JPH03281538A - Silicone aqueous emulsion composition and production of silicone particulate matter using the same composition - Google Patents

Abstract

PURPOSE:To obtain the title composition capable of providing particulate matter having excellent mechanical strength, small particle size and uniform shape as well as excellent dispersibility by blending a colloidal silica-silicone core shell body with a curing catalyst, emulsifying agent and water at a specific amount. CONSTITUTION:(A) 100 pts.wt. colloidal silica-silicone core shell body consisting of (i) 5-80wt.% core of colloidal silica and (ii) 20-95wt.% shell of polyorganosiloxane expressed by the average composition formula [R<1> is (substituted)1-8C monovalent organic group; (a) is 1.02-2.02] and having molecular ends blocked with OH is blended with (B) 0-5 pts.wt. curing catalyst, preferably dibutyltin dilaurate, (C) 1-20 pts.wt. emulsifying agent, preferably aliphatic substituted benzenesulfonic acid, etc., and (D) 50-1000 pts.wt. water to provide the objective composition. Furthermore, the composition is cured to from into fine particles by dispersing the composition into a heat medium of gas, etc., such as air heated to >=25 deg.C and bringing the composition into contact with the heat medium, thus providing the silicone particulate matter.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a silicone aqueous emulsion composition and a method for producing silicone granules using the same.

(Prior Art) In recent years, attempts have been made to use silicone granules as a modifying additive for alleviating internal stress and improving impact strength of various organic resins.

Conventionally, the manufacturing method for this type of silicone granules is as follows:
Methods of pulverizing silicone rubber either as it is or after freezing it have been used, but this method has poor productivity, large and uneven particle size, irregular shape and poor dispersibility, and lubrication. There were problems such as poor quality.

Therefore, various methods have been proposed to improve this problem.

For example, JP-A-59-88333 and JP-A-63-17959 disclose a method of spraying a liquid silicone rubber composition into hot air and curing it in the sprayed state to obtain a spherical cured product. Publication No. 82-243821, JP-A No. 62-257939, JP-A No. 63-7794
No. 2 and JP-A No. 63-202658 disclose a method of obtaining spherical particles by forming a liquid silicone rubber composition into an emulsion or suspension using water as a medium, and then hardening the composition by contacting it with a high-temperature liquid or gas. has been done.

However, the granules obtained by the above method lack mechanical strength because they do not contain reinforcing fillers such as various silicas and fumed titanium oxide, and when used as additives for modifying organic resins, The problem is that the shape changes due to the stress applied from the granules, and the granules themselves are destroyed. Furthermore, as a countermeasure to this problem, if a reinforcing filler is added to a liquid silicone rubber composition, it will not only lose its fluidity, but also have a large particle size and irregular shape due to the cohesive properties of the filler. cause problems.

(Problems to be Solved by the Invention) As described above, various methods for manufacturing silicone granules have been proposed in the past, but they have excellent mechanical strength, small particle size, uniform shape, and excellent dispersibility. At present, no method has been developed to obtain silicone granules.

The present invention has been made in response to these conventional circumstances, and is an aqueous silicone material that enables the production of silicone granules that have excellent mechanical strength, are small in particle size, uniform in shape, and have excellent dispersibility. An object of the present invention is to provide an emulsion composition and a method for producing silicone granules using the emulsion composition.

[Structure of the Invention] (Means for Solving the Problems) The silicone composition of the present invention includes (A) (a>80 to 5% by weight of colloidal silica core)
(b) Average compositional formula %Formula %) (wherein, R1 is a substituted or unsubstituted monovalent organic group having 1 to 8 carbon atoms, and a is a number of 1.02 to 8). 100 parts by weight of a colloidal silica silicone faciel body consisting of 20-95% by weight of a polyorganosiloxane shell whose ends are capped with hydroxyl groups, (B) 0-5 parts by weight of a curing catalyst, (C) 1-20 parts by weight of an emulsifier. , and (D) 50 to 1000 parts by weight of water, and the method for producing silicone granules of the present invention using this composition includes heating the composition at 25°C.
The method is characterized in that the silicone is hardened into fine particles by being brought into dispersion contact with the above heat medium.

The silicone aqueous emulsion composition according to the present invention can be produced as follows.

That is, (^) (a) colloidal silica, (b-1) general formula % formula % () (in the formula, R2 is a substituted or unsubstituted 1 having 1 to 8 carbon atoms)
a silicon atom number of 2 that has a structural unit represented by a valent organic group (indicates an integer from Ω to 3) and does not contain a hydroxyl group.
~10 organosiloxanes and optionally (b-2) a silane compound having 1 to 4 alkoxy groups are polycondensed in an aqueous medium in the presence of an emulsifier to form a colloidal silica-silicone core-shell body. It is obtained by preparing an aqueous emulsion and then adding the curing catalyst (B).

(Function) The silicone aqueous emulsion composition according to the present invention has a core-shell body in which a core of colloidal silica is covered with a shell of silicone via siloxane bonds, so that the reinforcing property of colloidal silica is sufficiently enhanced and the composition is effective. By evaporating volatile substances such as water at room temperature or by heating, a cured elastomer product with excellent mechanical strength can be obtained. And, by the manufacturing method according to the present invention, it is possible to obtain silicone granules having excellent mechanical strength, small particle size, uniform shape, and excellent dispersibility.

(Example) First, the components constituting the silicone aqueous emulsion composition according to the present invention will be explained.

The colloidal silica-silicone core-shell body of the component (A) used in the present invention is a component that forms a cured elastomer after water is removed, and one colloidal silica particle of the component (a) is combined with the colloidal silica particle of the component (b). covered with polyorganosiloxane. In more detail, this core-shell body is a simpler system: 1) both ends of polyorganosiloxane are bonded to the silica surface via a siloxane bond, and 2) one end of polyorganosiloxane is bonded to the silica surface. There are three types of polyorganosiloxane: one in which the polyorganosiloxane is bonded via a siloxane bond and the other end is blocked with a hydroxyl group, and 3) both ends of the polyorganosiloxane are blocked with a hydroxyl group and there is no siloxane bond with the silica surface. It is what was done. When a 3.4-functional alkoxysilane or a chain stopper is used in combination, the types of these forms increase and become complex.

