CN114340583A - Water-in-oil composition - Google Patents

Water-in-oil composition Download PDF

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Publication number
CN114340583A
CN114340583A CN202080061383.7A CN202080061383A CN114340583A CN 114340583 A CN114340583 A CN 114340583A CN 202080061383 A CN202080061383 A CN 202080061383A CN 114340583 A CN114340583 A CN 114340583A
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oil
water
powder
phase
silicone
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Inventor
氏本慧
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Shiseido Co Ltd
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Shiseido Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin

Abstract

The invention provides a water-in-oil composition in which aggregation/sedimentation of powder is less likely to occur in an oil phase in which a hydrophobized powder is blended. The invention therefore relates to a water-in-oil composition, characterized in that it comprises: an oil phase having a silicone oil/oil phase mass ratio of 0.65 or more; an organosilicon-treated powder dispersed in the oil phase and treated with an organosilicon surface-treating agent; a polyglycerol-modified silicone dispersant for dispersing the silicone-treated powder in an oil phase; an aqueous phase dispersed in the oil phase; and an emulsifier for dispersing the aqueous phase in the oil phase, wherein the mass ratio of the silicone-treated powder/the total powder is 0.7 or more.

Description

Water-in-oil composition
RELATED APPLICATIONS
This application claims priority from japanese patent application No. 2019-161685, filed on 5.9.9.2019, the contents of which are incorporated herein.
Technical Field
The present invention relates to a water-in-oil composition, and particularly to an improvement in dispersibility of a hydrophobized powder thereof.
Background
Hydrophobized powder is used in various cosmetics and the like because it exerts water resistance on its applied surface and is less likely to fall off due to sweat or the like. For example, sunscreen cosmetics are widely used to reduce the influence of ultraviolet rays on the skin, and are roughly classified into products using ultraviolet scattering powder as an ultraviolet screening agent and products using an organic ultraviolet absorber as an ultraviolet screening agent.
Organic ultraviolet absorbers are largely classified as ester oils, which are soluble in the oil phase and are easily spread evenly on the skin, but on the other hand, they are also sometimes irritating to the skin.
In contrast, fine zinc oxide particles and fine titanium dioxide particles are generally used for the ultraviolet scattering powder, and the particle size is adjusted to improve the visible light transmittance and obtain the ultraviolet scattering effect. Further, in order to obtain water resistance, the ultraviolet scattering powder is often blended in an oil phase with the surface of the powder being hydrophobized.
However, the inorganic powder subjected to the hydrophobic property-imparting treatment is likely to aggregate/sediment in the oil phase, and may cause cloudiness/unevenness of the composition and whitening in application to the skin.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4536538
Patent document 2: japanese patent laid-open No. 2006-213619
Patent document 3: japanese patent No. 4881961
Patent document 4: japanese laid-open patent publication No. 2010-159229
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above-mentioned conventional techniques, and an object of the present invention is to provide a water-in-oil composition in which aggregation and sedimentation of a hydrophobic powder are less likely to occur in an oil phase in which the powder is mixed.
Means for solving the problems
In order to solve the above problems, the present invention relates to a water-in-oil composition comprising:
an oil phase having a silicone oil/oil phase mass ratio of 0.65 or more;
an organosilicon-treated powder dispersed in the oil phase and treated with an organosilicon surface-treating agent;
a polyglycerol-modified silicone dispersant for dispersing the silicone-treated powder in an oil phase;
an aqueous phase dispersed in the oil phase; and
an emulsifier for dispersing the above aqueous phase in the oil phase,
the mass ratio of the organosilicon processing powder to the total powder is more than 0.7.
In addition, in the above-mentioned composition,
the water phase is 20 to 35% by mass in the composition,
the oil phase is 20 to 40% by mass of the composition,
furthermore, the organosilicon-treated ultraviolet-scattering powder is preferably contained in an amount of 10 to 35 mass% in the composition.
In the above composition, it is preferable that the average emulsified particle size of the aqueous phase is 10 μm or less.
Further, in the above composition, it is preferable to further contain an organically modified clay mineral.
In addition, in the above-mentioned composition,
