JP4101779B2 - Hair dye - Google Patents

Description

  The present invention relates to a hair dye, and more particularly to a hair dye having excellent coloring power, less secondary adhesion due to sweat, water and rubbing, and coloration continuing after washing.

  Temporary hair dyes such as hair mascara, color sticks, color gels, color sprays, and color rinses are easy to use, so they can make hair brighter and gray hair temporarily inconspicuous. Used for partial dyeing and fashion dyeing. The dyes used for such temporary hair dyes are generally carbon black, pigments, and acid dyes. Temporary hair dyes using carbon black and pigments have the disadvantage that the dye adheres to clothes and towels that are contact objects, or secondary adhesion that stains the skin and clothes due to the dye flowing down with sweat or water. In addition, since the specific gravity is large, precipitation or aggregation of the dye occurs in the hair dye, and the product stability may be deteriorated or the coloring may be uneven. Temporary hair dyes using direct dyes such as acid dyes are more permeable to hair than carbon black and pigments, and penetrate into cuticles in hair and cortex inside to dye the inside of hair. It is also used as a semi-permanent hair dye (hair dye that fades with several shampoos). However, these temporary hair dyes or semi-permanent hair dyes using direct dyes also have the disadvantage of secondary adhesion that stains clothes due to the dye running off with sweat or water.

  In order to solve these problems, various attempts have been made until now, for example, to temporarily color hair having a specific proportion of an amphoteric polymer resin having a betaine portion and an acid dye. The composition (for example, refer patent document 1) is disclosed. This was intended to improve secondary adhesion and dispersion stability by forming a complex between the cationic part of the amphoteric polymer resin and the acidic group of the acidic dye, The secondary adhesion was not sufficient, and in particular, the color dropped after shampooing and there was no persistence. Furthermore, as a further improvement, a hair cosmetic for coloring and coloring (for example, see Patent Document 2) in which a specific amphoteric polymer compound and an acidic dye are combined in a specific ratio is disclosed. This is to improve the secondary adhesion by using a betaine-type amphoteric polymer resin with a specific structure, but when an aromatic alcohol or the like is blended to make the dye penetrate into the hair, Aggregation of the polymer occurred and there was a limit to coloring, which was not satisfactory.

JP 54-67039 A Japanese Patent Laid-Open No. 9-87158

  Accordingly, an object of the present invention is to provide a hair dye having excellent coloring power, less secondary adhesion due to sweat, water, and rubbing and having a coloring power that persists even after washing.

  As a result of diligent research to achieve the object of the present invention, the inventor has combined a penetration agent such as an aromatic alcohol and a direct dye by combining an amphoteric resin and an amine oxide group-containing resin in a specific ratio. Even when contained, the present inventors have found that there is no aggregation of the polymer, excellent coloring power is exhibited, there is no secondary adhesion, and the coloring power persists even after shampooing.

That is, the present invention 1 comprises (A) an amphoteric resin, (B) an amine oxide group-containing resin, (C) one or more selected from aromatic alcohol and propylene carbonate, and (D) a direct dye. , (A) :( B) = 2: 1 to 1: 8, in which the component (B) comprises an acrylic ester of a long-chain aliphatic alcohol, ethylamine oxide methacrylate, acrylic acid and / or methacrylic acid It is a hair dye characterized by being an amine oxide group-containing resin having an amine oxide group as a structural unit . Further, the present invention 2 is the hair dye according to the present invention 1 or 2, wherein the pH of the hair dye is 2 to 6.

  The present invention can provide a hair dye that has excellent coloring power, little secondary adhesion due to sweat, water, and rubbing, and that maintains the coloring power after washing.

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

  As the zwitterionic resin as the component (A) in the present invention, 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 an unsaturated monomer containing an anionic group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group, and a group having a quaternary ammonium salt, or an unsaturated monomer containing a tertiary amino group As a specific example of a polymer having an unsaturated monomer containing a betaine structural group as an essential component, Yukaformer 204, 205, SM, AMPHOSET, 301, R102, R402 , 510, 201, W (Mitsubishi Chemical Co., Ltd.) and other dimethylaminoethyl methacrylate / methacrylic acid alkyl ester copolymer mono B methacrylic carboxymethyl betaine polymers can be mentioned is acetate modified product.

