JP4136964B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic, and more particularly to a hair cosmetic having high thixotropy, good stretchability to hair, and excellent hair fit, non-stickiness, setability and set retention.

  Conventionally, hair gels, hair creams, hair foams, set lotions, and the like have been used as hair cosmetics to adjust the hair style, and these hair cosmetics are generally polymeric compounds for setting hair. It is formulated by dissolving or emulsifying an oil agent or wax. These hair cosmetics have various functions such as setting power and feeling of use (gloss and unity) according to various styles.

  Among these, a gel type that is easy to apply on the hair and has an appropriate viscosity is often used as a dosage form. In order to give moderate viscosity to the gel, conventionally thickening such as polysaccharides such as guar gum, locust bean gum, xanthan gum, semi-synthetic polymers such as hydroxyethylcellulose, hydroxypropylcellulose, alginate, synthetic polymers such as polyvinylpyrrolidone An agent has been used (for example, see Patent Document 1).

  However, since the above thickener has a low viscosity at a low blending rate, it causes a problem such as separation even if an oil agent is blended. There was a problem with the usability. Therefore, in order to improve the feeling of use by imparting high thixotropy, inorganic powder such as silica gel is used (for example, see Patent Document 2). However, it was necessary to add a large amount of these, and there were problems in terms of poor handling, dispersibility, and stability.

  On the other hand, amine oxide group-containing resins (see, for example, Patent Document 3, Patent Document 4, and Non-Patent Document 1) are resins developed for the purpose of setting power, imparting gloss, and conditioning effects. As an example of application of a group-containing resin, a hair cosmetic that has excellent setting power, is non-sticky, and has a smooth feel and gloss by combining an amine oxide group-containing resin and a silicone compound (see, for example, Patent Document 5) .) Is disclosed. However, hair cosmetics prepared by these methods have no thixotropic properties, and therefore, when applied to hair, they do not spread well and cannot be uniformly applied to hair due to poor hair fit. The hair cosmetic was applied, causing stickiness, and did not reach a sufficiently satisfactory level in setting and holding power.

JP-A-6-92820 Japanese Patent Laid-Open No. 9-87158 JP-A-10-72323 JP 2001-310915 A JP 2000-336018 A Published by The Cosmetic Toiletry and Fragrance Association, “International Cosmetic Ingredient Dictionary and Handbook Ninth Edition” 2002, volume 1, p. 31

  Therefore, the object of the present invention is as a styling agent, excellent in use feeling at the time of application, cohesion and setability after application, feel after drying, etc., particularly high thixotropy, good stretch on the hair, and hair familiarity. Another object of the present invention is to provide a hair cosmetic excellent in non-stickiness, setability and set retention.

  As a result of diligent research to achieve the object of the present invention, the present inventor has found that the above problems are caused by a hair cosmetic containing an amine oxide group-containing resin, a carboxyl group-containing thickening polymer, and a specific film-forming resin. As a result, the present invention has been completed.

That is, the present invention 1 is a kind selected from the group consisting of (A) an amine oxide group-containing resin, (B) a carboxyl group-containing thickening polymer, (C) a nonionic film-forming resin and an amphoteric film-forming resin. It is a hair cosmetic characterized by containing the above.
The present invention 2 is the hair cosmetic composition of the present invention 1, wherein the (B) carboxyl group-containing thickening polymer is an acrylic acid / alkyl methacrylate copolymer.

  INDUSTRIAL APPLICABILITY The present invention can provide a hair cosmetic that has high thixotropy, good hair spreadability, excellent hair fit, non-stickiness, setability and set retention.

  Hereinafter, the configuration of the present invention will be described in detail.

The amine oxide group-containing resin which is the component (A) of the present invention is a copolymer having, as structural units, a long-chain fatty acid acrylic ester, ethyl methacrylate amine oxide, acrylic acid and / or methacrylic acid as structural units. It contains a group. Specifically, Acrylates / LaurylAcrylate / StearylAcrylate / Ethlamine Oxide Methacrylate copolymer, Acrylates / StearylAcrylate / Ethlamine Oxide Methacrylate copolymer, Acrylates / LaurylAcrylate / Ethlamine Oxide Methacrylate copolymer and the like, and among these, Acrylates / StearylAcrylate / Ethlamine Oxide Methacrylate copolymer Is particularly preferably used. These amine oxide group-containing resins are described in “International Cosmetic Ingredient Dictionary and Handbook” published by The Cosmetic Toiletry and Fragrance Association, and these amine oxide group-containing resins are commercially available. For example, Diaformer
Z711, Diaformer Z712, Diaformer Z731, Diaformer Z751 (manufactured by Clariant), Diaformer Z711, Diaformer Z712, Diaformer Z631, Diaformer Z732, Diaformer Z651, Diaformer Z731 Mer Z751 (manufactured by Mitsubishi Chemical Corporation) and the like.

