JPH11302140A - Cosmetic and treatment thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic having improved water resistance and cleansing resistance and excellent in makeup lasting quality by compounding a copolymer having a silyl group bound to a reactive functional group, a pigment and an acid dye. SOLUTION: This cosmetic contains a copolymer having at least one silyl group bound to a reactive functional group, a pigment and/or an acid dye. The copolymer comprises 25-99 wt.% monomer of formula I (R1 is H or methyl; R2 is a 1-6C alkylene; R3 to R5 are each a reactive functional group capable of cross-linking the copolymer molecules to each other by hydrolysis, preferably a 1-6C alkoxy, especially methoxy or ethoxy), >=1 wt.% monomer of formula II(R6 is H or metyl; R7 is a 1-18C alkyl) and >=1 wt.% monomer of formula III [R8 is H or methyl; R9 is a 1-6C alkylene X is a group of formula IV (R10 is a 1-6C alkyl) or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic and a method for treating the same, and more particularly to improving the color durability of a cosmetic containing a pigment or a dye.

[0001]

2. Description of the Related Art Pigments and dyes are blended in various cosmetics as coloring materials. Among such cosmetics, the hair dye is a temporary hair dye (color stick, color spray, etc.) that mixes a pigment as a main coloring component and adheres a dye only to the surface of hair, and an acid dye as a main coloring component. Semi-permanent hair dyes (acid hair dyes), some of which penetrate into the interior of the hair, and permanent hair dyes (oxidative hair dyes), which contain an oxidation dye as a main coloring component and dye deep into the hair.

[0002]

Of these, oxidative hair dyes have problems that, although the color lasts for a long time, they are liable to damage the hair, the scalp is rash or dyed, and the treatment is troublesome. On the other hand, temporary hair dyes and semi-permanent hair dyes do not cause damage to the hair or irritate the skin and are easy to treat, but have the drawback that they have poor color retention and are easily discolored by hair washing. Therefore, it has been desired to maintain the color durability of such temporary hair dyes and semi-permanent hair dyes.

[0003] Pigments and dyes are an essential component not only in such hair cosmetics but also in, for example, makeup cosmetics, and such makeup cosmetics have high water resistance and can improve the cosmetic durability. Requested. The present invention has been made in view of such problems of the related art, and an object of the present invention is to improve water resistance and washing resistance in a cosmetic containing a pigment and / or an acid dye,
An object of the present invention is to provide a cosmetic having excellent makeup durability and a method for treating the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, at least one reactive functional group has been added to a cosmetic containing a pigment and / or an acidic dye. By using a copolymer having a bonded silyl group, for example, a monomer having a trifunctional silyl group as a constituent monomer, and applying the cosmetic, hydrolyzing and cross-linking the cosmetic to significantly improve the cosmetic durability. Heading, the present invention has been completed.

That is, the cosmetic according to the present invention is characterized by blending a copolymer having a silyl group to which at least one reactive functional group is bonded, and a pigment and / or an acid dye. In the present invention, the silyl group to which the reactive functional group is bonded means, as described later, a compound capable of forming a siloxane bond Si—O—Si by hydrolysis and thereby cross-linking between copolymer molecules. I do. In the cosmetic of the present invention, it is preferable that the copolymer is a copolymer having the monomer (A) represented by the following general formula (I) as one of the constituent monomers.

The general formula (I):

Embedded image (In the general formula (I), R ₁ is a hydrogen atom or a methyl group;
₂ represents an alkylene group having 1 to 6 carbon atoms, and R ₃ , R ₄ and R ₅ each represent a reactive functional group capable of crosslinking between the copolymer molecules by being hydrolyzed. In the cosmetic of the present invention, it is preferable that the copolymer further has a monomer (B) represented by the following general formula (II) as a constituent monomer.

General formula (II):

Embedded image (In the general formula (II), R ₆ represents a hydrogen atom or a methyl group;
₇ means an alkyl group having 1 to 18 carbon atoms. In the cosmetic of the present invention, it is preferable that the copolymer further has a monomer (C) represented by the following general formula (III) as a constituent monomer.

The general formula (III)

Embedded image (In the general formula (III), R ₈ represents a hydrogen atom or a methyl group,
R ₉ represents an alkylene group having 1 to 6 carbon atoms. X means a group represented by any of the following formulas (IV) to (VI). )

General formula (IV):

Embedded image (In the general formula (IV), R ₁₀ means an alkyl group having 1 to 6 carbon atoms.)

General formula (V):

Embedded image (In the general formula (V), R ₁₁ and R ₁₁ ′ each have 1 carbon atom.
And alkyl groups x1 to x1 _each represent a positive integer. )

General formula (VI):

Embedded image (In the general formula (VI), R ₈ and R ₉ are as defined above.
R ₁₂ is an alkyl group having 1 to 6 carbon atoms, _{x 2} denotes a positive integer. )

In the cosmetic of the present invention, the proportion of the monomer (A) is preferably 25 to 99% by weight in the copolymer. In the cosmetic of the present invention, the proportion of the monomer (B) is preferably 1% by weight or more in the copolymer. In the cosmetic of the present invention, the proportion of the monomer (C) is preferably 1% by weight or more in the copolymer. In the cosmetic of the present invention, the copolymer further comprises a monomer (D) represented by the following general formula (VII):
Is preferable as a constituent monomer.

General formula (VII):

Embedded image (In the general formula (VII), R ₁₃ represents a hydrogen atom or a methyl group, and R ₁₄ represents an alkylene group having 1 to 6 carbon atoms.
Y is a group represented by ^-N + _{(R 15) 3} or _{-N (R 15) 2, R} 15 denotes an alkyl group having 1 to 6 carbon atoms. )

In the cosmetic of the present invention, the ratio of the monomer (D) is 1 to 100 with respect to the total weight of the monomers (A), (B) and (C) in the copolymer.
Preferably it is in the range of weight%. Also, R ₃ , R
It is preferable that ₄ and R ₅ are an alkoxy group having 1 to 6 carbon atoms. It is preferable that the cosmetic of the present invention further contains a siliconized polysaccharide compound. In addition, the cosmetic according to the present invention is preferably a hair dye. Further, the method of treating cosmetics according to the present invention is characterized in that after applying the cosmetics, the cosmetics are hydrolyzed to crosslink the copolymer molecules.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer blended in the cosmetic of the present invention has a silyl group to which at least one reactive functional group is bonded. As such a copolymer,
Copolymers having 1 to 3 functional silyl groups may be mentioned, but it is preferable to have a trifunctional silyl group from the viewpoint of the effect.

One of the preferred copolymers of the present invention is a copolymer having the monomer (A) represented by the above general formula (I) as a constituent monomer. The monomer (A) is an acrylic acid or methacrylic acid ester containing a trifunctional silyl group —SiR ₃ R ₄ R ₅ , and in the general formula (I), R ₁ is a hydrogen atom or a methyl group. R ₂ represents an alkylene group having 1 to 6 carbon atoms, and is preferably a propylene group.

R₃, R₄, R₅Can be hydrolyzed
Therefore, a siloxane-bonded Si—O—Si is formed,
Reactive functional groups capable of crosslinking between copolymer molecules of the present invention
For example, a hydrogen atom, an alkoxy group, a halogen atom
And an acyloxy group and an amino group.
Stability of coalescence and safety of by-products generated by hydrolysis
From the viewpoint of the reactivity, reactivity of the crosslinking reaction described below, etc.
An alkoxy group having a prime number of 1 to 6, particularly preferably
It is an xy group or an ethoxy group. Note that R₃, R ₄, R₅
May be the same or different. In addition, the copolymer of the present invention
In the body, one or more of the above monomers (A)
It can be a constituent monomer.

