JP2019178126A - Ultraviolet absorber-containing composition and cosmetics containing the same - Google Patents

Abstract

To provide crystal inhibiting compositions, specifically crystal inhibiting compositions capable of developing a variety of agents by having excellent usability without stickiness while stably compounding a poorly soluble UV absorber in a formulation.SOLUTION: Provided is a crystal inhibiting composition containing the following components (a) to (c): (a) a UV absorber that is solid at 25°C; (b) at least one selected from the group consisting of polysaccharide fatty acid esters (dextrin fatty acid esters, fructooligosaccharide fatty acid esters, inulin fatty acid esters, sucrose fatty acid esters); and (c) an oil agent with IOB value of 0.1-0.5.SELECTED DRAWING: None

Description

  The present invention relates to an oily composition containing an organic ultraviolet absorber, more specifically, an oily composition that can suppress crystal precipitation of a hardly soluble organic ultraviolet absorber by using a polysaccharide fatty acid ester, Furthermore, the cosmetic containing the oily composition is excellent in stability and feel.

  In recent years, the demand for sunscreen cosmetics has increased, and various sunscreen cosmetics have been developed according to the purpose of use. In particular, as the effects of UVA (long wavelength ultraviolet light with a wavelength of 320 to 400 nm) on the skin are understood, not only preventing UVB (medium wavelength ultraviolet light with a wavelength of 290 to 320 nm) but also preventing UVA is an important factor. ing. However, many UVA absorbers are solid at room temperature and poorly soluble (slightly soluble in water and non-polar oils), and the stability of the preparation over time is impaired due to crystal precipitation, particularly in the low temperature range. Due to the aggregation of components, problems such as failure to obtain the expected UV protection effect may occur. For this reason, various studies have been made on the stable blending of poorly soluble organic ultraviolet absorbers (see, for example, Patent Documents 1 to 3), but stickiness and the like occur due to an increase in the content of oils and surfactants. It was easy and there were cases where it was unsatisfactory in terms of usability.

  Also, in sunscreen cosmetics, a different touch is required, and not only water-in-oil emulsified cosmetics that have been commonly used, but also oil-in-water emulsified cosmetics, oil-based (solid) cosmetics, There is a history that dosage forms such as aerosol spray types have been diversified, and it is necessary to develop not only high UVA and UVB protection functions, but also sunscreen cosmetics of various dosage forms according to demand.

JP 2009-235046 A JP 2014-118383 A JP 2009-091307 A

  Therefore, in the present invention, an organic UV absorber that can be applied to various dosage forms and a cosmetic with excellent usability without crystal precipitation and stickiness, while blending a poorly soluble organic UV absorber. It is an object of the present invention to provide an oily composition containing

  In view of this situation, as a result of intensive investigations, the present inventors have found that an oily composition in which a polysaccharide fatty acid ester and an oil having an IOB value of 0.1 to 0.5 are mixed and dissolved when dissolving a poorly soluble organic ultraviolet absorber. As a result, the inventors have found that crystal precipitation of a hardly soluble organic ultraviolet absorber is remarkably suppressed and the stability of a cosmetic containing the same is improved, and the present invention has been completed.

That is, the present invention includes the following components (a) to (c):
(A) Solid ultraviolet absorber at 25 ° C. (b) Polysaccharide fatty acid ester (c) An oily composition containing an oil with an IOB value of 0.1 to 0.5, or a cosmetic containing the oily composition Further, the present invention relates to a method for suppressing crystal precipitation of a cosmetic containing a sparingly soluble organic ultraviolet absorber using the oily composition.

  The oil-based composition of the present invention can suppress the precipitation of crystals of a hardly soluble ultraviolet absorber. In addition, the oily composition can be easily blended into various types of cosmetics, and since a UV absorber can be stably blended, a cosmetic with a high UV protection effect can be provided. Furthermore, the long-term stability of the cosmetic can be easily estimated.

It is an evaluation standard in (Evaluation Method 2: Inhibition of Crystal Precipitation) in Examples.

  Hereinafter, the present invention will be described in detail. In the present specification, “to” means a range including numerical values before and after.

