JP6149788B2 - Film-forming silicone emulsion composition and film - Google Patents

Description

  The present invention relates to a silicone emulsion composition, and particularly to a film-forming silicone emulsion composition and a film that do not contain an organic tin compound and an inorganic tin compound as a curing catalyst.

  Regarding silicone emulsion compositions that form rubber films, those having various compositions have been conventionally known and are used as binders, weatherstrip agents, air bag coating agents, and the like.

  For example, an anionically stabilized hydroxylated diorganopolysiloxane, colloidal silica and a silicone emulsion composition comprising an organic tin compound or an organic amine compound (Japanese Patent Laid-Open No. 56-16553: Patent Document 1), dimethylsiloxane unit A silicone latex composition comprising a siloxane block copolymer comprising water and a monophenylsiloxane unit, water, a cationic surfactant, a filler, and an aminosilane (US Pat. No. 3,817,894: Patent Document 2), hydroxyl group Silicone emulsion composition comprising Si-H group-containing organopolysiloxane, Si-H group-containing organopolysiloxane, colloidal silica, amide group- and carboxyl group-containing silane, epoxy group-containing silane, and curing catalyst (JP-A-8-85760) : Patent Document 3), alkenyl group-containing organopolysiloxane, Si-H group-containing organopolysiloxane, colloidal silica, a reaction product of aminosilane and acid anhydride, epoxysilane, and addition reaction catalyst No. 9-208826: Patent Document 4), silicone emulsion composition comprising colloidal silica-silicone core shell, curing catalyst, emulsifier and water (Japanese Patent Laid-Open No. 9-208901: Patent Document 5), hydroxyl group-containing organopolysiloxane , Colloidal silica, amide group and carboxyl group-containing silane, epoxy group-containing silane, a curing catalyst and a photocatalytic oxide silicone emulsion composition (Japanese Patent Laid-Open No. 2002-363494: Patent Document 6) and the like have been proposed. .

  As functional group-containing silanes to be used for these, amino group-containing silanes, epoxy group-containing silanes, amide groups and carboxyl group-containing silanes, or combinations of these are shown. These functional group-containing silanes, colloidal silica that is a film reinforcing agent, and organotin compounds as curing catalysts are blended with silicone latex to have rubber strength and various agents such as deodorants and antibacterial agents for fiber base materials. It is possible to form a silicone film with improved adhesion.

  However, organotin compounds are becoming more restrictive and restricted by use, field, and country due to their toxicity problems.The replacement of dibutyltin compounds with octyltin compounds, and further changes from octyltin compounds to inorganic tin compounds, and others An alternative to metal compounds is needed.

  As curing catalysts other than tin compounds, bismuth compounds, titanium compounds and the like have been proposed. In the bismuth compound, it is described that a divalent bismuth carboxylate is effective as a curing catalyst for a polyoxyalkylene polymer having a hydrolyzable silicon group (Japanese Patent Laid-Open No. 2000-129126: Patent Document 7). ). As a titanium compound, a moisture curable composition comprising a hydrolyzable silyl group-containing organic polymer and titanium tetra (2-ethylhexanoate) has been proposed (Japanese Patent Laid-Open No. 2003-147220: Patent Document 8). .

  However, the bismuth compound has a problem that it is necessary to use the Si-H group-containing organopolysiloxane together, and the titanium compound has a problem that the curing rate is slow. For this reason, the composition which does not contain an organotin compound is also proposed. Silicone emulsion composition comprising hydroxyl group-containing organopolysiloxane, colloidal silica, amide group and carboxyl group-containing silane, and epoxy group-containing silane (Japanese Patent Laid-Open No. 2008-231276: Patent Document 9), hydroxy group-containing organopolysiloxane, colloidal A silicone emulsion composition composed of silica, an aminoxy group-containing organosilicon compound, an ionic emulsifier, a nonionic emulsifier, and water (International Publication No. 2012/002571: Patent Document 10) has been proposed. However, when the composition is used as a binder for deodorants, antibacterial agents, etc., a problem has been pointed out that the water absorption on the fiber surface after washing is lowered.

