JP2002332219A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair cosmetic which can impart wet flexibility, smoothness, oily touch, dry smoothness, flexibility and a combing property to hair. SOLUTION: This hair cosmetic contains an amine represented by the general formula (I) R<1> is a 8 to 40C alkyl or alkenyl, or R<5> O-(AO)n -Cm H2m [R<5> is a 8-40C alkyl or alkenyl; A is a 2 to 3C alkylene; (n) is an integer of 0 to 30 on the average; (m) is an integer of 2 to 3]; R<2> is a 1 to 5C alkylene; R<3> H, a 1 to 24C alkyl, an alkyl, a hydroxyalkyl, a 6 to 28C aryl or an arylalkyl; R<4> H, a 1 to 5C alkyl, an alkenyl or a hydroxyalkyl, a 6 to 28C aryl, an arylalkyl, or the like; (p) is an integer of 1 to 3; (q) and (r) are each an integer of 0 to 2; (p)+(q)+(r)=3}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides hair with sufficient flexibility and smoothness when wet, oily feeling, smoothness and softness after drying, and good combability. The present invention relates to a hair cosmetic which is made and has excellent environmental safety.

[0002]

2. Description of the Related Art Hair cosmetics impart to hair hair softness and smoothness when wet, oily feeling, smoothness and softness after drying, and combability. Is required. Due to such requirements, quaternary ammonium salts having a long-chain alkyl group, such as stearyltrimethylammonium chloride and distearyldimethylammonium chloride, have conventionally been used as surfactants. However, these do not fully satisfy the feeling of use of the hair when wet and after drying.

Japanese Patent Application Laid-Open Nos. 5-271035, 5-271036 and 2000-501430 disclose the use of a tertiary amine type amidoamine salt as a base for hair cosmetics. However, the above-mentioned requirements are not sufficiently satisfied, and there are drawbacks in that the feeling after drying and the like and the smoothness and oiliness when wet cannot be achieved at the same time.

[0004] An object of the present invention is to provide a hair cosmetic which can impart softness, smoothness, and oiliness when wet to hair, and smoothness, softness, and combability after drying. It is to be.

[0005]

The present invention provides a compound represented by the general formula (I):
A hair cosmetic comprising an amine represented by the formula (hereinafter referred to as amine (I)):

[0006]

Embedded image

Wherein R ¹ is a linear or branched alkyl or alkenyl group having 8 to 40 carbon atoms;
_{^{5 O- (AO) n -C m}} H 2m - (R 5 is a linear or branched alkyl or alkenyl group of 8 to 40 carbon atoms, A is an alkylene group having 2 to 3 carbon atoms, n represents an average value Wherein m is an integer of 2 to 3, n A's may be the same or different, and R ² is a linear or branched alkylene group having 1 to 5 carbon atoms. , R ³ is a hydrogen atom, having 1 to 1 carbon atoms
24 linear or branched alkyl groups, alkenyl groups or hydroxyalkyl groups, or aryl groups or arylalkyl groups having 6 to 28 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched chain having 1 to 5 carbon atoms. Alkyl group, alkenyl group or hydroxyalkyl group, or C6 to C2
8 represents an aryl group or an arylalkyl group, and R ³ and R ⁴ may form a ring singly or in combination. p is 1
An integer of ｑ3, q and r are integers of 0２2, and p + q + r is 3. Note that p R ¹ , R ² , q R ³ , r R ⁴
May be the same or different. ]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the amine (I), R ¹ is a linear or branched alkyl or alkenyl group having 10 to 28 carbon atoms, or a compound of the formula R ⁵ O— (AO) _n —C _m H _2m — In the group represented by, R ⁵ is preferably a linear or branched alkyl group or alkenyl group having 10 to 28 carbon atoms, and a group in which A, n and m have the same meaning as described above.
Straight or branched chain alkyl or alkenyl group of 24, or the formula _{^{R 5 O- (AO) n -C}} m H 2m - in a group represented by, R ⁵ is a linear or branched C12-24 alkyl or alkenyl group of chain, a, preferably a group that n and m are as defined above, in particular straight-chain alkyl group having 12 to 24 carbon atoms, or the formula _{^{R 5 O- (AO) n -C}} m H _2m - with a group represented by a linear alkyl group R ⁵ is a C12-24, a, a group n and m are as defined above preferable. The above n is preferably 0 to 20, and more preferably 5 or less. R ² is preferably a linear or branched alkylene group having 1 to 3 carbon atoms, more preferably a linear alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group. R ³ is preferably a straight-chain or branched-chain alkyl group having 1 to 22 carbon atoms, an alkenyl group or a hydroxyalkyl group, or an aryl group or an arylalkyl group having 6 to 28 carbon atoms. A branched alkyl or hydroxyalkyl group, or 6-1 carbon atoms
An aryl or arylalkyl group of 0 is more preferred. R ⁴ is preferably a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 1 to 5 carbon atoms, or an aryl group or arylalkyl group having 6 to 28 carbon atoms, Alkyl or hydroxyalkyl, phenyl or benzyl groups on the chain are more preferred. When R ³ and R ⁴ combine to form a ring, R ³ and R ⁴ preferably have a total carbon number of 4 to 28,
10 is more preferable, and a 5-membered ring or a 6-membered ring is particularly preferable. p is preferably an integer of 1 or 2. q and r are preferably 0 or 1, and particularly preferably a tertiary amine.

