JP2009280717A - Silicone resin aqueous emulsion composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone resin aqueous emulsion composition wherein a silicone resin is uniformly emulsified in water and which has excellent shelf stability and to provide a method for producing the same. <P>SOLUTION: The silicone resin aqueous emulsion composition includes a silicone resin having an average unit formula: R<SB>m</SB>R<SP>1</SP><SB>n</SB>Si(OX)<SB>p</SB>O<SB>(4-m-n-p)/2</SB>and ≤0°C softening point, an organo alkoxy silane or an alkoxy silane, a surfactant and water. The silicone resin aqueous emulsion composition further includes a water soluble and thickening polymer. In the method for producing the composition, the silicone resin and a mixture of the organo alkoxy silane or the alkoxy silane, the surfactant and water are mixed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to an aqueous silicone resin emulsion composition and a method for producing the same, and more particularly to an aqueous silicone resin emulsion composition having excellent storage stability and a method for producing the same.

Conventionally, silicone resins have excellent properties such as water repellency, weather resistance, heat resistance, antifouling properties, and flame retardancy, so many products and applications including paints, coating agents, and release agents Is used. However, since a silicone resin is generally solid at normal temperature, it is often used after being dissolved in an organic solvent and diluted from the viewpoint of workability. However, organic solvents tend to cause volatilization because they tend to volatilize, many are toxic to the human body, have a low flash point, and are flammable, so it is required to replace the dispersion medium with water from the organic solvent. ing. Therefore, various attempts have been made to emulsify a silicone resin in water to make an emulsion. However, since a silicone resin having a softening point higher than room temperature does not have fluidity at room temperature, it is difficult to emulsify in water, and even when emulsified, an aqueous emulsion having low storage stability is obtained.

for that reason,
(a) Japanese Patent Publication No. 5-87544 proposes a method in which an organic solvent (for example, toluene, xylene) solution of a polyorganosiloxane resin is emulsified in water with an emulsifier.
(b) In JP-A-7-291219, a linear polydimethylsiloxane solution in which polymethylsilsesquioxane powder is dispersed is prepared by mixing linear polydimethylsiloxane, isoparaffin and polymethylsilsesquioxane powder. A method of adding a nonionic surfactant and a small amount of water to form a grease and diluting with water has been proposed.
(c) Japanese Patent Application Laid-Open No. 2004-502017 proposes a method of mixing a mixture of polymethylhydrogensiloxane, silicone resin and alkyltrialkoxysilane, volatile methylsiloxane, surfactant and water.

(D) JP-T-08-504844 contains polyorganosiloxane oil, gum or resin, and has a silicone phase (A) of 100 parts by weight equal to at least 3 Pa · s, 2 to 20 parts by weight of water, and surface activity. 3 to 20 parts by weight of a combination of 0.5 to 10 parts by weight of agent (B) or 0.5 to 10 parts by weight of surfactant (B) and water-soluble thickening polymer (C) 2.5 × 10 ^{−4 to} 20 parts by weight A method for producing an oil-in-water emulsion (particle size of 0.1 to 5 μm) of a polyorganosiloxane oil and / or gum and / or resin has been proposed.

The silicone phase (A) has a viscosity equal to at least 3 Pa · s, at least one solvent of polyorganosiloxane oil and / or gum and / or resin and / or at least one silane and / or at least one siliceous or non-silica. A mixture of siliceous fillers (Claim 3); the polyorganosiloxane resin comprises RSiO _3/2 (T units) and / or SiO ₂ (Q units) and R ′ _{3 -a} R _a SiO _1/2 (M unit) and R ₂ SiO (D unit) (wherein, a is an integer of 0 to 3, R is a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, the number of carbon atoms 6 to 13 aromatic hydrocarbon group, polar organic group or hydrogen atom, and R ′ is a hydroxyl group, an alkoxy group, etc.) (Claim 7); Formula (R _b ) Si (OR ′) _4-b (In the formula, b is an integer of 0 to 4, and R and R ′ are as described above. Is present in an amount of 0 to 10 parts by weight per 100 parts by weight of the polyorganosiloxane oil and / or gum and / or resin, and the silane is a cross-linking agent or an adhesive (claim 8); at least one oil And / or gum and / or resin + optional solvent + optional silane into the water + surfactant + optional water soluble polymer mixture and then kneaded at a temperature in the range of 10-50 ° C. It is described as emulsifying (claim 14).

Japanese Patent Publication No. 5-87544 JP 7-291219 A Special table 2004-502017 gazette Japanese translation of PCT publication No. 8-504844, Japanese patent No. 3329816

However, the emulsion according to (a) still has the problem that it contains an organic solvent.
(b) is limited to a method for producing an emulsion in which polymethylsilsesquioxane powder, which is a special silicone resin, is dispersed, and there is a problem that it is essential to contain linear polydimethylsiloxane and isoparaffin. .
The production method according to (c) has a problem that it is essential to contain polymethylhydrogensiloxane and volatile methylsiloxane.
In [Detailed Description of the Invention] in (d), there are few explanations about the polyorganosiloxane resin, and both the aqueous emulsion composed of the polyorganosiloxane resin and the aqueous emulsion composed of the polyorganosiloxane resin and the silane are examples. However, it is not clearly and sufficiently described to the extent that a polyorganosiloxane resin aqueous emulsion having excellent storage stability can be produced by those skilled in the art.

Accordingly, the present inventor has reached the present invention as a result of earnest research to develop a silicone resin aqueous emulsion composition free from the above problems and a method for producing the same.
The object of the present invention is that the silicone resin is uniformly emulsified in water without containing an organic solvent, linear polydimethylsiloxane, polymethylhydrogensiloxane, volatile methylsiloxane, etc., and has excellent storage stability. An object is to provide an aqueous silicone resin emulsion composition and a method for producing the same.

The above purpose is
“[1] In an aqueous emulsion of a silicone resin comprising (A) a silicone resin, (B) a silane, (C) a surfactant and (D) water,
Component (A) is the average unit formula (1):
R _m R ¹ _n Si (OX) _p O _{(4-mnp) / 2} (1)
{In the formula, R is an alkyl group, R ¹ is an unsubstituted monovalent hydrocarbon group (excluding an alkyl group) or a substituted monovalent hydrocarbon group, and X is a hydrogen atom or an alkyl group. m, n, and p are numbers satisfying 0.5 ≦ m ≦ 1.8, 0 ≦ n ≦ 1.0, 0.7 ≦ m + n ≦ 1.8, and 0 <p ≦ 1.0. } And selected from the group consisting of R (XO) SiO _2/2 units and R ¹ (XO) SiO _2/2 units (wherein R, R ¹ and X are as defined above) A silicone resin having a softening point of 0 ° C. or lower,
Component (B) is composed of (b1) molecular formula (2): R ² _a Si (OY) _4-a (2)
(Wherein R ² is an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group, Y is an alkyl group, and a is 0, 1, 2, or 3) or Alkoxysilane, or (b2) a partially hydrolyzed condensate of organoalkoxysilane or alkoxysilane, which is blended in an amount of 3.5 to 30% by weight of component (A),
Component (C) is a water-based silicone resin emulsion composition characterized in that it is blended in an amount sufficient to emulsify component (A) and component (B) in component (D).
[2] The silicone resin aqueous emulsion composition according to [1], wherein the component (A) contains 1 to 50 mol% of the siloxane unit.
[3] The silicone according to [1] or [2], wherein n in the average unit formula (1) is 0 and R ² in the molecular formula (2) is an alkyl group or a phenyl group Resin aqueous emulsion composition.
[4] X in the average unit formula (1) is a hydrogen atom and / or an alkyl group having 1, 2 or 3 carbon atoms, and Y in the molecular formula (2) is an alkyl having 1, 2 or 3 carbon atoms The aqueous silicone resin emulsion composition according to [3], which is a group and a is 1. Is achieved.

