JP5271510B2 - Silicone-containing particles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone-containing particle rapidly releasing a silicone compound in water. <P>SOLUTION: The silicone-containing particle comprises a silicone mixture containing (B) 0.1-10 pts.mass of a polyoxyethylene-polyoxypropylene-modified silicone having &ge;6 HLB value and (C) 5-100 pts.mass of a surfactant and (D) an oil-absorbing carrier based on (A) 100 pts.mass of a dimethylpolysiloxane and/or a dimethylpolysiloxane derivative having &le;6 HLB value. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a silicone-containing particle and a method for producing the same. The present invention also relates to a powder detergent composition containing the silicone-containing particles.

  Silicone compounds have high lubricity and are widely used for the purpose of improving the texture of textile products. In general, it is known that a silicone compound has a higher texture improvement effect as the degree of polymerization, that is, the viscosity becomes higher. Further, it is known that a silicone compound having a low water solubility is preferable from the viewpoint of adsorptivity to fibers and prevention of detachment during rinsing. Such a silicone compound having a high texture-improving effect is a high-viscosity liquid, and thus is widely applied to liquid compositions such as liquid detergents, but is generally applied to powder compositions such as powder detergents. Is not done.

  It would be desirable to improve the function of the powder detergent if it can be applied to the silicone compound in the powder detergent, but when a silicone compound with high viscosity and low water solubility is added to the powder detergent, the handling at the time of manufacturing will be improved. Therefore, it is required to moderately reduce the viscosity of the silicone compound, to make it difficult to separate the reduced mixture, and to release the silicone compound quickly in water. In order to further improve the texture of the textile product, it is required that the released silicone compound be adsorbed by clothing even in a washing aqueous solution in which a surfactant coexists.

As a technique for powdering a silicone compound, techniques of Patent Documents 1 to 3 targeting a silicone compound as an antifoaming agent are known. Moreover, the technique of mix | blending a silicone compound as a self-emulsifiable composition and improving the dispersibility in water is also known (patent documents 4-5).
JP-A-3-186307 JP-A-7-70594 JP 2001-158900 A JP-A-53-34854 JP-A-56-129003

  However, conventional silicone compound pulverization techniques are mostly directed to silicone compounds as antifoaming agents having a relatively low viscosity, and powdery higher viscosity silicone compounds suitable for improving the texture of textile products. An appropriate method for this is not found in Patent Documents 1 to 3. Patent Documents 4 to 5 do not specifically refer to powdering a silicone compound, and powdering so that a high-viscosity silicone compound can be blended in a powder detergent or the like. No information can be obtained about the rapid release of water in water. In particular, at present, there is a tendency that the washing time tends to be shortened, and particles capable of quickly dispersing the silicone compound even in such a short time treatment are desired. Is hard to say. Furthermore, it is desirable for improving the texture of the textile product that the silicone compound is adsorbed by the textile product even in the washing aqueous solution in which the surfactant coexists, but Patent Documents 1 to 5 cannot find a solution to such a problem.

  An object of the present invention is to provide a silicone-containing particle that rapidly releases a silicone compound in water. In particular, it is to provide a silicone-containing particle which contains a silicone compound having a high viscosity and low water solubility suitable for improving the texture of a textile product, and rapidly releases the silicone compound in water. Furthermore, it is to provide silicone-containing particles in which the silicone compound is adsorbed by the fiber product even in a washing aqueous solution in which a surfactant coexists. Furthermore, it is providing the manufacturing method which can manufacture such a silicone containing particle | grain easily.

  The present invention relates to (A) dimethylpolysiloxane and one or more dimethylpolysiloxane derivatives having an HLB value of 6 or less and 100 parts by mass of (B) polyoxyethylene-poly (H) having an HLB value greater than 6. The present invention relates to a silicone-containing particle comprising 0.1 to 10 parts by mass of oxypropylene-modified silicone and (C) a silicone mixture containing 5 to 100 parts by mass of a surfactant and (D) an oil-absorbing carrier.

  The present invention also relates to a powder detergent composition containing 0.2 to 20% by mass of the silicone-containing particles of the present invention.

Moreover, this invention contains 0.2-20 mass% of silicone containing particle | grains of the said invention, and (E) content of the high molecular compound which has group represented by following formula (1) in a side chain at least. Relates to a powder detergent composition, wherein is from 0.001 to 10% by weight.
^{_{- (OX) n -E 2 -R}} (1)
(Wherein x is the same or different divalent saturated hydrocarbon group having 1 to 6 carbon atoms, n is a number of 5 to 300, E ² is an ether bond or an oxycarbonyl group, and R is a hydroxyl group. And an optionally substituted alkyl group having 4 to 30 carbon atoms.)

  Further, the present invention relates to (A) one or more dimethylpolysiloxane derivatives having an HLB value of 6 or less, and 100 parts by mass of (B) an HLB value greater than 6. -Production of silicone-containing particles, in which a liquid mixture obtained by mixing 0.1 to 10 parts by mass of polyoxypropylene-modified silicone and 5 to 100 parts by mass of (C) surfactant is mixed with (D) an oil-absorbing carrier. Regarding the method.

Further, the present invention relates to (A) one or more dimethylpolysiloxane derivatives having an HLB value of 6 or less, and 100 parts by mass of (B) an HLB value greater than 6. -A liquid mixture obtained by mixing 0.1 to 10 parts by weight of polyoxypropylene-modified silicone and 5 to 100 parts by weight of (C) a surfactant, (D) oil absorbing carrier and (E) at least in the side chain The present invention relates to a method for producing silicone-containing particles, which is mixed with a polymer compound having a group represented by formula (1).
^{_{- (OX) n -E 2 -R}} (1)
(Wherein x is the same or different divalent saturated hydrocarbon group having 1 to 6 carbon atoms, n is a number of 5 to 300, E ² is an ether bond or an oxycarbonyl group, and R is a hydroxyl group. And an optionally substituted alkyl group having 4 to 30 carbon atoms.)

