JPH06239718A - Makeup cosmetic - Google Patents

Abstract

PURPOSE:To obtain a makeup cosmetic, excellent in resistance to water, oil, rubbing and sticking to objects, makeup durability, usability and feeling of use and capable of being simply washed away without using a special cleansing agent such as a solvent. CONSTITUTION:This makeup cosmetic comprises a resin of a core-shell structure having a core part composed of a copolymer containing an acrylic acid ester and/or a methacrylic acid ester as principal component monomers and a shell part, covering the core part and composed of a copolymer containing styrene and/or alpha-methylstyrene and one or two or more selected from acrylic acid, methacrylic acid and esters thereof as principal component monomers and having a higher glass transition point than that of the core part in an amount of preferably 1-60wt.% based on the total amount of the makeup cosmetic.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a make-up cosmetic composition, and more specifically, it is blended with a resin having a specific core-shell structure and is excellent in water resistance and oil resistance, and particularly in abrasion resistance and object adhesion. Regarding excellent makeup cosmetics.

[0002]

2. Description of the Related Art Make-up cosmetics are generally used in the form of being applied onto the skin to form a cosmetic film. This cosmetic film causes sweating from inside the skin, secretory action of sebum, and rain from the outside. It is easily affected by water such as snow, seawater, and frictional force between hands and clothes, and the resulting makeup loss is a serious problem. Especially in recent years, sports activities such as tennis and golf have become popular.
Not only does it not lose makeup during normal operation, but it can withstand use during sports, that is, it withstands a lot of sweat and sebum secretion, and withstands a large amount of frictional force, does not lose makeup and adheres to the object. No makeup cosmetics are desired.

For example, the make-up cosmetics are formulated in oil-in-water emulsions, water-in-oil emulsions, non-aqueous emulsions,
There are various types such as water-based and powder-based, but the main components that form the cosmetic film on the skin are water-soluble polymers, oils, waxes, oil agents such as surfactants, powders, polyhydric alcohols, etc. Various attempts have been made to improve the water resistance and oil resistance of a makeup film composed of components, and to provide a makeup cosmetic having excellent physical abrasion resistance. As such attempts, there are means such as reducing the hydrophilic component by making the system a water-in-oil emulsion or a non-aqueous system, not using a surfactant, and modifying the powder surface to make it water repellent. Can be mentioned.

On the other hand, several cosmetics containing a resin emulsion for improving abrasion resistance have been disclosed centering on eye makeup cosmetics such as eyeliner and mascara. Original eyebrow (Japanese Patent Laid-Open No. 48-36347),
When a resin emulsion is blended with mascara (Japanese Patent Laid-Open No. 50-125043), the type of the resin emulsion is not particularly limited, and various polyvinyl chloride-based, polyacrylic acid-based, and polyvinyl acetate-based resins are used. Emulsion is featured. .

Recently, more research has been conducted, and the types of resin emulsions have been limited to a wide range of make-up cosmetics, for example, acrylic polymer emulsion (Japanese Patent Laid-Open No. 62-106006), styrene-acrylic acid. Ester copolymer resin emulsion (JP-A-1-203
313), a water-based non-emulsifier-polymerized resin emulsion which is a copolymer of an acrylic compound or another polymerizable compound mainly composed of an acrylic compound (JP-B-60-9692).
No.), an aqueous composite polymer emulsion having a multi-layered structure in which polymer particles have at least two layers having different compositions (JP-A-4-103510) and the like are blended with makeup cosmetics to improve the abrasion resistance.

[0006]

However, water-in-oil emulsions or non-aqueous emulsions of the above systems have good water resistance but poor sebum resistance. Each of them has problems such as poor usability due to poor compatibility, and poor abrasion resistance with a powder surface modified to have water repellency.

Further, even cosmetics containing a resin emulsion for improving the abrasion resistance have some abrasion resistance, but have sufficient abrasion resistance in the presence of a large amount of sebum. Yes I haven't got it yet. Not only that, but with cosmetics containing these resin emulsions,
It is inferior to the feeling of use that is emphasized in cosmetics such as a feeling of tightness and filminess such as thickness, and when removing the makeup film, there is a physical force such as dedicated solvent-based cleansing, cotton, or wiping with a tissue. There is also a problem that it becomes necessary, troublesome, and irritation to the skin is great.

