JPH06271427A - Temporary colorant composition for hair - Google Patents

Abstract

PURPOSE:To obtain a temporary colorant composition for the hair, using a pigment as a colorant and an amphoteric resin as a fixing agent, excellent in abrasion resistance and capable of imparting glass and smooth touch to the hair without causing problems in producing a resin. CONSTITUTION:This temporary colorant composition for the hair is obtained by dispersing (B) a pigment in a solution prepared by dissolving (A) an anionic resin which is a graft type or an alternating block type copolymer containing a constituent unit composed of a polysiloxane group bound through sulfide bond to a constituent unit, composed of a polymer of an unsaturated monomer and containing an unsaturated monomer unit having an amphoteric ionic part in (C) a cosmetic medium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a pigment as a colorant, and a copolymer containing a polysiloxane group and a polymer of an unsaturated monomer having a zwitterionic moiety, which is bonded through a specific bond. The present invention relates to a temporary colorant composition for hair, which uses a combined zwitterionic resin as a fixing agent and has excellent abrasion resistance and provides gloss and a smooth feel.

[0002]

2. Description of the Related Art Conventionally, when hair is temporarily dyed with a pigment as a colorant, a pigment solution is dispersed in a resin solution and applied to the hair and dried to fix the pigment to the resin for temporary hair dyeing. The approach is taken. The resin used is an anionic resin composed of a neutralized product of a copolymer of an anionic polymerizable unsaturated monomer such as acrylic acid and an alkyl ester of acrylic acid and / or methacrylic acid (JP-A-63-63). -218613, JP-A-63-218614) or a zwitterionic resin comprising a copolymer of a monochloroacetic acid amine salt modified product of a tertiary amine-containing methacrylate and an alkyl ester of acrylic acid and / or methacrylic acid ( JP-A-54-67039 and JP-A-60-36571) are generally used.

However, since the temporary colorant composition for hair using these resins does not have sufficient abrasion resistance, the pigment migrates and stains clothes and cloth when rubbed strongly on clothes and cloth. There was a problem. Further, when applied to hair, there is also a problem that the resin used for fixing may make the hair stiff or make the hair feel uncomfortable, thus deteriorating the feel.

In order to solve these problems, a polysiloxane group-grafted type obtained by copolymerizing a polysiloxane group-containing unsaturated monomer and a hydrophilic and / or hydrophobic unsaturated monomer Method using polymer (Japanese Patent Laid-Open No. 3-1
No. 41216) was proposed, but there is a problem in the production thereof because the polysiloxane group-containing unsaturated monomer is difficult to copolymerize, and in order to exert the effect of the polysiloxane group, It was necessary to increase the copolymerization ratio of the siloxane group-containing unsaturated monomer.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, is excellent in abrasion resistance, provides a gloss and a smooth feel, and has no problem in the production of resin. To provide a food composition.

[0006]

According to the present invention, the constitutional unit (A) consisting of a polysiloxane group and the constitutional unit consisting of a polymer of an unsaturated monomer are bonded via a sulfide bond, and A solution obtained by dissolving a zwitterionic resin, which is a graft-type or alternating block-type copolymer, in which a constitutional unit consisting of a polymer of a monomer contains an unsaturated monomer unit having a zwitterionic part, in (C) a cosmetic medium. And (B) a pigment dispersed therein to provide a temporary coloring composition for hair.

(A) Zwitterionic Resin The zwitterionic resin as the component (A) used in the present invention is an unsaturated monomer containing a constitutional unit composed of a polysiloxane group and an unsaturated monomer unit having a zwitterionic portion. It is a zwitterionic resin composed of a graft type or alternating block type copolymer in which the constitutional unit consisting of the polymer is bonded via a sulfide bond.

Generally, when radically polymerizing an unsaturated monomer in the presence of a mercapto group-containing compound, the mercapto group-containing compound acts as a radical scavenger, and as a result, the mercapto group-containing compound residue is polymerized with the unsaturated monomer. It is widely known that a polymer in which an object is bound via a sulfide bond is obtained. The zwitterionic resin as the component (A) utilizes this technique, and is unsaturated containing an unsaturated monomer having a zwitterionic group in the presence of a polysiloxane compound having at least one mercapto group in the molecule. It can be obtained by radically polymerizing a monomer.

