WO2012077731A1 - Gel-like hair cosmetic composition - Google Patents

Abstract

[Problem] To provide a novel gel-like hair cosmetic composition which can be stably sprayed in the form of mist and has high hair-arranging ability and excellent feeling of use (sense of light finish) for serving as a hair cosmetic composition, without causing flaking, said hair cosmetic composition having transparent appearance. [Solution] A non-emulsion gel-like hair cosmetic composition which contains, in an aqueous solvent, (a) a specific cationic polymer, (b) a non-stringy anionic polymer (such as a carboxyvinyl polymer) that has a thickening effect, (c) an adhesive polymer that has an adhesiveness as showing a ball number of 1-30 in an inclined ball tack test (inclination angle of 30°, at 25°C, at a humidity of 50%) in accordance with JIS Z-0237 and/or (d) one or more substances that are selected from at least one group among (d-1) sugar alcohols and sugar alcohol derivatives, (d-2) sugars and sugar derivatives and (d-3) polyalkylene glycols. The non-emulsion gel-like hair cosmetic composition has a viscosity of 500-3,000 mPa∙s (measured with a B-type viscometer at 30°C), and is sprayed in the form of mist when in use.

Description

Gel hair cosmetic

The present invention relates to a gel hair cosmetic. More specifically, it is a novel gel-like hair cosmetic that can be sprayed in a mist, has a high arranging power as a hair cosmetic, has an excellent feeling of use (light finish), has no flaking, and has a transparent appearance. About.

Conventionally, gel cosmetics are used by taking the preparation in the palm and applying it to the skin or hair. For this reason, there is a problem in terms of usability because it is necessary to wash away the residue on the palm after use. Further, even when such a gel cosmetic is accommodated in a spray container and sprayed, it has been difficult to spray as a mist because of a highly viscous preparation. A technique disclosed in Patent Document 1 solves the above-described problems.

Although the technique of this patent document 1 has the outstanding effect that a transparent gel-like composition can be sprayed in the shape of a mist, the composition of the hair can be freely adjusted to a shape according to preference with a handbrush or the like. The application as a hair cosmetic that combines effects such as the ability to arrange hair, the ability to rearrange hair (re-arrangement power), and the excellent feeling of use (light finish) has not been studied.

In general, in hair cosmetics, it is necessary to emulsify solid oil or liquid oil in order to exert an arranging power, but in that case, transparency cannot be obtained.

Thus, with the existing technology, it was technically difficult to achieve both a transparent gel shape that can be sprayed in mist and a high arrangement power.

As a document disclosing a technique close to the present invention, Patent Document 2 is further cited. In Patent Document 2, hair cosmetics having both fixing force and arranging power are described. However, it is a transparent gel that can be sprayed in a mist, has a high arranging power, and has a feeling of use (light finish). There is no description that suggests that an excellent hair cosmetic can be obtained. In addition, hair cosmetics generally have a high concentration of hair styling ingredients (mainly film-forming polymers) and try to increase flaking ( It is desirable to be able to prevent the occurrence of such a phenomenon because there is a problem in the formulation that a tendency that a powder-like product appears when the hairstyle is broken is likely to occur.

JP 2003-34614 A JP 2010-235499 A

The present invention has been made in view of the above circumstances, enables stable mist spraying, has high arranging power as hair cosmetics, excellent usability (lightness of finish), and does not cause flaking. An object of the present invention is to provide a novel gel-like hair cosmetic with a transparent appearance.

In order to solve the above problems, the present invention includes the following component (a), component (b), component (c) and / or component (d) in an aqueous solvent, and having a viscosity of 500 to 3000 mPa · s ( A non-emulsifying gel-like hair cosmetic that is used at 30 ° C. and a B-type viscometer).

(A) component: following formula (I)

[In the formula (I), R ₁ and R ₆ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ₂ represents an alkylene group having 1 to 10 carbon atoms; R ₃ , R ₄ and R ₅ each independently represents an alkyl group having 1 to 24 carbon atoms; A represents an oxygen atom, an NH group, or no A. X represents a halogen atom and R′SO ₄ (where R ′ is an alkyl group having 1 to 6 carbon atoms). Further, t / u = 2/8 to 8/2. ]
A cationic polymer having a structural unit represented by:
(B) component: a non-spinning anionic polymer having a thickening action,
Component (c): a tacky polymer having a tack number of 1 to 30 in a tilted ball tack test (slope angle 30 °, temperature 25 ° C, humidity 50%) according to JIS Z-0237 standard,
(D) Component: 1 selected from at least one group selected from (d-1) sugar alcohol and / or sugar alcohol derivative, (d-2) sugar and / or sugar derivative, and (d-3) polyalkylene glycol Seeds or two or more.

According to the present invention, a novel gel-like hair that is capable of stable mist spraying, has a high arranging power as a hair cosmetic, an excellent feeling of use (lightness of finish), does not cause flaking, and has a transparent appearance. Cosmetics are provided.

FIG. 2 is a schematic view showing an apparatus for an inclined ball tack test according to JIS Z-0237 standard.

[(A) component]
In the present invention, a cationic polymer having a structural unit represented by the following formula (I) is used as the component (a).

In the above formula (I), each substituent has the following meaning.

R ₁ and R ₆ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In the present invention, a methyl group as R _{1 and a} hydrogen atom as R ₆ are particularly preferable.

R ₂ represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. In the present invention, a methylene group is particularly preferred.

