JPH11255998A - New composite and water-in-oil type emulsified composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new composite with high emulsifying power for oils having a wide range of necessary HLB numbers by making the composite include a copolymer made from a specific amine-contg. (meth)acrylic monomer, (meth)acryloyl group-contg. monomer and others and a higher fatty acid liquid at normal temperature. SOLUTION: This new composite includes (A) a copolymer prepared by polymerizing a monomer composition comprising (i) 15.0-90.0 wt.% of an amine- contg. (meth)acrylic monomer of formula I (R<1> is H or methyl; R<2> and R<3> are each H, ethyl or the like; A is NH group; B is a 1-4C alkylene), (ii) 10.0-80.0 wt.% of a vinyl monomer of formula II [R<4> is a group of formula III ((p) is 3 or 4) or the formula CONH2 ], (iii) 1.0-60.0 wt.% of a (meth)acryloyl group- contg. monomer of formula IV [R<5> is a 8-17C alkylene or group of (Cn H2n O)q ((n) is 3 or 4; (q) is 10-25); R<6> is H or the like], and (iv) 0.1-25.0 wt.% of a crosslinkable vinyl monomer, and (B) a higher fatty acid liquid at normal temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel complex and a water-in-oil type emulsified composition, and more particularly, to a stable oil-in-oil type having excellent emulsifying power for oils having a wide range of required HLB. A novel complex that can be used as an emulsifier capable of forming an aqueous emulsion, and a wide range of required H
It can be easily manufactured even if it has an oil having LB, has high safety to skin and hair, has a good moist feeling, has excellent water resistance, and has good emulsion stability. It relates to an aqueous emulsion composition.

[0002]

2. Description of the Related Art Conventionally, oil-in-water emulsion compositions have been used as cosmetic emulsion compositions.
There were water-in-oil emulsion compositions and the like. These emulsified compositions are:
It is widely used as skin care creams, emulsions, sunscreen creams, foundations, hair creams and the like using various oily, aqueous components and surfactants.

[0003] However, in recent years, even higher safety is expected for cosmetics, and from this viewpoint, the presence of a surfactant may be a problem. Therefore, as a method of obtaining an oil-in-water emulsion composition without using a surfactant,
There has been a method of obtaining an oil-in-water emulsion composition using a specific polymer compound, for example, an alkyl-modified carboxyvinyl polymer (trade name: PEMULEN TR-1, TR-2, etc.). The alkyl-modified carboxyvinyl polymer is obtained by esterifying a part of the -COOH group of a carboxyvinyl polymer generally used as a thickener with a long-chain (C10-30) alcohol, and this long-chain hydrophobic group enables emulsification. Is what you do.

[0004] However, in general, an oil-in-water emulsion composition has a problem that it has a refreshing feel to skin and hair, but lacks a moist feel. There is also a method of blending a large amount of a solid or semi-solid oil component in an oil-in-water emulsion composition for the purpose of compensating for this moist feeling, but such an emulsion composition tends to give a sticky feel to skin and hair, Not desirable.

When an oil-in-water emulsion composition is used in a sunscreen cream, it generally has a problem in water resistance as compared with a water-in-oil emulsion composition, and the sunscreen effect is inferior in actual use. There was a problem. Furthermore, when an oil-in-water emulsion composition is used for a foundation, there is also a problem that the makeup lasts generally inferior to a water-in-oil emulsion composition.

Accordingly, an object of the present invention is to provide an emulsion having a water-in-oil type emulsifying ability, an excellent emulsifying power for oils having a wide range of required HLB, and a stable and low irritation to the skin. To provide a novel complex that can be used as an emulsifier capable of forming an oil, and can be easily manufactured using an oil having a wide range of required HLB, and has a moist and good use feeling; An object of the present invention is to provide a water-in-oil type emulsion composition which is excellent in water resistance and cosmetic durability, has good emulsification stability, and has low skin irritation.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, a novel complex comprising a specific cationic polymer and a liquid higher fatty acid has solved the above problems. They have found that they can be solved, and have completed the present invention.

