JPH04103515A - Water-based manicure cosmetic - Google Patents

Abstract

PURPOSE:To obtain a water-based manicure cosmetic having excellent adhesivity, water-resistance, abrasion resistance, aging stability, etc., and containing water as main component to be a substitute or organic solvent by using a cationic polymer emulsion and a hydrated oxide of a polyvalent metal element as essential components. CONSTITUTION:The objective manicure cosmetic is produced by using 5-60wt.% (in terms of solid) of a cationic polymer emulsion and 0.1-10wt.% of a hydrated oxide of a polyvalent metal element (e.g. boehmite) and properly compounding pigment, dye, antiseptic agent, perfumery, plasticizer, thickener, wetting agent, defoaming agent, filler, etc. The above emulsion can be produced by adding water to an organic solvent solution of a copolymer produced by the copolymerization of a cationic monomer and a hydrophobic nonionic monomer, and distilling off the organic solvent. It can be used as a nail enamel, nail enamel base coat, nail enamel overcoat and, further, eye liner, mascara, pack, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a water-based nail beauty product, and more specifically, a water-based nail beauty product that uses water as a main ingredient instead of the organic solvents conventionally used in nail beauty products. Regarding fees.

The nail beauty agent in the present invention includes nail enamel, nail enamel base coat, nail enamel overcoat, and the like.

[Prior art and its problems] Nail cosmetics such as nail enamel, nail enamel base coat, and nail enamel overcoat are widely used to color and decorate nails and to prevent scratches on nails. .

Conventional nail polishes are mainly based on resins such as nitrocellulose and alkyd resins as film-forming agents, as well as plasticizers and organic solvents. However, although these organic solvent-based nail polishes have excellent performance as coating film forming agents, they are organic solvents. It has serious drawbacks such as flammability, solvent odor, and adverse effects on the human body, especially on the nails themselves.

On the other hand, products using polymer emulsions or nail enamels are advantageous in terms of safety because they do not use solvents, and such technical numbers have been known for a long time (equity a).
o55-4s No. 445, JP-A No. 57-56410 and JP-A No. 54-28836, etc.).

However, nail enamels and the like using the above-mentioned polymer emulsions have problems with water resistance and durability, and improvements have been needed.

Furthermore, the above-mentioned durability,
In addition to film properties such as water resistance, storage stability is also required to be good.

Titanium, mica,
Inorganic pigments such as titanium mica and burl brighteners are added, but
These have a high specific gravity and settle over time, which may adversely affect the appearance, cosmetic effects, and usability of the nail polish, and may cause deterioration in quality.

Although it is possible to improve the storage stability of water-based nail polishes by adding a pigment anti-settling agent, the addition of this anti-settling agent further deteriorates the durability and water resistance of the formed film. Put it away.

As described above, it has been difficult to design a water-based nail polish that has good durability, water resistance, and storage stability.

[Means for Solving the Problems] In this situation, the inventors of the present invention have taken the initiative! As a result of research, we found that in a system using a polymer emulsion with a positive surface charge as a film forming agent, if a hydrous oxide of a polyvalent metal is used, the pigment can be stably dispersed, resulting in a nail polish with good durability and water resistance. The present invention was completed based on the discovery that the following can be obtained.

That is, the present invention uses the following components (A) and (B) (A) cationic polymer emulsion with a solid content of 5.
The present invention provides an aqueous nail beauty product characterized by containing 0.1 to 10% by weight of (B) a hydrous oxide of a polyvalent metal element.

The cationic polymer emulsion, component (A) of the present invention, is a Bommer emulsion obtained by performing a reaction such as emulsion polymerization in the presence of a cationic surfactant, a cationic monomer polymerized only, or a cationic monomer and a hydrophobic polymer emulsion. Examples include polymer emulsions obtained by copolymerization with nonionic monomers. The polymer emulsion obtained by emulsion polymerization in the presence of a cationic surfactant is synthesized by a known emulsion polymerization method by appropriately combining known cationic and nonionic monomers.

On the other hand, a cationic polymer emulsion produced by copolymerization of a cationic monomer and a hydrophobic nonionic monomer is produced by using an appropriate cationic monomer and a hydrophobic nonionic monomer.
It is produced by polymerization using known methods such as emulsion polymerization and emulsifier-free polymerization.