The polyorganosiloxane shell portion of component (b) in the colloidal silica silicone core body of component (A) is selected in the range of 20 to 95% by weight. If it is less than 20% by weight, the elastic modulus etc. will be greatly reduced, resulting in a cured product lacking elastomeric properties.

On the other hand, if it exceeds 95% by weight, it will not be possible to sufficiently impart the reinforcing properties of colloidal silica to the polyorganosiloxane,
This results in a cured elastomer that lacks mechanical properties.

In addition, the organic group bonded to the silicon atom of the polyorganosiloxane shell (b) in the core-shell body of component (A) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. .

Examples of unsubstituted organic groups include straight chain or branched alkyl groups such as methyl, ethyl, propyl, hexyl, octyl, decyl, hexadecyl, and octadecyl groups, phenyl, naphthyl, and xenyl groups. Examples include aralkyl groups such as an aryl group, benzyl group, β-phenylethyl group, methylbenzyl group, and naphthylmethyl group, and cycloalkyl groups such as cyclohexyl group and cyclobenzyl group.

Examples of the substituted organic group include groups in which the hydrogen atom of the unsubstituted organic group listed above is substituted with a halogen atom such as fluorine or chlorine. ．． Examples include 3-trifluoropropyl group and 3-fluoropropyl group.

(A) Another monovalent organic group in component (b) includes a carbon functional group and a group containing an ethylenically unsaturated group, and an emulsion using component (A) containing such an organic group can be mentioned. The composition has excellent adhesion (adhesion or fixation) when applied to base materials such as fibers and is advantageous, and the silicone granules obtained from such emulsion compositions are compatible with various organic resins, rubbers, etc. Since it has excellent compatibility and good interfacial adhesion, it is advantageous as a physical property modifier.

The carbon functional group here refers to carbon atoms, hydrogen atoms,
Furthermore, it refers to an organic group composed of at least one atom of nitrogen and oxygen, such as -CH2-Ctl 2-CH2-NH2, Ct(2-(
j(2-CH2-~H-CH2-CH2-NH2, -C
H2-CH2-CH2-NH-CH2-CH2-NH-
Examples include CH2-C)12-NH2, υ CH20H2-CO2-0-CH2-CH-CH2-0H01 (-CH2-CH2-CH2-3H).

In addition, as the ethylenically unsaturated group, those represented by CH2-CM-0-(Ct(2) general formula % formula %() 4 1 CI2 - C-CO-R' -... (V) Other examples of groups containing an ethylenically unsaturated group include those represented by the general formula % ().
(VI) In the formula, n represents an integer of 0 to 10.

Examples of the group containing ethylenically unsaturated represented by the above formula (m) include a vinyloxypropyl group, a vinyloxyethoxypropyl group, a vinyloxyethyl group, a vinyloxyethoxyethyl group, and preferably a vinyloxypropyl group. , vinyloxyethoxyprobyl group.

When the ethylenically unsaturated group is represented by the above formula (IV),
R3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom or a methyl group. Examples of the group represented by the formula (IV) include a vinylphenyl group, an isopropenylphenyl group, and a vinylphenyl group is preferable. Further, as the group containing an ethylenically unsaturated group represented by the formula (IV), vinylphenyl group, 1-(vinylphenyl)ethyl group, 2-(vinylphenyl)ethyl group, (vinylphenyl)methyl group,
Isopropenylphenyl group, 2-(vinylphenoxy)
Examples include ethyl group, 3-(vinylbenzoyloxy)propyl group, 3-(isopropenylhenzoylamino)propyl group, and preferably vinylphenyl group, ■-(
They are vinylphenyl)ethyl group and 2-(vinylphenyl)ethyl group.

When the ethylenically unsaturated group is represented by the above formula (V), R
4 is a hydrogen atom or a methyl group. R5 is an alkylene group having 1 to 6 carbon atoms, -O--S- or -N(R6
) R7-, R6 is a hydrocarbon group or (meth)acryloyl group having 1 to 6 carbon atoms, and R7 is an alkylene group having 1 to 6 carbon atoms. Groups containing an ethylenically unsaturated group represented by formula (V) include γ-acryloxypropyl group, γ-methacryloxypropyl group, N-
methacryloyl-N-methyl-γ-aminopropyl group,
Examples include N-acryloyl-N-methyl-γ-aminopropyl group, N,N-bis(methacryloyl)-γ-aminopropyl group, and preferably N-methacryloyl-
N-methyl-γ-aminopropyl group and N-acryloyl-N-methyl-γ-aminopropyl group.

Further, as the group containing an ethylenically unsaturated group represented by the above formula (Vl), vinyl group, allyl group, homoallyl group, 5
-hexenyl group, 7-octenyl group and the like, preferably vinyl group and allyl group.

Such a group containing a carbon functional group and an ethylenically unsaturated group usually accounts for 0.02 to 10%, Preferably it is within the range of 0.05 to 5%. If it is less than 0.02%, the effect of improving adhesion (adhesion or fixation) when applied to base materials such as fibers is small, and when silicone fine powder is manufactured, dispersibility and compatibility with various organic resins, rubbers, etc. The effect of improving solubility and even interfacial adhesion is small;
On the other hand, if it exceeds 1096, the final cured product may become too hard, and, for example, when silicone fine powder is used as a stress relaxation agent, its function will be insufficient.

The curing catalyst of component (B) is a catalyst capable of rapidly curing the silicone aqueous emulsion composition, and includes metal organic acid salts such as alkyltin organic acid salts and zinc organic acid salts;
Organometallic alcoholades such as tetrabutoxytitanium, n
Examples include amines such as -butylamine and imidazole. In the present invention, alkyltin organic acid salts are preferred, and dialkyltin dicarboxylates such as dibutyltin dilaurate and dioctyltin dilaurate are particularly suitable.

The amount of the curing catalyst (B) is usually 0.1 to 5 parts by weight per 100 parts by weight of the colloidal silicone core shell (A). If the amount is less than 0.1 part by weight, the curing speed will be slow and the strength of the cured product will be low.

However, when a tri- or tetrafunctional alkoxysilane is used when preparing a colloidal silica-silicone core-shell body, a desired elastomer (cured product) can be obtained without adding the curing catalyst. On the other hand, if the amount exceeds 5 parts by weight, the composition tends to increase in viscosity or gel in a short period of time, resulting in an unstable state.

