JPH05178734A - Solid-like water-in-oil type emulsified cosmetic - Google Patents

Abstract

PURPOSE:To provide the subject hard gel-like to solid-like cosmetic highly reduced in the difficult spreadability, tackiness, oiliness, etc., by emulsifying and dispersing an oily gel composition, a silicone gel composition and a specific fatty acid ester in water. CONSTITUTION:The objective solid-like water-in-oil type emulsified cosmetic contains an oily gel composition comprising an oiling agent (e.g. petrolatum, squalene) and an oily gelling agent (e.g. aluminum stearate), a silicone gel composition (e.g. a product produced by kneading and swelling a partially crosslinked organopolysiloxane polymer and a low viscous silicone oil) and/or a pasty silicone composition, a polyoxyethylene sorbite fatty acid ester of a nonionic surfactant and water. The cosmetic is a new and unique one exhibiting a hard gel-like to solid-like state, and simultaneously solves problems such as difficult spreadability, tackiness and oiliness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid water-in-oil type emulsified cosmetic composition, and more specifically to the weight of spreadability, stickiness,
The present invention relates to a hard gel-solid water-in-oil emulsion cosmetic having improved oiliness and the like.

[0002]

2. Description of the Related Art Generally, an emulsifying base has a soft paste form (so-called cream form) regardless of its emulsifying type (oil-in-water type, water-in-oil type or complex type). It is uniform and lacks novelty and uniqueness.

It is known that the water-in-oil type cream is superior to the oil-in-water type cream in the skin protecting effect, softening effect, moisturizing effect and the like which the base has.

However, the water-in-oil type cream, on the other hand, has drawbacks such as heavy spread, stickiness, and oiliness, but is not generally favored, and development of a product to correct these drawbacks. Was desired.

[0005]

Means for Solving the Problems As a result of intensive studies in view of such circumstances, the present inventor has found that an oil-based gel composition, a silicone gel composition, a specific fatty acid ester and water are emulsified and dispersed to give a hard gel-like composition. The inventors have found that a water-in-oil type emulsified cosmetic in which the weight, stickiness, oiliness and the like of solid-type spread are remarkably reduced can be obtained, and the present invention has been completed.

That is, the present invention provides the following components (a)-
(D) (a) Oily gel composition comprising oil agent and oil gelling agent (b) Silicone gel composition and / or pasty silicone composition (c) Polyoxyethylene sorbit fatty acid ester (d) Solid containing water A water-in-oil type emulsified cosmetic composition is provided.

The oil solution of the component (a) used in the present invention is
It is not particularly limited as long as it is usually used for cosmetics,
Mineral oil, vegetable oil, animal oil, higher fatty acid, higher fatty acid ester, higher alcohol and the like are used. Specifically, mineral oils such as liquid paraffin, petrolatum, solid paraffin wax, ceresin wax, and microcrystalline wax; squalane, lanolin, castor oil, hydrogenated castor oil,
Animal and vegetable oils such as olive oil, jojoba oil, macadamian nut oil, mink oil, turtle oil, almond oil, safflower oil, avocado oil, carnauba wax, candelilla wax, beeswax, mokuro, geiro; polyethylene wax, ethylene propylene copolymer Higher fatty acids such as oleic acid, stearic acid, lauric acid, myristic acid; isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, cetyl 2-ethylhexanoate, triglyceride 2-ethylhexanoate, trioctanoic acid Higher fatty acid esters such as glyceryl, diglyceryl isostearate, propylene glycol dicaprate, pentaerythritol rosinate and dipentaerythritol fatty acid ester; oleyl alcohol , Cetyl alcohol, stearyl alcohol, higher alcohols, and the like, such as lauryl alcohol, These one or two or more kinds are used in combination.

Examples of the oil gelling agent of component (a) include metal soaps such as aluminum stearate and magnesium stearate, polysaccharide fatty acid esters such as sucrose palmitate, starch palmitate, and bacmond oustearate. Examples thereof include organically modified clay minerals such as dioctadecyldimethylammonium salt-modified montmorillonite and dihexadecyldimethylammonium salt-modified montmorillonite.

The blending ratio of the oil gelling agent in the oily gel composition (a) is not particularly limited, but may be 8 to 30% by weight (hereinafter,%).
Is shown) is preferable. The blending ratio of the oily gel composition (a) to the cosmetic of the present invention is preferably 30 to 70%. Three
If it is less than 0%, it will be difficult to maintain a hard gel-solid form, and if it exceeds 70%, it will be too hard, and it will be difficult to remove it.

Examples of the silicone gel composition as the component (b) include those obtained by kneading a partially crosslinked organopolysiloxane polymer and a low-viscosity silicone oil and swelling them.

In the present invention, the partially crosslinked organopolysiloxane polymer used as the component (b) includes, for example, benzene which is insoluble in benzene and has a weight equal to or more than its own weight, which is obtained by crosslinking organopolysiloxane. An organopolysiloxane polymer partially having the obtained three-dimensional crosslinked structure can be mentioned.