As a method for synthesizing the amine (I), an amine represented by the formula (II) R ¹ —NH ₂ (II) (wherein R ¹ has the above-mentioned meaning) (hereinafter referred to as amine (II)) Reaction with a halogenated carboxylic acid or a lower alkyl ester or acid halide thereof, optionally using a catalyst, and then reacting the corresponding amine or the like, or reacting an amino acid or a derivative thereof with an amine (II) And the like.

[0010] The hair cosmetic composition of the present invention preferably contains at least one acid selected from the group consisting of inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid. As the organic acid, an organic acid having 1 to 5 carbon atoms is preferable, and acetic acid, glycolic acid, lactic acid, glutamic acid, malic acid, and succinic acid are specific. But hydrochloric acid, sulfuric acid, lactic acid, glutamic acid, malic acid and the like are particularly preferable.

When preparing the hair cosmetic of the present invention, the amine (I) and the acid may be separately blended, or may be blended after previously forming the acid salt of the amine (I).

[0012] The hair cosmetic composition of the present invention further comprises 10 carbon atoms.
It is preferred to contain up to 30 higher alcohols. The higher alcohol used in the present invention has 10 carbon atoms.
Higher alcohols having from 30 to 30 linear or branched alkyl or alkenyl groups, preferably having 12 carbon atoms
To 26 higher alcohols having a linear or branched alkyl or alkenyl group, more preferably higher alcohols such as cetanol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, calanavir alcohol, and seryl alcohol. Can be

[0013] The content of the amine (I) in the hair cosmetic composition of the present invention is 0.1 from the viewpoints of giving a good feeling to the hair and stabilizing the product during storage such as precipitation, solidification and layer separation. ~
It is preferably 15% by weight, particularly preferably 0.3 to 8% by weight. Further, the content of the acid is 0.3 to 0.3 to the amine (I).
It is preferably 10 mol times, particularly preferably 0.5 to 5 mol times. Further, the content of the higher alcohol is 0.5% from the viewpoint of exhibiting flexibility and moist feeling, and from the viewpoint of product stability.
It is preferably from 15 to 15% by weight, particularly preferably from 1 to 10% by weight.

The hair cosmetic composition of the present invention is used by replacing a part or all of the amine (I) with a salt by adjusting the pH in the composition.
It is preferable to use H3 to H6 from the viewpoint of good feel of hair and stability of the product.

