JP2000355523A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair cosmetic free from stickiness to hair, imparting hair with soft feeling and excellent gloss and having good set retainability by including a specific composite polymer and a film-forming polymer compound. SOLUTION: The objective composition contains (A) preferably 0.05-15 wt.% composite polymer produced by reacting 100 pts.wt. of a polysiloxane having at least one each of amino group or ammonium group and a phenyl-containing group (e.g. a compound of the formula) with preferably 20-5,000 pts.wt. of an anionic polymer (e.g. alkyl acrylate/alkyl methacrylate/diacetone acrylamide/ methacrylic acid copolymer) or an amphoteric polymer and (B) preferably 0.05-15 wt.% polymer compound having film-forming property (e.g. methyl vinyl ether maleic acid butyl ester).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair cosmetic composition which imparts non-stickiness, a supple feel, excellent luster, and good set retention to hair.

[0002]

2. Description of the Related Art Conventionally, hair cosmetics have been used by solubilizing, emulsifying and dissolving oil components such as silicone oil, ester oil, and hydrocarbon oil for the purpose of giving a supple feel and excellent gloss to hair. I have. In particular, silicone oil is excellent in non-stickiness and has been widely used in recent years. However,
With oils represented by silicone oils, the ability to set hair is poor and insufficient.

[0003] In addition, polymer compounds having various film-forming abilities have been used in hair cosmetics for the purpose of setting hair. However, although the polymer compound having film forming ability is excellent in set retention, it has a drawback that it is stiff, has poor combability, has an uncomfortable feeling, and is sticky during drying and under high humidity. was there.

Further, hair cosmetics comprising a combination of an oil component such as silicone and a polymer compound (Japanese Patent Laid-Open No. 2-1171).
No. 1) has been proposed, but this gives a supple feel to the hair, but reduces the set retention, and is not satisfactory.

[0005]

That is, an object of the present invention is to provide a hair cosmetic which has no stickiness, has a supple feel, an excellent luster, and a good set retention. Is to do.

[0006]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and as a result, have found that a hair cosmetic containing a specific composite polymer and a polymer compound having a film-forming ability has been obtained. The inventors have found that the above-mentioned difficulties can be solved, and have completed the present invention.

That is, the first aspect of the present invention is to provide (A) a composite polymer obtained by reacting a polysiloxane having at least one amino group or ammonium group and at least one phenyl group-containing group with an anionic or amphoteric polymer. Molecules and
(B) A hair cosmetic comprising a polymer compound having a film-forming ability.

[0008] Further, the second invention provides a compound represented by the following general formula (1):

[0009]

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Wherein R ¹ independently represents an alkyl group having 1 to 18 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or a trimethylsiloxy group;
Q ¹ is the following formula: -R ³ X ｛R ³ is a direct bond or 2 carbon atoms
Represents 6 to 6 alkylene groups, and X is of the following formula:
_{^{(NR 4 R 5) e NR}} 4 2, - (NR 4 R 5) e N + R 4 3 A - and _{^{- (NR 4 R 5) e}} N (R 4) COR 6 (R 4 independently of one another are A hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents an alkylene group having 2 to 6 carbon atoms, R ⁶ represents an alkyl group having 1 to 4 carbon atoms,
A ^- is Cl ^-, Br ^-, I ^- or COO ^- represents, and e
Represents an integer from 0 to 6), represents a group represented by｝ representing a group selected from the group consisting of: Q ² represents a phenyl group-containing group, and R ² independently of each other R ¹ and Q Represents the same meaning as defined for ¹ or Q ² , and x, y and z are each an integer of 0 or more, and 0 ≦ x + y + z ≦ 20
Wherein, when y = 0, at least one of R ² is Q ¹ , and when z = 0, at least one of R ² is Q ² ]; A hair cosmetic comprising: a composite polymer obtained by reacting an anionic or amphoteric polymer; and (B) a polymer compound having a film-forming ability.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the configuration will be described below.

The composite polymer used in the present invention is disclosed in JP-A-10-298043 and JP-A-11-79958.
It is synthesized by the production method disclosed in Japanese Patent Application Publication No.

