JP3480945B2 - Solid water-in-oil type emulsified cosmetic - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a solid water-in-oil type emulsification.
For more information on cosmetics,
Hard gel-solid water-in-oil milk with improved oiliness
About cosmetic cosmetics. [0002] 2. Prior Art and Problems to be Solved by the Invention
In addition, the emulsifying base is an emulsifying type (oil-in-water type, water-in-oil type or
Is a soft paste (so-called cream)
Shape), novelty and uniqueness
It lacks. [0003] Water-in-oil cream is used for
Oil-in-water cream with protective, softening and moisturizing effects
It is known to be better. [0004] However, water-in-oil creams
On the other hand, it has drawbacks such as heavy spread, sticky, oily, etc.
Is not generally favored because of
The development of a product that corrects this was desired. [0005] SUMMARY OF THE INVENTION The inventor of the present invention has proposed such a situation.
As a result of intensive studies in view of the above, the oil-based gel composition, silicone
Emulsifying and dispersing gel composition, specific fatty acid ester and water
Depending on the weight of the hard gel to solid mold,
Water-in-oil type emulsified cosmetics with significantly reduced oiliness
Was obtained, and the present invention was completed. That is, the present invention provides the following components (a) to
(D) (A) Oily gel composition comprising oil agent and oil gelling agent (B) partially crosslinked organopolysiloxane polymer and low
Silicone gel set made by kneading viscosity silicone oil and swelling
Product and / or organohydrogenpolysiloxane
And the aliphatic unsaturated group-containing compound have a viscosity at 25 ° C.
Silicone oil and / or polyhydric alcohol having a viscosity of 100 cs or less
Addition polymerization in the presence or absence of coal
Contains idrogen polysiloxane or aliphatic unsaturated group
Contains a polyoxyalkylene group in any of the compounds
100 parts by weight of silicone polymer and low viscosity silicone
5 to 1,000 parts by weight of oil kneaded under shearing force
G silicone composition (C) HLB10-16 polyoxyethylene sorbite
Fatty acid esters (D) water A solid water-in-oil type emulsified cosmetic characterized by containing
Is provided. The oil agent of the component (a) used in the present invention comprises:
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
Ter, higher alcohol, etc. are used. Specifically, flow
Paraffin, petrolatum, solid paraffin wax, selenium
Minerals such as thin wax and microcrystalline wax
Oils: squalane, lanolin, castor oil, hydrogenated castor oil,
Olive oil, jojoba oil, macadamian nut oil, mink
Oil, turtle oil, almond oil, safflower oil, avoca
Oil, carnauba wax, candelilla wax, mi
Animal and vegetable oils such as beeswax, mokuro, gay wax; polyethylene
Of wax and ethylene propylene copolymer
Oils: oleic, stearic, lauric, myristic
Higher fatty acids such as acetic acid; isopropyl myristate, pal
Isopropyl mitinate, octyldodecyl myristate
, Cetyl 2-ethylhexanoate, 2-ethylhexane
Acid triglyceride, glyceryl trioctanoate, jig
Lyseryl isostearate, Propylene dicaprate
Recall, rosin acid pentaerythritol ester, dipe
Higher fatty acid esthetics such as
Oleyl alcohol, cetyl alcohol, steari
Higher alcohols such as alcohol and lauryl alcohol
One or more of these are combined
Used to be forgotten. [0008] As the oil gelling agent of the component (a), stear
Gold such as aluminum phosphate and magnesium stearate
Genus soap, sucrose palmitate, starch palmi
Formic acid ester, Bacmond ostearic acid ester, etc.
Polysaccharide fatty acid ester, dioctadecyl dimethyl ammonium
Ammonium salt modified montmorillonite, dihexadecyl dimethy
Organically modified viscosity such as luammonium salt modified montmorillonite
Earth minerals and the like. The distribution of the oil gelling agent in the oil gel composition (a)
Although the mixing ratio is not particularly limited, 8 to 30% by weight (hereinafter referred to as%
Is preferable). Also, a book of the oily gel composition (a)
The mixing ratio to the inventive cosmetic is preferably 30 to 70%. 3
If it is less than 0%, it is difficult to maintain a hard gel state to a solid state.
If it exceeds 70%, it will be too hard.
Drawbacks such as heavy and sticky growth
come. [0010] The silicone gel composition of the component (b) is
Partially crosslinked organopolysiloxane polymer and low viscosity silicone
It is obtained by kneading and swelling coconut oil. In the present invention, component (b) is used.
Examples of partially crosslinked organopolysiloxane polymers include
For example, it can be obtained by crosslinking organopolysiloxane.
Insoluble in benzene and can contain more than its own weight of benzene
Organopolysiloxane partially having a three-dimensional crosslinked structure
Polymers may be mentioned. The polymer is represented by R_TwoSiO unit and RSiO_1.5Units
Have, R_ThreeSiO_0.5Unit and / or SiO_Twounit
May be included. This is insoluble in benzene
However, a three-dimensional cross-linking structure that can contain benzene
In order to obtain a structure with_1.5Units and / or S
iO_TwoUnit and R_TwoSiO unit and / or R_ThreeSiO_0.5Unit and ratio
Must be in an appropriate range. RSiO_1.5Unit
And / or SiO_TwoIf the unit is too small, the organopolysilo
The xanthate polymer does not have a sufficient three-dimensional cross-linked
It is soluble in
Also cannot be used. Also, R_TwoSiO unit and / or R_ThreeSiO
_0.5RSiO_1.5Unit and / or SiO_TwoUnit is
If too much, the organopolysiloxane polymer will
It has a bridge structure and is insoluble in benzene, but its own weight
Less than benzene can be contained.
