JPH08119836A - Cosmetic composition for nail - Google Patents

Abstract

PURPOSE: To provide a nail cosmetic composition which can solve the problems on deterioration, split or breakage and dullness after coating because the nails can sufficiently breathe. CONSTITUTION: This composition comprises the coating film-forming components and the additive components. The coating film-forming components contains a fluorine-containing polymer prepared from at least one of fluorine-containing methacrylate or fluorine-containing acrylate and a fluorine-free block copolymer formed from fluorine-free vinyl monomers. This block copolymer is prepared by 2-step polymerization of fluorine-free vinyl monomers and fluorine-containing methacrylate or fluorine-containing acrylate using a polymer peroxide. This composition can prevent nails from yellowing due to the xanthoprotein reaction with nitrate ion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nail cosmetic composition to be applied to the fingernails for cosmetic purposes.

[0002]

2. Description of the Related Art This type of nail cosmetic composition comprises a film-forming component, a solvent component, a coloring component, an anti-settling component and the like. Of these, nitrocellulose is usually used as the film-forming component. It is most important that the nail cosmetic composition does not come off easily, but nitrocellulose imparts this property. The nitrocellulose also imparts coating strength and gloss.

As a solvent component, it facilitates brush coating,
Solvents with a low boiling point are used to dry quickly and give the nails an aesthetic appearance. As the coloring component, pigments, dyes, pearlescent agents and the like having a desired color tone are used.

[0004]

However, the nail itself breathes like human skin breathes, and the conventional nail cosmetic composition as described above uses nitrocellulose, which lacks air permeability. Therefore, the nails themselves cannot breathe sufficiently. Therefore, there are problems such as deterioration of nails, cracking of nails, and dullness of fingers after application. in addition,
There was a problem that the yellow color of the nail was caused by the xanthoprotein reaction due to nitrate ions derived from nitrocellulose.

The present invention has been made by paying attention to such a problem of the prior art. An object of the invention is to provide a nail cosmetic composition capable of sufficiently breathing the nail itself and eliminating deterioration of the nail, cracking of the nail, dullness of the finger after application, and the like. Another object of the present invention is to provide a nail cosmetic composition capable of preventing yellowing of the nail due to a xanthoprotein reaction caused by nitrate ions.

[0006]

In order to achieve the above object, the nail cosmetic composition of the present invention is a nail cosmetic composition comprising a film-forming component and an additive component,
The film-forming component is a block copolymer composed of a fluoropolymer portion formed of at least one fluorine-containing methacrylate or a fluorine-containing acrylate and a non-fluoropolymer portion formed of a non-fluorine vinyl type monomer. It is contained.

The present invention will be described in detail below. First, the block copolymer contained as a film forming component will be described. Examples of the fluorine-containing methacrylate or fluorine-containing acrylate that forms the fluorine-containing polymer portion of the block copolymer include monomers represented by the following chemical formulas 1 to 25.

[0008]

Embedded image CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂

[0009]

Embedded image CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ OCOC (C
H ₃ ) = CH ₂

[0010]

Embedded image CF ₃ CH ₂ OCOCH═CH ₂

[0011]

[Chemical 4]

[0012]

Embedded image

[0013]

[Chemical 6]

[0014]

Embedded image HCF ₂ CF ₂ OCH ₂ CH ₂ OCOCH═CH ₂

[0015]

Embedded image C ₈ F ₁₇ OCH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂

[0016]

[Chemical 9]

[0017]

Embedded image CF ₃ (CF ₂ ) ₄ OCH ₂ CH ₂ OCOC
(CH ₃ ) = CH ₂

[0018]

[Chemical 11]

[0019]

Embedded image H (CF ₂ ) ₈ CH ₂ OCOCH═CH ₂

[0020]

Embedded image H (CF ₂ ) ₄ CH ₂ OCOCH═CH ₂

[0021]

Embedded image H (CF ₂ ) ₆ CH ₂ OCOC (CH ₃ ) ═CH ₂

[0022]

Embedded image C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ OCOC
(CH ₃ ) = CH ₂

