JPH10120903A - Silicone composition - Google Patents

Abstract

(57) [abstract] (with correction) [PROBLEMS] By applying to leather, synthetic rubber, natural rubber, textiles, hair, skin, etc. to form a coating film having excellent surface smoothness on them, A silicone composition that improves the smoothness, flexibility, combability, abrasion resistance, etc. SOLUTION: A silicone composition containing the following (A) and (B) as main components. (A) 100 parts by weight of a polyorganosiloxane represented by the general formula R ¹ _a SiO _{(4-a) / 2} and having a viscosity at 25 ° C. of 100 to 20 million cP (R ¹ is a monovalent compound having 1 to 20 carbon atoms) 1.95 <a <2.20) (B) 0.1-100 parts by weight of a composite silicone powder obtained by coating a silicone rubber spherical fine particle with a polyorganosilsesquioxane resin

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silicone which is applied to leather, synthetic rubber, natural rubber, textiles, hair, skin, etc. to improve the surface smoothness, flexibility, combability, abrasion resistance, etc. Composition.

[0002]

2. Description of the Related Art A polyorganosiloxane having a wide viscosity range is applied to natural leather, synthetic leather, textile fabric, spun yarn, etc. to improve their surface smoothness, or applied to synthetic rubber and natural rubber for abrasion resistance. Has conventionally been widely practiced. Furthermore, in recent years, it has been actively performed to add and blend the above-mentioned polyorganosiloxane to cosmetics for hair and skin to improve combability of hair and improve smoothness of skin surface. (JP
61-210022, JP-A-63-130512, JP-A-2-247113
No., JP-A-4-36226, JP-A-4-224309, JP-A-4-32
No. 7520, JP-A-4-364113, JP-A-5-13994, JP-A-5
5-39212, JP-A-5-163122, Japanese Patent Publication No. 4-2566, Japanese Patent Publication No. 4-2567, and Japanese Patent Publication No. 4-38723. But,
Even with these methods, the surface smoothness of the above-mentioned various substrates, hair, skin and the like cannot be sufficiently improved, and further improvement has been demanded. Examples of application of silicone powder to cosmetics include application of silicone rubber powder (Japanese Patent Publication Nos. 4-17162 and 4-66446) and application of polymethylsilsesquioxane powder ( 63-297
No. 313) has been reported, but sufficient effects have not been obtained even by the addition and blending of these conventional silicone powders.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a method for improving the surface smoothness, which has been a conventional problem, by adding and dispersing a composite silicone powder having excellent dispersibility to a polyorganosiloxane. An object of the present invention is to provide a silicone composition capable of forming an excellent coating film. Although the reason why the coating film comprising the silicone composition of the present invention exhibits excellent surface smoothness is not clear, it is clear that the composite silicone powder exhibits good dispersibility in polyorganosiloxane, and that the dispersed composite silicone is Morphology with stable powder
It is presumed to show the effect.

[0004]

Means for Solving the Problems The silicone composition of the present invention is a silicone composition containing the following (A) and (B) as main components. (A) 100 parts by weight of a polyorganosiloxane represented by the general formula R ¹ _a SiO _{(4-a) / 2} and having a viscosity at 25 ° C. of 100 to 20 million cP (R ¹ is a monovalent having 1 to 20 carbon atoms) (B) Silicone rubber spherical fine particles coated with polyorganosilsesquioxane resin 0.1 to 100 parts by weight Further, in the above composition, the composite silicone powder has an average particle size It is particularly effective to coat 100 parts by weight of silicone rubber spherical fine particles having a diameter of 0.1 to 100 μm with 1 to 500 parts by weight of a polyorganosilsesquioxane resin.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polyorganosiloxane of the component (A) in the present invention has a liquid or soft rubber-like appearance, and R ¹ is methyl, ethyl, propyl,
Alkyl group such as butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; cycloalkyl group such as cyclopentyl and cyclohexyl; one or two selected from aryl group such as phenyl group and tolyl group At least one kind of a monovalent organic group having 1 to 20 carbon atoms or a monovalent organic group in which a part of a hydrogen atom bonded to these carbon atoms is substituted with a halogen atom is exemplified. It is preferred that 90 mol% or more of these groups are methyl groups.

