JPH10139650A - Water-in-oil type emulsified composition and skin cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-viscosity water-in-oil type emulsified composition, good in extensibility and excellent in feeling of use and emulsification stability without becoming sticky even after the lapse of time by including a nonionic surfactant having an HLB within a prescribed range and a polymeric compound having orienting properties in the interface between the oil and the water therein. SOLUTION: This water-in-oil type emulsified composition comprises (A) a nonionic surfactant having 1-6 HLB such as a monoglyceride and (B) preferably 0.1-5wt.% polymeric compound which is a solid at normal temperature under atmospheric pressure, having orienting properties in the interface between the oil and the water, capable of producing intramolecular and intermolecular cross-linkages by bonds other than covalent bond and manifesting physical properties of causing no fracture or plastic deformation within the range of 0-15% elongational ratio at 20 deg.C temperature and 65% relative humidity such as a copolymer containing a hydrophilic segment and an organopolysiloxane segment. The water-in-oil type emulsified composition is preferably used to prepare a skin cosmetic.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-in-oil emulsified composition having low viscosity, good spreadability, non-stickiness with a refreshing feeling of use, and excellent emulsification stability, and a skin cosmetic containing the same.

[0002]

2. Description of the Related Art Conventionally, hydrocarbon-based oils such as liquid paraffin and squalane have been widely used as oil components in water-in-oil emulsion compositions. Covering with an oil film prevents water evaporation, which is effective for rough skin. Facial cosmetics using these oils have a high treatment effect, and make-up cosmetics have excellent water repellency and little makeup loss.

On the other hand, water-in-oil type emulsified cosmetics containing silicone oil as an oil component have smooth usability and are excellent in water repellency. In particular, cosmetics containing volatile silicone have good spreadability at the time of application, and as the volatile silicone oil evaporates as it is spread, reducing the amount of oil remaining on the skin surface, it has good adhesion, It is resistant to sweat and has the characteristic that it does not easily lose makeup. Furthermore, when lower alcohols such as ethanol are used in combination, a moderate cooling feeling can be obtained due to heat of vaporization due to their high volatility, and a refreshing feeling can be obtained. Further, by blending a fluorine-based oil agent having water repellency and oil repellency, makeup loss due to sebum can be prevented.

However, it is very difficult to obtain a stable water-in-oil type emulsifying system when a lower alcohol such as ethanol or a fluorinated oil is blended. Despite the strong demand for emulsified cosmetics, they have not been obtained. Up to now, methods of obtaining a water-in-oil type emulsion cosmetic having good stability include a method of increasing and solidifying waxes, a method of using silica, and a method of emulsifying stably using a clay mineral and a polyoxyalkylene-modified silicone. Method (JP-A-61-218)
No. 509, JP-A-64-63031 and JP-A-1-180237) are known. In any of the methods, a lower alcohol such as ethanol is blended in order to obtain a refreshing feeling. In the case where a fluorine-based oil agent was blended in order to prevent sebum loss, a stable emulsion could not be obtained, and there was a problem in the storage stability of the emulsion.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a water-in-oil oil having a low viscosity, good spreadability, a refreshing feel, no stickiness over time, and excellent emulsion stability. An object of the present invention is to provide a type emulsion composition and a skin cosmetic containing the same.

[0006]

Under these circumstances, the present inventors have conducted intensive studies and have found that HLB as an emulsifier is used.
Is a nonionic surfactant of 1 to 6 and a polymer compound having an orientation at the oil-water interface, for example, a copolymer that forms intramolecular and intermolecular crosslinks by a bond other than a covalent bond, dissolved in water or a lower alcohol, or It has been difficult to emulsify until now by using one or more polymer compounds selected from a copolymer having a hydrophilic segment to be dispersed and a copolymer containing a hydrophilic segment and an organopolysiloxane. Despite containing a lower alcohol such as ethanol and a fluorinated oil, etc., a water-in-oil emulsion composition having excellent stability was obtained, and when it was applied to skin cosmetics, The present invention has been found to be a cosmetic that has good viscosity and spreadability, has a refreshing feeling of use, and is not sticky over time.

That is, the present invention comprises the following components (A) and (B): (A) a nonionic surfactant having an HLB of 1 to 6 (B) a polymer compound having orientation at an oil-water interface A water-in-oil emulsion composition and a skin cosmetic containing the same.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the nonionic surfactant having an HLB of 1 to 6 as the component (A), a nonionic surfactant usually used in cosmetics and having an HLB of 1 to 6 is used. There is no particular limitation, for example, monoglyceride, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, alkanolamide, amine oxide, polyoxyethylene alkyl ether, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin Mono fatty acid ester, polyoxyethylene propylene glycol mono fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, alkyl saccharide,
α-monoalkyl glyceryl ether, dimethyl polysiloxane / polyoxyalkylene copolymer, dimethyl polysiloxane / monoalkyl glyceryl ether copolymer (see JP-A-6-135871), and the like.
One or more of such surfactants can be used.

The amount of the nonionic surfactant is as follows:
The content is preferably 0.05 to 10% by weight, more preferably 0.1 to 10% by weight.
It is 1 to 8% by weight, more preferably 0.1 to 5% by weight. Within this range, a stable water-in-oil emulsion composition can be obtained, and no stickiness occurs during use, and the feeling in use is good.

The polymer compound having an orientation at the oil-water interface of the component (B) is not particularly limited, but may be a viscous liquid or solid at room temperature and normal pressure at which intermolecular cross-linking is caused by a bond other than a covalent bond. It is a polymer. Preferably, it is dissolved in water or a lower alcohol, which is a copolymer which is a solid at room temperature and normal pressure and exhibits physical properties not causing breakage or plastic deformation at an elongation of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%. It is a copolymer containing a hydrophilic segment that disperses, and is more preferably a copolymer containing a hydrophilic segment and an organopolysiloxane.

It is desirable that such a high molecular compound is soluble or completely dispersible in water or lower alcohol, that is, that the crosslink is easily cleaved in water or lower alcohol. Here, the lower alcohol is preferably a C ₁ -C ₆ alcohol.

The bond other than the covalent bond includes a bond that is easily cleaved in water or a lower alcohol, such as an ionic bond, a hydrogen bond, a hydrophobic interaction, a dipole-dipole interaction, and a bond by van der Waals attractive force. Although ionic bonding, hydrogen bonding, and dipole-dipole interaction are preferable. The polymer compound of the present invention has one or more kinds of functional groups that cause such a bond.

Preferably, the polymer compound (B) is
The elongation ratio at a temperature of 20 ° C. and a relative humidity of 65% is 0 to 15
% In the range of not breaking or plastic deformation. Generally, it is known that a polymer recovers its original shape when the deformation is small, but hardly recovers when the deformation is large. Such deformation that does not return to its original shape is called plastic deformation. Some hard, brittle polymers break before plastic deformation occurs. Neither of them can maintain the original shape, and is unsuitable as a substance for protecting around water droplets in a water-in-oil emulsion. Therefore,
The above property of the polymer having orientation at the oil-water interface of the present invention is so-called rubber elasticity, orienting around water droplets,
It is extremely important in forming a protective film for water droplets and suppressing the separation of the emulsion.

Whether or not plastic deformation occurs when the elongation percentage is in the range of 0 to 15% can be confirmed by, for example, the following simple experiment. That is, about 0.2 mm thick, 20 mm long,
Prepare a 5mm wide specimen, temperature 20 ℃, relative humidity 65%
While recording the stress-strain curve under the conditions of (1), the crosshead is extended 3 mm (15%) at a crosshead speed of 20 mm / min. Ten minutes later, it was stretched again, and the stress-strain curve at the second stretching was 1
Following the same trajectory as the first curve indicates that it has completely recovered and no plastic deformation has occurred. In contrast,
When plastic deformation occurs, stress has been applied with a delay in the second elongation since it has already been elongated in the first reciprocating motion, and as a result, the stress-strain curve does not follow the same locus.

The polymer compound (B) is not particularly limited as long as it causes intramolecular and intermolecular crosslinks by bonds other than covalent bonds. It is necessary to have some kind of polar functional group at the terminal or side chain in the copolymer. then,
When the organopolysiloxane is contained in the copolymer,
Another polymer compound may be used as a linking group between the organopolysiloxane and the polar functional group.

Examples of such polar functional groups include those having a hydroxyl group such as N-acylalkyleneimine and pyrrolidone as those which cause a dipole-dipole interaction, and those having a hydroxyl group such as saccharides and polyvinyl alcohol as those which generate a hydrogen bond. And C ₁ -C ₄ such as poly (meth) acrylamide, polydimethylacrylamide, polydiethylacrylamide, etc.
A mono- or dialkyl (meth) acrylamide polymer,
Poly-N-morpholine (meth) acrylamide, poly-
Those having an amide group such as N-vinylpyrrolidone, poly-N-vinylacetamide, and polyamino acid are exemplified. Carbobetaine, which produces ionic bonds,
Betaine polymers such as sulfobetaine and phosphobetaine and anionic monomers such as (meth) acrylic acid and N,
N-dimethylaminoethyl (meth) acrylate and N,
Examples include amphoteric ionomers such as copolymers of cationic monomers such as N-dimethylaminopropyl (meth) acrylamide and amine oxides.