the surface treatment agent of the organosilicon-treated powder is preferably any one of a polydimethylsiloxane treatment agent, a hydrogenated polydimethylsiloxane treatment agent, and an octylethoxysilane treatment agent.
Further, in the above composition, it is preferable that the emulsifier is a polyether-modified silicone emulsifier.
In addition, in the above composition, it is preferable that the dispersant other than the polyglycerol-modified silicone dispersant is less than 0.5% by mass in the composition.
Further, in the above composition, it is preferable that the cyclic siloxane is less than 10% by mass in the composition.
In the above composition, it is preferable that the polyglycerin-modified silicone is dibutyl dimethicone polyglycerin-3.
ADVANTAGEOUS EFFECTS OF INVENTION
The water-in-oil composition according to the present invention is a water-in-oil composition in which a silicone-treated powder is dispersed in an oil phase mainly composed of a silicone oil, a polyglycerol-modified silicone dispersant is used as the dispersant, and an aqueous phase is dispersed in the oil phase, whereby the silicone-treated powder can be stably maintained in the composition and aggregation/sedimentation can be suppressed.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described.
The water-in-oil composition according to the present invention is a composition in which an aqueous phase and an organosilicon-treated powder are dispersed in an oil phase independently of each other.
[ oil phase ]
In the present invention, the dispersion medium is an oil phase, and particularly in the present invention, when the dispersion medium mainly contains a silicone oil and contains other oily components, the mass ratio of the silicone oil/the oil phase is preferably 0.65 or more, and more preferably 0.75 or more.
Examples of the silicone oil include dimethylpolysiloxane, octamethylsiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentapolysiloxane.
When the cyclic siloxane is contained, the amount of the cyclic siloxane to be mixed in the composition is preferably 10% by mass or less.
Examples of the other oily components include various liquid oils and fats, ester oils, hydrocarbon oils, and solid oils and fats.
Examples of the liquid oil and fat include avocado oil, camellia seed oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, almond oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, gossypium hirsutum seed oil, perilla oil, soybean oil, peanut oil, tea seed oil, torreya japonica oil, rice bran oil, paulownia oil, jatropha japonica oil, jojoba seed oil, germ oil, triglycerin, and the like.
Examples of the ester oil include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, acetylated lanolin, isocetyl stearate, isocetyl isostearate, isononyl isononanoate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyldiol monoisostearate, neopentyl glycol didecanoate, diisostearyl malate, glycerol di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, trimethylolpropane myristate, and the like, Pentaerythritol tetra-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, glycerol trioctanoate, glycerol triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glycerol trimyristate, glycerol tri-2-heptylundecanoate, methyl ricinoleate, oleyl oleate, acetin, 2-heptylundecyl palmitate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamate, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, glycerol tri-2-ethylhexanoate, glycerol tri-2-heptylundecanoate, methyl ricinoleate, oleyl oleate, glyceryl oleate, 2-heptylundecanoate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamate, di-2-heptylundecanoate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, glycerol tri-2-heptylundecanoate, glycerol tri-oleate, glycerol tri-2-heptylundecanoate, glycerol tri-oleate, glycerol tri-2-heptylundecanoate, glycerol tri-oleate, glycerol tri-2-oleyl-oleate, and/oleate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, and the like.
Examples of the hydrocarbon oil include liquid paraffin, ceresin, squalane, pristane, paraffin, ceresin, squalene, vaseline, microcrystalline wax, polyethylene wax, and fischer-tropsch wax.
[ Silicone-treated powder ]
In the present invention, the silicone-treated powder is particularly an inorganic powder having been subjected to a silicone surface treatment.
Preferably, titanium dioxide and/or zinc oxide treated with silicone are used.
When these silicone-treated powders are used as an ultraviolet scattering agent, titanium dioxide and zinc oxide are preferably prepared in the form of fine particles from the viewpoint of the ultraviolet scattering effect. The fine titanium dioxide particles preferably have an average primary particle diameter of 1 to 100nm, and the fine zinc oxide particles preferably have an average primary particle diameter of 1 to 100 nm. However, the present invention is not limited thereto.
The method of the organosilication treatment is not particularly limited, and the treatment can be performed by a known method. Examples thereof include treatments using silicones such as methylhydrogenpolysiloxane, a methylhydrogenpolysiloxane/dimethylpolysiloxane copolymer, and dimethylpolysiloxane; treatment with a silane compound such as octyltriethoxysilane or hexyltrimethoxysilane is used.
