JP2001039834A - Base for hair cosmetic and hair cosmetic using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject base capable of maintaining a natural feeling which the hair has itself free from stiffness and greasiness by combining a specific acrylic monomer composition with a specified silicone compound. SOLUTION: This base comprises a copolymer obtained by subjecting (A) an ethylenically unsaturated monomer component composed of (i) 10-40 wt.% of an ethylenically unsaturated monomer containing one or more carboxyl groups in a molecule, (ii) 5-20 wt.% of an ester of (meth)acrylic acid and a 10-18C aliphatic monohydric alcohol, (iii) 5-50 wt.% of an ester of (meth)acrylic acid and a 1-8C aliphatic monohydric alcohol and (iv) 5-60 wt.% of another ethylenically unsaturated monomer copolymerizable with the component i to the component iii to solution copolymerization in the presence of (B) 0.1-150 wt.% based on the total of the component A of a silicone compound having 2,000-100,000 mm2/s viscosity at 25 deg.C and (C) a hydrophilic solvent or a mixed solvent of the hydrophilic solvent and water by using (D) a radical polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a base for hair cosmetics, and more particularly to a base for hair cosmetics comprising a polymer obtained by polymerizing an acrylic monomer in the presence of a silicone compound. And hair cosmetics using the same.

[0002]

2. Description of the Related Art Anionic resin compositions used in hair cosmetics include half-esters of a copolymer of maleic acid and vinyl methyl ether, alkanolamine solutions of acrylic resins, or vinyl acetate-crotonic acid-vinyl neodecanoate. Polymers and the like are known, these are,
Although it is excellent in hair styling, it has high adhesiveness, and the texture is too hard, so it has an unnatural curl, and disadvantages such as flaking easily when passing through a comb or finger. It was not satisfactory, such as being seen. In order to alleviate these problems, it is common practice to add a silicone compound to the anionic resin composition.In this case, if the hair is used for a long time, the hair becomes sticky, There is a disadvantage that it becomes greasy. To cope with this, a high-molecular-weight silicone compound is dissolved in a solvent or a low-molecular-weight silicone oil or the like, or added as an emulsion using a polyether-modified silicone or a surfactant. However, there remain problems such as that the formed film becomes opaque and long-term storage stability is poor. Also, in the case of hair cosmetics using a polymer obtained by copolymerizing a silicone macromonomer, it was expected that a product without separation of silicone could be produced, but a macromonomer that can be expected to have a large silicone effect is dissolved in a hydrophilic solvent during polymerization. In many cases, the silicone effect is inferior, and the expected silicone effect is small when a macromonomer that dissolves in a hydrophilic solvent during polymerization is used, and the setting property is low when a large amount of silicone macromonomer is used. Had dropped.

[0003]

Therefore, the present applicant has
Japanese Patent Application No. 8-90159 proposed a hairdressing resin composition containing a polymer obtained by polymerizing an acrylic monomer in the presence of a specific silicone compound. This product had a strong hair-styling power of an acrylic resin and a good gloss of a film to be formed, and showed stable properties over a long period of time without a change in the effect of the silicone compound over time. However, the effect of imparting low tackiness and smoothness expected from the silicone compound was tentatively improved, but was still insufficient.

[0004] The object of the present invention is to maintain the natural texture of the hair itself without stiffness and stickiness, and to make the formed film transparent and have sufficient moisture resistance.
An object of the present invention is to provide a base for hair cosmetics, which can sufficiently exhibit low tackiness and a smoothing effect, and whose effect is not reduced by prolonged use on hair, and a hair cosmetic using the same.

[0005]

According to the present invention, when an acrylic resin is produced by polymerizing an acrylic comonomer by a solution polymerization method, the acrylic monomer is treated with a silicone compound and a hydrophilic solvent or water and a hydrophilic solvent. Polymerization using a commonly used radical polymerization initiator in the presence of a mixed solvent of a neutral solvent to form a complex in which an acrylic resin and a silicone compound can stably exist, thereby stabilizing the effect of the silicone compound over time. It provides a hair cosmetic base with excellent properties, but maximizes the unique properties of silicone compounds by combining a specific acrylic monomer composition with a specific silicone compound. That is.