  The said amine oxide group containing resin in this invention can be used individually or in mixture of 2 or more types, respectively, As the compounding quantity, it is 0.1-10 mass% with respect to the whole quantity of hair cosmetics ( Hereinafter, it is abbreviated as%), more preferably 0.2 to 5%. If it is less than 0.1%, an excellent setting property may not be obtained, and if it exceeds 10%, the cleaning properties may deteriorate or flaking may occur, which is not preferable.

  The carboxyl group-containing thickening polymer compound (B) of the present invention becomes water-soluble by neutralizing the carboxyl group with an alkaline substance and increases the viscosity of the aqueous system. Carboxyvinyl polymers such as CARBOPOL 940, 941, 980, 981 (above, manufactured by BF GOODRICH); acrylic acid / methacrylic such as PEMULEN TR-1, TR-2 (above, manufactured by BF GOODRICH) Acid alkyl copolymer; alkyl acrylate / methacrylic acid alkyl polyoxyethylene ester copolymer such as ACULYN 22, 23 (above, manufactured by ISP); alkyl acrylate itacone such as STRUCTURE series (above, manufactured by NSC) Acid alkylpolyoxyethylene ester copolymer; STA Examples thereof include methyl vinyl ether / maleic anhydride / decadiene copolymers such as BILEZE series (manufactured by ISP).

  Among these carboxyl group-containing thickening polymer compounds, acrylic acid / alkyl methacrylate copolymers such as PEMULEN TR-1 and TR-2 (manufactured by BF GOODRICH) are amine oxide group-containing resins. When combined, it has excellent thixotropy and is particularly preferred.

  The carboxyl group-containing thickening polymer compound in the present invention can be used alone or in admixture of two or more, and the blending amount is 0.01 to 5% with respect to the total amount of the hair cosmetic. Is more preferable, and 0.1 to 2% is more preferable. When it is 0.01 to 5%, a preferable viscosity for use can be obtained, the coating can be easily spread, and a desirable effect can be easily obtained with respect to stickiness and unity.

  Moreover, the carboxyl group-containing thickening polymer compound is generally used after being neutralized with an alkaline substance, for example, triethanolamine, diethanolamine, monoethanolamine, diisopropanolamine, monoisopropanolamine. Alkanolamines such as aminomethylpropanol, ammonia, potassium hydroxide, sodium hydroxide, basic amino acids (eg, arginine, lysine, etc.), basic polypeptides and the like. The blending amount of these alkaline substances is appropriately blended according to the blending amount of the carboxyl group-containing thickening polymer compound, and is usually adjusted to neutralize 50 to 150% equivalent of the carboxyl group.

  (C) component of this invention is 1 or more types chosen from nonionic film forming resin and amphoteric film forming resin. Anionic film-forming resins are poorly compatible with carboxyl group-containing thickening polymer compounds and amine oxide group-containing resins, and cationic film-forming resins form agglomerates with carboxyl group-containing thickening polymer compounds and aggregate. This is not preferable because the intended effect cannot be obtained.

Nonionic film-forming resin is a polymer comprising as an essential component an unsaturated monomer containing a pyrrolidone ring, an amide group, an N-alkyl-substituted amide group, a polyether group, or an acetamide group or a formamide group, and pyrrolidone Specific examples of the polymer containing a ring include rubiscol K-12, K-17, K-30, K-60, K-80, K-90 (above, manufactured by BASF), PVP K-15, Polyvinylpyrrolidone such as K-30, K-60, K-90, K-120 (above, manufactured by ISP); Rubiscol VA28, VA37, VA55, VA64, VA73 (above, manufactured by BASF), PVP / VA- 735, PVP / VA-635
, Vinyl pyrrolidone / vinyl acetate copolymers such as PVP / VA-535, PVP / VA-335, PVP / VA-235, and S-630 (manufactured by ISP); Lubiscol VAP343 (manufactured by BASF) And vinyl pyrrolidone / vinyl acetate / vinyl propionate copolymer. Specific examples of the polymer having an unsaturated monomer containing an amide group, an N-alkyl-substituted amide group, or a polyether group as essential components include (meth) acrylamide, N-octyl (meth) acrylamide, Homoradical polymers of unsaturated monomers such as hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (polypropylene glycol), or alkyl (meth) acrylate (C1 To C24) radical copolymers with esters, vinyl acetate and the like. Specific examples of the polymer containing an unsaturated monomer containing an acetamide group or a formamide group as an essential component include homo-radical polymers of unsaturated monomers such as N-vinylacetamide and N-vinylformamide, or ( Mention may be made of radical copolymers with (meth) acrylic acid alkyl esters, vinyl acetate and the like.

