JPH07206628A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic for hair and skin which comprises a reaction product from a silicon compound, other copolymerizable compounds and a difluoroalkanoyl peroxide as a radical polymerization initiator in a specific proportion. CONSTITUTION:The cosmetic contains a product resulting from the reaction between a silicon compound of formula I (R<1> is H, methyl; R<2> to R<4> are an alkyl, an alkoxy; n is 0 or 1), other copolymerizable compounds, a difluoroalkanoyl peroxide of formula II (l, m are 0 to 8) or formula III (X is H, F, Cl; p, q are l to 10) as a radical polymerization initiator where the molar ratio of the compound of formula I to the one of formula 11 or III is 1/(0.1 to 5,000) and the other copolymerizable compounds are less than 50 mole % based on the compound of formula I and the number-average molecular weight is 1,000 to 1,000,000. The compound of formula I is, for example, trimethoxyvinylsilane or triethoxy-vinylsilane and the other copolymerizable compounds are, for example, vinyl acetate, diisobutylene, styrene, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetics, and more particularly to hair and skin cosmetics.

[0002]

2. Description of the Related Art Hair cosmetics and skin cosmetics include oil-soluble or sparingly water-soluble polyalkylene glycol derivatives, paraffin wax, synthetic esters, water-soluble cationic cellulose derivatives, vinylpyrrolidone / alkyldialkylamino. Various compounds such as (meth) acrylate copolymers, unsaturated carboxylic acid (anhydride) derivatives / vinyl ether copolymers are used. Although these components have different purposes and forms of use depending on the type of cosmetics, they are generally used for imparting hair styling properties, moisturizing properties, adhesive properties, affinity to the skin, and the like.

[0003]

Recently, as a cosmetic for hair, a non-greasy and light-feeling hair tends to be preferred, but an oil-based cosmetic has a styling power but a sticky feel, and is not always suitable. is not. Further, since water-soluble copolymers and the like have strong adhesiveness and moisturizing properties, they give an unnatural appearance and are therefore not preferable. On the other hand, in the case of skin cosmetics, there is a demand for non-greasy, light-feeling and hard-to-remove cosmetics.However, oily cosmetics have the problem of stickiness, and water-soluble copolymers etc. It has the drawback of not lasting long.

[0004]

The present inventors have found that a cosmetic containing a compound having both a fluoroalkyl group and a silicon atom in the same molecule is non-greasy, has a light feel, and has a high degree of adhesion and The present invention has been completed by finding that it has a holding power and gives a natural appearance.

That is, the present invention has the general formula (1)

[Chemical 9] (R1 is a hydrogen atom or a methyl group, R2, R3 and R
4 each represents an alkyl group, an alkoxy group or an alkoxycarbonyl group having 1 to 10 carbon atoms, which may be the same or different, n is 0 or 1, and when n = 0, R1 is a hydrogen atom. ) And a silicon compound represented by the general formula (2)

[Chemical 10] (1 and m are the average addition mole numbers of hexafluoropropylene oxide, and are 0 to 8) or the general formula (3).

[Chemical 11] (X is a fluorine atom, a hydrogen atom or a chlorine atom, and p
And q are the numbers of difluoromethylene groups and are 1 to 10. )
Which is a reaction product of a difluoroalkanoyl peroxide and another copolymerizable compound, and the reaction molar ratio of the compound of the general formula (2) or (3) to the compound of the general formula (1) is 1: 0.1 to 1: 5,000, other copolymerizable compound is 50 mol% or less of the compound of the general formula (1),
A cosmetic containing a reaction product having a number average molecular weight of 1,000 to 1,000,000. Further, the structure of the main component of the reaction product containing a fluoroalkyl group used in the present invention has the following general formula (4):

[Chemical 12] (However, Rf is a residue derived from a radical decomposition product of the compound of the general formula (2) or the general formula (3),

[Chemical 13] Or

[Chemical 14] Or

[Chemical 15] Or

[Chemical 16] M is a monomer unit of the silicon compound of the general formula (1), S is another monomer unit, k is 1 to 5,000, and s is 0 to 2,500.
And the number average molecular weight of the polymer is 1,000 to 1,
It is, 000,000, and the inside of [] may be block or random. ] It is a cosmetic containing the reaction product shown by.

