JPS6031807B2 - variable color nail enamel - Google Patents

Description

[Detailed description of the invention] The present invention relates to variable color nail enamel.

More specifically, the present invention relates to a novel nail enamel that changes color or develops color when applied, giving an aesthetic sense, and allowing the naked eye to tell when makeup is finished due to the sudden color change. Conventionally, nail enamel consists of a film-forming agent, a film auxiliary agent, a plasticizer, a solvent, a coloring agent, etc. Nail enamel is applied onto the nail, and after about 1 to 5 minutes, the solvent components evaporate and the desired color is created. A resin film with color and gloss is formed on the nail.

In such nail enamel, the drying speed varies depending on the composition of the nail enamel or the ambient temperature and body temperature at the time of applying the nail enamel, so it is unclear when the nail enamel dries and hardens, and it is difficult to know the end point of film formation. When you touch it with your hands, it becomes sticky and not only sticks to your hands, but also leaves fingerprints on the film, degrading the appearance of the nail enamel and requiring reapplication. The present invention aims to improve such drawbacks.As a result of intensive studies, the present invention has been made by incorporating a pigment that changes color as the nail enamel dries and solidifies.
We have discovered and developed a new nail enamel that can visually detect the dry state of applied nail enamel and easily identify the end point of film formation, and have completed the present invention.

It is an object of the present invention to provide a variable color nail enamel that allows the drying period of the applied nail enamel to be accurately determined with the naked eye by color change.Another object of the present invention is to provide a variable color nail enamel that allows the drying period of the applied nail enamel to be accurately determined with the naked eye. The aim is to provide a variable color nail enamel that provides the user with the desired color.

That is, the present invention provides a nail enamel containing a coloring agent, in which a variable color substance having a different hue immediately after the nail enamel is applied to the nail and after drying and solidifying is present in a part or all of the colorant. It is characterized by comprising the following.

Such a variable color substance preferably has the general formula (1
) [In the formula, R2 and R2 represent an alkyl group, a hydroxyalkyl group, or an alkoxyalkyl group, R3 represents a day, and R4 represents a day, an alkyl group, an alkoxyl group, a nitro group, a halogen, or a condensed ring.

Further, A is each condensation reaction residue of an aromatic aldehyde, a polycyclic aldehyde, an aromatic nitroso compound or a polycyclic nitroso compound, Y is ○ or S, and Z has a substituent or has a substituent. represents an alkylene group having 2 to 4 carbon atoms. Examples include styryl-like compounds represented by:

Such a styryl analog compound has the general formula (0) [wherein R
,, R2, R3, R4, Y and Z are the same as those in general formula (1). ] and an aromatic aldehyde, a double ring aldehyde, an aromatic nitroso compound, or a heterocyclic nitroso compound in the presence or absence of an alkali catalyst, or a general formula plate. ) [In the formula, R,, R2, R3, R4, Y and Z are the same as those in general formula (1), and x represents an anion such as a halogen, an acid group, or an alkoxy anion.

] can be easily obtained by treating indolenium-type styryl pigments represented by the following with an alkali.

Here, the indoline conductor of general formula (0) is generally represented by general formula (W) [wherein R,, R2, R3 and R4 are the same as those in general formula (1).

], such as 2,3,3-trimethylindolenine, 2,3,
3,5-tetramethylindolenine, 2,3,3-trimethyl-4-methoxyindolenine, 2,3,3-trimethyl-5-methoxyindolenine, 2,3,3-trimethyl-6-methoxyindolenine, 2,3, 3-trimethyl-7-methoxyindolenine, 2,3,3-trimethyl-5-aminoindolenine, 2,3,3-trimethyl-5-acetaminoindolenine, 2,3,3-trimethyl-5-benzoylaminoindolenine, 2 ,3
, 3-trimethyl-5-dimethylaminoindolenine,
2,3,3-trimethyl-5-ethylaminoindolenine, 2,3,3-trimethyl-5-nitroindolenine, 2,3,3-trimethyl-6-nitroindolenine,
2,3,3-trimethyl-5-iodoindolenine, 2
, 3-trimethyl-7-bromoindolenine, 2,
3,3-trimethyl-5-ethoxycarbonylindolenine, 2,3,3-trimethyl-5-phenoxyindolenine, 2,3,3-trimethyl-5-anilinoindolenine, 2,3,3-trimethyl-5-carboxylindolenine, 2,3,3-trimethyl-5-cyanoindolenine, 2,3,3-trimethyl-5-phenylindoleniso, 2,3,3-trimethyl-4,5-dimethoxyindolenine, 2,3,3,5, 7-pentamethylindolenine, 2,3,3-trimethyl-5,6-dimethoxyindolenine, 2,3,3,7-tetramethyl-5-
Nitroindolenine, 2-methyl-3,3-diethylindolenine, 2,3-dimethyl-3-ethylindolenine, 2,5-dimethyl-3,3-diethylindolenine, 2,3-dimethyl-3-hydroxyethylindolenine , 2,3-dimethyl-3-ethoxymethylindolenine, 2,3-dimethyl-3-phenoxychetylindolenine, etc., or polycyclic fused indolenines such as naphthoindolenine, and general formula (V) XZYH
(V) [Wherein, X, Y and Z are the same as those in general formula (1).