In order to overcome the above problems, the present invention provides
Good water and oil resistance, especially excellent abrasion resistance, good makeup lasting, low object adhesion, good usability, good feeling, and no special cleansing agents such as solvents An object of the present invention is to provide a makeup cosmetic that can be easily washed off with an anionic cleansing agent, for example, a general alkaline soap or the like, and does not burden the skin.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has incorporated a resin having a core-shell structure composed of a specific copolymer component into a makeup cosmetic composition. Therefore, the water resistance and oil resistance are good,
In particular, it has been found that it is possible to obtain a makeup cosmetic which has excellent abrasion resistance, good makeup lasting, little object adhesion, good usability and feel, and can be easily washed off and has less burden on the skin. The present invention has been completed.

That is, according to the present invention, a core portion composed of a copolymer containing acrylic acid ester and / or methacrylic acid ester as a main component monomer, and coating the core portion with styrene and / or α-methylstyrene, Acrylic acid,
Makeup makeup containing a resin having a shell part having a glass transition point higher than that of the core part, which is made of a copolymer containing methacrylic acid and one or more kinds selected from these esters as a main component monomer. It is a fee. Less than,
The present invention will be described in detail.

<1> Resin Used in the Present Invention The resin used in the present invention covers a core portion composed of a copolymer containing an acrylic ester and / or a methacrylic ester as a main component monomer, and the core portion. A glass transition point higher than that of the core part, which is composed of a copolymer containing styrene and / or α-methylstyrene and one or more kinds selected from acrylic acid, methacrylic acid and esters thereof as a main component monomer. It is a resin having a core-shell structure composed of a shell portion having

The main component monomer in the core of the resin of the present invention is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, benzyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate. , Lauryl acrylate, stearyl acrylate,
2-hydroxyethyl acrylate, methoxy acrylate, ethoxy acrylate, butoxy acrylate,
Acrylic esters such as octyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, benzyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl meta. One or more kinds of methacrylic acid esters such as acrylate, lauryl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, methoxymethacrylate, ethoxymethacrylate, butoxymethacrylate and octylmethacrylate may be mentioned.

On the other hand, the shell portion of the resin of the present invention comprises the first essential component consisting of styrene and / or α-methylstyrene (hereinafter referred to as “styrene monomer”), acrylic acid, methacrylic acid and acrylic acid. A copolymer containing, as a main component monomer, a second essential component consisting of one or more selected from ester and methacrylic acid ester (hereinafter referred to as "acrylic monomer and / or methacrylic monomer"). is there. Further, the copolymer constituting the shell portion preferably has a glass transition point higher than the glass transition point of the copolymer forming the core portion, which is the kind of the main component monomer of the core portion or the shell portion, It can be adjusted by changing the compounding ratio.

Further, in the resin of the present invention, both the core portion and the shell portion are blended in addition to the above-mentioned main component monomer, or as a substituting sub-component monomer, acrylamide, methacrylamide, styrene sulfonic acid, and carboxy are contained. Ethylenically unsaturated acid-one or two of maleic anhydride, crotonic acid, itaconic acid, cinnamic acid, etc.
There are more than one species. Further, acrylic acid and / or methacrylic acid may be blended or used as a sub-component monomer in the core portion.

In the resin of the present invention, the relationship between the glass transition points of the copolymer constituting the core portion and the copolymer constituting the shell portion, the styrene monomer constituting the shell portion, the acrylic monomer and / or The weight ratio of the methacrylic monomer, the weight ratio of the monomer that forms the shell part and the monomer that forms the core part, and the acid value of the resin greatly affect the water resistance and abrasion resistance of the coating when blended into cosmetics. Affect.

The coating properties when the above resin is blended in cosmetics are as follows: the average molecular weight of the resin as a whole including the core portion and the shell portion of the resin, the glass transition point of the core portion, the shell portion and the resin, and the shell portion. It depends on its interaction with the monomer composition. In order to obtain a cosmetic film having appropriate film characteristics and a good feeling in use, the average molecular weight of the entire resin including the core part and the shell part is preferably 10,000 to 1,000,000. The glass transition point is higher than that of the core portion, and the glass transition point of the entire resin is preferably -10 to 100 ° C, more preferably -10 to 50 ° C.
On the other hand, the ratio of the weight of the styrene-based monomer in the shell portion to the weight of the acrylic-based monomer and / or the methacrylic-based monomer is preferably in the range of 30:70 to 80:20.

When the average molecular weight of the entire resin is less than 10,000 or the glass transition point is less than -10 ° C, the cosmetic material becomes too soft, the coating strength is weak, the abrasion resistance is deteriorated, and stickiness is generated in use. , Not preferable. Also,
If the average molecular weight of the resin as a whole exceeds 1,000,000 and the glass transition point exceeds 100 ° C, the decorative coating becomes porpo
It is difficult to adhere to the skin, and even if it adheres to the skin, the coating is stiff, resulting in a feeling of tightness or a coating when used, and the abrasion resistance becomes poor. Furthermore, when the glass transition point of the core portion is higher than that of the shell portion, the abrasion resistance is deteriorated and the object adhesion is increased,
Makeup stickiness also deteriorates.

