JPH04221306A - Solid cosmetic - Google Patents

Abstract

PURPOSE:To obtain a solid cosmetic, excellent in water and oil resistance, adhesion to the skin and feeling of use by combining a waxy fluorine-containing polymer with a volatile oiling agent and an oil gelling agent. CONSTITUTION:A solid cosmetic is obtained by blending (A) a waxy fluorine- containing polymer, e.g. a copolymer of a long-chain alkyl (meth)acrylate and an acrylic or a methacrylic acid ester having a bonded alkyl group in which at least one H atom is substituted with F atom with (B) a volatile oiling agent, e.g. a low-molecular chain polysiloxane, a low-molecular cyclic polysiloxane or light liquid isoparaffin and (C) an oil gelling agent, preferably a polyvalent metallic salt of dialkyl phosphate. The amounts of the ingredients are preferably 0.5-20wt.%, especially preferably 1.0-10wt.% ingredient (A), preferably 10-80wt.%, especially preferably 20-70wt.% ingredient (B) and preferably 0.1-10wt.%, especially preferably 0.5-5wt.% ingredient (C).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to solid cosmetics, and more particularly to solid cosmetics that have excellent water resistance, oil resistance, adhesion to the skin, and are comfortable to use.

0002

BACKGROUND OF THE INVENTION Cosmetics, especially make-up cosmetics and sunscreen cosmetics, are required to prevent fading of color over time and to maintain effects. Therefore, such cosmetics must be provided with water repellency, oil repellency, and secondary adhesion prevention functions. For this reason, conventional methods have been used to make the pigments used hydrophobic, increase the amount of oil in the formulation to improve water repellency, or conversely reduce the amount of oil to increase oil resistance. . However, with this method, the prevention of color fading over time and the improvement in the durability of the effect were not fully satisfactory. On the other hand, in recent years, the scope of use of make-up cosmetics has expanded, and people are increasingly wearing make-up not only during daily life, but also during sports, at the pool, at the beach, etc. The sports makeup cosmetics (also called waterproof makeup cosmetics) used in this case often contain large amounts of volatile oils such as silicone-based or light liquid isoparaffins, so the range of prescriptions is limited. Moreover, too much emphasis was placed on functionality, resulting in poor usability, and oil resistance and secondary adhesion prevention properties were not always satisfactory. Therefore, there has been a demand for makeup cosmetics that have excellent water resistance, oil resistance, and adhesion to the skin, and are free from dull color and have excellent usability and long-lasting effects.

0003

[Means for Solving the Problems] Under such circumstances, the present inventors have conducted intensive research and have found that a cosmetic product obtained by combining a waxy fluorine-containing polymer, a volatile oil agent, and an oil gelling agent is available. Excellent water resistance and oil resistance.
The present invention was completed by discovering that it has good adhesion to the skin, excellent secondary adhesion prevention function, and has a good feel when used.

[0004] That is, the present invention comprises the following components (A) to (C).
The present invention provides a solid cosmetic containing (A) a waxy fluorine-containing polymer, (B) a volatile oil agent, and (C) an oil gelling agent.

The wax-like fluorine-containing polymer (hereinafter referred to as "fluoropolymer") used in the present invention as component (A) is, for example, a long-chain alkyl (meth)acrylate and at least one hydrogen atom substituted with a fluorine atom. Examples include copolymers with (meth)acrylic acid esters that have bonded alkyl groups. Here, long chain alkyl (
The meth)acrylate is preferably an ester of a linear or branched long-chain alkyl alcohol having 8 or more carbon atoms and (meth)acrylic acid, such as octyl alcohol, decyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, etc. Examples include esters of long-chain alcohols and (meth)acrylic acid. Among these, esters with long chain alcohols having 18 or more carbon atoms are particularly preferred. In addition, examples of (meth)acrylic acid esters in which at least one hydrogen atom is bonded to an alkyl group substituted with a fluorine atom include known compounds having a polyfluoroalkyl group and a perfluoroalkyl group, for example,

[Chemical formula 1] etc. The copolymerization ratio of these long-chain alkyl (meth)acrylates and (meth)acrylic acid esters in which at least one hydrogen atom is bonded to an alkyl group substituted with a fluorine atom is determined in terms of solubility, stickiness, etc. from 1
0:1 to 1:5 (weight ratio), particularly 7:1 to 1:1 is preferred. The molecular weight of the copolymer is preferably 1,000 to 2,000,000, particularly preferably 10,000 to 500,000, from the viewpoint of friction resistance, sticky feeling, etc. These copolymers can be produced, for example, according to the description in JP-A-61-289009.