The emulsifier of component (C) has the role of stably existing the colloidal silica-silicone core-shell body in water;
It plays a role as a polycondensation catalyst when forming this core-shell body, and is an anionic emulsifier or a cationic emulsifier.

Examples of the anionic emulsifier include aliphatic substituted benzene sulfonic acid, aliphatic substituted naphthalene sulfonic acid, aliphatic sulfonic acid, silylalkyl sulfonic acid, aliphatic substituted naphthalene sulfonic acid in which the aliphatic substituent has a carbon chain having a length of 6 to 18 carbon atoms, Among them, aliphatic substituted benzenesulfonic acids are more preferred. However, when preparing a colloidal silica-silicone core-shell emulsion, these sulfonic acids are used in the form of sulfonic acids, but since they are later neutralized with an alkali, they are present in the form of sulfonic acid salts in the composition of the present invention.

On the other hand, examples of cationic emulsifiers include alkyltrimethylammonium salts such as octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride, dialkyldimethylammonium salts such as dioctadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, and didodecyldimethylammonium chloride. Examples include quaternary ammonium salt type emulsifiers such as benzalkonium chloride such as octadecyldimethylbenzylammonium chloride and hexadecyldimethylbenzylammonium chloride.

The blending ratio of the emulsifier (C) is usually 1 to 20 parts by weight per 100 parts by weight of the colloidal silica-silicone core shell (A). If the amount is less than 1 part by weight, it is difficult to form stable micelles, and if it exceeds 20 parts by weight, the viscosity of the emulsion increases, resulting in an unstable emulsion.

Furthermore, if necessary, a nonionic emulsifier may be used in combination as component (C). Examples of nonionic emulsifiers include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene (hereinafter abbreviated as POE) alkyl ether, POE sorbitan fatty acid ester, PO
Examples include E-glycerin fatty acid ester, POE alkylphenol ether, and POE polyoxypropylene broth copolymer.

Further, the amount of water as the component (D) is usually in the range of 50 to 1000 parts by weight per 100 parts by weight of the core-shell body of the component (A). (D) Component is less than 50 parts by weight or 10
If it exceeds 0.00 parts by weight, the emulsification state will be poor and the emulsion will become unstable.

Next, a method for producing a silicone aqueous emulsion composition according to the present invention will be explained.

The silicone aqueous emulsion composition of the present invention comprises (A)
Colloidal silica as component (a) and organosiloxane as component (A)(b-1), and optionally (AXb-
2) Prepare a colloidal silica silicone core-shell emulsion by polycondensing component alkoxysilane in an aqueous medium in the presence of an effective amount of an emulsifier or a mixture of emulsifiers, and then harden component (B). The main point is to add a catalyst.

The colloidal silica of component (A) (a) used in the present invention refers to an aqueous dispersion having SiO2 as a basic unit, and in the present invention, colloidal silica with a diameter of 4 to 400 nm.
, particularly preferably those having an average particle diameter of 30 to 150 r+m. Such colloidal silica includes both acidic and alkaline types, and is selected appropriately depending on the conditions. For example, when carrying out emulsion polymerization under acidic conditions using an anionic emulsifier, it is preferable to use acidic colloidal silica.

The organosiloxane (A) (b-1> component) used in the present invention has a structural unit represented by the above formula (II) and does not contain a hydroxyl group and has a silicon number of 1 to 1°. The structure is not particularly limited and may be linear, branched, or cyclic, but preferably has a cyclic structure.

If the number of silicon atoms exceeds 10, it will be difficult to incorporate colloidal silica particles into the siloxane micelles during emulsion polymerization, resulting in particles that cannot participate in the formation of the core-shell body, and as a result, in addition to the desired core-shell body, free particles will be generated. An emulsion is formed in which colloidal silica and polyorganosiloxane micelles coexist. Further, in the case of a siloxane containing a hydroxyl group, a polycondensation reaction occurs during initial emulsification, resulting in a siloxane having more than 10 silicon atoms, which causes the above-mentioned problems, so its use is not preferred.

(A) The substituted or unsubstituted monovalent organic group possessed by the organosiloxane component (b-1) includes the same organic groups as those in the polyorganosiloxane shell in the colloidal silica-silicone core-shell body. .

Examples of the organosiloxane of component (A) (b-1) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,5.7-titramethyl-1°3.5.
7-tetraphenylcyclotetrasiloxane, 1.3,
Examples include cyclic compounds such as 5.7-tetrabenzyltetramethylcyclotetrasiloxane and 1,3.5-tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane.

In addition to the cyclic compounds exemplified above, linear or branched organosiloxanes may also be used. however,
In the case of a linear or branched siloxane, the molecular terminal has an organic group other than a hydroxyl group, such as an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, 3,3.
Preferably, it is blocked with a 3-trifluoropropyldimethylsilyl group or the like.

In addition, the alkoxysilane as component (A) (b-2), which is used as necessary, is one of the components forming the shell part, but it is necessary to prevent the interfacial bond between the colloidal silica core and the organosiloxane shell. It is also effective as an intermediary.

Examples of such organic silane compounds having 1 to 4 alkoxy groups include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyltri(methoxyethoxy)silane, and γ-methacryloxyethyltrisilane. Methoxysilane, γ-methacryloxyethyltriethoxysilane, γ
-Acryloxyethyltrimethoxysilane, γ-acryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxyethyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane Methoxysilane, γ-acryloxypropyltriethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyl trimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane,
Ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoquinesilane, propyltributoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, dimethyldipropoxysilane, dimethylsibutquinsilane, diethyldimethoxysilane, diethyl Jetoxysilane, diethyldipropoxysilane, diethyljetoxycin,
Methyl ethyltrimethoxysilane, methylpropyljethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycid bovine dipropyltrimethoxysilane, γ Examples include -glycidoxypropylmethyldimethoxysilane and fluorinated alkoxysilanes such as fluoroalkylalkoxysilane.

The above-mentioned organone loxane as the component (A) (b-1) and the alkoxysilane as the component (A) (b-2) are the components of the colloidal silica-silicone core-shell body in the composition according to the present invention. The organosiloxane shell portion is 20 to 95% by weight, and (I)
The average composition formula of the formula RS i O (4-a) 72 (wherein R1 is a substituted or unsubstituted monovalent organic group having 1 to 8 carbon atoms, a is a number of 1.02 to 8) It is blended accordingly.