The copolymer of the present invention preferably has other constituent monomers together with the reactive silyl group-containing monomer such as the monomer (A) from the viewpoint of its effect. Although various monomers can be considered as such a monomer, a preferable one is the monomer (B) represented by the general formula (II).

The monomer (B) is an alkyl ester of acrylic acid or methacrylic acid. In formula (II), R ₆ represents a hydrogen atom or a methyl group, R ₇
Represents a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. In addition,
In the copolymer of the present invention, one or more of the above monomers (B) may be used as constituent monomers.

Further, in the copolymer of the present invention,
Having monomer (C) of general formula (III) as a constituent monomer
Is preferred. Monomer (C) contains siloxane
(Meth) acrylic acid ester. In general formula (III)
And R₈Is a hydrogen atom or a methyl group. R₉Is carbon
An alkylene group of the formulas 1 to 6, preferably ethylene
Group, propylene group, 2-hydroxypropylene group
You. X is a silo represented by any of the general formulas (IV) to (VI)
Means Xan. In the general formulas (IV) to (VI),
R ₁₀, R₁₁, R₁₁', R₁₂Is a straight chain having 1 to 6 carbon atoms
Represents a chain or branched alkyl group or a phenyl group. What
Note that R in each general formula₁₀, R₁₁, R₁₂Are multiple
Although there are numbers, they may be the same or different.
R₁₀, R₁₁, R ₁₂Is preferably a methyl group
You. R₁₁Preferably, 'is a butyl group.
When X is the general formula (V) or the general formula (VI),
(C) preferably has a molecular weight of 1,000 to 100,000.
2,000 to 20,000. It should be noted that the present invention
In the copolymer, one or two of the above monomers (C) are used.
The above can be used as constituent monomers.

The copolymer of the present invention may further have, as a constituent monomer, an amine-containing (meth) acrylate monomer (D) represented by the above general formula (VII). In the general formula (VII), R ₁₃ is a hydrogen atom or a methyl group. R ₁₄ represents an alkylene group having 1 to 6 carbon atoms, preferably an ethylene group or a propylene group. Y is a group represented by ^-N + _{(R 15) 3} or _{-N (R 15) 2, R} 1 5 denotes an alkyl group having 1 to 6 carbon atoms. In the case of -N ⁺ (R ₁₅ ) ₃ groups, a salt having a counter ion of a halogen, an inorganic acid, an organic acid or the like may be used.

Incidentally, as long as the effects of the present invention are not impaired, a monomer (E) other than the above-mentioned monomers (A) to (D) can be contained as a constituent monomer of the copolymer of the present invention. The copolymer according to the present invention can be obtained by polymerizing the above monomers using a known polymerization method, and for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or the like can be used. For example, in the case of the solution polymerization method, the copolymer of the present invention can be obtained by dissolving each monomer in a solvent with a desired monomer composition, adding a radical polymerization initiator under a nitrogen atmosphere, and heating and stirring. it can.

As the solvent used in the polymerization, any solvent can be used as long as it is capable of dissolving or suspending the monomer, and any organic solvent containing no water, such as methanol, ethanol, Alcohol solvents such as propyl alcohol, isopropyl alcohol and butyl alcohol, hexane, heptane, octane,
Hydrocarbon solvents such as isooctane, decane and liquid paraffin; ether solvents such as dimethyl ether, diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; methylene chloride Dimethylformamide, diethylformamide, dimethylsulfoxide, dioxane, and the like, in addition to chloride solvents such as chloroform, carbon tetrachloride and the like. These solvents may be used as a mixture of two or more kinds. Usually, it is preferable to select a solvent having a boiling point higher than the starting temperature of the polymerization initiator to be used.

The polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization. For example, peroxides such as benzoyl peroxide, azobisisobutyronitrile, 2,2'-azobis (Isobutyric acid) In addition to azo compounds such as dimethyl, persulfate polymerization initiators such as potassium persulfate and ammonium persulfate are exemplified. In addition, polymerization can be performed by photochemical reaction, irradiation of radiation, or the like, without using these polymerization initiators.

The polymerization temperature is not lower than the polymerization initiation temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, usually 7
The temperature may be set to about 0 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours. When it is desired to obtain a polymer having a relatively high molecular weight, the reaction is desirably performed for about one day. If the reaction time is too short, unreacted monomers will remain,
The molecular weight can also be relatively small.

The average molecular weight of the copolymer according to the present invention is not particularly limited, and a desired effect can be exerted as long as the copolymer has a degree of polymerization equal to or higher than that of the oligomer. However, if the degree of polymerization decreases, the rate of the crosslinking reaction described below decreases, and if the degree of polymerization is too high, the viscosity increases and the coating properties and workability deteriorate, so that the average molecular weight is 2,000 to 15
It is preferable to be about 000.

The thus obtained copolymer of the present invention has a functional silyl group in the molecule. For this reason,
By hydrolyzing this, the copolymer molecules are crosslinked with each other to form a crosslinked product. Then, after applying a hair dye obtained by blending the copolymer with a coloring material such as a pigment or an acid dye to hair, if such a crosslinking reaction is carried out, it is excellent in water resistance, washing resistance, and There is no adhesion to the dye, and the durability of the dyeing is remarkably improved. In addition, the feeling of use is not remarkable and flaking does not occur. Further, when the cosmetic of the present invention is applied as a makeup cosmetic, the same effect is exhibited, and the durability of the makeup is remarkably improved.

The mechanism by which such an effect is exhibited is considered as follows. FIG. 1 schematically shows the reaction of a copolymer having the monomer (A) as a constituent monomer. That is, the copolymer according to the present invention comprises a trifunctional silyl group -SiR derived from the monomer (A).
_{It has 3} R ₄ R ₅ . This trifunctional silyl group is water,
It is easily hydrolyzed by an acid, an alkali, or the like to form a trihydroxysilyl group —Si (OH) ₃ . This trihydroxysilyl group reacts with another trihydroxysilyl group to form a stable siloxane-bonded Si-O-Si, and as a result, a cross-linked copolymer in which copolymer molecules are cross-linked in a three-dimensional network. (In the present invention, it may be referred to as a crosslinked body).

Therefore, after the copolymer is coated and hydrolyzed, cross-linking occurs at the coated portion, and the cross-linked body firmly covers the coated portion in a network while embedding a coloring material such as a pigment or dye. And form a film having excellent water resistance and washing resistance. As a result, it is presumed that the coloring material does not flow or adhere to the contacted object, and the color durability of the hair dye and the makeup cosmetic is improved.

It should be noted that even if such a cross-linking reaction is not carried out after coating, but a cross-linked product is synthesized in advance and this is to be applied,
It is very difficult to apply the crosslinked product because it becomes a gel or a plastic.

The monomer composition of the copolymer blended in the cosmetic of the present invention is such that the proportion of the monomer (A) in the copolymer is 25 to 99% by weight, and more preferably 40 to 85% by weight. It is suitable. If the amount of the monomer (A) is too small, the number of crosslinking reaction sites is small, so that the water resistance and the washing resistance are low, and the effect of improving cosmetic durability may not be sufficiently exhibited. on the other hand,
Even when the amount of the monomer (A) is 100% by weight, water resistance, washing resistance, and cosmetic durability tend to be reduced. In addition, flaking tends to occur. This is probably because the cross-linking reaction does not proceed cleanly and the unreacted site remains in a large amount on the copolymer because the cross-linking reaction site is too many and dense.

The monomer (B) adjusts the ratio of the monomer (A) to contribute to water resistance and also suppress flaking. The proportion of the monomer (B) is 1% by weight or more, preferably 10% by weight or more in the copolymer.
When the proportion of the monomer (B) increases, the proportion of other monomers decreases, and the copolymer may become poorly soluble in alcoholic solvents. Therefore, the proportion of the monomer (B) is at most 75% by weight or less, preferably at most 75% by weight. It is 60% by weight or less.