Particularly preferred organosilication treatments include polydimethylsiloxane treatment, hydrogenated polydimethylsiloxane treatment, and octylethoxysilane treatment.
The amount of the organosilicon-treated powder is 10 to 35% by mass, preferably 15 to 30% by mass, based on the composition of the present invention. If the blending amount is less than 10% by mass, the effect of the organosilicon-treated powder such as water resistance is not sufficiently obtained, while if it exceeds 35% by mass, deterioration of usability such as a smell and a rough feeling with time may be concerned.
The organic silicon treatment agent is not particularly limited, and conventionally known organic silicon treatment agents can be used. Among these, preferred are organosilicon compounds, and preferred are, for example, various silicone oils such as dimethylpolysiloxane (polydimethylsiloxane), methylphenylpolysiloxane, methylhydrogenpolysiloxane, various alkylsilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, various fluoroalkylsilanes such as trifluoromethylethyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and the like. These may be used alone or in combination of two or more.
[ polyglycerol-modified Silicone dispersant ]
In the present invention, as the dispersant for the silicone-treated powder, a polyglycerol-modified silicone dispersant needs to be used.
The polyglycerol-modified silicone dispersant is preferably a polyglycerol skeleton having a polyglycerol chain at its main skeleton and silicone chains at both ends. The both-terminal silicone polyglycerin has almost no ability as a so-called emulsifier to form a water-in-oil composition, but in the present invention, the silicone treated powder exhibits excellent ability when dispersed in an oil phase.
More specifically, those having the following structures are preferably used.
Figure BDA0003525714430000061
m is 30 to 100, preferably 50 to 70 (average of 60 for the substances used in the test examples)
n is 1 to 5, preferably 2 to 3 (average of 3 for the substances used in the test examples)
In the present invention, the amount of the polyglycerol-modified silicone dispersant is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, based on the amount of the silicone-treated powder blended.
In addition, when a dispersant other than the polyglycerol-modified silicone dispersant is compounded, it is preferably less than 0.5% by mass in the composition.
[ Water phase ]
In the present invention, the water phase constituting the inner phase is dispersed in the oil phase of the outer phase, and the presence of the inner water phase suppresses the sedimentation of the silicone-treated powder.
Examples of the component contained in the aqueous phase include water, alcohol, and water-soluble polymer.
Examples of the alcohols include lower alcohols such as ethanol and isopropanol, higher alcohols such as isostearyl alcohol, octyldodecanol and hexyldecanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, 1, 3-butanediol, dipropylene glycol and polybutylene glycol.
Examples of the water-soluble polymer include homopolymers and copolymers of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as "AMPS"). The copolymer is formed by the copolymer and comonomers such as vinyl pyrrolidone, acrylamide, sodium acrylate, hydroxyethyl acrylate and the like. That is, examples include AMPS homopolymer, vinylpyrrolidone/AMPS copolymer, dimethylacrylamide/AMPS copolymer, acrylamide/AMPS copolymer, sodium acrylate/AMPS copolymer, and the like.
Further examples include carboxyvinyl polymers, ammonium polyacrylate, sodium acrylate/alkyl acrylate/sodium methacrylate/alkyl methacrylate copolymers, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan gum, mucopolysaccharide sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, cutin sulfate, locust bean gum, succinyl polysaccharide, chitin, chitosan, carboxymethylchitin, agar and the like.
In the present invention, the aqueous phase has an effect of suppressing the coagulation/sedimentation of the organosilicated powder in the composition, and the amount thereof is 10 to 35% by mass, preferably 20 to 30% by mass in the composition.
[ emulsifiers ]
In the present invention, as the water-in-oil emulsifier for dispersing the aqueous phase in the oil phase, an emulsifier having a low HLB is exemplified, but it is particularly preferable to use a polyether-modified silicone in which a polyoxyethylene group is bonded in a pendant group to the siloxane skeleton.
Figure BDA0003525714430000071
p=30~50
q=1~3
r=2~4
a=3~12
b=7~13
Figure BDA0003525714430000072
Polyether modification rate: about 20% by weight
The amount of the water-in-oil emulsifier to be blended in the composition of the present invention is preferably 0.5 to 7% by mass, and more preferably 2 to 5% by mass.
