JPH06256143A - Hair cosmetic - Google Patents

Abstract

PURPOSE:To provide a hair cosmetic holding good washability, preventing the easy deformation of a set hair shape by an outer force, and having an excellent set-holding force. CONSTITUTION:A hair cosmetic contains (A) a silicone resin comprising units of average formula I (R is alkyl, aryl; n is 1.0-1.8) and (B) a copolymer comprising B1: 30-80wt.% of a (meth)acrylamide monomer of formula II (R<1> is H, methyl; R<2>, R<3> are H, 4-12C alkyl, or form a ring together with the adjacent N atom), B2: 5-45wt.% of a (meth)acrylate ester monomer of formula III (R<4> is 1-4C alkyl), B3: 2-30wt.% of a (meth)acrylate ester monomer and/or a (meth) acrylamide monomer each having a tertiary amino group of formula IV (R<5> is 2-3C alkylene; R<6>, R<7> are methyl, ethyl; a is 0, 1), and B4; 0-30wt.% of a (meth)acrylate ester monomer of formula V (R<8>, R<9> are 2-4C alkylene; R<10> is H, methyl; b, c are 0-50).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hair cosmetic composition.
More specifically, the present invention relates to a hair cosmetic composition that exhibits excellent set-holding power while maintaining good hair washability.

[0002]

2. Description of the Related Art Conventionally, various hair cosmetics such as set lotion, hair spray, hair mist and hair foam have been used for the purpose of facilitating hairstyle making and long lasting. Each of these hair cosmetics is produced by dissolving a polymer compound for fixing hair in an appropriate solvent such as water, a lower alcohol or a water-lower alcohol mixed solvent.

However, the conventionally used hair-fixing polymer compounds have a certain set-holding power, but have a high hygroscopicity, so that they become sticky and become sticky under high-humidity conditions. There is also a problem that the property and gloss are also lowered, and also under high humidity conditions, the hair-fixing polymer compound is fluidized and the set holding power is lowered. For such a problem, it is necessary to use a polymer having a low hygroscopic property as a hair fixing polymer compound.

On the other hand, hair cosmetics are required to have hair washability that can be easily removed by washing with shampoo, and for that purpose, it is necessary to increase the water solubility of the hair fixing polymer compound.

However, it is required to lower the hygroscopicity of the hair-fixing polymer compound so that its performance does not deteriorate even under high humidity conditions, and to increase the water-solubility so that it can be easily removed by washing with shampoo. It is difficult to satisfy the contradictory requirements at the same time, which has been an important subject for the polymer compound for fixing hair.

By the way, liquefied gas is mixed as a propellant in hair spray type hair cosmetics. Conventionally, fluorocarbon has been used as a propellant, but in recent years, hydrocarbons (LPG) such as propane, butane, isobutane, or a mixture thereof have come to be used due to environmental problems. However, since LPG generally has a lower solubility for hair-fixing polymer compounds than CFCs, it is necessary to increase the amount of ethanol, isopropyl alcohol, or other solvent in the spray, which results in a large and heavy mist to be sprayed. There was also the problem that it was difficult to make the hair beautifully.

Further, in the conventional hair cosmetics, the feeling of dry or dry hair is reduced after setting and so-called flaking occurs, in which the resin film on the surface of the hair is peeled off during brushing. There was a problem such as a decrease in gloss.

[0008] The above-mentioned problems, namely, maintaining good hair washability while preventing performance deterioration under high humidity conditions, improving hair styling properties when using a propellant such as LPG, after setting In order to solve the problems such as improving the feel and luster of the hair, a specific acrylic or methacrylic copolymer and a silicone derivative are used in combination as the main component of the hair cosmetic (JP-A-4- 8282
No. 0) or a hair cosmetic containing a specific silicone resin and a volatile silicone oil (JP-A-61-1).
No. 61214) is proposed.

[0009]

However, even if the above hair cosmetics are used, there is a problem that the hairstyle easily collapses when various external forces are applied to the set hairstyle,
It has been desired to further improve the set holding power of hair cosmetics.

The present invention is intended to solve the problems of the prior art as described above, and an object thereof is to greatly improve the set holding power while maintaining good hair washability in hair cosmetics.

[0011]

Means for Solving the Problems The present inventors have prepared a hair cosmetic composition by combining a specific acrylic or methacrylic copolymer with a silicone resin having a specific average unit structure and blending them to obtain a set holding power. Was found to be significantly improved, and good hair washability was maintained, and the present invention was completed.