The above purpose is
"[5] In the method for producing an aqueous silicone resin emulsion composition according to claim 1, wherein the component (A) and the component (B) are emulsified in the component (D) by the action of the component (C), the component ( A), [3.5 to 30% by weight of component (A) (B), and component (C) in an amount sufficient to emulsify component (A) and component (B) in component (D) And a mixture of component (D)] at a temperature higher than 0 ° C. and not higher than 90 ° C., or [mixture of component (A) and its component (B) of 3.5 to 30% by weight] [A mixture of component (C) and component (D) in an amount sufficient to emulsify component (A) and component (B) in component (D)] at a temperature higher than 0 ° C. and lower than 90 ° C. The method for producing an aqueous silicone resin emulsion composition according to [1], which comprises mixing.
[6] The method for producing an aqueous silicone resin emulsion composition according to [5], wherein the temperature higher than 0 ° C. and not higher than 90 ° C. is 2 ° C. or higher and 75 ° C. or lower. Is achieved.

The above purpose is
"[7] In an aqueous silicone resin emulsion composition comprising (A) a silicone resin, (B) a silane, (C) a surfactant, (E) a water-soluble and thickening polymer, and (D) water,
Component (A) is the average unit formula (1):
R _m R ¹ _n Si (OX) _p O _{(4-mnp) / 2} (1)
{In the formula, R is an alkyl group, R ¹ is an unsubstituted monovalent hydrocarbon group (excluding an alkyl group) or a substituted monovalent hydrocarbon group, and X is a hydrogen atom or an alkyl group. m, n, and p are numbers satisfying 0.5 ≦ m ≦ 1.8, 0 ≦ n ≦ 1.0, 0.7 ≦ m + n ≦ 1.8, and 0 <p ≦ 1.0. } And selected from the group consisting of R (XO) SiO _2/2 units and R ¹ (XO) SiO _2/2 units (wherein R, R ¹ and X are as defined above) A silicone resin having a softening point of 0 ° C. or lower,
Component (B) is composed of (b1) molecular formula (2): R ² _a Si (OY) _4-a (2)
(Wherein R ² is an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group, Y is an alkyl group, and a is 0, 1, 2, or 3) or Alkoxysilane, or (b2) a partially hydrolyzed condensate of organoalkoxysilane or alkoxysilane, which is blended in an amount of 3.5 to 30% by weight of component (A),
Component (C) is blended in an amount sufficient to emulsify component (A) and component (B) in component (D),
The silicone resin aqueous emulsion composition, wherein the component (E) is added in an amount sufficient to improve the storage stability of the aqueous emulsion.
[8] The aqueous silicone resin emulsion composition according to [7], wherein the component (A) contains 1 to 50 mol% of the siloxane unit.
[9] The silicone according to [7] or [8], wherein n in the average unit formula (1) is 0 and R ² in the molecular formula (2) is an alkyl group or a phenyl group Resin aqueous emulsion composition.
[10] X in the average unit formula (1) is a hydrogen atom and / or an alkyl group having 1, 2 or 3 carbon atoms, and Y in the molecular formula (2) is an alkyl having 1, 2 or 3 carbon atoms The aqueous silicone resin emulsion composition according to [9], which is a group and a is 1.
[11] The aqueous silicone resin emulsion composition according to [7] or [8], wherein the component (E) is a carboxyvinyl polymer.
[12] The aqueous silicone resin emulsion composition according to [11], further comprising (F) an alkali metal hydroxide. Is achieved.

The above purpose is
“[13] In the method for producing the aqueous silicone resin emulsion composition according to [7], the component (A) and the component (B) are emulsified in the component (D) by the action of the component (C). (A), [3.5 to 30% by weight of component (A) (B), and component (A) and component (B) in an amount sufficient to emulsify component (D) (C And a mixture of component (D)] at a temperature higher than 0 ° C. and not higher than 90 ° C., or [mixture of component (A) and its component (B) of 3.5 to 30% by weight] [A mixture of component (C) and component (D) in an amount sufficient to emulsify component (A) and component (B) in component (D)] at a temperature higher than 0 ° C. and lower than or equal to 90 ° C. The method for producing an aqueous silicone resin emulsion composition according to [7], wherein the aqueous solution of the component (E) is added and mixed.
[14] The method for producing an aqueous silicone resin emulsion composition according to [13], wherein the component (E) is a carboxyvinyl polymer.
[15] The method for producing an aqueous silicone resin emulsion composition according to [14], wherein (F) an alkali metal hydroxide or an aqueous solution thereof is added and mixed together with an aqueous carboxyvinyl polymer solution.
[16] The method for producing an aqueous silicone resin emulsion composition according to [13], wherein the temperature higher than 0 ° C. and not higher than 90 ° C. is 2 ° C. or higher and 75 ° C. or lower. Is achieved.

The silicone resin aqueous emulsion composition of the present invention has a silicone resin uniformly emulsified in water without containing an organic solvent, linear polydimethylsiloxane, polymethylhydrogensiloxane, or volatile methylsiloxane, and is stable in storage. Excellent in properties.
According to the method for producing a silicone resin aqueous emulsion composition of the present invention, the silicone resin aqueous emulsion composition can be produced simply and efficiently.

The silicone resin aqueous emulsion composition according to claim 1 of the present invention comprises:
(A) In a silicone resin aqueous emulsion composition comprising a silicone resin, (B) silane, (C) a surfactant and (D) water,
Component (A) is the average unit formula (1):
R _m R ¹ _n Si (OX) _p O _{(4-mnp) / 2} (1)
{In the formula, R is an alkyl group, R ¹ is an unsubstituted monovalent hydrocarbon group (excluding an alkyl group) or a substituted monovalent hydrocarbon group, and X is a hydrogen atom or an alkyl group. m, n, and p are numbers satisfying 0.5 ≦ m ≦ 1.8, 0 ≦ n ≦ 1.0, 0.7 ≦ m + n ≦ 1.8, and 0 <p ≦ 1.0. } And selected from the group consisting of R (XO) SiO _2/2 units and R ¹ (XO) SiO _2/2 units (wherein R, R ¹ and X are as defined above) A silicone resin having a softening point of 0 ° C. or lower,
Component (B) is composed of (b1) molecular formula (2): R ² _a Si (OY) _4-a (2)
(Wherein R ² is an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group, Y is an alkyl group, and a is 0, 1, 2, or 3) or Alkoxysilane, or (b2) a partially hydrolyzed condensate of organoalkoxysilane or alkoxysilane, which is blended in an amount of 3.5 to 30% by weight of component (A),
Component (C) is characterized by being mixed in an amount sufficient to emulsify component (A) and component (B) in component (D).