In addition, when a compound having both an alkoxy group and a group containing a carbon functional group or an ethylenically unsaturated group is blended as component (A) (b-2), the cured elastomer product formed from the composition according to the present invention It is advantageous in that it can improve adhesion (adhesion or fixation) to base materials such as fibers, and in the case of silicone granules, it can improve compatibility with various organic resins, rubbers, etc., and interfacial adhesion. However, the blending amount is 0.02 to 10%, more preferably 0.05 to 5%, based on the total amount of organic groups bonded to silicon atoms in the average composition formula of formula (1) above. It is desirable to mix them.

Examples of organosilicon compounds having both a carbon functional group and an alkoxy group include 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -aminopropylmethyldimethoxysilane, N-diethylenetriaminepropylmethyldimethoxysilane, 3-glycidoxypropylmethylethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3-
Examples include mercaptopropylmethyldimethoxysilane.

On the other hand, examples of organosilicon compounds having both an ethylenically unsaturated group and an alkoxy group include (vinyloxypropyl)methyldimethoxysilane, (vinyloxyethoxypropyl)methyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, l- (m-vinylphenyl)
Methyldimethylisopropoxysilane, 2-(p-vinylphenyl)ethylmethyldimethoxine, 3-(p-vinylphenyl)ethylmethyldimethoxysilane,
-vinylbenzoyloxy)propylmethyldimethoxysilane, 1-(p-vinylphenylshicine, 1-(0-vinylphenyl)-1.1.2-)
Dimethyl-2,2-dimethoxydisilane, l-(p-vinylphenyl)-1,1-diphenyl-3-ethyl-3
, 3-jethoxydisiloxane, m-vinylphenyl [
3-(triethoxysilyl)propyl]diphenylsilane, [3-(p-isopropenylbenzoylamino)
[propyl] phenyldipropoxysilane, γ-acryloxypropylmethyljethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-methacryloyl-N-methyl-γ-aminopropylmethyldimethoxy Silane, N-acryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane, N. N-bis(methacryloyl)-γ-aminopropylmethyldimethoxysilane, N,N-bis(acryloyl)-γ-aminopropylmethyldimethoxysilane, N-methacryloyl-N-methyl-γ-aminopropylphenyldiethoxysilane,
l-(3-methacryloxypropyl)-1.1.3-trimethyl-3,3dimethoxydisiloxane, vinylmethyldimethoxylan, vinylethyldiisopropoxysilane, vinyldimethylnidoxinlanmethquinsilane, 5-hexenyl Examples include silane compounds such as methyljethoxysilane and 7-octynylethylsiethoxysilane, and siloxane compounds obtained by hydrolyzing the same, and these may be used alone or in a mixture of two or more.

The above-mentioned organosilicon compounds are preferably (vinyloxypropyl)methyldimethoxysilane, (vinyloxypropyl)methyldimethoxysilane, (
vinyloxyethoxypropyl)methyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, 2-(
p-vinylphenyl)ethylmethyldimethoxysilane,
3-(p-vinylbenzoyloxy)propylmethyldimethoxysilane, 1-(p-vinylphenyl)ethylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, N-methacryloyl-N-methyl-γaminopropylmethyldimethoxy silane, N-acryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, more preferably (
Silane compounds such as vinyloxypropyl)methyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, N-methacryloyl-N-methyl-γ-aminopropylmethyldimethoxysilane, and vinylmethyldimethoxysilane, and siloxane compounds obtained by hydrolyzing these. be.

As described above, the silicone aqueous emulsion composition according to the present invention comprises colloidal silica as the component (A)(a), organosiloxane as the component (A>(b-1)), and optionally (A)( A colloidal silica-silicone core-shell body is prepared by shear mixing the component b-2) with the alkoxysilane using a homogenizer in the presence of an emulsifier in an aqueous medium and polycondensing the mixture. It can be produced by adding a curing catalyst.

This emulsifier mainly plays the role of a surfactant to emulsify components (A) (b-1), and at the same time
) component, (A) (b-1) component and (A) (b
-2) It functions as a catalyst for the polycondensation reaction with component 2), and the anionic emulsifier is preferably an organic sulfonic acid emulsifier, and the anionic emulsifier is preferably a quaternary ammonium salt type. However, in the case of the quaternary ammonium salt type, the catalytic action is low depending on the type, so it is desirable to use an alkali catalyst such as sodium hydroxide or potassium hydroxide in combination.

In addition, the usage amount of this emulsifier is as follows: (A) component (a);
A total of 100 parts by weight of components (A) (b-1) and (A) (b-2) is preferred, and as the anionic emulsifier, a quaternary ammonium salt type is preferred. However, in the case of the quaternary ammonium salt type, the catalytic action is low depending on the type, so it is desirable to use an alkali catalyst such as sodium hydroxide or potassium hydroxide in combination.

In addition, the usage amount of this emulsifier is as follows: (A) component (a) and (
The amount is usually 1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on the total amount of IOO parts by weight of components A)(b-1) and (A)(b-2). In addition, a nonionic emulsifier may be used in combination if necessary.

In preparing the colloidal silica-silicone core-shell body, a combination of an acidic colloidal silica-anionic emulsifier and an alkaline colloidal cationic emulsifier is selected in order to maintain colloidal silica in a stable state.

The amount of water used in this case is (A) component (a) and (A) (
Usually 50 to 1000 parts by weight, preferably 1 to 100 parts by weight of the total amount of b-1) and (A) (b-2).
00 to 500 parts by weight, and the condensation temperature is usually 5 to 10 parts by weight.
It is 0°C.

In addition, when preparing the colloidal silica-silicone core-shell body in the composition according to the present invention, a crosslinking agent may be added as a third component in order to improve the strength of the silicone shell portion. Examples of the crosslinking agent include trifunctional trimethoxysilane such as methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, and (3,3,3-trifluoropropyl)trimethoxysilane. and tetrafunctional crosslinking agents such as tetraethoxysilane. The amount of this crosslinking agent added is (A) (b
-1) and (A) (b-2) It is usually 10% by weight or less, preferably 5% by weight or less, based on the total amount of components (b-2).

Since the colloidal silica-silicone core-shell emulsion in the composition according to the present invention obtained as described above is acidic or alkaline, it is necessary to neutralize it with an alkali or acid to maintain long-term stability. Examples of this alkaline substance include sodium hydroxide,
Potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine, etc. are used, and as acids, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid are used.