  Specific examples of the unsaturated monomer containing a betaine structural group and a polymer having a vinylpyrrolidone group as an essential component include acrylic acid / methacrylic acid such as AP polymer 560 and nature resin (manufactured by Osaka Organic Chemical Co., Ltd.). Acid / dimethylaminoethyl methacrylate / methacrylic acid alkyl ester / diacetone acrylamide / vinyl pyrrolidone copolymer; unsaturated monomer containing anionic group such as carboxyl group, sulfonic acid group, phosphoric acid group, and quaternary Specific examples of the polymer having both an ammonium salt-containing group and an unsaturated monomer containing a tertiary amino group as essential components include Anformer 28-4910, LV-71, LV-47 ( (National Starch Co., Ltd.) hydroxypropyl acrylate / butylaminoethyl methacrylate / acrylic A polymer comprising both an unsaturated monomer containing a carboxyl group which is an acid octylamide copolymer and an unsaturated monomer containing a tertiary amino group as an essential component; Marcote 295 (manufactured by Calgon) An unsaturated monomer containing a carboxyl group, such as diallyldimethylammonium chloride / acrylic acid copolymer such as Marquat Plus 3330 (manufactured by Calgon), and the like; The polymer etc. which have both the unsaturated monomers containing a quaternary ammonium salt as an essential component can be mentioned.

  In the hair dye of the present invention, in order to obtain dyeability after use, compatibility with an amine oxide group-containing resin, and good hair feel, among the above amphoteric resins, dimethylaminoethyl is preferable. A methacrylic carboxybetaine polymer that is a monohaloacetate modified product of a methacrylate / methacrylic acid alkyl ester copolymer, such as Yucaformer 205S, SM, AMPHOSET, 301, R102, R402, 510, 201, W, and the like. Of the methacrylic carboxybetaine polymers, Yucaformer SM having a long-chain alkyl ester group is more preferable.

In the present invention, the amphoteric resins can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected depending on the blending ratio of the amine oxide group-containing resin. 0.05 to 5% by mass (hereinafter referred to as%) is preferable based on the total amount of the hair dye, and further 0.1 to 2% is more preferable. If it is less than 0.05%, it may be inferior to secondary dyeing, and if it exceeds 5%, there may be a case where the wobbling during use becomes severe.

The amine oxide group-containing resin of component (B) in the present invention is a copolymer having, as structural units, an acrylic ester of a long-chain aliphatic alcohol, ethylamine oxide methacrylate, acrylic acid and / or methacrylic acid. It contains an amine oxide group. Specifically, acrylates / laurylacrylate / stealylacrylate / ethylamine oxidate acrylate.
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 (hereinafter, made by Clariant), Diamond former Z711, Diamond former Z712, Diamond former Z631, Diamond former Z731, Diamond former Z651 Diaformer Z751 (above, manufactured by Mitsubishi Chemical Corporation) and the like.

  The amine oxide group-containing resin in the present invention can be used alone or in combination of two or more, and the blending amount thereof is preferably 0.1 to 10% with respect to the total amount of the hair dye, More preferably, it is 0.2 to 5%. If the content is less than 0.1%, secondary adhesion may not be prevented. If the content exceeds 10%, the feeling of use may become worse and the object of the present invention may not be achieved.

  In the present invention, the (A) amphoteric resin and the (B) amine oxide group-containing resin are blended in the range of (A) :( B) = 2: 1 to 1: 8, more preferably (A): (B) = 1: 1 to 1: 7. If this range is exceeded, aggregation of the zwitterionic resin and the amine oxide group-containing resin occurs, and the objects of the present invention such as dyeing property and secondary adhesion cannot be achieved.

  (C) component in this invention is 1 or more types chosen from aromatic alcohol and a propylene carbonate. Aromatic alcohol and propylene carbonate have the effect of enhancing the dyeing property of the dye to the hair, increase the permeability to the hair, increase the dyeing power, improve the color fastness, and further, the dye is applied to the skin and It has multiple actions to prevent contamination of the scalp. Specific examples of the aromatic alcohol include 1 to 5 mol adducts of benzyl alcohol, benzyl alcohol ethylene oxide and / or propylene oxide, such as 2-benzyloxyethanol, polyoxyethylene / and / or polyoxypropylene benzyl ether. Is mentioned. The number of moles of polyoxyethylene / and / or polyoxypropylene added to polyoxyethylene / and / or polyoxypropylene benzyl ether is preferably n = 1 to 5, more preferably n = 1 to 3. In this case, n = 0 benzyl alcohol may be included, and benzyl alcohol alone can be suitably used in the present invention. Each of ethylene oxide and propylene oxide may be used alone or as a composite adduct, but in the case of a composite adduct, the total amount may be in the range of the above added mole number.

