JP4657324B2 - Water-containing composition - Google Patents

Description

  The present invention relates to a water-containing composition that can be used as cosmetics, external preparations for skin, and the like.

  Many of the UV absorbers that are difficult to dissolve in water (poorly water-soluble UV absorbers) are useful in the field of external use for skin, such as cosmetics and skin external preparations, and these UV absorbers can be stably incorporated into external compositions. Various techniques for inclusion are provided. As a representative technique, an emulsification technique or a solubilization technique can be given. And in terms of a technique that can distribute the ultraviolet absorbent to the skin with a refreshing feel, a solubilization technique and an underwater dispersion technique can be exemplified. In particular, the solubilization technique is an indispensable technique when the ultraviolet absorber is used in the form of a lotion or the like, and in general, as a solubilizer for the ultraviolet absorber, polyoxyethylene alkyl ether or polyoxyethylene curing Surfactants such as castor oil are used. However, when a UV absorber that has a large molecular weight and is hardly soluble in water having a bulky structure is used, these surfactants can solubilize a sufficient amount of the water-insoluble UV absorber. It was very difficult.

In the following Patent Document 1, use of ethoxylated phytosterol and phytostanol is reported as a means for dissolving a poorly water-soluble pharmaceutical agent. However, this preparation realizes an aqueous solution of a pharmaceutical agent for the purpose of preventing cell damage in living cells, and there is no description about the description and use of the ultraviolet absorber.
JP 2005-511586 A

  An object of the present invention is to provide a water-containing composition in which a poorly water-soluble UV absorber is solubilized or dispersed in water.

  In order to solve the above-mentioned problems, the present inventor has studied a surface-active substance capable of dissolving a poorly water-soluble UV absorber in water, and added phytosterol or phytostanol added with polyoxyethylene to an aqueous system. In particular, the present inventors have found that the ultraviolet absorbent can be dissolved by coexisting with a poorly water-soluble ultraviolet absorbent, and the present invention has been completed.

That is, the present invention
(1) Polyoxyethylene addition compound represented by the following formula (I) HO (CH ₂ CH ₂ O) _n -R (I)
[In formula, R shows a phytosterol residue or a phytostanol residue, and n shows the number of 5-100. ]
(2) bisethylhexyloxyphenol methoxyphenyl triazine and / or 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine , and
(3) contains water,
And (2) (1) polyoxy to bisethylhexyloxyphenol methoxyphenyl triazine and / or 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine The blending ratio of the ethylene addition compound is 1 or more by mass, the triazine-based UV absorber is solubilized or dispersed in water, and the L value is 70 or more when the transparency of distilled water is 100. The invention provides a transparent or translucent water-containing composition (hereinafter also referred to as the water-containing composition of the present invention).

  Compound (I) has the following formula:

  Can also be expressed. The group on the right side of the polyoxyethylene chain portion of this chemical formula is a phytosterol residue or a phytostanol residue that R can take.

  In the present invention, the “water-containing composition” means a composition containing water. In addition, the “dissolved state” referred to in the present specification means that the UV absorber is “transparent or translucent state” in the system when the visual observation is performed without the influence of other components. It means a state that is recognized to exist evenly. Examples of the “transparent or translucent state” include, for example, a “solubilized state” in which a poorly water-soluble UV absorber is thermodynamically stable, or the UV absorber is dispersed as fine particles in an aqueous phase. “Dispersed in water” can be mentioned.

  The water-containing composition of the present invention can typically be used as an external composition applicable to the skin or a base thereof. Specific product forms of the composition for external use include cosmetics and skin external preparations. Both cosmetics and external preparations for skin are forms that can be applied to the skin, and they are overlapping concepts. In particular, being a cosmetic means that it is also an external preparation for skin. . When it is a skin external preparation and not a cosmetic, the purpose of the skin external preparation is not “makeup” whose primary purpose is beauty, but its primary purpose is health, that is, “quasi-drug” Or the case of “medicine”.

  The present invention provides a water-containing composition in which a poorly water-soluble UV absorber is solubilized or dispersed in water.

[Formulation of polyoxyethylene addition compound (compound (I))]
In the water-containing composition of the present invention, as described above, compound (I) is blended together with water and a water-insoluble ultraviolet absorber. As will be described later, the compound (I) can be blended into the water-containing composition of the present invention as only one compound within the range of the above formula (I), and is a mixture of two or more different compounds. There may be.

  In compound (I), phytosterol, which is a parent compound of a phytosterol residue that R can take, is a plant-derived sterol (FDGunstone and BGHerslof, A Lipid Glossary, The Oily Press, Air, 1992), in particular. There is no limitation. That is, phytosterol residues that R can take include sitosterol residues, campesterol residues, stigmasterol residues, brassicasterol residues, avenasterol residues, ergosterol residues, and the like. Can be mentioned. In addition, as described above, the compound (I) to be blended in the water-containing composition of the present invention can be a mixture of two or more compounds having different phytosterol residues.

