JPS62198609A - Particle for compounding to cosmetic or quasi-drug - Google Patents

Abstract

PURPOSE:To provide spherical particle of a polymer having amino group at side chain and modified by ionic adsorption with a compound having anionic group and useful for coloring, imparting of ultraviolet absorptivity, prevention of chapped skin, etc., as an additive for cosmetic, soap, shampoo, etc. CONSTITUTION:The objective spherical polymer particle has an average particle diameter of 0.1-100mum (preferably 0.2-70mum), contains amino group at side chain and modified by ionic adsorption with a compound having anionic group (e.g. sulfone group, carboxyl group, phenolic OH group, etc.) such as acidic dye, ultraviolet absorber, L-ascorbic acid, colorant for food, colorant for cosmetic, colorant for quasi-drug, etc. The polymer is chitosan or a copolymer containing acrylic monomer or aromatic vinyl monomer having amino group. A cosmetic having high bleed-out resistance can be produced by the use of the polymer particle. The particle exhibits a function of slow-releasing agent by contacting with an aqueous solution of NaCl, etc.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The particles of the present invention can be used in head cosmetics, hair washing cosmetics, lotions, cream emulsions, packs, foundations, whitening powders, and lipsticks. Cosmetics such as layered cheek cosmetics, nail cosmetics, perfumes, bath cosmetics, cosmetic oils, face washes, soaps, toothpastes, shampoos, conditioners, etc.
Lotion, cream, emulsion, hand cream, cosmetic oil,
It is added to quasi-drugs such as shaving agents, sunscreens, masks, medicated soaps, and medicated toothpastes, and is used for purposes such as coloring, imparting UV absorption ability, and preventing skin irritation.

[Conventional technology]

In the past, dyes and ultraviolet absorbers were directly incorporated into cosmetics and quasi-drugs.

[Problem that the invention seeks to solve]

With conventional cosmetics and quasi-drugs that directly contain dyes and UV absorbers, the human body comes into direct contact with the dyes and UV absorbers, leading to problems such as skin staining and transdermal absorption. there were.

In the present invention, the above-mentioned problems have been solved by ionically adsorbing dyes, ultraviolet absorbers, etc. onto the particles to make them difficult to bleed out to water or organic solvents.

(Means for solving problems) The present invention is configured as follows.

``Cosmetic or pharmaceutical products, which are spherical particles of a polymer having a 7-mino group in the side chain, modified by ion adsorption with a compound having an anionic group, and having an average particle diameter of 0.1 to 100 μm. Particles for blending with non-Japanese products.'' The polymer having an amino group in the side chain that constitutes the present invention is not a polymer that contains an amino group on the polymer main chain, that is, a nitrogen atom, but a polymer that contains an amino group on the polymer main chain, that is, a nitrogen atom in the polymer main chain. Refers to polymers with amino groups either directly attached or attached to carbons on side chains.

By having an amino group in the side chain, the mobility of the amino group increases, and ion adsorption modification by a compound having an anionic group becomes extremely easy.

In achieving the present invention, the type of amino group may be any of primary to quaternary amino groups.

Examples of polymers that can be preferably used in the present invention include chitosans after insolubilization treatment, (meth)acrylates containing amino groups such as N-dimethylaminoethyl (meth)acrylate, and (meth)acrylic acid esters. copolymers with mono- or polyfunctional monomers copolymerizable with them, such as (meth)acrylonitrile and aromatic vinyl, (co)polymers of amino group-substituted aromatic vinyl monomers, (co)polymers of vinylpyridines These include polymers and polyamino acids. Generally, it is preferably used when the polymer has a monomer having an amino group that accounts for 5 mol% or more of the monomers.

The method for producing spherical particles having an average particle diameter of 0.1 to 100 μm from the above polymer is not particularly limited, but generally the following method can be used.

(1) A method in which a polymer solution is stirred into a non-solvent system or a coagulation bath system, and the polymer is precipitated as fine spherical particles. The more dilute the polymer solution is used, the finer the particles are generally obtained.

(2) A method of emulsion polymerization or suspension polymerization of monomers.

(3) A precipitation polymerization method in which the polymerization of Nanatsuma is started in a solution state and the resulting polymer is precipitated from the solution.

