KR830002531B1 - Make up cosmetics - Google Patents

Abstract

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Description

Make up cosmetics

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a make-up cosmetic product by blending a novel polymer emulsion, and is particularly suitable as an eye make-up cosmetic product.

Generally, make-up cosmetics, especially eye make-up cosmetics, are classified into water systems, oil systems, and powder systems according to their form.As a criterion for evaluating the products, they are easy to use, have a good feeling, and the stability of the products. It may be good, it is safe for skin, and especially the durability of makeup is good.

Conventional make-up cosmetics have poor makeup sustainability, and due to interactions with other cosmetic products used in combination with the action of human secretions such as sweat, tears, skin oil, and water such as rain, snow, pool water, and seawater, etc. In addition, the makeup is often broken by physical action such as friction by hands or clothing, and the improvement of the advantage as a far-line type in the oily or oil system can be seen. -27695, Japanese Patent Application Laid-Open No. 52-90637), water-based coating type, or other water-type types were not satisfactory. For example, water-based products contain a large amount of hydrophilic substances, and thus are susceptible to sweat, tears, and boiling, and have poor water resistance. In addition, the oil-based thing, on the contrary, is affected by skin oil or the oil content of the cosmetic product used in combination, and makeup is broken. In other words, oil resistance is poor. Moreover, neither water resistance nor oil resistance is enough in an emulsification system.

This cosmetic breakage is not only caused by interaction with water or oil, but also by the movement of the skin at the site of use, and by the friction of the hands or the outside. to be.

Until now, various products have been developed by the cosmetics researcher who have developed a product that satisfies these conditions, but none of the water systems have satisfied all the conditions.

Among these product forms, the film-type eye makeup cosmetics using polymer emulsification is one of widely used products because they have excellent properties such as ease of use and cosmetic effects.

Conventional cosmetic ingredients of this kind have been used as a film-forming agent, such as natural emulsion or polymer emulsion by emulsion polymerization using a water-soluble polymer or emulsifier, but it is difficult to obtain sufficient water resistance as cosmetics due to the poor water resistance of these high molecular materials themselves. It was.

In order to solve this problem, for example, the development of an emulsified coating type, such as cosmetics for solid, semi-solid, liquid oil-water-polymer emulsion-based eyelashes, can be found in Japanese Patent Application Laid-Open No. 50-125043. Although the water resistance of the polymer emulsion itself is not considered, it cannot necessarily be said to be complete.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete the outstanding makeup cosmetics which do not have the above faults by using the novel polymer emulsion excellent in water resistance.

The development and review of polymer emulsions with excellent water resistance have already been reviewed in the adhesive and paint industry, and various emulsions have been developed. However, for cosmetics, the following three points must be used. Original development is indispensable.

1. No harmful ingredients exist for human body (formalin, unreacted monomer, etc.)

2. Stable against microorganisms.

3. Have excellent coating properties.

(1) Form a continuous film. (3) Good adhesion to skin.

(2) The coating should have adequate hardness and flexibility. (4) The film should be excellent in water resistance.

Known techniques using polymer emulsions in cosmetics include, for example, British Patent No. 1110240, US Patent No. 3639572, and Japanese Patent Laid-Open No. 48-36347.

British Patent No. 1110240 discloses skin cosmetics containing neutral and non-toxic acrylate esters (3-7%) such as ethyl acrylate, methyl methacrylate, butyl methacrylate, and methacrylic acid, in particular, friction resistance, fouling resistance, water resistance, liquid As a shape eye makeup, US Patent No. 3939572 is from the same applicant as the above-mentioned UK patent, and a polymer emulsion containing butyl acrylate, ethyl acrylate, butyl methacrylate and methacrylic acid as 20: 15: 60: 5 It is -7% friction, stain and water resistant eyeliner.

Japanese Patent Application Laid-Open No. 48-3647 discloses a method for producing a liquid eyeliner mainly composed of 50% synthetic resin emulsion, especially copolymerized emulsion of vinylidene chloride and vinyl chloride or 60% methyl methacrylate emulsion. Neither of these are satisfactory in terms of water resistance and stability.