In addition, the present invention relates to (B) 100 parts by mass of (A) one or more of dimethylpolysiloxane and a dimethylpolysiloxane derivative having an HLB value of 6 or less (hereinafter referred to as “component (A)”). Polyoxyethylene-polyoxypropylene modified silicone having an HLB value greater than 6 [hereinafter referred to as component (B)] 0.1 to 10 parts by mass and (C) surfactant (hereinafter referred to as component (C)) 5 to 100 A liquid mixture obtained by mixing parts by mass is composed of (D) an oil-absorbing carrier (hereinafter referred to as component (D)), (E) a polymer compound having a group represented by the following formula (1) at least in the side chain The present invention relates to a method for producing silicone-containing particles, which is mixed with a surfactant (hereinafter referred to as component (E)) and a surfactant (hereinafter referred to as component (F)) that is the same as or different from (F) (C).
^{_{- (OX) n -E 2 -R}} (1)
(Wherein x is the same or different divalent saturated hydrocarbon group having 1 to 6 carbon atoms, n is a number of 5 to 300, E ² is an ether bond or an oxycarbonyl group, and R is a hydroxyl group. And an optionally substituted alkyl group having 4 to 30 carbon atoms.)

  According to the present invention, silicone-containing particles that rapidly release a silicone compound in water can be obtained. In particular, the present invention provides a silicone-containing particle containing a silicone compound having a high viscosity and low water solubility suitable for improving the texture of a textile product, and rapidly releasing the silicone compound in water. In addition, silicone-containing particles are also provided in which the silicone compound is adsorbed by a textile product even in a washing aqueous solution in which a surfactant coexists. Moreover, such a silicone-containing particle of the present invention can be easily produced by the production method of the present invention.

[Silicone-containing particles]
<(A) component>

  The component (A) is selected from one or more of dimethylpolysiloxane and a dimethylpolysiloxane derivative having an HLB value of 6 or less. The measuring method of HLB value is shown below.

* Measurement method of HLB value The HLB value is calculated by the following formula from the cloudy number A measured by the following method described on page 324 of the surfactant manual (edited by Nishiichiro et al., Published by Sangyo Tosho Co., Ltd., 1960). Calculate from
HLB value = 0.89 × A + 1.11
<Measuring method of cloud number A>
0.5 g of an evaluation sample (dimethylpolysiloxane derivative) is dissolved in 5 ml of 98% ethyl alcohol, titrated with a 2% aqueous phenol solution while stirring at 25 ° C., and the end point is when the liquid becomes turbid. The number of ml of 2% phenol aqueous solution required for this titration is defined as the cloud number A.

  The HLB value of the dimethylpolysiloxane derivative is 6 or less, preferably 4 or less, and more preferably 2 or less, from the viewpoint of adsorptivity to fibers and prevention of falling off during rinsing.

  Among the components (A), examples of the dimethylpolysiloxane derivative include alkyl-modified silicone, aralkyl-modified silicone, polyether-modified silicone (other than (B) component), fatty acid ester-modified silicone, fluoroalkyl-modified silicone, amino-modified silicone, Examples include modified silicones such as epoxy-modified silicone, carboxyl-modified silicone, methacryl-modified silicone, alcohol-modified silicone, mercapto-modified silicone, and vinyl-modified silicone. Among these, alkyl-modified silicone, polyether-modified silicone [other than component (B) ], Fatty acid ester-modified silicone and amino-modified silicone are preferred.

  The component (A) has a viscosity (25 ° C.) of 2000 mPa · s or more, more preferably 5000 mPa · s or more, and particularly preferably 10,000 mPa · s or more from the viewpoint of improving the texture to the textile product.

  The viscosity can be measured using a B-type viscometer (for example, DVM-B type manufactured by TOKYO KEIKI) by appropriately selecting the rotor and the number of rotations. For example, no. Measurement can be performed using four rotors, with a rotor rotation speed of 6 rpm, a measurement time of 1 minute, a sample temperature of 25 ° C., and a gap between the rotor and the inner surface of the sample container of 10 mm or more.

<(B) component>
(B) As a component, the compound represented by the following general formula (B-1) is preferable.

[Wherein, R is an alkylene group having 1 to 10 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms, n / (m + n) is 0.04 or more, a / b is 0.7 to 1.3. ]

In the formula, n / (m + n) is preferably 0.05 or more, more preferably 0.06 or more, and a / b is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. . The arrangement of C ₂ H ₄ O and C ₃ H ₆ O may be either block or random.

  The component (B) has a viscosity (25 ° C.) of less than 10,000 mPa · s, more preferably 8000 mPa · s or less, and particularly preferably 5000 mPa · s or less in view of handling properties. Further, the HLB value of the component (B) (measurement method: described in the column of the component (A)) is larger than 6, and more preferably 7 or more. The structure of the compound represented by the general formula (B-1) is preferably selected so that the viscosity and the HLB value are obtained.

The values of m, n, a and b of the component (B) can be calculated by ¹ H-NMR measurement using, for example, the following apparatus and conditions.
Solvent: Deuterated chloroform Sample concentration: 2% by mass
NMR apparatus: Mercury 400 (400 MHz) manufactured by Varian
NMR measurement conditions: observation width of 649.5 Hz
Data point 42052
Pulse width 4.5μs (45 ° pulse)
Pulse delay time 30 seconds
Measurement temperature Room temperature

  The component (B) is used in a proportion of 0.1 to 10 parts by mass, preferably 0.2 to 8 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A). .

<(C) component>
Examples of the component (C) include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

  Examples of the anionic surfactant include alkylbenzene sulfonic acid or a salt thereof, α-olefin sulfonic acid or a salt thereof, alkyl sulfate ester or a salt thereof, polyoxyalkylene alkyl ether sulfate or a salt thereof, α-sulfo fatty acid ester or a salt thereof, A fatty acid or its salt etc. are mentioned.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, alkyl polyglycoside, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyethylene / polyoxypropylene block polymer, polyoxyalkylene Examples include alkylenalalkylol (fatty acid) amide.

