JPH10231231A - Oil-in-water type emulsified composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful as a cosmetic by including a silicone oil and a specific macromolecular copolymer as an emulsifying agent therein. SOLUTION: This composition is obtained by including 0.1-50.0wt.% silicone oil and a macromolecular copolymer prepared by copolymerizing a composition containing (A) 15.0-90.0wt.% amine-containing (meth)acrylic monomer represented by formula I (R<1> is H or methyl; R<2> and R<3> are each H, methyl, etc.; B is a 1-4C alkylene), (B) 10.0-80.0wt.% vinyl monomer represented by formula II R<4> is a group represented by formula III [(p) is 3 or 4]}, etc., (C) 1.0-60.0wt.% (meth)acryloyl group-containing monomer represented by formula IV (R<5> is an 8-17C alkylene), etc., and (D) 0.1-25.0wt.% cross-linking vinyl monomer therein. The composition has a good feeling of use and is good in emulsification stability without substantially containing a surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-in-water emulsion composition, and more particularly, to an oil-in-water emulsion composition having low stickiness to the skin, excellent adaptability to skin and hair, and excellent emulsion stability. About things.

[0002]

2. Description of the Related Art As emulsifying compositions for cosmetics, creams and emulsions using various oily, aqueous components and surfactants have been widely used. However, in recent years, higher safety is expected for cosmetics, and from this viewpoint, the presence of a surfactant may be problematic. for that reason,
A method for obtaining a cosmetic emulsion using a specific polymer compound, for example, an alkyl-modified carboxyvinyl polymer as an emulsifier without using a general surfactant has been developed. The alkyl-modified carboxyvinyl polymer is generally a carboxyvinyl polymer used as a thickener, -COOH
A part of the groups is esterified with a long-chain (C10-30) alcohol, and emulsification is enabled by the long-chain hydrophobic groups. However, the carboxyvinyl polymer-based polymer has a problem that when incorporated into cosmetics, it gives an unpleasant feel such as stickiness and lack of familiarity with skin and hair.

[0003] Accordingly, an object of the present invention is to provide an oil-in-water type which does not use a general surfactant, has no stickiness, has a good feeling of use on skin and hair, and has good emulsion stability. It is to provide an emulsion composition.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have used a polymer copolymer obtained by polymerizing a specific monomer composition as an emulsifier, and a silicone resin. An oil-in-water emulsion composition containing oil has been found to be less sticky, excellent in conformity to skin and hair, and has good emulsification stability without using a surfactant, leading to the completion of the present invention. Was.

That is, the present invention provides a silicone oil,
An oil-in-water emulsified composition comprising a polymer copolymer represented by the following component (A) as an emulsifier.

(A) A polymer copolymer obtained by polymerizing a monomer composition containing the following (A) to (D). (A) General formula (I):

[0007]

Embedded image

Wherein R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a methyl group,
An ethyl group or a t-butyl group, A is an oxygen atom, or-
NH-group, B is a linear or side-chain carbon atom having 1 to 4 carbon atoms.
Represents an alkylene group. 15.0 to 90.0% by weight of an amine-containing (meth) acrylic monomer represented by
(B) General formula (II):

[0009]

Embedded image

(Wherein R ¹ is the same as above, and R ⁴ is a general formula:

[0011]

Embedded image

(Wherein p represents 3 or 4) or a group represented by the formula:

[0013]

Embedded image

The group represented by )) And 10.0 to 80.0% by weight of a vinyl monomer represented by the general formula (II)
I):

[0015]

Embedded image

(Wherein R ¹ and A are the same as described above, and R ⁵ is a linear or branched alkylene group having 8 to 17 carbon atoms or a compound represented by the general formula (IV):

[0017]

Embedded image

(Where n is an integer of 3-4, q is 10-2)
Represents an integer of 5. ), R ⁶ represents a hydrogen atom or a methyl group. )), And (D) 0.1 to 25.0% by weight of a crosslinkable vinyl monomer.

The oil-in-water emulsion composition of the present invention preferably contains substantially no surfactant, and is preferably a cosmetic composition.

