JPH06102614B2 - Hair cosmetics - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hair cosmetic composition, and more specifically, it has excellent set-retaining properties, and gives the hair after setting a good feel of smoothness, flexibility and the like. The present invention relates to a hair cosmetic that can be applied and can also prevent damage to hair due to brushing or the like.

[Conventional technology]

Conventionally, various hair cosmetics such as set lotion, hair spray, hair mist, and hair foam have been used for the purpose of making hairstyle easy and making hairstyle last longer. It was produced by dissolving a polymer compound for immobilization (hereinafter simply referred to as "polymer compound") in a suitable solvent such as water, a lower alcohol or a mixed solvent of water-lower alcohol. And, the obtained solution is used as it is as a hair lotion, and the solution is atomized with a pump or the like to be used as a hair mist, and a suitable liquefied gas is injected into the solution. What is mixed as an agent and used as an aerosol is a hair spray, and what is made to be sprayed as a foam is a hair foam.

Further, in recent years, along with the diversification and individualization of hairstyles, hair-type cosmetics that contain a large amount of polymer compounds to set hair more firmly have been demanded.

[Problems to be Solved by the Invention]

However, the conventionally used polymer compound is a film-forming resin, and under high humidity conditions, the conventional polymer has increased stickiness due to moisture absorption and becomes fluid even under high humidity conditions, I couldn't maintain a good set of hair. On the other hand, hair cosmetics must be easily removable by washing with shampoo. That is, water solubility on the one hand and low hygroscopicity on the other hand are required. It is difficult to satisfy these conflicting requirements at the same time, and conventionally, it was unavoidable that water solubility was abandoned and other solvents or solvent mixtures were used.

In the case of aerosol-type hair cosmetics, chlorofluorocarbon has been conventionally used as a propellant, but in recent years, it has been replaced with hydrocarbon (LPG) such as propane, butane, isobutane, and a mixture thereof due to environmental problems. But LPG
Has a tendency that the solubility of the film-forming resin is smaller than that of CFC gas, and when the present aerosol propellant is simply replaced with LPG, the film-forming resin in the aerosol product precipitates and cannot be used. Therefore, in order to dissolve the film-forming resin with LPG, the amount of solvent (ethanol, isopropyl alcohol, etc.) in the spray must be increased, and as a result the sprayed mist becomes large and heavy, and beautiful hair styling becomes difficult.

In addition, the conventional setting agent using a polymer compound has a bad feeling such as rough or dry hair after drying. In addition, there is a problem that the resin coating on the hair surface is peeled off by brushing or the like, so-called flaking occurs, and the gloss of the hair deteriorates.

Therefore, it has been desired to develop a hair cosmetic composition that has excellent set-holding power even when using a propellant such as LPG, has a good feel to the hair after setting, and does not damage the hair. .

[Means for Solving the Problems]

Under such circumstances, the inventors of the present invention have conducted intensive studies and found that, when a silicone derivative is added to a specific film-forming copolymer, in addition to good setting force, the feel of the hair after setting and the effect of preventing damage are set. They have found that an excellent hair cosmetic composition can be obtained, and completed the present invention.

That is, the present invention is a copolymer of the following components (A) and (B) (A) (a), (b), (c) and (d) (a) represented by the formula (I). (Meth) acrylamide monomer 30-80% by weight (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and represent a hydrogen atom or an alkyl group having 4 to 12 carbon atoms, or R ² and R ³ are combined. Forms a ring with adjacent nitrogen atoms) (b) 5 to 45% by weight of (meth) acrylic acid ester monomer represented by formula (II) (In the formula, R ¹ has the same meaning as described above, and R ⁴ has 1 to 4 carbon atoms.
2 to 30% by weight of (meth) acrylic acid ester-based monomer and / or (meth) acrylamide-based monomer having a tertiary amino group represented by the formula (III) (In the formula, R ¹ has the same meaning as described above, and R ⁵ has 2 to 3 carbon atoms.
Of the alkylene group, R ⁶ and R ⁷ are the same or different and represent a methyl group or an ethyl group, and a is 0 or 1) (d) A (meth) acrylic acid ester monomer 0 represented by the formula (IV) ~ 30% by weight (In the formula, R ¹ has the same meaning as described above, R ⁶ and R ⁹ are different alkylene groups having 2 to 4 carbon atoms, R ¹⁰ is a hydrogen atom or a methyl group, and b and c are 0 to respectively. The number of 50 is shown, but b and c do not become 0 at the same time.) (B) A hair cosmetic containing a silicone derivative is provided.