(Oil composition)
The oily composition in the present invention is a component (a) a solid organic ultraviolet absorber at 25 ° C., a component (b) a polysaccharide fatty acid ester, and a component (c) an oil agent having an IOB value of 0.1 to 0.5, As long as the organic UV absorber crystals are not precipitated, other components may be contained. The method of mixing and dissolving is not particularly limited. For example, after adding a certain amount of a volatile solvent to components (a) to (c) and heat-treating, the mixture is evaporated to dryness or no solvent is used. To melt.

  The component (a) UV absorber solid at 25 ° C. used in the present invention is for protecting the skin from UV rays, and is not particularly limited as long as it is solid at 25 ° C. For example, diethylamino Hexyl hydroxybenzoylbenzoate, ethyl paraaminobenzoate, benzophenone-1, benzophenone-3, benzophenone-6, benzophenone-9, ethylhexyltriazone, dioctylbutamidotriazone, t-butylmethoxydibenzoylmethane, bisethylhexyloxyphenolmethoxy Examples thereof include phenyltriazine, methylenebisbenzotriazolyltetramethylbutylphenol, and one or more of these can be used. Among these, hexyl diethylaminohydroxybenzoyl benzoate and bisethylhexyloxyphenol methoxyphenyl triazine are preferable because they have a high UVA protective effect.

  As a commercial item of component (a), UVINUL A PLUS GRANULAR (diethylaminohydroxybenzoyl hexyl benzoate; manufactured by BASF), TINOSORB S (bisethylhexyloxyphenol methoxyphenyl triazine; manufactured by BASF), UVINUL T150 (ethylhexyl triazone; BASF), TINOSORB M (methylene benzobenzotriazolyl tetramethylbutylphenol; BASF, Dainippon Kasei) and the like.

  The content of the component (a) in the present invention is not particularly limited, but is preferably 0.5 to 50% by mass (hereinafter simply referred to as “%”) in the oily composition, particularly preferably 2 to 35%. is there. This range is preferable because crystal precipitation can be suppressed.

  Component (b) polysaccharide fatty acid ester used in the present invention is an esterified product of polysaccharide and fatty acid, and preferred examples include sucrose fatty acid ester, dextrin fatty acid ester, fructooligosaccharide fatty acid ester, etc. One kind or two or more kinds can be used.

  The sucrose fatty acid ester is an ester of a saturated or unsaturated fatty acid having 6 to 32 carbon atoms, preferably 8 to 24 carbon atoms, and sucrose, and having an average substitution degree of 3 or more. preferable. In the case of a plurality of esters, the fatty acids may be single or different, and examples thereof include esters of saturated or unsaturated fatty acids having 8 to 24 carbon atoms and 2 to 4 carbon atoms with sucrose. Examples of commercially available products include Sugar Wax S-10E (Daiichi Kogyo Seiyaku), Sugar Wax A-10E (Daiichi Kogyo Seiyaku), Surf Hope SECOSME C-1800 (Mitsubishi Chemical Foods). .

  The dextrin fatty acid ester is an ester of dextrin with a straight or branched chain saturated or unsaturated fatty acid having 6 to 32 carbon atoms, preferably having an average degree of substitution of 1.5 or more per monosaccharide. The sugar average polymerization degree is preferably 10 to 50. Specific examples include dextrin myristate, dextrin palmitate, dextrin palmitate / 2-ethylhexanoate, dextrin stearate, dextrin palmitate / dextrin stearate, dextrin oleate, dextrin isopalmitate, dextrin isostearate and the like. The Commercially available products include Leopard MKL2 (produced by Chiba Flour Mills) which is a dextrin myristate, Leopard KL2 which is dextrin palmitate, Leopard TL2 (all produced by Chiba Flour Mills), Leopard which is palmitic acid / 2-ethylhexanoic acid dextrin. TT2 (manufactured by Chiba Flour Mills) and the like can be mentioned.

