JP2001213727A - Spherical resin particle and cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spherical resin particle having a higher water-adsorbing and oil-absorbing capacity than that of a conventional resin particle, this allows the spherical resin particle to act as a suitable component of a cosmetic, yielding such a high performed solid powder cosmetic that no conventional cosmetic can offer. SOLUTION: The solid powder cosmetic containing comparatively a small amount of oil, presents a smooth and creamy feeling and a refreshed feeling when it is applied with water; containing comparatively a large amount of oil, presents a moistening feeling of use which no conventional cosmetics have, extensibility and improvement of takeup, that is a caking and the like affecting badly. The oily solid powder cosmetic containing a large amount of oil, presents good adhesion to the skin and a refreshed stick-free feeling of use. The spherical resin particle has 2-50 μm of an average diameter, a water-absorbing capacity of 200-500 ml/100 g and oil-absorbing capacity, and cavities in its inside or on the surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to spherical resin particles and cosmetics using the same.

[0002]

2. Description of the Related Art Conventionally, many powders have been blended in cosmetics for the purpose of improving usability. Among them, a large number of inorganic powders such as talc, sericite, muscovite and other natural minerals and various metal oxides such as titanium oxide, lead oxide and zinc oxide have been compounded. On the other hand, natural organic substances, for example, finely divided cellulose and silk are also widely used.In recent years, finely divided various synthetic resins and finely divided ones by a special method have been synthesized. It is being actively developed for use. Examples include nylon powder, polyacrylonitrile powder, polyester powder, polystyrene powder, polypropylene powder, polyethylene powder, ethylene tetrafluoride powder, polymethyl methacrylate powder, and silicone powder.

[0003] Inorganic powders such as natural minerals and metal oxides have various shapes such as spheres, scales, needles, and amorphous particles, but they are not uniform. , From several microns to several tens of microns but non-uniform. In addition, it has a large specific gravity, has poor adaptation to the skin, and has various problems such as a feeling of roughness when used, and is not very preferable as a powder for cosmetics.
On the other hand, the organic fine particle powder is relatively easy to make the particle size and shape uniform as compared with the inorganic powder, and has a low specific gravity. And have been used in large quantities in recent years. Regarding the shape of the powder, when applied, a spherical or true sphere is preferred because an amorphous one such as a flake, a needle, or even a mechanically pulverized one has a rough feeling.

[0004] However, organic fine particle powders conventionally used, which are spherical or spherical, have a drawback that their water absorption and oil absorption are small, and thus have many restrictions on their formulation and usability. For example, when a solid powder cosmetic of a low oil content powdery type in a relatively low oil content region having an oil content of about 1 to 20% is used with water, the water absorption of resin particles is particularly small, so that a refreshing feeling is lost, There was a problem that it was difficult to obtain a smooth and creamy feel. The oil content is 2
In the case of high oil content powdery solid powder cosmetics in a relatively high oil content region of about 0 to 40%, the oil absorption of the resin particles is particularly small, so that the oil content increases and the removal rapidly deteriorates, so-called caking phenomenon. Problem. For this reason, there is a situation in which the amount of oil has to be limited, and it has been difficult to provide a moist feeling and smooth usability by the oil. Further, even in the case of an oily type solid powder cosmetic having an oil content of about 40 to 70%, especially when blended in a large amount due to the low oil absorption of the resin particles, the feel of spreading is improved, but the smoothness is improved. There was a limit because the feeling of use on the skin was too long to obtain a feeling of close contact with the skin.

[0005]

SUMMARY OF THE INVENTION The present invention provides a technique for obtaining spherical resin particles having a high water-absorbing and oil-absorbing property, for example, having a weight of 200 ml / 100 g or more. Further, the present invention is to obtain spherical resin particles excellent in adhesiveness to the skin with improved water absorption and oil absorption while having sliding properties (rolling effect) comparable to conventional spherical resin particles, Further, it is an object of the present invention to provide a cosmetic product which does not have the problems and caking phenomena at the time of using water as described above, and which can provide the usability and the finished feeling in each oil content region.