R ₃ , R ₄ and R ₅ each independently represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, preferably 1 to 4 carbon atoms. In the present invention, it is particularly preferred that R ₃ and R ₄ are each a methyl group and R ₅ is an ethyl group.

A represents an oxygen atom or NH group or does not have A. In the present invention, A is preferably an oxygen atom.

X represents a halogen atom and R′SO ₄ (where R ′ is an alkyl group having 1 to 6 carbon atoms). As the halogen atom, Cl, Br, and I are preferable. R ′ is preferably an alkyl group having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms. In the present invention, it is particularly preferred that X is C ₂ H ₅ SO ₄ .

Also, t / u = 2/8 to 8/2, preferably t / u = 3/7 to 7/3. If t / u is less than 2/8, film formability is inferior, and there is a problem in setting power. On the other hand, if t / u exceeds 8/2, solubility in aqueous solvents (alcohol, water, etc.) and hair There is a problem in terms of affinity and the like, and it is easy to flake. Further, the hygroscopicity is increased, and stickiness is felt, which is not preferable.

In the present invention, as the component (a), the following formula (II)

[In the formula (II), t / u = 2/8 to 8/2. ]
The vinyl pyrrolidone / N, N dimethylaminoethyl methacrylic acid copolymer diethyl sulfate having the structural unit represented by the formula is most preferably used.

In the gel-like hair cosmetic composition of the present invention, the molecular weight of the component (a) is preferably about 10,000 to 10,000,000, particularly preferably about 100,000 to 1,000,000. If the molecular weight is less than 10,000, it is difficult to obtain a firm feeling as a hair cosmetic, while if it exceeds 10 million, the solubility becomes poor and it is difficult to blend in the base.

The polymer represented by the above formula (I), in particular the polymer represented by the formula (II), is excellent in the flexibility of the film, and has excellent affinity and adhesion to the hair. It is a polymer with the characteristic which gives. In the present invention, it is also preferable in terms of transparency. These polymers are commercially available as “Guff Coat” series from GAF (USA), “HC Polymer” series from Osaka Organic Industry Co., Ltd., etc., and are commercially available. (A) A component can use 1 type (s) or 2 or more types.

The blending amount of the component (a) is preferably about 0.02 to 0.5% by mass, and particularly preferably about 0.05 to 0.2% by mass in the hair cosmetic composition of the present invention.

[Component (b)]
As the non-spinning anionic polymer having a thickening action as the component (b) used in the present invention, a carboxyvinyl polymer is preferably used. The carboxyvinyl polymer has no spinnability and has a property of increasing the viscosity by neutralization with alkali. However, since it has no spinnability, it has good “crisp” and is suitable for atomized spray. The carboxyvinyl polymer is mainly a polymer of acrylic acid, and is a synthetic polymer having a carboxyl group. Since the component (b) is “non-spinning”, a water-soluble cellulose derivative that is a spinnable thickener (for example, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, Etc.), sodium polyacrylate and the like are not included in the component (b) of the present invention.

The component (b) is preferably used by adjusting the pH with an alkali and neutralizing it to increase the viscosity. The alkali as the pH adjusting agent is not particularly limited, but potassium hydroxide, sodium hydroxide, triethanolamine, aminomethylpropanol, aminomethylpropanediol and the like are preferably used.

(B) Ingredients are “Sintalen” series (made by V3 SIGMA, Italy), “Carbopol” series (made by BF Goodrich, USA), “Hibiswako” (made by Wako Pure Chemical Industries, Ltd.) Etc., and are commercially available. (B) A component can use 1 type (s) or 2 or more types.

The blending amount of the component (b) is preferably about 0.05 to 1.0% by mass, and particularly preferably about 0.1 to 0.5% by mass in the hair cosmetic composition of the present invention.

[Component (c)]
The adhesive polymer as the component (c) used in the present invention has a ball number of 1 to 1 in an inclined ball tack test (inclination angle 30 °, temperature 25 ° C., humidity 50%) according to JIS Z-0237 standard. It is a tacky polymer having tackiness of 30.

The inclined ball tack test is an adhesive test measured using a measuring apparatus as shown in FIG. Specifically, the sample to be measured (adhesive substance) is provided on the inclined surface of the measuring apparatus shown in FIG. 1 by a method such as film formation (“adhesive surface”), and the inclined surface is formed on the adhesive surface. When the runway ("non-adhesive surface") is covered with a non-adhesive sheet from the top to 10 cm, and a ball of various materials and various sizes is rolled from the top of the inclined surface, the adhesive surface Of the balls stopped at any of the above positions, the stickiness is specified by the number (ball number) of the largest ball.

In the present invention, as the sample to be measured (adhesive substance), a polymer solution of 50% by mass of an adhesive polymer is prepared, and a film having a thickness of 0.1 mm is formed on the inclined surface of FIG. 1 with the polymer solution. After that, a ball tack test was performed using a sample surface (adhesive surface) that was dried at a temperature of 25 ° C. and a humidity of 50% for 1 day. The measurement conditions are as follows: the inclination angle of the inclined surface in the measuring apparatus shown in FIG. 1 is 30 °, the temperature is measured at 25 ° C. and the humidity is 50%, and the ball number is 1 to 30, more preferably 3 to 25 The adhesive polymer in the present invention is the one having the property. When the ball number is less than 1, no stickiness is obtained, and the arranging power cannot be expressed even on the hair. On the other hand, although the tackiness is high, the stickiness becomes high on the hair and hair styling becomes difficult, and the effects of the present invention are obtained. I can't.