The polymer has R ₂ SiO units and R SiO _1.5 units, and may contain R ₃ SiO _0.5 units and / or SiO ₂ units. This product is insoluble in benzene, but in order to have a structure having a three-dimensional crosslinked structure capable of containing benzene of its own weight or more, RSiO _1.5 unit and / or S
It is necessary that the ratio of the iO ₂ unit to the R ₂ SiO unit and / or the R ₃ SiO _0.5 unit is in an appropriate range. If the RSiO _1.5 units and / or SiO ₂ units are too small, the organopolysiloxane polymer does not have a sufficient three-dimensional crosslinked structure and is soluble in benzene, and even if it has an apparent crosslinked structure, it cannot be used. Also, R ₂ SiO units and / or R ₃ SiO
_If RSiO _1.5 units and / or SiO ₂ units are too much compared to _0.5 units, the organopolysiloxane polymer has a strong cross-linked structure and is insoluble in benzene, but contains less than its own weight of benzene. When it is mixed with a low-viscosity silicone oil, the organopolysiloxane polymer does not swell sufficiently, the silicone oil is separated and discharged, and stable maintenance cannot be performed, so that it cannot be used. Therefore, in order to obtain a soft and stable silicone gel composition, although it is affected by the molecular weight of the polymer,
Generally (R ₂ SiO units and / or R ₃ SiO _0.5 units): (R
SiO _1.5 unit and / or SiO ₂ unit) is 1: 1 to 30: 1
It is preferable to use one that is within the range. In each of the above structural units, R is, for example, a hydrogen atom; an alkyl group such as a methyl group, an ethyl group or a propyl group; an aryl group such as a phenyl group or a tolyl group; an aliphatic unsaturated group such as a vinyl group; and the like. , Or different types.

Such an organopolysiloxane polymer which is insoluble in benzene but has a three-dimensional crosslinked structure capable of containing benzene of its own weight or more can be synthesized, for example, by the following various methods. i) A dehydrogenation reaction and a condensation reaction are carried out by adding a catalytic amount of an alcoholic aqueous solution of an alkali metal hydroxide to an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to one silicon atom in one molecule and heating it. How to do. ii) a catalytic amount of an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to one silicon atom in one molecule and an organopolysiloxane having at least two hydroxyl groups bonded to at least two silicon atoms in one molecule. The method of carrying out the dehydrogenative condensation reaction by heating in the presence of an alkali metal hydroxide, a platinum compound or the like. iii) A method in which an organopolysiloxane having a hydroxyl group bonded to at least two silicon atoms in one molecule is heated in the presence of a catalytic amount of an alkali metal hydroxide, an organic tin compound or the like to carry out a dehydration condensation reaction. iv) A catalytic amount of an alkali polyorganosiloxane having a hydroxyl group bonded to at least two silicon atoms in one molecule and an organopolysiloxane having an alkoxyl group bonded to at least two silicon atoms in one molecule. A method of carrying out dealcoholization reaction by heating in the presence of a metal hydroxide, an organometallic tin compound or the like. By any of these methods, an organopolysiloxane polymer that is insoluble in benzene but has a three-dimensional crosslinked structure that can contain benzene of its own weight or more can be easily obtained.

Other examples of the partially crosslinked organopolysiloxane polymer other than those mentioned above include organopolysiloxane polymers which are insoluble in silicone oil but swell sufficiently, and (a) organohydrogenpolysiloxane and ( (B) A polymer obtained by addition-polymerizing an organopolysiloxane containing an aliphatic unsaturated group, which partially has a three-dimensional crosslinked structure. Used here (a)
The molecular structures of the organopolysiloxanes of (b) and (b) may be linear, branched, or cyclic, but in order to control the synthetic reaction of the target organopolysiloxane polymer, Is more preferable. Here, the hydrogen atom bonded to the silicon atom in the organohydrogenpolysiloxane of (a) which is a reactive group and the aliphatic unsaturated group in the organopolysiloxane containing an aliphatic unsaturated group of (b) are 1 molecule each. The presence of at least two of them is essential for forming a three-dimensional crosslinked structure in a part of the organopolysiloxane polymer obtained by polymerizing the both. The position of each of these reactive groups in the molecule is generally inside the molecular chain, but may be at the end of the molecular chain. The content of each of these reactive groups in the organopolysiloxane is 1 if the molecular structure is linear or branched in order to obtain a soft and stable silicone gel composition. ~ 20 mol%, and in the case of cyclic ones 1 to 50
It is preferably mol%. If the content exceeds the above range, it becomes a hard polymer and it becomes difficult for the low-viscosity silicone oil described later to be included in the three-dimensional crosslinked structure, resulting in separation and discharge, which makes it impossible to stably maintain. On the contrary, if the content is less than the above range, the structural viscosity of the silicone gel composition tends to be poor.

The organohydrogenpolysiloxane of (a) includes HSiO _1.5 units, RSiO _1.5 units, RHSiO units and R ₂ S.
It is composed of iO units, R ₂ HSiO _0.5 units, R ₃ SiO _0.5 units, and the like. Here, R is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an aryl group such as a phenyl group or a tolyl group, a cyclohexyl group, or one of hydrogen atoms bonded to carbon atoms of these groups. Illustrative are unsubstituted or substituted monovalent hydrocarbon groups excluding aliphatic unsaturated groups such as vinyl groups, which are selected from groups in which all or a part of them are substituted with halogen atoms, cyano groups and the like. Representative examples of such _{things, (CH 3) 3 SiO -} , - [(CH 3) 2 Si
O] _p −, − [CH ₃ HSiO] _q −, −Si (CH ₃ ) ₃ (where p = 10
.About.500, q = 2 to 50), and a preferred material is methylhydrogenpolysiloxane.

