JPS60149515A - Anti-sunburn cosmetic - Google Patents

Abstract

PURPOSE:To provide an anti-sunburn cosmetic containing a pigment coated with a polyvalent metal salt of p-dimethylaminobenzoic acid, and having extremely high ultraviolet-shielding capability, high transparent feeling, good durability on the skin, and excellent dispersability and stability. CONSTITUTION:The objective anti-sunburn cosmetic contains a pigment (e.g. talc, titanium oxide, titanium mica, magnesium silicate, nylon, polypropylene, etc.) coated with a compound of formula (M is Al, Mg, Zn, Ca or Zr; n is atomic valence of M). The anti-sunburn cosmetic is free of permeation into the skin, has extremely excellent spreadability and color-developability, and is resistant to degradation with time on the skin. The coated pigment can be prepared by dispersing a pigment in an aqueous solution of a water-soluble polyvalent metal salt, adding an aqueous solution of an alkali metal salt of p-dimethylaminobenzoic acid slowly and dropwise to the suspension under agitation, making the mixture alkaline, and continuing the agitation. The amount of the compound of formula applied to the pigment is 1-30wt% based on the pigment.

Description

[Detailed description of the invention] Misfire! The present invention relates to a sunscreen cosmetic containing a pigment whose surface is substantially treated by ultraviolet absorption and quality. More specifically, by containing the polyvalent metal salt of paradimethyl-1-minobenzoic acid-coated pigment, the pigment is substantially coated with the polyvalent metal salt of para-dimethyl-1-minobenzoic acid. This invention relates to a sunscreen cosmetic that has a high ability to block ultraviolet rays and has excellent transparency, makeup retention, dispersibility, and stability.

Conventionally, UV-cutting substances added to cosmetics include:
Paradimethyl 1-minobenzoic acid, benzophenone derivatives,
Examples include synthetic ultraviolet absorbers such as cinnamic acid derivatives, benzotriazole derivatives, and salicylic acid derivatives, and inorganic pigments such as titanium oxide, zinc oxide, and iron oxide. When compounding organic UV absorbers into cosmetics, increasing the amount added to the base causes problems with solubility, texture (for example, stickiness), and problems with skin transparency and UV absorption. There are many problems when used as a cosmetic raw material, such as a decrease in absorption capacity and coloring. On the other hand, the latter inorganic pigments are not absorbed transdermally, so there are no safety issues, but if they are blended in high concentrations to have effective UV blocking ability, the blocking power will be too great and if applied to the skin. It may turn white or become too pigmented, making it difficult to achieve a natural finish. Furthermore, regarding makeup linger, which is very important as a sunscreen cosmetic, it has drawbacks in adhesion to the skin (adhesiveness) and water resistance, making it impossible to achieve sufficient effects. Further, in order to improve these points, fine particle titanium oxide (Japanese Patent Publication No. 47-425
02), blending of fine particles of zinc oxide, etc., and hydrophobizing treatment thereof (e.g., metal soap treatment, JP-A-58-4930)
7. Pigment blending technology (silicon baking treatment) also has problems such as agglomeration of fine pigment particles, inconvenience in color tone, blueness due to interference colors, blackening due to ultraviolet absorption) and a decrease in ultraviolet blocking ability. No cosmetics have been produced that have a good finish) and have sufficient sunburn prevention effects.

The present invention has been developed as a result of intensive research to solve the problems of the conventional methods described above, and has been developed as a result of incorporation into cosmetics of pigments whose surface has been substantially treated with specific ultraviolet absorbing substances. It solves various problems, has extremely high UV protection ability, has no skin penetration, is safe, has transparency,
It was discovered that it exhibits extremely excellent properties such as makeup retention (adhesiveness), spreadability, dispersibility, stability, and color development, and based on this knowledge, the present invention was completed.

