JPH09118606A - Hair treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair treating agent containing a quaternary ammonium salt, low in skin irritation, good in touch feeling, and excellent in high temperature stability and brodegradability. SOLUTION: This hair treating agent contains, as active ingredient(s), 01-30wt.% of a quaternary ammonium organic acid salt of formula I (R1 is a 7-28C alkyl or alkenyl parted by an ester or amide group, including such a parting group; R2 is the same as R1 , or a 1-4C alkyl or hydroxyalkyl; R3 and R4 are each a 1-4C alkyl or hydroxyalkyl) and/or organic acid-netralized product of an amine of formula II (R5 is the same as R1 ; R6 is the same as R2 ; R7 is the same as R3 or R4 ). Each of these ingredients may be effective for hair treatment individually and also in combination. When the two kinds of ingredients are to be used, the weight ration is (99:1) to (50:50), and the greater proportion of the former ingredient is preferable in terms of touch feeling. This hair treating agent is useful as e.g. a setting agent such as shampoo, rinse, treatment, hair dye or mosse. This agent contains no halogen ion, thus preventing its container from rusting.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hair treatment agent.

[0002]

2. Description of the Related Art Conventionally, a quaternary ammonium salt having an alkyl group divided by an ester group or an amide group has been used as a quaternary ammonium salt for a hair treatment agent, and a halogen ion such as chlorine ion is used as a counter ion, Also known are those having a short-chain sulfate ion such as methosulfate and ethosulfate (for example, JP-A-6-9346 publication).

[0003]

However, these quaternary ammonium salts are highly irritating to humans, and their usability (the texture after use represented by the smoothness and moistness of hair) is not sufficient. It has many problems such as poor stability at high temperatures.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to solve these problems. That is, the present invention is a hair treatment agent comprising the following (a) and / or (b).

(A): Quaternary ammonium organic acid salt represented by the general formula (1)

[0006]

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(In the formula, R ₁ has 7 carbon atoms including the splitting group.
To an alkyl group or an alkenyl group which is cleaved with an ester group or an amide group, and R ₂ is an alkyl group or an alkenyl group which is cleaved with an ester group or an amide group having 7 to 28 carbon atoms, including a cleaved group, or a carbon atom. Alkyl groups or hydroxyalkyl groups having 1 to ₄ carbon atoms, and R ₃ and R ₄ are alkyl groups or hydroxyalkyl groups having 1 to ₄ carbon atoms. )

(B): Organic acid neutralized product of amine represented by the general formula (2)

[0009]

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(In the formula, R ₅ has 7 carbon atoms including the splitting group.
To an alkyl group or an alkenyl group cleaved by an ester group or an amide group, R ₆ includes an alkyl group or an alkenyl group cleaved by an ester group or an amide group having a carbon number of 7 to 28, including a cleaved group, or a carbon atom. An alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, and R ₇ is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. )

The quaternary ammonium salt used as (a) and / or the amine neutralized product used as (b) has an alkyl group or an alkenyl group divided by an ester group or an amide group shown in Chemical formula 5. . In the case of a di long chain alkyl group or a di long chain alkenyl group, they may be the same group or different groups.

[0012]

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(In the formula, R ₈ and R ₁₁ are alkyl groups or alkenyl groups having 5 to 23 carbon atoms, and R ₁₀ and R ₁₃ are 6 to 6 carbon atoms.
24 alkyl or alkenyl groups, R ₉ has 1 carbon atom
To 4 alkylene group, R _12, R ₁₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

R ₈ and R ₁₁ are residues obtained by removing COOH from higher fatty acids. The carbon number of the higher fatty acid is usually 6 to
24, and preferably 12 to 22. 6 carbon atoms
In the following, not only the texture is inferior, but also the irritation increases,
When the carbon number is 24 or more, the emulsifiability is poor. As the higher fatty acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid,
Examples thereof include margaric acid, stearic acid, nonadecyl acid, behenic acid, oleic acid, linoleic acid, and linolenic acid. These may be used alone or as a mixture of two or more. Further, coconut oil fatty acid, palm kernel oil fatty acid, tallow fatty acid, hardened tallow fatty acid and the like which are a mixture thereof can also be used.