[0023]

Embedded image C ₂ F ₅ CON (C ₂ H ₅ ) CH ₂ OCOCH═CH ₂

[0024]

Embedded image CF ₃ (CF ₂ ) ₂ CON (CH ₃ ) CH (CH ₃ )
CH ₂ OCOCH = CH ₂

[0025]

Embedded image

[0026]

Embedded image CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH
₂ OCOC (CH ₃ ) = CH ₂

[0027]

Embedded image CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH
₂ OCOCH = CH ₂

[0028]

Embedded image C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OC
OCH = CH ₂

[0029]

Embedded image C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂
OCOC (CH ₃ ) = CH ₂

[0030]

Embedded image C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₄ OC
OCH = CH ₂

[0031]

Embedded image C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂
OCOC (CH ₃ ) = CH ₂

[0032]

Embedded image C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C
₂ H ₅ ) HCH ₂ OCOCH═CH ₂ Among these, a monomer having 10 or more fluorine atoms in one molecule is preferable because the higher the fluorine content, the better the oxygen permeability.

Next, as the non-fluorine vinyl type monomer forming the non-fluorine polymer portion, methyl acrylate or methyl methacrylate [hereinafter, acryl and methacryl are generically referred to as (meth) acryl). ], Ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth)
Isopropyl acrylate, glycidyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
2-Ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid ester such as -N, N-dimethylaminoethyl, (meth) acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid-3-chloro-2-hydroxypropyl ester (Meth) acrylic acid hydroxyester, (meth) acrylic acid triethylene glycol ester, (meth) acrylic acid dipropylene glycol ester such as (meth) acrylic acid polyethylene glycol or polypropylene glycol ester, styrene, B Rutoruen, aromatic vinyl type monomers such as α- methylstyrene, vinyl formate, vinyl acetate,
Carboxylic acid vinyl esters such as vinyl propionate and vinyl stearate, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, 2-acrylamide-2. Examples include amide group-containing vinyl monomers such as methylpropanesulfonic acid, (meth) acrylic acid, and itaconic acid.

Among these, (meth) acrylic acid ester, (meth) acrylic acid hydroxy ester, (meth) acrylic acid hydroxy ester, (meth) acrylic acid polyethylene glycol or polypropylene glycol ester, and carboxylic acid vinyl ester. , (Meta)
Acrylamide, N, N-dimethyl (meth) acrylamide and the like are preferable because they have good polymerizability and do not irritate the living body.

The block copolymer can be efficiently obtained by a usual bulk polymerization method, suspension polymerization method, solution polymerization method or emulsion polymerization method using polymer peroxide. For example, in the case of a solution polymerization method, a non-fluorine vinyl type monomer that forms a fluorine-free polymer portion is added to the second step in the second step.
A block copolymer can be easily obtained by using a fluorine-containing methacrylate or a fluorine-containing acrylate that forms a fluorine-containing polymer portion in the step and performing polymerization in two steps.

That is, first, in the first step, by using a polymer peroxide as a polymerization initiator and polymerizing a non-fluorine vinyl type monomer in a solution, a peroxide bond containing a peroxide bond is introduced into the chain. A polymer is obtained. Next, in the second step, when a fluorinated methacrylate or a fluorinated acrylate is added to the production solution of the first step and polymerization is carried out, the peroxide bond-containing polymer is cleaved at the peroxide bond, resulting in efficient block copolymerization. A coalescence is obtained.

In the above two-step polymerization,
Fluorine-containing methacrylate or fluorine-containing acrylate may be used in the first step, and non-fluorine vinyl type monomer may be used in the second step.

The polymer peroxide used in the first step is a compound having two or more peroxy bonds in one molecule and has, for example, a structure represented by the following general formulas (1) to (7). is there.

