JPH11158040A - Manicuring agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solvent type manicuring agent capable of being easily coated on nails, having highly excellent dryability and gloss, giving a little feeling of pressure and not peeled even with the passage of days. SOLUTION: This manicuring agent comprises (A) a nitrocellulose, (B) a solvent, (C) a silicone resin expressed by an average composition of the formula: Ra SiO(4-a)/2 [R is a substituted or unsubstituted monovalent hydrocarbon group; (a) is a positive integer of the inequality: 0.8<(a)<1.8], and (D) a silicone graft copolymer obtained by radically polymerizing an acryl-modified silicone with a radically polymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nail enamel represented by nail enamel, nail enamel base coat, nail enamel overcoat and the like. For more information,
It is easy to apply to nails, has excellent drying properties and gloss, has little pressure on the nails, and does not easily peel off over time. It contains nitrocellulose and a solvent as a main ingredient. ").

[0002]

2. Description of the Related Art Conventionally, solvent-based nail polishes are easy to apply,
Drying property, smoothness of coating film, gloss, difficulty of scratching of coating film,
Various resins, plasticizers, and the like are blended in order to improve various properties such as a feeling of pressure on the nail at the time of application and a peeling property.

Japanese Unexamined Patent Publication (Kokai) No. 61-246113 discloses a nail polish having improved peeling properties by using an alkyd resin and a shoe-closed benzoate in combination.

[0004] Japanese Patent Application Laid-Open No. 5-213719 discloses that a combination of an alkyd-based resin, a shoe-closed benzoate, and a silicone-based graft copolymer improves the drying property and smoothness of a coating film while satisfying peeling properties. The disclosed nail polish is disclosed.

Japanese Unexamined Patent Publication (Kokai) No. 3-170409 discloses a nail polish having a high drying speed and no feeling of pressure on a fingertip by combining a specific silicone resin and a cellulose derivative in combination. Japanese Patent Application Laid-Open No. Hei 3-2793
Japanese Patent Publication No. 20 discloses a nail polish having a high drying rate and no feeling of pressure on a fingertip by combining a specific silicone resin with nitrocellulose and / or a highly volatile solvent.

[0006] Further, Japanese Patent Application Laid-Open No. 59-199621 discloses that a silicone resin having oxygen gas permeability is blended to form a film, a fingertip feel after application, and a degree of damage to a nail after long-term use. Are disclosed, but this is inferior in terms of aging, gloss, drying property and the like.

[0007] As described above, research and development of a product aiming at improvement of various properties required for the nail enamel are actively conducted.
In recent years, in particular, with the growing demand for higher quality nail polish from consumers and the diversification of tastes, there has been a demand for nail polish with many excellent properties. It is even better.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is easy to apply to nails, has excellent drying properties and gloss, has little pressure on nails, and is hard to peel off over time. It is an object of the present invention to provide a solvent-based nail polish.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, in a solvent-based nail polish, a specific silicone resin, an acryl-modified silicone and a radical polymerizable monomer were used. It has been found that the above problems can be solved by using a silicone-based graft copolymer obtained by radical polymerization of the above in combination, and the present invention has been completed.

That is, the present invention provides (a) nitrocellulose, (b) a solvent, and (c) an average composition formula represented by the following formula (I):

[0011]

## STR2 ## R_aSiO_{(4-a) / 2} (I)  (Wherein, R represents a substituted or unsubstituted monovalent hydrocarbon group;
A represents a positive number of 0.8 <a <1.8)
Silicone resin and (d) acrylic-modified silicone
Silico obtained by radical polymerization of radical polymerizable monomer
Nail polish containing
I do.

Here, it is preferable to further contain (e) sucrose acetate isobutyrate.

[0013]

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

The nitrocellulose as the component (a)
Known ones conventionally used can be used. For example, nitrocellulose RS1 / 2 second, nitrocellulose LIG1 / 2 second, nitrocellulose HIG1
/ 2 sec, nitrocellulose SS1 / 2 sec, nitrocellulose HIG1 sec, nitrocellulose HIG2 sec, nitrocellulose HIG7 sec, nitrocellulose HIG20
Second, nitrocellulose LIG1 / 4 second, nitrocellulose HIG1 / 4 second, nitrocellulose LIG1 / 8 second,
Nitrocellulose HIG 1/8 second, Nitrocellulose H
IG1 / 16 second. Nitrocellulose is 1
Species or two or more can be used.