  The aromatic alcohol and propylene carbonate in the present invention can be used alone or in admixture of two or more, and the blending amount is preferably 0.1 to 20% with respect to the total amount of the hair dye. More preferably, it is 1 to 10%. If it is less than 0.1%, the penetration of the dye into the hair may be inferior, and if it exceeds 20%, separation of the hair dye or the like may occur or the container packaging may be affected.

  As the direct dye which is the component (D) in the present invention, a basic dye, a nitro dye and a disperse dye are preferable from the viewpoint of dyeability on the skin. These basic dyes, nitro dyes, and disperse dyes are known dyes described in Cosmetic Ingredient Dictionary and Handbook (The Cosmetic, Toiletry, and Fragrance Association, Vol. 9, 2002).

  For example, as a nitro dye, HC BLUE NO. 2, HC BLUE NO. 4, HC BLUE NO. 5, HC BLUE NO. 6, HC BLUE NO. 8, HC BLUE NO. 9, HC BLUE NO. 10, HC BLUE NO. 11, HC BLUE NO. 12, HC BLUE NO. 13, HC BLUE NO. 14, HC BROWN NO. 1, HC BROWN NO. 2, HC GREEN NO. 1, HC ORANGE NO. 1, HC ORANGE NO. 2, HC ORANGE NO. 3, HC ORANGE NO. 5, HC RED NO. 1, HC RED NO. 3, HC RED NO. 7, HC RED NO. 8, HC RED NO. 9, HC RED NO. 10, HC RED NO. 11, HC RED NO. 13, HC RED NO. 14, HC VIOLET NO. 1, HC VIOLET NO. 2, HC YELLOW NO. 4, HC YELLOW NO. 5, HC YELLOW NO. 6, HC YELLOW NO. 7, HC YELLOW NO. 8, HC YELLOW NO. 9, HC YELLOW NO. 10, HC YELLOW NO. 11, HC YELLOW NO. 12, HC YELLOW NO. 13, HC YELLOW NO. 14, HC YELLOW NO. 15 etc. are mentioned.

  Examples of the anthraquinone dye include 1-amino-4-methylaminoanthraquinone and 1,4-diaminoanthraquinone.

  As acid dyes, Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Red No. 201, Red No. 227, Red No. 230, Red No. 232, Red No. 401, Red 502, Red 503, Red 504, Red 506, Orange 205, Orange 206, Orange 207, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 402, Yellow 403 , Yellow 406, Yellow 407, Green 3, Green 201, Green 204, Green 205, Green 401, Green 401, Green 402, Blue 1, Blue 2, Blue 202, Blue 205, Purple 401, Black 401, Acid Blue 1, Acid Blue 3, Acid Blue 62, Acid Black 52, Acid Brown 13, Acid Green 50, Acid Orange 6, Acid Dread 14, Acid Red 35, Acid Red 73, Acid Red 184, Brilliant Black 1, and the like.

  As oil-soluble dyes, red 215, red 218, red 225, orange 201, orange 206, yellow 201, yellow 204, green 202, purple 201, red 501 and red 505, Examples include orange No. 403, yellow No. 404, yellow No. 405, and blue No. 403.

As basic dyes, red 213, red 214, BASIC BLUE 3, BASIC BLUE 6, BASIC BLUE 7, BASIC BLUE 9, BAS
IC BLUE 26, BASIC BLUE 41, BASIC BLUE 99, BASIC BROWN 4, BASIC BROWN 16, BASIC BROWN 17, BASIC GREEN 1, BASIC GREEN 2, BASIC ORANGE 1, BASIC BORICS 22, BASIC RED 46, BASIC RED
76, BASIC RED 118, BASIC VIOLET 1, BASIC VIOLET 3, BASIC VIOLET 4, BASIC VIOLET 10, BASIC VIOLET 11: 1, BASIC VIOLET 14, BASIC VIWEL16, BASIC YWEL28, BASIC 11 It is done.

Disperse dyes include Disperse Black 9, Disperse Blue
1, Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, and the like.

  Among these direct dyes, acid dyes and basic dyes are preferable. Particularly, acid dyes include yellow No. 4, yellow No. 403, orange No. 205, green No. 3, green No. 201, green No. 204, red No. 2, red No. 104, Red No. 106, Red No. 201, Red No. 227, Blue No. 1, Blue No. 205, Purple No. 401 and Black No. 401 are preferable. Basic dyes such as Basic Blue-6, Basic Blue-7, Basic Blue-9, Basic Blue-26, Basic Blue-41, Basic Blue-99, Basic Brown-4, Basic Brown-16, Basic Brown-17, Basic Green-1, Basic Red-2, Basic Red-12, Basic Red-22, Basic Red-51, Basic Red-76, Basic Violet -1, Basic Violet -3, Basic Violet 10, Basic Violet 14, Basic Violet -57, Basic Yellow -57, Basic Yellow -87, Basic Orange -31 is preferred.

