JPH0329763B2 - - Google Patents

Abstract

PURPOSE:To obtain a hair cosmetic having excellent sebum absorbing ability, feeling in use and high reducing effects of oily feeling, containing an oil absorbing polymer having a large oil absorption amount of squalene prepared by polymerizing a vinyl monomer having a specific solubility parameter and making the polymer porous. CONSTITUTION:A hair cosmetic which is suitable for relieving an oily feeling of scalp and hair, has the above-mentioned effects and contains an oil absorbing polymer having >=1ml/g oil absorption amount of squalene prepared by polymerizing one or more vinyl monomers having 7-10 solubility parameter and making the polymer porous, 0.005-30mum average particle diameter and >=90wt.% particles with 0.005-30mum average particle diameter obtained by dissolving the monomer in a nonpolymerizable organic solvent which is a good solvent for the monomer but a poor solvent for the polymer formed from the monomer, polymerizing the monomer in a suspended or dispersed or emulsified state in water and by making the polymer porous by removing the solvent after the polymerization, as an active ingredient. The oil absorbing polymer is preferably crosslinked.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a hair cosmetic containing a porous vinyl-based oil-absorbing polymer that has excellent sebum absorption ability and a feeling of use, and is suitable for reducing the oily feel of the scalp and hair. [Prior art and its problems] Sebum gives shine and smoothness to the skin and hair when its secretion is moderate, but when it is secreted excessively, it causes glare and stickiness, and even damages the skin. When this happens, it causes makeup to come off, and when it comes to hair, it causes the hair to lose its volume, making it difficult to maintain the style. This excessively secreted sebum can be easily removed by washing, but the amount of sebum on the surface of the skin and hair returns to a certain level within a few hours for the skin and within a few days for the hair. Because of this, it must be cleaned frequently. For this reason, methods such as physiologically suppressing sebum secretion using medicinal agents and methods of physically absorbing excessively secreted sebum into powders and the like are being considered. However, no safe and effective medicinal agent has been found using the former method, and it has not yet been put to practical use. On the other hand, the method of physically absorbing sebum into powder etc. has few safety problems, but the sebum absorption ability and
There were problems with the effectiveness of the product, including the feeling of use. For example, JP-A-61-65807 discloses a method of controlling sebum using inorganic powders such as clay minerals and oxides. however,
In general, porous or layered inorganic materials have the disadvantage that their oil absorption ability is significantly reduced in the presence of sweat or dirt. JP-A-59-144710 discloses a method for reducing seborrhea using silanized silica gel. This method makes the surface of the inorganic powder hydrophobic and absorbs sebum into the interparticle spaces of aggregates of primary particles, and high oil absorption ability cannot be expected. U.S. Patent No. 4,489,058 uses a copolymer of stearyl methacrylate and styrene, which has high compatibility with sebum, to absorb sebum by swelling.
Disclosed are methods for inhibiting the appearance of acne.
Although this method is superior in that it absorbs sebum even in the presence of sweat and dirt, it has the disadvantage that the amount of absorption is still insufficient and that it does not feel good after absorbing sebum because it relies on simple swelling. . Furthermore, since particles with an average particle diameter of around 150 μm are used, they have the disadvantage that they are difficult to adhere to, especially when used for hair. [Means for solving the problems] In order to overcome these drawbacks, the present inventors have
As a result of extensive research, it was discovered that these drawbacks could be overcome by using a porous vinyl-based oil-absorbing polymer, and the present invention was completed. That is, in the present invention, squalene obtained by polymerizing and making porous one or more vinyl monomers having a solubility parameter of 7 to 10 has an oil absorption of 1.
