JPH0469320A - Hair cosmetic - Google Patents

Abstract

PURPOSE:To obtain a hair cosmetic having excellent smoothness, softness, moisture-retaining property and emulsion stability and giving good feeling in application by using an N-tris(hydroxymethyl)methyl-fatty acid amide and a cationic surfactant as essential components. CONSTITUTION:The objective cosmetic contains 0.01-80wt.% of an N-tris(hydroxymethy)methyl-fatty acid amide of formula (R1 is 7-27C alkyl or alkenyl) and 0.1-20wt.% of a cationic surfactant (e.g. quaternary ammonium salt). Preferably, the cosmetic is further compounded with 0.1-30wt.% of an oil or fat and proper amounts of conventional hair-cosmetic components by conventional cosmetic-preparation process. It can be used as hair rinse, hair conditioner, hair-treatment, hair cream, styling lotion, styling mousse, hair spray, etc. It is smoothly spreadable to hairs, free from stickiness and gives refreshing feeling.

Description

[Detailed Description of the Invention] [Industrial Application Field] Regarding the novel hair cosmetic of the present invention, more specifically, N-)
Contains lith(hydroxymethyl)methyl-fatty acid amide and a cationic surfactant, it spreads easily when applied, is non-sticky, gives a light feel, and has smoothness and
A hair rinse with excellent flexibility, moisture retention, and emulsion stability.
Hair conditioner hair treatment, hair cream, styling lotion, styling mousse,
Related to hair cosmetics such as conditioning mousse, hair spray, hair liquid, and styling gel.

[Prior art and problems to be solved by the invention] Conventionally, cationic surfactants, higher alcohols, glycerides, liquid paraffins, esters, etc. have been used to impart flexibility, smoothness, antistatic properties, etc. to hair. Hair cosmetics are used in combination with oils. However, when these oils are used in combination, the flexibility and smoothness are improved compared to when the cationic surfactant is used alone, but there is a drawback that the feeling of residual oil, that is, the feeling of greasiness and stickiness cannot be avoided.

On the other hand, emulsion-type hair cosmetics are widely used because their composition allows them to provide appropriate amounts of oil and moisture to hair and improve smoothness. By changing the type and amount of the oil component, various emulsions with different physical properties and texture can be obtained.

However, since emulsions are thermodynamically unstable systems, it is difficult to stabilize them, and many studies and attempts have been made to date. One of the countermeasures is the addition of an emulsifying agent. Such emulsification aids include cationic aids,
Although there are anionic auxiliaries, amphoteric auxiliaries and nonionic auxiliaries, nonionic auxiliaries are most preferred because of the wide range of oil components that can be incorporated.

As an example of adding a nonionic emulsifying agent, it is known that adding a higher alcohol such as cetanol or cetostetryl alcohol to a cosmetic emulsion improves the stability of the liquid crystal structure. . Although the method of adding higher alcohols is effective in preventing the crystallization of high-melting point oils, if they are added to the extent that they remain stable, the viscosity becomes extremely high, making it difficult to spread during application, resulting in an oily feel. The disadvantage is that it is strong and sticky.

Further, with regard to liquid crystal structures of higher alcohols, there have been problems such as precipitation of crystals with pearl-like luster due to destruction of the liquid crystal structure and reduction in viscosity.

For this reason, compositions have been developed in which a nonionic auxiliary agent that forms a lamellar liquid crystal structure is blended into the composition.

For example, in Japanese Patent Publication No. 38-5050, the following general formula (
n) [wherein l represents an integer of 1 to 3] A skin and hair care agent containing a triol represented by the following is disclosed. However, this triol has the disadvantage that it becomes an inverted middle liquid crystal in an aqueous solution, has a strong oily feel, and does not have a sufficient moisturizing effect.

Furthermore, JP-A No. 63-23737 discloses an aqueous dispersion of niosomes consisting of lipid lamellae using polyglycerol ether as a nonionic amphiphilic substance, and an aqueous dispersion of niosomes comprised between lipid layers. Water-soluble active substances are encapsulated within the membrane to improve stability. However, in forming niosomes that encapsulate active substances within vesicles, 8
The disadvantage is that the treatment must be carried out at a high temperature of 0° C. or higher, making it difficult to use active substances with poor high-temperature stability. Furthermore, Special Publication No. 58-8287, Special Publication No. 61-
56016, JP 57-77613, and JP 57-94326 also disclose aqueous dispersions of lipid globules using polyglycerol ether, but homogenization is required during production. However, the manufacturing method is complicated, such as dissolving the lipid in an organic solvent such as chloroform-methanol and evaporating the solvent, and has the drawback of being industrially difficult.