Examples of the alkylene group having 1 to 4 carbon atoms represented by R ₉ include methylene group, ethylene group, propylene group and butylene group. Ethylene group and propylene group are preferred. R < ₁₀ > and R < ₁₃ > usually have 6 to 24 carbon atoms, and preferably are linear or branched alkyl or alkenyl groups having 12 to 22 carbon atoms. When the carbon number is 6 or less, not only the texture is inferior, but also the irritancy is increased, and when the carbon number is 24 or more, the emulsifying property is inferior. Examples include amyl groups,
Hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group,
Octadecyl group, docosyl group, 2-ethylhexyl group,
2-hexyldecyl group, 2-octylundecyl group, pentene group, hexene group, heptene group, octene group, nonene group, decenyl group, dodecenyl group, tetradecenyl group,
Examples thereof include hexadecenyl group and octadecenyl group. These can also be used as one kind or as a mixed group of two or more kinds.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ₁₂ and R ₁₄ include methyl group, ethyl group, propyl group and butyl group. Of R ₁₂ and R ₁₄ , hydrogen atom and methyl group are preferable. 1 to 4 carbon atoms of R ₃ , R ₄ and R ₇
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the hydroxyalkyl group having 1 to 4 carbon atoms include hydroxymethyl group, hydroxyethyl group, hydroxypropyl group and hydroxybutyl group. Preferably a methyl group, an ethyl group,
It is a hydroxyethyl group.

Represented by the general formulas (1) and (2), in the case of a mono long-chain alkyl group type, R ₂ and R ₆ have 1 carbon atoms.
Examples of the alkyl group of to 4 usually include a methyl group, an ethyl group, a propyl group and a butyl group. 1 to 4 carbon atoms
Examples of the hydroxyalkyl group include hydroxymethyl group, hydroxyethyl group, hydroxypropyl group and hydroxybutyl group. Preferred are a methyl group, an ethyl group and a hydroxyethyl group.

The organic acid is not particularly limited, but usually at least one organic acid selected from the group consisting of carboxylic acids represented by the general formulas (3) to (13), sulfonic acid and phosphoric acid is used. Examples include the following, but preferably carboxylic acid. As the carboxylic acid, those having a carboxyl group in the molecule can be usually used. Preferred are compounds of the general formulas (3) to (7), which have good texture, good emulsification properties, and low irritation. General formula R ₁₅ COOH (3) General formula R ₁₆ O (AO) _n1 CH ₂ COOH (4) General formula

[0019]

[Chemical 6]

General formula

[0021]

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General formula

[0023]

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(In the formula, R ₁₅ , R ₁₇ and R ₁₈ have 6 to 2 carbon atoms.
4 is a residue obtained by removing COOH from the higher fatty acid, R ₁₆ is a residue obtained by removing OH from a higher alcohol having 6 to 24 carbon atoms, or R ₂₃ CONHCH ₂ CH ₂ , (R ₂₃ is a higher fatty acid having 6 to 24 carbon atoms. residue) obtained by removing COOH from, R ₂₀ is a linear or branched alkyl, alkenyl or hydroxyalkyl group, R ₁₉ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms 6 to 24 carbon atoms, R ₂₁ , R ₂₂ has at least one —— (CH ₂ ) _n3 —COOH and one is a hydrogen atom. A is an alkylene group having 2 to 4 carbon atoms, n1 is 0 to 20
, N2 and n3 represent 1 or 2. )

As the sulfonic acid, those having a sulfonic acid group or a sulfuric acid ester group in the molecule can be usually used. Preferred are compounds of the general formulas (8) to (11), which have good texture, good emulsification properties, and low irritation. Formula _{R 24 COX 1 (CH 2)} n4 -SO 3 H (8) formula