  The fructooligosaccharide ester is an ester of a C6-C32 linear or branched saturated or unsaturated fatty acid and a fructooligosaccharide, preferably having an average degree of substitution of 1 to 3 per monosaccharide. The sugar average polymerization degree is preferably 10-60. In addition, the measuring method of the sugar average degree of polymerization of fructooligosaccharide is, for example, L. De Leenheer, Starch 46 (5), p193-196 (1994), Carbohydrates as Organic Raw Materials, Vol. III, p67-92 (1996). In the present invention, fructooligosaccharide refers to an oligosaccharide having fructose as a main constituent sugar. Fructooligosaccharides are contained in various plants, for example, the roots, stems, leaves, seeds, etc. of the Asteraceae, Gramineae and Liliaceae, and the structure thereof is such that the main chain binding mode is 2 → 1 bond, There are two types, 2 → 6. Fructooligosaccharides derived from inulin, asparagosin, asphodelan, triticane, criticzan, bacmondow, etc. as 2 → 1 linkages, and Flaen, Levan, Seracan etc. as 2 → 6 linkages. Among these, inulin and / or hydrolyzed inulin are preferable. Inulin is composed of a chain of furanoid fructose units linked with β-1,2 and having α-D-glucose linked with sucrose at the reducing end, and preferably has about 2-60 furanoid fructose units. . Examples of commercially available products include Leopearl ISK2 and Leopearl ISL2 (both manufactured by Chiba Flour Milling Co., Ltd.), which are inulin stearate.

  The content of the component (b) in the present invention is not particularly limited and varies depending on the selection of the components (a) and (c), but is preferably 0.1 to 20%, more preferably 0.5 to 10%. . Within this range, crystal precipitation of the component (a) can be suppressed, the handling of the oily composition is good, and blending into a cosmetic is easy, which is preferable.

  The component (c) oil agent having an IOB value of 0.1 to 0.5 used in the present invention is not limited in its molecular structure and properties as long as the IOB value is in the range of 0.1 to 0.5. The IOB value is an index indicating the degree of polarity of an organic compound as a balance between inorganic and organic, and is expressed as IOB value = inorganic value / organic value, and this value is large. A compound can be said to be a more hydrophilic compound. In the present invention, an oil agent having an IOB value of 0.1 or less is inferior in solubility of the component (a), and an oil agent having an IOB value of 0.5 or more has a high polarity and is too biased toward hydrophilicity. Concerns about stability arise.

  In the present invention, the component (c) is preferably compatible with the components (a) and (b), and preferably has a melting point of 30 ° C. or less in terms of stability and handling of the oily composition. Ethylhexyl methoxycinnamate (IOB = 0.28), diethylhexyl succinate (IOB = 0.32), propylene glycol dicaprate (IOB = 0.26), methylphenylpolysiloxane (IOB = 0.28), triethyl Particularly preferred are glyceryl hexanoate (IOB = 0.36), cyclomethicone (IOB = 0.44), and the like.

  Examples of commercially available products of (c) above include UVINUL MC80 (ethylhexyl methoxycinnamate; manufactured by BASF), CRODAMOL OSU-LQ- (JP) (diethylhexyl succinate; manufactured by Croda Japan), Nikkor PDD (PGa dicaprate) Manufactured by Nippon Surfactant Co., Ltd.), KF-56 (methyl phenyl polysiloxane; manufactured by Shin-Etsu Chemical Co., Ltd.), FINSOLV TN (alkyl benzoate (C12-C15); INNOSPEC ACTIVE CHEMICAL), KF-995 (cyclomethicone; Shin-Etsu) Chemical Industry Co., Ltd.), MYRIITOL GTEH (glyceryl triethylhexanoate), and the like.

  Although content in particular of the component (c) in this invention is not restrict | limited, 3 to 80% is preferable, More preferably, it is 5 to 15%. Within this range, crystal precipitation of component (a) can be suppressed, solubility with (b) is good, and a stable oily composition is preferred.

  In the present invention, the content ratio (a) / (b) of the component (a) to the component (b) is preferably 0.15 to 100, more preferably 0.5 to 60, and still more preferably. 1.5-20. Further, the total mass ratio {(a) + (b)} / (c) of the component (a) and the component (b) to the component (c) is 0.01 to 3, preferably 0.03. It is -2, Especially preferably, it is 0.1-1. This range is preferable because the solubility of each component becomes good.

