JP2007314459A - Transparent solid composition and transparent solid cosmetic containing the same as substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent solid composition having transparency making the appearance beautiful even when formulating an ultraviolet light absorbent which is an ingredient which is slightly soluble in a nonpolar oil, having good feelings upon use and excellent in stability with time and to provide a transparent solid cosmetic containing the composition as a substrate. <P>SOLUTION: The transparent solid composition comprises (a) a lysine derivative-modified silicone represented by a specific structural formula, (b) a silicone oil, (c) a polar oil and (d) the ultraviolet light absorbent which is slightly soluble in the nonpolar oil. The transparent solid cosmetic comprises the transparent solid composition as the substrate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a transparent solid composition and a transparent solid cosmetic containing the same as a base, in particular, a transparent solid composition containing an amino acid derivative-modified silicone and a transparent solid cosmetic containing the same as a base.

  Oil-based transparent cosmetics mainly have advantages such as a beautiful appearance and a transparent finish when applied, and therefore various transparent bases have been studied. Furthermore, oily transparent solid cosmetics are required to have a feeling of use that spreads so as to melt on the skin even though it is solid. Therefore, many studies have been made on a base containing 12-hydroxystearic acid or dextrin fatty acid ester as a component for thickening or gelling an oil component.

  Specifically, cosmetics using a transparent base having a refractive index of 1.45 to 1.54 made of 12-hydroxystearic acid and an oil (see, for example, Patent Document 1), 12-hydroxystearic acid and heavy oil A transparent solid cosmetic comprising a liquid paraffin and a liquid oily component (see, for example, Patent Document 2), a transparent solid cosmetic containing 12-hydroxystearic acid, a transparent liquid oily component having a hydroxyl value of 120 or less, and methylphenylpolysiloxane (See, for example, Patent Document 3).

  Moreover, as a transparent cosmetic containing a dextrin fatty acid ester, a transparent solid cosmetic containing a dextrin fatty acid ester, a heavy liquid paraffin, and a liquid oil component (for example, Patent Document 4) See also), dextrin fatty acid ester, volatile oil, oil having a refractive index of 1.4 to 1.6, spherical powder having a refractive index of 1.3 to 1.6 and an average particle size of 3 to 30 μm, There is a transparent solid composition or the like containing (for example, see Patent Document 5).

  However, the type of oily component selected is limited by the compatibility with other active ingredients blended in order to exert an additional effect on the transparent solid cosmetic, and the thickener and the gelling agent described above However, the function may not be fully demonstrated. That is, there is a problem that the oily component to be blended is not sufficiently gelled, resulting in a fluid liquid cosmetic, or a phenomenon in which part of the oily component oozes out over time. More specifically, in a transparent cosmetic compounded with 12-hydroxystearic acid, the spread at the time of application is heavy, the sticky feeling of the oil remains and a refreshing feel is not obtained, and the feeling of use is inferior. The stability of was poor. In addition, in transparent cosmetics formulated with dextrin fatty acid esters, the moldability is not sufficient particularly in the case of sticks, and there is a problem that transparency decreases when a solidifying agent such as wax is added to compensate for this. there were.

On the other hand, in recent years, an oily cosmetic material in which an oily component such as silicone oil is thickened or gelled with an amino acid derivative-modified silicone has been developed as an oily cosmetic material with good growth (see, for example, Patent Document 6).
Japanese Patent No. 2584262 Japanese Patent No. 2791093 JP-A-4-91010 JP-A-9-235210 JP 2005-213145 A JP 2004-182680 A

However, an ingredient having low solubility in non-polar oils, particularly silicone oil, which is generally blended in cosmetics, is intended to be blended into a transparent solid cosmetic thickened or gelled with the amino acid derivative-modified silicone. In this case, it has not been sufficiently studied to realize stable gelation.
The present invention has been made in view of the above-mentioned circumstances, and its purpose is to have a beautiful appearance even when an ultraviolet absorber, which is a component that is hardly soluble in non-polar oils, is blended and has a good feeling of use. Another object is to provide a transparent solid composition having excellent stability over time and a transparent solid cosmetic containing the same as a base.

（式中、Ｒ^１およびＲ^２は互いに同一でも異なっても良く、下記式（IV）で表される基を表し、xは１〜９００の整数を表す。）

（式中、Ｒ^３は炭素数２〜３０のアルキル基を表し、nおよびmは１〜２０の整数を表す。） In order to achieve the above object, as a result of intensive studies by the present inventors, an oily component having a specific composition and a specific lysine derivative-modified silicone in a composition containing an ultraviolet absorber that is hardly soluble in nonpolar oils It has been found that a transparent solid composition having a sunscreen effect and excellent in a sense of transparency, a feeling of use and a stability can be obtained by gelling with a thickening agent, and the present invention has been completed.
That is, the transparent solid composition of the present invention is
(A) a lysine derivative-modified silicone represented by any one of the following general formulas (I) to (III);
(B) silicone oil;
(C) polar oil,
(D) a UV absorber that is sparingly soluble in nonpolar oils;
It is characterized by containing.