The monomer (C) has a siloxane moiety,
Thereby, the water resistance and washing resistance of the crosslinked product film can be improved, and the feeling of use can be made smooth and favorable. It also suppresses flaking. In the copolymer of the present invention, the amount of the monomer (C) is at least 1% by weight, preferably 5% by weight.
It is at least 70% by weight, but if the proportion of the monomer (C) is too large, the proportion of other monomers tends to be relatively low and the washing resistance tends to be inferior. It is 60% by weight or less.

When a copolymer having the monomer (D) as a constituent monomer is treated, a slimy feeling is imparted to the hair, and a moist feeling is obtained.
However, when the proportion of the monomer (D) is too large, the amine portion of the monomer (D) increases the hydrophilicity of the coating, resulting in poor water resistance, washing resistance and the like. The proportion of the monomer (D) is 1 to 100% by weight, preferably 5 to 50% by weight based on the total weight of the monomers (A) to (C).
% By weight. Preferred examples of the copolymer of the present invention include, for example, copolymers represented by formulas (VIII), (IX) or (X).

Formula (VIII):

Embedded image

General formula (IX):

Embedded image

Formula (X):

Embedded image In the general formulas (VIII) to (X), R ₁ , R ₂ , R ₃ , R
_{4, R 5, R 6,} R 7, R 8, R 9, R 13, R 14,
X and Y are as defined above. n, m, l, and p represent the molar ratio of monomer (A), monomer (B), monomer (C), and monomer (D), respectively.

There are no particular restrictions on the pigments and acid dyes to be incorporated into the cosmetic of the present invention, as long as they are usually incorporated into cosmetics.

As the acid dye, specifically, it can be used for coloring pharmaceuticals, quasi-drugs and cosmetics which do not show harmful effects on the human body. Legal dyes listed in "Ministerial Ordinance for Specifying Tar Dyes" can be used. For example, red 3
(Erythrosin), red 102 (new coccin), red 106 (acid red), red 201 (lithol rubin B), red 227 (fast acid magenta), red 230 (1) (erythrosin Y)
S), Red No. 203 (2) (erythrosin YSK),
Red No. 231 (Phloxin BK), Red No. 232 (Rose Bengal K), Red No. 401 (Violamin R), Red No. 502 (Bonsau 3R), Red No. 503 (Bonsau R), Red No. 504 (Bonsau SX), Red No. 506 (fast red S), yellow 202 (2) (uranin K), yellow 4 (tartrazine), yellow 402 (polar yellow 5G), yellow 403 (1) (naphthol yellow S), yellow 406 No. (metanyel yellow), green No. 3 (fast green FCF), green No. 201 (alizarin cyanine green F), green No. 204 (pyranine conch), green No. 205 (light green SF yellow),
Green No. 401 (Naphthol Green B), Green No. 402 (Ginea Green B), Blue No. 1 (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Blue 202
No. (Patent Blue NA), Blue No. 205 (Alphazurin FG), Brown No. 201 (Resorcinol Brown), Purple No. 401 (Alizur Purple), Black No. 401 (Naphthol Blue Black) and the like.

As the pigment used in the present invention, lakes can be used in addition to organic pigments and inorganic pigments. Examples of the organic pigment include azo pigments, indigo pigments, phthalocyanine pigments, and organic pigments such as β-carotene calsamine and cochineal. As inorganic pigments, Bengala,
Color pigments such as yellow iron oxide, black iron oxide, chromium oxide, ultramarine, navy blue, carbon black, etc., extenders such as mica, talc, kaolin, etc., white pigments such as titanium dioxide, zinc oxide, titanium mica, fish scale foil Pearl pigments, boron nitride, etc.
Special functional pigments such as photochromic pigments, synthetic fluorophlogopite, and fine particle composite powders, and the like can be given. As for the rake, red 202, 204, 206, 207, 2
In addition to lake pigments such as No. 20, dye lakes such as aluminum lakes may be mentioned.

The method of treating the cosmetic of the present invention is characterized in that the cosmetic of the present invention is applied and then hydrolyzed to crosslink the copolymer molecules. As a crosslinking method,
Examples of the reaction include a reaction with water, an acid, and an alkali and a reaction with heat. Specifically, there is a method in which, after the cosmetic of the present invention is applied, the applied portion is brought into contact with water (or water vapor or the like), an acid, or an alkali, or is hydrolyzed or crosslinked by heating. Alternatively, the cosmetic may be applied to a portion to be coated which has been previously treated with water, an acid, or an alkali to perform hydrolysis and crosslinking. A method of mixing the cosmetic of the present invention with water, an acid or an alkali and immediately applying the mixture is also conceivable, but a method of separately applying the cosmetic and water, an acid, an alkali or the like is more preferable. In the case of a reaction with water, an acid or an alkali, heating may be performed, but treatment at room temperature is usually sufficient. In addition,
When the progress of the crosslinking reaction may be slow, spontaneous crosslinking can also be performed with moisture in the atmosphere without contact with such acids, alkalis and water. Also,
In each case, a brush, a comb, a brush or the like can be used as appropriate for uniform application and treatment.

An acid used in the treatment method according to the present invention,
The alkali is not particularly limited as long as it can hydrolyze the copolymer to cause a crosslinking reaction, and organic and inorganic acids and alkalis can be used. Of course, one or more of these acids and alkalis can be used, and a mixture with water may be used.

The cosmetic according to the present invention comprises:
The present invention is characterized in that a pigment and / or an acid dye is blended as an essential component. One preferred embodiment thereof is a non-aqueous composition. Examples of the non-aqueous composition include those obtained by dissolving or dispersing the copolymer and a coloring material in a hydrophilic solvent. Examples of such a hydrophilic solvent include aliphatic 1 having 1 to 4 carbon atoms. To tetrahydric alcohol, ethyl cellosolve, butyl cellosolve, dioxane, methyl acetate, diformamide and the like. Among these, preferred as cosmetic raw materials are aliphatic 1
To dihydric alcohols such as methanol, ethanol, isopropanol and propylene glycol, and particularly preferred is ethanol and isopropanol from the viewpoint of safety.

When the cosmetic composition according to the present invention is used as a water-containing composition, a crosslinking reaction occurs in the product, so that it is preferable to appropriately prepare the composition at the time of application. Such a water-containing composition is also included in the cosmetic of the present invention. The amount of the copolymer in the cosmetic according to the present invention is not particularly limited, but is preferably 0.1 to 10% by weight, particularly preferably 1 to 5% by weight. If the amount is too small, sufficient effects may not be obtained in a single treatment. If the amount is too large, coatability, extensibility, etc. may be poor or flaking may occur.

The amount of the pigment or acid dye can be appropriately determined according to the desired coloring property, and is not particularly limited, but is usually 0.01 to 20% by weight, and more preferably 0.1 to 10% by weight. Preferably it is in the range of weight%. If the amount of the pigment or the dye is too large, secondary adhesion is likely to occur.

The dosage form of the cosmetic according to the present invention is not particularly limited, and may be in any form as long as the effects of the present invention can be exhibited. For example, liquid, milky, creamy,
Gel, solid, mist, spray, aerosol, mousse and the like can be mentioned. Applications include, for example, hair dyes such as color spray, color crayon, and color mousse,
Makeup cosmetics such as nail enamel, mascara, eyebrow and the like can be mentioned.

