JP2001048984A - Production of aryl group-containing silicone latex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a latex of an aryl group-containing polyorganosiloxane having a high molecular weight and regulated particle diameters in good productivity. SOLUTION: This method for producing a latex of an aryl group-containing polyorganosiloxane comprises emulsifying and polymerizing a mixture comprising an aryl group-containing linear organosiloxane having a substituent selected from a hydroxy group and an alkoxy group at the terminal, an emulsifier, an acid catalyst and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyorganosiloxane latex used as a raw material for a rubber source of an impact-resistant resin, a silicone-based flame retardant, an aqueous emulsion paint, and a sliding property modifier for a thermoplastic resin. About the method.

[0002]

2. Description of the Related Art Polyorganosiloxane is used as a rubber source for impact-resistant resins and a raw material for paints, taking advantage of its excellent impact absorption performance and water repellency.

Conventionally, polydimethylsiloxane, which is industrially easily available, has been generally used as a polyorganosiloxane used as a modifier for these resin materials.

However, polydimethylsiloxane has a low refractive index, and particularly in a resin composition mixed with a resin having a high refractive index, a pearl-like coloring defect due to a difference in refractive index between the two tends to occur, and the resin material is difficult to use. There is a disadvantage that the coloring property of the pigments and the like originally possessed is remarkably reduced.

A conventional method for producing a polyorganosiloxane by an emulsion polymerization method is disclosed in, for example,
Japanese Patent No. 69859 discloses a method for obtaining a polyorganosiloxane latex by mixing a polysiloxane precursor composed of an organosiloxane, a siloxane-based crosslinking agent and a siloxane-based graft-linking agent, a surfactant, a polymerization catalyst, and water and heating the mixture. Has been described.

Japanese Patent Application Laid-Open No. 5-194740 discloses a method for producing a polyorganosiloxane latex having a number average particle diameter of 0.1 μm or less.
No. 259696 proposes a method for reducing the viscosity of latex and improving the productivity of polyorganosiloxane latex.

However, JP-A-63-69859, JP-A-5-194740, and JP-A-8-194740
No. 259696 does not specifically suggest a method for obtaining a polyorganosiloxane latex containing an aryl group, and when a phenyl group-containing cyclic organosiloxane described in the specification is used,
Since the phenyl group-containing cyclic organosiloxane is a room temperature solid having a relatively high melting point, the temperature and pressure during emulsion polymerization must be kept high, and the reactivity of the aryl group-containing cyclic siloxane is poor. For,
There has been a problem that it is difficult to obtain a latex of an aryl group-containing polyorganosiloxane having a high molecular weight and a controlled particle diameter.

That is, a method for producing a polyorganosiloxane latex having a high molecular weight and a high refractive index having a controlled particle diameter with a high productivity has not been found so far, and the development of a production technique which overcomes this has been strongly developed. Was desired.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for obtaining a latex of an aryl group-containing polyorganosiloxane having a high molecular weight and a controlled particle size with high productivity.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have assiduously studied the emulsion polymerization method of an aryl group-containing polyorganosiloxane and the molecular weight of the obtained polyorganosiloxane and the particle size of the latex. The present inventors have found that by using an aryl group-containing organosiloxane having a specific structure, it has a high molecular weight, a controlled particle size, and exhibits unprecedented good productivity, and has reached the present invention.

That is, the present invention relates to an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal, an emulsifier, an acid catalyst, water and, if necessary, a vinyl polymerizable functional group-containing siloxane. And a method for producing an aryl group-containing silicone latex, which comprises emulsifying and polymerizing the mixture.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The aryl group-containing silicone produced by the method of the present invention is a silicone containing a siloxane repeating unit having at least one aryl group on a silicon atom.

The aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention is an organosiloxane having an aryl group on a silicon atom in at least one siloxane bond. And an organosiloxane having substituents at both ends selected from a hydroxyl group and an alkoxy group.

Specific examples of the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention include a linear polyorganosiloxane having the following structure.

[0015]

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Embedded image Specific examples of the alkoxy group in the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention include a methoxy group, an ethoxy group, and a normal propylyloxy group. No.

Specific examples of the aryl group in the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention include a phenyl group, a naphthyl group and an alkyl nucleus. Examples include a substituted phenyl group, an alkyl nucleus substituted naphthyl group, a halogen nucleus substituted phenyl group, and a halogen nucleus substituted naphthyl group.

