JPH06192045A - Hair cosmetic - Google Patents

Abstract

PURPOSE:To provide a hair cosmetic effective for imparting hair with smoothness and gloss without damaging the hair, having high adsorptivity to hair and resistant to shampooing and rubbing to keep its effect. CONSTITUTION:This hair cosmetic contains preferably 0.01-50wt.% (especially 0.05-30wt.%) of a sulfonic acid-modified silicone of the formula [R1 is lower alkyl or (substituted) phenyl; R2 is 2-11C hydrocarbon residue; the C-C single bond of the residue may be interrupted with a residue generated by a reaction; A is residue generated by the reaction of an isocyanate with a functional group having active hydrogen; R3 is arylene, alkylene, alkarylene or aralkylene; X is univalent metal, H or H.X1 (X1 is ammonia or amine); (m) is 50-200; (p) is 1-10]. The compound of formula can be produced by synthesizing a silicone having isocyanate group and reacting the silicone with a compound having SO3X group and active hydrogen.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hair cosmetic composition, and more particularly to a hair cosmetic composition containing a sulfonic acid-modified silicone.

[0002]

BACKGROUND OF THE INVENTION Various silicone derivatives have been used to impart smoothness and natural luster to hair. These silicone derivatives also have the advantage of being less sticky and less heavy than hydrocarbons and ester oil agents,
It is commonly used in hair cosmetics.

However, silicone derivatives generally have a low adsorbability to hair, are easily removed from hair by washing or rubbing, and have the problem that the above effects do not last.

Among the silicone derivatives, amino-modified silicone is said to have relatively high adsorptivity to hair, but the effect of general silicone to impart smoothness to hair is insufficient. .

Further, a hair treatment composition has been disclosed which has a long-lasting hair splitting prevention effect and a gloss imparting effect using a specific silicone compound or the like (Japanese Patent Laid-Open No. 4-66517). JP-A-4-66518,
JP-A-4-66519, JP-A-4-112813,
JP-A-4-112814, JP-A-4-112815, etc.), but these do not have a neutral pH,
There is a risk of damaging the hair due to the need for oxidizing and reducing agents. Furthermore, a cyclic Bunde salt-modified silicone is proposed in Japanese Patent Application Laid-Open No. 4-114037 as a conditioning component of a hair treatment composition capable of imparting gloss to the hair, and this and the sulfonic acid-modified silicone of the present invention have a structure. -The molecular weights are very different.

[0006]

SUMMARY OF THE INVENTION The present invention has been made from the above viewpoints, and imparts smoothness and luster to hair without damaging the hair, and has high adsorptivity to the hair, so that hair washing and An object of the present invention is to provide a hair cosmetic that is hard to be removed by friction and has a long-lasting effect.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor found that when a sulfonic acid-modified silicone represented by the following chemical formula 2 was added to a hair cosmetic composition, the hair became smooth. The present invention has been completed based on the finding that shine can be imparted and that it has high adsorptivity to hair.

That is, the present invention is a hair cosmetic containing a sulfonic acid-modified silicone represented by the following chemical formula 2.
Hereinafter, the present invention will be described in detail.

<1> Sulfonic Acid Modified Silicone Used in the Present Invention The sulfonic acid modified silicone used in the present invention is represented by the general formula of Chemical formula 2.

[0010]

[Chemical 2]

However, each R ₁ independently represents a lower alkyl group or an unsubstituted or substituted phenyl group, and R ₂ is 2 to 1
Indicates a monovalent hydrocarbon residue, the carbon-carbon single bond of which may be interrupted by a residue formed by the reaction of a functional group, and A is formed by the reaction of an isocyanate group with a functional group having an active hydrogen. Is a residue, R ₃ represents an arylene group, a linear or branched alkylene group, an alkali-ylene group or an aralkylene group, and X is a monovalent metal, a hydrogen atom or —H.
X ₁ (where X ₁ represents ammonia or amine), m represents an integer of 50 to 200, and p represents 1 to
Indicates an integer of 10.

