CN1894312A - Surface-coated powder and cosmetic containing said powder - Google Patents
Surface-coated powder and cosmetic containing said powder Download PDFInfo
- Publication number
- CN1894312A CN1894312A CNA200480037230XA CN200480037230A CN1894312A CN 1894312 A CN1894312 A CN 1894312A CN A200480037230X A CNA200480037230X A CN A200480037230XA CN 200480037230 A CN200480037230 A CN 200480037230A CN 1894312 A CN1894312 A CN 1894312A
- Authority
- CN
- China
- Prior art keywords
- powder
- hybrid
- organopolysiloxane
- metal oxide
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/58—Metal-containing linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
Abstract
A surface-coated powder which comprises a powder coated with a metal oxide-organopolysiloxane hybrid wherein an organopolysiloxane and a metal oxide form a composite at a molecular level. The surface-coated powder is prepared by coating a powder with a metal oxide-organopolysiloxane hybrid sol, to thereby form a thin film of the above hybrid on the surface of the powder. The metal oxide of the above metal oxide-organopolysiloxane hybrid is preferably one or more of metal oxides selected from among a titanium oxide, a zirconium oxide and silicon dioxide. The above metal oxide-organopolysiloxane hybrid can have a controlled water repellency by the adjustment of the proportion of the metal oxide to the organopolysiloxane, and thus the water repellency of the powder can be controlled with ease by the adjustment of the above proportion. In addition, a cosmetic containing the above surface-coated powder is excellent in natural appearance and in the feeling during the practice of application.
Description
Technical field
The present invention relates to the surface coated powder of a kind of process.More specifically, relate to metal oxide-organopolysiloxane hybrid and carry out surface coated powder.In addition, also relate to the used for cosmetic powder of making by this powder, and the makeup that contain this used for cosmetic powder.
Background technology
For the persistence that improves dressing, improve the sense of touch when smearing makeup, being used for the powder of makeup general is that surface coating is carried out in the hydrophobic surface treatments agent such as fluorine-containing material of representative in order to silicone, metallic soap, perfluoralkyl phosphate all.
And if the powder hydrophobicity that should the surface coats after handling is low, then dressing persistence can not get improving.Otherwise if hydrophobicity is too high, then with the affinity variation of skin, the result causes dressing persistence variation, make up that it is dirty to come off.So hydrophobic adjustment is extremely important.Though can adjust the hydrophobicity of this powder by changing treatment capacity that powder surface coats the hydrophobic surface treatments agent when handling, if treatment capacity very little powder surface can not be coated fully, also can cause streaking or aggegation.Even and under the situation that has increased treatment capacity, if the treatment capacity redundance that then can not be coated on the powder surface too much will separate out, so also exist the problem that can not manifest with the corresponding hydrophobicity of treatment capacity.And no matter treatment capacity is still too many very little, and sense of touch all can variation.That is have problems when, adjusting the hydrophobicity degree of powder by the treatment capacity that changes the hydrophobic surface treatments agent.
As the hydrophobic surface treatments agent of powder, consider that from aspects such as the difference of structure, the easy degree of obtaining, functional, securities general the most frequently used is the silicone or derivatives thereof.The applicant had before developed by a part of Siliciumatom of organopolysiloxane and had formed metal oxide-organopolysiloxane hybrid (TOHKEMY 2001-64395 number) that covalent linkage and homogeneous are composited by oxygen and atoms metal.This powder can directly be mixed in the makeup.
Summary of the invention
The inventor etc. think, when utilizing surface treatment to control the hydrophobicity of powder surface, do not carry out at the covering amount of powder surface by the agent of control hydrophobic surface treatments, and are preferably undertaken by the hydrophobicity of control hydrophobic surface treatments agent itself.
And the inventor etc. notice that metal oxide-organopolysiloxane hybrid is the hybrid of hydrophilic metal oxide and hydrophobic organopolysiloxane.That is, noticed by the ratio that changes metal oxide and organopolysiloxane and can adjust the hydrophobicity of hybrid, and expected that this hybrid is used for the powder surface treatment agent comes control surface to handle the hydrophobicity of powder, thereby finished the present invention.
That is, the present invention relates to coat by metal oxide and organopolysiloxane and carry out compound metal oxide-organopolysiloxane hybrid and the surface-coated powder that obtains at molecular level at powder surface.Metal oxide in above-mentioned metal oxide-organopolysiloxane hybrid is preferably the metal oxide that one or more are selected from titanium dioxide, zirconium white and silicon-dioxide.In addition, the organopolysiloxane in above-mentioned metal oxide-organopolysiloxane hybrid is preferably the residue of following general formula (1) expression.