In the water-in-oil emulsion composition of the present invention, the high molecular compound is formed into a continuous phase (W / O emulsion) by the action of the hydrophilic segment contained in the high molecular compound exhibiting orientation at the oil / water interface. (The external phase = oil phase)
It is possible to prevent coalescence or settling of water droplets. At this time, the polymer compound (B) becomes a protective film having an elastic property with respect to water droplets. In a W / O emulsion containing ethanol and silicone oil, the polymer compound (B) has a protective film with an elastic property, while water droplets coalesce or separate due to sedimentation due to destruction of an interface film, which is likely to occur with a normal emulsifier. As a result, coalescence and sedimentation of water droplets are suppressed, and a stable emulsion can be obtained. In order to obtain a protective film with an elastic property against such water droplets,
The polymer preferably contains a hydrophilic segment exhibiting special properties.

As the polymer compound (B), in the water-in-oil type emulsion composition, it is oriented at the interface between the water droplet and the oil phase, and the lower alcohol (when the oil phase contains a silicone oil, further has a higher silicone resistance). It is preferable to form a protective film for the strong water droplets of (1). It is preferable that the polymer compound (B) alone exhibits rubber elasticity at normal temperature and normal pressure, but a compound which does not exhibit rubber elasticity alone constitutes a water-in-oil emulsion composition such as a lower alcohol / silicone oil. When coexisting with substances that
The physical properties at normal temperature and normal pressure alone are not particularly limited as long as they are oriented at the interface between the water droplet and the oil phase and the same effect can be obtained.

Specific examples of the hydrophilic segment include N-acylalkyleneimine, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl, the terminal of which is blocked. Methacrylate, quaternary dimethylaminoethyl methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride, maleic anhydride half-esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, Diallyl dimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, vinyl alcohol , Vinyl caprolactam, N-
Examples thereof include segments derived from one or more selected from alkylenecarbobetaine and sugar-derived residues. Preferably, N-acylalkyleneimine, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternary dimethylaminoethyl methacrylate, vinylpyrrolidone, N-alkylenecarbobetaine and It is derived from one or more selected from those represented by sugar-derived residues.

In a polymer compound having a hydrophilic segment and exhibiting interfacial orientation, which is dissolved or dispersed in water or a lower alcohol, the ratio of the hydrophilic segment is determined by the ratio of the hydrophilic segment to the segment other than the hydrophilic segment (organopolysiloxane). Weight ratio of 1/50 to 20 /
1, preferably 1/40 to 2/1 and a molecular weight of 5
00 to 500,000, preferably 1,000 to 30
The one with a molecular weight of 000 is preferred for obtaining a stable emulsion.
Further, as the hydrophilic segment derived from N-acylalkyleneimine, a compound represented by the formula (1):

[0021]

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(Wherein R ¹ is a hydrogen atom, and has 1 to 22 carbon atoms)
Represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and n is 2 or 3. A) a poly (N-acylalkyleneimine) segment comprising a repeating unit represented by the formula (1) and an organopolysiloxane segment, wherein at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment is hetero- It is preferable that the poly (N-acylalkyleneimine) segment composed of the repeating unit represented by the formula (1) is bonded via an alkylene group containing an atom. In such a poly (N-acylalkylenimine) -modified silicone, the weight ratio of the segment of the poly (N-acylalkylenimine) to the segment of the organopolysiloxane is 1/50 to 20/1, preferably 1/40 to 20/1.
Those having a 2/1 molecular weight of 500 to 500,000, preferably 1,000 to 300,000 are preferable for obtaining a stable emulsion.

In the formula (1), the cycloalkyl group represented by R ¹ includes one having 3 to 6 carbon atoms; the aralkyl group includes phenylalkyl and naphthylalkyl; the aryl group includes Phenyl, naphthyl, alkyl-substituted phenyl and the like. Examples of the alkylene group containing a heteroatom bonded to at least one silicon atom at the terminal or side chain of the organopolysiloxane segment include a nitrogen atom, an oxygen atom or a sulfur atom having 1 to 3 carbon atoms having 2 to 20 carbon atoms. Examples of the alkylene group include specific examples of the formula (3);

[0024]

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And the group represented by

Preferred examples of the poly (N-acylalkyleneimine) -modified silicone include poly (N-acylalkylenimine).
Formylethyleneimine) modified silicone, poly (N-
Acetylethyleneimine) modified silicone, poly (N-
Propionylethyleneimine-modified silicone, poly (Nn-octanoylethyleneimine) -modified silicone, poly (Nn-dodecanoylethyleneimine) -modified silicone, poly (N-formylpropyleneimine) -modified silicone, poly (N- Acetyl propylene imine)
Modified silicone, poly (N-propionylpropyleneimine) -modified silicone, poly (Nn-octanoylpropyleneimine) -modified silicone, poly (Nn-dodecanoylpropyleneimine) -modified silicone, and the like.

The above poly (N-acylalkyleneimine)
The modified silicone can be prepared by a known method (Japanese Unexamined Patent Publication No. Hei 2-27682).
4, JP-A-4-85334, JP-A-4-8
No. 5,335, JP-A-5-112423, JP-A-7-133352, etc.)
For example, it is synthesized by the following method. First, a segment of poly (N-acylalkyleneimine) composed of the repeating unit represented by the formula (1) is represented by the formula (14);

[0028]

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(Wherein R ¹ is a hydrogen atom, having 1 to 22 carbon atoms)
Represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and n is 2 or 3. ) Is obtained by ring-opening polymerization of the cyclic imino ether compound represented by The cyclic imino ether compound represented by the formula (14) is a 2-oxazoline or a 2-oxazine as exemplified below. That is, 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2
-Oxazoline, 2-heptyl-2-oxazoline, 2
-Octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-undecyl-2-oxazoline, 2-dodecyl-2-oxazoline, 2-tridecyl-2-oxazoline, 2-tetradecyl -2-oxazoline, 2-pentadecyl-2-oxazoline, 2-hexadecyl-2-oxazoline, 2
-Heptadecyl-2-oxazoline, 2-octadecyl-2-oxazoline, 2-nonadecyl-2-oxazoline, 2-eicosyl-2-oxazoline, 2-heneicosyl-2-oxazoline, 2-docosyl-2-oxazoline, 2-benzyl -2-oxazoline, 2-phenyl-2-oxazoline, 2-naphthyl-2-oxazoline, 2-anthryl-2-oxazoline, 2-pyrenyl-2-oxazoline, 2-perylenyl-2-oxazoline, 2-cyclohexyl-2 -Oxazoline, 2-oxazine, 2-methyl-2-oxazine, 2-ethyl-2
-Oxazine, 2-propyl-2-oxazine, 2-butyl-2-oxazine, 2-pentyl-2-oxazine, 2-hexyl-2-oxazine, 2-heptyl-2
-Oxazine, 2-octyl-2-oxazine, 2-nonyl-2-oxazine, 2-decyl-2-oxazine,
2-undecyl-2-oxazine, 2-dodecyl-2-
Oxazine, 2-tridecyl-2-oxazine, 2-tetradecyl-2-oxazine, 2-pentadecyl-2-
Oxazine, 2-hexadecyl-2-oxazine, 2-
Heptadecyl-2-oxazine, 2-octadecyl-2
-Oxazine, 2-nonadecyl-2-oxazine, 2-
Eicosyl-2-oxazine, 2-heneicosyl-2
-Oxazine, 2-docosyl-2-oxazine, 2-benzyl-2-oxazine, 2-phenyl-2-oxazine, 2-naphthyl-2-oxazine, 2-anthryl-
2-oxazine, 2-pyrenyl-2-oxazine, 2-
Perylenyl-2-oxazine, 2-cyclohexyl-2
-Oxazine and the like.

These cyclic imino ethers are, for example, Li
ebigs Ann. Chem. , P996-p100
9 (1974). These compounds may be used alone as a monomer for ring-opening polymerization, or may be used in combination of two or more.

Examples of the polymerization initiator for ring-opening polymerization of the above cyclic imino ether include toluenesulfonic acid alkyl ester, dialkyl sulfate ester, trifluoromethanesulfonic acid alkyl ester and alkyl halide, but are not limited thereto. Absent. These initiators can be used alone or in a mixture.

The molecular chain of poly (N-acylalkyleneimine) can be obtained by ring-opening polymerization of the cyclic imino ether compound represented by the above formula (14) using these initiators. The chains may be homopolymer chains or copolymer chains, which may be random copolymer chains or block copolymer chains.

The above poly (N-acylalkyleneimine)
Is preferably 150 or more and 50,000 or less, more preferably 500 or more and 10,000 or less. When the molecular weight is smaller than 150, the properties of poly (N-acylalkylenimine) are lost, and 5
If it is larger than 000, production becomes difficult, which is not preferable.

In the polymer compound (B), those in which the hydrophilic segment is derived from N-acylalkyleneimine have a polymerization activity produced by ring-opening polymerization of a cyclic imino ether compound represented by the formula (14). It can be obtained by reacting a species with an organopolysiloxane having a functional group capable of reacting with the species.

Examples of the functional group capable of reacting with the above-mentioned polymerization active species include a primary, secondary or tertiary amino group, a mercapto group, a hydroxyl group and a carboxylate group. Among them, an amino group or a mercapto group is preferred. is there. The organopolysiloxane containing an amino group or a mercapto group in the molecule preferably has a molecular weight of 300 or more and 400,000 or less, more preferably 800 or more and 250,000 or less. May be provided. When the molecular weight of the organopolysiloxane is less than 300, it is not preferable in obtaining a stable emulsion,
If it is larger than 400,000, it becomes undesirably gel-like and difficult to react. The amino group or mercapto group contained may be introduced at any position of the main chain and the side chain.

The reaction between an organopolysiloxane containing an amino group or a mercapto group and the reactive terminal of poly (N-acylalkyleneimine) obtained by cationic polymerization of a cyclic imino ether can be carried out as follows. .

