JP2000016921A - Emulsion type hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject cosmetic causing no stickiness of the hair after finished, affording the hair with favorable luster and trimness, and good in preservability as well by including a specific thickening copolymer, an alkaline substance and a silicone derivative. SOLUTION: This hair cosmetic is obtained by including (A) a copolymer thickening in the presence of an alkaline substance, afforded by aqueous emulsion copolymerization of a monomer system composed of (i) 1-25 wt.% of a methylenesuccinic ester monomer of formula I [(a) is 1-150; (b) is 0-50; R is a 5-30C alkoxy, alkylphenoxy or sorbitan fatty acid ester of formula II ((c), (d), (e) and (f) are each an integer, totaling 0-100; R1 is H or the like)], (ii) 5-70 wt.% of a copolymerizable α,β-ethylenically unsaturated carboxylic acid monomer of formula III [R3 is H; R4 is a 1-4C alkyl or the like] and (iii) 10-90 wt.% of a nonionic copolymerizable α,β-ethylenically unsaturated monomer of the formula CH2=CYZ (Y is H; Z is CN or the like), (B) an alkaline substance, and (C) a silicone derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsified hair cosmetic composition which has no stickiness, gives luster, has good cohesion, and has good storage stability after finishing.

[0002]

2. Description of the Related Art Hair gels, hair creams, hair foams, set lotions and the like are used as hair cosmetics. These hair cosmetics are generally formulated by solubilizing, dispersing, or emulsifying an oil agent or a polymer compound. Among them, silicone oil is excellent in glossiness and non-stickiness, and is widely used.

However, it is difficult to uniformly emulsify silicone oil due to its properties, and there is a problem in long-term storage stability such as separation over time. Further, if a large amount of a surfactant is blended in order to ensure long-term storage stability, it may cause a sticky feeling to the finish. Accordingly, there has been a demand for an emulsified hair cosmetic composition which solves these problems and has no stickiness, gives gloss, is well united, and has good storage stability after finishing.

[0004]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies, and as a result, have found that an emulsified hair cosmetic containing a specific thickening copolymer, an alkaline substance, and a silicone derivative has been described above. Have been found to solve the above problem, and have completed the present invention.

That is, the present invention provides (i) a compound represented by the general formula (A):

[0006]

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Wherein a is an integer from 1 to 150;
Is an integer of 0 to 50, and R is alkoxy having 5 to 30 carbon atoms, alkylphenoxy, dialkylphenoxy, alkylcarbonyloxy or

[0008]

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(Wherein c, d, e and f are each an integer, the sum of the integers is 0 to 100, and R ₁ is H or C
OR ₂ where R ₂ is alkyl, alkylphenyl or dialkylphenyl having 5 to 30 carbon atoms. Sorbitan fatty acid ester). At least one kind of methylene succinate monomer 1 to 25
% By weight (hereinafter abbreviated as%) and the general formula (B):

[0010]

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(Wherein R ₃ is H, R ₄ is H, and has 1 to 1 carbon atoms)
An alkyl group of 4 or —CH ₂ COOX, or R ₃ is —COOX and R ₄ is H. X is H or an alkyl group having 1 to 4 carbon atoms. ) Copolymerizable α and β
- ethylenically unsaturated carboxylic acid monomer 5% to 70% and, the general formula _{(C): CH 2 = CYZ} ( wherein, Y is H, Z is CN, Cl, -COO
R _5, or _{-C 6 H 4 R 5, -OCOR} 6, or a -CONH ₂ or -CH = CH _2, or Y and Z are Cl, or Y is CH _3, Z is CN, -CONH
_{2, -CH = CH 2, -C} 6 H 4 R 5 or -COOR ₇
In and, R ₅ is H, Cl, Br or alkyl of 1 to 4 carbon atoms, R ₇ is a hydroxy alkyl alkyl or 2 to 8 carbon atoms having 1 to 12 carbon atoms, R ₆ is C 1 -C
~ 8 alkyl. ) At least one nonionic, copolymerizable α, β-ethylenically unsaturated monomer 1
A copolymer obtained by aqueous emulsion copolymerization of a monomer system containing 0 to 90% and, in some cases, 1% or less of a copolymerizable polyethylene unsaturated crosslinkable monomer, A copolymer which is made water-soluble by adding a substance and thickens an aqueous system in which the copolymer is present, (ii) an alkaline substance, and (iii) a silicone derivative. It is a characteristic emulsified hair cosmetic.

