JPH09286928A - Ultraviolet absorbent composite powder and method for producing the same - Google Patents

Abstract

(57) Abstract: An object of the present invention is to solve the problem of solubility in the oil phase and prevent the deterioration of the ultraviolet protection ability over time. SOLUTION: An ultraviolet absorbent composite powder obtained by uniformly adsorbing and coating an ultraviolet absorbent on a hydrophobic powder, and a method for producing the same.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet absorbing powder obtained by adsorbing and coating an ultraviolet absorbing agent on a hydrophobic powder, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, ultraviolet absorbers have been used in cosmetics, paints, containers and sheets.

There are many conventionally known ultraviolet absorbers, and among them, cinnamic acid-based compounds, benzophenone-based compounds and dibenzoylmethane-based compounds are often used. These compounds have UV protection ability, but some of them have low solubility in solvents and oils, or have problems such as dyeing property to clothes when the concentration is increased. It was limited.

There is also a method of immobilizing on a powder by a chemical bond described in JP-A-6-239732 (immobilized ultraviolet absorber and method for producing the same), but using a large amount of organic solvent, Also, it is not preferable in terms of environmental problems such as removal of unreacted substances in the immobilization reaction, and the operation is complicated.

[0005]

Therefore, the present invention solves the above-mentioned problems of the prior art, that is, the problems of solubility in the oil phase and dyeing property, thereby increasing the compounding amount and enhancing the ultraviolet protection ability. In addition, it is intended to be manufactured by a simple method.

[0006]

The above problems can be solved by developing a powder having an ultraviolet absorbing ability and dispersed in oil.

That is, the ultraviolet absorbent was uniformly coated on the hydrophobic powder surface-modified by the silicone polymer coating by utilizing adsorption / precipitation. As a result, the dispersibility in oil is good, and excellent ultraviolet absorbing ability is exhibited, and the surface activity of the powder is eliminated by coating with a silicone polymer (see Japanese Patent Publication No. 1-54380 relating to the prior application of the inventors). , Specifically described in Japanese Patent Publication No. 1-54381),
It was found that the stability of the coated ultraviolet absorber was improved, and since it was a very simple method, the present invention was completed.

The ultraviolet absorbent composite powder of the present invention and the method for producing the same will be specifically described.

Regarding the type of powder, for example, in the case of inorganic powder, extender pigment powders such as sericite, talc, mica, silica and kaolin, metal oxides such as zinc oxide, titanium oxide and ultramarine, or nylon. Examples include organic powders such as powders, but it goes without saying that the scope of the present invention is not limited to these examples.

The method of hydrophobizing a powder relating to the hydrophobic powder used in the present invention is known per se, and for example, a method of coating with a silicone polymer is disclosed in Japanese Patent Application Laid-Open No. 63-171678 related to the present inventors. Those specifically described in the publication can be mentioned. As the silicone polymer to be coated, for example, a silicone monomer or oricomer which is a precursor of the silicone polymer is adsorbed on the powder and polymerized on the surface thereof to form a uniform silicone polymer coating. As a convenient silicone monomer or oligomer for this coating, the silicone compound of the following formula 1 can be used.

[0011]

Embedded image (R ¹ HSiO) _a (R ² R ³ SiO) _b (R ⁴ R ⁵
R ⁶ SiO _1/2 ) _c (wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or have 1 to 10 carbon atoms which may be substituted with at least one halogen atom). Is a hydrocarbon group of
Provided that R ¹ , R ² and R ³ are not hydrogen atoms at the same time, and R ⁴ , R ⁵ and R ⁶ are each independently hydrogen atom or at least one halogen atom is substituted. Which is a hydrocarbon group having 1 to 10 carbon atoms, a is an integer of 1 or more, and c is 0 or 2, provided that when c is 0, a + b is 3 or more. Be an integer, and the maximum value of a + b + c is 10
000, and this compound contains at least one Si—H moiety).

In the above formula 1, the groups R ^{1 to} R ⁶ may be different from each other in each repeating unit.