(In the formula, R ¹ and R ² may be the same or different, represents a group represented by the following formula (IV), x represents an integer of from 1 to 900.)

(In the formula, R ³ represents an alkyl group having 2 to 30 carbon atoms, and n and m represent an integer of 1 to 20).

The transparent solid composition preferably includes (a) 1 to 20% by mass of a lysine derivative-modified silicone represented by any one of the general formulas (I) to (III).
The transparent solid composition preferably contains 10 to 70% by mass of (b) silicone oil.
The transparent solid composition preferably contains 20 to 50% by mass of (c) polar oil.
Furthermore, it is preferable that the ratio ((b) / (c)) of the blending amount of (b) silicone oil to the blending amount of (c) polar oil component is 0.2 to 2.7.

In the transparent solid composition, (c) the polar oil component is one or more selected from octyl methoxycinnamate, isononyl isononanoate, and tripropylene glycol dineopentanoate.
In the transparent solid composition, (d) an ultraviolet absorber that is hardly soluble in a nonpolar oil component is 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl]- 6- (4-methoxyphenyl) -1,3,5-triazine, 2,4,6-trianilino- (p-carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine, octocrylene , 4-tert-butyl-4′-methoxydibenzoylmethane, or one or more thereof.

The transparent solid composition further includes (e) a spherical powder having a refractive index of 1.3 to 1.6 and an average particle diameter of 3 to 30 μm.
The (e) spherical powder having a refractive index of 1.3 to 1.6 and an average particle diameter of 3 to 30 μm is preferably one or more selected from silicic anhydride, polyurethane and polyethylene. is there.
Moreover, this invention provides the transparent solid cosmetics which contain the said transparent solid composition as a base.

  According to the present invention, an oily component obtained by dissolving an ultraviolet absorber that is hardly soluble in a nonpolar oil in a mixed oil consisting of a polar oil and a silicone oil is thickened and gelled with a specific lysine derivative-modified silicone. Thus, a transparent solid composition having a sunscreen effect, excellent in transparency, feeling in use, and excellent in stability over time, and a transparent solid cosmetic containing the same as a base can be obtained.

（式中、Ｒ^１およびＲ^２は互いに同一でも異なっても良く、下記式（IV）で表される基を表し、xは１〜９００の整数を表す。）

（式中、Ｒ^３は炭素数２〜３０のアルキル基を表し、nおよびmは１〜２０の整数を表す。） Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited thereby.
In the present invention, the transparency of the transparent solid composition is such that the sample 88 is poured into a transparent resin container so as to have a thickness of 5 mm and placed under the container at 25 ° C. Can be evaluated by the transparency measuring method described later.
The “solid composition” means a composition having no fluidity at normal temperature (15 to 25 ° C.) and normal pressure.
Furthermore, the transparent solid cosmetic according to the present invention means a solid cosmetic which contains the transparent solid composition as a base and maintains the above-described transparency even after adding other compounding components.
(A) Lysine derivative-modified silicone The lysine derivative-modified silicone in the present invention is represented by any one of the following general formulas (I) to (III).

(In the formula, R ¹ and R ² may be the same or different, represents a group represented by the following formula (IV), x represents an integer of from 1 to 900.)

(In the formula, R ³ represents an alkyl group having 2 to 30 carbon atoms, and n and m represent an integer of 1 to 20).

本発明において、上記一般式（I）〜（III）で表されるリジン誘導体変性シリコーンの配合量（実分）は、１〜２０質量％、さらには２〜１５質量％であることが好適である。配合量が１質量％未満であると、増粘・ゲル化作用が十分でなく安定な固形組成物が得られない場合がある。また２０質量％を超えると、使用感触が悪いことがあり、かつ製剤処方上好ましくない。 Among the above compounds, particularly preferable compounds are compounds in which x is 50 to 200, n and m are 10, and R ³ is an ethyl group or an isobutyl group in the structures of the general formulas (I) and (II).
Specifically, it is a compound having a structure represented by the following formulas (V) to (VIII).

In the present invention, the blending amount (actual portion) of the lysine derivative-modified silicone represented by the general formulas (I) to (III) is preferably 1 to 20% by mass, and more preferably 2 to 15% by mass. is there. If the blending amount is less than 1% by mass, the thickening / gelling action is not sufficient and a stable solid composition may not be obtained. On the other hand, if it exceeds 20% by mass, the feeling in use may be poor, and it is not preferable in terms of formulation.

(B) Silicone oil Examples of the silicone oil used in the present invention include linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethyl. Various modified polysiloxanes such as cyclopolysiloxanes such as cyclohexasiloxane, silicone resins forming a three-dimensional network structure, silicone rubber, amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and fluorine-modified polysiloxane Etc. One or two or more of these silicone oils may be used in combination.

  In this invention, it is preferable that the compounding quantity of the said silicone oil is 10-70 mass%. More preferably, it is 10-50 mass%. If it is less than 10% by mass, a stable solid composition may not be obtained. In addition, good transparency and usability may not be obtained.

