JPS609692B2 - Make-up cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to make-up cosmetics, particularly eye make-up cosmetics.

The drawback of traditional makeup cosmetics was ``makeup discoloration'', which is the effect of natural substances on the human body such as sweat, tears, and sebum on cosmetics, and the weather conditions during use of cosmetics such as rain, snow, pool water, and seawater. , makeup discoloration mainly due to chemical effects such as the action of moisture due to the conditions of the place, the action of various ingredients in other cosmetics used together, and the movement of the skin in the area where the cosmetics are used.
The purpose is to solve various types of "makeup fading" caused mainly by physical effects such as friction from hands or clothing, and to obtain a makeup cosmetic that does not stain clothing and has good makeup retention. Furthermore, conventional makeup cosmetics come in a wide variety of formulations, including water-based, oil-based, emulsion-based, and powder-based formulations. , makeup tends to come off easily due to tears, rain, etc.

That is, the water resistance is poor. In addition, since oil-based products contain a large amount of lipophilic substances, they are likely to cause makeup to fade due to the skin or the oil content of the cosmetics used in combination. That is, oil resistance is poor. Emulsion type products do not have sufficient water resistance or oil resistance. Powder-based products have poor water resistance and oil resistance, and furthermore, makeup tends to come off due to movement of the skin at the application site or friction from hands or clothing. That is, the adhesion to the skin is poor.
In addition, clothing is also easily contaminated. In order to solve the above-mentioned drawbacks of make-up cosmetics, the present invention is based mainly on water-based and emulsion-based make-up cosmetics, and by blending resin emulsions polymerized using a special synthesis method as described below. The purpose of the present invention has been achieved, and a makeup cosmetic having excellent water resistance, oil resistance, and adhesiveness, and a long lasting makeup without smearing the makeup, has been obtained.

Conventional cosmetic ingredients of this type have used resin emulsions produced by emulsion polymerization using natural or synthetic water-moated polymers and emulsifiers as film-forming agents, but the water resistance of these polymeric substances themselves has been limited. Due to its poor properties, it has been difficult to obtain sufficient water resistance for use in cosmetics.

Furthermore, since cosmetics are applied and sprayed onto the human skin, sufficient consideration must be given to safety for the human body.

Among these, the safety of lipsticks and cosmetics used around the eyes must be thoroughly examined because they are applied immediately to mucous membranes. In particular, resin emulsions used as raw materials for eye make-up cosmetics generally use emulsifiers when making emulsions.

In this case, a nonionic emulsifier is mainly used, and in addition, a small amount of an anionic emulsifier is often used in combination. However, in this case, it is considered preferable to use as little emulsifier as possible or not use it as an ingredient in cosmetics from the viewpoint of safety and film properties. However, resin emulsions obtained by conventional manufacturing methods L Unless this type of emulsifier is used, it is not possible to create a stable emulsion with uniform particles. At the same time, the emulsifier in this case is mainly a nonionic emulsifier (polyoxyethylene alkyl ether type) in which the polyoxyethylene chain is relatively long, that is, a hydrophilic emulsifier is used in several percent.

Additionally, small amounts of anionic surfactants such as lauryl sulfate and inorganic salts such as peroxides are often used in combination. For this reason, in conventional resin emulsions, these hydrophilic substances affect the water resistance and adhesion after coating film formation, and at the same time, these emulsifiers can cause irritation. there were. The present invention uses a water-based resin emulsion that does not use an emulsifier at all, a so-called water-based emulsifier-free polymer resin emulsion (hereinafter simply referred to as an emulsifier-free polymer resin emulsion), thereby providing excellent makeup that does not have the above-mentioned drawbacks. It provides a fee.

At the same time, the amount of emulsifier in cosmetic ingredients can be reduced, making it possible to create cosmetics that are even less irritating.

