JPH0561246B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to hair treatment compositions such as perming agents and hair dyes, and more particularly to hair treatment compositions that prevent hair damage and have excellent conditioning effects. . [Prior Art and Problems] Perm agents, hair dyes, and the like contain oxidizing agents, reducing agents, and hair dyes for their purposes. However, when hair is treated with these, the cuticle part of the hair is severely damaged, the hair becomes damaged, and the hair becomes dry.
It had the disadvantage of causing split ends and hair breakage. As a way to improve this drawback, for example,
No. 52-96749 discloses a hair dye containing an oxidizing agent and a specific quaternary amine compound.
Publication No. 49340 describes a hair dye containing a fatty acid, an alkalizing agent, and a specific cationic polymer, but none of them had sufficient conditioning effects or durability. In addition, the above hair treatment agents require highly irritating oxidizing agents, reducing agents, hair dyes, etc.
Various thickeners have been devised to prevent adhesion to the skin due to dripping. However, if a large amount of oil, active agent, etc. are added, the spreadability and feel will deteriorate, and if the oil content is reduced and the viscosity is lowered, it will tend to drip, making it difficult to handle when applied. [Means for Solving the Problems] Under such circumstances, the present inventor conducted intensive research to solve the above-mentioned drawbacks and found that the above-mentioned hair treatment agent contains a branched quaternary ammonium salt and a branching ratio of 1 to 50%.
The inventors have discovered that the above-mentioned drawbacks can be solved by adding a higher alcohol to the composition, and have completed the present invention. Therefore, the present invention provides hair containing (A) a branched quaternary ammonium salt, (B) one or more of an oxidizing agent, a reducing agent, or a hair dye, and (C) a higher alcohol with a branching rate of 1 to 50%. The present invention provides a first invention relating to a processing agent composition. In other words, when components (A), (B) and (C) are used in combination, excellent hair protection and conditioning that cannot be obtained with ordinary mono- or dialkyl ammonium salts can be achieved even under harsh conditions. In addition, since the components (A) and (C) form a good liquid crystal state, it has excellent properties that do not cause dripping and can be easily spread by applying stress. can get. Examples of the branched quaternary ammonium as component (A) of the present invention include those represented by the following general formula (), (), or (). (In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ₃ represents an alkyl group having 1 to 3 carbon atoms or

[Formula], R ₄ and R ₅ represent an alkyl group having 2 to 16 carbon atoms, and X represents a halogen ion or an organic anion. 36 guerbet alcohol

It is synthesized using [Formula] as a raw material. Preferred examples of the branched quaternary ammonium salt include monoalkyl quaternary salts such as alkyltomethylammonium salts having an alkyl group derived from Guerbet alcohol, alkyldimethylhydroxyethylammonium salts, and alkyldimethylbenzyl ammonium salts; Dimethylammonium salts, dialkylmethylhydroxyethylammonium salts, dialkylmethylbenzylammonium salts and the like can be mentioned. Counter ions for these ammonium salts include halogen ions such as chlorine, iodine and bromine, and organic anions such as methosulfate, ethosulfate, metophosphate and ethophosphate. Examples of the alkyl group derived from Guerbet alcohol include 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, and 2-dodecylhexadecyl. Particularly preferable examples of the branched quaternary ammonium salts include 2-decyltetradecyltrimethylammonium chloride, 2-dodecylhexadecyltrimethylammonium chloride, di-2-hexyldecyldimethylammonium chloride, and di-2-octyldodecyl. Examples include ammonium chloride. [In the formula, R ₆ is the same or different, (a)