Because the polymer emulsions used as these well-known techniques, for example, in the US and UK patents contain considerably large amounts of ethyl acrylate and methacrylic acid, which are poor in water resistance, in the polymer composition, the film obtained from these polymer emulsions is extremely The lack of water resistance and the small amount used in cosmetics can not expect any effect on the makeup lasting effect, particularly the water resistance. Moreover, as the synthetic resin emulsion of Japanese Patent Laid-Open No. 48-36374, there are many problems in that the resin composition itself is safe for the human body and is not preferable as a raw material for cosmetics.

This invention provides the outstanding makeup cosmetics which do not have the above faults by using the special polymer emulsion which used the emulsifier.

Make-up cosmetics of the present invention is a copolymerized polymer emulsion obtained from one or two or more kinds of acrylic acid ester monomers having 4 to 18 carbon atoms in the ester portion and one or two or more kinds of methacrylic acid ester monomers, preferably 20-. It is obtained by mix | blending 10-25 weight% as 50 weight% and effective resin powder.

As the acrylic ester monomers, butyl acrylate (BA), isobutyl acrylate (ISOBA), hexyl acrylate (HA), 2-ethylhexyl acrylate (2EHA) and the like are contained, in particular 2-ethylhexyl acrylate alone It is most preferable to use together or with another acrylic acid ester monomer. When methyl acrylate or ethyl acrylate having 3 or less carbon atoms in the ester portion is used, the water resistance is extremely bad, and a good makeup cosmetic cannot be produced. Moreover, the acrylic acid ester whose carbon number of an ester part is 19 or more is bad in reactivity, and is not suitable for emulsion polymerization. Moreover, when the carbon number of an ester part becomes 9 or more, the obtained polymer emulsion will smell. Therefore, some restriction | limiting is added to the compounding condition to cosmetics.

Therefore, 4-8 are preferable and, as for carbon number of an ester part, 2-epolhexyl acrylate is the most preferable especially.

As a monomer used together with the above-mentioned acrylic ester monomer, methacrylic methacrylate (MMA), ethyl methacrylate (EMA), and butyl methacrylate (BMA) having a MFTC (minimum film formation temperature) of 0% or more when homopolymerized Methacrylic acid ester, such as these, is used. Vinyl acetate, styrene, acrylonitrile, vinyl chloride, and the like have defects in skin safety, water resistance and odor, and should not be used.

The amount of methacrylic ester monomer mixed with the acrylic acid ester monomer varies depending on the type of the acrylic acid ester monomer, the product form of the cosmetic to be produced, or other components to be incorporated into the cosmetic, for example, the amount of powder or oil, Although not limited to, for example, in the case of MMA, acrylic ester monomer / MMA = 5 / 5-8 / 2 is preferably 6 / 4-7 / 3, and in the case of EMA, acrylic ester Nomo / EMA = 3 / 7-7 / 3 Preferably it is 4 / 6-6 / 4.

Generally speaking, acrylic ester monomer / methacrylic acid ester monomer = 3 / 7-8 / 2, and it is 30 degreeC-20 degreeC, Preferably it is 10 degreeC-10 degreeC from the M.F.T. which a polymer has.

Synthesis of the emulsion can be carried out by a common known emulsion polymerization method. That is, an aqueous solution of an emulsifier is placed in a polymerization reactor, and then a monomer and a polymerization initiator (for example, hydrogen peroxide or ammonium persulfate, etc.) are added dropwise over several hours under conditions heated to 50-80 ° C. After polymerization and ripening for a while, unreacted monomer is removed under reduced pressure.

Generally, 0.2-5% of anionic and nonionic emulsifiers and 0.05-1.0% of polymerization initiators are used as the emulsifier to perform the polymerization completely. In some cases, it is needless to say in the prior art that coexistence of a small amount of carboxyl-containing monomers (for example, acrylic acid, methacrylic acid, etc.) is preferable.

Next, the manufacture example (synthesis example) of the polymer emulsion used for this invention is shown.

Synthesis Example 1

150 mι of water is placed in a 500 mι four-necked flask, and 3.0 g of polyoxyethylene lauryl ether and 0.3 g of lauryl sulfate are dissolved. Butyl acrylate 105mι methyl methacrylate 45mι, monomer mixed with 2mι acrylic acid and 10mι of 10% aqueous ammonium persulfate solution were each divided into several times, and dropped into a flask heated to 70-80 ° C, and in nitrogen stream, The polymerization reaction was carried out at a stirring speed of 250 rpm (torsional stirring rod) for 3 hours.