[in the formula, R is alkyl, the aryl or aralkyl of carbonatoms 1～22, can be the same or different separately.Y is-R ,-O-or-R
1-Si (O-)
3Shown in group (R wherein
1Alkylidene group for carbonatoms 1～5), can be the same or different, but have at least a Y for-O-or-R
1-Si (O-)
3In addition, n=1～100, m=0～5.]
In addition, the present invention relates to a kind of preparation method of surface-coated powder, it is characterized in that: make end or side chain have the partial hydrolystate reaction of the organopolysiloxane and the metal alkoxide of active function groups, with the hybrid colloidal sol that obtains thus powder is carried out the surface and coat processing, dry then.The preferred following general formula (2) of this organopolysiloxane:
[in the formula, R is alkyl, the aryl or aralkyl of carbonatoms 1～22, can be the same or different separately.X is-H ,-R or-R
1-Si (OR
2-)
3Shown in group (R wherein
1Be the alkylidene group of carbonatoms 1～5, R
2Alkyl for hydrogen or carbonatoms 1～5), can be the same or different, but have at least an X for-H or-R
1-Si (OR
2)
3In addition, n=1～100, m=0～5.]
In addition, the present invention relates to the used for cosmetic powder made through surface coated powder by above-mentioned and the makeup that contain this used for cosmetic powder.
The accompanying drawing summary
Fig. 1 represents the relation that is subjected to firing angle (acceptance angle) and brightness (Y) through surface coated titanium dioxide and untreated titanium dioxide of the present invention.
The best mode that carries out an invention
In the surface-coated powder of the present invention, the metal oxide-organopolysiloxane hybrid that is coated on powder surface is the product that compoundization taken place at molecular level by organopolysiloxane and metal oxide." in compoundization of molecular level " is meant herein, and organopolysiloxane and metal oxide this two-phase mutually mix at nano level.This hybrid has following character: because organopolysiloxane and metal oxide area size mutually be below visible wavelength (400nm), so can not confirm organopolysiloxane and metal oxide this two-phase mutually with opticmicroscope.In addition, at organopolysiloxane and metal oxide mutually at the interface, the covalent linkage that exists the Siliciumatom by a part of atoms metal and organopolysiloxane to form by oxygen.Owing to have such covalent linkage, just obtained the hybrid of metal oxide and compoundization of organopolysiloxane homogeneous.
Among the present invention, this metal oxide-organopolysiloxane hybrid is coated on powder surface with the state of precursor colloidal sol.And generated metal oxide-organopolysiloxane hybrid at powder surface.
In above-mentioned metal oxide-organopolysiloxane hybrid, titanium, zirconium, aluminium etc. can be listed, silicon can also be used with the metal of the metal oxide of organopolysiloxane generation hydridization.The oxide compound of these metals can be used alone, can also be 2 or more kinds in combination respectively.Preferred titanium dioxide, zirconium white in the metal oxide, preferred especially titanium dioxide.These metal oxides, as described below, preferably with metal alkoxide (compound that obtains with the hydrogen in the metal replacement alcohols hydroxyls such as titanium) as raw material.Metallic transition becomes metal oxide in the hydridization process.Alkoxide can list methylate, ethylate, propylate, butanolate, isopropoxide etc.
In addition, be used for the organopolysiloxane with metal oxide generation hydridization, get final product, there is no particular determination in addition so long as its end or side chain have the organopolysiloxane (being called active organopolysiloxane among the present invention) of active function groups.Active function groups such as alkoxyl group, silanol group, carboxyl, amino, epoxy group(ing) etc., the organopolysiloxane that preferably contains the organopolysiloxane of alkoxyl group and contain silanol group (herein, these contain the organopolysiloxane of alkoxyl group or silanol group, abbreviate as sometimes to contain the alkoxyl group organopolysiloxane, contain the silanol group organopolysiloxane).
Above-mentioned alkoxyl group is methoxyl group, propoxy-, butoxy, isopropoxy etc.The preferred especially organopolysiloxane derivative that uses the alkoxyl group that contains following general formula (2) expression.