], for example, ethylene chlorohydrin, ethylene bromohydrin, trimethylene chlorohydrin, trimethylene bromohydrin, tetra-ethylene chlorohydrin, tetra-ethylene bromohydrin, 1-chloro- 2-propyl alcohol, 2-chloro-1-propyl alcohol, 2-chloroethyl mercabutane, 3
- Chloropyrmercaptan, etc., can be reacted by heating.

On the other hand, examples of aromatic aldehydes to be reacted with indoline derivatives include benzaldehyde, p-acetaminobenzaldehyde, p-bromobenzaldehyde, m
- Brombenzaldehyde, o-brombenzaldehyde, p-dimethyl 'aminobenzaldehyde, p-diethylaminobenzaldehyde, p-dibutylaminobenzaldehyde, o-chlorobenzaldehyde, p-chlorobenzaldehyde, p-anisaldehyde, o -anisalde'hyde, p-tolualde 1 hyde, m-tolualdehyde, o-tolualde J hyde, o-ethoxybenzaldehyde, p-ethoxybenzaldehyde, p-fluorobenzaldehyde, o-fluorobenzaldehyde, p-nitrobenzalde, hydride, m-nitrobenzaldehyde, o-nitrobenzaldehyde, p-cyanobenzaldehyde, o-cyano/penzaldehyde, 2
, 4-dichlorobenzaldehyde, 2,6-dichlorobenzaldehyde, 3,4-dichlorobenzaldehyde,
3,5-dichlorobenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5
-dimethoxybenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 3
, 4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, veratraldehyde (3,4-dimethoxybenzaldehyde), 4-isopropylbenzaldehyde, o-(2-chloroethyl)penzaldehyde,
2,4,6-trimethylbenzaldehyde (mesicaldehyde), 2,4,6-triethoxybenzaldehyde, 3,4-dimethyl-p-anisaldehyde, 2,5-dimethyl-p-anisaldehyde, 2-chloro5-nitro Benzaldehyde, 2-chloro-6-nitrobenzaldehyde, 2-chloro-3-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, vanillin.

-Vanillin, isovanillin, 5-bromovanillin, 2-chloro-4-dimethylaminobenzaldehyde, 2-chloro-6-fluorobenzalde, hydro, 5-bromoveratraaldehyde, 6-fromeveratraaldehyde,
5-furomo-2-methoxybenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, p-dimethylaminocinnamaldehyde, p-diethylcinnamaldehyde, p-nitrocinnamaldehyde, o-nitrocinnamaldehyde, 2-chlorocinnamaldehyde, 9-
Examples include anthraldehyde, 10-chloro-9-anthraaldehyde, 9-phenanthrenecarboxaldehyde, and fluorenecarboxaldehyde. Examples of the heterocyclic aldehyde include furfural, 5-methylfurfural, 5-furfurfural, 4-isopropylfurfural, 2-thioquenecarboxaldehyde, 5-methylthioquenecarboxaldehyde, and 3-methoxybenzofurfural. Thioquene-2-carboxaldehyde, 2-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde, 4-pyridinecarboxaldehyde, 1-ethylindole-3-carboxaldehyde, 1-methylindole-3-carboxaldehyde , 1-methyl-2-
Phenylindole-3-carboxaldehyde, N-methylcarnozole-2-carboxaldehyde, N
-ethyl-7-furomocarbazole-2-carboxaldehyde, N-(n-octyl)-7-nitrocarbazole-2-carboxaldehyde, benzofuran-2-carboxaldehyde, dibenzofuran-2-carboxaldehyde, pyrrole-2-aldehyde, N-methylpyrrole-2-aldehyde, N-phenylpyrrole-2-aldehyde, 3-methylpyrrole-2-aldehyde, 2-ethylpyrrole-5-aldehyde, benzothiazole-2
-aldehyde, 6-methylbenzothiazole-2-aldehyde, 6-chlorobenzothiazole-2-aldehyde, 5-chlorobenzothiazole-2-aldehyde, 6-
Methoxybenzothiazole-2-aldehyde, 5,6-
Dichlorobenzothiazole-2-aldehyde, benzoselenazole-2-aldehyde, 6-methoxybenzozelenazole-2-aldehyde, 2,4-dimethylpyrrole-2-aldehyde, 4,6-dichloropyrimidine-5-
Ruboxaldehyde, 2-formyl-4,6-dimethylpyrimidine, quinoline-2-aldehyde, acridine-10-aldehyde, 2,4-diphenyl-5,6,7-hexahydrobenzopyran-8-ruboxaldehyde, 2,4-diphenyl- Examples include 6-methyl-5,6,7-bentahydrobenzopyran-8-carboxaldehyde.