Organopolysiloxane when mixed with high viscosity silicone oil
The polymer does not swell sufficiently and separates and discharges the silicone oil.
It cannot be used because it cannot maintain stability. this
Therefore, a silicone gel composition with good softness and stability
To obtain it (although it is also affected by the molecular weight of the polymer)
In general, (R_TwoSiO unit and / or R_ThreeSiO_0.5Unit): (R
SiO_1.5Unit and / or SiO_Two(Unit) is 1: 1 to 30: 1
It is preferable to use one that is within the range of
You. In each of the above structural units, R is a hydrogen atom;
Alkyl group such as group, ethyl group, propyl group; phenyl
Aryl groups, such as vinyl and tolyl groups; aliphatic unsaturated groups, such as vinyl groups
And the same kind or different kinds
There may be. Although insoluble in benzene,
Having a three-dimensional crosslinked structure that can contain benzene
Luganopolysiloxane polymer, for example, as shown below
It can be synthesized in various ways. i) bonded to at least two silicon atoms in one molecule
Organohydrogen polysiloxane having hydrogen atoms
In a catalytic amount of alcoholic water of alkali metal hydroxide.
Add solution and heat to perform dehydrogenation and condensation reactions
Method. ii) bonded to at least two silicon atoms in one molecule
Organohydrogen polysiloxane having hydrogen atoms
And at least two silicon atoms in one molecule
Hydroxylated organopolysiloxane with a catalytic amount
Heating in the presence of alkali metal hydroxides, platinum compounds, etc.
And performing a dehydrocondensation reaction. iii) bonded to at least two silicon atoms in one molecule
Hydroxylated organopolysiloxane in a catalytic amount
Heating in the presence of alkali metal hydroxides, organotin compounds, etc.
And performing a dehydration condensation reaction. iv) bonded to at least two silicon atoms in one molecule
Hydroxyl-containing organopolysiloxane and one molecule
Alkoxyl groups bound to at least two silicon atoms
With an organopolysiloxane having a catalytic amount of
Heating in the presence of metal hydroxide, organometallic tin compound, etc.
And performing a dealcoholation reaction. Any of these
In the method, benzene that is insoluble in benzene,
Organopolicies with three-dimensional crosslinked structure that can contain zen
A loxane polymer can be easily obtained. Further, a partially crosslinked organopolysiloxane
Other examples of the polymer include insoluble in silicone oil.
But swellable organopolysiloxane polymer
And (a) the organohydrogenpolysiloxane and
(B) With organopolysiloxane containing aliphatic unsaturated group
It is a polymer obtained by polymerization.
And those having a structure. Used here (a)
And (b) the molecular structure of the organopolysiloxane
Any of a chain, a branch, and a ring may be used.
Controls the synthesis reaction of organopolysiloxane polymer
It is more preferable that the resin be linear. This
Here, the organohydrogen of the reactive group (a)
Hydrogen atom bonded to silicon atom in polysiloxane
And (b) organopolysiloxa containing aliphatic unsaturated groups
Aliphatic unsaturated groups in the molecule
The presence of at least two is obtained by polymerizing both.
Three-dimensional cross-linked structure in part of luganopolysiloxane polymer
Indispensable for forming. In addition, that of these reactive groups
The position in each molecule is generally within the molecular chain.
However, it may be a molecular chain terminal. In addition, these reactions
Content of functional group in each organopolysiloxane
Obtains a soft and stable silicone gel composition
In order to achieve this, the molecular structure must be linear or branched.
1 to 20 mol% in the case of
Preferably it is mol%. If the content exceeds this range
It becomes a hard polymer and has low viscosity
Oil tends to be difficult to be encapsulated in the three-dimensional crosslinked structure.
Separation and discharge occur, and stable
U. Conversely, if the content is below this range, silicone gel
The structural viscosity of the composition tends to be poor. (A) Organohydrogen polysilo
Xan is HSiO_1.5Unit, RSiO_1.5Unit, RHSiO unit, R_TwoS
iO unit, R_TwoHSiO_0.5Unit, R_ThreeSiO_0.5Consisting of units, etc.
It is. Here, R represents a methyl group, an ethyl group,
Alkyl groups such as propyl and butyl, phenyl,
An aryl group such as a luyl group, a cyclohexyl group,
Some or all of the hydrogen atoms bonded to the carbon atoms of these groups
From a group whose part is substituted with a halogen atom, cyano group, etc.
Non-substituted except aliphatic unsaturated group such as vinyl group selected
A substituted or substituted monovalent hydrocarbon group is exemplified. like this
A typical example is (CH_Three)_ThreeSiO−, − [(CH_Three)_TwoSi
O]_p−, − [CH_ThreeHSiO]_q−, −Si (CH_Three)_Three(However, p = 10
To 500, q = 2 to 50)
Hydrogen polysiloxanes include suitable materials and
Become. Further, (b) an organo group containing an aliphatic unsaturated group
As the aliphatic unsaturated group of nopolysiloxane, vinyl
Group, an aryl group, etc., but a vinyl group is generally used.