Specific examples of the alkyl group optionally contained in the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention include a methyl group and an ethyl group. Group, normal butyl group, isobutyl group, normal propyl group, isopropyl group and the like.

Further, specific examples of the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention include an organosiloxane having the following structure.

[0019]

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Embedded image The aryl group content in the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention is not particularly limited, but the refractive index of the obtained silicone is not particularly limited. Considering the coloring property derived from the ratio, the molecular weight, or the utility of the resin modifier using the same as a flame retardant, the number of bonding groups other than the siloxane bond bonded to all silicon atoms in the organosiloxane is assumed to be 100. It is preferably 5 to 95, more preferably 5 to 50, and still more preferably 10 to 40.

The viscosity of the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention is not particularly limited. Considering the ease of controlling the particle size distribution and the ease of controlling the molecular weight, the viscosity measured at 25 ° C. is preferably 0.01 to 10 Pa · s, and more preferably measured at 25 ° C. Viscosity is 0.01-1 Pa
.S, and more preferably the viscosity measured at 25 ° C. is 0.01 to 0.2 Pa · s. In particular, when the viscosity measured at 25 ° C. exceeds 10 Pa · s, poor dispersion of the silicone occurs during the production of the silicone latex, and the stability of the latex tends to be poor.

The aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal used in the present invention is, for example, XF40-B6197 (polymethylphenylmethoxysiloxane) manufactured by Toshiba Silicone Co., Ltd. , YF3804 (polymethylphenylsiloxane) and XF40-B6626 (polymethylphenylmethoxysiloxane).

As the emulsifier used in the present invention, a usual anionic emulsifier or a nonionic emulsifier is used. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium lauryl sulfonate,
Sodium lauryl sulfate, sodium sulfosuccinate,
Sodium polyoxyethylene alkyl phenyl ether sulfate, N-lauroyl sarcosine soda, dipotassium alkenyl succinate, soap rosinate, sodium oleate, etc., among which sulfonates such as sodium alkyl benzene sulfonate, sodium lauryl sulfonate, etc. The use of a system emulsifier is preferred.
As the nonionic emulsifier, polyoxyethylene nonylphenyl ether, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, and the like are used.

The amount of the emulsifier used is not particularly limited. However, considering the stability of the emulsified latex at the time of polymerization and the heat coloring property when the obtained silicone is used as a modifier for a resin material, the amount used is not limited. The amount of the emulsifier is preferably in the range of 0.05 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 2 parts by weight, per 100 parts by weight of the siloxane compound. .

The acid catalyst used in the present invention includes sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzenesulfonic acids and aliphatic substituted naphthalenesulfonic acids, and mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. No. Among these, aliphatic substituted benzenesulfonic acid is preferred because of excellent stability of the emulsified latex during polymerization, and normal dodecylbenzenesulfonic acid is particularly preferred.

The vinyl-polymerizable functional group-containing siloxane used in the present invention is a graft-crosslinking component for complexing the obtained silicone with a vinyl polymer.
In particular, when used as a resin modifier, a rubber source of an impact-resistant resin, a flame retardant, and the like, it is effective as a cross-linking agent for both components when it is necessary to compound and use a vinyl polymer and silicone.

The siloxane containing a vinyl polymerizable functional group is not particularly limited as long as it has a vinyl polymerizable functional group and can be bonded to dimethyl siloxane through a siloxane bond. Then, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-
Methacryloyloxysiloxanes such as methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane; Examples thereof include vinyl siloxane such as tetramethyltetravinylcyclotetrasiloxane, and p-vinylphenyldimethoxymethylsilane, and mercaptosiloxane such as γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. In addition, these vinyl polymerizable functional group-containing siloxanes can be used as one kind or as a mixture of two or more kinds. When the obtained silicone is used as the rubber source of the impact-resistant resin, the preferred range of the amount of the siloxane unit containing a vinyl polymerizable functional group is based on the siloxane unit of the obtained polyorganosiloxane. Is in the range of 0.3 to 3 mol%, preferably 0.5 to 2 mol%, more preferably 0.5 to 1 mol%.

In the production method of the present invention, a cyclic diorganosiloxane compound can be used in combination as the siloxane component other than the aryl group-containing linear organosiloxane. The cyclic diorganosiloxane used is used in combination with an aryl group-containing linear organosiloxane, for example, to adjust the refractive index of the obtained silicone to a specific value or to control the aryl group content in the silicone.