In the average unit formula (1), R is an alkyl group and is directly connected to a silicon atom. m is an average of 0.5 ≦ m ≦ 1.8. That is, the average number of alkyl groups per silicon atom in the silicone resin is 0.5 or more and 1.8 or less. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group, decyl group, and dodecyl group. A lower alkyl group having 1 to 6 carbon atoms is preferable from the viewpoint of emulsification of the silicone resin, but a long chain alkyl group is preferable when a water repellent is required for the silicone resin.

R ¹ is an unsubstituted monovalent hydrocarbon group (excluding an alkyl group) or a substituted monovalent hydrocarbon group directly connected to a silicon atom.
The unsubstituted monovalent hydrocarbon group (excluding the alkyl group) is preferably one having 2 to 10 carbon atoms from the viewpoint of emulsifiability, and an alkenyl group such as a vinyl group, an allyl group, a 5-hexenyl group, or a 9-decenyl group; Examples thereof include aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group.
Of these, alkenyl groups such as vinyl groups and allyl groups are preferable when the silicone resin (A) is cured by a hydrosilylation reaction, and phenyl groups are preferable when the silicone resin (A) is required to have heat resistance.

R ¹ may be a substituted monovalent hydrocarbon group, and there is an unsubstituted monovalent hydrocarbon group described above, particularly one in which part or all of the hydrogen atoms of an alkyl group or a phenyl group are substituted with the following substituents.
As substituents, halogen atoms such as fluorine and chlorine; epoxy functional groups such as glycidyloxy group and epoxycyclohexyl group; (meth) acryl functional groups such as methacryloxy group and acryloxy group; amino group, aminoethylamino group and phenylamino group And amino functional groups such as dibutylamino group; sulfur-containing functional groups such as mercapto group and tetrasulfide group; alkoxy group; hydroxycarbonyl group; alkoxycarbonyl group.

Specific examples of the substituted monovalent hydrocarbon group include 3,3,3-trifluoropropyl group, perfluorobutylethyl group, perfluorooctylethyl group, 3-chloropropyl group, 3-glycidyloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 3-methacryloxypropyl group, 3-acryloxypropyl group, 11-methacryloxyundecyl group 3-aminopropyl group, N- (2-aminoethyl) aminopropyl group, 3- (N-phenylamino) propyl group, 3-dibutylaminopropyl group, 3-mercaptopropyl group; 3-hydroxycarbonylpropyl group; Examples include methoxypropyl group and ethoxypropyl group.

In the average unit formula (1), n is 0 ≦ n ≦ 1.0. That is, R ¹ is 0 or more and 1.0 or less on average per one silicon atom in the silicone resin. When n = 0, that is, when R ¹ is not contained, the silicone resin is an alkylpolysiloxane resin. When n exceeds 1.0, the R group content may decrease, the R ¹ group content may increase, and the emulsifiability may decrease.

In the average unit formula (1), X in the OX group is a hydrogen atom or an alkyl group. When X is a hydrogen atom, the OX group is a hydroxyl group, and when X is an alkyl group, the OX group is an alkoxy group. Both are directly connected to silicon atoms. In terms of emulsifiability, the number of carbon atoms in the alkyl group is preferably 10 or less, and more preferably 3 or less.
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, a pentanoxy group, and a methoxyethoxy group. The alkoxy group is often a residual group when a silicone resin is prepared by a hydrolytic condensation reaction of an organoalkoxylane.
The hydroxyl group directly bonded to the silicon atom is also referred to as a silanol group, and is generated when a silicone resin is prepared by a hydrolytic condensation reaction of organoalkoxylane or organohalosilane.

In the average unit formula (1), m + n is a number satisfying 0.7 ≦ m + n ≦ 1.8. m + n is an average value of the total number of R groups and R ¹ groups per silicon atom in the silicone resin.
If m + n is less than 0.7, the content of R group or R group and R ¹ group is low, and the silicone resin film becomes too hard and cracks are likely to occur. When m + n exceeds 1.8, the number of linear units increases and the silicone resin film becomes rubbery, which is not preferable. Preferably, m + n is in the range of 0.9 to 1.6.

In the average unit formula (1), p is a number satisfying 0 <p ≦ 1.0. p is the average number of OX groups per silicon atom in the silicone resin.
Since the OX group remains or is produced when the silicone resin is prepared by hydrolytic condensation reaction of organoalkoxylane or organohalosilane, it is usually larger than 0 on average per silicon atom in the silicone resin (A). However, if the amount is too large, the water-solubility of the silicone resin (A) becomes too large or unstable, so the average is 1.0 or less. There are three types of OX groups in one molecule of the silicone resin (A): all OH groups, all alkoxy groups, OH groups and alkoxy groups.

The OX group can be reduced by heating the OX group-containing silicone resin in the presence of a small amount of potassium hydroxide.
From the viewpoint of the emulsifiability of the silicone resin (A) and the storage stability of the aqueous emulsion, a more preferable range of p is 0.05 to 0.8, and more preferably 0.2 to 0.7.

As siloxane units constituting the silicone resin (A), triorganosiloxane units (abbreviated as M units), diorganosiloxane units (abbreviated as D units), monoorganosiloxane units (abbreviated as T units), and SiO _4/2 units (abbreviated as Q units). Unit).
The silicone resin (A) contains T units, Q units, or T units and Q units, but preferably further contains D units in order to lower the softening point thereof.
Preferred combinations of siloxane units include T unit and D unit; T unit, D unit and M unit; T unit, D unit and Q unit; T unit, D unit, Q unit and M unit; D unit, Q unit and M unit. There are units.

There are RSiO _3/2 units and R ¹ SiO _3/2 units as monoorganosiloxane units,
There are R ₂ SiO _2/2 units, RR ¹ SiO _2/2 units, R ¹ ₂ SiO _2/2 units as diorganosiloxane units,
Triorganosiloxane units include R ₃ SiO _1/2 units, R ₂ R ¹ SiO _1/2 units, and RR ¹ ₂ SiO _1/2 units.
Further, there are siloxane units in which one of R group or R ¹ group in the siloxane unit is substituted with OX group, for example, R (XO) SiO _2/2 unit, R ¹ (XO) SiO _2/2 unit. .
In order to improve the emulsifiability in water and the storage stability of the emulsion, the silicone resin (A) contains R (XO) SiO _2/2 units, R ¹ (XO) SiO _2/2 units, or both of these units. contains.
The content thereof is preferably 1 to 50 mol%, more preferably 2 to 30 mol%, and further preferably 4 to 25 mol% of the total siloxane units.

The silicone resin (A) has a softening point of 0 ° C. or less from the viewpoint of emulsification in water.
The softening point of the silicone resin (A) can be determined by measuring the glass transition point with a differential thermal analyzer.

