JP2000143449A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair cosmetic which is stable even in the coexistence of a water-compatible soluble solvent, having a good touch, having a good finger-combing property, when coated, giving excellent flexibility to hair when wetted, and giving a non-tacky dry touch to the hair in a drying process. SOLUTION: This hair cosmetic contains (A) a copolymer which has cationic groups and cross-linked structures in the molecule and whose 0.5 wt.% hydrogel has relations: 0.3<=η1<=20 (Pa.sec), 0. 01<=η2<=5 (Pa.sec), and η1>η2 wherein η1 is a viscosity at a shear rate of 1 sec-1 at 25 deg.C; η2 is a viscosity at a shear rate of 10 sec-1 at 25 deg.C, and (B) a water-compatible soluble solvent.

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 is stable even in a water-miscible solvent-compounded system and has excellent feeling in use.

[0002]

2. Description of the Related Art Conventionally, various hair cosmetics containing a general-purpose cationic polymer such as cationized cellulose have been used to improve the feel of hair. However, these have a problem that the fingers are poor at the time of application and the stickiness in the drying process from wet is remarkable.

In order to improve the stability and feeling of use of hair cosmetics, thickeners such as crosslinked polyacrylic acid and carrageenan are used. However, there is a problem that these thickeners cannot exhibit a sufficient thickening effect in the presence of a water-compatible solvent such as ethanol. Furthermore, when a water-insoluble component such as dimethylpolysiloxane is blended in order to improve the feel during drying, it is extremely difficult to stably disperse the component.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a stable and excellent feeling in use even in the presence of a water-compatible solvent, good fingering during coating, and a dry feeling without stickiness in the drying process. To provide a hair cosmetic that can be used.

[0005]

According to the present invention, there is provided a copolymer having the following components (A) and (B): 25% by weight hydrogel
° C, shear rate 1 sec ^-1 viscosity η ₁ , shear rate 1
The viscosity η _{2 at} ⁰ sec ⁻¹ is 0.3 ≦ η ₁ ≦ 20 (Pa · se
c), 0.01 ≦ η ₂ ≦ 5 (Pa · sec), and η ₁ > η ₂
(Hereinafter referred to as copolymer (A)) and (B) a hair cosmetic containing a water-compatible solvent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer (A) used in the present invention is such that, for the above η ₁ and η ₂ , 0.3 ≦ η ₁ ≦ 2
0 (Pa · sec), 0.01 ≦ η ₂ ≦ 5 (Pa · sec), and η ₁ > η ₂ . When the viscosity behavior is within this range, application to the hair is easy, a feeling of remaining on the hair is obtained, and the above-mentioned good feeling of use can be obtained. In particular, when the copolymer (A) is 0.4 ≦ η ₁ ≦ 10 (Pa · sec), 0.5
When ≦ η ₂ ≦ 3 (Pa · sec), a more favorable feeling in use is obtained.

Further, the copolymer (A) has a content of 2.0
Weight% ethanol gel, 25 ℃, shear rate 1sec
The viscosity of ^-1 eta _3, viscosity eta ₄ of shear rate 10 sec ^-1,
0.3 ≦ η ₃ ≦ 20 (Pa · sec), 0.01 ≦ η ₄ ≦ 5
When (Pa · sec) and η ₃ > η _4, it is possible to obtain a hair cosmetic which has an excellent feel and can maintain the feel even when ethanol is used in combination.

A 0.5% by weight hydrogel of the copolymer (A) has a complex elastic modulus ε _{1 at} 25 ° C., a strain frequency of 6.28 rad / sec, a strain of 1%, a loss tangent tan δ ₁ , and a strain of 5 at a strain of 1%.
The complex elastic modulus ε ₂ and the loss tangent tan δ ₂ at 00% are 1 ≦
ε ₁ ≦ 300 (N / m ² ), tan δ ₁ ≦ 2, and 0.
When 01 ≦ ε ₂ ≦ 30 (N / m ² ) and tan δ ₂ ≧ 1, a hair cosmetic with a more favorable feel can be obtained. Here, the loss tangent of the copolymer (A) is tan δ ₁ ≦
As the tan δ ₁ ≦ 1.0, it is possible to obtain a hair cosmetic with a more favorable feel.

The measurement of η _{1 to} η ₄ is performed by the following method.
The measurement method is the same for both samples 1 and 2. Specimen 1; a 0.5% by weight hydrogel prepared by adding a powder sample (average particle size of 50 μm or less) to ion-exchanged water and holding at 50 ° C. for half a day. Specimen 2; 2.0% by weight ethanol gel prepared in the same manner as above using ethanol instead of water. Measuring device: Viscometer manufactured by HAAKE, Rotovisco RV-20, Measuring conditions: M10 measuring head, coaxial double cylindrical rotor, measuring temperature 25 ° C., sample volume 15 ml, shear rate: ⁰ sec ⁻¹ to 15 sec in 2 minutes ⁻ Increased to ¹ , Number of measurement points; Measured 60 points over the above share rate range. Calculation method: Calculated from the above measured values using the Rotation Version 2.8 program.