(C) Polar oil component Examples of the polar oil component blended in the transparent solid composition according to the present invention include the following synthetic and natural ester oils.
Specifically, synthetic ester oils include, for example, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl dimethyloctanoate Decyl, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, Neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylol tri-2-ethylhexanoate Ropane, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, tri Glyceryl myristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2 -Octyldodecyl, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, palmitic acid 2-hexyldecyl, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2 , 5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate Octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-pheny Rucinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate.

  Examples of natural ester oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, permanent oil, wheat germ oil, and sasanqua oil. , Castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagari oil, jojoba oil, germ oil, triglycerin, glycerin trioctanoate, triiso Examples include glyceryl palmitate.

In the present invention, among the oils, polar oils having “IOB in the organic conceptual diagram of 0.17 to 0.63” are preferably used.
The organic conceptual diagram was proposed by Satoshi Fujita, and the details are "Pharmaceutical"
Bulletin ", vol.2, 2, pp.163-173 (1954)," Chemistry "vol.11,10, pp.719-725 (1957)," Fragrance Journal ", vol.50, pp.79 -82 (1981), “Organic Conceptual Diagram: Basics and Applications” (by Yoshio Koda, Sankyo Publishing, 1984).
That is, all the organic compounds are regarded as derivatives of methane (CH ₄ ), and certain numbers are set for the carbon number, substituent, transformation part, ring, etc., and the numbers are added to obtain an organic value or an inorganic value. The property value is obtained and plotted on a diagram with the organic value on the X axis and the inorganic value on the Y axis.

The IOB in the organic conceptual diagram means the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, “inorganic value (IV) / organic value (OV)”.
Since the oil component with an IOB of 0.17 to 0.63 in the organic conceptual diagram corresponds to a highly polar oil component, an ultraviolet absorber that is sparingly soluble in the nonpolar oil component blended in the transparent solid composition according to the present invention is dissolved. And is preferably used to provide excellent transparency.

In the present invention, one or more of octyl methoxycinnamate, isonononyl isononanoate, and tripropylene glycol dineopentanoate, among the above-mentioned “polar oils having an IOB in the organic conceptual diagram of 0.17 to 0.63”. Are preferably used in combination.
Moreover, in this invention, it is preferable that the compounding quantity of a polar oil component is 20-50 mass%. If it is less than 20% by mass, a stable solid composition may not be obtained. In addition, good transparency may not be obtained.

(D) Ultraviolet absorbers that are hardly soluble in nonpolar oils Examples of ultraviolet absorbers that are usually used in cosmetics include the following.
(1) Benzoic acid ultraviolet absorbers, for example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester and the like.
(2) Anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate.
(3) Salicylic acid ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, and the like.
(4) Cinnamic acid-based ultraviolet absorbers For example, octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4- Diisopropyl cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxy Ethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl -Diparametoki Sicinnamate etc.
(5) Triazine-based ultraviolet absorber, for example, bisresorcinyl triazine.
More specifically, bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine, 2,4,6-tris { 4- (2-ethylhexyloxycarbonyl) anilino} 1,3,5-triazine and the like.
(6) Other ultraviolet absorbers For example, 3- (4′-methylbenzylidene) -d, l-camphor, 3-d, l-camphor, 2-phenyl-5-methylbenzoxazole, 2,2′- Hydroxy-5-methylphenylbenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenylbenzotriazole), dianisoylmethane , Pyridazine derivatives such as 4-tert-butyl-4′-methoxydibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, dimorpholinopyridazinone.

  Among the ultraviolet absorbers, it is known that (5) triazine-based ultraviolet absorbers and (6) other ultraviolet absorbers have low solubility particularly in nonpolar oils. The term “nonpolar oil” as used herein corresponds to, for example, hydrocarbon oils, animal and vegetable oils and fats, waxes, and silicone oils having an IOB of 0.05 or less in the organic conceptual diagram. In the present invention, an ultraviolet absorber that is hardly soluble in these non-polar oils is dissolved in the oils (b) and (c), and is gelled with a specific (a) lysine derivative-modified silicone. Thus, one of the characteristics is that the ultraviolet absorber component is not precipitated in the solid composition and is excellent in stability.

Furthermore, in the present invention, among the ultraviolet absorbers, 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3 , 5-triazine, 2,4,6-trianilino- (p-carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine, octocrylene (2-ethylhexyl-2-cyano-3,3 -Diphenyl-2-propenoate), 4-tert-butyl-4'-methoxydibenzoylmethane, or one or more thereof.
It is preferable that the compounding quantity of the ultraviolet absorber which is hardly soluble in the (d) nonpolar oil component contained in the transparent solid composition concerning this invention is 0.5-4 mass%. If it is less than 0.5% by mass, the sunscreen effect may not be exhibited effectively, and if it exceeds 4% by mass, the stability of the solid composition may be inferior.