As the cyclic diorganosiloxane used in the present invention, a cyclic dialkylsiloxane having three or more membered rings is preferable in consideration of productivity during silicone polymerization. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or as a mixture of two or more.

By using a cyclic diorganosiloxane together with an aryl group-containing linear organosiloxane,
The molecular weight of the silicone in the obtained silicone latex can be increased, and the particle size of the silicone in the latex can be easily controlled.

In the present invention, a siloxane-based cross-linking agent can be used as required in addition to the above components. As the siloxane-based crosslinking agent, trifunctional or tetrafunctional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetra-n-propyloxysilane Is used.

In the present invention, an inorganic electrolyte such as sodium sulfate, magnesium sulfate, calcium sulfate, sodium chloride, and aluminum chloride can be added in order to suppress an increase in the viscosity of the latex during polymerization.

The amount of water used in the present invention is not particularly limited. However, considering the latex stability during emulsification and the productivity of silicone, the siloxane compound 1
100 parts by weight, preferably 100 to 1000 parts by weight, more preferably 150 to 500 parts by weight,
More preferably, it is in the range of 150 to 300 parts by weight.

In the present invention, an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal, an emulsifier, an acid catalyst, water and, if necessary, a cyclic diorganosiloxane, a vinyl polymerizable functional group. Methods for emulsifying a mixture of a group-containing siloxane and a siloxane-based crosslinking agent include mixing by high-speed stirring, mixing by a high-pressure emulsifier such as a homogenizer, membrane emulsification using a porous membrane, and fluid mixing using a static mixer. Although a method may be mentioned, a method using a homogenizer is preferable in consideration of easy control of the particle size distribution of siloxane in the latex.

Further, an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal, an emulsifier, an acid catalyst, water and, if necessary, a cyclic diorganosiloxane, and a vinyl polymerizable functional group-containing As a method of mixing siloxane and a siloxane-based crosslinking agent, first, an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at a terminal, a cyclic diorganosiloxane as necessary, a vinyl polymerizable functional group A method of mixing and homogenizing the siloxane-containing compound and the siloxane-based crosslinking agent to prepare a mixture of the siloxane-based compounds, then adding an emulsifier and an acid catalyst thereto, and then mixing with water is a preferable method for performing uniform emulsification. It is.

The polymerization in the present invention is carried out by heating the emulsion prepared by the above method. The heating temperature is preferably at least 50 ° C, more preferably at least 80 ° C. The heating time is at least 2 hours, more preferably at least 5 hours.

The polymerization can be stopped by cooling the reaction solution and neutralizing the latex with an alkaline substance such as caustic soda, potassium hydroxide, sodium carbonate and ammonia. Further, the time until the neutralization after cooling the heat-treated emulsion affects the molecular weight of the obtained silicone, and the longer the retention time until the neutralization, the higher the molecular weight tends to be. A preferred holding time until neutralization is 1 hour or more, and more preferably 10 hours or more.

As the polymerization method, an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal, an emulsifier, water and, if necessary, a cyclic diorganosiloxane, a vinyl polymerizable functional group After emulsifying the mixture of the contained siloxane and the siloxane-based cross-linking agent by the above-described method, the emulsion may be continuously dropped into an aqueous solution containing a heated acid catalyst to carry out polymerization. When polymerized by such a method, a silicone latex having a smaller particle diameter can be prepared.

[0038] The refractive index of the silicone produced by the method of the present invention is not particularly limited. In particular, in applications where the silicone composition is used by being mixed with another resin composition, the refractive index of the resin composition to be mixed is not particularly limited. By approaching the ratio, transparency and pigment coloring property can be improved.

The silicone latex produced by the method of the present invention is used as a rubber source for impact-resistant resin, a raw material for a silicone-based flame retardant, a raw material for an emulsion paint, and a raw material for a sliding property modifier for a thermoplastic resin. can do.

Hereinafter, the present invention will be described with reference to examples. In Examples and Comparative Examples, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

The absorbance of the polyorganosiloxane latex in each of the examples and comparative examples was measured at a solid concentration of 0.5 g.
/ L of the latex prepared at a wavelength of 700 nm using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation.
It measured on condition of.

The weight-average molecular weight of the polyorganosiloxane is determined by precipitating and collecting the polyorganosiloxane latex in isopropyl alcohol, drying this in vacuo at room temperature, and dissolving the solution in tetrahydrofuran in WA.
It was measured using GPC manufactured by TERS and determined from the retention time in terms of standard polystyrene.

