JP2003081775A - Hair cosmetic base and hair cosmetic using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair cosmetic base and a hair cosmetic which has excellent storage stability and homogeneous adhesivity, and with which the hair can be treated without giving stiffness and sticky feeling, and film having transparency, water resistance, moisture resistance, low stickiness, smoothing effect and long durability of effect is formed. SOLUTION: The hair cosmetic base is constituted with a copolymer obtained by copolymerizing (A) an ethylenic unsaturated monomer component with (B) an amino-modified silicone compound and (C) a phosphoric ester compound, of 0.1-120 wt.% in total of the components (B) and (C) based on the total of the ethylenic unsaturated monomer component (A) in (D) a hydrophilic solvent, or a solvent consisting of water and a hydrophilic solvent by a solution polymerization using (E) a radical polymerization initiator. The ethylenic unsaturated monomer component consists of (a) 10-40 wt.% of an ethylenic unsaturated monomer having one or more carboxylic groups in a molecule and (b) 60-90 wt.% of another polymeric ethylenic unsaturated monomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a base for hair cosmetics and a hair cosmetic using the same. More specifically, the present invention relates to a hair cosmetic base comprising a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a salt of a certain amino-modified silicone compound and a phosphoric acid ester compound. And a hair cosmetic using the same.

[0002]

BACKGROUND OF THE INVENTION Anionic resin compositions used in hair cosmetics include half-esters of a copolymer of maleic acid and vinyl methyl ether, acrylic resin alkanolamine liquid, or vinyl acetate-crotonic acid-vinyl neodecanoate copolymer. Polymers and the like are known, but these are
Although it is excellent in hair styling, it has high tackiness or has a too hard texture, so it has drawbacks such as being unnaturally stiff and flaking when passing through a comb or fingers. It was seen and not satisfactory. In order to reduce these problems, a silicone compound is generally added to the above-mentioned anion resin composition, but in this case, there is a drawback that the hair becomes sticky over time.

In order to solve these problems, a high molecular weight silicone compound is dissolved in a solvent or a low molecular weight silicone oil and added, or added as an emulsion using a polyether-modified silicone or a surfactant. Is being done. However, since silicone compounds are generally insoluble in water especially in aqueous cosmetics (meaning those containing water), a silicone containing a large amount of a surfactant or the like is used to stably mix the silicone compound. Since it is necessary to use an emulsion or the like, there are problems that the formed film becomes opaque, the water resistance and moisture resistance are reduced, and the long-term storage stability is poor.
When a water-soluble hydrophilic modified silicone is used, these water-soluble silicone compounds have a small effect of imparting the original effects of silicone, such as low tackiness, smoothness, water repellency and antifouling property. Therefore, a large amount must be used, and as a result, as in the case of using the silicone emulsion described above, the formed film becomes opaque, the water resistance and the moisture resistance are lowered, and the long-term storage stability is poor. There was a problem such as.

[0004]

Therefore, the applicant of the present invention is
Japanese Patent Application No. 11-215579 has proposed a base for hair cosmetics obtained by polymerizing an acrylic monomer in the presence of a specific silicone compound, and a hair cosmetic using the same. This is because the formed film is transparent and has sufficient water resistance and moisture resistance while maintaining the natural texture of the hair itself, and can sufficiently exhibit low tackiness and smoothing effect. It was intended to provide a base for hair cosmetics, in which the effect is not reduced by long-term use of

However, the base for hair cosmetics is
Although non-aqueous cosmetics (which do not contain water) have sufficiently improved the low-tackiness and smoothness imparting effect expected of silicone compounds, they are still insufficient in aqueous cosmetics. there were. In addition, Japanese Patent Application No. 11
In the case of the invention described in JP-A-215599, in which the acrylic monomer is polymerized in the presence of a large amount of a specific silicone compound, the long-term storage stability may be poor.

[0006] Therefore, the problem to be solved by the present invention, particularly in aqueous cosmetics, has good long-term storage stability, and the hair cosmetic ingredients are uniformly adhered to the hair and become stiff.
There is no stickiness, while maintaining the natural texture of the hair itself, the film formed is transparent and has sufficient water resistance and moisture resistance, and it is possible to sufficiently exhibit low tackiness and smoothing effect, It is an object of the present invention to provide a base for hair cosmetics that does not reduce the effect of long-term use on hair.