Further, the copolymer is composed of 5 to 15% of the monomer represented by (A), R ₃ is H in (B), and R _{4 is}
Is an alkyl group having 1 to 4 carbon atoms.
25 to 50% of an ethylenically unsaturated carboxylic acid monomer,
In (C), Y is H and Z is —COOR ₈ [wherein, R ₈ represents an alkyl group having 1 to 4 carbon atoms. And a nonionic copolymerizable α, β-ethylenically unsaturated carboxylic acid monomer of 30 to 70%, which is obtained by aqueous emulsion copolymerization of a monomer system. Emulsified hair cosmetics.

[0013]

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

The thickening copolymer used in the present invention is disclosed in US Pat. No. 4,616,074, and basically comprises three kinds of monomers, namely, (A): methylene succinic acid. Ester monomer, (B): α, β-ethylenically unsaturated carboxylic acid monomer, (C): nonionic α, β
-It can be easily produced by further adding an ethylenically unsaturated monomer and, in some cases, (D): a polyethylenically unsaturated crosslinkable monomer and emulsion-copolymerizing.
When (D) is additionally used, the content is preferably 0.0001 to 1%. The average molecular weight of the thickening copolymer is 100,000-
5,000,000. The proportion of each monomer can be varied within a certain range.

The (A) methylene succinate monomer used in the thickening copolymer is an ethylenically unsaturated copolymerizable monomer obtained by condensing a nonionic surfactant with methylene succinic acid. It is a body surfactant and is produced from an alcohol or the like and methylene succinic acid by a usual acid-catalyzed esterification reaction. Nonionic surfactants that can be esterified with methylene succinic acid include polyoxyethylene (2
0) Stearyl ether, polyoxyethylene (30)
Polyoxyethylene alcohols such as lauryl ether; ethoxylated alkylphenols such as polyoxyethylene (3) nonylphenol and polyoxyethylene (8) dinonylphenol; polyoxyethylene (8) stearate; polyoxyethylene (40) stearate Fatty acid esters such as sorbitan monooleate and sorbitan monostearate; polyoxyethylene (20)
And polyoxyethylene sorbitan fatty acid esters such as sorbitan monolaurate. The methylene succinate monomer accounts for 1 to 25%, preferably 5 to 15%, of the thickening copolymer.

(B) used in the thickening copolymer: α,
Examples of β-ethylenically unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, monobasic acids such as acyloxypropionic acid, maleic acid, fumaric acid, dibasic acids such as itaconic acid or the like. Monoester and the like. The α, β-ethylenically unsaturated carboxylic acid monomer accounts for 5 to 70% of the thickening copolymer, preferably 25 to 5%.
0%. Acrylic acid and methacrylic acid are particularly preferred.

(C) used in the thickening copolymer: Examples of the nonionic α, β-ethylenically unsaturated monomer include acrylic acid such as methyl acrylate, 2-ethylhexyl acrylate and butyl methacrylate; Examples include methacrylic acid alkyl esters or hydroxyalkyl esters, styrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylonitrile, vinyl caproate, and the like. The nonionic α, β-ethylenically unsaturated monomer accounts for 10 to 90% of the thickening copolymer, preferably 30 to 90%.
70%. Preferred monomers are the esters of acrylic and methacrylic acid, alone or in mixtures with styrene, acrylonitrile or vinyl acetate.