The lower alkyl group is preferably a methyl group, an ethyl group or a propyl group. R ₂ is 2 to 1
Indicates a monovalent hydrocarbon residue, preferably having 2 to 25 carbon atoms
Aliphatic residue, aromatic residue, aliphatic aliphatic residue having 1 to 5 carbon atoms or a residue having a repeating unit thereof, or aliphatic aromatic residue having 1 to 5 carbon atoms Alternatively, it represents a residue having the repeating unit. Further, the residue resulting from the reaction of these aliphatic carbon-carbon single bond interrupting functional group, for example, an ether bond generated by the reaction of alcohol and / or epoxide, a functional group having an isocyanate and active hydrogen, such as an amino group, Residue produced by reaction with hydroxyl group, mercapto group, or carboxyl group, for example,

[0013]

[Chemical 3] Etc.

The residue produced by the reaction between the isocyanate group represented by A and the functional group having active hydrogen is the same as above. R ₃ is preferably a phenylene group, having 1 to 4 carbon atoms.
Phenylene group substituted with lower alkyl group, having 1 carbon
~ 5 alkylene groups and

[0015]

[Chemical 4] Is.

As the monovalent metal represented by X,
Li, Na, and K are preferable. Also, the formula −H
When X ₁ in X ₁ is an amine, it has the general formula N
(R ₃ ) ₃ wherein each R ₃ is independently a hydrogen atom, preferably a linear or branched alkyl group having 1 to 5 carbon atoms, or preferably 1 to 5
3 represents a straight-chain or branched hydroxyalkyl group having 3 carbon atoms and preferably having 3 or less hydroxyl groups.

Examples of the amine include triethanolamine, 2-amino-2-methyl-1-propanol,
2-amino-2-methyl-1,3-propanediol,
Examples include monoethanolamine and the like. The value of m is 50
~ 200. The value of p is 1 to 10, preferably 1 to 5. The number average molecular weight (Mn) of the sulfonic acid-modified silicone is 5000 to 15000.

The sulfonic acid-modified silicone used in the present invention can be produced by synthesizing a silicone having an isocyanate group and then reacting the silicone with a compound having a —SO ₃ X group and active hydrogen.

Here, the silicone having an isocyanate group is represented by Chemical Formula 5.

[0020]

[Chemical 5]

Here, R ₁ , R ₂ , m and P are the same as above. The silicone having an isocyanate group can be produced by various methods, for example, by reacting a polyisocyanate containing at least two isocyanate groups having a functional group having active hydrogen.

The silicone having a functional group having active hydrogen is, for example,

[0023]

[Chemical 6]

(Here, m is an integer of 50 to 200) and the like. On the other hand, the polyisocyanate containing at least two isocyanate groups means, for example, hexane methylene diisocyanate (HDI), methylene diphenyl isocyanate (MDI), tolylene diisocyanate (TDI) and

[0025]

[Chemical 7]

(Here, n is preferably 1 to 9) and the like. The amount of the polyisocyanate containing at least two isocyanate groups used is preferably 1.0 to 1.2 in terms of an equivalent ratio to active hydrogen in the silicone having a functional group having active hydrogen.

The reaction conditions are preferably an inert gas atmosphere of nitrogen or the like, a reaction temperature of 0 to 150 ° C., particularly preferably 50 to 100 ° C., a reaction time of 2 hours to 20 hours, and particularly preferably 5 ~ 10 hours are used.

Next, a sulfonic acid-modified silicone is produced by reacting the above-mentioned silicone having an isocyanate group with a compound having a —SO ₃ X group and active hydrogen. Examples of the compound having a —SO ₃ X group and active hydrogen used here include sodium isethionate and sodium sulfanilate. The amount of the compound used is preferably 1.0 to 1.5 in an equivalent ratio to the isocyanate group in silicone.

In the reaction, a solvent such as 1,
4-dioxane, dimethoxyethane, diethyl ether, tetrahydrofuran, a hydrocarbon solvent having 5 to 8 carbon atoms (such as hexane), or the like, or a mixture of two or more thereof may be used. As an example of preferable reaction conditions, the reaction system is placed in an atmosphere of an inert gas such as nitrogen and the reaction temperature is 0 to 200 ° C., more preferably 50 to 150 ° C.
And the reaction time is about 5 to 50 hours, more preferably about 10 to 30 hours.