The polysiloxane having at least one amino group or ammonium group and at least one phenyl group-containing group used in the present invention has the general formula (1)

[0014]

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Wherein R ¹ independently represents an alkyl group having 1 to 18 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or a trimethylsiloxy group;
Q ¹ is the following formula: -R ³ X ｛R ³ is a direct bond or 2 carbon atoms
Represents 6 to 6 alkylene groups, and X is of the following formula:
_{^{(NR 4 R 5) e NR}} 4 2, - (NR 4 R 5) e N + R 4 3 A - and _{^{- (NR 4 R 5) e}} N (R 4) COR 6 (R 4 independently of one another are A hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents an alkylene group having 2 to 6 carbon atoms, R ⁶ represents an alkyl group having 1 to 4 carbon atoms,
A ^- is Cl ^-, Br ^-, I ^- or COO ^- represents, and e
Represents an integer from 0 to 6), represents a group represented by｝ representing a group selected from the group consisting of: Q ² represents a phenyl group-containing group, and R ² independently of each other R ¹ and Q Represents the same meaning as defined for ¹ or Q ² , and x, y and z are each an integer of 0 or more, and 0 ≦ x + y + z ≦ 20
00, provided that, when y = 0, at least one of R ² is Q ¹ , and when z = 0, at least one of R ² is Q ² ].

The group R ¹ in the above formula includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group,
Examples include a dodecyl group and a trimethylsiloxy group, preferably a methyl group or an ethyl group, and particularly preferably a methyl group or a trimethylsiloxy group [—OSi (C
H ₃ ) ₃ ]. Further, the groups R ₁ in the molecule may be the same or different.

The group Q in the above formula¹For example,
And the like. [-C_ThreeH₆NH_Two],
[-C_ThreeH₆N (CH_Three)_Two], [-C_ThreeH₆N⁺H_ThreeC
l^-], [-C _ThreeH₆N⁺H_ThreeCOO^-], [-C_ThreeH₆NHC
_TwoH_FourNH_Two], [-C_ThreeH₆N (CH_Three) C_TwoH_FourN (C
H_Three)_Two], [-C_ThreeH₆NHC_TwoH_FourN⁺H_ThreeCl^-], [-
C_ThreeH₆N (CH_Three) C_TwoH_FourN⁺(CH_Three)_ThreeCl^-], [-
C_ThreeH₆N (CH_Three) C_TwoH_FourN (CH_Three) COC_ThreeH₇]

The group Q ² in the above formula includes, for example, the following formula: —R ³ T (where R ³ has the same meaning as defined above, ie, a direct bond or an alkylene having 2 to 6 carbon atoms) Represents a group, especially an ethylene group, and T is a group represented by an unsubstituted or alkyl group, particularly a phenyl group substituted by a methyl group, and specifically, a phenyl group (hereinafter,- Ph)), a tolyl group [-
Ph (CH ₃ )], a xylyl group [—Ph (CH ₃ ) ₂ ],
Phenethyl group [-C ₂ H ₄ Ph], tolyl ethylene group [-
C ₂ H ₄ Ph (CH ₃ )]. In addition, the substituent on the phenyl ring can be bonded to any position. That is, when there is one substituent, it may be at the o, m- or p-position relative to a bond or a free bond to the group R ₃ , and when there are two substituents, they may be o, m It may be at the-or p-position, and may have any substituents even if it has more substituents.

The radicals R ² in the above formula independently of one another have the same meaning as defined for any of R ¹ , Q ¹ or Q ² above.

X, y and z in the above formula are integers within the above range. If the ratio is out of this range, the composite polymer which is a reaction product with the anionic or amphoteric polymer tends to gel, and it becomes difficult to prepare a stable hair cosmetic.

Examples of the polysiloxane having at least one amino group or ammonium group and at least one phenyl group-containing group used in the present invention include those represented by the following formulas (2) to (15). .