As described above, conventional nonionic auxiliary agents have problems in that the concentration range for forming liquid crystals is narrow and the temperature for forming liquid crystals is high, making it difficult to form liquid crystals on an industrial scale.

Normally, in hair cosmetics, due to the instability of emulsions, active ingredients with high melting points are not uniformly emulsified and dispersed and are separated, making it impossible to obtain sufficient effects such as moisturizing properties and smoothness. . Furthermore, some nonionic auxiliaries have a moisturizing effect, but this effect is not sufficient.

For this reason, it has been desired to develop hair cosmetics that are uniformly stable without changes such as crystal transition over a wide concentration range at the temperature at which hair cosmetics are used, have no oily feel, and have excellent smoothness and moisturizing effects. .

On the other hand, it is known that N-)lis(hydroxymethyl)methyl fatty acid amide can be used as a sub-cleaning component (US Pat. No. 2.927.081).

However, it has not yet been known that it has an excellent moisturizing effect.

[Means to solve the problem]

Under such circumstances, the present inventors have conducted extensive research to solve the above problems, and have found that using N-)IJs(hydroxymethyl)methyl-fatty acid amide and a cationic surfactant will result in a smooth surface. It is possible to obtain hair cosmetics with excellent properties and moisturizing properties, and if oils and fats are added to this to make emulsified hair cosmetics, in addition to good smoothness and moisturizing properties, it contributes to the stabilization of emulsions, etc. We discovered that it is possible to spread the uniformity of active ingredients with a high melting point, and that it is possible to obtain an excellent hair cosmetic that spreads well when applied and gives a light feel without stickiness. Completed the invention.

That is, the present invention provides the following components (A) and (B) (A) the following general formula (1) % formula %) where R1 is a straight or branched alkyl group having 7 to 27 carbon atoms or (B) A hair cosmetic containing a cationic surfactant and the following ingredients (C) A hair cosmetic containing oils and fats is provided.

N-tris (A) component used in the hair cosmetic of the present invention (
Hydroxymethyl)methyl-fatty acid amide is represented by the above general formula (I).

In the formula, R1 preferably has 7 to 23 carbon atoms, and L
- (Specific examples of 1-nee include straight-chain saturated acyl groups such as lauroyl group, myristoyl group, balmitoyl group, and stearoyl group; straight-chain unsaturated acyl groups such as oleoyl group; isostearoyl group, -2-octyldeca Examples include branched acyl groups such as noyl group and 2-hebutylundecanoyl group.Among them, in particular those of the following general formula (III), (TV) or (V)CHl [wherein m and n are each 0 Indicates an integer of ~24, m
and n is 4 to 24] [In the formula, R2 and R3 each represent an alkyl group having 2 to 12 carbon atoms] CH3-(C)1. ), (H=C1l(CH2), -(
A branched acyl group or a straight chain unsaturated acyl group represented by "-(V) [wherein X and y each represent an integer of 0 to 24, and the sum of X and y is 4 to 24]" is preferable. Further, more preferred R, -C- binding includes those of the general formula (II[) in which the sum of m and n is 10 to 16, and among these, an isostearoyl group in which the sum of m and n is 14 is particularly preferred. .

N-)lis(hydroxymethyl)methyl-fatty acid amide (I) in which R, -C- is represented by the above general formula (III) is a lamellar liquid crystal at room temperature, and is resistant to most solvents. It exhibits excellent compatibility with water, and has characteristics such as being almost uniformly dispersed when mixed with water.

N-tris(hydroxymethyl)methyl-fatty acid amide (I) in the present invention is produced, for example, according to the following reaction formula.

