JP2794033B2 - Cosmetics - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a cosmetic comprising a high-molecular-weight ultraviolet absorber in which an ultraviolet-absorbing polymer is adsorbed on the surface of a pigment, and more particularly to a pigment. By containing a high-molecular polymer that is a polycondensate of aminobenzoic acid and its derivatives adsorbed on, while maintaining the sunburn preventing effect derived from the ultraviolet absorption effect of the original aminobenzoic acid, also, An object of the present invention is to provide a cosmetic that has excellent stability and an excellent cosmetic effect.

[Problems to be Solved by the Prior Art and the Invention] Usually, sunburn is acute dermatitis that occurs when ultraviolet rays act out of the physiologically acceptable range of the skin in sunlight, and erythema ( Sunburn) and blackening (Suntan) are known. Generally, depending on the intensity and amount of ultraviolet rays received by the skin, the intensity of expression and the subsequent course differ,
First, edema due to hyperemia and subsequent swelling in the skin, and erythema (sunburn) with blisters occur. A few days later, the inflammation subsides, the erythema disappears, melanin pigments are deposited in the skin, and the skin shifts to black (santan).

Depending on the size of the ultraviolet light, the ultraviolet light has a short wavelength ultraviolet region (UV-C) of 280 nm or less, a medium wavelength ultraviolet region (UV-B) of 280 to 320 nm, and a long wavelength ultraviolet region (UV-C) of 320 to 400 nm.
Classified as A), but is usually absorbed by the ozone layer, atmosphere, etc.
UV light below 290 nm does not reach the surface, so 290-400n
m-ultraviolet radiation (UV-B and UV-A) is of biological significance, of which 290-320 nm ultraviolet radiation (UV-B) is mainly associated with acute erythema action (sunburn) and It is called ultraviolet rays, and ultraviolet rays of 320-400nm (UV-A)
It is called black region ultraviolet because it promotes blackening (suntan). Therefore, as an ultraviolet absorber, at least 290-320nm
It is essential to have an ultraviolet filter effect, and it is also required to absorb ultraviolet rays of 320 to 400 nm as required.

As is well known, aminobenzoic acid has excellent ultraviolet absorption ability,
It has the characteristic of having an absorption maximum wavelength near 290 nm.
This substance has been derivatized in many ways, and has been blended in various cosmetics for the purpose of preventing skin inflammation and sunburn due to sunlight, and stabilizing the content of components such as pigments and fragrances.

However, among these many derivatives, when incorporated in cosmetics in a large amount, there are substances that are questionable in terms of safety, and many have the problem of being unstable to light and causing coloration, etc. It has become possible to obtain an ultraviolet absorber excellent in stability and safety by polymerizing.
However, high-polymer UV absorbers have the problem that they are rough to the touch, and that the dispersibility deteriorates due to polymerization, resulting in insufficient UV absorption. Has become.

[Means for Solving the Problems] In view of such a current situation, the present inventor has conducted intensive studies in order to obtain an ultraviolet absorber that can solve the above-mentioned problems, and as a result, it has been found that pigments are one type of ultraviolet absorber. The present inventors have found that a pigment-adsorbed high-molecular-weight ultraviolet absorber obtained by polymerizing a certain aminobenzoic acid and a derivative thereof satisfies the above-mentioned conditions to be solved, and have completed the present invention based on such findings.

That is, in the present invention, the following general formulas (I) to
One or two or more monomers selected from the group consisting of (IV) are homopolymerized or copolymerized (the degree of polymerization is 15
To 7000) containing a pigment-adsorbed high-molecular-weight ultraviolet absorber to which a pigment is adsorbed.

Hereinafter, the present invention will be described in detail.

