JPH03240719A - Nail cosmetic - Google Patents

Abstract

PURPOSE:To provide a nail cosmetic having excellent touch and performance by compounding a specific resin having excellent gas permeability. CONSTITUTION:A resin comprising a polymer containing >=40mol% of units of the formula (R is >=3C alkyl, >=4C cycloalkyl, etc.) is dissolved in a low boiling point solvent (e.g. isopropyl alcohol) having a boiling point of <=150 deg.C and further suitably compounded with known cosmetic materials such as a pigment, a dye, a pearl agent, a perfume, an antioxidant and a deposition- preventing material to provide the objective cosmetic. A resin having a gas permeability of at least 5X10<-10>(cm<3> (STP).cm/cm<2>.sec.cmHg) (25 deg.C) as the value of the gas permeability of oxygen is employed as the above-mentioned resin. The nail cosmetic can be directly coated on nails and readily dried to give a beautiful finished product, has good stability and color tone stability, can be readily doubly coated to form a coating film having excellent luster, excellent odor, good permeability of a gas such as oxygen, etc., and capable of being fit to the nail for a long time without giving heavy weight and un-pleasant touch to the nail.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to nail cosmetics, and more particularly to nail cosmetics containing a resin with excellent gas permeability.

(Prior art) Nails, which are generally called underwater, are deformed epidermis like hair, and contain 7-12% water and 0.15-15% fat. It is a hard, translucent plate containing 0.76% cystine, and is made of high protein (keratin) whose main component is cystine.In this water, it is in close contact with the underlying tissue called the aqueous bed (axial layer). It is formed in the water matrix, and as the water bed grows, it grows towards the fingertips, producing 0.0% per day.
It has the property of being able to stretch by about 1 to 0.15 mm, and has been considered to be relatively durable. For this reason, various nail cosmetics have been on the market for a long time, but so far no particular problems have been reported.
Even if the underwater surface is covered with various nail enamel coatings,
It was thought that the nails would not be affected in any way.

However, although nails have been treated as "dead tissue," these nails (underwater) are supplied with water from the water bed and water matrix, and contain a moderate amount of water, making them highly elastic. If it leaves the water bed and lacks moisture, it quickly dries out and becomes brittle. For this reason, water can be said to be a "living tissue," and like the skin and other tissues, it can be said to breathe, albeit in a very small amount.

By the way, the constituent components of nail enamel are classified into film-forming components, solvent components, coloring components, and anti-sedimentation components, and the properties of nail enamel in particular largely depend on the nitrocellulose and resin in the film-forming components. The most important thing about nail enamel is that it is ``resistant to peeling.'' Nail enamel resin provides this property, but
Regarding the strength and gloss of the coating film, this resin plays a very important role, and many improvements have been made.

In the 1930s, nitrocellulose films were developed to have a glossy finish and increased resistance to soapy water.
A sulfonate-formamide type resin (trade name: Santorite) was developed and has been in use for a long time. However, this resin had safety problems and has been no longer used in Japan since 1972, and various resins have been developed to replace it.

For example, those containing acrylic ester resin (Chinoku Special Publication No. 46-43400) and those containing sucrose acetate isobutyrate (Special Publication No. 13336-1982)
, blended with methyl methacrylate/hexyl methacrylate copolymer (Japanese Patent Publication No. 139732/1983),
Compounded with polyester resin (Special Publication No. 53-187)
42), and one containing a modified alkyd resin (Japanese Patent Publication No. 57-27082).

However, these inventions were developed from the viewpoints of the adhesion of nail enamel to the nail (resistance to peeling), water resistance, scratch resistance, uniformity of the coating film, etc. It's not something that was given to me.