[0026]

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General formula

[0028]

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General formula R ₂₈ O (A ₂ O) _{n 6} —SO ₃ H (11) (wherein R ₂₄ , R ₂₅ and R ₂₇ are residues obtained by removing COOH from a higher fatty acid having 6 to 24 carbon atoms, R ₂₈ is a residue obtained by removing an OH group from a higher alcohol having 6 to 24 carbon atoms, R ₂₆ is a hydrogen atom or a methyl group, A ₁ and A ₂ are alkylene groups having 2 to 4 carbon atoms, and n 5 and n 6 are 0 to 20 integer, n4 is an integer of 1 to 3, X _1, X ₂ is _{-NH -, - N (CH 3} ) -, - N (C 2
H ₅₎ - represents a group or an oxygen atom represented by. )

As the phosphoric acid, one having a phosphoric acid ester group in the molecule can be usually used. Preferred are compounds of the general formulas (12) and (13), which have good texture, good emulsification properties, and low irritation. General formula

[0031]

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General formula

[0033]

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(In the formula, R ₂₉ , R ₃₀ and R ₃₁ have 6 to 2 carbon atoms.
4 is a residue obtained by removing OH from a higher alcohol, A _{3 to} A ₅ are alkylene groups having 2 to 4 carbon atoms, and n 7 to n 9 are integers 0 to 20. )

R ₁₅ , R ₁₇ , R ₁₈ , R ₂₃ , R ₂₄ , R ₂₅ , R
_The residue obtained by removing COOH from the higher fatty acid having ₂₇ to 24 carbon atoms is the same as R ₈ and R ₁₁ . 6 to 24 carbon atoms
Examples of higher alcohols forming R ₁₆ , R ₂₈ , R ₂₉ , R ₃₀ , and R ₃₁ include hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, and tetradecyl alcohol. Decyl alcohol,
Pentadecyl alcohol, hexadecyl alcohol, octadecyl alcohol, nonadecyl alcohol and the like can be mentioned.

Examples of the alkyl group having 1 to 4 carbon atoms for R ₁₉ include a methyl group, an ethyl group, a propyl group and a butyl group. Of these, preferred are a hydrogen atom and a methyl group. Examples of the linear or branched alkyl group having 6 to 24 carbon atoms of R ₂₀ include hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosyl group,
Examples thereof include a 2-ethylhexyl group, a 2-hexyldecyl group, a 2-octylundecyl group, and a 2-decyltetradecyl group. Examples of the linear or branched alkenyl group having 6 to 24 carbon atoms include hexene group, heptene group, octene group, nonene group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and the like. Examples of the linear or branched hydroxyalkyl group having 6 to 24 carbon atoms include hydroxyoctadecyl group. These can also be used as one kind or as a mixed group of two or more kinds.

Examples of the alkylene group having 2 to 4 carbon atoms of A _{3 to} A ₅ include ethylene group, propylene group and butylene group. In the above general formula, (AO) _n has 2 carbon atoms.
It represents that the alkylene oxide of ~ 4 has added n mol. The alkylene oxide may be used in combination of two or more (random addition or block addition). Preferred are ethylene oxide and propylene oxide. In addition, n1 and n5 to n9 are integers of 0 to 20, preferably 0 to 10.

Examples of the quaternary ammonium represented by the general formula (1) include those shown in Table 1.

[0039]

[Table 1]

Examples of the amine represented by the general formula (2) include those shown in Table 2.

[0041]

[Table 2]

The organic acids include those listed in Table 3.