[0006]

Means for Solving the Problems The present invention has an average particle size of 2 to 2.
50 μm, and the water absorption is 200 to 50 with respect to the resin particles.
0ml / 100g and / or oil absorption 200-500
ml / 100 g, having pores on the surface and inside,
The present invention relates to spherical resin particles and cosmetics containing the same.

The spherical resin particles having the characteristics used in the present invention are novel. The spherical resin particles having the characteristics of the present invention are obtained by suspension polymerization of acrylic acid, methacrylic acid (both are hereinafter referred to as (meth) acrylic acid) and their esters in a water / organic solvent in the presence of a crosslinking agent. Obtained by A method for producing spherical resin particles by suspension-polymerizing a polymerizable monomer in water is already known. However, the water absorption of the spherical resin particles obtained by this method is at most 80 m.
1/100 g.

In the present invention, spherical resin particles having a large number of pores on the surface and inside can be obtained by subjecting a polymerizable monomer to suspension polymerization in a liquid mixture of water and an organic solvent.

As the polymerizable monomer, a monomer selected from (meth) acrylic acid (salt), (meth) acrylic acid ester and (meth) acrylonitrile is particularly suitable. These monomers may be used alone or in combination of two or more to form a copolymer. Vinyl acetate, styrene, vinyl chloride, vinylidene chloride, itaconic acid, maleic acid and the like may be used in combination with these (meth) acrylic monomers.

The above monomers polymerize with the crosslinking agent.
Examples of the crosslinking agent include divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene di (meth) acrylate, allyl (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Is exemplified. Examples of (meth) acrylate esters include alkyl having 1 to 4 carbon atoms, benzyl and cyclohexyl. Two or more of these may be used in combination.

Particularly preferred combinations of monomers and crosslinking agents for obtaining the spherical resin particles of the present invention are methyl methacrylate and ethylene glycol dimethacrylate.

The spherical resin particles of the present invention can be obtained by suspension polymerization of a polymerizable monomer and a crosslinking agent in a liquid mixture of water and an organic solvent. Examples of the organic solvent include alcohol having a high affinity for water, Organic solvents selected from ethers, ketones, aldehydes, and nitrogen-containing compounds are particularly suitable. 2
More than one kind of organic solvent may be used in combination.

The mixing ratio of water and the organic solvent varies depending on the polymerizable monomer used, the crosslinking agent, the organic solvent, the reaction temperature and the like. When the mixing ratio of the organic solvent is small, the oil absorption and water absorption of the obtained spherical resin particles become small, and when the mixing ratio of the organic solvent is large, the shape of the obtained resin particles becomes non-spherical or tends to aggregate. There is.

The temperature at the time of the polymerization is not higher than the boiling point of the organic solvent used, preferably from 40 ° C. to 90 ° C. However, when the polymerization is carried out under pressure, the temperature may be higher than the boiling point of the organic solvent.

As the polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy 2,4 -Dimethylvaleronitrile), organic peroxides such as benzoyl peroxide and lauroyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate. Such a polymerization initiator is usually used in an amount of 0.1 to 100 parts by weight of the monomer.
It is used in an amount of 1 to 10 parts by weight.

A suspension stabilizer in a liquid mixture of water and an organic solvent,
For example, polyvinyl alcohol, gelatin, methyl cellulose, sodium alginate, calcium phosphate, colloidal silica, bentonite, aluminum oxide and the like may be added.

The resulting spherical resin particles are filtered and dried to obtain a product. By drying, the used organic solvent is completely removed from the resin particles. Drying is performed at a temperature lower than the softening temperature of the polymer, usually at 30 to 90 ° C.

According to the above method, the water absorption is 200 to 500.
Thus, spherical resin particles having an oil absorption of 200 to 500 ml / 100 g (resin powder) using oleic acid can be obtained.