  Of the nonionic surfactants, polyoxyalkylene alkyl ethers obtained by adding an average of 2 to 20 moles and further 3 to 16 moles of an alkylene oxide to an alcohol having 10 to 16 carbon atoms are preferable. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

  Cationic surfactants include dilong chain alkyl quaternary ammonium salts, mono long chain alkyl quaternary ammonium salts, dilong chain alkyl imidazolinamide quaternary salts, trialkylbenzylammonium salts, alkyl imidazolinium. Salts, N-alkyl-polyoxyalkylene trimethyl ammonium salts and the like.

  Examples of amphoteric surfactants include alkylcarboxybetaines, amidopropylbetaines, hydroxysulfobetaines, amide amino acid salts, alkylaminodicarboxylic acids, alkyldiaminoethylglycines, amine oxides, and the like.

  In the present invention, the temperature at which the silicone mixture containing the component (A), the component (B), and the component (C) is supported on the (D) oil-absorbing carrier is 40 to 160 ° C, further 50 to 120 ° C, and further 55. ~ 100 ° C is preferred, and the component (C) is preferably liquid at this temperature. As the component (C), a nonionic surfactant is preferable.

  (C) component is 5-100 mass parts with respect to 100 mass parts of (A) component, Preferably it is 10-80 mass parts, More preferably, it is used in the ratio of 15-50 mass parts.

  The mass ratio of the component (B) and the component (C) is (B) / (C), and is 1/2 to 1/100, more preferably 1/5 to 1/50. This is preferable.

  Further, the mass ratio of the component (A), the component (B), and the component (C) is [(B) + (C)] / (A), 10/1 to 1/10, and further 5/1 to 1/5 is preferable from the viewpoint of the balance between the viscosity reducing effect and the finish of the fiber.

<(D) component>
Examples of the oil-absorbing carrier (D) include silicates, aluminosilicates, sugars and polysaccharides. Specific examples of silicates and aluminosilicates include amorphous silicate ("Tokusil NR" manufactured by Tokuyama Corporation), bentonite ("Laundrosil EX0242" manufactured by Sud Chemie), calcium silicate ("Flolite" manufactured by Tokuyama Corporation) ), Aluminum silicate (“TIXOLEX 25” manufactured by Masatomo Chemical), among which amorphous silicate and calcium silicate are more preferable. Product names are shown in angle brackets.

  Specific examples of sugars and polysaccharides include cellulose, starch, and derivatives thereof. Specific examples of cellulose include carboxymethylcellulose (“Sunrose” manufactured by Nippon Paper Chemical Co., Ltd.), methylcellulose (“Metrozu” manufactured by Shin-Etsu Chemical Co., Ltd.), and hydroxypropyl methylcellulose (“Marporose” manufactured by Matsumoto Yushi Seiyaku Co., Ltd.). )), Cationized cellulose (Kao Co., Ltd. “Poise 60H”, Dow Chemical “JR30M”, “LR400”), and specific examples of starch include dextrin (Matsutani Chemical Industry Co., Ltd. “Pine Flow KH”). , Dextrin ("Paindex" manufactured by Matsutani Chemical Industry Co., Ltd.), and cationized starch ("Posiparin" manufactured by Matsutani Chemical Industry Co., Ltd.). Of these, dextrins are more preferred, those having a specific volume of 5 to 10 ml / g are more preferred from the viewpoint of oil absorption, and those having a glass transition temperature of 200 ° C. or more are particularly preferred from the viewpoint of stability at high temperatures. preferable.

  Also, sulfates, carbonates, bicarbonates, sesquicarbonates and phosphates can be used as the oil-absorbing carrier. Furthermore, particles obtained by spray-drying a surfactant or a builder component, particles obtained by mixing and granulating a plurality of detergent components, and the like may be used as the oil-absorbing carrier.

  These oil-absorbing carriers may be used alone or in combination.

  The mass ratio of the component (A), the component (B), the component (C), and the component (D) is 5/1 to 1/5 as [(A) + (B) + (C)] / (D). Further, 5 / 1.5 to 1/4, and more preferably 5/2 to 1/3 is preferable from the viewpoint of granulation suitability.

<(E) component>
The silicone-containing particle of the present invention further contains, as the component (E), a polymer compound having a group represented by the following formula (1) in at least a side chain, from the viewpoint of adsorption of the silicone compound to the fiber product To preferred.
^{_{- (OX) n -E 2 -R}} (1)

  In formula (1), n X represents the same or different divalent saturated hydrocarbon group having 1 to 6 carbon atoms. X may be linear, branched or cyclic. Specific examples of X include a methylene group, an ethylene group, a propylene group, a trimethylene group, various butylene groups, various pentylene groups, various hexylene groups, various cyclopentylene groups, various cyclohexylene groups, and the like. And an alkylene group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.

  n shows the number of 5-300, 5-200 are preferable and 8-120 are more preferable.

E ² represents an ether bond or an oxycarbonyl group (—OCO— or —COO—). In the oxycarbonyl group, the atom bonded to R may be a carbon atom or an oxygen atom.

  R represents an alkyl group having 4 to 30 carbon atoms which may be substituted with a hydroxyl group. R may be linear, branched or cyclic, but is preferably an alkyl group having 6 to 25 carbon atoms. Specific examples of R include various hexyl groups, octyl groups, decyl groups, dodecyl groups, tetradecyl groups, hexadecyl groups, octadecyl groups, icosyl groups, and cyclohexyl groups in which an alkyl group may be introduced on the ring, Examples include a cyclooctyl group and the like, and a group in which at least one hydrogen atom of these groups is substituted with a hydroxyl group.

  As a suitable example of the component (E), the polysaccharide derivative (e-1) having the group represented by the formula (1) and / or the group represented by the formula (1) may be used per main chain constituent monomer unit. And a water-soluble synthetic polymer compound (e-2) having a weight average molecular weight of 10,000 to 2,000,000 having an average of 0.0001 to 0.1.

<Polysaccharide derivative (e-1)>
As the polysaccharide derivative, a polysaccharide derivative (hereinafter referred to as polysaccharide derivative (e-1-a)) in which part or all of the hydrogen atoms of the hydroxy group of the polysaccharide or derivative thereof are substituted with the following group (α) is preferable.
(Α) Group represented by formula (2) -E ^1- (OX) _n1 -E ² -R (2)
(In the formula, E ¹ represents a linear, branched or cyclic divalent saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hydroxy group or an oxo group, and n1 is 8 to 300. X, E ² and R have the same meaning as described above, and n1 Xs may be the same or different.)