Examples of the aliphatic unsaturated group of the aliphatic unsaturated group-containing organopolysiloxane (b) include a vinyl group and an aryl group, and a vinyl group is common, and an organovinylpolysiloxane. As (CH ₂ = C
H) SiO _1.5 unit, RSiO _1.5 unit, R (CH = CH ₂ ) SiO unit, R ₂ SiO
Examples thereof include units, R ₂ (CH = CH ₂ ) SiO _0.5 units, R ₃ SiO _0.5 units, and the like. Here, R has the same meaning as in the case (a). A typical example of this is (C
_{H 2 = CH) (CH 3} ) 2 SiO -, - [(CH 3) 2 SiO] r - and -Si (CH _{3) 2}
Unit of (CH = CH ₂ ) (however, r = 10-100), or
_{(CH 3) 3 SiO -,} - [(CH 3) 2 SiO] m -, - [(CH = CH 2) CH 3 SiO] n
- and -Si (CH _{3) 3} (where, m = 10~500, n = 2~
Methyl vinyl polysiloxanes comprising units 50) are mentioned, which may be a mixture and are suitable materials.

The addition reaction between the organohydrogenpolysiloxane of (a) and the organopolysiloxane containing an aliphatic unsaturated group of (ii) may be carried out by a conventionally known general method. For example, appropriate organohydrogenpolysiloxane and organovinylpolysiloxane are blended in such a manner that the molar ratio of the hydrogen group bonded to the silicon atom which is each reactive group and the vinyl group is in the range of 1/3 to 3/1. After that, an addition polymerization catalyst such as platinum or palladium is added, and the mixture is heated and stirred to easily obtain the desired organopolysiloxane polymer insoluble in silicone oil. In particular, as the addition polymerization catalyst, Japanese Patent Publication Sho 3
It is preferable to use chloroplatinic acid described in JP-A-3-9969.

The low-viscosity silicone oil used as the component (b) is not particularly limited, but any one having a viscosity of about 50 cs or less can be preferably used. This is because as the viscosity becomes higher, a large amount of it is used, and as a result, it becomes oily to the touch, which is not preferable in terms of usability. And as the low-viscosity silicone oil, a chain-like dimethylpolysiloxane, methylphenylpolysiloxane, cyclic octamethylcyclotetrasiloxane having a low degree of polymerization,
Examples thereof include decamethylcyclopentasiloxane, and one or more of these can be appropriately selected and used as necessary.

Examples of the pasty silicone composition as the component (b) include the following silicone polymers in which the low viscosity silicone oil is encapsulated.

In the present invention, the pasty silicone composition used as the component (b) is a novel one, and has the general formula (1) R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} (1 ) (Wherein R ¹ is the same or different and is an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group or a halogenated hydrocarbon group, and R ² is a general formula C _n H _2n O (C ₂ H
₄ O) _d (C ₃ H ₆ O) _e R ³ [wherein R ³ is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms or-(CO) -R ⁵ (R
⁵ is a group represented by a saturated aliphatic hydrocarbon group having 1 to ⁵ carbon atoms, d is an integer of 2 to 200, e is an integer of 0 to 200, d
+ E is an integer of 3 to 200, n is 2 to 6], a is 1.0 ≦ a ≦ 2.5, b is 0.001 ≦ b ≦ 1.0, and c is 0. 001 ≦ c ≦ 1.
0} and / or the general formula (2) R ¹ _f H _g SiO _{(4-fg) / 2} (2) (where R ¹ is the same as above, and f is 1.0 ≦ f ≦ 3.0,
g is 0.001 ≦ g ≦ 1.5) and an organohydrogenpolysiloxane represented by the general formula (A) C _m H _2m-1 O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _i C _m H _2m-1 (A) (wherein h is an integer of 2 to 200, i is an integer of 0 to 200, h + i is an integer of 3 to 200, m is 2 to 6) and / Or the general formula (B) R ¹ _j R ⁴ _k SiO _{(4-jk) / 2} (B) (wherein R ¹ is the same as above, R ⁴ is a terminal 2-10 carbon atom having an aliphatic unsaturated group). 1 is a monovalent hydrocarbon group, j is 1.
0 ≦ j ≦ 3.0, k is 0.001 ≦ k ≦ 1.5) in combination with the organopolysiloxane, the component represented by the general formula (1) and / or the general formula (A) is added. A total amount of 100 parts by weight of the composition as an essential component is added to 25
100 parts by weight of a silicone polymer obtained by addition polymerization in the presence or absence of 3 to 200 parts by weight of a low viscosity silicone oil and / or polyhydric alcohol having a viscosity of 100 cs or less at 5 ° C. and a low viscosity silicone oil 5 to 1,00
This refers to a product obtained by kneading 0 part by weight under shearing force.

The silicone polymer constituting the pasty silicone composition of the component (b) of the present invention is a silicone oil in which the organohydrogenpolysiloxane and the compound containing an aliphatic unsaturated group have a viscosity at 25 ° C. of 100 cs or less, and And / or the addition polymerization is carried out in the presence or absence of a polyhydric alcohol, but it is essential that either the organohydrogenpolysiloxane or the compound containing an aliphatic unsaturated group contains a polyoxyalkylene group. It is a requirement.

