JPH09316492A - Cleaning agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cleaning agent containing a powdery silicone rubber having indefinite form and containing a specific polyorganosiloxane, having excellent cleaning power and storage stability and giving soft feeling in use. SOLUTION: This cleaning agent contains a powdery silicone rubber having indefinite form and containing a polyorganosiloxane having a polyoxyalkylene group of the formula R<1> (OR<2> )m OR<3> (R<1> and R<2> are each an alkylene; R<3> is H or an alkyl; (m) is 2-100) bonded to silicon atom (Si). The powder preferably has JIS A hardness of 20-45 and particle diameter of <=1mm. The powder is preferably produced by curing a silicone rubber composition curable by addition reaction and composed of a polyorganosiloxane having plural Si-bonded alkenyl groups, a polyorganosiloxane having Si-bonded H atom, a polyorganosiloxane having the above polyoxyalkylene group bonded to Si and free from bond between alkenyl group and H atom and a platinum-based catalyst, and finely pulverizing the cured silicone rubber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent containing a silicone rubber powder, and more particularly to a detergent having excellent detergency and storage stability and a soft feeling of use.

[0002]

2. Description of the Related Art A cleaning agent containing an inorganic powder, a silicone resin powder, or an organic resin powder as an abrasive for efficiently removing dirt has excellent detergency, but when it is used on the skin. Feel a foreign body or irritation,
Further, when used for a relatively soft base material, there is a problem that the base material is damaged.

Therefore, a cleaning agent containing a silicone rubber powder has been proposed as an abrasive. As such a cleaning agent, for example, a cleaning agent containing a silicone rubber powder having an inorganic powder adhered to its surface (JP-A-60-13).
No. 0698), and facial cleansing cosmetics containing silicone rubber powder (see JP-A-63-313710).

However, the detergent containing such a silicone rubber powder does not have sufficient detergency, and
There was a problem of poor storage stability.

[0005]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, an object of the present invention is to provide a cleaning agent having excellent cleaning properties, storage stability, and a soft feeling during use.

[0006]

The present invention provides a detergent containing a silicone rubber powder, wherein the silicone rubber powder is added to a silicon atom by the formula: -R ¹ (OR ² ) _m OR ³ (wherein R ¹ and R ² are the same or different alkylene groups, R ³ is a hydrogen atom or an alkyl group,
m is an integer of 2 to 100. And a polyoxyalkylene group-bonded polyorganosiloxane represented by the formula (1), which has an irregular shape.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The cleaning agent of the present invention will be described in detail below. The silicone rubber powder constituting the cleaning agent of the present invention has a silicon atom represented by the formula: —R ¹ (OR ² ) _m OR ³ (wherein R ¹ and R ² are the same or different alkylene groups, and R ³ is a hydrogen atom or an alkyl group,
m is an integer of 2 to 100. ), Which has an irregular shape containing a polyorganosiloxane having a polyoxyalkylene group bonded thereto. R ¹ in the above formula is an alkylene group, and examples thereof include an ethylene group, a propylene group and a butylene group, with an ethylene group and a propylene group being particularly preferable. R ² in the above formula is R ¹
And an alkylene group which is the same as or different from, and is particularly preferably an ethylene group. Further, R ³ in the above formula is a hydrogen atom or an alkyl group, and examples of the alkyl group of R ³ include a methyl group, an ethyl group and a propyl group. Further, m in the above formula is an integer of 2 to 100, and particularly preferably an integer of 5 to 20.

Examples of such a polyoxyalkylene group include the following groups. _{-C 2 H 4 (OC 2 H} 4) m OH -C 2 H 4 (OC 2 H 4) m OCH 3 -C 2 H 4 (OC 2 H 4) n (OC 3 H 6) p OH -C 2 _{H 4 (OC 2 H 4)} n (OC 3 H 6) p OCH 3 -C 3 H 6 (OC 2 H 4) m OH -C 3 H 6 (OC 2 H 4) m OCH 3 -C 3 H 6 _{(OC 2 H 4) n (} OC 3 H 6) p OH -C 3 H 6 (OC 2 H 4) n (OC 3 H 6) p OCH 3 ( where, m is an integer of 2 to 100, n is 0 or a positive integer, p is a positive integer, and n + p is 2 to
It is an integer of 100. ) Among such polyoxyalkylene groups, since the detergent of the present invention can be imparted with particularly excellent storage stability and soft feeling of use, the main chain thereof is composed of only the repeating unit of (OC ₂ H ₄ ). It is preferably a polyoxyethylene group. Such a polyorganosiloxane having a polyoxyalkylene group bonded to a silicon atom is simply contained in the silicone rubber powder and is a polyorganosiloxane that does not participate in the curing reaction for forming the silicone rubber.