[0007]

The base for hair cosmetics according to the present invention comprises (A) the following ethylenically unsaturated monomer (a).
And (b), that is, (a) 10 to 40% by weight of an ethylenically unsaturated monomer having at least one carboxyl group in the molecule, and (b) another polymerizable ethylenically unsaturated monomer of 60 to
90% by weight of the ethylenically unsaturated monomer component is added to the ethylenically unsaturated monomer component (A) in a total amount of 0.1 to 120% by weight of the (B) amino-modified silicone compound and (C). ) In the presence of a phosphoric acid ester compound and (D) a hydrophilic solvent or a solvent consisting of water and a hydrophilic solvent,
(E) It is composed of a copolymer obtained by performing a copolymerization reaction by solution polymerization using a radical polymerization initiator.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Ethylenically unsaturated monomer component: In the ethylenically unsaturated monomer component (A),
The ethylenically unsaturated monomer (a) having one or more carboxyl groups in the molecule is blended mainly for the purpose of introducing a carboxyl group into the copolymer. By blending this component, it becomes possible to impart appropriate hardness to the film.

When the base for hair cosmetics is neutralized with a basic compound before use, it is possible to impart water solubility to the film and improve the washability.
When the hair cosmetic using the hair cosmetic base according to the present invention is required to have hair washability, a part of the ethylenically unsaturated monomer (a) is neutralized with the basic compound (F). It is desirable to use. In this case, the amount of the ethylenically unsaturated monomer (a) used should be 10 to 40% by weight, preferably 15% by weight based on the total amount of the ethylenic monomer component (A) to be copolymerized. It is adjusted to be about 30% by weight. When the amount used is in the range of 10 to 40% by weight,
The obtained hair cosmetic base becomes easy to wash hair,
Further, the film formed by this base for hair cosmetics has appropriate moisture resistance, hardness and flexibility, and the set of hair lasts a long time. When the amount used is in the range of 15 to 30% by weight, the hair washability and moisture resistance and the hardness of the film are well balanced, and the hair can be easily washed off while washing hair while maintaining the setting force under high humidity. .

When the hair cosmetic using the base for hair cosmetics according to the present invention is not required to have a hair-washing property, the amount of the ethylenically unsaturated monomer (a) used may be decreased, The carboxyl group introduced into the united product may be used without being neutralized with the basic compound (F), but in order to impart appropriate hardness to the formed film, the ethylenically unsaturated monomer (a) is used. It is necessary that 10 to 40% by weight of the total amount of the ethylenic monomer component (A) used for the copolymerization be used.

Specific examples of the ethylenically unsaturated monomer (a) include (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, etc. These monomers may be used alone or in combination. Used.

In the ethylenically unsaturated monomer component (A), other polymerizable ethylenically unsaturated monomer (b)
Is involved in lipophilicity and flexibility of the hair cosmetic base according to the present invention, and mainly, hardness and flexibility of the formed film,
It is blended to control moisture resistance and adhesion to hair. The polymerizable ethylenically unsaturated monomer (b) is added in an amount of 60 to 90% by weight based on the total amount of the ethylenic monomer component (A).

The polymerizable ethylenically unsaturated monomer (b)
As, for example, methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-methacrylate
Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid Decyl, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, (meth)
Linear chains such as myristyl acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, oleyl (meth) acrylate, etc. Alternatively, (meth) acrylic acid ester of alcohol having a branched chain or alicyclic hydrocarbon group can be exemplified.

The polymerizable ethylenically unsaturated monomer (b) is an ethylenically unsaturated monomer other than the above-mentioned (meth) acrylic acid ester of a hydrocarbon monoalcohol, which is an ethylenically unsaturated monomer. The thing which can be copolymerized with a saturated monomer (a) can also be used. As the unsaturated monomer (b), for example, 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-octyl acrylamide, N-tersia Lioctyl acrylamide, N-tert-butyl acrylamide, acrylonitrile, vinyl acetate, styrene,
Examples thereof include vinylpyrrolidone. The polymerizable ethylenic monomer component (b) can be used alone or in combination.

The polymerizable ethylenically unsaturated monomer (b)
In particular, 2-ethylhexyl (meth) acrylate,
N-hexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate,
Tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, (meth)
Alcohols having straight or branched chain or alicyclic hydrocarbon groups such as palmityl acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and oleyl (meth) acrylate When (meth) acrylic acid ester, N-octyl acrylamide, N-tertiary octyl acrylamide, N-tertiary butyl acrylamide, etc. is used, the base for hair cosmetics according to the present invention is soluble in LPG (liquefied petroleum gas). Since LPG becomes particularly good, LPG
It is convenient when it is used for an aerosol product containing a propellant.