The present invention provides a hair cosmetic characterized by containing an oil-absorbing polymer of ml/g or more. The oil-absorbing polymer according to the present invention has an average particle size of
It is preferable that the particle size is 0.005 to 30 μm, contains 90% by weight or more of particles with a particle size of 0.005 to 30 μm, and is further crosslinked. In addition, for polymerization and porosity formation, the monomer is dissolved in a non-polymerizable organic solvent, and this solution is further polymerized while being suspended, dispersed, or emulsified in water, and after the polymerization is completed, the organic solvent is removed. It is preferable to carry out by doing. Polymerization can be carried out by known methods such as suspension, dispersion, or emulsion polymerization. Suspension polymerization depends on particle size
Suitable for obtaining polymer particles of 10 μm or more, dispersion polymerization is suitable for obtaining polymer particles of 1 to 10 μm, and emulsion polymerization is suitable for obtaining polymer particles of 1 to 10 μm.
Suitable for obtaining polymer particles of 1 μm or less. The smaller the particles, the better in terms of feel and adhesion to the skin and hair, but on the other hand, emulsion polymerization requires the use of a relatively large amount of surfactant, which has the disadvantage of being difficult to remove. Porous formation can be performed by a known method in which monomers and non-polymerizable substances such as organic solvents, plasticizers, linear polymers, etc. are dissolved and co-existed during polymerization, and these non-polymerizable substances are removed at the end of polymerization. In particular, a monomer is dissolved in a non-polymerizable organic solvent that is a good solvent for the monomer and a poor solvent for the polymer produced from the monomer, and the resulting monomer solution is suspended, dispersed, or emulsified in water and polymerized. However, it is preferable to remove the organic solvent after the polymerization is completed. The monomers used in the present invention are vinyl monomers with a solubility parameter of 7 to 10, such as esters of methacrylic acid and higher alcohols having 8 to 24 carbon atoms, esters of acrylic acid and higher alcohols having 8 to 24 carbon atoms, Styrene or styrene derivatives with linear or branched hydrocarbon substituents having 1 to 12 carbon atoms, vinyl esters of saturated carboxylic acids having 8 to 20 carbon atoms, acrylic acid, methacrylic acid, 4 carbon atoms
-6 diolefins, etc. If the solubility parameter of the vinyl monomer is outside the range of 7 to 10, the compatibility with sebum will be poor and sufficient sebum absorption capacity will not be obtained. These monomers may be used alone or in combination of two or more. When a monomer with a long-chain alkyl group such as stearyl methacrylate is used alone, it has good compatibility with sebum, but the glass transition temperature Tg is low and the degree of porosity is low. The Tg of the polymer is 100℃ (373〓)
It is preferable to copolymerize with the monomers listed above. A particularly preferred example of a monomer is an ester of a higher alcohol having 8 to 24 carbon atoms, such as stearyl alcohol, and acrylic acid or methacrylic acid, which may be polymerized alone, but as a polymer at 100°C. (373〓) or more
Styrene with Tg or carbon number 1-12
When copolymerized with linear or branched alkyl-substituted styrene, the degree of porosity is further increased and the oil absorption capacity is increased (see Synthesis Examples 1 and 2). When copolymerizing, the weight ratio of acrylate ester or methacrylate ester and styrene or styrene derivative is preferably 30/70 or more (if the weight ratio is less than this, the polymer becomes hard and feels undesirable, etc.) ). The oil-absorbing polymer according to the present invention is preferably tactilely swollen by sebum but not dissolved, and is therefore preferably crosslinked. Crosslinking can be carried out by adding a polyfunctional monomer during polymerization, by post-crosslinking, by self-crosslinking, or the like. Examples of polyfunctional monomers include polyvinyl aromatic compounds such as divinylbenzene, polyvinyl heterocyclic compounds such as divinylpyridine, dimethacrylates such as ethylene glycol dimethacrylate and triethylene glycol dimethacrylate, ethylene glycol acrylate, and triethylene. Examples include diacrylates such as glycol acrylate. When using these crosslinking agents, the amount added is
It is preferable to suppress it to 50% by weight or less. When the proportion of the crosslinking agent exceeds 50% by weight, the swelling ability of the polymer is greatly suppressed. A particularly preferred amount of crosslinking agent is 0.01 to 50% by weight based on the total weight of the polymer. In the present invention, organic solvents used for forming porosity include aromatic compounds such as toluene and benzene, ester compounds such as ethyl acetate and butyl acetate, alcohols such as isoamyl alcohol and methylisobutyl carbinol, n-
Examples include saturated hydrocarbons such as hexane, n-octane, and n-dodecane, and halogenated solvents such as dichloroethane and trichloroethylene, but in particular, the solubility parameters used in the present invention are 7 to 10.