The base for hair cosmetics according to the present invention comprises (A)
The following ethylenically unsaturated monomers (a) to (d), that is, (a) 10 to 40% by weight of an ethylenically unsaturated monomer having at least one carboxyl group in the molecule, (b) (meth) Esters of acrylic acid and aliphatic monoalcohols having a linear, alicyclic or branched chain having 10 to 18 carbon atoms 5 to 20
5% by weight of (c) an ester of (meth) acrylic acid with a linear, alicyclic or branched aliphatic monoalcohol having 1 to 8 carbon atoms and (d) the ethylenically unsaturated monomer An ethylenically unsaturated monomer component comprising 5 to 60% by weight of another ethylenically unsaturated monomer copolymerizable with the monomers (a) to (c), 0.1 to 150% by weight based on the total weight
Solution copolymerization using (D) a radical polymerization initiator in the presence of a silicone compound having a viscosity of 100 to 100,000 mm ² / s and (C) a hydrophilic solvent or a mixed solvent of water and a hydrophilic solvent. The hair cosmetic according to the present invention, which comprises a copolymer obtained by the above-mentioned method, comprises the above-mentioned hair cosmetic base.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Ethylenically unsaturated monomer component: Ethylenically unsaturated monomer having at least one carboxyl group in the molecule in the above ethylenically unsaturated monomer component (A) (A) is used to introduce a carboxyl group into a polymer and to neutralize the copolymer with a basic compound when used to impart water solubility to the formed film and improve hair washability. Is done. In addition, even when hair washing properties are not required, an appropriate amount is blended to give the film an appropriate hardness. The amount of the monomer (a) to be used must be 10 to 40% by weight, preferably 15 to 35% by weight, based on the total amount of the ethylenic monomer components used for polymerization. You. When the amount of the monomer (a) used is less than 10% by weight, the obtained hair cosmetic base becomes difficult to easily wash and remove at the time of washing the hair, and it is difficult to remove 40% by weight. If the amount exceeds the above range, the moisture resistance of the formed film is reduced, and the setting power of the hair does not last long when this base is used as a hair setting agent. Especially this usage is 15 ~
When the weight is 35% by weight, the balance between shampooing and moisture resistance is maintained,
When used as a hair setting agent, it can be easily washed off at the time of shampooing while maintaining the setting force under high humidity, and is formed when the copolymer is used after being neutralized with a basic compound. Sufficient water solubility can be imparted to the film. Specific examples of the monomer (a) include (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid and the like, and these monomers are used alone or in combination.

In the monomer component (A), a monomer (b) comprising an ester of (meth) acrylic acid and a linear, alicyclic or branched aliphatic monoalcohol having 10 to 18 carbon atoms. ) Relates to the lipophilicity and flexibility of the resin, and the amount used is 5 to 20% by weight, preferably 10 to 15% by weight. When the use amount is less than 5% by weight, the obtained hair cosmetic base has poor solubility in liquefied petroleum gas, easily causes a flaking phenomenon, and is used for hair cosmetics not using liquefied petroleum gas. Is insufficient in the flexibility of the resin, so that sufficient adhesion to the hair cannot be obtained. On the other hand, when it exceeds 20% by weight, the obtained film becomes very soft, has an increased tackiness, and has poor hair washability. In particular, when the used amount is 10 to 15% by weight, a flexible feel can be obtained in which the solubility in liquefied petroleum gas is appropriate and the film is not sticky. Specific examples of the monomer (b) include, for example, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, and (meth). ) Pentadecyl acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate,
(Meth) acrylates of alcohols having a linear or branched or alicyclic hydrocarbon group such as stearyl (meth) acrylate, isostearyl (meth) acrylate and oleyl (meth) acrylate alone or Can be used in combination.

In the above comonomer component (A), a monomer (ester) of (meth) acrylic acid and an aliphatic monoalcohol having a linear, alicyclic or branched chain having 1 to 8 carbon atoms ( c) is also involved in the lipophilicity, flexibility and hair washability of the resin, and the amount used is 5 to 50% by weight, preferably 10 to 40% by weight. When the used amount is less than 5% by weight, the obtained hair cosmetic base has poor solubility in liquefied petroleum gas, while when it exceeds 50% by weight, the obtained film has poor hair washability. . In particular, the amount used is 10 to 4
When the content is 0% by weight, a film having good solubility in liquefied petroleum gas and good film shampooing properties can be obtained. Specific examples of the monomer (c) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth)
N-butyl acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, (meth)
2-ethylhexyl acrylate, (meth) acrylic acid n
-Hexyl, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate and the like can be used alone or in combination.