  Similarly, phytostanol, which is a parent compound of a phytostanol residue that R can take, is a hydrogenated or saturated counterpart of phytosterol, and is not particularly limited. That is, examples of the phytostanol residue that R can take include sitostanol, campestanol, stigmasteranol, brassicastanol, avenastanol, ergostanol, and the like. Moreover, the compound (I) mix | blended in the water-containing composition of this invention can also be a mixture of 2 or more types of compounds which are phytostanol residues from which R differs as mentioned above.

  Further, the compound (I) is a water-containing composition of the present invention as a mixture of a compound in which R has one or more phytosterol residues and a compound having one or more phytostanol residues. It is also possible to blend in.

  Moreover, n which shows the number of the polyoxyethylene chains in a compound (I) is 5-100, Preferably it is 5-50.

  Compound (I) can be produced by a conventional method based on its chemical structure. For example, by adding ethylene oxide to phytosterol and removing the unreacted material, neutralization, dehydration, deodorization and filtration can be performed to easily produce compound (I).

  The compounding quantity of compound (I) in the water-containing composition of this invention is 10 mass% or less with respect to a composition, Preferably it is 3 mass% or less. Further, the compounding amount of the compound (I) largely depends on the relative relationship with the compounding amount of the poorly water-soluble UV absorber. The upper limit of the abundance ratio of the compound (I) to the poorly water-soluble UV absorber is preferably 1 or more in terms of mass ratio, with the upper limit of the compounding amount of the compound (I) as a limit index. Is particularly preferred. The suitable value of the minimum of the compounding quantity of compound (I) can also be prescribed | regulated by this compounding ratio. In addition, compound (I) is an essential compounding component of the water-containing composition of the present invention, and this compounding amount does not become 0% by mass.

[Formation of water-insoluble UV absorber]
In the water-containing composition of the present invention, it is necessary to blend one or two or more poorly water-soluble UV absorbers and solubilize or disperse them in water. The solubility in a solvent other than water in the poorly water-soluble UV absorber is not particularly limited. In addition, the blending of this poorly water-soluble UV absorber does not interfere with the selective blending of the water-soluble UV absorber.

  Examples of poorly water-soluble UV absorbers include triazine UV absorbers (typically bisresorcinyl triazine, more specifically bisethylhexyloxyphenol methoxyphenyl triazine (also known as 2,4-bis { [4- (2-Ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine, commercially available Tinosorb S, Ciba Specialty Chemicals) Octyltriazone (alias: 2,4,6-tris {4- (2-ethylhexyloxycarbonyl) anilino} 1,3,5-triazine or 2,4,6-trianilino-p- (carbo-2) '-Ethylhexyl-1'-oxy) -1,3,5-triazine, commercially available products Ubinal T150 (UVINUL T150), B SF), 2- [2-hydroxy-4- (2-ethylhexyl) phenoxy] -2H-benzotriazole, etc .; benzoic acid-based 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; anthranilic acid ultraviolet absorber (for example, homomenthyl-N -Acetyl anthranilate, etc.); salicylic acid-based ultraviolet absorbers (for example, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate) Cinnamic acid-based ultraviolet absorbers (for example, octyl cinnamate, ethyl-4-isopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-) Methoxycinnamate, isopropyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, etc.); benzophenone UV absorbers (eg, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy -4,4'-dimethoxybe Zophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4 ′ -Phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3- (4′-methylbenzylidene) -d, l-camphor, 3 -Benzylidene-d, l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) Benzotriazole; 2- (2′-hydroxy-5′- Dibenzalazine; dianisoylmethane; 4-methoxy-4′-tert-butyldibenzoylmethane; 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one; phenyl acrylate system UV absorber (for example, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate (also known as: Octocrylene), 2-ethyl-2-cyano-3,3-diphenyl acrylate, etc.); dibenzoylmethane UV absorber (For example, 4-tert-butyl-4′-methoxydibenzoylmethane); camphor derivatives (for example, 4-methylbenzylidene camphor, terephthalylidene dicamphor sulfonic acid, etc.); phenylbenzotriazole derivatives (for example, hydroxy- (ethylhexyl) ) Phenoxybenzotriazole, methylenebis-benzotriazolyltetramethylbutylphenol, etc.); benzalmalonate derivatives (for example, dimethicobenzalmalonate, etc.).

  Among the poorly water-soluble UV absorbers, it is preferable to have two or more 6-membered rings in the chemical structure. Examples of the UV absorber under the above conditions include bisethylhexyloxyphenol methoxyphenyl triazine, 2,4,6- And triazine derivatives such as tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine, 2- [2-hydroxy-4- (2-ethylhexyl) phenoxy] -2H-benzotriazole. Of these, bisethylhexyloxyphenol methoxyphenyltriazine is preferred.