It is preferable to use a solvent that is a good solvent for the vinyl monomer and a poor solvent for the polymer produced from the monomer. Specifically, aliphatic hydrocarbons such as hexane, octane, and dodecane, and aromatic hydrocarbons such as toluene and benzene are preferred. Examples include hydrocarbons. The ratio of the monomer to these organic solvents is preferably 1/1 to 1/4 (weight ratio). Examples of the plasticizer include dioctyl phthalate and dibutyl adipate, and examples of the linear polymer include polystyrene and polyvinyl acetate. As the polymerization initiator, commonly used oil-soluble polymerization initiators can be used. For example, benzoyl peroxide, lauroyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-
Peroxide-based initiators such as dimethylvaleronitrile), orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, and azo-based initiators can be used. As the dispersion and emulsion stabilizers used in the present invention, commonly used ones can be used. For example, gelatin, starch, hydroxyethyl cellulose,
Water-soluble polymers such as carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alkyl ether, polyvinyl alcohol, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate,
Examples include poorly water-soluble inorganic salts such as magnesium carbonate and calcium phosphate, surfactants such as sodium lauryl sulfate, sodium cetyl sulfate, and sodium polyoxyethylene lauryl ether sulfate. Monomers and diluents (porosity-enhancing agents) such as those mentioned above
A monomer solution consisting of a polymerization initiator and a polymerization initiator is dispersed or suspended in water according to a known method in the presence of a dispersion and emulsion stabilizer as described above to form droplets, and a polymerization reaction is performed to form the desired porosity. polymers can be produced. At this time, the monomer solution may be dispersed or suspended by any commonly used method, such as various types of normal stirring, forced stirring using a homogenizer or ultrasonic irradiation, and the like. A desired particle size can be obtained by appropriately using these methods. Further, although the appropriate polymerization temperature varies depending on the polymerization initiator used, it is generally sufficient to carry out the polymerization within a temperature range of 20 to 95°C. It is obvious that the polymerization temperature must be lower than the boiling points of the monomer and diluent at normal pressure. The polymer particles obtained in this way are separated by filtration after polymerization, the aqueous phase is removed, and after water washing and/or solvent washing to replace the high boiling point diluent with a low boiling point solvent, spray drying and vacuum drying are performed. It can be isolated as a powder by conventional means such as. By polymerizing in this way, the monomer, diluent, and initiator exist as uniformly dissolved droplets before polymerization, but as the polymerization progresses, the diluent, which is a voracious solvent for the polymer, undergoes microphase separation from the polymer. , during vacuum drying, vaporizes (desorbs) and produces a porous polymer. The oil absorption of the resulting oil-absorbing polymer is measured using squalene in accordance with the method for measuring oil absorption of pigments specified in JIS K5101 (1978). That is, 1 g of powder is placed on a glass plate, squalene is added little by little and kneaded using a spatula, and the end point is when the powder becomes paste-like.
The amount of squalene required per gram (ml) is defined as the oil absorption amount. According to the JIS method, boiled linseed oil is used as the oil.