In the hair cosmetic composition of the present invention, the copolymer of component (A) is
It is a film-forming resin and can be obtained by copolymerizing components (a) to (d). Examples of the monomer (I) used for producing the copolymer (A) include (meth) acrylamide, Nn-butyl (meth) acrylamide, N
-T-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N-lauryl (meth) acrylamide, (meth) acryloylmorpholine and the like can be mentioned, and among them, N-butyl (meth) acrylamide, N-octyl (meth). Acrylamide, N-lauryl (meth)
Acrylamide and the like are particularly preferable. 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 whole monomer.

Examples of the monomer (II) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and the like.
These are used alone or in combination of two or more, and are used in an amount of 5 to 45% by weight, preferably 10 to 40% by weight, based on the whole monomer.

Examples of the monomer (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 are used singly or in a combination of two or more kinds in an amount of 2 to 30% by weight, preferably 10 to 20% by weight, based on the whole monomer.

Examples of the monomer (IV) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, Methoxy polypropylene glycol mono (meth) acrylate and the like can be mentioned. These may be used alone or in combination of two or more, and may be 0 to
30% by weight, preferably 5 to 15% by weight is used.

The copolymerization reaction of these monomers (I) to (IV) is carried out by a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method in the presence of a radical polymerization initiator. Although it can be produced by polymerization, a solution polymerization method is particularly advantageous. The solvent used in the solution polymerization method is preferably a water-miscible organic solvent (may be a mixture with water). This organic solvent can be used alone or as a mixture of two or more components. Examples of this water-miscible organic solvent include aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol; ketones such as acetone, methyl ethyl ketone; ethers such as tetrahydrofuran, glyme, diglyme, dioxane, and the like.
Especially, methanol, ethanol, acetone or a mixture thereof with water is preferable.

The radical polymerization initiator that can be used in the present method, an azo compound, for example, 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. Also, an organic peroxide such as t-
Butyl peroctoate, dicumyl peroxide, di-
Although t-butyl peroxide and dibenzoyl peroxide can also be used, it is difficult to control the reaction, such as the need to polymerize at a low temperature of 40 ° C or less, because it may cause a redox reaction with the tertiary amino group of the monomer (III). However, it is not industrially preferable. The amount of the polymerization initiator used is preferably 0.001 to 2.0 mol%, and more preferably 0.01 to 1.0 mol%, based on the monomer mixture.

The polymerization may be carried out by heating after charging all of the monomer mixture and the polymerization initiator, or may be carried out by appropriately dropping or dividingly charging each monomer and / or the polymerization initiator.

The polymerization temperature is appropriately selected depending on the type of radical polymerization initiator, monomer, solvent, etc. used, but is usually 30 to 10
The temperature is 0 ° C, preferably 50 to 90 ° C. Further, the copolymerization can be carried out under an atmosphere of an inert gas such as nitrogen as is usually carried out.

After the polymerization step, the copolymer can be isolated from the polymerization reaction solution by a known method such as reprecipitation or solvent removal.
Further, reprecipitation can be repeated, or unreacted monomers can be removed from the copolymer obtained by a known method such as membrane separation, chromatographic method or extraction method. The molecular weight of the copolymer thus obtained (by gel filtration chromatography (in terms of polystyrene)) can be controlled in the range of 1,000 to 1,000,000 in terms of polymerization average molecular weight by selecting the polymerization conditions, but for the purpose of the present invention, the weight average molecular weight is 10,000. ~ 500,00
0, particularly preferably a weight average molecular weight of 20,000 to 200,000 is used.

Further, the copolymer (A) may be used as it is, or may be used in which the tertiary amino group is neutralized with an inorganic acid or an organic acid. Examples of the inorganic acid used for neutralization include hydrochloric acid, sulfuric acid, phosphoric acid and the like; examples of the organic acid include acetic acid, glycolic acid, lactic acid, dimethylolpropionic acid, tartaric acid, citric acid, maleic acid, malic acid. Etc.