The purpose of the present invention is to have an extremely excellent sun protection effect, excellent transparency, and natural color tone by blending a polyvalent metal salt coated pigment with baladimethylaminobenzoic acid. Another object of the present invention is to provide a sunscreen cosmetic that has very good adhesion to the skin and does not lose its makeup over time.

That is, in the present invention, the particle surface of the base pigment has the following formula (2
) (In the formula, M is ^l+ Mg+ Zn+ Ca or Z
(where r and n are the valences of M) A polyvalent metal salt of valadimethylaminobenzoic acid-coated pigment is substantially coated with a polyvalent metal salt of valadimethylaminobenzoic acid represented by A sunscreen cosmetic featuring the following.

In the polyvalent metal salt of baladimethylaminobenzoic acid-coated pigment of the present invention, the particle surface of the pigment (base pigment) is substantially coated with the polyvalent metal salt of baladimethylaminobenzoic acid, and the coating state is as follows: Substantially uniform.

The polyvalent metal salts of paradimethylaminobenzoic acid include aluminum salts, magnesium salts, zinc salts, calcium salts, and zirconium salts of paradimethylaminobenzoic acid. Their chemical structural formulas are as follows.

In addition, these polyvalent metal salts of baladimethylaminobenzoic acid are harmful to the skin in the UV-B region (280 to 3
The ultraviolet absorption ability at 20 nm) is extremely high, as shown in Table 1.

'-1゛, +, :J'' Valence metal salt (n m ) A l IMM g IMZ n salt C
a salt Zr salt 270' 15 1 0 0 15 275 10 0 0 0 10 280 6 0 0 0 6 285 3 0 0 0 3 290 2 0 0 0 2 295 '2 0 0 0 1 300 1 0 0 0 1 305 1 0 0 0 1 310 2 0 0 0 2 315 3 1 0 0 3 320 6 2 0 0 5 Note 1) For transmission spectra, a self-recording spectrophotometer model NFS-2000 manufactured by Shimadzu Corporation was used to measure the sample compound in ethanol. After 5 minutes of ultrasonication under 0.02 plate suspension,
Measurement was performed using a 10 m cell.

The amount of the polyvalent metal salt of paradimethylaminobenzoic acid coating the particle surface of the base pigment is 0.1 to 40% dish-shaped or 1 to 30% by weight based on the weight of the base pigment. be. If it is less than 1 weight, the particle surface of the base pigment will not be substantially coated, resulting in good adhesion, spreadability, dispersibility, covering power, durability of cosmetic effect, miscibility, ultraviolet absorption, It is difficult to impart sufficient anti-sun effect and feel, and if the amount exceeds 40% by weight, the particles of the base pigment will coagulate with each other, reducing the covering power of the pigment. There are cases where

The maximum particle size of the paradimethylaminobenzoic acid polyvalent metal salt-coated pigment of the present invention is 100 μm or less, and if it is larger than this, the adhesion and affinity for the skin will be poor and it will be felt as a foreign substance. .

The base pigment in the coated pigment of the present invention is a general term for white pigments, colored pigments, extender pigments, etc. for cosmetics, and examples include talc, kaolin, mica, calcium carbonate, titanium oxide, zinc oxide, titanium mica, and magnesium carbonate. , iron oxides, iron oxide-treated mica titanium, aluminum oxide, aluminum silicate, barium sulfate, bismuth oxychloride, silicon dioxide, magnesium silicate, nitrogen, polyethylene, Teflon, polypropylene, and other synthetic resin powders. These can be used alone or in combination of two or more.

The polyvalent metal salt of paradimethylaminobenzoic acid coated pigment of the present invention has a structure in which the particle surface of the base pigment is substantially covered with the polyvalent metal salt of paradimethylaminobenzoic acid, and is in the form of fine powder. ing. The state of the coating is recognized by scanning and transmission electron microscopy.

