method for producing an emulsion composition of a film-forming organopolysiloxane, it is possible to efficiently produce an emulsion composition having good film-forming properties, excellent strength and flexibility of the film after curing, and good storage stability of the emulsion.

[0068] In this case, as the (F) basic catalyst, either ammonia or an organic amine or both thereof can be used.

[0069] Such a catalyst can significantly suppress the by-products of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) and can reduce the content of each of the by-products to 1,000 ppm or less while satisfying the requirement that the viscosity of the organopolysiloxane in the emulsion composition of the film-forming organopolysiloxane be 300,000 mPa·s or more at 25°C.

[0070] Furthermore, it is preferred that: any one or both of the following (B-1) or (B-2) be used as the (B) cationic surfactant,

[0071] (B-1)Q 1 3(CH3)N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0072] (B-2)Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0073] Q1 is a monovalent organic group having 6 to 30 carbon atoms of the same or different types, Q 2 are monovalent organic groups having 6 to 30 carbon atoms of the same or different types, X are independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, α is an integer of 1 or 2, and the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

[0074] According to such a method for producing an emulsion composition, a composition having better storage stability of the emulsion can be produced efficiently.

[0075] In any one of the steps (I) to (III), 0.1 to 30 parts by mass of (E) a nonionic surfactant may be further added to 100 parts by mass of the total of (A-1) and (A-2).

[0076] According to such a method for producing an emulsion composition, a composition which is more easily emulsified and has dramatically improved emulsion stability can be efficiently produced by utilizing the supplementary emulsification ability of the component (E).

[0077] As the component (E), a nonionic surfactant represented by the following formula can be used:

[0078] R 3 O(EO) p (PO) q H

[0079] In the formula, R 3 It is a straight-chain or branched alkyl group having 8 to 30 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random; p and q are independently integers of 0 to 100, wherein p+q>0.

[0080] Such a component (E) has a property state that allows easy handling during production of an emulsion.

[0081] Furthermore, it is preferable to use colloidal silica whose particle surfaces are treated with an oxide of a metal other than silicon as the component (D).

[0082] When such a component (D) is used, electrical repulsion occurs between the surface-treated colloidal silica particles and the emulsion particles in the emulsion composition, and the particles are less likely to be integrated and aggregated, so that a more stable emulsion composition can be efficiently produced.

[0083] Furthermore, it is preferred to use a compound containing octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in an amount of 1,000 ppm or less as the component (A-1).

[0084] The method for producing an emulsion composition of the present invention can efficiently produce an emulsion composition containing a small amount of low-molecular-weight cyclic siloxane by using a raw material containing a small amount of such a low-molecular-weight cyclic siloxane.

[0085] The method for producing an emulsion composition of the present invention can make the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition 1,000 ppm or less, and can also make the total content of each of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecmethylcyclononasiloxane (D9) and eicosylcyclodecasiloxane (D10) contained in the emulsion composition 1,000 ppm or less.

[0086] According to the method for producing an emulsion composition of the present invention, an emulsion composition containing a small amount of such a low-molecular-weight cyclic siloxane can be produced efficiently.

[0087] (III) Beneficial effects

[0088] According to the film-forming organopolysiloxane emulsion composition of the present invention (hereinafter, also referred to as the emulsion composition), it is possible to provide an emulsion composition of the film-forming organopolysiloxane and a film having good film-forming properties, excellent strength and softness of the film after curing, and good storage stability of the emulsion. In addition, by treating various fibers or fiber products with the composition, softness and lubricity can be imparted to them. Furthermore, the fiber treatment agent containing the emulsion composition of the present invention as an active ingredient has excellent washing durability and can maintain softness and lubricity even after washing treatment. DETAILED DESCRIPTION

[0089] The inventors of the present application have conducted intensive studies to achieve the above-mentioned purpose, and as a result, have found that an emulsion composition of a film-forming organopolysiloxane containing (A) an organopolysiloxane having a viscosity of 300,000 mPa·s or more at 25°C, (B) a cationic surfactant, (C) water, and (D) colloidal silica in specific amounts has good film-forming properties, excellent strength and flexibility of the film after curing, and good storage stability of the emulsion, thereby completing the present invention.

[0090] That is, the present invention is an emulsion composition of a film-forming organopolysiloxane, characterized in that it contains the following (A) to (D).

[0091] (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 hydroxyl groups bonded to silicon atoms in one molecule, wherein the organopolysiloxane (A) is 100 parts by mass;

[0092] [Chemical formula 2]

[0093]

[0094] In formula (1), R 1 are independently a hydrogen atom, or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, 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, wherein 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 of 0 to 2,000, and these are values ​​that satisfy that the viscosity of the organopolysiloxane at 25° C. is 300,000 mPa·s or more;

[0095] (B) a cationic surfactant, which is 0.1 to 30 parts by weight;

[0096] (C) water, 30 to 3,000 parts by mass;

[0097] (D) Colloidal silica, in an amount of 0.5 to 50 parts by mass.

[0098] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0099] [Emulsion composition of film-forming organopolysiloxane]

[0100] The film-forming organopolysiloxane emulsion composition of the present invention contains:

[0101] (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 hydroxyl groups bonded to silicon atoms in one molecule, wherein the organopolysiloxane (A) is 100 parts by mass;

[0102] [Chemical formula 3]

[0103]

[0104] In formula (1), R 1 are independently a hydrogen atom, or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, 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, wherein 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 of 0 to 2,000, and these are values ​​satisfying that the viscosity of the organopolysiloxane at 25° C. is 300,000 mPa·s or more;

[0105] (B) a cationic surfactant, which is 0.1 to 30 parts by weight;

[0106] (C) water, 30 to 3,000 parts by mass;

[0107] (D) Colloidal silica, in an amount of 0.5 to 50 parts by mass.

[0108] It may be necessary to further contain components other than the components (A) to (D). Each component will be described below.

[0109] [(A) ingredient]

[0110] (A) An organopolysiloxane having a viscosity of 300,000 mPa·s or more at 25° C. and containing at least two alkoxy groups or hydroxyl groups bonded to silicon atoms in one molecule and represented by the following average composition formula (1). The emulsion composition of the present invention contains 100 parts by mass of the component (A).

[0111] [Chemical formula 4]

[0112]

[0113] In formula (1), R 1 are independently a hydrogen atom, or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, 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, c+d is an integer of 0 to 2,000, and these values ​​satisfy that the viscosity of the organopolysiloxane at 25° C. is 300,000 mPa·s or more.

[0114] In the above formula (1), R1 They are independently hydrogen atoms, or unsubstituted or substituted monovalent organic groups having 1 to 20 carbon atoms, which may be any of linear, branched or cyclic. Specifically, they include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, and naphthyl; alkenyl groups such as vinyl and allyl; or groups in which part of the hydrogen atoms in the structure of these organic groups is replaced with halogen atoms or organic groups containing polar groups such as amino, acryloyloxy, methacryloyloxy, epoxy, and mercapto groups. Here, it is desirable that R 1 More than 80% of the groups are methyl groups.

[0115] 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 hydroxyl group, which may be any of a linear, branched, or cyclic group. Specifically, in addition to a hydroxyl group, examples thereof include 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, and 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 hexyl group, a heptyl group, an octyl group, a decyl group, and a tetradecyl group; or groups in which a part or all of the hydrogen atoms bonded to these groups are replaced with halogen atoms, an amino group, a cyano group, and the like. Among them, R 2 A methyl group, a hydroxyl group, a methoxy group, and an ethoxy group are preferred, and the group is set so as to contain at least two alkoxy groups or hydroxyl groups bonded to a silicon atom in one molecule.

[0116] a, b, c, and d are integers satisfying that the viscosity of the organopolysiloxane at 25° C. is 300,000 mPa·s or more.

[0117] a is an integer of 2 to 1,000, preferably an integer of 2 to 500, and more preferably an integer of 2 to 100. If a is larger than 1,000, the silicone rubber coating may lack flexibility.

[0118] b is an integer of 10 to 10,000, preferably an integer of 50 to 7,000, and more preferably an integer of 10 to 5,000. If b is less than 10, the silicone rubber coating may lack flexibility or may not form a coating, while if b is greater than 10,000, the tear strength and tensile strength of the coating may decrease.

[0119] c is an integer of 0 to 1,000, preferably an integer of 0 to 200, and more preferably an integer of 0 to 100. If c is greater than 1,000, the silicone rubber film may lack flexibility or the tear strength and tensile strength of the film may decrease.

[0120] d is an integer of 0 to 1,000, preferably an integer of 0 to 200, and more preferably an integer of 0 to 100. If d is larger than 1,000, the silicone rubber coating may lack flexibility or the tear strength and tensile strength of the coating may decrease.

[0121] Furthermore, c+d is an integer of 0 to 2,000, preferably 0 to 400, and more preferably 0 to 200.

[0122] The viscosity of the organopolysiloxane of the component (A) at 25°C is 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 high viscosity that cannot be measured by the viscosity measurement method described below.

[0123] The viscosity (absolute viscosity) in the present invention is a value measured using a BM type rotational viscometer (TVB-10M) at 25° C. The viscosity of a substance whose viscosity cannot be measured even when using the M4 (measurement upper limit viscosity 2,000,000 mPa·s), which is the rotor that can measure the highest viscosity in the BM type rotational viscometer, or a substance that cannot be measured because it is entangled in the rotor of the BM type rotational viscometer, or a substance that cannot be measured because it is insoluble in toluene, is 300,000 mPa·s or more.

[0124] As specific examples of the organopolysiloxane of the component (A) in the present invention, the following average composition formula can be cited, but the invention is not limited thereto. In the following average composition formula, a, b, b1, b2, b3, c, c1, c2, c3, and d are values ​​satisfying that the viscosity of the polyorganosiloxane at 25° C. is 300,000 mPa·s or more, and a, b, c, and d are the same as those described above. b1, b2, and b3 are integers whose total satisfies b, that is, in the range of 10 to 10,000, and c1, c2, and c3 can be integers whose total satisfies c, that is, in the range of 0 to 1,000.

[0125] [Chemical formula 5]

[0126]

[0127] [Chemical formula 6]

[0128]

[0129] [Chemical formula 7]

[0130]

[0131] [(B) ingredient]

[0132] The component (B) is a cationic surfactant and contains 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, relative to 100 parts by mass of the component (A). If the amount of the component (B) is less than 0.1 parts by mass or more than 30 parts by mass, the emulsion may be unstable or it may be difficult to achieve a high degree of polymerization due to dealcoholization polycondensation or dehydration polycondensation of alkoxy groups or hydroxyl groups contained in the organopolysiloxane.

[0133] Furthermore, the component (B) preferably contains either or both of the following component (B-1) and component (B-2).

[0134] (B-1)Q 1 3(CH3)N + ·X - Cationic surfactants represented

[0135] (B-2)Q 2 α (CH3) 4-α N + ·X - Cationic surfactants represented

[0136] Q 1 is a monovalent organic group having 6 to 30 carbon atoms of the same or different types, Q 2 are monovalent organic groups having 6 to 30 carbon atoms of the same or different types, X are independently a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms, and α is an integer of 1 or 2.