[0006] The fluoropolymer can be used alone or in combination of two or more, and is present in the total composition in an amount of 0.5 to 20% by weight (hereinafter simply expressed as "%"), particularly 1.0 to 10%. It is preferable to mix them. If it is less than 0.5%, the expected water and oil resistance will not be achieved, and if it exceeds 20%, the feeling of use may be impaired, such as spreading or stickiness, which is not preferable.

The volatile oil agent (B) of the present invention is:
Polysiloxanes with a boiling point of 260°C or lower, such as low-molecular chain polysiloxanes such as hexamethyldisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane; Molecular cyclic polysiloxanes include light fluid isoparaffins such as Isopar (Esso Chemical), Shell Sol (Ciel Chemical), and IP Solvent (Idemitsu Petrochemical). Although each of these oils can be used alone, it is especially useful to use a mixture of silicone-based oils such as low-molecular chain polysiloxanes and low-molecular cyclic polysiloxanes, and hydrocarbon-based oils such as light fluid isoparaffin. It is preferable from the viewpoints of ease of use, usability, safety, etc. The weight ratio of silicone/hydrocarbon is preferably 10/1 to 1/2, particularly 5/1 to 1/1.

[0008] The blending amount of component (B) is 1 to 80% in the total composition.
%, particularly preferably 20 to 70%. If the amount is less than 1%, you will not be able to get a refreshing feel or finish, and if it exceeds 80%, it will take too long to evaporate, so the original effect of preventing makeup from fading may not be fully demonstrated. Undesirable due to its nature.

The oil gelling agent (C) is a substance that forms a three-dimensional network structure and solidifies (gels) it when added to liquid oil in a relatively small amount (usually 10% or less). Examples include, but are not limited to, 12-hydroxystearic acid; dibenzylidene sorbitol; higher fatty acid esters of dextrin such as palmitic acid and stearic acid (for example, Chiba Seifun Co., Ltd., Leopard); polyvalent metal dialkyl phosphates such as dicetyl aluminum phosphate. salts (for example, described in JP-A-1-41122); dialkyl phosphate polyaluminum salts (for example, as described in JP-A-1-193278); lauroylglutamic acid dibutylamide (for example, Ajinomoto, GP-1); metal soaps such as aluminum stearate, etc. can be mentioned. These may be used alone or in combination of two or more. Among these oil gelling agents, dialkyl phosphate polyvalent metal salts are particularly preferred. Here, the alkyl group is preferably a linear one having 12 to 18 carbon atoms, and the polyvalent metal is particularly preferably Al, Ca, or Fe (details thereof are described in Japanese Patent Publication No. 1-41122). The content of the oil gelling agent is preferably 0.1 to 10%, particularly preferably 0.5 to 5%, based on the total composition. If this amount is less than 0.1%, sufficient strength cannot be obtained when gelling a volatile oil agent, which is not preferable from the viewpoint of feel and stability. Also, 10
If it exceeds %, the gel becomes too strong, which is not preferable in terms of usability.

[0010] Furthermore, by incorporating pigments into the cosmetics of the present invention, makeup cosmetics with long lasting makeup can be obtained, and by incorporating ultraviolet absorbers, sunscreen cosmetics with excellent durability can be obtained. be able to. Examples of pigments include titanium oxide, zinc oxide (zinc white), iron oxide, ultramarine blue, sericite, silica alumina, silica gel, kaolin, talc, mica, clay, nylon powder, titanium mica, magnesium oxide, chromium oxide, antimony oxide, Magnesium carbonate, calcium carbonate, calcium phosphate, barium sulfate, aluminum hydroxide, boron nitride, chromium hydroxide, magnesium aluminate metasilicate, magnesium aluminate silicate, polyethylene powder, red 202
No., Red No. 204, Red No. 226, Orange No. 201,
Examples include Blue No. 404 and Yellow No. 401. Furthermore, these pigments may be used in the form of fine particles.
It is also possible to use a powder obtained by combining two or more of these pigments using mechanochemical means. Furthermore, it is also possible to use the above-mentioned powder whose surface has been subjected to metal soap treatment, silicon treatment, dialkyl phosphate treatment, treatment with a perfluoro group-containing compound, amino acid treatment, lecithin treatment, collagen treatment, etc. In addition to these pigments, powders of insoluble and soluble fungicides, ultraviolet absorbers, etc. can also be used. Specifically, insoluble disinfectants include trichlorocarbanilide, zinc pyrithione, etc., and insoluble ultraviolet absorbers include organic ultraviolet absorbers such as micronized titanium oxide, micronized zinc oxide, and para-aminobenzoic acid. Examples include polyvalent metal salts deposited on the surface of pigments such as mica. In addition, many known soluble disinfectants and ultraviolet absorbers can be used.