This polymer has at least one mercapto residue in the polysiloxane compound as long as it is bonded to a constitutional unit composed of a polymer of an unsaturated monomer through a sulfide bond and has a plurality of mercapto groups. When a polysiloxane compound is used, it is not necessary that all the mercapto groups in the compound participate in the bond with the structural unit composed of the polymer of the unsaturated monomer.

The graft type or alternating block type copolymer which is the zwitterionic resin has an average molecular weight of 5,000.
It is preferably in the range of 1,000,000.

(A-1) Polysiloxane compound containing mercapto group As the polysiloxane compound containing at least one mercapto group in the molecule, for example, the following general formula (Ia) can be used.
Or n or (2+) in the molecule represented by (IIa)
p) polysiloxane compounds containing mercapto groups.

[0012]

[Chemical 2]

When the compound represented by the general formula (Ia) is used, when the compound represented by the general formula (IIa) is used in the polysiloxane group represented by the following general formula (I), , A graft type copolymer or an alternating block type copolymer in which a constitutional unit composed of a polymer of an unsaturated monomer is bonded to a polysiloxane group represented by the following general formula (II) through a sulfide bond. Obtainable.

[0014]

[Chemical 3]

The above general formulas (Ia), (IIa), (I) and
And in (II), R₁Is a hydrogen atom, having 1 to 10 carbon atoms
Alkyl group, phenyl group, terminal hydroxyl group,
Substituted with alkyl ether group or fatty acid ester group
Polyoxyalkylene group, polyalkylene polyamid
R, a fatty acid group, or a polysiloxane group, R ₂
Represents an alkylene group having 1 to 10 carbon atoms, m, n and
p represents the following integer. However, m, n and p are poly
It shows the number of each group contained in the siloxane group.
However, it does not indicate a repeating unit. m = integer from 10 to 350 n = integer from 1 to 50 p = integer from 0 to 50

The compound represented by the above general formula (Ia) can be obtained as a commercial product, for example, trade name BX1.
6-838A (Toray Dow Corning Silicone Co., Ltd.);
In the general formula (Ia), m = 250, n = 5, R ₁
= Methyl group, R ₂ = propylene group), trade name X-22-
980 (Shin-Etsu Chemical Co., Ltd .; m = 100, n = 4, R ₁ = methyl group, R ₂ = propylene group in the general formula (Ia), and trade name KP-358 (Shin-Etsu Chemical Co., Ltd.) Co., Ltd .; In the general formula (Ia), m = 50, n =
4, R ₁ = methyl group, R ₂ = propylene group).

Examples of the compound represented by the general formula (IIa) include, for example, trade name X-22-167B (Shin-Etsu Chemical Co., Ltd .; in the general formula (IIa), m = 40, p =
0, R ₁ = methyl group, R ₂ = propylene group). The polysiloxane compound represented by the general formula (Ia) or (IIa) can be used in the group and in combination in both groups.

The amount of the mercapto group-containing polysiloxane compound used is such that, in the resulting copolymer, the weight ratio of the constitutional unit consisting of the polysiloxane group / the constitutional unit consisting of the polymer of the unsaturated monomer = 0. The range of 5 to 85 / 99.5 to 15 is preferable, and 1 to 75/99 to 2 is more preferable.
It is 5. If there are too few constitutional units consisting of polysiloxane groups, the resulting temporary coloring agent for hair cannot obtain gloss and smooth feel, and if it is too large, problems occur in abrasion resistance and pigment dispersibility, and However, it is not preferable because it causes a problem in removability of hair after repeated use for a long period of time.

(A-2) Unsaturated Monomer The amphoteric ion part (a) of the structural unit composed of a polymer of unsaturated monomer which is a constituent of the zwitterionic resin is (a-1)
Radical polymerization of an unsaturated monomer having a zwitterionic moiety,
Or (a-2) radical polymerization of a precursor unsaturated monomer that can be zwitterionized with a zwitterionizing agent to zwitterionize, or (a-3) an amine or amide derivative of (meth) acrylic acid It is obtained by copolymerizing an unsaturated monomer containing an unsaturated carboxylic acid monomer. The structural unit composed of a polymer of an unsaturated monomer includes (b) a hydrophobic unsaturated monomer and (c) another unsaturated monomer in addition to the unsaturated monomer that gives the (a) zwitterionic moiety. Saturated monomers can be used.