[0043]

[Table 3]

[0044] <Description of symbols in Tables 1~3> U: -COO- V: -CONH- W: -OCO- X: -NHCO- Y: - (CH 2) 2 - Z: - (CH 2) _{3 - C 11: n-C} 11 H 23 or _{C 11 H 21 C 12,:} n-C 12 H 25 C 15: n-C 15 H 31 C 16: n-C 16 H 33 or C ₁₆ H _{31, C 17: n-C 17 H} 35 C 21: n-C 21 H 43 C 22: n-C 22 H 45 or _{C 22 H 43 C 23,:} n-C 23 H 47

The quaternary ammonium salt (a) and the amine neutralized product (b) can be used alone, respectively.
The weight ratio in the case of using (b) and (b) is not particularly limited, but is usually 99/1 to 50/50, and the larger the ratio of (a), the more preferable in terms of texture.

(A) quaternary ammonium salt and (b)
The amine neutralized product has a mono long-chain alkyl group type and a di long-chain alkyl group type, and these may be used alone or in combination. When used in combination, the weight ratio is usually 100/0 to 50/50, and the larger the proportion of the mono-long-chain alkyl group type, the more preferable in terms of emulsifying property.

The quaternary ammonium salt represented by the general formula (1) is usually produced by an alkylamino alcohol such as dimethylaminoethanol or an alkylaminoalkyleneamine such as dimethylaminopropylamine and a carvone such as stearic acid. Dehydration condensation with acid,
Produced by quaternizing the obtained tertiary amine having an ester group or an amide group with an alkylating agent such as an alkyl halide such as methyl chloride or a dialkyl carbonate such as dimethyl carbonate, and treating it with an organic acid or a salt thereof. can do.

The amine neutralized product represented by the general formula (2) can be produced by synthesizing a tertiary amine in the same manner as the quaternary ammonium salt and neutralizing with an organic acid. can do.

In the dehydration condensation reaction, the amount of alkylaminoalcohol or alkylaminoalkyleneamine used is usually 0.1 to 5.0 times mol, preferably 0.3 to 3.0 times mol, of the carboxylic acid. Is. In the quaternization reaction, the amount of the alkylating agent such as alkyl halide or dialkyl carbonate used is usually 1.0 to 5.0 times, and preferably 1.3 to 2 times the molar amount of the produced tertiary amine. 0.0 times the molar amount. The amount of the organic acid used is usually 1.0 to 3.0 times mol, preferably 1.0 to 2.0 times the generated quaternary ammonium salt or tertiary amine.
It is twice the mole.

The dehydration condensation reaction temperature is usually 100 to 220.
C., preferably 150 to 190.degree. The reaction is very slow at 100 ° C or lower, and the coloring becomes severe at 220 ° C or higher. The quaternization reaction temperature is usually 50 to 150 ° C, preferably 80 to 120 ° C. If the temperature is 50 ° C or lower, not only the reaction is very slow, but also the product may be solidified and stirring may not be possible, and if the temperature is 150 ° C or higher, the coloring becomes severe. The treatment temperature with the organic acid is usually 50 to 150 ° C., preferably 8
0-100 ° C. If the temperature is 50 ° C or lower, it may be solidified and stirring may not be possible, and if it is 150 ° C or higher, the coloring may be severe.

The amount of the (a) quaternary ammonium salt and / or (b) amine neutralized product according to the present invention in the hair treatment composition of the present invention is not particularly limited, but is usually relative to the hair treatment composition. 0.1 to 30% by weight is blended. It is preferably 0.5 to 10% by weight. When it is 0.1% by weight or less, usability is deteriorated, and when it is 30% by weight or more, it tends to be left alone.

The use of the hair treatment agent of the present invention is not particularly limited, but it is useful for shampoo, conditioner, treatment, hair dye, mousse and the like. Further, by utilizing the excellent property of the quaternary ammonium salt, it can be applied to all the applications of the quaternary ammonium salt which has been conventionally used.