Yes, as organovinylpolysiloxane, (CH_Two= C
H) SiO_1.5Unit, RSiO_1.5Unit, R (CH = CH_Two) SiO unit, R_TwoSiO
Unit, R_Two(CH = CH_Two) SiO_0.5Unit, R_ThreeSiO_0.5Consists of units, etc.
Things. Here, R is the same as in the case of (a).
Show meaning. A typical example of this is (C
H_Two= CH) (CH_Three)_TwoSiO−, − [(CH_Three)_TwoSiO]_r-And -Si (CH_Three)_Two
(CH = CH_Two) (Where r = 10 to 100), or
(CH_Three)_ThreeSiO−, − [(CH_Three)_TwoSiO]_m−, − [(CH = CH_Two) CH_ThreeSiO]_n
-And -Si (CH_Three)_Three(However, m = 10 to 500, n = 2
50) Methylvinylpolysiloxane comprising units
These may be a mixture, suitable materials
Fees. Such an organohydrogen (a)
Organosiloxane and (B) Aliphatic Unsaturated Group Containing Organa
The addition reaction of nopolysiloxane is carried out by a conventionally known general method.
You can do it by law. For example, the appropriate organohydrogen
Polysiloxane and organovinylpolysiloxane
Is a hydrogen group bonded to each reactive silicon atom
In a molar ratio of 1/3 to 3/1 with the vinyl group.
After adding it, add weight such as platinum or palladium
By adding a mixed catalyst and stirring under heating,
Organopolysiloxane Polymerization Insoluble in Evolving Silicone Oil
Things are obtained. In particular, as the addition polymerization catalyst,
Using chloroplatinic acid described in JP-A-3-9969
Preferably. Low viscosity silicone used for component (b)
The oil is not particularly limited, but has a viscosity of about 50 cs
The following can be suitably used. This is high viscosity
As it becomes, as a result of using it in large quantities,
Because it gives a feeling of unpleasantness and is unfavorable in terms of usability.
is there. And as a low-viscosity silicone oil, it has a low polymerization degree and a chain.
Dimethylpolysiloxane, methylphenylpolysilo
Xane, cyclic octamethylcyclotetrasiloxane,
Decamethylcyclopentasiloxane
One or more of these may be appropriately selected and used according to
Can be Further, the paste-like silicone of the component (b)
The low-viscosity silicone composition is prepared in the following silicone polymer.
It contains corn oil. In the present invention, the component (b) is used.
Paste silicone compositions are novel and generally
Equation (1) R¹ _aR^Two _bH_cSiO_{(4-abc) / 2}        (1) ＲR here¹Is the same or different and has 1 to 18 carbon atoms
Substituted or substituted alkyl group, aryl group, aralkyl group
Or a halogenated hydrocarbon group, R^TwoIs the general formula C_nH_2nO (C_TwoH
_FourO)_d(C_ThreeH₆O)_eR^Three[Here R^ThreeIs a hydrogen atom or carbon number
1 to 10 saturated aliphatic hydrocarbon groups or-(CO) -R^Five(R
^FiveIs a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms)
A group, 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, and n is 2 to 6]
Oxyalkylene group, a is 1.0 ≦ a ≦ 2.5, b is
0.001 ≦ b ≦ 1.0, c is 0.001 ≦ c ≦ 1.
Organohydrogen polysiloxane represented by 0 °
And / or general formula (2) R¹ _fH_gSiO_{(4-fg) / 2}      (2) (Here R¹Is the same as above, f is 1.0 ≦ f ≦ 3.0,
g is an organohigh represented by 0.001 ≦ g ≦ 1.5)
Drogen polysiloxane and the general formula (A) C_mH_2m-1O (C_TwoH_FourO)_h(C_ThreeH₆O)_iC_mH_2m-1      (A) (Where h is an integer of 2 to 200, i is an integer of 0 to 200
A number, h + i is an integer of 3 to 200, and m is 2 to 6)
Polyoxyalkylene and / or general formula (B) R¹ _jR^Four _kSiO_{(4-jk) / 2}          (B) (Here R¹Is the same as above, R^FourIs aliphatically unsaturated at the end
A monovalent hydrocarbon group having 2 to 10 carbon atoms having a group, j is 1.
0 ≦ j ≦ 3.0, k is 0.001 ≦ k ≦ 1.5)
In combination with the organopolysiloxane,
Component represented by general formula (1) and / or general formula (A)
A total of 100 parts by weight of a composition comprising
Low viscosity silicone whose viscosity at 100 ℃ is 100cs or less
Oil and / or 3-200 parts by weight of polyhydric alcohol
Silicone obtained by addition polymerization in the presence or absence
100 parts by weight of a polymer and 5-1,000 low-viscosity silicone oil
0 parts by weight and kneaded under shearing force
Things. The pasty silicone of the component (b) of the present invention
The silicone polymer that constitutes the composition
Rogen polysiloxane and aliphatic unsaturated group-containing compound
Having a viscosity of 100 cs or less at 25 ° C.
In the presence or absence of oil and / or polyhydric alcohol
Addition polymerized, but organohydrogen
Polysiloxane or compounds containing aliphatic unsaturated groups
Either must contain a polyoxyalkylene group.