If necessary, a curing catalyst as component (B) is added to the colloidal silica-silicone core-shell body, and the mixture is stirred and mixed to complete the production of the silicone aqueous emulsion composition of the present invention. As the curing catalyst used in the present invention, dialkyltin dihydroborate is preferably used as described above. In addition, when using these curing catalysts, it is preferable that an emulsifier and water be used in advance in a conventional manner to form a 0/1 emulsion or an 10 type emulsion. It is preferably within the range of 25°C.

Next, a method for producing silicone granules using the silicone aqueous emulsion composition of the present invention will be explained.

In this method, the silicone aqueous emulsion composition according to the present invention is brought into dispersion contact with a heat medium of 25°C or higher, such as a liquid or gas, and the colloidal silica-silicone core-shell body, which is the main component in the composition, is transformed into fine particles. It consists of curing. If the heating temperature is less than 25°C, the curing speed of the core-shell body will be slow, making it difficult to obtain silicone granules with desired properties. A particularly preferred heating temperature is 50°C or higher. The liquid used as the heat medium may be any liquid that does not dissolve the core-shell body or inhibit its hardening, and examples thereof include liquid paraffin, waxes, dimethyl silicone oil, and phthalate esters.

As for the gas used as the heating medium, it is preferable to avoid anything that would dissolve the core-shell material or inhibit its hardening, as in the case of liquids, and it is also desirable to avoid flammable materials, such as air, nitrogen gas, and various other gases. Nonflammable gas is suitable.

The above silicone aqueous emulsion composition is brought into dispersion contact with a heat medium at a temperature of 25°C or higher, and the colloidal silica in the composition is
Methods for completing the curing of the silicone core shell body include, for example, spraying the composition into hot air to complete the curing, or adding the composition in small portions to a mixer equipped with an agitator filled with a heating medium set at a predetermined temperature. There is a method in which the composition is continuously supplied and continuously contacted and dispersed while stirring, or a method in which a heated liquid is poured into the composition and stirred.

The silicone granules thus obtained can be used either alone or in combination with other materials. When used in combination with other materials, the physical properties such as mechanical strength, water resistance, and lubricity of various materials to which it is added can be improved.

In such a case, the silicone granules may be applied to, for example, the following, but are not limited to these objects.

Namely, solid lubricants, water repellents, release agents, anti-stick agents,
Possible uses include grease, oil, cement, plaster, paint, casting materials, molding materials, films, agricultural chemicals, and medical uses. In addition, examples of target polymers particularly when mixed into polymer materials include natural rubber, polychloroprene rubber, polybutadiene rubber, 5BRSEPR, EPT rubber,
Polyisoprene rubber, polyisobutene rubber, polyacrylic ester rubber, polyurethane rubber, butadiene acrylonitrile copolymer rubber, polyester rubber, polysulfide rubber, fluororubber, silicone rubber, or copolymer rubber of these rubbers, or There are mixtures, and the resin materials include nylon-5 and nylon-5.
6. Nylon = 7, nylon-8, nylon-9, nylon-10, nylon-11, nylon-12, nylon-66, various polyamides represented by aromatic polyamides such as Kevlar, polyethylene terephthalate,
Saturated polyesters represented by polybutylene terephthalate, polyhydrogenated xylylene terephthalate, polycaprolactone, polycaprolactone, polycarbonate, ABS resin, AS resin, polystyrene, polyethylene, polypropylene, polybutane, polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride, Acrylonitrile, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polymethyl methacrylate, fluorine-containing resin,
Other polyolefin resins, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, bentone, polyphenylene oxide, polyethers such as polyacetal, phenol resin, polyurethane resin, acrylic resin, urea resin, unsaturated polyester resin, melamine resin, phthalate resin , BT resin,
Polyimide resin, silicone resin, celluloid, acetyl cellulose, epoxy acrylate, polyacrylate, various thermoplastic resins such as epoxy resin, thermosetting resin, cured by high energy rays such as ultraviolet rays, gamma rays, and electron beams. Examples include resins, block or random copolymers, or blends of these resins.

Of course, these resins contain various inorganic powder fillers, glass fibers, carbon fibers, and other fibrous fillers or reinforcing agents, heat resistance improvers, weather resistance improvers, other stabilizers, modifiers, pigments, dyes, etc. It goes without saying that it may be contained.

Examples of the present invention will be specifically shown below.

Note that parts and % in the examples represent parts by weight and % by weight unless otherwise specified.

In addition, the average particle diameter of colloidal silica as a raw material and colloidal silica-silicone core-shell body as an intermediate was measured using a laser particle size analysis system LPA-3000S 731.00 manufactured by Hibaku Denshi Co., Ltd., which uses a dynamic light scattering method. It was determined using

Furthermore, when the intermediate colloidal silica-silicone core-shell body is regarded as a graft polymer, that is, when the floidal silica core is regarded as a trunk polymer and the silicone shell is regarded as a technical polymer, the grafting ratio and grafting efficiency are determined by the following method. Ta. That is, the core-shell body-containing emulsion was heated at 40°C/0.5mmHg.

A constant pressure of ff1 (ff) of the dried core-shell body obtained by drying under reduced pressure for 5 hours is put into cyclohexane, shaken for 2 hours with a shaker to dissolve the free polyorganosiloxane, and then heated with a centrifuge. Rotation speed 23.00Or
Centrifuge at pm for 30 minutes to obtain insoluble matter.

Next, it was dried at 120° C. for 1 hour using a vacuum dryer to obtain the weight (m) of insoluble matter, and the grafting rate and grafting efficiency were calculated using the following formula.

Grafting ratio = (m) - (ρ) X Core fraction in core-shell body x 100 (ρ) ×
100 (g) 100 (X Core fraction in core shell body Example 1 Acidic colloidal silica Nortex OL (manufactured by Nissan Chemical Industries, Ltd., average particle diameter 84 nm SS i 022
0.66%, Na 200.019%, PH2,78
-, abbreviated as silica-1) i, ooo parts, 470 parts of distilled water, and 8.4 parts of dodecylbenzenesulfonic acid,
Octamethylcyclotetrasiloxane (abbreviated as b-1)
After adding 210 parts and pre-stirring with a homomixer,
The mixture was emulsified and dispersed by passing it through a homogenizer twice at a pressure of 300 kgf/cJ.