The measurement of δ ₁ , δ ₂ , ε ₁ , ε ₂ is performed by the following method. Sample: Same as Sample 1 above. Measuring device; Fluids Spectrometer RFS-II, manufactured by Rheometrics Co., Ltd. Measurement conditions: Dynamic Strain Sweep (dynamic strain sweep) mode Cone plate: diameter 50 mm, gap 0.05 mm, angle 0. 04 rad, strain frequency 6.2 rad / sec, strain 0.5-500%. Measurement temperature: 25 ° C.

The copolymer (A) having such rheological properties includes, for example, at least one kind of a vinyl monomer having a cationic group (hereinafter referred to as monomer (a ₁ )) and a compound represented by the general formula (1): ) Or (2)

[0012]

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Wherein R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ are the same or different and each represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms; Show. ]

[0014]

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[Wherein, R ¹ has the same meaning as described above;
¹ and A ² may be the same or different and have the formula — (CH ₂ ) _n —
6 represents an integer of 6), and B represents -O- or -CH
_2- represents a group. And a crosslinkable vinyl monomer having two or more vinyl groups in the molecule (hereinafter, referred to as monomer (a ₂ )). Hereinafter, a cationic group-containing copolymer (hereinafter, referred to as a copolymer (A ₁ )) obtained by subjecting at least one of the monomers (a ₃ )) to an essential constituent monomer and performing radical polymerization is exemplified. Can be

Among the monomers constituting the copolymer (A ₁ ), the monomer (a ₁ ) includes (meth) acrylic esters or (meth) acrylamides having a dialkylamino group, and (meth) acrylamides. Acroylalkyltrialkyl4
Quaternary ammonium salts, styrenes having a dialkylamino group, vinylpyridines, N-vinyl heterocyclic compounds, acid-neutralized or quaternary ammonium salts of monomers having an amino group, diallyl-type quaternary ammonium salts, etc. No.

Of these monomers (a ₁ ), compounds represented by the general formula (3) or (4) are preferred.

[0018]

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[Wherein R ¹ has the same meaning as described above;
⁴ and R ⁵ are the same or different and each represent an alkyl group or an alkenyl group having 1 to 4 carbon atoms, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y represents -O-, -NH-. , -CH _2-
Or _{-O-CH 2 CH (OH)} - represents a group, Z is 1 to 4 carbon atoms (provided that Y is -CH ₂ - when the number of 0-3 carbon) represents a linear or branched alkylene group And X represent a conjugate base of an acid, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. ]

[0020]

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Wherein R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a methyl group, and R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , X have the same meaning as described above. ]

Preferred acids used for obtaining the salt of the compound (3) or (4) include hydrochloric acid, sulfuric acid, acetic acid, citric acid, succinic acid, adipic acid and sulfamic acid, and quaternary ammonium salts. Preferred quaternizing agents to be obtained include alkyl halides such as methyl chloride and methyl iodide, diethyl sulfate, di-n-propyl sulfate and the like.

Preferred specific examples of the monomer (a ₁ ) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide as described in the above 4). Examples include quaternary ammonium salts quaternized with a grading agent, and dimethyldiallylammonium chloride.

As the monomer (a ₂ ), N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide,
N-n-propyl (meth) acrylamide, Nt-butylacrylamide, N- (meth) acryloylmorpholine and the like can be mentioned. Of these, the use feeling is preferable when N, N-disubstituted acrylamide is used, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like are particularly preferable.

As the monomer (a ₃ ), (meth) acrylates of polyhydric alcohols or unsaturated alcohols,
Acrylamide, divinyl compounds, polyallyl compounds and the like can be mentioned. Among these, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, allyl etherified pentaerythritol, vinyl (meth) acrylate, allyl (meth) acrylate, etc. Particularly preferred.

A preferred mixing ratio of the monomer (a ₁ ) and the monomer (a ₂ ) is 2/98 in a molar ratio of (a ₁ ) / (a ₂ ).
９８98/2, and more preferably 3 / 97-60 /
40. When the molar ratio is small, the thixotropic property is developed, and when the molar ratio is large, the viscosity retention at a low shear rate is facilitated, respectively.

The proportion of the monomer (a ₃ ) is preferably from 0.002 to 5% by weight, particularly preferably from 0.002% by weight to less than 0.1% by weight, based on the total amount of the monomer. When the ratio of the monomer (a ₃ ) is 0.002% by weight or more, the viscosity of the hydrogel formed from the copolymer (A ₁ ) is sufficient. The gel feels soft and slippery.