In the case of using LPG as a base for hair cosmetics for aerosol products, the polymerizable ethylenic monomers listed for LPG are contained in the total amount of the polymerizable ethylenically unsaturated monomer (b). It is preferable to add 20 to 40% by weight of the body component.

(B) Amino-modified silicone compound: The amino-modified silicone compound (B) mainly imparts low tackiness and smoothing effect to the film formed by the base for hair cosmetics according to the present invention, and gives a better feeling. It also imparts water resistance, moisture resistance and the like.

The amino-modified silicone compound (B) is not particularly limited, and known compounds can be used. In particular, the following general formula (I) is used.

[Chemical 4] (In the above formula, 1 represents 0 or a natural number, R ′ represents a linear or branched alkylene group, and R ¹ represents a linear or branched alkyl group, alkenyl group or aralkyl. Represents a group) and /
Or the following general formula (II)

[Chemical 5] (In the above formula, m represents 0 or a natural number, and R ″ and R ′ ″ each represent a linear or branched alkylene group.) The silicone effect is most effectively exhibited.

Specific examples of the amino-modified silicone compound (B) include those represented by the general formulas (I) and (II), "TSF4700" and "TSF4701".
(Both manufactured by Toshiba Silicone Co., Ltd.) and "X-22-16
1AS "," X-22-161A "," X-22-16 "
1B ”and“ KF-8012 ”(both manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and as those other than those represented by the general formulas (I) and (II),“ KF-8002 ”(Shin-Etsu Chemical Co., Ltd.). Manufactured) and the like. These amino-modified silicone compounds (B) are used alone or in combination.

(C) Phosphoric acid ester compound: The phosphoric acid ester compound (C) is used in combination with the amino-modified silicone compound (B) to prepare an amino-modified silicone compound for the solvent (D) during copolymerization. Of the amino-modified silicone compound, whereby the effect of the amino-modified silicone compound is effectively exhibited. This is because the phosphoric acid ester compound (C) forms a salt with the amino-modified silicone compound (B), whereby the amino-modified silicone compound (B) is formed on the surface and inside of the film formed by the base for hair cosmetics. ) Is reasonably distributed.

As the phosphoric acid ester compound (C), known compounds can be used, but in particular, the following general formula (III)

[Chemical 6] (In the above formula, n and p are each 0 or a natural number (however,
n and p must not be 0 at the same time. ) And R ² represents a linear or branched alkyl group, alkenyl group or aralkyl group. The above-mentioned silicone effect is most effectively exerted when the compound is represented by (1).

Specific examples of the phosphoric acid ester compound (C) include "Perlon EP-70", "EP-71" and "Gerazole E-50" (all manufactured by Kyowa Chemical Industry Co., Ltd.), and "phospha". Nord RS-410 "," R
S-610 "," RS-710 "," RD-510 "
Y ”,“ RB-410 ”,“ RL-210 ”,“ RA-
600 ”and“ ML-220 ”(both manufactured by Toho Chemical Industry Co., Ltd.) and the like.

As for the compounding ratio of the amino-modified silicone compound (B) and the phosphoric acid ester compound (C), if the former is neutralized by the latter, the amino group of the former amino-modified silicone compound (B) is Standardized neutralization rate is 20-
The proportion is preferably 200%, more preferably 60 to 150%, and particularly preferably 60.
~ 120%. Further, among these ranges, when the neutralization ratio exceeds 100% and the phosphoric acid ester compound (C) is in an excessive ratio, the mixture of the two has better solubility in the solvent (D) during the polymerization operation. From this point, a more optimal effect is exhibited.

The total amount of the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) used is 0. 1 with respect to the total amount of the ethylenically unsaturated monomer component (A) to be subjected to the copolymerization. It should be 1 to 120% by weight, particularly preferably adjusted to 1 to 50% by weight. If the amount of the mixture used is less than 0.1% by weight, the effect of silicone is difficult to be recognized, and if it exceeds 120% by weight, the polymerization reaction may be hindered. When the amount used is 1 to 50% by weight, the product has both stability over time and non-sticky slip.

In the copolymerization operation, the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) may be separately charged into the polymerization reaction system. However,
It is particularly preferable to prepare a mixture containing the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) in advance, and then subject this to the above-mentioned copolymerization reaction, whereby the solvent (D The solubility of the amino-modified silicone compound in (1) is further increased, but it is presumed that this is because the neutralization salt formation effectively occurs due to the mixing. In the mixing operation, water or a hydrophilic solvent exemplified as the solvent (D) component may be used for dilution.