Silicone rubber which constitutes such a silicone rubber powder is specified by JIS K 6301.
The ISA hardness is preferably 10 to 50, and particularly preferably 20 to 45. The particle size of such silicone rubber powder is 5 mm.
It is preferably not more than, and particularly preferably not more than 1 mm. The shape of such silicone rubber powder is indefinite.

As a method for producing this silicone rubber powder, a silicon atom is represented by the formula: --R ¹ (OR ² ) _m OR ³ (wherein R ¹ and R ² are the same or different alkylene groups, R ³ is a hydrogen atom or an alkyl group,
m is an integer of 2 to 100. It is preferable that the silicone rubber containing a polyorganosiloxane having a polyoxyalkylene group represented by the formula (1) is finely pulverized. As a method of finely pulverizing this silicone rubber,
Examples of the method include finely pulverizing silicone rubber with a pulverizer such as a stamp mill, a bell crusher, a roll mill, a hammer mill, a drum mill and a jet mill. When the silicone rubber is finely pulverized, the silicone rubber generates heat, so that it is preferable to perform cooling with water, liquid nitrogen or the like.

The curing reaction of the silicone rubber composition forming such a silicone rubber includes an addition reaction with an alkenyl group and a silicon atom-bonded hydrogen atom, a condensation reaction with a silicon atom-bonded hydroxyl group and a silicon atom-bonded hydrogen atom, and organic peroxide. Examples thereof include a radical reaction caused by a substance and a radical reaction caused by ultraviolet irradiation, and an addition reaction is particularly preferable. Examples of the silicone rubber composition curable by an addition reaction include (A) a polyorganosiloxane having at least two silicon-bonded alkenyl groups in one molecule.
100 parts by weight,
(B) Polyorganosiloxane having at least two silicon-bonded hydrogen atoms in one molecule {per 1 mol of alkenyl groups in the present composition, the silicon-bonded hydrogen atoms in component (B) are 0.1 To the amount of 10 mol}, and (C) the silicon atom has the formula: -R ¹ (OR ² ) _m OR ³ (wherein R ¹ and R ² are the same or different alkylene groups, and R ³ is A hydrogen atom or an alkyl group,
m is an integer of 2 to 100. ) A polyorganosiloxane having a polyoxyalkylene group bonded thereto and having neither an alkenyl group nor a hydrogen atom bonded thereto.
A silicone rubber composition comprising 0.001 to 20 parts by weight and (D) a platinum-based catalyst (a sufficient amount to cure the composition) is preferable.

The component (A) is the main component of this silicone rubber composition and is a polyorganosiloxane having at least two silicon-bonded alkenyl groups in one molecule. Examples of the molecular structure of the component (A) include linear, linear with some branched chains, branched, cyclic, and resinous,
In particular, a straight chain or a straight chain having a partially branched chain is preferable. Examples of the alkenyl group in the component (A) include a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group, and a vinyl group is particularly preferable.
In addition, as the group bonded to the silicon atom other than the alkenyl group in the component (A), an alkyl group such as a methyl group, an ethyl group, a propyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group; a benzyl group, Aralkyl group such as phenethyl group; Substituted or unsubstituted monovalent hydrocarbon group such as halogenated alkyl group such as 3,3,3-trifluoropropyl group; Alkoxy group such as methoxy group, ethoxy group, propoxy group; Hydroxyl group Are particularly preferable, and a methyl group, a phenyl group and a 3,3,3-trifluoropropyl group are particularly preferable.

The component (B) is a crosslinking agent for the silicone rubber composition, and is a polyorganosiloxane having at least two silicon-bonded hydrogen atoms in one molecule.
Examples of the molecular structure of the component (B) include linear, partially branched linear, branched, cyclic, and resinous, and particularly linear or partially branched linear. Is preferred. Examples of the group bonded to a silicon atom other than a hydrogen atom in the component (B) include an alkyl group such as a methyl group, an ethyl group and a propyl group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; a benzyl group and a phenethyl group. An aralkyl group such as; a substituted or unsubstituted monovalent hydrocarbon group such as a halogenated alkyl group such as a 3,3,3-trifluoropropyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group; and a hydroxyl group. In particular, a methyl group, a phenyl group and a 3,3,3-trifluoropropyl group are preferable.