Optionally used for thickening copolymers,
(D): Examples of the polyethylene-based unsaturated crosslinking monomer include diallyl phthalate, vinyl crotonate, allyl methacrylate, divinylbenzene, N, N′-methylenebisacrylamide, ethylene glycol diacrylate,
Examples include ethylene glycol dimethacrylate and 1,6-hexanediol diacrylate. The content of the polyethylene unsaturated monomer is 1% or less in the thickening copolymer.

The compounding amount of the thickening copolymer is preferably 0.01 to 5.0 as a pure component with respect to the total amount of the emulsified hair cosmetic.
0%, and more preferably 0.1 to 3.0%.
If it is less than 0.01%, the storage stability may deteriorate,
If it exceeds 5.0%, the viscosity may be too high and the usability may be deteriorated.

The alkaline substance used in the present invention includes, for example, alkanolamines such as triethanolamine, monoethanolamine, diisopropanolamine and triisopropanolamine, ammonia, potassium hydroxide, sodium hydroxide and 2-amino-2. -Methyl-1-propanol, 2-amino-2-methyl-1-propanediol, basic amino acids (lysine, arginine and the like), basic polypeptides and the like. The above alkaline substances can be used alone or in combination of two or more.

The alkaline substance is blended to make the thickening copolymer water-soluble and to adjust the pH of the hair cosmetic to a range of 3 to 10. The compounding amount is appropriately adjusted depending on the composition of the thickening copolymer and the compounding amount in the hair cosmetic.
If the pH is less than 3 or more than 10, it may not be desirable in terms of safety.

The silicone derivatives used in the present invention include, for example, those shown below. In the following chemical formula, both the block copolymer and the random copolymer are shown.

[0023] Dimethylpolysiloxane represented by the general formula (1)

[0024]

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(In the formula, g represents an integer of 3 to 20,000.)

[0026] Methylphenylpolysiloxane represented by general formulas (2) to (5)

[0027]

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[0028]

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[0029]

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[0030]

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(Where h is an integer of 1 to 20,000, j +
k is an integer of 1 to 500, l is an integer of 1 to 20,000, m
+ N represents an integer of 1 to 500. )

[0032] Epoxy-modified silicone represented by the general formula (6)

[0033]

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Wherein p is 1 to 500 (preferably 1 to 500)
250) and q each represent an integer of 1 to 50 (preferably 1 to 30), and R ₉ represents an alkylene group having 1 to 3 carbon atoms. ]

[0035] Fluorine-modified silicone represented by the general formula (7)

[0036]

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[Wherein r is 1 to 400 (preferably 1 to 400)
250). ]

[0038] Alcohol-modified silicone represented by the general formula (8) or (9)

[0039]

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[0040]

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Wherein s and t are 1 to 500, respectively.
(Preferably 1 to 200), and R ₁₀ is _Cu H
_2u (u represents a number from 0 to 4). ]

[0042] Alkyl-modified silicone represented by general formula (10) or (11)

[0043]

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[0044]

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Wherein v and w are 1 to 500, respectively.
(Preferably 1 to 200), R ₁₁ represents an alkyl group having 2 to 18 carbon atoms, and R ₁₂ represents C _x H _2x (x
Represents an integer of 0 to 4. ) And R ₁₃ is a carbon atom 10
Represents up to 16 alkyl groups. ]

[0046] Alkoxy-modified silicone represented by the general formula (12)

[0047]

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[In the formula, R ₁₄ represents a methyl group or a phenyl group, and R ₁₅ has 1 to 28 carbon atoms (preferably 12 to 2 carbon atoms)
2) represents an alkyl group, y represents an integer of 0 to 6,
Represents an integer of 1 to 3000, and a ′ and b ′ are a ′ +
An integer satisfying b ′ = 1 to 500 is shown. ]

[0049] Amino-modified silicone represented by formula (13) or (14)

[0050]

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[0051]

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[Wherein, R ₁₆ represents a methyl group or a hydroxy group, R ₁₇ represents a hydrogen atom or a methyl group, R ₁₈ represents a group represented by the following formula (15) or (16); ₁₉ represents a hydroxy group, hydroxyalkyl group, oxyalkylene group or polyoxyalkylene group, and c ′, d ′ and e ′ represent integers depending on the molecular weight. ]