The initiator may be used in combination with a polar solvent, preferably a single solvent such as acetonitrile, valeronitrile, dimethylformamide, dimethylacetamide, chloroform, methylene chloride, ethylene chloride, ethyl acetate, methyl acetate, or other solvents as required. Dissolved in a mixed solvent of 40-1
The temperature is raised to 50 ° C, preferably 60 to 100 ° C. Therein, the cyclic imino ether represented by the general formula (14) is added at once or, if the reaction is intense, dropped to carry out polymerization. The progress of the polymerization can be monitored by quantifying the residual amount of the cyclic imino ether which is a monomer using an analytical instrument such as gas chromatography. Even when the cyclic imino ether is consumed and the polymerization is completed, the active species at the growth terminal maintains the reactivity. Without isolating the polymer,
Subsequently, the polymer solution and an organopolysiloxane containing an amino group or a mercapto group in the molecule are mixed and reacted at 5 to 100 ° C, preferably 20 to 60 ° C. The mixing ratio can be appropriately selected as desired, but the reaction is carried out at a ratio of 0.1 to 1.3 mole equivalent of poly (N-acylalkylenimine) per mole of amino group or mercapto group in the organopolysiloxane. Is preferred. If it is less than 0.1 molar equivalent, it is difficult to impart the properties of the poly (N-acylalkylenimine) intended in the present invention due to a small modification rate, and more than 1.3 molar equivalent is unnecessary.

By the above-described reaction, a block copolymer or graft polymer having a poly (N-acylalkylenimine) segment as a hydrophilic segment added to an organopolysiloxane can be obtained.

Further, as the polymer compound (B), at least one silicon atom at the terminal or side chain of the organopolysiloxane segment has the following general formula (4):

[0040]

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(Wherein, m represents an integer of 1 to 8).

In this copolymer, the number of silicon atoms to which the group represented by the general formula (4) is bonded is 10 to 90% (more preferably 40 to 80%) of the total number of silicon atoms in the molecule, and the weight The average molecular weight is preferably from 1,000 to 500,000 (more preferably from 5,000 to 300,000).

When the weight average molecular weight of the organopolysiloxane containing the group (4) is smaller than 1,000, the emulsion stability becomes poor and the weight average molecular weight becomes 500,000.
Those exceeding the above are difficult to manufacture. When the number of silicon atoms to which the group represented by the general formula (4) is bonded is less than 10% of the total number of silicon atoms in the molecule, sufficient orientation to water droplets is not obtained, and emulsion stability is poor. Becomes 90
%, The water solubility becomes too high, and the emulsifiability becomes difficult to be exhibited.

The organopolysiloxane containing such a group (4) is, for example, a precursor represented by the following general formula (15):
Can be synthesized by a so-called hydrosilylation reaction in which an organohydrogenpolysiloxane represented by the following formula is reacted with an N-alkylenepyrrolidone represented by the following general formula (16). The hydrosilylation reaction is carried out using a halogen-based solvent such as dichloromethane, chloroform, or 1,2-dichloroethane, or an aliphatic ether such as tetrahydrofuran, diisopropyl ether, or dibutyl ether as a reaction solvent at room temperature to 100 ° C. And a transition metal complex such as chloroplatinic acid as a catalyst.

[0045]

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(Wherein R ¹¹ is the same or different and represents a saturated alkyl group having 1 to 22 carbon atoms or a phenyl group;
R ¹² , R ¹³ and R ¹⁴ each represent the same group as R ¹¹ or a group selected from a saturated alkyl group having 1 to 22 carbon atoms or a phenyl group, and p ² represents an integer of 30 to 3,000. shows, q ² is an integer of 60~1,500, m are as defined above)

Japanese Unexamined Patent Publication No. 5-32784 discloses a siloxane compound similar to the above-mentioned organopolysiloxane and a method for producing the same.
Further, there is no mention of an effect of suppressing the separation of a water-in-oil emulsion composition containing (silicone oil).

Further, as the polymer compound (B), a copolymer in which a sugar-derived residue is bonded to at least one silicon atom at the terminal or side chain of the organopolysiloxane segment can be used.

In this organopolysiloxane, the sugar-derived residue includes a sugar lactone amide alkyl group (a group in which a sugar lactone compound and an aminoalkyl group are amide-bonded). Also, as the organopolysiloxane,
40 to 97% by weight of silicone chain (more preferably 50 to 97% by weight)
９５95% by weight), having a weight average molecular weight of 1,000-
500,000 (more preferably 5,000 to 300,
000) is preferred. When the amount of the silicone chain is less than 40% by weight, the emulsion stability is deteriorated.
If it exceeds 300, the orientation to water droplets will decrease, and the emulsion stability will also deteriorate. If the weight average molecular weight is less than 1,000, the emulsion stability becomes poor, and the weight average molecular weight becomes 500,0.
Those exceeding 00 are difficult to manufacture.

The organopolysiloxane having a sugar-derived residue bonded thereto is, for example, an organopolysiloxane having at least one aminoalkyl group and a sugar lactone compound (in which aldonic acid or uronic acid is dehydrated and cyclized in the molecule).
To produce an amide bond.

Here, the aminoalkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, particularly an aminoalkyl group having 1 to 8 carbon atoms. Examples of lactone compounds in which aldonic acid or uronic acid is intramolecularly cyclized include D-glucose, D-galactose, D-allose, D-aldose, D-mannose, D-gulose, D-idose,
Lactone of aldonic acid derived from reducing monosaccharide such as talose; lactone of aldonic acid derived from reducing disaccharide such as maltose, cellobiose, lactose, xylobiose, isomaltose, nigerose, kojibiose; maltotriose, panose; Lactone of aldonic acid derived from reducing trisaccharide such as isomalttriose; lactone of aldonic acid derived from reducing oligosaccharide of four or more sugars; D
-Lactones of uronic acids such as -glucuronic acid, L-iduronic acid and mannuronic acid. These can be subjected to the reaction alone or as a mixture.

The reaction between the organopolysiloxane precursor having an aminoalkyl group and the sugar lactone is preferably carried out by using the sugar lactone in an amount of 1.0 to 1.3 times the mole of the amino group of the organopolysiloxane precursor in a solvent. And stirring at a solution concentration of 5 to 30% by weight under reflux for 3 to 20 hours. As the solvent used at this time, lower alcohols such as methanol, ethanol, 1-propanol and 2-propanol are suitable.

Further, at least one silicon atom in the terminal or side chain of the organopolysiloxane segment is linked via an alkylene group containing a hetero atom to the following general formula (2):

[0054]

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(Wherein R ² is a hydrogen atom, having 1 to 22 carbon atoms)
Represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group,
Represents a number of 1 to 5), and a copolymer formed by bonding poly (N-propylenecarbobetaine) composed of repeating units represented by the following formulas can also be used.

In this copolymer, the weight ratio of the organopolysiloxane segment to the poly (N-propylenecarbobetaine) segment is from 98/2 to 40 /
It is preferably 60 (more preferably 95/5 to 60/40) and the weight average molecular weight is 1,000 to 500,000 (more preferably 5,000 to 300,000). When the weight ratio between the organopolysiloxane segment and the poly (N-propylenecarbobetaine) segment is 9
When it is more than 8/2, when it is less than 40/60, or when the weight average molecular weight is less than 1,000, elasticity does not occur and the emulsion stabilizing action is insufficient, which is not preferable.
On the other hand, those having a weight average molecular weight exceeding 500,000 are difficult to produce.

Examples of the alkylene group containing a hetero atom interposed in the bond between the organopolysiloxane segment and the poly (N-propylenecarbobetaine) segment include a nitrogen atom, an oxygen atom and / or a sulfur atom.
Examples thereof include an alkylene group having 2 to 20 carbon atoms, and specific examples thereof include:

[0058]

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And the like. Examples of the cycloalkyl group represented by R ² include those having 3 to 6 carbon atoms; examples of the aralkyl group include phenylalkyl and naphthylalkyl; and examples of the aryl group include phenyl and
Naphthyl, alkyl-substituted phenyl and the like.

The above copolymer is composed of an organopolysiloxane and the following formula (17):

[0061]

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(Wherein R ² is the same as defined above), and the terminal-reactive poly (N-
First, an organopolysiloxane in which poly (N-propyleneimine) is bonded is produced. This is further reacted with sodium chloroacetate, β-propiolactone, γ-butyrolactone, and ε-caprolactone to produce an organopolysiloxane having poly (N-propylenecarbobetaine) bonded thereto.

As still another production method, the obtained poly (N-propyleneimine) -bonded organopolysiloxane is quaternized with an alkyl halide having 1 to 22 carbon atoms, a cycloalkyl halide, an aryl halide or the like. After the reaction, a hydrolysis reaction of an alkoxycarbonylethyl group or an alkoxycarbonylmethyl group is carried out under basic conditions to produce an organopolysiloxane to which poly (N-propylenecarbobetaine) is bonded.

Here, the ring-opening polymerization of a cyclic amine is carried out by a compound such as a Lewis acid, a protonic acid or an alkylating agent, for example, triethyloxonium tetrafluoroborate, benzyl chloride, benzyl bromide, benzyl iodide, methyl bromide, or the like. Methyl iodide, ethyl bromide, ethyl iodide, dimethyl sulfate, diethyl sulfate, trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, benzenesulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, p -Toluenesulfonic acid, p-toluenemethyl sulfonate, p-
It is carried out using ethyl toluenesulfonate or the like as an initiator. When N-substituted-azetidine is used as the cyclic amine, poly (N-substituted-propylenecarbobetaine) can be obtained.