[0015] The hair cosmetic composition of the present invention includes other cationic surfactants, anionic surfactants, nonionic surfactants,
Surfactants such as amphoteric surfactants, silicones, hydrocarbons, lanolin derivatives, higher fatty acid esters, higher fatty acids, fats and oils, glycerin, humectants, cationic polymers, polysaccharides, polypeptides, pearling agents, solvents A liquid crystal forming agent, an aromatic sulfonic acid, a dye, a fragrance, a propellant, a chelating agent, a pH adjuster, a preservative, an anti-dandruff agent and the like can be appropriately compounded within a range not to impair the object of the present invention.

The hair cosmetic composition of the present invention comprises an aqueous solution, an ethanol solution, an emulsion, a suspension, a gel, a liquid crystal,
A desired dosage form such as an aerosol can be obtained.

The hair cosmetic composition of the present invention comprises a hair rinse, a hair conditioner, a hair treatment, a hair pack,
It can be used for hair cream, conditioning mousse, hair mousse, hair spray, shampoo, leave-on treatment and the like.

[0018]

EXAMPLES The percentages in the examples are percentages by weight unless otherwise specified.

Synthesis Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a dehydrating tube, and a nitrogen inlet tube, 801.9 g of Farmin 80 (an alkyl primary amine manufactured by Kao Corporation) and N, N-dimethylglycine were added. 413.2 g of ethyl ester was charged, and 28
After adding 11.6 g of a methanol solution of sodium methylate at 100 ° C. and reacting while distilling off ethanol produced at 3 hours at 100 ° C., 21.3 g of Kyoward 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added. The catalyst was adsorbed, filtered and removed to obtain 1036.1 g of amine A shown in Table 1.

Synthesis Example 2 In a four-necked flask equipped with a stirrer, a thermometer, a dehydrating tube, and a dropping funnel, 325.6 g of Nissanamine VBS (an alkyl primary amine manufactured by NOF Corporation) and 90 mL of methanol
After adding 0 g and 3.9 g of a 28% sodium methylate methanol solution as a catalyst, 113.9 g of chloroacetic acid methyl ester was added dropwise over 1 hour while keeping the temperature at 15 to 20 ° C., and the mixture was reacted for 30 hours. After the reaction, the precipitated crystals were filtered, washed with 300 g of methanol, and dried to obtain 378.0 g of the corresponding chloroacetamide.

Next, the above-mentioned chloroacetamide 201. was placed in a four-necked flask equipped with a stirrer, thermometer and cooling tube.
0 g, 219.4 g of diethylamine and 500 g of isopropyl alcohol were added and reacted at 50 ° C. for 5 hours. After the reaction, 41.7 g of a 48% aqueous sodium hydroxide solution and 100 g of ion-exchanged water were added, and then excess diethylamine and the solvent were distilled off under reduced pressure. Further, after desalting and crystallization with acetone, and drying, amine B 201.
8 g were obtained.

Synthesis Example 3 In a four-necked flask equipped with a stirrer, a thermometer, a dehydrating tube, and a nitrogen introducing tube, 370.7 g of Farmin 20 (alkyl primary amine manufactured by Kao Corporation) and N-methyliminodiacetic acid 1
47.1 g was charged and reacted at 180 ° C. for 10 hours while distilling off generated water, followed by crystallization with acetone. After drying, 476.4 g of amine C shown in Table 1 was obtained.

Synthesis Example 4 316.0 g of chloroacetamide corresponding to the raw materials and conditions of Synthesis Example 2 except that 258.2 g of Farmin 86T (an alkyl primary amine manufactured by Kao Corporation) was used instead of Nissanamine VBS. I got

Next, the above-mentioned chloroacetamide 167. was placed in a four-necked flask equipped with a stirrer, thermometer and cooling tube.
3 g, 187.8 g of methylethanolamine and 500 g of methanol were added and reacted at 35 to 45 ° C. for 13 hours. After the reaction, 41.7 g of a 48% aqueous sodium hydroxide solution
After the addition, the excess methylethanolamine and the solvent were distilled off under reduced pressure. Further, desalting and crystallization with acetone were performed, and after drying, 328.5 g of amine D shown in Table 1 was obtained.