The method for producing the silicone resin (A) is not particularly limited. For example, hydrolytic condensation reaction of organoalkoxylane, hydrolytic condensation reaction of organohalosilane, hydrolytic condensation reaction of organoalkoxylane and organohalosilane, or partial hydrolyzate of monoorganotrialkoxysilane or monoorganotrihalosilane And a diorganopolysiloxane are prepared by an equilibration reaction.

(B) (b1) Molecular formula (2): R ² _a Si (OY) _4-a (2)
(Wherein R ² is an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group, Y is an alkyl group, and a is 0, 1, 2, or 3) or Alkoxysilane or (b2) the above-mentioned organoalkoxysilane or the partially hydrolyzed condensate of alkoxysilane has an action of assisting and stabilizing emulsification of component (A) in component (D).

R ² is an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group directly connected to a silicon atom.
The unsubstituted monovalent hydrocarbon group is preferably one having 1 to 10 carbon atoms from the viewpoint of emulsification assisting action.
As unsubstituted monovalent hydrocarbon, alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group, decyl group, vinyl group, allyl group Group, an alkenyl group such as 5-hexenyl group and 9-decenyl group; an aryl group such as phenyl group and tolyl group; and an aralkyl group such as benzyl.
Among these, when R ¹ in the silicone resin (A) is an alkyl group or an alkenyl group, an alkyl group or an alkenyl group is preferable. When R ¹ is an aryl group, an aryl group is preferable, and R ¹ is an alkyl group. In the case of a group and an aryl group, an alkyl group and an aryl group are preferred.

Examples of the substituted monovalent hydrocarbon group include the above-described unsubstituted monovalent hydrocarbon groups, particularly those in which part or all of the hydrogen atoms of the alkyl group or phenyl group are substituted with the following substituents.
As substituents, halogen atoms such as fluorine and chlorine; epoxy functional groups such as glycidyloxy group and epoxycyclohexyl group; (meth) acryl functional groups such as methacryloxy group and acryloxy group; amino group, aminoethylamino group and phenylamino group And amino functional groups such as dibutylamino group; sulfur-containing functional groups such as mercapto group and tetrasulfide group; alkoxy group; hydroxycarbonyl group; alkoxycarbonyl group.

Specific examples of the substituted monovalent hydrocarbon group include 3,3,3-trifluoropropyl group, perfluorobutylethyl group, perfluorooctylethyl group, 3-chloropropyl group, 3-glycidyloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 3-methacryloxypropyl group, 3-acryloxypropyl group, 11-methacryloxyundecyl group 3-aminopropyl group, N- (2-aminoethyl) aminopropyl group, 3- (N-phenylamino) propyl group, 3-dibutylaminopropyl group, 3-mercaptopropyl group; 3-hydroxycarbonylpropyl group; Examples include methoxypropyl group and ethoxypropyl group.

OY bonded to the silicon atom is an alkoxy group, and Y is an alkyl group.
The alkyl group preferably has 1 to 10 carbon atoms in view of emulsification assisting action in water, and is a methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group. , An octyl group, and a decyl group. The alkyl group may be an alkoxylated alkyl group.
a is 0, 1, 2 or 3, with 1 being most preferred, followed by 2.

Among the components (b1), tetraalkoxysilane is one in which a = 0. Examples of a = 1 include alkyltrialkoxysilane, alkenyltrialkoxysilane, aryltrialkoxysilane, and substituted alkyltrialkoxysilane.
Examples of a = 2 are dialkyl dialkoxysilanes; alkylalkenyl dialkoxysilanes; alkylaryl dialkoxysilanes and alkyl (substituted alkyl) dialkoxysilanes.

Examples of tetraalkoxysilane include tetraethoxysilane and tetrapropoxysilane.
As alkyltrialkoxysilanes, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, hexyltrimethoxysilane And octyltriethoxysilane and tetradecyltriethoxysilane.

Examples of the alkenyltrialkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy) silane.
Examples of the aryltrialkoxysilane include phenyltrimethoxysilane and phenyltriethoxysilane.

As substituted alkyltrialkoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltri Methoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, 2-amino-1-methylethyltriethoxysilane, N-methyl-γ-aminopropyltriethoxy Silane is exemplified.

Examples of the dialkyl dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, methylethyldimethoxysilane, methylethyldipropoxysilane, and methylethyldibutoxysilane.

Examples of the alkyl alkenyl dialkoxy silane include methyl vinyl dimethoxy silane, methyl vinyl diethoxy silane, methyl vinyl dipropoxy silane, methyl allyl dimethoxy silane, and methyl allyl diethoxy silane.
Examples of the alkylaryl dialkoxysilane include methylphenyldimethoxysilane, methylphenyldiethoxysilane, and methylphenyldipropoxysilane.

As alkyl (substituted alkyl) dialkoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylethyldiethoxysilane, γ -Aminopropylethyldimethoxysilane, gamma-aminopropylphenyldiethoxysilane, N-butyl-gamma-aminopropylmethyldiethoxysilane are exemplified.

Component (b2) is an organoalkoxysilane represented by molecular formula (2) or a partially hydrolyzed condensate of alkoxysilane. However, when triorganoalkoxysilane itself having a = 3 is hydrolyzed and condensed, it becomes a dimer having neither an alkoxy group nor a silanol group, and does not have an emulsifying assisting action. Therefore, component (b2) has a = 3. It does not contain hydrolysis condensate of triorganoalkoxysilane itself. Component (b2) is an organotrialkoxysilane in which a = 1, a diorganodialkoxysilane in which a = 2, a triorganoalkoxysilane in which a = 3 and a tetraalkoxy in which a = 0 in the molecular formula (2). Two to three partial cohydrolysis condensates selected from the group consisting of silanes may be used.

Component (B) may be used in combination of two or more of component (b1), two or more of component (b2), and one or more of component (b1) and component (b2).

Component (B) is blended in an amount of 3.5 to 30% by weight of component (A), preferably 4 to 15% by weight. If the blending amount of component (B) is less than 3.5% by weight of component (A), the storage stability of the resulting aqueous emulsion is poor, and if it exceeds 30% by weight, the amount of alcohol produced as a by-product increases, and the environment and human body. It is not preferable because it adversely affects the surface and the durability of the film is inferior.

Component (C) surfactant has the effect of stably emulsifying component (A) and component (B) in component (D), and the emulsifying effect of component (A) and component (B) is excellent. If it is, it will not be specifically limited. A nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant are appropriately selected from those having an excellent emulsifying action.

Examples of the nonionic surfactant include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene glycerin fatty acid ester. Examples of the alkyl group include higher alkyl groups such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a cetyl group, and a stearyl group. Examples of the fatty acid include high and intermediate fatty acids such as lauric acid, palmitic acid, stearic acid, and oleic acid.

Anionic surfactants include alkyl benzene sulfonate, alkyl ether sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl naphthyl sulfonate, unsaturated aliphatic sulfonate, hydroxylation Aliphatic sulfonates are exemplified. Examples of the alkyl group include high and intermediate alkyl groups such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a cetyl group, and a stearyl group. Examples of the unsaturated aliphatic group include an oleyl group, nonenyl group, and octynyl group. Examples of the counter ion include sodium, potassium, lithium, or ammonium ions, and sodium is common.