  Examples of the polysaccharides or derivatives thereof include cellulose, guar gum, starch, pullulan, dextran, fructan, mannan, agar, carrageenan, chitin, chitosan, pectin, alginic acid, hyaluronic acid and the like; these include methyl group, ethyl group , Derivatives substituted with a hydroxyethyl group, a hydroxypropyl group, and the like. These substituents can be substituted singly or in combinations of constituent monosaccharide residues.

  Specific examples of polysaccharide derivatives include hydroxyethyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl Examples include starch, hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum, hydroxypropyl methyl starch and the like.

  Among these polysaccharides or derivatives thereof, cellulose, starch, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, and hydroxypropyl cellulose are preferable, and hydroxyethyl cellulose is particularly preferable.

  The weight average molecular weight of these polysaccharides or derivatives thereof is preferably 10,000 to 10,000,000, more preferably 100,000 to 5,000,000, still more preferably 200,000 to 2,000,000.

In the group (α), E ¹ is preferably a linear or branched divalent saturated hydrocarbon group having 2 or 3 carbon atoms which may be substituted with a hydroxy group or an oxo group. Preferable examples thereof include ethylene, propylene, trimethylene, 2-hydroxytrimethylene, 1-hydroxymethylethylene, 1-oxoethylene, 1-oxotrimethylene, 1-methyl-2-oxoethylene and the like.

  X is preferably a linear or branched divalent saturated hydrocarbon group having 2 or 3 carbon atoms, specifically ethylene, propylene and trimethylene.

The average number of added moles of (—OX—) represented by n1 is preferably 8 to 120, more preferably 10 to 60, from the viewpoint of thickening effect and emulsion stability. The n1 Xs may be the same or different. E ² is an ether bond or an oxycarbonyl group, and an ether bond is preferred. R is preferably a linear or branched alkyl group having 5 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, which may be substituted with a hydroxy group, and from the viewpoint of stability. An unsubstituted alkyl group, particularly an unsubstituted linear alkyl group is preferred. Specifically, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, isostearyl group and the like are preferable.

The degree of substitution with the group (α) in the polysaccharide derivative (e-1-a) is preferably 0.0001 to 1.0, more preferably 0.0005 to 0.5, and still more preferably per constituent monosaccharide residue. Is 0.001 to 0.1.
In addition to the group (α), the polysaccharide derivative (e-1) in the present invention may be further substituted with one or more groups selected from the following groups (β), (γ) and (δ). In addition, the hydrogen atom of the hydroxy group of the groups (α) to (δ) may be further substituted with groups (α) to (δ).
(Β) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxy group or a salt thereof (γ) a carboxyalkyl group having 2 to 6 carbon atoms which may be substituted with a hydroxy group or a salt thereof (δ ) Group represented by general formula (3)

(In the formula, D ¹ represents a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, and R ¹ , R ² and R ³ are the same. Alternatively, it represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted with a hydroxy group, and Y ⁻ represents a hydroxy ion, a halogen ion or an organic acid ion.

  Examples of the group (β) include a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfo-2-hydroxypropyl group, and a 2-sulfo-1- (hydroxymethyl) ethyl group. From the viewpoint of production, a 3-sulfo-2-hydroxypropyl group is preferable. All or a part of these groups (B) may be a salt with an alkali metal such as Na, K, Ca, Mg or an alkaline earth metal, an amine, an organic cation such as ammonium.

  The degree of substitution with the group (β) is preferably 0 to 1.0 per constituent monosaccharide residue, more preferably 0 to 0.8, and still more preferably 0 to 0.5.

  Examples of the group (γ) include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, and a carboxypentyl group. Among these, a carboxymethyl group is preferable from the viewpoints of stability and production. All or part of the group (γ) may be a salt with an alkali metal such as Na, K, Ca, Mg or an alkaline earth metal, an amine, an organic cation such as ammonium.

  The degree of substitution with the group (γ) is preferably 0 to 1.0, more preferably 0 to 0.8, and particularly preferably 0 to 0.5 per constituent monosaccharide residue.

D ¹ in the group (δ) is preferably a linear or branched divalent saturated hydrocarbon group which may be substituted with a hydroxy group having 2 or 3 carbon atoms. Specifically, ethylene, propylene, trimethylene, 2-hydroxytrimethylene, 1-hydroxymethylethylene and the like are preferable.

Examples of R ¹ , R ^2, and R ³ include a methyl group, an ethyl group, a propyl group, and a 2-hydroxyethyl group, and among them, a methyl group and an ethyl group are preferable.

Among Y ⁻ , halogen ions include chlorine ion, bromine ion, iodine ion, etc., and organic acid ions include CH ₃ COO ⁻ , CH ₃ CH ₂ COO ⁻ , CH ₃ (CH ₂ ) ₂ COO ^{− and the} like. Can be mentioned. Y ^- The hydroxy ion, chloride ion and bromide ion are preferred.

  The degree of substitution with the group (δ) is preferably 0 to 0.5, particularly preferably 0 to 0.3 per constituent monosaccharide residue.

  The substitution of the polysaccharide or its derivative with the groups (α) to (δ), that is, polyoxyalkyleneation, sulfoalkylation, carboxyalkylation or cationization can be carried out by the method described in WO00 / 73351.

  The polysaccharide derivative (e-1) used in the present invention is exemplified by the following general formula (4) when the case where cellulose is used as the polysaccharide or its derivative is taken as an example.

(Wherein R ⁴ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group, a group selected from the above group (α), group (β), group (γ) and group (δ)). , Q represents an alkylene group having 2 to 4 carbon atoms, a, b and c are the same or different and each represents a number of 0 to 10, QO group, R ⁴ group, a, b and c are repeating Within the unit or between the repeating units, they may be the same or different, and the hydroxy groups of the groups (α) to (δ) may be further substituted with other groups (α) to (δ). At least one of R ^{4 in} the group is a group (α).)