In addition to the above essential components, the present invention preferably further comprises (e) a spherical powder having a refractive index of 1.3 to 1.6 and an average particle size of 3 to 30 μm. When the refractive index is in the above range, the difference in refractive index from the oily component used in the present invention is reduced, whereby high transparency of the base can be realized.
Examples of the spherical powder having a refractive index of 1.3 to 1.6 and an average particle diameter of 3 to 30 μm include polystyrene (about 1.59), PET (about 1.58), nylon (about 1. 53), polyethylene (about 1.51), polyurethane (about 1.50), silicic anhydride (about 1.45 to 1.50), hydrous silicic acid (about 1.40 to 1.50), polytetrafluoroethylene ( Spherical powder having an average particle diameter of 3 to 30 μm, such as about 1.35 to 1.38). Of these, spherical powders of silicic anhydride, polyurethane, and polyethylene are preferably used. The numerical value in the parentheses indicates a refractive index value.

  Moreover, the compounding quantity of the spherical powder whose (e) refractive index is 1.3-1.6 and whose average particle diameter is 3-30 micrometers contained in the transparent solid composition concerning this invention is 0.01-40 mass%. It is preferable that When it exceeds 40 mass%, when it is used as a base for cosmetics, it becomes difficult to spread the coating, and the feeling of use may be inferior.

Next, the transparent solid cosmetic containing the transparent solid composition according to the present invention as a base will be described below.
The transparent solid cosmetic according to the present invention can be obtained by adding an arbitrary component that does not impair the effects of the present invention to the transparent solid composition and preparing it according to a conventional method.
Examples of the optional component include oil, higher alcohol, higher fatty acid, POE / POP dimethyl ether, powder component, surfactant, moisturizer, metal sequestering agent, antioxidant, oil-soluble drug in a blending range that does not impair transparency. Etc.

Examples of the oil other than the silicone oil and polar oil include animal and vegetable oils and fats, waxes, hydrocarbon oils, higher fatty acids, and higher alcohols. You may mix | blend these oils in the range which does not impair the effect of this invention.
Examples of the animal and vegetable oils include cacao butter, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, owl kernel oil, hydrogenated oil, molasses, and hydrogenated castor oil.

Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, Examples include reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, ceresin, and microcrystalline wax.
Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, squalene, petrolatum and the like.

  The higher fatty acid is a fatty acid having an alkyl group having 9 to 30 carbon atoms, and examples thereof include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and melic acid. The alkyl group may be branched and may have a substituent such as an unsaturated bond, a hydroxyl group, a carboxyl group, or a phenyl group. For example, unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, petrothelic acid, elaidic acid, ricinoleic acid, linoelaidic acid, arachidonic acid; branched fatty acids such as isostearic acid; 12-hydroxystearic acid Examples thereof include hydroxycarboxylic acids such as acids.

Examples of the higher alcohol include higher alcohols having an alkyl group having 6 to 20 carbon atoms such as caproyl alcohol, capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and arakinyl alcohol. The alkyl group may be branched, and may have a substituent such as an unsaturated bond, a hydroxyl group, a carboxyl group, or a phenyl group.
Examples of POE / POP dimethyl ether include alkylene oxide derivatives described in JP-A No. 2003-113023.

Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, Aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, Ceramic powder, metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc .; Inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.); Inorganic red pigment (eg, iron oxide) (Bengara), titanium Iron, etc.); inorganic brown pigments (eg, γ-iron oxide, etc.); inorganic yellow pigments (eg, yellow iron oxide, ocher, etc.); inorganic black pigments (eg, black iron oxide, low-order titanium oxide, etc.) Inorganic purple pigments (eg, manganese violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, ultramarine blue, bitumen, etc.); -Pigment pigment (for example, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigment (for example, aluminum powder, copper) Powders); organic pigments such as zirconium, barium or aluminum lakes (for example, red 201, red 202) Organic pigments such as red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow 401, and blue 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3 No. and Blue No. 1); natural pigments (for example, chlorophyll, β-carotene, etc.) and the like.
In the transparent solid cosmetic according to the present invention, the powder component can be blended within a range in which the transparency of the cosmetic is maintained.

Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexyl); glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, monoglycerin monoerucate, glycerin sesquioleate, mono Glyceryl stearate, α, α′-oleic acid pyroglutamic acid glycerin, monostearic acid glycerin malic acid, etc.); propylene glycol fatty acid esters (for example, Nosutearin propylene glycol, etc.); hydrogenated castor oil derivatives; glycerol alkyl ethers, and the like.
Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate); POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerin) Monostearate, POE-glycerol monoisostearate, POE-monooleate such as POE-glycerol triisostearate, etc.); POE-fatty acid esters (for example, POE-distearate, P E-monodiolate, ethylene glycol distearate, etc.); POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-core) POE · POP-alkyl ethers (for example, POE · POP-cetyl ether, POE · POP-2-decyltetradecyl ether, POE · POP-monobutyl ether, POE · POP-hydrogenated lanolin, POE · POP-castor oil etc .; POE-castor oil hydrogenated castor oil derivatives (eg POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate) Allate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid, etc .; POE-honey bean lanolin derivatives (eg, POE-sorbite beeswax etc.); alkanolamide (eg, coconut oil fatty acid diethanolamine) POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; trioleyl phosphoric acid and the like.

Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate , Sodium lactate, bile salt, d, l-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, mellilot extract, trehalose, erythritol, POE POP random copolymer methyl ether and the like can be mentioned.
Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.
Examples of vitamins include vitamin A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

  Other ingredients that can be blended include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.); anti-inflammatory agents (for example, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, thiotaurine, hypotaurine, hinokitiol, zinc oxide, allantoin, etc.) Whitening agent (for example, Yukinosita extract, arbutin, tranexamic acid, L-ascorbic acid, L-ascorbic acid phosphate magnesium salt, L-ascorbic acid glucoside, potassium 4-methoxysalicylate, etc.); various extracts (for example, Owaku, Auren, Shikon, Peonies, Assemblies, Birch, Sage, Loquat, Carrot, Aloe, Zeniaoi, Iris, Grapes, Yokuinin, Loofah, Lily, Saffron, Senkyu, Ginger, Hypericum Ononisu, garlic, pepper, citrus unshiu peel, angelica, seaweed, etc.), activator (e.g., royal jelly, photosensitizer, cholesterol derivatives, etc.); blood circulation promoter, and the like.

The dosage form of the transparent solid cosmetic according to the present invention is gel or solid, and the product form is not particularly limited. For example, makeup cosmetics such as foundations, lipsticks, lip glosses, lip balms and eye shadows, makeup bases, skin care cosmetics, hair cosmetics such as hair sticks and pomades, and the like can be mentioned. It is also used as container filling and stick-shaped transparent solid cosmetics.
Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Unless otherwise specified, the blending amount indicates mass%.

で表されるＳｉ−Ｈ化合物９２．６ｇと１０−ウンデセノイルイソシアネート７．４ｇをトルエン１００ｇに加え、８５℃に加温した後、白金ジビニルテトラメチルジシロキサン錯体トルエン溶液（白金濃度０．３質量％）０．３３ｇを加え、３時間撹拌したートルエンと余剰のイソシアネート化合物を減圧留去した後、新たにトルエン１０００ｇとＮ^ε−ラウロイル−Ｌ−リジンイソブチルエステル１０．５ｇを加え、９０℃で６時間撹拌したートルエンを留去後、得られた透明ゴム状固体をヘキサン１０００ｇに加熱溶解させ、熱ろ過した。ろ液からヘキサンを留去後、固体を得た。
次に得られた固体を細かく砕き、２５℃のヘキサンでよく洗いながら吸引ろ過を行った後、減圧乾燥することで上記式（V）で表される粉末状のリジン誘導体変成シリコーン（Ｎ^ε−ラウロイル−Ｌ−リジンイソブチルエステル誘導体変性シリコーン）２０．３ｇを得た。 [Production Example 1] N ^epsilon - lauroyl -L- lysine isobutyl ester derivative-modified silicone (1) 20.1 g of N ^epsilon - lauroyl -L- lysine in 205ml ethanol - were suspended in Le. After cooling the reaction solution with ice, dry hydrogen chloride gas was introduced until saturation, and the mixture was stirred for 6 hours.
Next, ethanol was distilled off, 250 ml of diisobutyl ether was added, and after suction filtration, 300 ml of purified water was added. To this solution, 55 g of morpholine dissolved in 70 ml of purified water was slowly added with stirring, and the precipitated white powder was filtered off. The obtained white powder was recrystallized from n-hexane to obtain 20.1 g of N ^ε -lauroyl-L-lysine isobutyl ester.
(2) 150 g of purified water was added to 45.5 g of sodium azide, and the mixture was stirred to obtain a completely homogeneous solution while cooling in ice water. A solution obtained by mixing 101.4 g of 10-undecenoyl chloride and 150 ml of acetone was added dropwise little by little so that the temperature of the solution was in the range of 10 to 15 ° C. After completion of the addition, the mixture was stirred at around 12 ° C for 1 hour.
The solution was then transferred to a separatory funnel and the aqueous and organic layers were separated. The organic layer was slowly added to 500 ml of toluene maintained at 60 ° C., and stirred for 3 hours at a temperature in the range of 50 to 60 ° C. After distilling off the toluene and distilling under reduced pressure, 73.2 g of 10-undecenoyl isocyanate Got.
(3) The following formula

After adding 92.6 g of the Si—H compound represented by the following formula and 7.4 g of 10-undecenoyl isocyanate to 100 g of toluene and heating to 85 ° C., a platinum divinyltetramethyldisiloxane complex toluene solution (platinum concentration of 0.3 (Mass%) 0.33 g was added and stirred for 3 hours--toluene and excess isocyanate compound were distilled off under reduced pressure, and then 1000 g of toluene and 10.5 g of N ^ε -lauroyl-L-lysine isobutyl ester were newly added at 90 ° C. Stir for 6 hours--Toluene was distilled off, and the resulting transparent rubber-like solid was heated and dissolved in 1000 g of hexane and filtered hot. After removing hexane from the filtrate, a solid was obtained.
Next, the obtained solid is finely pulverized, suction filtered while thoroughly washing with hexane at 25 ° C., and then dried under reduced pressure, whereby powdered lysine derivative-modified silicone (N ^ε −) represented by the above formula (V) is obtained. 20.3 g of lauroyl-L-lysine isobutyl ester derivative-modified silicone) was obtained.