C) I20H R, C0OH+ H, N-C-CL[1H(Vl'
) C)1. OH (■) [In the formula, R1 has the same meaning as above] That is, fatty acid (VI) is reacted with tris(hydroxymethyl)aminomethane (■) to form a compound (■), which is hydrolyzed. Compound (I) is produced by this.

Among the fatty acids (VI) used in this reaction, those obtained industrially are usually mixtures in which the total number of carbon atoms in the alkyl group and the position of the branched methyl group have a certain distribution, for example, in the production of oleic acid dimer. The isostearic acid with methyl branches obtained as a by-product of the process contains about 75% or more of carbon atoms with a total number of 18 carbon atoms (the sum of m and n is 14), and the remainder contains 14 carbon atoms and 16 carbon atoms. 20, and the branched methyl group is located approximately in the center of the alkyl main chain [Journal of the American Oil and Chemical Society (J, ^mer.

Oil [:hem, Sac,) Vol, 51
．． 522. (1974) ; Vol. 5
6. 823A, (1979)].

The first step of this reaction, the reaction between fatty acid (VI) and tris(hydroxymethyl)aminomethane (■), is an oxazolination reaction, and it is preferably carried out using approximately equal moles of these. This reaction is carried out without a solvent or in an inert solvent such as xylene, mesitylene, cumene, decane, etc.
~250°C, especially 130-220°C, even 150-20°C
Preferably, the reaction is carried out at a temperature of 0° C. while removing the water produced. If the temperature is low, the reaction will not proceed; if the temperature is high, coloration will be severe and side reactions will occur. Further, it may be carried out under a nitrogen atmosphere or an air atmosphere. The reaction time varies depending on various conditions, but is usually preferably 1 to 24 hours.

The second step, the hydrolysis reaction of oxazoline, consists of carbon atoms ranging from 1 to
It is preferable to carry out the reaction in a mixed solvent of the lower alcohol of No. 6 and water. A method for hydrolyzing oxazolines having a direct alkyl group using only water as a solvent is described in U.S. Patent No. 2.8.
No. 77,242. However, this method requires a large excess of water, about 20 times the weight of the oxazoline, and there was a problem that the reaction yield was low if the amount of water was small. According to the present invention, by using the above mixed solvent, it is possible to hydrolyze oxazoline in a high yield with a small amount of solvent. The ratio of lower alcohol to water is 1 = 10 to IO = 1, especially 2:
5-5:2, more preferably 1:2-2:1. When this range is exceeded, there is less water in the system, and when it is below this range, hydrolysis slows down due to heterogeneity within the system. Moreover, the ratio of this mixed solvent to compound (■) is preferably 0.1:l to 20:l in terms of weight ratio. When it exceeds this range, productivity is poor and impractical, and when it falls below this range, the hydrolysis reaction becomes slow. Examples of lower alcohols used here include methanol, ethanol, isopropanol, propazol, butanol, isobutanol,
5eC-butanol, t-butanol, amyl alcohol, t-amyl alcohol, neopentyl alcohol,
Examples include hexyl alcohol.

The reaction may be carried out under a nitrogen atmosphere or an air atmosphere.
Preferably it is carried out at a temperature of 150°C, particularly 60-130°C, more preferably 70-120°C. If the temperature is low, the reaction will not substantially proceed, and if the temperature is high, coloring will be severe and side reactions will occur. The reaction time varies depending on the reaction temperature, etc., but is usually preferably 1 to 15 hours. Further, an alkaline substance or an acidic substance may be present in this hydrolysis reaction.

Compound (I) can be isolated from the reaction mixture by conventional methods such as solvent distillation, recrystallization, chromatography, etc. alone or in combination.

The N-)lis(hydroxymethyl)methyl-fatty acid amide thus obtained can be used alone or in combination of two or more, and the amount incorporated into the hair cosmetic of the present invention is not particularly limited, but Usually 0.01-80% by weight
(hereinafter simply expressed as %), particularly preferably 0.1 to 60%.

As the cationic surfactant as component (B) used in the hair cosmetic of the present invention, for example, the following general formula [wherein R1-
One or two of R7 is a linear or branched alkyl group having 8 to 28 carbon atoms, a hydroxyalkyl group, or R8 is CH, CH, Oi (R is an alkyl group having 8 to 24 carbon atoms or hydroxy represents an alkyl group, r represents a number from 1 to 10), the remainder represents a benzyl group, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group, and X- represents a halokene ion or an organic anion] Examples include quaternary ammonium salts.