In the present invention, if the viscosity of (A) is less than 10 cP at 25 ° C., sufficient surface smoothness cannot be obtained,
If it exceeds 20 million cP, it becomes difficult to disperse the composite silicone powder of (B), so it is necessary to be 10 to 20 million cP, preferably 1 to 10 million cP,
More preferably, it is 1,000 to 1,000,000 cP.

The composite silicone powder (B) in the present invention is obtained by coating spherical particles of silicone rubber with a polyorganosilsesquioxane resin. In order to achieve the object of the present invention, the average particle size of the silicone rubber spherical fine particles in (B) is preferably from 0.1 to 100 μm, particularly preferably from 1 to 30 μm. If the average particle size of the silicone rubber spherical fine particles is less than 0.1 μm, the surface smoothness is poor. If the average particle size exceeds 100 μm, the roughness becomes large and the touch becomes poor. Further, it is preferable to coat 1 to 500 parts by weight of the polyorganosilsesquioxane resin with respect to 100 parts by weight of the silicone rubber spherical fine particles, and it is particularly preferable to coat 5 to 100 parts by weight. When the amount of the polyorganosilsesquioxane resin is less than 1 part by weight, the obtained powder has a high cohesiveness, so that the dispersibility in the component (A) is poor. The coating film of the composition has poor surface smoothness. The method for producing the composite silicone powder in the present invention is described in, for example, JP-A-7-19
No. 6815, the polyorganosilsesquioxane may be added to the surface of the silicone rubber spherical fine particles by hydrolyzing and condensing the organotrialkoxysilane while maintaining the aqueous dispersion of the silicone rubber spherical particles alkaline. Can be coated.

The silicone rubber spherical fine particles in the present invention are spherical cured products having a linear polyorganosiloxane block represented by the general formula-(R ² ₂ SiO) _{b-in the} molecular structural formula. Here, R ² is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; a cycloalkyl group such as cyclopentyl, cyclohexyl, cyclooctyl; phenyl, tolyl One or more monovalent organic groups having 1 to 20 carbon atoms selected from aryl groups and the like, or monovalent organic groups in which some of the hydrogen atoms bonded to these carbon atoms are substituted with halogen atoms It is selected from organic groups and the like, and preferably 90% by mole or more is a methyl group. If b is less than 5, the surface smoothness is poor, and if it exceeds 5,000, it is difficult to produce. Therefore, b is 5 to 5,000, preferably 10 to 1,000.

The composite silicone powder used in the present invention is obtained by coating a polyorganosilsesquioxane resin on spherical particles of silicone rubber. The polyorganosilsesquioxane has the general formula R ³ SiO _It is a solid resin polymer having a siloxane unit represented by _3/2 as a constituent unit. Here, R ³ is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; a cycloalkyl group such as cyclopentyl, cyclohexyl, cyclooctyl; phenyl, tolyl One or more monovalent organic groups having 1 to 20 carbon atoms selected from aryl groups and the like, or monovalent organic groups in which some of the hydrogen atoms bonded to these carbon atoms are substituted with halogen atoms It is selected from organic groups, and preferably 90% by mole or more is a methyl group.

In the present invention, (A) and (B) are mixed in an amount of (B) component per 100 parts by weight of (A) component.
If it is less than 0.1 part by weight, sufficient surface smoothness is not obtained, and if it exceeds 100 parts by weight, the viscosity of the composition becomes too high, and handling becomes difficult, so 0.1 to 100 parts by weight is required, and it is preferable. Is 1 to 10 parts by weight. This (A),
As a method for mixing (B), a general stirrer having an anchor blade, a propeller blade, a flat plate blade, or the like, or an ultra mixer, a planetary mixer, a combination mixer, or the like suitable for mixing a high-viscosity material can be used.