[0039]

-(COR ₁ CO ₂ R ₂ OCOR ₁ COOO) _n -... (1) In the formula, R ₁ is an alkylene group having 1 to 18 carbon atoms, or a substituted alkylene group, and 3 to 15 carbon atoms. A cycloalkylene group, a substituted cycloalkylene group, a phenylene group, or a substituted phenylene group, R ₂ has 2 to 1 carbon atoms
An alkylene group of 0, or a substituted alkylene group,

[0040]

Embedded image - _{[C (R 3) HCH 2 O} ) m R 4 - wherein, R ₃ is a hydrogen atom or a methyl group, R ₄ is alkylene or substituted alkylene group having 2 to 10 carbon atoms,
m = 1 to 13.

[0041]

[Chemical 28]

Or

[0043]

[Chemical 29]

Represents Also, n = 2 to 30.

[0045]

Embedded image - _{[COR 1 COOOC (CH 3) 2} R 5 C (CH 3) 2 OO) n - in (2) wherein, R ₁ is the same as R ₁ in the general formula (1) It is a base. R ₅ represents an ethylene group, a phenylene group, or an acetylene group. Also, n = 2 to 30.

[0046]

Embedded image (CH ₃ ) ₃ COO (COR ₁ COOO) _n C (CH ₃ ) ₃ (3) In the formula, R ₁ is the same group as R ₁ in the general formula (1). Also, n = 2 to 30.

[0047]

Embedded image - _{[COR 1 COOOC (CH 3) 2} CH 2 CH 2 - -C (CH 3) 2 OOCOR 1 COOO) n - ··· (4) wherein, R ₁ is the general formula (1) It is the same group as R ₁ in the above. Also, n = 2 to 30.

[0048]

-(COR ₁ COOO) _n -... (5) In the formula, R ₁ is the same group as R ₁ in the general formula (1). Also, n = 2 to 30.

[0049]

Embedded image

(6) In the formula, X represents a hydrogen atom, a methyl group, or a chlorine atom. Also, n = 2 to 30.

[0051]

Embedded image - _{[C (R 6) 2 R 5} C (R 6) 2 OOCONHR 1 NHCO- - (OCH 2 CR 7 H) P OCONHR 1 NHCOOO) n - ··· (7) In the formula, R ₁ Is the same group as R ₁ in the general formula (1). R ₅ is the same group as R ₅ in the general formula (2).
R ₆ and R ₇ represent a hydrogen atom or a methyl group. Also, n =
2-30 and p = 1-100.

Specific examples of the polymer peroxide represented by the general formula (1) include those represented by the following chemical formulas 36 to 51. In any equation, n
= 2 to 30.

[0053]

Embedded image

[0054]

Embedded image

[0055]

[Chemical 38]

[0056]

[Chemical Formula 39]

[0057]

[Chemical 40]

[0058]

Embedded image

[0059]

Embedded image

[0060]

[Chemical 43]

[0061]

[Chemical 44]

[0062]

Embedded image

[0063]

Embedded image

[0064]

[Chemical 47]

[0065]

Embedded image

[0066]

[Chemical 49]

[0067]

Embedded image

[0068]

[Chemical 51]

Of these, the decomposition temperature is too low,
Polymer peroxides represented by the general formulas 36 to 45, 48, and 51, which do not cause excessively high temperatures or are difficult to manufacture, are suitable.

Further, specific examples of the polymer peroxide represented by the general formula (2) include the compounds shown in the following chemical formulas 52 to 63. In both formulas, n = 2 to 30.

[0071]

Embedded image

[0072]

Embedded image

[0073]

[Chemical 54]

[0074]

[Chemical 55]

[0075]

[Chemical 56]

[0076]

[Chemical 57]

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

[Chemical formula 61]

[0081]

Embedded image

[0082]

[Chemical formula 63]

Of these, the polymer peroxides represented by the general formulas 52, 53, 56, 61 and 62 are preferable for the same reason as above. Further, specific examples of the polymer peroxide represented by the general formula (3) include the compounds represented by the following chemical formulas 64 to 69. In both formulas, n = 2 to 30.

[0084]

[Chemical 64]

[0085]

Embedded image

[0086]

[Chemical formula 66]

[0087]

Embedded image

[0088]

[Chemical 68]

[0089]

[Chemical 69]

Among these, the general formula 64 is used for the above reason.
Polymer peroxides represented by ~ 66 are preferred. Further, specific examples of the polymer peroxide represented by the general formula (4) include the compounds represented by the following chemical formulas 70 to 75. In any equation, n
= 2 to 30.