The mixture of the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) is preferably dissolved in the solvent (D) at the time of copolymerization, but other silicone compounds, surfactants and the like may be added. It may be used together and adjusted so as to be dissolved in the solvent (D) at the time of copolymerization. Further, for the purpose of suppressing foaming during copolymerization and adjusting the appearance, water solubility, foaming property, defoaming property and the like of the copolymer, other silicone compounds, surfactants and the like may be used in combination.

The silicone compound that can be used in combination with the mixture of the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) is not particularly limited, but for example, dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified. Examples thereof include silicone, fluorine-modified silicone, alcohol-modified silicone and the like. The surfactant that can be used in combination with the mixture of the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) is not particularly limited, but from the viewpoint of foam suppression during copolymerization, a high molecular weight poly A nonionic polymer surfactant of oxyethylene / polyoxypropylene / block copolymer system may be used.

(D) Hydrophilic solvent or solvent composed of water and hydrophilic solvent: As a solvent for copolymerization, a hydrophilic solvent or a solvent (D) composed of water and a hydrophilic solvent is used. The hydrophilic solvent has a solubility in water of 10 g / 100 water.
An organic solvent having a temperature of g (25 ° C.) or higher is meant. Specific examples of such a hydrophilic solvent include aliphatic 1-4 hydric alcohols having 1 to 4 carbon atoms such as methanol, ethanol, 2-propanol, ethylene glycol and glycerin, and glycols such as ethyl cellosolve and butyl cellosolve. Examples thereof include ether, dioxane, and dimethylformamide, which can be used alone or in combination.

Since the base for hair cosmetics of the present invention is widely involved in the human body such as the eye mucous membrane, considering that it is applied to the human body, ethanol or 2-propanol alone or as a hydrophilic solvent is used. It is preferable that they are used together and, if necessary, used together with water to form the solvent (D).

The amount of the solvent (D) to be blended is not particularly limited, but in the copolymerization step, it is used in an amount of 50 to 150% by weight based on the total amount of the ethylenically unsaturated monomer component (A). In this range, a stable copolymerization state and a high polymerization rate can be obtained. The solvent (D) used in the neutralization step and the dilution step after the copolymerization
There is no particular limitation on the compounding amount of. The solvent (D)
When the base for hair cosmetics is used in an aqueous cosmetic, it may be further added in the neutralization step or the dilution step after the completion of the copolymerization step.

The solvent (D) at the time of copolymerization is not particularly limited, but is a mixture of the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) present at the time of copolymerization, a surfactant, ethylene. It is important to dissolve the water-soluble unsaturated monomer component (A) and the copolymer obtained by polymerization, whereby the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) can be dissolved. It is presumed that the copolymerization of the ethylenically unsaturated monomer component (A) proceeds around the salt molecule to form a complex of the silicone compound and the acrylic polymer.

(E) Radical polymerization initiator: The radical polymerization initiator (E) is not particularly limited as long as it is used in the solution polymerization method. Specific examples thereof include peroxides represented by benzoyl peroxide, lauroyl peroxide and hydrogen peroxide, persulfates represented by ammonium persulfate and potassium persulfate, and 2,2′-azobis. Known compounds such as azo compounds represented by isobutyronitrile, 2,2′-azobisisovaleronitrile and the like can be mentioned, and any of them may be used. The amount of the radical polymerization initiator (E) used is not particularly limited, but is preferably in the range of 0.01 to 10% by weight based on the total amount of the ethylenically unsaturated monomer component (A). In this range, a high polymerization rate can be obtained and the performance of the final product can be kept high.

The copolymerization method for obtaining the base for hair cosmetics according to the present invention is not particularly limited, and a known solution polymerization method can be used. For example, the ethylenically unsaturated monomer component (A) composed of the ethylenically unsaturated monomer (a) and (b) is included in the amino-modified silicone compound (B) and the phosphoric acid ester compound (C). The mixture is put into a reaction vessel together with the solvent (D), stirred and mixed, then the radical polymerization initiator (E) is added, and the mixture is heated under a nitrogen stream while stirring, that is, a so-called batch polymerization method or the ethylenic non-polymerization method. The saturated monomer component (A) was dropped into a reaction vessel containing a solvent (D) containing an amino-modified silicone compound (B) and a phosphoric acid ester compound (C) and the radical polymerization initiator (E). Then, a so-called dropping polymerization method of heating while stirring under a nitrogen stream, and a polymerization method of separately charging the ethylenically unsaturated monomer component (A) can be mentioned.