  Moreover, the ultraviolet absorber which has absorption in a UVA area | region has the tendency for the stabilization effect of a water-soluble pigment | dye or a water-soluble chemical | medical agent to be excellent. Examples of such a poorly water-soluble UV absorber include bisethylhexyloxyphenol methoxyphenyltriazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine, 2 -[2-hydroxy-4- (2-ethylhexyl) phenoxy] -2H-benzotriazole, 4-tert-butyl-4'-methoxydibenzoylmethane, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid An acid hexyl ester etc. can be mentioned.

  The blending amount of the poorly water-soluble ultraviolet absorber in the water-containing composition of the present invention is as long as the poorly water-soluble ultraviolet absorber in the composition can maintain the state of being solubilized or dispersed in water at room temperature. There is no particular limitation. The relationship between the amount of the poorly water-soluble UV absorber and the amount of compound (I) is as described above. It is also possible to determine the specific blending amount in consideration of the properties of each ultraviolet absorber within the limits of the blending amount relationship.

[Formulation of water]
The water in the water-containing composition of the present invention is usually ion-exchanged water, purified water, or tap water. Total amount of compound (I) and poorly water-soluble UV absorber in the whole composition, or compound (I), poorly water-soluble UV absorber and general ingredients in the whole composition The remaining amount with respect to can be contained.

[Specific Embodiments of the Present Invention]
In the water-containing composition of the present invention, due to the presence of the compound (I), the inherently poorly soluble ultraviolet absorber is easily solubilized or dispersed in water. Preferably, for example, a part in which a poorly water-soluble UV absorber is dissolved or dispersed in Compound (I) is prepared, and this is mixed with an aqueous phase containing a water-soluble drug or water-soluble dye to be stabilized. The water-containing composition of the present invention can be produced by solubilizing or dispersing.

  The water-containing composition of the present invention containing only the above essential components can be used as an external composition used as a cosmetic or a skin external preparation. In the composition for external use, properties such as a medicinal effect and an ultraviolet ray shielding action of the poorly soluble ultraviolet absorbent solubilized or dispersed in water can be utilized for the outer skin.

  Moreover, the water-containing composition of the present invention containing only these essential components can be used as a base for an external composition containing other general components. That is, first, the water-containing composition of the present invention can be produced, and secondly, general components can be blended to produce an external composition of the final target aspect.

  Common ingredients here include excipients, buffers, salts, antioxidants, for the addition of medicinal properties, coloring, adjustment of manufacturing parameters, adjustment of ionic strength, adjustment of pH, stability of the formulation, etc. Preservatives, fragrances, surfactants, water-soluble vitamins and the like can be mentioned. As a general component, a water-soluble substance is usually used, but an ultraviolet absorber may be acceptable depending on the final product form. For example, a liquid oil that does not have a six-membered ring due to its structure can be used as the general component.

  Moreover, it is also possible to manufacture the external composition of the final target form, without going through manufacture of the water-containing composition of this invention of the aspect containing only said essential component. In this case, for example, an aqueous phase in which a water-soluble component selected as a general component is dissolved in water is prepared, and a poorly water-soluble UV absorber is added to the compound (I). By mixing the dissolved or dispersed parts, the ultraviolet absorber can be solubilized or water-dispersed to produce an external composition in the final form, but it is not limited to this production method. However, the production method can be appropriately selected or devised according to the nature of the necessary and selected general components.

  Hereinafter, examples of the present invention will be disclosed and the present invention will be described more specifically, but the present invention is not limited thereby. Unless otherwise specified, the blending amount is mass% relative to the blending target.

[Test example]
In accordance with a conventional method, compound (I) or other surfactant and an ultraviolet absorber are mixed and dissolved, and the test parts shown in Tables 1 to 6 (Examples) are prepared by mixing the parts in water. Or a comparative example) was obtained and a test according to the following criteria was performed. The results are listed separately for each table. In addition, "-" in the column which shows the compounding quantity of each table | surface shows that it is 0 mass%. Furthermore, “POE” is an abbreviation for “polyoxyethylene”, and “POP” is an abbreviation for “polyoxypropylene”.

(1) Test immediately after preparation of test product (a) Confirmation of dissolution state Each test product was subjected to a visual confirmation test of the dissolution state. Judgment criteria are as follows.
A: Transparent state.
○: Almost transparent.
Δ: Cloudy to translucent.
X: Separation is observed.