Transfer this mixed solution to a separable flask equipped with a condenser, nitrogen inlet, and stirrer, and stir and mix.
Condensation was completed by heating at 5°C for 5 hours and cooling at 5°C for 48 hours. Next, this polyorganosiloxane emulsion was neutralized to pH 7 with an aqueous sodium carbonate solution to complete the condensation. The condensation rate of octamethylcyclotetrasiloxane in the obtained polyorganosiloxane was 99.6%.

Furthermore, it was confirmed by particle size analysis based on dynamic light scattering and electron microscopy that the polyorganosiloxane was a colloidal silica-silicone core-shell material. That is, when the particle size was analyzed using a racer particle size analysis system (LPA-300OS/3100 manufactured by Hibaku Denshi Co., Ltd.), it was found that 84r of the raw material colloidal silica
The monodisperse particle size distribution with a peak around v completely disappeared, and a monodisperse particle size distribution with a peak around 155 parts m newly appeared. Further, when observed using an electron microscope, only silicone particle images were confirmed, and no raw material silica particle images were observed at all.

On the other hand, a part of this core-shell body emulsion was poured into a large amount of acetone to precipitate a core-shell body, and after a day,
It was dried in a vacuum dryer at 50°C for 12 hours to obtain a core-shell aggregate. As a result of elemental analysis, IR and IH129SINMR analysis of this core-shell aggregate, the proportion of silicone shell was 49.2%. Furthermore, when the core-shell body was considered to be a graft polymer, the grafting rate and grafting efficiency were 40 and 2%, respectively.

Next, the colloidal silica-silicone core-shell aqueous emulsion prepared above (solid content 24.
0%) to a 50% aqueous emulsion of dibutyltin dilaurate (50 parts dibutyltin dilaurate, 5 parts sodium dodecylbenzenesulfonate and 4 parts distilled water)
A silicone aqueous emulsion composition was obtained by adding 0.24 parts (prepared with 5 parts) at 25° C. and mixing and stirring.

The above silicone aqueous emulsion composition was poured into a fluororesin container and placed in an atmosphere at a temperature of 25°C and a relative temperature of 60%.
A rubber-like sheet with a thickness of approximately 1 mm+ was obtained by allowing the mixture to stand for one week and proceeding with casting and curing. The hardness, tensile strength, 100% tensile stress, and elongation of this rubber sheet were evaluated according to Tsuki SK 6301, and the results shown in Table 1 were obtained.

In addition, Table 1 shows the above silicone aqueous emulsion composition.
After casting on the various substrates shown in Figure 1, rubber-like sheets were obtained on each of the various substrates when left under the same conditions. Table 1 also shows the results of examining the adhesion between these rubber sheets and various base materials.

[Determination of adhesion: Pull one end of the rubber-like sheet provided on the base material in a direction almost perpendicular to the base material at a speed of about 300 mm/min, and observe the state of the rubber-like sheet and base material at this time. It was evaluated as follows.

◎... Extremely excellent adhesion, not interfacial peeling, but destruction of the rubber sheet O... Interfacial peeling occurs, but considerable force is required to peel △... Interfacial peeling occurs, but no peeling occurs The force used for drying is slightly smaller than the O mark above. Using Kagaku Co., Ltd. product name), the inlet temperature was 250℃,
When the colloidal silica silicone core shell body was cured by spraying under conditions of an outlet temperature of 100° C. and a discharge rate of fil/hr, 110 g of silicone granules were obtained from the product container at the bottom of the cyclone. When this silicone granule was observed under an electron microscope, the average particle size was 3.
．． It was found that the particles were 0 μm in shape and had a shape similar to a pearl.

Next, 10 parts of this silicone granule and the intrinsic viscosity [η
] or 100 parts of polybutylene terephthalate of 05 were mixed to prepare a thermoplastic resin composition. and,
This composition was prepared using a twin-screw extruder at a cylinder temperature of 2
Extrusion processing was performed at 30°C to obtain a pellet. When the fractured surface of the obtained pellet was observed with a scanning electron microscope, it was found that the silicone particles were uniformly dispersed in the resin layer, and that the shape was maintained as spherical before mixing without being deformed or destroyed. I was able to confirm that it was there.

Also, using this pellet, the cylinder temperature 231)
℃, injection molding was performed at a mold temperature of 60℃ to prepare test pieces for physical property evaluation. The results of the impact resistance test conducted on this test piece are also shown in Table-1. In addition, the impact resistance test is A
Izot impact strength was measured at a temperature of 23° C. with a 1/4′ notch according to STM-D256.

Example 2.3 A polyorganosiloxane emulsion was prepared under the same conditions as in Example 1, except that the blending ratio of various components was changed. These obtained polyorganosiloxanes were confirmed to be colloidal silica silicone core-el bodies having a monodisperse particle size distribution by particle size analysis based on dynamic light scattering and observation using an electron microscope. These core-shell bodies were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Next, dibutyltin dilaurate was added to the core-shell aqueous emulsion under the same conditions as in Example 1 to obtain a silicone aqueous emulsion composition.

The silicone aqueous emulsion composition thus obtained was cured in the same manner as in Example 1 to prepare a rubber sheet, and its physical properties were investigated. The results are shown in Table-1.

In addition, the above silicone aqueous emulsion composition was prepared in Example 1.
Using the same method as in Example 1, the adhesiveness between the rubber sheet and various substrates was evaluated for the rubber sheets on various substrates obtained by casting and curing on various substrates. The results of the investigation are also shown in Table 1.

Furthermore, the above silicone aqueous emulsion composition was spray-cured in the same manner as in Example 1 to obtain silicone granules, and various physical properties of the obtained silicone granules were investigated and under the same conditions as in Example 1. A pellet was prepared by mixing with polybutylene terephthalate and extrusion processing, and the same evaluation as in Example 1 was performed. These results are also shown in Table-1.