[0137] The cationic surfactants as these components (B-1) and (B-2) are substances that emulsify and disperse the organopolysiloxane in water. However, regarding the mechanism of action of components (B-1) and (B-2), the inventors of the present application believe that in addition to the mechanism of action as emulsifiers, there is also the following mechanism of action.

[0138] It is considered that in the method for producing the organopolysiloxane emulsion composition of the present invention, after the organopolysiloxane is emulsified and dispersed in water, when the alkaline catalyst (base catalyst) is added, OH generated in the aqueous phase - By exchanging counter ions with the cationic surfactants as the components (B-1) and (B-2), the cationic surfactant itself also functions as a catalyst, and as a result, the degree of polymerization of the organopolysiloxane as the component (A) can be more effectively increased.

[0139] The cationic surfactant as component (B-1) is as described above. 1 3(CH3)N + ·X - The cationic surfactant represented by Q 1 are the same or different types of monovalent organic groups having 6 to 30 carbon atoms, preferably monovalent organic groups having 7 to 20 carbon atoms, and more preferably monovalent organic groups having 8 to 18 carbon atoms. 1 If the number of carbon atoms in Q is 6 or more, the hydrophilicity of the surfactant is appropriate, the contact frequency with the organopolysiloxane of component (A) is sufficient, and the organopolysiloxane can be highly polymerized without taking time to achieve a high degree of polymerization. 1 When the number of carbon atoms is 30 or less, the emulsifying power as a surfactant is sufficient and a stable emulsion can be obtained.

[0140] As Q 1 Specific examples include alkyl groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl; alkenyl groups such as oleyl, etc. Among them, octyl, dodecyl, hexadecyl, and octadecyl are preferred.

[0141] In addition, X - is a halogen ion or a monovalent carboxyl ion having 1 to 6 carbon atoms, and specific examples thereof include Cl - Br - ,I - Isohalogen ions; HCOO - 、CH3COO - 、C2H5COO - Among them, Cl - Br - HCOO - 、CH3COO - .

[0142] Specific examples of the component (B-1) include, but are not limited to, trihexylmethylammonium chloride, triheptylmethylammonium chloride, trioctylmethylammonium chloride, trinonylmethylammonium chloride, tridecylmethylammonium chloride, trilaurylmethylammonium chloride, trioctylmethylammonium acetate, and trilaurylmethylammonium acetate.

[0143] The amount of the cationic surfactant as component (B-1) can be 0 to 30 parts by mass, preferably 0.2 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of component (A). When the amount is 0 to 30 parts by mass, the stability of the emulsion is good.

[0144] In addition, the cationic surfactant of the component (B-2) is Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented by can improve the stability of the emulsion. 2 are the same or different monovalent organic groups having 6 to 30 carbon atoms, preferably a monovalent organic group having 12 to 28 carbon atoms, and more preferably a monovalent organic group having 18 to 26 carbon atoms. 2 If the number of carbon atoms in Q is 6 or more, the stability of the emulsion is good. 2 If the number of carbon atoms is less than 30, then 1 The same as the case of Q, the emulsifying power of the surfactant is sufficient to obtain a stable emulsion. 2 X - With the above Q 1 X - α is an integer of 1 or 2.

[0145] 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, eicosyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexyltrimethylammonium acetate, phenyltrimethylammonium acetate, heptyltrimethylammonium acetate, benzyltrimethylammonium chloride, decyltrimethylammonium chloride, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, eicosyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexyltrimethylammonium acetate, phenyltrimethylammonium acetate, heptyltrimethylammonium acetate, benzyltrimethylammonium chloride, dec ... trimethylammonium acetate, octyl trimethylammonium acetate, nonyl trimethylammonium acetate, decyl trimethylammonium acetate, lauryl trimethylammonium acetate, myristyl trimethylammonium acetate, hexadecyl trimethylammonium acetate, stearyl trimethylammonium acetate, eicosyl trimethylammonium acetate, behenyl trimethylammonium acetate, dihexyl dimethylammonium chloride, diphenyl dimethylammonium chloride, hexyl phenyl dimethylammonium chloride, heptyl phenyl dimethylammonium chloride, octyl phenyl dimethylammonium chloride, nonyl phenyl dimethylammonium chloride, decyl phenyl dimethylammonium chloride, lauryl phenyl Dimethylammonium chloride, myristylphenyldimethylammonium chloride, hexadecylphenyldimethylammonium chloride, stearylphenyldimethylammonium chloride, eicosylphenyldimethylammonium chloride, behenyldimethylammonium chloride, diheptyldimethylammonium chloride, di(benzyl)dimethylammonium chloride, dioctyldimethylammonium chloride, dinonyldimethylammonium chloride, didecyldimethylammonium chloride, dilauryldimethylammonium chloride, dimyristyldimethylammonium chloride, hexadecyldimethylammonium chloride, distearyldimethylammonium acetate, di(eicosyl)dimethylammonium chloride The present invention includes, but is not limited to, methyl 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, dieicosyl dimethyl ammonium acetate, and dibehenyl dimethyl ammonium acetate.

[0146] The amount of the cationic surfactant as component (B-2) can be 0 to 30 parts by mass, preferably 0.2 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass relative to 100 parts by mass of component (A). If it is 30 parts by mass or less, the stability of the emulsion is good.

[0147] In addition, as described above, the emulsion composition of the present invention contains 0 to 30 parts by mass of the component (B-1) and 0 to 30 parts by mass of the component (B-2) relative to 100 parts by mass of the component (A), but the total amount of the 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 is good.

[0148] Compared with component (B-2), component (B-1) has high hydrophobicity, so the contact frequency with the organopolysiloxane of component (A) is high, and a faster polymerization rate can be expected. On the other hand, component (B-2) has high hydrophobicity and poor emulsification ability. Therefore, when only (B-1) is used, although it varies depending on the composition, particle size, viscosity, pH and other conditions of the emulsion, it is also necessary to further improve the time stability of the emulsion. Therefore, by simultaneously using component (B-2) having a higher emulsification ability than component (B-1), the stability of the emulsion can be improved on the basis of accelerating the polymerization rate.

[0149] As described above, only component (B-1) can be used, but by using component (B-1) and component (B-2) together, the stability of the emulsion can be improved while accelerating the polymerization rate. 1 3(CH3)N + ·X - The cationic surfactant represented by (B-2) is Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented by (B-1) is a quaternary ammonium with three substituents Q 1 Characterization, (B-2) with 1 or 2 substituents Q of quaternary ammonium 2 Characterization. Monovalent organic group Q 1 , Q 2 The more carbon atoms there are, the higher the hydrophobicity is, because its bulkiness leads to greater steric hindrance. 1 , Q 2 To adjust their effects, the polymerization rate and the stability of the emulsion are set to be optimal.

[0150] In the combination of component (B-1) and component (B-2), the total number of carbon atoms of the substituents of the quaternary ammonium is not particularly limited. From the perspective of obtaining a suitable emulsion, the total number of carbon atoms of the substituents of the quaternary ammonium of (B-1) (3 Q 1 The total number of carbon atoms in the methyl group is N (B-1) , the total number of carbon atoms (1 or 2 Q 2 The total number of carbon atoms in the remaining methyl groups is N (B-2) , N (B-1) With N (B-2) The difference of is preferably 0 to 35, the lower limit can be any integer in the range of 0 to 4, and the upper limit can be any integer in the range of 30 to 34. (B-1) With N(B-2) By setting the difference of to an appropriate value, a suitable emulsion can be obtained.

[0151] In addition, Q 1 The number of carbon atoms and Q 2 There is no particular restriction on the number of carbon atoms in the combination. From the perspective of obtaining a suitable emulsion, Q 1 The number of carbon atoms and Q 2 The difference in the number of carbon atoms is preferably 0 to 15, the lower limit may be any integer from 0 to 4, and the upper limit may be any integer from 10 to 14. 1 The number of carbon atoms and Q 2 By setting the value of the number of carbon atoms of to an appropriate value, the hydrophilicity of the surfactant, the contact frequency with the organopolysiloxane of the (A) component, and the emulsifying power can be set to appropriate values, and the degree of polymerization of the organopolysiloxane can be increased by polycondensation to make the polymerization rate appropriate, thereby obtaining a stable and appropriate emulsion.

[0152] [(C) ingredient]

[0153] The emulsion composition of the present invention contains 30 to 3,000 parts by mass, preferably 40 to 2,400 parts by mass of water as the component (C) relative to 100 parts by mass of the component (A). If the amount of water is too small, an oil-in-water emulsion will not be obtained, and if the amount is too large, the economic efficiency will be poor.

[0154] [(D) ingredient]

[0155] The component (D) is colloidal silica, and contains 0.5 to 50 parts by mass of the component (D) based on 100 parts by mass of the component (A).

[0156] The colloidal silica of the component (D) acts as a film strengthening agent. Even if the strength (especially hardness and tensile strength) of the film is weak and the emulsion composition cannot be used for applications such as those seeking durability, the use of colloidal silica can dramatically improve the strength (especially hardness and tensile strength) of the film formed by the emulsion composition.

[0157] In the present invention, colloidal silica is preferably hydrophilic and can be used as an aqueous dispersion. The type of colloidal silica is not limited as long as it can be mixed with the emulsion composition and used, and commercially available products can be used.

[0158] In particular, as colloidal silica, by using colloidal silica whose particle surface is treated with an oxide of a metal other than silicon, the stability of the emulsion can be greatly improved. As the oxide of the metal other than silicon, aluminum oxide, titanium oxide, iron oxide, zinc oxide, magnesium oxide, etc. are preferably substances with an isoelectric point of 5 or more. By using such colloidal silica, the surface of the colloidal silica particles is positively charged in a wide pH range, so that an electrical repulsion is generated between the emulsion particles in the emulsion composition, and it is not easy to be integrated and aggregated, so it can be dispersed more stably. In addition, the isoelectric point can be measured, for example, according to JIS R1638: 1999. In addition, when a film is formed by removing the use of such colloidal silica, an electrical repulsion is generated between the emulsion particles in the emulsion composition and the colloidal silica, and it is not easy to be integrated and aggregated, so a more uniform (more dispersed particles) film can be obtained, thereby being able to more dramatically improve the strength (especially hardness, tensile strength) of the film formed by the emulsion composition.

[0159] Specific colloidal silica includes 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, SNOWTEX AK-YL (manufactured by Nissan Chemical Corporation), etc. Among the above, SNOWTEX AK, SNOWTEX AK-L, and SNOWTEX AK-YL in which the colloidal silica surface is treated with alumina are particularly preferred, but the present invention is not limited to these.

[0160] The average particle size of the colloidal silica is not particularly limited, and the above-mentioned average particle size of the colloidal silica can be adopted.