The cosmetics according to the present invention may be blended with components normally contained in cosmetics as long as the effects of the present invention are not impaired. For example, surfactants, humectants, ultraviolet ray protective agents, pH adjusters, preservatives, antioxidants, chelating agents, thickeners, film-forming agents, oily components, polymer compounds, propellants, powders, and the like. . It is preferable that water, acid, and alkali are separately prepared from the copolymer, but if appropriately prepared at the time of coating, water, acid, and alkali are mixed in the composition together with the copolymer of the present invention as described above. It is also possible. When another film-forming agent is incorporated into the cosmetic along with the copolymer of the present invention, preferred film-forming agents include a siliconized polysaccharide compound represented by the following general formula (XI).

Formula (XI):

Embedded image (In the general formula (XI), Glu is a sugar residue of the polysaccharide compound, and P is 2
R ₁₆ is a monovalent organic group having 1 to 8 carbon atoms, and R ₁₇ , R ₁₈ and R ₁₉ are each a monovalent organic group having 1 to 8 carbon atoms. Or -OSiR ₂₀ R
A siloxy group represented by ₂₁ R ₂₂ is meant. However,
R ₂₀ , R ₂₁ , and R ₂₂ each represent a monovalent organic group having 1 to 8 carbon atoms, a represents 0, 1 or 2, and b represents a positive integer. )

In the general formula (XI), Glu represents a saccharide residue of a polysaccharide compound. As such a polysaccharide compound, various known polysaccharide compounds can be used, such as cellulose, hemicellulose, gum arabic, Tragacanth gum, tamarind gum, pectin, starch, mannan,
Guar gum, locust bean gum, quince seed gum, alginic acid, carrageenan, agar, xanthan gum, dextran, pullulan, chitin, chitosan, hyaluronic acid, chondroitin sulfate, and derivatives of these polysaccharide compounds, for example, carboxymethylation, sulfated, phosphorus Examples include polysaccharide compound derivatives that have been subjected to oxidation, methylation, ethylation, addition of alkylene oxides such as ethylene oxide and propylene oxide, acylation, cationization, and molecular weight reduction. Among them, preferred is ethyl cellulose or pullulan, and particularly preferred is pullulan. In the present invention, the average molecular weight of the polysaccharide compound varies depending on the type of the polysaccharide compound, but is usually about 1,000 to 5.0.
00,000 is preferred.

These polysaccharide compounds contain at least one or more reactive functional groups such as a hydroxyl group and a carboxyl group depending on the type. The divalent linking group represented by P is a linking group derived from A formed by reacting a reactive functional group of the polysaccharide compound with a silicone compound represented by the following general formula (XII).

[0051]

Embedded image General formula (XII):

In the general formula (XII), Q, R ₁₆ , R ₁₇ , R
₁₈ , R ₁₉ and a are the same as those in the general formula (XI). A is a functional group capable of reacting with the reactive functional group of the polysaccharide compound, and examples thereof include an isocyanate group, an epoxy group, a vinyl group, an acryloyl group, a methacryloyl group, an amino group,
Examples include an imino group, a hydroxyl group, a carboxyl group, and a mercapto group. For the reaction between the silicone compound and the polysaccharide compound, a conventionally known method, for example, a method described in JP-A-8-134103 can be used.

Examples of P include a carbamoyl group, -CH
₂ CH (OH)-, a carbonyl group, an amino group, an ether group, and the like. From the viewpoint of reactivity, the compound of the general formula (XII) wherein A is an isocyanate group (O = C = N-) And a carbamoyl group (—CONH—) formed by reacting a hydroxyl group of a polysaccharide compound. In this case, the sugar residue of the polysaccharide compound means the remaining portion of the polysaccharide compound excluding the hydrogen atom of the hydroxyl group that has reacted with the isocyanate group. Further, in the case of other reactions, the sugar residue of the polysaccharide compound means the same.

Examples of the divalent aliphatic group represented by Q include an alkylene group, an alkylene group having an oxygen atom, a nitrogen atom, a sulfur atom and the like in the main chain, and an alkylene group having an arylene group such as a phenylene group in the main chain. Groups and alkylene groups having a carbonyloxy group or an oxycarbonyl group in the main chain. These divalent aliphatic groups can have a substituent such as a hydroxy group, an alkoxy group, or an alkyl group, and the terminal atom of the aliphatic group is a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Is also good. To illustrate the _{Q, - (CH 2) 2} -, - (CH 2) 3 -, -
_{(CH 2) 4 -, -} (CH 2) 6 -, - (CH 2)
_{8 -, - [CH 2 CH} (CH 3)] -, - (CH 2) 2
O (CH ₂ ) ₃ —, —CH ₂ CH (OH) —CH ₂ — and the like are exemplified, and a propylene group represented by — (CH ₂ ) ₃ — is preferable.

In the general formula (XI), R ₁₆ ,
Examples of the monovalent organic group having 1 to 8 carbon atoms found in R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group.
Cyclopentyl group, cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group, aralkyl group such as benzyl group, vinyl group, alkenyl group such as allyl group, 3,3,
Examples thereof include a fluorinated alkyl group such as a 3-tolufluoropropyl group. Such an organic group is preferably an alkyl group, and more preferably a methyl group.

Further, R ₁₇ , R ₁₈ and R ₁₉ may each be a siloxy group represented by —OSiR ₂₀ R ₂₁ R ₂₂ . Such siloxy groups include trimethylsiloxy, ethyldimethylsiloxy, phenyldimethylsiloxy, vinyldimethylsiloxy, 3,3,3-
Examples thereof include a trifluoropropyldimethylsiloxy group. R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ ,
R ₂₁ and R ₂₂ may be the same or different. In the siliconized polysaccharide compound of the present invention, when a = 0 and R
It is preferred that ₁₇ , R ₁₈ and R ₁₉ are methyl groups. In the present invention, a particularly preferred siliconized polysaccharide compound is a siliconized pullulan represented by the following general formula (XIII).

[0057]

Embedded image General formula (XIII): (In the general formula (XIII), B represents a hydrogen atom or -CONH (C
H ₂ ) ₃ Si [OSi (CH ₃ ) ₃ ], the substitution degree of which is 0.5 to 2.5, c is 100 to 20,
000 number. In the present invention, the degree of substitution of the siliconized polysaccharide compound means the average number of bonds of the silicone compound per unit sugar constituting the polysaccharide compound. For example, the substitution degree of the siliconized pullulan is determined by the substituent -CONH (CH ₂ ) ₃ attached to the basic unit of pullulan represented by the following general formula (XIV).
Indicates the average number of Si [OSi (CH ₃ ) ₃ ].

[0058]

Embedded image General formula (XIV):

When the reactive silyl group-containing copolymer and the silicone-containing polysaccharide compound are used in combination, the longevity and feeling of use can be enhanced, and further, the flaking when the composition is overlaid can be suppressed. . When a silicone-containing polysaccharide compound is blended, it is dissolved in low molecular weight silicone oil or light isoparaffin as a solvent and blended.
The ease of compounding and the feeling of use during application can be enhanced. As the low molecular weight silicone oil, a linear dimethylpolysiloxane having 2 to 7 carbon atoms and a cyclic dimethylpolysiloxane having 3 to 7 carbon atoms are preferable. The amount of the siliconized polysaccharide compound in the composition is not particularly limited, but is usually 0.01 to 20% by weight, preferably 0.2 to 10% by weight.
It is. Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the structure of each monomer used below is as follows.

Monomer A1:

Embedded image

Monomer A2:

Embedded image

Monomer B1:

Embedded image

Monomer C1 (average molecular weight 422) and monomer C2 (average molecular weight 12,000):

Embedded image

Monomer C3 (average molecular weight 5,000):

Embedded image

Monomer C4:

Embedded image

Monomer D1:

Embedded image

[0067]Synthesis of copolymer Copolymer 1  3-methacryloxypropyltrimethoxysilane (mo
Nomer A1) 2.0 g (8 mmol) and methacrylic acid
8.0 g (80 mmol) of methyl (monomer B1) was added.
Dissolve in 100 ml of ethanol, and in a nitrogen stream at 70 ° C.
After heating and stirring for 0.05 hours, add 0.05 g of potassium persulfate
The reaction was allowed to take place overnight to complete the copolymerization reaction. Reaction solution at room temperature
And concentrated under reduced pressure. Residue is ethanol 10ml
And added to 500 ml of n-hexane. Settling
The product was separated to obtain the desired copolymer.