All of the above-mentioned quaternary ammonium salts are preferably used, but among these, as branched quaternary ammonium salts, the following general formula (X) or (Xi) described in JP-A-61-267505 is preferred. It is preferable to contain one or more of the following.

[In the formula, R3 is (a) CH3(CH2), CHCH2-
An alkyl group selected from a branched alkyl group represented by R1□ and (b) a straight alkyl group represented by CLf-[:Lh- (in the formula, R+2 is a methyl group or an ethyl group, p and q are an alkyl group) The total number of carbon atoms is 8 to 16), and the branching rate of group R9 (a
) / (a) + (b) is 10 to 100%, R3゜ and RI + represent a group selected from a benzyl group and an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X- represents a halogen ion or an organic anion] [In the formula, R13 and R+4 represent an alkyl group having 2 to 12 carbon atoms, and RI5 represents a group R, C)1. CH2CHCN, -
or an alkyl group having 1 to 3 carbon atoms, RI OSR
l 1 and X have the same meaning as in (X)] These cationic surfactants can be used alone or in combination of two or more, and the ingredient in the hair cosmetic of the present invention , usually 0.1 to 20%, particularly preferably 0.5 to 5%.

In addition, the oils and fats of component (C) used in the hair cosmetic of the present invention are not particularly limited as long as they are commonly used, such as higher alcohols having straight or branched alkyl groups or alkenyl groups. ; Hydrocarbons such as liquid paraffin, vaseline, and solid paraffin; Lanolin derivatives such as liquid lanolin and lanolin fatty acids; Silicones such as dimethylpolysiloxane; Higher alcohol higher fatty acid esters, higher fatty acids, and alkyl or alkenyl groups. fats and oils such as long-chain amidoamine; animal and vegetable fats and oils such as mink oil and olive oil; Among these oils and fats, suitable for hair rinses or hair conditioners are monoglycerides derived from saturated or unsaturated straight-chain or branched fatty acids having 12 to 24 carbon atoms, and straight-chain or branched alkyl chains having 12 to 26 carbon atoms. Particularly preferred are higher alcohols having groups or alkenyl groups. Preferred specific examples thereof include fatty acid monoglycerides such as oleic acid monoglyceride, valmitic acid monoglyceride, stearic acid monoglyceride, behenic acid monoglyceride, and isostearic acid monoglyceride, and heptyl alcohol, stearyl alcohol monoglyceride,
Higher alcohols such as behenyl alcohol, caranervir alcohol, and seryl alcohol can be mentioned. These oils and fats can be used alone or in combination of two or more, and the amount blended into the hair cosmetic of the present invention is usually 0.1 to 0.1.
30%, especially 1-10% is preferred.

Furthermore, the hair cosmetic of the present invention may contain ingredients normally used in cosmetics, pharmaceuticals, foods, etc., such as anti-dandruff agents, bactericides, medicinal agents such as vitamins; preservatives such as parabens, etc., as necessary. Thickeners such as perfluoropolyether and water-soluble polymers; Coloring agents such as dyes and pigments; Conditioning agents such as cationic polymers; Burling agents such as glycol esters; Hair setting polymers such as acrylic resin liquid; Various Mixed fragrances; other encyclopedias, fragrances, conditioning, rinses, and indredients [BNCY
CLOPεDIA OF C0NDITIONIN
G RINS BINGRE[1JBNTS (MIC
ELLE PRBSS, 1987)] may be appropriately blended within a range that does not impair the effects of the present invention.

The hair cosmetic of the present invention can be manufactured according to a conventional method, such as hair rinse, hair conditioner, etc.
It can be applied to hair treatments, hair creams, styling lotions, styling mousses, conditioning mousses, hair sprays as aliquids, styling gels, etc.

〔Effect of the invention〕

Since the hair cosmetic of the present invention uses N-tris(hydroxymethyl)methyl-fatty acid amide, which has excellent performance as a moisturizing ingredient, and a cationic surfactant, it has a low oily feel and spreads easily. Furthermore, since high melting point substances such as oils and fats are stably incorporated into the system, the active ingredients work effectively and exhibit excellent effects.