In the water-in-oil composition of the present invention, in addition to the essential components described above, components used in general skin external preparations such as cosmetics and medicines, for example, whitening agents, moisturizers, antioxidants, oily components, other ultraviolet absorbers, surfactants, thickeners, alcohols, powder components, colorants, aqueous components, water, various skin nutrients, and the like can be appropriately blended as necessary, and the water-in-oil composition can be produced by a conventional method.
The water-in-oil composition of the present invention can be prepared by a conventional method used for the production of a water-in-oil emulsion composition. For example, a method of uniformly dissolving the oil phase by heating it appropriately, dispersing the silicone-treated powder in the oil phase by a homomixer, and emulsifying the silicone-treated powder by a homomixer while slowly adding a separately prepared aqueous phase to the oil phase.
Hereinafter, the production method and the evaluation method will be described before the description of the specific embodiments.
[ production method ]
After dispersing the powder in the oil component mixed by the homomixer, the well-mixed aqueous component was added to obtain a composition.
[ evaluation method ]
At 2mg/cm on a PMMA plate simulating skin (SPFMASTER-PA01)2The coating film was formed by dropping the amount of (A) and applying the coating film for 60 seconds with a finger and drying the coating film for 15 minutes. The absorbance (400 to 280nm) of the coating film was measured using a model U-3500 self-recording spectrophotometer, manufactured by Hitachi, K.K., using an uncoated plate as a control, and the integrated value of absorbance and the absorbance at 300nm were determined from the obtained measurement data. Further, a uniform film having a thickness of 10 to 50 μm was produced, and the transparency of the sample having the same film thickness was visually confirmed.
Further, the transparency was evaluated by the following criteria.
A: is extremely transparent
B: is transparent
C: although transparent, has a little white color
D: less transparent and white
Hereinafter, specific embodiments of the present invention will be described.
First, the present inventors have studied the dispersibility of a hydrophobized powder when the hydrophobized powder is mixed in a water-in-oil composition.
The results are shown in table 1.
TABLE 1(A)
Figure BDA0003525714430000091
TABLE 1(B)
Figure BDA0003525714430000101
As is clear from comparison of test examples 1-1 to 1-3 in Table 1, the formation of aggregates was hardly confirmed in test examples 1-1 and 1-2 in which the silicone treatment (the coating treatment with hydrogenated polydimethylsiloxane) was performed, and the transparency of the composition was high, but the transparency was lowered in test example 1-3 in which the stearic acid treatment was performed, and the aggregation of the powder was confirmed. Similarly, when test examples 1-4 to 1-6 were compared, it was found that, if no aggregate was formed in the hydrogenated polydimethylsiloxane coating (test example 1-4), and if triethoxyoctylsilane coating (test example 1-5) and dextrin palmitate coating (test example 1-6), aggregate was formed, and transparency was reduced.
Based on the above results, in the present invention, the hydrophobization treatment needs to be a silicone treatment.
Next, the present inventors studied the mass ratio of silicone-treated powder/total powder.
As shown in test examples 1-7 to 1-9 in Table 1(B), when the organosilicon-treated powder/total powder was less than 0.7, a decrease in transparency was observed. Therefore, the silicone-treated powder/total powder is preferably 0.7 or more.
The present inventors have also studied the mass ratio of the silicone oil in the oil phase. The results are shown in table 2.
TABLE 2
Figure BDA0003525714430000111
As is clear from table 2, basically, the oil phase of the present invention is preferably a silicone oil, but when other oil components (diisopropyl sebacate) are included, the mass ratio of the silicone oil is preferably 0.65 or more, preferably 0.75 or more.
The present inventors have further studied a dispersant for dispersing the silicone-treated powder in the oil phase. The results are shown in table 3.
TABLE 3
Figure BDA0003525714430000121
As is clear from table 3 above, it is particularly preferable to use a polyglycerin-modified silicone dispersant, and a sufficient dispersing effect cannot be obtained with a general dispersant such as isostearic acid.
The present inventors have studied the water-in-oil composition for water phase ratio. The results are shown in table 4.
TABLE 4
Figure BDA0003525714430000131
The redispersibility of the powder was evaluated as follows.
C: can not redisperse even if vibrated for a plurality of times
B: redispersion if vibrated several times
A: redispersing if vibrated 1, 2 times
As is clear from table 4, agglomeration of the powder occurred if the aqueous phase in the composition was less than 20 mass%. Therefore, the water phase of the water-in-oil composition of the present invention is preferably 20% by mass or more.