(A) An example of the unsaturated monomer having a zwitterionic moiety is an amine of acrylic acid or methacrylic acid (hereinafter referred to as (meth) acrylic acid) represented by the following general formula (III), and Amide derivatives {for example, amine derivatives such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and amides such as dimethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide Derivative}
Monochloroacetic acid / Aminomethyl propanol neutralized product,
Monochloroacetic acid / triethanolamine neutralized product; zwitterionized product of halogenated fatty acid salts such as potassium monochloroacetate and sodium monochloropropionate; and zwitterionized product of propanesultone of amine and amide derivative of the above (meth) acrylic acid. There is.

[0021]

[Chemical 4]

In the above formula, R ^{3 to} R ⁸ , A, and D have the following meanings independently in each formula. R ³ = hydrogen atom, or methyl group R ⁴ = alkylene group having 1 to ⁴ carbon atoms R ⁵ and R ⁶ = hydrogen atom, alkyl group having 1 to 4 carbon atoms R ⁷ = alkylene group having 1 to 4 carbon atoms R ⁸ = An alkyl group having 1 to 24 carbon atoms, or an alkylene group A = -O- group, or -NH- group

In the copolymer used as the zwitterionic resin, these unsaturated monomers may be subjected to the copolymerization in the above-mentioned form, but as an alternative method, the copolymerization may be carried out in the form of a precursor,
Next, it is also possible to perform zwitterionization with a so-called zwitterionizing agent. Explaining with specific examples, it is subjected to copolymerization in the form of dimethylaminoethyl (meth) acrylate as a precursor, and then a zwitterionizing agent (potassium monochloroacetate,
It is also possible to zwitterionic ionize by adding propane sultone etc.). Further, the salt produced as a by-product of the amphoteric conversion is optionally filtered at a monomer stage, or a stage after copolymerization-amphoteric conversion,
It can be removed by ion exchange or the like. These techniques are described in detail in JP-A-56-92809.

Further, the amine or amide derivative of (meth) acrylic acid and (meth) acrylic acid, maleic acid,
An unsaturated monomer having an amphoteric ion portion can be substituted by copolymerizing with an unsaturated carboxylic acid monomer such as itaconic acid and crotonic acid.

(A) The amount of the unsaturated monomer having an amphoteric ion portion used is preferably 10 to 50% by weight, and more preferably 15 to 45% by weight, based on all the monomers. If the amount is too small, the copolymer obtained will be poorly soluble in water, making it difficult to remove the hair from the temporary colorant composition after coating and drying.If the amount is too large, the water resistance of the temporary colorant composition after coating and drying will be poor. Will be enough.

The (b) hydrophobic unsaturated monomer is a radical-polymerizable unsaturated monomer used for the purpose of imparting hydrophobicity and film strength, hardness, and flexibility to the resulting polymer. And generally has a solubility in water of 1
It is less than 0 (g / 100g water; 25 ° C).

For example, methyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Alkyl (meth) acrylates such as lauryl (meth) acrylate, tridecyl (meth) acrylate, oleyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate; butoxyethyl (meth) acrylate, benzyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate,
1,3-butylene glycol di (meth) acrylate,
Examples include (meth) acrylic derivatives such as diacetone (meth) acrylamide; aromatic unsaturated monomers such as styrene, chlorostyrene, and vinyltoluene; and vinyl acetate.

The amount of the hydrophobic unsaturated monomer used is preferably 50 to 90% by weight based on the total monomers. If too little, the resulting copolymer lacks flexibility and wear resistance,
The water resistance of the temporary colorant composition after coating and drying is insufficient, and when the amount is too large, it is difficult to remove hair from the temporary colorant composition after coating and drying, which is not preferable.

The unsaturated monomer (c) other than the unsaturated monomers (a) and (b) is used to change the feel and texture of the zwitterionic resin and to improve the affinity for hair. Further, it can be used as one component of the copolymer.

Examples of the unsaturated monomer (c) include, for example, hydroxyethyl (meth) acrylate,
Nonionic (meth) acrylic derivatives such as hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylamide,
There are vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, and polymerizable vinyl monomers such as N-vinylpyrrolidone. These unsaturated monomers should be below 20% by weight, based on the total monomers used. The monomers of the above groups (a), (b), and (c) can be used together in each group.