Therefore, the hair cosmetic composition of the present invention has excellent smoothness, flexibility, and moisturizing properties, spreads well when applied, is free from stickiness, provides a light feel, and has good emulsion stability.

〔Example〕

Next, the present invention will be described with reference to Reference Examples and Examples, but the present invention is not limited to these Reference Examples and Examples.

Reference Example I Synthesis of N-)lith (hydroxymethyl)methyl-isostearamide [Compound (Ia)] = (1) 2
-heptanedecyl-4,4-bis(hydroxymethyl)
-2-Oxacillin [Compound (■a)] Into a reaction vessel of capacity Ii equipped with a thermometer, reflux condenser, Dean-Stark trap and stirrer, 300 g (1,055 g mole) and tris(hydroxymethyl)aminomethane 127
．． 75 g (1,055 mol) was charged. The temperature was raised while stirring, and the temperature was increased to 140-160% for 3 hours, and then the temperature was increased to 160-160%.
The reaction was carried out at 96°C for 3 hours, and the calculated amount of water was distilled off to obtain 386.25 g of the title compound (■a) (yield 99.1%).
).

This substance is a viscous yellow liquid at 140°C, but solidifies into a waxy state at room temperature. m, p, 53-58°C.

Gas chromatography: purity 90.7% (2)N-)
Lis(hydroxymethyl)methyl-isostearic acid amide compound (I a)) 150 g of the compound (■a) obtained in (1) was placed in a reaction vessel with a capacity of 11 equipped with a thermometer, a reflux condenser, and a stirrer. (0,368 mol) and 300 d of ethanol were charged. Raise the temperature while stirring to 76℃
450 d of water was added dropwise over 15 minutes. The reaction solution becomes cloudy. After stirring under reflux for 5 hours at 83-84°C, the mixture was cooled to room temperature. At this time, the reaction solution becomes almost transparent. After adding ethanol and repeating evaporation several times for dehydration, 157.67 g of crude compound (Ia) was obtained. This product had a purity of 87.6% as determined by gas chromatography. The residue was dissolved in 1,000 ml of chloroform and evaporated after removing insoluble materials, and the residue was dissolved in 50 ml of hexane (1-
After recrystallizing and washing with hexane, the obtained solid was heated at 50°C.
The product was dried under reduced pressure to obtain 79.62 g of compound (Ia) (
yield 55.8%).

Gas chromatography purity: 95.2% This product was a thermotropic liquid crystal that was colorless and transparent at room temperature.

Acid value: 1.42 Hydroxyl value: 414.1, (theoretical value 434.26) [
R (KBr, cm-') 3380 (0-H stretching), 3300 (NH stretching)
, 2928, 2860 (C-H stretching), 1626
(C=O stretching), 1536 (NH bending), 1468
, 1380 (C-H bending angle), 1050 , 102
6 (C-0 expansion/contraction), 722 (CH, lateral sway), 68
8 (N-H out-of-plane bending angle) NMR (['DC!!3,
δppm>0, 65-1.05 (6)1. Broad, -C113) 2.02-2.58 (2H,
Broad, -('H,C-)3, 32-3.99 (6
H, broad, -CH2DH)4.77-5.48
(3H, broad, -CH,OH)6J5-6.
65 (IH, Broad, -C-N)I-) Example 1 A hair rinse composition having the composition shown in Table 1 was prepared, and its rinsing performance was investigated. The results are shown in Table 1. The test method used in the examples is as follows.

[Hair treatment]

Place 20g (15cm in length) of the hair of a Japanese woman who has never undergone beauty treatments such as cold perm or bleach on a table, and apply 2g of the rinse-type hair cosmetic product evenly to this hair bundle. It was applied, then rinsed with running water for 30 seconds, towel dried, and then dried with a hair dryer. For non-rinsing type hair cosmetics, a predetermined amount of the agent was applied to the hair bundles and then air-dried. Various evaluations were performed on this hair bundle.

[Higher alcohol adsorption amount]

Take 0.5g of hair rinsed by the above method,
Higher alcohols were extracted with chloroform.

After concentration, it was dissolved in a certain amount of chloroform containing an internal standard substance, and the amount of higher alcohol adsorbed was determined from the peak area by gas chromatography.