[in the formula, R is alkyl, the aryl or aralkyl of carbonatoms 1～22, can be the same or different separately.X is-H ,-R or-R
1-Si (OR
2)
3Shown in group (R wherein
1Be the alkylidene group of carbonatoms 1～5, R
2Alkyl for hydrogen or carbonatoms 1～5), can be the same or different, but have at least an X be-H or-R
1-Si (OR
2)
3n＝1～100，m＝0～5。]
The alkyl of above-mentioned R is methyl, ethyl, propyl group etc., especially preferably uses methyl compound.In addition, the aryl of above-mentioned R is phenyl, tolyl etc., and aralkyl is a styroyl etc.These organopolysiloxane derivatives can be enumerated as general formula (the 3) (R in the general formula (3)
1, R
2, n is identical with the definition in the general formula (2)).Specifically can list the compound of following formula (4), (5) expression.
The preparation method of surface-coated powder of the present invention below is described.Among the present invention, metal oxide-organopolysiloxane hybrid is coated on powder surface with the state of its precursor colloidal sol, and forms final metal oxide-organopolysiloxane hybrid at powder surface.Select titanium dioxide for use with metal oxide wherein, as its raw material, active organopolysiloxane uses the situation that contains the alkoxyl group polydimethylsiloxane to describe as example with the alkoxide of titanium.
In the alkoxide of titanium, drip water, organic solvent, sour three's mixed solution, make its partial hydrolysis, generate TiO 2 sol.This moment, the preferred mixed solution that slowly drips was to obtain transparent colloidal sol.In this TiO 2 sol, add and contain the alkoxyl group polydimethylsiloxanederivative derivative, generation hybrid colloidal sol.Do not finish fully at this stage hydrolytic polymerization.The surface that this hybrid colloidal sol is used for powder coats.
This hybrid colloidal sol has the character that forms transparent film.This hybrid colloidal sol is coated on powder surface,, can obtains carrying out surface coated surface-coated powder through metal titanium dioxide-polydimethylsiloxane hybrid at the further hydrolytic polymerization of powder surface by hybrid colloidal sol.
Among the present invention, hybrid colloidal sol is coated on powder surface, and can exemplifies following method: with the method for hybrid colloidal sol and powder mixes after drying in the method for powder surface formation metal titanium dioxide-polydimethylsiloxane hybrid; With the molten method that is sprayed to after drying on the powder surface of hybrid; With hybrid colloidal sol and powder mixes, add alkaline reagentss such as ammoniacal liquor afterwards hybrid is separated out at powder surface, then exsiccant method etc.
The hybrid film that uses hybrid colloidal sol to form is a kind of even overlay film of transparent and tool flexibility.Change the proportion of composing of titanium dioxide and polydimethylsiloxane, can control the hydrophobicity and the specific refractory power of this hybrid film.In addition, polymerization generates titanium dioxide if the alkoxide of titanium is hydrolyzed separately, is difficult to form clear films usually.On the other hand,, also just only obtain high molecular, can not form firm overlay film even contain the polymerization that is hydrolyzed separately of alkoxyl group organopolysiloxane.
Carry out surface coated powder with metal oxide-organopolysiloxane hybrid among the present invention, so long as the powder of using always in the makeup, except that particle structures such as shapes such as tabular, spindle shape, needle-like and particle diameter, porous, atresia, do not have particular determination, can list inorganic powder class, light powdery type, organic dust class, pigment powdery type, composite powder class etc.Specifically can list inorganic powder classes such as dark blue, ultramarine, red iron oxide, iron oxide yellow, iron oxide black, titanium dioxide, zinc oxide, aluminum oxide, cerium oxide, silicon-dioxide, magnesium oxide, zirconium white, magnesiumcarbonate, lime carbonate, chromic oxide, chromium hydroxide, carbon black, magnesium aluminum silicate, mica, synthetic mica, synthetic sericite, sericite, talcum, kaolin, silicon carbide, barium sulfate, bentonite, montmorillonite, boron nitride; Pearl white, mica titanium, iron oxide encapsulated mica, ferric oxide mica titanium, pigment dyestuff are handled light powdery type such as mica titanium, aluminium powder; Organic dust classes such as Magnesium Stearate, Zinic stearas, N-acyl-lysine, nylon; The pigment powdery type such as pigment lake of organic tar class pigment, organic pigment; Coated by titanium dioxide mica titanium particulate, zinc oxide coat mica titanium particulate, barium sulfate coating mica titanium, contain the silicon-dioxide of titanium dioxide, contain the composite powders such as silicon-dioxide of zinc oxide etc.These powder can be used alone, and also can be used in combination of two or more.In addition, can also use one or more materials that are composited in these powder.