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

[Chemical 74]

[0096]

[Chemical 75]

Of these, the general formula 70
Polymer peroxides represented by ~ 72 are preferred. In addition, specific examples of the polymer peroxide represented by the general formula (5) include compounds represented by the following chemical formulas 76 to 83. In either formula,
n = 2-30.

[0098]

[Chemical 76]

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

[Chemical 81]

[0104]

[Chemical formula 82]

[0105]

[Chemical 83]

Of these, the general formula 76
Polymer peroxides represented by are preferred. Further, specific examples of the polymer peroxide represented by the general formula (6) include the compounds represented by the following Chemical formulas 84 to 86, which are preferably used. In both formulas, n = 2 to 30.

[0107]

[Chemical 84]

[0108]

Embedded image

[0109]

[Chemical 86]

Further, specific examples of the polymer peroxide represented by the above general formula (7) are shown below.
The compound shown in Chemical formula 94 is given. In both formulas, n = 2 to 30.

[0111]

[Chemical 87]

[0112]

Embedded image

[0113]

[Chemical 89]

[0114]

[Chemical 90]

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

Of these, the general formula 8
Polymer peroxides represented by 7, 89, 91 and 93 are suitable. The above polymer peroxides can be used alone or in combination of two or more when used.

The amount of the polymer peroxide used in the first step is usually 0.5 to 20 with respect to 100 parts by weight of the monomer.
Parts by weight, polymerization temperature is 60 to 130 ° C., polymerization time is 2-1
It is about 0 hours. The polymerization temperature in the second step is 60-14.
The temperature is 0 ° C. and the polymerization time is about 3 to 15 hours.

The ratio of the fluorine-containing polymer portion to the non-fluorine polymer portion in this block copolymer is 1/1 by weight.
The range of 9 to 19/1 is preferable, and the range of 1/9 to 9-1 is more preferable. The ratio of the fluoropolymer part is 1/1
If it is less than 9, the oxygen permeability coefficient, which will be described later, becomes too small, resulting in deterioration of the nails. If it exceeds 19/1, precipitation occurs during polymerization, which makes production difficult.

The block copolymer thus obtained has an oxygen permeation coefficient of 1 × 10 ⁻¹⁰ [cm ³ (STP) in order to prevent deterioration of the nail, cracking of the nail, dullness of the finger after application, and the like. ) ・
cm / cm ² · sec · cmHg] (25 ° C) or higher is desirable. This oxygen permeability coefficient is based on a gas permeability measuring method by a high vacuum method used as a method for evaluating gas permeability of a polymer.

That is, the block copolymer solution was placed in a smooth petri dish, the solvent was slowly evaporated to prepare a film having a thickness of about 50 μm without defects, and the film was sufficiently dried under reduced pressure, and then the oxygen permeability was measured. . The higher the oxygen permeability coefficient, the better, but the upper limit is 6 × 1 for silicone rubber.
0 ^-8 [cm ³ (STP) ・ cm / cm ²・ sec ・ cmHg], polytrimethylsilylpropyne 5 × 10 ^-7 [cm ³ (STP) ・ cm / cm ²
・ Sec ・ cmHg]. The higher the fluorine content in the block copolymer, the higher the oxygen permeability.

Next, the additive components include solvents, pigments, dyes, pearlescent agents, fragrances and the like. The solvent has a boiling point of 150 because it evaporates early after applying the nail cosmetic composition to the nails.
A low boiling point solvent having a temperature of ℃ or less is desirable. Examples of the low boiling point solvent include ethyl alcohol, propyl alcohol, and 2
-Propyl alcohol, 1-butyl alcohol, 2-butyl alcohol, 2-methyl-1-propanol, 2-
Methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol,
2-hexanol, 3-hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, acetone, 2-butanone, 3-methyl-2-butanone, 2-pentanone, 3-pentanone, 2-methyl-3-pentanone, 3-methyl -2-pentanone, 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, 4,4
-Dimethyl-2-pentanone, 2-hexanone, 3-hexanone, cyclopentanone, cyclohexanone, 2-
Heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-hexanone, 5-methyl-2-hexanone,
5-methyl-3-hexanone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, trimethyl methyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propion Propyl acid, butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, 2-methyl-methyl butyrate, methyl caproate, toluene, Examples include ethylbenzene and xylene. These low boiling solvents are used alone or in combination of two or more.