As an amphoteric film-forming resin, a polymer containing an unsaturated monomer containing a betaine structural group such as a carboxybetaine group, a sulfobetaine group, or a phosphobetaine group as an essential component, or a carboxyl group or a sulfonic acid group , A polymer having both an unsaturated monomer containing an anionic group such as a phosphate group and a group having a quaternary ammonium salt or an unsaturated monomer containing a tertiary amino group as essential components It is. Specific examples of the polymer having an unsaturated monomer containing a betaine structural group as an essential component include Yucaformer 205S, SM, AMPHOSET, 301, R102, R402, 510, 201, and W (manufactured by Mitsubishi Chemical Corporation). Methacrylic carboxybetaine polymer which is a monohaloacetate modified product of dimethylaminoethyl methacrylate / methacrylic acid alkyl ester copolymer such as Specific examples of the polymer having a pyrrolidone group as an essential component include AP polymer 560, natural resin (manufactured by Osaka Organic Industry Co., Ltd.), etc. acrylic acid / methacrylic acid / dimethylaminoethyl methacrylate / methacrylic acid alkyl ester / diacetone acrylamide. / Vinylpyrrolidone copolymer , An unsaturated monomer containing an anionic group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an unsaturated monomer containing a group having a quaternary ammonium salt or a tertiary amino group Specific examples of the polymer having an essential component include hydroxyform acrylate / butylaminoethyl methacrylate / octyl acrylate such as Anformer 28-4910, LV-71, and LV-47 (manufactured by NSC). Polymers having both an unsaturated monomer containing a carboxyl group as an amide copolymer and an unsaturated monomer containing a tertiary amino group as essential components; such as Marquat 295 (manufactured by Calgon) Diallyldimethylammonium chloride / acrylic acid copolymers, diallyldimethylammonium chloride / acrylic acid such as Marquat Plus 3330 (Calgon) Is acrylamide copolymer, an unsaturated monomer containing a carboxyl group, and polymers and the like can be mentioned that both the unsaturated monomer containing a quaternary ammonium salt as an essential component.

  In the hair cosmetic composition of the present invention, among the above-mentioned film-forming resins, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate, which are nonionic film-forming resins, are used for obtaining setting power after use and a good feel of hair. A copolymer, a methacrylic carboxybetaine polymer that is a monohaloacetate modified product of a dimethylaminoethyl methacrylate / methacrylic acid alkyl ester copolymer that is an amphoteric film-forming resin, an unsaturated monomer that contains a betaine structural group, and A copolymer of acrylic acid / methacrylic acid / dimethylaminoethyl methacrylate / methacrylic acid alkyl ester / diacetone acrylamide / vinyl pyrrolidone, which is a polymer having a vinylpyrrolidone group as an essential component, is preferred.

In the present invention, these nonionic film-forming resins and amphoteric film-forming resins can be used alone or in admixture of two or more, and the blending amount is 0 with respect to the total amount of the hair cosmetic. 0.1 to 20% is preferable, and 0.2 to 5% is more preferable. If it is less than 0.1%, the desired setting property may not be obtained, and if it exceeds 10%, the stickiness during use becomes severe.

  In addition to the above essential components, the hair cosmetic of the present invention, if necessary, components generally used in cosmetics, for example, other surfactants, polymer compounds, fats and oils, powders, silicones, pH adjusting agent, moisturizing agent, ultraviolet absorber, ultraviolet dispersing agent, pigment, liquid alcohol, plant extract, bactericidal agent, preservative, antioxidant, chelating agent, drug, perfume, etc., within the range not impairing the effect of the present invention Can be used.

  The form of the hair cosmetic composition of the present invention is not particularly limited, and is usually an emulsion, a blowing agent, a mist agent, a lotion agent, a hair rinse, a hair treatment, a hair foam, a hair essence, a cream, It can be in the form of wax or the like.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited by this.

  Test methods relating to thixotropy, setability, set retention and sensory evaluation (expansion to hair, hair conformance, non-stickiness) described in Examples are shown below. Moreover, the compounding quantity of the composition of hair cosmetics shown in the following table | surfaces is each shown by the mass%.