Further, the cosmetic of the present invention contains, in addition to the above-mentioned fluoroalkyl group-containing reaction product as a main component,
As a by-product, with the radical termination reaction, the general formula (4)
Also, those in which one or both of Rf are substituted with a hydrogen atom, a chlorine atom, or other substituents derived from a solvent are included. Furthermore, a fluoroalkyl compound of a self-decomposition product of difluoroalkanoyl peroxide is also included.

Specific compounds of the general formula (1) include trimethoxyvinylsilane, triethoxyvinylsilane,
Diacetoxymethylvinylsilane, diethoxymethylvinylsilane, triacetoxyvinylsilane, triisopropoxyvinylsilane, trimethylvinylsilane, tri-t-butoxyvinylsilane, ethoxydiethylvinylsilane, diethylmethylvinylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane, 3-methacryloxypropyldiacetoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, 3-methacryloxypropyltriacetoxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltrimethylsilane , 3-methacryloxypropyltree t-butoxysilane, 3-methacryloxypropylethoxydiethylsilane, 3-meta Lilo propyl diethyl methyl silane,
3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyldiacetoxymethylsilane, 3-acryloxypropyldiethoxymethylsilane, 3-acryloxypropyltriacetoxysilane, 3-acryl Silicone compounds such as Roxypropyltriisopropoxysilane, 3-acryloxypropyltrimethylsilane, 3-acryloxypropyltree t-butoxysilane, 3-acryloxypropylethoxydiethylsilane, 3-acryloxypropyldiethylmethylsilane Can be raised.

The reaction product used in the present invention uses the compound of the general formula (2) or the general formula (3) as a radical polymerization initiator, and is capable of copolymerizing with the compound of the general formula (1) if necessary. The molar ratio of the compound of the general formula (2) or (3) and the compound of the general formula (1) obtained by reacting with the compound is in the range of 1: 0.1 to 1: 5,000, preferably 1 The range is from 1 to 1: 1,000. When the molar ratio of the compound of the general formula (1) is less than 0.1, a large amount of products are generated due to the self-decomposition of peroxide, and when it exceeds 5,000, the target fluoroalkyl group-containing compound is contained. It is not preferable because the yield of the compound is lowered. Further, the reaction product used in the present invention has at least one fluoroalkyl group at the terminal, and the addition mole number of the monomer of the general formula (1) is 1 to 1,000, preferably 1 to 500. The number average molecular weight is in the range of 1,000 to 1,000,000, preferably 1,000 to 50,000. Further, the molecular weight of the obtained reaction product can be adjusted by adjusting the charged molar ratio of the compound of the general formula (2) or the general formula (3). That is, when the charged molar ratio of the compound of the general formula (2) or the general formula (3) is increased, a reaction product having a low molecular weight is obtained, and the molar ratio of the compound of the general formula (2) or the general formula (3) is obtained. If is low, a high molecular weight reaction product is obtained.

Further, during the reaction, other copolymerizable compound may be added if necessary. At this time, the amount of the other copolymerizable compound is 50 mol% or less of the amount of the compound of the general formula (1). If the amount of the other copolymerizable compound exceeds 50 mol%, the characteristics of the fluoroalkyl group do not appear, which is not preferable.

Other copolymerizable compounds include vinyl compounds such as vinyl acetate, vinyl propionate, vinyl butyrate and vinylpyrrolidone; vinyl chloride, vinylidene chloride,
Halogen compounds such as vinyl fluoride and vinylidene fluoride; olefin compounds such as isobutylene and diisobutylene; aromatic vinyl compounds such as styrene and methylstyrene; acrylic compounds such as acrylonitrile and acrylamide; general formula (9)

[Chemical 17] (Y is a hydrogen atom or a methyl group, AO is one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms,
When two or more kinds are added, they may be added in a block form or in a random form, and R5 is a hydrogen atom or a carbon number.
1 to 24 hydrocarbon groups or acyl groups, and r is 0 to 1,000 in terms of the average number of moles of added oxyalkylene groups. ) Acrylic acid, methacrylic acid and their derivatives,
Further examples include unsaturated monocarboxylic acids such as itaconic acid and crotonic acid.

