JP2002255756A - Hair-setting agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair-setting agent composition having no tackiness in spite of having hair dressing power, light finish excellent smooth feeling, gloss combing properties, capable of maintaining a hair style for many hours. SOLUTION: This hair-setting agent composition comprises (A) 0.01-10 wt.% of a vinyl alcohol/vinylamine-based copolymer composed of a specific structure, (B) a powder component and (C) an inorganic acid and/or an organic acid, and has pH 4-9 of system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hair setting composition. More specifically, despite having an excellent hair-styling effect, there is no stickiness and a light finish,
The present invention relates to a hair setting composition which has a smooth feeling, is glossy, has good combability, and can maintain a hairstyle for a long time.

[0002]

2. Description of the Prior Art Conventionally, as a hair setting agent, a film-forming polymer compound dissolved in water, a lower alcohol or a mixed solvent thereof has been widely used. Film-forming polymer compounds have the effect of fixing hair and holding the set, but those that have been used in the past have caused stickiness in the process of being applied to the hair and dried. However, there was a disadvantage that the hairstyle was crushed. In order to eliminate such disadvantages, attempts have been made to improve the usability by adding cosmetic oils, surfactants, alcohols, etc. to the film-forming polymer compound. A hair setting agent having both holding power and feeling of use was not obtained.

[0003] In recent years, hair treatment agents (JP-B-2-44446, JP-B-3-14805) in which an amphoteric polymer and a cationic polymer are blended, and an amphoteric polymer compound and an anionic polymer are blended. Hair treatment agent (3-2)
No. 1524). However, these treatment agents are also insufficient in terms of the feeling of use such as tackiness in the process from application to drying and smoothness and the like, and also have a problem that the hairstyle is destroyed with time. Yes, not fully satisfactory.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object the problem that the hair has an excellent adhesion to each other, and that the formed film is rich in elasticity and does not stick, and is smooth and has good combability. An object of the present invention is to provide a hair setting agent composition which is excellent in imparting gloss, is non-sticky in a process from application to drying, and can maintain a hairstyle for a long time, and is easily cursed.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific vinyl alcohol / vinylamine copolymer and a powder are used in combination and a specific vinyl alcohol / vinylamine copolymer is used. It has been found that by setting the pH in the pH range, a hair setting composition having both excellent set holding power and good feel can be obtained, and the present invention has been completed.

That is, the present invention relates to (A) the following formula (I)

[0007]

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Where m: n: x: y = 0 to 15:50
0.01 to 10% by weight of a vinyl alcohol / vinylamine copolymer having a structural unit represented by the following formula (B): C) A hair setting composition containing an inorganic acid and / or an organic acid, wherein the pH of the system is 4 to 9.

Here, the amount of component (B) is 0.01 to 1
It is preferably 0% by weight.

[0010] The present invention also provides an aerosol-type hair setting composition using a solution containing the above-mentioned hair setting composition as a stock solution for aerosol.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The vinyl alcohol / vinylamine copolymer as the component (A) used in the present invention has the following formula (I)

[0013]

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Has a structural unit represented by

In the above formula (I), m is the following formula (I-1) occupying the above copolymer.

[0016]

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The value is such that the proportion of the structural unit represented by the formula is 0 to 15 mol%, preferably 0 to 5 mol%.

N is the following formula (I-
2)

[0019]

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The value is such that the proportion of the structural unit represented by the formula is 50 to 99 mol%, preferably 55 to 95 mol%.

X represents the following formula (I-
3)

[0022]

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The ratio of the structural unit represented by the formula is 0 to 40 mol%, preferably 0.5 to 35 mol%.

Y is the following formula (I-
Four)

[0025]

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The value is such that the proportion of the structural unit represented by is 1 to 50 mol%, preferably 1 to 35 mol%.

The component (A) is represented by the formulas (I-1) and (I-
2) A copolymer in which the structural units represented by (I-3) and (I-4) are linearly arranged. The mode of such copolymerization is arbitrary, and random copolymers and block copolymers can be used. It includes any copolymer such as a polymer. In the present invention, a random copolymer is preferred.

The molecular weight of the component (A) is preferably about 60,000 to 150,000, particularly about 80,000 to 120,000. If the molecular weight is too small, the set holding power tends to be weak, while
If the molecular weight is too large, the solubility tends to deteriorate, which is not preferable.