(Cosmetics)
The cosmetic of the present invention contains the oily composition described above. The production method is not particularly limited, and is prepared by a conventional method according to the dosage form. For example, the oily composition may be prepared in advance and used as it is as an oil phase of cosmetics, or other oil-soluble properties. It can also be mixed and dissolved with the components. The content ratio of the oily composition in the cosmetic is not particularly limited, and varies depending on the dosage form of the cosmetic. However, the content of the component (a) in the total cosmetic is 0.5 to 30%. , Preferably 5 to 15%.

  In addition to the oily composition described above, the cosmetics of the present invention include components used in ordinary cosmetics, such as oily components other than components (a) to (c), cationic surfactants, and nonionic interfaces. Surfactants such as active agents, anionic surfactants, amphoteric surfactants, water, water-soluble polymers, polyhydric alcohols, lower alcohols and other aqueous components, antibacterial agents, preservatives, pH adjusters, cooling agents, Cosmetic ingredients such as powders, vitamins and amino acids, fragrances and the like can be appropriately contained as long as the effects of the present invention are not impaired.

  The cosmetic of the present invention can be carried out in various forms such as liquid, emulsion, cream, solid, gel, and paste. The cosmetics of the present invention are not particularly limited in their dosage forms such as oil-based, water-in-oil emulsified systems, oil-in-water emulsified systems, and are emulsions, creams, serums, cosmetic oils, lip balms, sunscreens. Various cosmetics such as skin care cosmetics such as cosmetics, foundations, makeup bases, makeup cosmetics such as cheeks, eye shadows, lipsticks, lip gloss, etc., and scalp or hair cosmetics such as hair creams and hair stylings Can be implemented. Moreover, the usage method includes a method of using with hands, fingers and cotton, a method of using it by impregnating a non-woven fabric and the like, a method of using as a spray agent and an aerosol agent, and the like.

  EXAMPLES Hereinafter, although an Example, a test example, etc. are given and this invention is demonstrated more concretely, this invention is not restrict | limited at all by these Examples.

[Examples 1 to 5 and Comparative Examples 1 to 3: Oily Composition]
An oily composition was prepared by the composition shown in Table 1 and the following production method. About the obtained oil-based composition, the presence or absence of crystal | crystallization precipitation was evaluated by the following method, and it showed in Table 1 with the result.

(Production method)
A: Components 1 to 10 are heated to 90 ° C. and dissolved uniformly.
B: Allow A to cool to room temperature.

(Evaluation method: Suppression of crystal precipitation)
About each said sample, what was left still for 3 days in a -20 degreeC thermostat is left still at room temperature for 1 day, Then, an upright type microscope (made by Olympus Co., Ltd.) by magnification 40times and exposure time 1/200 second ) Was observed under polarized light. A small amount of the sample was placed on a glass plate, diluted with an appropriate amount of cyclomethicone, and then prepared with a preparation to obtain a sample for microscopic observation. When the hardly soluble ultraviolet absorber is present as a crystal in the oily composition, it is observed as an amorphous glitter under polarized light. Therefore, the presence or absence of the glitter was evaluated according to the following criteria.
<Criteria>
(Judgment): (Evaluation)
(Double-circle): The ultraviolet-ray absorber or the base crystal glitter is not observed at all.
○: An ultraviolet absorber or base glitter is observed, but crystals are not felt when applied to the skin.
X: A clear ultraviolet absorber or base crystal glitter is observed.

[Examples 6 to 15 and Comparative Examples 4 to 6: Sunscreen cosmetics (oil-in-water emulsion type)]
The sunscreen cosmetics shown in Table 2 were prepared by the following production method. About the obtained sunscreen cosmetics, the following evaluation items were evaluated by the following methods, and the results are shown in Table 2 together with the results.

(Production method)
A: Components 4 to 18 are heated to 90 ° C. and mixed and dissolved.
B: Components 1 to 3 are mixed uniformly at room temperature and heated to 75 ° C.
C: A is added to B and emulsified.
D: After cooling C to 50 ° C., components 19 to 20 were sequentially added and uniformly mixed to obtain a sunscreen cosmetic.

