JP3071222B2 - Skin cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a skin cosmetic containing a specific polysiloxane-oxyalkylene copolymer. More specifically, the present invention relates to a cleansing cream,
A linear polysiloxane which is used in skin cosmetics such as cold cream, hand cream, powder, lotion, foundation, mascara, eye shadow, lotion, lipstick, nail polish and has no stickiness and has good durability. The present invention relates to a skin cosmetic comprising a non-hydrolyzable block copolymer having a polyoxyalkylene block as a repeating unit.

[0002]

2. Description of the Related Art Skin cosmetics include cleansing cream, cold cream, hand cream, powder, lotion, foundation, mascara,
There are various types such as eyeshadow, lotion, lipstick, nail polish, sunscreen cream, etc., which have clean feeling, good skin feel, good feeling of use, no sweating, durability and durability In addition, when it is no longer necessary, it is required to have a property that it can be easily removed from the skin with facial cleanser, water, etc., but there are conflicting properties among these properties, and there is no cosmetic that combines all of these properties. Development has been desired.

[0003] The main components of these cosmetics are liquid paraffin, paraffin wax, fatty acids, higher alcohols,
Animal and vegetable fats and oils, synthetic esters, polyalkylene glycol derivatives, silicone compounds, etc. are employed. In particular, silicone compounds have unique properties (eg, durability, water resistance, affinity with skin, moisture retention, gloss) Application properties, water repellency, flexibility, water vapor permeability, gas permeability, film forming properties, filler retention, lubricity, etc.), and have been highlighted as components of skin cosmetics. Applications to skin cosmetics have been proposed. For example,
Dialkylpolysiloxane (JP-A-54-1903)
6), an amino group-containing polysiloxane (JP-A-57-58).
605), pendant polysiloxane-polyoxyalkylene copolymers (JP-A-58-131910 and JP-A-59-197432), silicone resins (JP-A-62
-298518), esterified polysiloxane (JP-A-63-150288), cyclic dimethylpolysiloxane (JP-A-63-159489), and the like. Polysiloxanes that do not have hydrophilic groups are difficult to dissolve in aqueous solvents and must be used with a large amount of emulsifiers to dissolve them.These emulsifiers impair the transparency of the emulsion or cause irritation to the skin. Or adversely affect water resistance. Amino group-containing polysiloxanes can turn yellow, which is undesirable. Many pendant polyalkylene groups having dioxyalkylene groups have been proposed, but their water resistance, retention, skin contact feeling, gloss, and the like are insufficient. Silicone resins also have to use low molecular weight cyclic siloxane, isopentane, etc. as a solvent, and their uses are limited. Esterified polysiloxanes also improve performance, but significantly increase costs.

[0004]

SUMMARY OF THE INVENTION The present invention improves the balance of water resistance, durability, retention, skin contact feeling, gloss, etc., which has improved the disadvantages of conventional skin cosmetics containing a silicone compound as an organic component. An object of the present invention is to provide a skin cosmetic that has been obtained.

[0005]

Means for Solving the Problems The present inventors have conducted experiments on silicone compounds having a large number of chemical structures in order to find effective silicone compounds as components of skin cosmetics, and have been proposed as skin cosmetics. The present inventors have found that a silicone-based block copolymer having a specific chemical structure which has never been used is effective, and completed the present invention.

That is, the present invention is a skin cosmetic comprising a non-hydrolyzable block copolymer having a linear polysiloxane-polyoxyalkylene block as a repeating unit.

The block copolymer of the present invention has the general formula

Embedded image (Wherein, R represents a monovalent hydrocarbon group containing no aliphatic unsaturation, n is an integer of 2 to 4, and b is at least 4
Wherein c is an integer of at least 5; a is an integer of at least 4; Y is a divalent divalent linked to the adjacent silicon atom by a carbon-silicon bond and to the polyoxyalkylene block by an oxygen atom. Represents an organic group,
The average molecular weight of each siloxane block is from about 500 to about 1
000, the average molecular weight of each polyoxyalkylene is from about 300 to about 10,000, the siloxane blocks make up from about 10 to about 90% by weight of the copolymer, and the block copolymer has at least about With an average molecular weight of 3,000).

In particular, the general formula (A):

Embedded image (Wherein R ″ represents a monovalent hydrocarbon group and a is an integer of at least 4) and a compound represented by the general formula (B):

Embedded image (Wherein, R ′ represents a monovalent hydrocarbon group, and n represents 2 to 4)
And b is an integer of at least 4).