On the other hand, a styrene-based monomer in the shell part,
If the weight ratio of the acrylic monomer and / or the methacrylic monomer is less than 30/70, the effect of producing a cosmetic film having a suitable film strength and a good feeling of use is reduced, and the weight ratio is 80%. When it exceeds / 20, the cosmetic coating becomes fluffy, and it is difficult to adhere to the skin, and even if it adheres to the skin, the coating is hard and a feeling of tightness is likely to be generated in use.

Next, the weight ratio of the resin of the shell portion to the resin of the core portion is preferably 99: 1 to 1:99, more preferably 10:90 to 50:50. The acid value of the resin in the shell part is preferably 60 to 350, and the total acid value of the resin in which the core part and the shell part are combined is preferably 10 to 350, more preferably 10 to 150. When the acid value of the resin in the shell portion is less than 60 or the total oxidation of the resin is less than 10, it becomes difficult to wash off the cosmetic containing the resin with soap. If the acid value of the shell portion or the total acid value of the resin exceeds 350, the water resistance will deteriorate.

The determination of the acid value affects the ease with which the soap can remove the decorative coating. Resins satisfying the above range are more excellent in water resistance and abrasion resistance than resins conventionally used for improving makeup lasting, and are easily anionic detergents without using a special cleansing agent, For example, a makeup cosmetic that can be washed off with a general alkaline soap can be obtained.

Next, an example of the method for producing the resin used in the present invention will be described. The resin used in the present invention is a resin having a core-shell structure, and can be obtained as a resin emulsion containing the resin as a dispersed phase by two steps of manufacturing the shell part and the core part.

First, as a first step, a styrene-based monomer and an acrylic-based monomer and / or a methacrylic-based monomer are used as main components, and if necessary, a sub-component monomer, a solvent, and a polymerization initiator are added, and a usual method is used. After the reaction, aging and cooling, only the copolymer is taken out by filtration and neutralized with an aqueous ammonia solution or the like to obtain an aqueous solution of the shell part.

Examples of the solvent include isopropyl alcohol, and examples of the polymerization initiator include benzoyl peroxide. The reaction may be mixed at 80 ° C. for about 3 hours.

Next, in the second step, an acrylic ester and / or a methacrylic ester is used as a main component monomer, a sub-component monomer is added if necessary, and further a resin aqueous solution in the shell part and a polymerization initiator are added, The resin of the present invention can be obtained by performing ordinary emulsion polymerization, aging and cooling. The resin thus produced is obtained as an emulsion having this as a dispersed phase, and thus can be added to the makeup cosmetics as it is or after being filtered as an emulsion of another solvent.

<2> Makeup Cosmetic of the Present Invention The makeup cosmetic of the present invention contains the above resin preferably in an amount of 1 to 60% by weight based on the total amount of the cosmetic. When used as a resin emulsion, it is preferable that the effective resin amount is 1 to 60% by weight. If the blending amount is less than this range, the desired water resistance,
Oil resistance, abrasion resistance, etc. cannot be expected, and if it exceeds this range, the stability over time as a cosmetic may not be maintained.

Examples of the makeup cosmetics of the present invention include base materials such as emulsion, cream and water-based gel, as well as finishes such as foundations and control colors. These cosmetics can be produced by the same method as that for ordinary cosmetics except that the above resin is blended.

Further, the makeup cosmetic of the present invention comprises:
In order to adjust the flexibility of the coating film or to improve the adhesion to the skin, it is preferable to blend the polyhydric alcohol so that the ratio of the polyhydric alcohol and the resin is 1:99 to 70:30. If this ratio is less than 1:99, the effect of enhancing the adhesion to the skin cannot be expected. If this ratio exceeds 70:30, the film becomes too soft,
The film strength decreases and the abrasion resistance deteriorates.

Further, the makeup cosmetic of the present invention is
For the same purpose as the above polyhydric alcohol, it is preferable to add a nonionic surfactant in an amount of 1 to 30% by weight, more preferably 5 to 20% by weight, based on the amount of the effective resin component of the resin emulsion. It is desirable to mix them. If the blending amount is less than 1%, the effect of enhancing the adhesion to the skin cannot be expected. On the other hand, if the blending amount exceeds 30%, the coating strength will be reduced, and the water resistance and abrasion resistance will be poor.