That is, the present invention provides the following average expression (A)

[0013]

[Chemical 6] (Wherein R represents an alkyl group or an aryl group, and n represents a numerical value of 1.0 to 1.8) and at least one silicone resin, and (a) to (d) shown below. Hair cosmetics characterized by containing a copolymer composed of a monomer: (a) the following formula (I)

[0014]

[Chemical 7] (In the formula, R ¹ is hydrogen or a methyl group, R ^{2 and} R ³ are independently hydrogen or an alkyl group having 4 to 12 carbon atoms, or a ring formed by R ² and R ³ together with an adjacent nitrogen atom. 30 to 80% by weight of an acrylamide-based or methacrylamide-based monomer represented by the formula (II)

[0015]

[Chemical 8] (In the formula, R ¹ is hydrogen or a methyl group, and R ⁴ has 1 to 4 carbon atoms.
5 to 45% by weight of an acrylic acid ester-based or methacrylic acid ester-based monomer represented by the formula (III).

[0016]

[Chemical 9] (In the formula, R ¹ is hydrogen or a methyl group, R ⁵ is a carbon number of 2 to 3
Alkylene group, R ⁶ and R ⁷ independently represent a methyl group or an ethyl group, and a represents 0 or 1), and an acrylic acid ester-based or methacrylic acid ester-based monomer having a tertiary amino group And / or 2 to 30% by weight of acrylamide or methacrylamide monomer; and (d) the following formula (IV)

[0017]

[Chemical 10] (In the formula, R ¹ is hydrogen or a methyl group, R ⁸ and R ⁹ are independently an alkylene group having 2 to 4 carbon atoms, R ¹⁰ is a hydrogen or a methyl group, and b and c are independently an integer of 0 to 50. , But b and c do not become 0 at the same time)
30% by weight.

The present invention will be described in detail below.

The hair cosmetic composition of the present invention contains a specific acrylic or methacrylic copolymer and a silicone resin having a specific average unit.

The acrylic or methacrylic copolymer used in the present invention is a film-forming resin and can be obtained by copolymerizing the above-mentioned monomer components (a) to (d).

Among such monomers, the component (a),
That is, as the monomer represented by the formula (I), for example,
(Meth) acrylamide (means a generic term for acrylamide and methacrylamide. Hereinafter, similarly, acrylic acid residue CH ₂ ═CH—CO— and methacrylic acid residue CH ₂ ═C are similarly described.
_(CH 3) -CO- collectively as the called (meth) acrylic. ), N-n-butyl (meth) acrylamide, N
Examples thereof include -t-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N-lauryl (meth) acrylamide, (meth) acryloylmorpholine. Among them, N-n-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N-
Lauryl (meth) acrylamide is preferred. These are used alone or in combination of two or more, and are used in an amount of 30 to 80% by weight, preferably 40 to 70% by weight, based on the total amount of monomers constituting the copolymer.

Examples of the component (b), that is, the monomer represented by the formula (II) include, for example, methyl (meth) acrylate,
Examples thereof include ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. These may be used alone or in combination of a plurality of types in an amount of 5 to 45% by weight, preferably 1
It is used in an amount of 0 to 40% by weight.

Examples of the component (c), that is, the monomer represented by the formula (III) include (meth) acrylic acid-N, N.
-Dimethylaminoethyl, (meth) acrylic acid-N, N
-Diethylaminoethyl, (meth) acrylic acid-N, N
-Dimethylaminopropyl, N, N-dimethylaminopropyl (meth) acrylamide and the like can be mentioned. These may be used singly or in combination of two or more kinds in an amount of 2 to 30% by weight of the total amount of monomers constituting the copolymer, preferably 1
It is used in an amount of 0 to 20% by weight.

Examples of the component (d), that is, the monomer represented by the formula (IV), include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono. (Meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate,
Methoxy polypropylene glycol mono (meth) acrylate etc. can be mentioned. These may be used singly or in combination of two or more kinds in the total amount of 0
-30% by weight, preferably 5-15% by weight is used.

The copolymerization reaction of these monomers (I) to (IV) can be carried out, for example, in the presence of a radical polymerization initiator by a known polymerization method such as bulk polymerization method, solution polymerization method or suspension polymerization method.
It can be produced by an emulsion polymerization method or the like, and it is particularly advantageous to copolymerize it by a solution polymerization method.