(F) Basic compound: The composition comprising the copolymer obtained by the above-mentioned copolymerization can be suitably used as it is as a base for hair cosmetics, but the basic compound (F) is used. By neutralizing with, it is possible to impart particularly good hair washability to the base for hair cosmetics.

Of the above basic compounds (F), specific examples of organic basic compounds include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, morpholine, triisopropanolamine, ethanolamine, 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 can be mentioned. Further, specific examples of the inorganic basic compound include ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. These basic compounds (F) are used alone or in combination.

The composition comprising the above copolymer preferably contains 30 to 95% of the carboxyl groups in the copolymer as the basic compound (F) when it is desired to impart appropriate PH and hair washability. ), It can be neutralized and used as a base for hair cosmetics. Particularly preferably, it is adjusted so that 40 to 75% of the carboxyl groups in the copolymer are neutralized with the basic compound (F), and in this range, a high setting force is maintained even under high humidity. Moreover, the hair washability is improved.

When the hair cosmetic composition is not washed off after use, it is not necessary to neutralize the hair cosmetic composition when it is used for applications requiring hair wash resistance. However, even in that case, it is possible to neutralize and use, and the neutralization rate at that time is preferably 50% or less, and particularly preferably 0.01 to 30%. In addition to the above-mentioned components, the base for hair cosmetics according to the present invention may contain additives such as an ultraviolet ray inhibitor, an antioxidant and a hair nutrient.

The base for hair cosmetics according to the present invention thus obtained is dissolved in a hydrophilic solvent or water and a hydrophilic solvent, and various additives for hair cosmetics are added thereto to prepare a hair cream or hair lotion. , A non-gas aerosol (hair mist), a hair foam (hair armose), etc. Further, the above-mentioned base for hair cosmetics can be mixed with a hair coloring agent as a coloring fixing agent for hair, and can be used in color spray, color foam, mascara and the like. Furthermore, when the base for hair cosmetics according to the present invention is used as a hair styling agent for aerosol, a hydrophilic solvent or water and a hydrophilic solvent using the base for hair cosmetics as the solvent (D) for polymerization, for example. What was melt | dissolved in is pressurized and filled in an aerosol container with a propellant, such as natural gas and dimethyl ether, and other additives, and may be enclosed. In this case, it is usually desirable to appropriately adjust the blending ratio of various components to be filled in the aerosol container according to each purpose, application, and the like. In addition to the above applications, the base for hair cosmetics can also be suitably used as a coating agent for the skin wound surface such as a film-forming component of a facial pack, a barrier-forming component of a hand cream, and a shampoo or a rinse. It is also useful as an additive for improving finger passing and as a conditioner component.

[0039]

[Examples] The present invention will be specifically described below by comparing Examples and prescription examples using the same with Comparative Examples and Comparative Prescription Examples, but the present invention is not limited to these Examples. Absent. The parts and percentages used below are
All are by weight unless otherwise indicated.

[Production of Base for Hair Cosmetics] [Example 1] A raw material shown in Table 1 was charged into a 1-liter four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement tube and a stirrer. It is. The amino-modified silicone compound (B) and the phosphoric acid ester compound (C) were mixed with each other in advance, dissolved in the solvent (D), and charged. Next, the radical polymerization initiator (E) was added, and the mixture was refluxed (about 8
Copolymerization was carried out at 0 ° C. for 8 hours. After the completion of the copolymerization,
The basic compound (F) is diluted with the same amount of ethanol at 50 ° C., added and neutralized, and after neutralization, diluted with purified water so that the solid content becomes 40%, and the hair cosmetic base is prepared. Obtained.

[Examples 2 to 6] The raw materials shown in Table 1 were subjected to copolymerization and neutralization in the same manner as in Example 1 and diluted with ethanol so that the solid content after neutralization was 40%. A base material for cosmetics was obtained.

<Example 7> As shown in Table 1, copolymerization was carried out in the same manner as in Example 2 except that the neutralization with the basic compound (F) was not performed, and the mixture was diluted with ethanol to give a solid content of 40%. A base for hair cosmetics was obtained. Further, a part of the hair cosmetic base and carbon black are kneaded in a composition such that the weight ratio of the solid content of the hair cosmetic base to carbon black is 65:35, using a three-stage roll. Then, a color paste for color spray was separately prepared.