[0010] In the comonomer component (A), the other ethylenically unsaturated monomer (d) is mainly used for the hardness and flexibility of the film formed by the obtained hair cosmetic base. It is blended to control moisture resistance and adhesion to hair. The amount of the monomer (d) to be used is 5 to 60% by weight, preferably 15 to 60% by weight of the total amount of the comonomer components used for the polymerization.
It is adjusted to be 50% by weight. If the amount of the monomer (d) is less than 5% by weight, it is impossible to adjust the film hardness, flexibility, moisture resistance and adhesion to hair to desired ones. If the amount exceeds 60% by weight, the hardness and flexibility of the film become inappropriate and the properties important as hair cosmetics may be significantly impaired. When the use amount of this component is particularly 15 to 50% by weight,
The adhesiveness between the film and the hair and the flexibility of the film are optimized, and inappropriate properties such as gum up and flaking that occur when used in hair cosmetics can be suppressed. The monomer (d) may be an acrylic monomer other than the (meth) acrylic monomer corresponding to the monomers (a) to (c), but an acrylic monomer Other ethylenically unsaturated monomers that can be copolymerized with these monomers (a) to (c) may be used. The above polymerizable monomer (d)
Specific examples of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Glyceryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate,
Methoxydiethylene glycol (meth) acrylate,
Methoxytetraethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, (meth) acrylamide, diacetone acrylamide, N-octylacrylamide, N-tert-octylacrylamide, N-tert-butylacrylamide, acrylonitrile, vinyl acetate ,styrene,
Vinylpyrrolidone, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) )
Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like can be mentioned, and these can be used alone or in combination. Further, as the monomer (d), the following general formula (I)

[0011]

Embedded image (Wherein, R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched hydroxyalkyl group, or General formula (II) of

[0012]

Embedded image Represents a group represented by When the composition contains the ethylenically unsaturated monomer represented by the formula (1) or acrylonitrile, vinyl acetate, styrene, or vinylpyrrolidone, a hard and less sticky film can be obtained. Among them, the monomer (d) preferably contains the compound represented by the general formula (I) in an amount of 15 to 50% by weight in all the ethylenic monomer components.
Particularly, the compound represented by the general formula (I) is diacetone acrylamide, N-tertiary octyl acrylamide,
When N-tert-butyl acrylamide is contained, it contributes to the improvement of the setting power under high temperature and high humidity without inhibiting the solubility of the hair cosmetic base in liquefied petroleum gas.
It also has good hair washability, and is also involved in film hardness.
Since it acts to efficiently develop the smoothness and the adhesion resistance of the silicone effect, it is desirable to use the above monomers alone or in combination, and particularly when N-tert-butylacrylamide is used. Optimal results are obtained. Further, as the monomer (d), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glyceryl (meth) acrylate, methoxyethyl (meth) acrylate, (meth) acrylic acid By using monomers such as ethoxyethyl, methoxydiethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, and ethoxydiethylene glycol (meth) acrylate, the dispersibility of the pigment and the adhesion to hair are adjusted. be able to. From these facts, when the hair cosmetic base of the present invention is used as a base for a hair coloring agent such as a hair color spray or a hair color foam, an alkylene glycol of (meth) acrylic acid, a polyalkylene glycol, It is desirable to use an ester of an alkylene glycol monoalkyl ether or a polyalkylene glycol monoalkyl ether in combination with the compound represented by the general formula (I).

(B) Silicone compound: The silicone compound (B) gives the film formed by the hair cosmetic base of the present invention a low tackiness and a smoothing effect, and furthermore has a good touch, water resistance and moisture resistance. It imparts properties and the like. As the silicone compound (B), known compounds can be used, but in order to form a non-sticky film,
2,000-100,000 mm ² / s at 25 ° C
Silicone compound having a viscosity of
A silicone compound having a viscosity of more than 100,000 mm ² / s is difficult to handle, and a silicone compound which is solid at room temperature, as seen in polyoxyethylene-modified silicone, has a high hydrophilicity and is therefore a film to be formed. May be inferior in moisture resistance and water resistance. Further, the silicone compound (B) has the following general formula (III)

[0014]

Embedded image 中 In the formula, a and b each independently represent 0 or a natural number (however, a and b must not be 0);
m and n each independently represent a natural number. Also, R4,
R5 each independently represents a linear or branched alkyl group having 1 to 18 carbon atoms. It is preferable to use a polyether-modified silicone having the structure represented by シ リ コ ー ン, since the effect of the silicone compound (B) is exhibited by using a small amount.

The amount of the silicone compound (B) used is
0.1 to 1 based on the total amount of the comonomer components used for the polymerization
50% by weight, preferably 0.5 to 10%
It is adjusted to be% by weight. When the amount of the silicone compound (B) used is less than 0.1% by weight, the film formed from the obtained base for hair cosmetics cannot achieve the original purpose in terms of smoothness and low tackiness.
It is not much different from the conventional hair cosmetic base. On the other hand, if this component exceeds 150% by weight, the polymerization reaction is hindered due to thickening and foaming during the polymerization, and the appearance, odor and viscosity stability of the obtained base material are significantly impaired and formed. The adhesion of the film to the hair may be poor and may cause flaking. Particularly when this component is used in an amount of 0.5 to 10% by weight, polymerization is not hindered, and the obtained base has good appearance, odor and viscosity stability, and is excellent in smoothness and low adhesion to hair. And good hair washability. In addition, applications that do not require hair washability, for example,
In the case of a cosmetic for imparting a semi-permanent conditioning effect to hair, the amount of this component is adjusted to 10 to 150% by weight in order to make full use of the water resistance and the like of the silicone compound (B). You can also.