A method for converting a sulfonic acid group into an ammonium salt or an amine salt is known. For example, a sulfonic acid-modified silicone in which X in the formula 2 is a monovalent metal prepared as described above is dissolved in hexane or heptane, and an aqueous solution of hydrochloric acid or sulfuric acid is added thereto, preferably at a reaction temperature of 0 to
After acidic hydrolysis at 50 ° C., preferably for a reaction time of 5 minutes to 1 hour, the silicone phase is removed and the amine is added to it to give a sulfonic acid-modified silicone in the form of an amine salt.

<2> Hair Cosmetic of the Present Invention The hair cosmetic of the present invention contains the sulfonic acid-modified silicone, and may be used as a mixture of two or more of the sulfonic acid-modified silicone. Good.

The content of the sulfonic acid-modified silicone is preferably 0.01 to 50%, more preferably 0.05.
~ 30%. If the blending amount is less than 0.01%, the effect of imparting smoothness and gloss to the hair is poor. On the other hand, if it exceeds 50%, it may be difficult to stably mix it in a dosage form due to easy separation, or the produced cosmetic may have too high a viscosity to be applied to hair.

Examples of the hair cosmetics in the present invention include shampoo, rinse, treatment, hair oil, hair cream, split ends coat agent, hair styling agent, hair color, permanent wave agent, bleaching agent and the like. The dosage form is not particularly limited.

In the hair cosmetic composition of the present invention, in addition to the above-mentioned sulfonic acid-modified silicone, oils, surfactants, alcohols, polymer compounds, which are usually blended in hair cosmetic compositions,
Water and other components can be appropriately mixed depending on the use, dosage form, purpose and the like.

The above oils include liquid paraffin,
Liquid oils such as squalane, cetyl 2-ethylhexanoate, isopropyl myristate, olive oil, castor oil; semi-solid to solid fats such as petrolatum, solid para, beef tallow, lanolin, beeswax, whale wax, cholesterol; cetanol, behenyl alcohol, etc. And higher fatty acids such as palmitic acid and stearic acid; fluorine-based oil agents such as perfluoropolyether; and silicone derivatives other than the sulfonic acid-modified silicone used in the present invention.

As the above-mentioned surfactant, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene (hereinafter abbreviated as "POE") sorbitan fatty acid ester, POE glycerin fatty acid ester, POE alkyl ether, POE polyoxypropylene alkyl ether, POE Nonionic surfactants such as polyoxypropylene copolymer, POE alkyl phenyl ether, POE hydrogenated castor oil, polyethylene glycol fatty acid ester, decaglycerin fatty acid ester, alkyl diethanolamide; alkyl sulfate, POE alkyl ether sulfate, POE alkyl ether Acetate, alkyl phosphate, POE alkyl ether phosphate, higher fatty acid salt, higher fatty acid hydrolyzed collagen salt, amino acid anionic surfactant; sulfosuccinic acid surfactant, olefin Anionic surfactants such as ruphonate; amphoteric surfactants such as lecithin, betaine acetate, imidazolinium betaine; cationic such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride Surfactants may be mentioned.

Alcohols include monohydric alcohols such as ethanol, propanol and benzyl alcohol;
1,3-butylene glycol, propylene glycol,
Examples thereof include polyhydric alcohols such as dipropylene glycol, glycerin, polyethylene glycol and sorbitol.

Examples of the polymer compound include polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, acrylic resin alkanolamine, vinyl acetate-crotonic acid copolymer, methyl vinyl ether-maleic acid monoalkyl ester copolymer, N-methacryloyl. Ethyl N, N-dimethylammonium α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer, diethyl vinylpyrrolidone sulfate-N, N'-dimethylaminoethyl methacrylic acid copolymer, hydroxyethylcellulose dimethyldiallylammonium chloride, hydroxy Examples include ethyl cellulose hydroxypropyl trimethyl ammonium chloride ether, carboxyvinyl polymer, carboxymethyl cellulose salt, xanthan gum, hydroxyethyl cellulose and the like.