Therefore, as an example of the combination of the organohydrogenpolysiloxane and the compound containing an aliphatic unsaturated group, one is represented by the general formula (1) R ¹ _a R ² _b H _c SiO ₍ containing a polyoxyalkylene group). _{4-abc) / 2} (1) an organohydrogenpolysiloxane represented by
R ¹ is bonded to an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an aryl group such as a phenyl group or a tolyl group, an aralkyl group such as a benzyl group or a phenethyl group, or a carbon atom of these groups. Chloromethyl group in which some or all of the hydrogen atoms present are replaced with halogen atoms,
The same or different C1-C18 unsubstituted or substituted alkyl group, aryl group, aralkyl group or halogenated hydrocarbon group selected from trifluoropropyl group and the like, R ² is a general formula (3) C _n H _2n O (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e -R ³ (3), wherein R ³ is a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group and other saturated aliphatic hydrocarbon groups having 1 to 10 carbon atoms, or a group represented by the formula-(CO) -R ⁵ , wherein R ⁵ is saturated aliphatic hydrocarbon having 1 to ⁵ carbon atoms Group, and d is 2 to 20
An integer of 0, an integer of 0 to 200, and an integer of d + e of 3 to 200
Is a polyoxyalkylene group in which n is 2 to 6.

Regarding a of the a, b and c values, 1.
When it is less than 0, the obtained polymer does not swell sufficiently in silicone oil, and when it is more than 2.5, the polymer obtained is kneaded with silicone oil under shearing force to give a paste-like composition with water content. It is necessary to set 1.0 ≦ a ≦ 2.5, preferably 1.0 to 2.0 because b cannot be sufficiently dispersed, and when b is less than 0.001, the obtained polymer is silicone. The paste composition obtained by kneading with oil under shearing force is not sufficiently dispersed in water, and if it is more than 1.0, the swelling property of the obtained polymer into silicone oil becomes insufficient, so 0.001 ≦ b ≦ 1.0, preferably 0.005 to 1.0, and c is 0.0
If it is less than 01, it will be difficult to form a three-dimensional structure in the polymer obtained by addition polymerization, and the viscosity of the silicone oil will be poor. If it is more than 1.0, the cross-linking density of the three-dimensional structure formed by addition polymerization will be poor. Is too high to hold silicone oil stably, so 0.00
1 ≦ c ≦ 1.0, preferably 0.005 to 1.0.

Therefore, the combination with the organohydrogenpolysiloxane represented by the general formula (1) is represented by the general formula (B) R ¹ _j R ⁴ _k SiO _{(4-jk) / 2} (B). R ¹ is the same as above, R ⁴ is a vinyl group at the terminal,
If the monovalent hydrocarbon group having 2 to 10 carbon atoms and having an aliphatic unsaturated group such as an allyl group, j is less than 1.0, the crosslinking density of the three-dimensional structure formed by addition polymerization becomes too high. Therefore, a polymer that stably holds silicone oil cannot be obtained, and if it exceeds 3.0, the formation of a three-dimensional structure in the polymer obtained by addition polymerization becomes insufficient and the viscosity increase of silicone oil is poor. Therefore, 1.0 ≦ d ≦
It is 3.0, preferably 1.0 to 2.5, and when k is less than 0.001, it becomes difficult to form a three-dimensional structure in the target polymer, and the viscosity increase of silicone oil If it is less than 1.5, the cross-linking density of the three-dimensional structure formed by addition polymerization becomes too high, and a polymer capable of stably holding silicone oil cannot be obtained. 001 ≦ k ≦ 1.
The organohydrogenpolysiloxane having an aliphatic unsaturated group of 5, preferably 0.005 to 1.0 is used. The organohydrogenpolysiloxane represented by the general formula (1) and the general formula (B) are used. The mixture with the organopolysiloxane represented by the following is abbreviated as mixture-I hereinafter.

It is also possible to use a combination of the organohydrogenpolysiloxane represented by the general formula (1) and the polyoxyalkylene represented by the general formula (A).

Another combination of the organohydrogenpolysiloxane and the compound containing an aliphatic unsaturated group is represented by the general formula (2) R ¹ _f H _g SiO _{(4-fg) / 2} (2). When R ¹ is the same as above and f is less than 1.0, the swelling property of the obtained polymer in silicone oil cannot be sufficiently obtained, and when it is more than 3.0, in the polymer obtained by addition polymerization, Since it becomes difficult to form a three-dimensional structure in the above, and the viscosity increase of the silicone oil becomes poor, 1.0 ≦ f ≦ 3.
0, preferably 1.0 to 2.5, and g is 0.001
If it is less than 3, it will be difficult to form a three-dimensional structure in the polymer obtained by addition polymerization, and the viscosity increase of the silicone oil will be poor. Since the cross-linking density becomes too high and the resulting polymer does not retain silicone oil stably, 0.001 ≦ g ≦ 1.5, preferably 0.005
An organohydrogenpolysiloxane of 1.0 and a compound represented by the general formula (A) C _m H _2m-1 (C ₂ H ₄ O) _h (C ₃ H ₆ O) _i C _m H _2m-1 (A) , H is 2 to 200, preferably 5 to 100, i
Is 0 to 200, preferably 0 to 100, and in order to sufficiently disperse water in the obtained polymer, it is desirable that h / i ≧ 1, and m is 2 to 6, preferably 3 to 6. A mixture with a certain polyoxyalkylene (hereinafter abbreviated as mixture-II) is exemplified.