The blending amount of the component (B) is (B) based on 1 mol of the total of the alkenyl groups in the silicone rubber composition, that is, the alkenyl groups contained in the components (A) and (C).
The amount of silicon atom-bonded hydrogen atoms in the component is 0.1 to 10 mol, and particularly, the amount is preferably 0.5 to 2.0 mol. This is because if the amount of silicon atom-bonded hydrogen atoms in the component (B) is less than 0.1 mol with respect to 1 mol of alkenyl groups in the silicone rubber composition, curing will not proceed sufficiently. This is also because even if this exceeds 10 moles, curing does not proceed sufficiently.

The component (C) has excellent hydrophilicity to the silicone rubber powder obtained by curing the silicone rubber composition,
And a component for imparting a soft feel, to the silicon atom, the formula: —R ¹ (OR ² ) _m OR ³ (wherein R ¹ and R ² are the same or different alkylene groups, and R ³ is a hydrogen atom or an alkyl group,
m is an integer of 2 to 100. ) Is a polyorganosiloxane having a polyoxyalkylene group bonded thereto, and no alkenyl group or hydrogen atom bonded thereto.
Other groups bonded to the silicon atom in the component (C) include alkyl groups such as methyl group, ethyl group and propyl group;
Aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; 3,3,3
A substituted or unsubstituted monovalent hydrocarbon group such as a halogenated alkyl group such as a trifluoropropyl group; a methoxy group,
An alkoxy group such as an ethoxy group and a propoxy group; a hydroxyl group is exemplified, and particularly, a methyl group, a phenyl group, 3,3,3-
It is preferably a trifluoropropyl group. Examples of the molecular structure of the component (C) include linear, partially branched linear, branched, cyclic, and resinous, and particularly linear or partially branched linear. Is preferred.
Examples of the component (C) include polyorganosiloxane represented by the following general formula.

Embedded image

Embedded image

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Embedded image (In the formula, m is an integer of 2 to 100, x is a positive integer, and y is a positive integer.)

The amount of component (C) blended is 0.001 to 20 parts by weight per 100 parts by weight of component (A). this is,
The component (C) is 0.001 with respect to 100 parts by weight of the component (A).
This is because if the amount is less than parts by weight, sufficient hydrophilicity cannot be imparted to the obtained silicone rubber powder, and if it exceeds 20 parts by weight, the obtained silicone rubber powder becomes sticky. Is. When the component (i) is blended as the component (C), the component (A)
It is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the component, and when the component (ii) is compounded,
It is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the component.

Component (D), a platinum-based catalyst, is a catalyst for curing this silicone rubber composition, and is, for example, chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum. , Platinum-supported silica fine powder, platinum-supported activated carbon fine powder, and platinum black.

The blending amount of the component (D) is an amount sufficient to cure the silicone rubber composition, and, for example, in the component (D) based on the total weight of the components (A) and (B). It is preferable that the amount of platinum metal is 0.1 to 1,000 ppm in weight unit, and it is particularly preferable that the amount is 1 to 500 ppm.

In this silicone rubber composition, other optional components such as fumed silica, precipitated silica, quartz powder, fused silica, titanium dioxide, talc,
Inorganic fillers such as mica and carbon black, and inorganic fillers obtained by surface-treating these inorganic fillers with organosilicon compounds such as organoalkoxysilanes, organochlorosilanes and organosilazanes; 3-methyl-1-butyne-3 -Ol, 3,5-dimethyl-1-hexyn-3-ol, alkyne alcohol such as phenylbutynol; 3-methyl-3-penten-1-yne,
Enyne compounds such as 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3
5,7-Tetravinylcyclotetrasiloxane, 1,
Addition reaction inhibitors such as 3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole; preservatives, antibacterial agents, antioxidants, fragrances, pigments and dyes are mixed. be able to. In order to adjust the specific gravity of the silicone rubber powder, it is preferable to blend at least one inorganic filler selected from the group consisting of talc, mica, and fused silica. The specific gravity of the silicone rubber powder is 0.97 to 1 It is preferably 0.20, and particularly preferably 0.97 to 1.10. Therefore, the blending amount of these inorganic fillers is preferably less than 100 parts by weight, and particularly preferably 0.01 to 20 parts by weight, relative to 100 parts by weight of the component (A). Further, in order to improve the handling workability of this silicone rubber composition, it is preferable to add the above-mentioned addition reaction inhibitor, and the amount of this addition agent is 10 to 50,000 ppm by weight in the silicone rubber composition.
It is preferable that the amount is such that

In the detergent of the present invention, the content of the above silicone rubber powder is not limited, and may be, for example, 0.01 to
It is preferably in the range of 20% by weight, and particularly preferably 0.
It is preferably in the range of 1 to 10% by weight.