[0161] In addition, as an example of a similar composition containing silica / organopolysiloxane / water, a Pickering emulsion composition can be mentioned.

[0162] A Pickering emulsion is an emulsion stabilized by adsorbing (orienting) solid fine particles at a liquid / liquid interface. Therefore, it is possible to produce an emulsion composition without using an emulsifier, and thus has attracted attention in recent years.

[0163] As solid particles used in the Pickering emulsion composition, hydrophobic silica, hydrophobic cellulose, silicone resin powder, hollow hemispherical silicone particles, polyamide resin, talc, hydrophobic pigments, etc. are generally used. Among them, as for silica, hydrophobic silica formed by modifying and hydrophobizing the surface of hydrophilic silica with hydrocarbons, etc. by reacting the hydroxyl groups on the surface of the hydrophilic silica with trifunctional silanes, etc. is generally used. On the other hand, the colloidal silica preferably used in the present invention is an aqueous dispersion of hydrophilic silica particles having a large number of silanol groups (Si-OH) on the surface, and preferably its surface is coated with a metal oxide other than silicon, so the Pickering emulsion composition is different from the emulsion composition of the present invention in composition.

[0164] Furthermore, in the present invention, colloidal silica is not adsorbed (oriented) at the liquid / liquid (organopolysiloxane / water) interface, but is stably dispersed in the aqueous phase (continuous phase) while being repelled by charges, and therefore the dispersion mechanism is also different from that of the Pickering emulsion composition.

[0165] [(E) ingredient]

[0166] The component (E) is a nonionic surfactant and can be contained in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the component (A).

[0167] The nonionic surfactant as the component (E) has a function of supplementing the insufficient emulsifying ability of the components (B-1) and (B-2) alone, and thus facilitates emulsification and can dramatically improve the stability of the emulsion.

[0168] The nonionic surfactant as component (E) preferably has the following structure,

[0169] R 3 O(EO) p (PO) q H

[0170] In the formula, R 3 It is a straight-chain or branched alkyl group having 8 to 30 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random; p and q are independently integers of 0 to 100, wherein p+q>0.

[0171] As the nonionic surfactant of the component (E), as described above, it is preferred that R 3 O(EO) p (PO) q H represents a nonionic surfactant, R 3It is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably a linear or branched alkyl group having 12 to 22 carbon atoms, and more preferably a linear or branched alkyl group having 13 to 18 carbon atoms.

[0172] If R 3 The number of carbon atoms in R is 8 or more, the hydrophilicity of the surfactant is appropriate, and the compatibility with the components (B-1) and (B-2) is also good, and there is no worry about separation of light and dark or separation into two layers even after 2 months. 3 The number of carbon atoms in the R is 30 or less, so the hydrophobicity is not too high and sufficient emulsification is possible. 3 If the number of carbon atoms of the nonionic surfactant is less than 30, the polymerization degree of the ethylene oxide group (p in the formula) will be increased, and there is no need to deliberately increase the hydrophilicity. Therefore, the polymerization degree of the ethylene oxide group can be lower, and the property state of the nonionic surfactant itself will also be easy to handle when making the emulsion.

[0173] As R 3 Specific examples of include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl. Among them, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl are preferred, and tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl are more preferred.

[0174] EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random. p and q are independently integers of 0 to 100, preferably integers of 2 to 80, and more preferably integers of 4 to 60. Wherein, p+q>0. In addition, as the degree of polymerization of PO (wherein, q) increases, the hydrophobicity increases, and the emulsification of the nonionic surfactant tends to decrease, so p>q is preferred.

[0175] Specific examples of the 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, polyoxyethylene (60) stearyl ether, and the like.

[0176] In addition, for the purpose of improving the stability of the emulsion, there is no problem in adding the following substances: cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkyl imidazolines other than components (B-1) and (B-2).

[0177] In the present invention, in addition to the cationic surfactant, the above-mentioned nonionic or amphoteric surfactant may be added, but the anionic surfactant having a strong catalytic effect may not be added. In the present invention, since the emulsion polymerization emulsion can be obtained without adding the anionic surfactant, the emulsion composition of the present invention can be used together with the cationic emulsion and chemical reagent used in fiber treatment applications or hair cosmetic applications, etc., and has good stability and usefulness that the conditions of use and blending are not limited. This is a feature of the present invention that has not been found in conventional emulsion polymerization emulsions using anionic surfactants.

[0178] [Other ingredients]

[0179] The emulsion composition of the present invention may further contain a salt composed of a basic substance and an acidic substance, wherein the basic substance is composed of either or both of ammonia and an organic amine.

[0180] The emulsion composition of the present invention desirably contains a salt consisting of an alkaline substance and a strongly acidic substance or / and a weakly acidic substance, wherein the alkaline substance consists of ammonia or / and an organic amine. The salt consisting of an alkaline substance consisting of ammonia or / and an organic amine and a strongly acidic substance or / and a weakly acidic substance refers to a salt produced by neutralizing an alkaline catalyst (base catalyst) used for polymerization in the manufacture of the emulsion composition of the present invention described later.

[0181] When ammonia and / or an organic amine is used as a catalyst, the viscosity of the organopolysiloxane in the organopolysiloxane emulsion composition of the present invention at 25° C. is 300,000 mPa·s or more, and the by-production of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) can be significantly suppressed, and the content of each can be made 1,000 ppm or less.

[0182] Therefore, in the present invention, when a strong acid or / and a weak acid is added as a neutralizing agent for terminating polymerization, a salt composed of a basic substance composed of ammonia or / and an organic amine and a strong acid or / and a weak acid is generated in the emulsion composition.

[0183] Even if the emulsion composition of the present invention contains the above-mentioned salt, it has good film forming properties, excellent strength and flexibility of the film after curing, and good storage stability of the emulsion. However, in order to make the stability of the emulsion composition better, the less the content of the above-mentioned salt, the more preferred. The salt concentration in the emulsion composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.

[0184] In addition, in order to suppress separation of the emulsion composition, it is preferred not to contain a large amount of components such as alcohol that generally have the effect of reducing the stability of the emulsion. The concentration of alcohol in the emulsion composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.

[0185] In addition, the cationic surfactant of component (B-1) and component (B-2) is sometimes sold in the form of being diluted in a solvent (especially alcohol) such as ethanol or IPA (isopropyl alcohol), but the concentration of the preferred solvent (especially alcohol) is 20% by mass or less, more preferably 13% by mass or less, and more preferably 7% by mass or less. When the concentration of the solvent (especially alcohol) is greater than 20% by mass, the stability of the emulsion decreases and it is easy to separate over time. In addition, the above-mentioned alcohol refers to an aliphatic alcohol having a carbon number of 1 to 20. In addition, the numerical range shown above only shows an example and is not limited thereto, and other components may also be included and set in consideration of the stability of the emulsion composition.

[0186] In addition, the particle size of the emulsion composition of the present invention is not particularly limited. From the perspective of the stability of the emulsion, the average particle size of the emulsion composition is preferably 1 μm or less, and more preferably 500 nm or less. If the average particle size is 1 μm or less, the buoyancy of the emulsion corresponding to the volume of the particles is reduced, and the particles can be uniformly dispersed in the emulsion, and the aggregation or integration of the particles can be suppressed. Even if stored for a long time, the particles will not separate into light and dark or separate into two layers.

[0187] In the present specification, the average particle size refers to a particle size at which the cumulative value is 50% in a volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution measuring apparatus.

[0188] The film-forming organopolysiloxane emulsion composition of the present invention can contain octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in an amount of 1,000 ppm or less.

[0189] Furthermore, the total content of each of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9) and eicosylcyclodecasiloxane (D10) contained in the emulsion composition can be 1,000 ppm or less.

[0190] In the method for producing an emulsion composition described below, as the low molecular weight siloxane supplied to the emulsion polymerization, a cyclic siloxane oligomer such as octamethylcyclotetrasiloxane is used because it is easily available and easily emulsified and ring-opening polymerized. However, the ring-opening polymerization of the cyclic siloxane oligomer is an equilibrium reaction, and in the emulsion after the emulsion polymerization, the cyclic siloxane oligomer represented by octamethylcyclotetrasiloxane usually remains in the polysiloxane.

[0191] Therefore, the oligomer may volatilize from the emulsion during storage or use, thereby damaging the physical stability of the emulsified system. In addition, when such an emulsion is used in large quantities as a hair cosmetic, for example, for hair treatment, especially when accompanied by a heat blowing treatment, the volatilized oligomer may sometimes pollute the surrounding environment or cause a contact failure of an electronic device. Furthermore, if such an emulsion is used for skin cosmetics, etc., the volatile characteristics of the low molecular weight cyclic siloxane oligomer contained therein may sometimes damage the touch. Therefore, it is sought to suppress the amount of the cyclic siloxane oligomer in the emulsion. In particular, among the cyclic siloxanes, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are easily generated in an equilibrium reaction, and they are stable compounds and have volatility, so it is sought to suppress their content.

[0192] Such silanol-terminated polyorganosiloxanes are synthesized, for example, by hydrolyzing and polycondensing dimethyldichlorosilane, or by ring-opening polymerization of corresponding cyclic siloxane oligomers in the presence of an acidic catalyst such as sulfuric acid, or a basic catalyst such as potassium hydroxide or potassium silanol. Unreacted cyclic siloxane oligomers, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc., are present in the product. However, in order to avoid the above-mentioned problems caused by the cyclic siloxane oligomers remaining after the emulsion polymerization, it is preferred to suppress the content of cyclic siloxane oligomers in the raw materials. In order to suppress the cyclic siloxane oligomers of component (A) in this way, it can be achieved by, for example, distilling off the existing cyclic siloxane oligomers under reduced pressure from the polymer obtained by the ring-opening polymerization.

[0193] As described above, since products having reduced contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like have been sought in recent years, the content of the cyclic siloxane in the emulsion composition is preferably within the above range.

[0194] The contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in the emulsion composition of the present invention after storage at 25°C for 6 months are almost unchanged from those immediately after production, and the contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) immediately after production are less than 1,000 ppm. The contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in the emulsion composition of the present invention after storage at 25°C for 6 months are also less than 1,000 ppm.

[0195] The emulsion composition of the present invention has film-forming properties. The method for forming the film is not particularly limited, and by removing water from the emulsion composition, the organopolysiloxane in the emulsion composition will condense to form a uniform film. The method for removing water is not particularly limited, and for example, the water may be removed at 100° C. or above in a short time, or the water may be removed slowly at 25° C.

[0196] For the coating, for example, the emulsion composition was weighed into a 15 cm×10 cm PP (polypropylene) tray so that the nonvolatile component was 8.0 g, and dried at 25° C. for 48 hours, and then further dried at 105° C. for 1 hour to form a coating. The hardness, tensile strength and elongation of the above-prepared coating were measured according to JIS K6249 to evaluate the coating physical properties.