Solvents used for the ring-opening polymerization of cyclic amines and the production of the copolymer of the present invention include acetic esters such as ethyl acetate and propyl acetate, and ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran. Ketones such as acetone, methyl ethyl ketone, etc .; halogen solvents such as chloroform and methylene chloride; nitrile solvents such as acetonitrile and benzonitrile; aprotic polar such as N, N-dimethylformamide, N, N-dimethylacetamide and dimethyl sulfoxide Solvents can be used.

The method for connecting the poly (N-propyleneimine) chain and the silicone chain can be the same as the method for connecting the poly (N-acylalkyleneimine) chain and the silicone chain.

JP-B-63-16418 discloses a siloxane having a betaine group similar to the organopolysiloxane to which the above-mentioned poly (N-propylenecarbobetaine) is bonded, and a method for producing the same. Also in the examples, the effect of suppressing the separation of the water-in-oil emulsion composition containing a lower alcohol (or further silicone oil) is not shown. Further, as a polymer compound (B) having an orientation at an oil-water interface, a copolymer comprising a hydrophilic segment and an organopolysiloxane, the copolymer comprising the following three segments (i), (ii) and (iii) Those which are coalesced can also be used because they suppress the separation of a water-in-oil emulsion composition containing a lower alcohol (or furthermore, a silicone oil) and exhibit an emulsion stabilizing effect.

(I) 1 to 98% by weight of a segment derived from a radical polymerizable vinyl monomer (ii) 1.5 to 60% by weight of a hydrophilic segment (iii) 0.1 to 90% by weight of an organopolysiloxane segment

The segments (i), (ii) and (ii)
The copolymer comprising i) is described in JP-A-3-128311, JP-A-3-128312, WO95 / 060.
78, WO95 / 06079, etc., disclose similar copolymers and a method for producing the same, but the field of application of the copolymers relates to hair cosmetics and includes lower alcohols (or silicone oils). It does not relate to the effect of improving the emulsification stability of the water-in-oil type emulsified composition, nor does it relate to a refreshing skin cosmetic comprising these. Further, these copolymers exhibit orientation around water droplets in a water-in-oil emulsion composition containing a lower alcohol (or, further, silicone oil) to form a protective film for the water droplets. There is no description on the effect of suppressing separation and improving the emulsion stability.

The copolymer comprising the above segments (i), (ii) and (iii) will be described below.

Representative examples of the radically polymerizable vinyl monomer used for constituting the segment (i) include acrylic acid and salts, esters and amides thereof. Acrylates include those derived from normal non-toxic metal ions, ammonium ions or substituted ammonium ions. Examples of the acrylate include those derived from an alcohol having a C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched or C ₃ -C ₄₀ cyclic structure, and 2 to 8 hydroxyl groups. Derived from a C ₂ -C ₈ polyhydric alcohol (eg, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, 1,2,6-hexanetriol, etc.), and an amino alcohol (eg, amino Examples thereof include those derived from ethanol, dimethylaminoethanol, diethylaminoethanol, and quaternized derivatives thereof, and those derived from alcohol ethers (eg, methoxyethanol, ethoxyethanol, and the like). Examples of the acrylamide include unsubstituted acrylamide, N-alkylmonosubstituted or N-alkylaminomonosubstituted acrylamide, N, N-dialkyldisubstituted or N, N-dialkylaminodisubstituted acrylamide (as the alkyl group or alkylamino group). Is C ₁ −
Straight-chain C _40, of branched C ₃ -C _40, or may be mentioned those having a cyclic structure C ₃ -C _40, also the alkylamino groups may optionally be quaternized. ).

Further, a substituted acrylic acid (for example, methacrylic acid, α-amino acid) in which a substituent selected from a C ₁ -C ₄ alkyl group, a cyano group and a carboxyl group is bonded to the 2- or 3-position carbon atom of the acrylic acid. Ethyl acrylic acid, 3-cyanoacrylic acid and the like), and salts, esters and amides thereof can also be used. Examples of the salts, esters and amides of these substituted acrylic acids include those similar to the salts, esters and amides of acrylic acid. Other radically polymerizable vinyl monomers that can be used include C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched or C
Vinyl esters or allyl esters of carboxylic acids having a cyclic structure ₃ -C _40, vinyl halides or allyl halides (e.g. vinyl chloride, allyl chloride), vinyl-substituted or allyl-substituted heterocyclic compounds (such as vinyl pyridine, allyl pyridine, etc.) , Vinylidene chloride, hydrocarbons having at least one carbon-carbon double bond (e.g.,
Styrene, α-methylstyrene, t-butylstyrene,
Butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, vinyltoluene, etc.), and mixtures thereof.

Of these, preferred radically polymerizable vinyl monomers include acrylic acid, methacrylic acid,
α-ethylacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid n-butyl, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid 2
-Ethylhexyl, decyl methacrylate, methyl α-ethyl acrylate, ethyl α-ethyl acrylate, n-butyl α-ethyl acrylate, isobutyl α-ethyl acrylate, t-butyl α-ethyl acrylate, α-ethyl acryl 2-ethylhexyl acid, decyl α-ethyl acrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate 2-hydroxyethyl α-ethyl acrylate, glyceryl acrylate, glyceryl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl α-ethyl acrylate, 2-ethoxyethyl acrylate, Methacrylic acid - ethoxyethyl, 2-ethoxyethyl alpha-ethyl acrylate, acrylamide, methacrylamide, alpha-ethyl acrylamide, N- methylacrylamide, N, N- dimethylacrylamide,
N, N-dimethylmethacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, Nt-butylacrylamide,
N, N-di-n-butylacrylamide, N, N-diethylacrylamide, N-octylacrylamide, N
-Octadecylacrylamide, N-phenylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylamide, N, N
-Dimethylaminoethylacrylamide, quaternized N, N
-Dimethylaminoethyl acrylamide, N, N-dimethylaminoethyl methacrylamide, quaternized N, N-dimethylaminoethyl methacrylamide, acrylic acid N,
N-dimethylaminoethyl, quaternized acrylate N, N-
Dimethylaminoethyl, N, N-dimethylaminoethyl methacrylate, quaternized N, N-dimethylaminoethyl methacrylate, maleic acid, maleic anhydride, maleic acid half ester, crotonic acid, itaconic acid, angelic acid, chloride Diallyl dimethyl ammonium, vinyl pyrrolidone, methyl vinyl ether, methyl vinyl ketone,
Maleimide, vinylpyridine, vinylimidazole, vinylfuran, styrenesulfonic acid, allyl alcohol,
Examples include vinyl alcohol, vinyl caprolactam, and mixtures thereof. As more preferred radical polymerizable monomers, methyl acrylate, methyl methacrylate,
α-ethyl methyl acrylate, ethyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl α-ethyl acrylate, 2-ethylhexyl acrylate, methacrylic acid 2 -Ethylhexyl, 2-ethylhexyl α-ethylacrylate, N-octylacrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N, N-dimethylaminoethyl acrylate,
And quaternized N, N-dimethylaminoethyl acrylate and mixtures thereof. The most preferred radically polymerizable monomers are n-butyl acrylate and acrylate 2
-Ethylhexyl, N-octylacrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N, N-dimethylaminoethyl acrylate, quaternized acrylate N, N-dimethylacrylamide, and mixtures thereof. .

A preferred radical polymerizable monomer used for constituting the segment (i) can be represented by the following general formula (5):

[0075]

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Wherein X ¹ is —OH, —NH ₂ , —OM (M is Na
⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , NH ₄ ⁺ , cations such as alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium), —OR ³ , —NHR ³ and -N (R ³ ) ₂ (R ³ has 1 to 1 carbon atoms)
8 linear or branched alkyl groups, N, N-dimethylaminoethyl groups, methyl quaternized N, N-dimethylaminoethyl groups, 2-hydroxyethyl groups, 2-methoxyethyl groups or 2-ethoxyethyl groups Wherein R ⁴ and R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a methoxyl group, an ethoxyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group. Or a group selected from an ethoxyethyl group).

Examples of the hydrophilic segment (ii) include the same as described above.

The segment composed of the organopolysiloxane of (iii) is represented by the following general formula (6): E (Y) _s Si (R ⁶ ) _3-t (Z) _t (6) A monomer constituting (i) or (ii) or a vinyl group copolymerizable with the macromonomer thereof (optionally having a substituent), Y represents a divalent linking group, and R ⁶ represents hydrogen Represents an atom, a lower alkyl group, an aryl group or an alkoxyl group, Z represents a monovalent siloxane polymer portion having an average molecular weight of 500 or more, and s represents 0 or 1
And t represents an integer of 1 to 3]. The weight average molecular weight of the organopolysiloxane (6) is from about 1,000 to about 50.
Of about 5,000 to about 4,000 to about 400,000.
0 is particularly preferred, and about 5,000 to about 300,000 is more preferred. Examples of the organopolysiloxane (6) include dimethylpolysiloxane represented by the following formulas (7) to (12).

[0079]

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[Wherein t has the same meaning as described above;⁷
Represents a hydrogen atom or an alkyl group; ⁸Is a hydrogen atom or
A carboxyl group (preferably a hydrogen atom);⁹Is
Hydrogen atom, methyl group or carboxymethyl group (preferably
Represents a methyl group), and R^TenIs an alkyl group, alkoxyl
Group, alkylamino group, aryl group or hydroxyl group
(Preferably an alkyl group), and x represents a number of 2 to 6.
And y represents a number from 5 to 700 (preferably about 250).
And u represents 0 or 1]

The copolymer comprising the segments (i), (ii) and (iii) contains 1 to 98% by weight of the segment (i).
(Preferably 1 to 90% by weight, more preferably 50 to 9% by weight.
0% by weight), segment (ii) 1.5 to 60% by weight (preferably 7.5 to 50% by weight) and segment (iii)
0.1 to 90% by weight (preferably 0.5 to 90% by weight,
(More preferably 2 to 60% by weight).