Specific examples of the component (c) used in the present invention include acrylic polymers such as acronal YJ2720D, acronal V215ap, acronal N285, acronal V210, acronal V212 (above, BASF products), plus size L- 2700 (manufactured by Kyodo Chemical Co., Ltd.), NCOR38-088A, Duro-Tak87-200A, Duro-Tak387-2054 / 87-2054 (above, National StarchN & Chemical), MG-0560, MG-0580 (above, Dow Corning) Made by Daito Kasei Kogyo Co., Ltd., Yodosol AH955 belonging to methacrylic acid alkyl ester / acrylic acid alkyl ester copolymer, PRIMALＩＭPS83D (Rohm & HA) SS).

In addition, a monomer represented by the following formula (A) and / or a monomer represented by the following formula (B), a monomer represented by the following formula (C), and a monomer represented by the following formula (D) A preferred example is an adhesive polymer obtained by polymerization of

Hereinafter, the monomer represented by formula (A) is monomer A, the monomer represented by formula (B) is monomer B, the monomer represented by formula (C) is monomer C, and the monomer represented by formula (D) Is also referred to as monomer D. Monomers A, B, C and D can be used alone or in combination of two or more.

<Monomer A>

[In the formula (A), R ₇ is H or CH ₃ , n is an integer of 0 to 30 and (CH ₂ ) _n includes a branched chain, and R ₈ is H, OH, OCH ₃ , OCH ₂ CH ₃ or a phenyl group. ]

Specific examples of monomer A include butyl acrylate, ethyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, methoxyethyl acrylate, and the like.

<Monomer B>

[In the formula (B), R ₉ is H or CH ₃ , R ₁₀ and R ₁₁ are each independently H or (CH ₂ ) _k R ″ {where k is an integer of 1 to 3 , R ″ is H, OH or —NR ′ ″ R ″ ″ (where R ′ ″ and R ″ ″ are each independently H or an alkyl group having 1 to 3 carbon atoms)} . ]

Specific examples of monomer B include dimethylacrylamide (DMAA), dimethylaminopropylacrylamide (DMAPAA), and the like.

<Monomer C>

[In the formula (C), R ₁₂ is H or CH ₃ , p is an integer of 1 to 100, m is an integer of 0 to 30, and R ₁₃ is H, OH, OCH ₃ , OCH ₂ CH ₃ or a phenyl group, and Z is an oxyethylene group (EO), an oxypropylene group (PO), an oxybutylene group (BO), or a glyceryl group. ]

Specific examples of monomer C include polyoxyethylene glycol acrylate.

<Monomer D>

[In the formula (D), R ₁₄ and R ₁₅ are each independently H or CH ₃ , q is an integer of 1 to 100, Y is an oxyethylene group (EO), oxypropylene group (PO), oxy It is a butylene group (BO), a linear or branched oxyalkylene group having 5 or more carbon atoms, or a glyceryl group (provided that when Y is a linear or branched oxyalkylene group having 5 or more carbon atoms, q is 1.) ]

Specific examples of the monomer D include polyoxyethylene glycol diacrylate, polyoxyethylene glycol dimethacrylate, and glycerin dimethacrylate.

Preferred examples of the adhesive polymer obtained by polymerizing the monomer A and / or B, the monomer C, and the monomer D include an adhesive polymer represented by the following formula (III).

[In the formula (III), R ₇ to R ₁₅ , n, m, p, q, Y, Z are the same as those in the above formulas (A) to (D); a, b, c, d are It represents the number of moles of each monomer, 40 <a <400, b is 80 ≦ b ≦ 300, c is 30 <c <300, and d is a number in the range of 0 <d <10. ]
The mass% of each monomer represented by the formula (III) that satisfies the adhesive condition of the ball number of 1 to 30 of the present invention is approximately as follows. 7.5 <monomer A <62.5 (mass%), 20 ≦ monomer B ≦ 45 (mass%), 7.5 <monomer C <60 (mass%), 0 <monomer D <10 (mass%).

The above-mentioned adhesive polymer is polymerized by mixing a monomer A and / or B, a monomer C, and a monomer D in an appropriate ratio and using a standard polymerization method in an appropriate solvent as necessary. Can be prepared. For example, it can be obtained by performing thermal polymerization in ethanol at about 80 ° C. for 8 hours using a polymerization initiator such as 2,2′-azobisisobutyronitrile in ethanol. Can be used. However, it is not limited to this manufacturing method.

Silicone-based adhesive polymers can also be used, and addition reaction type silicones SD4584PSA, SD4560, SD4570, SD4580, SD4585, SD4587L (above, manufactured by Toray Dow Silicone), TSR1512, TSR1516 (above, manufactured by MOMENTIVE) ) And the like.

The component (c) in the present invention is not limited to the specific examples listed above as long as it is a polymer that satisfies the above-described adhesive conditions. From the viewpoint of transparency of hair cosmetics, compared to silicone-based adhesive polymer, an adhesive obtained by polymerizing the above acrylic polymer, monomer A and / or monomer B, monomer C, and monomer D A functional polymer is preferably used. In this invention, 1 type, or 2 or more types can be used for (c) component.

The amount of component (c) is preferably 0.05 to 13% by mass, more preferably 0.1 to 10% by mass in the hair cosmetic composition of the present invention. If it is less than 0.05% by mass, the arranging power, re-styling power, etc. may be insufficient. On the other hand, if it exceeds 13% by mass, it may be difficult to obtain a light finish, which is not preferable.