Subsequently, the present inventors synthesized various lysine derivative-modified silicones according to the above synthesis examples, and evaluated transparent solid compositions containing the lysine derivative-modified silicones. The compounding composition and evaluation result of the transparent solid composition of each test example are shown below.
In the following examples and test examples, as the component (b), methylphenylpolysiloxane is silicone KF56 (manufactured by Shin-Etsu Chemical Co., Ltd., refractive index: 1.405 to 1.595, viscosity: 10 to 20 mm ² / As for s), silicone KF96A-6T (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the dimethylpolysiloxane. As component (c), octyl methoxycinnamate is Parsole MCX (DSM Nutrition Japan Co., Ltd.), Octocrylene is Parsole 340 (DSM Nutrition Japan Co., Ltd.), and bis (resorcinyl) triazine is Chinosorb S (Ciba Specialty Chemicals). 4-tert-butyl-4′-methoxydibenzoylmethane was Parsol 1789 (Roche Vitamin Japan Co., Ltd.).

The evaluation criteria are as follows.
(1): “Transparency”
The sample was poured into a transparent resin container so as to have a thickness of 5 mm, and the visibility of the font 88 Times New Roman characters placed under the container at 25 ° C. was evaluated by a professional panel.
5: The characters look very clear and the sharpness is very high.
4: Characters are clearly visible and sharpness is high.
3: Characters are visible, but sharpness is slightly inferior.
2: The characters are barely visible, but the sharpness is inferior.
1: The character cannot be read and is opaque.

(2): “Usability”
Sensory evaluation was conducted by 20 specialist panels on the lightness of each sample and the non-stickiness after application. Very good (5 points), good (4 points), normal (3 points), a little bad (2 points), bad (1 point), evaluated in five stages, rounded off the average score of 20 people Asked.

(3): “Stability”
After filling each sample, it was allowed to stand at room temperature (25 ° C.) for 1 month, and the appearance state was evaluated every week.
○: No change in appearance and excellent stability.
(Triangle | delta): Some changes, such as oil floating, are seen.
×: Not acceptable due to drastic changes such as oil floating.

<Types of lysine derivative-modified silicone>
In order to examine the suitability of lysine derivative-modified silicones, the following various lysine derivative-modified silicones were synthesized in accordance with Production Example 1 described above, and blended into a transparent solid composition for evaluation. The results are shown in Table 1 below.
Structure of synthetic lysine derivative-modified silicone

（製法）室温にて成分（１）〜（１３）を９５℃にて加熱混合して分散させ、脱気して室温にて固化させた。

(Production Method) Components (1) to (13) were dispersed by heating and mixing at 95 ° C. at room temperature, deaerated and solidified at room temperature.

As is apparent from the results in Table 1 above, in Test Examples 5 and 6 in which dextrin palmitate, which is one of 12-hydroxystearic acid or dextrin fatty acid ester, is used as a thickening or gelling agent, high transparency is obtained. The oil floats over time and is inferior in stability. Also, the feeling of use such as stretch and stickiness is not satisfactory.
On the other hand, a transparent solid composition having excellent transparency and stability was obtained in Test Examples 1 to 4 in which various lysine derivative-modified silicones were blended. Moreover, these transparent solid compositions have a sunscreen effect on both UVB and UVA by containing, as an ultraviolet absorber, a component (10) that is sparingly soluble in nonpolar oils that have a UVA absorbing effect. It is. Moreover, the feeling of use was also very excellent.

（製法）室温にて成分（１）〜（７）を９５℃にて加熱混合して分散させ、脱気して室温にて固化させた。 <Amount of lysine derivative-modified silicone>
Then, the compounding quantity of the lysine derivative modified silicone mix | blended with the transparent solid composition concerning this invention was examined. The results are shown in Table 2 below.

(Production Method) Components (1) to (7) were heated and mixed at 95 ° C. to disperse at room temperature, deaerated and solidified at room temperature.

As is clear from the results of Table 2 above, it is clear that the transparent solid composition has excellent transparency and stability when the blending amount of the lysine derivative-modified silicone of component (a) is 1 to 20% by mass. It is.
In Test Example 7 in which the blending amount of the lysine derivative-modified silicone is less than 1% by mass, thickening or gelation is not sufficiently achieved, and a stable solid composition cannot be obtained, and when it exceeds 20% by mass, There was a tendency for the feeling of use to decrease.