(A-3) Polymerization As described above, the zwitterionic resin of the present invention is produced by the bulk polymerization method, the solution polymerization method, the suspension polymerization method, the emulsion polymerization method or the like in the presence of the mercapto group-containing polysiloxane compound. It can be produced by polymerizing an unsaturated monomer by a known radical polymerization method. A preferred polymerization method is a solution polymerization method,
The mercapto group-containing polythyroxine compound and the unsaturated monomer are dissolved in a solvent, a polymerization initiator is added, and the mixture is heated and stirred under a nitrogen stream. The mercapto group-containing polysiloxane compound and the unsaturated monomer are usually present in all kinds and all amounts from the beginning of the polymerization, but they may be added separately in terms of those kinds and / or amounts.

The solvent is water, and methanol, ethanol,
It can be selected from alcohols such as isopropanol, ethylene glycol, and butyl cellosolve, and acetone, toluene, ethyl acetate, and the like. These solvents may be mixed and used. The amount of the solvent used is preferably such that the polymer concentration of the resulting copolymer solution is 10 to 70% by weight.

The polymerization initiator is preferably a peroxide such as benzoyl peroxide or lauroyl peroxide, or an azo compound such as azobisisobutyronitrile. As for the molecular weight of the polymer, the mercapto group-containing polysiloxane compound acts as a chain transfer agent, but the polymerization temperature, the type and amount of the polymerization initiator, the amount of the solvent, and the polymerization conditions such as other chain transfer agents should be appropriately selected. Can obtain a desired molecular weight.

The obtained polymer solution can be used as it is as a solution in which a zwitterionic resin is dissolved in a cosmetic medium, but from the polymer solution, for example, a spray drier, a belt drier, an extrusion drier, a vacuum drier can be used. It is also possible to remove the solvent with a method such as the above to take out the copolymer polymer as a solid, and dilute it with an arbitrary solvent before use.

(B) Pigment As the pigment used in the present invention, for example, carbon black, Gunjou, titanium oxide, zinc oxide, chromium hydroxide, kaolin, talc, silicic anhydride, magnesium silicate,
Inorganic pigments such as aluminum silicate and titanium mica; red 20
No. 4, Red 404, Yellow 205, Blue 404 and other legal dyes for cosmetics and pharmaceuticals; aluminum foil, or colored aluminum foil and / or finely cut aluminum foil coated with epoxy resin, acrylic resin, etc. , A polyester film, a polypropylene film, or the like, which is vapor-deposited on aluminum, or those which are colored and / or laminated and coated with an epoxy resin, an acrylic resin, or the like and are finely cut, and the like.

The weight ratio of the (A) zwitterionic resin to the (B) pigment is preferably (A) / (B) = 50/1 to 1/1, and the relative amount of the (A) component is too large. If the relative amount of the component (A) is too small, the abrasion resistance is deteriorated because the hair becomes insufficiently colored temporarily, and the hair becomes stiff and the hair feels uncomfortable. Is insufficient, which is not preferable.

(C) Solvent for Cosmetics The solvent for cosmetics used in the temporary hair coloring composition of the present invention is water, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and butyl cellosolve, hexane, There are hydrocarbons such as heptane, and cyclic silicones such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. These solvents may be mixed and used. The amount of the solvent used depends on the type of use (A) zwitterionic resin and (B)
The concentration of the total amount of the pigment is preferably 1 to 30% by weight in the usage form.

Temporary Coloring Composition for Hair The preparation of the temporary coloring composition for hair of the present invention is carried out by mixing (A) a zwitterionic resin with a cosmetic solvent and mixing (B) a pigment. Alternatively, it may be prepared as a masterbatch at a high concentration in advance and diluted with a solvent until the usage form, or may be mixed and mixed at a mixing ratio of the usage form before use. In any case, these may be mixed by ordinary stirring or, if necessary, may be pulverized and mixed by a homogenizer, a ball mill, a sand mill, a roll mill, a disper mill or the like.