Hereinafter, the constitution of the oil-in-water emulsion composition of the present invention will be described. The polymer copolymer (A) which is the emulsifier of the present invention is obtained by polymerizing the monomer composition containing the above (A) to (D). Hereinafter, each component constituting the emulsifier will be described in detail.

Representative examples of the amine-containing (meth) acrylic monomer represented by the general formula (I) include, for example, N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate. Examples thereof include acrylate and N, N-dimethylaminopropyl (meth) acrylamide, but the present invention is not limited to these examples. In the present invention, the amine-containing (meth) acrylic monomers are used alone or in combination of two or more.

Particularly preferred are amine-containing (meth) compounds.
The acrylic monomer is represented by the following general formula (V).

[0023]

Embedded image

The proportion of the amine-containing (meth) acrylic monomer in the monomer composition is from 15.0 to 9
0.0% by weight, preferably 25.0-75.0% by weight,
It is more preferably adjusted to 41.0 to 52.0% by weight. When the proportion of the amine-containing (meth) acrylic monomer is less than the above range, the emulsion stability is not good, and when it exceeds the above range, a feeling of tightness in use feeling is apt to occur, which is not preferable.

Representative examples of the vinyl monomer represented by the general formula (II) include, for example, N-vinylpyrrolidone,
Examples thereof include N-vinylpiridone, acrylamide, methacrylamide, and the like, but the present invention is not limited to such examples. In the present invention, the vinyl monomers are used alone or in combination of two or more.

Particularly preferred vinyl monomers are:
It is represented by the following general formula (VI).

[0027]

Embedded image

The ratio of the vinyl monomer in the monomer composition is 10.0 to 80.0% by weight, preferably 2%.
0.0 to 75.0% by weight, more preferably 40.0 to
It is adjusted to be 48.0% by weight. When the ratio of the vinyl monomer is less than the above range, the emulsion stability is not good, and when the ratio exceeds the above range, the viscosity becomes difficult to be obtained, and the emulsion stability deteriorates, which is not preferable.

Specific examples of the (meth) acryloyl group-containing monomer represented by the general formula (III) include, for example, 2
-Ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, Nt-octyl (meth) acrylamide, and the like. It is not limited only to the illustration. In the general formula (III), the group —R ⁵ —
R ⁶ must be hydrophobic, so that R ⁵ has 8 or more carbon atoms, and _{n of the} — (C _n H _2n ) _q — group has 3 or more, q
Must be at least 10. In the present invention, the (meth) acryloyl group-containing monomers are used alone or in combination of two or more.

Among them, particularly preferred (meth) acryloyl group-containing monomers are those represented by the following general formula (VII).

[0031]

Embedded image

The proportion of the (meth) acryloyl group-containing monomer in the monomer composition is 1.0 to 60.0% by weight, preferably 1.0 to 55.0% by weight, more preferably 1.5 to 3.5%. It is prepared so as to be% by weight. When the ratio of the (meth) acryloyl group-containing monomer exceeds the above range, the solubility in water is reduced, and the like, which is not preferable in the production process of the emulsion. When the ratio is less than the above range, the emulsion stability is not good. .

The crosslinkable vinyl monomer as the component (D) is a compound having two or more carbon-carbon unsaturated double bonds in one molecule, and has a property of crosslinking with other monomers. is there.

Representative examples of the crosslinkable vinyl monomer include, for example, ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and polypropylene. (Meth) having two or more carbon-carbon unsaturated double bonds in one molecule such as glycol di (meth) acrylate
Acrylic monomers; methylenebis (meth) acrylamide, 1,2-bis (meth) acrylamideethane,
1, such as 1,5-bis (meth) acrylamidopentane
(Meth) acrylamide monomers having two or more carbon-carbon unsaturated double bonds in the molecule; vinyl monomers having two or more carbon-carbon unsaturated double bonds in one molecule such as divinylbenzene; However, the present invention is not limited only to such an example. In the present invention, the crosslinkable vinyl monomers are used singly or as a mixture of two or more.

Particularly preferred crosslinkable vinyl monomers are those represented by the following formula (VIII).