In order to provide a base for hair cosmetics having a long-term storage stability without separation of the silicone compound, and to provide a hair cosmetic which does not cause a time-dependent change in the effect of the silicone compound when applied to hair cosmetics In order to provide a base for use, the ethylenically unsaturated monomer such as a silicone compound or a surfactant present at the time of polymerization and a polymer obtained by polymerization may be soluble in a solvent at the time of polymerization. is necessary. This is because it is necessary that the polymerization of the ethylenically unsaturated monomer progresses around the silicone compound molecule to form a complex in which the silicone compound molecule and the grown polymer molecule are entangled. Presumed.
In the case of the emulsion polymerization method in the presence of a silicone emulsion or using a polyether-modified silicone as an emulsifier, it is difficult to obtain excellent effects as in the case of the hair cosmetic base of the present invention. This is presumed to be because it is difficult to form a complex in which the silicone compound molecules and the grown polymer molecules are sufficiently entangled.

The silicone compound (B) is desirably a silicone compound which dissolves in a hydrophilic solvent at the time of polymerization or a mixed solvent of water and a hydrophilic solvent, but may be used in combination with another silicone compound or a surfactant. The solvent may be adjusted so as to be dissolved in a hydrophilic solvent at the time of polymerization or a mixed medium of water and a hydrophilic solvent. In addition, other silicone compounds for the purpose of suppressing foaming during polymerization, adjusting the appearance of the base, and adjusting the water solubility of the base and the foaming and defoaming properties when used as a hair cosmetic. Or a surfactant may be used in combination. Specific examples of the silicone compound (B) include FZ-2203, FZ-2207, and FZ-2222 manufactured by Nippon Unicar Co., Ltd., and these compounds are used alone or in combination. The silicone compound used in combination with the silicone compound (B) is not particularly limited. Examples thereof include dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, fluorine-modified silicone, trimethylsiloxysilicane, alcohol-modified silicone, and amino-modified silicone. Modified silicone and the like may be mentioned, and a co-modified silicone in which two or more types of modifications have been made may be used.
In particular, it is preferable to adjust the HLB of the system by combining polyether-modified silicones having different HLBs. The surfactant used in combination with the silicone compound (B) is not particularly limited, but from the viewpoint of preventing stickiness and suppressing foaming during polymerization, a high molecular weight polyoxyethylene / polyoxypropylene / block copolymer system is used. May be used.

(C) A hydrophilic solvent or a mixed solvent of water and a hydrophilic solvent: Here, the hydrophilic solvent has a solubility in water of 10 g.
/ Means an organic solvent that is at least 100 g (25 ° C.) water. Specific examples of such a hydrophilic solvent include, for example, aliphatic 1 having 1 to 4 carbon atoms such as methanol, ethanol, 2-propanol, ethylene glycol and glycerin.
To 4-hydric alcohols, glycol ethers such as ethyl cellosolve and butyl cellosolve, dioxane, dimethylformamide and the like, and these can be used alone or in combination. In addition, in consideration of the possibility that the hair cosmetic base of the present invention may adhere to human skin, water, ethanol or 2-propanol is particularly used alone or in combination among the hydrophilic solvents, and polymerization is performed. As the solvent at this time, it is preferable to use ethanol or 2-propanol alone or in combination. When the hair cosmetic base is used in an aqueous cosmetic, water may be added in the neutralization step or the dilution step after the polymerization step.

(D) Radical polymerization initiator: The radical polymerization initiator (D) is not particularly limited as long as it is used in a solution polymerization method. Specific examples thereof include peroxides represented by benzoyl peroxide, lauroyl peroxide, hydrogen peroxide and the like, and persulfates represented by ammonium persulfate and potassium persulfate, and 2,2′-azobis Known compounds such as azo compounds typified by isobutyronitrile and 2,2′-azobisisovaleronitrile and the like can be mentioned, and any of them may be used.