Further, as the above-mentioned other components, humectants such as amino acids and hyaluronic acid; ultraviolet absorbers such as oxybenzone and para-aminobenzoic acid ester; antioxidants such as tocopherol and dibutylhydroxytoluene; paraben, phenoxyethanol and the like. Antiseptic; bactericides such as isopropylmethylphenol and trichlorocarban; hydrolysates of proteins such as collagen, keratin, silk (eg hydrolyzed collagen: Promois W42R manufactured by Seiwa Kasei Co., Ltd.); citric acid, citric acid PH adjusting agents such as sodium, anti-dandruff agents such as zinc pyrithione and piroctone olamine, plant extract, anti-inflammatory agents such as dipotassium glycyrrhizinate; propellants such as dimethyl ether and LPG; Na
Inorganic salts such as Cl; pearling agents such as triethylene glycol distearate, chelating agents, dyes, and fragrances.

[0040]

The hair cosmetic composition of the present invention is applied to the hair and dried as it is, or when applied to the hair and rinsed and then dried, the sulfonic acid-modified silicone is adsorbed on the hair and is hard to remove even after washing. It forms a smooth film and gives the hair a smooth feel and shine for a long time.

[0041]

EXAMPLES The production examples of the sulfonic acid-modified silicone used in the present invention and the examples of the present invention are described below, but the present invention is not limited to these sulfonic acid-modified silicones and examples.

[0042]

[Production Example] A production example of the sulfonic acid-modified silicone used in the present invention will be described.

[0043]

[Production Example 1] 500 ml round bottom flask 6
150 parts by weight and 2.7 parts by weight of silicone having a structure shown in the formula (4) and having a hydroxyl group at one end having an average molecular weight of 10,000 (Cilaplane FM0425 manufactured by Chisso Corporation) and HDI, respectively. (Isocyanate has an equivalent ratio of 1.07 to active hydrogen in the silicone), 1
The reaction was carried out at 00 ° C with stirring. The reaction was followed by IR spectrum, and the reaction was continued until the absorption intensity attributed to the isocyanate of 2200 to 2300 cm ^-1 became half of that at the start of the reaction to produce a silicone having an isocyanate group at the terminal.

Next, 2.3 parts by weight of sodium isethionate (active hydrogen in the compound has an equivalent ratio of 1.03 with respect to isocyanate groups in silicone) and 50 parts by weight of 1,4-dioxane are added. The reaction was continued until the absorption of isocyanate disappeared. After the reaction is completed, the product is filtered, and then the low-boiling substance is removed by distillation to obtain a colorless transparent oil 120.
Got gram. This oil has an IR spectrum
It was confirmed to be a sulfonic acid-modified silicone represented by Chemical formula 8.

[0045]

[Chemical 8] However, m is 130 and p is 1.

[0046]

[Production Example 2] In a 500 ml round bottom flask, a silicone 15 having a hydroxyl group at one end as in Production Example 1 was used.
Contains 0 part by weight and 3.95 parts by weight of MDI (isocyanate has an equivalent ratio of 1. to active hydrogen in the silicone).
The reaction was carried out at 80 ° C. with stirring. The reaction was followed by IR spectrum in the same manner as in Production Example 1 to produce a silicone having an isocyanate group at the terminal, and then 2.34 parts by weight of sodium isethionate (active hydrogen in the compound was based on the isocyanate group in the silicone). The equivalent ratio is 1.05), and 100 parts by weight of 1,4-dioxane are added and reacted until the absorption of isocyanate disappears.

After completion of the reaction, filtration was carried out, and then low-boiling substances were removed by distillation to obtain 100 g of a pale yellow oil. It was confirmed by IR spectrum that this oil was a sulfonic acid-modified silicone represented by Chemical formula 9.

[0048]

[Chemical 9] However, m is 130 and p is 1.

[0049]

Production Example 3 In a 500 ml round bottom flask, a silicone having a structure represented by the chemical formula (4) in chemical formula 6 and having a hydroxyl group at one end and an average molecular weight of 5,000 (X-22 manufactured by Shin-Etsu Chemical Co., Ltd.) -170D) 100 parts by weight and MDI 5.3
6 parts by weight (isocyanate has an equivalent ratio of 1.07 to active hydrogen in the silicone) were reacted at 80 ° C. with stirring.