(1) Thixotropic properties For the hair cosmetics shown in the examples and comparative examples, the viscosity was changed by changing the rotor and rotation speed under a temperature condition of 20 ° C. using a viscometer (manufactured by Shibaura System Co., Ltd., bismetron viscometer). It was measured. As for the relationship of the viscosity (η) to the shear stress (S), the case where η clearly decreases as S increases is referred to as “thixotropic property; yes”, and the others are referred to as “thixotropic property;

(2) Setting power 0.5 g of the hair cosmetic shown in the examples and comparative examples was uniformly applied to a hair bundle (a sample in which a virgin hair having a length of 15 cm and a weight of 1 g was wound on a rod having a diameter of 2 cm). It was left to stand in a high-temperature room at 6 ° C. for 6 hours to be completely dried. After drying, the rod was removed and the apparent length (L1) of the hair bundle was measured. According to the following formula, the setting force was calculated by the following formula.
Setting force (%) = (15−L1) ÷ 15 × 100

(3) Set retention effect 0.5 g of the hair cosmetics shown in Examples and Comparative Examples was evenly applied to a hair bundle in which virgin hair having a length of 15 cm and a weight of 1 g was bundled, and wound around a rod having a diameter of 2 cm. It was left to stand in a high-temperature room at 6 ° C. for 6 hours to be completely dried. After drying, the rod was removed and the apparent length (L1) of the hair bundle was measured. Next, the hair bundle was hung in a constant temperature and humidity chamber at a temperature of 25 ° C. and a humidity of 90%, taken out after 30 minutes, and the apparent length (L2) of the hair bundle was measured again. According to the following formula, the set retention effect was determined by the following formula.
Set retention effect (%) = (15−L2) ÷ (15−L1) × 100
The closer this value is to 100, the higher the set holding effect.

(3) Sensory evaluation Using the hair cosmetics shown in the examples and comparative examples using 10 specialist panels, sensory evaluation was performed on the items of spread, hair familiarity, and non-stickiness at the time of application. The evaluation criteria are as follows.
◎: Very good [more than 8 subjects answered good]
○: Good [6 or more and less than 8 subjects answered that it was good]
△: Slightly bad [4 or more and less than 6 subjects answered good]
×: Bad [less than 4 subjects answered good]

-Examples 1-7 and Comparative Examples 1-5
A hair cosmetic composition having the composition shown in Table 1 was prepared by a conventional method, and the above tests were conducted. The results are also shown in Table 1.

As apparent from Table 1, Examples 1 to 7 using the components of the present invention all showed excellent performance. On the other hand, Comparative Examples 1 to 5 are inferior in any of thixotropy, setability, set retention, and sensory evaluation (expansion to hair, hair familiarity, non-stickiness), and can achieve the object of the present invention. There wasn't.

  Hereinafter, other formulation examples of the hair cosmetic composition of the present invention will be given as examples. In addition, for these examples, the above thixotropic properties, set properties, set retention properties and sensory evaluation (expansion to hair, hair familiarity, non-stickiness) were examined. It had excellent properties and was good.

Example 8 (styling gel)
Compounding amount (%)
(1) Amine oxide group-containing resin 2.0
(Product name: Diaformer Z732, manufactured by Mitsubishi Chemical Corporation)
(2) Acrylic acid / alkyl methacrylate copolymer 0.6
(Product name: PEMULEN TR-1
, B. F. GOODRICH)
(3) Nonionic film-forming resin 4.0
(Product name: PVP / VA S600, manufactured by BASF)
(4) Amphoteric film forming resin 2.0
(Product name: AP polymer 560, manufactured by Osaka Organic Industry Co., Ltd.)
(5) Ethanol 30.0
(6) Triethanolamine 0.5
(7) POE (60) hydrogenated castor oil 0.1
(8) Sage extract 0.2
(9) Fragrance 0.1
(10) Purified water balance

(Production method) (3) to (4) and (10) are uniformly dissolved, and (2) is added and dispersed. Next, the solution which mixed (1) and (5)-(9) was added, and it dispersed uniformly with the homomixer, and obtained the styling gel.

Example 9 (mist spray)
Compounding amount (%)
(1) Amine oxide group-containing resin 0.5
(Product name: Diaformer Z732, manufactured by Mitsubishi Chemical Corporation)
(2) Acrylic acid / alkyl methacrylate copolymer 0.2
(Product name: PEMULEN TR-1
, B. F. GOODRICH)
(3) Carboxyvinyl polymer 0.1
(Product name: Carbopol 980
, B. F. GOODRICH)
(4) Nonionic film-forming resin 0.5
(Product name: PVP K-30, manufactured by ISP)
(5) Ethanol 30.0
(6) Octyl methoxycinnamate 0.1
(7) Dimethylpolysiloxane emulsion 0.5
(Product name: BY22-070
, Manufactured by Toray Dow Corning Silicone)
(8) Triethanolamine 0.5
(9) Perfume 0.02
(10) Purified water balance

(Production method) (2) to (3) are added to (10) and dispersed. Next, a solution in which (1) and (4) to (9) were uniformly mixed was added, uniformly dispersed with a homomixer, and filled into a pump mist container to obtain a mist spray.