The refractive index of the polyorganosiloxane was measured by precipitating and recovering the polyorganosiloxane latex in isopropyl alcohol, drying it in a vacuum at room temperature, and measuring it at 20 ° C. using an Abbe refractometer manufactured by Shimadzu Corporation. I asked.

The phenyl content of the polyorganosiloxane was determined by precipitating and recovering the polyorganosiloxane latex in isopropyl alcohol, drying it in a vacuum at room temperature, and then NMR analysis of a heavy acetone solution (GSX manufactured by JEOL Ltd.). -400) By measurement, the molar amounts of the methyl group (M) and the phenyl group (P) bonded to the silicon atom were determined, and the phenyl group content was determined from the following equation.

Phenyl content (mol%) = P / (P + M) × 100

[0046]

EXAMPLES (Example 1) Production of polyorganosiloxane latex (S-1) 95 parts of terminal methoxydiphenyldimethylsiloxane (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%) and γ-methacryloyloxypropyldimethoxy Five parts of methylsilane were mixed to obtain 100 parts of a siloxane mixture. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were added to the siloxane mixture, and after stirring, 200 parts of distilled water was added, and 1 part was added using a homomixer.
After preliminary stirring at 000 rpm, the mixture was treated four times with a homogenizer at a pressure of 40 MPa to emulsify and disperse to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and stirring blades, heated at 80 ° C. for 5 hours with mixing and stirring, and then left at 20 ° C. After 16 hours, the pH of the latex was adjusted with a 5% aqueous sodium hydroxide solution. Neutralized to 7.4, polymerization was completed and polyorganosiloxane latex (S-
1) was obtained. The polyorganosiloxane latex (S-1) thus obtained had a solid content of 29.1% and an absorbance of 0.58. The weight average molecular weight of the polyorganosiloxane in S-1 was 16,000,
The refractive index measured at 20 ° C. was 1.515. Table 1 shows the above results.

(Example 2) Preparation of polyorganosiloxane latex (S-2) 95 parts of terminal silanol diphenyldimethylsiloxane (YF3804 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 17 mol%) and γ-methacryloyloxypropyldimethoxymethylsilane 5 Were mixed to obtain 100 parts of a siloxane mixture. Next, 1 part each of sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid was added to the siloxane mixture, and the mixture was stirred.
Add 200 parts of distilled water and use a homomixer for 10,000
After preliminarily stirring at rpm, 40M using a homogenizer.
The mixture was emulsified and dispersed by treating at a pressure of Pa 4 times to obtain an organosiloxane latex. The mixture was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours while mixing and stirring, and then heated at 20 ° C.
After 16 hours, the pH of this latex was neutralized to 7.4 with a 5% aqueous sodium hydroxide solution to complete the polymerization, and a polyorganosiloxane latex (S-2) was obtained.
The polyorganosiloxane latex (S-2) thus obtained has a solid content of 29.3% and an absorbance of 0.5.
It was 2. The weight average molecular weight of the polyorganosiloxane in S-2 was 62,000, and the refractive index measured at 20 ° C. was 1.471. Table 1 shows the above results.

Example 3 Production of polyorganosiloxane latex (S-3) 76.3 parts of methoxydiphenyldimethylsiloxane terminated (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%), octamethylcyclotetrasiloxane (TSF-40 manufactured by Toshiba Silicone Co., Ltd.
4) 18.7 parts and γ-methacryloyloxypropyldimethoxymethylsilane 5 parts were mixed to obtain 100 parts of a siloxane mixture. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were added to the siloxane mixture, and the mixture was stirred.
After adding 00 parts and preliminarily stirring with a homomixer at 10,000 rpm, the mixture was emulsified and dispersed by treating it four times with a homogenizer at a pressure of 40 MPa to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and then left at 20 ° C. After 16 hours, the pH of this latex was adjusted with a 5% aqueous sodium hydroxide solution. After neutralization to 7.4, the polymerization was completed to obtain a polyorganosiloxane latex (S-3). The polyorganosiloxane latex (S-3) thus obtained had a solid content of 28.6% and an absorbance of 0.31. The weight average molecular weight of the polyorganosiloxane in S-3 was 67000, and the refractive index measured at 20 ° C was 1.491. Table 1 shows the above results.