JP 56-16553 A US Pat. No. 3,817,894 JP-A-8-85760 JP-A-9-208826 JP-A-9-208901 JP 2002-363494 A JP 2000-129126 A JP 2003-147220 A JP 2008-231276 A International Publication No. 2012/002571

  In view of the above-mentioned problems of the prior art, the present invention has a good film-forming property without using an organic tin compound and an inorganic tin compound, and is excellent in the strength and flexibility of a film after curing. When a film having good adhesion is formed and a film is formed on the fiber surface, a decrease in water absorption on the fiber surface after washing is small, and a silicone emulsion composition having a good emulsion storage stability and film The purpose is to provide.

  As a result of diligent study to achieve the above-mentioned object, the present inventor has studied various functional group-containing silanes. As a result, by adding a specific long-chain alkyl group-containing organoalkoxysilane to the emulsion composition, an organotin compound In addition, it exhibits good film-formability without using inorganic tin compounds, has excellent strength and flexibility of the film after curing, and has good adhesion to various substrates. When formed, it was found that the decrease in water absorption on the fiber surface after washing can be reduced, and that the storage stability of the emulsion can be further improved, and the present invention has been made.

（式中、ａは１０〜１０，０００の整数であり、ｂは０〜１，０００の整数であり、ｃは０〜１，０００の整数である。）
で表されるものから選択される[１]記載の皮膜形成性シリコーンエマルション組成物。
[３]．（Ｃ）成分が、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、デシルトリメトキシシラン、デシルトリエトキシシランである[１]又は[２]記載の皮膜形成性シリコーンエマルション組成物。
[４]．繊維処理剤である[１]〜[３]のいずれかに記載の皮膜形成性シリコーンエマルション組成物。
[５]．[１]〜[３]のいずれかに記載の皮膜形成性シリコーンエマルション組成物を硬化させてなる皮膜。 Accordingly, the present invention provides the following silicone emulsion composition and film.
[1]. (A) The following general formula (2)
X ₃ SiO— (R ⁴ ₂ SiO) _a — (Y ₂ SiO) _b —SiX ₃ (2)
( Wherein R ⁴ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, the number of carbon atoms. An aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, Y is a group represented by X or — (O—X ₂ Si) _c —X, and R ⁴ , X, Y May be the same or different, a is an integer of 10 to 10,000, b is an integer of 0 to 1,000, and c is an integer of 0 to 1,000. , X, Y, b, and c are selected to contain at least two hydroxyl groups bonded to a silicon atom in one molecule, and the ends are blocked with hydroxyl groups.)
In indicated the organopolysiloxane containing hydroxyl group attached to at least two silicon atoms in one molecule 100 parts by weight,
(B) Surfactant: 0.1 to 50 parts by mass (C) Long-chain alkyl group-containing organoalkoxysilane represented by the following general formula (1): 1 to 15 parts by mass,
R ¹ _x R ² _y Si (OR ³ ) _4-xy (1)
(Wherein R ¹ is a monovalent alkyl group having 6 to 15 carbon atoms, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ³ is a monovalent alkyl group having 1 to 6 carbon atoms. R ^{1 to} R ³ may be the same or different from each other, x is an integer of 1 to 3, y is an integer of 0 to 2, and x + y is an integer of 1 to 3.
(D) Colloidal silica: 0.5 to 50 parts by mass, and (E) water: 50 to 500 parts by mass, and does not contain an organic tin compound and an inorganic tin compound. object.
[2].
(A) component is a following formula

(In the formula, a is an integer of 10 to 10,000, b is an integer of 0 to 1,000, and c is an integer of 0 to 1,000.)
[1] The film-forming silicone emulsion composition described in [1].
[3]. The film-forming silicone according to [1] or [2] , wherein the component (C) is hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane. Emulsion composition.
[4]. The film-forming silicone emulsion composition according to any one of [1] to [3], which is a fiber treatment agent.
[5]. [1] A film formed by curing the film-forming silicone emulsion composition according to any one of [3] .