(B) Confirmation of transparency (L value) For each test product, the transparency was confirmed by measuring the L value. The L value was measured as a transparency using a spectrophotometer (UV-160) manufactured by Shimadzu Corporation as a control when the transparency of distilled water was taken as 100. Judgment criteria are as follows.
90 or more: Transparent state.
70 to less than 90: almost transparent.
Less than 70: Cloudy to translucent.
Inability to measure: Separation is observed.

(C) Usability test Each test product immediately after preparation was subjected to a usability test by 10 professional panels. Judgment criteria are as follows.

○: When 5 or more out of 10 people evaluate that there is no stickiness. △: When 3-4 people out of 10 evaluate that there is no stickiness. ×: 0-2 people out of 10 have no stickiness. When evaluating

(2) Test over time The test product prepared as described above was stored at 50 ° C. for 1 month (hereinafter also referred to as “50 ° C. 1M”), and the L value was measured again in the above manner. Then, the stability over time was evaluated based on the difference between the L value measured immediately after the preparation of the test product and the L value measured this time. Judgment criteria are as follows. The L value measured this time is also listed in each table.
◎: L value change ± 2 or less ○: L value ± 5 or less △: L value ± 10 or less ×: L value change ± 10 or more, or a separation is observed

  <Test system 1>

  In Table 1, since Comparative Examples 1-2 used the surfactant which does not have a phytosteryl skeleton, it became clear that solubilization ability was low and it was not suitable for solubilization of a ultraviolet absorber. Examples 1 to 3 use the compound (I) having a phytosteryl skeleton as a surfactant, and solubilize a triazine-based UV absorber that is a water-insoluble UV absorber at a sufficiently practical level. I was able to.

  <Test system 2>

  In Table 2, Comparative Example 3 had some problems in stability over time because the number of moles of polyoxyethylene groups in the blended polyoxyethylene-added phytosterol was less than 5.

  In Example 4, the polyoxyethylene group of the compound (I) was 5 to 50 mol, and the appearance, usability, and stability over time were good.

  In Example 5, since the polyoxyethylene group of the compound (I) was 50 or more, stickiness was observed during use.

<Test system 3>
In the test system shown in Table 3, since the ratio (mass ratio) of the compound (I) and the poorly water-soluble substance becomes a problem, the ratio is also shown in the table.

  In Example 9, since the ratio of compound (I) / ultraviolet absorber was 1 or less, it was slightly translucent.

  In Examples 6 to 8, since the ratio of compound (I) / ultraviolet absorber was 1 or more, the appearance, usability and stability were good.

  <Test system 4>

  Compound (I) used in Example 10 is an ultraviolet absorber having only one 6-membered ring in the chemical structure and can be solubilized, but the stability over time is the best result. It did not come.

  Since the compound (I) used in Examples 11 to 13 is an ultraviolet absorber having two or more 6-membered rings in the chemical structure, the appearance and stability were good.

<Test system 5>
In the test system shown in Table 5, in addition to the essential components of the water-containing composition of the present invention, each test was conducted using a formulation (external preparation) using general components. Each general component is water-soluble. Prepare each test product by mixing with ion-exchanged water to prepare aqueous phase parts and mixing with UV absorber and compound (I) dissolving parts in advance. It was.

  From the results of Examples 14 to 17, it was revealed that the original effect in the water-containing composition of the present invention was not impaired even in a system in which general components were blended.

Claims (6)

(1) Polyoxyethylene addition compound represented by the following formula (I) HO (CH ₂ CH ₂ O) _n -R (I)
[In formula, R shows a phytosterol residue or a phytostanol residue, and n shows the number of 5-100. ]
(2) bisethylhexyloxyphenol methoxyphenyl triazine and / or 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine , and
(3) contains water,
And (2) (1) polyoxy to bisethylhexyloxyphenol methoxyphenyl triazine and / or 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine The blending ratio of the ethylene addition compound is 1 or more by mass, the triazine-based UV absorber is solubilized or dispersed in water, and the L value is 70 or more when the transparency of distilled water is 100. A transparent or translucent water-containing composition. The phytosterol residue or phytostanol residue R in the polyoxyethylene adduct (I) is a sitosterol residue, a campesterol residue, a stigmasterol residue, a brassicasterol residue, an avenasterol residue Group consisting of a group, an ergosterol residue, a sitostanol residue, a campestanol residue, a stigmasteranol residue, a brassicastanol residue, an avenastanol residue, and an ergostanol residue The water-containing composition of Claim 1 which is 1 type, or 2 or more types chosen from. The water-containing composition according to claim 1 or 2, wherein n in the polyoxyethylene addition compound (I) is a number of 5 to 50. The water-containing composition according to any one of claims 1 to 3 , wherein the water-containing composition is an external composition. The hydrous composition of Claim 4 whose form of an external composition is cosmetics or a skin external preparation. The water-containing composition according to any one of claims 1 to 5 , wherein the water-containing composition is a composition used as a base for producing a composition for external use.