In this method, squalene is used because of its similarity to sebum. The oil absorption amount of the polymer related to the present invention is 1ml/g
More preferably, it is 2 ml/g or more. Further, the degree of porosity can be determined as the pore volume by measuring the pore distribution by mercury porosimetry. Details of the measurement method are described in, for example, "Powder Engineering Handbook" edited by the Powder Engineering Society, Nikkan Kogyo Shimbun (1988). Pore volume is 0.1ml/g or more, even 0.15
It is preferable that it is ml/g or more. The porous oil-absorbing polymer thus obtained can be used as a lotion hair cosmetic by dispersing it in water, lower alcohol, or a mixture thereof. The most preferable base for the hair cosmetic of the present invention is a water/ethanol mixed system, with a weight ratio of 99/1 to 20/80, more preferably
Used as 95/5 to 40/60. The preferred amount of oil-absorbing polymer in lotion hair cosmetics is
0.05-5% by weight, more preferably 0.1-2% by weight
It is. In the above lotion system, various water-soluble polymers can be used for dispersion stabilization or hair styling. Specifically, nonionic water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and hydroxyethyl cellulose, and anionic water-soluble polymers such as carboxymethyl cellulose, crosslinked polyacrylic acid (carboxy vinyl polymer), xanthan gum, and guar gum may be used. I can do it. The amount of these polymers is preferably
0.01-5% by weight, more preferably 0.05-1% by weight
It is. In addition to the above ingredients, the hair cosmetic of the present invention includes:
Other commonly included ingredients, such as polyhydric alcohols such as glycerin, dipropylene glycol, 1,3-butylene glycol, nonionic activators, cationic activators, anionic activators, dyes, preservatives, fragrances, oxidants drugs such as inhibitors, chelating agents, fungicides, vitamins, hormones, astringents,
Ultraviolet absorbers and the like can be added within a qualitative and quantitative range that does not impair the effects of the present invention. [Effects of the Invention] As mentioned above, the porous vinyl polymer contained in the hair cosmetic of the present invention exhibits a significantly higher amount of squalene absorption than conventional inorganic powders and water-insoluble polymers. A hair cosmetic containing the following shows a high effect of alleviating oiliness, as shown in the examples below. [Examples] The present invention will be explained in more detail below using synthesis examples and examples, but the present invention is not limited to these examples. Synthesis Example 1 40 g of stearyl methacrylate, 40 g of divinylbenzene, 80 g of toluene, 2 g of benzoyl peroxide, and 700 g of a 0.6% polyvinyl alcohol aqueous solution were placed in the separable flask of Synthesis Example 1 2, and dispersed for 5 minutes at 11,000 rpm using a homomixer, and then,
Polymerization was carried out at 80° C. for 8 hours under a nitrogen atmosphere while stirring at 300 rpm. After the polymerization was completed, it was filtered, washed with water and then with acetone, and after drying, 40 g of porous vinyl polymer was obtained (average particle size: 6.7 μm). This polymer has pores of 347 Å or less on the particle surface, as determined by pore distribution measurement using mercury porosimetry.
Its pore volume was 0.151 ml/g. Synthesis Example 2 Put 20 g of stearyl methacrylate, 20 g of styrene, 40 g of divinylbenzene, 30 g of toluene, 90 g of n-dodecane, 0.8 g of benzoyl peroxide, and 470 g of 3.3% sodium dodecyl sulfate aqueous solution into the separable flask from 2, and stir at 300 rpm. ,
Polymerization was carried out at 65° C. for 9 hours under a nitrogen atmosphere. After the polymerization was completed, 50 g of a porous vinyl polymer was obtained according to Synthesis Example 1 (average particle size: 2.0 μm). This polymer has pores of 725 Å or less on the particle surface, as determined by pore distribution measurement using mercury porosimetry.
Its pore volume was 0.299ml/g. Synthesis Example 3 Into the separable flask from Step 2, add 17 g of stearyl methacrylate, 17 g of divinylbenzene, 34 g of toluene, 1 g of potassium persulfate, and 1.0% polyoxyethylene (35 moles of ethylene oxide added).