Embedded image Wherein a is an integer of at least 4, b is an integer of at least 4, c is an integer of at least 5,
R ′ represents a monovalent hydrocarbon group, and R ″ represents a monovalent hydrocarbon group.) A high molecular weight non-hydrolyzable block copolymer having a linear polysiloxane-polyoxyalkylene block represented by the following formula: Good results are obtained with the use of coalescence.

Examples of R, R ', R "and the like in the above formula include an alkyl group (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, eicosyl, etc.), an aryl group (For example, phenyl, naphthyl, etc.), an aralkyl group (for example, benzyl, phenylethyl, etc.), a tolyl group, a xylyl group, and a cyclohexyl group. Is -R '''-,-R'''-CO-, -R '''-NHCO-,-R'''-NHCON
H-R ""-NHCO-, -R '"-OOCNH-R""-NHCO-, where
R ′ ″ is a divalent alkylene group, for example, ethylene, propylene, butylene, etc., and R ″ ″ is a divalent alkylene group, for example, R ′ ″ or a divalent arylene group, for example, —C ₆ H _4- ,
_{-C 6 H 4 -C 6 H 4} -, -C 6 H 4 -CH 2 -C 6 H 4 -, -C 6 H 4 -CH (CH 3) 2 -C 6
H _{4- and the} like, and preferably, R ″ ′ is a phenylene group)
Group. More preferred examples of the divalent organic group include -C
H ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH ₂ -,-(CH ₂ ) ₂ CO-
,-(CH ₂ ) ₃ NHCO-,-(CH ₂ ) ₃ NHCONHC ₆ H ₄ NHCO-,-(CH
_{2) 3} OOCNC ₆ H ₄ NHCO-, and the like. The most preferred Y is a divalent alkylene group, in particular -CH ₂ CH ₂ CH ₂ - is.

The above-mentioned non-hydrolyzable copolymer reacts a polyoxyalkylene compound having a reactive terminal group with a dihydrocarbylsiloxane liquid having a terminal group which reacts with the reactive terminal group of the polyoxyalkylene compound. Can be manufactured.

The nature of these reactive groups determines the structure of the divalent organic group represented by Y as described above, and, of course, the nature of the end groups of the product generally depends on the end groups of the reactants. Such a reaction can be represented by the following reaction formulas (a) to (f).

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image In the above, the polyoxyalkylene compound includes polyoxyethylene, polyoxypropylene, polyoxybutylene, mixed polyoxyethylene-oxypropylene, and the like.

The most desirable example is CH ₂ = C (CH ₃ ) -CH ₂
-A polyoxyalkylene compound having groups at both ends and H
Dimethyl having Si a (CH _{3) 2} O- groups at both ends - obtained by reaction of a polysiloxane

Embedded image Is a block copolymer represented by (In the above formula, Me represents a methyl group, n is an integer of 2 to 4, a is an integer of at least 4, and b is at least 4
And c is an integer of at least 4. )

The block copolymer used in the present invention is used alone or dissolved in water or various organic solvents (ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, pentane, hexane, octane, nonane, decane, etc.).

In addition, oils (camellia oil, rapeseed oil, sesame oil, safflower oil,
Cottonseed oil, castor oil, soybean oil, coconut oil, palm oil, beeswax, montan wax, lanolin, squalene, silicone oil, etc., surfactants (alkylbenzene sulfonates, polyoxyalkylene alkyl sulfates, alkyl sulfates, alkane sulfones) Acid salt, alkylethoxycarboxylate, succinic acid derivative, alkylamine oxide, imidazoline type compound, polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof), high Molecular compounds (hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, cationized cellulose, cationized polymer, polyvinyl Rupyrrolidone, copolymer of vinylpyrrolidone and vinyl acetate, vinylpyrrolidone-vinyl acetate-alkylaminoacrylate copolymer, lower alkyl half ester of methyl vinyl ether-maleic anhydride copolymer, vinyl acetate-crotonic acid copolymer, Acrylic acid-acrylic ester-N-alkylacrylamide copolymer, etc.), humectants (glycerin, ethylene glycols, propylene glycols, sorbitol, maltitol, sodium pyrrolidonecarboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl) Glucosides, glycols), amino acids (glycine, serine, proline), powders (sericite, silica alumina, silica gel, kaolin, talc, bengara, gunjo, mica, mica titanium, iron oxide, Titanium oxide, magnesium oxide, chromium oxide, antimony oxide, zinc monoxide, zinc dioxide, magnesium carbonate, calcium carbonate, calcium phosphate, barium sulfate, aluminum hydroxide, chromium hydroxide, magnesium metasilicate aluminate, magnesium silicate , Polyethylene powder, etc.), antioxidants, UV absorbers, fragrances, dyes, pigments,
It is blended with components such as pigments, preservatives, vitamins, hormones, deodorants, fixing agents, anti-inflammatory agents and the like, which are blended in ordinary skin cosmetics, to form skin cosmetics.