Examples of the component (B) silicone derivative used in the present invention include the following (1) to (12).

(1) Dimethylpolysiloxane represented by the formula (V) (CH ₃ ) SiO [(CH ₃ ) ₂ SiO] n ₁ Si (CH ₃ ) ₃ (V) (In the formula, n ₁ represents an integer of 3 or more. As the methyl polysiloxane represented by the general formula (V), for example, one commercially available under the trade name of KF96 of Shin-Etsu Chemical Co., Ltd. can be used.

(2) Methylphenyl polysiloxane represented by the formula (VI) (In the formula, a, b, and c represent numbers such that their sum is 1 to 5000. However, when b is 0, c is not 0, and c
When b is 0, b is not 0) Methylphenyl polysiloxane represented by the general formula (VI) is also widely known. For example, use a commercially available product under the trade name of Shin-Etsu Chemical Co., Ltd. KF50. You can

(3) An amino-modified silicone polymer which is a polymer of an organosiloxane having at least one aminoalkyl group in one molecule.

Among the organosiloxanes forming this amino-modified silicone polymer, those containing a methyl group as a functional group other than an aminoalkyl group are generally used, but other alkyl groups such as ethyl group, propyl group; vinyl group, allyl group, etc. An alkenyl group such as a group; an aryl group such as a phenyl group or a naphthyl group; a cycloalkyl group such as a cyclohexyl group; a hydroxy group, a hydroxyalkyl group, an oxyalkylene group or a polyoxyalkylene group can also be included.

Representative examples of the aminoalkyl group contained in the amino-modified silicone polymer are shown below by the general formula (VII) or (VIII).

[In the formula, R ¹¹ represents a divalent hydrocarbon group, and R ¹² represents a group —OCH ₂
CH ₂ −, Are shown, R ¹³ and R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group, d and e is an integer of Less than six, Z ^- represents a halogen ion or an organic anion] divalent R ¹¹ of Examples of the hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene _{group, -CH 2 CH (CH 3)} CH 2
Examples thereof include an alkylene group such as — and an alkylenearylene group such as — (CH ₂ ) ₂ —C ₆ H ₄ —. Of these, an alkylene group, particularly a propylene group is preferable. R ¹³
Examples of the monovalent hydrocarbon group represented by R ¹⁴ include a methyl group, an ethyl group, a propyl group, a hexyl group, and a phenyl group. Further, both R ¹³ and R ¹⁴ may be a hydrogen atom or a monovalent hydrocarbon group, or R ¹³ is a hydrogen atom and R ¹⁴ is 1
It may be a valent hydrocarbon group. Furthermore, the preferred values of d and e are d = 0 and e = 1.

A typical example of the hydroxyalkyl group is the following general formula (IX)
Indicated by.

—R ¹¹ OH (IX) [wherein R ¹¹ has the same meaning as described above] Representative examples of the oxyalkylene group and the polyoxyalkylene group are represented by the following general formula (X).

R ¹¹ fOChH ₂ hOqH (X) [wherein R ¹¹ has the same meaning as described above, and f is 0 or 1]
And g represents an integer of 1 to 100 and h represents an integer of 1 to 5] Among the hydroxyalkyl groups represented by the formula (X), preferred is f = 1 and g is an integer of 3 to 70. , H is 2 or 3. Here, those having h of 2 or 3 may be bonded in a block or random manner. This also applies to other combinations of integers of h.

A typical amino-modified silicone polymer has the general formula (X
It is represented by I) or (XII).

[In the formula, R ¹⁵ represents a methyl group or a hydroxy group, and R ¹⁶
Represents a methyl group or a hydrogen atom. R ¹⁷ represents the above-mentioned aminoalkyl group (VII) or (VIII), R ¹⁸ represents a hydroxy group, a hydroxyalkyl group, an oxyalkylene group or a polyoxyalkylene group, and i, j, k
Represents an integer depending on the molecular weight] Of these, a particularly preferred amino-modified silicone polymer is represented by the following general formula (XIII).