The polymerization method for obtaining the hair cosmetic base of the present invention is not particularly limited, and a known polymerization method can be used. For example, a comonomer component is charged into a reaction vessel together with a hydrophilic solvent containing the silicone compound or a mixed solvent of water and a hydrophilic solvent, and after stirring and mixing, the radical polymerization initiator is added, and the mixture is added under a nitrogen stream. Heating while stirring, or a so-called batch polymerization method, or a comonomer component is previously charged in a dropping funnel or the like, and a hydrophilic solvent containing the silicone compound or a mixed solvent of water and a hydrophilic solvent and the polymerization initiator are mixed. A so-called drop polymerization method, in which the mixture is dropped into a reaction vessel containing the mixture and heated while stirring under a nitrogen stream, a polymerization method in which a comonomer component is dividedly charged, and the like. The polymerization temperature cannot be unequivocally specified because it varies depending on the type of the radical polymerization initiator to be used and the like. However, it is usually preferable to set a 10-hour half-life temperature of the radical polymerization initiator, and particularly, the temperature is determined by the solvent used. When the temperature is close to the reflux temperature, polymerization with high reproducibility can be carried out, which is optimal. If the polymerization time is shorter than 8 hours, the polymerization may be incomplete and unreacted monomers may remain, so the polymerization time may be 8 hours or more, particularly 12 to 24 hours. desirable.

(E) Basic compound: The polymer obtained by the above-mentioned polymerization can be usually used as it is or without solvent, but in order to further impart water solubility, The base for hair cosmetics can be neutralized by adding an organic and / or inorganic basic compound (E).
For example, when 50 to 95% of the carboxyl group equivalent of the polymer is neutralized with an organic or inorganic basic compound, a suitable hair washability can be imparted to the hair cosmetic base. Particularly preferred is a case where the neutralization ratio is 55 to 75%. If the neutralization ratio is less than 50%, the obtained hair cosmetic base may have poor shampooing properties.
%, The set retention under high humidity is weak, and the alkalinity of the hair cosmetic base may be too strong. In particular, when the neutralization ratio is 55 to 75%, a high setting force is maintained even under high humidity, and the hair washability is improved.
However, when the hair cosmetic is not washed off after use and the present hair cosmetic base is used for applications requiring hair washing resistance, it is not always necessary to neutralize as described above. Among the organic and / or inorganic basic compounds, specific examples of the organic basic compound include morpholine, triisopropanolamine, ethanolamine, and the like.
Diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-
Ethyl-1,3-propanediol, 2-amino-2-
Methyl-1,3-propanediol, trishydroxyethylaminomethane and the like. Specific examples of the inorganic basic compound include ammonia, lithium hydroxide,
Examples include sodium hydroxide and potassium hydroxide.
These basic compounds are used alone or in combination.

The hair cosmetic base of the present invention may contain additives such as an ultraviolet ray inhibitor, an antioxidant and a hair nutrient in addition to the above-mentioned components. The composite of the acrylic resin and the silicone compound thus obtained is
It is used as a base for hair cosmetics in a state of a resin solution or a state in which a solvent is removed. The base for hair cosmetics according to the present invention is dissolved in water and a hydrophilic organic solvent and various additives of hair cosmetics are added to the base for hair cream, hair lotion, non-gas aerosol (hair mist), hair foam (hair mousse). ), And hair cosmetics such as split hair coating agents. The hair cosmetic base may be mixed with a hair coloring agent as a coloring fixing agent for the hair, and used as a hair cosmetic such as a color spray, a color foam, and a mascara. Further, when the hair cosmetic base of the present invention is used for an aerosol hairdressing agent, the base dissolved in a hydrophilic solvent used as the polymerization solvent may be liquefied petroleum gas (LPG) or dimethyl ether. (DM
The aerosol container may be pressurized and sealed together with a propellant such as E) and other additives. In this case, the mixing ratio of the various components filled in the aerosol container is usually
It is desirable to make appropriate adjustments according to the respective purposes and applications. In addition to the above uses, the hair cosmetic base can be suitably used as a film forming component of a facial pack, a coating material for a skin wound surface such as a barrier forming component of a hand cream, and a shampoo and a rinse. It is also useful as an additive.

[0023]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, and Formulation Examples and Comparative Formulation Examples, but the present invention is not limited to these Examples. All parts and percentages used below are by weight unless otherwise indicated.

[Production of hair cosmetic base] Example 1 was prepared based on the production composition of the hair cosmetic base shown in Table 1 below.
To 8 and Comparative Examples 1 to 10 were prepared respectively.

[0025]

[Table 1] <Note> * 1: FZ-2203 is a polyether-modified silicone (viscosity at 5,000 mm ² / s at 25 ° C.) having a structure represented by the general formula (III) manufactured by Nippon Unicar Co., Ltd. * 2: FZ-2222 is a polyether-modified silicone (viscosity at 25 ° C .: 35,000 mm ² / s) having a structure represented by the general formula (III) manufactured by Nippon Unicar Co., Ltd. * 3: SH3775M is a polyether-modified silicone (25%) manufactured by Toray Dow Corning Silicone Co., Ltd.
° C viscosity: 1,600 mm ² / s). * 4: SH244 is a cyclic dimethylpolysiloxane (viscosity at 25 ° C: 2.3 mm ² / s) manufactured by Dow Corning Toray Silicone Co., Ltd. * 5: KF96-10 is a dimethylpolysiloxane manufactured by Shin-Etsu Chemical Co., Ltd. (viscosity at 25 ° C .: 10 mm ² / s).