Among the present invention, metal oxide-organopolysiloxane hybrid not being had particular determination with respect to the amount of powder, is 1～99 quality % (following brief note is " % ") with respect to powder preferably, more preferably more than 3%.
Surface-coated powder of the present invention can be used as powder and is used for coating, printing ink, makeup etc.Especially be suitable for and make the cosmetic powder.
Estimate its hydrophobicity with surface-coated powder of the present invention for the easy wetness degree of the mixing solutions of water and organic solvent 2-propyl alcohol.Add powder in mixed solution, powder swims on the liquid level when nonwetting, increases the 2-propyl alcohol with respect to the then final powder sedimentation of the ratio of water.The 2-propyl alcohol of this moment is defined as the hydrophobization degree with respect to the volume ratio of water.For example, with respect to 25ml water, when the amount of 2-propyl alcohol was 10ml, the hydrophobization degree was 0.4.The hydrophobization degree is big more, and the hydrophobicity of powder is high more.When surface-coated powder was used for makeup, the hydrophobization degree was too low, then can be wetting by sweat, and dressing persistence variation.On the other hand, hydrophobization Du Taigao, because of with the affinity variation of skin, the dressing persistence is variation also.Particularly, the value of hydrophobization degree is preferably more than 0.6 but less than 1.2.
When exploitation was used for the powder of foundation cream etc. of makeup, the natural look when realizing coating was generally all controlled the optical characteristics of powder.Particularly, for example, the ratio of the surface reflection during by minimizing light incident powder increases scattered light, can eliminate factitious gloss when being coated with, and can cover the shortcoming of skin.Coat different silicon-dioxide of specific refractory power and titanium dioxide etc. at powder surface, can increase scattered light relatively.But when the mixture that forms with these inorganic oxides, directly use then has hard sensation, for further hydrophobic property must carry out surface treatment.At above situation, among the present invention, with metal oxide-organopolysiloxane hybrid cladding powder,, utilize the transparent metal oxide-organopolysiloxane hybrid layer that forms at powder surface can increase scattered light in flexibility of giving sense of touch and appropriate hydrophobic while.
Below describe with regard to the makeup that mixed surface-coated powder of the present invention.Carry out surface coated surface-coated powder of the present invention by mixing with metal oxide-organopolysiloxane hybrid, can make the makeup that dressing persistence and usability are good, dressing effect is natural.The formulation of makeup mainly contains cosmetics such as foundation cream, white powder, also can be used for skin protection cosmeticss such as sun care preparations, emulsion, astringent, hair cosmetic etc.Combined amount to surface-coated powder is not particularly limited, more than the preferred 0.1 quality %.
And, in makeup of the present invention, for composition commonly used in keeping formulation and other all purposes, can in the scope that does not influence effect of the present invention, make applying some make up.For example, can suitably mix the oiliness composition to give lubricated sense, mix powder such as organic dust, inorganic powder, pigment to give coloring effect and powder sense, water compositions such as mixing water soluble macromolecular, alcohols, water can suitably mix overlay films such as adjusting powder disperses, the tensio-active agent of sense of touch, polymer emulsion and form agent, UV light absorber, wetting Agent for Printing Inks, antioxidant, beauty treatment composition, pH regulator agent, defoamer, anti-fading agent, sanitas, spices etc. to reach various effects to give moisture feeling.
Below enumerate embodiment the present invention is described, but the present invention is not limited to these embodiment.
The preparation example 1. of hybrid colloidal sol
Get 1mol tetraisopropoxy titanium (with the pure medicine system of light) in glass beaker, when stirring, drip the mixed solution of 1mol water, 0.06mol hydrochloric acid, 400ml Virahol with the speed of about 2mL/min with magnetic stirring apparatus, transparent TiO 2 sol.Drip to finish, add the mixed solution that alkoxyl group polydimethylsiloxane and 200ml Virahol are formed that contains at once, obtain titanium dioxide-polydimethylsiloxane hybrid colloidal sol by the above-mentioned chemical formula of 0.2mol (4) expression.Tetraisopropoxy titanium is mol ratio 5: 1 with the feed ratio that contains the alkoxyl group polydimethylsiloxane, and the colloidal sol that just this example is made later is called 5/1 hybrid colloidal sol.