The content of the low boiling point solvent is preferably 30 to 90% by weight, more preferably 50 to 80% by weight. Furthermore, as an additive component, for example, an acrylic resin, a styrene resin, a urethane resin, an epoxy resin, a vinyl chloride resin, or a vinyl acetate resin may be blended. These resins are used in all properties such as water-soluble resins, emulsion resins, solvent-soluble resins and the like.

[0126]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. (Example 1) A) Production of polymer containing peroxide bond A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 300 parts by weight of xylene and heated to 70 ° C while blowing nitrogen gas. To this, a mixed solution having the following composition was charged for 2 hours. Then, a polymerization reaction was performed for 3.5 hours to obtain a solution having 34.3% by weight of a polymer containing a peroxide bond.

Methyl ethyl ketone 150 parts by weight xylene 49 parts by weight Methyl methacrylate 120 parts by weight Butyl methacrylate 120 parts by weight Polymer peroxide represented by the following formula- [CO (CH ₂ ) ₄ COO (C ₂ H ₄ O) ₃ CO ( CH _{2) 4} COOO] ₁₀ - 35 parts by weight B) block copolymer with a thermometer, a reactor equipped with a stirrer and a reflux condenser, was charged with the following mixture.

140 parts by weight of the polymerization solution obtained in the above A) CH ₂ ═CHCOO (C ₂ H ₄ ) ₂ (CF ₂ ) ₇ CF ₃ 43 parts by weight Methyl ethyl ketone 80 parts by weight While blowing nitrogen gas into the solution, 70 Heat to ℃,
The polymerization reaction was carried out for 6 hours. As a result, a semitransparent bluish white polymer dispersion containing 34.5% by weight of the block copolymer was obtained.

The ratio of the fluorine-containing monomer in the block copolymer, that is, the ratio of the fluorine-containing polymer portion in the block copolymer was 49.8%. The oxygen permeability coefficient of this block copolymer is 2.37 × 10 ⁻⁹ [cm ³ (STP) · cm
/ Cm ² · sec · cmHg].

C) Preparation of Nail Cosmetic Composition 35 parts by weight of the block copolymer obtained as described above, 25 parts by weight of n-butyl acetate, 15 parts by weight of ethyl acetate, 10 parts by weight of acetone, 10 parts by weight of ethanol. Parts, 5 parts by weight of isopropyl alcohol, and further antioxidants, anti-settling agents, colorants and the like were appropriately added to obtain a nail cosmetic composition.

D) Evaluation of Nail Cosmetic Composition A film of the nail cosmetic composition, a feeling of wearing, and a damage property of nails after long-term use were examined by monitoring 10 women.
It evaluated by the following evaluation criteria. The results are shown in Table 1.

8 out of 10 female monitors feel good ○ 5 out of 10 female monitors feel good △ less than 5 out of 10 female monitors feel good X (Example 2) A nail cosmetic composition was prepared in the same manner as in Example 1 except that the block copolymer obtained in Example 1 was replaced with the block copolymer obtained by the following method.

The following mixed solution was charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser. This resulting polymer solution 120 parts by weight of _{CH 2 = CHCOO (C 2 H} 4) 2 (CF 2) 7 CF 3 9.1 parts by weight of xylene 19.6 parts by weight A) of Example 1, nitrogen gas While blowing, heat to 70 ℃,
The polymerization reaction was carried out for 4 hours. As a result, a semitransparent bluish-white polymer dispersion liquid containing 34.3% by weight of the block copolymer was obtained.