The development of this new emulsifier-free polymeric resin emulsion was mainly conducted in the fields of paints, adhesives, etc., with the aim of transitioning from an organic solvent type to an aqueous emulsion type, improving the water-resistant adhesion of the film, and making it pollution-free. This is something that is attracting attention.

A film obtained from a resin emulsion using a conventional emulsifier has a heterogeneous structure that is not completely fused due to the emulsifier and other water-soluble substances contained therein.

The film exhibits water absorption and solubility due to the dissolution and diffusion of these emulsifiers, which significantly reduces the water resistance of the film itself. This emulsifier-free polymer resin emulsion was developed to improve this fundamental drawback of the aqueous emulsion type.

However, even with conventional resin emulsions, it was easily possible to synthesize resin emulsions without using emulsifiers due to the protective colloidal action of water-soluble polymers, such as vinyl acetate resin emulsions. As mentioned above, there is a fundamental difference in that the objective is water resistance.

The resin composition applied to the present invention includes copolymers of various acrylic compounds, or other polymerizable compounds mainly composed of various acrylic compounds, such as styrene, vinyl acetate,
It is a copolymer with vinylversite, alkyd, etc.

Emulsifier-free polymeric resins are generally synthesized without using emulsifiers by using the following three stabilizing means alone or in combination. m. Introduction of a relatively hydrophilic monomer (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, sodium 2-sulfoethyl methacrylate, etc.) as part of the resin composition.

(2) Copolymerizing unsaturated acid monomers such as acrylic acid and methacrylic acid into the resin composition to introduce free luponic acid groups.

{3i Less than polymer produced by polymerization initiator - SOZ
Increase of surface charge of emulsion by stem.

Since the resin emulsion synthesized in this way does not use any emulsifier, it has a film with better water resistance and adhesiveness than any conventional resin emulsion that uses an emulsifier and has a different monomer composition. can be formed.

In particular, acrylic resins copolymerized with styrene, which is effective in water resistance, have extremely good water resistance and adhesion, and are significantly superior to conventional resin emulsions. Table 1 compares the water resistance (whitening degree, film solubility) and adhesion (peelability) of conventional resin emulsions and this emulsifier-free polymer resin emulsion.The emulsifier-free polymer resin emulsion has extremely superior film performance. I know that there is.

Table 1 BA: Butyl acrylate MMA: Methyl methacrylate St: Stellene 28HA: 2-ethylhexyl acrylate [Production method] Part 1 As an emulsifier, sodium dodenyl sulfate 0
．． Produced by general emulsion polymerization with persulfate using 5%, voriquinethylene (30 mol) and 2.0% lauryl ether.

×2 Manufactured on the same machine as *1 using boroxyshetylene nonifer ether as an emulsifier.

Lost 3, younger brother 4 Manufactured according to Manufacturing Example 1 described below.

[Method for determining water resistance and adhesion] Each resin emulsion was applied to a nylon plate, dried at 25°C and 50% for 12 hours, then immersed in water, shaken, and left for 1 day to evaluate the degree of whitening and swelling solubility of the film. and the removability is evaluated sensually.

〔Evaluation criteria〕

○ Good, △ Fair, × Poor, *Extremely poor The resin emulsion polymerized in this way has superior film properties compared to conventional resin emulsions, and other than the fact that it does not contain an emulsifier, it has the following properties as shown in Table 2. As such, there is no essential difference at all from conventional resin emulsions.

Table 2 1 Loss of the conventional acrylic (BA/MMA) resin emulsion in Table 1 2 Pharmatex E Yama 142 (Mitsui Toatsu Chemical Co., Ltd.) Also, ``One of the drawbacks of conventional resin emulsions is that they cannot be mixed with various thickeners. The properties of the resin emulsion are extremely poor, and the types of thickeners that can be used in combination are limited depending on the properties of the resin emulsion.