A particularly preferred cationic polymer emulsion contains 0.5 to 15% by weight of a nitrogen-containing monomer (cationic monomer) having a positively chargeable salt-forming group and a polymerizable double bond, and a polymer copolymerizable with the nitrogen-containing monomer (cationic monomer). Nonionic, water-insoluble monomers with possible double bonds (hydrophobic nonionic monomers)
After adding water to an organic solvent solution of a copolymer obtained by copolymerizing 85 to 99.5% by weight, the organic solvent is distilled off (phase inversion emulsification method). Here, the organic solvent refers to a solvent that has a boiling point lower than that of water and is miscible with water, such as methyl ethyl ketone and lower alcohol.

It is also possible to perform seed polymerization in multiple stages to produce a composite polymer emulsion with a multilayer structure, which can then be used.

Examples of the cationic monomer include (meth)acrylic acid esters or (meth)acrylamides having a dialkylamino group such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropylacrylamide; N,N- dimethylaminostyrene, N,
Styrenes having a dialkylamino group such as N-dimethylaminomethylstyrene; 4-vinylpyridine, 2-
Examples include vinylpyridines such as vinylpyridine, or those obtained by quaternizing these with a known quaternizing agent such as an alkyl halide, a pencil halide, an alkyl or arylsulfonic acid, or a dialkyl sulfate.

In addition, examples of hydrophobic nonionic monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate,
Isobutyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyl versatic acid , vinyl acetate, styrene, acrylonitrile, dibutyl maleate, and other diene and olefinic unsaturated hydrocarbons.

The cationic polymer emulsion obtained in this way is contained in the nail preparation of the present invention in an amount of 5 to 60% by weight (solid content).
The solid content (hereinafter expressed in %) is blended.

If the amount is less than 5%, it will be necessary to apply several layers to obtain the coating film required for practical use, and if it exceeds 60%, the viscosity of the nail polish will increase, resulting in poor brushability, etc. A decrease in coating properties is observed.

Hydrous oxides of polyvalent metal elements which are component (B) of the present invention include divalent to hexavalent metal elements such as magnesium, beryllium, potassium, indium, iron (■), aluminum, lanthanum, manganese (■), Antimony (III)
, bismuth (■), titanium (■), tin (TV), zirconium, cerium (■), thorium, silicon, manganese (IV) niobium, tantalum, antimony (■), molybdenum, tungsten, etc. It will be done.

In this specification, the hydrated oxide is also referred to as a hydrated oxide, and is a hydrate of a metal oxide containing a so-called hydroxide, and is represented by the general formula MnO,.XH20 (wherein, M is metal, n and m are integers, and X is a positive number).

Examples of hydrous oxides of polyvalent metal elements include BeO.1.
7H20, Hg (OH), Ga 203-2.4
H20, In203-3.5H20,5b203・3H
20, Bi203-3H20, La203-3H20,
Fe203-2H20, β-Fe203・H2O, A1
203-3H,, ○, Al2O3・1.2H20, Al
2O3・H2O, Mn0-OH, Mn ○2-0.6
H20, 5i02-1.2H20, a-TiO2-1,
6H20, β-T i O2・0, 8 H20, T
i O2・0, 5H20 (rutile), Z rO2・
2.8H20, αS n 02 ・1, 8 H2O,
β-5nO2-1, 6H20, Ce 02 ・2, 6
H20, T h O2'3.5H20, Nb203-
4.6H20, Ta203-3.4H20, S b 2
03 ・4 H20, HBi03, MOO3・2H20
, WO3-3H20, WO3-1, 8H20, and the like.

Of these, when blending into nail enamel,
Hydrous oxides of aluminum, titanium, and iron are preferred, and boehmite, which is a type of alumina hydrate sol, is particularly preferred. In addition, when using a sol of a hydrated oxide of a polyvalent metal element, peptize it by treating a few drops of water of the hydrated oxide of a polyvalent metal element with a monobasic acid, and then add the monobasic acid. Alternatively, it is preferable to adjust the viscosity of the sol by adding water-soluble salts. If further thickening is required, a known water-soluble polymer may be blended.

The polyvalent metal hydrated oxide preferably has a particle size of 100 μm or less, particularly preferably 10 μm or less.

Moreover, it is preferable to use a hydrous metal oxide dispersion liquid, and the pH thereof is preferably 1 to 7.

It is preferable to use volatile acids such as hydrochloric acid, nitric acid, acetic acid, and formic acid to adjust the pH of the dispersion liquid, but metal hydrated oxides exhibit buffering properties in their own specific pH range depending on the amount of acid added. It is necessary to keep this in mind. The amount of acid added is preferably about 0.001 to 5 in molar ratio to the metal hydrated oxide.

When the pH of the system is in the above pH range of 1 to 7, the metal hydrated oxide is dispersed in a colloidal state, and in this state, the interface of the colloidal particles is positively charged.