<Water-soluble synthetic polymer compound (e-2)>
The water-soluble synthetic polymer compound is a compound having a molecular weight of 10,000 to 2,000,000 having an average of 0.0001 to 0.1 group of the formula (1) per main chain constituting monomer unit.

  As the group of formula (1), X is an ethylene group, n is a number of 5 to 200, and R is a linear, branched or cyclic alkyl group having 4 to 30 carbon atoms. Further, the average number of groups of the formula (1) is more preferably 0.001 to 0.05 on average per main chain constituting monomer unit, and the weight average molecular weight is more preferably 30,000 to 1,500,000.

The water-soluble synthetic polymer compound can be obtained by reacting a compound represented by the general formula (5) with a water-soluble synthetic polymer compound having a hydroxyl group such as polyvinyl alcohol and polyglycidol.
E ^3- (OX) _n -E ² -R (5)
(In the formula, E ³ represents an epoxidized alkyl group having 3 to 6 carbon atoms, a linear or branched halogenated alkyl group having 1 to 6 carbon atoms which may be substituted by a hydroxy group, or a carboxy group or A carboxyalkyl group having 2 to 6 carbon atoms or a derivative thereof, and X, n, R and E ² have the same meaning as described above.

  It can also be obtained by copolymerizing a water-soluble monomer and a monomer having a hydrophobic group having 4 to 30 carbon atoms via a 5-200 oxyethylene (EO) linking chain.

  As said water-soluble monomer, the compound represented by General formula (6) or the compound represented by General formula (7) is mentioned.

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or a methyl group, and x represents an average of 2 to 100.)

(Wherein R ⁸ and R ⁹ are the same or different and represent a hydrogen atom or a methyl group, R ¹⁰ and R ¹¹ represent a methyl group or an ethyl group, y represents 0 or an integer of 2 to 5, and Z represents —N (R ¹² ) — group (R ¹² represents a hydrogen atom or a methyl group), an oxygen atom or a direct bond.

  Specific examples thereof include methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropylacrylamide, N, N -Dimethylacrylamide and the like, and these compounds can be synthesized by known methods.

  Examples of the monomer having a hydrophobic group having 4 to 30 carbon atoms via 5 to 200 EO linking chains include compounds represented by the general formula (8).

Wherein R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom or a methyl group, z represents a number of 5 to 200, R ¹⁵ has 4 to 30 carbon atoms which may be substituted with a hydroxy group, Preferably 8-30 linear, branched or cyclic alkyl groups are shown.)

  Specific examples include lauroxy polyethylene glycol monoacrylate, stearoxy polyethylene glycol monomethacrylate and the like, and these compounds can be synthesized by known methods.

  (E) A component is 1-50 mass parts with respect to 100 mass parts of (A) component, Preferably it is 2-30 mass parts, More preferably, it is used in the ratio of 5-20 mass parts.

<(F) component>
In addition to the component (C), the silicone-containing particle of the present invention preferably further contains a surfactant as a component (F) for assisting the dissolution of the silicone-containing particle in water and quickly dispersing it in water. . Examples of the component (F) include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, with anionic surfactants being preferred. Specific examples of the component (F) include sodium laurate, linear alkyl (carbon number 8-14) sodium benzenesulfonate, alkyl (carbon number 12-18) sodium sulfate, polyoxyethylene alkyl ether sodium sulfate (average EO addition mole number 0.2 to 3), α-olefin (carbon number 12 to 18) sodium sulfonate powder, fatty acid (carbon number 14 to 18) diethanolamide powder and the like, among which sodium alkyl sulfate is more preferable. .

  (F) A component is 5-80 mass parts with respect to 100 mass parts of (A) component, Preferably it is 20-60 mass parts, More preferably, it is used in the ratio of 30-50 mass parts.

  The component (F) may be liquid or solid at normal temperature (20 ° C.). Further, the component (F) may be the same as the component (C).

<(G) Binder [hereinafter referred to as (G) Component>]
The silicone-containing particles of the present invention preferably further contain a binder as the component (G). It is preferable to obtain the silicone-containing particles of the present invention by extrusion granulation using a binder. Examples of the binder of component (G) include thermoplastic water-soluble binders, and at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, and the like. preferable. In the present invention, the water-soluble binder having a melting point or softening point of 35 to 80 ° C. is preferably used, preferably 45 to 70 ° C., particularly preferably 50 to 65 ° C.

  The weight average molecular weight of the binder is preferably 4000 to 20000, more preferably 6000 to 13000, and particularly preferably 7000 to 9000 in terms of viscosity when granulated by GPC method using polystyrene as a standard.

  The component (G) is preferably used in a proportion of 10 to 300 parts by mass, more preferably 30 to 200 parts by mass, particularly 50 to 150 parts by mass with respect to 100 parts by mass of (A).

  In addition to the above components, the silicone-containing particles of the present invention can contain pigments (dyes, pigments), fragrances, soil release agents, recontamination inhibitors, bleaches, bleach activators, antibacterial agents, enzymes, and the like. .

  These components may be mixed in advance with the silicone mixture and then mixed with the oil absorbing carrier, or may be mixed with the silicone mixture after mixing with the oil absorbing carrier in advance, or may be added after mixing the silicone mixture and the oil absorbing carrier. May be.

  The preferable content of each component in the final silicone-containing particles of the present invention is (A) component is 15 to 60% by mass, further 20 to 50% by mass, (B) component is 0.05 to 10% by mass, and further 0.1 to 5% by mass, component (C) 1 to 30% by mass, further 5 to 20% by mass, component (D) 1 to 60% by mass, further 10 to 40% by mass, component (E) 0 .01-20% by mass, further 0.1-10% by mass, component (F) 1-30% by mass, further 5-20% by mass, component (G) 15-50% by mass, further 20-40% by mass. %.