Example 4 Snowtex OZL as acidic colloidal silica
(Manufactured by Yasan Kagaku Kogyo Co., Ltd., average particle size 122 nIl, S
i 0221.14%, Na 200.1.01%
A polyorganosiloxane emulsion was prepared with the same composition and under the same conditions as in Example 1, except that silica-2 (abbreviated as silica-2) was used. The obtained polyorganosiloxane was confirmed to be a colloidal silica silicone core-shell material having a monodisperse particle size distribution by particle size analysis based on dynamic light scattering and observation using an electron microscope. This core-shell body was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Next, dibutyltin dilaurate was added to the core-shell aqueous emulsion under the same conditions as in Example 1 to obtain a silicone aqueous emulsion composition.

The thus obtained aqueous silicone emulsion composition was cured in the same manner as in Example 1 to prepare a rubber-like sheet, and its physical properties were investigated. The results are shown in Table-1.

In addition, the above silicone aqueous emulsion composition was prepared in Example 1.
Using the same method as in Example 1, the adhesiveness between the rubber sheet and various substrates was evaluated for the rubber sheets on various substrates obtained by casting and curing on various substrates. The results of the investigation are also shown in Table 1.

Furthermore, the above silicone aqueous emulsion composition was spray-cured in the same manner as in Example 1 to obtain silicone granules, and various physical properties of the obtained silicone granules were investigated and under the same conditions as in Example 1. The pellets were mixed with polybutylene terephthalate and extruded to form pellets, and evaluated in the same manner as in Example]. These results are also shown in Table-1.

Example 5.6 In the case of Example 1, 3-aminopropylmethyldimethoxysilane (abbreviated as b-2a) (Example 5) or (p-vinyl phenyl)methyldimethoxysilane (
b-2b) (Example 6) A polyorganosiloxane emulsion was prepared with the same composition and under the same conditions as in Example 1, except that 4.2 parts were added in advance.

This polyorganosiloxane emulsion obtained is
Colloidal silica with a monodisperse particle size distribution was determined by particle size analysis based on dynamic light scattering and electron microscopy observation.
It was confirmed that it was a silicone core shell body. This core-shell body was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Next, dibutyltin dilaurate was added to the core-shell aqueous emulsion under the same conditions as in Example 1 to obtain a silicone aqueous emulsion composition.

The silicone aqueous emulsion composition thus obtained was cured in the same manner as in Example 1 to prepare a rubber-like sheet, and its physical properties were investigated. The results are shown in Table-1.

In addition, the above silicone aqueous emulsion composition was prepared in Example 1.
Using the same method as in Example 1, the adhesiveness between the rubber sheet and various substrates was evaluated for the rubber sheets on various substrates obtained by casting and curing on various substrates. The results of the investigation are also shown in Table 1.

Furthermore, the above silicone aqueous emulsion composition was spray-cured in the same manner as in Example 1 to obtain silicone granules, and various physical properties of the obtained silicone granules were investigated and under the same conditions as in Example 1. The mixture was mixed with polybutylene terephthalate and extruded to form pellets, and the same evaluation as in Example 1 was conducted. These results are also shown in Table-1.

Example 7 In the case of Example 1, Snowtex 20L of alkaline colloidal silica was used instead of acidic colloidal silica.
(Manufactured by Yasan Kagaku Kogyo Co., Ltd., average particle size 72r+m, S
i O220, 3 parts%, Na 200.022%
, PH9,93...abbreviated as silica-3), 30 parts of dioctadecyldimethylammonium chloride and 6.0 parts of potassium hydroxide were used in place of dodecylbenzenesulfonic acid, and octamethylcyclotetrasiloxane (abbreviated as silica-3) was used in advance. b-1), 3-mercaptopropylmethyldimethoxysilane (abbreviated as b-2C)4.
A polyorganosiloxane emulsion was prepared with the same composition and under the same conditions as in Example 1, except that 2 parts of the emulsion was added (hydrochloric acid was used for neutralization).

This polyorganosiloxane emulsion obtained is
Colloidal silica with a monodisperse particle size distribution was determined by particle size analysis based on dynamic light scattering and electron microscopy observation.
It was confirmed that it was a silicone core shell body. This core-shell body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Next, dibutyltin dilaurate was added to the core-shell aqueous emulsion under the same conditions as in Example 1 to obtain a silicone aqueous emulsion composition.

The silicone aqueous emulsion composition thus obtained was cured in the same manner as in Example] to prepare a rubber-like sheet, and its physical properties were investigated. The results are shown in Table-2.

Examples of the above silicone aqueous emulsion composition]
Using the same method as in Example 1, the adhesiveness between the rubber sheet and various substrates was evaluated for the rubber sheets on various substrates obtained by casting and curing on various substrates. The results of the investigation are also shown in Table 2.

Furthermore, the above silicone aqueous emulsion composition was spray-cured in the same manner as in Example 1 to obtain silicone granules, and various physical properties of the obtained silicone granules were investigated and under the same conditions as in Example 1. The mixture was mixed with polybutylene terephthalate and extruded to form pellets, and the same evaluation as in Example 1 was conducted. These results are also shown in Table-2.

Example 8 Snowtex as alkaline colloidal silica
20L (abbreviated as liquor 3) 1000 parts, distilled water 47
0 parts, dioctadecyldimethylammonium chloride 3
0 parts of potassium hydroxide and 6.0 parts of potassium hydroxide, 21 parts of octamethylcyclotetrasiloxane (abbreviated as b-1)
A mixture of 1 part and 4.2 parts of 3-glyndoxypropylmethyldimethoxysilane (abbreviated as b-2d) was added, and a polyorganosiloxane emulsion was prepared and neutralized under the same conditions as in Example 1. (using hydrochloric acid), a polyorganosiloxane emulsion with a condensation rate of 95.3% of octamethylcyclotetrasiloxane was obtained.

This polyorganosiloxane emulsion obtained is
Colloidal silica with a monodisperse particle size distribution was determined by particle size analysis based on dynamic light scattering and electron microscopy observation.
It was confirmed that it was a silicone core shell body. This core-shell body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Next, dibutyltin dilaurate was added to the core-shell aqueous emulsion under the same conditions as in Example 1 to obtain a silicone aqueous emulsion composition.

The thus obtained aqueous silicone emulsion composition was cured in the same manner as in Example 1 to prepare a rubber-like sheet, and its physical properties were investigated. The results are shown in Table-2.

In addition, the above silicone aqueous emulsion composition was prepared in Example 1.
Using the same method as in Example 1, the adhesiveness between the rubber sheet and various substrates was evaluated for the rubber sheets on various substrates obtained by casting and curing on various substrates. The results of the investigation are also shown in Table 2.