In the copolymer comprising the segments (i), (ii) and (iii), the segment (i) is preferably selected from t-butyl acrylate, t-butyl methacrylate and a mixture thereof. This is because such polymers dissolve directly in cyclomethicone solvents without the need for co-solvents.

Particularly preferred copolymers containing segments (i), (ii) and (iii) include the following (weight percents below relate to the amount of reactants added to the polymerization reaction and are not necessarily in the final polymer It is not about the amount of).

Acrylic acid / n-butyl methacrylate /
Polydimethylsiloxane (PDMS) macromer-molecular weight 20,000 (10/70/20 v / v / v) (I) N, N-dimethylacrylamide / isobutyl methacrylate / PDMS macromer-molecular weight 20,000 (2
0/60/20 v / v / v) (II) t-butyl acrylate / t-butyl methacrylate /
PDMS macromer-molecular weight 10,000 (56/24
/ 20 v / v / v) (III) n-butyl acrylate / 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 36/22/40/2 (IV) n-butyl acrylate / 2- Methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 33/22/40/5 (V) n-butyl acrylate / 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 30 0.5 / 22/40 / 7.5
(VI) n-butyl acrylate / 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 28/22/40/10 (VII) n-butyl acrylate / 2-methoxyethyl acrylate / poly (N -Propionylethyleneimine) / polydimethylsiloxane 23/22/40/15 (VIII) n-butyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 53/40/7
(IX) n-butyl acrylate / 2-ethylhexyl methacrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 35/20/40/5 (X) n-butyl acrylate / 2-methoxyethyl acrylate / poly (ethylene glycol ) / Polydimethylsiloxane 36/22/40/2 (XI)

The segments (i), (ii) and (ii)
The copolymer containing i) can be synthesized at a time by a radical polymerization method, or each macromonomer can be polymerized in advance and finally made into a copolymer. For example, it can be synthesized by a radical polymerization method as follows.

The general principles are well understood [eg Odian; "Principles of polymerization", 2nd edition,
John Wiley & Sons, 1
981, 179, 318]. The desired monomers are all introduced into the reactor with sufficient amounts of mutual solvent to ensure that the viscosity of the reaction is reasonable when the reaction is complete. Typical monomer concentrations are from about 20 to about 50% by weight. It is desirable to remove undesired terminators, especially oxygen. This is done by purging or evacuation with an inert gas such as argon or nitrogen. An initiator is introduced, but if a thermal initiator is used, the reaction is brought to the temperature required for initiation. On the other hand, redox or radical initiation can also be applied if desired. The polymerization is allowed to proceed for hours to days as needed to achieve high levels of conversion. The solvent is then removed, usually by evaporation or by precipitating the polymer with the addition of a non-solvent. The polymer is further purified if necessary.

The amount of the polymer having orientation at the oil-water interface is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and further preferably 0.1 to 5% by weight. . Within this range, a stable water-in-oil emulsion composition can be obtained, the viscosity of the oil phase, which is a continuous phase, does not increase, and no stickiness occurs during use, and the feeling of use is good.

The water-in-oil emulsion composition and the skin cosmetic containing the same of the present invention contain various oils and water in addition to the above components (A) and (B). Here, the oil content is not particularly limited and includes, for example, vaseline, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, higher fatty acids, solid and semi-solid oil components such as higher alcohols; and olive oil, jojoba oil, castor oil,
And liquid oils such as squalane, liquid paraffin, ester oil, diglyceride, triglyceride, silicone oil, and fluorine-based oil. These oils are present in the composition of the present invention or the skin cosmetic in an amount of 10 to 80% by weight, especially 20% by weight.
６０60% by weight is preferred. Water is contained in the composition of the present invention or the skin cosmetic in an amount of 15 to 90% by weight, especially
It is preferable to mix it by 70 to 70% by weight.

The water-in-oil emulsified composition of the present invention and the skin cosmetic containing it, if necessary, in addition to the above-mentioned components, may have a qualitative and quantitative range which does not impair the object and effect of the present invention. Within the composition, components that are blended with ordinary cosmetics can be blended. Such components include, for example, water-soluble and oil-soluble polymers;
Coloring agents such as inorganic and organic pigments, inorganic and organic pigments treated with metal soap or silicone, inorganic and organic pigments and organic dyes treated with fluorine compounds; surfactants such as cationic activators and anionic activators Agents: ethanol, preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances, ultraviolet absorbers, humectants, blood circulation promoters, cooling agents, antiperspirants, skin activators, and the like.

The skin cosmetic of the present invention can be produced according to a usual method, and can be a cream, an emulsion, a foundation, a lipstick and the like.

[0091]

Industrial Applicability The water-in-oil emulsion composition and the skin cosmetic containing the same according to the present invention show excellent emulsification stability, are excellent in refreshing feeling and refreshing feeling, and have no stickiness.

[0092]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited thereto. still,
The percentages in the examples are on a weight basis unless otherwise specified. In this synthesis example, the weight average molecular weight was determined by gel permeation type liquid chromatography using chloroform as a developing solvent, and the value is a value in terms of polystyrene.

Synthesis Example 1 (Synthesis of poly (N-acetylethyleneimine) -modified silicone) 13.03 g (0.070 mol) of methyl-p-toluenesulfonate (methyl tosylate), 2-methyl-2
A mixture of 70 g (0.82 mol) of oxazoline, 10 ml of acetonitrile, and 30 ml of chloroform was refluxed for 6 hours to synthesize a poly (N-acetylethyleneimine) terminal reactive polymer (molecular weight: 1,000). To this reaction solution, polydimethylsiloxane substituted with 3-aminopropyl at both ends (FM3311, molecular weight 1,000, manufactured by Chisso Corporation).
A solution prepared by dissolving 31.8 g in 50 ml of chloroform was added thereto, and reacted at 55 ° C. for 24 hours. By distilling off the solvent under reduced pressure, a block copolymer (molecular weight: 3,000) having poly (N-acetylethyleneimine) chains at both ends of polydimethylsiloxane was obtained. The copolymer was a pale yellow brittle solid (yield 110.2 g,
Yield 96%).

Synthesis Example 2 (Synthesis of poly (Nn-dodecanoylpropyleneimine) -modified silicone) 1.45 g (7.8 × 10 ⁻³ mol) of methyl tosylate
7.8 g of 2-n-undecyl-2-oxazine (0.0
33 mol) and 10 ml of dimethylacetamide in 1
While maintaining the temperature at 00 ° C. for 24 hours, poly (Nn-dodecanoylpropyleneimine) (molecular weight: 1,000) was synthesized. This reaction solution was mixed with a polydimethylsiloxane substituted at both ends with 3-aminopropyl (manufactured by Chisso, FM3325, molecular weight 1).
A solution of 38.9 g of (0000) dissolved in 50 ml of chloroform was added and refluxed for 72 hours. Then, it was reprecipitated with methanol, and the residue was dried under reduced pressure. The obtained polymer was a yellow viscous liquid and had a molecular weight of 12,000 (yield 45.7 g, 95%).

Synthesis Example 3 (Synthesis of poly (N-acetylethyleneimine) -modified silicone) 3.26 g (0.018 mol) of methyl tosylate, 2-
A mixture of 70 g (0.82 mol) of methyl-2-oxazoline, 10 ml of acetonitrile and 40 ml of chloroform was added to 6
After refluxing for an hour, poly (N-acetylethyleneimine) (molecular weight: 4,000) was synthesized. In this reaction solution, 3
Polydimethylsiloxane substituted with an aminopropyl group (KF865, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 4,40)
0, molecular weight 2,000) 63.6 g of chloroform 15
The solution dissolved in 0 ml was added and reacted at 55 ° C. for 24 hours. By evaporating the solvent under reduced pressure, a graft polymer (molecular weight: 6,000) having a poly (N-acetylethyleneimine) chain attached to polydimethylsiloxane and a molecular weight of 2,0
A mixture of 100 silicones formed. This polymer was a pale yellow brittle solid (134.1 g, yield 9).
8%).

Synthesis Example 4 Synthesis of (N-acetylethyleneimine). (Nn-octanoylethyleneimine) random copolymer-modified silicone 1.86 g (0.01 mol) of methyl tosylate, 2-n
-Heptyl-2-oxazoline 10 g (0.059 mol), 2-methyl-2-oxazoline 10 g (0.11 mol)
A mixture of (N-acetylethyleneimine) and (Nn-octanoylethyleneimine) random copolymer (molecular weight 2,000) was synthesized by refluxing a mixture of 74 mol) and 20 ml of chloroform for 6 hours. Polydimethylsiloxane having a 2-aminoethylaminopropyl group substituted on the side chain (KF857, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 830, viscosity 7)
0cs (25 ° C)) 43.34 g in chloroform 150 g
Put the above random copolymer solution in the solution dissolved in,
Refluxed for 10 hours. The solvent was distilled off under reduced pressure to obtain a copolymer (molecular weight: 19,000) in which poly (N-acylethyleneimine) was grafted to polydimethylsiloxane. This copolymer was a pale yellow viscous liquid (yield 64.5 g, 99%).