[Method for producing silicone-containing particles]
The silicone-containing particle of the present invention is a mixture obtained by mixing 0.1 to 10 parts by mass of (B) component and 5 to 100 parts by mass of surfactant to 100 parts by mass of (A) component. , (D) It can manufacture by mixing with a component. The silicone-containing particles of the present invention were obtained by mixing 0.1 to 10 parts by mass of component (B) and 5 to 100 parts by mass of surfactant (C) with respect to 100 parts by mass of component (A). It can manufacture by mixing a mixture with (D) component and (E) component. The silicone-containing particles of the present invention were obtained by mixing 0.1 to 10 parts by mass of component (B) and 5 to 100 parts by mass of surfactant (C) with respect to 100 parts by mass of component (A). It can manufacture by mixing a mixture with (D) component, (E) component, and (F) component. At that time, the mixture is preferably a liquid mixture from the viewpoint of oil absorption to the component (D), and a temperature condition is employed so that the components (A), (B), and (C) can maintain a liquid state. It is preferable. As above-mentioned, the temperature at the time of carrying | supporting the silicone mixture containing (A) component, (B) component, and (C) component on (D) component is 40-160 degreeC, Furthermore, 50-120 degreeC, Furthermore, 55-100 ° C is preferred. In the present invention, the component (G) is further added to the component (D) carrying the components (A) to (C) and mixed as appropriate to perform granulation. In the present invention, the (G) component is further added to the (D) component and (E) component carrying the (A) to (C) components and mixed as appropriate to perform granulation. In the present invention, the (G) component is further added to the (D) component carrying the (A) to (C) component, the (E) component, and the (F) component, and mixed appropriately, and granulation is performed. Do. The granulation method is not particularly limited, and a general granulation method can be used using a conventionally known granulation apparatus. For example, it can be produced by a stirring rolling granulation method, an extrusion granulation method, a spray cooling method or the like. Examples of the apparatus used for granulation include a high-speed mixer manufactured by Fukae Kogyo Co., Ltd. and a pro-shear mixer manufactured by Taiheiyo Kiko Co., Ltd. Examples include Pelleter Double and Twin Dome Gran manufactured by NIPOWAL. As another granulation method, a tablet shape by a briquetting machine can be cited as a preferable granulation method. Among these, it is preferable to produce the silicone-containing particles of the present invention by consolidation by extrusion granulation. By using a manufacturing method in which extrusion granulation and consolidation are used, there is an advantage that stability during transportation and storage is enhanced. That is, the silicone-containing particles of the present invention contain (A) component, (B) component, (C) component, (D) component, (E) component, (F) component and (G) component, and are extruded. Particles that are consolidated by granulation are preferred.

  In the case of extrusion granulation, for example, each component is sufficiently premixed in advance using a known mixer such as a Henschel mixer, a high-speed mixer, or a nauter mixer, and then the resulting mixture is mixed with pelleter double (Fujitsu It can be obtained by extrusion granulation with a known extruder such as Powdal Co., Ltd. or Twin Dome Gran (Fuji Paudal Co., Ltd.). Further, a kneading and extruding apparatus such as Extrude Ohmics (manufactured by Hosokawa Micron Co., Ltd.) can also be used. In this case, the above-mentioned premixing can be omitted.

  The short axis particle diameter of the silicone-containing particles obtained through extrusion granulation is preferably 0.3 to 2.5 mm, more preferably 0.5 to 2.0 mm, still more preferably about 0.7 to 1.0 mm. And can be extruded in the form of a cylindrical or noodle-shaped granulated product.

  The silicone-containing particles obtained as described above may be pulverized or sized by a known method and apparatus. The equipment used when pulverizing or sizing is not particularly limited, and a known pulverizer (or pulverizer) can be used. For example, high-speed mixer (Fukae Kogyo Co., Ltd.), Malmerizer, Fitzmill (Dalton Co., Ltd.), Power Mill (Paurec Co., Ltd.), Comil (Quadro Co.), etc. From the viewpoint of the amount of fine powder generated that affects the properties and productivity, it is preferable to use a pulverizer such as a power mill using a knife cutter or a comil that pulverizes particles by pressing the impeller and screen.

  Examples of the power mill include an apparatus disclosed in Japanese Patent Laid-Open No. 5-96195. This device is a device with a cutter blade and a cylindrical screen. Particles thrown into the power mill inlet fall freely inside the power mill, and are crushed and adjusted by a pulverizing blade disposed on the cutter blade during this natural fall. Be grained.

  Examples of the comil include an apparatus disclosed in US Pat. No. 4,759,507. This device is an instrument having an impeller and a screen, and particles thrown into the comil inlet are pressed against the screen by the centrifugal force generated by the rotating impeller. The small particles are instantaneously and also lifted by the swirl generated due to the conical shape, and the particles that have risen are pulverized and sized by the impeller.

  The degree of pulverization of the obtained silicone-containing particles is determined while evaluating the long axis particle diameter and short axis particle diameter by, for example, an image analysis method as described in JP-A-2003-130785. To do. If the pulverization conditions are determined, silicone-containing particles having a desired shape can be produced with good reproducibility for the same extruded granulated product.

[Powder detergent composition]
The silicone-containing particles of the present invention can be applied to various products for the purpose of treating textile products. Among these, it is preferably blended in a powder detergent composition. The powder detergent composition preferably contains 0.2 to 20% by mass, further 0.5 to 10% by mass, and 1 to 5% by mass of the silicone-containing particles of the present invention. As the components other than the silicone-containing particles of the present invention, those known as components of powder detergent compositions for textile products can be used. Such a powder detergent composition has a total content of the component (E) derived from the silicone-containing particles and other components, 0.001 to 10% by mass, and further 0.001 to 1% by mass. It is preferable that

[1] Preparation of silicone mixture (1-1) Compounding component (A) Dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., “KF96-30,000 cs”, viscosity (25 ° C.) 29200 mPa · s), (C ) A nonionic surfactant (“Emulgen 106” manufactured by Kao Corporation) was used as a component. As the component (B) and other polyether-modified silicones, the following (both manufactured by Toray Dow Corning) were used.
Polyether-modified silicone (I): “L-7001” (viscosity (25 ° C.) 2440 mPa · s, HLB value = 7.8, R in the general formula (B-1) is propylene ((CH ₂ ) ₃ ) , R ′ is a methyl group (CH ₃ ), n / (m + n) = 0.0653, a / b = 0.94)
Polyether-modified silicone (II): “SH-3749” (viscosity (25 ° C.) 1440 mPa · s, HLB value = 7.8, R in the general formula (B-1) is propylene ((CH ₂ ) ₃ ) , R ′ is an acetyl group (CH ₃ CO), n / (m + n) = 0.0765, a / b = 1.04)
Polyether-modified silicone (III): “FZ-2166” (viscosity (25 ° C.) 1180 mPa · s, HLB value = 5.4, a / b = 0.34 in general formula (B-1))
Polyether-modified silicone (IV): “FZ-2130” (viscosity (25 ° C.) 440 mPa · s, HLB value = 6.9, b = 0 in the general formula (B-1))

