JPH04103513A - Water-based manicure cosmetic - Google Patents

Abstract

PURPOSE:To obtain a water-based manicure cosmetic having excellent adhesivity, water-resistance, abrasion resistance, etc., and containing water as main component to be a substitute for manicures using organic solvents by using plural kinds of acrylic polymer emulsions having different glass transition temperatures. CONSTITUTION:The objective manicure cosmetic is produced by using 5-60wt.% of two kinds of acrylic polymer emulsions composed of an acrylic polymer emulsion having at least relatively high glass transition temperature and an acrylic polymer emulsion having a glass transition temperature lower than that of the former emulsion by >=10 deg.C and properly compounding film-forming assistant, plasticizer, pigment, dye, antiseptic agent, perfumery, thickener, etc. It can be used as a nail enamel, nail enamel base coat, nail enamel overcoat, etc.

Description

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

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 film-forming agents, they have problems with flammability, solvent odor, and effects on the human body due to the use of organic solvents, especially negative effects on the nails themselves. It has serious drawbacks.

In order to solve these drawbacks, water-based nail polishes that do not use organic solvents have been developed and proposed in recent years.

For example, Japanese Patent Publication No. 54-28836 and Japanese Patent Publication No. 55-43
Publication No. 445 discloses nail beauty products made of acrylic polymer emulsions, but as far as the present inventors have tested, they have poor brush handling properties, film forming properties (particularly low hybridization film properties), and coating properties. The film is inferior in terms of gloss, etc.

Also, JP-A-56-131513 and JP-A-57-
No. 56410 discloses nail cosmetics made of acrylic polymer microemulsions, but the coating films obtained with these nail cosmetics have the drawback of being completely brittle against mechanical friction.

Furthermore, JP-A-56-131513 and JP-A-62-
Although Japanese Patent No. 63507 discloses a peel-off water-based nail polish, it has the drawback that it peels off easily during daily use, so it cannot be said to be practical.

Furthermore, all of the above nail polishes use polymer emulsions produced by emulsion polymerization using natural or synthetic water-soluble polymers and emulsifiers as film-forming agents, and these film materials themselves have poor water resistance, making them difficult to put into practical use. It has been difficult to obtain sufficient performance as a long-lasting nail polish.

[Means for Solving the Problems] In view of the above situation, the present inventors have improved gloss, adhesion, water resistance,
We conducted intensive research to obtain a water-based nail polish that has excellent coating strength, is flammable, and has no solvent odor.

As a result, they discovered that the above object could be achieved by using a combination of a plurality of acrylic polymer emulsions having different glass transition temperatures, and completed the present invention.

That is, in the present invention, the difference in glass transition temperature is 10°C.
The present invention provides an aqueous nail polish containing two or more of the above acrylic polymer emulsions.

The acrylic polymer emulsion used in the present invention is an acrylic polymer emulsion having at least a relatively high glass transition temperature (Tg) (hereinafter referred to as r high Tg).
(hereinafter referred to as "low Tg emulsion") and an acrylic polymer emulsion (hereinafter referred to as "low Tg emulsion") whose Tg is 10°C or more lower than that of the high Tg emulsion.
It consists of a seed acrylic polymer emulsion.

High Tg emulsion and low Tg emulsion are polymer emulsions obtained by the sole or copolymerization of acrylic acid-based or methacrylic acid-based monomers, respectively, and can be copolymerized with acrylic acid-based or methacrylic acid-based monomers as necessary. It is also possible to add vinyl monomers.

Examples of acrylic acid monomers include acrylic acid,
Methyl acrylate, ethyl acrylate, n-acrylate
Propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, N,N-dimethylamine ethyl acrylate, etc.; examples of methacrylic acid monomers include methacrylic acid, methyl methacrylate, methacrylate; ethyl acid, n-propyl methacrylate, isopropyl methacrylate,
Examples include n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, N,N-dimethylaminoethyl methacrylate, and the like.