Requirements. Therefore, the organohydrogenpolysilo
On the Combination of Xane and Aliphatic Unsaturated Group-Containing Compound
To illustrate, first one contains a polyoxyalkylene group
General formula (1) R¹ _aR^Two _bH_cSiO_{(4-abc) / 2}      (1) An organohydrogenpolysiloxane represented by
R¹Is methyl, ethyl, propyl, butyl, etc.
Aryl such as alkyl group, phenyl group and tolyl group
Aralkyl groups such as benzyl, phenethyl, etc.
Or one of the hydrogen atoms bonded to the carbon atoms of these groups.
A chloromethyl group partially or wholly substituted with a halogen atom,
Selected from trifluoropropyl groups and the like,
Is an unsubstituted or substituted alkyl having 1 to 18 carbon atoms
Group, aryl group, aralkyl group or halogenated hydrocarbon
Group, R^TwoIs the general formula (3) C_nH_2nO (C_TwoH_FourO)_d(C_ThreeH₆O)_e-R^Three          (3) And R^ThreeIs a hydrogen atom or a methyl, ethyl,
Ropyl, butyl, pentyl, hexyl, hepti
And saturated aliphatic carbons having 1 to 10 carbon atoms such as octyl group
Hydride group or formula-(CO) -R^FiveAnd R^FiveIs carbon
A saturated aliphatic hydrocarbon group represented by Formulas 1 to 5, wherein d is 2 to 20;
An integer of 0, e is an integer of 0 to 200, and d + e is 3 to 200
Is a polyoxyalkylene group wherein n is 2 to 6.
It is assumed that. The a of the a, b, and c values is as follows.
If it is less than 0, the obtained polymer is sufficient for silicone oil.
If it is larger than 2.5, the resulting polymer will not swell
Paste obtained by kneading with corn oil under shearing force
Because it cannot disperse enough water in the composition
1.0 ≦ a ≦ 2.5, preferably 1.0 to 2.0
It is necessary that b is less than 0.001.
Kneading the resulting polymer with silicone oil under shearing force
The obtained paste-like composition is not sufficiently dispersed in water,
The swelling of the resulting polymer in silicone oil
0.001 ≦ b ≦ 1.0, because it is not sufficient
Is 0.005 to 1.0, and c is 0.0
When the molecular weight is less than 01, the polymer obtained by addition polymerization has a three-dimensional structure.
The formation of the structure becomes difficult and the viscosity of the silicone oil is poor.
When it is larger than 1.0, it is formed by addition polymerization.
Cross-linking density of the three-dimensional structure is too high
Oil cannot be held stably,
1 ≦ c ≦ 1.0, preferably 0.005 to 1.0
Things. Thus, the following equation (1) can be used.
Combined with Lugano hydrogen polysiloxane
Is the general formula (B) R¹ _jR^Four _kSiO_{(4-jk) / 2}          (B) And R¹Is the same as above, R^FourIs a vinyl group at the end,
The number of carbon atoms having an aliphatic unsaturated group such as an allyl group is
A monovalent hydrocarbon group of 2 to 10;
The crosslink density of the three-dimensional structure formed by
Too long to obtain a polymer that holds silicone oil stably
If it is larger than 3.0, the polymer obtained by addition polymerization
Formation of a three-dimensional structure in
1.0 ≦ d ≦
3.0, preferably 1.0 to 2.5, and for k
Is less than 0.001 in the intended polymer
Thickening of silicone oil due to difficulty in forming three-dimensional structure
If it is larger than 1.5, it will cause addition polymerization.
Cross-link density of the three-dimensional structure formed
Polymer that can hold silicone oil stably
Cannot be obtained, so that 0.001 ≦ k ≦ 1.
5, preferably aliphatic unsaturation of 0.005 to 1.0
It is considered to be an organopolysiloxane containing a sum group.
An organohydrogenpoly represented by the general formula (1)
Siloxane and organopolysilo represented by the general formula (B)
The mixture with the xane is abbreviated hereinafter as mixture-I. Incidentally, the organo high represented by the general formula (1)
Drogen polysiloxane and poly (A)
Can be used in combination with lioxyalkylene
You. Further, the organohydrogen policy
Other combinations of loxane and compounds containing aliphatic unsaturated groups
For the set, the general formula (2) R¹ _fH_gSiO_{(4-fg) / 2}        (2) And R¹Is the same as above, and f is less than 1.0.
Swelling of silicone polymer in silicone oil
If it is larger than 3.0, the polymer obtained by addition polymerization
It becomes difficult to form a three-dimensional structure inside
1.0 ≦ f ≦ 3.
0, preferably 1.0 to 2.5, and g is 0.001
If it is less than three dimensions in the polymer obtained by addition polymerization
It is difficult to form the structure, and the viscosity of the silicone oil increases.
The properties are poor, and if it is larger than 1.5,
The cross-link density of the three-dimensional structure formed by the
The resulting polymer does not hold silicone oil stably
Therefore, 0.001 ≦ g ≦ 1.5, preferably 0.005 to
An organohydrogenpolysiloxane of 1.0
General formula (A) C_mH_2m-1(C_TwoH_FourO)_h(C_ThreeH₆O)_iC_mH_2m-1      (A) And h is 2 to 200, preferably 5 to 100, i
Is 0 to 200, preferably 0 to 100, and is obtained
In order to sufficiently disperse water in the polymer, h / i ≧ 1
M is 2 to 6, preferably 3 to 6.