  The said direct dye can be used 1 type or in combination of 2 or more types, As the compounding quantity, 0.01-5% with respect to the whole quantity of hair dye, Especially 0.1-1% is preferable. If it is less than 0.01, the coloring property to the hair may be poor, and if it exceeds 5%, the dye may not be dissolved and may be deposited, or secondary adhesion may not be prevented. There are times when you cannot achieve.

  Furthermore, the pH of the hair dye in the present invention is intended to enhance the dyeing property of the dye to the hair by making the hair acidic, i.e., by setting the acid side to the amino acid residue in the hair protein. A certain carboxyl group is dissociated, and it is easy to bond with a dye. The preferred pH is 2-6, more preferably 3-5. If the pH exceeds this range, the dyeing property is inferior, and the durability of the hair dyeing state is also inferior, and it is not preferable because it is easily washed off with shampoo or the like.

  Moreover, in order to set pH to the said range, normally, an organic acid, an inorganic acid, and those salts are used. Specifically, citric acid, malic acid, acetic acid, lactic acid, oxalic acid, tartaric acid, formic acid, levulinic acid, malonic acid and other organic acids and their salts (for example, sodium salt, potassium salt, organic base salt) And phosphoric acid, sulfuric acid, hydrochloric acid and salts thereof. These pH adjusters are appropriately selected within a range that does not impair the stability and hair dyeing effect of the hair dye, and among these, lactic acid or lactate is preferable from the viewpoint of the hair dyeing effect and the like. Moreover, 0.01 to 10% of the compounding quantity of these pH adjusters is preferable normally, and 0.1 to 5% is still more preferable.

In addition to the above essential components, the hair dye of the present invention, if necessary, components generally used in cosmetics, for example, other surfactants, polymer compounds, fats and oils, powders, silicones, moisturizing agents. Agents, ultraviolet absorbers, ultraviolet dispersants, pigments, liquid alcohols, plant extracts, bactericides, preservatives, antioxidants, chelating agents, drugs, fragrances, and the like can be used as long as the effects of the present invention are not impaired. .

  The dosage form of the hair dye of the present invention is not particularly limited, and is a liquid, emulsion, cream, oil, gel, aerosol, solid preparation, or stick preparation used as a normal hair dye. Specific examples include hair lotion, hair liquid, hair tonic, hair cream, hair oil, hair gel, hair mist, color creon, shampoo, hair rinse, hair treatment, hair foam, hair spray, wax and the like.

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

  The test methods for dyeing property, secondary adhesion, film fastness and wrinkle described in Examples are shown below. Moreover, the compounding quantity of the composition of the hair dye shown in the following table | surfaces is each shown by the mass%.

(1) Dyeing property 0.5 g of the hair dye shown in Examples and Comparative Examples is evenly applied to a hair bundle obtained by bundling white hair of 10 cm in length and 1 g in weight, and dried for 10 minutes using a dryer. I let you. After drying, the dyeing property (white hair hiding power) was evaluated by 10 professional inspectors. 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]

(2) Secondary adhesion The hair bundle prepared in (1) above is placed on a white cloth for JIS dyeing fastness test (according to JIS L0803), 2 mL of purified water is applied to the hair bundle and left for 10 minutes. The degree of secondary adhesion to the skin was evaluated using 10 professional inspectors. 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]

(3) Fastness of film The hair bundle prepared in (1) above is sandwiched with a white cloth for JIS dyeing fastness test (according to JIS L0803), and the operation of rubbing 10 times while applying a certain pressure is repeated. The degree was evaluated using 10 professional inspectors. 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]

(4) Coloring durability The hair bundle prepared in the above (1) was rinsed with a 5% aqueous sodium lauryl sulfate solution for 1 minute, washed with water, and then dried with a dryer. The remaining color of the hair bundle dyed after drying was evaluated using 10 professional inspectors. 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 1-11 and Comparative Examples 1-6
A hair dye 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 11 using the components of the present invention all showed excellent performance. On the other hand, Comparative Examples 1 to 6 were inferior in any of dyeing property, secondary adhesion, film fastness, and color persistence, and the object of the present invention could not be achieved.