[0011] In the present invention, the amount of the pigments etc. to be blended is preferably 1 to 70%, particularly 10 to 60% of the total composition.
is preferred. If the amount is less than 1%, it will feel sticky,
If it exceeds 70%, the purpose of the present invention will not be achieved and formulation will become difficult.

[0012] In addition to the above-mentioned essential ingredients, the solid cosmetic of the present invention may contain an oil agent commonly used in cosmetics. Examples of such oils include liquid paraffin, squalane, polybutene, paraffin wax, microcrystalline wax, ceresin wax, polyethylene, petrolatum, castor oil, jojoba oil, macadamian nut oil, isopropyl myristate, isopropyl palmitate, stearic acid. Examples include isocetyl, cetyl palmitate, cetyl 2-ethylhexanoate, octyldodecyl myristate, glyceryl trioctanoate, lanolin, dimethylpolysiloxane, oleic acid, oleyl alcohol, and the like.

[0013] In addition, the solid cosmetic of the present invention may contain optional ingredients other than the above-mentioned ingredients that are used in ordinary cosmetics, depending on its dosage form and purpose, within a quantitative and qualitative range that does not impair the effects of the present invention. Can be used together. Such optional ingredients include:
Surfactants such as polyether-modified silicone, other ultraviolet absorbers, antioxidants, preservatives, humectants, anti-inflammatory agents,
Examples include drugs such as vitamins and hormones, and water. When water is used here, it is preferable to use a water-in-oil (W/O) emulsified cosmetic and to use oil as the outer phase.

[0014] The solid cosmetic of the present invention is produced by a conventional method and can be used as a blusher, an eyeliner, an eye shadow, a mascara,
It can be used as a wide variety of cosmetics such as foundation, eyebrow, lipstick, etc.

[0015]

[Effects of the Invention] The solid cosmetic of the present invention has excellent water resistance, oil resistance, and adhesion to the skin, and is also excellent in feel when used.

[0016]

EXAMPLES Next, the present invention will be further explained with reference to synthesis examples and examples, but the present invention is not limited by these in any way.

Synthesis Example 1 Perfluoroalkyl methacrylate [CH2=C(C
H3) 26.7 g of COOC2H4 C8 F17], 80.0 g of stearyl methacrylate, and 30 g of toluene were placed in a four-necked flask, and after melting and mixing, the mixture was heated to 0.5 at 50°C.
After stirring under a nitrogen stream for an hour, 2,2′-azobis-2
, 4-dimethylvaleronitrile (1.1 g) was added thereto, and polymerization was carried out at 65° C. for 5 hours and then at 80° C. for 1 hour under a nitrogen stream to obtain a cloudy viscous solution. After polymerization, the copolymer was diluted with toluene and poured into ethanol to precipitate the copolymer, separated by filtration, and then dried under reduced pressure to obtain 102.4 g of a copolymer of perfluoroalkyl methacrylate and stearyl methacrylate. The monomer composition in the copolymer was almost the same as the charged composition (equivalent to 25.1% by weight of perfluoroalkyl methacrylate from F%)
.

Synthesis Example 2 Copolymerization was carried out in the same manner as in Synthesis Example 1 except that stearyl methacrylate in Synthesis Example 1 was replaced with behenyl methacrylate to obtain 103.5 g of a copolymer of perfluoroalkyl methacrylate and behenyl methacrylate. The monomer composition in the copolymer was almost the same as the charged composition (perfluoroalkyl methacrylate was 24% based on F%).
(equivalent to 9% by weight).

Examples 1 and 2 Oil-based solid cosmetics having the compositions shown in Table 1 were prepared by the following manufacturing method. This was evaluated using the following evaluation criteria. The results are shown in Table 1.

[0020]

[Table 1]

(Manufacturing method) The above ingredients [A] are mixed and heated to 80 to 90°C to melt, and the previously mixed formulation [B] is added thereto and mixed uniformly. After defoaming, pour into a container and cool.