The pigment-adsorbed high molecular weight ultraviolet absorber applied to the present invention comprises, as monomers, p-aminobenzoic acid and its derivatives to m-aminobenzoic acid and its derivatives represented by the above general formulas (I) to (IV). And a polymer obtained by homopolymerizing or copolymerizing the same on the surface of the pigment, and specifically includes 4-aminobenzoic acid, 2-methoxy-4-aminobenzoic acid, and 2-acetoxy-4. -Aminobenzoic acid, 2-acetoamino-4-aminobenzoic acid, 2-dimethylamino-4-aminobenzoic acid, 3-acetoamino-4-aminobenzoic acid, 3-methyl-4-aminobenzoic acid, 3-dimethylamino -4-aminobenzoic acid, 4-methyl-3-aminobenzoic acid, 3-aminobenzoic acid, 5-acetoamino-3-aminobenzoic acid, 5-dimethylamino-3-amino Polymer or copolymer formed from Ikiko acid.

The degree of polymerization of these polymers or copolymers is 15-70
It is preferably in the range of any number of 00, with any number of caps of 50-3000 being more preferred. If the degree of polymerization is less than 15, even if an insoluble solvent is added, the polymer will not be insolubilized and an adsorbed pigment cannot be obtained.If the degree of polymerization is greater than 7000, insolubilization such as gelation will occur at the stage of polymerization polymerization. Is caused, resulting in a mere mixture of polymer and pigment rather than being adsorbed on the pigment surface, which is not preferable.

Regarding the characteristics of these polymers or copolymers, although slight variations are seen depending on the type and degree of polymerization of the monomers used, they are generally found in the examples of poly-4-aminobenzoic acid. Like, benzene, toluene,
THF, DMF, water, methanol, ethanol, dioxane,
It is insoluble or sparingly soluble in solvents and oils such as triglyceride and squalane at room temperature and 80 ° C., and has a yellowish white appearance. It does not dissolve when heated and has the property of decomposing at 300 ° C or higher.

The pigment is not particularly limited, and the support of the present invention is specifically applicable to any pigment such as a soluble azo pigment, an insoluble azo pigment, a polycyclic pigment, a carbon black inorganic pigment, an extender pigment, and a white pigment. It is valid. More specifically, as soluble azo pigments, Lake Red C, Brilliant Carmine 6B, Permanent Red F5R, Bordeaux 10B, Lake Red R, Lake Red R, Orange Lake, Brilliant Carmine 3B, Lisor Red, Lisor Rubin GX , Brilliant Scarlet G, Helio Bordeaux BL, etc., and insoluble azo pigments include benzidine yellow, benzidine orange, naphthol red, pyrazolone orange, pyrazolone red, sulfamide azo yellow, permanent orange and the like, and polycyclic ones. Pigments include phthalocyanine buzo yellow, permanent orange and the like, and polycyclic pigments include phthalocyanine blue, phthalocyanine green, fast sky blue, quinacridone red, Quinacridone magenta, dioxazine violet, isoindolinone Erogu Lee Nish,
Isoindolinone yellow redish, perinone orange, perylene-based pigment, thioindigo-based pigment, herringdon, anthraquinone-based pigment, and inorganic pigments include titanium dioxide, red iron oxide, chromium hydroxide, leadtan, ultramarine, navy blue, and cobalt hydroxide. , Graphite, chromium oxide, iron oxide yellow, iron oxide black, etc., and as extender pigments, fish scale foil, bismuth titanium oxychloride mica foil, pearl pigment, barite powder, precipitated barium sulfate, barium carbonate, carbonated coal Powder, precipitated calcium carbonate, gypsum, asbestos, clay, mica, silica powder, finely divided silicic acid, diatomaceous earth, talc, basic magnesium carbonate, alumina white, gloss white, satin white, and the like. , Lead white, basic lead sulfate, zinc sulfate, antimony oxide and the like.

The ratio of these polymers or copolymers and pigments is
1: 9 to 9: 1, preferably 3: 7 to 1: 1. When the amount of the pigment is larger than 1: 9, the ultraviolet absorbing ability is reduced, and when the amount of the pigment is smaller than 9: 1, the dispersibility is deteriorated, and the usability is deteriorated. In addition, the method for obtaining these polymers or copolymers may be in accordance with a usual self-condensation reaction, that is, p-aminobenzoic acid and its derivatives to m-aminobenzoic acid and its derivatives as monomers, For example, pyridine, DMF, dissolved in DMSO, etc., lithium bromide, lithium iodide and other solubilizers and allyl sulfonic acid chloride, triphenyl phosphite and other condensing agents are added,
It is heated and reacted and condensed on an oil bath.