The ratio of the fluorine-containing monomer in the block copolymer, that is, the ratio of the fluorine-containing polymer portion in the block copolymer was 19.7%. The oxygen permeability coefficient of this block copolymer is 3.17 × 10 ⁻¹⁰ [cm ³ (STP) ·
cm / cm ² · sec · cmHg]. Example 3 A nail cosmetic composition was prepared in the same manner as in Example 1 except that the block copolymer obtained in Example 1 was replaced with the block copolymer obtained by the following method.

The following mixed solution was charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser. Polymerization solution obtained in A) of Example 1 100 parts by weight CH ₂ ═CHCOO (C ₂ H ₄ ) ₂ (CF ₂ ) ₇ CF ₃ 45 parts by weight Methyl ethyl ketone 70 parts by weight While blowing nitrogen gas, 70 Heat to ℃,
The polymerization reaction was carried out for 6 hours. As a result, a semitransparent bluish white polymer dispersion containing 34.5% by weight of the block copolymer was obtained.

The ratio of the fluorinated monomer in the block copolymer, that is, the ratio of the fluorinated polymer portion in the block copolymer was 59.2%. The oxygen permeability coefficient of the block copolymer is 3.18 × 10 ⁻⁹ [cm ³ (STP) · cm / cm
² · sec · cmHg]. (Example 4) A nail cosmetic composition was prepared in the same manner as in Example 1 except that the block copolymer obtained in Example 1 was replaced with the block copolymer obtained by the following method.

The following mixed solution was charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser. Polymerization solution obtained in A) of Example 1 100 parts by weight CH ₂ ═CHCOOCH ₂ (CF ₂ ) ₈ H 30 parts by weight xylene 41 parts by weight While blowing nitrogen gas into the solution, it was heated to 70 ° C.
The polymerization reaction was carried out for 4 hours. As a result, a semitransparent bluish white polymer dispersion containing 34.1% by weight of the block copolymer was obtained.

The ratio of the fluorinated monomer in the block copolymer, that is, the ratio of the fluorinated polymer portion in the block copolymer was 49.2%. The oxygen permeability coefficient of the block copolymer is 3.00 × 10 ⁻⁹ [cm ³ (STP) · cm / cm
² · sec · cmHg]. (Example 5) A nail cosmetic composition was prepared in the same manner as in Example 1 except that the block copolymer obtained in Example 1 was replaced with the block copolymer obtained by the following method.

The following mixed solution was charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser. Polymerization solution obtained in A) of Example 1 100 parts by weight CH ₂ ═C (CH ₃ ) COOCH ₂ (CF ₂ ) ₆ H 30 parts by weight Methyl ethyl ketone 41 parts by weight While blowing nitrogen gas, the temperature was raised to 70 ° C. Heat
The polymerization reaction was carried out for 6 hours. As a result, a semitransparent bluish white polymer dispersion containing 34.5% by weight of the block copolymer was obtained.

The ratio of the fluorinated monomer in the block copolymer, that is, the ratio of the fluorinated polymer portion in the block copolymer was 49.2%. The oxygen permeability coefficient of the block copolymer is 1.77 × 10 ⁻⁹ [cm ³ (STP) · cm / cm
² · sec · cmHg]. Example 6 The procedure of Example 1 was repeated except that the block copolymer was changed to 20 parts by weight, n-butyl acetate 30 parts by weight, acetone 25 parts by weight, ethanol 15 parts by weight, and isopropyl alcohol 10 parts by weight. A nail cosmetic composition was obtained in the same manner as in Example 1. This composition was tested in the same manner as in Example 1. The results are shown in Table 1. (Example 7) In the composition of Example 1, 40 parts by weight of the block copolymer, 15 parts by weight of toluene, and 20 parts of ethyl acetate.
A nail cosmetic composition was obtained in the same manner as in Example 1 except that parts by weight, acetone 15 parts by weight, and ethanol 10 parts by weight were used instead. This composition was tested in the same manner as in Example 1. The results are shown in Table 1. (Example 8) In Example 1, a block copolymer was obtained by changing the compounding amounts of the monomer and the solvent as follows.