In the NMR spectrum data (solvent CDCl ₃ or DMSO-d ₆ ) of the obtained copolymer, a peak of a CH ₂ ＣC hydrogen atom derived from a raw material monomer, which is observed at about _{6 to} 7 ppm, was recognized. No formation was confirmed from this. Further, in the present invention, the formation of a copolymer was similarly confirmed for other copolymers.

[0069]Copolymer 2  3. 3-methacryloxypropyltrimethoxysilane
0 g (16 mmol) and 8.0 g of methyl methacrylate
(80 mmol), except that copolymer 1 was used.
Thus, the desired copolymer was obtained.

[0070]Copolymer 3  7. 3-methacryloxypropyltrimethoxysilane
0 g (32 mmol) and 4.0 g of methyl methacrylate
(40 mmol) except that copolymer 1 was used.
Thus, the desired copolymer was obtained.

[0071]Copolymer 4  3-methacryloxypropyltrimethoxysilane 1
0.0 g (40 mmol) and methyl methacrylate
Same as copolymer 1 except that 0 g (20 mmol) was used.
Thus, the desired copolymer was obtained.

[0072]Copolymer 5  3-methacryloxypropyltrimethoxysilane 1
0.0 g (40 mmol) and methyl methacrylate 0.
Same as copolymer 1 except that 4 g (4 mmol) was used
To obtain the desired copolymer.

[0073]Copolymer 6  3-methacryloxypropyltrimethoxysilane 1
The above copolymerization was used except that only 0.0 g (40 mmol) was used
A target copolymer was obtained in the same manner as in Preparation 1.

[0074]Test example 1  i) Sample preparation Formula 1: (1) Copolymer 2 or 3 wt% (2) Carbon black 2 (3) Ethanol 44.8 or 43.8 (4) Beeswax 10 (5) Mokurou 10 (6) Castor Oil 30 (7) POE (20) Sesquioleate 1.2 (8) Appropriate amount of fragrance (9) Appropriate amount of antioxidant

(Preparation method) An oil and carbon black were sequentially added to an ethanol solution of the copolymer, and after adding a fragrance and an antioxidant, the mixture was sufficiently stirred to obtain a temporary hair dye.

Ii) Test method Each sample was applied to gray hair, left for 3 minutes, washed with water, and air-dried. At this time, the presence or absence of flaking was evaluated. Thereafter, the hair was washed and dried naturally with a commercially available shampoo every day, and the durability was visually evaluated. In addition, a hair dye containing ethanol instead of the copolymer was also prepared as a control, and the test was performed in the same manner. The evaluation criteria are as follows.

[0077]Evaluation standard for dyeing durability  A: The staining effect was maintained for 7 days or more. ：: The staining effect was maintained for 4 to 6 days. Δ: The dyeing effect was maintained for 2 to 3 days or more. X: No persistence.

[0078]Flaking evaluation criteria  ◎: No flaking at all. Δ: Slight flaking is observed. ×: Clear flaking is observed.

[0079]

[Table 1]  Copolymer monomer [wt%]A1 / B1 2% by weight 3% by weight 3% by weight  1 20/80 △ ○ ◎ 233/67 ○ ◎ ◎ 3 67/33 ○ ◎ ◎ 4 83/17 ○ ◎ ◎ 5 96/4 ○ ◎ ◎6 100/0 △ ○ △  None − × × ◎(ethanol)

As can be seen from Table 1, the temporary hair dye containing the copolymer has excellent washing resistance and markedly improved durability over the case where no copolymer is used. Understood.

[0081]Test example 2  A liquid acidic hair dye was prepared according to the following formula 2, and the test example 1 was used.
Test for dye retention and flaking in the same manner as
Tested. Formulation 2 Copolymer 2 or 3% by weight Acid dye (Natrozole) 1 Ethanol 20.7 or 19.7 Benzyl alcohol 6 Isopropyl alcohol 20 Lactic acid 0.3 Silicon KF-56 (Shin-Etsu Chemical Co., Ltd.) 50 Amount Antioxidant Appropriate amount

[0082]

[Table 2]  Copolymer monomer [wt%]A1 / B1 2% by weight 3% by weight 3% by weight  1 20/80 △ ○ ◎ 233/67 ○ ◎ ◎ 3 67/33 ○ ◎ ◎ 4 83/17 ○ ◎ ◎ 5 96/4 ○ ◎ ◎6 100/0 △ ○ △  None − △ △ ◎(ethanol)

As can be seen from Table 2, even when the copolymer of the present invention is blended with an acidic hair dye, excellent washing resistance is exhibited, and dye durability is improved. If the amount of the monomer (A) in the copolymer is too small or too large, the washing resistance tends to be low, and the effect of improving the dye durability tends to be low. Therefore, in the present invention, the proportion of the monomer (A) in the copolymer is 25 to 99% by weight, and more preferably 40 to 8% by weight.
5% by weight is preferred.

[0084]Test example 3  Next, the copolymer having the monomer composition shown in Table 3 was mixed with the copolymer.
Synthesized in the same way as the union, and temporarily
Hair dyes and acid hair dyes were prepared respectively. In addition, copolymerization
The amount of each body was 2% by weight. Same as Test Example 1
The test was performed as described above. Also, for smoothness and slimy feeling
This was evaluated by the following method.

[0085]Smoothness  In the dyeing durability test, apply the sample, wash with water, and
We conducted a questionnaire about the smoothness of the hair after drying,
Evaluation was made according to the following criteria. ：: Of the 20 persons, 16 or more persons had smooth use feeling.
I answered. ：: 12 to 15 out of 20 persons felt smooth in use
I answered. Δ: 6 to 11 out of 20 persons had smooth use feeling.
I answered. ×: 0 to 5 out of 20 people feel smooth in use
I answered.

[0086]Slimy feeling  In the dyeing durability test, apply the sample, wash with water, and
A questionnaire was asked about the sliminess of the hair after drying.
The evaluation was based on the following criteria. ◎: 15 or more of the 20 respondents answered that they were good. ：: Out of the 20 persons, 10 to 14 persons answered that they were good. B: Out of the 20 persons, 5 to 9 persons answered that they were good. ×: Out of 20 persons, 0 to 5 persons answered that they were good.

[0087]

[Table 3]Temporary hair dye (Formulation 1, copolymer 2% by weight)  Copolymer monomer [% by weight] Dyeing Smoothness FlakingA2 B1 C * 7 67 33-○ ○ ◎  8 50 10 40 (C1) ◎ ◎ ◎ 9 50 10 40 (C2) ◎ ◎ ◎ 10 50 40 10 (C3) ◎ ◎ ◎11 60 35 5 (C4) ◎ ◎ ◎  12 50-50 (C2) ○ ◎ ◎13 25-75 (C4) △ ◎ ◎  * () Indicates the used monomer (C)

[0088]

[Table 4]Acid hair dye (Formulation 2, copolymer 2% by weight)  Copolymer monomer [% by weight] Dyeing Smoothness FlakingA2 B1 C * 7 67 33-○ ○ ◎  8 50 10 40 (C1) ◎ ◎ ◎ 9 50 10 40 (C2) ◎ ◎ ◎ 10 50 40 10 (C3) ◎ ◎ ◎11 60 35 5 (C4) ◎ ◎ ◎  12 50-50 (C2) ◎ ◎ ◎13 25-75 (C4) ○ ◎ ◎  * () Indicates the used monomer (C)

As can be seen from Tables 3 and 4, by introducing the monomer (C) into the copolymer, the color durability of the hair dye is improved and the feeling of use of the treated hair is smoothened. it can. Further, in the copolymers 12 and 13 composed of the monomers (A) and (C), although the copolymer was sticky and difficult to handle, the dyeing durability and smoothness were sufficiently satisfactory.