[0036]

Embedded image

The proportion of the crosslinkable vinyl monomer in the monomer composition is from 0.1 to 25.0% by weight, preferably from 1.0 to 10.0% by weight, and more preferably from 6.5 to 6.5% by weight.
It is prepared to be 7.5% by weight. When the ratio of the crosslinkable vinyl monomer is less than the above range,
If the emulsification stability is not good, and if it exceeds the above range, the solubility in water is reduced, so that it is difficult to emulsify.

The polymerization reaction of the monomer composition containing the amine-containing (meth) acrylic monomer, vinyl monomer, (meth) acryloyl group-containing monomer and crosslinkable vinyl monomer is carried out by a general solution polymerization method or a bulk polymerization method. The reaction can be performed, for example, by a precipitation polymerization method, which is a polymerization method for obtaining a powder, and is usually performed while heating in a non-aqueous solvent under an atmosphere of an inert gas such as nitrogen gas. The reason why the polymerization reaction is carried out in a non-aqueous solvent under an inert gas atmosphere is to prevent the ester groups present in the monomer or the formed copolymer from being hydrolyzed. .

In the present invention, a good solvent alone or a mixed solvent of a good solvent and a poor solvent is used as the non-aqueous solvent.

In the present invention, the good solvent is used
This is because the formation of a homopolymer due to the difference in reactivity of each monomer is suppressed, and a uniform copolymer is obtained. In the present specification, the good solvent means the good solvent 1 at 25 ° C.
A solvent in which a copolymer having a molecular weight of 10,000 or more is dissolved in an amount of 20 g or more per 00 ml and no turbidity is observed. Specific examples of the good solvent include, for example, methanol, ethanol, isopropanol, acetone,
Examples include ethyl acetate, benzene, toluene, xylene and the like. Among these good solvents, ethanol, isopropanol and benzene are particularly preferable since they can obtain a copolymer having a relatively high molecular weight. Since benzene and the like are harmful, ethanol and isopropanol are most preferable.

The reason why the poor solvent is used in the present invention is that the produced copolymer is easily precipitated from the polymerization solution. The poor solvent means a solvent which dissolves a copolymer having a molecular weight of 10,000 or more in 5 g or less in 100 ml of the poor solvent at 25 ° C. Specific examples of the poor solvent include linear, branched or cyclic aliphatic hydrocarbons having 15 or less carbon atoms, such as n-pentane, n-hexane, and cyclohexane. Among these poor solvents, linear, branched or cyclic aliphatic hydrocarbons having a relatively high boiling point and 7 or less carbon atoms are preferred. Among them, straight-chain, branched-chain or cyclic aliphatic hydrocarbons having 6 or 7 carbon atoms are particularly preferable because of their high boiling points. Further, n-hexane, cyclohexane, and the like are preferable because they are inexpensive and industrially easy to handle.

In order to synthesize a high molecular weight copolymer without impairing the properties of the obtained emulsifier, it is preferable to mix the good solvent and the poor solvent in appropriate ratios. If the proportion of the poor solvent is too large, the polymerization proceeds promptly, and it becomes difficult to obtain a polymer copolymer having desired physical properties by depositing powder in a short time. The ratio of the poor solvent to the mixed solvent of the good solvent and the poor solvent is 9
It is desirable that the content of the good solvent is 8% by weight or less, preferably 97% by weight or less, and the proportion of the good solvent is 2% by weight or more, preferably 3% by weight or more.

In order to efficiently obtain a high molecular weight copolymer from the reaction solution, it is preferable to use a reaction device for improving stirring during polymerization. When a commonly used stirrer for solution polymerization is used as such a reaction apparatus, it is preferable to dilute the monomer composition with the solvent so that the concentration of the monomer composition becomes 30% by weight or less. At the time of the reaction, it is preferable to sufficiently stir using a stirrer or the like in order to prevent the reaction solution from stagnating. The polymerization reaction is preferably performed under heating at 50 to 100 ° C., and is generally performed at the reflux temperature of the solvent used in the reaction. The time required for the polymerization reaction is usually 10 hours or more. In the polymerization reaction, the amount of the remaining monomer was 1
When the content becomes 0% by weight or less, the process can be arbitrarily terminated. The amount of the remaining monomer is, for example, PS
It can be determined by adding an oxygen to a double bond by a known method such as a DB method and measuring the double bond content.