As specific compounds of the above general formula, there can be mentioned, for example, compounds represented by the following formulas 2, 3, 4, and 5.

[0014]

Embedded image (Wherein R ⁷ is a lower alkyl group such as a methyl group or an ethyl group or an aryl group such as a phenyl group, and d
= 3 to 7)

[0015]

Embedded image (In the formula, R ⁸ and R ⁹ are a lower alkyl group or an aryl group, R ¹⁰ is an alkyl group or an aryl group, and e
+ F is 3 to 100)

[0016]

Embedded image (In the formula, g is preferably 1 to 500, particularly preferably 2
~ 5)

[0017]

Embedded image (In the formula, h + i is 1 to 500, and h ≧ 2)

It is also possible to use one in which one or more methyl groups in Chemical formulas 4 and 5 are replaced with one or more such as ethyl group, propyl group or phenyl group.

Examples of such compounds include dihydrogen hexamethylcyclotetrasiloxane, trihydrogen pentamethylcyclotetrasiloxane, tetrahydrogen tetramethylcyclotetrasiloxane, dihydrogen octyl cyclopentasiloxane, and tetrahydrogen. Cyclic silicone compounds such as hexamethylcyclopentasiloxane and pentahydrogenpentamethylcyclopentasiloxane and 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,1,1,3,5 , 7, 9, 9, 9
-Nonamethylpentasiloxane and 1,1,1,3
Mention may be made of linear silicone compounds such as 5,7,9,11,11,11-decamethylhexasiloxane. These silicone compounds can form a silicone polymer coating deposited on the solid surface, for example by polymerization on the solid surface as disclosed in the above-mentioned publication.

In the present invention, the contact with the silicone compound and the polymerization are most preferably carried out by a gas phase treatment. However, the silicone compound is dissolved in a solvent to disperse the powder and then dried to obtain a silicone on the surface of the powder. A polymer coating can be formed, or a silicone compound dissolved in a solvent can be directly sprayed and dried by heating to form a silicone polymer coating. That is, a liquid phase treatment can be used, and in the case of the liquid phase treatment, a silicone polymer coating is formed on the surface by drying after the treatment,
Stable powder can be obtained by itself. In the case of gas phase treatment, even a drying step is unnecessary. For example, a suitable mixer (rotary ball mill, vibrating ball mill, planetary ball mill,
Sand mill, attritor, pug mill, poni mixer,
Charge the powder into a planetary mixer, crusher, etc.,
It is carried out by processing into mechanochemicals.

Next, a method for coating the surface of the silicone-coated powder with the ultraviolet absorber will be described. First, an ultraviolet absorber is dissolved in an organic solvent, silicone-coated powder is further added, and the mixture is stirred and well dispersed. After that, the solubility of the ultraviolet absorber is lowered by gradually dropping water, and the ultraviolet absorber is deposited and coated on the surface of the silicone-coated powder.

Further, the coating amount of the ultraviolet absorber coated by the above method can be arbitrarily adjusted by selecting the amount of the silicone-coated powder, the ultraviolet absorber or the dropped water. The treatment temperature is not particularly limited as long as it is not higher than the boiling point of the organic solvent.

Organic solvents used for coating the surface of the silicone-coated powder with the ultraviolet absorber are acetone, ethanol,
Any material may be used as long as it can dissolve an ultraviolet absorber such as toluene. If necessary, two or more kinds of organic solvents may be used in combination.

Next, deposit and deposit on the surface of the silicone-coated powder.
Examples of the ultraviolet absorber to be coated will be given.