[0197] [Method for producing emulsion composition]

[0198] Next, the method for producing the emulsion composition of the present invention is carried out through the following steps. That is,

[0199] A method for producing an emulsion composition of a film-forming organopolysiloxane, which is a method for producing the above-mentioned emulsion composition of a film-forming organopolysiloxane, characterized in that it comprises the following steps (I) to (III), after step (I), steps (II) and (III) are carried out in any order or simultaneously,

[0200] Furthermore, the water (C) is added so that the total amount of the following (C-1), (C-2) and (C-3) becomes 30 to 3,000 parts by mass.

[0201] and adding the water (C) so that the total amount of the following (C-1), (C-2) and (C-3) is 30 to 3,000 parts by mass;

[0202] (I) a step of emulsifying a mixture comprising the following components (A-1), (A-2), (B) and (C-1) to prepare an emulsion composition;

[0203] (A-1) an organopolysiloxane having a viscosity of 300,000 mPa·s or less at 25° C. and terminally blocked with an alkoxy group or / and terminally blocked with a silanol group;

[0204] (A-2) an alkoxysilane represented by the following formula (3);

[0205] R 4 e Si(OR 5 ) 4-e (3)

[0206] In formula (3), R 4 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, R 5 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms; e is 0 or 1;

[0207] In addition, the total amount 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;

[0208] (B) a cationic surfactant, which is 0.1 to 30 parts by weight;

[0209] (C-1) water, 30 to 3,000 parts by mass;

[0210] (II) further adding (C-2) water to the obtained emulsion composition as needed, polymerizing at 0 to 40° C. for 1 to 150 hours in the presence of (F) a basic catalyst, and further neutralizing the mixture;

[0211] (III) A step of further adding 0.5 to 50 parts by mass of (D) colloidal silica and, if necessary, further adding (C-3) water.

[0212] In addition, as long as the steps (II) and (III) are performed after the step (I), the order is arbitrary and they may be performed simultaneously.

[0213] [(A-1) Ingredient]

[0214] First, (A-1) an organopolysiloxane having a viscosity of 300,000 mPa·s or less at 25°C and terminally blocked with alkoxy groups or / and terminally blocked with silanol groups is a raw material of the organopolysiloxane as the component (A). The viscosity of the organopolysiloxane terminally blocked with alkoxy groups or / and terminally blocked with silanol groups at 25°C is preferably 150,000 mPa·s or less, and more preferably 50,000 mPa·s or less. If the viscosity at 25°C is 300,000 mPa·s or less, the particle size of the emulsion becomes smaller and the emulsion becomes highly stable. In addition, if the viscosity at 25°C is 300,000 mPa·s or less, a branched structure may be provided. In addition, when the terminal is an alkoxy group such as a methoxy group or an ethoxy group, since it can be hydrolyzed in the emulsion composition to become a silanol group, polymerization can be performed even if the organopolysiloxane terminally blocked with an alkoxy group is used.

[0215] As the component (A-1), a compound containing octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in an amount of 1,000 ppm or less can be used.

[0216] In the method for producing an emulsion composition of the present invention, by using a raw material containing a small amount of such a low-molecular-weight cyclic siloxane, an emulsion composition containing a small amount of a low-molecular-weight cyclic siloxane can be produced efficiently.

[0217] As specific examples of component (A-1), the following average composition formula can be cited, but it is not limited thereto. In the following average composition formula, g, h+i, and h+i+j are values ​​satisfying that the viscosity of the organopolysiloxane terminally blocked with an alkoxy group or / and a silanol group at 25°C is less than 300,000 mPa·s. In addition, g, h+i, and h+i+j in the following general formula can typically take values ​​of 1 to 2000.

[0218] [Chemical formula 8]

[0219]

[0220] [(A-2) Ingredient]

[0221] The organoalkoxysilane as the component (A-2) is a raw material for the organopolysiloxane as the component (A), and is an organoalkoxysilane represented by the following formula (3).

[0222] R 4 e Si(OR 5 ) 4-e (3)

[0223] In formula (3), R 4are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, R 5 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms; and e is 0 or 1.

[0224] Among them, R 4 They are independently hydrogen atoms or substituted or unsubstituted monovalent organic groups 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; alkenyl groups such as vinyl and allyl; or groups in which a portion of hydrogen atoms in the structure of these organic groups is replaced with halogen atoms or organic groups containing polar groups such as amino, acryloyloxy, methacryloyloxy, epoxy, and mercapto groups. Among them, R is desirable in terms of industry and properties. 4 More than 80% of the R 5 are independently a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. 5 The carbon number of the monovalent organic group is 1 to 20, and the above R 4 The same is preferred, and methyl, ethyl, propyl and butyl are preferred, and methyl and ethyl are more preferred.

[0225] The amount of component (A-2) 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, relative to 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, sufficient strength and durability are obtained during film coating.

[0226] 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-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, p-phenylyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, The present invention also includes, but is not limited to, propyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, and 3-isocyanate propyl triethoxysilane.

[0227] [Component (B), component (D), component (E)]

[0228] In the method for producing an emulsion composition of a film-forming organopolysiloxane of the present invention, as the cationic surfactant (B), any one or both of the following (B-1) and (B-2) can be used.

[0229] (B-1)Q 1 3(CH3)N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0230] (B-2)Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0231] Q 1 is a monovalent organic group having 6 to 30 carbon atoms of the same or different types, Q 2is 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, and the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

[0232] In any of the steps (I) to (III), 0.1 to 30 parts by mass of (E) a nonionic surfactant may be further added to 100 parts by mass of the total of (A-1) and (A-2).

[0233] Furthermore, as the component (E), a nonionic surfactant represented by the following formula can be used:

[0234] R 3 O(EO) p (PO) q H

[0235] In the formula, R 3 It is a straight-chain or branched alkyl group having 8 to 30 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random; p and q are independently integers of 0 to 100, wherein p+q>0.

[0236] Furthermore, as the component (D), colloidal silica whose particle surfaces are treated with an oxide of a metal other than silicon can also be used.

[0237] The (B) component, the (D) component, and the (E) component used in the method for producing the emulsion composition of the present invention are the same as those described above.

[0238] [Component (C-1), component (C-2), component (C-3)]

[0239] Component (C-1), component (C-2) and component (C-3) are water used in step (I) and, if necessary, step (II) and step (III). The amount of water used as component (C) is the sum of the amounts of component (C-1), component (C-2) and component (C-3).

[0240] In step (I), the amount of water 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.

[0241] For example, when an emulsifier such as a high-pressure homogenizer that reduces the size of emulsion particles by pressure is used, the amount of the component (C-1) used is not particularly limited to 30 to 3,000 parts by mass relative to 100 parts by mass of the component (A). However, when an emulsifier such as a homodisper (an emulsifier composed of a circular disk having serrated teeth on the outer circumference) that reduces the size of emulsion particles by shearing force is used, a homomixer (an emulsifier composed of a rotor and a stator), a colloid mill (an emulsifier that emulsifies the components by feeding them into a gap between a high-speed rotating disk and a fixed disk), the amount of the 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 relative to 100 parts by mass of the component (A).

[0242] When an emulsifier that reduces the size of emulsion particles by shearing force is used, if 200 parts by mass or less of the component (C-1) is added, the shearing force acts efficiently, the size of the emulsion particles is reduced, and the stability of the emulsion composition is improved.

[0243] Moreover, when it is 1 part by mass or more, it is easy to form an O / W type emulsion.

[0244] In step (II), component (C-2) may or may not be added. The total amount of component (C-1), component (C-2) and component (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).

[0245] When adding component (C-2), the amount of component (C-2) may be appropriately adjusted to obtain a concentration and viscosity suitable for the intended use. In addition, when an emulsifier such as a homodispersor, homomixer, or colloid mill is generally used, water is preferably added as component (C-2).

[0246] In step (III), component (C-3) may or may not be added. The total amount of component (C-1), component (C-2) and component (C-3) used (water of component (C)) is preferably 30 to 3,000 parts by mass relative to 100 parts by mass of component (A).

[0247] When the component (C-3) is added, the amount of the component (C-3) can be appropriately adjusted to obtain a concentration and a viscosity suitable for the intended use. In addition, when the colloidal silica of the component (D) is an aqueous dispersion, the water in the aqueous dispersion of the colloidal silica is also included in the component (C-3).

[0248] [(F)INGREDIENT]

[0249] In the method for producing an emulsion composition of a film-forming organopolysiloxane of the present invention, (C-2) water may be further added to the emulsion composition obtained in step (II) as necessary, and polymerization may be performed at 0 to 40° C. for 1 to 150 hours in the presence of (F) a basic catalyst, and further neutralization may be performed.

[0250] In this case, as the (F) basic catalyst, either ammonia or an organic amine or both thereof can be used.

[0251] Examples of the alkaline catalyst (base catalyst) of the component (F) include alkali metal hydroxides or alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; ammonia, organic amines, etc. Examples of organic amines include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and alkylamines such as monomethylamine, diethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine.

[0252] In order to adjust the content of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in the emulsion composition to 1,000 ppm or less, the base catalyst is preferably ammonia and / or triethanolamine, and more preferably ammonia.

[0253] A large number of reports have used emulsion polymerization of common cationic surfactants represented by trimethylammonium chloride of hexadecyltrimethylammonium chloride and tallow, but the catalytic effect of these cationic emulsifiers is weak, so in order to supplement them, a strong base of an alkali metal hydroxide or an alkaline earth metal hydroxide is usually used as a catalyst as described above. However, in the present invention, since the catalytic effect can be greatly improved by using component (B-1), there is no need to use a strong base, and only ammonia or / and an organic amine as a weak base can be fully polymerized. Therefore, in order to polymerize and almost not generate cyclic siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6), etc.), as a base catalyst, ammonia (ammonia water) or / and an organic amine is preferably used, and ammonia (ammonia water) is more preferably used.

[0254] In the method for producing an emulsion composition of a film-forming organopolysiloxane of the present invention, it is preferred that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition is 1,000 ppm or less, and it is preferred that the total content of each of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecmethylcyclononasiloxane (D9) and eicosylcyclodecasiloxane (D10) contained in the emulsion composition is 1,000 ppm or less.

[0255] The amount of the base catalyst used is preferably 0.1 to 10 equivalents, more preferably 0.2 to 5 equivalents, based on the total molar amount of the cationic surfactant as the component (B-1) and the cationic surfactant as the component (B-2).

[0256] When 0.1 equivalent or more is used relative to the total molar amount of the cationic surfactant as the component (B-1) and the cationic surfactant as the component (B-2), an emulsion composition containing a highly polymerized organopolysiloxane can be obtained in a short time.

[0257] Furthermore, when 10 equivalents or less is used relative to the total molar amount of the cationic surfactant as the component (B-1) and the cationic surfactant as the component (B-2), the stability of the emulsion composition is good, and the by-product amount of cyclic siloxane (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) etc.) can be suppressed to 1,000 ppm or less.