The hair treatment agent of the present invention is used in an amount of anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, and hair treatment agent of the present invention which does not impair the effects of the present invention. The organic acids such as carboxylic acids, sulfonic acids and phosphoric acids represented by the general formulas (3) to (13) or salts thereof may be used in combination. Examples of the anionic surfactant include sodium lauryl sulfate, sodium polyoxyethylene lauryl sulfate, triethanolamine polyoxyethylene lauryl sulfate, sodium polyoxyethylene lauryl ether acetate, sodium polyoxyethylene coconut oil fatty acid monoethanolamide sulfate, and polyoxyethylene. Lauryl sulfosuccinate disodium, sulfosuccinic acid polyoxyethylene lauroyl ethanolamide disodium, coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid methyl taurine magnesium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid Acyl-L-glutamate sodium, N-coconut oil fatty acid acyl-L-glutamate triethanolamine, laurilo Rumechiru -β- sodium alanine, N- lauroyl -N- methyl -β-
Examples include alanine triethanolamine and sodium lauryl phosphate.

As the amphoteric surfactant, coconut oil fatty acid amide propyl dimethylamino acetic acid betaine, lauryl dimethyl amino acetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl hydroxysulfobetaine, lauroyl. Examples thereof include sodium amidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl phosphate and sodium β-laurylaminopropionate. As the nonionic surfactant, 1: 1 type coconut oil fatty acid diethanolamide, lauryl dimethylamine oxide, glyceryl monostearate, ethylene glycol monostearate, polyethylene glycol monostearate, polyethylene glycol distearate, sorbitan monolaurate, monolaurin Acid polyoxyethylene sorbitan, polyoxyethylene dioleic acid methyl glucoside, polyoxyethylene beef tallow alkylhydroxymyristyrene ether, ethylene glycol monostearate, ethylene glycol distearate and the like. Examples of the cationic surfactant include stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid aminopropylethyldimethylammonium ethylsulfate, and a lactate of stearic acid diethylaminoethylamide.

Further, higher alcohols such as cetyl alcohol, stearyl alcohol and behenyl alcohol are used as emulsion stabilizers, and glycerin, sodium pyrrolidonecarboxylate and the like are used as moisturizers, and cationized cellulose, cationized guar gum and polyethylene are used as polymer compounds. Glycol, sodium polyacrylate, hydroxyethyl cellulose, protein derivatives and the like, as the silicone, dimethyl polysiloxane, modified silicone in which various organic groups are introduced into a part of the methyl group of dimethyl polysiloxane, cyclic dimethyl siloxane, As a chelating agent, sodium ethylenediaminetetraacetate,
1-hydroxyethane-1,1-diphosphonate sodium, etc., lower alcohols such as ethanol, propylene glycol, dipropylene glycol, etc., fragrances, colorants, preservatives, UV absorbers, water, etc. Any of those described in the cosmetics type permission standard '94 issued by Nippo, which does not impair the effects of the present invention can be used in combination.

The form of the hair treatment agent of the present invention is not particularly limited, such as liquid, paste, solid and powder, but liquid and paste are preferred because they are easy to use. In the case of liquid and paste-like rinses, the quaternary ammonium salt according to the present invention is usually 0.5 to 30% by weight, the emulsifying aid such as glyceryl monostearate is 1 to 5% by weight, and the emulsifying agent is cetyl alcohol. Stabilizers 1 to 10% by weight, polymer compounds and silicones 0 to 10% by weight, humectants, chelating agents and lower alcohols 0 to 1
5% by weight and 30-97.5% by weight of water are used.

The pH of the hair treatment composition of the present invention is usually 3-9.
It is. When it is 3 or less and 9 or more, hydrolysis of the ester or the like occurs, and the performance of the quaternary ammonium salt of the present invention is poor.