At the time of mixing (A) and (B), a solvent can be used. For example, cyclic dimethylpolysiloxane and chain dimethylpolysiloxane have a boiling point of 760 mmHg
250 ° C. or less, or petroleum light fractions such as petroleum ether, ligroin, gas oil or hydrocarbon solvents such as n-pentane, n-hexane, cyclohexane, light liquid isoparaffin, benzene, toluene, xylene, ethanol, Examples include alcohol solvents such as isopropanol and butanol.

The silicone composition of the present invention can be used as an aqueous emulsion using an emulsifier.
The emulsifier is not particularly limited, but for example, a nonionic emulsifier such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan alkylate, polyoxyethylene sorbitan alkylate, alkyl sulfate, alkylbenzene sulfonate, alkyl It may be selected from anionic emulsifiers such as phosphates, cationic emulsifiers such as quaternary ammonium salts and alkylamine salts, and amphoteric emulsifiers such as alkyl betaines and alkyl imidazolines.

The emulsification can be carried out by using a known emulsifying machine such as a homomixer, a high-pressure homogenizer, an ultra mixer, a planetary mixer, a combi-mixer, and a homo-mixer.

[0014]

Next, the present invention will be described with reference to examples. Here, “part” indicates “part by weight” and “viscosity” indicates a measured value at 25 ° C.

(Production Example 1) The viscosity represented by Chemical Formula 1 is 60
500 g of a 0 cSt polyorganosiloxane and 20 g of a 30 cSt polyorganosiloxane represented by the following chemical formula were placed in a glass beaker having a capacity of 1 liter, and stirred and mixed at 2,000 rpm using a homomixer, followed by polyoxyethylene octyl. 5 g of phenyl ether (additional mole number 9), water
When 150 g was added and stirring was continued at 6,000 rpm, phase inversion occurred and thickening was recognized. However, while stirring at 2,000 rpm, 325 g of water was added, and an O / W emulsion was obtained. Was.

[0016]

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[0017]

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Next, the emulsion was transferred to a glass flask equipped with an anchor-type stirring blade, and a 2-ethylhexanol solution of chloroplatinic acid (with a platinum content of 2.
0% by weight) and 1 g of polyoxyethylene octyl phenyl ether (additional mole number 9) was added.
When the reaction was carried out for a time, an aqueous dispersion of silicone spherical fine particles was obtained (hereinafter referred to as dispersion 1). The average particle diameter of the particles in this dispersion 1 was measured using a Coulter counter (manufactured by Coulter Electronics Co., Ltd.). Measured 3
μm. 2,290 water in a 3 liter glass flask
g, 580 g of the dispersion 1 obtained above and 60 g of aqueous ammonia (concentration 28% by weight) were charged, and the water temperature was set to 10 ° C.
The mixture was stirred with an anchor-type stirring blade at a blade rotation speed of 200 rpm. At this time, the pH of the solution was 11.2, and 65 g of methyltrimethoxysilane was added dropwise to the solution over 20 minutes. During this time, the solution temperature was maintained at 5 to 15 ° C., and the mixture was further stirred for 4 hours. ~
The mixture was heated to 60 ° C. and stirred for 1 hour, and the obtained liquid was formed into a cake having a water content of about 30% by weight using a pressure filter.

Then, the cake was dried at 105 ° C. in a circulating hot air drier, and the dried product was pulverized by a jet mill. Observation of the obtained composite silicone powder with an optical microscope confirmed that it was spherical. To 0.1 g of this composite silicone powder, 0.3 g of polyoxyethylene octylphenyl ether (10 moles of EO added) was added. After mixing, 20 g of water was further added to obtain an aqueous dispersion of the composite silicone powder, and the average particle size was measured using a Coulter counter to be 3 μm. By weight analysis, the composite silicone powder was found to be 100 parts by weight of silicone rubber spherical fine particles coated with 10 parts by weight of a polyorganosilsesquioxane resin (hereinafter referred to as composite silicone powder 1). ).