In the general formula (9), the oxyalkylene group represented by AO is an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, an oxystyrene group, an oxydecylene group, an oxytetradecylene group, Examples thereof include an oxyhexadecylene group and an oxyoctadecylene group. These may be added alone or in combination of two or more. When two or more kinds are added at the same time, block-shaped addition or random-shaped addition may be performed.

The reaction for obtaining the reaction product used in the present invention can be carried out at normal pressure, and the reaction temperature is not particularly limited, but the reaction time becomes long at -20 ° C or lower, and 150 ° C is selected. If it exceeds, the pressure during the reaction becomes high and the reaction operation becomes complicated, so -20 to 150 ° C, preferably
It is in the range of 0 to 100 ° C. Although the reaction time varies depending on the charged molar ratio and the reaction temperature, it is usually in the range of 30 minutes to 20 hours.

In addition, it is preferable to use a solvent in order to facilitate the handling and reaction of the compound of the general formula (2) or the general formula (3) in the reaction. Although various solvents can be used as the solvent, halogenated aliphatic solvents and halogenated aromatic solvents are particularly preferable in order to make the reaction system uniform. Specific examples of these solvents include methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoro. Ethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1, 1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, 1,1,1,2,2, -pentafluoro-3,3-
Dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride, hexafluoroxylene, pentafluorobenzene, 1-fluoro-1,1-dichloroethane, 1,1,
1,2,2-pentafluoropropanol and the like, particularly 1,1,2-trichlorotrifluoroethane, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride and the like are preferable. When these solvents are used, the concentration of the compound of the general formula (2) or the general formula (3) in the usual solvent is preferably about 0.1 to 30% by weight. Also,
If 1 or m in the general formula (2) exceeds 8, and p or q in the general formula (3) exceeds 10, the reaction system will not be uniform even if a solvent is used, which is not preferable.

The reaction product used in the present invention appropriately changes R 1, R 2, R 3 and R 4 in the general formula (1), l and m in the general formula (2) or p and q in the general formula (3). By changing the reaction temperature, the reaction time, the charging ratio of the compound of the general formula (1) and the compound of the general formula (2) or the general formula (3), and the like, from a low molecular weight to a high molecular weight. Because you can get things
It can be used in various forms of cosmetics. Further, since a reaction product having surface activity can be obtained, it can be used as an emulsifier.

The blending amount of the above reaction product in the cosmetic of the present invention varies depending on the kind of the cosmetic, but generally,
An amount of 0.1 to 50% by weight, preferably 0.5 to 30% by weight is sufficient to exert the effect.

The purpose of use, the form of use, etc. of the above-mentioned reaction product differ depending on the type of cosmetics, but they are used as the main agent or auxiliary agent, and are used alone or in combination with other conventionally used cosmetic ingredients. Can be used. That is, in addition to water, alcohols and other solvents or solid diluents such as titanium oxide, talc and kaolin, coupling agents, plasticizers, emollients, thickeners, lubricants, film-forming resins, penetrants, buffers, anionic agents, Cationic, amphoteric or nonionic surfactants, fragrances, dyes, preservatives, preservatives, propellants, foam stabilizers, UV absorbers, softeners, gloss control agents, antistatic agents, moistureproofing agents, fining agents. , Evaporation promoters, etc.

The types of cosmetics include hair spray, set lotion, cold wave liquid, hair tonic,
Hair liquid, hair blow, pomade, hair cream,
Hair cosmetics such as hair mousse, hair oil and tic, or skin makeup such as packs, cleansing cream, lotion, cold cream, hand cream, powder, foundation, mascara, eye shadow, lotion, lipstick, eyeliner, nail lacquer You can give a fee.

[0018]

The cosmetic of the present invention contains a reaction product having a silicon atom and a fluoroalkyl group directly bonded by a carbon-carbon bond in the same molecule, so that it is not sticky and has a light feel. Moreover, it is an excellent cosmetic having a high degree of adhesion and holding power and giving a natural appearance.