The present invention further relates to cosmetics containing the above spherical resin particles. When the spherical resin particles of the present invention are incorporated into a solid powder cosmetic, the content is 0.5 to 60% by weight (hereinafter referred to as%), preferably 2 to 30%. If it is less than 0.5%, the effect of blending the spherical resin particles cannot be sufficiently exhibited, and
If it exceeds 0%, the finish becomes powdery, and the impact resistance also deteriorates.

[0020] The powder cosmetics are blended with other conventional components. Specifically, talc, kaolin, sericite, muscovite,
Synthetic mica, phlogopite, phlogopite, biotite, vermulite,
Inorganic powders such as magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, silica, hydroxyapatite, zeolite, and boron nitride;
Spherical resin powders such as nylon powder and polyethylene powder, inorganic white pigments such as titanium oxide and zinc oxide, iron oxides, iron titanate, carbon black, chromium oxide, cobalt titanate, inorganic coloring pigments such as ultramarine and navy blue, oxychloride Pearl pigments such as bismuth, fish scale, colored titanium coated mica, clay minerals such as penton, metal powders such as aluminum powder and copper powder, red No. 201, red 202, red 204, red 205 and red 226
And organic pigments such as No. 203, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404, and powders obtained by hydrophobizing these powders with silicones, fatty acid esters and the like. One or more of these are arbitrarily selected. The compounding amount is generally 0.5 to 7
0%.

The solid oily cosmetic of the present invention may further contain, if necessary, a surfactant, a humectant, an antioxidant, an ultraviolet absorber, a dye, a fragrance, and the like, in addition to the above-mentioned components. Of course, these must be used under qualitative and quantitative conditions that do not impair the effects of the present invention.

[0022]

Next, the present invention will be described in more detail with reference to production examples of spherical resin particles. The present invention is not limited by this. Example 1 An oil phase and an aqueous phase were prepared with the following composition. (Oil phase) parts by weight methyl methacrylate 45 ethylene glycol dimethacrylate 5 2,2'-azobisisobutyronitrile 0.25 (aqueous phase) parts by weight deionized water 60 ethanol 60 colloidal silica 1 (solid content) adipic acid- Ethanolamine condensate 1

The above oil phase and aqueous phase are combined with T. K. High-speed stirring was performed using a homomixer (manufactured by Tokushu Kika Kogyo) to disperse the oil phase in the aqueous phase. This dispersion was charged into a 2 liter autoclave, purged with nitrogen, and stirred at 200 rpm for 8 hours.
Polymerization was carried out at 0 ° C. for 7 hours. Filter the product to 70% solids
Was obtained. Further, the cake-like substance is heated to 80 ° C.
For 5 hours to obtain white spherical fine particles having an average particle diameter of 10 μm. The water absorption of the fine particles is 380 m per 100 g.
1 was much higher than that of ordinary spherical fine particles. The oil absorption of oleic acid of these fine particles was 41 g / 100 g.
0 ml, which was much higher than that of ordinary spherical fine particles.

The amount of water absorption and the amount of oil supply were measured by the following methods. About 1 g of fine particles are precisely weighed (Wg) on a glass plate having a smooth water absorption , water is dropped from a burette, and kneaded with a metal spatula. This is repeated, and the amount of water dripping (Vml) immediately before the water seeps out when pressed with a spatula is measured. The amount of water absorption is determined from the following equation. Water absorption = (V / W) × 100 (ml / 100 g) Oil absorption : About 1 g of fine particles are precisely weighed on a glass plate (Wg), oleic acid is dropped from a burette, and kneaded with a metal spatula. By repeating this, the drop amount (Vml) of oleic acid immediately before the oleic acid seeps out when pressed with a spatula is measured. Obtain the oil absorption from the following formula. Oil absorption = (V / W) × 100 (ml / 100g)

Example 2 An aqueous phase was prepared with the following composition. (Aqueous phase) parts by weight deionized water 96 methyl ethyl ketone 24 colloidal silica 1 (solid content) adipic acid-ethanolamine condensate 1

Using the above oil phase and the aqueous phase of Example 1, white spherical fine particles having an average particle diameter of 10 μm were obtained in the same manner as in Example 1. The water absorption of the fine particles is 350 per 100 g.
ml and very high compared to ordinary spherical fine particles. or,
The oil absorption of oleic acid in these fine particles is 4 per 100 g.
00 ml, which was much higher than ordinary spherical fine particles.