As cationic surfactants, alkyltrimethylammonium salts such as octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride; dialkyldimethylammonium salts such as dioctadecyldimethylammonium chloride, dihexadecyltridiammonium chloride and didecyldimethylammonium chloride Quaternary ammonium type salt surfactants are exemplified.

Examples of amphoteric surfactants include alkylbetaines and alkylimidazolines.
One kind of such a surfactant may be used alone, or two or more kinds of surfactants of different types may be used in combination.

The amount of component (C) is sufficient to emulsify component (A) and component (B) in component (D). Usually, it is 1 to 20% by weight of the total amount of the component (A) and the component (B), and preferably 2 to 15% by weight. This is because if it is less than 1% by weight, the emulsifying power for component (A) and component (B) may be insufficient, and the stability of the aqueous emulsion composition may be insufficient. On the other hand, if it exceeds 20% by weight, the durability of the silicone resin film may be inferior.

The water that is component (D) is preferably one that does not contain emulsification and a component that inhibits the stability of the emulsion, and examples include ion-exchanged water, distilled water, well water, and tap water.
The component (D) may be an amount sufficient to maintain a stable aqueous emulsion state, and the content is not particularly limited. Usually, 10 to 99% by weight is contained in the aqueous silicone resin emulsion.

A silicone resin aqueous emulsion composition according to claim 7 of the present invention comprises:
In a silicone resin aqueous emulsion composition comprising (A) a silicone resin, (B) a silane, (C) a surfactant, (E) a water-soluble and thickening polymer, and (D) water,
Component (A) is the average unit formula (1):
R _m R ¹ _n Si (OX) _p O _{(4-mnp) / 2} (1)
{Wherein, R represents an alkyl group, R ¹ represents an unsubstituted monovalent hydrocarbon group (excluding an alkyl group) or a substituted monovalent hydrocarbon group, and X represents a hydrogen atom or an alkyl group. m, n, and p are numbers satisfying 0.5 ≦ m ≦ 1.8, 0 ≦ n ≦ 1.0, 0.7 ≦ m + n ≦ 1.8, and 0 <p ≦ 1.0. } And selected from the group consisting of R (XO) SiO _2/2 units and R ¹ (XO) SiO _2/2 units (wherein R, R ¹ and X are as defined above) A silicone resin having a softening point of 0 ° C. or lower,
Component (B) is composed of (b1) molecular formula (2): R ² _a Si (OY) _4-a (2)
(Wherein R ² is an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group, Y is an alkyl group, and a is 0, 1, 2, or 3) or Alkoxysilane, or (b2) a partially hydrolyzed condensate of organoalkoxysilane or alkoxysilane, which is blended in an amount of 3.5 to 30% by weight of component (A),
Component (C) is blended in an amount sufficient to emulsify component (A) and component (B) in component (D),
Component (E) is characterized in that it is added in an amount sufficient to improve the storage stability of the aqueous emulsion.

Component (A), component (B), component (C) and component (D) are as described above.
The water-soluble and thickening polymer as component (E) has the effect of improving the storage stability of an aqueous silicone resin emulsion comprising component (A), component (B), component (C) and component (D). .

As component (E), gum arabic, carrageenan, quince seed, casein, dextrin, gelatin, sodium pectate, sodium alginate, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone Examples include sodium polyacrylate, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, and xanthan gum. Among these, a carboxyvinyl polymer is preferable in terms of an effect of improving storage stability.

It is preferable that the component (E) is previously made into an aqueous solution and then mixed with other components. The carboxyvinyl polymer is preferably improved in water solubility by an alkali metal hydroxide such as sodium hydroxide.

The content of component (E) in the silicone resin aqueous emulsion composition comprising component (A), component (B), component (C), component (D), and component (E) is The amount is sufficient to improve the storage stability, specifically 0.01 to 10% by weight, and more preferably 0.02 to 4% by weight.

The above-mentioned two types of silicone resin aqueous emulsion compositions include, as necessary, known inorganic thickeners (for example, smectite clay), inorganic binders (for example, colloidal silica), condensation reaction catalysts, buffers, pH adjusters, Preservatives, ultraviolet absorbers, dyes, penetrants, antistatic agents, chelating agents, inorganic powders and the like can be contained. When colloidal silica (2 to 15% by weight in the composition) is contained, the strength of the film formed by drying the aqueous silicone resin emulsion composition is improved.
When a silicone resin aqueous emulsion composition contains a catalytic amount of a condensation reaction catalyst (for example, an organic titanium compound catalyst such as tetrabutyl titanate or an organic tin catalyst such as dibutyltin dilaurate), it becomes room temperature curable and forms a cured film. can do.

The silicone resin aqueous emulsion composition according to claim 1 of the present invention comprises:
It can be produced by emulsifying component (A) and component (B) in component (D) by the action of component (C).
It is necessary to mix component (A) with other components at a temperature higher than 0 ° C. and lower than the boiling point of water which is component (D). Since water freezes when the water temperature reaches about 0 ° C., 2 ° C. or higher is preferable. When the water temperature is close to the boiling point, the evaporation rate increases, so it must be 90 ° C. or lower, and preferably 75 ° C. or lower.
As a method for more uniformly emulsifying component (A) and component (B) in component (D), there is the following method (1).

Method (1)
Ingredient (A) is charged into a container. In a separate container, mix component (B), component (C) and component (D) until they are almost uniform.
The mixture of component (B), component (C), and component (D) is charged into a container containing component (A). Next, the mixture is stirred with a propeller type electric stirrer, and the component (A) and the component (B) are emulsified into the component (D) in the form of fine particles to obtain an aqueous emulsion. Or high-speed stirring with an emulsifier that can apply high-speed shearing such as colloid mill, homomixer, homogenizer, combination mix, sand grinder, in-line continuous emulsifier, vacuum emulsifier, or shake at high speed with ultrasonic emulsifier. Component (A) and component (B) are emulsified in component (D) in the form of fine particles to form an aqueous emulsion.
When mixing component (B), component (C) and component (D), a small amount of component (D) may be used, and the remaining component (D) may be used for diluting the aqueous emulsion.

There are the following method (2) and method (3) as methods according to method (1).
Method (2)
Ingredient (A) and ingredient (B) are mixed in a container. In a separate container, component (C) and component (D) are mixed to dissolve component (C). The solution is put into a container containing a mixture of component (A) and component (B). Next, the mixture is stirred with a propeller type electric stirrer, and the component (A) and the component (B) are emulsified into the component (D) in the form of fine particles to obtain an aqueous emulsion. Or high-speed stirring with an emulsifier that can apply high-speed shearing such as colloid mill, homomixer, homogenizer, combination mix, sand grinder, in-line continuous emulsifier, vacuum emulsifier, or shake at high speed with ultrasonic emulsifier. The component (A) and the component (B) are emulsified in the component (D) in the form of fine particles to form an aqueous emulsion.
In mixing the component (C) and the component (D), a small amount of the component (D) may be used, and the remaining component (D) may be used for diluting the aqueous emulsion.