The component (A) may be used alone or in combination of two or more. The compounding amount is sufficient for a good feeling such as set holding power and non-stickiness which are the objects of the present invention. As a result of examining a range in which the film of the copolymer is not peeled off and powdered), it was found that 0.1% of the total amount of the composition of the present invention.
0.01 to 10% by weight, preferably 0.5 to 5% by weight
It is. If the amount is too small, the effect as a hair setting agent cannot be obtained, while if the amount is too large, flaking occurs.

The method for producing the component (A) is not particularly limited. For example, the component (A) can be produced by the following steps (i) to (vii) as shown in Japanese Patent Publication No. 6-51741. However, the present invention is not limited to this manufacturing method.

(I) A vinyl acetate monomer and N
-Continuous supply of vinylformamide monomer.

(Ii) A vinyl acetate monomer and N-vinylformamide are copolymerized, and poly (vinyl acetate) -co-poly (N-vinylformamide) [PVA
c / PNVF].

(Iii) The reaction mixture containing PVAc / PNVF is continuously taken out of the reaction vessel.

(Iv) In a medium of methanol, PVAc /
Hydrolysis of the acetate function of PNVF produces a vinyl alcohol copolymer as a gel swollen with methanol and methyl acetate.

(V) grinding the gel to obtain a granular copolymer product, optionally rinsing with methanol and washing.

(Vi) Poly (vinyl alcohol) -co-poly (vinylamine) [PVOH / PVAm] particles are obtained by hydrolyzing the copolymer particles in a mixture of isopropyl alcohol and water with an acid or a base in the form of a slurry. Get.

(Vii) The particulate PVOH / PVAm is washed with methanol to remove soluble salts and by-products, and the solvent is removed from the copolymer product, especially by vacuum or hot stripping.

Through the above-mentioned production step, a copolymer having the structural unit represented by the above formula (I), that is, a copolymer containing vinyl alcohol and vinylamine and optionally containing vinyl acetate and / or vinylformamide Is obtained.

The powder component (B) used in the present invention is not particularly limited as long as it can be generally used in cosmetics. For example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, phlogopite, biotite, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, silicate Calcium, magnesium silicate, calcium carbonate, strontium silicate,
Inorganic powders such as silica, zeolite, fluorapatite, hydroxyapatite, ceramic powder, and boron nitride; polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene-acrylic acid copolymer powder, Organic powders such as benzoguanamine resin powder, polytetrafluoroethylene powder, and cellulose powder; titanium oxide coated mica,
Pearl pigments such as titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil; red 201, red 202, orange 203, orange 204
Organic pigments such as No. 205, Yellow No. 205 and Blue No. 404;
Natural pigments such as chlorophyll and β-caroline; inorganic polymer powders such as bentonite, rabonite, and silicic anhydride; and the like, but are not limited thereto.

One or more types of the component (B) can be used, and the amount of the component (B) is in the total amount of the composition of the present invention from the viewpoint of eliminating stickiness of hands and improving combability. , 0.01 to 10% by weight, particularly 0.1 to 10% by weight.
5% by weight.

The inorganic acid and / or organic acid as the component (C) used in the present invention is used as a pH adjuster. Examples of the inorganic acid include hydrochloric acid, phosphoric acid and the like. Examples of the organic acid include lactic acid, citric acid, oxalic acid, nitric acid, boric acid and the like. These acids may be used in the form of a salt. Salts include hydrochlorides, metal salts (sodium salts,
Potassium salt), amine salt and the like.

One or more components (C) can be used, and are blended so that the pH of the whole system of the composition of the present invention is 4 to 9, preferably 5 to 8. Composition pH
If it is less than 4, the acidity is too strong, which affects the outer container such as corrosion and causes hair trouble due to denaturation of the hair protein in actual use. On the other hand, if the pH is higher than 9, the alkalinity is too strong, which again affects the outer container such as corrosion and causes hair troubles, which is not desirable.