The above nonionic surfactant has an HLB of 5
It is above, and it is preferable that it has a property of being dispersed or dissolved in water. Such nonionic surfactants include, for example, polyoxyethylene (4.2) lauryl ether, polyoxyethylene (7) oleyl ether, polyoxyethylene (5) nonylphenyl ether, polyethylene glycol monooleate ( 10E.
O. ), Polyoxyethylene (10) hydrogenated castor oil, and further poly-modified silicone.

In the cosmetic of the present invention, various components generally used in cosmetics, such as an aqueous component, an oil component, a powder component, a surfactant, a moisturizer, a thickener, a coloring agent, a fragrance, and an antioxidant are used. An agent, a pH adjusting agent, a chelating agent, an antiseptic agent, an ultraviolet protective agent, an anti-inflammatory agent, and a whitening agent can be added.

[0031]

EXAMPLES Examples of the present invention will be described below. In addition,
The compounding amounts used below are all by weight.

First, a production example of the resin emulsion used in the examples of the present invention is shown below.

[0033]

[Production Example] Styrene 30 which is a raw material monomer for the shell part
g, α-methylstyrene 10 g, methacrylic acid 40
g, 20 g of methyl methacrylate, 100 g of isopropyl alcohol, 1 g of benzoyl peroxide at 80 ° C.
While maintaining at 3, the mixture was mixed for 3 hours to cause a polymerization reaction. This was aged, cooled, and filtered to take out the copolymer. To this copolymer, 16 g of a 25% aqueous ammonia solution and 200 g of water were added, neutralized, and further stirred and mixed at 90 ° C. for 2 hours. This was cooled to give an aqueous solution of the shell part.

To the aqueous solution of the shell part, 50 g of methyl acrylate as a raw material monomer of the core part, 50 g of butyl methacrylate, 1 g of ammonium persulfate and 200 g of water were added, and the mixture was stirred at 90 ° C. for 10 hours to cause a polymerization reaction. After aging, cooling, and filtration, a resin emulsion having a core-shell structure is obtained.

The resin thus obtained has an average molecular weight of 30.
The total acid value was 130 and the glass transition point was 7 ° C in the core part and 20 ° C in the shell part. This was used for the following evaluations and examples.

On the other hand, as a comparative example, an average molecular weight of 400,000,
An emulsion having a total acid value of 360 and a glass transition point of 3 ° C. was produced as follows. Hereinafter, this is referred to as a comparative emulsion.

10 g of styrene, 44 g of 2-ethylhexyl acrylate, 46 g of acrylic acid, 1.5 g of an anion activator, 100 g of water and 1.5 g of ammonium persulfate were mixed and stirred, and a polymerization reaction was carried out for 3 hours while maintaining at 90 ° C. After aging and cooling, the mixture was filtered to obtain a comparative emulsion.

Further, as another comparative example, an aqueous composite polymer was produced according to Synthesis Example 1 of JP-A-4-10351. Hereinafter, this is referred to as an aqueous complex polymer emulsion.

<Evaluation of Resin Emulsion> The film characteristics of the resin emulsion of the above-mentioned production examples are water resistance / rub resistance, sebum resistance / rub resistance, object adhesion, touch (flexibility), usability (adhesion to skin). And the ease of removing makeup. Evaluation was made with the above resin emulsion and 1 as a pigment.
It was carried out using a sample composition containing 0% by weight of the mixed powder.

The coating properties of the commonly used film forming agent and the above-mentioned aqueous composite polymer emulsion were evaluated in the same manner as the resin emulsion of the above Production Example.

(1) Water resistance / rub resistance Each sample was applied to the skin, and 20 minutes later, the skin was wetted with running water. Immediately after that, a white tissue was rubbed 5 times with a certain strength, and the degree of coloring on the tissue was sensory-evaluated as the adhesion amount.

(2) Sebum resistance and abrasion resistance Each sample was applied to the skin, and 20 minutes later, artificial sebum was applied to the skin. Immediately after that, a white tissue was rubbed 5 times with a certain strength, and the degree of coloring on the tissue was sensory-evaluated as the adhesion amount.

(3) Objective Adhesion Each sample was applied to the skin, and 20 minutes later, it was rubbed with a white cotton cloth 5 times with a constant strength, and the degree of coloring on the cotton cloth was sensory-evaluated as the adhesion amount. It should be noted that the good adherence to the objective means that the adherence to the objective is small.

(4) Feel (Pliability) Tightness and coat feeling were sensory evaluated immediately after the sample was applied to the skin and after 20 minutes.