The average particle diameter preferably used in the present invention is 0°1 to 10
0 μm, and in particular, those in the range of 0.2 to 70 μm are preferably used. If the average particle size is smaller than this, it will be difficult to collect the particles by sieving, etc. If the average particle size is larger than this, the anionic property used in the present invention is undesirable because it will give a strong foreign body feeling when added to cosmetics or quasi-drugs. Compounds having groups include one or more sulfone groups, carboxyl groups, phenolic OH groups, etc. in the molecule.

Particularly, compounds preferably used in the present invention are listed as follows:
Among acid dyes, red No. 104, No. 106, blue No. 1,
Food-added dyes, cosmetic-added dyes, or quasi-drug-added dyes such as Green No. 204 are preferred. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, and benzoic acid-based compounds, and particularly preferred are 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2,2-dihydroxy-4,4'- It is a compound having a sulfonic group such as dimethoxybenzophenone-5-sulfonic acid. Compounds preferably used in the present invention include L-ascorbic acid and its monoesters of phosphoric acid and sulfuric acid. Mono-, silicic acid esters, and mono-sulfuric esters of alcohols and glycols are also preferably used.

The method of ion adsorption of the above-mentioned compound having an anionic group onto the above-mentioned spherical particles of the polymer having an amino group in the side chain is not particularly limited, but the following method is generally used.

(1) A compound having an anionic group is added to a water or organic dispersion medium slurry of spherical particles, dissolved, and heat-treated as necessary.

(2) When the compound having an anionic group is a salt with an alkali metal, etc., an acidic compound such as sulfuric acid, phosphoric acid, or acetic acid is added to the slurry, and if necessary, heat treatment is performed.

The amount of ion adsorption of a compound having an anionic group varies depending on the type of polymer having an amino group in the side chain, the type of compound having an anionic group, the purpose of adsorption, etc., but is generally 1% or more.

Before, at the same time, or after the adsorption treatment of the above-mentioned compound having an anionic group, the particles of the polymer having an amino group in the side chain used in the present invention are adsorbed onto the surface of the polymer particles, and the particles after drying are prepared. It can prevent blocking, give a feeling of slippage, improve dispersibility, etc.

Examples of adsorbed fine particles used for this purpose include silica sol, alumina sol, fine particles TiO2, TiO2, 5n02, acidic calcium phosphate, barium sulfate, carbon black, and pigments. D is particularly preferably adsorbed when there is a relationship of D≧5d, where d is the average particle diameter of the fine particles adsorbed thereon.

As a method for adsorbing the above-mentioned fine particles to spherical particles of a polymer having an amino group in a side chain, the following method can generally be used.

(1) After the adsorption fine particles are well dispersed in advance, they are added to a slurry of spherical particles, stirred, and heated if necessary.

<2) After adding the fine particles, the slurry is made acidic or alkaline, and heated if necessary.

Although the amount of fine particles adsorbed on the spherical particles is not particularly limited, generally an amount of 10% or less can prevent blocking, impart a feeling of slippage, and improve dispersibility. However, especially when the purpose is to impart opacity or color, 2
In some cases, 0% or more is adsorbed.

〔Example〕

Example 1 A dilute solution of chitosan (Kurita Industries, Press Aid 101) in hydrochloric acid and a dilute solution of caustic soda were brought into contact with each other under high speed stirring,
Chitosan spherical particles with an average particle diameter of 5 μm were obtained. Approximately 40% of the amino groups of the particles were crosslinked with glutaraldehyde to make them insoluble, and then dyed under the following conditions.

Dye: Red No. 104 in 20% by weight bath
Ratio: 1:10 Sulfuric acid: pH 3 Temperature x time = 95°C x 1 hr The dyed particles were suctioned and filtered, thoroughly washed and air-dried. The filtrate was almost colorless, and most of the dye used was adsorbed to the particles.

Colored particles after air drying are mixed with hot water, ethyl alcohol, parasulfur,
There was almost no discoloration in castor oil.

Example 2 A UV absorber was adsorbed onto the insolubilized chitosan spherical particles obtained in Example 1 under the following conditions.