[0058]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Additives and test methods used in Examples and Comparative Examples are as follows. Emulsion Stabilizer A: Cetyl Alcohol Emulsion Stabilizer B: Stearyl Alcohol Emulsion Stabilizer C: Behenyl Alcohol Emulsification Aid: Glycerin Monostearate Moisturizer: Glycerin Silicone: Dimethylpolysiloxane Chelating Agent: EDTA-2Na PG: Propylene Glycol

Skin irritation A 1.0% aqueous surfactant solution of the composition shown in Table 5 to Table 7 was prepared, and a closed patch test (after 48 hours, inside the upper arm) was conducted by 5 men and women. It was evaluated according to the standard. The result was shown by the total value. -Evaluation criteria- 0; No reaction (erythema) 1; Very mild erythema 2; Clear erythema 3; Medium to strong erythema 4;

Texture 4 g of hair rinse having the composition shown in Tables 5 to 7 is taken, and water is added to make 200 cc. A hair bundle (length 15 cm, weight 5 g) washed with shampoo was immersed at 40 ° C. for 5 seconds.
Then, the substrate was rinsed twice with warm water (200 ° C., 40 ° C.) for 30 seconds, and then dried overnight at 25 ° C. × 65% RH. The texture is 10 with regard to the flexibility, moistness and smoothness of the hair bundle after rinsing and after being dried overnight.
It was scored by the following criteria using the name panelists, and evaluated by the total score. <Scoring Criteria> 0: Inferior to the standard rinse 1; Slightly inferior to the standard rinse 2; Equivalent to the standard rinse 3; Slightly superior to the standard rinse 4: Superior to the standard rinse In addition, Comparative Example 1 was used as the standard rinse.

Emulsion stability The rinses shown in Tables 5 to 7 were checked for emulsion stability after 3 days at 25 ° C. ○: stable △: slightly separated ×: separated

[0062]

【Example】

Examples 1 to 15 and Comparative Examples 1 to 3 Using the compounds described in Tables 1 to 4, appropriate amounts of perfume and dye were added to the compositions (parts by weight) described in Tables 5 to 7 to obtain pH with citric acid. Adjust and add water (the rest) to bring the total volume to 10
By setting the content to 0 part, the hair treatment agent of the present invention and the hair treatment agent of the comparative example were prepared and tested for skin irritation, usability and emulsification. The results are shown in Tables 5 to 7.

[0063]

[Table 4]

[0064]

[Table 5]

[0065]

[Table 6]

[0066]

[Table 7]

From Table 5, it can be seen that the quaternary ammonium salt and / or amine neutralized product of the present invention has very low skin irritation, good texture, and is extremely excellent.

[0068]

EFFECTS OF THE INVENTION The quaternary ammonium salt of the present invention has a good texture after use, represented by the smoothness and moisturizing feel of hair, is less irritating to humans and is useful as an environmentally and human friendly hair treatment agent. Is. Further, since it does not contain halogen ions, it is possible to prevent rusting of the container. Further, it is excellent in high temperature stability and biodegradability and is extremely useful as a hair treatment agent.

Claims (2)

[Claims] 1. A hair treatment agent comprising the following (a) and / or (b): (A): Quaternary ammonium organic acid salt represented by the general formula (1) (In the formula, R ₁ is an alkyl group or an alkenyl group which is cleaved by an ester group or an amide group having a carbon number of 7 to 28 including a cleaving group, and R ₂ is an ester having a carbon number of 7 to 28 including a cleaving group. An alkyl group or an alkenyl group divided by a group or an amide group, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and R ₃ and R ₄ are an alkyl group having 1 to ₄ carbon atoms or a hydroxyalkyl group.) (B): Neutralized organic acid of amine represented by the general formula (2) (In the formula, R ₅ is an alkyl group or an alkenyl group which is cleaved with an ester group or an amide group having a carbon number of 7 to 28 including a cleaving group, and R ₆ is an ester having a carbon number of 7 to 28 including the cleaving group. An alkyl group or an alkenyl group divided by a group or an amide group, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and R ₇ is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group.) 2. The hair treatment agent according to claim 1, wherein the organic acid is carboxylic acid, sulfonic acid or phosphoric acid.