In the present invention, the viscosity at 25 ° C. used in the addition polymerization of the mixture -I or -II is 10
Low viscosity silicone oils of 0 cs or less include linear or branched methyl polysiloxane, methylphenyl polysiloxane, ethyl polysiloxane, ethyl methyl polysiloxane, ethyl phenyl polysiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopenta. Cyclic dimethylpolysiloxanes such as siloxane are listed, but these have a viscosity of 100cs at 25 ℃.
The viscosity is not particularly limited as long as it is as follows, and it is preferable that the viscosity is 50 cs or less, but these may be used alone or as a mixture of two or more kinds.

Examples of the polyhydric alcohol include ethylene glycol, 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin and diglycerin. These may be used alone or in combination of two or more. You may use together.

The amount of the low-viscosity silicone oil and / or polyhydric alcohol is preferably 3 to 200 parts by weight with respect to 100 parts by weight of the above-mentioned mixture -I or -II. When addition polymerization is carried out in the presence of a low-viscosity silicone oil and / or a polyhydric alcohol, a polymer containing these is obtained, which is higher than that obtained by addition polymerization in the absence thereof. It exhibits swelling properties and exhibits excellent thickening properties.

The addition polymerization of this mixture -I or -II is carried out in the presence of a known platinum compound catalyst or rhodium compound catalyst such as chloroplatinic acid, alcohol-modified chloroplatinic acid or chloroplatinic acid-vinylsiloxane complex. The reaction may be carried out at room temperature or under heating at 50 to 150 ° C.

In this case, if necessary, an organic solvent may be used, and examples thereof include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as benzene, toluene and xylene, and n. -Aliphatic or alicyclic hydrocarbons such as pentane, n-hexane, cyclohexane, dichloromethane, chloroform,
Carbon tetrachloride, trichloroethane, trichloroethylene,
Illustrative are halogenated hydrocarbons such as fluorochlorinated hydrocarbons.

The ratio of the partially crosslinked organopolysiloxane in the above silicone gel composition and the ratio of the silicone polymer in the above pasty silicone composition are both 1.
It is 0 to 30%.

The silicone gel composition and / or the pasty silicone composition (b) thus obtained is preferably blended in the cosmetic composition of the present invention in an amount of 10 to 40%, preferably 15 to 40%.
35% is more preferable. If it is less than 10%, the effect of improving the feeling of use is not observed, and if it exceeds 40%, it becomes difficult to maintain a hard gel-solid form.

The component (c), polyoxyethylene sorbite fatty acid ester, is a colorless to pale yellow, liquid to pasty nonionic surfactant, and commercially available products are Nikkor GO-4, GO-430 and GO-440. , GO-46
0, GL-1, GS-460 (all manufactured by Nippon Surfactant Industry) and the like. The HLB of the polyoxyethylene sorbite fatty acid ester (c) is preferably 4 or more, more preferably 10-16. When two or more compounds (c) are used in combination, the combined HLB may be in the above range.

The amount of the polyoxyethylene sorbitol fatty acid ester (c) to be incorporated in the cosmetic of the present invention is preferably 0.5 to 5%. If it is less than 0.5%, the effect of the present invention cannot be obtained.
Further, even if the content exceeds 5%, the effect is not improved and the usability may be deteriorated.

The content of the component (d) in the cosmetic of the present invention is preferably 5 to 35%. If it is less than 5%, the usability is not improved, and if it exceeds 35%, the stability over time deteriorates. An aqueous component usually used in cosmetics can be appropriately added to the component (d).

The solid water-in-oil type emulsified cosmetic composition of the present invention comprises polyoxyethylene sorbit in a mixed oil comprising the oily gel composition (a) and the silicone gel composition or the pasty silicone composition (b). It can be produced by emulsifying and dispersing water (d) using the fatty acid ester (c) and cooling and solidifying.

The solid water-in-oil type emulsion cosmetic of the present invention comprises:
In addition to the above components (a) to (d), a moisturizing agent, a preservative, an antioxidant, an ultraviolet absorber, an emollient, a beauty ingredient, a fragrance, a water-soluble polymer, in addition to the components (a) to (d).
Ingredients usually used in cosmetics such as a quality-retaining pigment, a coloring pigment, a bright pigment, an organic powder, a hydrophobized pigment, and a tar dye can be blended.

[0039]

The solid water-in-oil type emulsion cosmetic of the present invention comprises:
It is a novel and unique one that exhibits a hard gel to solid form, and it solves all the problems that conventional water-in-oil type creams have such as spread weight, stickiness, and oiliness. ..

[0040]

EXAMPLES The present invention will be described below in greater detail by giving Examples, but the present invention is not limited thereto.