The UV absorber used in this treatment is, for example, 4-aminobenzoic acid (hereinafter abbreviated as PABA), PABA butyl ester, PABA glyceryl ester, N, N-diisopropoxy PABA ethyl ester, N, N-. Diethoxy
PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA amyl ester, N, N-
PABA UV absorbers such as dimethyl PABA isooctyl ester, anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranilate, salicylic acid, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate. , Dipropylene glycol salicylate, ethylene glycol salicylate, p-
Salicylic acid-based UV absorbers such as isopropanol phenyl salicylate, octyl cinnamate, ethyl-4-
Isopropyl cinnamate, 4-isopropyl cinnamate, 2,5-diisopropyl cinnamate, 2,4-
Diisopropylcinnamate, p-methoxycinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate Mate,
2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-
Cyano-β-phenylcinnamate, mono-2-ethylhexanoyl-di (-p-methoxycinnamoyl) glycerin, 3,4,5-trimethoxycinnamate, 3,
Cinnamic acid-based UV absorbers such as 4,5-trimethoxycinnamate and 1-methylallyl-3,4,5-trimethoxycinnamate, 2,4-dihydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2- Hydroxy-4′-methoxybenzophenone, 2,2′-dihydroxy-4′-methoxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-2′-methyl-4-methoxybenzophenone, 2-hydroxybenzophenone sulfonate, 4- Phenylbenzophenone,
2-hydroxy-4- (n-octoxy) benzophenone, 2-hydroxy-4′-chlorobenzophenone,
Benzophenone-based UV absorbers such as 2,2′-dihydroxy-4-methoxybenzophenone-3,3-disulfonate, 3-benzylidene-d, l-camphor, urocanic acid, urocaniethyl ester, 4-imidazole acrylic acid [Urocanic acid derivative], 2-phenyl-5
-Methylbenzohexazole, 2-phenylbenzimidazole-5-sulfonic acid, benzylphthalide, anthracene, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-5)
-T-octylphenyl) benzotriazole, benzotriazolyl carbonate, dianisoylmethane, 2-
Hydroxy-4'-hydroxydibenzoylmethane, 2
-Hydroxy-4'-t-butyldibenzoylmethane,
4-methoxy-4′-hydroxydibenzoylmethane,
4-hydroxy-4'-t-butyldibenzoylmethane, 4-methoxy-3'-allyl-4'-t-butyldibenzoylmethane, 2-hydroxy-4'-t-butyldibenzoylmethane, 4-methoxy -4'-t-butyldibenzoylmethane, 3-allyl-4-methoxy-4 '
-T-butyldibenzoylmethane, 2,3-dihydroxy-4'-t-butyldibenzoylmethane, 2,3-dimethoxy-4'-t-butyldibenzoylmethane, 3,
4-dimethoxy-4 ', 5'-di-t-butyldibenzoylmethane, 3,5-di-t-butoxy-4', 5'-di-
Dibenzoylmethane-based UV absorbers such as t-butyldibenzoylmethane and 3,4,5-trimethoxy-4′-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3- Penten-2-on,
Guanine, cinchonidine, veratrol, 4- (3,4
Examples include UV absorbers such as imidazolidine derivatives such as -dimethoxyphenylethylene) -2,5-dioxoimidazolidine-1-propionic acid 2-ethylhexyl ester.

In the present invention, the coating amount of the ultraviolet absorbent is not particularly limited, but is preferably 5 to 40% by weight, more preferably 10 to 20% by weight based on the total amount of the ultraviolet absorbing composite powder of the present invention. If the coating amount is less than 5% by weight, the absorbency may be weakened, and if the coating amount exceeds 40% by weight, the particles may aggregate and become rough.

Thus, the ultraviolet absorbent composite powder of the present invention is obtained. Incidentally, the ultraviolet absorbent composite powder according to the present invention, cosmetics, paints, containers, plastics, paper, fibers,
It can be used for sheets, glass, prisms, lenses and the like.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples.

Preparation Example 1: Silicone of fine particle silica gel
Particle size of 5 in a rotary double-cone type reaction vessel (stainless steel, with heat insulation jacket) with a polymer coating volume of 100 liters.
4 kg of 0 nm silica gel was added. The temperature of the reaction tank and the treatment liquid supply tank (stainless steel, with a heat insulation jacket) directly connected to it with a volume of 10 liters, the heat medium heated to 80 ° C. is supplied to each heat insulation jacket from the heat medium heating tank by a circulation pump. By doing, 80 ℃
Held. Nitrogen gas was supplied to the treatment liquid supply tank at 1.5 liter / min to bubble the treatment liquid.
A condenser was attached to the reaction tank so that nitrogen gas was released from the condenser and unreacted treating agent could be recovered.
The reaction tank is rotated at 10 minute intervals for 1 minute, and the operation of mixing the fine particle silica gel in the reaction tank is repeated for 8 hours.
The treated powder was taken out.