On the other hand, in the present invention, which uses a non-emulsifier polymerized resin emulsion, the types of thickeners that can be used are expanded, the viscosity can be easily stabilized, and cosmetics with excellent stability over time can be produced. You can get it. In other words, it provides the convenience of freely selecting thickeners when producing cosmetics with various desired viscosities and textures. Table 3 shows the miscibility of the conventional type and this emulsifier-free polymeric resin emulsion with various thickeners.

Table 3 Loss 1 Conventional acrylic yarn (B-MMA) resin emulsion in Table 1 2 Acrylic/based resin emulsion with monomer ice formation of BA/St = 7/3 and manufactured according to Production Example 1 described below [Evaluation criteria] ○: Good miscibility △: 〃 Fair ×: Poor *: Coagulation This emulsifier-free polymer resin emulsion is used in makeup cosmetics, preferably 5-95%, preferably 10-6
By using 0%, the desired product properties such as water resistance and strong adhesiveness can be obtained.

In other words, the above-mentioned characteristic of not using an emulsifier is clearly reflected in the product properties, and it is possible to obtain a makeup cosmetic that has excellent water resistance, oil resistance, and adhesion, and has good makeup retention without smudging. Table 4 compares the product characteristics of a conventional film type eyeliner and a film type eyeliner using this emulsifier-free polymerized resin emulsion, and clearly shows the effects of use.

Table 4 Loss 1 An eyeliner in which the conventional acrylic resin (BA/MMA) resin emulsion shown in Table 1 was used in place of the emulsifier-free polymerized resin emulsion shown in Example 2.

Husband 2 An eyeliner using the emulsifier-free polymerized acrylic (BA/st) resin emulsion shown in Table 3 instead of the emulsifier-free polymerized resin emulsion of Example 2. Test method: The peelability test using a nylon plate shown in the note in Table 1 and the results of the actual use test on the human body are evaluated by sensory evaluation. Evaluation criteria:
〇: Good ×: Poor *: Extremely poor Conventionally, various makeup cosmetics using synthetic resin emulsions have already been published in Japanese Patent No. 481-36347, US Pat. & Peh mountain mehi 89 27
~29 ('74) NordaSChimmeIBrie
fsNO. 407 gu 69) etc.,
All of these use conventional resin emulsions using emulsifiers, and are insufficient as water-resistant makeup cosmetics that do not smudge, which is the object of the present invention.

In short, there are no known examples in the literature of blending an emulsifier-free polymer resin emulsion into cosmetics as in the present invention, and in particular, if an emulsifier-free polymer resin emulsion is used in cosmetics, the thickener used in combination can be arbitrarily selected. There are no examples to suggest this effect. Next, a production example of the emulsifier-free polymer resin emulsion used in the present invention will be shown.

Production example 1 130% water, 70% butyl acrylate, 30% styrene, 2% acrylic acid in 300% four-necked fufusco
10 parts of aqueous ammonia (28%) and 40 parts of potassium persulfate as a polymerization initiator were charged, and the mixture was stirred at a stirring rate of 25 pm (twisted type stirrer) in a nitrogen stream.
The polymerization reaction was carried out at 0°C for 3 hours.

Thereafter, dialysis was performed using cellophane paper to remove ionic impurities and a resin emulsion with good film properties was obtained.
Production example Distilled water 13 in a 2300' four-necked flask
0 top, 30' styrene, 70' butyl acrylate,
Sodium 2-sulfoethyl methacrylate 5,
Then, as a polymerization initiator, ammonium persulfite 50 9 9 hydrogen peroxide (30%) aqueous solution 0.5 ml and ascorbic acid 30 ml were prepared, and the mixture was heated under conditions of 65 to 70°C for 3 hours under a nitrogen stream. Polymerization was carried out using

After the reaction was completed, the system was depressurized to 10 mHg and
The mixture was treated for 0 minutes to remove unreacted monomers. Thereafter, the polymerization initiator was removed by dialysis to obtain a resin emulsion. Next, examples of the present invention will be shown.