When used for an aerosol type spray, a propellant such as propane, butane, trichloromonofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, carbon dioxide or nitrogen gas is used in combination.

[0016]

EXAMPLES [Synthesis example of non-hydrolyzable block copolymer having a linear polysiloxane-polyoxyalkylene block as a repeating unit (hereinafter abbreviated as "alternate block copolymer")] Synthesis example 1 Mechanical stirrer In a 500 ml three-necked flask equipped with a condenser, a thermometer and a nitrogen inlet, dimethallyl polyether (CH ₂ CC (CH ₃ ) CH ₂ O (C ₂ H ₄ O) ₁₈ (C ₃ H ₆ O) ₃₃ CH ₂ C (CH ₃ ) = C
H ₂ ) 100 g, toluene 350 g, chloroplatinic acid
20 ppm of Pt was added. The temperature of this mixture is 80 to 10
109 g of dihydropolydimethylsiloxane (HMe ₂ SiO (MeSiO) ₄₀ SiMe ₂ H) was slowly added at such a rate as to maintain the temperature at 0 ° C. The end of this reaction was determined by the negative result of the AgNO ₃ test for SiH. The reaction mixture was then neutralized with NaHCO ₃ , filtered and rotary evaporated at 50 ° C./1 mmHg.
After removing the solvent with, 203 g of an alternating block copolymer having a molecular weight of 52,000 and having the following repeating unit was obtained.

Embedded image

Synthesis Example 2 Dimethallyl polyether (CH ₂ CC (CH ₃ ) CH ₂ O (C ₂ H ₄ O) ₂₀ (C
With _{20ppm 3 H 6 O) 29 CH} 2 C (CH 3) = CH 2) 70g and dihydro polydimethylsiloxane _{HMe 2 SiO (MeSiO) 30 SiMe} 2 H 61g and toluene 350 g, a platinum group addition catalyst of platinum, synthetic The same experiment as in Example 1 was performed. 126 g of a product with a molecular weight of 36,000 having the following repeating unit were obtained.

Embedded image

Synthesis Example 3 Dimethallyl polyether CH ₂ = C (CH ₃ ) CH ₂ O (C ₂ H ₄ O) ₂₀ (C
₃ H ₆ O) ₂₉ CH ₂ C (CH ₃ ) = synthesis using 150 g of CH ₂ , 43 g of dihydropolydimethylsiloxane HMe ₂ SiO (MeSiO) ₃ —SiMe ₂ H, 340 g of toluene, and 20 ppm of platinum as a platinum-based addition catalyst. The same experiment as in Example 1 was performed. 186 g of a product with a molecular weight of 48,000 having the following repeating unit were obtained.

Embedded image

Synthesis Example 4 Dimethallyl polyether CH ₂ CC (CH ₃ ) CH ₂ O (C ₂ H ₄ O) ₁₈ (C
_{3 H 6 O) 20 CH 2} C (CH 3) = CH 2 120g and dihydro polydimethylsiloxane _{HMe 2 Si (MeSiO) 15 SiMe} 2 H 72g and toluene 330 g, using a platinum 20ppm as platinum group addition catalyst, Synthesis Examples The same experiment as in Example 1 was carried out to obtain 184 g of a product having a molecular weight of 38,000 having the following repeating unit.

Embedded image

Synthesis Example 5 Dimethallyl polyether CH ₂ CC (CH ₃ ) CH ₂ O (C ₂ H ₄ O) ₅ CH ₂
C (CH ₃ ) = 180 g of CH ₂ , 95 g of dihydropolydimethylsiloxane HMe ₂ SiO (MeSiO) ₈ SiMe ₂ H, and 350 g of toluene
g, using 20 ppm of platinum as a platinum-based addition catalyst,
The same experiment as in Synthesis Example 1 was performed. 261 g of a 5,000 molecular weight product having the following repeating unit was obtained.