[0015] The amount of nitrocellulose is preferably 5 to 25% by weight, more preferably 7 to 25% by weight, based on the total amount of the nail enamel. If the amount is less than 5% by weight, the drying speed may decrease, and the gloss may decrease over time. On the other hand, if the amount exceeds 25% by weight, the viscosity may increase and coating may be difficult. In addition, in this specification, the compounding amount of nitrocellulose means the state wet with 30% isopropyl alcohol (hereinafter, referred to as "30% IPA").

As the solvent as the component (b), known solvents such as ester type, alcohol type and hydrocarbon type which are conventionally used can be used. For example, methyl acetate,
Examples include ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, butyl lactate, ethyl alcohol, isopropyl alcohol, butyl alcohol, toluene, isobutyl acetate, propyl acetate, isopropyl acetate, and propyl alcohol. Among them, butyl acetate, ethyl acetate, isopropyl alcohol, butyl alcohol, ethyl alcohol and the like are preferably used. One or more solvents can be used.

The amount of the solvent varies depending on the useability, color, etc., but is generally about 50 to 85% by weight based on the total amount of the nail polish.

The silicone resin as the component (c) has an average composition formula of the following formula (I)

[0019]

Embedded image R_aSiO_{(4-a) / 2} (I)  (Wherein, R represents a substituted or unsubstituted monovalent hydrocarbon group;
A represents a positive number of 0.8 <a <1.8)
You.

Here, the hydrocarbon group means a group consisting of a carbon atom and a hydrogen atom, and any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group can be used.

In the definition of R in the above formula (I), the "monovalent hydrocarbon group" is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted. Alternatively, it may not be substituted.

Specific examples of R include an alkyl group such as a methyl group, an ethyl group and a propyl group; a vinyl group, an allyl group,
Alkenyl groups such as hexenyl group; cycloalkyl groups such as cyclohexyl group and cycloheptyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenylethyl group; chlorophenyl group, tetrachlorophenyl group; Halogen-substituted monovalent hydrocarbon groups such as chloromethyl group, pentafluorobutyl group and trifluoropropyl group; and others, γ-glycidoxy group, β-
(3,4 epoxycyclohexyl) group, cyanoethyl group, γ-aminopropyl group, N-β- (aminoethyl)
γ-aminopropyl group and the like. Among them, a methyl group and a phenyl group are particularly preferred. These are one or two
More than one species can be used.

The number of these substituted or unsubstituted monovalent hydrocarbon groups (R) directly bonded to silicon is preferably 0.8 to 1.8 on average per silicon atom. 0 to 1.5 pieces. If it is less than 0.8, it is hard and brittle, cannot follow the bending of the nail, and its aging is poor. On the other hand, if it is more than 1.8, the drying speed becomes slow and the coating film becomes sticky. Absent.

The above silicone resin can be produced by a known method. That is, the average formula R _b SiX _4-b
Wherein R is as defined above; b is 0-3
X represents a hydrolyzable group), is mixed at a ratio corresponding to the target siloxane structure, is hydrolyzed in a conventional manner, and then proceeds with polymerization. To obtain a polymer (silicone resin).

Various combinations are conceivable for the selection of the silane, and are not particularly limited as long as they are within the range of the above average formula. Among them, the combination of R ₂ SiX ₂ and RSix ₃ is particularly preferable. In the above average formula, X represents a silanol group generated by hydrolysis (SiOH
Group) and the residue of a hydrolyzable group X such as an alkoxy group.

The silicone resin used in the present invention preferably has a molecular weight in the range of 250 to 100,000. If the molecular weight is too low, the drying rate will be slow, while if it is too high, the coating will be brittle and will tend to peel off over time, which is not preferred.