The treated powder obtained showed a marked hydrophobicity.

Preparation Example 2 The particulate silica gel of Preparation Example 1 was changed to particulate titanium dioxide, and the same treatment was carried out to obtain silicone polymer-coated particulate titanium dioxide.

Preparation Example 3 The fine particle silica gel of Preparation Example 1 was changed to 10 kg of sericite and the same treatment was carried out to obtain a silicone polymer-coated sericite.

Preparation Example 4 The particulate silica gel of Preparation Example 1 was changed to 10 kg of talc, and the same treatment was carried out to obtain a silicone polymer-coated talc.

Preparation Example 5 20 g of fine particle titanium dioxide was placed in a planetary ball mill, and 5
After mixing and milling for 1 minute, 1 g of methyl hydrogen polysiloxane (molecular weight 6000) was added and further mixed and milled for 3 hours.

The obtained silicon-coated fine-particle titanium dioxide showed a remarkable hydrophobic property.

Preparation Example 6 Substituting the fine particle titanium dioxide of Preparation Example 5 with sericite,
The same treatment was performed to obtain a silicone polymer-coated sericite.

Preparation Example 7 The particulate titanium dioxide of Preparation Example 5 was changed to silica gel,
The same operation was performed to obtain a silicone polymer-coated silica gel.

Preparation Example 8 The fine particle titanium dioxide of Preparation Example 5 was changed to zinc white, and the same operation was performed to obtain a silicone polymer-coated zinc white.

Example 1-1: Silicone polymer coating
UV absorber coating on particulate silica gel 4-methoxy-4'-t-butyldibenzoylmethane 2
0 g was dissolved in 150 mL of acetone, and 60 g of the silicone polymer-coated fine particle silica gel of Preparation Example 1 and 400 mL of ethanol were placed in a 3 liter beaker and stirred and dispersed. Then 900 with quick stirring
mL of water was slowly added dropwise. After completion of the dropping, filtration and drying were performed to obtain a composite powder coated with 4-methoxy-4′-t-butyldibenzoylmethane.

Example 1-2 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 2, the same treatment as in Example 1-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 1-3 Using the silicone polymer-coated sericite of Preparation Example 3, the same treatment as in Example 1-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 1-4 Using the silicone polymer-coated talc of Preparation Example 4, the same treatment as in Example 1-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 1-5 Using the silicone polymer-coated fine particles of titanium dioxide of Preparation Example 5, the same treatment as in Example 1-1 was carried out to obtain an ultraviolet absorbent composite powder.

Examples 1-6 Using the silicone polymer-coated sericite of Preparation Example 6, the same treatment as in Example 1-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 1-7 Using the silicone polymer-coated silica gel of Preparation Example 7, the same treatment as in Example 1-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 1-8 Using the silicone polymer-coated zinc oxide of Preparation Example 8, the same treatment as in Example 1-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 2-1 Using the silicone polymer-coated silica gel of Preparation Example 1, the same operation as in Example 1-1 was carried out with 3,4,5-trimethoxycinnamate to obtain a composite powder of ultraviolet absorber. Got the body

Example 2-2 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 2, the same operation as in Example 2-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 2-3 Using the silicone polymer-coated sericite of Preparation Example 3, the same operation as in Example 2-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 2-4 Using the silicone polymer-coated talc of Preparation Example 4, the same procedure as in Example 2-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 2-5 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 5, the same operation as in Example 2-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 2-6 Using the silicone polymer-coated sericite of Preparation Example 6, the same operation as in Example 2-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 2-7 Using the silicone polymer-coated silica gel of Preparation Example 7, the same operation as in Example 2-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 2-8 Using the silicone polymer-coated zinc oxide of Preparation Example 8, the same operation as in Example 2-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 3-1 Using the silicone polymer-coated silica gel of Preparation Example 1, the same operation as in Example 1-1 was carried out with 2- (2-hydroxy-5-methylphenyl) benzotriazole,
An ultraviolet absorbent composite powder surface-modified with benzotriazole was obtained.