Thereafter, the mixture was further heated and stirred for 1 hour, depressurized to 500 mm Hg, and the unreacted monomer was removed. After cooling, the cellophane dialysis membrane was transferred and dialyzed to remove ionic impurities, thereby obtaining a polymer emulsion having good coatability.

Synthesis Example 2

Into a 500 ml four-necked flask, 150 ml of water is placed and 4.5 g of polyoxyethylene lauryl ether and 0.2 g of lauryl sulfate are dissolved. Monomer mixed with 45mι of butyl acrylate, 45mι of 2ethylhexyl acrylate, 60mι of methyl methacrylate and 3mι of acrylic acid, and 10mι of 10% aqueous ammonium persulfate solution were divided into several times or several times, respectively, at 70-75 ° C. The flask was added dropwise into an aqueous solution of a heated flask and subjected to polymerization for 3 hours at a stirring speed of 250 rpm (torsional stirring rod) in a nitrogen stream.

After that, heating and stirring were carried out for 1 hour, and deodorization was carried out at 500 mmHg.

After cooling, dialysis is performed using a cellophane dialysis membrane to remove ionic impurities, thereby obtaining a polymer emulsion film having good coatability.

Next, in order to clarify the range of a polymer composition, the physical property value of the polymer emulsion in various monomer ratios was recorded in Table 1.

Table-1

Coating characteristics of the polymer emulsion film at various monomer ratios

The evaluation criteria of Table-1 are as follows.

◎ Extremely good

○ good

△ normal

× bad

In addition, the evaluation test method of the film characteristics of Table-1 is as follows.

(1) Transparency: A sample is applied on the skin and the transparent glass plate with a width of 5 × 15 mm, and the transparency after drying is evaluated.

(2) Adhesion: A sample is applied on the skin and a nylon plate of 0.5 × 20 × 50mm size under the condition of temperature 25 ° C. and 50% humidity, and the adhesiveness of the skin after 30 minutes is functional as a micro spatular. Determine.

(3) Whitening degree: A sample is applied on a nylon plate of 0.5 × 20 × 50mm size, dried for 5 hours, immersed in distilled water, and after 1 day, the whitening degree and swelling degree of the film after 7 days are visually determined.

(4) Water-Adhesive Resistance: For the samples of the whitening degree of (3), the degree of adhesion and peeling of the sample on the nylon plate are evaluated in the same manner.

(5) Dry adhesiveness: The sample is uniformly applied on the skin and on a nylon plate of 0.5 × 20 × 50mm size under the condition of temperature 25 ° C. and 50% humidity, and the adhesiveness after 30 minutes is removed from the surface by a micro spatula. Peel off and evaluate.

By using this polymer emulsion in an eye makeup cosmetic, 15-90% (as an emulsion of 50% resin concentration), preferably 20-50%, depending on the use, the product which has the outstanding product characteristic can be obtained.

That is, it becomes possible to reflect the said characteristic which a polymer emulsion has to a product characteristic, and the make-up cosmetics which satisfy various conditions are obtained.

If the amount of the polymer emulsion added in the product is less than 15%, the polymer emulsion may not function due to the film forming property of the polymer itself or other hydrophilic additives in the prescription.

Table 2 shows the product characteristics when the addition amount of the emulsion is changed, but the addition amount is preferably 15% or more, preferably 20-50%.

As mentioned above, the addition of the above-mentioned polymer emulsion obtained by an emulsion synthesis method using an emulsifier such as a surfactant and a protective colloidal agent to obtain an eye makeup cosmetic that satisfies various conditions is not yet known in the literature.

Next, the use effect of the cosmetics by this invention is described.

Since this invention aims at the improvement of the cosmetic persistence in time-lapse of cosmetics especially eye makeup cosmetics, it is necessary to evaluate the effect of actual cosmetic persistence. For this reason, the effect of use was examined by the practical use test and physical measurement shown next.

[Test Product] A file-off eyeliner product corresponding to Example 1 described later and a commercially available similar product.