(Evaluation Criteria) (1) Lightness of stretch A sample was taken with a finger and applied to the upper arm, and the lightness of stretch was sensory evaluated. ◎ Very light, ○ Light, △ Not very light, × Heavy (2) Non-stickiness A sensory evaluation was made of the sticky feeling when touching the sample with fingers. ◎ Not sticky, ○ Not very sticky, △ Slightly sticky, × Sticky (3) A makeup stick sample was taken with a finger, applied to the eyelids, and sensory evaluated 6 hours later. ◎Very good, ○Good, △Not very good, ×Bad

Example 3 Oil-based eyeshadow:

(%) [A] Glyceryl tribehenate
5.0 Squalane

5.0 Light fluid isoparaffin
15.0 Decamethylcyclopentasiloxane 45.0
Waxy fluorine-containing polymer (synthesis example 2)
10.0 Dicetyl Calcium Phosphate
2.0 Dibutylhydroxytoluene (BHT) 0.02 [
B] Mica titanium
8.9
8 Nylon powder
3
．． 0 Silicon processing Gunjo
5.0
Silicon treated red iron
1.0


100.00 (Manufacturing method) The ingredients of [A] above are mixed and heated to 80 to 90°C to melt, and the premixed formulation of [B] is added thereto and mixed uniformly. After defoaming, pour into a container and cool. The resulting eyeshadow had a refreshing feel without stickiness, and spread well. Also, water resistance,
It had good oil resistance, no fading or fading, and long-lasting makeup.

Example 4 Oil-based eyeshadow

(%) [A] Microcrystalline wax 2.
0 carnauba wax

0.5 Glyceryl tribehenate
4.
0 liquid paraffin

4.0 Light fluid isoparaffin
7.
0 Decamethylcyclopentasiloxane 25.0
Waxy fluorine-containing polymer (synthesis example 1)
4.0
〃 ( 〃 2)
2.0 Dicetyl Calcium Phosphate
1.0 BHT

0.02 [B] Mica titanium
20.0 Bengala
10.0
nylon powder
5.0
Gunjou
2.0
talc

13.48

100.00 (Manufacturing method) The formulation [A] above is mixed and heated to 80 to 90°C to melt, and the previously mixed formulation [B] is added thereto and mixed uniformly. After defoaming, it is poured into a mold or metal plate, cooled, and molded. The obtained oil-based eyeshadow was a makeup cosmetic with excellent water resistance and oil resistance, and did not cause makeup smearing, and had a refreshing feel without stickiness.

Example 5 Oil-based foundation

(
%) [A] Candelilla wax
5.0
solid paraffin
2
．． 0 Waxy fluorine-containing polymer (
Synthesis example 2) 2.0
〃
(〃 1) 4.0
Dicetyl aluminum phosphate
3.0 Light fluid isoparaffin
10.0 Dodecamethylcyclohexasiloxane
29.98 BHT

0.02 [B] Talc

31.5 Silicon-treated yellow iron oxide
4.0 Silicon treated red iron
2.0 Silicon treated black iron oxide
2.0 Silicon treated titanium oxide
4.5

100.00 (Manufacturing method) The formulation [A] above is mixed and heated to 80 to 90°C to melt, and the previously mixed formulation [B] is added thereto and mixed uniformly. After defoaming, it is poured into a mold or metal plate, cooled, and molded. The obtained oil-based foundation was a makeup cosmetic with excellent water resistance and oil resistance, which caused less makeup smearing, and had a refreshing feel without stickiness.

Example 6 Lipstick:
(
%) [A] Candelilla wax
3.0
Ceresin

1.0 Waxy fluorine-containing polymer (synthesis example 2) 6.0
〃
(〃 1) 4.0
Light liquid isoparaffin
10.0
Dodecamethylcyclohexasiloxane
41.98 Jojoba oil

10.0 Octyldodecyl myristate
8.0 Dicetyl Calcium Phosphate
2.0 BHT

0.02 [B] Mica titanium
12.0 Silicon treated titanium oxide
1.0 red 22
No. 6
1.0

100.0
0 (Manufacturing method) The ingredients of [A] above are mixed and heated to 80 to 90°C to melt the mixture, and the previously mixed formulation of [B] is added thereto and mixed uniformly. After defoaming, pour into a container and cool. The resulting lipstick was non-sticky, had a refreshing feel, and spread well. It also had good water resistance and oil resistance, did not fade or fade, and had long makeup life. Note that it is preferable to use a highly airtight container for this lipstick.