Hereinafter, the present invention will be described in detail.
The silicone emulsion composition of the present invention contains the above components (A) to (E) in a specific amount.
Component (A) The organopolysiloxane of the component (A) is not particularly limited as long as it contains a hydroxyl group bonded to at least two silicon atoms in one molecule, one type alone or two or more types. They can be used in appropriate combinations. Especially, what is shown by following General formula (2) is preferable.
X ₃ SiO— (R ⁴ ₂ SiO) _a — (Y ₂ SiO) _b —SiX ₃ (2)
(Wherein R ⁴ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, the number of carbon atoms. An aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, Y is a group represented by X or — (O—X ₂ Si) _c —X, and R ⁴ , X, Y May be the same or different, a is an integer of 10 to 10,000, b is an integer of 0 to 1,000, and c is an integer of 0 to 1,000. , X, Y, b, and c are selected so that each molecule contains at least two hydroxyl groups bonded to silicon atoms.

R ⁴ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. , Heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; cyclopentyl, cyclohexyl, cycloheptyl; phenyl, tolyl, naphthyl, or these groups And a group in which part or all of the hydrogen atoms to be substituted are substituted with a halogen atom, an amino group, a cyano group, or the like. Of these, a methyl group is preferable.

  X 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. Specifically, in addition to the hydroxyl group, a methyl group , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; phenyl group, Tolyl group, naphthyl group; methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group or a part of hydrogen atoms bonded to these groups or Examples thereof include groups that are all substituted with halogen atoms, amino groups, cyano groups, and the like.

Y is a group represented by X or — (O—X ₂ Si) _c —X. R ⁴ , X and Y may be the same or different.

  a is an integer of 10 to 10,000, preferably an integer of 100 to 10,000, more preferably an integer of 1,000 to 5,000. When a is less than 10, the flexibility of the silicone rubber film may be poor, and when it is more than 10,000, the tensile strength of the film may decrease.

  b is an integer of 0 to 1,000, preferably an integer of 0 to 200. c is an integer of 0 to 1,000, preferably an integer of 0 to 200. However, the above X, Y, b and c are selected from the viewpoint of curability so as to contain at least two, preferably 2-3 hydroxyl groups, bonded to a silicon atom in one molecule. The

  Specific examples of the organopolysiloxane of component (A) in the present invention include the following.

（式中、ａは１０〜１０，０００の整数であり、ｂは０〜１，０００の整数であり、ｃは０〜１，０００の整数である。）

(In the formula, a is an integer of 10 to 10,000, b is an integer of 0 to 1,000, and c is an integer of 0 to 1,000.)

Among them, the average composition formula is preferably represented by HO [(CH ₃ ) ₂ SiO _2/2 ] _d [C ₆ H ₅ SiO _3/2 ] _e , and d / e (molar ratio) is 100/0. 0.05 to 0.5 is preferable.

  The organopolysiloxane of component (A) can be synthesized by a known method. For example, in the presence of a catalyst such as an alkali metal hydroxide, a cyclic siloxane such as octamethylcyclotetrasiloxane, or an α, ω-dihydroxysiloxane oligomer, an α, ω-dialkoxysiloxane oligomer, or an organoalkoxysilane. Obtained by equilibration reaction. It can also be obtained by subjecting α, ω-dihydroxydimethylpolysiloxane and organoalkoxysilane to dehydration and dealcoholization condensation in the presence of a catalyst such as an alkali metal hydroxide. Examples of the organoalkoxysilane include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane.