From the above, the proportion of the monomer (C) in the copolymer is preferably 1% by weight or more, more preferably 5% by weight or more. Further, the monomer (B) in the copolymer also contributes to prevention of stickiness of the copolymer, and the proportion of the monomer (B) in the copolymer is preferably 1% by weight or more, more preferably 10% by weight or more. It was suggested that there is.

[0091]

[Table 5]Temporary hair dye (Formulation 1, copolymer 2% by weight)  Copolymer monomer [wt%]A2 B1 C4 D1 11 60 35 5-◎ △  14 60 35 5 10 ◎ ◎ 15 60 35 5 20 ○ ◎ 16 60 35 5 50 ○ ◎17 60 35 5 100 × ◎

For the copolymer synthesized with the monomer composition shown in Table 5, a temporary hair dye (formulation 1, copolymer blending amount 2% by weight) was prepared. As can be seen from Table 5, the monomer (A)
When the copolymer consisting of-(D) is blended with a temporary hair dye,
It can give the hair a slimy feel and a moist feel. When the proportion of the monomer (D) increases, the hydrophilicity of the crosslinked body coating increases, and the dye holding effect tends to decrease. This tendency was the same for the acidic hair dye. Therefore, the ratio of the monomer (D) is 1 to 100% by weight, preferably 5 to 50% by weight based on the total weight of the monomers (A) to (C) in the copolymer.
It is.

The present inventors have further studied the effect of the case where another film-forming agent is used in combination with a cosmetic containing a copolymer and a pigment and / or an acidic dye. As the film-forming agent, siliconized pullulan (a substitution degree of 1.7, molecular weight of the raw material pullulan of about 200,000), which is one of the siliconized polysaccharide compounds, was used.

[0094]Test example 4  Formulation 3 (temporary hair dye): Copolymer 5% by weight Siliconized pullulan 1 Carbon black 1 Ethanol 22.8 Light isoparaffin 70 Silicone rubber 0.2 Perfume Appropriate amount Preservative Appropriate amount

A temporary hair dye was prepared according to Formula 3 above. In addition, a hair dye containing ethanol instead of the siliconized pullulan was also prepared as a control. The test was performed by the following method using each hair dye as a sample. The sample was applied to gray hair, left for 3 minutes, washed with water, and air-dried. Thereafter, the hair was washed and dried naturally with a commercially available shampoo every day, and the dyeing durability after 10 days was visually evaluated. The criteria are as follows. A: Very good as compared to the control. ○: Equal to or slightly better than the control. Δ: Slightly inferior to control. X: Inferior to control.

(Smoothness) The smoothness on the first and tenth days of the above dyeing durability test was evaluated by touch. The criteria are as follows. A: Very good as compared to the control. ○: Equal to or slightly better than the control. Δ: Slightly inferior to control. X: Inferior to control.

(Flaking at the time of stacking) About 2 g of a sample was sprayed on the hair of 20 specialized panels, and then washed with water and air-dried. After further three cycles of spraying, washing the hair, and air drying the sample, the presence or absence of flaking was visually determined. The evaluation criteria are as follows. ◎: No flaking at all. Δ: Slight flaking is observed. ×: Clear flaking is observed.

[0098]

[Table 6]  Copolymer Monomer [wt%] Dyeing Smoothness StackedA2 B1 C * D1 Day 1 Day 10 Flaking  Copolymer 19 60 35 5 (C3) 20 ◎ ◎ ◎ ◎ Copolymer 20 50 40 10 (C1)-○ ◎ ◎ ◎ Copolymer 21 50 25 25 (C2)-○ ◎ ◎ ◎ Copolymer 22 67 37--○ ◎ ◎ ◎Copolymer 23 50-50 (C3)-○ ◎ ◎ ◎

As shown in Table 6, when the copolymer and the siliconized pullulan are used in combination, the dye retention effect can be made equal to or higher than that of the copolymer alone.
In addition, the feel can be made smoother than the case of using the copolymer alone, and the effect is particularly remarkable for damaged hair. And these effects persisted after repeated shampooing. Further, in the case of the copolymer alone, flaking sometimes occurred when the copolymer was superimposed, but it could be suppressed by the combined use with the siliconized pullulan. In addition, such an effect was the same also in the case of an acidic hair dye.

[0100]

[Table 7] Ingredients Amount  Copolymer 19 5 5 5 2 2 1 0.1 −Siliconized ferulan − 0.1 0.5 0.5 2 5 5 5 Dye holding − ○ ◎ ◎ ◎ ○ △ △  Smoothness Day 1-○ ◎ ◎ ◎ ◎ ◎ ◎Day 10 − ○ ◎ ◎ ◎ ◎ ◎ ◎ Flaking during stacking △ △ ◎ ◎ ◎ ◎ ◎ ◎ ◎

Table 7 shows the results of a test performed in the same manner as in Test Example 4 except that the mixing ratio of the copolymer and the siliconized pullulan was changed. The amount of change in the copolymer and the siliconized pullulan was adjusted with ethanol. When the amount of the copolymer is small, the dyeing durability tends to decrease. On the other hand, when the amount of the siliconized pullulan is small, the durability and smoothness of the dyeing are not sufficiently improved, and flaking may occur during superposition. Thus, the preferred weight ratio of copolymer to siliconized pullulan is 100: 1 to 1: 100, and even more preferably 50: 1 to 1: 1.
1: 1.

As described above, by using the reactive silyl group-containing copolymer and the silicone-containing polysaccharide compound in combination with the pigment and / or the acid dye, the color retention and the feeling of use are extremely good, and the flaking due to superposition is achieved. Less cosmetics can be obtained. In the case of using the silicone-containing polysaccharide compound alone, since the dye-holding effect is lower than that of using the copolymer alone, the effect is improved by using the silicone-containing polysaccharide compound in combination, because a crosslinked film of the copolymer is formed. It is presumed that the emulsification of the siliconized polysaccharide compound at the time of synthesizing contributes synergistically to the crosslinked product film and the film of the siliconized polysaccharide compound.

[0103]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, all compounding amounts are weight%.

[0104]Examples 1 to 3 Color spray  Using the color spray of Table 8, the same as in Test Example 1
As a result of the test, all of Examples 1 to 3 were compared with Comparative Example 1.
High washing resistance and excellent dye durability.

[0105]

[Table 8] Components Example 1 Example 2 Example 3 Comparative Example 1  (1) Copolymer 4 135-(2) Polyvinylpyrrolidone / vinyl acetate copolymer-5-(3) Black iron oxide 111 (4) Ethanol 46 44 42 42 (5) POE (40) ) Hardened castor oil 1 1 1 1 (6) Octyl palmitate 1 1 1 1 (7) LPG (3.5 kg / cm^Two at 20 ℃) 50 50 50 50(8) Fragrance proper amount proper amount proper amount proper amount Dyeing ○ ◎ ◎ ×  (Manufacturing method) (1) to (6) and (8) are uniformly stirred and mixed
Later, this is filled into an aerosol container, and (7) is filled
A color spray was obtained.

[0106]Examples 4 to 6 Hair mist  Using the hair mist of Table 9, the same test as in Test Example 1 was performed.
As a result, all of Examples 4 to 6 were more resistant than Comparative Example 2.
The washing property was high and the dyeing durability was excellent.