Thus, a reaction solution containing a precipitate of the polymer copolymer is obtained. The mixed solvent can be removed by, for example, filtering the obtained polymer copolymer precipitate and drying it in vacuo. Alternatively, it can be carried out by distillation under normal pressure or reduced pressure.

In the polymerization reaction, a polymerization catalyst may be used. Such polymerization catalysts include, for example, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), azo compounds such as dimethyl-2,2'-azobisisobutyrate, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, and di-t-butylperoxide There are peroxides represented by dialkyl peroxides such as oxides, peroxycarbonates such as diisopropylperoxydicarbonate, and peroxyesters such as t-butylperoxypivalate. These catalysts are used alone or in combination of two or more. These are used in combination. In addition, the present invention is not limited only to such an example. In addition, when a large amount of an amine-based monomer is used in the monomer composition, an excessive use of a peroxide catalyst may cause undesirable side reactions such as an oxidation reaction at the same time, and may hinder polymerization. Cost. In general, it is preferable to mainly use an azo-based catalyst, but it depends on the boiling point of the solvent used. For example, when ethanol or benzene is used, 2,2′-azobisisobutyronitrile is not easily handled. Most preferred because it is good. The amount of the polymerization catalyst to be used is preferably 0.05 to 3.0% by weight, and more preferably 0.1 to 1.0% by weight, based on the total weight of the monomers in the monomer composition.

In the course of the polymerization of the monomers,
Various aspects are exhibited. For example, when only the above-mentioned good solvent is used, the appearance is similar to that in the case where general solution polymerization is performed in the initial stage of the polymerization reaction, but the crosslinking reaction proceeds with the progress of the reaction, and the gel-like state is obtained. And a grease-like product without a precipitate is obtained as the reaction further proceeds.

When a mixed solution of the above-mentioned good solvent and poor solvent is used, the initial stage of the polymerization exhibits the same appearance as that of the case where a general solution polymerization method is employed. As the reaction proceeds, the crosslinking reaction progresses and the mixture becomes gel-like. As the reaction further progresses, the obtained polymer can no longer be dissolved in the mixed solvent, becomes insoluble, and precipitates as a precipitate.

Thus, (a) a high molecular weight copolymer is obtained.
No. 1 and JP-A-6-316510.

The amount of the high molecular copolymer in the emulsion composition is preferably 0.01 to 10.0% by weight, more preferably 0.05 to 5.0% by weight. If the amount is less than 0.01%, the stability of the emulsified composition is insufficient. If the amount exceeds 10.0% by weight, the effect of improving the stability is small and not suitable.

When using the above-mentioned high molecular weight copolymer, it is desirable to neutralize it with a suitable acidic substance. Examples of the neutralizing agent include mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid, citric acid, lactic acid, succinic acid, malic acid, dimethyl sulfate, and diethyl sulfate.

The silicone oil used in the present invention includes, for example, chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexa. There are cyclic silicones such as siloxane. Of these, volatile silicone oils having a boiling point of 300 ° C. or less are preferred. The amount of the silicone oil is preferably 0.1 to 50.0% by weight. 0.
If the amount is less than 1% by weight, the effect is not exhibited.

For the oil-in-water emulsion composition used in the present invention, various raw materials usually used for cosmetics can be used.

The liquid oils and fats include linseed oil, camellia oil,
Macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, triglycerin, glycerin trioctanoate And glycerin triisopalmitate. Examples of solid fats and oils include cocoa butter, coconut oil, palm oil, palm kernel oil, hardened oil, hardened castor oil, mokuro, shea butter and the like. As waxes, beeswax,
Carnauba wax, lanolin, reduced lanolin, hard lanolin, jojoba wax, shellac wax and the like.

The higher alcohols include, for example, linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, and cetostearyl alcohol, glyceryl monostearyl ether (batyl alcohol), and glyceryl monocetyl ether (kimyl alcohol). And other branched alcohols.