In order to explain the production method in more detail, a polymer of talc-adsorbed 4-aminobenzoic acid and a copolymer of talc-adsorbed 4-aminobenzoic acid and 3-aminobenzoic acid are also shown as typical examples according to the present invention. The production example of is shown below.

Production Example 1 4-Aminobenzoic acid (0.5 mol was dissolved in 1 liter of pyridine and refluxed on an oil bath. 70 g of talc was added thereto, stirred, and lithium bromide (0.2 mol) and allyl sulfone were further added. One liter of pyridine in which acid chloride (1 mol) was dissolved was added dropwise, and the mixture was stirred for 4 hours, poured into a large amount of methanol to precipitate, filtered, washed with water, dried, and dried.
4 g (yield 93.4%) of a polymer of talc-adsorbed 4-aminobenzoic acid (polymerization degree and in the range of 1800 to 2200) (hereinafter, in the case of a polymer, poly is attached like poly-4-aminobenzoic acid) Call.) See FIG. 1 for UV absorption.

 See Fig. 2 for the absorption of Seto Line.

Production Example 2 4-aminobenzoic acid (0.25 mol) and 3-aminobenzoic acid (0.25 mol) were dissolved in 1 liter of pyridine and refluxed on an oil bath. Add 70g of talc to this, stir,
Further, 1 liter of pyridine in which lithium bromide (0.2 mol) and allylsulfonic acid chloride (1 mol) were dissolved was added dropwise. After the dropwise addition, the mixture was stirred for 4 hours, poured into a large amount of methanol to precipitate, filtered, washed with water and dried, and 133 g (yield 92.0%)
Of talc-adsorbed 4-aminobenzoic acid and 3-aminobenzoic acid (the degree of polymerization was in the range of about 800 to 1600).

Since the product of the present invention is a cosmetic containing a pigment-adsorbed high molecular weight ultraviolet absorber, it may contain one type of polymer or copolymer-adsorbed pigment, or may contain two or more types of polymer or copolymer-adsorbed pigment. May be.

The product of the present invention is added to cosmetics in a total amount of 0.00
The content is 1 to 50% by weight, preferably 1 to 30% by weight. If it is less than 0.001%, the ultraviolet absorbing power is not sufficient,
If the content exceeds% by weight, the feeling of use will deteriorate. In the cosmetic of the present invention, examples of cosmetic ingredients other than the pigment having a high molecular weight ultraviolet absorber adsorbed thereon include polyhydric alcohols such as glycerin, squalane, oils such as fatty acids, and the like.
Other active agents, various active ingredients, preservatives, antioxidants and the like are used.

There are a wide variety of cosmetics of the present invention provided in this manner, and specifically, makeup cosmetics such as foundation, undermakeup, lipstick, and basic cosmetics such as cream and lotion, and sunscreen cosmetics And the like.

[Feeling of use] As typical examples, poly-4-aminobenzoic acid and talc-adsorbed poly-4-aminobenzoic acid were applied with a puff, and then sensory evaluation was performed by 10 panelists. The results are shown in Table 1.

Sample (1) Talc-adsorbed poly-4-aminobenzoic acid (2) Poly-4-aminobenzoic acid As described above, it was found that the talc-adsorbed poly-4-aminobenzoic acid had a better feeling in use.

 Examples will be described below. The mixing ratio is% by weight.

Example 1. Powder foundation (A) Hydrophobized talc 17.3 Hydrophobized sericite 30 Nylon powder 10 Talc-adsorbed poly-4-aminobenzoic acid 10 obtained in Production Example 10 Titanium oxide 10 Iron oxide 2 Preservative 0.2 (B) Silicon oil 8 Glycerin tri-2-ethylhexylate 4 Solid paraffin 0.5 Carnauba wax 1.5 Isopropyl myristate 4 Squalane 2 (C) Compounding flavor 0.5 (Method) (A) was mixed for 15 minutes with a ribbon mixer. Thereafter, the pulverized material is transferred to a Henschel mixer, and the separately dissolved (B) is added thereto, followed by stirring for 8 minutes. When the temperature reaches 40 ° C., add (C) and press through a blower shifter.