[In the formula, R ¹⁷ represents the above-mentioned aminoalkyl group (VII) or (VIII), and j and k represent integers depending on the molecular weight] Further, typical examples of the amino-modified silicone polymer of the present invention are: A polymer represented by the following general formula (XIV) having an average molecular weight of about 3,000 to 100,000, which is described in the CTFA Dictionary (US Cosmetic Ingredient Dictionary) 3rd edition under the name of Amodimethicone. ing.

[In the formula, s and t are integers depending on the molecular weight of 3,000 to 100,000] As the amino-modified silicone represented by the general formula (XIV), Toray Silicone Co., Ltd., SM8702C, Dow.
Amodimethicone emulsion and the like, which are commercially available from Chemical under the trade names DC929 and the like, can be used.

(4) Fatty acid-modified polysiloxane represented by the formula (XV) [In the formula (XV), g, h, and i are numbers from 1 to 1000, and j is 0.
To 10 and R ¹⁹ represents an alkyl group having 9 to 21 carbon atoms] (5) Alcohol-modified silicon represented by formula (XVI-1) or (XVI-2) [In the formula, k and 1 represent a number of 1 to 1000 (preferably 1 to 200), and R ²⁰ represents Cn ₄ H ₂ n ₄ (n ₄ represents a number of 0 to 4)] (6) Aliphatic alcohol-modified silicon represented by formula (XVII) [In the formula (XVII), m is 1 to 1000 (preferably 1 to 10)
0), o is 1 to 500 (preferably 1 to 50), q is 0 to 500
(Preferably 0 to 50), and r represents a number of 0 to 5,
R ²¹ represents Cn ₅ Hn _{5 + 1} (n ₅ represents a number of 4 to 22)] (7) Represented by formula (XVIII-1), (XVIII-2), (XIX) or (XX) Polyether modified silicone [In the formula (XVIII-1), s is a number from 0 to 35, u is a number from 1 to 45, v is a number from 0 to 1000, and R ²² is Cn ₆ H ₂ n _{6 + 1} (n ₆ is 1
~ Number 4)] [In the formula (XVIII-2), t ′ is 1 to 6 (preferably 2 to
3) number, w is 2 to 500 (preferably 20 to 80), x
Is a number of 1 to 50 (preferably 1 to 30), y is a number of 0 to 50 (preferably 1 to 30), and z is 0 to 50 (preferably 0 to 35).
Where D is an alkyl group having 1 to 12 carbon atoms or a formula OC
n ₇ H ₂ n _{7 + 1} (n ₇ represents a group of 0 to 6) or a hydrogen atom] [In the formula, R ²³ is CH ₂ a ″ OC ₂ H ₄ b ″ OC ₃ H ₆ c ″
OH or methyl group, x ″ is 1 to 500 (preferably 1
0 ″ to 200) and y ″ is 0 to 100 (preferably 0 to 1)
0 ", a" is a number from 0 to 6 (preferably 2 to 3), b "is a number from 1 to 100 (preferably 2 to 10), and c" is 0 to 100 ( Preferably 0 to 20)] [Wherein, e "is 1 to 300 (preferably 1 to 50), f" is 2 to 500 (preferably 2 to 50), g "is 0 to 6 (preferably 2 to 3), h" is 1 ~ 50 (preferably 2-20),
i ″ represents a number of 0 to 50 (preferably 0 to 20)] General formulas (XVIII-1), (XVIII-2), (XIX), (X
Silicone ether copolymers represented by X) are also widely known. For example, KF351, KF352 from Shin-Etsu Chemical Co., Ltd.
Etc. from Japan Unicar Co., Ltd. SILWET L-7002, SILVET
It is commercially available under the trade name of FZ-2110, and these can be used.