[0053]

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[0054]

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[Wherein, R ₂₀ represents a divalent hydrocarbon group;
R ₂₁ represents a group —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH
_{2 -, - OCH 2 CH (} OH) CH 2 -, or -OCH
₂ CH (CH ₂ OH) - indicates, R ₂₂ and R ₂₃ represents a hydrogen atom or a monovalent hydrocarbon group, f 'and g' are each an integer of Less than six, W ^- is a halogen ion or Shows organic anions. ]

[0056] Polyether-modified silicone represented by general formulas (17) to (21)

[0057]

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[Wherein R ₂₄ represents a hydrogen atom or a carbon atom 1 to
Represents 12 alkyl groups, h 'is 1 to 100 (preferably 3 to 30), j' is 1 to 50 (preferably 1 to 3)
0) and k 'each represent an integer of 1 to 50 (preferably 3 to 30), and l' represents an integer of 0 to 50 (preferably 0 to 30). However, the sum of h ′ and j ′ is an integer of 15 or more,
The sum of k ′ and l ′ is an integer of 5 or more. ]

[0059]

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[0060]

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[0061]

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Wherein R ₂₅ is — (CH ₂ ) ₃ —O— (C
_{2 H 4 O) p '-} (C 3 H 6 O) q' -A (A is a hydrogen atom or a carbon atom 1-12 alkyl group, p 'and q' integers of 0 to 50 And p ′ + q ′ ≧ 1
It is. ), M ′ represents an integer of 1 to 2000,
n 'represents an integer of 1 to 1000. ]

[0063]

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(Wherein r ′ represents an integer of 1 to 1000, s ′ represents an integer of 1 to 100, and t ′ and u ′ each represent an integer of 0 to 1000).

These silicone derivatives can be used alone or in combination of two or more.

The compounding amount of the silicone derivative is 0.1.
It is preferably from 0.5 to 20%, particularly preferably from 0.1 to 10%. If the amount is less than 0.05%, the luster may be insufficient. If the amount is more than 20%, shampooing may be unfavorably deteriorated.

The hair cosmetic composition of the present invention may contain, in addition to the above essential components, alcohols, oily substances, surfactants, propellants, preservatives, chelating agents, as long as the effects of the present invention are not impaired. It is also possible to add an antioxidant, an ultraviolet absorber, a pH adjuster, a dye, a fragrance and the like.

[0068]

The present invention will be described below with reference to examples and comparative examples. The present invention is not limited by these.

The thickening copolymers used in Examples and Comparative Examples were (A) polyoxyethylene methylene succinate (20) stearyl ester 10%, (B) acrylic acid 40%, and (C) ethyl acrylate 50%. And its pure content (solid content) is 30%. The average molecular weight is about 1,000,000.

The sensory test and the test method of storage stability shown in Examples and Comparative Examples are as follows. In addition, the compounding quantity of the composition shown in the following tables is each shown by weight%. Hereinafter, the viscosity-increasing copolymer is shown in terms of pure components.

Sensory test Hair styling was performed by 20 subjects using hair cosmetic samples. After that, the subject himself was not sticky,
Sensory evaluation was performed on the gloss and the unity. The evaluation criteria are as follows.

◎: Very good 18 or more subjects who answered good ○: Good 12 or more but less than 18 subjects who answered good △: Somewhat bad The number of subjects who answered good was 8 No less than 12 ×: Poor Less than 8 subjects answered good

Storage stability A hair cosmetic sample was stored in a thermostat at 40 ° C. for 6 months and observed. The evaluation criteria are as follows. ：: no change ×: change such as separation is observed.

Examples 1 to 5 and Comparative Examples 1 to 4 Hair cosmetics having the formulations shown in Table 1 were prepared by a conventional method, and the above tests were carried out. The results are shown in Table 1.

[0075]

[Table 1]

As is clear from Table 1, all the hair cosmetics of the examples using the components of the present invention had excellent performance.