Claims (9)

1. A water-in-oil composition comprising:
an oil phase having a silicone oil/oil phase mass ratio of 0.65 or more;
an organosilicon-treated powder dispersed in the oil phase and treated with an organosilicon surface-treating agent;
a polyglycerol-modified silicone dispersant for dispersing the silicone-treated powder in an oil phase;
an aqueous phase dispersed in the oil phase; and
an emulsifier for dispersing the aqueous phase in the oil phase,
the mass ratio of the organosilicon processing powder to the total powder is more than 0.7.
2. A water-in-oil composition according to claim 1,
the water phase is 20 to 35% by mass in the composition,
the oil phase is 20 to 40% by mass of the composition,
in addition, the content of the organosilicon-treated ultraviolet scattering powder in the composition is 10-35% by mass.
3. A water-in-oil composition according to claim 1 or 2,
the average emulsified particle size of the aqueous phase is 10 μm or less.
4. A water-in-oil composition according to any of claims 1 to 3,
further comprising an organically modified clay mineral.
5. A water-in-oil composition according to any of claims 1 to 4,
the surface treating agent of the organosilicon treating powder is any one of a polydimethylsiloxane treating agent, a hydrogenated polydimethylsiloxane treating agent and an octyl ethoxy silane treating agent.
6. A water-in-oil composition according to any of claims 1 to 5, wherein the emulsifier is a polyether modified silicone emulsifier.
7. The water-in-oil composition according to any one of claims 1 to 6, wherein the dispersant other than the polyglycerol-modified silicone dispersant is less than 0.5% by mass in the composition.
8. A water-in-oil composition according to any of claims 1 to 7, wherein the cyclic siloxane is present in the composition in an amount of less than 10% by mass.
9. The water-in-oil composition according to any one of claims 1 to 8, wherein the polyglycerin-modified silicone is dibutyl dimethicone polyglycerin-3.
CN202080061383.7A 2019-09-05 2020-08-28 Water-in-oil composition Pending CN114340583A (en)

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Publication number Priority date Publication date Assignee Title
JP2007161650A (en) * 2005-12-14 2007-06-28 Shiseido Co Ltd Water-in-oil type emulsified cosmetic
WO2011055761A1 (en) * 2009-11-06 2011-05-12 花王株式会社 Oil-in-water-type emulsion cosmetic
JP2012246446A (en) * 2011-05-30 2012-12-13 Dow Corning Toray Co Ltd Novel liquid organopolysiloxane and use of the same
JP2013010935A (en) * 2011-05-30 2013-01-17 Dow Corning Toray Co Ltd Organopolysiloxane elastomer modified with mono-/diglycerin derivative, and use therefor
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