The amount of the silicone resin depends on the molecular weight of the silicone resin, but is preferably from 0.2 to 50% by weight, more preferably from 1 to 30% by weight, based on the total amount of the nail polish.
It is. If the amount is less than 0.2% by weight, the effect of improving the gloss and the feeling of pressure on the nail is not sufficient, while if it exceeds 30% by weight, peeling over time tends to be poor.

The silicone-based graft copolymer as the component (d) is synthesized by radically copolymerizing the acrylic-modified silicone (A) and the radically polymerizable monomer (B).

The acrylic-modified silicone (A) is, for example, a silicone represented by the following general formula (II) and an acrylic compound represented by the following general formula (III) and / or the following general formula (IV). , Si- of the general formula (II)
It can be obtained by subjecting Si—X of the general formula (III) and / or (IV) to a condensation reaction at a ratio of 0.25 to 1 equivalent per equivalent of OH, but is not limited to this method.

[0030]

Embedded image

(Wherein, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group or a hydroxyl group; R ² and R ³ each independently represent a substituted or unsubstituted monovalent hydrocarbon group;
n represents an integer of 1 or more)

[0032]

Embedded image

[Wherein, R ⁴ represents a hydrogen atom or a methyl group; R ⁵ represents a divalent saturated hydrocarbon group (which may be optionally interrupted by one or two ether bonds)] R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms or a phenyl group; X represents an alkoxy group having 1 to 6 carbon atoms or a halogen atom)

[0034]

Embedded image

[In the formula, R ⁷ represents a hydrogen atom or a methyl group; R ⁸ represents a divalent saturated hydrocarbon group (which may be optionally interrupted by one or two ether bonds). X represents an alkoxy group having 1 to 6 carbon atoms or a halogen atom) In the above general formula (II), in the definition of R ¹ , R ² and R ³ , “substituted or unsubstituted monovalent hydrocarbon group” "Is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms (such as an alkyl group), a phenyl group, or a monovalent halogenated hydrocarbon group.

In the above general formulas (III) and (IV), in the definition of R ⁵ and R ⁸ , the term “divalent saturated hydrocarbon group” means the number of carbon atoms having a straight or branched carbon chain. 1 to 10 are preferable, and specific examples include an alkylene group and the like. These may be blocked by one or two ether bonds (-O-).

In the definition of R ⁶ , the alkyl group having 1 to 6 carbon atoms is particularly preferably a methyl group or an ethyl group.

In the definition of X, the alkoxy group having 1 to 6 carbon atoms is particularly preferably a methoxy group or an ethoxy group.

On the other hand, as the radical polymerizable monomer (B), methacrylic acid, methyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
Stearyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, styrene,
Substituted styrene, vinyl esters of organic acids such as vinyl acetate, ethylene, low molecular weight linear hydrocarbons such as propylene,
Examples thereof include vinyl chloride, vinylidene chloride, and polyoxyethylene monomethacrylate.

The copolymerization of the acrylic-modified silicone and the radical polymerizable monomer proceeds very smoothly, and a silicone-based graft copolymer can be obtained. The molecular weight can be controlled by a known polymerization technique. Specifically, for example, JP-B-60-30715, JP-B-1
It can be manufactured by the method described in JP-A-60162. This silicone-based graft copolymer is commercially available, for example, as "Aron GS-30" (manufactured by Toagosei Co., Ltd.), and is commercially available.

The silicone content in the silicone-based graft copolymer is preferably from 5 to 80% by weight, more preferably from 10 to 70% by weight, based on the total amount of the copolymer. The molecular weight of the silicone-based graft copolymer is GP
The weight average molecular weight in terms of polystyrene in C (gel permeation chromatography) is preferably about 3,000 to about 200,000, and particularly about 5,000.
0 to about 100,000.

The blending amount of the silicone-based graft copolymer depends on its molecular weight, but when the weight average molecular weight in terms of polystyrene by GPC is about 30,000, the solid content is 0.2 to 0.2% based on the total amount of the nail enamel. It is preferably 10% by weight, particularly 0.5 to 3% by weight. If the amount is less than 0.2% by weight, the effect of improving the drying property and the smoothness of the coating film is not sufficient, and the gloss tends to decrease. On the other hand, if it exceeds 10% by weight, the applicability may not be good. Not preferred.