Examples of aromatic nitroso compounds include p-dimethylaminonitrobenzene, p-diethylaminonitrosobenzene, p-methylnitrosobenzene (p-nitrosotoluene), p-nitronitrosobenzene, o-nitronitrosobenzene, Examples include 3-nitroso-2-nitotoluene.

Further, as the double ring nitroso compound, for example, 3-
Examples include nitrosoindole, 2-methyl-3nitrosoindole (3-nitrosomethylketol), and 3nitroso-2-phenylindole.

In the styryl analogous compound applied to the present invention, in the above general formula (1), R and R2 are represented by an alkyl group, a hydroxyalkyl group, or an alkoxyalkyl group, and when these alkyl groups become higher, The stability of styryl-like compounds deteriorates, and the manufacturing method becomes difficult.
Moreover, it is expensive.

Preferably, R2 and/or R2 are lower alkyl groups. Furthermore, R3 represents a day in the general formula (1), and as the number of carbon atoms in these groups increases, such styryl-like compounds become difficult to produce and expensive.

Preferably R2 is days. Furthermore, Z has the general formula (1
), with or without a substituent, the number of carbon atoms is 2 to
4 alkylene group, but the number of carbon atoms in the alkylene group is 2
When it is less than 5 or more than 5, the stability of the obtained styryl-like compound becomes poor, the manufacturing method becomes difficult, and it becomes high-grade.

Preferably Z is an ethylene group or a propylene group.
In the nail enamel according to the present invention, all base materials for nail enamel that have been conventionally used can be used.

That is, such base materials for nail enamel include, for example, film forming agents such as nitrocellulose and ethyl cellulose, and film forming agents such as dammar, ceramics, alkyl sulfamide formaldehyde resins, rosin modified resins, acrylic resins, urethane resins, and epoxy resins. agent resins, such as dibutyl phthalate, plasticizers such as camphor, solvents such as methyl acetate, acetone, ethyl acetate, methyl ethyl ketone, impronognol, ethanol, toluene, butyl acetate, xylene, butanol, amyl acetate, diacetone alcohol, For example, inorganic pigments such as titanium oxide, zinc oxide, iron rhombic oxide, and gunjiro, and organic pigments such as azo pigments, phthalocyanine pigments, indigo pigments, and lake pigments can be mentioned. The styryl-like compound applied to the present invention can be incorporated into nail enamel by dissolving it in the solvents listed above. Examples of such solvents include acetate esters, aromatic or aliphatic hydrocarbons, ketones, It is preferable to use something with low polarity such as ethers, and o For nail enamel in which a styryl-like compound is dissolved in a highly polar solvent such as alcohol, the styryl-like compound will develop a slight color in the nail enamel solution. This is because the color change during the process of applying nail enamel to the nail and drying and solidifying it may lack clarity.

In such a case, it is preferable to add a small amount of NH3 as an auxiliary agent until the pH of the nail enamel reaches 10.
In this way, the color development of the nail enamel solution disappears, and the color change after drying becomes clear. Furthermore, in addition to alcohols, if it is necessary to use an additive that develops color before drying, NH3 can be similarly used to clarify the color change. The amount of styryl-like compound contained in the nail enamel according to the present invention is 0.001 to 1.0% based on the total amount of nail enamel. % by weight is preferred.