[Comparative Examples 1, 4, 5] As shown in Table 1, Example 1 was repeated except that the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) were not blended.
Copolymerization and neutralization were carried out in the same manner as in 2 and 3, and both were diluted with ethanol to obtain a hair cosmetic base having a solid content of 40%.

[Comparative Example 2] As shown in Table 1, copolymerization and neutralization were carried out in the same manner as in Example 1 except that the phosphoric acid ester compound (C) was not blended, and diluted with ethanol to give a solid content of 40. % Hair cosmetic base was obtained. The amino-modified silicone compound (B) was premixed with the ethylenically unsaturated monomer (a) of the ethylenically unsaturated monomer component (A).

Comparative Example 3 As shown in Table 1, Example 1 was repeated except that the amino-modified silicone compound (B) was not blended.
Copolymerization and neutralization were carried out in the same manner as above, and diluted with ethanol to obtain a base for hair cosmetics having a solid content of 40%.

[Comparative Examples 6 to 9] Raw materials shown in Table 1 were charged, copolymerization and neutralization were carried out in the same manner as in Example 3, and all were diluted with ethanol to give a hair cosmetic base having a solid content of 40%. I got an agent. Comparative Example 6 contains an ethylenically unsaturated monomer (a) in an amount less than the lower limit, and Comparative Example 7 contains an ethylenically unsaturated monomer (a) in an amount exceeding the upper limit. Comparative Examples 8 and 9 contain the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) in a total amount exceeding the upper limit.

[Comparative Examples 10 to 12] The copolymers obtained in Comparative Examples 1, 4 and 5 were added to the respective copolymers after the same amount of amino-modified silicone compound as those in Examples 1, 2 and 3. (B) and the phosphoric acid ester compound (C) were dissolved and mixed in ethanol, neutralized in the same manner as in Examples 1, 2 and 3,
Both were diluted with ethanol to obtain a base for hair cosmetics having a solid content of 40%. That is, each subsequent compounding amount of the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) was 4 parts by weight of “TSFE700” in Comparative Example 10.
4 parts by weight of "Parlon EP-70", and in Comparative Example 11 "T
4 parts by weight of SFE700, 6 parts by weight of "Parlon EP-70", 2 parts by weight of "TSFE700" in Comparative Example 12,
3 parts by weight of "Parlon EP-70".

<Comparative Example 13> As shown in Table 1, copolymerization was carried out in the same manner as in Comparative Example 4 except that the neutralization with the basic compound (F) was not performed, and the mixture was diluted with ethanol to give a solid content of 40%.
To obtain a base for hair cosmetics. Further, a part of the hair cosmetic base and carbon black are kneaded in a composition such that the weight ratio of the solid content of the hair cosmetic base to carbon black is 65:35, using a three-stage roll. Then, a color paste for color spray was separately prepared.

[0049]

[Table 1]

[Evaluation of Change in Properties of Hair Cosmetic Base with Time] Next, the appearance and aqueous solution of each of the hair cosmetic bases obtained in Examples 1 to 7 and Comparative Examples 1 to 13 were evaluated. Status,
Changes in the transparency of the film and the feel of the film over time were evaluated according to the following methods. The evaluation results are shown in Table 2.

(1) Appearance The appearance of the obtained base material for hair cosmetics was visually observed, and further left at 20 ° C for 10 days, and its time-dependent appearance was visually determined. The evaluation criteria are shown below. ◯: It was transparent. Δ: There was haze. X: Cloudy or separated.

(2) State of aqueous solution An aqueous solution was prepared so that the non-volatile component was 10% by using the obtained base for hair cosmetics, and the state of the solution at 20 ° C was visually observed. The evaluation criteria are shown below. ◯: It was transparent. Δ: Milky white was exhibited. X: Cloudy or separated.

(3) Transparency of the film The obtained base for hair cosmetics was diluted with ethanol so that the non-volatile component was 10%, and this solution was thinly applied to a glass plate so that dust was not applied at room temperature. The film obtained by drying for 20 minutes in a dryer at 50 ° C. was visually evaluated for transparency over time for 10 days. The evaluation criteria are shown below. ◯: It was 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. X: Opaque white turbidity or non-uniform translucency during the drying process and after standing for 10 days.