The detergent of the present invention preferably contains a surface-active agent which is usually used in detergents. As the surfactant, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid,
Anionic surfactants such as myristyl benzene sulfonic acid and its sodium salt; octyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide, octyl dimethyl benzyl ammonium hydroxide, decyl dimethyl benzyl ammonium hydroxide, di Cationic surfactants such as octadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide, coconut oil trimethylammonium hydroxide; polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenols, polyoxyalkylene alkyl esters, polyoxyalkylene sorbitan esters, polyethylene Glycor, polypropylene Glyco , Nonionic surfactants ethylene oxide adducts of diethylene of glycol trimethyl nonanol, mixtures of two or more of these surfactants can be exemplified. In the cleaning agent of the present invention, the content of these surfactants is not limited and is, for example, 0.01 to 80.
It is preferably in the range of wt%, and particularly 0.1 to
Preferably it is in the range of 50% by weight.

An oil agent may be added to the detergent of the present invention. This oil agent is solid or semi-solid such as beeswax, carnauba wax, candelilla wax, ozokerite, ceresin, rice wax, mokuro, montane wax, paraffin wax, microcrystalline wax, hydrogenated castor oil, lanolin, petrolatum, cholesteryl stearate, etc. Solid wax; liquid paraffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, oleic acid. 2-octyldodecyl, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, avocado oil, a Mondo oil,
Olive oil, cacao oil, jojoba oil, sesame oil, safflower oil, soybean oil, camellia oil, squalane, persic oil, castor oil, mink oil, cottonseed oil, coconut oil, egg yolk oil, beef tallow, pork fat; polypropylene glycol monooleate, Glycol esters such as neopentyl glycol-2-ethylhexanoate; isostearic acid triglyceride,
Polyhydric alcohols such as coconut oil fatty acid triglyceride; polyoxyalkylene ether oils such as polyoxyethylene lauryl ether and polyoxypropylene cetyl ether; alcohols such as ethanol, octyldodecanol, cetyl alcohol, oleyl alcohol; dimethylsiloxane, polymethyl Phenyl siloxane, polymethyl hydrogen siloxane, dimethyl siloxane / methyl stearoxy siloxane copolymer, dimethyl siloxane / methyl cetyloxy siloxane copolymer,
Dimethyl siloxane / methyl (polyoxyethylene) siloxane copolymer, dimethyl siloxane / methyl (polyoxyethylene / polyoxypropylene) siloxane copolymer, dimethyl siloxane / methyl (polyoxypropylene) siloxane copolymer, cyclic polydimethyl siloxane , Cyclic polymethylphenyl siloxane, cyclic polymethyl hydrogen siloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, polyoxyalkylene-modified polysiloxane, alkoxy-modified polysiloxane, alkyl-modified polysiloxane, and other silicone oils; Examples include mixtures of two or more species. further,
Cyclic diorganosiloxane oligomers such as octamethyltetracyclosiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, diorganosiloxane oligomers such as decamethyltetrasiloxane; methyl alcohol, ethyl Alcohol, n-
Lower alcohols such as propyl alcohol and isopropyl alcohol; and volatile oil agents such as paraffin hydrocarbons may also be added. In the cleaning agent of the present invention, the content of these oil agents is not limited, and for example, 0 to
It is preferably in the range of 80% by weight, and particularly preferably 0.
It is preferably in the range of 1 to 50% by weight.