As the solvent used in the solution polymerization method, a water-miscible organic solvent or a mixed solvent of such an organic solvent and water can be used. In this case, the organic solvent may be used alone or in combination of plural kinds. You may use it. Examples of water-miscible organic solvents include aliphatic alcohols having 1 to 3 carbon atoms (eg, methanol, ethanol, propanol), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, glyme, diglyme, dioxane). And the like, and particularly, methanol, ethanol, acetone or a mixture thereof with water is preferable.

As the radical polymerization initiator usable in the copolymerization reaction, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-
2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile) and the like are preferable. Further, organic peroxides such as t-butyl peroctoate, dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide and the like can also be used. When such an organic peroxide is used, there is a possibility of causing a redox reaction with the tertiary amino group of the above-mentioned monomer (III), so the reaction is carried out at a low temperature of 40 ° C. or lower while controlling the reaction. In general, the amount of the polymerization initiator used is preferably 0.001 to 2.0 mol% and more preferably 0.01 to 1.0 mol% with respect to the monomer mixture.

At the time of polymerization, as a method of charging the monomers and the polymerization initiator, the monomer mixture and the polymerization initiator may be charged in all amounts and then heated, or each monomer and / or the polymerization initiator may be appropriately added dropwise. Alternatively, heating may be performed while charging in divided portions.

The copolymerization temperature is appropriately selected depending on the type of polymerization initiator, monomer, solvent, etc. used, but is usually 30.
-100 to 100 ° C, preferably 50 to 90 ° C. Moreover, the atmosphere of the copolymerization can be an inert gas atmosphere such as nitrogen.

After the copolymerization reaction, the copolymer can be isolated from the reaction solution by a known method such as reprecipitation or solvent distillation. The unreacted monomer can be removed from the obtained copolymer by a known method such as repeated reprecipitation, membrane separation, chromatography or extraction. The thus obtained copolymer has a weight average molecular weight of 1,000 to 1,000 depending on the selection of polymerization conditions.
It can be controlled in the range of 10,000 (molecular weight by gel filtration chromatography (polystyrene conversion)). The copolymer used in the hair cosmetic composition of the present invention preferably has a weight average molecular weight of 10,000 to 500,000, particularly preferably a weight average molecular weight of 20,000 to 200,000.

As the copolymer, the one obtained as described above can be used as it is, but the one obtained by neutralizing the tertiary amino group with an inorganic acid or an organic acid can also be used. . Here, examples of the inorganic acid that can be used for neutralization include hydrochloric acid, sulfuric acid, phosphoric acid, and the like, and examples of the organic acid include acetic acid, glycolic acid, lactic acid, citric acid, maleic acid, malic acid, and the like. You can

On the other hand, the silicone resin used in the hair cosmetic composition of the present invention has the following formula (A):

[0033]

[Chemical 11] As an average unit. Here, R is an alkyl group or an aryl group, and n represents the numerical value of 1.0-1.8. Examples of the alkyl group include linear, branched,
A cyclic alkyl group is preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable, and a methyl group is particularly preferable. The aryl group includes a hydrocarbon aromatic such as a phenyl group, a naphthyl group and a toluyl group, and a phenyl group is particularly preferable. In addition, these alkyl groups and aryl groups may have various substituents as needed.

On the other hand, a silicone resin having an average unit represented by the formula (A), R ₃ SiO _1/2 units, R ₂ SiO
It consists of a suitable combination of units and SiO ₂ units, the proportions of which are chosen to satisfy the value of n in formula (A) above. The average molecular weight of the silicone resin is preferably 1500-10000.

Such a silicone resin can be manufactured by various methods. For example, the general formula R ₃ Si
X, R ₂ SiX ₂ , RSiX ₃ and RSiX ₄ (wherein
X represents a hydrolyzable group such as chlorine, bromine, fluorine, alkoxy (methoxy, ethoxy, etc.), acyloxy, etc.)
The compound represented by is mixed with a suitable solvent such as toluene, benzene, and xylene at a mixing ratio according to the composition of the desired silicone resin, and then this is mixed with water for hydrolysis or condensation, and then the aqueous phase Can be obtained by neutralizing the obtained resinous substance with an alkali such as sodium bicarbonate and removing the solvent.