Example 10 (aerosol type mist spray)
Compounding amount (%)
(1) Amine oxide group-containing resin 0.6
(Product name: Diaformer Z732, manufactured by Mitsubishi Chemical Corporation)
(3) Carboxyvinyl polymer 0.3
(Product name: Carbopol 980,
B. F. GOODRICH)
(4) Nonionic film-forming resin 0.5
(Product name: PVP K-90, manufactured by ISP)
(5) Ethanol 30.0
(6) Amodimethicone emulsion 0.5
(Product name: BY22-007,
(Toray Dow Corning Silicone)
(7) Aminomethylpropanol 0.3
(8) Perfume 0.02
(9) Liquefied petroleum gas 5.0
(10) Dimethyl ether 15.0
(11) Purified water balance

(Manufacturing method) (1) to (7) and (11) are uniformly mixed with a homomixer, filled in an aerosol pressure-resistant container, and put into the propellant of (8), (9) and (10), and aerosol type A mist spray was obtained.

Example 11 (hair cream)
Compounding amount (%)
(1) Amine oxide group-containing resin 1.0
(Product name: Diaformer Z732, manufactured by Mitsubishi Chemical Corporation)
(2) Acrylic acid / alkyl methacrylate copolymer 1.0
(Product name: PEMULEN TR-1,
B. F. GOODRICH)
(3) Amphoteric film forming resin 1.0
(Product name: AP polymer 560, manufactured by Osaka Organic Industry Co., Ltd.)
(4) Amphoteric film forming resin 0.3
(Product name: LUVISE CLEAR, manufactured by BASF)
(5) Isostearic acid 1.0
(6) Polyoxyethylene (60) hydrogenated castor oil 1.0
(7) Ethanol 5.0
(8) Light liquid isoparaffin 3.0
(9) Dimethylpolysiloxane (100,000 cs) 2.0
(10) Octyl paramethoxycinnamate 0.5
(11) Sodium hydroxide 0.08
(12) Fragrance 0.05
(13) Balance of purified water

(Production Method) (3) to (4) and (11) are dissolved in (13), and then (2) is added and dispersed. Next, a solution in which (1) and (5) to (10) and (12) were uniformly mixed was added, and the mixture was uniformly dispersed with a homomixer to obtain a hair cream.

Example 12 (hair essence)
Compounding amount (%)
(1) Amine oxide group-containing resin 0.4
(Product name: Diaformer Z732, manufactured by Mitsubishi Chemical Corporation)
(2) Amine oxide group-containing resin 0.1
(Product name: Diaformer Z-712, manufactured by Clariant)
(3) Acrylic acid / alkyl methacrylate copolymer 0.2
(Product name: PEMULEN TR-1,
B. F. GOODRICH)
(4) Amphoteric film forming resin 0.5
(Product name: AP polymer 560, manufactured by Osaka Organic Industry Co., Ltd.)
(5) Ethanol 20.0
(6) Decamethylpentasiloxane 5.0
(7) Dimethylpolysiloxane (1 million cs) 2.0
(8) Tetosodium edetate 0.01
(9) Triethanolamine 0.2
(10) Polyoxyethylene (40) hydrogenated castor oil 0.5
(11) Purified water balance

(Production method) (8) is dissolved in (11), and then (3) is added and dispersed. Next, a solution in which (1), (2), (4) and (9) are mixed is added and dispersed uniformly with a homomixer, and then (5) to (7) and (10) are mixed. In addition, the hair essence was obtained by dispersing again with a homomixer.

In addition, the fragrance | flavor used by said each prescription is the following.

  According to the present invention, it is possible to provide a hair cosmetic composition that has high thixotropy, good stretchability to hair, excellent hair fit, non-stickiness, and unity, and little flaking.

Claims (1)

(A) Amine oxide group-containing resin which is a copolymer having a long-chain fatty acid acrylic ester, ethylamine oxide methacrylate and acrylic acid and / or methacrylic acid as constituents , and (B) an acrylic acid / alkyl methacrylate copolymer And (C) at least one selected from the group consisting of a nonionic film-forming resin and an amphoteric film-forming resin.