[0019]

EXAMPLES The effects of the present invention will be described below with reference to examples and comparative examples. In each example,% is based on weight,
The average molecular weight is the number average molecular weight. Examples 1 to 6 and Comparative Examples 1 to 3 (hair spray) Examples 1 to 6 shown in Table 1
Using the compounds of Comparative Examples 1 to 3, hair sprays were prepared according to the formulations shown below. <Process> (%) Compound shown in Table 1 3.0 Absolute ethanol 36.0 Dimethylpolysiloxane 0.6 2-Methyl-2-amino-1-propanol 0.3 Trichloromonofluoromethane 30.0 Dichlorodifluoro Methane 30.0 Perfume 0.1

[0020]

[Table 1]

<Evaluation Method> About this hair spray,
A sensory test for appearance, set holding power, feel, stickiness and comb-like sensory test was conducted on 10 men and women aged 15 to 55 years. The results are shown in Table 2.

[0022]

[Table 2]

From Table 2, it can be seen that the hair spray of the present invention is excellent.

Example 7 (pack) A pack was prepared according to the following formulation. <Method> (%) A Purified water 64.0 Propylene glycol 5.0 B Compound of Table 1 No. 6 14.0 Ethanol 5.0 C Sorbitan monolaurate 2.0 Polyoxyethylene (20 mol) Sorbitan Monostearate 1.5 Squalane 5.0 D Ethanol 3.0 Fragrance 0.5 Preservative Appropriate amount Phase B was added to phase A and heated to 60 ° C. to dissolve. Next, this was heated to 60 ° C. and added to the dissolved phase C, cooled to room temperature with stirring, and then phase D was mixed to obtain a pack. The obtained pack had good compatibility with the skin, was easy to apply, and was excellent in film-forming ability and its releasability.

Example 8 (emollient lotion) An emollient lotion was prepared according to the following formulation. <Method> (%) A Stearic acid 2.0 Cetyl alcohol 1.5 Vaseline 5.0 Liquid paraffin 10.0 B Table 1 No. Compound of 2 2.5 Glycerin 3.5 Propylene glycol 5.0 Purified water 70.0 C Fragrance 0.5 Preservative, antioxidant Proper amount Phase B is heated and mixed, to which phase A heated and dissolved is added. ,
Further, phase C was added, mixed while heating to 70 ° C., uniformly emulsified with a homomixer and cooled to room temperature to obtain an emollient lotion. The obtained emollient lotion had good compatibility with the skin, had no stickiness, and was refreshing.

Example 9 (Cream Foundation) A cream foundation was prepared according to the following formulation. <Process> (%) A Stearic acid 0.5 Squalane 11.0 Compound No. 2 in Table 1 2.0 Cetyl alcohol 1.5 Liquid paraffin 5.0 Isopropyl myristate 4.0 B Triethanolamine 1.2 Propylene Glycol 4.5 Purified water 53.3 Preservative A suitable amount C Titanium oxide 8.0 Talc 7.0 Kaolin 2.0 Coloring pigment Appropriate amount D Fragrance Appropriate amount A phase is heated to 80 ° C to dissolve it, and then the pigment of C is dissolved. Added and dispersed evenly. The phase B melted by heating at 80 ° C. was gradually added to this to emulsify, then cooled with stirring, the fragrance of D was added at 50 ° C., and further cooled to room temperature with stirring. The cream foundation thus obtained was a lightly stretched product and had good skin compatibility.

Example 10 (Cleansing Cream) A cleansing cream was prepared according to the following formulation. <Processing> (%) A Paraffin 5.5 Cetyl alcohol 1.5 Vaseline 17.0 Liquid paraffin 28.0 Polyoxyethylene (5 mol) Sorbitan monolaurate 3.0 Preservative Suitable amount B No. 5 in Table 1 Compound 3.0 Propylene glycol 4.0 Glycerin 1.5 Purified water 36.0 C Fragrance 0.5 Phase A is heated to melt to 65 ° C. Phase B is also heated to 6
The temperature was adjusted to 5 ° C., phase B was added to phase A, and the mixture was stirred, homogenized with a homomixer and then cooled, then the flavor of C was added at 50 ° C., and the mixture was cooled to room temperature with stirring. The cleansing cream thus obtained had a good spread and a smooth feel.