(Hereinafter referred to as mixture-II)
Abbreviated). In the present invention, the mixture -I or -II is
The viscosity at 25 ° C. used in addition polymerization is 10
Low viscosity silicone oils of 0 cs or less are linear or
Branched methylpolysiloxane, methylphenylpolysilo
Xane, ethyl polysiloxane, ethyl methyl polysiloxane
Xane, ethylphenylpolysiloxane, octamethyl
Cyclotetrasiloxane, decamethylcyclopentasilo
Cyclic dimethylpolysiloxane such as xan
These have a viscosity at 25 ° C. of 100 cs.
The viscosity is not particularly limited as long as:
Preferably, the viscosity should be 50 cs or less.
However, these are mixtures of two or more even when used alone.
Is also good. As the polyhydric alcohol, ethylene glycol is used.
Recall, 1,3-butylene glycol, propylene glycol
Recall, dipropylene glycol, glycerin, jig
Lyserine and the like are exemplified, but these are used alone
May be used in combination of two or more. Low viscosity silicone oil and / or polyhydric alcohol
The amount of coal is 100 weight
The amount is preferably 3 to 200 parts by weight based on parts by weight. Low viscosity slurry
Addition polymerization in the presence of corn oil and / or polyhydric alcohol
Is carried out to obtain a polymer containing these,
Compared to those obtained by addition polymerization in the absence of
High swelling property for oils and excellent viscosity
become. The addition polymerization of the mixture -I or -II
Is, for example, chloroplatinic acid, alcohol-modified chloroplatinic acid or
Are known such as chloroplatinic acid-vinylsiloxane complex
In the presence of a platinum or rhodium compound catalyst
At room temperature or at a temperature of 50 to 150 ° C.
Just do it. In this case, an organic solvent is used if necessary.
Methanol, ethanol, 2-pro
Aliphatic alcohols such as panol and butanol, benzase
Aromatic hydrocarbons such as toluene, xylene, n-pe
Aliphatic, such as n-hexane, n-hexane, and cyclohexane.
Or alicyclic hydrocarbon, dichloromethane, chloroform,
Carbon tetrachloride, trichloroethane, trichloroethylene,
Examples are halogenated hydrocarbons such as fluorinated hydrocarbons
It is. Partially crosslinked type in the above silicone gel composition
Ratio of organopolysiloxane polymer and the above paste
Of silicone polymer in the silicone composition
These are also 10 to 30%. The silicone gel composition thus obtained and
And / or paste-like silicone composition (b) of the present invention
The proportion of the cosmetic is preferably 10 to 40%, more preferably 15 to 40%.
35% is more preferred. If it is less than 10%, it will improve the feeling of use
No fruit is seen, and if it exceeds 40%, it is hard gel to solid
Will be difficult to maintain. The polio of HLB 10 to 16 of the component (c)
Xyethylene sorbite fatty acid ester is colorless to pale yellow
A non-ionic surfactant that is liquid to paste in color.
Nikkol GO-4, GO-430, GO
-440, GO-460, GL-1, GS-460 (I
Deviation is also manufactured by Nippon Surfactant Industries).
When two or more of the above compounds (c) are used in combination
Suffices if the combined HLB is within the above range. Polyoxyethylene sorbite fatty acid S
The content of the ter (c) in the cosmetic of the present invention is 0.5 to 5%.
preferable. If less than 0.5%, the effect of the present invention cannot be obtained,
In addition, even if it exceeds 5%, the effect is not improved.
In fact, the feeling of use may be deteriorated. Amount of water of component (d) in the cosmetic of the present invention
Is preferably 5 to 35%. If less than 5%
No improvement in usability is observed, and over 35% stability over time
The sex worsens. The component (d) is usually used in cosmetics.
The resulting aqueous component can be appropriately blended. The solid water-in-oil type emulsified cosmetic of the present invention comprises an oil
Gel composition (a) and silicone gel composition or
Into a mixed oil comprising the silicone composition (b)
Polyoxyethylene sorbite fatty acid ester (c)
Water (d) is emulsified and dispersed and solidified by cooling.
Can be built. The solid water-in-oil type emulsified cosmetic of the present invention includes:
In addition to the above components (a) to (d), the effects of the present invention are not hindered.
Humectants, preservatives, antioxidants, UV absorption
Agents, emollients, beauty ingredients, fragrances, water-soluble polymers,
Extender, coloring pigment, glitter pigment, organic powder, hydrophobic treatment
Components commonly used in cosmetics such as pigments and tar pigments
Can be combined. [0039] The solid water-in-oil type emulsified cosmetic of the present invention comprises:
It is a novel and unique hard gel to solid
The weight, stickiness, and greasyness
Solving the problems of the water-in-oil type cream at once
Things. [0040] The present invention will be specifically described below with reference to examples.