Examples 3 and 4 Spherical fine particles were obtained using the monomer formulations shown in Table 1.

[0028]

[Table 1]

Next, the present invention will be described in more detail with reference to working examples of cosmetics containing spherical fine particles. The present invention is not limited by this. All compounding rates are% by weight. The organoleptic evaluation of the solid powder cosmetics for removal, sticking, spreading, adhesion to skin, finish moistness, finish tackiness, refreshing sensation (when using water), and creamy feeling (when using water) was performed according to the following criteria.

Evaluation Criteria (1) Removal Very good ◎ Somewhat good ○ Somewhat bad △ Very bad × (2) With Very good ◎ Somewhat good ○ Somewhat bad △ Very bad × ( 3) Noisy Very good ◎ Somewhat good 〇 Somewhat bad △ Very bad × (4) Feeling of adhesion to skin Very good ◎ Somewhat good ○ Somewhat bad △ Very bad × (5) Moist feeling of finish Very moist Yes ◎ Somewhat moist ○ Not very moist △ Not very moist × (6) Finished sticky Very no sticky ◎ Somewhat sticky ○ Somewhat sticky △ Very sticky × (7) Refreshing feeling (When using water) Very refreshing ◎ Somewhat refreshing ○ There is no refreshing △ No refreshing at all × (8) Creamy (when using water) Very creamy That ◎ do not have a little there is a creamy feeling ○ slightly there is no creamy feeling △ exactly the creaminess ×

Example 5 and Comparative Examples 1 and 2 Preparation of a Low-oil Powdery Foundation for Dual Use Components 1 to 6 shown in Table 2 were mixed with a Henschel mixer.
Add components 7 to 10 which have been heated and mixed in advance, and mix the oil uniformly. After crushing and sieving this,
The mixture was punched on a middle plate to obtain a low-oil powdery type dual-use solid foundation. The results are also shown in Table 2.

[0032]

[Table 2]

As can be seen from Table 2, Comparative Example 1 containing a conventionally used spherical EDMA-crosslinked polymethyl methacrylate (average particle size of 5 to 15 μm, water absorption of 60 ml / 100 g) was prepared by taking a sponge and spreading it. Although it was excellent in point, it lacked the adhesion to the skin, and did not feel any refreshing feeling and creamy feeling especially when using water. On the other hand, Comparative Example 2, which does not contain the spherical resin powder, has a refreshing feeling and a creamy feeling that are slightly superior to Comparative Example 1, but is not sufficient, but has poor spread when used in dry use and lacks adhesion to the skin. It was use feeling. On the other hand, Example 5 in which the spherical resin particles of the present invention were blended was very excellent in removing to a sponge, sticking to the skin, and spreading, and also excellent in adhesion to the skin as compared with the comparative example. . It should be further noted that when using water, the spherical resin particles of the present invention contain plenty of water, so that a refreshing sensation that gives the skin a crisp feel and a creamy feel like using an emulsified cream foundation are given. This is a point that can be felt on the skin, and that a completely new dual-use foundation that has never been seen before is obtained.

Example 6 and Comparative Examples 3 and 4 Preparation of high oil content powdery type solid foundation Components 1 to 6 shown in Table 3 were mixed with a Henschel mixer.
Add components 7 to 10 which have been heated and mixed in advance, and mix the oil uniformly. After crushing and sieving this,
The mixture was punched on a middle plate to obtain a high oily powdery solid foundation.