That is, if it is less than 0.001% by weight, the color change that is a feature of the present invention after the nail enamel applied to the nail dries and forms a film becomes difficult to clearly distinguish with the naked eye.
Also 1. This is because even if it is used in an amount exceeding 20% by weight, the cost of the nail enamel will only increase, and in particular, no noticeable difference in color change will be observed. More preferably 0.
01 to 0.1% by weight. Most of the styryl-like compounds applied to the present invention have light absorption in the ultraviolet region, and the nail enamel according to the present invention is white (including colorless).
Since it is a pale yellow compound, it will be colorless or pale yellow immediately after being applied to the nail unless a colored coloring material is added, but after drying and solidifying, the styryl-like compound used Depending on the type, blue, green, yellow, light,
It produces vivid colors such as purple and red.

In addition, when colored coloring materials are used, the dried nail enamel film exhibits a color tone that is a combination of the coloration of the coloring materials and the unique coloring of styryl-like compounds, so you can use various colors depending on your preference. It is also possible to select changes. This color change can be easily detected with the naked eye, and is not affected by the composition of the nail enamel, the ambient temperature during use, body temperature, etc., and it is possible to determine when the nail enamel film is formed based on this color change. Since it can be determined clearly and accurately, there is no need to rely on the user's personal touch as with conventional nail enamel.

Moreover, it can be said that such a color change can provide the user with an aesthetic sense that has not been recognized by conventionally used nail enamels.

Hereinafter, the variable color nail enamel according to the present invention will be specifically explained based on Examples, but the present invention is not limited thereto. Example 1 Methyl methacrylate-butyl methacrylate copolymer 25
parts by weight (molar ratio 1/1, average molecular weight 70,000) and parts by weight of ethyl methacrylate-methyl acrylate copolymer 1 (molar ratio 2/1, average molecular weight 85,000) were mixed with 15 parts by weight of ethyl acetate, acetic acid n The resin solution was dissolved in a mixed solvent consisting of 4 parts of -phthyl and 5 parts by weight of acetyltributyl citrate, and the resin solution was designated as liquid A.

Next, 0.1 parts by weight of each of the styryl-like compounds shown in Table 1 was dissolved in 5 parts by weight of ethyl acetate, and the solution was added to the above solution A to prepare nail enamel.

As shown in Table 2, the resulting nail enamels were colorless and transparent or pale yellow when applied to the nails, but when the nail enamels dried and solidified, the styryl-like content contained in each nail enamel appeared. It changed to a unique color based on the compound.

The color tone of the nail enamel film thus changed in color did not change in color or change in color even after 5 days had passed, and the color tone was maintained as it was. Table 1 Table 2 Example 2 2 parts by weight of ethyl cellulose (Hercules N-7), 1 part by weight of ethyl acetate, 17 parts by weight of butyl acetate,
4 parts by weight of toluene, 2 parts by weight of acetyltributyl stalate
．． A solution of A solution was obtained by dissolving the lily pads in a mixed solvent consisting of 5 parts by weight.

Next, 3,3-dimethyl-2-{4-(
0.01 part by weight of p-dimethylaminophenyl)1,3-butadienylene}indolino[2,11b]oxazolidine was dissolved to obtain Solution B.

Claims (1)

[Scope of Claims] 1. In a nail enamel containing a coloring agent, a part of the coloring agent is a variable color substance that has a different hue immediately after the nail enamel is applied to the nail and after it dries and hardens. Alternatively, variable color nail enamel is characterized in that it constitutes the entire amount. 2 The color-changing substance has a general formula ▲ Numerical formula, chemical formula, table, etc.
, R_4 is H, alkyl group, alkoxy group, nitro group,
Indicates a halogen or a fused ring. or each condensation reaction residue of an aromatic aldehyde, a heterocyclic aldehyde, an aromatic nitroso compound, or a heterocyclic nitroso compound, Y is O or S, and Z has 2 to 4 carbon atoms with or without a substituent. represents an alkylene. The variable color nail enamel according to claim 1, which is a styryl-like compound represented by: 3. The variable color nail enamel according to claim 2, wherein a styryl-like compound is dissolved in a solvent that is a base material for nail enamel. 4. The variable color nail enamel according to claim 3, wherein the solvent is composed of one or more selected from acetate esters, aromatic or fatty acid hydrocarbons, ketones, and ethers. 5. The variable color nail enamel according to claim 2, wherein the content of the styryl-like compound in the nail enamel is 0.001 to 1.0% by weight. 6. The variable color nail enamel according to claim 2, wherein R_1 and/or R_2 in the general formula is a lower alkyl group. 7. The variable color nail enamel according to claim 2, wherein R_3 in the general formula is H or a lower alkyl group. 8. The variable color nail enamel according to claim 2, wherein Z in the general formula is an ethylene group or a propylene group.