The reaction was followed by IR spectrum in the same manner as in Production Example 1 to produce a silicone having an isocyanate group at the terminal, and then 4.95 parts by weight of sodium sulfaniate (active hydrogen in the compound was the isocyanate in the silicone). 100 parts by weight of 1,4-dioxane were added and reacted until the absorption of isocyanate disappeared. After the reaction was completed, the reaction mixture was filtered, and low-boiling substances were subsequently removed by distillation to obtain a light yellow oil 100.
Got gram.

The IR spectrum of this oil is
It was confirmed to be a sulfonic acid-modified silicone represented by 0.

[0052]

[Chemical 10] However, m is 60 and p is 1.

[0053]

[Production Example 4] Silicone 100 having a hydroxyl group at one end as in Production Example 1 was placed in a 500 ml round bottom flask.
Part by weight and 7.5 parts by weight of PMDI (a mixture of n = 1 to 5) are contained (isocyanate has an equivalent ratio of 1.0 to active hydrogen in the silicone), and reacted at 70 ° C. with stirring. It was

The reaction was followed by IR spectroscopy, 220
After the intensity of the absorption attributed to the isocyanate 0~2300cm ^{over 1} ends the reaction continued until no change has preparing isocyanates of silicone, 6.5 part by weight of sodium isethionate (active hydrogen in the compound Equivalent ratio to isocyanate group in silicone is 1.05
30 parts by weight of 1,4-dioxane and reacted until the absorption of isocyanate disappeared.

After the reaction was completed, the reaction mixture was filtered, and then low-boiling substances were removed by distillation to obtain 90 g of a pale yellow viscous oil. It was confirmed by IR spectrum that this oil was a sulfonic acid-modified silicone represented by Chemical formula 11.

[0056]

[Chemical 11] However, m is 130 and p is 2 or more and 10 or less.

[0057]

Production Example 5 50 g of the sulfonic acid-modified silicone produced in Production Example 1 was dissolved in 50 ml of hexane, and 1N HCl was added.
The mixture was reacted with 50 ml of an aqueous solution at room temperature for 20 minutes while stirring. After the reaction, the silicone phase was taken out, 1 g of triethanolamine was added, and the mixture was reacted for 30 minutes while stirring,
The unreacted portion was distilled off to obtain 47 g of a milky white oil.

This oil was a triatanolamine salt of a sulfonic acid-modified silicone represented by Chemical formula 12.

[0059]

[Chemical 12]

Next, examples using the sulfonic acid-modified silicone obtained in these production examples will be described.

[0061]

Examples 1 to 4 Hair Oil <Production Method> Each silicone compound shown in Table 1 was used, and Table 2 was used.
Hair oil of the formula Each silicone compound, ethyl alcohol, and fragrance are added to decamethylcyclopentasiloxane, and dissolved by stirring or dispersed by stirring.

[0062]

[Table 1]

[0063]

[Table 2]

<Evaluation> The hair oil of each of the above Examples and Comparative Examples was applied to a hair bundle, and after washing, the amount adsorbed to hair and the effect of imparting smoothness were evaluated.

(1) Measurement of Adsorption Amount on Hair A hair bundle having a length of 12 cm and a weight of about 2 g was washed with a 35% aqueous solution of sodium polyoxyethylene lauryl ether sulfate (LES),
After drying at 40 ℃ for 1 day, leave at 20 ℃ and 50% humidity for 1 day. After that, the weight of the hair bundle is measured and used as the weight (W ₀ ) before the treatment. After this hair bundle is immersed in 50 g of the hair oil of the above Examples and Comparative Examples for 1 hour, excess hair oil attached to the hair bundle is lightly wiped with a towel and dried at 40 ° C. for 1 day. Then the above LE
Wash 3 times with S aqueous solution while passing through comb, dry again at 40 ° C for 1 day, leave at 20 ° C, 50% humidity for 1 day, and measure the weight (W ₁ ) after treatment. From W ₀ and W ₁ , the amount of each silicone compound adsorbed on the hair was determined by the following formula.

Adsorption amount = (W ₁ −W ₀ ) × 100 / W ₀ −A _B1 where A _B1 represents the rate of change in weight when hair oil is not used.