Further, the cleaning agent of the present invention may contain other optional components as long as the object of the present invention is not impaired. Examples of such components include water; quaternary ammonium salt, alkyldiaminoethylglycine chloride solution, isopropylmethylphenol, triclosan (trichlorohydroxydiphenyl ether), bactericidal agents such as hinokitiol; fluororesin powder, silk powder, polyethylene resin Powder, polypropylene resin powder, polyamide resin powder, acrylic resin powder, vinyl chloride resin powder, epoxy resin powder, polystyrene resin powder, cellulose powder,
Organic resin powder such as polymethylsilsesquioxane resin powder; talc, sericite, mica, colloidal silica, kaolin, zinc white, magnesium carbonate, calcium carbonate,
Inorganic powders such as bentonite, hectorite, colloidal magnesium aluminum silicate, pumice, alumina, calcium phosphate; clay minerals such as montmorillonite, nontronite, savonite, hectorite, permiculite, sepiolite; carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinyl Alcohol, polyvinylpyrrolidone, polyacrylic acid,
Examples thereof include water-soluble polymers such as salts, enzymes, flavors, dyes, preservatives and fungicides.

The detergent of the present invention is prepared by mixing the above components with a homomixer, paddle mixer, colloid mill, propeller stirrer, homogenizer, in-line continuous emulsifier, ultrasonic emulsifier, vacuum stirrer and the like. It Examples of the form of the detergent of the present invention include a solid form; a semisolid form such as cream; a liquid form such as a liquid form and an emulsion form; and a foam form, and a liquid form such as a liquid form and an emulsion form is particularly preferable. The cleansing agent of the present invention can be used as a skin cleansing agent such as a facial cleanser and a body cleansing agent, a hair cleansing agent, a household cleansing agent, and an industrial cleansing agent.

[0025]

EXAMPLES The cleaning agent of the present invention will be described in detail with reference to Examples. The viscosity in the examples is a value measured at 25 ° C. In addition, the physical properties and hydrophilicity of silicone rubber powder,
And the feel was evaluated as follows. [Average Particle Diameter of Silicone Rubber Powder] The average particle diameter was determined from the weight of the silicone rubber powder that passed through several kinds of meshes having different sieves. [Maximum Particle Diameter of Silicone Rubber Powder] The maximum particle diameter of the silicone rubber powder was obtained by observing with an electron microscope. [Hydrophilicity of silicone rubber powder] Silicone rubber powder 1
An aqueous dispersion consisting of 00 parts by weight, 4 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1), and 1000 parts by weight of ion-exchanged water was prepared. The appearance was observed after the aqueous dispersion was allowed to stand for 1 week at room temperature.
If the silicone rubber powder is not aggregated in the aqueous dispersion and can be easily redispersed, the hydrophilicity is good, and the silicone rubber powder is aggregated in the aqueous dispersion. When the redispersion did not occur, the hydrophilicity was poor and indicated by x. [Feeling of Silicone Rubber Powder] The feel of the silicone rubber powder when the above aqueous dispersion is applied to the skin of the hand is ○ when the silicone rubber powder has a soft feel, and the feeling of foreign matter is somewhat stiff. The case of having a foreign matter is shown by Δ, and the case of having a feeling of a foreign substance is shown by x.

Reference Example 1 100 parts by weight of polydimethylsiloxane capped with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 100 centistokes, and 0.85 mol of silicon atom-bonded hydrogen atoms per 1 mol of this vinyl group. A polymethyl hydrogen siloxane endcapped with trimethylsiloxy groups at both molecular chain ends, an isopropanol solution of chloroplatinic acid in an amount of 5 ppm by weight of platinum metal based on the total amount of these siloxanes, formula:

Embedded image 4 parts by weight of polyoxyethylene group-containing polymethylsiloxane represented by and an average particle diameter of about 4 μm, and 10 parts by weight of mica treated with polymethylhydrogensiloxane are uniformly mixed to obtain an addition reaction curing type A silicone rubber composition was prepared. This silicone rubber composition was heated at 150 ° C. for 30 minutes to mold a silicone rubber. The JIS A hardness and specific gravity of this silicone rubber were measured. Next, apply this silicone rubber to a turning radius of 20.
The powder was finely pulverized with a cm cm hammer mill to prepare an irregularly shaped silicone rubber powder. The characteristics of this silicone rubber powder are shown in Table 1.

Reference Example 2 100 parts by weight of polydimethylsiloxane capped with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 500 centistokes, and 0.95 mol of silicon atom-bonded hydrogen atoms per 1 mol of this vinyl group. The average unit formula for

[Chemical 6] A polymethylsiloxane represented by the following formula, a solution of chloroplatinic acid in isopropanol in an amount of 10 ppm by weight of platinum metal based on the total amount of these siloxanes, formula:

[Chemical 7] 0.5 parts by weight of polymethylethylene group-containing polyoxysiloxane represented by and 14 parts by weight of talc having an average particle size of about 0.5 μm and treated with polymethylhydrogensiloxane are uniformly mixed and added. A reaction-curable silicone rubber composition was prepared. This silicone rubber composition was heated at 150 ° C. for 30 minutes to mold a silicone rubber. The JIS A hardness and specific gravity of this silicone rubber were measured. Next, the silicone rubber was finely pulverized with a hammer mill having a radius of gyration of 20 cm to prepare an indefinite shape silicone rubber powder. The characteristics of this silicone rubber powder are shown in Table 1.