Example 9 In the case of Example 1, 42 parts of 3-aminopropylmethylcymethquine silane (abbreviated as b-2a) and tetraethoxysilane (abbreviated as b-1) were added in advance to octamethylcyclotetrasiloxane (abbreviated as b-1). A polyorganosiloxane emulsion was prepared with the same composition and under the same conditions as in Example 1, except that 8.4 parts (abbreviated as 2e) were blended.

This polyorganosiloxane emulsion obtained is
Colloidal silica with a monodisperse particle size distribution was determined by particle size analysis based on dynamic light scattering and electron microscopy observation.
It was confirmed that it was a silicone core shell body. This core-shell body was evaluated in the same manner as in Example], and the results are shown in Table 2.

Next, dibutyltin dilaurate was added to the core-shell aqueous emulsion under the same conditions as in Example 1 to obtain a silicone aqueous emulsion composition.

The thus obtained aqueous silicone emulsion composition was cured in the same manner as in Example 1 to prepare a rubber-like sheet, and its physical properties were investigated. The results are shown in Table-2.

In addition, the above silicone aqueous emulsion composition was prepared in Example 1.
Using the same method as in Example 1, the adhesiveness between the rubber sheet and various substrates was evaluated for the rubber sheets on various substrates obtained by casting and curing on various substrates. The results of the investigation are also shown in Table 2.

Comparative Example 1 The same conditions as in Example 1 were carried out without using colloidal silica, but using 210 parts of octamethylcyclotetrasiloxane (abbreviated as b-1), 4.2 parts of dodecylbenzenesulfonic acid, and 630 parts of distilled water. A polyorganosiloxane emulsion was prepared.

The siloxane micelle particle size in this emulsion is 275
The condensation rate of octamethylcyclotetrasiloxane was 953%.

Next, using this polyorganosiloxane emulsion, dibutyltin dilaurate was added under the same conditions as in Example 1 to obtain a silicone aqueous emulsion composition.

The obtained silicone aqueous emulsion composition was prepared in Example 1.
A comb-shaped sheet was prepared by curing in the same manner as in the case of , and its physical properties were investigated. The results are shown in Table-2.

In addition, the above silicone aqueous emulsion composition was prepared in Example 1.
Using the same method as in Example 1, the adhesiveness between the rubber sheet and various substrates was evaluated for the rubber sheets on various substrates obtained by casting and curing on various substrates. The results are also shown in Table 2.

Furthermore, the above silicone aqueous emulsion composition was spray-cured in the same manner as in Example 1 to obtain silicone granules, and various physical properties of the obtained silicone granules were investigated and under the same conditions as in Example 1. A pellet was prepared by extrusion processing with polybutylene terephthalate, and the same evaluation as in Example 1 was performed. These results are also shown in Table-2.

Comparative Example 2.3 Same as in Example 1, without using colloidal silica and using 210 parts of octamethylcyclotetrasiloxane (abbreviated as b-1), 8.4 parts of dodecylbenzene sulfonic acid, and 470 parts of distilled water. A polyorganosiloxane emulsion was prepared under the same conditions.

The siloxane micelle particle size in this emulsion is 280
nli, and the condensation rate of octamethylcyclotetrasiloxane was 963%.

Next, to 69 parts of this polyorganohydrodiene siloxane emulsion, the above Snowtex 01,
(Silica-1) and dibutyltin dilaurate 50% aqueous emulsion were prepared by blending 100 parts and 0.40 parts (Comparative Example 2) and 50 parts and 0.40 parts (Comparative Example 3), respectively. did.

The compound prepared above was cured in the same manner as in Example 1 to prepare a rubber sheet, and its physical properties were investigated. The results are shown in Table-2.

In addition, the above silicone aqueous emulsion composition was prepared in Example 1.
Using the same method as in Example 1, the adhesiveness between the rubber sheet and various substrates was evaluated for the rubber sheets on various substrates obtained by casting and curing on various substrates. The results of the investigation are also shown in Table 2.

Furthermore, the above silicone aqueous emulsion composition was spray-cured in the same manner as in Example 1 to obtain silicone granules, and various physical properties of the obtained silicone granules were investigated and under the same conditions as in Example 1. A pellet was prepared by mixing with polybutylene terephthalate and extrusion processing, and the same evaluation as in Example 1 was performed. These results are also shown in Table-2.

Comparative Example 4 An attempt was made to prepare a rubber-like sheet without adding dibutyltin dilaurate as a curing catalyst to the colloidal silica silicone core-shell aqueous emulsion prepared in Example 1. However, the physical properties could not be evaluated because it did not harden even after being left for one month.

Reference Example A test piece for evaluating physical properties was prepared under the same conditions as in Example 1 without adding silicone granules to polybutylene terephthalate, and its impact resistance was tested.The Izot impact strength was 6. Okgf Italian c+n/c
It was m.

(The following is a blank space) [Effects of the Invention] As explained above, the silicone aqueous emulsion composition according to the present invention has a core-shell body in which a core of colloidal silica is covered with a shell of silicone through siloxane bonds. , it is possible to sufficiently and effectively bring out the reinforcing properties of colloidal silica, and by evaporating volatile substances such as moisture at room temperature or by heating, a cured elastomer product with excellent mechanical strength can be obtained. .

And, by the method according to the present invention, it has excellent mechanical strength,
Furthermore, silicone granules having a small particle size, uniform shape, and excellent dispersibility can be obtained.

Claims (2)

[Claims] (1) (A) (a) Colloidal silica core 80-5% by weight (
b) Average compositional formula R^1_aSiO_(_4_-_a_)_/_2...(
I) (wherein R^1 is a substituted or unsubstituted monovalent organic group having 1 to 8 carbon atoms, and a represents a number of 1.02 to 2.02)
100 parts by weight of a colloidal silica-silicone core-shell body consisting of 20 to 95% by weight of a polyorganosiloxane shell whose molecular terminals are blocked with hydroxyl groups, (B) 0 to 5 parts by weight of a curing catalyst, (C) Emulsifier 1 20 parts by weight, and (D) 50 to 1000 parts by weight of water. (2) A method for producing silicone granules, which comprises bringing the aqueous silicone emulsion composition according to claim 1 into dispersion contact with a heat medium at 25° C. or higher to harden the silicone into fine particles.