（製法）室温にて成分（１）〜（９）を９５℃にて加熱混合して分散させ、脱気して室温にて固化させた。 <Amount of silicone oil>
Then, the compounding quantity of the silicone oil mix | blended with the transparent solid composition concerning this invention was examined. The results are shown in Table 3 below.

(Production Method) Components (1) to (9) were heated and mixed at 95 ° C. to disperse at room temperature, degassed and solidified at room temperature.

As is clear from Table 3 above, when the blending amount of the silicone oil is 10% by mass or more, and the ratio of the blending amount of the silicone oil to the blending amount of the polar oil is in the range of 0.2 to 2.7. Excellent transparency and stability can be obtained (Test Example 12). When the blending amount of the silicone oil exceeds 50% by mass, the blending ratio of other oily components, particularly polar oils, decreases, and the UV absorber that is hardly soluble in nonpolar oils is not sufficiently dissolved in the composition. , Transparency tends to decrease.
Further, in Test Example 14 in which part of the silicone oil blended in Test Example 13 was changed to a hydrocarbon oil and blended with a polar oil, transparency and stability could be maintained well. However, when all of the silicone oil was changed to hydrocarbon oil (Test Example 15), the stability was extremely deteriorated, and transparency and usability were inferior.
From the above results, in the transparent solid composition according to the present invention, the blending of the silicone oil is a necessary component for the stability of the composition, and the suitable blending amount is 10 to 70% by mass. Is clear.

（製法）室温にて成分（１）〜（７）を９５℃にて加熱混合して分散させ、脱気して室温にて固化させた。 <Polar oil content>
The amount of polar oil blended in the transparent solid composition according to the present invention was examined. The results are shown in Table 4 below.

(Production Method) Components (1) to (7) were heated and mixed at 95 ° C. to disperse at room temperature, deaerated and solidified at room temperature.

As apparent from Table 4 above, when the blending amount of isononyl isononanoate (IOB: 0.2) and octyl methoxycinnamate (IOB: 0.28), which are polar oils, is 20% by mass or more, transparency and stability are improved. It becomes the solid composition which was excellent also in the property. When it exceeds 50% by mass, the stability is lowered, and the evaluation tends to be slightly lowered in terms of the feeling of use (Test Example 20 and Test Example 12 in Table 3 above).
Therefore, it is clear that a suitable blending amount of the polar oil blended in the transparent solid composition according to the present invention is 20 to 50% by mass.

Moreover, from the examination result of the suitable compounding quantity of the said silicone oil, and the suitable compounding quantity of a polar oil, the ratio (the compounding quantity of a silicone oil / the compounding quantity of a polar oil) of silicone oil with respect to polar oil is 0.2-2. 7 shows that the composition is excellent in all of transparency, stability and feeling of use.
When the ratio of the silicone oil to the polar oil is about 0.2 to 2.7 in the total amount of the silicone oil and the polar oil as the main components of the transparent solid composition according to the present invention, it is hardly soluble in the nonpolar oil. The solubility of a certain ultraviolet absorber becomes good, gives an excellent transparency to the solid composition, and has excellent stability when the oily component is thickened and gelled.
In addition, the light feel of silicone oil is added to improve the stickiness and spread.

（製法）室温にて成分（１）〜（１２）を９５℃にて加熱混合して分散させ、脱気して室温にて固化させた。 <Types of spherical powder>
Next, the amount of polar oil blended in the transparent solid composition according to the present invention was examined. The results are shown in Table 5 below.

(Manufacturing method) Components (1) to (12) were dispersed by heating and mixing at 95 ° C at room temperature, deaerated and solidified at room temperature.

From Table 4 above, silicone-treated spherical silicic anhydride powder (refractive index: 1.45 to 1.50), spherical silicic anhydride, which is a spherical powder having a refractive index of 1.3 to 1.6 and an average particle size of 3 to 30 μm. In Test Examples 21 to 23 in which powder (1.45 to 1.50) and urethane powder (about 1.50) were blended, a transparent solid composition having excellent transparency and stability was obtained. This transparent solid composition was found to have a sunscreen effect by containing an ultraviolet absorber. Moreover, the feeling of use was also extremely excellent.
In the powder dispersion system, the transparency is improved when the refractive index of the external phase and the powder agree to some extent. Accordingly, when a powder having a refractive index considerably higher than that of the external phase, kaolin (about 1.62), titanium oxide (2.3 to 2.55) (Test Examples 23 and 25) is dispersed, the transparency is poor. Is.

EXAMPLES Hereinafter, although the Example of the transparent solid cosmetics which contain the transparent solid composition concerning this invention as a base is given and this invention is demonstrated further in detail, this invention is not limited to these.
Example 3-1: Sunscreen cosmetic (1) Lysine derivative-modified silicone (VI) 10.0% by mass
(2) Decamethylcyclopentasiloxane 28.1
(3) Methylphenylpolysiloxane 20.0
(4) Isononyl isononanoate 20.0
(5) Stearyl alcohol 4.0
(6) Octyl methoxycinnamate 7.5
(7) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy}
-Phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine 2.2
(8) Spherical anhydrous silicic acid powder (average particle size: 4-6 μm) 10.0
(9) EDTA · 3Na · 2H ₂ O 0.3
(10) Citric acid 0.1
(Manufacturing method) Components (1) to (10) were dispersed by heating and mixing at 95 ° C at room temperature, deaerated and solidified at room temperature.
The obtained transparent solid cosmetic is excellent in the appearance transparency, has a good feeling of use, and has a sunscreen effect.