That is, the present invention provides a polymer copolymer obtained by polymerizing a monomer composition containing the following (A) to (D):
A novel complex comprising a higher fatty acid that is liquid at normal temperature. (A) General formula (I):

[0009]

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(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):

[0011]

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

[0013]

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

[0015]

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

[0017]

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

[0019]

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(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.

Further, according to the present invention, there is provided a water-in-oil emulsion composition comprising the novel complex described above.

Hereinafter, the configuration of the present invention will be described in detail. (Polymer Copolymer) The polymer copolymer used in the present invention is obtained by polymerizing the monomer composition containing (A) to (D) described above. Hereinafter, each component constituting the polymer copolymer 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).

[0025]

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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).

[0029]

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The proportion of the vinyl monomer in the monomer composition is 10.0 to 80.0% by weight, preferably 2% by weight.
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 formula (VII).

[0033]

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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 another monomer. is there.

Representative examples of the crosslinkable vinyl monomer include 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.

Among them, particularly preferred crosslinkable vinyl monomers are those represented by the following general formula (VIII).

[0038]

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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, a 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, for example, by filtering the obtained polymer copolymer precipitate, followed by vacuum drying. Alternatively, it can be carried out by distillation under normal pressure or reduced pressure.

At the time of 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, at the initial stage of the polymerization, the same aspect as when a general solution polymerization method is employed is exhibited. 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 polymer copolymer is obtained. The polymer copolymer is described, for example, in JP-A-5-140531 and JP-A-6-316510.

(Higher Fatty Acid Liquid at Room Temperature) Examples of the higher fatty acid liquid at room temperature used in the present invention include straight-chain fatty acids such as caproic acid, enanthic acid, caprylic acid and pelargonic acid, and branched chains such as isostearic acid. Examples thereof include straight-chain monoenoic acids such as fatty acids, oleic acid, myristoleic acid, and palmitoleic acid, and di, tri, and tetraenoic acids. Of these, isostearic acid and oleic acid are particularly preferred. When a higher fatty acid which is solid at room temperature is used, it is difficult to stabilize the emulsion. In the present invention, any one or more of the above higher fatty acids are selected and used.

(Example of New Composite and Method for Producing the Same) The present inventor has found that when the above-mentioned polymer copolymer and a higher fatty acid which is liquid at normal temperature are mixed, a composite insoluble in water or oil is formed. I found to do. The new composite has a completely different chemical composition from the polymer copolymer and the liquid higher fatty acid, and is not a mixture of both. The melting point of this complex is 100 ° C. or higher, and the carboxyl group of the higher fatty acid is bonded to the amino group of the polymer copolymer.

This complex can be produced, for example, as follows. That is, the polymer copolymer and water are mixed to prepare an aqueous solution of the polymer copolymer. A liquid higher fatty acid is added to the aqueous solution of the polymer copolymer. In addition,
The addition is preferably performed while stirring with a stirrer, if necessary. When a liquid higher fatty acid is added to an aqueous solution of a polymer copolymer, the polymer copolymer is adsorbed to the liquid higher fatty acid and binds at the carboxyl group of the liquid higher fatty acid. The adsorption of the polymer copolymer to the liquid higher fatty acid increases with the passage of time and saturates after a certain period of time. If the solution obtained after the addition is subjected to a centrifugal separation treatment, the novel complex according to the present invention becomes a solid and precipitates, so that it can be easily taken out.

(Examples of use of the novel composite) The novel composite according to the present invention has use as, for example, an emulsifier. In the presence of oil, this complex is oriented at the interface between water and oil and acts as a strong interfacial film at the interface of the emulsified particles, preventing coalescence of the particles and a wide emulsifying power independent of the required HLB fluctuation of the oil. Is obtained.

(Preparation of a water-in-oil emulsion composition) A water-in-oil emulsion composition is prepared by adding the above-mentioned novel complex to a liquid containing an oil while stirring or heating as necessary. It can be carried out.