Synthesis Example 5 (Synthesis of poly (N-formylpropyleneimine) -modified silicone) 13.03 g (0.070 mol) of methyl tosylate, 2
A mixture of 70 g (0.82 mol) of oxazine, 10 ml of acetonitrile and 30 ml of chloroform was refluxed for 6 hours,
A terminally reactive polymer of poly (N-formylpropyleneimine) (molecular weight 1,000) was synthesized. This reaction solution was mixed with polydimethylsiloxane having a 3-mercaptopropyl group substituted on the side chain (X-22-980, manufactured by Shin-Etsu Chemical Co., Ltd.).
1.7% sulfur content, 150 cs viscosity (25 ° C) 50
g in 100 ml of chloroform,
The reaction was carried out at a temperature of 60 ° C for 3 hours and then at 60 ° C for 24 hours. By evaporating the solvent under reduced pressure, a graft polymer (molecular weight: 6,200) having poly (N-formylpropyleneimine) chain attached to polydimethylsiloxane was obtained. This copolymer was a pale yellow viscous liquid (yield: 129.0 g, 97%).

Synthesis Example 6 (Synthesis of Amino-Modified Silicone Containing Tertiary Amino Group in Side Chain (Precursor of Synthesis Example 7)) 6.00 g (0.031 mol) of N, N-dimethylaminopropylmethyldimethoxysilane 1.46 g of water (0.
(081 mol) at 60 ° C. for 5 hours, and the resulting methanol and water are removed under reduced pressure at 60 ° C. and 2-5 mmHg. After the temperature was raised to 80 ° C., 228 g (0.769 mol) of octamethylcyclotetrasiloxane, 1.92 g (1.18 × 10 ⁻² mol) of hexamethyldisiloxane and 0.90 g of polymerization catalyst (tetramethylammonium hydroxide 0 .12 g (1.32 × 10 ⁻³ mol) contained; tetramethylammonium hydroxide pentahydrate dissolved in octamethylcyclotetrasiloxane and toluene, reacted at 80 ° C. for 12 hours, and dried in vacuum at 80 ° C./2 mmHg The tetramethylammonium hydroxide content was determined by a hydrochloric acid titration method), and the mixture was heated under a nitrogen atmosphere for 72 hours. 1
By removing the oligomer at 20 ° C. under a vacuum of 2 to 5 mmHg, an amino-modified silicone having a tertiary amino group in the side chain represented by the following formula was synthesized. The product was a clear, colorless oil (225 g). The weight average molecular weight is 22,
000. The amine equivalent was determined by a hydrochloric acid titration method to be 7,200.

[0099]

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Synthesis Example 7 (Synthesis of poly (N-propionylethyleneimine) -modified silicone) 2.36 g (0.0153 mol) of diethyl sulfate and 30.3 g (0.306 mol) of 2-ethyl-2-oxazoline
Was dissolved in 43 ml of chloroform and heated under reflux in a nitrogen atmosphere for 5 hours to obtain poly (N-propionylethyleneimine).
Was synthesized (molecular weight: 2,000). A solution of 100 g of the tertiary amino-modified silicone synthesized in Synthesis Example 6 (0.0139 mol as an amino group) in 270 ml of chloroform was added all at once, and the mixture was heated under reflux for 16 hours. The reaction mixture was concentrated under reduced pressure, and a graft copolymer (molecular weight: 28,90) having N-propionylethyleneimine chain attached to polydimethylsiloxane represented by the following formula:
0) was obtained. This polymer was a pale yellow rubbery solid (yield 129 g, 97%).

[0101]

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Synthesis Example 8 (Synthesis of poly (N-propionylethyleneimine) -modified silicone) 3.55 g (0.0230 mol) of diethyl sulfate and 27.4 g (0.276 mol) of 2-ethyl-2-oxazoline
Was dissolved in 60 g of dehydrated ethyl acetate, and the solution was dissolved in a nitrogen atmosphere.
The mixture was heated under reflux for an hour to synthesize a poly (N-propionylethyleneimine) terminal-reactive polymer (molecular weight 1,200). Here, a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 110,000, amine equivalent 2
(0,800) 400 g (0.0192 mol based on amino group) of a 50% ethyl acetate solution was added all at once, and the mixture was refluxed for 8 hours. The reaction mixture was concentrated under reduced pressure to obtain a graft copolymer (molecular weight 115,000) in which N-propionylethyleneimine chain was attached to polydimethylsiloxane. This copolymer was a pale yellow rubbery solid (yield 4
27g, 99% yield).

Synthesis Example 9 (Synthesis of poly (N-propionylethyleneimine) -modified silicone) 3.77 g (0.0244 mol) of diethyl sulfate and 48.4 g (0.488 mol) of 2-ethyl-2-oxazoline
Was dissolved in 107 g of dehydrated chloroform, and the mixture was heated under reflux in a nitrogen atmosphere for 5 hours to synthesize a poly (N-propionylethyleneimine) terminal-reactive polymer (molecular weight: 2,000). Here, a 50% ethyl acetate solution of 400 g (0.0407 mol in terms of amino group) of side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 110,000, amine equivalent 9,840) was added all at once, and the mixture was added for 13 hours. Heated to reflux. The reaction mixture was concentrated under reduced pressure to obtain a graft copolymer (molecular weight: 137,000) having N-propionylethyleneimine chain attached to polydimethylsiloxane. The obtained copolymer was a pale yellow rubbery solid (yield 444).
g, 98% yield).

Synthesis Example 10 (Synthesis of alkylpyrrolidone-modified silicone) 500 g of methyl hydrogen polysiloxane (SiH
2.91 mol, weight average molecular weight 100,000,
2.0 g of a 5% isopropyl alcohol solution of chloroplatinic acid was added to the SiH equivalent 172), and N- (3-propenyl) pyrrolidone 382 was added thereto while stirring under a nitrogen atmosphere.
g (3.06 mol) was added dropwise at such a rate that the temperature in the system did not exceed 60 ° C. After the completion of the dropping, the inside of the system is kept at 65 ° C.
Stirring was continued for another 3 hours to return to room temperature. To this, 3,530 g of ethanol was added to make a homogeneous solution, and 10 g of activated carbon powder was further added. The obtained solution is concentrated under reduced pressure, ethanol and unreacted N- (3-propenyl) pyrrolidone are distilled off, and 847 g (yield 98%) of methylpolysiloxane having an alkylpyrrolidone group in a side chain is colorless. Obtained as a clear rubbery solid. The weight average molecular weight was 155,000. In the FT-IR spectrum, no Si-H stretching vibration absorption (2125 cm ^-1 ) was observed.

Synthesis Example 11 (Synthesis of Silicone Containing Residue Derived from Sugar) The amine equivalent was 996 and the weight average molecular weight was 108,000.
Of γ-aminopropyl-modified dimethylpolysiloxane (0.201 mol in terms of amino group), 39.3 g (0.221 mol) of δ-gluconolactone, and 200 g of methanol were mixed and stirred vigorously under a nitrogen atmosphere. While heating, the mixture was refluxed for 8 hours. The solution was diluted three times with methanol and added dropwise to 10 liters of vigorously stirred water at room temperature. The stirring was stopped, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain 204 g (86% yield) of a saccharide-derived residue-containing dimethylpolysiloxane as a colorless transparent elastic solid.
As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained. The content of the silicone segment was 86%.

Synthesis Example 12 (Synthesis of Carbobetaine-Modified Silicone) 30.6 g (0.198 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 1498.2 g
(9.53 mol) was dissolved in 3058 g of dehydrated ethyl acetate, and the mixture was heated under reflux in a nitrogen atmosphere for 15 hours to synthesize a terminal-reactive poly (N-propylene imine). Here, 800 g of side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 110,000, amine equivalent 4,840)
A 50% ethyl acetate solution (0.165 mol based on amino group) was added all at once, and the mixture was refluxed for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (2,212 g, yield 95
%). The resulting reaction mixture was dissolved in 5,000 g of diethyl ether, and β-propiolactone 824 was dissolved.
g (11.4 mol) was added at room temperature, and reacted at room temperature for 24 hours. The obtained solution was concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 13 [Synthesis of Poly (2-ethyl-2-oxazoline) Macromonomer End-Capped with Vinylbenzyl (Precursor of Synthesis Example 14)] 50 g of 2-ethyl-2-oxazoline (0.5044 mol) ), Meta-paravinylbenzyl chloride 0.381
6 g (0.0025 mol) [manufactured by Aldrich Chemical Co.], sodium iodide 0.562 g (0.0037 mol), N, N'-diphenyl-p-phenylenediamine 0.06 g (0.00023 mol), acetonitrile 5
0 ml of the mixture was refluxed for 16 hours at 90 ° C. and the reaction was terminated by adding 100 ml of dichloromethane. The mixed solution containing the synthesized product was filtered, further precipitated in 800 ml of ether, filtered out with suction, and dried under vacuum to obtain a poly (2-ethyl-2-oxazoline) macromonomer ( (40 g, 90% yield).

Synthesis Example 14 [n-butyl acrylate /
Synthesis of 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane copolymer (36/22/40/5)] 3.6 g (0.0281 mol) of n-butyl acrylate, 2-methoxy 2.2 g of ethyl acrylate (0.
0169 mol), dimethylpolysiloxane (Mw = 10,
000 (manufactured by Chisso), 0.2 g (0.00002 mol) of the poly (2-ethyl-2-oxazoline) macromonomer prepared in Synthesis Example 13, 4.0 g (0.001 mol), and 90 ml of acetone as an initiator. As azobisisobutyronitrile (AIBN) 0.015 g (0.0
001 mol), and refluxed for 24 hours.
Was added to stop the synthesis. The reaction mixture is poured into a Teflon coat pan and placed in a vacuum drier to dry the acetone at room temperature. The obtained synthesized product was dissolved in ethanol, the insolubles were filtered, the filtrate was taken out, and the ethanol was distilled off under reduced pressure to obtain [n-butyl acrylate / 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / Polydimethylsiloxane copolymer].
This copolymer was a rubbery solid (yield 9.0 g).