Example 3-2 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 2, the same operation as in Example 3-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 3-3 Using the silicone polymer-coated sericite of Preparation Example 3, the same operation as in Example 3-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 3-4 Using the silicone polymer-coated talc of Preparation Example 4, the same operation as in Example 3-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 3-5 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 5, the same operation as in Example 3-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 3-6 Using the silicone polymer-coated sericite of Preparation Example 6, the same operation as in Example 3-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 3-7 Using the silicone polymer-coated silica gel of Preparation Example 7, the same operation as in Example 3-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 3-8 Using the silicone polymer-coated zinc white of Preparation Example 8, the same operation as in Example 3-1 was carried out to obtain an ultraviolet absorbent composite powder.

Next, examples of various skin external preparations containing the ultraviolet absorbent composite powder according to the present invention will be described.

No skin irritation or allergenicity was observed in any of the external preparations for skin of each Example, and the safety to the skin was extremely high.

Example 4-1 Using the silicone polymer-coated silica gel of Preparative Example 1, the same procedure as in Example 1-1 was repeated to give 2-hydroxy-4-.
This was performed with methoxybenzophenone to obtain an ultraviolet absorbent composite powder surface-modified with benzophenone.

Example 4-2 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 2, the same operation as in Example 4-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 4-3 Using the silicone polymer-coated sericite of Preparation Example 3, the same operation as in Example 4-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 4-4 Using the silicone polymer-coated talc of Preparation Example 4, the same operation as in Example 4-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 4-5 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 5, the same operation as in Example 4-1 was carried out to obtain an ultraviolet absorbent composite powder.

Examples 4-6 Using the silicone polymer-coated sericite of Preparation Example 6, the same operation as in Example 4-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 4-7 Using the silicone polymer-coated silica gel of Preparation Example 7, the same operation as in Example 4-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 4-8 Using the silicone polymer-coated zinc oxide of Preparation Example 8, the same operation as in Example 4-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 5-1 Using the silicone polymer-coated silica gel of Preparation Example 1, the same procedure as in Example 1-1 was carried out to obtain 4- (3,4-dimethoxyphenylethylene) -2,5-dioxoimidazolidine. This was carried out with -1-propionic acid 2-ethylhexyl ester to obtain an ultraviolet absorbent composite powder.

Example 5-2 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 2, the same operation as in Example 5-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 5-3 Using the silicone polymer-coated sericite of Preparation Example 3, the same operation as in Example 5-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 5-4 Using the silicone polymer-coated talc of Preparation Example 4, the same operation as in Example 5-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 5-5 Using the silicone polymer-coated fine particle titanium dioxide of Preparation Example 5, the same operation as in Example 5-1 was carried out to obtain an ultraviolet absorbent composite powder.

Examples 5-6 Using the silicone polymer-coated sericite of Preparation Example 6, the same operation as in Example 5-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 5-7 Using the silicone polymer-coated silica gel of Preparation Example 7, the same operation as in Example 5-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 5-8 Using the silicone polymer-coated zinc white of Preparation Example 8, the same operation as in Example 5-1 was carried out to obtain an ultraviolet absorbent composite powder.

Example 6: Foundation composition weight% (1) UV absorbent composite powder of Example 2-3 10.0 (2) Titanium dioxide 13.0 (3) Colloidal kaolin 25.0 (4) Talc 34.7 (5) ) Red iron oxide 1.0 (6) Yellow iron oxide 2.5 (7) Black iron oxide 0.1 (8) Liquid paraffin 8.0 (9) Sorbitan sesquioleate 3.5 (10) Glycerin 2.0 (11) Ethylparaben 0.2

(Manufacturing Method) The above components (1) to (7) were mixed and pulverized with a pulverizer to an average particle size of 1 to 5 μm.
This was transferred to a high speed blender, and component (10) was added and mixed. Separately, mix the components (8), (9) and (11),
The homogenized product was added to the above mixture and further homogenized. This was treated with a crusher, passed through a sieve to adjust the particle size, and then compression-molded to obtain a cake-type foundation.