Reference Example 3 100 parts by weight of polydimethylsiloxane capped with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 500 centistokes, and 1.2 mol of silicon atom-bonded hydrogen atoms per 1 mol of this vinyl group. A polymethyl hydrogen siloxane endcapped with trimethylsiloxy groups at both molecular chain ends, an isopropanol solution of chloroplatinic acid in an amount of 5 ppm by weight of platinum metal based on the total amount of these siloxanes, formula:

Embedded image 1 part by weight of polyoxyethylene group-containing polymethylsiloxane represented by and an average particle diameter of about 4 μm, and 10 parts by weight of mica treated with polymethylhydrogensiloxane are uniformly mixed to obtain an addition reaction curing type. A silicone rubber composition was prepared. This silicone rubber composition was heated at 150 ° C. for 30 minutes to mold a silicone rubber. The JIS A hardness and specific gravity of this silicone rubber were measured. Next, apply this silicone rubber to a turning radius of 20.
The powder was finely pulverized with a cm cm hammer mill to prepare an irregularly shaped silicone rubber powder. The characteristics of this silicone rubber powder are shown in Table 1.

[Reference Example 4] 100 parts by weight of polydimethylsiloxane endblocked by dimethylvinylsiloxy groups at both molecular chains having a viscosity of 100 centistokes, and 0.85 mol of silicon atom-bonded hydrogen atoms per 1 mol of this vinyl group. A polymethyl hydrogen siloxane endcapped with trimethylsiloxy groups on both ends of the molecular chain, an isopropanol solution of chloroplatinic acid in an amount of 10 ppm by weight of platinum metal relative to the total amount of these siloxanes, formula:

Embedded image 1 part by weight of a polyoxyethylene group-containing polymethylsiloxane represented by the formula (1) and 10 parts by weight of fused silica having an average particle size of about 5 μm and treated with polymethylhydrogensiloxane are uniformly mixed to obtain an addition reaction curing type A silicone rubber composition was prepared. This silicone rubber composition was heated at 150 ° C. for 30 minutes to mold a silicone rubber. The JIS A hardness and specific gravity of this silicone rubber were measured. Next, the silicone rubber was finely pulverized with a hammer mill having a radius of gyration of 20 cm to prepare an indefinite shape silicone rubber powder. The characteristics of this silicone rubber powder are shown in Table 1.

Reference Example 5 100 parts by weight of polydimethylsiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain having a viscosity of 100 centistokes, and 1.20 moles of silicon atom-bonded hydrogen atoms per 1 mole of this vinyl group. The amount of polymethyl hydrogen siloxane capped with trimethylsiloxy groups at both ends of the molecular chain, the amount of platinum metal to the total amount of these siloxanes is 5 ppm by weight in isopropanol, and the average particle size is about 5 ppm. An addition reaction-curable silicone rubber composition having a thickness of 4 μm and 10 parts by weight of mica treated with polymethylhydrogensiloxane was uniformly mixed. This silicone rubber composition was heated at 150 ° C. for 30 minutes to mold a silicone rubber. This silicone rubber JI
S A hardness and specific gravity were measured. Next, the silicone rubber was finely pulverized with a hammer mill having a radius of gyration of 20 cm to prepare an indefinite shape silicone rubber powder. The characteristics of this silicone rubber powder are shown in Table 1.