Reference Example 1 Synthesis of partially crosslinked organopolysiloxane polymer: trimethylsilyl end-capped dimethylmethylhydrogenpolysiloxane [molecular weight 2300, CH ₃ HSiO vs. (CH ₃ ) ₂ SiO =
1 to 4 (molar ratio)], 1% potassium hydroxide solution (ethanol to water = 2 to 1) was added in an appropriate amount, heated and refluxed to carry out a polymerization reaction to obtain a reaction product. Next, this reaction product is washed with water to remove the alkaline agent, and then naturally dried.
An organopolysiloxane polymer which can contain 0% was obtained.

Reference Example 2 Synthesis of partially crosslinked organopolysiloxane polymer: trimethylsilyl end-blocked dimethylmethylhydrogenpolysiloxane (average molecular weight 2340, Si-H 4.5 mol%) was added to a planetary mixer having an internal volume of about 5 l. 1790
g, and dimethylvinylsilyl end-capped dimethylpolysiloxane (average molecular weight 930, vinyl group 7.7 mol%)
710 g was added and mixed with stirring. 0.5 g of a 2% isopropanol solution of chloroplatinic acid was added to the mixed solution, the temperature was raised to 70 to 80 ° C., and stirring was continued for 2 hours. Thereafter, the pressure inside the system was reduced to 5 to 10 mmHg, and stripping was continued for 30 minutes to obtain a solid organopolysiloxane polymer having colorless flexibility.

Reference Example 3 Synthesis of Partially Crosslinked Organopolysiloxane Polymer: Trimethylsilyl end-blocked dimethylmethylhydrogenpolysiloxane (average molecular weight 2340, Si-H 4.5 mol%) was added to a planetary mixer having an internal volume of about 5 l. 1790
g, and 4240 g of dimethylvinylsilyl end-blocked dimethylmethylphenylpolysiloxane (average molecular weight 5560, vinyl group 1.5 mol%) were added and mixed with stirring.
0.5 g of a 2% isopropanol solution of chloroplatinic acid was added to the mixed solution, the temperature was raised to 70 to 80 ° C., and stirring was continued for 2 hours. Thereafter, the pressure inside the system was reduced to 5 to 10 mmHg, and stripping was continued for 30 minutes to obtain a solid organopolysiloxane polymer having colorless flexibility.

Reference Example 4 (1) Average composition formula (4) in the reactor

[0045]

[Chemical 1]

68 g of an organohydrogenpolysiloxane represented by: 100 g of ethanol, the average composition formula is C
H ₂ = CHCH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ 32 g of polyoxyalkylene and 3% by weight of chloroplatinic acid in ethanol solution.
After charging 3 g, stirring the mixture for 2 hours while maintaining the internal temperature at 70 to 80 ° C., and removing the solvent under reduced pressure, the average composition formula (5) was obtained.

[0047]

[Chemical 2]

An organohydrogenpolysiloxane represented by the following formula was obtained. (2) In the reactor, 100 g of the organohydrogenpolysiloxane obtained in (1) above, 100 g of ethanol and the average composition formula (6).

[0049]

[Chemical 3]

28.9 g of dimethylvinylsilyl end-capped dimethylpolysiloxane represented by and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged, and the internal temperature was 70 to
After maintaining at 80 ° C. and stirring for 2 hours, the solvent was removed under reduced pressure to obtain an elastic polymer.

After 20 parts by weight of this polymer and 80 parts by weight of dimethylpolysiloxane (viscosity 6 cS) were dispersed and mixed,
A three-roll mill was sufficiently kneaded under shearing force to prepare a silicone composition. The composition had a smooth feel and was a uniform pasty composition with a viscosity of 32,000 cP.

Reference Example 5 In the reactor, the average composition formula (7)

[0053]

[Chemical 4]

Organohydrogenpolysiloxane 100 g, ethanol 62 g, average composition formula
CH ₂ = CHCH ₂ O- (C ₂ H ₄ O) ₁₀ -CH ₂ CH = CH ₂ 23.6 g of polyoxyalkylene represented by (8) and 3% by weight of chloroplatinic acid
0.3g of ethanol solution was charged and the internal temperature was 70-80
After maintaining the temperature at 0 ° C. and stirring for 2 hours, the solvent was removed under reduced pressure to obtain a granular polymer.

33 parts by weight of the obtained polymer and 67 parts by weight of dimethylpolysiloxane (viscosity 6 cS) were dispersed and mixed, and then sufficiently kneaded under a shearing force by a three-roll mill and swollen to prepare a silicone composition. did. The composition had a smooth feel and was a uniform pasty composition with a viscosity of 24,800 cP.

Reference Example 6 The average compositional formula (4) obtained in (1) of Reference Example 1 was placed in a reactor.
Organohydrogenpolysiloxane 10 represented by
0 g, 75 g of ethanol, 49.4 g of the polyoxyalkylene represented by the average composition formula (8) used in Reference Example 2 and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged, and the internal temperature was adjusted to 70 to 80 ° C. After maintaining and stirring for 2 hours,
The solvent was removed under reduced pressure to obtain a granular polymer.

After 33 parts by weight of this polymer and 67 parts by weight of dimethylpolysiloxane (viscosity 6 cS) were dispersed and mixed,
The mixture was sufficiently kneaded by a three-roll mill under shearing force and swollen to prepare a silicone composition. The composition had a smooth feel and was in the form of a uniform paste with a viscosity of 10,600 cP.