Example 7 Emulsion Foundation Composition Weight% (A) Ion-exchanged water 43.5 Sodium chondroitin sulfate 1 Sodium lactate 0.5 1,3-butylene glycol 3 Methylparaben Appropriate amount (B) Dimethylpolysiloxane (20cs) 16 Decamethyl Cyclopentasiloxane 5 Silicone resin 1 Cetyl isooctanate 1 Polyoxyalkylene modified organopolysiloxane (modification rate 20%) 4 Antioxidant proper amount Fragrance proper amount (C) Yellow iron oxide 1 Red iron oxide 0.45 Black iron oxide 0.2 Example 1 -2 UV absorbent composite powder 11.7 UV absorbent composite powder of Example 1-3 11.65

(Manufacturing method) After the component (B) is dissolved by heating, the powder of the component (C) is added and dispersed. Further, the component (A) previously dissolved and heated was added and emulsified and cooled to room temperature to obtain an emulsified foundation.

[0085] Example 8: Pressed Powder Constitutive Ingredients wt% (1) Example UV absorber composite powder 30 1-6 (2) UV absorption of Example 1-4 agent composite powder 65.8 ( 3) Iron oxide pigment 0.1 (4) Squalane 2.0 (5) 2-Ethylhexyl palmitate 2.0 (6) Perfume 0.1

(Manufacturing method) Components (1), (2) and (3) were mixed with a Henschel mixer, and a mixture of components (4) and (5) with heat was sprayed onto the mixture.
Molded into a medium plate to obtain pressed powder.

Example 9: UV protection stick composition weight% (1) UV absorbent composite powder 20.0 of Example 3-2 (2) UV absorbent composite powder 10.0 of Example 3-4 (3) UV absorbent composite powder 11.0 of Example 3-3 (4) Iron oxide (red, yellow, black) 0.5 (5) Carnauba wax 1.0 (6) Solid paraffin 3.0 (7) Liquid paraffin 45.0 (8) Isopropyl myristate 8.0 (9) Sorbitan sesquioleate 1.5 (10) Perfume

(Production method) Components (7) to (9) are poured into a kettle, heated to 80 to 90 ° C., and components (5) and (6) are added and dissolved. Ingredients (1) to (4) are added to this and uniformly dispersed. After degassing, ingredient (10) is added and gently stirred.
This was poured into a container at 80 ° C. and cooled to room temperature to obtain an ultraviolet protection stick.

[0089] In the formulation of Comparative Example 1 Example 7, similarly to the ultraviolet absorber in Comparative Example 1 except that replacing the ultraviolet absorbent composite powders of Examples 3-2 to untreated titanium dioxide Example 7 An agent composite powder was obtained.

In Example 7, the dispersibility of titanium dioxide was better than that in Comparative Example 1, the finish was good, and the sunscreen effect was high.

Example 10: Lipstick composition % by weight (1) Hydrocarbon wax 3.0 (2) Carnauba wax 1.0 (3) Glyceryl isostearate 40.0 (4) Liquid paraffin 45.8 (5) UV rays of Example 2-2 Absorbent composite powder 4.0 (6) Iron oxide, sericite mixed powder 6.0 (7) Perfume 0.2

(Production Method) Components (1) to (4) were melted at 85 ° C., and components (5) and (6) were added thereto with stirring.
Finally, component (7) was added under stirring. The resulting mixture was placed in a container. The desired lipstick with excellent dispersibility was thus obtained.