  Since the organopolysiloxane of component (A) is preferably used in the form of an oil-in-water emulsion, it may be made into an emulsion by a known emulsion polymerization method. Therefore, the cyclic siloxane, α, ω- Dihydroxysiloxane oligomer, α, ω-dialkoxysiloxane oligomer, or organoalkoxysilane, etc. are emulsified and dispersed in water using a surfactant such as an anionic surfactant or a cationic surfactant, and then as necessary. It can be easily synthesized by carrying out an emulsion polymerization reaction by adding a catalyst such as an acid or an alkaline substance. In this case, the solid content concentration of the component (A) in the emulsion is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.

(B) component (B) A component can also be mix | blended as a surfactant at the time of preparing the organopolysiloxane emulsion of the said (A) component. There is no restriction | limiting in particular as surfactant of (B) component, It can use individually by 1 type or in combination of 2 or more types. Examples of the surfactant include nonionic surfactants and anionic surfactants.

  Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan alkyl ester, polyethylene glycol, polypropylene glycol, diethylene glycol and the like.

Among these, polyoxyalkylene alkyl ethers represented by the following general formula (3) are preferable.
RO (EO) _n (PO) _m H (3)
Wherein R is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms, n and m are 0 to 50, preferably 0 to 25, and n + m = 5 to 20 EO is a polyoxyethylene group and PO is a polyoxypropylene group.)

As the anionic surfactant, an alkyl sulfate represented by the following general formula (4) and an alkylbenzene sulfonate represented by the following general formula (5) are preferable.
R-OSO ₃ M (4)
With R-Ph-OS ₃ M (5)
(Wherein R is a linear or branched alkyl group having 8 to 30 carbon atoms, preferably 8 to 12 carbon atoms, and M is hydrogen or a metal element, preferably hydrogen, an alkali metal element or an alkaline earth metal element. Ph is a phenyl group.)

  Examples of the alkyl sulfate include sodium lauryl sulfate. Examples of the alkylbenzene sulfonate include salts of hexyl benzene sulfonic acid, octyl benzene sulfonic acid, decyl benzene sulfonic acid, dodecyl benzene sulfonic acid, cetyl benzene sulfonic acid, myristyl benzene sulfonic acid, and the like.

Examples of the anionic surfactant include higher fatty acids such as lauric acid, stearic acid, oleic acid and linolenic acid and salts thereof, polyoxyethylene monoalkyl ether sulfate represented by the following general formula (6), and the following general formula The polyoxyethylene alkylphenyl ether sulfate ester salt represented by (7) is mentioned.
RO (EO) _n (PO) _m SO ₃ M (6)
R-Ph-O (EO) _n (PO) _m SO ₃ M (7)
(In the formula, R is a linear or branched alkyl group having 8 to 30 carbon atoms, M is hydrogen or a metal element, n and m are 0 to 30, and n + m = 5 to 20. EO is a polyoxyethylene group. PO is a polyoxypropylene group, and Ph is a phenyl group.)

  (B) The compounding quantity of a component is 0.1-50 mass parts with respect to 100 mass parts of (A) component, 0.5-25 mass parts is preferable, and 1-10 mass parts is more preferable.

Component (C) The component (C) is a long-chain alkyl group-containing organoalkoxysilane represented by the following general formula (1), and can be used singly or in appropriate combination of two or more. This component (C) is a component for improving the adhesion between the silicone rubber film and the substrate. It is a component that exhibits the same effect as a conventional epoxy group-containing silane, a reaction product of an amino group-containing organoalkoxysilane and an acid anhydride, and this is a new finding of the present inventors.
R ¹ _x R ² _y Si (OR ³ ) _4-xy (1)
(Wherein R ¹ is a monovalent alkyl group having 6 to 15 carbon atoms, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ³ is a monovalent alkyl group having 1 to 6 carbon atoms. R ^{1 to} R ³ may be the same or different from each other, x is an integer of 1 to 3, y is an integer of 0 to 2, and x + y is an integer of 1 to 3.