Synthesis Example 15 [Acrylic acid / n-butyl methacrylate / polydimethylsiloxane copolymer (10
Synthesis of / 70/20)] Polymer I: 10 parts of acrylic acid, 70 parts of n-butyl methacrylate and 20 parts of 20K PDMS macromer were placed in a flask. Add enough ethyl acetate to obtain a final monomer concentration of 40%. The initiator benzoyl peroxide was added to a level of 0.1% by weight relative to the amount of monomer. The vessel was evacuated and refilled with nitrogen. Heated to 60 ° C. and maintained this temperature under stirring for 48 hours. The reaction was terminated by cooling to room temperature, and the reaction mixture was poured into a Teflon coat pan and placed in a vacuum oven to dry out ethyl acetate, and acrylic acid / n-butyl methacrylate / polydimethylsiloxane (= 10/70/20) ) (Molecular weight 100,000).

Examples 1 to 13 and Comparative Examples 1 to 4 Water-in-oil emulsion compositions (skin cosmetics) having the compositions shown in Tables 1 and 2 were produced by the following method, and the emulsion storage stability and spreadability were excellent. The evaluation was performed for a refreshing feeling. The results are shown in Tables 1 and 2.

(Production method) Components (1) to (14) are mixed. The mixture of (15) to (17) is slowly stirred to emulsify the mixture. This was defoamed and filled in a polyethylene container to prepare an emulsion.

(Evaluation method) (1) Emulsion storage stability: A polyethylene container containing 100 ml of each emulsion was filled with about 70 g and charged at 5 ° C. and room temperature (20 to 25).
° C) and storage at 40 ° C for one month, the stability of each emulsion was judged from the appearance according to the following criteria. ：: No change △: Unevenness on the surface ×: Separation

(2) Good spreadability: Each of the water-in-oil type emulsified cosmetics was applied to the face by 15 expert panelists, evaluated according to the following criteria, and judged by the average score. Bad ... Score 1 Slightly bad ... Score 2 Normal ... Score 3 Slightly good ... Score 4 Good ... Score 5

(3) Refreshing feeling: Evaluated according to the following criteria in the same manner as in (2) Good spreadability described above, and judged by the average score. Bad ... Score 1 Slightly bad ... Score 2 Normal ... Score 3 Slightly good ... Score 4 Good ... Score 5

(Judgment Criteria) A: Average score of 4.5 or more and 5.0 O: Average score of 3.5 or more and less than 4.5 Δ: Average score of 2.5 or more and less than 3.5 X: Average score of 1.5 Not less than 2.5 and XX: average score of not less than 1.0 and less than 1.5

[0116]

[Table 1]

[0117]

[Table 2]

Tables 1 and 2 show that the HLB of the present invention is 1 to
6 water-in-oil type emulsified cosmetic comprising a nonionic surfactant and a polymer having orientation at the oil-water interface (Example 1)
Nos. To 13) had excellent storage stability at each temperature, had a good feeling in use, and were excellent in refreshing feeling. On the other hand, when the above two components are not used together (Comparative Examples 1 to 5)
4) had a refreshing feeling, but was poor in stretchability and storage stability.

Example 14 (cream emulsified cosmetic)

[0120]

(Table 3) (Ingredients) (1) 10% dimethylpolysiloxane (KF-96L, 2cs, manufactured by Shin-Etsu Chemical Co., Ltd.) (2) 10% decamethylcyclopentasiloxane (3) Perfluoropolyether (FOMBLIN, manufactured by Asimont Inc.) HC-04) 5% (4) Squalane 5% (5) Lanolin 5% (6) Poly (N-propionylethyleneimine) -modified silicone (Synthesis Example 7) 1% (7) Dimethylpolysiloxane / methylpolyoxyethylene siloxane Copolymer (KF-6015, HLB4.5, manufactured by Shin-Etsu Chemical Co., Ltd.) 2% (8) Purified water balance (9) Ethanol 10% (10) 1,3-butylene glycol 5% (11) Sodium hyaluronate 0 .1%

The above components (1) to (7) are mixed. The mixture of (8) to (11) is added to this with stirring slowly over 30 minutes, and further stirred for 10 minutes with a homomixer to emulsify. This was defoamed and filled in a polyethylene container to prepare a creamy emulsified cosmetic.

Example 15 (creamy foundation)

[0123]

(Table 4) (Components) (1) Isoparaffin (C ₁₀ -C ₁₂ ) 15% (2) Octamethylcyclotetrasiloxane 8% (3) Dimethylpolysiloxane (KF-96A, 6cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 7 % (4) Cetanol 1% (5) Diisostearyl malate 6% (6) Aluminum stearate 1% (7) α-monoisostearyl glyceryl ether (HLB2.5) 1% (8) Dimethylsiloxane methylpoly Oxyethylene siloxane copolymer (Shin-Etsu Chemical Co., Ltd., KF-6015, HLB4.5) 1% (9) Poly (N-propionylethyleneimine) -modified silicone (Synthesis Example 8) 1% (10) Silicone-treated fine particle oxidation Titanium ^{* 1} (Taica) 5% (11) Siliconized spherical silica ^{* 1} 1% (12) Siliconized titanium oxide ^{* 1} 5% (13) Siliconized iron oxide (red, yellow, black) ^{* 1} 3% (14) Glycerin 3% (15) Ethanol 5% (16) Methyl paraoxybenzoate 0.1% (17) Purified water balance (* 1) 2% coated with methyl hydrogen polysiloxane

The components (1) to (9) are heated and mixed at 80 ° C. Separately, the components (10) to (13) are mixed with a Henschel mixer, and this is added to (1) to (9), which have been mixed in advance, and dispersed and mixed with a stirrer. The mixture of (14) to (16) heated to 40 ° C. is added to this with stirring slowly over 30 minutes, and further stirred for 10 minutes with a homomixer to emulsify. The emulsion was cooled to room temperature while slowly stirring, defoamed and filled into a bottle to prepare a creamy foundation.

Example 16 (Sunscreen emulsion)

[0126]

(Table 5) (Components) (1) Octamethylcyclotetrasiloxane 3% (2) Decamethylcyclopentasiloxane 10% (3) Dimethylpolysiloxane (KF-96L, 2cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 3% (4 ) Octyldodecyl myristate 8% (5) Stearic acid 0.5% (6) Octyl methoxycinnamate 2% (7) Poly (N-propionylethyleneimine) -modified silicone (Synthesis Example 8) 2% (8) Dimethylsiloxane・ Methyl polyoxyethylene siloxane copolymer (manufactured by Dow Corning Toray, SH3775C, HLB3.5) 2% (9) Silicon-treated fine titanium oxide ^{* 1} (manufactured by Teica) 3% (10) Silicon-treated fine zinc oxide ^{* 2} 5% (11) Nylon powder 2% (12) Ethanol 8% (13) Glycerin 4% (14) Mag sulfate Nesium 1% (15) Purified water balance (* 1) 2% coated with methyl hydrogen polysiloxane (* 2) 5% coated with methyl hydrogen polysiloxane

The components (1) to (11) are mixed by heating at 70 ° C. In addition, components (12) to (15) are added
The mixture that has been heated and mixed at 0 ° C. is added over 30 minutes while slowly stirring, and further stirred for 10 minutes with a homomixer to emulsify. The emulsion was cooled to room temperature with slow stirring, defoamed and filled into a bottle to prepare a sunscreen emulsion.

Example 17 (Liquid foundation)

[0129]

(Table 6) (Components) (1) Octamethylcyclotetrasiloxane 15% (2) Dimethylpolysiloxane (KF-96L, 2cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 8% (3) Octyl methoxycinnamate 2% (4) 12-hydroxystearic acid 1% (5) Octyldodecyl myristate 7% (6) Dimethylsiloxane / methylpolyoxyethylenesiloxane copolymer (manufactured by Dow Corning Toray, SH3775C, HLB3.5) 3% (7) Poly (N-propionylethyleneimine) modified silicone (Synthesis Example 9) 0.5% (8) Silicone-treated fine particle titanium oxide ^{* 1} (manufactured by Teica) 7% (9) Spherical silicone resin powder (manufactured by Toshiba Silicone Co., Tospearl 120) 2% (10) lecithin treated mica titanium ^* 3 1% (11) silicone-treated titanium oxide ^* 1 5% (12) silicone-treated iron oxide (red, yellow, 3% (13) Ethanol 13% (14) 1,3-butylene glycol 2% (15) Magnesium sulfate 1% (16) Purified water balance (* 1) 2% coated with methyl hydrogen polysiloxane ( * 3) 5% coated with soy lecithin

The components (1) to (7) are heated and mixed at 70 ° C. Separately, the components (8) to (12) are mixed with a Henschel mixer, and the components (1) to (7), which have been mixed in advance, are added and dispersed and mixed with a stirrer. The mixture of (13) to (16) heated to 40 ° C. is added to this with stirring slowly over 30 minutes, and further stirred for 10 minutes with a homomixer to emulsify. The emulsion was cooled to room temperature with slow stirring, defoamed and filled into a bottle to prepare a liquid foundation.