Example 11: Composition of sunscreen cream wt% (A) Decamethylcyclopentasiloxane 42.0 Polyethylene glycol 5.0 Dispersant Appropriate amount (B) Cetyl alcohol 5.0 Vaseline 10.0 Dimethylpolysiloxane (10cs / 25 ° C) 15.0 Methyl Phenylpolysiloxane (20cs / 25 ℃) 5.0 Microcrystalline wax 5.0 Glyceryl monostearate 3.0 Polyoxyethylene sorbitan monostearate 3.0 Fragrance Suitable amount Preservative Suitable amount Antioxidant Suitable amount (C) UV absorber composite of Example 4-2 Powder 5.0 Coloring pigment Appropriate amount

(Production method) (A) Phase was heated and dissolved (C)
Add the phases and homogenize with a homomixer. What melt | dissolved the (B) phase by heating was added to it, and it stirred well, and after homogenizing with a homomixer, stirring and cooling obtained the sunscreen cream.

Example 12: Body powder composite component wt% (A) Talc 50.0 UV absorber composite powder of Example 5-4 39.0 Pearling agent 1.0 Coloring pigment Appropriate amount (B) Zinc white 3.0 (C) Stearine Magnesium acid 4.0 Liquid paraffin 1.0 Bactericide Suitable amount (D) Perfume Suitable amount

(Production Method) (A) is mixed with a blender.
(B) is added to this and mixed well, then (C) is added and after the color is adjusted, the fragrance (D) is sprayed and uniformly mixed. This was crushed with a crusher and passed through a sieve to obtain a body powder.

Example 13 20 g of the composite powder of the ultraviolet absorber obtained in Coating Example 3-5 and an acrylic resin solution (Mn 48, 200, Mw / Mn 2.5)
6) 18 g was kneaded with 70 g of glass beads in a paint shaker for 20 minutes to obtain a paint.

It was found that the obtained paint had improved light resistance.

Example 14 Container 2% by weight of the ultraviolet absorbent composite powder obtained in Example 1-3 was mixed in polyethylene to form a white polystyrene wide-mouth bottle by injection molding.

Comparative Example 2 As Comparative Example 2, a white polystyrene wide-mouth bottle was injection-molded without mixing the ultraviolet absorbent composite powder.

Pieces each having a size of 4 cm × 4 cm were cut out from the wide-mouth bottles of Example 14 and Comparative Example 2 and the ultraviolet absorption spectrum (diffuse reflection method) was measured.
The piece obtained in No. 4 had a higher ultraviolet absorption effect.

(Confirmation of coating state of the composite powder of the present invention)
FIG. 1 shows the thermal analysis (DTA curve) of the composite powder of the present invention, a UV absorber and a simple mixture prepared by mixing the powder in a mortar.

As shown in the figure, in the case of the simple mixed product, 8
While the peak of the melting point of the absorbent is observed at around 5 ° C., the composite powder of the present invention does not have the peak like that of the simple mixed product, and it can be seen that the composite powder is uniformly coated in an amorphous state. .

(Evaluation 1 of Ultraviolet Absorbing Ability) In this evaluation, each powder of the composite powder of the present invention and the simple mixed product was added to silicone oil.
% Dispersion, and coated on a quartz plate for 5 μm, and the ultraviolet absorption spectrum was measured. The results are shown in FIG.

As shown in the same figure, it was found that the composite powder of the present invention has remarkably improved ultraviolet absorption ability as compared with the simple mixed product.

(Evaluation 2 of UV Absorption Ability) In the measuring method of this evaluation, a certain amount of the following three kinds of powders were uniformly applied to an adhesive tape, and then the transmission spectrum was measured.

A: The present invention (using the powder described in Examples 1-3 in the present specification) B: 3-allyl-4-methoxy on the silicone-coated powder by the method described in JP-A-6-239732. −
Chemically bound 4'-t-butyldibenzoylmethane C: Mica treated only with silicone (using the powder described in Preparation Example 3 herein) The results are shown in FIG.

As shown in the same figure, the composite powder (A) of the present invention was formed on a silicone-coated powder as disclosed in JP-A-6-239.
UV light compared to those obtained by chemically bonding 3-allyl-4-methoxy-4′-t-butyldibenzoylmethane (B) by the method described in Japanese Patent No. 732, and mica (C) that has been treated only with silicone. It was found that the absorption capacity was remarkably improved.