[0025]

[Table 1]

Examples 1 to 8 and Comparative Examples 1 to 2 The amines A to D according to the present invention obtained in Synthesis Examples 1 to 4,
Alternatively, using the comparative compound Y (trimethylstearyl ammonium chloride manufactured by Tokyo Chemical Industry Co., Ltd.) and the comparative compound Z (NIKKOL amidoamine MPS manufactured by Nikko Chemicals Co., Ltd.) shown in Table 2, the compositions shown in Tables 3 and 4 were used. A hair rinse was produced by a conventional method. These hair rinse agents were evaluated by the following methods. The results are shown in Tables 3 and 4.

[0027]

[Table 2]

<Evaluation method> Emulsifiability After the hair rinse was produced, the emulsified state after standing at room temperature (25 ° C) for 3 hours was evaluated according to the following criteria.

○: Emulsion gel is kept stable △: Slightly separated ×: Separation ・ Emulsion storage stability As an accelerated test of storage of the hair rinse agent, the hair rinse was stored at 50 ° C. for 3 weeks, and the gel emulsified state was evaluated according to the following criteria. Was evaluated.

○: Emulsified gel is kept stable △: Slightly separated ×: Separated ・ Performance at the time of application to hair, rinsing and after drying For Japanese women who have never undergone chemical treatment such as cold perm 20 g of hair (length 20 cm, average diameter 60 μm) were bundled and washed with 5 g of shampoo. This shampoo composition is polyoxyethylene alkyl (C12)
Sodium ether sulfate (average number of moles of ethylene oxide added: 2.5) 15%, diethanolamide 3%, the balance being water.

Thereafter, the prepared hair rinse was heated at 50 ° C.
Apply 2.0 g of the stored product for 3 weeks, and apply for 40 seconds for about 40 seconds.
Rinse with running water. At the time of this coating, the rich feeling at the time of rinsing and its persistence, flexibility, smoothness, and the softness and combing feeling after drying were sensory evaluated by five expert panelists according to the following criteria.

A: 4 or more respondents B: 3 respondents C: 2 respondents D: 1 or less respondents

[0033]

[Table 3]

[0034]

[Table 4]

Synthesis Example 5 An autoclave equipped with a stirrer and a thermometer was charged with Calcol 6850 (higher alcohol manufactured by Kao Corporation).
5 g and 0.1 g of potassium hydroxide were added, and the temperature was 120 ° C.
After dehydration at a degree of vacuum of 2.6 kPa for 1 hour, the temperature was increased to 60 ° C.
, And 58.4 g of acrylonitrile was introduced over 1 hour, and maintained for 1 hour to complete the reaction. Next, 1.9 g of Raney nickel and 0.3 of sodium hydroxide
g and ion-exchanged water (16.1 g) were added thereto, and a hydrogenation-reduction reaction was performed at a temperature of 130 ° C. for 3 hours, followed by filtration to remove the catalyst. Further purification by distillation gave 288.5 g of the corresponding ether primary amine.

Next, 156.8 g of the above ether primary amine and 61.9 g of N, N-dimethylglycine were placed in a four-necked flask equipped with a stirrer, a thermometer, a dehydrating tube and a nitrogen introducing tube.
And heated to 180 ° C. After reacting at the same temperature for 8 hours while distilling off generated water, crystallization with acetone was carried out, and after drying, amine E15 shown in Table 5
9.5 g were obtained.

Synthesis Example 6 The same raw materials and conditions as in Synthesis Example 5 were used except that 407.1 g of an adduct of 3.1 mol of octadecanol ethylene oxide was used in place of calcol 6850, and distillation purification was not carried out. The resulting primary amine was 445.6.