On the other hand, from the viewpoint of ease of preparation, it is preferable to carry out a method of preparing a novel complex in a system by blending a polymer copolymer and a liquid higher fatty acid as raw materials for an emulsion composition. . That is, a liquid higher fatty acid is added to the oil, the mixture is stirred at room temperature using a disper, and an aqueous solution of a polymer copolymer is added little by little while stirring is continued to prepare a water-in-oil emulsion composition. The additive components other than the emulsifier may be added immediately after the preparation of the emulsified composition and stirred gently.

(Mixing ratio, blending amount) In the water-in-oil type emulsion composition of the present invention, the blending amount of the above-mentioned novel complex in the emulsion composition is suitably from 0.02 to 10.0% by weight. is there.
If the amount is less than 0.02% by weight, the stability of the emulsified composition is insufficient, and if the amount exceeds 10.0% by weight, the effect of improving the stability is small and not suitable. On the other hand, when the preparation of the water-in-oil emulsion composition is carried out by a method of preparing a novel composite in the system, the amount of the polymer copolymer in the emulsion composition is preferably from 0.01 to 10%. 0.0% by weight, and more preferably 0.1 to 5.0% by weight. If the amount is less than 0.01% by weight, the stability of the emulsified composition is insufficient. If the amount exceeds 10.0% by weight, the effect of improving the stability is too small to be suitable.

The amount of the liquid higher fatty acid is as follows:
Preferably it is 1.0 to 30.0% by weight, more preferably 2.0 to 20.0% by weight. If the content is less than 1.0% by weight, the water-in-oil type has insufficient emulsification stability due to insufficient hydrophobicity based on the hydrophobic group of the liquid higher fatty acid.
Even if the amount is more than 0.0% by weight, the effect of improving the emulsion stability is unfavorably small.

In the water-in-oil emulsion composition of the present invention, the blending ratio of the liquid higher fatty acid and the polymer copolymer is preferably liquid higher fatty acid / polymer copolymer> 1 (weight ratio), More preferably, the liquid higher fatty acid / polymer copolymer is> 2 (weight ratio). When the ratio of the liquid higher fatty acid / polymer copolymer is 1 or less, the emulsion stability may be poor and an oil-in-water type may be obtained.

Further, the total amount of the polymer copolymer and the liquid higher fatty acid is preferably 0.1 to 30.0% by weight, more preferably 0.5 to 20.0% by weight. If the content is less than 0.1% by weight, the stability of the emulsion is insufficient, and if the content exceeds 30.0% by weight, the effect is saturated, so the upper limit is 30.0% by weight from an economic viewpoint. Is preferred.