As ester oils, cetyl octoate,
Hexyl laurate, isopropyl myristate, octyl palmitate, isocetyl stearate, isopropyl isostearate, octyl isopalmitate, isodecyl oleate, glyceryl tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, succinic acid 2 -Ethylhexyl, diethyl sebacate and the like. Examples of the hydrocarbon oil include liquid paraffin, squalane, squalene, paraffin, isoparaffin, ceresin, vaseline, and microcrystalline wax.

The lower alcohol includes methanol, ethanol, propanol, isopropanol and the like.

As humectants, polyethylene glycol, propylene glycol, dipropylene glycol,
1,3-butylene glycol, hexylene glycol,
There are glycerin, diglycerin, xylitol, maltitol, maltose, D-mannitol and the like.

Examples of the water-soluble polymer include plant polymers such as gum arabic, carrageenan, pectin, agar, quince seed (quince), starch, alge colloid (brown algae extract), and microbial polymers such as dextran and pullulan. Animal polymers such as collagen, casein and gelatin; starch polymers such as carboxymethyl starch and methylhydroxypropyl starch; alginic acid polymers such as sodium alginate; vinyl polymers such as carboxyvinyl polymer (such as CARBOPOL); Polyoxyethylene polymer, polyoxyethylene polyoxypropylene copolymer polymer, acrylic polymer such as sodium polyacrylate, polyacrylamide, inorganic water-soluble polymer such as bentonite, aluminum magnesium silicate, laponite, etc. A.

Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers such as para-aminobenzoic acid; anthranilic acid-based ultraviolet absorbers such as methyl anthramylate; salicylic acid-based ultraviolet absorbers such as octyl salicylate and phenyl salicylate; Isopropyl acid, octyl paramethoxycinnamate, mono-2-diparamethoxycinnamate
Cinnamic acid UV absorbers such as glyceryl ethylhexanoate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-
Benzophenone-based ultraviolet absorbers such as 4-methoxybenzophenone-5-sulfonic acid, urocanic acid, 2- (2 ′
-Hydroxy-5'-methylphenyl) benzotriazole, 4-tert-butyl-4'-methoxybenzoylmethane and the like.

The sequestering agents include sodium edetate, sodium metaphosphate, phosphoric acid and the like.

As antioxidants, ascorbic acid, α
-Tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like.

As antibacterial agents, benzoic acid, salicylic acid,
Examples include carboxylate, sorbic acid, paraoxybenzoate, parachloromethcresol, chlorhexidine chloride, and trichlorocarbanilide.

The drugs include vitamin A oil, retinol, retinol palmitate, inosit, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, DL-α-tocopherol nicotinate, magnesium phosphate ascorbate, vitamin D2 (ergocasiferol) ), Vitamins such as dl-α-tocopherol, dl-α-tocopherol acetate, pantothenic acid, biotin,
Hormones such as estradiol and ethinyl estradiol, amino acids such as arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine and tryptophan; anti-inflammatory agents such as allantoin and azulene;
Examples include whitening agents such as arbutin, astringents such as zinc oxide and tannic acid, cooling agents such as L-menthol and camphor, sulfur, lysozyme chloride, pyridoxine hydrochloride, and γ-oryzanol.

As various extracts, dokudami extract,
Oak extract, melilot extract, bonito extract, liquorice extract, peonies extract, bonsai extract, loofah extract, kina extract, saxifrage extract,
Clara extract, Kouhone extract, Fennel extract, Primrose extract, Rose extract, Jiao extract, Lemon extract, Sikon extract, Aloe extract, Shobu root extract, Eucalyptus extract, Japanese cedar extract, Sage extract, Thyme extract, Tea extract, Seaweed extract, Cucumber extract, Clove Extracts, raspberry extract, melissa extract, carrot extract, carrot extract, maroni extract, peach extract, peach extract, mulberry extract, cornflower extract, hamamelis extract, placenta extract, thoracic extract, silk extract and the like.