As nail enamel has become more commonplace today, various problems have begun to appear. It seems that the problem is not specifically about nail enamel, but about nail makeup itself. For example, you apply enamel every morning and then use nail remover to remove it after you get home or before you go to bed, but in doing so, you also remove the fat contained in your nails, causing the surface of your nails to become glossy. Not only is this problem disappearing, but the nails are getting rougher and there is a need for new nail care. To solve this problem, methods such as improving the enamel itself or replacing the nail remover solution with a milder one have been taken. Furthermore, after treating the nail with nail remover, the nail is further coated with oil or the like to protect the nail, but this is not a fundamental solution. This does not mean that the number of nail removals has decreased, and even if better nail removers or better nail care methods are developed, it is still a nuisance.

On the other hand, gas-permeable resins have been studied as nail enamels that take into consideration the properties of nails.
99621), but since it is a silicone resin, there are many problems with gloss, adhesion, surface hardness, etc.
Furthermore, there are only a limited number of solvent-soluble silicone resins that are permitted for use in cosmetics, and considerable improvement is required before they can actually be used as nail enamel. However, as a result of the improvement, the gas permeability of the silicone resin has decreased significantly, and the gas permeability has become comparable to that of conventional silicone resins, so it is difficult to say that the problem has been solved.

(Problems to be Solved by the Invention) Nitrocellulose, which has been used in the past, has the properties necessary for nail enamel, such as high surface hardness, sufficient strength of the nail coating, and ability to dissolve or dissolve in water. It is an excellent material that does not swell, is soluble in low-boiling organic solvents that are approved for use in cosmetics, and has a low viscosity that allows it to be applied with a brush. However, it is not a very good material from the perspective of gas permeability, and it is not desirable when considering physiological effects such as nail breathing, especially if nail resin is left on the nail for a long period of time. Many problems have been pointed out, such as not only is it not good for your nails, but your nails feel heavy, you don't feel well, and your nails feel heavy.

From these viewpoints, we have developed a resin that does not affect physiological functions such as nail respiration, has gloss, water resistance, excellent surface hardness and coating strength, and is soluble in low boiling point solvents that can be used in cosmetics.
There is a need for a nail cosmetic that can be applied with a brush and is made of a gas-permeable resin that can sufficiently permeate oxygen, water vapor, etc. that are necessary for nails to breathe.

(Means for Solving the Problems) The present invention provides the following general 2: 1% CH2-CHF C-R 1 (However, R group in the formula is a branched alkyl group having 3 or more carbon atoms, 4 carbon atoms or more cycloalkyl group, or 3 carbon atoms
This represents an aromatic group having the above-mentioned branched alkyl group or cycloalkyl group having 4 or more carbon atoms, and some or all of the hydrogen atoms of the alkyl group or cycloalkyl group may be substituted with fluorine atoms. ) is the unit shown by 4
A resin consisting of a polymer containing 0 mol% or more, the gas permeability of which is at least 5 XIXlo-1O(' (STP) ・cs/cm
・sec-aaHg) (25°C) This is an excellent nail makeup that does not cause any discomfort or discomfort even when applied with a large amount of water for a long time. Fees will be provided.

The polymer used in the present invention is a vinyl ester of an aliphatic carboxylic acid having a branched alkyl group having 3 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms, or a vinyl ester of an aliphatic carboxylic acid having 3 or more carbon atoms.
A vinyl ester of an aromatic carboxylic acid having the above-mentioned branched alkyl group or a cycloalkyl group having 4 or more carbon atoms, or a vinyl ester having a combination of the above-mentioned alkyl groups, wherein one of the hydrogen atoms of the alkyl group is Part or all may be substituted with a fluorine atom,
These are polymers obtained by polymerizing one or more of these vinyl esters, and the corresponding vinyl esters alone or as a mixture can be easily synthesized by an appropriate polymerization method, such as a radical polymerization method.