[0258] However, the amount of the base catalyst is not limited to the above, and if necessary, it can be outside the above range. In addition, when the content of the cyclic siloxane (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) etc.) is not particularly limited due to the use, the base catalyst used can also be the above-mentioned alkali metal hydroxide or alkaline earth metal hydroxide.

[0259] In addition, when adding an alkali catalyst to the emulsion composition, the alkali catalyst may be diluted with water in advance before use. In this case, the amount of water used for dilution is not particularly limited as long as it is within the range of 30 to 3,000 parts by mass of the component (C) relative to 100 parts by mass of the component (A). If this is done, the concentration of the alkali catalyst is appropriate, and the emulsion composition is stabilized and easy to handle.

[0260] The organopolysiloxane having silanol groups at the end as the component (A-1), the organoalkoxysilane as the component (A-2), the cationic surfactant as the component (B), and the water as the component (C-1) are prepared into a uniform emulsion composition using an emulsifier such as a homogenizer, a homodispersor, a homomixer, a colloid mill, a line mixer, etc., and the water as the component (C-2) is further added to the obtained emulsion composition as required, and then polymerization is carried out at 0 to 40° C. for 1 to 150 hours in the presence of an alkali catalyst as the component (F), and further neutralization is carried out. Then, colloidal silica as the component (D) and (C-3) water are further added as required.

[0261] In addition, the polymerization temperature is 0 to 40° C., preferably 5 to 30° C. If the polymerization temperature is 0° C. or higher, the polymerization progresses quickly and practically, the emulsion does not freeze, and the stability is good. If the polymerization temperature is 40° C. or lower, the stability of the emulsion is good, and the by-product of cyclic siloxane (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), etc.) can be suppressed to less than 1,000 ppm.

[0262] The polymerization time is 1 to 150 hours, preferably 1 to 120 hours. If it is 1 hour or longer, the polymerization is sufficient, and if it is 150 hours or shorter, it is industrially sufficient.

[0263] The polymerization reaction can be terminated by neutralizing after a specified polymerization time. Neutralization here can be performed by adding an acidic compound. Examples of the acidic compound (neutralizer) include hydrochloric acid, formic acid, acetic acid, propionic acid, lactic acid, etc., preferably hydrochloric acid, formic acid, and acetic acid. In addition, ion exchange resins can be used instead of acidic compounds for neutralization.

[0264] The high polymerization degree organopolysiloxane emulsion composition of the present invention obtained by the above method is suitable for use as a fiber treatment agent, a mold release agent, a hydrophobic agent, a cosmetic raw material, etc., and can be used to treat various fibers, leather, paper, hair, etc. to impart excellent softness, lubricity, hydrophobicity, weight, etc. In addition, examples of fibers include 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, but are not limited thereto.

[0265] The high polymerization degree organopolysiloxane emulsion composition of the present invention can be appropriately blended with various thickeners, pigments, dyes, penetrants, antistatic agents, defoamers, flame retardants, antibacterial agents, preservatives, hydrophobic agents, crosslinking agents, adhesion improvers or other silicone oils, silicone resins, silica, acrylic resins, urethane resins, etc.

[0266] The high polymerization degree organopolysiloxane emulsion composition of the present invention can form a coating after drying, and can be used by treating or impregnating the surface of various substrates such as fiber, paper, metal, wood, rubber, plastic, glass, etc. The coating method for the substrate can be various coating methods known in the art such as dipping, spraying, roller coating, rod coating, brush coating, etc.

[0267] In addition, the antiviral activity value Mv in JIS L 1922 of the high-polymerization organopolysiloxane emulsion composition of the present invention is 2.0 or more, so that it can have antiviral performance. This antiviral performance is believed to be exhibited by the cationic surfactant in the emulsion composition. In addition, the high-polymerization organopolysiloxane emulsion composition of the present invention has a film-forming ability, so by applying the emulsion composition to a target material such as a substrate to be imparted with antiviral properties to form a film, a film containing a substance that exhibits antiviral performance can be formed, so it is excellent in durability and can be expected to have long-term antiviral performance.

[0268] Example

[0269] 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 "mass %" unless otherwise specified.

[0270] [Examples 1 to 25, Comparative Examples 1 to 8]

[0271] 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. In addition, 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).

[0272] [Example 1]

[0273] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol-terminated at both ends (component (A-1-1)) and 6.0 g of triethoxyphenylsilane (component (A-2-1)) and 95% ethanol of trioctylmethylammonium chloride (component (B-1-1)) were mixed by heating at 150° C. and under a reduced pressure of 10 mmHg or less to reduce the amount of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) to less than 10 ppm (detection limit), and the active ingredient was 95% (TOMAC: Linyi Connect Chemical Technology Co., Ltd.) and 45.0 g of ion exchange water (component (C-1)), and uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion exchange water (component (C-2)) was further added, and uniformly dispersed using a homogenizer. Then, an aqueous solution of potassium hydroxide prepared by diluting 1.4 g of 85% potassium hydroxide (component (F-1)) with 60.0 g of ion exchange water (component (C-2)) was added. Then, the solution temperature was lowered to 15°C, polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 1.4 g of acetic acid. Next, 120.0 g of an aqueous dispersion (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.: containing component (C-3), the same below) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and uniformly dispersed using a homogenizer to obtain emulsion A. The nonvolatile content of emulsion A after drying at 105°C for 3 hours was 39.3%.

[0274] [Example 2]

[0275] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol-terminated at both ends (component (A-1-1)) and 6.0 g of triethoxyphenylsilane (component (A-2-1)) and 95% ethanol of trioctylmethylammonium chloride (component (B-1-1)) were mixed by heating at 150° C. and under a reduced pressure of 10 mmHg or less to reduce the amount of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) to less than 10 ppm (detection limit), and the active ingredient was 95% (TOMAC: Linyi Connect Chemical Technology Co., Ltd.) and 45.0 g of ion exchange water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion exchange water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 1.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion exchange water (component (C-2)) in advance. Then, the solution temperature was lowered to 15°C, polymerization was carried out for 24 hours, and 1.4 g of acetic acid was used to neutralize and terminate the polymerization. Next, 120.0 g of an aqueous dispersion (SNOWTEXAK-YL: manufactured by Nissan Chemical Co., Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and uniformly dispersed using a homogenizer to obtain emulsion B. The non-volatile component of emulsion B after drying at 105°C for 3 hours was 40.0%.

[0276] [Example 3]

[0277] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol-terminated at both ends (component (A-1-1)) and 6.0 g of triethoxyphenylsilane (component (A-2-1)) and 95% ethanol of trioctylmethylammonium chloride (component (B-1-1)) were mixed by heating at 150° C. and under a reduced pressure of 10 mmHg or less to reduce the amount of cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) to less than 10 ppm (detection limit), and the active ingredient was 95% (TOMAC: Linyi Connect Chemical Technology Co., Ltd.) and 45.0 g of ion exchange water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion exchange water (component (C-2)) was further added and uniformly dispersed using a homogenizer. Then, an aqueous solution of triethanolamine prepared by diluting 3.2 g of triethanolamine (component (F-3)) with 60.0 g of ion exchange water (component (C-2)) was added. Then, the solution temperature was 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 Co., Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added and uniformly dispersed using a homogenizer to obtain emulsion C. The nonvolatile content of emulsion C after drying at 105° C. for 3 hours was 40.2%.

[0278] [Example 4]

[0279] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.) 9.0 g, ion exchange water ((C-1) component) 45.0 g, and uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion, to which 330.0 g of ion exchange water ((C-2) component) was further added, and uniformly dispersed using a homogenizer, and then an ammonia aqueous solution prepared by diluting 2.2 g of a 30% ammonia aqueous solution ((F-2) component) with 60.0 g of ion exchange water ((C-2) component) was added. Then, the solution 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 Co., Ltd.) containing 30% of the active ingredient of colloidal silica ((D-1) component) was added, and uniformly dispersed using a homogenizer to obtain an emulsion D. The nonvolatile content of emulsion D after drying at 105°C for 3 hours was 40.4%.

[0280] [Example 5]

[0281] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene lauryl ether (component (E-1)) (EMULGEN 109P: manufactured by Kao Corporation), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion E. The nonvolatile content of emulsion E after drying at 105° C. for 3 hours was 42.0%.

[0282] [Example 6]

[0283] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion F. The nonvolatile content of emulsion F after drying at 105° C. for 3 hours was 42.0%.

[0284] [Example 7]

[0285] 294.0 g of an organopolysiloxane (component (A-1-2)) with a viscosity of 50,000 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion G. The nonvolatile content of emulsion G after drying at 105° C. for 3 hours was 42.0%.

[0286] [Example 8]

[0287] 294.0 g of an organopolysiloxane (component (A-1-3)) having a viscosity of 200,000 mPa·s at 25° C. and silanol-terminated at both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion H. The nonvolatile content of emulsion H after drying at 105° C. for 3 hours was 42.0%.

[0288] [Example 9]

[0289] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 2.6 g of acetic acid. Next, 30.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion I. The nonvolatile content of emulsion I after drying at 105° C. for 3 hours was 43.4%.

[0290] [Example 10]

[0291] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 2.6 g of acetic acid. Next, 100.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion J. The nonvolatile content of emulsion J after drying at 105° C. for 3 hours was 40.0%.

[0292] [Example 11]

[0293] 298.5 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (detection limit) 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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion K. The nonvolatile content of emulsion K after drying at 105° C. for 3 hours was 42.0%.

[0294] [Example 12]

[0295] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 90.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 285.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and 2.6 g of acetic acid was used to neutralize and terminate the polymerization. Next, 120.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion L. The nonvolatile content of emulsion L after drying at 105° C. for 3 hours was 42.0%.

[0296] [Example 13]

[0297] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene stearyl ether (component (E-3)) (EMULGEN 350: manufactured by Kao Corporation), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion M. The nonvolatile content of emulsion M after drying at 105° C. for 3 hours was 42.0%.

[0298] [Example 14]

[0299] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 30.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 30.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 0.4 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 0.4 g of acetic acid. Next, 120.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion N. The nonvolatile content of emulsion N after drying at 105° C. for 3 hours was 41.1%.

[0300] [Example 15]

[0301] 294.0 g of an organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25° C. and having cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) reduced to less than 10 ppm (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)), 1.5 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and an ethanol compound containing 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 1.5 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniformly dispersing using a homogenizer, 7.4 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 8.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion O. The nonvolatile content of emulsion O after drying at 105° C. for 3 hours was 44.3%.

[0302] [Example 16]

[0303] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether ((E-2) component) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water ((C-1) component) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water ((C-2) component) was further added and uniformly dispersed using a homogenizer. Then, an ammonia aqueous solution prepared by diluting 11.1 g of a 30% ammonia aqueous solution ((F-2) component) with 60.0 g of ion-exchanged water ((C-2) component) was added. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 12.9 g of acetic acid. Next, 120.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain an emulsion P. The nonvolatile content of the emulsion P after drying at 105° C. for 3 hours was 42.6%.