An alkyl group selected from a branched alkyl group represented by the formula and (b) a linear alkyl group represented by CH ₃ (-CH ₂ - _q (in the formula)
R ₇ is a methyl or ethyl group, p and q are numbers such that the total number of carbon atoms in the alkyl group is 8 to 16), and the branching rate (a)/(a) + (b) of the group R ₆ is 10 to 100 wt%. It is something that is
R ₁ , R ₂ , and X have the same meanings as above] The branched quaternary ammonium salt of formula () is usually synthesized using an oxo alcohol having 8 to 16 carbon atoms as a raw material, and examples thereof include: , dialkyldimethylammonium salts, dialkylmethylhydroxyethylammonium salts, and dialkylmethylbenzylammonium salts having an alkyl group derived from the alcohol. Counter ions for these ammonium salts include halogen ions such as chlorine, iodine and bromine, and organic anions such as methosulfate, ethosulfate, metophosphate and ethophosphate. In formula (), the alkyl group R ₆ has a total number of carbon atoms of 8 to 16 (a)

[Formula] and (b) CH ₃ (a group selected from --CH ₂ -- _q , and R ₇ is a methyl or ethyl group. Branching rate of _{R 6} (a)/
(a)+(b) is determined from the branching rate of the oxo alcohol used as a raw material, and is generally 10 to 100 wt%, preferably 10 to 50 wt%. Further, the total number of carbon atoms in the alkyl group R ₆ may be 8 to 16, but those having a certain distribution are preferable, and those having the following distribution are particularly preferable. C _8-11 : 5 wt% or less C ₁₂ : 10-35 wt% C ₁₃ : 15-40 wt% C ₁₄ : 20-45 wt% C ₁₅ : 5-30 wt% C ₁₆ : 5 wt% or less A particularly preferred example is a carbon number of 8 ~16 with branching rate 10
It is a dialkyldimethylammonium chloride of the formula () having -50 wt% of alkyl groups _R6 . [In the formula, R ₉ is (c)