[0107]

[Table 9] Ingredients Example 4 Example 5 Example 6 Comparative Example 2  (1) Copolymer 11 35-(2) Polyvinyl alcohol / vinyl acetate copolymer-5 (3) Carbon black 11 11 (4) Ethanol 96 94 92 92 (5) POE (9) Lauryl ether 1 1 1 1 (6) Dimethylpolysiloxane (5cps) 1 1 1 1(7) Fragrance proper amount proper amount proper amount proper amount ○ ○ ◎ ×  (Production method) (1) to (7) are uniformly stirred and mixed, and filled in a container.
To obtain a hair mist.

[0108]Examples 7 to 9 Color spray  As in Test Example 1 above, using the color sprays in Table 10.
In Examples 7 to 9, all of Examples 7 to 9 were compared with Comparative Example 3.
The washing resistance was high, and the dyeing durability was excellent.

[0109]

[Table 10] Ingredients Example 7 Example 8 Example 9 Comparative Example 3  (1) Copolymer 5 13 5-(2) Polyvinyl peritritol / vinyl acetate copolymer-5-(3) Resorcinol brown 111 (1) Ethanol 48.2 46.2 44.2 49.2 (5) Benzyl alcohol 55 5 5 (6) Citric acid 0.3 0.3 0.3 0.3 (7) POE (100) hydrogenated castor oil 1 1 1 1 (8) High molecular weight methylpolysiloxane 0.5 0.5 0.5 0.5 (9) Dimethylpolysiloxane (5cps) 3 3 3 3 (10) LPG (3.5kg / cm^Two at 20 ℃) 40 40 40 40(11) Fragrance proper amount proper amount proper amount proper amount ◎ ◎ ◎ △  (Manufacturing method) (1) to (9) and (11) are uniformly stirred and mixed
Later, this is filled into an aerosol container, and (10) is filled.
To get a color spray.

[0110]Example 10 Nail enamel  Using the copolymers 1 to 6, the following formulation 4
Was prepared. Apply this to female paneler's nails and dry
After washing with water. After that, daily observations revealed that copolymerization
When ethanol is added instead of the body (control
), Cracking and peeling were observed within 3 days,
In the case of blending a copolymer, any of the copolymers should be 7 days or more.
No cracking or peeling is observed at all, and the color lasts
Was.

Formulation 4: Nitrocellulose 10% by weight Alkyd resin 10 Acetyltributyl citrate 5 Ethyl acetate 10 Butyl acetate 5 Copolymer 1 to 65 Ethanol 55 Rhodamine B Appropriate amount Precipitating inhibitor Appropriate amount

(Production method) Rhodamine B was added to a part of the alkyd resin and a part of acetyltributyl citrate, and they were kneaded well. Other components were mixed and dissolved, and the above mixture was added thereto and uniformly dispersed to obtain a nail enamel.

[0113]Example 11 Mascara  The copolymers 1 to 6 were used to prepare
Kara was prepared. Apply each mascara to eyelashes, dry and apply water
I washed. After that, washing and drying are repeated with a commercially available cleaning agent.
did. As a result, as apparent from Table 11, the copolymer
Is clearly prevented from discoloration,
Has improved.

Formulation 5: Black iron oxide 10% by weight Solid paraffin 5 Lanolin wax 5 Light isoparaffin 5 Ethanol 70 Copolymer 1 to 65 Perfume Appropriate amount (Production method) I got mascara.

[0115]

[Table 11]Copolymer color retention *  Copolymer 1 ○ Copolymer 2 ◎ Copolymer 3 ◎ Copolymer 4 ◎ Copolymer 5 ◎Copolymer 6 ◎ None (control) ×  * Evaluation criteria for color durability: ：: Discoloration occurred after washing 5 times or more. …: Discoloration was caused by washing three or more times. X: Discoloration occurred after one washing.

[0116]Examples 12 to 14 Color Spray  As in Test Example 1 above, using the color sprays in Table 12.
And Examples 12 to 14 were all comparative examples 4
Washing resistance is higher than that of
It was also smooth.

[0117]

[Table 12] Ingredients Example 12 Example 13 Example 14 Comparative Example 4  (1) Copolymer 91---(2) Copolymer 11-1--(3) Copolymer 12--1-(4) Polyvinylpyrrolidone / Polyvinyl acetate copolymer---1 (5 ) Black iron oxide 1 1 1 1 (6) Ethanol 46 46 46 46 46 (7) POE (40) Hardened castor oil 1 1 1 1 (8) Octyl palmitate 1 1 1 1 (9) LPG (3.5 kg / cm^Two at 20 ℃) 50 50 50 50(10) Flavor appropriate amount appropriate amount appropriate amount appropriate amount  ◎ ◎ ◎ ×Smoothness ◎ ◎ ◎ ×  (Manufacturing method) (1) to (8) and (10) are uniformly stirred and mixed
Later, this is filled into an aerosol container, (9) is filled
A color spray was obtained.

[0118]Examples 15 to 17 Hair mist  Using the hair mist shown in Table 13, a test was performed in the same manner as in Test Example 1.
As a result, all of Examples 15 to 17 were compared with Comparative Example 5.
High washing resistance, excellent dyeing durability, and smooth feeling
It was.

[0119]

[Table 13] Ingredients Example 15 Example 16 Example 17 Comparative Example 5  (1) Copolymer 81---(2) Copolymer 9-1--(3) Copolymer 13--1-(4) Polyvinyl alcohol / vinyl acetate copolymer---5 (5 ) Carbon black 111 (1) (6) Ethanol 96 96 96 96 (7) POE (9) Lauryl ether 111 (11) Dimethylpolysiloxane (5cps) 111(9) Fragrance proper amount proper amount proper amount proper amount  ◎ ◎ ◎ ×Smoothness ◎ ◎ ◎ ×  (Production method) (1) to (9) are uniformly stirred and mixed, and filled in a container.
To obtain a hair mist.

[0120]Examples 18 to 20 Color Spray  As in Test Example 1 above, using the color sprays in Table 14.
And Examples 18 to 20 were all Comparative Example 6.
The washing resistance was higher than that of, and the dyeing durability was excellent.

[0121]

[Table 14] Ingredients Example 18 Example 19 Example 20 Comparative Example 6  (1) Copolymer 11 1---(2) Copolymer 13-1--(3) Copolymer 14--1-(4) Polyvinyl alcohol / Polyvinyl acetate copolymer---1 (5 ) Resorcinol brown 1 1 1 1 (6) Ethanol 48.2 48.2 48.2 48.2 (7) Benzyl alcohol 5 5 5 5 (8) Citric acid 0.3 0.3 0.3 0.3 (9) POE (100) hydrogenated castor oil 1 1 1 1 (10) High molecular weight polydimethylsiloxane 0.5 0.5 0.5 0.5 (11) Dimethylpolysiloxane (5cps) 3 3 3 3 (12) LPG (3.5kg / cm^Two at 20 ℃) 40 40 40 40(13) Fragrance appropriate amount appropriate amount appropriate amount appropriate amount  ◎ ◎ ◎ ×Smoothness ◎ ◎ ◎ ×  (Manufacturing method) (1) to (11) and (13) are uniformly stirred and mixed.
After combining, fill this into aerosol container and fill (12)
To give a color spray.

[0122]Example 21 Nail enamel  Using the copolymers 11, 12, and 14, the following formulation 6
A wool enamel was prepared. Apply this to the female paneler's nails
The cloth was dried, washed with water after drying. After that, we observed every day
In addition, when ethanol is blended in place of the copolymer (co
Cracks and peeling were observed within 3 days
However, when a copolymer was blended,
No cracking or peeling for more than 10 days
Lasted.