The above-mentioned drugs can be used in a free state, those capable of forming a salt can be used in the form of an acid or base salt, and those having a carboxylic acid group can be used in the form of an ester thereof. .

Further, if necessary, suitable fragrances, dyes and the like can be added to the emulsion composition of the present invention as long as the emulsion stability is not impaired.

When the emulsifier of the present invention is used, an emulsion composition having good emulsion stability can be obtained without using a surfactant. Therefore, from the viewpoint of safety, it is desirable that the emulsified composition of the present invention does not contain a surfactant.

The oil-in-water emulsion composition of the present invention is a cream,
It can be in the form of all possible emulsified cosmetics, such as emulsions, translucent lotions, sunscreens, makeup cleansers, emulsified foundations, hair creams and the like.

[0069]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to this. All amounts are by weight.

Production Example 1 (Production of high molecular weight copolymer) In a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube, 50 g of N, N-dimethylaminoethyl methacrylate as a monomer, N-vinylpyrrolidone 47.5
g, 2.5 g of stearyl acrylate and 1.9 g of tripropylene glycol diacrylate, and a mixed solvent (mixing ratio (weight ratio) of 4:96) of 23.1 g of ethanol and 554.3 g of cyclohexane were added. While refluxing, the mixture was stirred for 2 hours under a nitrogen stream to degas.

Next, 0.41 g of 2,2'-azobisisobutyronitrile was added to a three-necked flask, and polymerization was started at 80 ° C. After a lapse of 45 minutes from the start of the polymerization, 1.9 g of tripropylene glycol diacrylate was added, and after a lapse of 45 minutes, 1.9 g of tripropylene glycol diacrylate was added. After performing a polymerization reaction for about 10 hours while stirring under a nitrogen stream, the obtained polymer slurry solution was filtered under reduced pressure, and the solid component was dried under reduced pressure. The obtained dried polymer was pulverized with a pulverizer to obtain a white powdery polymer copolymer.

Production Example 2 (Production of high molecular weight copolymer) In a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube, 50 g of N, N-dimethylaminoethyl methacrylate as a monomer, 47. 5g,
2.5 g of stearyl acrylate, 1.9 g of tripropylene glycol diacrylate and 37 ethanol
6.2 g was added to adjust the monomer concentration to 21% by weight, and the mixture was stirred for 2 hours under a nitrogen stream while refluxing at 80 ° C. to be deaerated.

Next, 0.41 g of 2,2′-azobisisobutyronitrile was added to a three-necked flask, and polymerization was started at 80 ° C. After a lapse of 45 minutes from the start of the polymerization, 1.9 g of tripropylene glycol diacrylate was added.
After 5 minutes, 1.9 g of tripropylene glycol diacrylate was added. Approximately 1 while stirring under a nitrogen stream
After conducting the polymerization reaction for 0 hour, the obtained polymer slurry solution was filtered under reduced pressure, and the solid component was dried under reduced pressure.
The dried polymer was pulverized with a pulverizer to obtain a white powdery polymer copolymer.

Examples 1 to 3 and Comparative Examples 1 and 2 (skin care creams) Oil-in-water emulsified compositions having the composition shown in Table 1 were obtained by using the polymer copolymers produced in Production Examples 1 and 2 as emulsifiers. It was manufactured and evaluated for stickiness and familiarity when applied to the skin. Further, the emulsion stability of the emulsified composition was evaluated. Each evaluation method and manufacturing method are as follows.

(1) Evaluation method Sensory test by a female panel A sensory test was conducted by 15 female panels on the feeling of use as an emulsion composition. (Evaluation criteria of stickiness) ：: Very good (13 or more of 15 persons are evaluated as good) ○: Good (10 or more and less than 13 of 15 persons are evaluated as good) △: Somewhat good (5 of 15 persons) Not less than 10 and less than 10 were evaluated as good. ×: Inferior (less than 5 out of 15 evaluated as good) (Familiarity evaluation criteria) ◎: Very good (13 or more out of 15 evaluated as good) ○: Good (10 to less than 13 out of 15 rated good) Δ: Somewhat good (5 to less than 10 out of 15 rated good) ×: Poor (less than 5 out of 15 rated good) Stability test The emulsified composition was allowed to stand in a thermostat at 50 ° C., and the state after one month was observed. (Evaluation criteria for stability) ：: No oil separation was observed. Δ: Oil separation was slightly observed. X: Oil separation is clearly recognized. (2) Production method Emulsification is carried out with an emulsifier while adding the oil phase component to the water phase component.