[Formula] (where r is an integer from 2 to 14, x is an integer from 3 to 11,
The sum of r and x represents 9-21) or an alkyl group having 1-3 carbon atoms. R ₁ , R ₂ , and X have the same meanings as above.] The methyl branched quaternary ammonium salt represented by the formula () is preferably one in which the sum of r and x is 15, and isostearyltrimethylammonium chloride, Examples include isostearyldimethylammonium chloride. These branched quaternary ammonium salts can be used alone or in combination of two or more, and the total amount of the branched quaternary ammonium salts is 0.01 in the hair treatment composition.
~10% by weight (hereinafter simply expressed as %), especially 0.03~
5% is preferred. The oxidizing agent, reducing agent, and hair dye of component (B) can be arbitrarily selected as long as they are normally used in perm agents and hair dyes. Examples of oxidizing agents include hydrogen peroxide, sodium persulfate, ammonium persulfate, Sodium perborate, urea peroxide, sodium percarbonate, sodium peroxide tripolyphosphate, sodium bromate,
Potassium bromate, sodium peroxide pyrophosphate,
Examples include sodium peroxide orthophosphate, sodium silicate-hydrogen peroxide adduct, sodium sulfate chloride hydrogen peroxide adduct, etc.
It is blended in an amount of about 0.1 to 10%. As the reducing agent, thioglycolic acid, cysteine, sulfite, etc. are used, and are blended in the composition in an amount of about 0.05 to 10%. Hair dyes are mainly divided into oxidative hair dyes, non-oxidative permanent or semi-permanent hair dyes, and non-oxidative hair dyes. Oxidative hair dyes oxidize the dye intermediate with an oxidizing agent and dye the hair with the generated pigment.Cuppler (Modifier) does not produce pigment even when oxidized alone, but in the presence of the dye intermediate It produces a pigment when oxidized. Therefore, the oxidized hair dye base includes a dye intermediate, an oxidizing agent, and a reactive compound as a coupler (modifier) used in combination as necessary. Among these, as dye intermediates, p-phenylenediamine, toluene-2,5-diamine, N
-Phenyl-p-phenylenediamine, 4,4'-
Diaminodiphenylamine, p-aminophenol, p-methylaminophenol, o-phenylenediamine, toluene-3,4-diamine, o-
Aminophenol, p-chloro-o-phenylenediamine, p-amino-o-cresol, o-chloro-p-phenylenediamine, phloroglucin, pyrogallol, 3,3'-iminodiphenol, diphenylamine, 2,6 Para and ortho components such as -diaminopyridine and p-aminophenylsulfamic acid: Modifiers include m-phenylenediamine, toluene-2,4-diamine, and p-methoxy-m-phenylene. Meta components and phenols such as diamine, m-aminophenol, α-naphthol, resorcinol, hydroquinone, and catechol are generally used. Furthermore, in addition to the above-mentioned components, the oxidative hair dye base contains, in order to maintain the quality of the product and increase its usefulness, dyes that do not participate in the pigment-forming reaction but affect the color tone of the hair, such as: Nitro
p-phenylenediamine, p-nitro-o-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 4-
Examples include nitro dyes such as amino-2-nitrophenol and direct dyes such as picramic acid, picric acid, and 1,4-diaminoanthraquinone. Typical non-oxidative permanent or semi-permanent hair dyes are vegetable hair dyes and metallic hair dyes.
Vegetable hair dyes use extracts of ``henna'', ``walnuts'', ``soybeans'', etc. as a hair dye base, and the pigment components of the extracts have a dyeing effect on hair keratin. On the other hand, metallic hair dyes utilize the chemical reaction of metals to produce insoluble metal salts, and iron, copper, lead, manganese, nickel, cadmium, etc. can be used as hair dye bases. Particularly preferred are iron salts. Non-oxidative temporary hair dyes are those in which hair dye bases such as acid dyes and pigments are directly adhered to the hair, or hair is coated with a resin containing these to dye the hair. There are no particular restrictions on the dyes and pigments used in the hair dye base, but examples include pigments such as titanium oxide and carbon black; triphenylmethane dyes, azo dyes,
quinoline dye, xanthen dye, acridine dye,
Examples include tar-based dyes such as azine dyes, oxazine dyes, indigoid dyes, anthraquinone dyes, stilbene dyes, and thiazole dyes. The hair dye is added in an amount of 0.1 to 5% in the treatment agent. The higher alcohol with a branching rate of 1 to 50% as component (C) is
It is obtained by mixing a linear higher alcohol and a branched higher alcohol. In the present invention, the branching rate is a value obtained by the following formula. Branching rate (%) = X / X + Y × 100 Specific examples include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol,
Examples include behenyl alcohol. On the other hand, examples of branched higher alcohols include iso-branched, multi-branched, Guerbet-branched, and monomethyl-branched. The iso-branched type is a branched higher alcohol obtained by subjecting an α-olefin to an oxo reaction, and iso-branched alcohols have different branch chain lengths and branching rates depending on the reaction conditions. Specifically, Dovanol 23 (carbon number 12-13, branching rate 20-30%: manufactured by Mitsubishi Yuka), Dovanol 45 (carbon number 13-15, branching rate 20-30)
%: Mitsubishi Yuka), Dovanol 23i (carbon number 12-13,
Branching rate 93%: produced by Mitsubishi Yuka), Oxokol 710 (7 to 10 carbon atoms: produced by Nissan Chemical), and the like. The hyperbranched type is a branched higher alcohol with a carbon number of 7 to 13 and has multiple methyl branches obtained by oxo-reacting α-olefin obtained by dimerizing to tetramerizing 1-propylene, and the branching rate is It is 100%.
Specific examples of these include Nissan heptanol, Nissan decanol, Nissan tridecanol (all manufactured by Nissan Chemical), and the like. Also, 2, 4, 4
-Nissan nonanol derived from trimethylpentene and fine oxocol 180 (manufactured by Nissan Chemical) are also mentioned. Guerbet branched type can be obtained by dimerizing higher alcohols by the carburet method. General formula (),