Reference Example 6 100 parts by weight of polydimethylsiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain having a viscosity of 100 centistokes, and 1.20 mol of silicon atom-bonded hydrogen atoms per 1 mol of this vinyl group. Of polymethyl hydrogen siloxane blocked with trimethylsilyl groups at both ends of the molecular chain, and an addition reaction by uniformly mixing an isopropanol solution of chloroplatinic acid in an amount of 5 ppm of platinum metal with respect to the total amount of these siloxanes. A curable silicone rubber composition was prepared. This composition was treated with pure water at 25 ° C. (electrical conductivity = 0.2 μS / cm)
200 parts by weight and formula:

Embedded image 4 parts by weight of polyoxyethylene group-containing polymethylsiloxane represented by
A uniform water-based emulsion of addition reaction-curable silicone rubber composition was prepared at a pressure of 100 kgf / cm ² . This aqueous emulsion was allowed to stand at 30 ° C. for 6 hours to prepare an aqueous dispersion of silicone rubber powder. 80 this aqueous dispersion
Although the mixture was heated at ℃ for 1 hour, a large amount of gel-like substance was generated, so this was filtered through a mesh (150 mesh) and then dried by a spray dryer to prepare a spherical silicone rubber powder. The characteristics of this silicone rubber powder are shown in Table 1.

[0032]

[Table 1]

[Examples 1 to 4, Comparative Examples 1 to 4] Reference Example 1
6 to 6, the silicone rubber powder has an average particle size of 11
0 μm, JIS A hardness 78, specific gravity 0.93 polyethylene resin powder, or average particle size 70 μm, specific gravity 2.2 amorphous silica powder 3 parts by weight each, deca A liquid cleaning agent was prepared by uniformly mixing 10 parts by weight of methylcyclopentasiloxane, 0.3 parts by weight of polyoxyethylene (20 mol adduct) sorbitan monolaurate, and 86.7 parts by weight of ion-exchanged water. Next, 40 parts by weight of titanium oxide treated with trimethylsiloxy group-blocked polymethylhydrogensiloxane at both molecular chain ends, 20 parts by weight of polydimethylsiloxane blocked with trimethylsiloxy group at both molecular chain ends having a viscosity of 200 centistokes, decamethyl Liquid paraffin 20 having 30 parts by weight of tetrasiloxane and a melting point of 70 ° C.
A detergency evaluation foundation consisting of 10 parts by weight of fumed silica having a specific surface area of 200 m ² / g was prepared. 0.1 g of this foundation was uniformly spread on a circular collagen film having a diameter of 7 cm by a finger for 30 seconds to apply the foundation, and the excess foundation on the collagen membrane was wiped off with a dry towel. 10 g of the above-mentioned cleaning agent was dropped on this collagen film, and the pressing pressure at the time of cleaning was adjusted to 50 g / cm ² and 200 g / cm ² , and the cleaning was performed by rubbing 10 times. The brightness of the collagen film after washing was measured with a color difference meter (CR100 manufactured by Minolta Camera Co., Ltd.), and the contact angle of water was measured with a contact angle measuring machine (manufactured by Elmer Optical Co., Ltd.). Table 2 shows the results.

Further, the silicone rubber powders prepared in Reference Examples 1 to 6 have an average particle diameter of 110 μm, and JIS A
5 parts by weight of polyethylene resin powder having a hardness of 78 and a specific gravity of 0.93, or 5 parts by weight of amorphous silica powder having an average particle size of 70 μm and a specific gravity of 2.2, and 10 parts by weight of potassium laurate, Triethanolamine 10 parts by weight, propylene glycol 10 parts by weight, ethanol 5 parts by weight, glycerin 10 parts by weight, formula:

Embedded image 0.3 parts by weight of the polyoxyethylene group-containing organopolysiloxane represented by the formula (4) and 49.7 parts by weight of ion-exchanged water were uniformly mixed to prepare an emulsion-like detergent. After the detergent was allowed to stand at 25 ° C. for 1 week, the appearance of the detergent was observed, and the storage stability of the detergent was found to be good when the silicone rubber powder was uniformly dispersed. If yes, the case where the silicone rubber powder was separated was shown as x, because the storage stability was poor. In addition, the cleanability of 10 panelists when washing their face with this cleaning agent,
And the feeling of use was evaluated. After cleaning the cleaning property of the cleaning agent,
When the feel was refreshed, the cleanability was good, and when the slimy feel remained, the cleanability was fair, and when the slimy feel remained, the cleanability was poor. In addition, the feeling of use of this cleaning agent is ○ when a soft rub feeling is felt, △ when a foreign sensation or irritation is occasionally felt but a soft rub feeling is felt occasionally, and × when a foreign sensation or irritation is always felt. Indicated. Table 2 shows the results.