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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Examples of the anionic or amphoteric polymer used in the present invention include an acrylate / methacrylate copolymer (plus size, manufactured by Ryo Kagaku Co., Ltd.) and a vinyl acetate / crotonic acid copolymer (resin 28-
1310, manufactured by NSC), vinyl acetate / crotonic acid / vinyl neodecanoate copolymer (28-2930, NSC
), Methyl vinyl ether maleic acid half ester (Gantrez ES, ISP), t-butyl acrylate / ethyl acrylate / methacrylic acid copolymer (Rubimer, manufactured by BASF), vinyl pyrrolidone / vinyl acetate / vinyl propio Nate copolymer (Rubiscol VAP, manufactured by BASF), vinyl acetate / crotonic acid copolymer (Rubiset CA, manufactured by BASF),
Vinyl acetate / crotonic acid / vinyl pyrrolidone copolymer (Rubiset CAP, manufactured by BASF), vinyl pyrrolidone / acrylate copolymer (Rubiflex, BA
SF), acrylate / acrylamide copolymer (Ultrahold, BASF), vinyl acetate / butyl maleate / isobornyl acrylate copolymer (Advantage, ISP), octylamide acrylate / acrylic acid Anionic polymers such as ester copolymers (Dermacril 79, manufactured by NSC) and amphoteric polymers such as octylacrylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer (AMPHOMER, manufactured by NSC) can be used. And a carboxyl group-containing polymer is particularly preferable.

The composite polymer used in the present invention is obtained by reacting 20 to 5000 parts by weight of the above anionic or amphoteric polymer with 100 parts by weight of the above polysiloxane.

The composite polymer used in the present invention is:
It is preferable to use it after neutralization with an alkaline agent such as diisopropanolamine, triethanolamine, aminoethylpropanol, ammonia, sodium hydroxide, potassium hydroxide, or a basic amino acid.

The compounding amount of the composite polymer used in the present invention is 0.05 to 1 based on the total amount of the hair cosmetic.
It is preferably 5% by weight, more preferably 0.1 to 10% by weight. If the amount is less than 0.05% by weight, non-stickiness and combability may be insufficient. Further, when the amount is more than 15% by weight, washing off may be deteriorated during hair washing.

The polymer compound having a film-forming ability used in the present invention is preferably a water-soluble one, but is not limited thereto. For example, acrylic acid ester / methacrylic acid ester copolymer (plus size, manufactured by Yoyo Kagaku), vinyl acetate / crotonic acid copolymer (resin 28-1310, manufactured by NSC), vinyl acetate / crotonic acid / vinyl neodeca Nate copolymer (28-293)
0, manufactured by NSC), methyl vinyl ether maleic acid half ester (Gantrez ES, manufactured by ISP), t-
Butyl acrylate / ethyl acrylate / methacrylic acid copolymer (Rubimer, manufactured by BASF), vinyl pyrrolidone / vinyl acetate / vinyl propionate copolymer (Rubiscol VAP, manufactured by BASF), vinyl acetate / crotonic acid copolymer Merging (Rubi set CA, BASF
Co., Ltd.), vinyl acetate / crotonic acid / vinyl pyrrolidone copolymer (Rubiset CAP, manufactured by BASF), vinyl pyrrolidone / acrylate copolymer (Rubiflex, manufactured by BASF), acrylate / acrylamide copolymer (Ultrahold, Anions such as vinyl acetate / butyl maleate / isobornyl acrylate copolymer (Advantage, manufactured by ISP) and octylamide acrylate / acrylate copolymer (Damacryl 79, manufactured by NSC) Polymer, dialkylaminoethyl methacrylate acetic acid amphoteric acetic acid polymer (Yukaforma, manufactured by Mitsubishi Chemical Corporation), octylacrylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer (A
Amphoteric polymers such as MPHOMER, NSC), quaternized vinylpyrrolidone / dimethylaminoethyl methacrylate (GAFQUAT, ISP), methylvinylimidazolium chloride / vinylpyrrolidone copolymer (Rubicoat, BASF), etc. Cationic polymers such as polyvinylpyrrolidone (Rubiscol K, BAS
F), vinylpyrrolidone / vinyl acetate copolymer (Rubiscol VA, manufactured by BASF), vinylpyrrolidone /
Nonionic polymers such as dimethylaminoethyl methacrylate copolymer (Copolymer 937, manufactured by ISP) and vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (Copolymer VC713, manufactured by ISP). In addition, naturally occurring polymer compounds such as cellulose or derivatives thereof, keratin and collagen or derivatives thereof can also be suitably used.
The above polymer compounds can be used alone or in combination of two or more.