[Formula] [In the formula, R ₁₀ and R ₁₁ represent a number of carbon atoms of 2 to 16, more preferably 12 to 16]], specifically 2-hexyldecanol (trade name, N-diecol 160A) : Manufactured by New Japan Chemical Co., Ltd.), 2-
Heptylundecanol (trade name, Diadol)
18G: manufactured by Mitsubishi Kasei), 2-octyldodecanol (trade name, NGECOL 200A: manufactured by Shin Nihon Rika),
Examples thereof include 2-decyltetradecanol (trade name, ND-Ecol 240A: manufactured by Shinnihon Rika), 2-dodecylhexadecanol, and the like. In addition, the monomethyl branched type has the general formula

〔Effect of the invention〕

The hair treatment composition of the present invention is excellent in protecting hair under harsh conditions and imparting conditioning effects, and furthermore, by forming a good liquid crystal emulsion state, it can prevent dripping when applied to hair. It has good operability and is easy to spread. Furthermore, since the conditioning effect on hair lasts for a long time even after repeated hair washing, it exhibits excellent performance in effectively protecting hair after treatments such as perming and hair dyeing until it is treated again. [Example] Next, an example will be given and explained. Example 1 A hair dye composition having the following composition was prepared and evaluated for appearance, ease of application, and ease of rinsing. (First agent)

[Table] (Second agent) (wt%) (1) Hydrogen peroxide 6.0 (2) PEO(20) cetyl ether 8.0 (3) Cetostearyl alcohol 8.0 (4) Propylene glycol 2.0 (5) Liquid paraffin 0.5 (6 ) Phosphoric acid Adjusted to PH3.5 (7) Water Balance amount (evaluation method) Appearance: Emulsified state was observed with the naked eye. Ease of application: Evaluated by having five expert panelists mix equal amounts of the first and second agents, apply the mixture to the hair, leave it for 30 minutes, and then wash with water. (result)