Example 18 (Hand cream)

[0132]

(Table 7) (Components) (1) Dimethylpolysiloxane (KF-96L, 1cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 10% (2) Decamethylcyclopentasiloxane 10% (3) Dimethylsiloxane / methylstearoxysiloxane Coated 3% (4) Solid paraffin 1% (5) Cetanol 1% (6) Lanolin 5% (7) Poly (N-propionylethyleneimine) -modified silicone (Synthesis Example 9) 2% (8) Glycerin monostearate ( HLB3.5) 2% (9) Ethanol 5% (10) Glycerin 5% (11) Sodium hyaluronate 0.1% (12) Purified water balance

The components (1) to (8) are heated and mixed at 70 ° C. The mixture of (9) to (12) is added to this with stirring slowly over 30 minutes, and further emulsified by stirring with a homomixer for 10 minutes. This was defoamed and filled in a polyethylene container to prepare a hand cream.

Example 19 (Emulsion cream)

[0135]

[Table 8] (Components) (1) Dimethylpolysiloxane (KF-96L, 2cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 10% (2) Decamethylcyclopentasiloxane 10% (3) Fluorine-containing silicone (Asahi Glass Co., Ltd. FSL-300) 5% (4) Squalane 5% (5) Lanolin 1% (6) Copolymer (Synthesis Example 10) 1.5% (7) Dimethylsiloxane / methylpolyoxyethylenesiloxane copolymer (Toray Co., Ltd.) Dow Corning SH3775C, HLB3.5) 2% (8) Purified water balance (9) Sodium hyaluronate 0.1% (10) Glycerin 5%

The components (1) to (7) are mixed. The mixture of (8) to (10) is added to this with stirring slowly over 30 minutes, and further stirred for 10 minutes with a homomixer to emulsify. This was defoamed and filled in a polyethylene container to prepare a cream emulsion cosmetic.

Example 20 (Cream emulsified cosmetic) A cream emulsified cosmetic was prepared in the same manner as in Example 19 except that the copolymer of component (6) used in Synthesis Example 11 was used.

Example 21 (Cream emulsified cosmetic) A cream emulsified cosmetic was prepared in the same manner as in Example 19 except that the copolymer of component (6) used in Synthesis Example 12 was used.

Example 22 (Cream emulsified cosmetic) A cream emulsified cosmetic was prepared in the same manner as in Example 19 except that the copolymer of component (6) used in Synthesis Example 14 was used.

Example 23 (Cream emulsified cosmetic) A cream emulsified cosmetic was prepared in the same manner as in Example 19, except that the copolymer of component (6) used in Synthesis Example 15 was used.

The skin cosmetics comprising the water-in-oil emulsion compositions of Examples 14 to 23 were excellent in storage stability, good in use feeling, good in refreshing feeling, and non-sticky.

Claims (21)

[Claims] 1. A water-in-oil containing the following components (A) and (B): (A) a nonionic surfactant having an HLB of 1 to 6 (B) a polymer compound having orientation at an oil-water interface -Type emulsion composition. 2. The component (B) causes intramolecular and intermolecular crosslinks due to bonds other than covalent bonds, and breaks or undergoes plastic deformation at an elongation of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%. The water-in-oil emulsion composition according to claim 1, which is a polymer compound that is a solid at ordinary temperature and normal pressure and has physical properties that do not occur. 3. The water-in-oil emulsion composition according to claim 1, wherein the polymer compound (B) contains a hydrophilic segment and is dissolved or dispersed in water or a lower alcohol. 4. The water-in-oil emulsion composition according to claim 1, wherein the polymer compound (B) is a copolymer containing a hydrophilic segment and an organopolysiloxane segment. 5. The polymer compound (B), wherein the hydrophilic segment of the polymer compound (B) has a terminal-blocked N-acylalkyleneimine, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, methacrylic acid, N,
N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternary dimethylaminoethyl methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride, half esters of maleic anhydride, crotonic acid, itaconic acid, acrylamide, Acrylic alcohols, hydroxyethyl methacrylate, diallyl dimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam, N-alkylenecarbobetaine, and residues derived from sugars 5. The water-in-oil emulsion composition according to claim 3, which is derived from one or more kinds. 6. The weight ratio of the hydrophilic segment of the polymer compound (B) to the segment of the organopolysiloxane is 1
The water-in-oil emulsion composition according to claim 4 or 5, wherein the polymer compound has a weight average molecular weight of 500 to 500,000. 7. A segment in which the hydrophilic segment of the polymer compound (B) is bonded to at least one terminal or side chain silicon atom of the organopolysiloxane segment via an alkylene group containing a hetero atom, The following general formula (1): (Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and n represents a number of 2 or 3). The water-in-oil emulsion composition according to any one of claims 1 to 6, which is (N-acylalkyleneimine). 8. A segment in which the hydrophilic segment of the polymer compound (B) is bonded to at least one silicon atom in the terminal or side chain of the organopolysiloxane segment via an alkylene group containing a hetero atom, The following general formula (2): (Wherein, R ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, and r represents a number of 1 to 5). Poly (N-
The water-in-oil emulsion composition according to any one of claims 1 to 6, which is propylene carbobetaine). 9. An alkylene group containing a hetero atom bonded to at least one silicon atom at the terminal or side chain of the organopolysiloxane segment is represented by the formula (3): 9. The water-in-oil emulsion composition according to claim 7, which is selected from the groups represented by the following formulae. 10. The polymer compound (B) is added to at least one terminal or side chain silicon atom of an organopolysiloxane segment by the following general formula (4): The water-in-oil emulsion composition according to any one of claims 1 to 4, wherein a group represented by the following formula (where m represents an integer of 1 to 8) is bonded. 11. The polymer compound (B) is represented by the general formula (4)
Is 10 to 90% of the total number of silicon atoms in the molecule, and has a weight average molecular weight of 1,000.
The water-in-oil emulsion composition according to claim 10, wherein the composition is from 0 to 500,000. 12. The high molecular compound (B) is a copolymer in which a sugar-derived residue is bonded to at least one terminal or side chain silicon atom of an organopolysiloxane segment. The water-in-oil emulsion composition according to any one of the above. 13. The water-in-oil emulsion composition according to claim 12, wherein the sugar-derived residue is a sugar lactone amide alkyl group. 14. The polymer compound (B) contains 40 to 97% by weight of a silicone chain and has a weight average molecular weight of 1,000 to 1,000.
The water-in-oil emulsion composition according to claim 12, which is 500,000. 15. The weight ratio of the organopolysiloxane segment of the polymer compound (B) to the poly (N-propylenecarbobetaine) segment is from 98/2 to 40/60.
Having a weight average molecular weight of 1,000 to 500,000.
The water-in-oil emulsion composition according to claim 14, which is: 16. Component (B) is a segment derived from the following segments (i), (ii) and (iii): (i) a radical polymerizable vinyl monomer 1 to 98% by weight (ii) a hydrophilic segment The water-in-oil type emulsion composition according to any one of claims 1 to 4, which is a copolymer comprising 1.5 to 60% by weight (iii) 0.1 to 90% by weight of an organopolysiloxane segment. 17. The segment (i) has the following general formula (5): [In the formula, X ¹ represents —OH, —NH ₂ , —OM (M represents a cation), —OR ³ , —NHR ^3, and —N (R ³ ) ₂ (where R ³ represents 1 to 8 carbon atoms) A linear or branched alkyl group, N, N-dimethylaminoethyl group, methyl quaternized N, N-dimethylaminoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group or 2-ethoxyethyl group And R ⁴ and R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a methoxyl group, an ethoxyl group,
Or a group selected from 2-hydroxyethyl, 2-methoxyethyl and ethoxyethyl groups]. 18. A segment (ii) having a terminal-blocked N-acylalkyleneimine, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate , Quaternary dimethylaminoethyl methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride, maleic anhydride half-esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyl Dimethylammonium chloride, vinylpyrrolidone,
17. It is derived from one or more selected from vinyl ethers, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam, N-alkylenecarbobetaine and residues derived from sugars. The water-in-oil emulsion composition according to the above. 19. The segment (iii) is represented by the following general formula (6): E (Y) _s Si (R ⁶ ) _3-t (Z) _t (6) wherein E is a segment (i) or ( ii) a vinyl group (which may have a substituent) which can be copolymerized with the monomer constituting the monomer or its macromonomer, Y represents a divalent linking group, R ⁶ represents a hydrogen atom, a lower alkyl group , An aryl group or an alkoxyl group, Z represents a monovalent siloxane polymer portion having an average molecular weight of 500 or more, and s represents 0 or 1.
And t represents an integer of 1 to 3]. The water-in-oil emulsion composition according to claim 16, wherein 20. An organopoly represented by the general formula (6)
The siloxane is represented by the following general formulas (7) to (12);(Wherein t has the same meaning as described above;⁷Is a hydrogen atom or
Represents an alkyl group; ⁸Is a hydrogen atom or carboxyl
A group represented by R⁹Represents a hydrogen atom, a methyl group or a carboxy group.
A tyl group;^TenRepresents an alkyl group, an alkoxyl group,
Shows a rukylamino group, aryl group or hydroxyl group
And x represents a number of 2 to 6, and y represents a number of 5 to 700.
And u represents 0 or 1).
Silicone containing with a weight average molecular weight of 00000
17. The water-in-oil according to claim 16, comprising a macromer.
-Type emulsion composition. 21. A skin cosmetic comprising the water-in-oil emulsion composition according to any one of claims 1 to 20.