(8) Epoxy-modified silicon represented by formula (XXI) [In the formula (XXI), α represents a number of 1 to 500 (preferably 1 to 250), β represents a number of 1 to 50 (preferably 1 to 30), and R
²⁴ represents an alkylene group having 1 to 3 carbon atoms] (9) Fluorine-modified silicon represented by the formula (XXII) [In the formula (XXII), γ represents a number of 1 to 400 (preferably 1 to 250)] (10) Cyclic silicon represented by the formula (XXIII) [In formula (XXIII), δ represents a number of 3 to 8 and R ²⁵ represents an alkyl group having 1 to 3 carbon atoms] (11) represented by formula (XXIV-1) or formula (XXIV-2) Alkyl modified silicone [In the formula (XXIV-1), ε and η each represent a number of 1 to 500 (preferably 1 to 200), R ²⁶ is an alkyl group having 2 to 18 carbon atoms, and R ²⁷ is Cn ₈ H ₂ n ₈ (n ₈ is the number of 0-4) shows a] [In the formula (XXIV-2), θ and κ each represent a number of 1 to 1000 (preferably 1 to 200), and R ²⁸ represents an alkyl group having 10 to 16 carbon atoms] (12) Formula (XXV) Or Bunte salt-modified silicone represented by (XXVI) [In the above general formulas (XXV) and (XXVI), X is an alkali metal, an alkaline earth metal, ammonia, an amine or a fourth group.
Represents a primary ammonium salt, n is an integer of 1 to 20, m is 1 to
It is an integer of 20 and (n / m)> 1, and l is an integer of 1 to 20] The above silicone derivative can be used alone or in combination of two or more, and both are preferably used. However, (2) methylphenyl polysiloxane, (3) amino-modified polysiloxane, and (6) aliphatic alcohol-modified polysiloxane are preferable.

Examples of the hair cosmetic composition of the present invention include hair sprays, set foams, set lotions, gels, shampoos and rinses, and are used in various dosage forms such as aqueous solutions, hydroalcoholic solutions, emulsions, creams and gels. be able to.

The hair cosmetic composition of the present invention is blended so that the component (A) is preferably contained in an amount of 0.01 to 20% by weight, particularly preferably 1 to 7% by weight, and the component (B) is one or two types thereof. The above is mixed in a hair cosmetic composition, preferably 0.01 to
It is blended so as to contain 10% by weight, particularly preferably 0.1 to 5% by weight.

If the content of the component (A) is less than 0.01% by weight, the holding power for the set is insufficient, and if it exceeds 20% by weight, the feeling of stiffness is increased and the feeling is lowered. Further, if the content of the component (B) is less than 0.01% by weight, the feeling of stiffness is increased and flaking is more likely to occur, and if it exceeds 10% by weight, the oily feeling and the sticky feeling are increased and the feeling is deteriorated. Also makes it difficult to achieve the object of the present invention.

The hair cosmetic composition of the present invention comprises the components (A) and (B) described above.
Manufactured by dissolving in a solvent such as water, a lower alcohol or a mixed solvent of water-lower alcohol in the above-mentioned proportion by a conventional method, further mixing with a propellant as necessary and filling a pressure resistant container. To be done.

The solvent is preferably selected according to the form of the hair cosmetic composition of the present invention, and in the case of a set lotion, it is preferable to use water or a monohydric alcohol-water mixed solvent having 2 to 3 carbon atoms. When using a pump spray type hair mist, it is preferable to use a monohydric alcohol-water mixed solvent having 2 to 3 carbon atoms as a solvent, and when using a hair spray, 1 having 2 to 3 carbon atoms is used. Preference is given to using polyhydric alcohols, especially ethanol.

In the case of a hair spray, the stock solution prepared in the above proportion is used as the stock solution, and the ratio of the stock solution and the propellant is preferably 5/95 to 70/30 weight ratio, and particularly preferably 20/80 to 50/50 weight ratio. In the case of, the ratio of undiluted solution to propellant is 97 / 3-70 / 30 weight ratio, especially 95/5
A weight ratio of ~ 85/15 is preferred.

As the propellant, for example, fluorocarbon gas such as trichloromonofluoromethane, dichlorodifluoromethane can be used, but liquefied petroleum gas (LPG), dimethyl ether (DM
E), carbon dioxide gas, nitrogen gas or mixtures thereof are preferred. Particularly, LPG, DME or LPG / DME mixed gas is preferable. These propellants have an internal pressure of 2.
Preparation and filling to be 0 to 4.5 kg / cm ² G.