  Hereinafter, other prescription examples of the hair dye of the present invention will be given as examples. In addition, for these examples, examinations on the above-described dyeing property, secondary adhesion, film fastness, and color persistence were examined. In any of these examples, excellent characteristics were obtained. Met.

Example 12 (hair foam)
Compounding amount (%)
(1) Yellow No. 4 0.05
(2) Green No. 3 0.1
(3) Red No. 106 0.2
(4) Amphoteric resin 1.5
(Product name: Yuka Former SM, manufactured by Mitsubishi Chemical Corporation)
(5) Amine oxide group-containing resin 3.0
(Product name: Diaformer Z732, manufactured by Mitsubishi Chemical Corporation)
(6) Benzyl alcohol 5.0
(7) Carbon black 0.1
(8) Dimethylpolysiloxane (10 cs) 1.0
(9) Ethanol 30.0
(10) Polyoxyethylene (15E.O.) cetyl ether 0.5
(11) POE (60E.O.) hydrogenated castor oil 2.0
(12) Lactic acid 2.0
(13) Sodium lactate 0.25
(14) Fragrance 0.1
(15) Balance of purified water
(16) Liquefied petroleum gas (0.4 mPa) 8.0

(Manufacturing method) (1)-(3) was melt | dissolved in (15), and what melt | dissolved (5)-(14) uniformly in this was added and it was set as the undiluted | stock solution. This stock solution was filled into an aerosol pressure-resistant container, and (16) was added to obtain a foam preparation.

Example 13 (mist spray)
Compounding amount (%)
(1) Black 401 No. 0.01
(2) Color 205 No. 0.02
(3) Green No. 3 0.06
(4) Purple No. 401 0.08
(5) Amphoteric resin 1.0
(Product name: Yuka Former SM, manufactured by Mitsubishi Chemical Corporation)
(6) Amine oxide group-containing resin 1.0
(Product name: Diaformer Z732, manufactured by Mitsubishi Chemical Corporation)
(7) Benzyl alcohol 1.0
(8) Carbon black 0.1
(9) Polyoxyethylene (2E.O.) benzyl ether 0.5
(10) Ethanol 30.0
(11) Lactic acid 3.0
(12) Sodium lactate 0.38
(13) Octyl methoxycinnamate 0.1
(14) Perfume 0.02
(15) Balance of purified water

(Manufacturing method) The solution which added (1)-(4) to (15) and melt | dissolved was added, the solution which mixed (5)-(14) was added, and it filled with the container for pump mists, and obtained the mist spray.

Example 14 (aerosol type mist spray)
Compounding amount (%)
(1) Basic Blue-99 0.2
(2) Basic brown 16 0.1
(3) Basic Brown 17 0.12
(4) Amphoteric resin 2.0
(Product name: Yuka Former SM, manufactured by Mitsubishi Chemical Corporation)
(5) Amine oxide group-containing resin 2.0
(Product name: Diaformer Z732, manufactured by Mitsubishi Chemical Corporation)
(6) Benzyl alcohol 3.0
(7) Ethanol 50.0
(8) Amodimethicone emulsion 0.5
(Product name: BY22-009, manufactured by Toray Dow Corning Silicone)
(9) Aminomethylpropanol 0.3
(10) Polyoxyethylene (1E.O.) benzyl ether 5.0
(11) Lactic acid 2.0
(12) Sodium lactate 0.25
(13) Liquefied petroleum gas 5.0
(14) Dimethyl ether 15.0
(15) Balance of purified water

(Production method) (1) to (3) and (15) were uniformly mixed, and a mixture of (4) to (12) was added to obtain a stock solution. The stock solution was filled into an aerosol pressure vessel, and the propellant (13) and (14) was added to obtain an aerosol type mist spray.

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 dye having excellent coloring power, less secondary adhesion due to sweat, water and rubbing, and having no hair stiffness after dyeing.

Claims (2)

(A) an amphoteric resin, (B) an amine oxide group-containing resin, (C) one or more selected from aromatic alcohol and propylene carbonate, and (D) a direct dye. B) A hair dye having a ratio of 2: 1 to 1: 8, wherein the component (B) is a long chain aliphatic alcohol acrylic ester, ethylamine oxide methacrylate, acrylic acid and / or methacrylic acid as a constituent component. A hair dye characterized by being an amine oxide group-containing resin having an amine oxide group as a structural unit . Furthermore, pH of hair dye is 2-6, Hair dye of Claim 1 characterized by the above-mentioned.