[0035]

[Table 2]

[Examples 5 to 6 and Comparative Examples 5 to 7] The silicone rubber powders prepared in Reference Examples 1, 2 and 5 had an average particle diameter of 110 μm, a JIS A hardness of 78 and a specific gravity. Polyethylene resin powder of 0.93, or amorphous silica powder having an average particle size of 70 μm and a specific gravity of 2.2, 3 parts by weight each, decamethylcyclopentasiloxane 10 parts by weight, polyoxyethylene (20 mol addition) ) 0.3 parts by weight of sorbitan monolaurate and 86.7 parts by weight of ion-exchanged water were uniformly mixed to prepare a liquid detergent. 1 part by weight of a dimethylpolysiloxane endcapped with trimethylsiloxy groups at both molecular chain ends having a viscosity of 100 centistokes in advance, 0.2 part by weight of caranauba wax, 0.5 part by weight of carbon black, and 98.3 of toluene were added. 1 g on a white acrylic resin coated steel sheet made by drying it after immersing it in a mixed solution consisting of parts by weight
/ 100 cm ^{2 was} dropped and the surface was rubbed with a case at a pressure of 500 g / cm ² 30 times. Then, water is dropped onto the coated steel sheet after cleaning, and the case where the water droplets are non-spherical with a diameter of 1 cm or more is regarded as having good cleanability, and the water droplets have a diameter of 5 mm.
A sample having a spherical shape or a non-spherical shape of ˜1 cm was evaluated as a good cleaning property, and a sample having a water droplet having a spherical shape having a diameter of 5 mm or less was evaluated as poor cleaning property and shown as a cross. In addition, observing the surface of the coated steel sheet after cleaning, it is indicated that there is no damage when no trace of coating is observed, and if the trace of coating is slightly observed due to carbon black, there is some damage. When the rubbing trace was clearly observed, it was shown as being damaged and indicated by x. Table 3 shows the results.

[0037]

[Table 3]

[0038]

The cleaning agent of the present invention is a cleaning agent containing a silicone rubber powder, and the silicone rubber powder having an irregular shape containing a polyorganosiloxane having a polyoxyalkylene group bonded to a silicon atom. Since it is used, it is characterized by having excellent cleaning properties, storage stability, and a soft feeling of use.

Continued Front Page (72) Inventor Asao Harashima 2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow Corning Silicone Co., Ltd.

Claims (7)

[Claims] 1. A detergent containing a silicone rubber powder, wherein the silicone rubber powder contains silicon atoms,
_{^{Formula: -R 1 (OR 2) m}} OR 3 ( wherein, R ¹ and R ² are the same or different alkylene groups, R ³ is a hydrogen atom or an alkyl group,
m is an integer of 2 to 100. ) A detergent having an irregular shape containing a polyorganosiloxane having a polyoxyalkylene group represented by the formula (1). 2. The cleaning agent according to claim 1, wherein the silicone rubber powder has a particle size of 5 mm or less. 3. The cleaning agent according to claim 1, wherein the JIS A hardness of the silicone rubber powder is 10 to 50. 4. The silicone rubber powder contains silicon atoms,
_{^{Formula: -R 1 (OR 2) m}} OR 3 ( wherein, R ¹ and R ² are the same or different alkylene groups, R ³ is a hydrogen atom or an alkyl group,
m is an integer of 2 to 100. The cleaning agent according to claim 1, which is obtained by finely pulverizing a silicone rubber containing a polyorganosiloxane having a polyoxyalkylene group represented by the formula (1). 5. The cleaning agent according to claim 4, wherein the silicone rubber is obtained by curing an addition reaction-curable silicone rubber composition. 6. A silicone rubber composition comprising: (A) a polyorganosiloxane having at least two silicon atom-bonded alkenyl groups in one molecule.
100 parts by weight, (B) a polyorganosiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule (based on 1 mol of the alkenyl group in the present composition, a silicon atom-bonded hydrogen atom in the component (B)) Is 0.1-1
0 mol}, (C) on the silicon atom, the formula: —R ¹ (OR ² ) _m OR ³ (wherein R ¹ and R ² are the same or different alkylene groups, and R ³ is hydrogen. An atom or an alkyl group,
m is an integer of 2 to 100. ) A polyorganosiloxane having a polyoxyalkylene group bonded thereto and having neither an alkenyl group nor a hydrogen atom bonded thereto.
The cleaning agent according to claim 5, which comprises 0.001 to 20 parts by weight and (D) a platinum-based catalyst (a sufficient amount to cure the composition). 7. The cleaning agent according to claim 1, wherein the cleaning agent containing the silicone rubber powder is liquid.