% is shown in weight %. Example 1 Creamy eye shadow (blue) Light liquid paraffin 10.0% Lanolin conductor 5.0% Peace wax 2.0% Stearic acid 3.0 Cetyl alcohol 0.5 Sorbitan monostearate 1.0 Propylene glycol 5. 0 Ion exchange water 48.0 Triethanolamine 1.5 V-Gum
1.0 emulsifier-free polymerized resin emulsion (manufacturing example 2) 10.0 bar pigment
10.0 tone ultramarine
3.0 preservative
Appropriate amount of fragrance
Appropriate amount <Production method> Decompose and dissolve Veegum, propylene glycol, and triethanolamine in ion-exchanged water,
Thereafter, it is heated to uniformly disperse the pearl pigment and the pigment.

Next, an oil phase component such as peace wax is heated and dissolved, and is gradually added to the already prepared aqueous phase while being mixed to emulsify it.
After cooling, the resin emulsion is mixed uniformly, and then preservatives and fragrances are added to form a blue cream eyeshadow. Example 2 Liquid film type eyeliner carbon black 5.0% titanium dioxide (anatase) 2.0 Sodium polyphosphate 0.1 Polyoxyethylene sorbitan monooleate 0.5 Ion exchange water
26.6 Propylene glycol 5.0 Carboxymethyl cellulose Na salt 0.8 Emulsifier-free polymerized resin emulsion (product name: Julimar SE series. Nippon Pure Chemical Industries, Ltd.) 60.0 Preservative
Appropriate amount of fragrance
Appropriate amount <Production method> Sodium polyphosphate and polyoxyethylene sorbitan monooleate are dissolved in ion-exchanged water, carbon black and titanium dioxide are mixed therein, and the mixture is uniformly ground and dispersed using a colloid mill.

Propylene glycol, carboxymethyl cellulose and resin emulsion are sequentially added to this, mixed uniformly, and finally a preservative and fragrance are added to form a black film type eyeliner. Example 3 Creamy Mascara Piece Wax 3.0% Solid Paraffin Wax 2.0 Stearic Acid 3.5 Ion Exchange Water 34.0 Vee Gum
3.0 Triethanolamine 1.5 Talc
5-0 Black iron oxide 15.0 Emulsifier-free polymerized resin emulsion (Product name: Almatex E-142
, Mitsui Toatsu Chemical Co., Ltd.) 30.0 Glycerin
30 fragrances
Appropriate amount of preservative
Appropriate amount <Production method> Disperse and dissolve glycerin, trietanoamine, and vougum in ion-exchanged water, add turk and pigment, disperse uniformly, and overflow to 70 qo.

A dissolved oil phase component such as peace wax is gradually added to this and uniformly emulsified. After emulsification, the resin emulsion is added and mixed uniformly, and a preservative and fragrance are added to form a black mascara. The present invention is applicable to other foundations, eye make-up cosmetics such as eyebrows, eye shadows, eyeliners, and mascaras, and skin cosmetics such as body paint, nail enamel, barrier creams, packs, lipsticks, hair colorants, and leg make-up cosmetics. It is widely applied to cosmetics and hair cosmetics.

Claims (1)

[Scope of Claims] 1. Contains a water-based non-emulsifier polymerized resin emulsion whose resin composition is a copolymer of an acrylic compound or a copolymer of an acrylic compound with other polymerizable compounds. Make-up cosmetics featuring the following. 2 The amount of water-based emulsifier-free polymerized resin emulsion is 10
60%. 3. The makeup cosmetic according to claim 1, wherein the acrylic compound copolymer is an acrylic ester-methacrylic ester copolymer. 4. The makeup cosmetic according to claim 1, wherein the copolymer containing an acrylic compound as a main component with another polymerizable compound is an acrylic ester-styrene copolymer. 5. The make-up cosmetic according to claim 1, wherein the copolymer containing an acrylic compound as a main component with other polymerizable compounds is an acrylic ester-methacrylic ester-styrene copolymer.