Example 11 (Soft lotion) A soft lotion was prepared by the following formulation. <Method> (%) A ethanol 10.0 oleyl alcohol 0.1 polyoxyethylene (20 mol) sorbitan monolaurate 1.5 polyoxyethylene (20 mol) lauryl ether 0.5 preservative proper amount perfume 0.1 B Compound No. 1 in Table 1 2.5 Glycerin 2.5 Propylene glycol 4.0 UV absorber Adequate amount Purified water 78.8 Mix phase A at room temperature to dissolve, and mix phase B at room temperature as well. After dissolution, the phase A was added to the phase B to solubilize it. The softening lotion thus obtained has a good affinity with the skin,
It was not sticky and was refreshing.

Example 12 (emollient cream) An emollient cream was prepared according to the following formulation. <Process> (%) A Stearic acid 2.0 Stearyl alcohol 7.0 Reduced lanolin 2.0 Squalane 5.0 Octyldodecanol 6.0 Polyoxyethylene (25 mol) Stearyl ether 3.0 Monostearic acid glyceride 2 0.0 Fragrance 0.3 Preservative Suitable amount Antioxidant Suitable amount B No. 1 in Table 1 Compound of 4 3.0 Propylene glycol 2.0 Purified water 67.7 Phase B was mixed and heated to 70 ° C. Phase A was mixed and heated at 70 ° C. and melted, and this was added to phase B to carry out preliminary emulsification, uniformly emulsified with a homomixer, and then cooled to room temperature. The emollient cream thus obtained had a good spread and a smooth feel.

Example 13 (Emulsion type eyeliner) An emulsion type eyeliner was prepared according to the following formulation. <Process> (%) A Stearic acid 3.5 Beeswax 2.0 Carnauba wax 0.5 Microcrystalline wax 5.0 B Table 1 No. Compound of 3 2.0 Butylene glycol 5.0 Triethanolamine 1.5 Purified water 50.5 C 3% Bentonite dispersion 20.0 D Pigment 10.0 Preservative proper amount Perfume proper amount Phase B is mixed and heated to 70 ℃. Phase A was mixed and melted at 70 ° C., and phase B was added to this with stirring to emulsify. The C phase and D phase swollen in advance were added to the emulsion, dispersed through a colloid mill, and then cooled.
The emulsion-type eyeliner thus obtained was easy to draw lines, and the coating film had good gloss and flexibility.

From Examples 1 to 13 of the present invention and Comparative Examples 1 to 3, it can be seen that the cosmetics of the present invention have excellent performance.

Claims (2)

[Claims] 1. The following general formula (1): (R1 is a hydrogen atom or a methyl group, R2, R3 and R
4 each represents an alkyl group, an alkoxy group or an alkoxycarbonyl group having 1 to 10 carbon atoms, which may be the same or different, n is 0 or 1, and when n = 0, R1 is a hydrogen atom. ) And a silicon compound represented by the following general formula (2): (1 and m are the average number of moles of hexafluoropropylene oxide added, which is 0 to 8) or the general formula (3): (X is a fluorine atom, a hydrogen atom or a chlorine atom, and p
And q are difluoromethylene groups and are integers of 1 to 10. ) Is a reaction product of difluoroalkanoyl peroxide and another copolymerizable compound, and the reaction molar ratio of the compound of the general formula (2) or (3) to the compound of the general formula (1) is 1 : 0.1 to 1: 5,000, the other copolymerizable compound is 50 mol% or less of the compound of the general formula (1), and the number average molecular weight is 1,000 to 1,000,000.
A cosmetic containing the reaction product of 2. The structure of the main component of the reaction product containing a fluoroalkyl group is represented by the following general formula (4): (However, Rf is a residue derived from a radical decomposition product of the compound of the general formula (2) or the general formula (3), and Or Or [Chemical 7] Or M is a monomer unit of the silicon compound of the general formula (1), S is another monomer unit, k is 1 to 5,000, and s is 0 to 2,500.
And the number average molecular weight of the polymer is 1,000 to 1,
It is, 000,000, and the inside of [] may be block or random. ) The cosmetic according to claim 1, which comprises a reaction product represented by