On the other hand, Comparative Examples lacking any of the essential components are inferior in terms of non-stickiness, gloss, cohesion, and storage stability (emulsion stability), and can achieve the object of the present invention. Did not.

Example 6 (Hair Cream) A hair cream having the following composition was prepared by a conventional method.

Thickening Copolymer 2.0 Diisopropanolamine 2.0 Dimethylpolysiloxane 1.0 Silicon KF-96H (1,000,000 cs) Polyvinylpyrrolidone (K-90; ISP) 1.0 Poly, manufactured by Shin-Etsu Chemical Co., Ltd. Oxyethylene oleyl ether (2EO) 0.2 Ethanol 5.0 Purified water Remainder

The composition of Example 6 had no stickiness, imparted excellent luster to hair, had good cohesion, and had excellent emulsion stability.

[0081]

As described above, according to the present invention, there is provided an emulsified hair cosmetic composition which has no stickiness to the finished hair, imparts luster, has good cohesion, and has good storage stability. it can.

Claims (3)

[Claims] (I) General formula (A): Wherein a is an integer of 1 to 150, b is an integer of 0 to 50, and R is an alkoxy, alkylphenoxy, dialkylphenoxy, alkylcarbonyloxy or alkylcarbonyloxy having 5 to 30 carbon atoms. 2] (Wherein c, d, e and f are each an integer, the sum of the integers is 0 to 100, R ₁ is H or COR ₂ , and R ₂ is an alkyl having 5 to 30 carbon atoms. , Alkylphenyl or dialkylphenyl)). And 1 to 25% by weight of at least one methylene succinic acid ester monomer represented by the general formula (B): (Wherein R ₃ is H, R ₄ is H, an alkyl group having 1 to 4 carbon atoms or —CH ₂ COOX, or R ₃ is —C
OOX, R ₄ is H. X is H or an alkyl group having 1 to 4 carbon atoms. 5) to 70% by weight of a copolymerizable α, β-ethylenically unsaturated carboxylic acid monomer of the formula (C): CH ₂ ＣCYZ (where Y is H, Z is CN, Cl, -COO
R _5, or _{-C 6 H 4 R 5, -OCOR} 6, or a -CONH ₂ or -CH = CH _2, or Y and Z are Cl, or Y is CH _3, Z is CN, -CONH
_{2, -CH = CH 2, -C} 6 H 4 R 5 or -COOR ₇
In and, R ₅ is H, Cl, Br or alkyl of 1 to 4 carbon atoms, R ₇ is a hydroxy alkyl alkyl or 2 to 8 carbon atoms having 1 to 12 carbon atoms, R ₆ is C 1 -C
~ 8 alkyl. ) At least one nonionic, copolymerizable α, β-ethylenically unsaturated monomer 1
0 to 90% by weight, is a copolymer obtained by aqueous emulsion copolymerization of a monomer system, which becomes water-soluble by the addition of an alkaline substance and thickens the aqueous system in which the copolymer is present. An emulsified hair cosmetic comprising: a copolymer characterized by the following: (ii) an alkaline substance; and (iii) a silicone derivative. 2. The copolymer (A), (B) or (C)
Further, (D): a copolymer obtained from aqueous emulsion copolymerization of a monomer system containing 0.0001 to 1% by weight of a copolymerizable polyethylene-based unsaturated crosslinking monomer. An emulsified hair cosmetic according to the above. 3. A copolymer comprising the monomer 5 represented by (A)
And 15% by weight, R ₃ is H in (B), R ₄
Is an alkyl group having 1 to 4 carbon atoms.
25 to 50% by weight of ethylenically unsaturated carboxylic acid monomer
And in (C), Y is H and Z is -COOR
_{8 wherein} R ₈ represents an alkyl group having 1 to 4 carbon atoms, and 30 to 70% by weight of a nonionic copolymerizable α, β-ethylenically unsaturated carboxylic acid monomer. ,
The emulsified hair cosmetic according to claim 1 or 2, which is a copolymer obtained by aqueous emulsion copolymerization of a contained monomer system.