[Examples 1, 2, 5, 6, 7 and 8] In a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen purging tube and a stirrer, an ethylenically unsaturated unit shown in Table 1 was added. A total of 100 parts of the monomers (a) to (d), a silicone compound, 100 parts of ethanol, and a polymerization initiator (initial charge) were added, and polymerization was carried out for 8 hours under a nitrogen stream at reflux (about 80 ° C.). After the polymerization, an organic basic substance was diluted with the same amount of ethanol at 50 ° C. for neutralization by addition, and diluted with ethanol so as to have a nonvolatile content of 40% to obtain a hair cosmetic base.

Example 3 A four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen purging tube and a stirrer was charged with 100 parts of ethanol and the silicone compound shown in Table 1.
The mixture was heated under a nitrogen stream, and a polymerization initiator (initial charge) was added at 70 ° C. or higher. Under reflux, a total of 100 parts of the ethylenically unsaturated monomers (a) to (d) shown in Table 1 were added dropwise from the dropping funnel over 2 hours. During this time, 0.25 parts of the same type of polymerization initiator was added one hour after the start of the dropping and at the end of the dropping. After completion of the dropwise addition, heating was continued for 6 hours to complete the polymerization. After the polymerization, an organic basic substance was diluted with the same amount of ethanol at 50 ° C. and neutralized by adding the same, followed by dilution with purified water so as to have a nonvolatile content of 40% to obtain a hair cosmetic base.

Example 4 A hair cosmetic base was obtained in the same manner as in Example 1, except that purified water was used in place of ethanol for dilution after neutralization.

[Comparative Examples 4, 5, 6, and 8] As shown in Table 1, hair cosmetics were prepared in the same manner as in Example 1, except that some of the silicone compounds and ethylenically unsaturated monomers were different. A base was obtained.

[Comparative Examples 7, 9 and 10] As shown in Table 1, the same procedures as in Example 3 were carried out except that some of the silicone compounds and ethylenically unsaturated monomers were different. Agent was obtained.

[Comparative Examples 1 and 2] As shown in Table 1, hair cosmetics were performed in the same manner as in Example 1 except that no silicone compound was added and some of the ethylenically unsaturated monomers were different. A material base was obtained.

Comparative Example 3 As shown in Table 1, the same procedure as in Example 3 was carried out except that no silicone compound was used and some of the ethylenically unsaturated monomers were different. A base was obtained.

[Evaluation of Changes Over Time in Physical Properties of Hair Cosmetic Base] Next, the hair cosmetic bases obtained in Examples 1 to 8 and Comparative Examples 1 to 10, and Comparative Example 1 Example 1 corresponding to the hair cosmetic base obtained in 2, 3,
The appearance, the state of the aqueous solution, the transparency of the film, and the change over time in the feel of the film were obtained by dissolving and mixing the same kind and the same amount of the silicone compound as in 2, 3 in ethanol (Comparative Examples 11, 12, and 13). Evaluation was performed according to the following method. (1) Appearance The appearance of the obtained hair cosmetic base was visually observed, left at 20 ° C. for 10 days, and the appearance over time was visually judged. The evaluation criteria are shown below. ：: Transparent. Δ: There was haze. X: Cloudy or separated. (2) State of Aqueous Solution Using the obtained hair cosmetic base, an aqueous solution was prepared so as to have a nonvolatile component content of 10%, and the state of the solution at 20 ° C. was visually observed. The evaluation criteria are shown below. ：: Transparent. Δ: Milky white was exhibited. X: Cloudy or separated. (3) Transparency of film The obtained hair cosmetic base was diluted with ethanol so as to have a nonvolatile component content of 10%, and this solution was thinly applied to a glass plate and dried at room temperature without dust. The film was dried for 20 minutes in a dryer at 50 ° C., and the transparency with time was visually determined over 10 days at room temperature. The evaluation criteria are shown below. ：: Uniform and transparent during the drying process and after standing for 10 days. Δ: whitish during drying, but transparent after drying and after standing for 10 days. C: Opaque white turbidity or uneven translucency during the drying process and after standing for 10 days. (4) Temporal stability of feel of the film Simultaneously with the evaluation of the above (3), the change of the feel over time was determined by finger touch using the film. The evaluation criteria are shown below. ：: There was no change in slipperiness and stickiness throughout the 10 days. Δ: The slipperiness decreased over time, and the stickiness became stronger after standing for 10 days. X: The stickiness was strong from the beginning or an oily substance adhered to the finger. Examples 1 to 8 and Comparative Examples 1 to 1 thus obtained
Table 2 below shows the results of the performance evaluation of the hair cosmetic base in Example 3.