The hair setting composition of the present invention may contain, in addition to the above essential constituents, a quantitative and qualitative range which does not impair the effects of the present invention depending on the purpose. Components that can be used may be blended. Such optional components include, for example, liquid paraffin, squalane, lanolin derivatives, higher alcohols, various ester oils, avocado oil, palm oil, silicone oil, high molecular silicone oil, polyalkylene glycol polyether and its carboxylic acid oligo. Oils such as ester compounds and terpene hydrocarbons; ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin,
Water-soluble polyhydric alcohols such as sorbitol and polyethylene glycol; humectants such as hyaluronic acid, chondroitin sulfate, and pyrrolidone carboxylate; ultraviolet absorbers; resins such as acrylic resins, silicone resins, and polyvinylpyrrolidone; soy protein, gelatin, Proteins such as collagen, silk fibroin and elastin or protein hydrolysates; preservatives such as ethylparaben and butylparaben;
Activators such as various amino acids, biotin and pantothenic acid derivatives; γ-oryzanol, dextran sodium sulfate,
Antiseborrheic agents such as vitamin E; diluents such as ethanol, isopropanol, and tetrachlorodifluoroethane; thickeners such as carboxyvinyl polymer, as well as drugs, flavors, coloring materials, and the like.

The dosage form of the hair setting composition of the present invention is arbitrary, and may be any of an emulsion system, a powder dispersion system, and a three-layer system of oil-water-powder.

The hair setting composition of the present invention comprises:
It is preferable to use a solution obtained by blending the components (A) to (C) in a solvent as a stock solution for aerosol, and use it together with an aerosol propellant as an aerosol-type hair setting agent.

The propellant for aerosol is not particularly limited as long as it can be used for aerosol cosmetics. For example, dichlorodifluoromethane, difluoromonochloroethane, monochlorodifluoromethane, dichlorotetrafluoroethane, tetrafluoroethane , Dimethyl ether (DME), propane, isobutane, n
-Butane, isopentane, liquefied petroleum gas (LPG; mainly composed of propane, isobutane, mn-butane), or mixtures thereof. One or more propellants for aerosol can be used.

The aerosol-type hair setting composition of the present invention is prepared by emulsifying (dispersing) the components (A) to (C) in a solvent together with other optional components such as a surfactant, if desired. It is obtained by adding a propellant. The propellant is usually filled into a known pressure-resistant container for aerosol by an ordinary method.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition, the compounding amount is weight% unless otherwise specified.

In each of the following examples, “vinyl alcohol / vinylamine copolymer” is referred to as
It is manufactured according to the method described in JP-A-17441, and has a composition represented by the above formula (I).

Example 1 Hair blow (combination component) (% by weight) (1) Decamethylcyclopentasiloxane 15.0 (2) High molecular weight polysiloxane (molecular weight 800,000) 3.0 (3) Polyoxyethylene curing Castor oil (60EO) 2.0 (4) 1,3-butylene glycol 2.0 (5) Vinyl alcohol / vinylamine copolymer 3.0 (in the general formula (I), m: n: x: y = 3: 63: 13: 21 (molar ratio); molecular weight 100,000) (6) ethanol 3.0 (7) spherical silica 1.5 (8) ion-exchanged water 70.4 (9) fragrance 0.1 (10) Lactic acid appropriate amount (adjusted to pH 6.5) (Preparation method) Dissolve (2) in (1) and add (3), (4),
After emulsifying by adding a part of (8), this is added to (5) to
It was mixed with (7), the rest of (8), (9) and (10).

Example 2 Misty aerosol cosmetic for hair (combination component) (% by weight) (1) Decamethylcyclopentasiloxane 0.4 (2) Propylene glycol 0.3 (3) Polyoxyethylene-cured castor Oil (60EO) 0.03 (4) Vinyl alcohol / vinylamine copolymer 1.0 (in the general formula (I), m: n: x: y = 0: 61: 7: 32 (molar ratio); molecular weight (150,000) (5) Ethanol 12.0 (6) Cellulose powder 1.0 (7) Deionized water 45.17 (8) Fragrance 0.1 (9) Lactic acid Suitable amount (adjusted to pH 6.5) (10) Dimethyl ether ( (Propellant) 40.0 (Production method) After dissolving (3) in (2) and adding a part of (1) and (7) to the mixture and emulsifying the same, this was added to (4) to (6), ( The remainder of 7) was mixed with (8) and (9) to obtain a stock solution for aerosol. This stock solution was put in an aerosol container, and after filling the valve, (10) was filled.