Embedded image

Synthesis Example 6 for Comparative Example Hydrosilyl group-containing dimethylpolysiloxane Me ₃ SiO [S
iMe ₂ O] ₁₀₀ [SiMe ₂ HO] ₁₃ SiMe ₃ 27 g and allyl polyether CH ₂ = CHCH ₂ O (C ₂ H ₄ O) ₁₈ (C ₃ H ₆ O) ₂₀ CH ₃ 94 g and toluene 330 g, platinum-based addition The same experiment as in Synthesis Example 1 was carried out using 20 ppm of platinum as a catalyst to obtain 120 g of a product having a molecular weight of 35,000 and having the following chemical structural formula.

Embedded image

Synthesis Example 7 for Comparative Example Dihydropolydimethylsiloxane HMe ₂ SiO [Me ₂ SiO] ₂₀₀ S
iMe ₂ H 97 g, allyl polyether CH ₂ = CHCH ₂ O (C ₂ H ₄ O)
₂₇ (C ₃ H ₆ O) _{30 The} same experiment as in Synthesis Example 1 was carried out using 43 g of CH ₃ , 320 g of toluene and 20 ppm of platinum as a platinum-based addition catalyst, and 133 g of a molecular weight of 21,000 having the following chemical structural formula. Got the product.

Embedded image

Example 1 : Hand cream The following composition was mixed by a conventional method to produce a hand cream. · 10 parts by weight of the alternating block copolymer according to Synthesis Example 1 · Cyclic siloxane 24 〃 · Squalane 5 〃 · Lanolin 3 〃 · Microcrystalline wax 3 〃 · Propylene glycol 5 〃 · Citric acid 0.8 〃 · Preservative 0.2 〃 ・ Purified water 48 〃 ・ Fragrance 1 〃 ・ Polyoxyethylene stearate 3 〃 Evaluation: When applied to hands, there was no sticky feeling, and dishwashing was performed for 30 minutes, but no rough skin occurred.

Comparative Example 1 A similar hand cream was prepared except that the polyether pendant dimethylpolysiloxane prepared in Synthetic Example 6 for Comparative Example was used instead of the alternating block copolymer according to Synthetic Example 1 in Example 1. . Evaluation: Compared to the hand cream of Example 1, when applied to hands, there was a sticky feeling and dishwashing was performed for 30 minutes, but the hand cream was completely removed, the fat of the hands was removed, and the hand was felt.

Example 2 : Sunscreen cream The following composition was mixed by a conventional method to produce a sunscreen cream. • 10 parts by weight of the alternating block copolymer according to Synthesis Example 2 • Cyclic siloxane 40 〃 • Squalane 3 〃 • Microcrystalline wax 1 〃 • Silica 5 〃 • UV inhibitor 0.5 〃 • Citric acid 0.8 〃 • Urogenic acid 1.0〃 Preservative 0.4〃 Purified water 30.3〃 Polyoxyethylene stearate 3３ Glycerin 5〃 Evaluation: When applied to the back, it spreads well and has no sticky feeling. 10 minutes in seawater, 5 times the initial application after swimming
0% remained.

Comparative Example 2 A similar sunscreen cream was prepared except that the polyether pendant dimethylpolysiloxane prepared in Comparative Example 7 was used in place of the alternating block copolymer according to Synthetic Example 2 in Example 2. . Evaluation: Compared with the sunscreen cream of Example 2, applied to the back, but spreads poorly and has a sticky feeling. After swimming for 10 minutes in seawater, only 20% of the originally applied amount remains. .

Example 3 Lipstick The following composition was mixed by a conventional method to produce a lipstick. -Alternating block copolymer according to Synthesis Example 37 37 parts by weight-Microcrystalline wax 20 〃-Citric acid 0.5 〃-Titanium oxide fine powder 8 〃-Shikonin 0.01 〃-Preservative 0.2 〃-Purified water 34 .29〃 Evaluation: Applied to skin, but gloss was good. The skin to which a shower of water was applied was aged for 3 minutes, but the purple color of shikonin remained.

Comparative Example 3 A similar lipstick was produced except that the polyether pendant dimethylpolysiloxane prepared in Synthesis Example 6 for Comparative Example was used instead of the alternating block copolymer of Synthesis Example 2 in Example 2. . Evaluation: When applied to skin, gloss was inferior to that of Example 3. I irritated my skin for 3 minutes,
The purple color of shikonin was almost spilled.