[0076]

[Table 1] ────────────────────────────────── Example Comparative Example Component ─────── ─ ───── 1 2 3 1 2 ────────────────────────────────── A. Oil phase flow Paraffin 22.0 22.0 22.0 22.0 22.0 Decamethylcyclopentasiloxane 5.0 − 5.0 − 5.0 Methylphenylpolysiloxane (20cs) − 5.0 − − − B. Aqueous phase Polymer copolymer (Production Example 1) 0.3 0.3 − 0.3 − Polymer copolymer Polymer (Production Example 2)--0.3--PEMULEN TR-2 ^{* 1)} ----0.3 Lactic acid 0.1 0.1 0.1 0.1-Potassium hydroxide----0.1 Deionized water Residue Residue Residue Residue ──── ────────────────────────────── Emulsion stability ○ ○ ○ ○ ○ Familiar ○ ○ ○ ○ × Sticky ◎ ○ ◎ × ○ ────────────────────────────────── * 1): Product name (alkyl Modified carboxyvinyl polymer)

From Table 1, it can be seen that the oil-in-water emulsion composition of the present invention has a low stickiness, a good fit, an excellent feeling upon use,
It can be seen that the emulsion has excellent emulsion stability.

Example 4, Comparative Examples 3 and 4 (Hair Styling Cream) An oil-in-water emulsion composition having the composition shown in Table 2 was produced and evaluated based on the above criteria. The manufacture is the same as in Example 1. Table 2 also shows the results.

[0079]

Table 2 Component Ingredient Example 4 Comparative Example 3 Comparative Example 4 A. Oil phase Isoparaffin 2.0 2.0 2.0 Octamethylcyclotetrasiloxane 4.0-4.0 Aqueous phase polymer copolymer (Production Example 1) 5.0 5.0-PEMULEN TR-2 ^{* 1)} --5.0 Lactic acid 1.0 1.0-Potassium hydroxide--1.0 Ion-exchanged water Residue Residue ─────────乳化 Emulsion stability ○ ○ ○ Familiar ○ ○ × Sticky ○ △ ○ ─────────── ─────────────────────── * 1): Product name (alkyl-modified carboxyvinyl polymer) manufactured by BFGoodrich

From Table 2, it can be seen that the oil-in-water emulsion composition of the present invention has a low stickiness, a good conformability, an excellent feeling upon use,
It can be seen that the emulsion has excellent emulsion stability.

Example 5 (Skin care emulsion) A. Oil phase Dimethylpolysiloxane (6cs) 1.0% by weight Isooctyl myristate 5.0 Squalane 3.0 Vitamin E acetate 0.05 Cetostearyl alcohol 2.0 B. Water Phase Citric acid 0.04 Propylene glycol 11.0 Methyl parahydroxybenzoate 0.3 Sodium hexametaphosphate 0.1 Polymer copolymer (Production example 1) 0.05 Xanthan gum 0.1 Ion-exchanged water Residue (Preparation method) Oil phase The components are heated and dissolved, and emulsified by an emulsifier while being added to the aqueous phase components.

Example 6 (Skin Care Cream) A. Oil Phase Jojoba Oil 3.0% by Weight Vitamin A Acetate 0.01 Ethyl Paraoxybenzoate 0.3 Behenyl Alcohol 5.0 Methylphenyl Polysiloxane (20cs) 47.0 B. Aqueous phase Glycerin 2.0 Trisodium edetate 0.2 Polymer copolymer (Preparation Example 1) 1.0 Lactic acid 0.5 Ethanol 1.0 Ion-exchanged water Residue (Preparation method) Same as in Example 5.