Example 3 Hair Cream (Blend Component) (% by Weight) (1) Decamethylcyclohexasiloxane 25.0 (2) Di-2-ethylhexyl succinate 6.0 (3) Polyoxyethylene hydrogenated castor oil (40EO) 2.0 (4) Propylene glycol 3.0 (5) Vinyl alcohol / vinylamine copolymer 0.1 (in the general formula (I), m: n: x: y = 5: 58: 32: 5 (molar ratio); molecular weight 80,000) (6) carboxyvinyl polymer 0.6 (7) kaolin 1.5 (8) ethanol 10.0 (9) ion-exchanged water 51.75 (10) perfume 0.05 ( 11) Citric acid suitable amount (adjusted to pH 7.5) (Production method) Dissolve (2) in (1), and add (3), (4),
After emulsifying by adding a part of (9), this is added to (5) to
It was mixed with (8), the remainder of (9), (10) and (11).

Comparative Example 1 Hair blow (combination component) (% by weight) (1) Decamethylcyclopentasiloxane 15.0 (2) High molecular weight polysiloxane (molecular weight 800,000) 3.0 (3) Polyoxyethylene curing Castor oil (60EO) 2.0 (4) 1,3-butylene glycol 2.0 (5) N-methacryloylethyl-N, N-dimethylammonium α-N-methylcarboxybetaine alkyl methacrylate copolymer liquid 10. 0 (actual 3.0) ("SM Polymer"; manufactured by Mitsubishi Chemical Corporation) (6) Ethanol 3.0 (7) Deionized water 64.9 (8) Fragrance 0.1 (9) Lactic acid (Adjusted to pH 6.5) (Production method) Dissolve (2) in (1) and add (3), (4),
After emulsifying by adding a part of (7), this is added to (5),
It was mixed with (6), the remainder of (7), (8) and (9).

Comparative Example 2 Misty aerosol cosmetic for hair (combination component) (% by weight) (1) Decamethylcyclopentasiloxane 0.4 (2) Propylene glycol 0.3 (3) Polyoxyethylene-cured castor Oil (60EO) 0.03 (4) Vinylpyrrolidone / vinyl acetate copolymer 3.0 (“PVP / VA · S-630”; manufactured by ISP) (5) Ethanol 12.0 (6) Ion-exchanged water 45 .17 (7) Fragrance 0.1 (8) Lactic acid appropriate amount (adjusted to pH 6.5) (9) Dimethyl ether (propellant) 40.0 (Production method) Dissolve (3) in (2) and (1) , (6) was added and emulsified, and then mixed with (4), (5), and the remainder of (6), (7) and (8) to obtain a stock solution for aerosol. This stock solution was put into an aerosol container, and after filling the valve, (9) was filled.

Comparative Example 3 Hair cream (combination component) (% by weight) (1) Decamethylcyclohexasiloxane 25.0 (2) Di-2-ethylhexyl succinate 6.0 (3) Polyoxyethylene hydrogenated castor oil (40EO) 2.0 (4) Propylene glycol 3.0 (5) Vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymer 0.1 ("Stylase CC-10"; manufactured by ISP) (6) Methylcellulose 5.0 (7) Ethanol 0.5 (8) Deionized water 58.3 (9) Fragrance 0.1 (10) Citric acid Appropriate amount (adjusted to pH 8.0) (Production method) Dissolve (2) in (1) (3), (4),
After emulsifying by adding a part of (8), this is added to (5) to
It was mixed with (7), the rest of (8), (9) and (10).

Comparative Example 4 Atomized Aerosol Cosmetic for Hair (Blend Component) (% by Weight) (1) Decamethylcyclopentasiloxane 0.4 (2) Propylene Glycol 0.3 (3) Polyoxyethylene Cured Castor Oil (60EO) 0.03 (4) Vinyl alcohol / vinylamine-based copolymer 3.0 (in the general formula (I), m: n: x: y = 0: 61: 7: 32 (molar ratio); molecular weight (150,000) (5) Ethanol 12.0 (6) Deionized water 45.17 (7) Fragrance 0.1 (8) Lactic acid Appropriate amount (adjusted to pH 6.5) (9) Dimethyl ether (propellant) 40.0 (Production method) (3) is dissolved in (2), and a part of (1) and (6) is added and emulsified, and then emulsified, and the remainder of (4), (5) and (6) is added to (7) , (8) to give a stock solution for aerosol. This stock solution was put into an aerosol container, and after filling the valve, (9) was filled.