It is sufficient that at least one kind of such silicone resin is contained in the hair cosmetic composition of the present invention, and a plurality of kinds of silicone resins may be appropriately combined and contained.

In the hair cosmetic composition of the present invention, the compounding ratio of the (meth) acrylic copolymer and the silicone resin as described above is 0.01 in the hair cosmetic composition for the (meth) acrylic copolymer. ~ 20% by weight, especially 1-10% by weight
It is preferable that Generally, if the content of the (meth) acrylic copolymer is less than 0.01% by weight, the set holding power becomes insufficient, and if it exceeds 20% by weight, the feeling of stiffness is increased and the feeling is deteriorated, which is not preferable.

On the other hand, the silicone resin content in the hair cosmetic composition is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. Generally, silicone resin is 0.0
If it is less than 1% by weight, the feeling of stiffness is increased or flaking tends to occur, and if it exceeds 10% by weight, the oily feeling or the sticky feeling is increased and the feeling is deteriorated, which is not preferable.

The hair cosmetic composition of the present invention comprises hair spray, set foam, set lotion, gel, cream,
Various forms of use such as shampoo and conditioner can be adopted, and depending on such forms of use, it can be made into a dosage form such as an aqueous solution, a hydroalcoholic solution, an emulsion or a gel.

The method for producing the hair cosmetic composition of the present invention includes:
The (meth) acrylic copolymer and the silicone resin may be mixed according to a conventional method so as to form a uniform solution system in the above-mentioned mixing ratio. At that time, the (meth) acrylic copolymer and the silicone resin are (i) water, a lower alcohol,
Alternatively, it may be dissolved or dispersed in a water-lower alcohol mixed solvent to form a solution system, or (ii) a volatile oil (low boiling point oil) may be used to form a solution system, and (iii) injection as necessary. You may mix | blend an agent and other additives.

In the case of (ii), the volatile oil used is a low-boiling chain silicone, a cyclic silicone,
Examples thereof include low-boiling isoparaffinic hydrocarbons. Here, as the low-boiling chain silicone, the following formula

[0042]

[Chemical 12] (In the formula, n represents an integer of 0 to 5) can be used, and specific examples thereof include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and hexadecamethyl. Heptasiloxane etc. can be mentioned.

The cyclic silicone has the following formula:

[0044]

[Chemical 13] (In the formula, n represents an integer of 3 to 7) can be used, and specific examples thereof include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tetradecamethylcycloheptasiloxane. Etc. can be given.

As the low-boiling isoparaffinic hydrocarbon, an isoparaffinic hydrocarbon having a boiling point in the range of 60 to 260 ° C. under normal pressure can be used. Specific examples thereof include those manufactured by Exxon Co. Isobar (registered trademark) A, the same C, the same E, the same G, the same H, the same K, the same L, the same M, Shell Zol (registered trademark) 7 manufactured by Shell Co.
1. Salt roll (registered trademark) 100 manufactured by Phillip Co.
Alternatively, the same 130, the same 220 and the like can be cited.

In producing the hair cosmetic composition of the present invention, the above
When compounding a propellant and other additives as in (iii),
The solvent, propellant and other additives to be used are appropriately selected according to the dosage form imparted to the hair cosmetic.

For example, in the case of a set lotion, it is preferable to use water or a mixed solvent of water and a monohydric alcohol having 2 to 3 carbon atoms as a solvent in the above method (i). Also in the case of the hair mist of the formula, it is preferable to use a mixed solvent of water and a monohydric alcohol having 2 to 3 carbon atoms as the solvent.

In the case of a hair spray, the above (i)-
Although it can be suitably produced by any of the methods (iii), for example, in the case of the above method (i), it is preferable to use a monohydric alcohol having 2 to 3 carbon atoms, particularly ethanol as a solvent. preferable. Then, a solution obtained by mixing the silicone resin and the (meth) acrylic copolymer in a solvent in the above-described proportion is used as a stock solution, and the stock solution and the propellant are mixed. The mixing ratio of the stock solution and the propellant is 5/95 to 7 by weight.
It is preferably 0/30, particularly preferably 20/80 to 50/50.

Also in the case of hair foam, a stock solution prepared by mixing a silicone resin and a (meth) acrylic copolymer in a solvent is mixed with a propellant. In this case, the mixing ratio of the stock solution and the propellant is a weight ratio. 97/3 to 70/30, especially 95/5 to
It is preferably 80/20.