The amount of the polymer compound having a film-forming ability used in the present invention is preferably 0.05 to 15% by weight, more preferably 0.1 to 10% by weight. If the amount is less than 0.05% by weight, the set retention may be insufficient. Further, when the content is more than 15% by weight, stiffness may be felt and suppleness may be insufficient.

The hair cosmetic composition of the present invention may contain, in addition to the above essential components, alcohols, oily substances, silicones and derivatives thereof, surfactants, propellants, water, preservatives as long as the effects of the present invention are not impaired. Agents, chelating agents, antioxidants, ultraviolet absorbers, pH adjusters, pigments, fragrances, and the like can be added.

The hair cosmetic composition of the present invention can be in various forms such as aerosol form, liquid form, gel form, and the like.

[0044]

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

<Synthesis Method of Composite Polymers Used in Examples and Comparative Examples> Alkyl acrylate / alkyl methacrylate / diacetone acrylamide / methacrylic acid copolymer liquid (commercially available product plus size L-53) was used as an anionic polymer. (Manufactured by Ryogaku Kagaku Co., Ltd.) was put into 80 parts by weight of ethanol, and the mixture was stirred and dissolved at room temperature.
Next, a polysiloxane having at least one amino group or ammonium group and at least one phenyl group-containing group is represented by the following formula:

[0046]

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8 parts by weight of the polysiloxane represented by the formula (1) was added and mixed and stirred at room temperature. Further, the mixture was heated and refluxed at 80 ° C. for 3 hours while stirring under a nitrogen gas atmosphere, and then the solvent was discharged to adjust the solid content to 20% by weight to obtain a composite polymer.

The test methods of set retention and sensory test 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%.

(1) Set Retention Evaluation Test 0.5 g of a hair cosmetic sample was evenly applied to a hair bundle having a length of 15 cm and a weight of 1 g, and wound on a rod having a diameter of 2 cm.
It was left in a high-temperature room at 45 ° C. for 6 hours and completely dried. After drying, the rod was removed and the apparent length (L) of the hair bundle was measured. Next, the hair bundle was suspended in a thermo-hygrostat at a temperature of 25 ° C. and a humidity of 90%, taken out 30 minutes later, and the apparent length (L ₀ ) of the hair bundle was measured again.

The set retention was determined by the following equation.

Set retention (%) = [(15−L ₀ ) /
(15-L)] × 100 (The closer this value is to 100, the higher the set retention.)

The evaluation criteria are as follows.

◎: very good set retention of 80% or more ○: good set retention of 50% or more and less than 80% Δ: slightly poor set retention of 30% or more and less than 50% ×: poor set retention of less than 30%

(2) Sensory test Hair styling was performed on 20 subjects using hair cosmetic samples. Thereafter, the subject himself / herself carried out a sensory evaluation on non-stickiness, suppleness (no stiffness), and good gloss.

The evaluation criteria are as follows.

No stickiness ：: Very good The number of subjects who answered that there was no stickiness was 18 or more ○: The number of subjects who answered that there was no sticky was 12 or more and less than 18 △: Somewhat bad stickiness The number of subjects who answered that there was no response was 8 or more and less than 12 ×: Bad The number of subjects who answered that there was no stickiness was less than 8

Suppleness ：: Very good The number of subjects who answered that there was no stiffness was 18 or more ○: Good The number of subjects who answered that there was no stiffness was 12 or more and less than 18 △: Somewhat bad There was no stiffness 8 or more and less than 12 ×: Poor Less than 8 subjects with no stiffness

Good gloss ◎: Very good The number of subjects who answered that the gloss was good was 18 or more ○: Good The number of subjects who answered that the gloss was good was 12 or more and less than 18 △: Somewhat bad The number of subjects who answered good was 8 or more and less than 12 ×: Poor The number of subjects who answered good gloss was less than 8

Examples 1 to 5 and Comparative Examples 1 to 4 Aerosol compositions having the compositions shown in Table 1 were prepared by a conventional method, and the above-mentioned tests were carried out. The results are shown in Table 1.