(Evaluation item)
(A) Freshness to start (b) No stickiness after the skin (c) Suppression of crystal precipitation (ii) Emulsion stability (e) UV protection effect

(Evaluation method 1: Sensory evaluation)
10 cosmetic panel evaluation specialists use each of the above-mentioned sunscreen cosmetics, and for each of the items (a) freshness to start and (b) no stickiness of the back skin, the following evaluation criteria 1a The sensory evaluation was performed in five stages according to the above, and the average score of all the panels was determined according to the following criteria 1b.
<Evaluation criteria 1a>
(Evaluation): (Grade)
Good: 5 points Somewhat good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point <Criteria 1b>
(Judgment): (Average score)
◎: 4.0 or more ○: 3.0 or more and less than 4.0 △: 2.0 or more and less than 3.0 ×: Less than 2.0

(Evaluation method 2: Suppression of crystal precipitation (oil-based composition))
About the said Examples 6-15 and Comparative Examples 4-6, the sample which heat-dissolved to the components 4-16 of Table 2 was created, and it left still for 3 days in a -20 degreeC thermostat, and set it to room temperature 1 After standing still, it was observed under polarized light using an upright microscope (manufactured by Olympus) at a magnification of 40 times and an exposure time of 1/200 seconds. A small amount of the sample was placed on a glass plate, diluted with an appropriate amount of cyclomethicone, and prepared by overlaying a preparation. When the hardly soluble organic ultraviolet absorber is present as a crystal in the oily composition, it is observed as an amorphous glitter under polarized light. Therefore, the presence or absence of the glitter is evaluated according to the following criteria 2.
<Criteria 2>
(Judgment): (Evaluation)
(Double-circle): The ultraviolet-ray absorber or the base crystal glitter is not observed at all.
○: An ultraviolet absorber or base glitter is observed, but crystals are not felt when applied to the skin.
X: A clear ultraviolet absorber or base crystal glitter is observed.

(Evaluation method 3: emulsion stability)
The samples of Examples 6 to 15 and Comparative Examples 4 to 6 were placed in a glass standard bottle, and the appearance was visually observed. The state after storage at room temperature for 2 weeks was observed, compared with the appearance immediately after filling, and judged using the following criteria 3.
<Criteria 3>
(Judgment): (Evaluation)
A: Separation, precipitation, crystals, etc. cannot be confirmed even after 2 weeks at room temperature.
○: After 2 weeks at room temperature, slight separation is observed, but there is no problem in use.
Δ: No problem immediately after filling, but separation, precipitation, crystals, etc. are confirmed at room temperature for 2 weeks.
X: Separation, precipitation, crystals, etc. are confirmed immediately after production and from filling.

(Evaluation method 4: UV protection effect (SPF))
Each sample was applied to a PMMA plate (manufactured by Helio screen) so as to be 1.3 mg / cm ² , dried for 20 minutes, then set on an SPF analyzer (manufactured by Labsphere), and measured at 9 points. Calculated from the values.
<Criteria 4>
(Judgment): (Evaluation)
◎: Calculated value of SPF analyzer is 15 or more ○: Calculated value of SPF analyzer is 10 or more and 15 or less △: Calculated value of SPF analyzer is 5 or more and 10 or less ×: Calculated value of SPF analyzer is 5 or less

  As is clear from the results in Table 1, the sunscreen cosmetics of Examples 6 to 15 can suppress the crystal of the organic ultraviolet absorber and have good stability as an emulsified cosmetic. It is a sunscreen cosmetic that can fully exert its protective effect, and is excellent in both freshness and stickiness of the back skin. On the other hand, the comparative example 1 which does not mix | blend a component (b) resulted in the organic ultraviolet absorber depositing immediately after manufacture, and produced a problem in emulsion stability. In addition, Comparative Examples 2, 3 using squalane (IOB value = 0) having an IOB value of 0.1 or less and dipropylene glycol (IOB value = 1.8) exceeding 0.5 instead of the component (c) The oil-based composition was unable to suppress crystal precipitation of the organic ultraviolet absorber, and was inferior in stability as an emulsified cosmetic.