In the nail enamel of the present invention, the above (a) to (d)
It is preferable that the composition further contains (e) sucrose acetate isobutyrate in addition to the components.

The sucrose acetate isobutyrate used in the present invention has the following formula (V)

[0045]

Embedded image (Wherein R ⁹ represents COCH ₃ ; R ¹⁰ represents COCH (CH
₃ ) Represents ₂ ).

The compounding amount of sucrose butyric acid isobutyrate is
The content is preferably 1 to 10% by weight based on the total amount of the nail polish. By adding sucrose butyric acid isobutyrate, the peeling property and the lack of pressure on the nail can be further improved without impairing the ease of application and gloss.

In general, in the case of a solvent-based nail polish, particularly when a high volatile solvent is added in a large amount to increase the drying speed of the nail polish, the nail starts to be dried from the side where the brush is applied, so that it becomes difficult to apply it to the nail. It is in. In addition, if the brush is dried before the trace of the brush disappears, the surface of the coating film loses its smoothness and the gloss becomes poor. However, in the nail enamel of the present invention, even though the drying property is improved, the ease of application is equal to or higher than that of the conventional product, and extremely excellent luster is obtained, and peeling over time. There is no feeling of pressure on nails.

The solvent-based nail polish of the present invention widely includes nail coating agents generally used in the cosmetics industry as nail varnishes, nail polish products, and the like. For example, base coat, nail enamel, top coat ( Overcoats) and nail care products such as nail guards, etc., but are not limited to these examples.

The nail polish of the present invention may further comprise other resins, plasticizers, pigments, fragrances, dyes, pearlescent agents, lamellas and the like, if necessary, in addition to the above-mentioned components so long as the effects of the present invention are not impaired. Raw materials that are generally blended in nail polishes, such as agents, drugs, humectants, ultraviolet absorbers, matting agents, fillers, surfactants, and metal soaps, can be blended.

[0050]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition, the compounding amount is weight%. All nitrocellulose amounts are 30% IPA products.

Prior to the examples, each evaluation method used in this example will be described.

[Ease of application] Each sample was filled into a 10 ml glass bottle with a brush, and this was filled with a specialized panel (10 persons).
To be used, easy to apply to nails (apply once,
(Double coating) was comprehensively evaluated according to the following criteria. <Evaluation criteria> ○: good (paints smoothly and smoothly) △: slightly poor (slightly difficult to apply) ×: poor (very difficult to apply)

[Drying speed] In actual use, the time from immediately after the application until the fingerprint did not stick when touched with a fingertip was measured. <Evaluation criteria> ：: 2-3 minutes ○: 3-4 minutes ○ △: 4-5 minutes △: 5-6 minutes ×: 6-7 minutes

[Gloss] A sample was placed on a glass plate at 0.35 m.
m, and then dried at room temperature for 24 hours. The gloss of the coating film was measured using a D-2 type gloss meter at an angle of incidence of 60 ° and a reflection angle of 60 °. <Evaluation Criteria> A: The value of incident angle 60 ° -reflection angle 60 ° is 90 or more to 1
00 Δ: The value of incident angle 60 ° -reflection angle 60 ° is 70 or more to 9
Less than 0 ×: Value of incident angle 60 ° -reflection angle 60 ° is less than 70

[Peeling Over Time] Each sample was used by a specialized panel (10 persons), and the peeling after three days had passed was comprehensively evaluated according to the following criteria. <Evaluation criteria> ◎: Very difficult to peel ○: Somewhat hard to peel ○ △: Somewhat easy to peel △: Easy to peel ×: Very easy to peel

[Sense of Pressure on Nail] Each sample was prepared using a specialized panel (1
0), and a comprehensive evaluation was made on the feeling of pressure on the nail during application according to the following criteria. <Evaluation criteria> ◎: No feeling of pressure at all ○: Slightly no feeling of pressure ○ △: Slightly feeling of pressure △: There is a feeling of pressure ×: There is a feeling of pressure very much

(Examples 1 to 5, Comparative Examples 1 to 5) Tables 1 and 2
The nail polish was prepared by a conventional method with the composition shown in Table 1 and the ease of application, gloss, drying speed, peeling over time, and feeling of pressure on the nail were evaluated by the above-described evaluation methods. The results are shown in Tables 1 and 2.