Comparative Example 5 Misty aerosol cosmetic for hair (combination component) (% by weight) (1) Decamethylcyclopentasiloxane 0.4 (2) Propylene glycol 0.3 (3) Polyoxyethylene-cured castor Oil (60EO) 0.03 (4) Vinyl alcohol / vinylamine copolymer 0.005 (in the general formula (I), m: n: x: y = 0: 61: 7: 32 (molar ratio); molecular weight (150,000) (5) Ethanol 12.0 (6) Deionized water 42.165 (7) Cellulose powder 5.0 (8) Fragrance 0.1 (9) Lactic acid Appropriate amount (adjusted to pH 6.5) (10) Dimethyl ether ( (Propellant) 40.0 (Production method) After dissolving (3) in (2), adding a part of (1) and (6) and emulsifying it, and then emulsifying it, (4), (5), (5) The remaining part of 6) was mixed with (7) to (9) to obtain a stock solution for aerosol. This stock solution was put in an aerosol container, and after filling the valve, (10) was filled.

Using the hair setting compositions of Examples 1 to 3 and Comparative Examples 1 to 5 as samples, the following test methods were used to determine the stickiness of hands, ease of combing, smoothness, gloss of hair, and set holding power. The evaluation was based on evaluation criteria. Table 1 shows the results.

[Tackiness of Hands] Using a panel (30 persons), 1 g of a sample was placed on the palm of the hand, rubbed with the hand for 30 seconds, and the stickiness of the hand was subjected to a sensory evaluation according to the following criteria to comprehensively evaluate the results. (Evaluation criteria) ○: Not sticky at all △: Slightly sticky ×: Slightly sticky

[Ease of combing] Hair strand (4 g)
2 g of a sample was applied thereto, the shape was adjusted with a comb, and immediately after and 6 hours later, the ease of combing was organoleptically evaluated. (Evaluation criteria) ○: Good combability △: Slightly caught ×: Caught

[Smoothness] 2 g of a sample was applied to a hair strand (4 g), the shape was adjusted with a comb, and immediately and after 6 hours, the smoothness of the hair strand was organoleptically evaluated. (Evaluation criteria) ○: Smooth △: Smooth ×: Not smooth

[Gloss of Hair] A 2 g sample was applied to a hair strand (4 g), the shape was adjusted with a comb, and immediately after and 6 hours later, the gloss of the hair strand was sensory evaluated. (Evaluation criteria) ○: Glossy △: Glossy ×: Glossy

[Set holding power] A hair bundle having a length of 25 cm and a weight of 2 g was wetted with water, 0.5 g of a sample was applied, and the diameter was 15 m.
m and air-dried. After drying, remove the curled hair bundle from the rod, and place it in a thermo-hygrostat (28
(C, 90% humidity) for 3 hours, and the length of the curl was measured. The set holding force was calculated from the following formula based on the curl length (L ₁ ) of the hair bundle immediately after being removed from the rod and the curl length (L ₂ ) of the hair bundle after standing for 3 hours.

[0064]

[Formula 1] Set holding force = ｛(25−L ₂ ) / (25−
L ₁ )｝ × 100 (%) (Evaluation criteria) ○: Set holding force 67 to 100% △: Set holding force 34 to 66% ×: Set holding force 0 to 33%

[0065]

[Table 1]

In Table 1, the evaluation of “set holding power” of Examples 1 to 3 “○ ^(*) ” indicates that the length of the curl after leaving the hair bundle from the rod for 6 hours was (L ₂ )
The evaluation calculated by the following is shown.

As is clear from the results in Table 1, Example 1
Each of ~ 3 is non-sticky, easy to comb,
It is excellent in smoothness and gloss of hair, and has extremely excellent set holding power. On the other hand, none of Comparative Examples 1 to 5 exhibited all the effects of the present invention.

[0068]

As described in detail above, according to the present invention, the hair is provided with a rich luster, has excellent set holding power, and has a smooth feel and excellent feel when wet and dry. Provided is a hair cosmetic composition which has a non-sticky feeling in spite of having a hair styling property and can maintain a style for a long time.

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Claims (3)

[Claims] (A) The following formula (I): (Where m: n: x: y = 0 to 15:50 to 99: 0)
A vinyl alcohol / vinylamine copolymer having a structural unit represented by the following formula: (B: 40: 1 to 50 (molar ratio)): 0.01 to 10% by weight; (B) a powder component; And / or an organic acid.
A hair setting composition, wherein H is 4 to 9. 2. The hair setting composition according to claim 1, wherein the amount of component (B) is 0.01 to 10% by weight. 3. An aerosol-type hair setting composition using a solution containing the hair setting composition according to claim 1 or 2 as a stock solution for aerosol.