Method (3)
Ingredient (A), ingredient (B) and ingredient (C) are mixed in a container.
Ingredient (D) is charged into a container containing a mixture of ingredient (A), ingredient (B) and ingredient (C). Next, the mixture is stirred with a propeller type electric stirrer, and the component (A) and the component (B) are emulsified into the component (D) in the form of fine particles to obtain an aqueous emulsion. Or high-speed stirring with an emulsifier that can apply high-speed shearing such as colloid mill, homomixer, homogenizer, combination mix, sand grinder, in-line continuous emulsifier, vacuum emulsifier, or shake at high speed with ultrasonic emulsifier. Component (A) and component (B) are emulsified in component (D) in the form of fine particles to form an aqueous emulsion.

In the said manufacturing method, the compounding quantity of a component (B) is 3.5 to 30 weight% of a component (A).
The amount of component (C) is sufficient to emulsify component (A) and component (B) in component (D). Usually, it is 1 to 20% by weight of the total amount of the component (A) and the component (B), and preferably 2 to 15% by weight.
The amount of component (D) is not particularly limited as long as it is sufficient to emulsify component (A) and component (B) and maintain a stable aqueous emulsion state. The amount is 10 to 99% by weight.

When a W / O type emulsion is formed, it can be phase-shifted into an O / W type emulsion by applying high-speed shearing. In that case, you may dilute with water.

The aqueous silicone resin emulsion composition thus obtained contains a predetermined amount of the component (B), so that the uniformity of the aqueous emulsion is excellent, and it is stable for one week or more when left at room temperature. The average particle size of the emulsion is about 0.1-5 μm.
When component (B) is not contained, component (A) cannot be emulsified in component (D). Even if contained, if it is less than 3.5% by weight of component (A), the aqueous emulsion lacks uniformity or lacks storage stability.

The aqueous silicone resin emulsion composition according to claim 7 of the present invention is obtained by emulsifying component (A) and component (B) in component (D) by the action of component (C) to form an aqueous silicone resin emulsion composition. In the manufacturing process, component (A), [3.5-30% by weight of component (A), component (B), sufficient to emulsify component (A) and component (B) in component (D) A mixture of component (C) and component (D)] at a temperature higher than 0 ° C. and not higher than 90 ° C., or [component (A) and its component of 3.5 to 30% by weight (B ) And [a mixture of component (C) and component (D) in an amount sufficient to emulsify component (A) and component (B) in component (D)] above 0 ° C. It can be produced by mixing at a temperature of 90 ° C. or lower and then adding and mixing the aqueous solution of component (E).
Component (A), [Component (B) in an amount of 3.5 to 30% by weight of Component (A), and an amount of component sufficient to emulsify Component (A) and Component (B) in Component (D) ( C) and a mixture of component (D)] at a temperature higher than 0 ° C. and lower than 90 ° C., and [mixture of component (A) and its component (B) of 3.5 to 30% by weight] And [mixture of component (C) and component (D) in an amount sufficient to emulsify component (A) and component (B) in component (D)] above 0 ° C. and below 90 ° C. The conditions for mixing at the temperature are as described above.

When component (E) is a carboxyvinyl polymer, it is preferable to further improve solubility in water and thickening by further coexisting (F) alkali metal hydroxide.
Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and cesium hydroxide.
The compounding amount of the alkali metal hydroxide may be a so-called catalytic amount, preferably 10 to 10,000 ppm by weight of the aqueous silicone resin emulsion composition.

It is preferable that the alkali metal hydroxide is previously made into an aqueous solution and then added to the emulsion composition produced above. The alkali metal hydroxide or an aqueous solution thereof is preferably added after the emulsion composition produced above is cooled to room temperature (for example, 30 ° C.). The stirring time after charging may be sufficient as long as it becomes uniform.

A water-soluble polymer aqueous solution may be added before or after the alkali metal hydroxide or its aqueous solution is added.
Further, colloidal silica may be added, or water may be added for dilution.

When a W / O type emulsion is formed, it can be phase-shifted into an O / W type emulsion by applying high-speed shearing. In that case, you may dilute with water.

The silicone resin aqueous emulsion composition thus obtained contains a predetermined amount of component (B) and component (E), so it has excellent uniformity and is stable for 3 months or more when left at room temperature. . The average particle size of the emulsion is about 0.1-5 μm.
The aqueous silicone resin emulsion composition thus produced exhibits basicity and may be partially neutralized or neutralized with an organic acid (eg, acetic acid) or a mineral acid (eg, hydrochloric acid, sulfuric acid).

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. In the examples, the part representing the blending amount means part by weight, and the percentage representing the content means weight%. The softening point of the silicone resin is a value obtained by measuring the glass transition point with a differential thermal analyzer. The average particle size of the emulsion particles was calculated by measuring the particle size distribution with a submicron particle analyzer (COULTER MODEL N4 MD manufactured by Coulter Electronics Co., Ltd.).

[Example 1]
Average composition formula (CH ₃ ) _1.2 (OH) _0.1 (OCH ₂ CH ₃ ) _0.1 SiO _{1.3 The} average unit formula [(CH ₃ ) ₂ SiO _2/2 ] _0.16 [(CH ₃ ) (HO) SiO _{2 / 2} ] _0.10 [(CH ₃ ) (CH ₃ CH ₂ O) SiO _2/2 ] _0.06 [(CH ₃ ) SiO _3/2 ] _0.68 , and 100 parts of a silicone resin having a softening point of 0 ° C. or less. After heating to 50 ° C., a solution in which 6 parts of n-octyltriethoxysilane, 4.3 parts of polyoxyethylene (7 mol) isodecyl ether and 8.5 parts of water at 50 ° C. were uniformly mixed was added. Subsequently, high-speed stirring was performed at 50 ° C. using a propeller-type electric stirrer (HEIDON three-one motor, rotation speed: 700 rpm) to obtain an O / W type methylpolysiloxane resin aqueous emulsion. After cooling to 30 ° C., 94 parts of water was added to obtain an aqueous emulsion composition of an O / W type methylpolysiloxane resin. The obtained aqueous emulsion composition was uniform with no non-emulsified product, and was stable for more than one week.

[Example 2]
An O / W type methylpolysiloxane resin aqueous emulsion composition was prepared under the same conditions as in Example 1 except that n-octyltriethoxysilane used in Example 1 was changed to n-hexyltrimethoxysilane. . The obtained aqueous methylpolysiloxane resin emulsion composition was uniform without any non-emulsified product and was stable for one week or more.

[Example 3]
An O / W type methylpolysiloxane resin aqueous emulsion composition was prepared under the same conditions as in Example 1 except that n-octyltriethoxysilane used in Example 1 was changed to methyltriethoxysilane. The obtained silicone resin aqueous emulsion composition was uniform without any non-emulsified product, and was stable for one week or more.

[Example 4]
An O / W type methylpolysiloxane resin aqueous emulsion composition was prepared under the same conditions as in Example 1 except that n-octyltriethoxysilane used in Example 1 was changed to phenyltrimethoxysilane. The obtained aqueous methylpolysiloxane resin emulsion composition was uniform without any non-emulsified product and was stable for one week or more.