Table 1 of polyvalent metal salt of paradimethylaminobenzoic acid-coated pigment The polyvalent metal salt of paradimethylaminobenzoic acid forming the layer (coating layer) contains water, an organic solvent, an oily substance,
Since it is insoluble in sebum and exhibits a so-called pigment state, it is not absorbed through the skin (skin permeation), does not cause skin irritation to the human body, and is extremely safe. It has a water-repellent effect, water resistance, oil absorption, and heat resistance.

Therefore, the polyvalent metal salt of paradimethylaminobenzoic acid-coated pigment is extremely safe for the human body, and has a synergistic effect with the pigment's inherent ultraviolet reflection ability in terms of ultraviolet light absorption. It exhibits extremely high UV-cutting ability, and at the same time exhibits extremely excellent properties such as transparency, makeup retention (adhesiveness), spreadability, safety, and color development, making it extremely effective as a base for sunscreen cosmetics. Useful.

Moreover, it does not have the disadvantages of conventional cosmetic pigments, such as dehydration, degreasing, dryness, and alkalinization of the skin surface, and can protect the skin in a healthy manner.

Therefore, a sunscreen cosmetic containing this coated pigment exhibits extremely high UV-cutting ability, has good spreadability (extensibility) and adhesion (adhesion) to the skin, and is easy to apply. It has good feel when applied, makeup finish after application, makeup durability, and water resistance, and can develop and maintain desirable and beautiful cosmetic effects.

The polyvalent metal salt-coated pigment of baladimethylaminobenzoic acid used in the present invention is produced, for example, in the following manner.

Base pigment, 0.1 to 20% by weight based on its weight
, preferably 0.5 to 5% by weight of a water-soluble polyvalent metal salt, and then suspended in an aqueous solution containing 1 to 4 equivalents of baladimethyl based on the water-soluble polyvalent metal salt under stirring. 0.01~20Jliage% containing aminobenzoic acid alkali salt
, preferably an aqueous solution of 0.5 to 5% Tf Paradimethylaminobenzoic acid polyvalent metal salt is sequentially orientated and adsorbed. The target coated pigment can be isolated from the reaction mixture by filtering the reaction mixture to remove the polyvalent metal salt of valadimethylaminobenzoic acid-coated pigment, and then thoroughly washing the precipitate with water. Unreacted alkali paradimethylaminobenzoic acid salt and the polyvalent metal salt adhering to the precipitate are completely removed. After this washing step, it may be dried and, if necessary, ground.

The polyvalent metal salt-coated pigment of Baladimethylaminobenzoic acid of the present invention obtained by drying has a Fourier transform infrared absorption (F
Analysis by T-IRI spectroscopy and observation by electron microscopy revealed that the pigment surface was uniformly coated with polyvalent metal salt of valadimethylaminobenzoic acid.

The effects of the polyvalent metal salt of baladimethylaminobenzoic acid coated pigment used in the present invention will be shown below using Examples. In the Examples, 1 part means part by weight, and % means % by weight.

The measure of sun protection effectiveness is the SPF value (Sun Pro
fection Factor) was used.

The SPF value is the minimum erythema generation energy Ea when 1 ml of cosmetic sample is uniformly applied to the backs of 20 panelists, and the minimum erythema production energy Ea when no cosmetic sample is applied at all. It was determined from the comparison with the group generation energy Ec.

SPF value=Ea/Ec In the measurement, five Toshiba F' L-20S E-30 lamps were connected to an M-IJMI type ultraviolet irradiation device for clothing manufactured by Toshiba Apparel Products Co., Ltd., and irradiation was performed from a distance of 15 cm. The irradiation energy was measured using an ultraviolet light intensity meter (UVIt-305/365) manufactured by Toshiba Optical Machinery Co., Ltd. (
In addition, the definition of SPF value is Federal Register
er 43. (166), 38206-38269
(1978) Statement Example 1 Sanryoku Soto Pressed Powder - Present Invention Comparative Example 12 "BarashimetinoblEnom Aluminum Benzoate 94.
0 -- -I -Coated talc (coating amount 25%) 12-ethylhexylparadimethylaminobenzoic acid-s
, ss ~AI titanium oxide - -6,58 I talc - 87.42 87.421 Red iron 0
．． 6 0.6 0.6 1 Yellow iron oxide 1.2 1.2 1.2 Black iron oxide 0.2 0.2 0.2 [Flow/f5':#) 2.02.02.OB+palmitic acid Isopropyl 1.8 1.8 1.81 Fragrance
0.2 0.2 0.2 A is mixed with a Henschel mixer, B is added, mixed, stirred and pulverized, then filled into a mold container and molded to form a product.