Examples of R ¹ include linear alkyl groups such as hexyl group, octyl group, nonyl group, decyl group, dodecyl group, and tetradecyl group, cyclic alkyl groups such as cyclohexyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group; -Branched alkyl groups such as an ethylhexyl group. Of these, a linear alkyl group is particularly preferred. When an organosilane having an alkyl group with less than 6 carbon atoms in R ¹ is used, the film-forming property is not sufficient and the storage stability of the emulsion is not sufficient. In addition, when an organosilane in which R ^{1 has} an alkyl group having more than 15 carbon atoms is used, the film-forming property is lowered.

Examples of R ² include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and an aryl group such as a phenyl group and a tolyl group.

R ³ is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, and a methyl group or an ethyl group is particularly preferable.

  a is an integer of 1 to 3, 1 is preferable, b is an integer of 0 to 2, and 0 is preferable.

As the long-chain alkyl group-containing organoalkoxysilane represented by the general formula (1),
_{Hexyltrimethoxysilane: 6 H 13 Si (OCH 3} ) 3, hexyl _{triethoxysilane: C 6 H 13 Si (OC} 2 H 5) 3, _{octyltrimethoxysilane: C 8 H 17 Si (OCH} 3) 3, octyl _{triethoxysilane: C 8 H 17 Si (OC} 2 H 5) 3, decyl _{trimethoxysilane: C 10 H 21 Si (OCH} 3) 3, decyl _{triethoxysilane: C 10 H 21 Si (OC} 2 H 5) 3 , dodecyl trimethoxy _{silane: C 12 H 25 Si (OCH} 3) 3, dodecyl triethoxy _{silane: C 12 H 25 Si (OC} 2 H 5) 3 and the like, hexyl trimethoxysilane, hexyl triethoxysilane, Okuchirutori Methoxysilane, octyltriethoxysilane, decyltrimethoxysilane, and decyltriethoxysilane are preferred.

  (C) The compounding quantity of a component is 1-15 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-10 mass parts. When the blending amount of the component (C) is less than 1 part by mass, the effect of improving the adhesion to the substrate is weakened, and when it exceeds 15 parts by mass, the film is hard and brittle, and the flexibility is also lowered.

Component (D) Colloidal silica is added as a film reinforcing agent. In the present invention, colloidal silica can be used as an aqueous dispersion. As the aqueous dispersion of colloidal silica, a commercially available one may be used, and there is no limitation on the type thereof. For example, it may be one having an average particle size of 5 to 50 nm and stabilized with sodium, ammonium, aluminum or the like. Specifically, Snowtex (manufactured by Nissan Chemical Industries), Ludox (manufactured by Grace), silica doll (Japan) Chemical Industry Co., Ltd.), Adelite AT (manufactured by ADEKA), Cataloid S (manufactured by Catalytic Chemical Industry Co., Ltd.) and the like.

  (D) The compounding quantity of component is 0.5-50 mass parts in conversion of the pure part of colloidal silica with respect to 100 mass parts of (A) component, Preferably it is 1-30 mass parts. When the blending amount of colloidal silica is less than 0.5 parts by mass, there is no effect of improving the strength and flame retardancy of the film, and when it exceeds 50 parts by mass, the film becomes hard and brittle, and elongation and flexibility are lowered.

(E) component (E) The compounding quantity of water is 50-500 mass parts with respect to 100 mass parts of (A) component, Preferably it is 100-200 mass parts.

Component (F) The film-forming silicone emulsion composition of the present invention has an amide group and carboxyl group-containing organoalkoxysilane and / or its hydrolytic condensation from the viewpoint of further improving the adhesion between the silicone rubber film and the substrate. It is preferable to contain a product. In particular, those represented by the following formula and oligomers thereof are preferred.
_{(C 2 H 5 O) 3} SiC 3 H 6 -NHCO-CH = CHCOOH,
_{(C 2 H 5 O) 3} SiC 3 H 6 NH 3 + -OCOCH = CHCOOC 2 H 5

  (F) The compounding quantity of a component is 0.5-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 2-5 mass parts.