Examples of raw material monomers for the vinyl ester polymer used in the present invention include vinyl pivalate, vinyl 2.2-dimethylbutanoate, vinyl 2.2-dimethylpentanoate, and vinyl 2.2-dimethylbutanoate.
-Aliphatic carboxylic acids having a branched alkyl group having 4 or more carbon atoms, such as vinyl methyl-2-ethylbutanoate, vinyl 2,2-diethylpenkunate, vinyl fluoroacetate, and vinyl 3-trifluoromethylpropionate. Vinyl esters, or vinyl p-tert-butylbenzoate, vinyl p-tert-amylbenzoate, p-(3-
There are vinyl esters of aromatic monocarboxylic acids having a branched alkyl group having 4 or more carbon atoms, such as pentyl>vinyl benzoate.

One or more of these monomers are mixed with a commonly used radical polymerization initiator in a suitable organic solvent,
For example, azo radical polymerization initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobisvaleronitrile, benzoyl peroxide, ter
Organic peroxide radical polymerization initiators such as t-butyl hydroperoxide, cumene peroxide, diacyl peroxide, inorganic radical polymerization initiators such as ammonium persulfate, potassium persulfate, and many other radical polymerizations. It is synthesized by polymerization using an initiator system, for example, a redox system such as a hydrogen peroxide-sodium hydroxide system.

As the polymerization method, many polymerization methods commonly used for radical polymerization of vinyl monomers such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and radiation polymerization can be used.

Further, a polymer containing 40 mol% or more of repeating units derived from the various vinyl ester monomers can be obtained by radical homopolymerization of the various vinyl esters, or by combining 40 mol% or more of the vinyl ester monomers with other monomers, e.g. Styrene derivatives, (meth)acrylic acid and their esters, vinyl ethers, itaconic acid and its esters, fumaric acid or maleic acid and their esters, butadiene, isoprene, acrylonitrile, etc. as copolymerization partner monomers, 60 It is obtained by copolymerization using less than mol%. At this time, the unit represented by the general formula derived from the vinyl ester monomer is 40 mol%
Polymers with a molecular weight of less than 10% are not preferred because their gas permeability decreases.

Among the polymers thus obtained, the gas permeability is at least 5×10-” (c
m” (STP) ・cm/cm2・sec-cmHg)
(25°C) was used to make a nail cosmetic.

The nail cosmetic of the present invention uses the highly gas permeable vinyl ester resin as a solvent with a low boiling point of 150°C or less, such as ethyl alcohol, isopropyl alcohol, methylcellosolve, acetone, ethyl acetate, butyl acetate, toluene, etc. Nail cosmetics can be prepared by dissolving the nail cosmetics in the following manner and adding appropriately known cosmetic materials such as pigments, dyes, burrs, fragrances, antioxidants, and antisettling agents.

(Effects of the invention) The nail cosmetics obtained in this way were actually applied to the nails, and the feeling of use and long-term feeling were investigated using 10 monitors, and the results were highly evaluated. . That is, the nail cosmetic of the present invention can be applied directly to the nail, the coating film dries easily, does not leave scratches, fingerprints, clothing marks, etc., provides a beautiful finish, and has stability, color stability, It was found that the product has properties comparable to those of conventionally used nail cosmetics whose main ingredient is nitrocellulose, including ease of layering, gloss, and odor. What's more, this nail cosmetic has good permeability to gases such as oxygen, so it won't make your nails feel heavy even if you leave it on your nails for more than 3 days.
You can wear it for a long time without feeling any discomfort.

(Examples) The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples.The units of formulation in the Examples are all units by weight. Also, the evaluation test method for nail enamel was conducted as follows.

The performance of the gas-permeable nail enamel was evaluated by measuring gas permeability using the high vacuum method, which has traditionally been used as a method for evaluating the gas permeability of polymers.

That is, a nail enamel solution was placed in a smooth petri dish, and the solvent was slowly evaporated to form a defect-free film with a thickness of about 50 μm. After sufficient vacuum drying, gas permeability was measured.

The pencil hardness was measured in accordance with JTS K5400r Paint General Test Method. However, the load of the weight is 300
g, apply nail enamel evenly to the nylon plate,
After air drying at room temperature for 24 hours, pencil hardness was measured.