Also, in the gel form such as hair setting gel,
0.5-10.0% by weight of film-forming resin, preferably 1.0-3.0
It is preferable to use 0.5 to 2.0% by weight of a thickening agent comprising a water-soluble polymer such as polyacrylic acid and hydroxyethyl cellulose, and a solvent comprising water and optionally a lower alcohol.

In the hair cosmetic composition of the present invention, in addition to the above-mentioned components, glycerides such as castor oil, cocoa oil, mink oil, avocado oil and olive oil; beeswax, whale wax and lanolin, in addition to the above components. , Waxes such as carnauba wax; alcohols such as cetyl alcohol, oleyl alcohol, hexadecyl alcohol, lauryl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, propylene glycol, polypropylene glycol, glycerin; isopropyl myristate, laurin Esters such as hexyl acid salt, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, octyldodecyl myristate; polyoxyethylene ethyl ether, Oxypropylene cetyl ether, higher alcohol propylene oxide and ethylene oxide adducts of polyoxyethylene polyoxypropylene stearic ether; dialkyl dimethyl ammonium chloride,
Cationic surfactants such as distearyl dimethyl ammonium chloride, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride; polyvinyl pyrrolidone type, vinyl acetate type, acidic polyvinyl acetate type, acidic acrylic type, amphoteric acrylic type, etc. It is possible to add the high molecular compound and the like. Moreover, in order to enhance the commercial value, a fragrance or a coloring agent is added as necessary. Further, a preservative or an antioxidant may be added to prevent the hair cosmetic from deteriorating over time.

〔Example〕

Hereinafter, the configuration and effects of the present invention will be specifically described with reference to examples.

Synthesis Examples 1 to 5 Ethanol in a four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introducing pipe and a stirring device.
100 parts was added and heated to 60 ° C. Then, a monomer solution consisting of 100 parts of the monomer mixture and 200 parts of ethanol (water is also added if necessary) and an initiator solution prepared by dissolving the initiator in 33 parts of ethanol were added in a nitrogen atmosphere for 1.5 hours. At the same time, the mixture was dropped and maintained at 60 ° C. for 8 hours for reaction. After polymerization, reprecipitation and purification with water, at 80 ℃, 20mmHg
Vacuum dried for 12 hours. The obtained polymer was a pale yellow solid. The polymer of Synthesis Example 1 has an average molecular weight of 104,300.
(GPC in tetrahydrofuran solution: polystyrene conversion)
Met. The polymers of Synthesis Examples 2 to 5 have an average molecular weight of
It was in the range of 60,000 to 160,000. Table 1 shows the monomer composition ratio of each polymer.

Example 1 1.5 parts by weight of the copolymer obtained in Synthesis Example 1 was added to anhydrous ethanol 57.
It was dissolved in 5 parts by weight, and 0.15 parts by weight of lactic acid, 0.3 parts by weight of methylphenylpolysiloxane (100 centistokes) and 0.15 parts by weight of fragrance were added thereto. The obtained solution was put in an aerosol container, and 40 parts by weight of liquefied petroleum gas (LPG) was injected under pressure to prepare an aerosol composition. The set test, the moist feeling of hair after setting, the presence or absence of stickiness, and the slipperiness of the obtained composition were evaluated by the following test methods. The results are shown in Table 2.

Test method: (1) Holding power of set Wet a hair bundle with a length of 18 cm and a weight of 1.5 g with water, wind it on a rod and let it dry naturally, then remove the rod from the curled hair bundle and curl it 4 for each composition on hair
It was sprayed from the direction and naturally dried. After that, dry curled hair is kept in a constant temperature and humidity box (20 ° C, 98% R
H) was hung for 30 minutes, the curl spread was observed, and the holding power of the set was judged. Judgment is made by measuring the length of curled hair and setting the length of the hair when sprayed.
100%, the length of the original hair without curl (18 cm) was set as the holding power of 0%.

Holding power ◎ 81% or more ○ 61-80% △ 21-60% × 0-20% (2) Moisture, stickiness, and slipperiness Each composition is sprayed onto a hair bundle curled in the same manner as in (1) above. Then, after being naturally dried, a comparison was made with a hair bundle (control) to which the composition was not applied by sensory evaluation by 10 professional female panels.