〔sensory evaluation〕

The treated hair tresses were sensory evaluated by expert panelists according to the following criteria.

・Smoothness: Especially excellent ◎, good ○, fair △, poor △, Strong oily feeling × ・Moisturizing properties: Excellent moisturizing feeling ◎, Moisturizing feeling ○, Neutral △, No moisturizing feeling Observation was made using a polarizing microscope.

○: Forms uniform liquid crystal.

×: Uniform liquid crystal is not formed.

Margin Example 2 Hair rinse agent compositions having the compositions shown in Table 2 were prepared below, and their rinsing performance was examined. The results are shown in Table 2.

(Manufacturing method) To the mixture of (phases) and (2) heated to 70°C, the mixture of (1) to (2) heated and dissolved at the same temperature was added and stirred to emulsify, and then cooled to 45°C while stirring. , (2) were added and further cooled to room temperature while stirring to obtain a hair rinse composition.

All of the obtained hair rinse agent compositions exhibited good rinsing performance and good stability.

Sensory evaluation was performed in the same manner as in Example 1.

[Storage stability]

The sample was placed in a 100-capacity transparent glass container, and after storage, the appearance was observed with the naked eye. The evaluation was based on the following criteria.

○: Uniform throughout, with no abnormalities such as dispersion or aggregation.

X: Non-uniform, with separation, aggregation, etc. observed.

Example 3 Hair treatment composition: (Product 6 of the present invention) ■ Cetostearyl alcohol 3.0 ■ Liquid paraffin 3.0 *3: Commercially available oxo synthetic alcohols having 12 to 15 carbon atoms (such as Dopanol 23 and Dopanol 45) A branched quaternary ammonium salt derived from a quantity mixture manufactured by Mitsubishi Yuka Co., Ltd.
Its branching rate is 20% *4: Obtained in Reference Example 1 ■ Methylparaben ■ Fragrance 0.2 0.4 Total 100.0 bottles 5: Reference Example 1
A hair treatment composition was obtained which has excellent smoothness and flexibility, has little oily feel, is light, and has a moist and good feel.

Example 4 Hair cream composition = (Invention product 7) ■ Heptyl alcohol 5.0 ■ Dipropylene glycol 6. O■ Glycerin
10.0 ■ Liquid paraffin 3.
0 ■ Fragrance 0
．． 4 Total: 100.0 Zero 6: Obtained in Reference Example 1 A hair cream composition was obtained that was excellent in smoothness and flexibility, had no sticky feeling, and had a good feel.

Example 5 Styling lotion composition: (Product of the present invention ■Liquid paraffin 0.5■Methacrylic acid ester polymer" 1.0■Polyethylene glycol 1.0■Ethanol
20.0 ■ Fragrance
0.4■ Water balance meter 100.0 pieces 7: Obtained in Reference Example 1 Pass: Yukaformer A Door 5, manufactured by Mitsubishi Yuka ■ A setting agent that provides excellent hair style retention with a good feel A composition was obtained.

Example 6 Conditioning mousse composition = (Product of the present invention ■ Dialkyldimethylammonium chloride $3 0.5 (%) ■
Methylphenylpolysiloxane (300cs) 1.0 ■ Isotridecyl myristate ■ 3-methyl-1,3-butanediol ■ Glycerin ■ Liquid paraffin 1.0 1.0 2.5 2.5 Procedural amendment (voluntary)

Claims (1)

[Claims] 1. The following components (A) and (B) (A) The following general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 is carbon number 7 ~27 linear or branched alkyl group or alkenyl group] N-tris(hydroxymethyl)methyl-
A hair cosmetic containing one or more fatty acid amides (B) a cationic surfactant. 2. The following components (A), (B) and (C) (A) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 has a carbon number of 7 to 27 represents a straight-chain or branched alkyl group or alkenyl group] N-tris(hydroxymethyl)methyl-
A hair cosmetic containing one or more fatty acid amides (B) a cationic surfactant (C) oils and fats. 3. Claim 1 or 2, wherein R_1 in general formula (I) is a branched alkyl group or alkenyl group having 13 to 19 carbon atoms.
The hair cosmetics mentioned.