As the propellant to be mixed in this way, for example, chlorofluorocarbons such as trichloromonofluoromethane and dichlorodifluoromethane can be used, but liquefied petroleum gas (LPG), dimethyl ether (DME), carbon dioxide gas,
It is preferable to use nitrogen gas, or a mixture thereof. Particularly, LPG, DME, or a mixed gas of LPG and DME is preferable. These propellants are used by filling an aerosol can with an internal pressure of 2.0 after filling.
Adjust to be ~ 4.5 kg / cm ² G.

In the case of a gel form such as a hair setting gel, it is preferable to use water or a lower alcohol as a solvent, and further, a thickening agent composed of a water-soluble polymer such as polyacrylic acid or hydroxyethyl cellulose. It is preferable to add 0.5 to 2.0% by weight of the agent.

Additives that can be contained in the hair cosmetic composition of the present invention include castor oil, cocoa oil, mink oil,
Glycerides such as avocado oil and olive oil; waxes such as beeswax, whale wax, lanolin and carnauba wax; cetyl alcohol, oleyl alcohol, hexadecyl alcohol, lauryl alcohol, stearyl alcohol,
Alcohols such as isostearyl alcohol, 2-octyldodecanol, propylene glycol, polypropylene glycol, glycerin; isopropyl myristate, isopropyl laurate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, 2-ethyl. Esters of hexadecyl hexanoate, octyldodecyl myristate, etc .; Addition products of alcohols such as polyoxyethylene ethyl ether, polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene stearate ether with propylene oxide or ethylene oxide; dialkyldimethyl chloride Ammonium, distearyl dimethyl ammonium chloride, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride Um, cationic surfactants such as stearyl trimethyl ammonium chloride; polyvinyl pyrrolidone type, acetate vinyl ether, acidic polyvinyl acetate, amphoteric acrylic, can be mentioned amphoteric acrylic polymer compounds such like. Further, if necessary, additives such as fragrances, dyes, preservatives and antioxidants can be added.

[0053]

According to the hair cosmetic composition of the present invention, a specific (meth)
Since it contains an acrylic copolymer and a silicone resin having a specific average unit structure, it exhibits excellent set holding power even when a propellant such as LPG is used, and imparts good feel and gloss to hair. Furthermore, it becomes possible to maintain a good hair condition immediately after setting even under high humidity conditions. In particular, the set holding power is remarkably improved, and the hairstyle set using this hair cosmetic composition is less likely to collapse even when an external force is applied.

[0054]

EXAMPLES The present invention will be specifically described below based on examples.

Example 1 (1) Synthesis of (meth) acrylic copolymer Ethanol 1 was placed in a four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introducing tube and a stirrer.
00 parts by weight was added and the mixture was heated to 60 ° C. On the other hand, Nt-
100 parts by weight of a monomer mixture consisting of 52% by weight of butyl acrylamide, 18% by weight of ethyl acrylate, 20% by weight of N, N-dimethylaminopropylacrylamide and 10% by weight of methoxypolyethylene glycol (PEG400) methacrylate, 200 parts by weight of ethanol and further necessary. A monomer solution was accordingly prepared from water. Further, 2,2'-azobis- (2,4-
Dimethyl valeronitrile is 0.26 based on all monomers
A solution of the polymerization initiator was prepared by dissolving it in 33 parts by weight of ethanol in an amount of mol%. Then, the monomer solution and the polymerization initiator solution are simultaneously dropped into ethanol heated to 60 ° C. described above under a nitrogen atmosphere for 1.5 hours,
The reaction was carried out at 60 ° C. for 8 hours. After that, the product is purified by reprecipitation with water, and then 12 at 80 ° C. and 20 mmHg.
Vacuum dried for an hour. This gives an average molecular weight of 1043
The copolymer of 00 (GPC in a tetrahydrofuran solution: polystyrene conversion) was obtained.

(2) Preparation of hair cosmetics 1.5 parts by weight of the copolymer obtained in (1) above was dissolved in 57.5 parts by weight of absolute ethanol, and 0.15 parts by weight of lactic acid was added to the solution.
1.0 part by weight of a silicone resin was dissolved. in this case,
As the silicone resin, an average formula (CH ₃ ) _0.30 (C ₆ H ₅ ) _0.85 Si composed of (C ₆ H ₅ ) SiO _3/2 unit: (CH ₃ ) ₂ SiO unit = 5.67: 1
A silicone resin with O _1.43 (molecular weight about 8000) was used.