(5) Usability (Adhesion to the Skin) When the sample was applied to the skin, a sensory evaluation was made on the ease of application including the drying speed and the familiarity with the skin.

(6) Ease of makeup removal A sample was applied to the skin, and after 20 minutes, the ease of removal when washed with soap was subjected to a sensory evaluation.

Table 1 shows the results of a sensory evaluation conducted by 10 female panelists on the following criteria in each of the above tests. ◎: Very good ○: Good △: Normal ×: Poor

[0048]

[Table 1] From these results, it is clear that the cosmetics using the resin emulsion used in the present invention are excellent in water abrasion resistance, sebum abrasion resistance, objective adhesion, feel and usability, and can be easily washed off with soap.

Next, examples of the makeup cosmetics of the present invention using the resin emulsions obtained in the above production examples will be described.

[0050]

Example 1 Aqueous Foundation Using the components shown in Table 2, an aqueous foundation was produced by the following method. Polyethylene glycol monooleate (10 EO) was dissolved in purified water, and the pigment was dispersed and mixed in this, and uniformly pulverized and dispersed using a colloid mill. To this, 1,3-butylene glycol, glycerin, and a thickener were added, and the resin emulsion, preservative, and fragrance of Production Example were added while mixing with stirring, and mixed until uniform.

Similarly, the water-based foundation of Comparative Example 1 using a silicone / acrylic resin emulsion having an effective resin amount of 30% by weight and the Comparative Example emulsion having an effective resin amount of 50% by weight were used in place of the resin emulsion of Production Example. Aqueous foundation of Comparative Example 3, effective resin amount 35
Aqueous Foundation of Comparative Example 4 Using Wt% by Weight of Aqueous Composite Resin Emulsion and Production Example An aqueous foundation of Comparative Example 2 was produced in which the resin emulsion was blended outside the preferred blending amount range.

[0052]

[Table 2]

[0053]

Example 2 Liquid Eyeliner Next, a liquid eyeliner will be described as the makeup cosmetic of the present invention.

The components of Table 3B were preheated and dissolved, and the heated and dissolved components of C were mixed. Component A, which was mixed and dispersed using a three-roll mill, was mixed to this until uniform, and then resin emulsion as component D was added with stirring and mixing until uniform.

[0055]

[Table 3]

<Evaluation of Makeup Cosmetics of the Present Invention> The makeup cosmetics of the respective Examples and Comparative Examples obtained above were evaluated in the same manner as the resin emulsion of the above Production Examples. The results are shown in the bottom columns of Tables 2 and 3.

As is clear from these results, the cosmetic material of Example 1 is excellent in water resistance / rub resistance, sebum resistance / rub resistance, and object adhesion, and has a very good feel and usability. It was excellent and easy to remove with soap. Also, with regard to the cosmetic material of Example 2, good evaluation was obtained in all tests.

[0058]

The make-up cosmetic composition of the present invention is excellent in water resistance, oil resistance, abrasion resistance, and adhesion to an object, has a long lasting makeup, and has good usability and usability. Further, even if a special cleansing agent such as a solvent is not used, it can be easily washed off with an anionic detergent, for example, general alkaline soap.

Claims (7)

[Claims] 1. A core portion comprising a copolymer having an acrylic ester and / or a methacrylic ester as a main component monomer, and a core portion coated with styrene and / or α-methylstyrene, and acrylic acid, Makeup makeup containing a resin having a shell part having a glass transition point higher than that of the core part, which is made of a copolymer containing methacrylic acid and one or more kinds selected from these esters as a main component monomer. Fee. 2. In the shell portion of the resin, the weight of styrene and / or α-methylstyrene, acrylic acid,
The makeup cosmetic according to claim 1, wherein the weight ratio of one or more selected from methacrylic acid and these esters is 30:70 to 80:20. 3. The acid value of the shell portion of the resin is 60 to 35.
3. The acid value of the whole resin including the core portion and the shell portion is 10 to 350, and the acid value is 10 to 350.
Makeup cosmetics listed. 4. The glass transition point of the resin is −10 to 10.
The makeup cosmetic according to any one of claims 1 to 3, which has a temperature of 0 ° C and an average molecular weight of 10,000 to 1,000,000. 5. The compounding amount of the resin is 1 to 60% by weight based on the total amount of the cosmetics.
The makeup cosmetic according to any one of 1. 6. The make-up according to claim 1, wherein the polyhydric alcohol is blended in a ratio of the polyhydric alcohol and the resin of 1:99 to 70:30. Cosmetics. 7. The makeup cosmetic according to any one of claims 1 to 6, wherein 1 to 30% by weight of the resin is mixed with a nonionic surfactant.