(4) Stability of film feel over time Simultaneously with the evaluation of (3) above, the film was used to determine the change in feel over time by finger touch. The evaluation criteria are shown below. ◯: There was no change in the feeling of slippage and stickiness throughout the 10 days. Δ: The slippery feeling decreased with time, and the sticky feeling became stronger after leaving for 10 days. X: Sticky feeling was strong from the beginning, or oily matter adhered to the finger.

[0055]

[Table 2]

From the results shown in Table 2, Examples 1 to 1 of the present invention
6 and the bases for hair cosmetics obtained in Comparative Examples 1 and 4 to 5 are all excellent in appearance, state of aqueous solution, and transparency of the film, and the feel of the film is stable over time. I knew it was. The hair cosmetic bases obtained in Example 7 and Comparative Example 13 could not be made into an aqueous solution because the copolymer was not neutralized with the basic compound (F). The nature was fine.

[Evaluation of Performance of Hair Cosmetics of Various Dosages Using Hair Cosmetic Base] Next, using each of the hair cosmetic bases obtained in the above-mentioned Examples and Comparative Examples, It was formulated into various types of hair cosmetics such as styling foam, hair styling water, hair styling spray, hair spray, hair styling mist and color spray, and their performances were evaluated. Tables 3 to 8 show the results of prescription and performance evaluation of hair cosmetics of various dosage forms.
The method for evaluating the performance of each hair cosmetic composition is as shown below. Unless otherwise indicated, all the formulation compositions in the respective formulation examples and comparative formulation examples are on a weight basis, and the compounding amount as a non-volatile component is shown except for the compounding amounts of the compounding components whose concentrations are shown in parentheses. In addition, the judgment criteria when there is no particular definition is as follows. A: Very good. ○: Good. Δ: Somewhat dissatisfied. X: Bad.

(A) Set holding power (curl retention) Hair having a length of 22 cm and a weight of about 2 g was washed with a commercial shampoo, treated with a commercial rinse, air-dried, and then 1 was applied to the lower end of the hair.
A 0 g clip was attached and attached to the rotary shaft of a motor rotating at 30 rpm. Next, while rotating the hair,
The test formulation was sprayed evenly from a distance of about 15 cm for 10 seconds, the deposited droplets were immediately spread with a finger, wound on a rod having a diameter of about 1.2 cm, and fixed with a clip. After drying it for 30 minutes in a desiccator, cool it well, and then attach it to a vertically graduated glass plate that has been unwound in a spiral shape at 30 ° C, 9 ° C.
5% R. H. The hair was allowed to stand in a thermo-hygrostat regulated to 1, the tip position of the hair was recorded after 10 hours, and the curl retention was calculated based on the following equation. The larger the value, the stronger the setting power. Curl retention (%) = {(L-Lt) / (L-L
0)} × 100 L: Length of the test hair when stretched Lt: Tip position of the test hair after leaving for 10 hours in a constant temperature and humidity chamber L0: Test hair before being put in the constant temperature and humidity chamber Tip position

(B) Smoothness (combability) A dry hair bundle was prepared, and the test formulation was sprayed or applied to evaluate the difficulty of comb passage when it was solved with a comb.

(C) Sticky feeling A dry hair bundle was prepared, and the test formulation was sprayed or applied, and the sticky feeling when the dried hair bundle was gripped with the palm was evaluated.

(D) The amount of resin dropped off when the hair bundle prepared in the same manner as in the flaking set holding power evaluation was disentangled was evaluated as follows. ○: There was no dropout. Δ: There was some loss. X: Many were dropped off and were in a powder blown state.

(E) The feeling of touching the hair prepared in the same manner as in the case of evaluating the texture set holding power was evaluated as follows by a sensory test using an in-house monitor, and the same after 1 day. The change with time when the test was conducted was also evaluated. A: Smooth and dry touch. ◯: There was some feeling of stiffness, but it was satisfactory. Δ: Stiff or sticky. X: Quite stiff or strongly adhered.

(F) Hair Washability The test formulation is uniformly sprayed onto a test hair bundle to give 50 to 6
It was dried at 0 ° C., immersed in warm water at 40 ° C., and the state was observed and evaluated as follows. ◯: The resin component could be removed from the hair within 1 minute. Δ: The resin component could be removed from the hair in about 5 minutes. X: The resin component remained on the hair after 5 minutes.

(G) Stability over time After the test formulations were allowed to stand at room temperature for the preparation for 1 month, the degree of separation of the formulation components was visually observed. A: No separation occurred at all. ◯: Slightly separated, shaken for 1 minute, and allowed to stand for 7 days, but no separation occurred. Δ: Slightly separated, and by shaking for 1 minute,
It was redispersible, but after 1 hour, separation occurred again. X: Separation occurred, and it could not be dispersed again even if shaking was added.