[0035]

[Table 3]

Conventional spherical EDM of Comparative Example 3
A cross-linked polymethyl methacrylate (average particle size 5 to 10μ)
m, oil-absorbing amount 55 ml / 100 g), the high oil content powdery type solid foundation has good spreadability but very poor take-off, and with continuous use with a sponge, the compact surface becomes hard and the take-off is significantly deteriorated. Caking phenomenon occurred. For this reason, the adhesion to the skin deteriorated, and the feeling of adhesion and moistness were not sufficient.
Comparative Example 4, in which no spherical resin powder was blended, had a serious defect that the spread was very poor and the foundation could not be evenly spread on the skin. On the other hand, in Example 6 in which the spherical resin particles of the present invention were blended, although the prescription system was a high oil type powdery type, it was much better than the Comparative Example in terms of removal, sticking, and spreading. And excellent adhesion to the skin. Further, since the spherical resin particles of the present invention have a very large oil absorption and can sufficiently contain the oil component in the prototype, they are extremely excellent in the moist feeling after application, and a completely new high An oily powdery solid foundation was obtained.

Example 7 and Comparative Example 5 Preparation of Oily Stick Foundation Components 3 to 7 and 14 in Table 4 were heated and dissolved, and components 8 to 13 were added.
And disperse. This product is treated by TK Mill manufactured by Special Machinery Co., Ltd. and heated to 85 ° C. 90 ° C in advance
The components 1 and 2 which have been heated and dissolved and mixed in are added thereto, and after mixing, degassed. After filling in a predetermined stick container, it was rapidly cooled to 5 ° C. and molded. Table 4 shows the evaluation results.

[0038]

[Table 4]

Conventional spherical EDM of Comparative Example 5
A cross-linked polymethyl methacrylate (average particle size 5 to 10μ)
m, oil absorption 55ml / 100g), the oily stick foundation, although lightly spread, has a slippery feel and slips on the skin, and has no adhesion to the skin,
The finish was also very sticky. In contrast, Example 7 in which the spherical resin particles of the present invention were blended,
The stickiness was good, the spreadability was light, and the finish was very close. Furthermore, since a large amount of spherical resin particles having a large oil absorption is blended, the oily foundation is a new type of oily stick foundation which does not feel sticky while retaining the unique moist skin feel of the oily foundation.

[0040]

The spherical resin particles of the present invention have a very high water- and oil-absorbing performance as compared with conventional resin particles and are therefore very suitable as a compounding material for cosmetics. The solid powder cosmetic composition of the present invention provided a smooth, creamy feel and a refreshing feeling when using water in a system having a relatively low oil content. Further, in a system having a relatively high oil content, it has a moist feeling and extensibility, which has not been achieved conventionally, and the deterioration of removal such as caking is improved. Further, in an oily system having a large oil content, the present invention provides an unprecedented epoch-making solid powder cosmetic having a strong adhesion to the skin and a refreshing, non-greasy feel. .

Continued on the front page F-term (reference) 4C083 AA122 AB232 AB242 AB432 AC012 AC022 AC352 AC392 AC422 AC442 AD091 AD092 AD152 AD512 BB26 CC01 CC12 DD11 DD17 DD21 DD31 EE01 EE06 EE07 4F070 AA32 AB13 AB14 DA33 DC03 DC06 DC07 DC16 4J0107 JA04 JA05 JA05 JA05

Claims (3)

[Claims] 1. Spherical resin particles having pores on the surface and inside. The average particle size is 2 to 50 μm, the water absorption is 200 to 500 ml / 100 g and / or the oil absorption is 200 to 500 ml / 100 g based on the resin particles. 2. A polymerizable monomer whose outer shell is selected from (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylonitrile, divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol di ( The resin particles according to claim 1, which are obtained from a crosslinking agent selected from (meth) acrylate, 1,3-butylene (meth) acrylate, allyl (meth) acrylate, and trimethylolpropane tri (meth) acrylate. 3. A cosmetic containing the resin particles according to claim 1.