The temporary coloring composition for hair of the present invention comprises a softening lubricant such as lanolin, a lanolin derivative, glycerin, a glycerin derivative, isopropyl or butyl myristate, oleyl alcohol, dibutyl phthalate, and pantothenyl alcohol, if necessary. Silicone compounds such as dimethyl polysiloxane, alkylene oxide addition polysiloxane, fatty acid modified polysiloxane, fragrance,
Additives known to hair cosmetics such as UV absorbers and antioxidants, and known polymers for hair cosmetics such as polyvinylpyrrolidone and zwitterionic or anionic acrylic polymers can be used in combination.

The temporary coloring composition for hair of the present invention is in the form of a spray or foam aerosol by adding a propellant such as petroleum liquefied gas such as propane or butane, dimethyl ether or freon liquefied gas to the above composition. Can also be used as The temporary coloring composition for hair of the present invention can be used for decoration of window glass other than hair, clothes, furniture and the like.

[0041]

【Example】

<Production Example 1> A five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a glass tube for nitrogen substitution, and a stirrer was placed in a mercaptopolysiloxane BX16 (trade name BX16-838, Toray Dow Corning Silicone Co., Ltd.).
A): 20 parts, dimethylaminoethyl methacrylate:
20 parts, methyl methacrylate: 20 parts, normal butyl methacrylate: 20 parts, lauryl methacrylate:
20 parts and absolute ethanol: 150 parts were added, azobisisobutyronitrile: 0.4 part was added, and the mixture was heated under reflux at 80 ° C. under a nitrogen stream to carry out polymerization for 8 hours.

Next, a 40% anhydrous ethanol suspension of a potassium hydroxide neutralized product of monochloroacetic acid in an equimolar amount to dimethylaminoethyl methacrylate was dropped into a five-necked flask with a dropping funnel, and further, under a nitrogen stream at 80 ° C. The mixture was heated at reflux for 12 hours for amphoteric reaction.

The resulting viscous suspension was filtered with a pressure filter to obtain a suspension, and the filtrate was regenerated by a cation exchange resin (Mitsubishi Kasei Co., Ltd., trade name: Diaion PK-220; after regeneration, the system). Through an anion exchange resin (Mitsubishi Kasei Co., Ltd.).
Trade name Diaion PA-416; After regeneration, the system is passed through a column filled with absolute ethanol). Then, the ethanol content was adjusted to obtain a polymer solution "P-1" having a polymer content of 30%. The average molecular weight of the obtained polymer measured by gel permeation chromatography (GPC) was 150,000.

<Production Example 2> In a five-necked flask similar to Production Example 1, mercaptopolysiloxane BX16: 3 parts, dimethylaminoethyl methacrylate: 14 parts, methacrylic acid: 16 parts, aminomethylpropanol: 5 parts, isobutyl. Methacrylate: 25 parts, stearyl methacrylate: 32 parts, cyclohexyl methacrylate: 10
And 200 parts of ethanol were added, and copolymerization was carried out in the same manner as in Production Example 1 using 1 part of azobisisobutyronitrile as a polymerization initiator.

After cooling, aminomethyl propanol% corresponding to 30% of an equimolar amount of methacrylic acid was dropped into the five-necked flask with a dropping funnel and stirred. Next, ethanol was added to the polymer solution "P-2" having a polymer content of 30%.
Got The average molecular weight of the obtained polymer was 60,0.
It was 00.

<Production Example 3> In a five-necked flask similar to Production Example 1, mercaptopolysiloxane BX16: 50 parts,
Diethylaminoethyl methacrylate: 30 parts, normal butyl acrylate: 10 parts, palmityl acrylate: 10 parts, and absolute ethanol: 100 parts,
Azobisisobutyronitrile: Copolymerization was carried out in the same manner as in Production Example 1 using 1 part of a polymerization initiator.

Then, a 50% ethanol solution of a neutralized aminomethyl propanol of monochloroacetic acid equimolar to diethylaminoethyl methacrylate was dropped into a five-necked flask with a dropping funnel, and heated under reflux at 80 ° C. under a nitrogen stream. For 6 hours. Then, the ethanol content was adjusted and the polymer solution "P-
I got 3 ”. The average molecular weight of the obtained polymer was 4
It was 10,000.