Example 3-2: Sunscreen cosmetics (1) Lysine derivative-modified silicone (VI) 10.0% by mass
(2) Decamethylcyclopentasiloxane 25.2
(3) Methylphenylpolysiloxane 5.0
(4) Dimethylpolysiloxane (6 mPa · s) 15.0
(5) Isononyl isononanoate 20.0
(6) Cetyl isooctanoate 2.0
(7) Isostearic acid 4.0
(8) Octyl methoxycinnamate 7.5
(9) Octocrelin 1.0
(10) Silicone-treated spherical anhydrous silicic acid powder (average particle size: 4 to 6 μm) 10.0
(11) EDTA · 3Na · 2H ₂ O 0.3
(Production Method) Components (1) to (11) were dispersed by heating and mixing at 95 ° C. at room temperature, deaerated and solidified at room temperature.
The obtained transparent solid cosmetic is excellent in the appearance transparency, has a good feeling of use, and has a sunscreen effect.

Example 3-3: Makeup base (1) Lysine derivative-modified silicone (VI) 8.0% by mass
(2) Decamethylcyclopentasiloxane 20.9
(3) Methylphenylpolysiloxane 10.0
(4) Dimethylpolysiloxane (6 mPa · s) 10.0
(5) Isononyl isononanoate 5.0
(6) Dineeopentanoic acid tripropylene glycol 5.0
(7) Olive oil 2.0
(8) Squalane 1.0
(9) Isostearic acid 4.0
(10) Octyl methoxycinnamate 3.0
(11) 4-tert-butyl-4′-methoxydibenzoylmethane 0.7
(12) Hydrophobized spherical silica powder (average particle size: 4 to 6 μm) 30.0
(13) EDTA · 3Na · 2H ₂ O 0.3
(14) Citric acid 0.1
(Manufacturing method) Components (1) to (14) were dispersed by heating and mixing at 95 ° C at room temperature, deaerated and solidified at room temperature.
The obtained transparent solid cosmetic is excellent in the appearance transparency, has a good feeling of use, and has a sunscreen effect.

Claims (10)

(A) a lysine derivative-modified silicone represented by any one of the following general formulas (I) to (III);
(B) silicone oil;
(C) polar oil,
(D) a UV absorber that is sparingly soluble in nonpolar oils;
A transparent solid composition comprising:

(In the formula, R ¹ and R ² may be the same or different, represents a group represented by the following formula (IV), x represents an integer of from 1 to 900.)

(In the formula, R ³ represents an alkyl group having 2 to 30 carbon atoms, and n and m represent an integer of 1 to 20).   The transparent solid composition according to claim 1, wherein the transparent solid composition comprises (a) 1 to 20% by mass of a lysine derivative-modified silicone represented by any one of the general formulas (I) to (III). Composition.   The transparent solid composition according to claim 1 or 2, wherein 10 to 70% by mass of (b) silicone oil is contained.   The transparent solid composition according to any one of claims 1 to 3, further comprising (c) 20 to 50% by mass of a polar oil.   The transparent solid composition according to any one of claims 1 to 4, wherein a ratio ((b) / (c)) of (b) silicone oil to (c) polar oil is 0.2 to A transparent solid composition characterized by being 2.7.   The transparent solid composition according to any one of claims 1 to 5, wherein (c) the polar oil is one or more selected from octyl methoxycinnamate, isononyl isononanoate, and tripropylene glycol dineopentanoate. A transparent solid composition characterized by that.   The transparent solid composition according to any one of claims 1 to 6, wherein (d) an ultraviolet absorber that is hardly soluble in a nonpolar oil component is 2,4-bis-[{4- (2-ethylhexyloxy). ) -2-Hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4,6-trianilino- (p-carbo-2′-ethylhexyl-1′-oxy) A transparent solid composition, which is one or more selected from -1,3,5-triazine, octocrylene, and 4-tert-butyl-4′-methoxydibenzoylmethane.   The transparent solid composition according to any one of claims 1 to 7, further comprising (e) a spherical powder having a refractive index of 1.3 to 1.6 and an average particle size of 3 to 30 µm. A transparent solid composition.   The transparent solid composition according to any one of claims 1 to 8, wherein (e) a spherical powder having a refractive index of 1.3 to 1.6 and an average particle size of 3 to 30 µm is silicic anhydride, polyurethane, polyethylene. The transparent solid composition characterized by being 1 type, or 2 or more types selected from. A transparent solid cosmetic comprising the transparent solid composition according to claim 1 as a base.