[Example 5]
An O / W type methylpolysiloxane resin aqueous emulsion composition was prepared under the same conditions as in Example 1 except that the n-octyltriethoxysilane used in Example 1 was changed to tetraethoxysilane. The obtained aqueous methylpolysiloxane resin emulsion composition was uniform without any non-emulsified product and was stable for one week or more.

[Comparative Example 1]
An O / W type aqueous emulsion composition was tried under the same conditions as in Example 1 except that n-octyltriethoxysilane used in Example 1 was not added. The obtained aqueous composition was mostly non-emulsified, and the silicone resin was precipitated.

[Example 6]
100 parts of the methylpolysiloxane resin used in Example 1 was put into a vacuum emulsifier (MIZUHO type vacuum emulsifier PVQ-3, manufactured by Mizuho Kogyo Co., Ltd., the same applies hereinafter) and heated to 50 ° C. Next, a liquid in which 6 parts of n-octyltriethoxysilane, 4.6 parts of 70% aqueous solution of polyoxyethylene (35 mol) undecyl ether, 1.1 parts of polyoxyethylene (2 mol) lauryl ether and 8.5 parts of water were uniformly mixed was prepared. The mixture was charged and stirred at 50 ° C at high speed. The obtained aqueous emulsion of O / W type methylpolysiloxane resin was cooled to 30 ° C., 42.6 parts of water was added, and the mixture was stirred and diluted. Furthermore, after adding 15 parts of 0.9% carboxyvinyl polymer aqueous solution, 1.1 parts of 1% sodium hydroxide aqueous solution was added and stirred. Finally, 41.5 parts of water was added and stirred to obtain an aqueous emulsion composition of an O / W type methylpolysiloxane resin. The average particle size of the emulsion particles was 347 nm. The resulting aqueous methylpolysiloxane resin emulsion composition was uniform without any non-emulsified product and was stable for 3 months or more.

[Example 7]
The methylpolysiloxane resin used in Example 6 is represented by the average composition formula (CH ₂ CH ₂ CH ₃ ) _1.0 (OH) _0.4 SiO _1.3 and the average unit formula [(CH ₂ CH ₂ CH ₃ ) SiO _3/2 ] _0.92 [(CH ₂ CH ₂ CH ₃ ) (HO) SiO _2/2 ] _0.08 , except that the softening point was changed to a propylpolysiloxane resin of 0 ° C. or less, and the emulsification temperature was changed to 65 ° C. Under the same conditions as in Example 6, an O / W type silicone resin aqueous emulsion composition was prepared. The average particle size of the emulsion particles was 363 nm. The obtained propylpolysiloxane resin aqueous emulsion was uniform with no non-emulsified product and was stable for 3 months or more.

[Comparative Example 2]
An attempt was made to prepare an aqueous propylpolysiloxane resin emulsion under the same conditions as in Example 7 except that n-octyltriethoxysilane used in Example 7 was not used. The obtained aqueous composition was mostly non-emulsified, and propylpolysiloxane resin was precipitated.

[Example 8]
100 parts of the silicone resin used in Example 7 was put into a vacuum emulsifier and heated to 65 ° C. Next, a liquid in which 4.5 parts of n-octyltriethoxysilane, 4.6 parts of a 70% aqueous solution of polyoxyethylene (35 mol) undecyl ether, 1.1 parts of polyoxyethylene (2 mol) lauryl ether and 8.5 parts of water were uniformly mixed was prepared. The mixture was added and stirred at 65 ° C. at high speed. The obtained O / W type propylpolysiloxane resin aqueous emulsion was cooled to 30 ° C. and then diluted by adding 42.6 parts of water. Furthermore, after adding 12 parts of 1% carboxyvinyl polymer aqueous solution, 1.1 parts of 1% sodium hydroxide solution was added and stirred. Finally, 12.7 parts of water and 21.3 parts of colloidal silica (concentration 30%, particle size 10 nm, pH 10) were added and stirred to obtain an O / W type propylpolysiloxane resin aqueous emulsion composition. The average particle size of the emulsion particles was 322 nm. The resulting propylpolysiloxane resin aqueous emulsion composition was uniform with no non-emulsified product and was stable for 3 months or more.

[Example 9]
An O / W type propylpolysiloxane resin aqueous emulsion composition was prepared under the same conditions as in Example 8 except that the amount of n-octyltriethoxysilane added in Example 8 was changed to 9 parts. The average particle size of the emulsion particles was 311 nm. The resulting propylpolysiloxane resin aqueous emulsion composition was uniform with no non-emulsified product and was stable for 3 months or more.

[Example 10]
100 parts of the propylpolysiloxane resin used in Example 7 was put into a vacuum emulsifier and heated to 65 ° C. Next, 6 parts of n-octyltriethoxysilane, 5.8 parts of a 70% aqueous solution of polyoxyethylene (35 mol) undecyl ether, 1.7 parts of polyoxyethylene (3 mol) isodecyl ether and 8.1 parts of water were uniformly mixed. The solution was added and stirred at 65 ° C. at high speed. The obtained O / W type propylpolysiloxane resin aqueous emulsion was cooled to 30 ° C., 41.9 parts of water was added, and the mixture was stirred and diluted. Furthermore, after adding 14 parts of 0.9% carboxyvinyl polymer aqueous solution, 1.1 parts of 1% sodium hydroxide solution was added and stirred. Finally, 12.3 parts of water and 21.3 parts of colloidal silica (concentration 30%, particle diameter 10 nm, pH 10) were added and diluted by stirring to obtain an O / W type propylpolysiloxane resin aqueous emulsion composition. The average particle size of the emulsion particles was 373 nm. The resulting propylpolysiloxane resin aqueous emulsion composition was uniform with no non-emulsified product and was stable for 3 months or more.

[Comparative Example 3]
An attempt was made to prepare an aqueous propylpolysiloxane resin emulsion under the same conditions as in Example 8, except that n-octyltriethoxysilane of Example 8 was not added. The obtained aqueous composition was mostly non-emulsified, and propylpolysiloxane resin was precipitated.

[Comparative Example 4]
An aqueous propylpolysiloxane resin emulsion was tried under the same conditions as in Example 8 except that the amount of n-octyltriethoxysilane added in Example 8 was 3 parts. The obtained aqueous composition had many non-emulsified materials, and propylpolysiloxane resin was precipitated.

[Comparative Example 5]
In a container, 6 parts of n-octyltriethoxysilane, 4.3 parts of polyoxyethylene (7 mol) isodecyl ether and 8.5 parts of water at 50 ° C. are uniformly mixed, and the softening point is 45 ° C., which is a dimethylsiloxane unit. Was added in an amount of 100 mol of solid methylphenylpolysiloxane resin (silicon atom-bonded hydroxyl group content: 7% by weight). Subsequently, the mixture was stirred at a high speed using a propeller type electric stirrer (HEIDON three-one motor, rotating at 700 rpm) at 50 to 70 ° C. and then diluted with 94 parts of water, but did not become an emulsion.