(Selective Ingredients) For the water-in-oil emulsion composition used in the present invention, various raw materials usually used for cosmetics can be used. Liquid oils 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, glycerin triisopalmitate, etc. . As solid fats and oils, cocoa butter, coconut oil,
There are palm oil, palm kernel oil, hardened oil, hardened castor oil, molle, shea butter and the like. As waxes, beeswax,
Carnauba wax, lanolin, reduced lanolin, hard lanolin, jojoba wax, shellac wax and the like. Examples of ester oils include cetyl octanoate, hexyl laurate, isopropyl myristate, octyl palmitate, isocetyl stearate, isopropyl isostearate, octyl isopalmitate, isodecyl oleate, glyceryl tri-2-ethylhexanoate, and tetra-2-ethyl. Examples include pentaerythritol hexanoate, 2-ethylhexyl succinate, and diethyl sebacate. Examples of the hydrocarbon oil include liquid paraffin, squalane, squalene, paraffin, isoparaffin, ceresin, vaseline, and microcrystalline wax. As higher alcohols, for example, lauryl alcohol, cetyl alcohol,
Examples include straight-chain alcohols such as stearyl alcohol, behenyl alcohol, myristyl alcohol, and cetostearyl alcohol, and branched-chain alcohols such as glyceryl monostearyl ether (bacyl alcohol) and glyceryl monocetyl ether (kimyl alcohol).
Lower alcohols include methanol, ethanol, propanol, isopropanol and the like. As humectants, polyethylene glycol, propylene glycol,
Dipropylene glycol, hexylene glycol, glycerin, diglycerin, xylitol, maltitol,
Maltose, D-mannite and the like. Examples of the water-soluble polymer include plant gums such as gum arabic, carrageenan, pectin, agar, quince seed (quince), starch, alge colloid (brown algae extract), microbial polymers such as dextran and pullulan, collagen, casein , Animal polymers such as 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-based polymer, acrylic polymer such as sodium polyacrylate and polyacrylamide, and inorganic water-soluble polymer such as bentonite, aluminum magnesium silicate, and laponite.
As the ultraviolet absorber, benzoic acid ultraviolet absorbers such as para-aminobenzoic acid, anthranilic acid ultraviolet absorbers such as methyl anthramylate, octyl salicylate, salicylic acid ultraviolet absorbers such as phenyl salicylate, isopropyl paramethoxycinnamate, Cinnamic acid ultraviolet absorbers such as octyl paramethoxycinnamate and glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy Benzophenone ultraviolet absorbers such as -4-methoxybenzophenone-5-sulfonic acid, urocanic acid, 2- (2'-hydroxy-
5′-methylphenyl) benzotriazole, 4-tert
-Butyl-4'-methoxybenzoylmethane.
Sequestering agents include edetate sodium salt, sodium metaphosphate, phosphoric acid and the like. Examples of the antioxidant include ascorbic acid, α-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like. Drugs include vitamin A oil, retinol, retinol palmitate, inosit, pyridoxine hydrochloride,
Benzyl nicotinate, nicotinamide, nicotinic acid D
L-α-tocopherol, magnesium ascorbate phosphate, ascorbic acid 2-glucoside, vitamin D2
(Ergocasiferol), dl-α-tocopherol 2-L potassium ascorbic acid diester potassium salt, d
Vitamins such as l-α-tocopherol, dl-α-tocopherol acetate, pantothenic acid and biotin; hormones such as estradiol and ethinyl estradiol; anti-inflammatory agents such as allantoin and azulene; whitening agents such as arbutin; zinc oxide; tannic acid And astringents such as L-menthol and camphor, and sulfur, lysozyme chloride, pyridoxine hydrochloride, and γ-oryzanol. As various extracts, there are a dokudami extract, a oak extract, a melilot extract, a bonito extract, a licorice extract,
Peony extract, Soapwort extract, Loofah extract,
Kina extract, Saxifraga extract, Clara extract, Kouhone extract, Fennel extract, Primrose extract, Rose extract, Geo extract, Lemon extract, Sicon extract,
Aloe extract, shobu root extract, eucalyptus extract, horsetail extract, sage extract, thyme extract, tea extract,
Seaweed extract, cucumber extract, clove extract,
There are raspberry extract, melissa extract, carrot extract, carrot extract, marronje extract, peach extract, peach leaf extract, mulberry extract, cornflower extract, hamamelis extract, placenta extract, chest line extract, silk extract and the like. In addition, the drug is used in a free state,
Those capable of forming a salt can be used in the form of a salt of an acid or a base, and those having a carboxylic acid group can be used in the form of an ester thereof. Further, in the water-in-oil emulsion composition of the present invention,
If necessary, appropriate fragrances, dyes and the like can be added within a range that does not impair the emulsion stability.

(Uses of Emulsion Composition) The water-in-oil emulsion composition of the present invention can be used as all possible emulsified cosmetics such as skin care creams, emulsions, sun creams, make-up cleansers, emulsified foundations and hair creams. Can be taken.

[0063]

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.

Example 1 The polymer copolymer (10 mM) obtained in Production Example 1 and isostearic acid (10 mM) were used as the liquid higher fatty acid. Isostearic acid was added to the aqueous solution of the polymer copolymer, and the mixture was stirred with a stirrer and then centrifuged to obtain a composite remaining below the mixture.