[Component (d)]
The component (d) of the present invention comprises at least one group selected from (d-1) sugar alcohols and / or sugar alcohol derivatives, (d-2) sugars and / or sugar derivatives, and (d-3) polyalkylene glycols. It is 1 type, or 2 or more types chosen from.

<(D-1) component>
The sugar alcohol is a polyhydric alcohol that is obtained by reducing the carbonyl group of the saccharide and is solid at room temperature. Specifically, maltitol (“Malbit”; product food science Co., Ltd.), sorbitol (“sorbitol C”; product food science Co., Ltd.), ribitol, mannitol, arabitol, galactitol, xylitol, erythritol, Inositol and the like can be exemplified. Of these, sorbitol and maltitol are preferable from the viewpoints of stickiness and non-stickiness.

Examples of the sugar alcohol derivative include an adduct obtained by adding polyoxyethylene (POE) and / or polyoxypropylene (POP) to the sugar alcohol, an adduct obtained by adding an alkyl group to the sugar alcohol, a cationized product obtained by cationizing the sugar alcohol, An anionized product obtained by anionizing a sugar alcohol, a silylated product obtained by silylating a sugar alcohol, and the like can be mentioned. Specifically, POP sorbit (“Uniol HS-1600D”, “Uniol HS-2000D” (manufactured by NOF Corporation)), POEPOP pentaerythritol ether (“UNILUBE 5TP-300KB” (manufactured by NOF Corporation)) ) And the like.

<(D-2) component>
Examples of the sugar include monosaccharides and oligosaccharides. Specifically, monosaccharides include tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-threose, etc.); For example, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; hexose (eg, D-glucose, D-talose, D-bucose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); heptacarbon (eg, aldheptose, heproose, etc.); octose (eg, octulose, etc.); (For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose Amino sugar (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acid (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturon) Acid, L-iduronic acid, etc.).

Sugar derivatives include POE and / or POP additions to sugars, additions of alkyl groups to sugars, cationizations obtained by cationizing sugars, anionizations obtained by anionizing sugars, and silyls obtained by silylation of sugars. And the like. Specifically, POE (10) methyl glucoside (= methyl gluces-10) (“Macbiobride MG-10E” (manufactured by NOF Corporation), Glucam E-10 (manufactured by Lubrizol Corporation)), POE (20) Methyl glucoside (“Macbiobride MG-20E” (manufactured by NOF Corporation)), POP (10) Methylglucoside (“Macbiobride MG-10P” (manufactured by NOF Corporation), Glucam P -10 (manufactured by Lubrizol Co., Ltd.)), POE (20) methyl glucoside (“Macbiobride MG-20P” (manufactured by NOF Corporation), “Glucam P-20” (manufactured by Nippon Lubrizol Corporation) ) Etc.)) etc. Among these, POE (10) methyl glucoside, POP (10) methyl glucoside, and the like are preferable from the viewpoints of arranging power when applied to hair, re-styling power over time, and the like.

<(D-3) component>
The polyalkylene glycol as component (d-3) means an addition polymer of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). In the present invention, those having a molecular weight of about 200 to 20000 are preferably used from the viewpoints of arranging power when applied to hair and lightness after finishing. As the component (d-3), a commercially available product can be used. For example, as an EO addition polymer, polyethylene glycol (PEG) 200, PEG300, PEG400, PEG600, PEG1000, PEG1540, PEG2000, PEG4000, PEG6000, PEG11000, PEG 20000 (manufactured by NOF Corporation or Toho Chemical Co., Ltd.) and the like, and PO addition polymers include UNIOR D-700, UNIOR D-1000, UNIOR D-1200, UNIOR D-2000 (all Also available from NOF Corporation). Among them, polyethylene glycol having a molecular weight of 1000 to 15000 is most preferable from the viewpoint of the arranging power when applied to hair.

As the component (d), any one type or two or more types can be used from the group of the components (d-1), (d-2), and (d-3). As the component (d), either a room temperature solid or a room temperature liquid can be used, but a room temperature solid is more preferable. However, it is not limited to this.
The blending amount (total amount) of component (d) is preferably 0.05 to 13% by mass, more preferably 0.1 to 10% by mass in the hair cosmetic composition of the present invention. If it is less than 0.05% by mass, the arranging power, re-styling power, etc. may be insufficient. On the other hand, if it exceeds 13% by mass, it may be difficult to obtain a light finish, which is not preferable.

In the present invention, the component (a), the component (b), the component (c) and / or the component (d) are dissolved in an aqueous solvent. Examples of the aqueous solvent include water, alcohol solvents such as ethanol, and mixed solvents thereof.

The hair styling cosmetic composition of the present invention has a system viscosity of 500 to 3000 mPa · s (30 ° C., B-type viscometer), preferably 600 to 2000 mPa · s, particularly preferably 700 to 1500 mPa · s.

The hairdressing cosmetic composition of the present invention is water-based and has a low viscosity. However, the adjustment of the viscosity is, for example, controlling the degree of copolymerization of the copolymer to be blended, adjusting the amount of addition of a polymer or the like, and adjusting the blending amount of the aqueous solvent. Etc.

In the gel-like hair cosmetic composition of the present invention, the component (a) and the component (b) form a complex, and adjacent complexes form weak bonds due to cohesive force. This makes it possible to form a uniform gel that is elastic and yet has a low viscosity compared to a normal gel-like composition, and can be shaken or passed through pores (for example, spray holes of a cosmetic sprayer). Since weak bonds due to aggregation between the composites are easily broken by an external force of the degree of passage, etc., it can be easily sprayed in the form of a mist during use.