The preparation example 2. of hybrid colloidal sol
Get 1mol tetraisopropoxy titanium (with the pure medicine system of light) in glass beaker, with in the magnetic stirrer, the mixed solution with the speed dropping 1mol water of about 2mL/min, 0.06mol hydrochloric acid, 400ml Virahol obtains transparent TiO 2 sol.Drip to finish, add the mixed solution that alkoxyl group polydimethylsiloxane and 100ml Virahol are formed that contains at once, make titanium dioxide-polydimethylsiloxane hybrid colloidal sol by the above-mentioned chemical formula of 0.1mol (4) expression.Tetraisopropoxy titanium is mol ratio 10: 1 with the feed ratio that contains the alkoxyl group polydimethylsiloxane, and the colloidal sol that just this example is made later is called 10/1 hybrid colloidal sol.
Embodiment 1.
In 100 parts of titanium dioxide (rutile-type, special grade chemical, Northeast chemistry system), add 5/1 hybrid colloidal sol of 20 parts of preparation examples 1, mix, add Virahol again to forming pulpous state.Consider the Virahol in the hybrid colloidal sol and the alkoxyl group of disengaging, the solids component amount that makes the titanium dioxide/polydimethylsiloxane hybrid that is coated on powder surface is about 5% quality with respect to resultant (powder after promptly handling, down with).With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is made 5/1 hybrid cladding titanium dioxide.
Embodiment 2.
In 100 parts of titanium dioxide (rutile-type, special grade chemical, Northeast chemistry system), add 10/1 hybrid colloidal sol of 25 parts of preparation examples 2, mix, add Virahol again to forming pulpous state.Consider the Virahol in the hybrid colloidal sol and the alkoxyl group of disengaging, making the solids component amount of the titanium dioxide/polydimethylsiloxane hybrid that is coated on powder surface is about 5% quality with respect to resultant.With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is made 10/1 hybrid cladding titanium dioxide.
Comparative example 1.
In 100 parts of titanium dioxide (rutile-type, special grade chemical, Northeast chemistry system), the alkoxyl group polydimethylsiloxane that contains of 4 parts of above-mentioned chemical formulas (4) is mixed with isopropanol, continue to add Virahol to forming pulpous state.With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is made the silicone cladding titanium dioxide.
Comparative example 2.
In 98.2 parts of titanium dioxide (rutile-type, special grade chemical, Northeast chemistry system), 0.8 part of methyl hydrogen polydimethylsiloxane is mixed with isopropanol, continue to add Virahol to forming pulpous state.With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is made 0.8% methyl hydrogen polydimethylsiloxane cladding titanium dioxide.
Comparative example 3.
In 100 parts of titanium dioxide (rutile-type, special grade chemical, Northeast chemistry system), 4 parts of methyl hydrogen polydimethylsiloxanes are mixed with isopropanol, continue to add Virahol to forming pulpous state.With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is made 3.8% methyl hydrogen polydimethylsiloxane cladding titanium dioxide.
[hydrophobicity test]
Estimate the hydrophobicity of embodiment 1,2 and comparative example 1～3.Hydrophobic evaluation is carried out by the following method.
Get 25ml water and 0.05g working sample in the 100ml beaker, under magnetic stirrer, drip the 2-propyl alcohol with drop-burette.Reading the sample that floats on liquid level under the whipped state becomes by visual titer can not confirm the time.The result is summarized as follows table 1.Hydrophobization degree in the table is meant the titer of 2-propyl alcohol and the capacity ratio of water.The hydrophobization degree is high more, shows that hydrophobicity is strong more.
Table 1
| The hydrophobization degree | Less than 0.6 | 0.6 above but less than 0.8 | 0.8 above but less than 1.0 |
| Working sample | Comparative example 1 | Embodiment 1 | |
| The hydrophobization degree | 1.0 above but less than 1.2 | 1.2 above but less than 1.6 | 1.6 more than |
| Working sample | Embodiment 2, comparative example 2 | Comparative example 3 | |
From the result of embodiment 1,2 as can be known, by changing starting raw material than (tetraisopropoxy titanium and the feed ratio that contains the alkoxyl group polydimethylsiloxane), even adopt same treatment capacity also can control hydrophobicity.From the result of comparative example 1 as can be known, only, can not show sufficient hydrophobicity with the raw material of hybrid-contain the alkoxyl group polydimethylsiloxane.
Use the angle colour-difference meter to estimate embodiment 1,2 and coat and handle preceding titanium dioxide.On the bonding plane of translucent adhesive tape (Sumitomo 3M system), be coated with assess sample with brush, use angle colour-difference meter (the many spectroginiophotometers of techworld society system) to measure.Input angle is decided to be-5 °, is subjected to firing angle in 5 °～80 ° scope (Fig. 1).From the brightness (Y) of this moment and the graph of a relation that is subjected to firing angle as can be known, the titanium dioxide after the coating of embodiment 1,2 is handled is compared with undressed titanium dioxide, and low angle one side brightness descends, and the brightness of high angle one side is risen relatively.The corresponding specular reflection light of low angle one side, the corresponding scattered light of high angle one side can confirm that thus scattering of light can be risen after hybrid colloidal sol coats.