FIG. 1 shows the results of measuring the IR (infrared absorption spectrum; KBr) of the obtained composite, together with the IR of the polymer copolymer (Preparation Example 1) and the isostearic acid. From FIG. 1, the signal pattern of the complex is different from that of both alone.
That is, the signal around 1710 cm ⁻¹ derived from the C ＝ O stretching of —COOH of isostearic acid disappears by mixing, and a signal around 1560 cm ⁻¹ derived from the C ＝ O stretching of —COO ⁻ is newly added instead. Is recognized.
From this, it can be seen that a product in which the carboxyl group of isostearic acid was bonded to the high molecular weight copolymer was obtained. From the above, it can be seen that the composite comprising the high molecular weight copolymer and the liquid higher fatty acid is a completely different substance from both components. When the melting point of this composite was examined, it was 100
It was found to be above ℃.

Example 2, Comparative Examples 1-3 An emulsion composition having the composition shown in Table 1 was prepared by the following procedure. The polymer copolymer according to Production Example 1 is dispersed in an aqueous phase, and then the other aqueous phase components are dissolved and emulsified by an emulsifier while being added to the oil phase components.

The skin care cream prepared as described above was subjected to a sensory test (feel of use) and an evaluation of emulsion stability as follows. Table 1 also shows the results.

Sensory Test A sensory test was conducted by 15 female panels on the feeling of use as an emulsion composition. Evaluation criteria for moist feeling or long-lasting makeup ○: Good (10 or more of 15 persons are evaluated as good) △: Somewhat good (5 or more of 15 or less than 10 persons are evaluated as good) ×: Poor (5 of 15 persons) Less than first name is good)

Emulsion Stability Test The emulsified composition was allowed to stand in a constant temperature bath at 40 ° C., and the state after one month was observed. Evaluation criteria for stability ：: No separation of water or oil was observed. Δ: Separation of water or oil was slightly observed. ×: Separation of water or oil is clearly recognized.

[0072]

[Table 1] Component Ingredient Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 ───────────────────────────────── A. Oil phase Liquid paraffin 18.0 18.0 18.0 18.0 Isostearic acid 6.0-6.0 6.0 B. Aqueous phase Polymer copolymer (Preparation example 1) 1.0 1.0 − − PEMULEN TR-2 − − − 1.0 Sodium hydroxide − − − 0.2 Glycerin 5.0 5.0 5.0 5.0 Methyl parahydroxybenzoate 0.2 0.2 0.2 0.2 Ion exchange water Residue Residue Residue ───────────────────────────────── emulsified water-in-oil- ^*) - ^*) oil-in-water emulsification stability ○ × × ○ Moist feeling ○ − ^*) − ^*) △ ─────────────────────────────────

*) Comparative Examples 1 and 2 could not be emulsified.

From Table 1, it can be seen that Example 2 of the present invention is a water-in-oil type emulsified composition having a moist and good feeling in use and excellent emulsification stability without using a surfactant. You can see that.

Example 3, Comparative Examples 4 to 6 The polymer copolymer of Production Example 1 was dispersed in an aqueous phase, the aqueous phase component was dissolved, powder was added, and the mixture was stirred and dispersed. Subsequently, the aqueous phase component in which the powder was dispersed was emulsified with an emulsifier while being added to the oil phase component which was heated and dissolved, and cooled to room temperature to produce a foundation having the formulation shown in Table 2. The obtained foundation was evaluated based on the above criteria. The results are also shown in Table 2.

[0076]

[Table 2] 例 Example Comparative Example Ingredient ──── ──── ────── 3 4 5 6 ───────────────────────────────── A. Powdered titanium dioxide 5.0 5.0 5.0 5.0 Iron oxide (yellow) 1.0 1.0 1.0 1.0 Iron oxide (black) 0.2 0.2 0.2 0.2 B. Oil phase Liquid paraffin 3.0 3.0 3.0 3.0 Decamethylcyclopentasiloxane 10.0 10.0 10.0 10.0 Microcrystalline wax 2.0 2.0 2.0 2.0 Isostearic acid 8.0 8.0-2.0 C. Aqueous phase High molecular copolymer (Preparation example 1) 2.0-2.0-PEMULEN TR-2---2.0 Sodium hydroxide---0.5 Methyl paraben 0.2 2.0 2.0 2.0 Ion-exchanged water Residue Residue Residue ── ─────────────────────────────── emulsion type water-in-oil - ^*) - ^*) oil-in-water emulsion Qualitative ○ × × ○ makeup ^{○ - *) - *) ×} ─────────────────────────────────

*) Comparative Examples 4 and 5 could not be emulsified.