The sun protection effects and sensory test results (by 20 panelists) of the present composition and Comparative Examples 1 and 2 are as follows.

Present invention Comparative example 12 Sun protection effect 20 6.0 3.0 (SPF value) Spreading on skin 4.8 2.6 4.6 Lucent feeling
4.7 4.7 4.7 Makeup finish 4.8 3.2
2.8 Adhesion 4. j 3.2 2.7 Makeup fading 4.7 3.6 2.5 Water resistance 4.8 4.1 2.1 Oiliness 4.7 2.5 4.3 (Note) Listed in the table The numerical value shown is the evaluation score for the relevant effect of the test item. and very good 5
, 4 for good, 3 for average, 2 for bad, 1 for very poor
This is the average score of the 20 panelists in case a.

As described above, the composition of the present invention has cosmetic effects (spreading on the skin, lucent feeling, adhesion, makeup fading, makeup finish,
It also has excellent water resistance and oiliness.

Example 2 Sunscreen cream Foundation Shiron (Wl
o) Present invention Comparative example f-xf7! Iy acid 1.51°゛A "Norbitanesesquioleic acid ester 4.0 4
．． O■Liquid paraffin, 0 34.0 L lanolin 2.0 2.0 Purified water 3''''゛ 3''°Pa B1 Propylene glycol 4.0 4.01 Triethanolamine 0.2 0.2 Zinc aminobenzoate 10.0 -1-Coated fine particle titanium oxide (
Coating amount: 10%) C1 Particulate titanium oxide -10,0 1 Kaolin 5.0 5.0 1 Red iron oxide 0.3 0.3 1 Yellow iron oxide 1.0, 1.0 L Black iron oxide 0.05 0. 05 D Flavor 0.2 0.2 C is uniformly ground. A dissolved at 75° C. is added to B dissolved at 70° C. to emulsify it, C and D are added at 60° C., cooled to 30° C., and the product is filled into a container.

The results of a sensory test (by 20 panelists) of the sunscreen effect of the present composition and comparative examples are as follows.

Present invention Comparative example Sun protection effect (SPF value) 20.0? , 0' Spreading on the skin 4.6.4.2 Lucent feel 4.5 4.4 Makeup fading 4.4 3.2 Makeup finish 4.4 4.0 Water resistance 4.8 3. As shown in the figure, the present composition has a remarkable sun protection effect compared to the comparative example. , 10 A1 lanolin 2525 I and male oil 21.58 21.58 L isopropyl myristate ester 10 10 de 5
') f-yt'zinc benzoate 51-Coated fine particle titanium oxide' 1 (coverage rate 10%) Blya particle zinc oxide -5 1 Red No. 204 33 1 Red No. 223 0.4 0.4 L Orange No. 201 0.02 0.02 Dissolve A at about 80°C, add uniformly mixed B, mix with a roller, and pour into a mold to form a product.

The sun protection effect and sensory test results (by 20 panelists) of this composition are as follows.