(H) As an evaluation of only the color-developing color spray formulation, 2 g of a white hair bundle was sprayed with each of the test formulations for 10 seconds, then sufficiently dried, and the state of hiding the base was visually observed. ⊚: The color of the white hair as the base was completely hidden, and the coating film was black. ◯: The appearance of the coating film was slightly grayish due to the effect of the color of the white hair as the base. Δ: The appearance of the coating film became light gray due to the influence of the color of the white hair as the base. X: The color of the white hair as the base was hardly hidden, and color unevenness occurred.

(I) Non-transfer color As an evaluation of the color spray formulation only, a test formulation was sprayed onto a bundle of 2 g of white hair for 10 seconds each to be sufficiently dried, and a weight of 100 g was applied using a Gakushin-type friction tester. After rubbing with the cotton cloth for 30 times, the stain on the cotton cloth was visually observed. A: The cotton cloth was not soiled at all. ◯: Slight stains were confirmed on the cotton cloth. Δ: A clear black color transfer was confirmed on the cotton cloth. ×: A thick black color transfer was confirmed on the cotton cloth,
Part of the color of the coating film on the hair was also lost.

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

[Table 5]

[0070]

[Table 6]

[0071]

[Table 7]

[0072]

[Table 8]

[0073]

As described above, the base for hair cosmetics according to the present invention maintains the properties of the acrylic resin alkanolamine solution having particularly strong hair styling property among the anionic resin compositions for hair cosmetics. , The transparency of the formed film, good gloss and the low tackiness and smoothing effect which are the properties of the silicone compound, and the gloss of the film formed by this,
There is no problem of low tackiness and change of smoothing effect with time, and even when the composition is made into an aqueous solution or an alcohol solution, it is stable without producing insoluble matter with time.

Further, the film formed by the hair cosmetic using the hair cosmetic base according to the present invention has no problems of adhesion and flaking, is excellent in smoothness and is excellent in high temperature and high humidity. The hair can be easily removed by washing, while exhibiting an excellent hair styling effect such that the hair retainability is exerted and the touch is not impaired, and the copolymer is neutralized.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C083 AC102 AC442 AC542 AC901                       AC902 AD161 AD162 CC32                       CC36 EE01 EE06 EE07

Claims (6)

[Claims] 1. (A) 10 to 40 parts by weight of the following ethylenically unsaturated monomers (a) and (b), that is, (a) an ethylenically unsaturated monomer having at least one carboxyl group in the molecule. % And (b) other polymerizable ethylenically unsaturated monomer (60 to 90% by weight), the total amount of the ethylenically unsaturated monomer component (A) based on the total amount of the ethylenically unsaturated monomer component (A). (E) radical in the presence of 0.1 to 120% by weight of (B) amino-modified silicone compound and (C) phosphoric acid ester compound, and (D) hydrophilic solvent or solvent consisting of water and hydrophilic solvent A base for hair cosmetics comprising a copolymer obtained by a copolymerization reaction by solution polymerization using a polymerization initiator. 2. The amino-modified silicone compound (B) is
The following general formula (I): (In the above formula, 1 represents 0 or a natural number, R ′ represents a linear or branched alkylene group, and R ¹ represents a linear or branched alkyl group, alkenyl group or aralkyl. Represents a group) and /
Alternatively, the following general formula (II): (In the above formula, m represents 0 or a natural number, and R ″ and R ′ ″ each represent a linear or branched alkylene group.), And a phosphoric acid ester compound ( C) is represented by the following general formula (III): (In the above formula, n and p are each 0 or a natural number (however,
n and p must not be 0 at the same time. ) And R ² represents a linear or branched alkyl group, alkenyl group or aralkyl group. The base for hair cosmetics according to claim 1, which is a compound represented by the formula (1). 3. The hair cosmetic composition according to claim 1, wherein upon copolymerization, the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) are mixed in advance and then the copolymerization reaction is carried out. Base material. 4. A solvent (D) which dissolves the ethylenically unsaturated monomer component (A), the amino-modified silicone compound (B) and the phosphoric acid ester compound (C) is used in the copolymerization. The base for hair cosmetics according to any one of 1. 5. The base for hair cosmetics according to claim 1, wherein the copolymer is neutralized with a basic compound (F). 6. A hair cosmetic comprising the base for hair cosmetics according to claim 1.