From Table 2, it can be seen that Example 3 of the present invention is an excellent water-in-oil emulsion composition having good cosmetic durability and excellent emulsification stability without using a surfactant.

Example 4, Comparative Examples 7 to 9 The polymer copolymer of Production Example 1 was dispersed in an aqueous phase, the aqueous phase component was dissolved, and the mixture was emulsified with an emulsifier while being added to the oil phase component. Was prepared, and the emulsion stability was evaluated based on the above criteria, and the water resistance was evaluated based on the following criteria. Table 3 also shows the results.

Water Resistance Test A certain amount of sample is applied to the forearm and washed with ion-exchanged water. Thereafter, the sample remaining on the skin was extracted with ethanol, and the remaining amount was measured by absorbance using octyl paramethoxycinnamate as an index. Evaluation criteria for water resistance ：: Sample remains at least 80% Δ: Sample remains at least 50% and less than 80% ×: Sample remains at less than 50%

[0081]

[Table 3] 例 Example Comparative Example Ingredient ──── ─────── ─── 4 7 8 9 ────────────────────────────── A. Oil phase Octyl paramethoxycinnamate 8.0 8.0 8.0 8.0 Hydrophobized titanium dioxide 5.0 5.0 5.0 5.0 Glycerin diisostearate 5.0 5.0 5.0 5.0 Oleic acid 10.0 10.0 − − B. Aqueous phase Polymer copolymer (Production example 1) 0.5 − 0.5 − PEMULEN TR-2 − − − 0.5 Water Sodium oxide---0.3 Methyl paraoxybenzoate 0.2 0.2 0.2 0.2 Ion-exchanged water Residual Residual Residual ─────────────────────────────乳化 Emulsified water-in-oil − ^*) − ^*) Oil-in-water Emulsion stability ○ × × ○ Water resistance ○ − ^*) − ^*) △ △ ────── ────

*) Comparative Examples 7 and 8 could not be emulsified.

From Table 3, it can be seen that Example 4 of the present invention is a water-in-oil emulsion composition having excellent water resistance and excellent emulsion stability without using a surfactant.

Example 5 Emulsion A. Oil phase Liquid paraffin 20.0% by weight Squalane 5.0 Isostearic acid 1.0 B. Aqueous phase Polymer copolymer (Preparation example 1) 0.1 Citric acid 0.1 1 , 3-Butylene glycol 8.0 Arbutin 0.1 Phenoxyethanol 0.3 Ion-exchanged water Residue -Preparation method- The polymer copolymer according to Production example 1 is dispersed in an aqueous phase, the aqueous phase component is dissolved and added to the oil phase component While emulsifying with an emulsifier.

Example 6 Skin Care Cream A. Oil Phase Glyceryl Tri-2-ethylhexanoate 2.0% by Weight Hardened Oil 1.0 Phytosterol 0.1 Vitamin A Acetate 0.5 Isostearic Acid 20.0 B. Water Phase Polymer Copolymer (Production Example 1) 5.0 Propylene glycol 5.0 Ethylparaben 0.1 Sodium edetate 0.2 Ion-exchanged water Residue -Production method- The polymer copolymer according to Production Example 1 was dispersed in an aqueous phase. The aqueous phase component is dissolved and emulsified by an emulsifier while being added to the oil phase component dissolved by heating, followed by cooling.

Example 7 Sunscreen Cream A. Oil Phase Squalane 3.0% by weight 2-ethylhexyl succinate 3.0 Isopropyl myristate 7.0 Octyl paramethoxycinnamate 10.0 Butylparaben 0.2 Isostearic acid 5 B. Aqueous phase Polymer copolymer (Production example 1) 0.5 Glycerin 10.0 Ion-exchanged water Residue -Production method- The polymer copolymer according to Production example 1 is dispersed in the aqueous phase, and the aqueous phase component is dispersed. Emulsify with an emulsifier while dissolving and adding to the oil phase component.