(1-2) Measurement of viscosity of silicone mixture Silicone mixture [(A) component + (B) component + (C) in the blending ratio of Table 1 (the ratio in Table 1 is the ratio in the final silicone-containing particles)] ) Component] was prepared, and the silicone mixture was heated to 60 ° C. with stirring, and then a B-type viscometer (DVM-B type manufactured by TOKYO KEIKI), rotor No. The viscosity was measured at 4, 60 r / min. In Comparative Examples 3 and 4, since the viscosity was high, measurement was not possible at 60 r / min, so measurement was performed at 30 r / min. The results are shown in Table 1.

(1-3) Evaluation of Stability of Silicone Mixture After the silicone mixture was heated to 60 ° C. with stirring, it was allowed to stand for 24 hours in a thermostatic bath at 60 ° C., and then the state of the liquid was observed. Evaluation was made according to the following criteria. The results are shown in Table 1.
○: Liquid separation is not observed ×: Liquid separation is observed

[2] Preparation and Evaluation of Silicone-Containing Particles (2-1) Preparation of Silicone-Containing Particles According to the ratio shown in Table 1, silicone mixture, dextrin (“Pine Flow KH”, manufactured by Matsutani Chemical Co., Ltd.), silicon dioxide ( "Toceal NR", manufactured by Tokuyama Corporation), calcium silicate ("Fluorite R", manufactured by Tokuyama Corporation), hydrophobized hydroxyethyl cellulose ("Softa SA-ED", manufactured by Kao Corporation), anion A surfactant (“E-10P-HD”, manufactured by Kao Indonesia Chemical Co., Ltd.) was charged into a Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), mixed at a jacket temperature of 75 ° C., and heated. Next, when the temperature of the powder reached 60 ° C., polyethylene glycol (“KPEG6000LA” manufactured by Kao Corp.) previously melted was added and further mixed, and then the mixture was extracted. Next, the obtained mixture was extruded through a screen having a pore diameter of 0.7 mm by an extrusion granulator (“Peletter Double EDX-60 type”, manufactured by Fuji Powder Co., Ltd.) and consolidated. Further, after the extruded granulated product was cooled, it was pulverized by a granulator (pulverized once by a power mill), and passed through a sieve to remove particles having a particle size of 355 μm or less to obtain silicone-containing particles.

(2-2) Measuring Method of Silicone Dissolution from Silicone-Containing Particles Place 1 L of distilled water at 20 ° C. and a stir bar in a 1 L beaker and add about 0.1 g of silicone-containing particles for 7 minutes while stirring with a stirrer. Immediately thereafter, filtration was performed under reduced pressure using filter paper (grade: 5C, manufactured by ADVANTEC). After the filter paper was dried, the filter paper was immersed in chloroform, and ultrasonic waves were applied for 10 minutes to elute the silicone into chloroform. After removing the filter paper, chloroform was removed, and 1 mL of deuterated chloroform containing 0.1% by mass of dinitrobenzene was added as an internal standard to prepare a sample for ¹ H-NMR measurement. ¹ H-NMR measurement was performed using Mercury 400BB (400 MHz) manufactured by Varian under the following conditions, and the silicone was quantified by the area ratio of the peak of the internal standard and the peak of silicone.
NMR measurement conditions: observation width of 649.5 Hz
Data point 42052
Pulse width 4.5μs (45 ° pulse)
Pulse delay time 30 seconds
Measurement temperature Room temperature

The silicone elution rate was measured by the following formula. The results are shown in Table 1.
Silicone elution rate (%) = [1-C / (A × B / 100)] × 100
A: Mass of charged silicone-containing particles (g)
B: Ratio (%) of silicone contained in the silicone-containing particles subjected to the test
C: Mass of silicone remaining on filter paper calculated by NMR measurement (g)

(2-3) Evaluation method of silicone adsorption amount (Preparation of evaluation cloth)
Using a commercially available cotton knitted fabric (100% cotton) with a fully automatic washing machine ("NA-F70AP" manufactured by National), a commercial laundry detergent (attack) at a standard usage amount, water temperature 20 ° C, water volume 40L, bath The treatment was repeatedly washed 5 times with a standard course under the condition of ratio 20, and the treatment agent adhering to the cloth was removed, cut into a size of 30 cm × 40 cm, and used as an evaluation cloth.

(Processing of evaluation cloth)
To 7 L of water at 20 ° C., 5.71 g of the powder detergent composition described in Example 3 of Japanese Patent No. 312757, 0.12 g of silicone-containing particles shown in Table 1, and 0.3 kg of evaluation cloth (8 sheets at 40 cm × 30 cm). Charged and washed for 7 minutes. After dehydration, it was rinsed with 5 L of water for 3 minutes, dehydrated, rinsed for 3 minutes, dehydrated and air-dried.

(Silicone extraction and quantification from treated fabric)
Using ASE manufactured by DIONEX, the solvent was chloroform, and the silicone was extracted under conditions of a temperature of 120 ° C., a pressure of 1500 psi, FLUSH of 20%, and 3 cycles. After extraction, chloroform was evaporated in a hot water bath, and 1 mL of deuterated chloroform containing 0.1% by mass of dinitrobenzene was added as an internal standard to prepare a sample for ¹ H-NMR measurement. ¹ H-NMR measurement was performed under the following conditions using Mercury 400BB (400 MHz) manufactured by Varian, and the amount of adsorption per unit amount of the cloth for evaluation was determined by quantifying silicone by the area ratio of the peak of the internal standard and the peak of silicone. Converted into The results are shown in Table 1.
NMR measurement conditions: observation width of 649.5 Hz
Data point 42052
Pulse width 4.5μs (45 ° pulse)
Pulse delay time 30 seconds
Measurement temperature Room temperature

In addition, 4% by mass of the silicone-containing particles of Reference Examples 1 to 3 and Example 1 was added to the powder detergent composition described in Example 3 of Patent Registration No. 312757, and a fully automatic washing machine (manufactured by Matsushita Electric Industrial Co., Ltd.). , NA-F60E) was washed on a standard course, and showed a better finish than when no silicone-containing particles were added. Among them, the one washed with the silicone-containing particles of Example 1 was the best. It showed finish.