[0034]

[Table 2] <Note> * In Comparative Example 11, the same kind and amount of the silicone compound blended in Example 1 were mixed with Comparative Example 1 after polymerization. * Comparative Example 12 is a mixture of the same kind and the same amount of silicone compound blended in Example 2 after polymerization in Comparative Example 2. * Comparative Example 13 is a mixture of the same type and the same amount of silicone compound blended in Example 3 after polymerization in Comparative Example 3.

From the results shown in Table 2, Example 1 of the present invention was obtained.
The bases for hair cosmetics obtained in Comparative Examples 1 to 5 and Comparative Examples 1 to 5 and 7 to 10 are all excellent in appearance, aqueous solution state, and transparency of the film, and stability with time of the feel of the film. Was also found to be good.

[Evaluation of Performance of Hair Cosmetic Base in Various Formulations as Hair Cosmetic] Next, using the hair cosmetic bases obtained in the above Examples and Comparative Examples, hair spray, hair Formulated into various dosage forms such as color spray, hair styling foam, hair styling mist, etc.
The performance as various dosage forms was evaluated. The evaluation method of each performance is as shown below. Unless otherwise indicated, the composition in each of the formulation examples using the base according to the examples and the comparative formulation examples using the base according to the comparative examples is based on weight unless otherwise indicated, and the concentration is indicated in parentheses. Other than the amount of the compounding component, the compounding amount as the nonvolatile component is shown. The criterion in the case where there is no particular definition is as follows. A: Very good. ：: Good. Δ: Somewhat dissatisfied. X: Poor. (A) Set retention power (curl retention) Hair having a length of 22 cm and a weight of about 2 g was washed with a commercially available shampoo, treated with a commercial rinse, air-dried, and placed on the lower end of the hair.
A 0 g clip was attached and attached to the rotating shaft of a motor that rotated 30 times per minute. Next, while rotating the hair,
The test formulation was sprayed evenly for about 10 seconds from a distance of about 15 cm, and immediately adhered droplets were rubbed with a finger, wound around a rod having a diameter of about 1.2 cm, fixed with a clip, and then heated to 50 to 60 ° C. After drying in a desiccator for 30 minutes, it was unscrewed and attached to a vertically graduated glass plate at 30 ° C, 9 ° C.
5% R. H. The hair was allowed to stand in a constant-temperature and constant-humidity chamber, and after 10 hours, the tip position of the hair was recorded, and the curl retention was calculated based on the following equation. The larger the value, the greater the setting power. Curl retention (%) = ｛(L−Lt) / (LL)
0)｝ × 100 L: Length of test hair when stretched Lt: Left end of test hair after 10 hours in a thermo-hygrostat L0: Test hair before placing in thermo-hygrostat Tip position (b) Smoothness (comb passability) As in the case of evaluation of set holding power, prepare a dry hair bundle by spraying the test prescription and evaluate the difficulty of comb passing when untangled with a comb Then, the change over time when the same test was performed after one day had elapsed was also evaluated. (C) Adhesion Resistance In the same manner as in the evaluation of the set holding power, a dry hair bundle was prepared by spraying the test formulation, and the stickiness when the hair bundle was squeezed with the palm was evaluated. (D) Flaking The amount of resin that had fallen off when the hair bundle was unbound with a comb was evaluated in the same manner as in the case of the evaluation of set holding power. ：: No dropout occurred. Δ: There was some dropout. C: Many drops were found and the powder was blown. (E) Texture As in the case of the set holding power evaluation, the sensory evaluation when the created hair is touched by hand is evaluated as follows, and the change over time when the same test is performed one day later is also evaluated. did. ◎: Smooth and dry touch. ：: There was some stiffness, but it was satisfactory. Δ: Stiff or sticky. X: considerably stiff or strongly adhered. (F) Hair washability The test formulation was sprayed evenly on the test hair bundle,
It was dried at 0 ° C., immersed in warm water at 40 ° C., and its state was observed and evaluated as follows. ○: The resin component was removed from the hair within one minute. Δ: The resin component was removed from the hair in about 5 minutes. X: The resin component remained on the hair even after 5 minutes. (G) Abrasion resistance (in hair color spray) A friction tester for dyeing fastness (manufactured by Toyo Seiki Seisakusho Co., Ltd.) A cotton cloth was sprayed on the stage and a hair bundle was sprayed on the upper part to dry the hair bundles. Wear, temperature 25 ℃, humidity 60% R. H. The measurement was carried out by rubbing both of them with a load of 300 g and a reciprocating motion 30 times. The judgment was made by visually observing the degree of transfer of the dye to the cotton cloth after the friction.