These hydrated oxides of polyvalent metals are preferably used in an amount of 0.01 to 20%, particularly 0.1 to 10%, in the aqueous nail preparation of the present invention. Examples of monobasic acids for treating metal hydrated oxides include acetic acid, formic acid, sulfamic acid, carboxylic acid, nitric acid, and hydrochloric acid.

Further, the water-soluble salts may be either organic or inorganic as long as they are water-soluble and non-toxic.

Among these, water-soluble inorganic salts include alkali metal, alkaline earth metal, or aluminum salts of inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. Among these inorganic salts, preferred are potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, potassium nitrate, sodium nitrate, magnesium nitrate, calcium nitrate, aluminum nitrate, potassium chloride, sodium chloride, magnesium chloride, calcium chloride, aluminum chloride, Mention may be made of potassium carbonate, sodium carbonate, aluminum carbonate, among which particular mention may be made of sodium sulfate, potassium nitrate, sodium nitrate, potassium chloride, and sodium chloride.

Examples of water-soluble organic salts include alkali metal salts of acetic acid, citric acid, and tartaric acid.

These water-soluble salts vary depending on the ionic value of the salt, but
Usually 0.001 to 10% based on metal hydrated oxide
It is preferable to use g=0.01 to 5%.

In addition to the above-mentioned ingredients, the aqueous nail preparation of the present invention includes pigments,
Dyes, preservatives, fragrances, plasticizers, film-forming aids, thickeners, wetting agents, antifoaming agents, fillers, etc. can be blended.

As pigments, especially R-221, R-226, B-40
4, Y-401, and other known organic pigments. In addition to such organic colorants, inorganic materials such as titanium dioxide, brown iron oxide, red iron oxide, titanium mica, and bismuth oxychloride can also be used.

As plasticizers and film-forming aids, known ones such as cellosolve, methyl cellosolve, butyl cellosolve, carpitol, butyl carpitol, cellosolve acetate, butyl cellosolve acetate, butyl carpitol acetate, hexylene glycol, etc. can be used. From the viewpoint of storage stability and water resistance of the coating film, the blending amount is preferably 0 to 15%.

Known thickeners can be used, but since the polymer emulsion is cationically charged, nonionic water-soluble thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene oxide, methylcellulose, hydroxyethylcellulose, and hydroxypropylmethylcellulose are used. Cationically modified products such as thickeners, cationized guar gum, and cationized cellulose can also be used.

[Effects of the Invention] Since the nail beauty preparation of the present invention is water-based without using organic solvents, it is highly safe and has good water resistance, durability, and adhesion.

Furthermore, it is an excellent product that keeps the pigments etc. blended in the system stable and does not cause problems such as sedimentation even when stored for a long period of time.

Therefore, it is expected to be used as an alternative to conventional nail polishes that use organic solvents.

[Examples] Next, the present invention will be explained in more detail by giving synthesis examples, examples, and comparative examples, but the present invention is not limited in any way by these examples.

Synthesis Example 1 50 parts of methyl ethyl ketone was charged into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube, and nitrogen gas was passed through the reactor to remove dissolved oxygen.

Meanwhile, 35 parts of methyl ethyl ketone, 56 parts of methyl methacrylate, and 4 parts of n-butyl acrylate were added to the dropping funnel.
0 parts, N,N-dimethylaminoethyl methacrylate
4 parts and 0.2 parts of azobisisobutyronitrile were charged.

While stirring, the temperature inside the reactor was raised to 80°C, and a solution of the monomers and radical initiator in methyl ethyl ketone was added dropwise from the dropping funnel over 2.5 hours. Two hours after the completion of the dropwise addition, a solution of 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of methyl ethyl ketone was added.

After aging at the same temperature for 3 hours, a solution of 0.1 part of azobisisobutyronitrile dissolved in 5 parts of methyl ethyl ketone was added again, and the reaction was continued for an additional 5 hours to obtain a copolymer.

A part of the obtained copolymer was isolated and its molecular weight was measured by gel permeation chromatography, and the weight average molecular weight was 75,000. The calibration curve for Kölpermeation chromatography was prepared using polystyrene as a standard substance (solvent: tetrahydrofuran).

After the winter reaction period, the copolymer solution was cooled to room temperature and added with lactic acid.
Add 5.6 parts to neutralize, and further stir at 300 rpm.
400 parts of ion-exchanged water was added. Methyl ethyl ketone was distilled off at 40° C. under reduced pressure, and water was further distilled off at 50° C. to obtain a polymer emulsion with a solid content of 30%.