(Production Example 2) Silicone was prepared in the same manner as in Production Example 1 except that 1 g of polyoxyethylene octyl phenyl ether (additional number of 9) used in preparing the O / W emulsion was changed to 1 g. An aqueous dispersion of rubber spherical fine particles (hereinafter referred to as Dispersion 2) was obtained. The average particle size of the particles in this dispersion 2 was measured using a Coulter counter and found to be 15 μm. The weight of the composite silicone powder was determined by weight analysis to be 100 parts by weight of silicone rubber spherical fine particles coated with 10 parts by weight of a polyorganosilsesquioxane resin (hereinafter referred to as composite silicone powder 2). ).

(Examples 1 to 7 and Comparative Examples 1 to 3) With the composition shown in Table 1, (A) and (B) were uniformly mixed, and the obtained silicone composition was treated with octamethylcyclotetrasiloxane. 5% was mixed and dispersed therein to obtain a test liquid. Sheep tanned leather (30 mm × 150 mm × 1 mm thick) is immersed in this test solution for 5 minutes, pulled up, dried at room temperature for 20 hours, and further heated at 105 ° C.
After heating and drying in a hot air circulating thermostat adjusted for 3 hours,
The coefficient of kinetic friction between this and untreated sheep tanned leather was measured with an autograph (manufactured by Shimadzu Corporation) (load: 200 g, pulling speed: 300 mm / min) (see Fig. 1). The measurement results are shown in Table 1. Was.

(Examples 8 to 12 and Comparative Examples 4 to 6) Table 2
(A) and (B) are uniformly mixed with the composition shown in
1,200 g of the obtained silicone composition was mixed with 120 g of polyoxyethylene lauryl ether (9 moles of EO added), 4 g of a 25% aqueous solution of sodium polyoxyethylene lauryl ether sulfate (3 moles of EO added) and 120 g of purified water in 5 liters. Into a planetary mixer (manufactured by Inoue Manufacturing Co., Ltd.)
After stirring at room temperature for 30 minutes to confirm phase inversion emulsification, purified water
540 g was added and the mixture was stirred at room temperature for 1 hour to obtain a white emulsion. A 8% aqueous solution of the obtained emulsion was used as a test solution, and surface treatment was applied to sheep tanned skin in the same manner as in Examples 1 to 7 to measure the coefficient of kinetic friction between this and untreated sheep tanned skin. Table 2 shows the measurement results.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

The silicone composition of the present invention is applied to leather, synthetic rubber, natural rubber, textiles, hair, skin, etc.
By forming a coating film having excellent surface smoothness on them, their smoothness, flexibility, combability, abrasion resistance and the like are improved.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a method of measuring a coefficient of dynamic friction between a sheep tanned skin treated with a silicone composition and an untreated sheep tanned skin in an example of the present invention.

[Explanation of symbols]

 1. 1. Sheep tanned skin treated with a silicone composition; 2. Untreated sheep tanned skin, Aluminum plate 4. 200g load.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoshinori Iguchi 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (2)

[Claims] 1. A silicone composition containing the following (A) and (B) as main components. (A) 100 parts by weight of a polyorganosiloxane represented by the general formula R ¹ _a SiO _{(4-a) / 2} and having a viscosity at 25 ° C. of 100 to 20 million cP (R ¹ is a monovalent having 1 to 20 carbon atoms) 1.95 <a <2.20) (B) 0.1-100 parts by weight of a composite silicone powder comprising silicone rubber spherical fine particles coated with a polyorganosilsesquioxane resin 2. The composite silicone powder has an average particle size of 0.1 to 0.1.
2. The silicone composition according to claim 1, wherein 100 parts by weight of 100 μm silicone rubber spherical fine particles are coated with 1 to 500 parts by weight of a polyorganosilsesquioxane resin.