Flexibility is nylon plate (thickness 0.5 x width 151 x length 40
Apply nail enamel evenly to 24 mm) at room temperature.
After air-drying for a while, overlap the two ends of the nylon plates,
The 180-degree bending operation was repeated, and the evaluation was made based on the state of crack occurrence: ◎ is excellent, ○ is good, Δ is fair, and × is bad.

Adhesion is determined by applying nail enamel evenly to a nylon plate.
After air-drying at room temperature for 24 hours, use a knife to mark 11 lines in the vertical and horizontal directions at 2 mm intervals, apply adhesive cellophane tape with a width of 25+ m while pressing, and peel off this cellophane tape at once. Adhesion was evaluated based on the number of nail enamel films applied. In other words, when the number of peeled films is 5 or less, it is excellent (◎), and 6 to 1.
0 sheets were rated good (0), 11 to 30 sheets were rated fair (Δ), and 30 or more sheets were rated poor (x).

Glossiness was measured using a Gardner type gloss meter at an incident angle of 20 degrees.
The determination was made by measuring the specular gloss at 45 degrees and 75 degrees. That is, nail enamel was applied uniformly to a smooth glass plate, and after air-drying at room temperature for 24 hours, the specular reflection intensities of the three types mentioned above were measured.
The specular glossiness at each incident angle was set as 00. Here, the glossiness evaluation is shown as acceptable (Δ) when the average value of the three types of specular glossiness is 50 or less, good (○) when it is 51 to 55, and excellent (◎) when it is 56 or more. Ta.

The feeling of wearing was evaluated by applying the nail enamels prepared in Examples and Comparative Examples to the nails of 10 female monitors, and evaluating the feeling of wearing after one day using the following criteria.

In other words, among the 10 monitors, those who felt that 8 Å or more were good were rated excellent (◎), and those who felt that 4 Å or more were good were rated good (○).
If at least one person felt that it was good, it was judged as acceptable (△), and if not everyone felt that it was good, it was judged as unacceptable (×).

Example 1 Oxygen permeability coefficient (po,) is PO□=2.65X10-'
cm' (STP) ・cs / cm" ・5ec-c
n + Hg), 35 parts of a radical homopolymer of vinyl pivalate (number average molecular weight approximately 140,000), 25 parts of n-butyl acetate, 15 parts of ethyl acetate, 10 parts of acetone, 5 parts of isopropyl alcohol, 10 parts of ethanol, and Nail enamel was prepared by appropriately adding an antioxidant, an antisettling agent, a coloring agent, and the like.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are shown in Table 1.

As a comparative example, the characteristic values of nitrocellulose nail enamel made with the formulation shown in Table 2 are also shown.