[0058]

[Table 1]

[Table 2]

In Tables 1 and 2, the average composition of the silicone resin ^(*) used was R _1.2 SiO _1.4 , R: phenyl group / methyl group = 2.5 (molar ratio), molecular weight 3000
Met. (Preparation method) Dissolve (1) to (4) in (5) to (7),
Samples (8) and (9) were mixed by stirring.

As is clear from Tables 1 and 2, Examples 1 to 5 of the present invention in which a silicone resin and a silicone-based graft copolymer were blended together were excellent in separation stability, ease of application, gloss and drying speed. It can be seen that it is hard to be peeled off even with the elapse of time and the feeling of pressure on the nail is small.

On the other hand, Comparative Examples 2 and 3, in which the silicone resin was blended and the silicone-based graft copolymer was not blended, showed less pressure on the gloss and nails than Comparative Example 1 in which neither of them was blended. Although there was an improvement in the drying speed, there was no change in the difficulty in peeling over time, and the effect of improving the drying speed was not sufficient. In Comparative Examples 4 and 5, in which the silicone-based graft copolymer was blended and the silicone resin was not blended, the gloss and drying speed were remarkably improved, but the sense of pressure on the nails was rather increased.

(Example 6: overcoat) (combination component) (% by weight) Nitrocellulose 1/4 second (30% IPA) 15 Nitrocellulose 1/2 second (30% IPA) 4 Alkyd resin (Versatic) Acid glycidyl ester modified) 4 sucrose benzoate 4 silicone graft copolymer (“Aron GS-30”) (solid content) 2 sucrose acetate isobutyrate 3 acetyl triethyl citrate 5 isopropyl alcohol 3 n-butyl alcohol 1 acetic acid Ethyl 25 n-butyl acetate 34 An overcoat was obtained by a conventional method. It had good drying properties, was easy to apply, had excellent gloss, was difficult to peel off over time, and had little pressure on the nails.

Example 7: Basecoat (combination component) (% by weight) Nitrocellulose ４ second (30% IPA) 7 Nitrocellulose 秒 second (30% IPA) 5 Alkyd resin (versatic acid) (Glycidyl ester modification) 6 Sucrose benzoate 6 Silicone graft copolymer ("Aron GS-30") (solid content) 2 Sucrose acetate isobutyrate 3 Acetyl triethyl citrate 5 Isopropyl alcohol 3 n-butyl alcohol 1 Ethyl acetate 25 n-butyl acetate 37 A base coat was obtained by an ordinary method. It had good drying properties, was easy to apply, had excellent gloss, was difficult to peel off over time, and had little pressure on the nails.

[0064]

As described above in detail, according to the present invention, a beautiful nail which is excellent in drying property, gloss of a coating film, and ease of application, is resistant to peeling over time, and has little pressure on the nail. Fees are obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshiharu Nakao 1050 Nippa-cho, Kohoku-ku, Yokohama, Kanagawa Prefecture Inside Shiseido Daiichi Research Center (72) Inventor Miwa Soyama 1050 Nippa-cho, Kohoku-ku, Yokohama, Kanagawa Inside Shiseido Daiichi Research Center

Claims (2)

[Claims] 1. A nitrocellulose (a) and a solvent (b)
And (c) the average composition formula is represented by the following formula (I):_aSiO_{(4-a) / 2} (I)  (Wherein, R represents a substituted or unsubstituted monovalent hydrocarbon group;
A represents a positive number of 0.8 <a <1.8)
Silicone resin and (d) acrylic-modified silicone
Silico obtained by radical polymerization of radical polymerizable monomer
Nail polish, comprising a wax-based graft copolymer. 2. The nail enamel according to claim 1, further comprising (e) sucrose acetate isobutyrate.