The copolymer (A ₁ ) contains at least one of the above-mentioned three types of vinyl monomers which are essential structural units,
Other vinyl monomers copolymerizable therewith can be used as constituents. Other vinyl monomers include, for example, (meth) acrylic acid derivatives such as methyl (meth) acrylate and ethyl (meth) acrylate; anionic group-containing monomers such as acrylic acid and methacrylic acid; N- (3 -Sulfopropyl) -N-acryloyloxyethyl-N, N
Betaines such as -dimethylammonium betaine and N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine.

The method for producing the copolymer (A ₁ ) is preferably an aqueous solution polymerization method, a reversed phase suspension polymerization method, a precipitation polymerization method, or the like. For example, when an aqueous solution polymerization method as described in JP-A-4-230250, page 12, column 22, lines 28-34 is used, the polymerization initiation temperature is 20-90 ° C., and the reaction time is 1-1.
It is preferably performed in about 0 hours.

As the polymerization initiator, JP-A-4-2302
No. 50, page 12, column 22, line 46 to page 13, page 23
An azobis compound as shown in column line 18 is used alone or in combination with a reducing agent.

The production of the copolymer (A ₁ ) by an aqueous solution polymerization method is described, for example, in JP-A-53-34101, page 3, upper right column, line 14 to lower right column, line 8; Is used.

One or more copolymers (A) can be used, and 0.005 to 20% by weight, especially 0.1 to 20% by weight in the total composition.
It is preferable to mix it in an amount of from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight, from the viewpoint of appearance and feel.

The water-miscible solvent of the component (B) used in the present invention is not particularly limited as long as it has a solubility in water at 20 ° C. of 5 or more. For example, lower alcohols, polyhydric alcohols and glycol ethers may be used. No. Examples of lower alcohols include ethanol, isopropanol, and the like;
For example, ethylene glycol, propylene glycol, isoprene glycol, hexylene glycol, 1,3-
Butylene glycol, diethylene glycol, dipropylene glycol, glycerin, pentaerythritol,
Sorbitol.

Examples of the glycol ether include ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monoethyl ether.

As the component (B), lower alcohols and polyhydric alcohols are preferable, and ethanol, propylene glycol and glycerin are particularly preferable.

One or more water-miscible solvents of component (B) can be used, and 0.1 to 99.9% by weight, especially 1 to 70% by weight, and further 3 to 50% by weight in the total composition. Mixing is preferred in terms of appearance and feel.

The hair cosmetic composition of the present invention contains, in addition to the above essential components, anionic surfactants, amphoteric surfactants, nonionic surfactants, cationic surfactants, anionic surfactants used in ordinary cosmetics. Polymer, nonionic polymer,
Cationic polymers, ethylene oxide / propylene oxide block copolymers, oils, powders, functional beads / capsules, silicones, metal chelators, antioxidants,
An ultraviolet absorber, a humectant, a fragrance, and the like can be appropriately compounded.

The hair cosmetic of the present invention can be produced according to a usual method. The dosage form is not particularly limited, and can be applied, for example, as a shampoo, a dry shampoo, a hair rinse, a conditioner, a hair treatment, a hair cream, a styling agent, a hair gel, a setting agent, a perm agent, a hair dye, etc. It is suitable as a hair cosmetic.

[0039]

EFFECT OF THE INVENTION The hair cosmetic composition of the present invention is stable and excellent in use feeling even in a water-miscible solvent compounding system, has good finger feel during application, and has softness, coat feeling and finger feeling when wet. Excellent, and in the drying process, there is no stickiness and a dry feeling can be obtained. Further, even when a water-insoluble component is blended, it can be stably dispersed for a long period of time.

[0040]

EXAMPLE Production Example 1 N, N-dimethylaminoethyl methacrylate diethyl sulfate (MOEDES: manufactured by Nitto Chemical Industry Co., Ltd.) was placed in a reaction vessel.
3.85 g, N, N-dimethylacrylamide 71.3
7g, polyethylene glycol dimethacrylate (NK-9
G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.0429 g, ion-exchanged water 3
A pre-nitrogen-substituted monomer aqueous solution consisting of 50 g is added,
Nitrogen was further blown in for 20 minutes, and the temperature was raised to 55 ° C. while replacing the inside of the reaction system with nitrogen. Next, the polymerization initiator (2,
0.22 g of 2'-azobis (2-amidinopropane) dihydrochloride) was added. After 30 minutes to 1 hour, it starts to polymerize,
The whole became a soft gel. Continue stirring as it is,
Four hours after the addition of the polymerization initiator, the polymerization was stopped. The mochi-like contents were taken out, washed by stirring in 5 liters of ethanol for 10 minutes, and dried. Thereafter, the mixture was pulverized with a coffee mill and a jet mill, and the pulverized particles were classified with a high volter to obtain a cationic group-containing copolymer No. 1. 1 was obtained.