However, the present invention is not limited by these. Reference Example 1 Synthesis of Partially Crosslinked Organopolysiloxane Polymer: Tri
Methylsilyl endblocked dimethylmethylhydrogenpo
Lisiloxane [Molecular weight 2300, CH_ThreeHSiO pair (CH_Three)_TwoSiO =
1: 4 (molar ratio)] in 1% potassium hydroxide solution (ethanol
Of water to water = 2: 1), heat and reflux to polymerize
The reaction was performed to obtain a reaction product. Then the reaction product
After washing with water to remove the alkaline agent, air dry
Is insoluble in benzene, and benzene has its own weight of 18
An organopolysiloxane polymer which can contain 0% was obtained. Reference Example 2 Synthesis of partially crosslinked organopolysiloxane polymer: Content
Trimethylsilyl in a planetary mixer
End-blocked dimethyl methyl hydrogen polysiloxane
(Average molecular weight 2340, Si-H 4.5 mol%) 1790
g, and dimethylvinylsilyl end-blocked dimethylpolysiloxane
Loxane (average molecular weight 930, vinyl group 7.7 mol%)
710 g was charged and mixed by stirring. In the same mixed solution, chloride
0.5 g of a 2% solution of platinic acid in isopropanol was added.
No, the temperature was raised to 70-80 ° C., and stirring was continued for 2 hours. So
After that, the pressure inside the system is reduced to 5 to 10 mmHg, and stripping is performed.
By continuing for 30 minutes, a colorless flexible solid
An organopolysiloxane polymer having a shape was obtained. Reference Example 3 Synthesis of partially crosslinked organopolysiloxane polymer: Content
Trimethylsilyl in a planetary mixer
End-blocked dimethyl methyl hydrogen polysiloxane
(Average molecular weight 2340, Si-H 4.5 mol%) 1790
g, and dimethylvinylsilyl end-blocked dimethylmethyl
Phenylpolysiloxane (average molecular weight 5560, vinyl
(Based on 1.5 mol%) was added and stirred and mixed.
2% isopropanol solution of chloroplatinic acid
Of 0.5 g and heated to 70-80 ° C.,
Stirring was continued for a while. Then, the pressure inside the system was reduced to 5-10 mmHg.
And by continuing the stripping for 30 minutes,
Solid organopolysiloxane with color flexibility
Compound was obtained. Reference Example 4 (1) Average composition formula (4) in the reactor [0045] Embedded imageAn organohydrogen policy represented by
Roxane 68g, ethanol 100g, average composition formula is C
H_Two= CHCH_TwoO (C_TwoH_FourO)_TenCH_ThreePolyoxyalkylene represented by
Solution of 32 g of chloroplatinic acid and 32% by weight of ethanol.
3 g, and maintained for 2 hours while maintaining the internal temperature at 70 to 80 ° C.
After stirring, the solvent was removed under reduced pressure.
Equation (5) [0047] Embedded image An organohydrogen policy represented by
Loxane was obtained. (2) In the reactor, the organohydrogen obtained in (1) above
100 g of genpolysiloxane, 100 g of ethanol
And average composition formula (6) [0049] Embedded image Dimethylvinylsilyl end-blocking represented by
28.9 g of dimethylpolysiloxane and triple chloroplatinic acid
0.3 g of an ethanol solution at a concentration of 70%
After stirring at 80 ° C for 2 hours, the solvent was removed under reduced pressure.
This gave a resilient polymer. 20 parts by weight of this polymer and dimethyl
80 parts by weight of roxane (viscosity 6 cS) were dispersed and mixed.
Mix well with a three-roll mill under shearing force
A composition was prepared. This composition has a smooth feel
And a uniform paste-like composition with a viscosity of 32,000 cP
there were. Reference Example 5 In the reactor, the average composition formula (7) [0053] Embedded image An organohydrogen policy represented by
Loxane 100g, ethanol 62g, average composition formula is
 CH_Two= CHCH_TwoO- (C_TwoH_FourO)_Ten-CH_TwoCH = CH_TwoPos indicated by (8)
23.6 g of lioxyalkylene and 3% by weight of chloroplatinic acid
0.3 g of an ethanol solution of
After stirring at 2 ° C for 2 hours, the solvent was removed under reduced pressure
Thus, a granular polymer was obtained. 33 parts by weight of the obtained polymer and
67 parts by weight of siloxane (viscosity 6 cS) were dispersed and mixed.
After that, knead well under a shearing force with a three-roll mill and swell.
Thus, a silicone composition was prepared. This composition is lubricated
A uniform paper with a smooth feel and a viscosity of 24,800 cP
It was a strike composition. Reference Example 6 In the reactor, the average composition formula (4) obtained in (1) of Reference Example 1 was used.
An organohydrogenpolysiloxane 10 represented by the formula:
0 g, ethanol 75 g, average composition used in Reference Example 2
49.4 g of the polyoxyalkylene represented by the formula (8)
And 0.3 g of chloroplatinic acid in 3% by weight ethanol solution
After stirring for 2 hours while maintaining the internal temperature at 70 to 80 ° C,
The solvent was removed under reduced pressure to obtain a granular polymer. 33 parts by weight of this polymer and dimethyl
After mixing and dispersing 67 parts by weight of roxane (viscosity 6 cS),
Knead well under a shearing force with a three-roll mill to
Then, a silicone composition was prepared. This composition is smooth
Paste with uniform feel and viscosity of 10,600 cP
It was. Reference Example 7 In the reactor, the average composition formula (9) [0059] Embedded image An organohydrogen policy represented by
Loxane 100g, ethanol 57g, used in Reference Example 2
Polyoxyalkylene represented by the average composition formula (8)
An ethanol solution of 13.5 g and 3% by weight of chloroplatinic acid
Charge 0.3g, keep the internal temperature at 70-80 ° C, 2 o'clock
After stirring for a while, the solvent was removed under reduced pressure to remove the granular polymer.