Reference Example 7 In the reactor, the average composition formula (9)

[0059]

[Chemical 5]

100 g of the organohydrogenpolysiloxane represented by the formula, 57 g of ethanol, 13.5 g of the polyoxyalkylene represented by the average composition formula (8) used in Reference Example 2 and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid. Was charged, the internal temperature was maintained at 70 to 80 ° C., and the mixture was stirred for 2 hours, then, the solvent was removed under reduced pressure to obtain a granular polymer.

20 parts by weight of this polymer and 80 parts by weight of dimethylpolysiloxane (viscosity 6 cS) were dispersed and mixed, then sufficiently kneaded under a shearing force by a three-roll mill and swollen to prepare a silicone composition. The composition had a smooth feel and was in the form of a uniform paste with a viscosity of 22,800 cP.

Reference Example 8 In the reactor, 100 g of the organohydrogenpolysiloxane of the average composition formula (7) used in Reference Example 2, 103 g of ethanol, and the poly of the average composition formula (8) used in Reference Example 2 were used. 23.6 g of oxyalkylene, dimethylpolysiloxane 82.4 having a viscosity at 25 ° C. of 6 cS
g and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged, the internal temperature was maintained at 70 to 80 ° C., and the mixture was stirred for 2 hours, and then the solvent was removed under reduced pressure to obtain a silicone polymer. ..

Next, 100 parts by weight of this silicone polymer was dispersed and mixed with 100 parts by weight of dimethylpolysiloxane having a viscosity of 6 cS at 25 ° C., and then sufficiently kneaded and swelled by a three-roll mill under a shearing force to give a silicone composition. I made things. This was a homogeneous paste-like composition with a smooth feel and a viscosity of 82,800 cP.

Reference Example 9 Organohydrogenpolysiloxane 100 represented by the average composition formula (9) used in Reference Example 4 was placed in a reactor.
g, ethanol 95 g, polyoxyalkylene 13.5 g of the average compositional formula (8) used in Reference Example 2, and dimethylpolysiloxane 75.7 having a viscosity at 25 ° C. of 5 cS.
g and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged and treated in the same manner as in Reference Example 5 to prepare a polymer.

Next, 100 parts by weight of this polymer and 200 parts by weight of octamethylcyclotetrasiloxane were dispersed and mixed, and then sufficiently kneaded under a shearing force by a three-roll mill to prepare a swollen silicone composition. This was a uniform paste-like composition having a smooth feel and a viscosity of 44,000 cP.

Reference Example 10 Average composition formula (10)

[0067]

[Chemical 6]

Organohydrogenpolysiloxane 100 g, ethanol 74 g, average composition formula:
CH ₂ ═CHCH ₂ O (C ₂ H ₄ O) ₃₀ CH ₂ CH═CH ₂ 18.5 g of polyoxyalkylene represented by (11), 29.6 g of dimethylpolysiloxane having a viscosity of 6 cS at 25 ° C. and platinum chloride 0.3 g of an ethanol solution containing 3% by weight of acid was charged and treated in the same manner as in Reference Example 5 to prepare a polymer.

Then, 100 parts by weight of this polymer and 200 parts by weight of phenyltris (trimethylsiloxy) silane were dispersed and mixed, and then sufficiently kneaded under a shearing force by a three-roll mill to make a swollen silicone composition. .. This was a uniform paste-like composition having a smooth feel and a viscosity of 25,500 cP.

Reference Example 11 The average compositional formula (5) obtained in (1) of Reference Example 1 was placed in a reactor.
Organohydrogenpolysiloxane 10 represented by
0 g, ethanol 72 g, average composition formula (12)

[0071]

[Chemical 7]

28.9 g, 25 of dimethylpolysiloxane end-capped with a dimethylvinylsilyl group represented by
A polymer was prepared by charging 14.3 g of dimethylpolysiloxane having a viscosity of 30 cS at 0 ° C. and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid and treating in the same manner as in Reference Example 5.

Then, 22.2 parts by weight of this polymer and 25 ° C.
Dimethylpolysiloxane 7 having a viscosity of 6 cS at
7.8 parts by weight were dispersed and mixed, and then sufficiently kneaded with a three-roll mill under shearing force to prepare a silicone composition.
This product has a smooth feel and a viscosity of 48,000 cP
Was a uniform paste composition.

Reference Example 12 100 g of the organohydrogenpolysiloxane of the average composition formula (7) used in Reference Example 2, 103 g of ethanol, and the polyoxyalkylene of the average composition formula (8) used in Reference Example 2 were placed in a reactor. 23.6 g, 1,3-butylene glycol 82.4 g, and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged, the mixture was stirred for 2 hours while maintaining the internal temperature at 70 to 80 ° C, and then the solvent was added under reduced pressure. Was removed,
A silicone polymer was obtained.

Next, 100 parts by weight of this silicone polymer was dispersed and mixed with 100 parts by weight of dimethylpolysiloxane having a viscosity of 50 cS at 25 ° C., and then sufficiently kneaded and swelled by a three-roll mill under shearing force to give a silicone composition. I made things. This was a homogeneous pasty composition with a smooth feel and a viscosity of 65,000 cP.