(2) Measurement of Adsorption Amount on Hair Hair bundles treated in the same manner as above are further washed 3 times with a LES aqueous solution (total of 6 washing treatments), and dried at 40 ° C. for 1 day.
Then, leave it at 20 ° C and 50% humidity for 1 day,
Measure (W ₂ ). The adsorption amount of various silicone derivatives on hair was determined from W ₀ and W ₂ by the following formula.

Adsorption amount = (W ₂ −W ₀ ) × 100 / W ₀ −A _B2 where A _B2 represents the rate of change in weight when hair oil is not used.

(3) Providing smoothness to hair The degree of smoothness of a hair bundle that has been treated in the same manner as the measurement of the amount adsorbed to the hair was sensory-evaluated into five levels by six skilled evaluators. . In addition, "smooth" was 5 points and "not smooth" was 1 point.

Table 3 shows the results of the above evaluations.

[0071]

[Table 3]

[0072]

Examples 5 to 7 Shampoo Using each silicone compound shown in Table 4, shampoo was prepared according to the formulation shown in Table 5. The components are mixed, heated to 80 ° C., and homogenized with stirring. Then, it is cooled to room temperature with stirring.

After washing the same hair bundle with these shampoos 3 times, further washing 3 times while passing through a comb with an LES 35% aqueous solution, and drying, the smoothness of the hair bundle and the luster were evaluated by 6 evaluators. The sensory evaluation was carried out in 5 steps. "Glossy" was given as 5 points and "Glossy" was given as 1 point. The results are shown in Table 4.
Shown in.

[0074]

[Table 4]

[0075]

[Table 5]

[0076]

Examples 8 to 10 Hair rinses Using the silicone compounds shown in Table 6, hair rinses having the formulations shown in Table 7 were produced. Phases A and B are each dissolved by heating at 80 ° C., phase B is added to phase A with stirring, and then cooled to room temperature with stirring.

After applying a certain amount of this rinse to the same bundle of hair as described above, rinsing with tap water was repeated 3 times, and then LES3
The product was washed three times while being combed with a 5% aqueous solution, dried, and then subjected to a sensory evaluation of smoothness and gloss on a scale of 5 by 6 assessors. The results are shown in Table 6.

[0078]

[Table 6]

[0079]

[Table 7]

[0080]

[Examples 11 to 13] Foam-shaped hair styling agent A silicone-based compound shown in Table 8 was used to produce a foam-shaped hair styling agent having the formulation shown in the cover sheet 9. 80 ° C for A phase and B phase
It is dissolved by heating with, and phase B is added to phase A with stirring, then cooled to room temperature with stirring, and phase C is further added. This emulsion is filled in an aerosol can, and LPG is further filled.

A fixed amount of this foam-shaped hair styling material was applied to a hair bundle similar to that described above, dried and then washed 3 times with a LES 35% aqueous solution.
After drying, the smoothness and gloss of the hair bundle were evaluated by 6 evaluators.
Sensory evaluation was performed at the stage. The results are shown in Table 9.

[0082]

[Table 8]

[0083]

[Table 9]

From the evaluation results of the above-mentioned respective execution rows, the hair cosmetic composition of the present invention is smoother than the hair cosmetic composition of Comparative Example,
It is clear that it is remarkably excellent in imparting luster and remaining on the hair. In particular, it is not lost from the hair after multiple washes with a surfactant.

[0085]

EFFECTS OF THE INVENTION The hair cosmetic composition of the present invention has an excellent effect of imparting smoothness and luster to hair, has high adsorptivity to hair, and is hard to be removed by washing or rubbing.

Claims (1)

[Claims] 1. A hair cosmetic containing the sulfonic acid-modified silicone represented by Chemical formula 1. [Chemical 1] However, each R ₁ independently represents a lower alkyl group or an unsubstituted or substituted phenyl group, R ₂ represents a hydrocarbon residue having a valence of ₂ to 11, and its carbon-carbon single bond is a residue generated by reaction of a functional group. May be interrupted by a group, A is a residue formed by the reaction of an isocyanate group and a functional group having active hydrogen, R ₃ is an arylene group, a linear or branched alkylene group, an alkali-alkylene group or an aralkylene group. Group, X represents a monovalent metal, a hydrogen atom or —H · X ₁ (where X ₁ represents ammonia or an amine), m represents an integer of 50 to 200, and p represents 1 Indicates an integer of -10.