Embodiment 3,4
Preparation has mixed the powder foundation cream of the foregoing description 1,2 and comparative example 1～3, shown in their table composed as follows, carry out use test from " ductility ", " adherence sense ", " dressing persistence ", " outward appearance of nature " four aspects by 40 specialized review persons.According to being judged to be good number, estimate by following standard.Evaluation result is summed up as table 2.
[evaluation]
◎: more than 35
Zero: 25～34
△: 15～24
*: 15 of less thaies
Table 2
| The composition name | Embodiment | Comparative example | ||||
| 3 | 4 | 4 | 5 | 6 | ||
| 1 | 5/1 hybrid cladding titanium dioxide (embodiment 1) | 15 | - | - | - | - |
| 2 | 10/1 hybrid cladding titanium dioxide (embodiment 2) | - | 15 | - | - | - |
| 3 | Contain alkoxyl group polydimethylsiloxane cladding titanium dioxide (reference examples 1) | - | - | 15 | - | - |
| 4 | Methylhydrogenpolysi,oxane cladding titanium dioxide (reference examples 2) | - | - | - | 15 | - |
| 5 | Methylhydrogenpolysi,oxane cladding titanium dioxide (reference examples 3) | - | - | - | - | 15 |
| 6 | | 10 | 10 | 10 | 10 | 10 |
| 7 | | 5 | 5 | 5 | 5 | 5 |
| 8 | | 5 | 5 | 5 | 5 | 5 |
| 9 | Zinc oxide | 10 | 10 | 10 | 10 | 10 |
| 10 | Tinting pigment | 8 | 8 | 8 | 8 | 8 |
| 11 | Sericite | Surplus | Surplus | Surplus | Surplus | Surplus |
| 12 | | 5 | 5 | 5 | 5 | 5 |
| 13 | Vaseline | 4 | 4 | 4 | 4 | 4 |
| 14 | Silicone oil | 3 | 3 | 3 | 3 | 3 |
| 15 | Sanitas | In right amount | In right amount | In right amount | In right amount | In right amount |
| 16 | Spices | In right amount | In right amount | In right amount | In right amount | In right amount |
| (assessment item) ductility | ◎ | ◎ | △ | △ | ○ | |
| The adherence sense | ○ | ◎ | ○ | △ | × | |
| The woman's persona situation of taking off that takes place in time | ◎ | ◎ | △ | △ | × | |
| Natural look | ◎ | ◎ | △ | × | △ | |
(preparation method)
A: composition 1～11 is mixed, disperses.
B: composition 12～16 is mixed.
C: in A, add B, mix, pulverize and obtain the powder foundation cream.
From the table the result as can be known, example 3,4 of the present invention has all been obtained good result on all items.
In 100 parts of iron oxide yellow, add 5/1 hybrid colloidal sol of 20 parts of preparation examples 1, mix, add Virahol again to forming pulpous state.Consider the Virahol in the hybrid colloidal sol and the alkoxyl group of disengaging, making the solids component amount of the titanium dioxide/polydimethylsiloxane hybrid that is coated on powder surface is about 5% quality with respect to resultant.With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is got 5/1 hybrid coated iron oxide Huang.The same operation makes red, the iron oxide black of 5/1 hybrid coated iron oxide.These that make 5/1 hybrid coated iron oxide, the color and luster clarification is compared at peer-level with the material of only handling with the silicone coating.The hydrophobization degree is all more than 0.6, in the scope of less than 0.8.
Embodiment 6.
In 100 parts of iron oxide yellow, add 10/1 hybrid colloidal sol of 25 parts of preparation examples 2, mix, add Virahol again to forming pulpous state.Consider the Virahol in the hybrid colloidal sol and the alkoxyl group of disengaging, making the solids component amount of the titanium dioxide/polydimethylsiloxane hybrid that is coated on powder surface is about 5% quality with respect to resultant.With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is got 10/1 hybrid coated iron oxide Huang.The same operation gets red, the iron oxide black of 10/1 hybrid coated iron oxide.These that make 10/1 hybrid coated iron oxide, the color and luster clarification is compared at peer-level with the material of only handling with the silicone coating.The hydrophobization degree is all more than 0.8, in the scope of less than 1.0.