Component (G) The film-forming silicone emulsion composition of the present invention may contain an epoxy group-containing organoalkoxysilane and / or a partially hydrolyzed condensate thereof from the viewpoint of improving the flexibility and elongation of the silicone rubber. preferable. Among these, γ-glycidoxypropyltrimethoxysilane is preferable.

  (G) The compounding quantity of a component is 0.5-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 2-5 mass parts.

  The film-forming silicone emulsion composition of the present invention is a rubber having excellent strength and flexibility of a film after curing and good adhesion to various substrates without using an organic tin compound and an inorganic tin compound. When a film is formed and a film is formed on the fiber surface, a silicone emulsion composition having a small decrease in water absorption on the fiber surface after washing can be obtained, and does not contain an organic tin compound and an inorganic tin compound.

  The method for preparing the film-forming silicone emulsion composition of the present invention may follow a conventionally known emulsion polymerization method and phase inversion emulsification method. The emulsifier is not particularly limited, and for example, a homomixer, a homogenizer, a colloid mill, a universal mixing stirrer, a combination mix, a line mixer, and the like can be used. Moreover, after preparing an emulsion composition by (A) component and (B) component, you may mix | blend another component. The solid content concentration of the film-forming silicone emulsion composition is preferably 30 to 70% by mass, particularly 40 to 60% by mass.

  If necessary, the film-forming silicone emulsion composition of the present invention is usually added to a fiber treatment agent or an aqueous paint, for example, a thickener, an antifoaming agent, a pigment, an inorganic powder, a penetrating agent, An antistatic agent, a preservative, etc. can be mix | blended suitably.

  There is no restriction | limiting in particular as a processing method of the film formation silicone emulsion composition of this invention, It can carry out by well-known methods, such as brush coating, roll coating, spray coating, knife coating, dip coating. In this case, in order to improve the workability at the time of application, it is possible to adjust the liquid viscosity by adding a thickener or the like. Examples of the thickening agent include carboxymethyl cellulose, sodium polyacrylate, starch, casein, cellulose acetate, hydroxyethyl cellulose, and polyvinyl alcohol. Then, it hardens | cures by drying at normal temperature, and a membrane | film | coat is formed, but it is effective for shortening of processing time to accelerate hardening by heating as needed.

  The present invention can provide a film comprising a cured product of the above film-forming silicone emulsion composition. The composition of the present invention can be widely applied as an inorganic or organic binder, a fiber treatment agent, a paint, a release agent, a back treatment agent for an adhesive sheet, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition represents mass%, and “part” represents mass part.

[Production Example 1: (A-1)]
498 g of octamethylcyclotetrasiloxane (D4), 2 g of phenyltriethoxysilane, 50 g of 10% aqueous sodium lauryl sulfate solution and 50 g of 10% aqueous solution of dodecylbenzenesulfonic acid were charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer. 400 g of water was gradually added for dilution, and emulsification was performed twice with a high-pressure homogenizer at a pressure of 30 MPa to obtain a uniform white emulsion. This emulsion was transferred to a 1 liter ratchet type polybin, subjected to a polymerization reaction at 50 ° C. for 24 hours, aged at 10 ° C. for 24 hours, and then neutralized to pH 6.2 with 12 g of a 10% aqueous sodium carbonate solution. This emulsion had a non-volatile content of 45.4% after drying at 105 ° C. for 3 hours. The organopolysiloxane in the emulsion was subjected to instrumental analysis such as NMR, GPC, IR and the like, and the average composition formula was HO [(CH _{3) 2 SiO 2/2] d [} C 6 H 5 SiO 3/2] e H, [(CH 3) 2 SiO 2/2] / [C 6 H 5 SiO 3/2] = d / e = 100 The terminal represented by /0.1 (molar ratio) was a non-flowable soft gel in which the terminal was blocked with a hydroxyl group. Thus, an emulsion (A-1) containing the organopolysiloxane of component (A) was obtained.