Add 530g of nonyl phenyl ether aqueous solution,
Polymerization was carried out at 75° C. for 8 hours under nitrogen atmosphere while stirring at 300 rpm. After polymerization, 100-150mm
Topping was performed with Hg for 2 to 3 hours to obtain a water-suspended porous vinyl polymer (average particle size <
0.7μm). Synthesis Examples 4 and 5 Vinyl polymers were obtained in the same manner as in Synthesis Example 1 except that the amount of toluene was changed to 160 g (Synthesis Example 4) and 0 g (Synthesis Example 5). The polymer obtained in Synthesis Example 5 is a comparative product. The oil absorption amount of the oil-absorbing polymers produced in Synthesis Examples 1 to 5 above was measured by a method according to the JIS K 5101 method described above. In addition, as a comparison, polymer No. 14 of Example 1 (t-butyl styrene 65%, stearyl methacrylate 35%
Weight %, divinylbenzene as crosslinker 0.0125
The oil absorption amount was measured in the same manner using (% by weight). The results are shown in Table 1.

[Table] Example 1 A paste hair cosmetic having the following composition was prepared. Porous vinyl polymer obtained according to Synthesis Example 1 15 wt% Carboxymethyl cellulose 0.5 Ethyl alcohol 30 Perfume 0.1 Make up to 100% with purified water. As a comparative product, a cosmetic was prepared in which the polymer of Synthesis Example 1 was replaced with Polymer No. 14 of US Pat. No. 4,489,058, talc, and kaolin. Each hair cosmetic was applied to the subject's cheeks, peeled off after 1 hour, and the amount of absorbed sebum was determined gravimetrically. The results are shown in Table 2.

[Table] As is clear from Table 2, the product of the present invention exhibited higher sebum absorption ability than the comparative product. Example 2 A hair cosmetic having the following composition was prepared. Water-insoluble porous vinyl polymer obtained according to Synthesis Example 2 0.3 wt% Carboxyvinyl polymer (Carbopol 941,
Gutdoritsuchi) 0.04 L-menthol 0.05wt% Fragrance 0.2 Ethyl alcohol 48 Make 100% with purified water. This hair cosmetic was applied to one side of the heads of six subjects, and a hair cosmetic containing no polymer (comparative product) was applied to the other side. After 1 day, 2 days, and 3 days, the difference in oiliness between the left and right sides was sensory evaluated using a monitor. The results are shown in Table 3.

[Table] Example 3 A hair conditioner having the following composition was prepared. Porous vinyl polymer dispersion corresponding to Synthesis Example 3 (as solid content) 1.0wt% Stearyltrimethylammonium chloride
1.5 Setanol 2.3 Propylene Glycol 5.0 Methylparaben 0.2 Hydroxyethylcellulose 0.8 Blue No. 1 Appropriate amount Fragrance Appropriate amount Purified water Balance amount This hair cosmetic was applied to one side of the heads of five subjects, and a comparison product without polymer was applied to the other side. After application and rinsing, the oiliness over time was evaluated according to Example 2. The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1. Contains an oil-absorbing polymer in which the oil absorption amount of squalene obtained by polymerizing and making porous one or more vinyl monomers having a solubility parameter of 7 to 10 is 1 ml/g or more. A hair cosmetic characterized by: 2. The hair cosmetic according to claim 1, wherein the oil-absorbing polymer has an average particle size of 0.005 to 30 μm and contains 90% by weight or more of particles with a particle size of 0.005 to 30 μm. 3 The oil-absorbing polymer has a solubility parameter of 7 to 10
A vinyl monomer is dissolved in a non-polymerizable organic solvent that is a good solvent for the monomer and a poor solvent for the polymer produced from the monomer, and suspended in water.
Claims 1 or 2 are polymerized in a dispersed or emulsified state and made porous by removing the organic solvent after the polymerization is completed.
Hair cosmetics as described in section. 4. The hair cosmetic according to any one of claims 1 to 3, wherein the oil-absorbing polymer is crosslinked. 5. Hair according to any one of claims 1 to 4, wherein the vinyl monomer is selected from esters of higher alcohols having 8 to 24 carbon atoms and acrylic acid or methacrylic acid, and styrene. Cosmetics.