Obtained. 20 parts by weight of this polymer and dimethylpolysilo
80 parts by weight of xane (viscosity 6 cS) were dispersed and mixed.
Knead sufficiently under shearing force with this roll mill and swell
A silicone composition was made. This composition has a smooth
A uniform paste with a feel and viscosity of 22,800 cP
Met. Reference Example 8 In the reactor, the compound of average composition formula (7) used in Reference Example 2 was used.
Lugano hydrogen polysiloxane 100 g, ethanol
103 g, according to the average composition formula (8) used in Reference Example 2.
23.6 g of the indicated polyoxyalkylene, at 25 ° C.
Dimethylpolysiloxane having a viscosity of 6 cS
g and 0.3 g of a 3 wt% chloroplatinic acid ethanol solution.
Charged and stirred for 2 hours while maintaining the internal temperature at 70 to 80 ° C.
After removing the solvent under reduced pressure, the silicone polymer
was gotten. Then, 100% by weight of the silicone polymer
In the part, dimethyl polysilo having a viscosity of 6 cS at 25 ° C.
After dispersing and mixing 100 parts by weight of xan, a three-roll mill
Knead well under shearing force and swell to form a silicone
A product was made. It has a smooth feel, viscosity
Is 82,800 cP.
Was. Reference Example 9 In the reactor, the average composition formula (9) used in Reference Example 4 was used.
Organohydrogenpolysiloxane 100
g, ethanol 95 g, average composition formula used in Reference Example 2
13.5 g of the polyoxyalkylene of (8) at 25 ° C.
Dimethylpolysiloxane having a viscosity of 5 cS
g and 0.3 g of a 3 wt% chloroplatinic acid ethanol solution.
The polymer was prepared and treated in the same manner as in Reference Example 5 to produce a polymer. Next, 100 parts by weight of this polymer and octame
Disperse and mix 200 parts by weight of tylcyclotetrasiloxane
After that, knead well under shearing force with a three roll mill
A swollen silicone composition was made. This one is slippery
Uniform paper with a viscous feel and a viscosity of 44,000 cP
It was a strike composition. Reference Example 10 In the reactor, the average composition formula (10) [0067] Embedded image An organohydrogen policy represented by
Roxane 100g, ethanol 74g, average composition formula is
 CH_Two= CHCH_TwoO (C_TwoH_FourO)₃₀CH_TwoCH = CH_TwoPos indicated by (11)
Lioxyalkylene 18.5 g, viscosity at 25 ° C.
29.6 g of 6 cS dimethylpolysiloxane and chloride
Charge 0.3 g of a 3% by weight ethanol solution of platinic acid,
A polymer was prepared in the same manner as in Example 5. Next, 100 parts by weight of this polymer and phenyl
200 parts by weight of tris (trimethylsiloxy) silane
After mixing and dispersing, the
A silicone composition swollen by mixing and kneading was prepared. This
Has a smooth feel and a viscosity of 25,500 cP
It was a uniform paste-like composition. Reference Example 11 In the reactor, the average composition formula (5) obtained in (1) of Reference Example 1 was used.
An organohydrogenpolysiloxane 10 represented by the formula:
0 g, ethanol 72 g, average composition formula (12) [0071] Embedded image With a dimethylvinylsilyl group represented by
28.9 g of dimethylpolysiloxane blocked with 25
Dimethylpolysiloxane having a viscosity at 30 ° C of 30 cS
An ethanol solution of 14.3 g and 3% by weight of chloroplatinic acid
0.3 g was charged and treated in the same manner as in Reference Example 5 to obtain a polymer.
Had made. Then, 22.2 parts by weight of this polymer and 25 ° C.
Dimethylpolysiloxane 7 having a viscosity of 6 cS
7.8 parts by weight, and then mixed with a three-roll mill.
The mixture was sufficiently kneaded under shearing force to produce a silicone composition.
It has a smooth feel and a viscosity of 48,000 cP
Was a uniform paste-like composition. Reference Example 12 In the reactor, the compound of average composition formula (7) used in Reference Example 2 was used.
Lugano hydrogen polysiloxane 100 g, ethanol
103 g of the average composition formula (8) used in Reference Example 2.
23.6 g of polyoxyalkylene, 1,3-butylene
82.4 g of recall and 3% by weight of chloroplatinic acid in ethanol
Of the solution, and maintain the internal temperature at 70 to 80 ° C.
After stirring for 2 hours, the solvent was removed under reduced pressure.
A silicone polymer was obtained. Then, 100% by weight of the silicone polymer
In the part, a dimethyl policy having a viscosity of 50 cS at 25 ° C.