Ultraviolet absorber: 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid to 5% bath Ratio: 1:10 Phosphoric acid: pH3 Temperature x time = 95°C x 1hr Examples of particles after adsorption Air-dried particles were obtained in the same manner as in 1.

Almost no ultraviolet absorber used was detected in the adsorption filtrate. In addition, the ultraviolet absorption spectrum measured by molding air-dried particles into kBr tablets was approximately 290 nm and 330 nm.
An absorption peak was observed.

Example 3 To a dilute Salt V solution of chitosan (the same as that used in Example 1), silica sol (Yasan Kagaku, Snowtex N) was added in a solid content of 5% by weight based on chitosan, and as in Example 1, caustic soda was added. This was brought into contact with a dilute solution under high-speed stirring to obtain chitosan spherical particles with an average particle diameter of 1 μm. The surface of the particles was covered with silica sol.

After insolubilization treatment was carried out in the same manner as in Example 1, staining was carried out under the following conditions.

Dye: Blue No. 1 to 12% by weight of particles Bath ratio: 1:10 Phosphoric acid: pH 2.5 parts x Time: 98°C x 1 hr The dyed filtrate is almost colorless, and the particles after air drying are washed with hot water. ,
The color hardly faded against ethyl alcohol and castor oil.

Example 4 During dyeing in Example 1, silica sol (Snowtex N) was added in a solid content of 2% by weight based on particles, and dyeing was carried out in the same manner (however, only the dye was 5% by weight based on particles).

The air-dried particles after dyeing were extremely easy to crush and had a noticeable smooth feel.

Example 5 0.9 part of lauroyl peroxide and 1.2 parts of sodium lauryl sulfate were added to 7,100 parts of raw materials containing 90 mol% of styrene and 10 mol% of N-dimethylaminobutyl methacrylate.
1 part was dissolved and suspended in 250 parts of water. Then, after equalization treatment with a homomixer, 75°C under a nitrogen seal.
The temperature was raised to , and the mixture was allowed to react for 15 hours with gentle stirring.
Spherical particles with an average particle diameter of approximately 10 μm were obtained.

The particles showed similar dyeing and adsorption results when subjected to dyeing and UV absorber adsorption treatment under the same conditions as shown in Example 2.4.

Example 6 The spherical particles obtained in Example 5 were allowed to adsorb [-ascorbic acid] under the following conditions.

[-ascorbine 1!2 two pair particles 10 weight ffi% bath
Ratio: 1:10 pH: 4.5 Temperature x Time: 80'C It was adsorbed.

〔Effect of the invention〕

According to the present invention, spherical particles for blending in cosmetics and quasi-drugs with high bleed-out resistance, in which acid dyes, ultraviolet absorbers, etc. are ionically bonded, have been obtained.

Cosmetics and quasi-drugs containing these particles have characteristics such as beautiful hue, non-staining properties on the skin, and non-transdermal absorbability.

Furthermore, it was found that when the particles of the present invention come into contact with an aqueous solution of dodecylbenzenesulfonic acid or sodium chloride, a portion of the adsorbed dye, etc. is released from the particles, and functions as a sustained release agent.

Claims (5)

[Claims] (1) Cosmetics or pharmaceuticals, characterized in that they are spherical particles of a polymer having an amino group in the side chain, are modified by ion adsorption with a compound having an anionic group, and have an average particle diameter of 0.1 to 100 μm. Particles for blending external products. (2) The spherical particles of a polymer having an amino group in the side chain are chitosan or particles of a copolymer containing an acrylic or aromatic vinyl monomer having an amino group. Particles for blending into cosmetics or quasi-drugs as described in section 1). (3) The particles for blending into cosmetics or quasi-drugs according to claim (1), wherein the anionic group is selected from a sulfonic group, a carboxyl group, and a phenolic OH group. (4) The particles for blending into cosmetics or quasi-drugs according to claim (1), wherein the compound having an anionic group is selected from acid dyes, ultraviolet absorbers, and L-ascorbic acids. (5) The cosmetic or non-medicinal product according to claim (1), wherein the compound having an anionic group is selected from food additive dyes, cosmetic additive dyes, and quasi-drug additive dyes. Particles for product formulation.