Embodiment 7.
In 100 parts of sericites, add 5/1 hybrid colloidal sol of 20 parts of preparation examples 1, mix, add Virahol again to forming pulpous state.Consider the Virahol in the hybrid colloidal sol and the alkoxyl group of disengaging, making the solids component amount of the titanium dioxide/polydimethylsiloxane hybrid that is coated on powder surface is about 5% quality with respect to resultant.With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is made 5/1 hybrid and coat sericite.The same operation gets 5/1 hybrid coated talc powder, mica.The hydrophobization degree is all more than 0.6, in the scope of less than 0.8.
Embodiment 8.
In 100 parts of sericites, add 10/1 hybrid colloidal sol of 25 parts of preparation examples 2, mix, add Virahol again to forming pulpous state.Consider the Virahol in the hybrid colloidal sol and the alkoxyl group of disengaging, making the solids component amount of the titanium dioxide/polydimethylsiloxane hybrid that is coated on powder surface is about 5% quality with respect to resultant.With automatic mortar it is mixed on one side and pulverize, Yi Bian make the Virahol volatilization.It in 100 ℃ of crushed after being dried, is got 10/1 hybrid and coat sericite.The same operation makes 10/1 hybrid coated talc powder, mica.The hydrophobization degree is all more than 1.0, in the scope of less than 1.2.
Embodiment 9. powder foundation creams
(composition) (%)
1.5/1 hybrid cladding titanium dioxide (embodiment 1) 10.0
2.10/1 hybrid cladding titanium dioxide (embodiment 2) 10.0
3.10/1 hybrid coated talc powder (embodiment 8) 15.0
4.10/1 hybrid coats sericite (embodiment 8) surplus
5. spherical nylon powder 5.0
6. silicon-dioxide 5.0
7.10/1 hybrid coated iron oxide Yellow iron oxides is red
Iron oxide black (embodiment 6) 5.0
8. whiteruss 4.0
9. polyisobutene 2.0
10. three Unimac 5680s, two glyceryl ester 3.0
11. the beauty treatment composition is an amount of
12. spices is an amount of
(preparation method)
A: composition 1～7 is mixed.
B: with composition 8～10 heating for dissolving, to added ingredients 11 and 12 wherein.
C: add B in A, pulverize with impactor mixing back.
D: extrusion molding in metalware obtains the powder foundation cream.
Gained powder foundation cream ductility, good with the affinity of skin, the adherence sense of tool appropriateness, the dressing effect nature, the dressing persistence is good.
Embodiment 8. oiliness foundation creams
(composition) (%)
1.5/1 hybrid cladding titanium dioxide (embodiment 1) 8.0
2.10/1 hybrid cladding titanium dioxide (embodiment 2) 6.0
3. zinc oxide 10.0
4.5/1 hybrid coats sericite (embodiment 7) surplus
5.5/1 hybrid coats mica (embodiment 7) 10.0
6.5/1 hybrid coated iron oxide Yellow iron oxides is red
Iron oxide black embodiment 5) 7.0
7. squalane 15.0
8. carnauba wax 3.0
9. Microcrystalline Wax 5.0
10. methyl polysiloxane 10.0
11. decamethylcyclopentasiloxane 10.0
12. the beauty treatment composition is an amount of
13. spices is an amount of
(preparation method)
A: composition 1～6 is mixed.
B: with composition 7～10 90 ℃ of dissolvings, to added ingredients 11 wherein.
C: B is added among the A, mixing.
D: composition 12～13 is added among the C uniform mixing.
E:, obtain the oiliness foundation cream with D hot briquetting in metalware.
Gained oiliness foundation cream tool ductility and adherence sense, the dressing effect nature, the dressing persistence is good.
Embodiment 9. oil-in-water emulsify foundation creams
(composition) (%)
1.5/1 hybrid cladding titanium dioxide (embodiment 1) 5.0
2.10/1 hybrid cladding titanium dioxide (embodiment 2) 3.0
3.5/1 hybrid coats sericite (embodiment 7) 5.0
4.5/1 hybrid coated iron oxide Yellow iron oxides is red
Iron oxide black (embodiment 5) 4.0
5. the neopentyl glycol dicaprate 6.0
6. soybean lecithin 1.0
7. NOFABLE SO-992 2.0
8. the surplus of purifying waste water
9. propylene glycol 9.0
10. sanitas is an amount of
11. decamethylcyclopentasiloxane 20.0
12. squalane 5.0
13. polyalkyl acrylate powder 3.0
14. the beauty treatment composition is an amount of
15. spices is an amount of
(preparation method)
A: after composition 5～7 dissolvings, added ingredients 1～4, thorough mixing.