Furthermore, even if the weak bond due to aggregation between the composites breaks down during use, the composites have the property of aggregating each other by allowing them to stand after use. A weak bond due to aggregation is made between the bodies, forming a gel with elasticity. Therefore, according to the present invention, the gel is formed at the time of standing, and can be easily sprayed in the form of a mist by spraying with a sprayer at the time of use. In addition, an entirely new type of gel-like hair cosmetic that is excellent in arranging power and usability is provided. This gel-like hair cosmetic is excellent in the appearance of the appearance (gel feeling), and is also excellent in the touch during use. Also, the transparency is good.

The hair cosmetic composition of the present invention is a non-emulsifying type. In the present invention, it is preferable that the oil component (however, excluding the fragrance and phenoxyethanol) and the surfactant are not substantially contained. By substantially not containing an oil component, a reduction in stickiness can be obtained more effectively, and by not emulsifying, the appearance can be adjusted to be transparent. Moreover, in this invention, sufficient smoothness can be obtained even if oil content is not included.

The hair cosmetic of the present invention may be blended with other components conventionally used in hair cosmetics, for example, depending on the form thereof, as long as the effects of the present invention are not impaired. Examples of such a component include a film-forming polymer. The film-forming polymer usually has a lower ball number in the ball tack test than the component (c).

The film-forming polymer is not particularly limited, and any film-forming polymer conventionally used in hair cosmetics such as hair styling agents can be arbitrarily used. In the present invention, acrylic, vinyl, and urethane film-forming polymers are preferably used from the viewpoint of re-styling and the like.

<Acrylic and vinyl film-forming polymers>
As anionic ones, alkyl acrylate / diacetone acrylamide copolymers (plus size L-53P, plus size L-9909B, plus size L-9948B etc. (all manufactured by Kyoyo Chemical Co., Ltd.)), alkyl acrylate・ Octylacrylamide copolymer (Dermacryl 79 (made by NSC Japan)), polyethylene glycol ・ polypropylene glycol-25 ・ Dimethicone ・ Acrylates copolymer (Rubiflex SILK (made by BASF)), acrylic acid / acrylic acid amide・ Ethyl acrylate copolymer (Ultrahold 8, Ultrahold Strong (manufactured by BASF)), alkyl acrylate copolymer (aniset NF-1000, aniset HS-3000, etc.) Etc.)) etc.

As amphoteric ones, acrylic acid octylamide / hydroxypropylpropyl acrylate / butylaminoethyl methacrylate copolymer (AMPHOMER SH30, AMPHOMER LV-71 (made by NSC Japan)), methacryloyloxyethylcarboxybetaine / methacrylic acid Alkyl copolymers (Yukaformer R205, Yukaformer 301, Yukaformer SM, Yukaformer 104D, etc. (manufactured by Mitsubishi Chemical Corporation), RAM Resin-1000, RAM Resin-2000, RAM Resin-3000, RAM Resin-4000 (Osaka Organic Chemical Co., Ltd.) Company)), dimethyldiallylammonium chloride / acrylic acid copolymer (Mercoat 280, Marcoat 295 (Nalco)), dimethyldiallylammonium chloride Um acrylamide-acrylic acid copolymer (mer coat plus 3330, Ma coat plus 3331 (Nalco Co., Ltd.)), and the like.

As a cationic substance, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer diethyl sulfate (HC Polymer 1S (M), HC Polymer 2 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Guff Coat 755N ( ISP)), vinylpyrrolidone / dimethylaminopropyl methacrylamide / lauryl dimethylaminopropyl methacrylamide copolymer (Styrise W-20 (ISP)), vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate / acrylic Alkyl diacrylate / tripropylene glycol copolymer (Coscut GA467, Koscut GA468 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), polydimethylmethylenepiperidinium chloride (Mercoat 100 (manufactured by Nalco)), dimethyldiallylammonium chloride Um acrylamide copolymer (manufactured by Merquat 550 (Nalco)), trimethyl amino propyl acrylamide chloride-dimethylacrylamide copolymer.

Nonionic materials include polyvinylpyrrolidone [rubiscol K17, rubiscol K30, rubiscol K90 (manufactured by BASF), PVP K (ISP)], vinylpyrrolidone / vinyl acetate copolymer [PVP / VA S -630, PVP / VA E-735, PVP / VA E-335 (above, made by ISP), Rubiscor VA73W, Rubiscol 37E (above, made by BASF), PVA-6450 (Osaka Organic Chemical Co., Ltd.) ), Vinyl methyl ether / alkyl maleate copolymer [Gantrez A-425, Gantrez ES-225, Gantrez ES-335 (all manufactured by ISP)], vinylpyrrolidone / methacrylamide / vinyl imidazole copolymer [ Ruby Set Clear (BASF)) That.

<Urethane-based film-forming polymer>
Examples of urethane-based film-forming polymers include silicone / polyether-based polyurethane resins (Yodosol PUD; manufactured by Akzo Nobel), “Rubiset PU” (manufactured by BASF), and Japanese Patent Application Laid-Open No. 2006-. Examples thereof include silylated urethane polymers described in Japanese Patent No. 213706. Examples of the acrylic-urethane film-forming polymer include “DynamX” (manufactured by Akzo Nobel Co., Ltd.).

When the film-forming polymer is blended, it is preferably blended in the hair cosmetic composition of the present invention at about 0.1 to 15% by mass, more preferably 1 to 4% by mass.

Also, silicone derivatives and polyhydric alcohols can be listed as optional additional components. Silicone derivatives and polyhydric alcohols are not particularly limited, and those conventionally used in cosmetics and the like can be used.