Claims (11)

(A) 0.1 or 10 parts by mass of polyoxyethylene-polyoxypropylene-modified silicone having an HLB value greater than 6 and (C) interface with respect to 100 parts by mass of one or more dimethylpolysiloxanes A silicone comprising a silicone mixture containing 5 to 100 parts by mass of an activator, (D) an oil-absorbing carrier, and (E) a polymer compound having a group represented by the following formula (1) in at least a side chain. Containing particles,
(B) is Ri compound der represented by the following general formula (B-1),
(E) is a polymer compound in which part or all of the hydrogen atoms of the hydroxy group of hydroxyethyl cellulose are substituted with a group represented by the following formula (1).
Silicone-containing particles.
^{_{- (OX) n -E 2 -R}} (1)
(Wherein x is the same or different divalent saturated hydrocarbon group having 1 to 6 carbon atoms, n is a number of 5 to 300, E ² is an ether bond or an oxycarbonyl group, and R is a hydroxyl group. And an optionally substituted alkyl group having 4 to 30 carbon atoms.)

[Wherein, R is an alkylene group having 1 to 10 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms, n / (m + n) is 0.04 or more, a / b is 0.7 to 1.3. ] The silicone-containing particles according to claim 1, further comprising a surfactant different from (F) (C) in addition to the surfactant (C) blended in the silicone mixture. The silicone-containing particles according to claim 1 or 2, further comprising (G) a binder. The silicone-containing particle according to any one of claims 1 to 3, wherein the viscosity (25 ° C) of (A) is 2000 mPa · s or more. The silicone-containing particle according to any one of claims 1 to 4, wherein (C) is a nonionic surfactant. A powder detergent composition containing 0.2 to 20% by mass of the silicone-containing particles according to any one of claims 1 to 5. Containing 0.2 to 20% by mass of the silicone-containing particles according to any one of claims 1 to 5, and (E) containing a polymer compound having a group represented by the following formula (1) in at least a side chain It is a powder detergent composition whose amount is 0.001-10 mass%,
(E) is a polymer compound in which part or all of the hydrogen atoms of the hydroxy group of hydroxyethyl cellulose are substituted with a group represented by the following formula (1).
Powder detergent composition.
^{_{- (OX) n -E 2 -R}} (1)
(Wherein x is the same or different divalent saturated hydrocarbon group having 1 to 6 carbon atoms, n is a number of 5 to 300, E ² is an ether bond or an oxycarbonyl group, and R is a hydroxyl group. And an optionally substituted alkyl group having 4 to 30 carbon atoms.) (A) 0.1 or 10 parts by mass of polyoxyethylene-polyoxypropylene-modified silicone having an HLB value greater than 6 and (C) interface with respect to 100 parts by mass of one or more dimethylpolysiloxanes A liquid mixture obtained by mixing 5 to 100 parts by mass of an activator is mixed with (D) an oil-absorbing carrier and (E) a polymer compound having a group represented by the following formula (1) in at least a side chain. A method for producing silicone-containing particles, comprising:
(B) is Ri compound der represented by the following general formula (B-1),
(E) is a polymer compound in which part or all of the hydrogen atoms of the hydroxy group of hydroxyethyl cellulose are substituted with a group represented by the following formula (1).
A method for producing silicone-containing particles.
^{_{- (OX) n -E 2 -R}} (1)
(Wherein x is the same or different divalent saturated hydrocarbon group having 1 to 6 carbon atoms, n is a number of 5 to 300, E ² is an ether bond or an oxycarbonyl group, and R is a hydroxyl group. And an optionally substituted alkyl group having 4 to 30 carbon atoms.)

[Wherein, R is an alkylene group having 1 to 10 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms, n / (m + n) is 0.04 or more, a / b is 0.7 to 1.3. ] (A) 0.1 or 10 parts by mass of polyoxyethylene-polyoxypropylene-modified silicone having an HLB value greater than 6 and (C) interface with respect to 100 parts by mass of one or more dimethylpolysiloxanes A liquid mixture obtained by mixing 5 to 100 parts by mass of an activator is obtained by (D) an oil-absorbing carrier, (E) a polymer compound having a group represented by the following formula (1) at least in the side chain, and (F ) A method for producing silicone-containing particles, which is mixed with a surfactant different from (C),
(B) is Ri compound der represented by the following general formula (B-1),
(E) is a polymer compound in which part or all of the hydrogen atoms of the hydroxy group of hydroxyethyl cellulose are substituted with a group represented by the following formula (1).
A method for producing silicone-containing particles.
^{_{- (OX) n -E 2 -R}} (1)
(Wherein x is the same or different divalent saturated hydrocarbon group having 1 to 6 carbon atoms, n is a number of 5 to 300, E ² is an ether bond or an oxycarbonyl group, and R is a hydroxyl group. And an optionally substituted alkyl group having 4 to 30 carbon atoms.)

[Wherein, R is an alkylene group having 1 to 10 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms, n / (m + n) is 0.04 or more, a / b is 0.7 to 1.3. ] The method for producing silicone-containing particles according to claim 8, wherein (G) a binder is added to the mixture of the liquid mixture, (D) the oil-absorbing carrier, and (E) the polymer compound, and then extruded and granulated. The silicone-containing particles according to claim 9, wherein (G) a binder is added to the mixture of the liquid mixture and (D) an oil-absorbing carrier, (E) a polymer compound, and (F) a surfactant, followed by extrusion granulation. Manufacturing method.