(Example 4) Preparation of polyorganosiloxane latex (S-4) Except that the amount of terminal methoxydiphenyldimethylsiloxane used in Example 3 was changed to 57 parts and the amount of octamethylcyclotetrasiloxane was changed to 38 parts Conducts polymerization in the same manner and obtains a polyorganosiloxane latex (S
-4) was obtained. The polyorganosiloxane latex (S-4) thus obtained has a solid content of 29.0%,
The absorbance was 0.11. The weight average molecular weight of the polyorganosiloxane in S-4 was 110,000, and the refractive index measured at 20 ° C. was 1.469. Table 1 shows the above results.

Example 5 Preparation of polyorganosiloxane latex (S-5) Except that the amount of terminal methoxydiphenyldimethylsiloxane used in Example 3 was changed to 38 parts and the amount of octamethylcyclotetrasiloxane was changed to 57 parts Conducts polymerization in the same manner and obtains a polyorganosiloxane latex (S
-5) was obtained. The polyorganosiloxane latex (S-5) thus obtained has a solid content of 29.4%,
The absorbance was 0.07. The weight average molecular weight of the polyorganosiloxane in S-5 was 154000, and the refractive index measured at 20 ° C. was 1.448. Table 1 shows the above results.

(Example 6) Preparation of polyorganosiloxane latex (S-6) 75.6 parts of methoxyphenylmethylsiloxane at terminal (XF40-B6626 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 47 mol%), octamethylcyclotetrasiloxane (TSF-404 manufactured by Toshiba Silicone Co., Ltd.)
19.4 parts and γ-methacryloyloxypropyldimethoxymethylsilane 5 parts were mixed to obtain 100 parts of a siloxane mixture. Next, sodium dodecylbenzenesulfonate and dodecylbenzenesulfonate were added in 1 part each.
Parts of the siloxane mixture, and after stirring, 200 ml of distilled water
The mixture was preliminarily stirred with a homomixer at 10,000 rpm, and then treated four times with a homogenizer at a pressure of 40 MPa to emulsify and disperse to obtain an organosiloxane latex. The mixture was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours while mixing and stirring, and then left at 20 ° C.
Six hours later, the pH of this latex was neutralized to 7.4 with a 5% aqueous sodium hydroxide solution to complete the polymerization, and a polyorganosiloxane latex (S-6) was obtained. The polyorganosiloxane latex (S-
The solid content of 6) was 30.0%, and the absorbance was 0.43. The weight average molecular weight of the polyorganosiloxane in S-6 was 17000, and the refractive index measured at 20 ° C. was 1.510. Table 1 shows the above results.

(Example 7) Preparation of polyorganosiloxane latex (S-7) 38 parts of methoxydiphenyldimethylsiloxane terminated (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%), octamethylcyclotetrasiloxane (Toshiba Silicone TSF-404)
57 parts and 5 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to form a siloxane mixture 10
0 parts were obtained. Next, 1 part of sodium dodecylbenzenesulfonate was added to the siloxane mixture, and after stirring, 310 parts of distilled water was added, and the mixture was mixed at 10,000 rpm with a homomixer.
After preliminary stirring at 40MPa with a homogenizer
The mixture was emulsified and dispersed by treating at a pressure of 4 times to obtain a premixed organosiloxane latex.

On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device.
A 0% by weight aqueous solution of dodecylbenzenesulfonic acid was prepared.

While the aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after completion of the addition, the temperature was maintained for 1 hour and the system was cooled. The reaction was left at 20 ° C. and after 16 hours the pH of this latex was neutralized to 7.4 with 5% aqueous sodium hydroxide,
The polymerization is completed and the polyorganosiloxane latex (S-
7) was obtained. The polyorganosiloxane latex (S-7) thus obtained had a solid content of 17.3% and an absorbance of 0.06. The weight average molecular weight of the polyorganosiloxane in S-7 was 160,000, and the refractive index measured at 20 ° C was 1.450. Table 1 shows the above results.

(Example 8) Production of polyorganosiloxane latex (S-8) 63 parts of terminal silanol diphenyldimethylsiloxane (YF3804 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 17 mol%), octamethylcyclotetrasiloxane (Toshiba Silicone Co., Ltd.) 32 parts of TSF-404) and 5 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. Then add sodium dodecylbenzenesulfonate to 1
Parts of siloxane mixture and stirred, then distilled water 310
The mixture was preliminarily stirred with a homomixer at 10,000 rpm, and then treated and treated four times with a homogenizer at a pressure of 40 MPa to obtain a premixed organosiloxane latex.

On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer.
A 0% dodecylbenzenesulfonic acid aqueous solution was prepared.