<Production Example 4> In a five-necked flask similar to that of Production Example 1, 10 parts of mercaptopolysiloxane (trade name X-22-980, manufactured by Shin-Etsu Chemical Co., Ltd.), monochloroacetic acid salt of dimethylaminoethyl methacrylate. Amphoteric compound by: 20 parts, ethyl acrylate: 15 parts, methyl methacrylate: 30 parts, tridecyl methacrylate:
20 parts, N-vinylpyrrolidone: 5 parts, and isopropyl alcohol: 100 parts were added, and benzoyl peroxide:
1 part was added, and the mixture was heated under reflux at 80 ° C. under a nitrogen stream to carry out polymerization for 8 hours. Then, the polymer solution “P-4” having a polymer content of 30% by adjusting the isopropyl alcohol content
Got The average molecular weight of the obtained polymer was 70,0.
It was 00.

<Production Example 5> A mercaptopolysiloxane (trade name: X-22-167B, manufactured by Shin-Etsu Chemical Co., Ltd.): 30 parts, diethylaminoethyl acrylate: 40 parts, and isobutyl were placed in a five-neck flask similar to that of Production Example 1. Methacrylate: 15 parts, 2-ethylhexyl methacrylate: 15 parts, and absolute ethanol: 200 parts,
Copolymerization was carried out in the same manner as in Production Example 1 using azobisisobutyronitrile as a polymerization initiator.

Next, a 40% anhydrous ethanol suspension of propanesarton in an equimolar amount of diethylaminoethyl acrylate was added dropwise to the five-necked flask with a dropping funnel,
Further, the mixture was heated under reflux at 80 ° C. under a nitrogen stream to carry out an amphoteric reaction for 6 hours. Then, the ethanol content was adjusted to obtain a polymer solution "P-5" having a polymer content of 30%. The average molecular weight of the obtained polymer was 70,000.

<Production Example 6> A mercaptopolysiloxane BX-16: 90 was placed in the same five-necked flask as in Production Example 1.
Parts, dimethylaminoethyl methacrylate: 5 parts, normal butyl methacrylate: 5 parts, and absolute ethanol: 150 parts, and copolymerization is carried out in the same manner as in Production Example 1 using azobisisobutyronitrile as a polymerization initiator.

Then, a 40% anhydrous ethanol suspension of a potassium hydroxide neutralized product of monochloroacetic acid in an equimolar amount of dimethylaminoethyl methacrylate was added dropwise to the five-necked flask with a dropping funnel to prepare Production Example 1. In the same manner, amphoteric reaction, pressure filtration and ion exchange treatment are performed. Then, the ethanol content was adjusted to obtain a polymer solution "P-6" having a polymer content of 30%. The average molecular weight of the obtained polymer was 20,000.

<Production Example 7> A 5-neck flask similar to Production Example 1 was charged with 60 parts of dimethylaminoethyl methacrylate.
Methyl methacrylate: 20 parts, normal butyl methacrylate: 20 parts, and absolute ethanol: 150 parts were added, and copolymerization was carried out in the same manner as in Production Example 1 using azobisisobutyronitrile as a polymerization initiator.

Then, a 40% anhydrous ethanol suspension of a potassium hydroxide neutralized product of mol chloroacetic acid in an equimolar amount of dimethylaminoethyl methacrylate was dropped into a five-necked flask using a dropping funnel to prepare Production Example 1. In the same manner, amphoteric reaction, pressure filtration, and ion exchange treatment were performed. Then, the ethanol content was adjusted to obtain a polymer solution "P-7" having a polymer content of 30%. The average molecular weight of the obtained polymer was 180,000.

<Examples 1 to 10 and Comparative Examples 1 and 2> Polymer solutions, pigments and solvents were added to a sand mill at the blending ratios shown in Table 1 and treated for 5 hours to prepare master batches "M-1" to "M-".
I got 7 ”. Next, the masterbatch, the polymer solution and the solvent were uniformly mixed at the blending ratio shown in Table 2 to prepare a coating type temporary colorant. Incidentally, regarding Examples 2, 4 and 9,
Liquefied petroleum gas was further added to the colorant composition, and the mixture was filled into a spray bottle and mixed to prepare a spray type temporary colorant.

The water resistance, washability and abrasion resistance of this coloring agent,
Table 2 shows the results of evaluation of the feel by the method described below.

[0057]

[Table 1]

[0058]

[Table 2]

<Examples 11 to 13 and Comparative Example 3> Mixing ratios shown in Table 3 were uniformly mixed to prepare a coating type temporary colorant. When evaluating this temporary colorant, the evaluation results shown in Table 3 are shown. The evaluations in the above examples were made according to the following methods.