Evaluation ◎ Very good compared to the control ○ Slightly better than the control △ Equal to the control × Poor compared to the control (3) Hair damage prevention effect Make a bundle of 1000 hairs, spray each composition, and brush The number of split ends and broken hairs after counting 5000 times was counted, and ranked according to the following evaluation.

Rating ◎: 20 or less ○: 21 to 50 △: 51 to 100 ×: 101 or more Comparative products 1 and 2 were prepared by using the following compounds instead of the component (B) in the invention product, comparative product 3 was obtained by removing the component (B), and comparative product 4 was prepared from the product (A) of the invention. ) The components are excluded.

Comparative product 1; Octyldodecyl myristate Comparative product 2; Propylene glycol Example 2 An aerosol composition having the following composition was prepared, and its set holding power, moist feeling, tackiness and slipperiness were evaluated in the same manner as in Example 1.

Composition (% by weight) Polymer 1.5 Methylphenylpolysiloxane (100 centistokes) 0.3 Perfume 0.15 Anhydrous ethanol balance propellant (LPG) 40 100.0 Example 3 A hair mist having the following composition was prepared.

Composition (wt%) Polymer compound of Synthesis Example 3 4.0 Amodimethicone aqueous emulsion ^{* 4} 0.5 Fragrance 0.2 Water 10.0 Ethanol balance 100.0 * 4: SM8702C Toray Silicone Co., Ltd. modified silicone polymer, active ingredient 40% Inclusion Example 4 A hair-blowing agent having the following composition was prepared.

Composition (wt%) Polymer compound of Synthesis Example 4 0.5 Aliphatic alcohol-modified polysiloxane ^{* 5} 1.2 Perfume 0.2 Water balance ethanol 10.0 100.0 * 5: KF7002 manufactured by Shin-Etsu Chemical Co., Ltd. Example 5 Hair gel having the following composition Prepared.

Composition (wt%) Polymer compound of Synthesis Example 5 3.5 Methylphenylpolysiloxane (50cs) 0.8 Sodium polyacrylate (Carbopol 940 ^{* 6} ) 0.8 Triethanolamine 0.8 Perfume 0.2 Ethanol 15.0 Water balance 100.0 * 6: BFGoodrich The compositions of Examples 3 to 5 manufactured by Chemical Campany were excellent in holding power of the set, and the hair after setting was moist and smooth, did not become sticky, and was not damaged.

〔The invention's effect〕

The hair cosmetic composition of the present invention has excellent set holding power, imparts a good feel to the hair after setting, and has an excellent hair damage preventing effect, and was used as a hair spray, a set lotion or a hair mist. In that case, the effect is particularly remarkable.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08F 299/02 MRS

Claims (1)

[Claims] 1. A copolymer of the following components (A) and (B) (A) (a), (b), (c) and (d) (a) represented by the formula (I). (Meth) acrylamide monomer 30-80% by weight (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and represent a hydrogen atom or an alkyl group having 4 to 12 carbon atoms, or R ² and R ³ are combined. Forms a ring with adjacent nitrogen atoms) (b) 5 to 45% by weight of (meth) acrylic acid ester monomer represented by formula (II) (In the formula, R ¹ has the same meaning as described above, and R ⁴ has 1 to 4 carbon atoms.
2 to 30% by weight of (meth) acrylic acid ester-based monomer and / or (meth) acrylamide-based monomer having a tertiary amino group represented by the formula (III) (In the formula, R ¹ has the same meaning as described above, and R ⁵ has 2 to 3 carbon atoms.
Of the alkylene group, R ⁶ and R ⁷ are the same or different and represent a methyl group or an ethyl group, and a is 0 or 1) (d) A (meth) acrylic acid ester monomer 0 represented by the formula (IV) ~ 30% by weight (In the formula, R ¹ has the same meaning as described above, R ⁸ and R ⁹ are different alkylene groups having 2 to 4 carbon atoms, R ¹⁰ is a hydrogen atom or a methyl group, and b and c are 0 to respectively. The number of 50 is shown, but b and c do not become 0 at the same time.) (B) A hair cosmetic containing a silicone derivative.