Example 16: Cream (ingredient) (%)
1. N-stearoyl-N-methyltaurine sodium 0.1
2. Phospholipid / cholesterol mixture 2.2
3. Glycerin 10.5
4.1,3-Butylene glycol 5.0
5. Diglycerin 1.0
6). Sucrose fatty acid ester 2.0
7). Cetyl ethylhexanoate 3.0
8). Ethylhexyl methoxycinnamate 5.0
9. Diethylaminohydroxybenzoylbenzoic acid hexyl ester 1.0
10. Oil-soluble licorice extract 0.1
11. Rice germ oil 0.02
12 Tocopherol 0.01
13. Purified water remaining amount 14. Xanthan gum 0.1
15. Carbomer 0.5
16. Sodium hydroxide appropriate amount17. Ethanol 6.5
18. Antiseptic suitable amount 19. Trehalose 0.05
20. Seaweed extract 0.01
21. Citric acid 0.02
22. Sodium monohydrogen phosphate 0.15
23. Hydroxyproline 0.05
24. Kawara mugwort extract 0.05

(Production method)
A: Components 1 to 5 and 13 are heated to 70 ° C. and mixed uniformly.
B: Components 6 to 12 are heated to 80 ° C. and mixed uniformly.
C: Add B to A and stir.
D: Components 14 to 24 heated to 70 ° C. are added to C and emulsified.
E: D was cooled to room temperature with stirring to obtain a cream.

  The cream of Example 16 is a cosmetic that can suppress the crystals of the poorly soluble ultraviolet absorber, can sufficiently exhibit the ultraviolet protective function of the poorly soluble ultraviolet absorber, and is excellent in emulsion stability. Met.

Example 17: Shaking type sunscreen (water-in-oil type)
(Ingredient) (%)
1. Bisethylhexyloxyphenol methoxyphenyl triazine 1.5
2. Paramethoxycinnamic acid ethyl ester 7.5
3. (Palmitic acid / ethylhexanoic acid) dextrin 1.5
4). Diethylaminohydroxybenzoyl hexyl benzoate 3.0
5. Diethylhexyl succinate 3.5
6). Polysilicone 15 3.0
7). Methyl polysiloxane 0.5
8). Safflower oil 0.1
9. Silylated Anhydrous Silicic Acid 4.0
10. Zinc oxide 7.0
11. Mica 2.0
12 Polyhydroxystearic acid 1.0
13. Cyclomethicone 5.0
14 Light isoparaffin 4.0
15. Ethanol 7.0
16. Preservative appropriate amount17. Perfume appropriate amount 18. Purified water remaining amount 19. Hydrolyzed hyaluronic acid 0.01
20. Hydrolyzed collagen 0.01

(Production method)
A: Components 1 to 8 are heated to 80 ° C. and mixed uniformly.
B: Components 9 to 14 are uniformly roller-mixed.
C: Add B to A and mix uniformly.
D: Components 15 to 17 are added to C and mixed uniformly.
E: Add 18 to 20 to D and emulsify.
F: E was cooled to room temperature to obtain a shaking type sunscreen.

  The shaking type sunscreen of Example 17 can suppress the crystals of the hardly soluble UV absorber, can fully exhibit the UV protection function possessed by the hardly soluble UV absorber, and is stable in emulsion. It was a cosmetic with excellent properties.

Claims (4)

An oily composition containing the following components (a) to (c).
(A) Organic UV absorber solid at 25 ° C. (b) Polysaccharide fatty acid ester (c) Oil with IOB value of 0.1 to 0.5   The mass ratio (a) / (b) of the component (a) to the component (b) is 0.15 to 100, and the component (a) and the component (b) with respect to the component (c) Total oil content ratio {(a) + (b)} / (c) is 0.02-20, The oil-based composition of Claim 1 characterized by the above-mentioned.   Cosmetics containing the oil-based composition of Claim 1 or 2.   A method for suppressing crystal precipitation of a cosmetic containing a solid organic ultraviolet absorber at 25 ° C., using the oil-based composition according to claim 1.