Present invention Comparative example Sun protection effect 102 (SPF' value) Adhesion to skin 4.6 3.6 Lucent feel 4.2 3.6 Makeup finish 4.3 3.8 Unnatural feeling 4.6 3. 2. Makeup fading 4.6 2.8 Water resistance 4.8 4.2 As described above, compared to the comparative example, this composition has a remarkable sun protection effect, and has excellent water resistance and makeup fading resistance. Example 4 Cake foundation that prevents sunburn The present invention Comparative example 12 r'f5 i>/ftL-1E/0 lead benzoate 3
0.0 - -1- Coverage, 9 (coverage rate ″%) ■ Magnesium dimethylaminobenzoate 30.3
----1-Coating "A" (coverage rate '%) 1-paradimethylaminobenzoic acid aluminum 10--
I-W! Fine particle titanium oxide (coverage rate 9%) A I
! -3,0,03,0 titanium oxide 10.
0 10.0 10.01 Aluminum myristate treatment -10.0-1 Fine particle titanium oxide (coverage rate 2%) Mica - 30.3 35.3 1 Red iron oxide 1.0 1.0 1.0 Yellow iron oxide 3.0 3.0 3. OL black iron oxide 0.5 0.5 0.5 F! rllll/f571 :/ 10 10 1゜1 Squalane 2 2 2 B1 Sesquisorbicun 4 leate 2 2 21 Glycerin 1 1 1 12-Ethylhequinlparadimethylanoan M1 Froic acid-
-sL fragrance 0.2 0.2 0.2 A is mixed and stirred with a Henschel mixer, B is uniformly dissolved and mixed, then added to A, mixed and pulverized, and then filled into a mold container and molded. Product.

The sun protection effects and sensory test results (by 20 panelists) of the present composition and Comparative Examples 1 and 2 are as follows.

Present invention Comparative example 12 Sun protection effect 25.0? , 0 7.0 (SPF value) Extension to skin 4.5 3.8 3.9 Lucent lJ
4.3 4.2 4.1 Adhesion 4.8 3.2 3.
6 Makeup fading 4.7 2.7 2.8 Makeup finish 4.4 3.6 3.5 Water resistance 4.8
3.2 3.4 Oiliness 4.5 4.5 2.5 As described above, the present composition showed remarkable sun protection effect, water resistance, and resistance to makeup smearing compared to the comparative example. .

Example 5 Sunscreen lotion Invention Comparative Example 12 Aluminum paradimethylaminobenzoate coating 4.0
- - Particulate titanium oxide (coverage rate 10%) Particulate titanium oxide treated with zinc myristate -4,0- (
Coverage rate 2%) 2-ethylhexylparadimethylaminoamine 11tiM
-4,.

Denatured alcohol 16.0 16.0 16.0 Polyethylene hydrogenated castor oil (60E, 0.l O, 5o, s
o, s Propylene glycol 4.0 4.0 4.0
Fragrance 0.1 0.1 0.1 Pure water 75.4 S'5.4 75.4 Product appearance and sun protection effect of each composition in this example and the present invention
Comparative Example 12 Product Appearance Pigment is uniformly dispersed and aggregates Oil droplets are formed and do not easily settle from sunburn (anti-tanning effect) 4.Q 1.0 1.0 Oiliness
4.6 4.5 2.6 Water Resistance 4.7 4.1 3.2 As described above, the present composition has a remarkable sunscreen prevention effect and (decreased sensory properties) compared to the comparative example. Indicated.

1-

Claims (2)

[Claims] (1) The particle surface of the base pigment is expressed by the following formula (1) (where M is ^11 Mg+ Zn+ Ca or Zr
, n is the valence of M). Features sunscreen cosmetics. (2) The base pigment is talc, mica, kaolin, titanium oxide, zinc oxide, iron oxide, silicon dioxide, aluminum oxide, aluminum silicate, titanium mica, titanium mica treated with iron oxide, magnesium carbonate, calcium carbonate, barium sulfate, oxy The sunscreen cosmetic according to claim 1, which is a powder of inorganic pigments such as bismuth chloride and magnesium silicate, and synthetic resins such as nylon, polyethylene, Teflon, polypropylene, and methyl methacrylate.