Next, in a four-necked flask equipped with a stirrer, a thermometer, a dehydrating tube, and a nitrogen introducing tube, 232.1 g of the above-mentioned primary ether amine and 72.2 N, N-dimethylglycine were placed.
g, and the temperature was raised to 190 ° C. After reacting at the same temperature for 8 hours while distilling off generated water, excess N, N-dimethylglycine was removed by washing with water to obtain 297.1 g of amine F shown in Table 5.

Synthesis Example 7 323.2 g of chloroacetamide corresponding to the raw materials and conditions of Synthesis Example 2 except that 267.3 g of Farmin 80 (an alkyl primary amine manufactured by Kao Corporation) was used instead of Nissanamine VBS. I got

Next, the above-mentioned chloroacetamide 138. was placed in a four-necked flask equipped with a stirrer, thermometer, and cooling tube.
4 g, 170.69 g of pyrrolidine and 400 g of isopropyl alcohol were added and reacted at 40 ° C. for 6 hours. After the reaction, 33.1 g of a 48.3% aqueous sodium hydroxide solution and 50 g of ion-exchanged water were added, and then excess pyrrolidine and the solvent were distilled off under reduced pressure. Further, after desalting and crystallization with acetone and drying, amine G 108.3 shown in Table 5 was obtained.
g was obtained.

Synthesis Example 8 In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube,
Chloroacetamide 13 obtained in the same manner as in Synthesis Example 7
8.4 g, 257.2 g of N-methylaniline, and 395 g of isopropyl alcohol were added and reacted at 60 to 70 ° C. for 30 hours. After the reaction, 33.1 g of a 48.3% aqueous sodium hydroxide solution and 80 g of ion-exchanged water were added.
Excess N-methylaniline and the solvent were distilled off under reduced pressure.
Further, after desalting and crystallization with acetone, and drying,
132.7 g of amine H shown in the following was obtained.

[0042]

[Table 5]

Examples 9 to 12, Comparative Example 3 Using the amines E to H according to the present invention obtained in Synthesis Examples 5 to 8 and the comparative compound Z similar to Comparative Example 2, a hair rinse agent having the composition shown in Table 6 Was produced by a conventional method. These hair rinse agents were evaluated in the same manner as in Example 1. Table 6 shows the results.

[0044]

[Table 6]

Example 13 A hair rinse having the following composition was produced.

Amine A 3.0% Lactic acid 2.0% Cetanol 4.0% Isopropyl palmitate 2.0% Dimethylpolysiloxane (average molecular weight 9000) 1.0% Polyether-modified silicone (KF6015 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 2.0% Propylene glycol 1.5% 50% citric acid aqueous solution 0.2% Fragrance, methyl paraben Appropriate amount Purified water Balance (pH 3.5) This rinse agent emulsifies into a gel, and the storage stability of the emulsion is good. there were. Furthermore, at the time of application, rich feeling at the time of rinsing and its persistence, flexibility, smoothness, and softness after drying,
The combing feeling was also good.

Example 14 A hair treatment agent having the following composition was produced.

Amine B 2.5% 35% aqueous hydrochloric acid 0.7% cetanol 6.5% dimethylpolysiloxane (average molecular weight 9000) 5.0% polyoxyethylene sorbitan monostearate 0.5% (average ethylene oxide addition) Number of moles 20) Behenic acid 0.1% Dipropylene glycol 6.0% Glycerin 8.0% 50% Citric acid aqueous solution 0.2% Fragrance, methyl paraben Appropriate amount Purified water balance (pH 3.5) This hair treatment agent is a gel The emulsion was emulsified in a state, and the storage stability of the emulsion was good. Furthermore, the rich feeling at the time of coating and rinsing and its persistence, flexibility, smoothness, and the softness after drying and the combing feeling were also good.

Example 15 A hair treatment agent having the following composition was produced.