[Production Example 2: (A-2)]
_{H- [O-Si (CH 3} ) 2] 40 -OH
Dimethylpolysiloxane blocked with hydroxyl groups at both ends represented by the formula (viscosity: 65 mPa · s, D4 content: 300 ppm, D5 (decamethylcyclopentasiloxane) content: 700 ppm) 492 g, phenyltriethoxysilane 8 g, 10% sodium lauryl sulfate 50 g of the aqueous solution was charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer, then 400 g of water was gradually added for dilution, and emulsified three times with a high-pressure homogenizer at a pressure of 50 MPa to obtain a uniform white emulsion. The emulsion was transferred to a 1 liter ratchet type polybin, cooled at 15 ° C. for 10 hours, charged with 50 g of 10% aqueous dodecylbenzenesulfonic acid solution, aged at 15 ° C. for 48 hours, and then pH 6 with 12 g of 10% aqueous sodium carbonate solution. Neutralized to .5. This emulsion had a non-volatile content of 47.5% after drying at 105 ° C. for 3 hours. The organopolysiloxane in the emulsion was subjected to instrumental analysis such as NMR, GPC, IR and the like, and the average composition formula was HO [(CH _{3) 2 SiO 2/2] d [} C 6 H 5 SiO 3/2] e H, [(CH 3) 2 SiO 2/2] / [C 6 H 5 SiO 3/2] = d / e = 100 The terminal represented by /0.5 (molar ratio) was a non-flowable soft gel in which the terminal was blocked with a hydroxyl group. Thus, an emulsion (A-2) containing the organopolysiloxane of component (A) was obtained.

[Production Example 3: Component (F)]
After dissolving 154 g of maleic anhydride in 500 g of ethanol, 346 g of 3-aminopropyltriethoxysilane was added dropwise at room temperature for 1 hour, and further reacted at 80 ° C. under reflux of ethanol for 24 hours to obtain a pale yellow transparent (F) An F solution containing 50% of the components was obtained. This solution had a non-volatile content of 45.1% after drying at 105 ° C. for 3 hours, and the reaction product in the solution was subjected to instrumental analysis such as IR, GC, NMR, and GCMS, and about 60% A mixture of those represented by the formula below with the remaining about 40% being oligomers derived from them.
_{(C 2 H 5 O) 3} SiC 3 H 6 -NHCO-CH = CHCOOH,
_{(C 2 H 5 O) 3} SiC 3 H 6 NH 3 + -OCOCH = CHCOOC 2 H 5

[Examples 1-4, Comparative Examples 1-3]
Emulsions (A-1), (A-2), (C-1) hexyltrimethoxysilane containing the component (A) obtained in the above production example with the composition shown in Table 1, (C-2) Octyltriethoxysilane, (C-3) decyltrimethoxysilane, (C-4: comparison) hexyldecyltrimethoxysilane, (C-5: comparison) propyltrimethoxysilane, (D) colloidal silica containing component ( Snowtex C, manufactured by Nissan Chemical Industries, Ltd., active ingredient: 20%), solution containing component (F), and composition of each silicone emulsion using γ-glycidoxypropyltrimethoxysilane as component (G) The product (non-volatile content 40%) was obtained. In addition, (B) component is the quantity contained in the said (A-1) component etc., (E) component is the quantity contained in the said (A-1) component etc.

1. Evaluation of Film Properties 20 g of each silicone emulsion composition was poured into a polypropylene resin disposable tray (150 mm × 105 mm × 19 mm), left in an atmosphere of a temperature of 25 ° C. and a relative humidity of 60% for 48 hours, and then heated at 105 ° C. for 1 hour. Thus, a cured film having a thickness of about 1 mm was produced. About this film, hardness, tensile strength, and elongation were measured according to JIS K6249. The evaluation results are shown in Table 1.