Example 7 Highlight color
(%) [A]
Waxy fluorine-containing polymer (synthesis example 1)
3.0 Light fluid isoparaffin
6.0 Decamethylcyclopentasiloxane 79.48
dicetyl calcium phosphate
3.0
BHT
0
．． 02 [B] Silicon-treated mica titanium
1.0
siliconized talc
7.0
Red No. 226
0.
5

100.00 (Manufacturing method) The ingredients of [A] above are mixed and heated to 80 to 90°C to melt, and the premixed formulation of [B] is added thereto and mixed uniformly. After defoaming, pour into a container and cool. The resulting highlight color had a refreshing feel without stickiness, and spread well. It also had good water resistance and oil resistance, did not fade or fade, and had long makeup life. This highlight color is preferably filled in a highly airtight container, such as a tube.

Example 8 Eyeliner:
(%) [A
] Hardened oil
5.
0 Microcrystalline wax
4.0
Waxy fluorine-containing polymer (synthesis example 1)
10.0 Dicetyl aluminum phosphate
3.0 Light fluid isoparaffin
10
．． 0 Decamethylcyclopentasiloxane 37.98
BHT
0.
02 [B] Silicon treated black iron oxide
20.0
Silicon treated mica
10.0


100.00 (Manufacturing method) The formulation [A] above is mixed and heated to 80 to 90°C to melt, and the previously mixed formulation [B] is added thereto and mixed uniformly. After defoaming, it is poured into a mold or metal plate, cooled, and molded. The obtained eyeliner was a makeup cosmetic with excellent water resistance and oil resistance, which caused less makeup smearing, and had a refreshing feel without stickiness.

Example 9 Eyebrow:
(%) [
A] Hardened oil
5
．． 0 Candelilla Row

2.0 Microcrystalline wax 4.0
Waxy fluorine-containing polymer (synthesis example 2
) 2.0
〃 (
〃 1) 4.0 Dicetyl aluminum phosphate
3.0 Light fluid isoparaffin
10.0 Decamethylcyclopentasiloxane 39.
98BHT

0.02 [B] Silicon treated red iron

5.0 〃 Black iron oxide
15.0 〃
mica
10.0

100.00 (Manufacturing method) The formulation [A] above is mixed and heated to 80 to 90°C to melt, and the premixed formulation [B] is added thereto and mixed uniformly. After defoaming, it is poured into a mold or metal plate, cooled, and molded. The obtained oil-based eyebrow was a makeup cosmetic with excellent water resistance and oil resistance, which caused less makeup smearing, and had a refreshing feel without stickiness.

Example 10 Eye color
(%) [
A]1 Decamethylcyclopentasiloxane
22.9 2 Light fluid isoparaffin
10.0 3 Squalane

10.0 4 Preservatives

0.1 5 Waxy fluorine-containing polymer (Synthesis Example 1)
8.0 6 Dicetyl calcium phosphate
3.0
7 Hydrophobized pigment (composition below) *
30.0 [B] 8 Glycerin fatty acid ester
4.0 (Glycerol monooleate) 9 Propylene glycol
2.0 10 water

10.0

100.00
*7-(1) Silicon-treated talc
(10.5)
7-(2) Silicon-treated mica
(10.0) 7-(
3) Silicon treated red iron
(8.0) 7-(4) Silicon processing gunjo (1
．． 5) (Manufacturing method) (1) Mix and dissolve components 1 to 6. (2) Add the hydrophobized pigment from step 7 to (1) and mix thoroughly. (3) Mix 8 to 10, add to (2), and emulsify. After deaerating this, pour it into a container. The obtained eye color had excellent water resistance and oil resistance, and had a refreshing feel without stickiness.

Example 11 Cream eyebrow
(%) [A] 1
Light liquid isoparaffin
30.0 2 Dimethylpolysiloxane
13.9 3 Paraffin wax
5.0 4 Vaseline

5.0 5 Waxy fluorine-containing polymer (synthesis example 1) 10.0
6 Dicetyl calcium phosphate
5.0
7 Glycerin fatty acid ester
3.0
(Glycerol monooleate) [B] 8 Black iron oxide
3.0 9
kaolin
10.0
10 water
15.
0 11 Preservatives

0.1

100.00 (Manufacturing method) (1) Components 1 to 7 are heated and dissolved. (2) Components 8 to 11 are added to (1), stirred and dispersed, and then cooled.

Claims (1)

[Claims] 1. A solid cosmetic comprising the following components (A) to (C) (A) a waxy fluorine-containing polymer (B) a volatile oil agent (C) an oil gelling agent.