(Evaluation of UV-A Transmission Amount) Next, the UV-A transmission amount of the following components was evaluated for the present invention and the conventional example.

The present invention A includes 4-methoxy-4'-t.
-Butyldibenzoylmethane was used as a composite powder coated with 10% by weight, and the coating amount was 20%.
The present invention B was defined as the weight percent. As a conventional example,
The 4-methoxy-4′-t-butyldibenzoylmethane was changed to titanium oxide, which was designated as Conventional Example A.

Composition (% by weight) Inventive A Inventive B Conventional Example A Ion-exchanged water 52.65 52.65 52.65 Isostearic acid 1 1 1 1,3-butylene glycol 5 5 5 Methylparaben 0.15 0.15 0.15 Phenoxyethanol 0.2 0.2 0.2 Dimethyl poly Siloxane (20cs) 5 5 5 Decamethylcyclopentasiloxane 25 25 25 Polyoxyalkylene-modified organopolysiloxane (modification rate 20%) 2 2 2 Mica 1 1 1 UV absorbent composite powder of Example 1-1 (4 -Methoxy-4'-t-butyldibenzoyl methane coating amount 10% by weight) 8 --- UV absorbent composite powder of Example 1-1 (of 4-methoxy-4'-t-butyldibenzoyl methane 20% by weight)-8-Titanium oxide--8

(Evaluation Results) UV-A Transmittance (μW / cm ² ) 802 566 1060 As described above, the present invention A and the present invention B are more U than the conventional example A.
It was found that the VA transmission amount was suppressed to a low level and that it showed an excellent ultraviolet absorbing ability.

(Coloring Degree of Various Composite Powders According to Different Coating Methods) The coating state was compared depending on the coloring degree of the absorbent with and without silicone treatment. FIG. 4 shows the results.

UV-A was added to the titanium oxide treated with silicone.
The powder composited with the absorbent (the powder described in Example 1-2 in the present specification is used) (□) is not colored as compared with the composite powdered with untreated titanium oxide (●). It is considered that this is because the UV-A absorber is not decomposed on the surface. The composite of untreated titanium oxide (●) was more yellowish than the color of the UV-A absorber itself (■).

From these results, the silicone-treated (□) was not colored and therefore the absorbent was not decomposed, and the untreated (●) was colored and the absorbent was decomposed. all right.

[0116]

EFFECTS OF THE INVENTION According to the present invention, the solubility in the oil phase can be enhanced, the coating can be performed stably, the usability can be improved, and the solubility in the oil phase can be enhanced. It is possible to provide an ultraviolet absorbing powder having no dyeing property and a simple manufacturing method.

[Brief description of drawings]

FIG. 1 is a graph showing thermal analysis (DTA curve) of powder.

FIG. 2 is a graph showing a UV absorption spectrum of powder.

FIG. 3 is a graph showing a UV absorption spectrum of powder.

FIG. 4 is a diagram showing the degree of coloring of various composite powders depending on the coating method.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 5/32 PPB C09D 5/32 PPB 7/12 PSK 7/12 PSK PSL PSL C09K 3/00 104 C09K 3/00 104Z

Claims (6)

[Claims] 1. An ultraviolet absorbent composite powder, which is obtained by uniformly adsorbing and coating an ultraviolet absorbent on a hydrophobic powder. 2. The ultraviolet absorbent composite powder according to claim 1, wherein the adsorption / coating is precipitation / coating. 3. A cosmetic comprising the ultraviolet absorbent composite powder according to claim 1. 4. A coating material containing the ultraviolet absorbent composite powder according to claim 1. 5. A container containing the ultraviolet absorbent composite powder according to claim 1. 6. An ultraviolet absorbent characterized in that an ultraviolet absorbent is dissolved in an organic solvent, hydrophobic powder is added, water is added, and precipitation and coating are carried out to produce an ultraviolet absorbent composite powder. Method for producing absorbent composite powder.