Formulation 6: Nitrocellulose 10% by weight Alkyd resin 10 Acetyltrityl citrate 5 Ethyl acetate 10 Butyl acetate 5 Copolymer 11, 12, or 145 Ethanol 55 Rhodamine B Appropriate amount Precipitating inhibitor Appropriate amount

(Preparation method) Rhodamine B was added to a part of the alkyd resin and a part of the acetyltrityl citrate, and they were kneaded well. Other components were mixed and dissolved, and the above mixture was added thereto and uniformly dispersed to obtain a nail enamel.

[0125]Example 22  The copolymers 24-26 were synthesized by the following method, and
The test was performed in the same manner as in Example 1. As a result, as shown in Table 15
In addition, all of the copolymers have a high dye holding effect,
Was also good. In addition, flaking was recognized in each case
Did not.

[0126]Copolymer 24  12.0 g of monomer A2 and 6.0 g of monomer B1
Was dissolved in 100 ml of ethanol, and heated to 70 ° C under a nitrogen stream.
After heating and stirring for 1 hour, 2,2'-azobis (isobutyric acid)
After adding 0.05 g of dimethyl and reacting overnight, a copolymerization reaction was performed.
Was completed. The reaction was cooled to room temperature and concentrated under reduced pressure.
The residue was dissolved in 10 ml of ethanol, and n-hexane 50 was dissolved.
Added in 0 ml. Precipitate is separated, and
A coalescence was obtained.

[0127]Copolymer 25  10.0 g of monomer A2, 2.0 g of monomer B1,
Except that 1.0 g of monomer D1 was used,
In the same manner as in the above, the desired copolymer was obtained.Copolymer 26  10.0 g of monomer A2, 10.0 g of monomer C4
g and the above copolymer except that 0.5 g of monomer D1 was used.
In the same manner as in No. 24, the desired copolymer was obtained.

[0128]

[Table 15]Acid hair dye (Formulation 2, copolymer 2% by weight)  Copolymer Monomer [% by weight] Dyeing Smoothness SmoothnessA2 B1 C4 D1  24 67--33 ○ ○ ◎ 25 77 15-8 ◎ ○ ◎26 49-49 2 ◎ ◎ ◎

[0129]Example 23 Color spray  Red iron oxide 1% by weight Copolymer 19 4 Siliconized pullulan 1 Silicon rubber 0.2 Light isoparaffin 70 Ethanol 23.8 Perfume Appropriate Preservative Appropriate

(Production method) Silicon rubber and siliconized pullulan were dissolved in light isoparaffin, and an ethanol solution of the copolymer 19 and other components were added to prepare a stock solution for spraying. A can was filled with 70 parts of the stock solution, and after attaching a valve, 30 parts of dimethyl ether gas was charged to obtain a color spray. This color spray had better color retention and feeling of use, and was able to suppress flaking at the time of superposition, as compared with the case where no siliconized pullulan was blended.

[0131]Example 24 Nail enamel  Pigment 2% by weight Copolymer 22 7 Siliconized pullulan 0.5 Light isoparaffin 45 Ethanol 45.5 Perfume Appropriate Preservative Appropriate

(Production method) After dissolving the siliconized pullulan in light isoparaffin, an ethanol solution of the copolymer 22 and other components were added to obtain a nail enamel. This nail enamel had better color retention and feeling of use, and was able to suppress flaking at the time of stacking, as compared with the case where silicone-containing pullulan was not blended.

[0133]Example 25 Oil-based water-proof mascara  Iron oxide 10% by weight Copolymer 20 2 Siliconized pullulan 2 Light isoparaffin 50 Ethanol 20 Solid paraffin 5 Lanolin wax 5 Glycerin 6 Fragrance Appropriate amount Antioxidant Appropriate amount

(Production method) Silicone pullulan, solid paraffin, and lanolin wax were dissolved in light isoparaffin, and an ethanol solution of the copolymer 20 and a glycerin dispersion of iron oxide were added to obtain a mascara. The present mascara had better color retention and feeling of use, and was able to suppress flaking at the time of stacking, as compared with the case where silicone-containing pullulan was not blended.

[0135]

The cosmetic according to the present invention comprises a pigment and / or an acid dye in which a specific copolymer is blended, and after coating, the copolymer is crosslinked to provide water resistance and washing resistance. By forming a crosslinked body film having excellent adhesiveness, the adhesion to a contacted object is extremely small, and the effect of keeping the makeup lasting is exerted.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a crosslinking reaction of a copolymer according to the present invention.

Claims (13)

[Claims] 1. A cosmetic comprising a copolymer having a silyl group to which at least one reactive functional group is bonded, and a pigment and / or an acidic dye. 2. The cosmetic according to claim 1, wherein the copolymer is a copolymer having a monomer (A) represented by the following general formula (I) as one of constituent monomers. Fees. General formula (I): (In the general formula (I), R ₁ is a hydrogen atom or a methyl group;
₂ represents an alkylene group having 1 to 6 carbon atoms, and R ₃ , R ₄ and R ₅ each represent a reactive functional group capable of crosslinking between the copolymer molecules by being hydrolyzed. ) 3. The cosmetic according to claim 1 or 2,
A cosmetic, wherein the copolymer further comprises a monomer (B) represented by the following general formula (II) as a constituent monomer. General formula (II): (In the general formula (II), R ₆ represents a hydrogen atom or a methyl group;
₇ means an alkyl group having 1 to 18 carbon atoms. ) 4. The cosmetic according to claim 1, wherein the copolymer further comprises a monomer (C) represented by the following general formula (III) as a constituent monomer. . General formula (III): (In the general formula (III), R ₈ represents a hydrogen atom or a methyl group,
R ₉ represents an alkylene group having 1 to 6 carbon atoms. X means a group represented by any of the following formulas (IV) to (VI). General formula (IV): (In the general formula (IV), R ₁₀ means an alkyl group having 1 to 6 carbon atoms.) General formula (V): (In the general formula (V), R ₁₁ and R ₁₁ ′ each have 1 carbon atom.
And alkyl groups x1 to x1 _each represent a positive integer. General formula (VI): (In the general formula (VI), R ₈ and R ₉ are as defined above.
R ₁₂ is an alkyl group having 1 to 6 carbon atoms, _{x 2} denotes a positive integer. ) 5. The cosmetic according to claim 2, wherein the proportion of the monomer (A) is 25 to 9 in the copolymer.
Cosmetics characterized by being 9% by weight. 6. The cosmetic according to claim 3, wherein the proportion of the monomer (B) is 1% by weight or more in the copolymer. 7. The cosmetic according to claim 4, wherein the proportion of the monomer (C) is 1% by weight or more in the copolymer. 8. The cosmetic according to claim 1, wherein the copolymer further comprises a monomer (D) represented by the following general formula (VII) as a constituent monomer. . General formula (VII): (In the general formula (VII), R ₁₃ represents a hydrogen atom or a methyl group, and R ₁₄ represents an alkylene group having 1 to 6 carbon atoms.
Y is a group represented by ^-N + _{(R 15) 3} or _{-N (R 15) 2, R} 15 denotes an alkyl group having 1 to 6 carbon atoms. ) 9. The cosmetic according to claim 8, wherein the proportion of the monomer (D) is 1 to 10 with respect to the total weight of the monomers (A), (B) and (C) in the copolymer.
Cosmetics characterized by being in the range of 0% by weight. 10. The cosmetic according to claim 2, wherein
In, R₃, R ₄And R₅Is an alcohol having 1 to 6 carbon atoms
Cosmetics characterized by being a xyl group. 11. The cosmetic according to claim 1, further comprising a silicone-containing polysaccharide compound. 12. The hair dye according to any one of claims 1 to 11. 13. A treatment method comprising applying the cosmetic composition according to claim 1 and hydrolyzing the composition to crosslink the copolymer molecules.