CH ₂ ═CHCOO (C ₂ H ₄ ) ₂ (CF ₂ ) ₇ CF ₃ 1.5 parts by weight Methyl ethyl ketone 3 parts by weight As a result, a polymer solution containing 32.3% by weight of a block copolymer was obtained. Using this block copolymer solution, a nail cosmetic composition was prepared in the same manner as in Example 1. (Comparative Example 1) A nail cosmetic composition was prepared in the same manner as in Example 1 except that the block copolymer of Example 1 was replaced with the copolymer obtained by the following method.

A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 60 parts by weight of methyl ethyl ketone, heated to 75 ° C. while blowing nitrogen gas, and the following mixed solution was supplied thereto over 2 hours.

Methyl ethyl ketone 40 parts by weight Methyl methacrylate 24 parts by weight Butyl methacrylate 24 parts by weight CH ₂ = CHCOO (C ₂ H ₄ ) ₂ (CF ₂ ) ₇ CF ₃ 48 parts by weight CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) COOO-t-Bu 4 parts by weight This is further subjected to a polymerization reaction at 75 ° C. for 5 hours and 50 ° C. for 3 hours to obtain a semitransparent white polymer solution containing 49.5% by weight of the polymer. Obtained. (Comparative Example 2) 100 parts by weight of nitrocellulose, 50 parts by weight of ethyl acetate, 50 parts by weight of toluene, and further antioxidants, anti-settling agents, coloring agents and the like were appropriately added to obtain a nail cosmetic composition. This composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0144]

[Table 1]

As shown in Table 1, the nail cosmetic compositions of Examples 1 to 8 are excellent in film-forming property, and the surface of the film is smooth and the feeling of wearing is good. Moreover, damage to the nails after long-term use is prevented. On the other hand, when the fluorine-containing random copolymer is used (Comparative Example 1), the damage to the nail after long-term use is great. In addition, when nitrocellulose is used (Comparative Example 2), the feeling of wearing is poor and the damage to the nails after long-term use is great.

Incidentally, the nail cosmetic composition using the silicone-based copolymer has a poor film-forming property as compared with the fluorine-based block copolymer of the present invention, and the surface of the formed film is not smooth. .

Technical ideas other than the claims will be described below along with their effects. (1) The oxygen permeability coefficient of the block copolymer is 1 × 10 ⁻¹⁰
The nail cosmetic composition according to claim 1, wherein the composition is at least [cm ³ (STP) · cm / cm ² · sec · cmHg] (25 ° C). According to this configuration, the nail itself can be sufficiently breathed, and deterioration of the nail, cracking of the nail, dullness of the finger after application, and the like can be effectively eliminated. (2) As the block copolymer, a polymer peroxide is used, and a fluorine-containing methacrylate or a fluorine-containing acrylate or a non-fluorine vinyl-type monomer is polymerized to obtain a peroxide bond-containing vinyl polymer. The nail cosmetic composition according to claim 1, which is obtained by polymerizing a monomer or a fluorine-containing methacrylate or a fluorine-containing acrylate. According to this structure, the block copolymer can be easily obtained with a high block rate. (3) The nail cosmetic composition according to claim 1, wherein the additive component contains a low boiling point solvent. According to this structure, the nail cosmetic composition can be quickly dried after being applied to the nails.

[0148]

As described above in detail, according to the nail cosmetic composition of the present invention, the nail itself can be sufficiently breathed, the nail is deteriorated, the nail is cracked, and the finger dries after application. It can be resolved. In addition, it is possible to effectively prevent yellowing of the nail due to the xanthoprotein reaction caused by nitrate ions.

Claims (1)

[Claims] 1. A nail cosmetic composition comprising a film-forming component and an additive component, wherein the film-forming component is a fluorine-containing polymer portion formed of at least one fluorine-containing methacrylate or fluorine-containing acrylate. A nail cosmetic composition containing a block copolymer comprising a non-fluorine polymer portion formed of a non-fluorine vinyl type monomer.