Example 2. Liquid foundation (A) Squalane 10 Vaseline 5 Stearyl alcohol 3 Isopropyl myristate 1 Stearic acid 2 Glycerin monooleate 0.5 POE (25) Monostearate 1.5 (B) Iron oxide 2.2 Talc adsorption obtained in Production Example 2 Copolymer of 4-aminobenzoic acid and 3-aminobenzoic acid 16 Sericite 2 (C) Propylene glycol 5 Glycerin 5 Potassium hydroxide 0.2 Preservative 0.2 Purified water 46.1 (D) Compound flavor 0.3 (Method) (B) The material pulverized by the pulverizer is uniformly dispersed in (A) heated to 80 ° C., and (C) heated to 80 ° C. is added to the dispersion and emulsified. Cool to ℃, add (D) and fill container.

Example 3 Oily stick foundation Talc adsorbed poly-3-acetoamino-4-aminobenzoic acid 10 (produced in the same manner as in Production Example 1) Talc 18 palmityl-2-ethylhexinate 4 Silicon oil 16 Squalane 22 Microcrystalline wax 4.5 Solid paraffin 7 Ozokerite 2 Activator 3 Titanium oxide 5 Iron oxide 8 (B) Compounded flavor 0.5 (Method) (A) was heated to 80 ° C., uniformly dispersed and dissolved, vacuumed and defoamed. Then, with slow stirring (B)
Was added, and when the mixture became uniform, it was directly filled into a container and solidified.

Example 4. Lipstick (A) Talc-adsorbed poly-2-astoxy-4-aminobenzoic acid 12 (produced in the same manner as in Production Example 1) Squalane 15 Candelilla wax 7 Liquid lanolin 28 Diisostearyl malate 10 Dibutylhydroxyl Toluene 0.1 Isopropyl myristate 24 Sorbitan monostearate 0.8 Tar dye 2.5 Titanium oxide 0.5 (B) Compounded fragrance 0.2 (Method) Performed in the same manner as in Example 3.

Example 5 Cream (A) Talc-adsorbed poly-4-methyl-3-aminobenzoic acid 7 (manufactured in the same manner as in Production Example 1) Stearic acid 8 Gaylow 4 Cetanol 4 Lanolin 2 Squalane 7 Olive oil 2 Activator 6 Propylene glycol 5 butylparaben 0.1 methylparaben 0.1 fragrance 0.2 purified water 54.5 Example 6. Lotion talc adsorbed poly-3-aminobenzoic acid 7 (produced in the same manner as in Production Example 1) ethanol 7 propylene glycol 5 activator 5 citric acid 0.2 citric Sodium acid salt 0.1 Methyl paraben 0.1 Fragrance 0.2 Purified water 75.4

[Brief description of the drawings]

FIG. 1 is an ultraviolet absorption spectrum of poly-4-aminobenzoic acid and poly-4-aminobenzoic acid adsorbed on kaolin. FIG. 2 is an infrared absorption spectrum of poly-4-aminobenzoic acid.

Claims (2)

(57) [Claims] Claims: 1. A method in which one or two or more monomers selected from the group consisting of the following general formulas (I) to (IV) are homopolymerized or copolymerized on a pigment surface (having a polymerization degree of 15 to 7000). A cosmetic comprising a pigment-adsorbed high-molecular-weight ultraviolet absorber to which (arbitrary number) has been adsorbed. 2. Pigment surfaces obtained by homopolymerizing or copolymerizing one or two or more monomers selected from the group consisting of the general formulas (I) to (IV) (polymerization degree: 15 to 70).
00 arbitrary number), the content ratio of the pigment-adsorbed high-molecular-weight ultraviolet absorber which is adsorbed is 0.001 to 5% in the total cosmetics.
The cosmetic according to claim 1, which is 0% by weight.