Example 7 (Make Cleansing) A. Oil Phase Decamethylcyclopentasiloxane 10.0% by Weight Macadamia Nut Oil 5.0 Ethyl Parahydroxybenzoate 0.3 Vitamin A Oil 0.1 Bacyl Alcohol 0.5 B. Water Phase 1,3-butylene glycol 5.0 Propylene glycol 2.0 Arbutin 2.0 Magnesium phosphate ascorbate 1.0 Placenta extract 0.5 High molecular copolymer (Production example 1) 0.8 Lactic acid 0.4 Edet Trisodium acid salt 0.1 Methyl parahydroxybenzoate 0.1 Deionized water Residue (Preparation method) Same as in Example 5.

Example 8 (Emulsified Foundation) A. Powder Talc 1.0% by Weight Titanium Dioxide 4.0 Iron Oxide (Yellow) 1.8 Iron Oxide (Black) 0.05 B. Oil Phase Liquid Paraffin 10.0 Liquid lanolin 2.0 Microcrystalline wax 1.0 Methylphenyl polysiloxane (20cs) 1.0 C. Aqueous phase polymer copolymer (Production Example 1) 4.0 Lactic acid 1.5 1,3-butylene glycol 8. 0 Methylparaben 0.2 Ion-exchanged water Residue (Preparation method) Disperse with an emulsifier while adding sufficiently pulverized powder to the aqueous phase component. The oil phase component is heated to a liquid state, added to the water phase component, and emulsified by an emulsifier. Subsequently, it is cooled with stirring.

[0085]

As described above, the oil-in-water emulsion composition of the present invention does not require the use of a surfactant, has no stickiness, is excellent in conformability, and has excellent emulsion stability. It is.

Claims (9)

[Claims] 1. An oil-in-water emulsion composition comprising a silicone oil and a polymer copolymer represented by the following component (A) as an emulsifier. (A) A polymer copolymer obtained by polymerizing a monomer composition containing the following (A) to (D). (A) General formula (I): (Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³
Are each independently a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, A is an oxygen atom, or a -NH- group, B
Represents a linear or branched alkylene group having 1 to 4 carbon atoms. 15.0 to 90.0% by weight of an amine-containing (meth) acrylic monomer represented by the following formula (B):
I): (In the formula, R ¹ is the same as described above, and R ⁴ is a general formula: (Wherein p represents 3 or 4) or a group represented by the following formula: Represents a group represented by Vinyl monomer 1)
0.0 to 80.0% by weight, (C) general formula (III): (Wherein R ¹ and A are the same as above, and R ⁵ is a linear or side chain alkylene group having 8 to 17 carbon atoms or a general formula (IV): (Wherein, n represents an integer of 3 to 4, q represents an integer of 10 to 25), and R ⁶ represents a hydrogen atom or a methyl group. )), And (D) 0.1 to 25.0% by weight of a crosslinkable vinyl monomer. 2. The (A) amine-containing (meth) acrylic monomer of the formula (V): The oil-in-water emulsion composition according to claim 1, which is: 3. The method according to claim 1, wherein the vinyl monomer (B) is of the formula (V)
I): The oil-in-water emulsion composition according to claim 1 or 2, wherein 4. The (meth) acryloyl group-containing monomer (C) is represented by the formula (VII): The oil-in-water emulsion composition according to any one of claims 1 to 3, wherein 5. The crosslinkable vinyl monomer of the formula (D) is a compound of the formula (VIII): The oil-in-water emulsion composition according to any one of claims 1 to 4, wherein 6. A silicone oil in an amount of 0.1 to 50.0% by weight and a polymer copolymer represented by the component (A) in an amount of 0.0
2. The composition of claim 1, further comprising 1 to 10.0% by weight.
6. The oil-in-water emulsion composition according to any one of items 1 to 5. 7. The oil-in-water emulsion composition according to claim 1, wherein the silicone oil is a volatile silicone oil having a boiling point of 300 ° C. or lower. 8. The method of claim 1, wherein the composition is substantially free of a surfactant.
8. The oil-in-water emulsion composition according to any one of items 1 to 7. 9. The oil-in-water emulsion composition according to claim 1, which is a cosmetic composition.