[0304] [Example 17]

[0305] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 22.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 25.8 g of acetic acid. Next, 120.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion Q. The nonvolatile content of emulsion Q after drying at 105° C. for 3 hours was 43.2%.

[0306] [Example 18]

[0307] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 2.6 g of acetic acid. Next, 180.0 g of an aqueous dispersion containing 20% ​​of the active ingredient of colloidal silica (component (D-2)) (SNOWTEX C, manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion R. The nonvolatile content of emulsion R after drying at 105° C. for 3 hours was 39.4%.

[0308] [Example 19]

[0309] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was raised to 30°C, 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion S. The nonvolatile content of emulsion S after drying at 105° C. for 3 hours was 42.0%.

[0310] [Example 20]

[0311] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 2 hours, and the polymerization was terminated by neutralization with 2.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion T. The nonvolatile content of emulsion T after drying at 105° C. for 3 hours was 42.0%.

[0312] [Example 21]

[0313] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 144 hours, and the polymerization was terminated by neutralization with 2.6 g of acetic acid. Next, 120.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion U. The nonvolatile content of emulsion U after drying at 105° C. for 3 hours was 42.0%.

[0314] [Example 22]

[0315] 300.0 g of an organopolysiloxane (component (A-1-4)) having a viscosity of 1,500 mPa·s at 25° C. and having a branched unit, wherein cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were previously reduced to less than 10 ppm (detection limit) by heating and mixing at 150° C. under a reduced pressure of 10 mmHg or less (in the general formula (1), R 1 =Methyl, R 2= methoxy, a = 3, b = 450, c = 1, d = 0), 9.0 g of ethanol containing 95% of the active ingredient of trioctyl methyl ammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), 9.0 g of ethanol containing 80% of the active ingredient of behenyl trimethyl ammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.) 24.0 g, ion exchange water ((C-1) component) 45.0 g, and uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion exchange water ((C-2) component) was further added, and uniformly dispersed using a homogenizer, and then an ammonia aqueous solution prepared by diluting 2.2 g of a 30% ammonia aqueous solution ((F-2) component) with 60.0 g of ion exchange water ((C-2) component) was added. Then, the solution temperature was lowered to 15°C, 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 Co., Ltd.) containing 30% of the active ingredient of colloidal silica ((D-1) component) was added, and uniformly dispersed using a homogenizer to obtain an emulsion V. The nonvolatile content of emulsion V after drying at 105°C for 3 hours was 42.0%.

[0316] [Example 23]

[0317] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol-terminated at both ends, wherein cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol product containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 98% of stearyltrimethylammonium chloride (component (B-2-2)) (Tokyo Chemical Industry Co., Ltd.) Ltd.), 8.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPONNYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution (component (F-2)) was diluted with 60.0 g of ion-exchanged water (component (C-2)) in advance. Then, the solution temperature was lowered to 15° C., 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion W. The nonvolatile content of emulsion W after drying at 105° C. for 3 hours was 41.3%.

[0318] [Example 24]

[0319] 294.0 g of an organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25° C. and having cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) reduced to less than 10 ppm (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)), 9.0 g of trioctadecylmethylammonium chloride (component (B-1-2)) containing 95% of active ingredients (manufactured by AstaTech), 8.0 g of stearyltrimethylammonium chloride (component (B-2-2)) containing 98% of active ingredients (manufactured by Tokyo Chemical Industry Co., Ltd.), and polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: NIPPON NYUKAZAI CO., LTD.) 24.0 g, ion exchange water ((C-1) component) 45.0 g, and uniformly emulsified and dispersed using a homomixer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion exchange water ((C-2) component) was further added, and uniformly dispersed using a homomixer. Then, an ammonia aqueous solution prepared by diluting 2.2 g of a 30% ammonia aqueous solution ((F-2) component) with 60.0 g of ion exchange water ((C-2) component) was added. Then, the solution temperature was lowered to 15° C., 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 Co., Ltd.) containing 30% of the active ingredient of colloidal silica ((D-1) component) was added, and uniformly dispersed using a homomixer to obtain an emulsion X. The nonvolatile content of emulsion X after drying at 105°C for 3 hours was 40.3%.

[0320] [Example 25]

[0321] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of trioctadecylmethylammonium chloride (component (B-1-2)) (manufactured by AstaTech) containing 95% of the active ingredient, and 80% of the active ingredient of behenyltrimethylammonium chloride (component (B-2-1)) in ethanol (LIPOQUAD 22-80: LION SPECIALTY CHEMICALS) CO., LTD.), 9.0 g of polyoxyethylene tridecyl ether ((E-2) component) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water ((C-1) component) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water ((C-2) component) was further added, and after uniform dispersion using a homogenizer, 2.2 g of a 30% ammonia aqueous solution ((F-2) component) was diluted with 60.0 g of ion-exchanged water ((C-2) component) in advance. Then, the solution temperature was lowered to 15° C., 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 containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion Y. The nonvolatile content of emulsion Y after drying at 105° C. for 3 hours was 41.1%.

[0322] [Comparative Example 1]

[0323] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol-terminated at both ends (component (A-1-1)) (component (A-2-1)) and 6.0 g of triethoxyphenylsilane (component (A-2-1)) (component (E-2)) (Newcol 1310: NIPPON NYUKAZAI CO., LTD.) 24.0 g, ion exchange water ((C-1) component) 45.0 g, and uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion exchange water ((C-2) component) was further added, and uniformly dispersed using a homogenizer, and then an ammonia aqueous solution prepared by diluting 2.2 g of a 30% ammonia aqueous solution ((F-2) component) with 60.0 g of ion exchange water ((C-2) component) was added. Then, the solution temperature was lowered to 15°C, 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 Co., Ltd.) containing 30% of the active ingredient of colloidal silica ((D-1) component) was added, and uniformly dispersed using a homogenizer to obtain an emulsion CA. The nonvolatile content of the emulsion CA after drying at 105°C for 3 hours was 41.1%.

[0324] [Comparative Example 2]

[0325] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homogenizer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and uniformly dispersed using a homogenizer. Then, an ammonia aqueous solution prepared by diluting 2.2 g of a 30% ammonia aqueous solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was added. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 2 hours, and the polymerization was 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 homogenizer to obtain an emulsion CB. The nonvolatile content of emulsion CB after drying at 105°C for 3 hours was 39.6%.

[0326] [Comparative Example 3]

[0327] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol groups blocking both ends, wherein the cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (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)), 9.0 g of an ethanol compound containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homomixer and a disperser to prepare an emulsion. To the emulsion, 330.0 g of ion-exchanged water (component (C-2)) was further added, and uniformly dispersed using a homomixer. Then, an ammonia aqueous solution prepared by diluting 2.2 g of a 30% ammonia aqueous solution (component (F-2)) with 60.0 g of ion-exchanged water (component (C-2)) was added. Then, the solution temperature was lowered to 15° C., polymerization was carried out for 24 hours, and the polymerization was 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 to obtain an emulsion CC. The nonvolatile content of emulsion CC after drying at 105°C for 3 hours was 39.6%.

[0328] [Comparative Example 4]

[0329] 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and silanol-terminated at both ends (component (A-1-1)) (component (A-2-1)) and 6.0 g of triethoxyphenylsilane (component (A-2-1)) (component (E-2)) (Newcol 1310: NIPPON NYUKAZAI CO., LTD.) 24.0g, ion exchange water ((C-1) component) 45.0g, using a homogenizer and a disperser to uniformly emulsify and disperse, thereby preparing an emulsion, further adding ion exchange water ((C-2) component) 330.0g to the emulsion, after uniformly dispersing using a homogenizer, adding an ammonia aqueous solution prepared by diluting 2.2g of a 30% ammonia aqueous solution ((F-2) component) with 60.0g of ion exchange water ((C-2) component) in advance. Then, the solution temperature was lowered to 15°C, polymerization was carried out for 24 hours, and the polymerization was terminated by neutralization with 2.6g of acetic acid. Next, ion exchange water ((C-3) component) 84.0g was added, and uniformly dispersed using a homogenizer to obtain an emulsion CD. The non-volatile component of emulsion CD after drying at 105°C for 3 hours was 38.6%.

[0330] [Comparative Example 5]

[0331] An attempt was made to prepare an emulsion by uniformly emulsifying and dispersing 294.0 g of an organopolysiloxane (component (A-1-1)) with a viscosity of 1,500 mPa·s at 25° C. and cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) at 150° C. and having a viscosity of 1,500 mPa·s at 25° C., 6.0 g of triethoxyphenylsilane (component (A-2-1)), 120.0 g of an ethanol product (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)), and 45.0 g of ion-exchanged water (component (C-1)) using a homomixer and a disperser, but separation was rapid and a uniform emulsion could not be obtained, so the emulsion was not evaluated.

[0332] [Comparative Example 6]

[0333] 300.0 g of dimethylpolysiloxane (component (A-3)) with a viscosity of 1,500 mPa·s at 25° C. and trimethylsilyl-terminated dimethylpolysiloxane (component (A-3)) in which cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were reduced to less than 10 ppm (detection limit) by heating at 150° C. and under a reduced pressure of 10 mmHg or less, 9.0 g of ethanol containing 95% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.), and 80% of the active ingredient of docosyltrimethylammonium chloride (component (B-2-1)) (LIPOQUAD 22-80: manufactured by Lion Specialty Chemicals Co., Ltd.) were mixed in advance at 150° C. and under a reduced pressure of 10 mmHg or less, and 9.0 g of ethanol containing 80% of the active ingredient of trioctylmethylammonium chloride (component (B-1-1)) (TOMAC: manufactured by Linyi Connect Chemical Technology Co., Ltd.) were mixed in advance. LTD.), 9.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPONNYUKAZAI CO., LTD.), 24.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homomixer and a disperser to prepare an emulsion, and 390.0 g of ion-exchanged water (component (C-2)) was further added to the emulsion and uniformly dispersed using a homomixer. Then, 120.0 g of an aqueous dispersion of colloidal silica (component (D-1)) containing 30% of the active ingredient (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion CE. The nonvolatile content of emulsion CE after drying at 105° C. for 3 hours was 41.9%.

[0334] [Comparative Example 7]

[0335] 300.0 g of dimethylpolysiloxane (component (A-3)) having a viscosity of 1,500 mPa·s at 25° C. and having a viscosity of 1,500 mPa·s at both ends and having cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) reduced to less than 10 ppm (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 NIPPONNYUKAZAI CO., LTD.), and 45.0 g of ion-exchanged water (component (C-1)) were uniformly emulsified and dispersed using a homomixer and a disperser to prepare an emulsion, and 390.0 g of ion-exchanged water (component (C-2)) was further added to the emulsion and uniformly dispersed using a homomixer. Then, 120.0 g of an aqueous dispersion containing 30% of the active ingredient of colloidal silica (component (D-1)) (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) was added and uniformly dispersed using a homomixer to obtain emulsion CF. The nonvolatile content of emulsion CF after drying at 105° C. for 3 hours was 41.0%.