Vinyl monomers (hereinafter referred to as "vinyl monomers") that can be copolymerized with such acrylic acid or methacrylic acid monomers include styrene, acrylonitrile, methacrylate, vinyl chloride, vinylidene chloride, and acetic acid. Examples include vinyl, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, N,N-dimethylamine propylacrylamide, and the like.

The acrylic polymer emulsion of the present invention is a high Tg emulsion and a low Tg emulsion obtained by polymerizing the above monomers.
A mixture of emulsions, each usually provided in the form of a 5-60% emulsion (as solids).

The mixing ratio of high Tg emulsion and low Tg emulsion varies depending on the type of each emulsion used, but the apparent Tg of the polymer emulsion after mixing is 10.
It is desirable to set the temperature to about 50°C.

Note that Tg (K) of the copolymer can be derived from the following formula.

1 / T g = W + / T g l + W 2
/ T g 2+...Tg+, 1g2,...: Composition Tg of the homopolymer of each monomer (K) Wl, W2,...: Weight fraction of each component: Absolute temperature Acrylic of the present invention High T in system polymer emulsion
The difference in Tg between the g emulsion and the low Tg emulsion is, as described above, 10°C or more, but preferably 20°C or more.

In addition, the manufacturing method includes emulsifier-free polymerization in which each of the necessary monomers is polymerized by a known method such as soap-free polymerization using a reactive emulsifier or aqueous medium heterogeneous polymerization without an emulsifier.

A particularly preferred method is to polymerize these monomers by solution polymerization or the like in a hydrophilic organic solvent that has a lower boiling point than water and is miscible with water, such as methyl ethyl ketone or lower alcohol, and then, after adding water, the organic solvent This is a method to obtain a polymer emulsion by distilling off.

The water-based nail beauty preparation of the present invention is prepared by blending the above-mentioned acrylic polymer emulsion as a film-forming base.

The amount of the acrylic polymer emulsion blended in the water-based nail polish is 5 to 60% by weight (hereinafter simply expressed as %) (as solid content).

If the amount is less than 5%, it will be necessary to apply several coats to obtain the coating film required for practical use, and if it exceeds 60%, the viscosity of the nail polish will become high and the brushability will deteriorate. A decrease in applicability is observed.

Moreover, it is preferable to further add a film-forming aid and a plasticizer to the water-based nail beauty preparation of the present invention. Film-forming aids and plasticizers are those that lower the film-forming temperature, and examples include ethylene glycol, propylene glycol, pentaerythritol, glycerin, liquid paraffin, chlorinated paraffin, machine oil, dioctyl phthalate, dibutyl phthalate. , tricresyl phosphate, cellosolve, butyl cellosolve, cellosolve acetate,
Examples include carpitol, butyl carpitol, carpitol acetate, butyl carpitol acetate, texanol, xylene, hexylene glycol, benzyl alcohol, phenethyl alcohol, 1,3-dibutylene glycol, dipropylene glycol, isoprene glycol, and the like.

These film forming aids and plasticizers are used in an amount of 0 to 25 parts by weight per 100 parts by weight of the acrylic polymer emulsion.
It is preferable to further add 3 to 20 parts by weight.

The nail beauty product of the present invention further includes pigments, dyes,
Preservatives, fragrances, thickeners, etc. can be added.

As pigments, especially R-221, R-226, R-22
0, B-I Al lake, Y-4 Al lake, and other known organic pigments. In addition to such organic colorants,
Inorganic materials such as titanium dioxide, brown iron oxide, red iron oxide, mica titanium bismuth oxychloride can also be used.

[Effects of the Invention] The nail beauty preparation of the present invention obtained as described above contains two or more types of acrylic polymer emulsions with a Tg difference of 10°C or more. Good gloss, adhesion, water resistance, coating strength, etc., which cannot be obtained with acrylic polymer emulsions, can be obtained. This nail polish also has advantages such as being flammable and free of solvent odor.