Example 8 Hair Cream A. Oil Phase Liquid Paraffin 10.0 wt% Vaseline 8.0 Salami Beeswax 2.0 Butylparaben 0.1 Isostearic Acid 2.0 B. Water Phase Polymer Copolymer (Production Example) 1) 2.0 Glycerin 30.0 Purified water Residue -Preparation method- Emulsify and cool with an emulsifier while adding the aqueous phase component to the oil phase component dissolved by heating.

Example 9 Cream A. Oil phase Glyceryl 2-ethylhexanoate 10.0% by weight Squalane 8.0 Isostearic acid 5.0 New complex (Example 1) 2.0 B. Aqueous phase glycerin 8.0 Ethanol 1.0 Hyaluronic acid 0.3 Ion-exchange water Residue -Preparation method- Dissolve the aqueous phase component, emulsify with an emulsifier while adding the new complex to the heat dispersed oil phase component, and cool.

Example 10 Emulsion A. Oil phase Isostearyl palmitate 20.0% by weight Vaseline 5.0 Cetostearyl alcohol 1.0 New complex (Example 1) 0.5 B. Aqueous phase Dipropylene glycol 3. 0 Ascorbic acid palmitate 0.3 Ion-exchanged water Residue -Preparation- Dissolve the aqueous phase component, emulsify with an emulsifier while adding the new complex to the heat dispersed oil phase component, and cool.

[0090]

As described above, the water-in-oil emulsion composition of the present invention has good emulsification stability without using a surfactant. For this reason, a water-in-oil type emulsion composition having excellent water resistance is obtained, and when used as a sunscreen cosmetic, the sunscreen effect is maintained, and when used as a foundation, the cosmetic has a good hold. There is an advantage that it becomes. Furthermore, it has a moist and good use feel, which is a characteristic of the water-in-oil type, and it can be used widely from non-polar oils to polar oils regardless of the type of oil. In addition, it can have refreshing usability.

[Brief description of the drawings]

FIG. 1 shows the infrared absorption spectrum of the novel composite of the present invention.
It is a figure shown with an infrared absorption spectrum of a polymer copolymer and a higher fatty acid which are raw materials.

Claims (8)

[Claims] 1. A novel complex comprising a polymer copolymer obtained by polymerizing a monomer composition containing the following (A) to (D), and a higher fatty acid which is liquid at ordinary temperature. (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 novel complex according to claim 1, wherein the higher fatty acid liquid at room temperature is isostearic acid or oleic acid. 3. The amine-containing (meth) acrylic monomer of (A) is of the formula (V): Wherein the vinyl monomer of (B) is of the formula (VI): Wherein the (meth) acryloyl group-containing monomer (C) is represented by the formula (VII): Wherein the crosslinkable vinyl monomer of (D) is of the formula (VII)
I): The novel conjugate according to claim 1 or 2, wherein 4. The content of the monomers (A), (B), (C) and (D) is as follows: (A): 41.0 to 52.0% by weight (B): 40.0 to 48% The novel composite according to any one of claims 1 to 3, wherein the content is 0.0% by weight (C): 1.5 to 3.5% by weight (D): 6.5 to 7.5% by weight. 5. A water-in-oil type emulsion composition comprising the novel composite according to claim 1. 6. The water-in-oil emulsion composition according to claim 5, wherein the novel complex is prepared in a system by blending a polymer copolymer and a liquid higher fatty acid as raw materials for the emulsion composition. 7. The water-in-oil type emulsion composition according to claim 6, wherein the mixing ratio of the liquid higher fatty acid and the polymer copolymer is such that the liquid higher fatty acid / polymer copolymer is> 1 (weight ratio). 8. The method of claim 5, wherein the composition is substantially free of a surfactant.
8. The water-in-oil emulsion composition according to any one of items 1 to 7.