[0336] [Comparative Example 8]

[0337] 300.0 g of an organopolysiloxane (component (A-1-1)) having a viscosity of 1,500 mPa·s at 25° C. and having silanol groups capped at both ends and having a viscosity of 1,500 mPa·s, (component (A-1-1)) and a reduced pressure of 10 mmHg or less and heated and mixed at 150° C. under 150° C., 6.0 g of polyoxyethylene tridecyl ether (component (E-2)) (Newcol 1310: manufactured by NIPPON NYUKAZAICO., LTD.), 10.5 parts of sodium dodecylbenzenesulfonate as an anionic surfactant, and 18.0 g of ion-exchanged water (component (C-1)) were emulsified using a homodisper. 254.7 g of ion exchange water (component (C-2)) was further added to the emulsion, and after being uniformly dispersed using a homogenizer, 3.6 g of concentrated hydrochloric acid was added as an acid catalyst. Then, the solution temperature was lowered to 10°C, polymerization was carried out for 22 hours, and 7.2 g of triethanolamine was used for neutralization to terminate the polymerization. Next, 120.0 g of an aqueous dispersion (SNOWTEX AK-YL: manufactured by Nissan Chemical Co., Ltd.) containing 30% of the active ingredient of colloidal silica (component (D-1)) was added, and an attempt was made to uniformly disperse it using a homogenizer, but it was quickly separated and a uniform emulsion could not be obtained, so the emulsion was not evaluated.

[0338] [Evaluation of lotion]

[0339] 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 by the following evaluation methods. The results are shown in Tables 1 to 3.

[0340] In addition, each of the obtained emulsion compositions was weighed into a 15 cm × 10 cm PP (polypropylene) tray so that the non-volatile component was 8.0 g, and dried at 25°C for 48 hours to volatilize the water. As a result, Examples 1 to 25 and Comparative Example 3 formed a rubber-like film, and Comparative Examples 1, 2, and 4 were liquids with fluidity. In the column "Extraction viscosity (mPa·s)" of Tables 1 to 3, the extraction viscosity is shown for the emulsions whose viscosity can be measured by the following method, and the property state of the film is shown for the emulsions whose viscosity cannot be measured.

[0341] [Viscosity of extracted organopolysiloxane]

[0342] 300 g of each emulsion composition was added to 2 L of IPA while stirring, the emulsion was broken to extract the organopolysiloxane, and the organopolysiloxane was dried at 105° C. for 3 hours and then measured using a BM type rotational viscometer (TVB-10M) at 25° C. In addition, the viscosity of the substance that could not be measured even when using the rotor M4 (measurement upper limit viscosity 2,000,000 mPa·s) that can measure the highest viscosity in the BM type rotational viscometer, the substance that was entangled in the rotor of the BM type rotational viscometer and could not be measured, or the substance that was insoluble in toluene and could not be measured was 300,000 mPa·s or more.

[0343] [Average particle size of emulsion]

[0344] This is a particle size at a cumulative value of 50% in a volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer (Partica LA-960 manufactured by HORIBA Ltd.).

[0345] [Content of cyclic siloxane]

[0346] 0.1 g of each emulsion composition was extracted with 10 mL of acetone containing 20 ppm (mass) of tetradecane as an internal standard (vibrated for 3 hours) and then left overnight. Then, the acetone layer was used to quantify (mass conversion value) cyclic siloxanes (hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecmethylcyclononasiloxane (D9) and eicosylcyclodecasiloxane (D10)) by gas chromatography (Agilent 7890B (manufactured by Agilent Technologies)).

[0347] [Film forming properties]

[0348] Each emulsion composition was weighed into a 15 cm×10 cm PP (polypropylene) tray so that the nonvolatile component was 8.0 g, and dried at 25° C. for 48 hours and then at 105° C. for 1 hour to evaluate whether a film was formed.

[0349] A: A uniform coating was formed, and the coating had a strength sufficient to be easily peeled off from the disposable tray.

[0350] B: A uniform coating was formed, but the coating could not be peeled off from the disposable tray, or the coating was deformed during peeling.

[0351] C: A uniform film was not formed.

[0352] [Evaluation of physical properties of coating]

[0353] The hardness (C-type durometer hardness), tensile strength and elongation during cutting of the film prepared above were measured in accordance with JIS K6249. The evaluation results are collectively recorded in Tables 1 to 3.

[0354] [Storage stability of emulsion (25°C)]

[0355] 100 g of each emulsion composition was put into a glass bottle and stored in a thermostatic chamber at 25° C. The appearance was visually observed and the nonvolatile components of the upper and lower layers were measured after 3, 6, and 12 months. The storage stability was evaluated according to the following evaluation criteria.

[0356] (Evaluation Criteria)

[0357] A: No separation of light and dark colors was observed in either the upper layer or the lower layer.

[0358] B: Slight separation of light and dark was observed between the upper layer and the lower layer.

[0359] C: Completely separated into two layers.

[0360] [Storage stability of emulsion (40°C)]

[0361] 100 g of each emulsion composition was put into a glass bottle and stored in a thermostatic chamber at 40° C. for 30 days. The appearance was visually observed and the nonvolatile components in the upper and lower layers were measured. Storage stability was evaluated according to the following evaluation criteria.

[0362] (Evaluation Criteria)

[0363] A: No separation of light and dark colors was observed in either the upper layer or the lower layer.

[0364] B: Slight separation of light and dark was observed between the upper layer and the lower layer.

[0365] C: Completely separated into two layers.

[0366] [Table 1]

[0367]

[0368] [Table 2]

[0369]

[0370] [Table 3]

[0371]

[0372] In the column of “Extracted viscosity (mPa·s)” in Tables 1 to 3, “rubber-like” means that the viscosity cannot be measured by the above method, the property state of the coating is rubber-like, and the viscosity at 25° C. is 300,000 mPa·s or more.

[0373] As shown in Tables 1 and 2, the emulsion compositions of the film-forming organopolysiloxane (high polymerization degree organopolysiloxane) of the present invention of Examples 1 to 25 have the ability to form a strong film and are also excellent in storage stability.

[0374] In contrast, as shown in Table 3, in Comparative Examples 1 and 4 in which no cationic surfactant was used, the viscosity of the extracted organopolysiloxane was low and the molecular weight was low, so the film forming property was poor. In Comparative Examples 2 and 3 in which a cationic surfactant was used but colloidal silica was not used, the viscosity of the extracted organopolysiloxane was high, but in Comparative Example 2, the viscosity at 25°C was less than 300,000 mPa·s, and a uniform film was not formed. In Comparative Example 3, the viscosity was sufficient, but the hardness and tensile strength of the film were insufficient. In Comparative Example 5 in which the (B) component was excessively blended, the emulsion was unstable and a uniform emulsion could not be obtained. In Comparative Examples 6 and 7 in which a low-viscosity dimethylpolysiloxane with trimethylsilyl groups capped at both ends that could not be polymerized (condensation polymerization by dehydration or dealcoholization) was used instead of the (A) component of the present invention, although silica was contained, a film having sufficient physical properties could not be obtained even if a cationic surfactant was used alone or even if a nonionic surfactant was further combined. In Comparative Example 8, in which an anionic surfactant with a strong catalytic effect was used instead of a cationic surfactant, high-viscosity anionic emulsion polymerization was performed at a lower temperature (10° C.), but the addition of colloidal silica made the emulsion unstable and a uniform emulsion could not be obtained. Therefore, the emulsion compositions obtained by the compositions of Comparative Examples 1 to 8 could not obtain a uniform emulsion at all, or a film was not formed, or even if a film was formed, the film strength was weak.

[0375] In addition, the emulsion A of Example 1 prepared using potassium hydroxide as the alkaline catalyst (F) has a content of cyclic siloxanes D4 to D6 greater than 5000 mass ppm, but the obtained film has good physical properties (hardness, tensile strength, and elongation when cut) and storage stability. Thus, even if the emulsion composition of the present invention has residual low molecular weight cyclic siloxane, the obtained film has good physical properties and storage stability, and the process of removing low molecular weight cyclic siloxane can be omitted, so that the manufacturing cost can be reduced.

[0376] In contrast, in the emulsion B of Example 2 prepared using ammonia as the (F) alkaline catalyst, the content of cyclic siloxanes D4 to D6 is greatly reduced to less than 200 mass ppm, and the physical properties and storage stability of the obtained coating are good. It can be seen that by the method for manufacturing the emulsion composition of the present invention, by using the organic polysiloxane in which the ends of the low molecular weight cyclic siloxanes are preliminarily reduced by alkoxy groups or / and the ends are blocked by silanol groups in combination with an appropriate alkaline catalyst, not only can the respective contents of cyclic siloxanes D4 to D6 contained in the obtained emulsion composition be made less than 1000 ppm, but also the respective contents of cyclic siloxanes D3 to D10 contained in the emulsion composition can be easily made less than 1,000 ppm in total. Therefore, the emulsion composition of the present invention and its method for manufacturing the same have high industrial application value.

[0377] [Antiviral performance test of treated cloth]

[0378] Ion exchange water was added to emulsion compositions F and Z and diluted to 1% solid content to prepare test solutions. Standard cotton cloth for antiviral performance test was immersed in the test solution for 10 seconds, then wrung out with a roller at a wringing rate of 100%, and dried at 150°C for 2 minutes to prepare each test cloth. The antiviral performance test was performed on each test cloth using the following test method. The specifications / standards are shown in Table 4, and the results are shown in Table 5.

[0379] [Test method] JIS L 1922: 2016

[0380] Method for determining virus titer: plaque assay

[0381] [Test virus] Influenza A virus

[0382] (H3N2): ATCC VR-1679

[0383] [Table 4]

[0384]

[0385] [Table 5]

[0386]

[0387] It can be confirmed from the above table that lotion F has antiviral properties.

[0388] [Industrial Applicability]

[0389] The film-forming organopolysiloxane emulsion composition of the present invention can provide a film-forming organosilicone emulsion composition and a film having good film-forming properties, excellent strength of the film after curing, and good storage stability of the emulsion. In addition, since the content of the cyclic siloxane can be extremely low, when a substrate or the like is subjected to a heat treatment, there is no need to worry about the cyclic siloxane volatilizing and contaminating the inside of the device, or the cyclic siloxane and the cyclic siloxane-derived silica powder causing contamination of the product itself, so the film-forming organopolysiloxane emulsion composition of the present invention is useful in industry and has excellent versatility. Therefore, in addition to a fiber treatment agent, it can also be widely used in a mold release agent or a hydrophobic agent, a cosmetic, a hair cosmetic, and the like.

[0390] This specification contains the following protocols.