Example 2 Oxygen permeability coefficient (pot) is POz=2.59X 10-
9cm' (STP)・C11170m2・sec-CI
IIHg), a radical homopolymer of 2,2-dimethylbutanoic acid vinyl ester (number average molecular weight approximately 180,000) 3
Nail enamel was produced in the same manner as in Example 1, except that 5 parts were used.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Example 3 Oxygen permeability coefficient (PO□) is POz = 9.36 X
10-”cm’ (STP) ・cta 7cm”
Nail enamel was prepared in the same manner as in Example 1, except that 35 parts of a radical homopolymer of 2,2-dimethylpenconic acid vinyl ester (number average molecular weight of approximately 200,000) was used (sec-cmHg). did.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Example 4 Oxygen permeability coefficient (PO2) is POz = 2.10
10-9cm3 (STP) ・am 7cm” ・se
Example 1 was carried out in the same manner as in Example 1, except that 35 parts of a radical homopolymer of 2-methyl-2-ethylbutanoic acid vinyl ester (number average molecular weight of about 160,000) was used.
Created nail enamel.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Example 5 Oxygen permeability coefficient (pot) is POz=4.48X10-9
cm3(STP) ・cm 7cm” ・sec-cm
In addition to using 35 parts of a radical copolymer (number average molecular weight approximately 240,000) of vinyl 2,2-dimethylbutanoate (85 mol%) and di-tert-butyl fumarate (15 mol%), which is Hg), Nail enamel was created in the same manner as in Example 1.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Example 6 Oxygen permeability coefficient (poz) is POz=4.20X10-'
cm' (STP) ・cs / am2- sec-c
Vinyl p-tert-butylbenzoate (80 mol%) and di-tert-butyl fumarate (ffI)Ig)
20 mol%> radical copolymer (number average molecular weight approximately 19
Nail enamel was prepared in the same manner as in Example 1, except that 35 parts of Nail Enamel was used.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Example 7 Oxygen permeability coefficient (POZ) is P (h = 1, 26
10-'cm3(STP) ・c+i/cI11"
・sec-cmHg) 2,2-dimethylbutanoic acid vinyl ester (75 mol%) and methacrylic acid 5ec
A nail enamel was prepared in the same manner as in Example 1, except that 35 parts of a radical copolymer (number average molecular weight: about 350,000) of -butyl (25 mol %) was used.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Example 8 Oxygen permeability coefficient (po,) is POz = 7.63
10-” Cm3(STP)・cm/cm”
・sec-cmHg) 2-methyl-2ethylbutanoic acid vinyl ester (85 mol%) and styrene (15 mol%) copolymer (number average molecular weight about 320,000) 35 parts was used, except that the same example was used. Nail enamel was created in the same manner as in 1.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Example 9 Oxygen permeability coefficient (PO□) is PO, = 7.16 x 1
0-” cm' (STP) ・cm 7cm2・s
In addition to using 35 parts of a radical copolymer (number average molecular weight approximately 170,000) of vinyl fluoroacetate (85 mol%) and styrene (15 mol%), which is ec-cm) Ig),
Nail enamel was created in the same manner as in Example 1.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Example 10 Oxygen permeability coefficient (pot) is POz=9.68X10-1
0co+3(STP) ・cn /cn+" ・sec
-cmHg) and 3-trifluoromethylpropionic acid vinyl ester (75 mol%) and fumaric acid di-tert
- Copolymer of butyl (25 mol%) (number average molecular weight approx. 2
Nail enamel was prepared in the same manner as in Example 1, except that 35 parts (80,000) were used.

The hardness, flexibility, adhesion, gloss, and gas permeability of nail enamel were investigated. Their characteristic values are summarized in Table 1.

Comparative Example As a comparative example, nail enamel using typical nitrocellulose as a film-forming agent was prepared at the mixing ratio shown in Table 2.
The same performance evaluation as in Example 1 was performed. The results are also summarized in Table 1.

Table 1 Table 2 Nitrocellulose (R3I/4 seconds) Alkyd resin (Arachid 400T manufactured by Arayo Kagaku Kogyo)
Dibutyl phthalate camphor ethyl acetate n-butyl isopropyl alcohol Toluene 16.3 parts 12.5 parts 6.2 parts 2 parts 5 parts 30 parts 2 parts 24 parts PO, Xl0-"Cm" (STP) ・Cll/Cl1
l”・sec-aiHgat25℃

Claims (1)

[Claims] The following general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, the R group in the formula is a branched alkyl group having 3 or more carbon atoms, a cycloalkyl group having 4 or more carbon atoms, Or carbon number 3
This represents an aromatic group having the above-mentioned branched alkyl group or cycloalkyl group having 4 or more carbon atoms, and some or all of the hydrogen atoms of the alkyl group or cycloalkyl group may be substituted with fluorine atoms. ) is the unit shown by 4
A resin consisting of a polymer containing 0 mol% or more, the gas permeability of which is at least 5 x 10^-1^0 (cm^3 (STP) cm/cm) as the value of the gas permeability coefficient for oxygen.
A nail cosmetic characterized by containing a gas permeable resin having a gas permeability of 2.sec.cmHg) (at 25° C.).