Specific examples of silicone derivatives include dimethicone copolyol (polyether-modified silicone). Examples of commercially available products include Silicone SC1014M, Silicone KF-6017P (both Shin-Etsu Chemical), SILWET-10E, SILWET-10P (both Nippon Unicar), and Silicone SH-3771 (Toray Dow Corning).

Specific examples of the polyhydric alcohol include dihydric alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol). Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohols (eg, glycerin, trimethylolpropane, etc.); polyhydric alcohol polymers (eg, diethylene glycol, Dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol Alkyl ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol) Benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.); dihydric alcohol alkyl ethers (eg, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethyl) Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, Dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); dihydric alcohol ether esters (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol Nobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerin monoalkyl ether (eg, xyl alcohol, ceralkyl alcohol, batyl alcohol, etc.); glycolide; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP -Butyl ether ; POP · POE- ether; Tripoli polyoxypropylene glycerol ether; POP-glycerin ether; POP-glycerol ether phosphoric acid; poly glycerin.

When the silicone derivative and the polyhydric alcohol are blended, the blending amount thereof is preferably 0.1 to 10% by mass, more preferably 0.2 to 5.0% by mass in the hair cosmetic composition of the present invention.

In addition to the above-mentioned components, other components that are usually used in cosmetics and pharmaceuticals can be optionally added to the hair cosmetic of the present invention within a range that does not impair the effects of the present invention.

The dosage form of the gel hairdressing cosmetic composition of the present invention is an aerosol hair spray, a non-aerosol hair spray, a hair mist, a hair styling gel, etc., which is sprayed at the time of use. Specifically, for example, the hair can be easily misted and stored in a normal spray cosmetic container such as a dispenser type, a trigger type, etc., without being soiled. It can be applied easily.

Since the hair cosmetic composition of the present invention is water-based and has a low viscosity, even when sprayed in the form of a mist during use, the spray nozzle of the spray container is not clogged and has excellent arranging power and re-styling power (re-arranging power). It can be applied to hair widely and uniformly. In the case of an aerosol type, the spray container is usually filled together with a propellant. As the propellant, a propellant known in the aerosol field such as liquefied gas such as propane, butane, pentane and dimethyl ether, and compressed gas such as nitrogen and compressed air can be arbitrarily used. The blending amount of these propellants is preferably about 30 to 60% by mass with respect to 100% by mass of the hair cosmetic (stock solution).

Next, the present invention will be further described in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, the blending amount is expressed in mass% (actual amount).

First, the evaluation method used in this example will be described.

[viscosity]
A sample (100 to 200 mL) was placed in a B-type viscometer (rotor No. 2, rotation speed 60 rpm, 30 ± 2 ° C.), and the sample viscosity after 1 minute from the start of rotor rotation was measured.

[Atomized spray]
Each sample was accommodated in a dispenser type sprayer (“Y-150”: manufactured by Yoshino Kogyo Co., Ltd.), and each sample was sprayed up to 10 times to confirm whether it could be sprayed in a mist form. The evaluation was performed using the 10 evaluation containers according to the following evaluation criteria in terms of the total score.
<Evaluation point>
5 points: Can be neatly atomized from the first time 4 points: Can be neatly atomized from the second time 3 points: Can be neatly atomized from the 3rd to 5th time 2 points: Beautifully atomized nebulized from the 6th to 9th time 1 point to be able to: Clean mist spray at the 10th time 0 point: Can not be mist spray <Evaluation criteria>
◎: Total evaluation score is 40 points or more ○: Total evaluation point is 30 points or more and less than 40 points Δ: Total evaluation point is 20 points or more and less than 30 points ×: Total evaluation point is less than 20 points

[Transparency (appearance)]
Each sample was accommodated in the glass container, and transparency (appearance) was determined visually. Evaluation was performed by 10 people, and the following evaluation criteria were evaluated by the total score.
<Evaluation point>
5 points: Translucent 4 points: Slightly transparent 3 points: Normal 2 points: Slightly transparent 1 point: Transparency is not felt <Evaluation criteria>
◎: Total evaluation score is 40 points or more ○: Total evaluation point is 30 points or more and less than 40 points Δ: Total evaluation point is 20 points or more and less than 30 points ×: Total evaluation point is less than 20 points

[Arrangement power]
Applying 0.5g of a sample to a bundle of black virgin hair (length 20cm, mass 2g) In the test, the total evaluation points were evaluated according to the following evaluation criteria.
<Evaluation point>
5 points: Easy to arrange 4 points: Slightly easy to arrange 3 points: Normal 2 points: Slightly difficult to arrange 1 point: Difficult to arrange <Evaluation criteria>
◎: Total evaluation score is 40 points or more ○: Total evaluation point is 30 points or more and less than 40 points Δ: Total evaluation point is 20 points or more and less than 30 points ×: Total evaluation point is less than 20 points

[Light finish]
Applying 0.5g of the sample to a bundle of black virgin hair (length 20cm, mass 2g), and finishing the hair bundle after drying at room temperature, the professional panelists (10 persons) In the sensory test according to), the total evaluation points were evaluated according to the following evaluation criteria.
<Evaluation point>
5 points: Light finish 4 points: Slightly light finish 3 points: Normal 2 points: Slightly heavy 1 point: Heavy <Evaluation criteria>
◎: Total evaluation score is 40 points or more ○: Total evaluation point is 30 points or more and less than 40 points Δ: Total evaluation point is 20 points or more and less than 30 points ×: Total evaluation point is less than 20 points