[Comparative Example 6]
In Comparative Example 5, 2.9 parts of a 70% aqueous solution of polyoxyethylene (18 mol) undecyl ether was used instead of 2.0 parts of polyoxyethylene (7 mol) isodecyl ether, and 3.1 parts of water was used instead of 4.0 parts of water. Attempts were made to prepare an aqueous emulsion under the same conditions except that it did not result in an emulsion.

The aqueous silicone resin emulsion composition of the present invention is useful as a paint vehicle, a coating agent, a water repellent, an impregnating agent and the like because it forms a silicone resin film when moisture is evaporated by applying or impregnating on an object.
The method for producing a silicone resin aqueous emulsion composition of the present invention is useful for easily producing the silicone resin aqueous emulsion composition with high productivity.

Claims (16)

(A) In a silicone resin aqueous emulsion composition comprising a silicone resin, (B) silane, (C) a surfactant and (D) water,
Component (A) is the average unit formula (1):
R _m R ¹ _n Si (OX) _p O _{(4-mnp) / 2} (1)
{In the formula, R is an alkyl group, R ¹ is an unsubstituted monovalent hydrocarbon group (excluding an alkyl group) or a substituted monovalent hydrocarbon group, and X is a hydrogen atom or an alkyl group. m, n, and p are numbers satisfying 0.5 ≦ m ≦ 1.8, 0 ≦ n ≦ 1.0, 0.7 ≦ m + n ≦ 1.8, and 0 <p ≦ 1.0. } And selected from the group consisting of R (XO) SiO _2/2 units and R ¹ (XO) SiO _2/2 units (wherein R, R ¹ and X are as defined above) A silicone resin having a softening point of 0 ° C. or lower,
Component (B) is composed of (b1) molecular formula (2): R ² _a Si (OY) _4-a (2)
(Wherein R ² is an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group, Y is an alkyl group, and a is 0, 1, 2, or 3) or Alkoxysilane, or (b2) a partially hydrolyzed condensate of organoalkoxysilane or alkoxysilane, which is blended in an amount of 3.5 to 30% by weight of component (A),
Component (C) is a water-based silicone resin emulsion composition characterized in that it is blended in an amount sufficient to emulsify component (A) and component (B) in component (D). The silicone resin aqueous emulsion composition according to claim 1, wherein the component (A) contains 1 to 50 mol% of the siloxane unit. The aqueous silicone resin emulsion according to claim 1 or 2, wherein n in the average unit formula (1) is 0 and R ² in the molecular formula (2) is an alkyl group or a phenyl group. Composition. X in the average unit formula (1) is a hydrogen atom and / or an alkyl group having 1, 2 or 3 carbon atoms, and Y in the molecular formula (2) is an alkyl group having 1, 2 or 3 carbon atoms , A is 1, The aqueous silicone resin emulsion composition according to claim 3, wherein In the method for producing an aqueous silicone resin emulsion composition according to claim 1, wherein component (A) and component (B) are emulsified in component (D) by the action of component (C), component (A), and [3.5 to 30% by weight of component (A) (B), a component (C) in an amount sufficient to emulsify component (A) and component (B) in component (D), Or a mixture of component (A) and its component (B) of 3.5 to 30% by weight] and [component (A And a mixture of component (C) and component (D)] in an amount sufficient to emulsify component (B) in component (D) at a temperature higher than 0 ° C and lower than 90 ° C. 2. The method for producing an aqueous silicone resin emulsion composition according to claim 1, wherein 6. The method for producing an aqueous silicone resin emulsion composition according to claim 5, wherein a temperature higher than 0 ° C. and lower than or equal to 90 ° C. is 2 ° C. or higher and 75 ° C. or lower. In a silicone resin aqueous emulsion composition comprising (A) a silicone resin, (B) a silane, (C) a surfactant, (E) a water-soluble and thickening polymer, and (D) water,
Component (A) is the average unit formula (1):
R _m R ¹ _n Si (OX) _p O _{(4-mnp) / 2} (1)
{In the formula, R is an alkyl group, R ¹ is an unsubstituted monovalent hydrocarbon group (excluding an alkyl group) or a substituted monovalent hydrocarbon group, and X is a hydrogen atom or an alkyl group. m, n, and p are numbers satisfying 0.5 ≦ m ≦ 1.8, 0 ≦ n ≦ 1.0, 0.7 ≦ m + n ≦ 1.8, and 0 <p ≦ 1.0. } And selected from the group consisting of R (XO) SiO _2/2 units and R ¹ (XO) SiO _2/2 units (wherein R, R ¹ and X are as defined above) A silicone resin having a softening point of 0 ° C. or lower,
Component (B) is composed of (b1) molecular formula (2): R ² _a Si (OY) _4-a (2)
(Wherein R ² is an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group, Y is an alkyl group, and a is 0, 1, 2, or 3) or Alkoxysilane, or (b2) a partially hydrolyzed condensate of organoalkoxysilane or alkoxysilane, which is blended in an amount of 3.5 to 30% by weight of component (A),
Component (C) is blended in an amount sufficient to emulsify component (A) and component (B) in component (D),
The silicone resin aqueous emulsion composition, wherein the component (E) is added in an amount sufficient to improve the storage stability of the aqueous emulsion. The silicone resin aqueous emulsion composition according to claim 7, wherein the component (A) contains 1 to 50 mol% of the siloxane unit. The aqueous silicone resin emulsion according to claim 7 or 8, wherein n in the average unit formula (1) is 0 and R ² in the molecular formula (2) is an alkyl group or a phenyl group. Composition. X in the average unit formula (1) is a hydrogen atom and / or an alkyl group having 1, 2 or 3 carbon atoms, and Y in the molecular formula (2) is an alkyl group having 1, 2 or 3 carbon atoms The silicone resin aqueous emulsion composition according to claim 9, wherein a is 1. The silicone resin aqueous emulsion composition according to claim 7 or 8, wherein the component (E) is a carboxyvinyl polymer. The silicone resin aqueous emulsion composition according to claim 11, further comprising (F) an alkali metal hydroxide. The method for producing an aqueous silicone resin emulsion composition according to claim 7, wherein the component (A) and the component (B) are emulsified in the component (D) by the action of the component (C). [3.5 to 30% by weight of component (A) (B), a component (C) in an amount sufficient to emulsify component (A) and component (B) in component (D), And a mixture of component (A) and its component (B) of 3.5 to 30% by weight] and [component (A And a mixture of component (C) and component (D) sufficient to emulsify component (B) in component (D) at a temperature above 0 ° C. and below 90 ° C. The method for producing an aqueous silicone resin emulsion composition according to claim 7, wherein an aqueous solution of the component (E) is added and mixed. The method for producing an aqueous silicone resin emulsion composition according to claim 13, wherein the component (E) is a carboxyvinyl polymer. The method for producing an aqueous silicone resin emulsion composition according to claim 14, wherein (F) an alkali metal hydroxide or an aqueous solution thereof is added and mixed together with an aqueous carboxyvinyl polymer solution. 14. The method for producing an aqueous silicone resin emulsion composition according to claim 13, wherein a temperature higher than 0 ° C. and lower than or equal to 90 ° C. is 2 ° C. or higher and 75 ° C. or lower.