After 100 parts by weight of roxane are dispersed and mixed,
Mix well under shearing force with
A composition was made. It has a smooth feel,
A uniform paste-like composition having a degree of 65,000 cP
Was. Reference Example 13 In the reactor, the average composition formula (13) [0077] Embedded image An organohydrogen policy represented by
Loxane 100 g, ethanol 160 g, average composition formula
 CH_Two= CHCH_TwoO (C_TwoH_FourO)₃₀-(C_ThreeH₆O)_Ten-CH_TwoCH = CH_Two(14)
34.7 g of polyoxyalkylene represented by
20 g of glycol, viscosity at 25 ° C. is 10 cS
13.7 g of dimethylpolysiloxane and 3 weight of chloroplatinic acid
% Ethanol solution, and the same as in Reference Example 5
To produce a polymer. Next, 100 parts by weight of this polymer and decamethyl
300 parts by weight of cyclopentasiloxane was dispersed and mixed
Then, swell by kneading well under shearing force with a three-roll mill
Thus, a silicone composition was prepared. This one is smooth
Uniform paste with a viscosity of 52,000 cP with a pleasant feel
Composition. Examples 1-4, Comparative Examples 1-4 Table 1 (Examples 1-3, Comparative Examples 1-3) and Table 2 (Example
4. Solid water-in-oil type emulsified cosmetic having the composition shown in Comparative Example 4)
Was prepared by the following production method. (Manufacturing method) (A) Heat-dissolve (1) to (8). (B) (a), (9) or (10), and (11)-
(18) is heated and mixed. (C) Add (19) and (20) to (b) and emulsify
You. (D) Fill the container and cool to obtain the product. Each of the obtained products is placed in a thermostat at 15 ° C.
Leave in the bulk after 1 day, 1 week and 2 weeks
The presence or absence of water separation at the bottom of the vessel was examined. The result is no separation
、, stability with time as △ for slight separation and × for separation
Were evaluated and shown in Tables 1 and 2. [0083] [Table 1][0084] [Table 2]The silicone gels in Tables 1 and 2
Composition (9) is the organopoly obtained in Reference Example 2 above.
A viscosity at 25 ° C. of 1 is added to 25 parts by weight of the siloxane polymer.
Disperse 75 parts by weight of dimethylpolysiloxane of 0 cs
After mixing, it was kneaded well and swelled to prepare. Table 1
The paste-like silicone composition (10) in the reference
25 ° C. to 25 parts by weight of the silicone polymer obtained in Example 8
Dimethylpolysiloxane 7 having a viscosity of 10 cs
After dispersing and mixing 5 parts by weight, apply shear force with a three-roll mill.
And swelled. As is clear from Tables 1 and 2, the product of the present invention
(Examples 1 to 4) show good temporal stability. Further, the products obtained in the above Examples 1 to 3 were prepared.
Product, commercial water-in-oil nourishing cream (Comparative Example 5) and
And commercially available oil-in-water cream (Comparative Example 6) are shown in Table 3.
For the evaluation items, according to the following evaluation methods and evaluation criteria
Sensory evaluation was performed for each. Table 3 shows the results. Rheometer penetration: (Evaluation method) Using a rheometer (manufactured by Fudo Kogyo)
The penetration was measured (diameter: 1 cm, speed: 6 cm / min, depth)
1.5 mm, temperature; 15 ° C.). (Evaluation criteria) The results are shown by numerical values. Maintenance of solid form: (Evaluation method) Solid state can be maintained at 50 ° C in a metal dish container
Was observed. (Evaluation criteria) Good for maintaining solid state, not good
Was evaluated as x. Ease of removal and feeling of use: (Evaluation method) Use test by 10 expert panels
No, the average of the absolute evaluation results of each person was averaged. (Evaluation criteria) Very good 3 points, good 2 points, ordinary 1
0 points for points, bad, 2 points or more on average, 1 point on average
Less than 2 points were rated as Δ, and less than 1 point on average was rated as x. [0091] [Table 3] As is clear from Table 3, the product of the present invention (implementation
Examples 1) to 3) have moderate hardness and a water-in-oil type.
But it's easy to spread, greasy, and sticky
In addition, the protection effect was excellent. Against this
Then, the creams of Comparative Examples 5 and 6 are also present invention products in appearance.
Are not hard gels or solids like
The solid state cannot be maintained at the temperature,
Does not satisfy all of the evaluation items in Table 3.
Was.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI // C08L 83/12 C08L 83/12 (58) Investigated field (Int.Cl. ⁷ , DB name) A61K 7/48 A61K 7 / 00

Claims (1)

(57) Claims 1. An oily gel composition comprising the following components (a) to (d): (a) an oil agent and an oil gelling agent; and (b) a partially crosslinked organopolysiloxane polymer. Silicone oil and / or polyhydric alcohol having a viscosity at 25 ° C. of not more than 100 cs with a silicone gel composition and / or an organohydrogenpolysiloxane and a compound having an aliphatic unsaturated group, which are kneaded and swollen with a low-viscosity silicone oil. Is added and polymerized in the presence or absence of 100 parts by weight of a silicone polymer containing a polyoxyalkylene group in either an organohydrogenpolysiloxane or a compound containing an aliphatic unsaturated group, and a low-viscosity silicone oil 5 to 5 parts by weight. 1,000 parts by weight of a paste-like silicone composition (c) kneaded under shearing force Solid-like water-in-oil emulsified cosmetic which is characterized by containing the bit fatty acid ester (d) water.