TABLE 2

Addition amount and product characteristics of polymer emulsion

Evaluation standard

X: The effect is not seen (* the effect is too bad)

△: effect can be seen somewhat

○: good

[Test Method]

(1) Practical use test by 50 panelists

(2) Evaluation by physical measurement

Samples were applied to a nylon sheet of 10 × 40 mm and dried at room temperature for 3 hours.

(Vi) 10 g of Duracon beads were added to a 50 ml sample tube, and the sample was added and shaken with a mixer for 5 hours to evaluate the degree of abrasion of the coating film (friction adhesiveness).

(Ii) 10 g of Duracon beads and 20 ml of ion-exchanged water were placed in a 50 ml sample tube, and the sample pieces were inserted and shaken with a mixer for 5 minutes to evaluate the adhesion and dissolution of the coating film. Water friction adhesion).

TABLE 3

Evaluation standard

0 Good Normal × Bad ＃ Extremely poor

Table-3 compares the product characteristics of the commercially available eyeliner and the film-type eyeliner using the polymer emulsion obtained in the present invention, and the apparent effect is shown.

Next, the Example which concerns on this invention is shown.

Example-1

quite

Sodium polyphosphate and polyoxyethylene sorbitan monooleate are dissolved in ion-exchanged water, and carbon black iron oxide and titanium dioxide dispersion are mixed and mixed therein, and uniformly ground and dispersed using a colloid mill.

A glycerol and a midpoint agent are added to it, and a polymer emulsion, a preservative, and a fragrance | flavor are added sequentially, stirring and mixing, and mixing until it becomes uniform, and a black peel-off eyeliner can be obtained.

Example 2

Clinic Mascara

[Prescription] Beeswax 3.0 (Weight) Talc 5.0

Solid Paraffin Wax 3.0 Black Iron Oxide 13.0

Stearic Acid 2.5 Polymer Emulsion 25.0

Hard Flow Paraffin 5.0 EMA / BA = 40/60 Resin Content 50%

Ion-Exchange Water 36.5 Propylene Glycol 3.0

Triethanolamine 1.0 perfume

Preservative of Polyvinyl Alcohol 1.0

Bentonite 2.0

quite

Dissolve and dissolve propylene glycol, triethanolamine, bentonite and polyvinyl alcohol in ion-exchanged water. And talc and a pigment are added, it disperse | distributes uniformly, and it warms up to 70 degreeC. The heat-dissolved oil phase component is added to this, while stirring gradually, and it emulsifies uniformly. After emulsification, a polymer emulsion is added, the mixture is uniformly mixed, and then, a preservative and a flavoring agent are added, and the mixture is cooled to 40 ° C to give a black cream-like mascara.

Example-3

foundation

[Prescription] Hard Flow Paraffin 10.0 (by weight) Bentonite 2.0

Lanolin derivative 2.0 polymer emulsion 30.0

Solid paraffin wax 2.0 MMA / 2EHA = 3/70

Stearic acid 3.0 resin 50%

Cetyl Alcohol 0.5 Talc 15.5

Sorbitan sesquioleate 1.0 black iron oxide 0.2

Propylene Glycol 2.0 Iron Oxide 2.0

Polyethylene Glycol 3.0 Red Iron Oxide 0.5

Ion-exchanged water 25.3 Preservative

Triethanolamine 1.0 perfume

quite

Bentonite-based midpoints soaked in propylene glycol and polyethylene glycol are dispersed in ion-exchanged water, and triethanol amine is added to disperse and dissolve uniformly.

It is then warmed up to 70 ° C. to add talc and pigment and to disperse uniformly. Next, the applied oil phase component is gradually added to the aqueous phase prepared while stirring, and then emulsified uniformly.

After cooling, the polymer emulsion is uniformly mixed, and then, preservatives and fragrances are added to give a fleshy creamy foundation.

The present invention is widely applicable to skin cosmetics and hair cosmetics such as lip balm, packs, body paints, barrier creams, rag makeup cosmetics and hair colorants in addition to the eye makeup cosmetics foundation based on the embodiment.

Claims (1)

20-50 to a copolymer polymer emulsion wherein one or two or more acrylic ester monomers having 4 to 18 carbon atoms and one or two or more methacrylic acid ester monomers are formed in a ratio of 3 / 7-8 / 2. Makeup cosmetics blended by weight.