Amine E 2.5% 90% Lactic acid 0.9% Cetanol 4.0% Dimethylpolysiloxane ^{* 1} 3.0% Amino-modified silicone ^{* 2} 0.5% Polyoxyethylene sorbitan monostearate 0.5% (Average number of moles of ethylene oxide added: 20) Liquid paraffin 2.0% Dipropylene glycol 3.0% Glycerin 7.0% 50% citric acid aqueous solution 0.2% Hydroxyethyl cellulose ^{* 3} 0.1% Flavor, methyl paraben Appropriate amount Purified water Balance (pH 3.7) * 1: KF96A-5000cs manufactured by Shin-Etsu Chemical Co., Ltd. * 2: Aminoalkyl silicone emulsion SM8702C manufactured by Dow Corning Silicone Toray Co., Ltd. * 3: SE- manufactured by Daicel Chemical Industries, Ltd. 850 This hair treatment agent is emulsified into a gel and has good storage stability of the emulsion. It was. Furthermore, the rich feeling at the time of coating and rinsing and its persistence, flexibility, smoothness, and the softness after drying and the combing feeling were also good.

[0051]

The hair cosmetic composition of the present invention has a very good emulsifying property such as an oil agent such as a feel improving agent and an excellent long-term stability of the emulsified gel. In addition, the hair can be provided with a good rich feeling when wet and its durability, flexibility, smoothness, softness after drying, and good combability.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tohru Kato 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term (reference) 4C083 AB282 AB332 AC022 AC072 AC122 AC172 AC302 AC352 AC442 AC482 AC581 AC582 AD042 AD152 AD162 AD282 CC31 CC39 EE06 EE07 EE28

Claims (5)

[Claims] 1. A hair cosmetic containing an amine represented by the general formula (I) (hereinafter referred to as amine (I)). Embedded image [Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 40 carbon atoms, or a compound represented by the formula R ⁵ O- (AO) _n
-C _m H _2m - (R ⁵ is a linear or branched alkyl or alkenyl group of 8 to 40 carbon atoms, A is the number of 0 to 30 by the number 2-3 alkylene group, n averages atoms, m is 2-3
R ² is a linear or branched alkylene group having 1 to 5 carbon atoms, R ³ is a hydrogen atom, and 1 to 24 carbon atoms. A linear or branched alkyl group, alkenyl group or hydroxyalkyl group, or an aryl or arylalkyl group having 6 to 28 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl having 1 to 5 carbon atoms group, alkenyl group or hydroxyalkyl group, or an aryl group or an arylalkyl group having a carbon number of 6 to 28, R ³ and R ⁴ may form a ring alone or combined with. p is an integer of 1-3, q and r are integers of 0-2, and p + q + r is 3. Note that p
R ¹ , R ² , q R ³ , and r R ⁴ may be the same or different. ] 2. In the general formula (I), R ¹ has ¹ carbon atom.
Straight or branched chain alkyl or alkenyl group of 2 to 24, or the formula _{^{R 5 O- (AO) n -C}} m H 2m - (R 5 is a straight chain or branched chain alkyl group having 12 to 24 carbon atoms or alkenyl group, a, group n and m is expressed by indicating) defined above, R ² is a straight-chain alkylene group having 1 to 3 carbon atoms, R ³
And R ⁴ is a linear or branched alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or 6 to 28 carbon atoms.
An aryl group or an arylalkyl group (R ³ and R ⁴ may form a ring alone or in combination), p is 1 or 2,
The hair cosmetic according to claim 1, wherein q and r are 0 or 1. 3. The hair cosmetic composition according to claim 1, which contains at least one acid selected from the group consisting of inorganic acids and organic acids. 4. The hair cosmetic composition according to claim 1, which contains an alcohol having 10 to 30 carbon atoms. 5. An amine (I) content of 0.1 to 15% by weight, an acid content of 0.3 to 10 mole times the amine (I) and an alcohol content of 10 to 30 carbon atoms. Is 0.5
The hair cosmetic according to claim 4, wherein the amount is from 15 to 15% by weight.