[0060]

[Table 1]

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

On the other hand, the hair cosmetic composition of Comparative Example, which lacked any of the essential components, was inferior in terms of set retention, non-stickiness, supple feel and gloss, and could not achieve the object of the present invention. .

Example 6 (Gel Hair Cosmetic) A gel hair cosmetic having the following composition was prepared by a conventional method.

Ingredients Ingredients Amount-Composite polymer 2.0-Alkyl-modified carboxyvinyl polymer 0.5 (PEMULEN TR-1, manufactured by BF GOODRICH)-Tetrahydroxypropylethylenediamine 1.0-Polyvinylpyrrolidone / vinyl Acetate copolymer 2.0 (Ruviscol VA HM, manufactured by BASF) ・ Polyether-modified silicone 0.3 (Silwet FZ-2222, manufactured by Nippon Unicar) ・ Diglycerin 0.5 ・ Zinc paraphenolsulfonate 0・ 1 ・ Disodium edetate 0.05 ・ Remaining water with purified water as 100

Example 7 (Hair spray) A hair spray having the composition shown below was prepared by a conventional method.

Ingredients Ingredients Ingredients • Composite polymer 5.0 • Quaternized dialkylaminoethyl methacrylate 5.0 (Yukaformer 205, manufactured by Mitsubishi Chemical Corporation) • Triethyl citrate 0.2 • Aminomethylpropanol 0.3 • Liquefied petroleum gas 45.0 ・ Ethanol Remaining amount when total amount is 100

Example 8 (Hair lotion) A hair lotion having the following composition was prepared by a conventional method.

Ingredients Ingredients Ingredients • Composite polymer 3.0 • Polyquaternium-46 2.0 (Rubicut Hold, manufactured by BASF) • Hydroxyethylcellulose 0.3 (SP-400, manufactured by Daicel Chemical) • Lemon extraction Material 0.5 (Lemon Extra Liquid, manufactured by Ichimaru Falcos) ・ Methyl paraoxybenzoate 0.1 ・ Ethanol 20.0 ・ Purified water The remaining amount with the total amount being 100

Each of the compositions of Examples 6 to 8 provided hair with no stickiness, a supple feel, excellent gloss, and good set retention.

[0070]

As described above, the present invention is to provide a hair cosmetic which imparts no stickiness, a supple feel, excellent luster to hair, and good set retention. it can.

Claims (2)

[Claims] 1. A composite polymer obtained by reacting (A) a polysiloxane having at least one amino group or ammonium group and at least one phenyl group-containing group with an anionic or amphoteric polymer, and (B) a coating film A hair cosmetic comprising a polymer compound having a forming ability. 2. The composite polymer of (A) is represented by the general formula (1): Wherein R ¹ is independently of each other C ¹ -C 18
Represents an alkyl group, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or a trimethylsiloxy group, wherein Q ¹ represents the following formula:
-R ³ X {R ³ is a direct bond or C 2 -C represents a 6 alkylene group, and X is the formula :-( NR ⁴ R ⁵⁾ _{e
^{NR 4 2, - (NR 4}} R 5) e N + R 4 3 A - and - (NR
_{^{4 R 5) e N (R}} 4) COR 6 (R 4 represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4 independently of one another, R ⁵
Represents an alkylene group having 2 -C 6, R ⁶ represents an alkyl group of 1 to 4 carbon atoms, A ^- is C
l ^-, Br ^{-, I -} or COO ^- and represents, and e represents a group represented by 0 to represent a group selected from the group consisting of an integer of 6)}, Q ² is-containing phenyl group R ² independently of one another, has the same meaning as defined for R ¹ , Q ¹ or Q ² above, and x, y and z are each an integer of 0 or more, and 0 ≦ x + y + z ≦ 2000, provided that when y = 0, at least one of R ² is Q ¹ , and when z = 0, at least one of R ² is Q ²
The hair cosmetic according to claim 1, which is a composite polymer obtained by reacting a polysiloxane represented by the following formula with an anionic or amphoteric polymer.