Synthesis Example 2 50 parts of isopropanol was charged into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube, and dissolved oxygen was removed by flowing nitrogen gas.

Meanwhile, 35 parts of isopropanol, 50 parts of styrene, 46 parts of ethyl acrylate, 4 parts of N,N-dimethylaminopropylacrylamide, and 0.2 parts of azobisisobutyronitrile were charged into a dropping funnel.

While stirring, the temperature inside the reactor was raised to 80° C., and the isopropanol solution containing the above monomer and radical initiator was added dropwise from the dropping funnel over 2.5 hours. After 2 rf of monomer dropwise addition, a solution of 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of isopropanol was added. After aging at the same temperature for 3 hours, a solution of 0.1 part of azobisisobutyronitrile dissolved in 5 parts of isopropanol was added again, and the reaction was continued for another 5 hours to obtain a copolymer.

When a part of the obtained copolymer was isolated and its molecular weight was measured by gel permeation chromatography, its weight average molecular weight was 75,000. The calibration curve for gel permeation chromatography was prepared using polystyrene as a standard substance (solvent: tetrahydrofuran).

After the reaction, the copolymer solution was cooled to room temperature, and acetic acid 5.
6 parts were added to neutralize the mixture, and 400 parts of ion-exchanged water was further added while stirring at 30 rpm. Methyl ethyl ketone was distilled off at 40°C under reduced pressure, and water was further distilled off at 50'C to obtain a polymer emulsion with a solid content of 33%.

Examples 1-4 Nail enamel was prepared according to the formulation shown in Table 1.

(Manufacturing method) A film-forming aid was added to ion-exchanged water, pigments, polymer emulsions, boehmite gel, and other ingredients were added, stirred and mixed uniformly, and finally degassed to prepare nail enamel.

(Composition) (Left below) Table 1 (Manufacturing method) Add ion-exchanged water, a film-forming aid, pigment, Bommer emulsion, and other ingredients, stir and mix uniformly, and finally degas. , and prepared enamels.

(Composition) Table 2 Ratio Examples 1 to 4 Nail enamels were prepared according to the formulations shown in Table 2. In Comparative Example 3.4, commercially available DIANAL LX-125 (anionic acrylic emulsion, solid content 35%, manufactured by Mitsubishi Rayon) was used as the polymer emulsion.

Test Examples The physical properties of the nail enamels obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated by the following method. The results are shown in Table 3.

(Evaluation method) (1) Drying property A sample is applied to the nail with a nail enamel brush under conditions of a temperature of 25° C. and a relative humidity of 60%, and the drying time to the touch is measured.

O; Within 3 minutes Δ; 3 to 6 minutes x; 6 minutes or more (2) Gloss During drying evaluation, drying after 30 minutes Visually evaluate the gloss of the paint film.

(3) When evaluating adhesion and drying properties, evaluate the adhesion to the nail after 30 minutes by scraping off the film from the surface with a micro spatula (4) Water resistance 0.5 x 15 x 40 mm nylon plate Apply the sample uniformly with a nail enamel brush and heat at 25°C.
After drying for 1 hour at 60% relative humidity, soak in water at 35°C.
Is there any deterioration of the paint film after soaking for a long time (cloudiness, swelling, softening, etc.)?
peeling, etc.).

(5) Abrasion resistance During drying evaluation, drying after 30 minutes The condition after rubbing the coating film 50 times with a cotton cloth is observed.

(6) Smell I smell the nail enamel bottle around my mouth. Evaluate your abilities.

In addition, regarding the above evaluation items (2) to (6), The judgment was made as follows.

O; Very good 0; Good △; Average ×: Poor (7) Stability over time The sample was left in a constant temperature bath at 40°C for one month, and the appearance was visually observed for the presence or absence of precipitation of the pearlescent agent and pigment.

O: Extremely good ○, Good ×: Sedimentation Table 1 Results) Margin below As is clear from the results, the nail polish of the present invention has better adhesiveness, water resistance, abrasion resistance, and stability over time than the comparative example. She was excellent in all respects including sex.

The present invention is widely applicable to other eye makeup cosmetics such as eyeliners and mascaras, skin cosmetics such as bags and hair colorants, and hair cosmetics.

Below Up Out wish Man transformation king KK formula

Claims (1)

[Claims] (1) The following two components (A) and (B), (A) Solidify the cationic polymer emulsion 5-60% by weight as a form component (B) Hydrous oxide of polyvalent metal element 0.1~ 10% by weight A water-based nail beauty product characterized by containing.