[0391] [1] An emulsion composition of a film-forming organopolysiloxane, characterized in that it contains the following (A) to (D):

[0392] (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 hydroxyl groups bonded to silicon atoms in one molecule, wherein the organopolysiloxane (A) is 100 parts by mass;

[0393] [Chemical formula 9]

[0394]

[0395] In formula (1), R 1 are independently a hydrogen atom, or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, 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, wherein 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 of 0 to 2,000, and these are values ​​satisfying that the viscosity of the organopolysiloxane at 25° C. is 300,000 mPa·s or more;

[0396] (B) a cationic surfactant, which is 0.1 to 30 parts by weight;

[0397] (C) water, 30 to 3,000 parts by mass;

[0398] (D) Colloidal silica, in an amount of 0.5 to 50 parts by mass.

[0399] [2] The film-forming organopolysiloxane emulsion composition according to [1], wherein the cationic surfactant (B) comprises either or both of the following (B-1) and (B-2):

[0400] (B-1)Q 1 3(CH3)N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0401] (B-2)Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0402] Q 1 is a monovalent organic group having 6 to 30 carbon atoms of the same or different types, 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; wherein the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

[0403] [3] The film-forming organopolysiloxane emulsion composition according to [1] or [2], further comprising 0.1 to 30 parts by mass of (E) a nonionic surfactant per 100 parts by mass of the component (A).

[0404] [4] The film-forming organopolysiloxane emulsion composition according to [3], wherein the (E) nonionic surfactant is a compound represented by the following formula:

[0405] R 3 O(EO) p (PO) q H

[0406] In the formula, R 3 It is a straight-chain or branched alkyl group having 8 to 30 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random; p and q are independently integers of 0 to 100, wherein p+q>0.

[0407] [5] The film-forming organopolysiloxane emulsion composition according to any one of [1] to [4], wherein the particle surface of the colloidal silica (D) is treated with an oxide of a metal other than silicon.

[0408] [6] The film-forming organopolysiloxane emulsion composition according to any one of [1] to [5], further comprising a salt composed of a basic substance and an acidic substance, wherein the basic substance is composed of either or both of ammonia and an organic amine.

[0409] [7] The emulsion composition of a film-forming organopolysiloxane as described in any one of [1] to [6], characterized in that the content of each of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) contained in the emulsion composition is 1,000 ppm or less.

[0410] [8] The emulsion composition of a film-forming organopolysiloxane according to any one of [1] to [7], characterized in that the total content of each of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecylcyclononasiloxane (D9) and eicosylcyclodecasiloxane (D10) contained in the emulsion composition is 1,000 ppm or less.

[0411] [9] The film-forming organopolysiloxane emulsion composition according to any one of [1] to [8], wherein the average particle size of the emulsion contained in the emulsion composition is 1 μm or less.

[0412]

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

[0413]

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

[10] , wherein the antiviral activity value Mv of the emulsion composition according to JIS L 1922 is 2.0 or more.

[0414]

[12] A method for producing an emulsion composition of a film-forming organopolysiloxane, which is a method for producing an emulsion composition of a film-forming organopolysiloxane according to [1], characterized in that it comprises the following steps (I) to (III), and after step (I), steps (II) and (III) are carried out in any order or simultaneously,

[0415] and adding the water (C) in an amount of 30 to 3,000 parts by weight of the total amount of the following (C-1), (C-2) and (C-3);

[0416] (I) a step of emulsifying a mixture comprising the following components (A-1), (A-2), (B) and (C-1) to prepare an emulsion composition;

[0417] (A-1) an organopolysiloxane having a viscosity of 300,000 mPa·s or less at 25° C. and terminally blocked with an alkoxy group or / and terminally blocked with a silanol group;

[0418] (A-2) an alkoxysilane represented by the following formula (3);

[0419] R 4 e Si(OR 5 ) 4-e (3)

[0420] In formula (3), R 4 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, R 5 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms; e is 0 or 1;

[0421] In addition, the total amount 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;

[0422] (B) a cationic surfactant, which is 0.1 to 30 parts by weight;

[0423] (C-1) water, 30 to 3,000 parts by mass;

[0424] (II) further adding (C-2) water to the obtained emulsion composition as needed, polymerizing at 0 to 40° C. for 1 to 150 hours in the presence of (F) a basic catalyst, and further neutralizing the mixture;

[0425] (III) A step of further adding 0.5 to 50 parts by mass of (D) colloidal silica and, if necessary, further adding (C-3) water.

[0426]

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

[12] , wherein either ammonia or an organic amine or both are used as the (F) basic catalyst.

[0427]

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

[12] or

[13] , characterized in that one or both of the following (B-1) and (B-2) are used as the (B) cationic surfactant,

[0428] (B-1)Q1 3(CH3)N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0429] (B-2)Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented is 0 to 30 parts by mass;

[0430] Q 1 is a monovalent organic group having 6 to 30 carbon atoms of the same or different types, 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, and the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

[0431]

[15] A method for producing an emulsion composition of a film-forming organopolysiloxane as described in any one of

[12] to

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

[0432]

[16] The 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 the component (E):

[0433] R 3 O(EO) p (PO) q H

[0434] In the formula, R 3 It is a straight-chain or branched alkyl group having 8 to 30 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random; p and q are independently integers of 0 to 100, wherein p+q>0.

[0435]

[17] A method for producing an emulsion composition of a film-forming organopolysiloxane as described in any one of

[12] to

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

[0436]

[18] A method for producing an emulsion composition of a film-forming organopolysiloxane as described in any one of

[12] to

[17] , characterized in that a compound containing octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in an amount of 1,000 ppm or less is used as the component (A-1).

[0437]

[19] A method for producing an emulsion composition of a film-forming organopolysiloxane as described in any one of

[12] to

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

[0438]

[20] A method for producing an emulsion composition of a film-forming organopolysiloxane as described in any one of

[12] to

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

[0439] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are examples, and all technical solutions having substantially the same configuration and achieving the same technical effects as the technical concept described in the claims of the present invention are included in the technical scope of the present invention.

Claims

1. An emulsion composition of a film-forming organopolysiloxane, characterized in that: It is composed of the following (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 hydroxyl groups bonded to silicon atoms in one molecule, wherein the organopolysiloxane (A) is 100 parts by mass; [Chemical formula 1] In formula (1), R 1 are independently a hydrogen atom, or an unsubstituted or substituted monovalent organic group having 1 to 20 carbon atoms, 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, wherein 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 of 0 to 2,000, and these are values ​​satisfying that the viscosity of the organopolysiloxane at 25° C. is 300,000 mPa·s or more; (B) a cationic surfactant, which is 0.1 to 30 parts by weight; (C) water, 30 to 3,000 parts by mass; (D) Colloidal silica, in an amount of 0.5 to 50 parts by mass.

2. The film-forming organopolysiloxane emulsion composition according to claim 1, characterized in that The cationic surfactant (B) comprises any one or both of the following (B-1) or (B-2), (B-1)Q 1 3(CH3)N + ·X - The cationic surfactant represented is 0 to 30 parts by mass; (B-2)Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented is 0 to 30 parts by mass; Q 1 is a monovalent organic group having 6 to 30 carbon atoms of the same or different types, 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; wherein the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

3. The film-forming organopolysiloxane emulsion composition according to claim 1, characterized in that: The (E) nonionic surfactant is further contained in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the (A) component.

4. The film-forming organopolysiloxane emulsion composition according to claim 3, characterized in that The (E) nonionic surfactant is a compound represented by the following formula: R 3 O(EO) p (PO) q H In the formula, R 3 It is a straight-chain or branched alkyl group having 8 to 30 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random; p and q are independently integers of 0 to 100, wherein p+q>0.

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

6. The film-forming organopolysiloxane emulsion composition according to claim 1, wherein The compound further contains a salt composed of a basic substance and an acidic substance, wherein the basic substance is composed of either or both of ammonia and an organic amine.

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

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

9. The film-forming organopolysiloxane emulsion composition according to claim 1, characterized in that: 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 claim 9, characterized in that: The average particle size of the emulsion contained in the emulsion composition is 500 nm or less.

11. The film-forming organopolysiloxane emulsion composition according to claim 1, characterized in that: The emulsion composition has an antiviral activity value Mv in accordance with JIS L 1922 of 2.0 or more.

12. A method for producing an emulsion composition of a film-forming organopolysiloxane, which is a method for producing the emulsion composition of a film-forming organopolysiloxane according to claim 1, characterized in that: The method comprises the following steps (I) to (III), and after step (I), steps (II) and (III) are carried out in any order or simultaneously. and adding the water (C) in an amount of 30 to 3,000 parts by weight of the total amount of the following (C-1), (C-2) and (C-3), (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) an organopolysiloxane having a viscosity of 300,000 mPa·s or less at 25° C. and terminally blocked with an alkoxy group or / and terminally blocked with a silanol group; (A-2) an alkoxysilane represented by the following formula (3), R 4 e Si(OR 5 ) 4-e (3) In formula (3), R 4 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, R 5 are independently a hydrogen atom, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms; e is 0 or 1, In addition, the total amount 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) a cationic surfactant, which is 0.1 to 30 parts by weight; (C-1) water, 30 to 3,000 parts by mass; (II) further adding (C-2) water to the obtained emulsion composition as needed, polymerizing at 0 to 40° C. for 1 to 150 hours in the presence of (F) a basic catalyst, and further neutralizing the mixture. (III) A step of further adding 0.5 to 50 parts by mass of (D) colloidal silica and, if necessary, further adding (C-3) water.

13. The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein: As the (F) basic catalyst, either ammonia or an organic amine or both are used.

14. The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein: Using any one or both of the following (B-1) or (B-2) as the (B) cationic surfactant, (B-1)Q 1 3(CH3)N + ·X - The cationic surfactant represented is 0 to 30 parts by mass; (B-2)Q 2 α (CH3) 4-α N + ·X - The cationic surfactant represented is 0 to 30 parts by mass; Q 1 is a monovalent organic group having 6 to 30 carbon atoms of the same or different types, 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, and the total amount of (B-1) and (B-2) is 0.1 to 30 parts by mass.

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), 0.1 to 30 parts by mass of (E) a nonionic surfactant is further added to 100 parts by mass of the total of (A-1) and (A-2).

16. The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 15, wherein: As the component (E), a nonionic surfactant represented by the following formula is used: R 3 O(EO) p (PO) q H In the formula, R 3 It is a straight-chain or branched alkyl group having 8 to 30 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group, and their arrangement may be block-shaped or random; p and q are independently integers of 0 to 100, wherein p+q>0.

17. The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein: As the component (D), colloidal silica whose particle surfaces are treated with an oxide of a metal other than silicon is used.

18. The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein: As the component (A-1), a compound containing octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) in an amount of 1,000 ppm or less is used.

19. The method for producing an emulsion composition of a film-forming organopolysiloxane according to claim 12, wherein: 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 claim 12, wherein: The total content of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8), octadecamethylcyclononasiloxane (D9), and eicosylcyclodecasiloxane (D10) contained in the emulsion composition is 1,000 ppm or less.

Images