Reference Example 13 Average composition formula (13)

[0077]

[Chemical 8]

Organohydrogenpolysiloxane of 100 g, ethanol 160 g, average composition formula
CH ₂ = CHCH ₂ O (C ₂ H ₄ O) _30- (C ₃ H ₆ O) ₁₀ -CH ₂ CH = CH ₂ (14)
In the same manner as in Reference Example 3, 34.7 g of polyoxyalkylene represented by the formula, 20 g of ethylene glycol, 13.7 g of dimethylpolysiloxane having a viscosity of 10 cS at 25 ° C. and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged. Processed to make polymer.

Next, 100 parts by weight of this polymer and 300 parts by weight of decamethylcyclopentasiloxane were dispersed and mixed, and then sufficiently kneaded and swollen by a three-roll mill under shearing force to prepare a silicone composition. This was a homogeneous paste-like composition with a smooth feel and a viscosity of 52,000 cP.

Examples 1 to 5 and Comparative Examples 1 to 4 Solid compositions having the compositions shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 3) and Table 2 (Examples 4 to 5 and Comparative Example 4) A water-in-oil type emulsion cosmetic was prepared by the following production method.

(Manufacturing Method) (a) (1) to (8) are heated and dissolved. (B) (a), (9) or (10), and (11)-
Heat and mix (18). (C) Add (19) and (20) to (B) and emulsify. (D) Fill the container and cool to obtain the product.

Each of the obtained products was allowed to stand in a thermostat at 15 ° C., and the presence or absence of water separation in the bulk and the container bottom after 1 day, 1 week and 2 weeks was examined. The results are shown in Tables 1 and 2 with ◯ indicating no separation, Δ indicating slight separation, and x indicating separation.

[0083]

[Table 1]

[0084]

[Table 2]

The silicone gen composition (9) in Tables 1 and 2 had a viscosity of 10 parts at 25 ° C. in 25 parts by weight of the organopolysiloxane polymer obtained in Reference Example 2 above.
It was prepared by dispersing and mixing 75 parts by weight of dimethylpolysiloxane which is CS, sufficiently kneading and swelling. In addition, the pasty silicone composition (10) in Table 1 is the same as in Reference Example 8 above.
To 25 parts by weight of the silicone polymer obtained in Step 1, 75 parts by weight of dimethylpolysiloxane having a viscosity at 25 ° C. of 10 CS was dispersed and mixed, and then sufficiently kneaded and swelled by a three-roll mill under a shearing force to prepare.

As is clear from Tables 1 and 2, the products of the present invention (Examples 1 to 5) show good stability over time.

Further, the products obtained in Examples 1 to 3, the commercially available water-in-oil type nourishing cream (Comparative Example 5) and the commercially available oil-in-water type cream (Comparative Example 6) are shown in Table 3. With respect to the items, sensory evaluation was performed according to the following evaluation methods and evaluation criteria. The results are shown in Table 3.

Rheometer Penetration: (Evaluation Method) A rheometer (manufactured by Fudo Kogyo Co., Ltd.) was used to measure the penetration (diameter: 1 cm, speed: 6 cm / min, depth: 1.5 mm, Temperature; 15 ° C). (Evaluation criteria) The results are shown numerically.

Maintaining Solid Form: (Evaluation Method) It was observed in a gold dish container at 50 ° C. whether the solid form could be maintained. (Evaluation Criteria) One that could maintain the solid state was rated as O, and one that could not be maintained was rated as X.

Ease of taking and feeling of use: (Evaluation method) A use test was conducted by a panel of 10 persons, and the absolute evaluation results of each person were averaged. (Evaluation criteria) 3 points are very good, 2 points are good, and 1 is normal.
A point and a bad point were 0 points, an average of 2 points or more was ◯, an average of 1 point or more and less than 2 points was Δ, and an average of less than 1 point was x.

[0091]

[Table 3]

As is clear from Table 3, the products of the present invention (Examples 1 to 3) have appropriate hardness and, while being water-in-oil type, have good spreadability, oilyness and sticky feeling. Moreover, the protection effect was excellent in durability. On the other hand, the creams of Comparative Examples 5 and 6 are not hard gel-solid type like the product of the present invention in appearance, and neither of them can maintain the solid state at high temperature, The feeling of use did not satisfy all the evaluation items in Table 3.

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[Procedure amendment]

[Submission date] June 9, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

[0084]

[Table 2]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction content]

The silicone gel composition (9) in Tables 1 and 2 had a viscosity of 10 parts at 25 ° C. in 25 parts by weight of the organopolysiloxane polymer obtained in Reference Example 2 above.
It was prepared by dispersing and mixing 75 parts by weight of dimethylpolysiloxane which is CS, sufficiently kneading and swelling. Further, the pasty silicone composition (10) in Table 1 was prepared by adding 25 parts by weight of the silicone polymer obtained in Reference Example 8 to dimethylpolysiloxane 75 having a viscosity of 10 CS at 25 ° C.
After parts by weight were dispersed and mixed, they were sufficiently kneaded and swelled by a three-roll mill under shearing force to prepare.

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Claims (1)

[Claims] 1. An oily gel composition comprising the following components (a) to (d) (a) an oil agent and an oil gelling agent (b) a silicone gel composition and / or a pasty silicone composition (c) polyoxy Ethylene sorbite fatty acid ester (d) A solid water-in-oil type emulsified cosmetic containing water.