The obtained solution was placed in an aerosol container and 40 parts by weight of liquefied petroleum gas (LPG) was injected to prepare an aerosol type hair cosmetic.

(3) Evaluation The obtained aerosol type hair cosmetics were evaluated for (i) set holding power and (ii) hair washability as follows. The results are shown in Table 1.

(I) Set holding power A hair bundle having a length of 18 cm and a weight of 1.5 g is moistened with water, wound on a rod having a diameter of 2 cm to be naturally dried, and after curling the hair, remove it from the rod. The curled hair was sprayed with an aerosol type hair cosmetic from four directions, and was naturally dried again. Then, the hair is attached to a vibrator (SHAKER MS-1, manufactured by Inei Seieidou) and hung in a constant temperature and constant humidity box (20 ° C., 98% RH) at a rotation speed of 1
The curl elongation after rotating at 50 rpm for 30 minutes was observed, the set holding force was determined by the following formula, and the set holding force was evaluated according to the following evaluation criteria.

Set holding force = (L−L ₁ ) / (L−
L ₀ ) × 100 (%) (In the formula, L: initial hair bundle length (18 cm), L ₀ : hair bundle length when the rod is removed, L ₁ : rotated in constant temperature and humidity box for 30 minutes Evaluation criteria for hair bundle length after: ◎: 80% or more ○: 60% or more and less than 80% △: 20% or more and less than 60% ×: Less than 20% (ii) Washability The same as the hair targeted for the evaluation of set holding power. Aerosol-type hair cosmetics were sprayed onto the hair for 2 seconds from the front and back, dried with a dryer, then lightly massaged with plain shampoo, and dried again with a dryer. Sensory evaluation was performed by 10 professional female panels based on the following criteria, using the hair shampooed and dried in the same manner without applying the cosmetics as a control.

Evaluation Criteria A: Equivalent to control B: Slightly worse than control X: Better than control Example 2 As a silicone resin, (CH ₃ ) ₃ SiO _1/2 unit: SiO ₂ unit = 0.
An aerosol-type hair cosmetic composition was prepared in the same manner as in Example 1 except that a silicone resin having an average formula (CH ₃ ) _1.33 SiO _1.34 of 8: 1 was used, and its set-holding power and washability were evaluated. did. The results are also shown in Table 1.

Comparative Example 1 Example 1 except that a copolymer of polyvinylpyrrolidone (PVP) and vinyl acetate (VAc) (PVP / VAc = 6/4) was used instead of the (meth) acrylic copolymer.
Prepare an aerosol type hair cosmetic in the same manner as
The set holding power and the hair washability were evaluated. This result is also shown in Table 1.
It was shown to.

Comparative Example 2 An aerosol type hair cosmetic composition was prepared in the same manner as in Example 1 except that a copolymer of ethyl maleic anhydride and methyl vinyl ether was used instead of the (meth) acrylic copolymer. Then, the set holding power and the hair washability were evaluated. The results are also shown in Table 1.

Comparative Example 3 An aerosol-type hair cosmetic composition was prepared in the same manner as in Example 1 except that the (meth) acrylic copolymer was not used, and its set holding power and hair washability were evaluated. The results are also shown in Table 1.

Comparative Example 4 Instead of the silicone resin having the average formula (CH ₃ ) _0.30 (C ₆ H ₅ ) _0.85 SiO _1.43 , methylphenyl polysiloxane (KF-50 (1000c, manufactured by Shin-Etsu Silicone Co., Ltd.) was used.
An aerosol-type hair cosmetic composition was prepared in the same manner as in Example 1 except that s)) was used, and its set holding power and hair washability were evaluated. The results are also shown in Table 1.

Comparative Example 5 Example 1 was repeated except that an amodimethicone aqueous emulsion (Toray Silicone, SM8702C) was used instead of the silicone resin having the average formula (CH ₃ ) _0.30 (C ₆ H ₅ ) _0.85 SiO _1.43. An aerosol-type hair cosmetic composition was prepared in the same manner as in 1. above, and its set holding power and hair washability were evaluated.
The results are also shown in Table 1.