<Water resistance> In the case of a coating type temporary colorant, the colorant is coated on a glass plate with a 65 mil bar coater,
In the case of a spray type temporary colorant, the colorant is spray-applied on the glass plate from a distance of about 15 cm for about 3 seconds, dried with a hair dryer for about 1 minute, and then at 23 ° C., 6 ° C.
The sample was left to stand overnight in a constant temperature and humidity room at 0% RH. Next, warm water of 23 ° C. was dropped on the glass plate in the same constant temperature and constant humidity chamber, and after 5 minutes, it was rubbed lightly with a finger to evaluate whether or not the film was dissolved. ◯: The film did not dissolve ×: The film started to dissolve or completely dissolved

<Detergency> A 2% aqueous solution of polyoxyethylene (addition mol number: about 3 mol) sodium lauryl ether sulfate was prepared. Next, this aqueous solution was kept at 40 ° C., the glass plate prepared in the same manner as in the water resistance evaluation was immersed for about 10 minutes, and then lightly rubbed with a finger to evaluate whether or not the film was dissolved. ○: Film dissolution started or completely dissolved ×: Film not dissolved

<Abrasion resistance> In the case of a coating type temporary colorant,
A coat of the coating type temporary colorant is applied to a hair bundle having a weight of 1 g and a length of 20 cm with a brush, then dried for about 1 minute using a hair dryer, and left to stand overnight in a constant temperature and humidity chamber at 23 ° C. and 60% RH for one day. And For spray-type temporary coloring, weight 1
g, a 20 cm long hair bundle is rotated at 30 rpm, sprayed for about 5 seconds from a distance of 15 cm, the whole hair is smoothed with fingers, then dried for about 1 minute using a hair dryer, 23 ° C., 60% The test piece is left for one day in a constant temperature and humidity room of RH. Next, a cotton cloth was rubbed on the test piece, and the amount of the pigment attached to the cloth was visually judged. ○: No or almost no transfer ×: Large transfer amount

<Feeling> The feeling was evaluated by using a test piece prepared in the same manner as in the abrasion resistance evaluation using a finger. ○: There is little feeling of stiffness, and it has a smooth feel. ×: There is a feeling of stiffness, and lacks a smooth feel.

[0064]

[Table 3]

Claims (6)

[Claims] 1. A constitution comprising a polymer of an unsaturated monomer in which a constitutional unit of (A) a polysiloxane group and a constitutional unit of a polymer of an unsaturated monomer are bonded via a sulfide bond. (B) Pigment is dispersed in a solution of a graft-type or alternating block-type zwitterionic resin, which is an unsaturated monomer unit having a zwitterionic part, in a cosmetic medium (C). A temporary coloring composition for hair. 2. A constitutional unit comprising a polysiloxane group,
The composition according to claim 1, which is selected from the compounds represented by the following general formula (I) and general formula (II). [Chemical 1] In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
It represents a phenyl group, a polyoxyalkylene group, a polyalkylenepolyamine group, a fatty acid group, and a polysiloxane group in which a terminal is substituted with a hydroxyl group, an alkyl ether group, or a fatty acid ester group, and R ₂ is 1 to 1
10 represents an alkylene group, m, n and p represent the number of each group contained in the polysiloxane group and represent the following integers: m = 10 to 350 integer n = 1 to 50 integer p = An integer from 0 to 50 3. The composition according to claim 1, wherein the weight ratio of the zwitterionic resin (A) and the pigment (B) is 50/1 to 1/1. 4. The (A) zwitterionic resin has a constitutional unit comprising a polysiloxane group / a constitutional unit comprising a polymer of an unsaturated monomer (weight ratio) = 0.5 to 85 / 99.5 to 15. 2. The composition of claim 1, which is: 5. The unsaturated monomer having (A) a polymer of unsaturated monomers of a zwitterionic resin has (a) an unsaturated monomer having at least one zwitterionic group in the molecule: 10 to 10. 5
0% by weight, (b) a hydrophobic unsaturated monomer: 50 to 90% by weight, and (c) an unsaturated monomer other than the above (a) and (b): 0 to 20% by weight. The composition according to 1. 6. A jet-type temporary colorant composition for hair, which is obtained by adding a liquefied gas to the composition according to claim 1.