Example 4 : Lotion A lotion was prepared by mixing the following compositions in a conventional manner. 3 parts by weight of the alternating block copolymer according to Synthesis Example 4 stearic acid 0.2 〃 cetanol 1.5 〃 vaseline 3.0 ラ lanolin alcohol 2.0 〃 liquid paraffin 7.0 〃 polyoxyethylene Monooleic acid ester (10 EO) 2.0〃 ・ Fragrance 0.5〃 ・ Preservative 0.3〃 ・ Glycerin 3.0〃 ・ Propylene glycol 5.0〃 ・ Triethanolamine 1.0〃 ・ Purified water 72 0.0 Rating: When applied to the skin, it could be applied very smoothly, and sweat did not cause makeup loss. In addition, the lotion emulsion was stable without phase separation.

Comparative Example 4 A similar lotion liquid was prepared except that the polyether pendant dimethylpolysiloxane prepared in Synthetic Example 7 for Comparative Example was used instead of the alternating block copolymer according to Synthetic Example 4 in Example 4. . Evaluation: When applied to the skin, the lotion solution of Example 4 was slightly less smooth. By sweating,
Makeup loss occurred.

Example 5 : Lotion ・ Alternative block copolymer according to Synthesis Example 3.0 3.0 parts by weight ・ Glycerin 2.0２．０ ・ Propylene glycol 6.0〃 ・ Dipropylene glycol 1.0〃 ・ Ethanol 20.0 〃 ・ Purified water 68.0 〃 Evaluation: When applied to the skin, it spreads well and feels good, gives gloss to the skin and gives a firm feeling to the skin.

Comparative Example 5 A similar lotion was prepared except that the polyether pendant dimethylpolysiloxane prepared in Synthetic Example 6 for Comparative Example was used instead of the alternating block copolymer according to Synthetic Example 5 in Example 5. . Evaluation: Lack of spread when applied to skin, little gloss, and little tightness to skin.

[0033]

A number of polyether pendant dimethylpolysiloxanes or linear polyether-polysiloxane-polyether block copolymers have been proposed and used as main components of cosmetics. In the present invention, since a non-hydrolyzable block copolymer having a linear polysiloxane-polyol alkylene block as a repeating unit is used as a main component of skin cosmetics for the first time, cleansing cream, cold cream, and hand cream are used. , Powder, lotion, foundation, mascara, eye shadow, lotion,
When used in skin cosmetics such as lipstick, nail polish, sunscreen cream, lipstick, etc., the application feeling to the skin is smooth, there is no stickiness, there is a moist feeling, glossiness, the effect of holding on the skin, It is superior to conventional products in holding effect and the like.

Claims (3)

(57) [Claims] 1. A skin cosmetic comprising a non-hydrolyzable block copolymer having a linear polysiloxane-polyoxyalkylene block as a repeating unit. 2. A compound of the general formula (Wherein, R represents a monovalent hydrocarbon group containing no aliphatic unsaturation, n is an integer of 2 to 4, and b is at least 4
C is an integer of at least 4; a is an integer of at least 6; Y is a divalent divalent linked to an adjacent silicon atom by a carbon-silicon bond and to the polyoxyalkylene block by an oxygen atom. Represents an organic group,
The average molecular weight of each siloxane block is from about 400 to about 1
000, the average molecular weight of each polyoxyalkylene is from about 300 to about 10,000, the siloxane blocks make up from about 10 to about 90% by weight of the copolymer, and the block copolymer has at least about The skin cosmetic according to claim 1, wherein a linear polysiloxane-polyoxyalkylene block copolymer represented by the following formula (having an average molecular weight of 3,000) is used. 3. General formula (A): (Wherein R ″ represents a monovalent hydrocarbon group, and a is an integer of at least 4) and a compound represented by the general formula (B): (Wherein, R ′ represents a monovalent hydrocarbon group, n is an integer of 2 to 4, and b is an integer of at least 4). 4] Wherein a is an integer of at least 4, b is an integer of at least 4, c is an integer of at least 5,
R ′ represents a monovalent hydrocarbon group, and R ″ represents a monovalent hydrocarbon group.) A high molecular weight non-hydrolyzable block copolymer having a linear polysiloxane-polyoxyalkylene block represented by the following formula: The skin cosmetic according to claim 1, wherein the skin cosmetic is used.