Comparative Example 6 Example 1 was repeated except that an aliphatic alcoholic polysiloxane (general formula :) was used in place of the silicone resin having the average formula (CH ₃ ) _0.30 (C ₆ H ₅ ) _0.85 SiO _1.43. Similarly, an aerosol-type hair cosmetic composition was prepared, and its set holding power and hair washability were evaluated. The results are also shown in Table 1.

[0068]

[Table 1] From Table 1, the hair cosmetics of the examples of the present invention show good hair washing.
It has excellent set holding power while maintaining
Recognize.

[0069]

According to the hair cosmetic composition of the present invention, excellent set holding power can be obtained even when a propellant such as LPG is used.
It is possible to impart a good feel and luster to the hair and maintain a good hair condition immediately after setting. In particular, it is possible to obtain an excellent set-holding force in which the set hairstyle is not easily broken even when an external force is applied, while maintaining good hair washability.

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[Procedure amendment]

[Submission date] April 17, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

Evaluation Criteria A: Equivalent to control B: Slightly worse than control X: Better than control Example 2 As a silicone resin, (CH ₃ ) ₃ SiO _1/2 unit: SiO ₂ unit = 0.
An aerosol-type hair cosmetic composition was prepared in the same manner as in Example 1, except that a silicone resin having an average formula (CH ₃ ) _1.33 SiO _1.34 (molecular weight: about 3000) of 8: 1 was used. The set holding power and the hair washability were evaluated.
The results are also shown in Table 1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction content]

Comparative Example 4 The average formula (CH ₃ ) _0.30 (C ₆ used in Example 1 was used.
Instead of the silicone resin having a H _{5) 0.85} SiO _1.43, methylphenyl polysiloxane (Shin-Etsu Silicone Co., KF-50 (1000cs)) a but using in the same manner as in Example 1 of the aerosol type hair A cosmetic was prepared and its set holding power and hair washability were evaluated. The results are also shown in Table 1.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction content]

Comparative Example 5 The average formula (CH ₃ ) _0.30 (C ₆ used in Example 1 was used.
H ₅ ) _0.85 SiO 1 In place of the silicone resin having _1.43 , an amodimethicone aqueous emulsion (Toray Silicone, SM8702C) was used in the same manner as in Example 1 except that an aerosol type hair cosmetic preparation was prepared. Then, the set holding power and the hair washability were evaluated. The results are also shown in Table 1.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

Comparative Example 6 The average formula (CH ₃ ) _0.30 (C ₆ used in Example 1 was used.
H ₅ ) _0.85 SiO _1.4 An aerosol-type hair cosmetic composition was prepared in the same manner as in Example 1 except that an aliphatic alcoholic polysiloxane was used in place of the silicone resin, and the set holding power was obtained. And the hair washability was evaluated. The results are also shown in Table 1.

Claims (1)

[Claims] 1. The following average formula (A): (Wherein R represents an alkyl group or an aryl group, and n represents a numerical value of 1.0 to 1.8) and at least one silicone resin, and (a) to (d) shown below. Hair cosmetics characterized by containing a copolymer composed of a monomer: (a) the following formula (I): (In the formula, R ¹ is hydrogen or a methyl group, R ^{2 and} R ³ are independently hydrogen or an alkyl group having 4 to 12 carbon atoms, or a ring formed by R ² and R ³ together with an adjacent nitrogen atom. Represents 80% by weight of an acrylamide monomer or a methacrylamide monomer represented by the formula: (b) the following formula (II): (In the formula, R ¹ is hydrogen or a methyl group, and R ⁴ has 1 to 4 carbon atoms.
5 to 45% by weight of an acrylic acid ester-based or methacrylic acid ester-based monomer represented by the formula (III): (c) the following formula (III): (In the formula, R ¹ is hydrogen or a methyl group, R ⁵ is a carbon number of 2 to 3
Alkylene group, R ⁶ and R ⁷ independently represent a methyl group or an ethyl group, and a represents 0 or 1), and an acrylic acid ester-based or methacrylic acid ester-based monomer having a tertiary amino group And / or 2 to 30% by weight of acrylamide or methacrylamide monomer; and (d) the following formula (IV): (In the formula, R ¹ is hydrogen or a methyl group, R ⁸ and R ⁹ are independently an alkylene group having 2 to 4 carbon atoms, R ¹⁰ is a hydrogen or a methyl group, and b and c are independently an integer of 0 to 50. , But b and c do not become 0 at the same time)
30% by weight.