Tables 3 to 7 below show the formulations and evaluation results of the performance as various dosage forms. According to them, it is clear that the formulation example using the base according to the example is superior to the formulation example using the base according to the comparative example. [Preparation and Evaluation of Hair Spray] A hair spray was prepared by a conventional method using the composition shown in the upper part of Table 3 below, and the evaluation results are shown in the lower part of the same table.

[0038]

[Table 3]

[Preparation and Evaluation of Hair Color Spray] A hair color spray was prepared by a conventional method using the composition shown in the upper part of Table 4 below, and the evaluation results are shown in the lower part of the table.

[0040]

[Table 4] <Note> * Each color paste was obtained by kneading 55 parts of the base for hair cosmetics of Examples 2, 6 and Comparative Example 2, 8 parts of carbon black and 37 parts of ethanol in an alumina ball mill for 10 hours. It is.

[Preparation of Hair Styling Foam and Evaluation Thereof] A hair styling foam was prepared by a conventional method using the composition shown in the upper part of Table 5 below, and the evaluation results are shown in the lower part of the table.

[0042]

[Table 5]

[Preparation and Evaluation of Hair Styling Mist] A hair styling mist was prepared by a conventional method using the composition shown in the upper part of Table 6 below, and the evaluation results are shown in the lower part of the table.

[0044]

[Table 6]

[Preparation of Hair Styling Gel and Its Evaluation] A hair styling gel was prepared by a conventional method using the composition shown in the upper part of Table 7 below, and the evaluation results are shown in the lower part of the table.

[0046]

[Table 7] <Note> *: Carbopol 940 liquid is used for Carbopol 940 (B
F Goodrich's carboxyvinyl polymer) was swelled and dissolved in an appropriate amount of purified water.
0%, 2-amino-2-methyl-1-propanol 0.
The gel was prepared by adding 25% and gelling, and then prepared with purified water to obtain a gel solution containing 0.5% of Carbopol 940.

[0047]

As described above, the hair cosmetic base according to the present invention is formed while maintaining the properties of an acrylic resin having particularly strong hair styling power among the anionic hair cosmetic resin compositions. The film has low tackiness and smoothness, which are the properties of silicone compounds, as well as transparency and good gloss of the film. Is stable without producing insoluble matter over time even when it is made into an aqueous solution or an alcohol solution. Furthermore, the film formed by the hair styling agent using the hair cosmetic base of the present invention has no problems of adhesion and flaking, has excellent smoothness, and exhibits excellent set holding power even under high temperature and high humidity. In addition, it has an excellent hair styling effect such as not impairing its feel and can be easily washed and removed.

Claims (5)

[Claims] (A) The following ethylenically unsaturated monomers (a) to (d), that is, (a) 10 to 40% by weight of an ethylenically unsaturated monomer having at least one carboxyl group in the molecule. %, (B) 5-20% by weight of an ester of (meth) acrylic acid and a linear, alicyclic or branched aliphatic monoalcohol having 10 to 18 carbon atoms, (c) (meth) acrylic acid 5 to 50% by weight of an ester with a linear, alicyclic or branched aliphatic monoalcohol having 1 to 8 carbon atoms and (d) the ethylenically unsaturated monomers (a) to (c) (B) 0.1 to 150% by weight based on the total amount of the monomer components, ,
2,000-100,000 mm ² / s at 25 ° C
A copolymer obtained by solution copolymerization using a radical polymerization initiator in the presence of a silicone compound having a viscosity of (C) and (C) a hydrophilic solvent or a mixed solvent of water and a hydrophilic solvent. A base for hair cosmetics. 2. The monomer (d) has the following general formula (I): (Wherein, R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched hydroxyalkyl group, or General formula (II) Represents a group represented by The hair cosmetic base according to claim 1, which is an ethylenically unsaturated monomer represented by the formula: 3. The silicone compound (B) is represented by the following general formula (III): 中 In the formula, a and b each independently represent 0 or a natural number (however, a and b must not be 0);
m and n each independently represent a natural number. Also, R4,
R5 each independently represents a linear or branched alkyl group having 1 to 18 carbon atoms. The hair cosmetic base according to claim 1, comprising a polyether-modified silicone having a structure represented by｝. 4. The hair cosmetic base according to claim 1, wherein the copolymer is neutralized with the basic compound (E). 5. A hair cosmetic comprising the hair cosmetic base according to any one of claims 1 to 4.