[Re-hair styling (arrangement after 1 hour)]
When a hair bundle after applying 0.5 g of a sample to a bundle of black virgin hair (length 20 cm, mass 2 g) and drying at room temperature, the hair is straightened immediately after application, and then after 1 hour, the hair is re-styled. The ease of arrangement (re-hairing ability) was evaluated according to the following evaluation criteria in terms of the total score of the sensory tests by female panelists (10 persons).
<Evaluation criteria>
5 points: Re-styling ability 4 points: Slight re-styling ability 3 points: Normal 2 points: Slight re-styling ability 1 point: No re-styling ability <Evaluation criteria>
◎: Total evaluation score is 40 points or more ○: Total evaluation point is 30 points or more and less than 40 points Δ: Total evaluation point is 20 points or more and less than 30 points ×: Total evaluation point is less than 20 points

[Flaking]
A 0.5 g sample is applied to a bundle of black virgin hair (length: 20 cm, mass: 2 g), dried at room temperature, and then a white powdery substance is formed on the hair when the hair bundle is broken (frame It was evaluated according to the following evaluation criteria in terms of the total of the evaluation points in a sensory test by female panelists (10 persons).
<Evaluation point>
5 points: Flaking does not occur 4 points: Flaking hardly occurs 3 points: Normal 2 points: Slight flaking occurs 1 point: Flaking occurs <Evaluation criteria>
◎: Total evaluation score is 40 points or more ○: Total evaluation point is 30 points or more and less than 40 points Δ: Total evaluation point is 20 points or more and less than 30 points ×: Total evaluation point is less than 20 points

1. Production Example 1 (Preparation of component (c))
Polymerization was performed using the monomers A to D shown below to prepare the component (c) used in this example.
Monomer A: 30 parts of butyl acrylate (made by Idemitsu Kosan Co., Ltd.)
Monomer B: 30 parts of dimethylacrylamide (DMAA) (manufactured by Kojin Kasei Co., Ltd.)
Monomer C: 15 parts of polyoxyethylene glycol acrylate (p = 10, Blemmer AE-400, manufactured by NOF Corporation), and polyoxypropylene glycol acrylate (p = 6, Blemmer AP-400. NOF ( 20 parts (total: 35 parts)
Monomer D: 5 parts of polyoxyethylene glycol diacrylate (q = 6, NK ester 14G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(Production method)

A mixture prepared by mixing 100 parts of the above monomers A to D was prepared in advance, and added to a 1 L five-neck flask equipped with a dropping funnel containing the mixture, reflux cooling air, thermometer, nitrogen replacement tube, and a stirrer. Then, 100 parts of ethanol was charged, and the temperature was raised under a nitrogen stream. When the mixture was refluxed (about 80 ° C.), 1 part of a polymerization initiator (2,2′-azobisisobutyronitrile) was added to the ethanol. The mixture was added dropwise continuously for 2 hours. Thereafter, the polymerization reaction was allowed to proceed in a reflux state for 8 hours. Next, the solvent content of this solution was adjusted by distilling off the solvent from the solution in the five-necked flask and adding ethanol to obtain a solution of the component (c) having a solid content concentration of 50%.

When an inclined ball tack test was conducted on the tackiness of the component (c) (Production Example 1), the tackiness of the ball number 5 was obtained.

2. Comparative Examples 1-5, Examples 1-7
Using the samples shown in Table 1 below, viscosity, mist spray, transparency (appearance), arranging power, lightness of finish, hair styling power (arranging power after 1 hour), and flaking are evaluated according to the above evaluation methods. did. The results are shown in Table 1. In Table 1, the amount of component (c) is shown in terms of the actual amount. The “vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate ^(*) ” used was a polymer represented by the above formula (II) (molecular weight of about 1,000,000).

As is apparent from the results shown in Table 1, Examples 1 to 7 which are hair cosmetics of the present invention were able to have all the effects of the present invention. On the other hand, Comparative Examples 1 to 3 outside the scope of the present invention could not achieve the effects of the present invention. Comparative Example 4 was an emulsified hair cosmetic compounded with an oil and a surfactant, and transparency was not obtained and the lightness of the finish was not obtained.

3. Preferred blending amount of each blending component In order to investigate the preferred blending amount of component (c) and component (d), using the samples shown in Tables 2 to 4 below, viscosity, mist spray, transparency (Appearance), arrangement power, light finish, hair styling power (arrangement power after 1 hour), and flaking were evaluated. The results are shown in Tables 2-4. In Tables 2 to 4, the amount of component (c) is shown in terms of the actual amount. The “vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate ^(*) ” used was a polymer represented by the above formula (II) (molecular weight of about 1,000,000).

The following are examples of prescriptions.

(Example 8: Mist-like styling agent)
(Mixed component) (mass%)
(1) Ion exchange water Residual (2) Ethanol 30
(3) Carboxyvinyl polymer 0.2
(4) Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate 0.14
(5) Methyl Gluces 10 3
(6) Propylene glycol 5
(7) Adhesive polymer (component (c) in Production Example 1) 1
(8) Vinylpyrrolidone / vinyl acetate copolymer 1
(9) Perfume appropriate amount (10) EDTA-2Na · 2H ₂ O appropriate amount (11) 2-acrylamido-2-methylpropane 0.2
<Production method>
Add (3), (5), (6), and (10) to (1) under room temperature conditions and dissolve sufficiently to obtain an aqueous phase part. Add (9) to (2) and solubilize to make alcohol parts. Add alcohol parts to the water phase parts and stir well, then add (11) to neutralize. Next, add (4) and stir well. Furthermore, (7) and (8) are added and stirred sufficiently to obtain a gel-like composition. These are filled in a container with a mist dispenser to obtain a mist sprayable gel composition.