Therefore, it can be widely used as an alternative to conventional nail polishes based on 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 Synthesis of Polymer Emulsion A 2. 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, 71.7 parts of methyl methacrylate, 20.1 parts of n-butyl acrylate, and N were placed in the dropping funnel.

8.2 parts of N-dimethylaminoethyl methacrylate and 0.2 parts of azobisisobutyronitrile were charged.

While stirring, the temperature inside the reactor was raised to g o 'c, and a solution of the monomers and radical initiator in methyl ethyl ketone was added dropwise from the dropping funnel over a period of 15 ii. 2 hours after the completion of dripping, add 0.2 azobisisobutyronitrile.
A solution of 1 part 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 a further 5 hours to obtain a copolymer.

After the reaction, the copolymer solution was cooled to room temperature, and lactic acid 4.
After adding 300 parts of ion-exchanged water with stirring at 300 rpm, methyl ethyl ketone was distilled off at 40"C under reduced pressure, and water was further distilled off at 50 °C. A copolymer was obtained.

The obtained copolymer emulsion A had a solid content of 30% and a Tg of 50°C.

Synthesis Example 2 Synthesis of Polymer Emulsion B: In the same manner as in Synthesis Example 1, 49 parts of methyl methacrylate and 42.8 parts of n-butyl acrylate were used in 1,000 parts.
part, N, N-dimethylaminoethyl methacryate 8
．． Two parts were copolymerized in methyl ethyl ketone.

Next, 4.5 parts of acetic acid was added to this copolymer to neutralize it, and the phase was inverted to water in the same manner as in Synthesis Example 1 to obtain a copolymer.

The obtained copolymer (polymer emulsion B) had a solid content of 30% and TglO''C.

Synthesis Example 3 Synthesis of Polymer Emulsion C: In a 300 ml four-bottle flask, 130 parts of water, 73 parts of methyl methacrylate, n-acrylic acid
23 parts of butyl, 4 parts of acrylic acid, aqueous ammonia (28%
)20 parts and 0.0 parts ammonium persulfate as a polymerization initiator.
05 parts, stirred at 300 rpm in a nitrogen stream,
The polymerization reaction was carried out at 65°C for 3 hours. The mixture was then subjected to dialysis using cellophane paper to remove ionic impurities and obtain polymer emulsion C.

The obtained polymer emulsion C had a solid content of 35% and 7
There was a g50"CT.

Synthesis Example 4 Synthesis of Polymer Emulsion D 2 In the same manner as in Synthesis Example 3, the composition was 62 parts of methyl methacrylate, 34 parts of butyl acrylate, 4 parts of acrylic acid.
part was copolymerized.

The obtained polymer emulsion D had a solid content of 35% and T
There was a g30"CT.

Synthesis Example 5 Synthesis of Polymer Emulsion E 2 In the same manner as in Synthesis Example 3, the monomer composition was 75 parts of methyl methacrylate, 21 parts of butyl acrylate, and 4 parts of acrylic acid.
part was copolymerized.

The obtained polymer emulsion E had a solid content of 35% and a Tg
was 56°C.

Example 1 A water-based enamel was prepared using the recipe shown below.

(Formulation) Polymer emulsion A (7g 50℃) 90 parts Polymer emulsion B (7g 10℃) 10 parts pigment (red pigment R-221) 3 parts ion exchange water 10 parts calpitol)
10 parts diethyl phthalate 5 parts hydroxyethyl cellulose 0.5 parts fragrance
0.1 part preservative
0.1 part silicone antifoaming agent 0.1 part (method 12) Pigment slurry, polymer emulsion, thickener, which was prepared by adding a film forming aid and a plasticizer to ion-exchanged water and grinding it with a sand grinder. Add other ingredients,
The mixture was stirred and mixed uniformly and finally degassed to prepare nail enamel.

Example 2 A water-based enamel was prepared using the recipe shown below.