2. Emulsion Storage Stability 100 g of each silicone emulsion composition is placed in a glass bottle and stored in a constant temperature bath at 40 ° C. for 30 days. The appearance and non-volatile content of the upper and lower layers are visually observed and stored according to the following criteria. Stability was evaluated.
A: No light / dark separation is observed at the upper and lower layers.
B: Slight density separation is confirmed in the upper layer and the lower layer.
C: It is completely separated into two layers.

3. Film Formability The state of the film prepared above was evaluated.
A: It has a strength that forms a uniform film and can be easily peeled from the disposable tray.
B: A uniform film is formed, but cannot be peeled from the disposable tray.
C: A uniform film is not formed.

4). Water absorption ○ Water absorption before washing Ion exchange water was added to the silicone emulsion composition and diluted to a solid content of 2% to prepare a test solution. A polyester / cotton broad cloth (65% / 35%, manufactured by Tanigami Shoten) was immersed in the test solution for 1 minute, then squeezed with a roll under the condition of a squeezing rate of 100%, dried at 100 ° C. for 2 minutes, and further A heat-treated evaluation cloth was prepared by heat treatment at 150 ° C. for 2 minutes.
Drop water droplets (mass: approx. 0.02 g) from 2 to 3 cm from the height of the treated cloth on four places with a dropper, measure the time until the cloth is completely absorbed, and calculate the average value. did.
Water absorption after washing Washing was performed once by a test method based on JIS L0217 103, and then heat treatment was performed at 150 ° C. for 2 minutes to prepare a treated cloth for water absorption evaluation.
Drop water droplets (mass: approx. 0.02 g) from 2 to 3 cm from the height of the treated cloth on four places with a dropper, measure the time until the cloth is completely absorbed, and calculate the average value. did.

Claims (5)

(A) The following general formula (2)
X ₃ SiO— (R ⁴ ₂ SiO) _a — (Y ₂ SiO) _b —SiX ₃ (2)
( Wherein R ⁴ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, the number of carbon atoms. An aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, Y is a group represented by X or — (O—X ₂ Si) _c —X, and R ⁴ , X, Y May be the same or different, a is an integer of 10 to 10,000, b is an integer of 0 to 1,000, and c is an integer of 0 to 1,000. , X, Y, b, and c are selected to contain at least two hydroxyl groups bonded to a silicon atom in one molecule, and the ends are blocked with hydroxyl groups.)
In indicated the organopolysiloxane containing hydroxyl group attached to at least two silicon atoms in one molecule 100 parts by weight,
(B) Surfactant: 0.1 to 50 parts by mass (C) Long-chain alkyl group-containing organoalkoxysilane represented by the following general formula (1): 1 to 15 parts by mass,
R ¹ _x R ² _y Si (OR ³ ) _4-xy (1)
(Wherein R ¹ is a monovalent alkyl group having 6 to 15 carbon atoms, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ³ is a monovalent alkyl group having 1 to 6 carbon atoms. R ^{1 to} R ³ may be the same or different from each other, x is an integer of 1 to 3, y is an integer of 0 to 2, and x + y is an integer of 1 to 3.
(D) Colloidal silica: 0.5 to 50 parts by mass, and (E) water: 50 to 500 parts by mass, and does not contain an organic tin compound and an inorganic tin compound. object. (A) component is a following formula

(In the formula, a is an integer of 10 to 10,000, b is an integer of 0 to 1,000, and c is an integer of 0 to 1,000.)
The film-forming silicone emulsion composition according to claim 1, which is selected from those represented by: The film-forming silicone emulsion composition according to claim 1 or 2 , wherein the component (C) is hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane. object. The film-forming silicone emulsion composition according to any one of claims 1 to 3, which is a fiber treatment agent. The film | membrane formed by hardening | curing the film-forming silicone emulsion composition of any one of Claims 1-3.