While the aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the completion of the addition, the temperature was maintained for 1 hour, followed by cooling. The reaction was left at 20 ° C. and after 16 hours the pH of this latex was neutralized to 7.4 with 5% aqueous sodium hydroxide,
The polymerization is completed and the polyorganosiloxane latex (S-
8) was obtained. The polyorganosiloxane latex (S-8) thus obtained had a solid content of 17.9% and an absorbance of 0.12. The weight average molecular weight of the polyorganosiloxane in S-8 was 200000, and the refractive index measured at 20 ° C was 1.449. Table 1 shows the above results.

Comparative Example 1 Production of Polyorganosiloxane Latex (T-1) 95 parts of octamethylcyclotetrasiloxane (TSF-404 manufactured by Toshiba Silicone Co., Ltd.) and 5 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed.
100 parts of a siloxane mixture were obtained. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were added to the siloxane mixture, and the mixture was stirred.
After preliminarily stirring at 00 rpm, the mixture was stirred for 4 hours with a homogenizer.
The mixture was emulsified and dispersed by treating at a pressure of 0 MPa four times to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and then left at 20 ° C. After 16 hours, the pH of this latex was adjusted with a 5% aqueous sodium hydroxide solution. After neutralization to 7.4, the polymerization was completed to obtain a polyorganosiloxane latex (T-1). The polyorganosiloxane latex (T-1) thus obtained had a solid content of 29.4% and an absorbance of 0.08. The weight average molecular weight of the polyorganosiloxane in T-1 was 210,000,
The refractive index measured at ° C was 1.409. Table 1 shows the above results.

[0059]

[Table 1] The following is clear from the examples and the comparative examples.

1) In the methods of Examples and Comparative Examples, a high-molecular-weight polyorganosiloxane can be obtained in a high yield in any case.

2) The polyorganosiloxane contained in the polyorganosiloxane latex produced by the method of Examples 1 to 8 has a phenyl group content corresponding to the charged raw material composition.

3) The polyorganosiloxane contained in the polyorganosiloxane latex produced by the methods of Examples 1 to 8 has a high refractive index. The polyorganosiloxane latex having such a high refractive index has excellent design properties when used, for example, as a rubber source of an impact-resistant resin or a raw material for a water-based paint, and has high industrial utility value.

4) On the other hand, the refractive index of the polyorganosiloxane contained in the polyorganosiloxane latex produced by the method of Comparative Example 1 is low, and the polyorganosiloxane latex containing the polyorganosiloxane having such a low absorbance is, for example, Poor design when used as a rubber source of impact-resistant resin or as a raw material for water-based paints, and its industrial utility value is low.

5) In particular, in the method of using the linear phenyl group-containing organosiloxane and the cyclic dimethylsiloxane of Examples 3 to 5, 7 and 8, a high molecular weight polyorganosiloxane containing a phenyl group can be obtained.

[0065]

As described above, the present invention has the following remarkable effects, and its industrial value is extremely large.

1) A polyorganosiloxane latex having a high molecular weight and a high refractive index can be produced with good production stability.

2) An aryl group-containing polyorganosiloxane useful as a raw material for a rubber source of an impact-resistant resin, a silicone-based flame retardant, an aqueous emulsion paint, and a slidability modifier for a thermoplastic resin can be produced. .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CP061 CP142 CP162 FD13 GH01 GT00 4J035 BA02 CA05U CA06U CA13M CA131 CA14M CA14N CA141 FB01 FB02 LA04 LA08 LB01

Claims (4)

[Claims] 1. An aryl group, which is obtained by emulsifying and polymerizing a mixture of an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at an end, an emulsifier, an acid catalyst, and water. A method for producing a silicone latex. 2. A method comprising emulsifying and polymerizing a mixture comprising an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at a terminal, a cyclic diorganosiloxane, an emulsifier, an acid catalyst and water. A method for producing an aryl group-containing silicone latex. 3. A method comprising emulsifying and polymerizing a mixture of an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at an end, an emulsifier, an acid catalyst, water, and a vinyl polymerizable functional group-containing siloxane. A method for producing an aryl group-containing silicone latex. 4. A mixture comprising an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at a terminal, a cyclic diorganosiloxane, an emulsifier, an acid catalyst, water, and a vinyl polymerizable functional group-containing siloxane. A process for producing an aryl group-containing silicone latex, which comprises emulsifying and polymerizing the compound.