(Example 9: Mist-like styling agent)
(Mixed component) (mass%)
(1) Ion exchange water Residual (2) Ethanol 30
(3) Carboxyvinyl polymer 0.30
(4) Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate 0.14
(5) Sorbitol 2
(6) Glycerin 5
(7) Adhesive polymer (component (c) in Production Example 1) 1
(8) PEG-10 methyl ether dimethicone 0.5
(9) Perfume appropriate amount (10) EDTA-2Na appropriate amount (11) 2-acrylamido-2-methylpropane 0.2
<Production method>
Add (3), (5), (6), and (10) to (1) under room temperature conditions and dissolve sufficiently to obtain an aqueous phase part. Add (9) to (2) and solubilize to make alcohol parts. Add alcohol parts to the water phase parts and stir well, then add (11) to neutralize. Next, add (4) and stir well. Furthermore, (7) and (8) are added and stirred sufficiently to obtain a gel-like composition. These are filled in a container with a mist dispenser to obtain a mist sprayable gel composition.

The gel-like hair cosmetic composition of the present invention is transparent in appearance, can be sprayed stably and has high arranging power as a hair cosmetic composition, excellent usability (light finish), and flaking. Does not occur.

Claims (6)

1. The following component (a), component (b), component (c) and / or component (d) are contained in an aqueous solvent, and the viscosity is 500 to 3000 mPa · s (30 ° C., B-type viscometer), A non-emulsifying gel-like hair cosmetic used by spraying in the form of a mist during use.
   (A) component: following formula (I)
   

   

   [In the formula (I), R ₁ and R ₆ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ₂ represents an alkylene group having 1 to 10 carbon atoms; R ₃ , R ₄ and R ₅ each independently represents an alkyl group having 1 to 24 carbon atoms; A represents an oxygen atom, an NH group, or no A. X represents a halogen atom and R′SO ₄ (where R ′ is an alkyl group having 1 to 6 carbon atoms). Further, t / u = 2/8 to 8/2. ]
   A cationic polymer having a structural unit represented by:
   (B) component: a non-spinning anionic polymer having a thickening action,
   Component (c): a tacky polymer having a tack number of 1 to 30 in a tilted ball tack test (slope angle 30 °, temperature 25 ° C, humidity 50%) according to JIS Z-0237 standard,
   (D) Component: 1 selected from at least one group selected from (d-1) sugar alcohol and / or sugar alcohol derivative, (d-2) sugar and / or sugar derivative, and (d-3) polyalkylene glycol Seeds or two or more.
2. The gel-like hair cosmetic composition according to claim 1, wherein the aqueous solvent is water and / or an alcohol solvent.
3. (A) The component is represented by the following formula (II)
   

   

   [In the formula (II), t / u = 2/8 to 8/2. ]
   The gel-like hair cosmetic composition according to claim 1 or 2, which is a vinyl pyrrolidone / N, N dimethylaminoethyl methacrylic acid copolymer diethyl sulfate having a structural unit represented by:
4. The gel hair cosmetic according to claim 1, wherein the component (b) is a carboxyvinyl polymer.
5. The component (c) is a monomer represented by the following formula (A) and / or a monomer represented by the following formula (B), a monomer represented by the following formula (C), and the following formula (D). The gel-like hair cosmetic composition according to claim 1, which is an adhesive polymer obtained by polymerizing the monomer represented.
   

   

   [In the formula (A), R ₇ is H or CH ₃ , n is an integer of 0 to 30 and (CH ₂ ) _n includes a branched chain, and R ₈ is H, OH, OCH ₃ , OCH ₂ CH ₃ or a phenyl group. ]
   

   

   [In the formula (B), R ₉ is H or CH ₃ , R ₁₀ and R ₁₁ are each independently H or (CH ₂ ) _k R ″ {where k is an integer of 1 to 3 , R ″ is H, OH or —NR ′ ″ R ″ ″ (where R ′ ″ and R ″ ″ are each independently H or an alkyl group having 1 to 3 carbon atoms)} . ]
   

   

   [In the formula (C), R ₁₂ is H or CH ₃ , p is an integer of 1 to 100, m is an integer of 0 to 30, and R ₁₃ is H, OH, OCH ₃ , OCH ₂ CH ₃ or a phenyl group, and Z is an oxyethylene group (EO), an oxypropylene group (PO), an oxybutylene group (BO), or a glyceryl group. ]
   

   

   [In the formula (D), R ₁₄ and R ₁₅ are each independently H or CH ₃ , q is an integer of 1 to 100, Y is an oxyethylene group (EO), oxypropylene group (PO), oxy It is a butylene group (BO), a linear or branched oxyalkylene group having 5 or more carbon atoms, or a glyceryl group (provided that when Y is a linear or branched oxyalkylene group having 5 or more carbon atoms, q is 1.) ]
6. The gel-like hair cosmetic composition according to claim 5, wherein the component (c) is an adhesive polymer represented by the following formula (III).
   

   

   [In the formula (III), R ₇ to R ₁₅ , n, m, p, q, Y, Z are the same as those in the above formulas (A) to (D); a, b, c, d are It represents the number of moles of each monomer, 40 <a <400, b is 80 ≦ b ≦ 300, c is 30 <c <300, and d is a number in the range of 0 <d <10. ]

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