[Table] As a result, products 1 and 2 of the present invention had good feel on hair after dyeing, that is, smoothness, softness, and moisturizing feeling. Example 2 Apple pectin was added to the composition corresponding to the product 1 of the present invention.
Inventive product 4 contained 0.05% OM (manufactured by Helpshutrite). For product 4 of the present invention, test hair was dyed in the same manner as in Example 1. As a result, there is no dripping during the hair dyeing process.
It also spread well. In addition, this test hair had extremely good smoothness, softness, and moisturizing feeling.
Its effect is 7 times (sodium dodecyl sulfate 5%
Even after repeating the aqueous solution + rinsing process, almost no changes were observed. Example 3 A cream hair dye having the following composition was prepared. (First agent) (wt%) (1) p-phenylenediamine 2.0 (2) o-aminophenol 1.0 (3) m-phenylenediamine 0.2 (4) Stearyltrimethylammonium chloride 2.5 (5) 2-octyl chloride Dodecyltrimethylammonium 1.5 (6) POE(20) Cetyl ether 1.0 (7) Cetostearyl alcohol 6.0 (8) 2-hexyldecanol 0.4 (9) Propylene glycol 5.0 (10) Sodium sulfite 0.1 (11) Methylparaben 0.1 (12) Aqueous ammonia Adjusted to PH10 (13) Fragrance 0.3 (14) Apple Pectin OM (manufactured by Help Suit Light) 0.05 (15) Water Balance This hair dye exhibits excellent fluidity when mixed with the two ingredients, does not drip, and is easy to apply. It also lasted well and was extremely easy to rinse. Moreover, the hair treated with this hair dye showed an excellent conditioning effect, and the effect remained almost unchanged even after seven repeated shampoo treatments. Example 4 The following cream hair dye was prepared. (First agent) (1) p-phenylenediamine 2.0 (2) o-aminophenol 0.5 (3) m-phenylenediamine 0.2 (4) Resorcinol 1.0 (5) Stearyltrimethylammonium chloride 2.0 (6) Isostearyl chloride Methylammonium 1.0 (7) POE(20) Cetyl ether 1.0 (8) Cetostearyl alcohol 6.0 (9) 2-heptylundecanol 0.6 (10) Propylene glycol 5.0 (11) Sodium sulfite 0.1 (12) Methylparaben 0.1 (13) Ammonia water Adjusted to PH10 (14) Fragrance 0.3 (15) Apple pectin OM (manufactured by Help Suit Light) 0.1 (16) Water Balance This hair dye shows excellent fluidity when mixed with the two ingredients, and does not drip. It spread well during application and was extremely easy to rinse. In addition, hair treated with bleaching agents shows excellent conditioning effects,
The effect remained almost unchanged even after seven repeated shampoo treatments. Example 5 A cream depigmentant having the following composition was prepared. (First agent) (1) Stearyltrimethylammonium chloride 1.5 (2) Dialkyldimethylammonium chloride (same as component (7) in Example 1) 1.0 (3) PEO (23) lauryl ether 5.0 (4) Cetostearyl alcohol 6.0 (5) 2-octyldodecanol 0.5 (6) Propylene glycol 4.5 (7) Methylparaben 0.1 (8) Ammonia water Adjusted to PH10 (9) Xanthan gum (manufactured by Kelco) 0.2 (10) Water Balance This decolorizer has two agents. It exhibited excellent fluidity during mixing, no dripping, spread well during application, and was extremely easy to rinse. Furthermore, the hair treated with the bleaching agent showed an excellent conditioning effect, and the effect remained almost unchanged even after seven repeated shampoo treatments. Example 6 A permanent wave composition having the following composition was prepared. (First agent) (wt%) (1) Thioglycolic acid 6.0 (2) Cetostearyl alcohol 0.2 (3) POE(20) cetyl ether 0.7 (4) 2-hexyldecyltrimethylammonium chloride 0.2 (5) Apple pectin OM (manufactured by Help Shutrite) 0.05 (6) Ammonia water Adjusted to PH9.0 (7) Water balance (second agent) (wt%) (1) Sodium bromate 10.0 (2) Water balance This composition for permanent waves Hair treated with shows excellent conditioning effects,
The effect lasted for more than 15 days. Example 7 A creamy acidic hair dye composition having the following composition was prepared. (Weight%) (1) Red No. 102 0.3 (2) Yellow No. 4 0.1 (3) Behenyltrimethylammonium chloride 1.5 (4) -2-octyldodecyltrimethylammonium chloride 1.5 (5) POE(20) cetyl ether 1.0 (6 ) Cetostearyl alcohol 4.5 (7) 2-octyldodecanol 0.3 (8) Propylene glycol 5.0 (9) Citric acid Adjusted to PH3.0 (10) Methylparaben 0.1 (11) Fragrance 0.3 (12) Water Balance This acidic hair dye It exhibited good fluidity, had no dripping during application, spread well, was extremely easy to rinse, and had an excellent feel on the hair after dyeing. Example 8 A liquid hair dye composition having the following composition was prepared. (First agent) (wt%) (1) p-phenylenediamine 2.0 (2) o-aminophenol 1.0 (3) m-phenylenediamine 0.2 (4) 2-hexyldecyltrimethylammonium chloride 1.0 (5) POE (6) Stearyl ether 1.0 (6) Apple pectin OM (manufactured by Helpshutrite) 0.05 (7) Propylene glycol 10.0 (8) Fragrance 0.3 (9) Sodium sulfite 0.1 (10) Oleic acid 8.0 (11) Oleyl alcohol 1.0 ( 12) Ammonia water Adjusted to PH10.0 (13) Water Balance amount (second agent) (wt%) (1) Hydrogen peroxide 6.0 (2) Water 94.0 Hair dyed with the above composition has excellent condition. It exhibited a shockening effect, and the effect remained almost unchanged even after seven repeated shampoo treatments.

Claims (1)

[Scope of Claims] 1. The following three components (A), (B) and (C) (A) One or more branched quaternary ammonium salts (B) An oxidizing agent, a reducing agent, or a hair dye. A hair treatment composition comprising one or more (C) higher alcohols having a branching rate of 1 to 50%. 2. The following three components (A), (D) and (B) (A) One or more branched quaternary ammonium salts (D) Anionic polymer (B) Oxidizing agent, reducing agent or hair dye A hair treatment composition comprising one or more of the following.