Production Examples 2 to 14 In the same manner as in Production Example 1 except that the monomers shown in Table 1 were used, copolymer No. 1 containing a cationic group was used. 2-No. 14 were produced.

Test Example 1 For the cationic group-containing copolymer obtained in Production Examples 1 to 14, 0.5% by weight of hydrogel at 25 ° C.
And dynamic viscoelasticity were measured by the above method. Table 1 shows the results.

[0043]

[Table 1]

Example 1 A hair cosmetic composition having the composition shown in Table 2 was produced by a conventional method, and the resulting product was used (feeling during application and rinsing,
Softness during rinsing, stickiness during the drying process, dry feeling during drying) and stability were evaluated. The results are shown in Table 2.

(Evaluation method) (1) Feeling of use: After 10 g of each hair cosmetic was applied to hair by a panel of 10 persons and uniformly spread, the hair was rinsed with tap water and dried with a dryer. The sensory evaluation of the feeling during the process was performed according to the following criteria. The average point was determined, and 4.5 points or more were indicated as ◎, 4 points or more and less than 4.5 points as ○, 2.5 points or more and less than 4 points as Δ, and less than 2.5 points as ×.

(I) Finger passing at the time of coating and rinsing: 5; 4: Slip. 3: Normal. 2: Does not slip much. 1: No slip. (Ii) Softness during rinsing: 5; very soft. 4: soft. 3: Normal. 2: Not very soft. 1; not soft. (Iii) Stickiness in the drying process: 5; 4: Not very sticky. 3: Normal. 2: Somewhat sticky. 1; sticky. (Iv) Dry feeling upon drying: 5; very dry. 4; 3: Normal. 2: Do not rustle much. 1: Do not rustle.

(2) Stability: The condition when the hair cosmetic was stored at room temperature for one week to one month was visually judged according to the following criteria. A: Stable for one month or more. ；: Stable for 1 week or more (separated within 1 month). ×: separated within one week.

[0048]

[Table 2]

Examples 2 to 13 Hair cosmetic compositions having the compositions shown in Tables 3 and 4 were produced by a conventional method.

[0050]

[Table 3]

[0051]

[Table 4]

Each of the hair cosmetics obtained in Examples 2 to 13 was stable without being separated for more than one month even in the coexistence of a water-compatible solvent, was excellent in use feeling, and had good finger wiping when applied. In addition, the hair had excellent softness when wet, and had a dry feeling without stickiness in the drying process.
In addition, even when a water-insoluble component was blended, it could be stably dispersed for a long period of time.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoshi Onizuka 2-1-3 Bunka, Sumida-ku, Tokyo F-term in Kao Corporation Research Laboratory F-term (reference) 4C083 AB432 AC022 AC072 AC102 AC112 AC122 AC152 AC182 AC352 AC392 AC422 AC432 AC442 AC642 AC692 AC932 AD112 AD131 AD132 AD152 AD162 AD192 AD212 AD532 CC31 CC38 DD23 EE01 EE06

Claims (3)

[Claims] 1. The following components (A) and (B): (A) a copolymer having a cationic group and a crosslinked structure in a molecule, wherein 0.5% by weight of a hydrogel,
° C, shear rate 1 sec ^-1 viscosity η ₁ , shear rate 1
The viscosity η _{2 at} ⁰ sec ⁻¹ is 0.3 ≦ η ₁ ≦ 20 (Pa · se
c), 0.01 ≦ η ₂ ≦ 5 (Pa · sec), and η ₁ > η ₂
A hair cosmetic containing (B) a water-compatible solvent. 2. Component (A) is a 2.0% by weight ethanol gel having a viscosity η _{3 at} 25 ° C. and a shear rate of 1 sec ⁻¹ ,
The viscosity η _{4 at} a shear rate of 10 sec ⁻¹ is 0.3 ≦ ε ₃ ≦ 2
The hair cosmetic according to claim 1, wherein 0 (Pa · sec), 0.01 ≦ ε ₄ ≦ 5 (Pa · sec), and η ₃ > η ₄ . 3. The following components (A) and (B): (A) at least one kind of a cationic group-containing vinyl monomer, and a compound represented by the general formula (1) or (2): [Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms. [Chemical formula 2] [Wherein, R ¹ has the same meaning as described above, and A ¹ and A ² are the same or different and each represents a group represented by the formula-(CH ₂ ) _n- (n represents an integer of 2 to 6). And B represents an —O— or —CH ₂ — group. And at least one kind of a hydrophilic nonionic group-containing vinyl monomer represented by the formula and at least one kind of a crosslinkable vinyl monomer having two or more vinyl groups in a molecule. And a cationic group-containing copolymer obtained by radical polymerization, and (B) a hair cosmetic containing a water-compatible solvent.