(Formulation) Polymer emulsion A (7g at 50°C) 10 parts Polymer emulsion B (7g at 10°C) 90 parts Pigment (red pigment R-221) 3 parts ion-exchanged water 1 part Calpitol
10 parts diethyl phthalate 5 parts hydroxyethyl cellulose 0.5 parts fragrance
0.1 part preservative
0.1 part Silicone antifoaming agent 0.1 part (Production method) Produced in the same manner as in Example 1.

Actual IM example 3 A water-based enamel was prepared using the recipe shown below.

(Prescription Polymer Emulsion C (7g 50℃) 50 parts Polymer Emulsion D (Tg 30℃) 50 parts Pigment (Red Pigment R-221) 3 parts Ion exchange water 10 parts Calpitol
10 parts diethyl phthalate 5 parts bentonite 0.5 parts fragrance
0.1 part preservative
0.1 part Silicone antifoaming agent 0.1 part (manufacturing method) Manufactured in the same manner as in Example 1.

Comparative example 1 A water-based enamel was prepared using the recipe shown below.

(Formulation) Polymer Emulsion C (7g 50°C) 100 parts am<red pigment R-221) 3 parts ion-exchanged water 1 part calpitol
10 parts diethyl phthalate 5 parts bentonite 0.5 parts fragrance
0.1 part preservative
0.1 part Silicone antifoaming agent 0.1 part (manufacturing method) Manufactured in the same manner as in Example 1.

Comparative example 2 A water-based enamel was prepared using the recipe shown below.

(prescription) Polymer emulsion D (Tg30℃) Pigment (red pigment R-221) ion exchange water calpitol diethyl phthalate bentonite fragrance Preservative Silicone antifoaming agent (Manufacturing method) It was manufactured in the same manner as in Example 1.

100 copies Part 3 10 copies 10 copies 5th part 0.5 part 0.1 part 0.1 part 0.1 part Comparative example 3 A water-based enamel was prepared using the recipe shown below.

(prescription) Polymer emulsion C (Tg50℃) 50 parts Volimer emulsion eye E (Tg56℃) 50 parts Pigment (red pigment R-221) 3 parts ion exchange water calpitol diethyl phthalate bentonite fragrance Preservative Silicone antifoaming agent (Manufacturing method) It was manufactured in the same manner as in Example 1.

10 parts 10 parts 5 parts 0.5 parts 0.1 part 0.1 part 0.1 part Test Examples Regarding the water-based nail enamels obtained in Examples 1 to 3 and Comparative Examples 1 to 3, drying properties, gloss, and adhesion The properties, water resistance, abrasion resistance, and odor were examined using the following methods. This result is the first
Shown in the table.

(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: 3 minutes or less 623-6 minutes ×: 6 minutes or more (2) Gloss At the time of drying property evaluation, the gloss of the dried coating film after 30 minutes is evaluated with the naked eye.

(3) Adhesiveness At the time of drying evaluation, the adhesion to nails was evaluated after 30 minutes by scraping off the film from the surface with a micro spatula.

(4) Water resistance 0.5 x 15 x 40 layers Apply the sample evenly with a nail enamel brush to a nylon plate of 0.5 x 15 x 40 layers. After drying for 1 hour at a temperature of 25 °C and a relative humidity of 60%, water at 35 °C. The film is immersed in water for 1 hour and the presence or absence of deterioration of the coating film (cloudiness, swelling, softening, peeling, etc.) is evaluated.

(5) Abrasion resistance When evaluating drying properties, observe the condition after rubbing the dried coating film 50 times with a cotton cloth after 30 minutes.

(6) Smell Sensory evaluation of the odor of the nail enamel bottle at the mouth.

The above evaluation items (2) to (6) were determined as follows.

■ = Extremely good O: Good Δ: Fair It was excellent in terms of hardness, water resistance, abrasion resistance, etc.

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Claims (1)

[Claims] (1) A water-based nail polish containing two or more types of acrylic polymer emulsions whose glass transition temperatures differ by 10°C or more.