B: after the mixing of composition 11～15 usefulness homomixers, add A, dispersing and mixing.
C: add dissolving blended composition 8～10 in addition in B, emulsification mixes.
D: after C deaeration processing, promptly get the water-in-oil-type foundation cream.
Gained water-in-oil-type foundation cream, tool ductility and adherence sense, the dressing effect nature, the dressing persistence is good.
(composition) (%)
1.10/1 hybrid coats sericite (embodiment 8) 35.0
2.10/1 hybrid coated talc powder (embodiment 8) surplus
3.10/1 hybrid cladding titanium dioxide (embodiment 2) 5.0
4.10/1 hybrid coated iron oxide Yellow iron oxides is red
Iron oxide black (embodiment 6) 10.0
5. red iron oxide coats mica titanium 10.0
6. the spherical polystyrol powder 5.0
7. the atresia spherical silicon dioxide 5.0
8. oxysuccinic acid two isostearoyl esters 4.0
9. squalane 4.0
10. three Unimac 5680s, two glyceryl ester 4.0
11. the beauty treatment composition is an amount of
12. spices is an amount of
(preparation method)
A: composition 1～7 is mixed.
B: with composition 8～10 heating for dissolving, to added ingredients 11 and 12 wherein.
C: add B in A, pulverize with impactor mixing back.
D: extrusion molding in metalware obtains eye shadow cream.
The gained eye shadow cream develops the color, and is good with the affinity of skin, tool appropriateness adherence sense, and the dressing persistence is good.
Embodiment 11. mascara
(composition) (%)
1. carnauba wax 4.0
2. beeswax 4.0
3. pentaerythritol abietate 2.0
4. behenyl alcohol 1.5
5. sucrose fatty ester 1.5
6. NOFABLE SO-992 2.0
7. polyoxyethylene sorbitan monooleate (20E.0.) 1.0
8.5/1 hybrid cladding titanium dioxide (embodiment 1) 2.0
9. contain perfluoroalkyl ester coated iron oxide black 8.0
10.5/1 hybrid coats mica (embodiment 7) 6.0
The surplus 11. purify waste water
12. sodium hydroxide 0.5
13.1,3-butyleneglycol 8.0
14. sanitas is an amount of
15. polyalkyl acrylate aqueous dispersions 30.0
16. nylon end 4.0
17. the beauty treatment composition is an amount of
18. spices is an amount of
(preparation method)
A: 100 ℃ of heating for dissolving, added ingredients 5～7 dissolves with composition 1～4.To wherein adding 8～10, the fully mixing powder that makes disperses, with temperature regulation to 75 ℃.
B: composition 11～17 is mixed, and dissolving is with temperature regulation to 75 ℃.
C: add B in A, emulsification mixes.Deaeration then, cooling, added ingredients 18 promptly gets mascara.
Gained mascara colour developing and good to the tack of eyelashes.
Embodiment 12. lipsticks
(composition) (%)
1. Microcrystalline Wax 10.0
2. ceresin 5.0
3. the polyethylene polypropylene copolymer 5.0
4. liquid lanolin 7.0
5. Vaseline 5.0
6. the isocaprylic acid cetyl 10.0
7. whiteruss She measures
8. tinting pigment 10.0
9. mica titanium 10.0
10.5/1 hybrid cladding titanium dioxide (embodiment 1) 5.0
11. dyestuff 1.0
12. the beauty treatment composition is an amount of
13. spices is an amount of
(preparation method)
A: with composition 1～7 110 ℃ of heating for dissolving.
B: added ingredients 8～13 in A, 90 ℃ of dispersions, deaerations afterwards.
C: B is installed in the container, and cooling promptly gets lipstick.
Gained lipstick spreadability is good, suitable sliding, and usability is good.
Embodiment 13. sun care preparationss
(composition) (%)
1.5/1 hybrid cladding titanium dioxide (embodiment 1) 10.0
2.10/1 hybrid cladding titanium dioxide (embodiment 2) 10.0
3. decamethylcyclopentasiloxane 20.0
4. the neopentyl glycol dicaprate 5.0
5. p-methoxycinnamic acid 2-ethylhexyl 10.0
6.4-the tertiary butyl-4 '-methoxy dibenzoyl methane 5.0
7. polyoxyethylene methyl polysiloxane multipolymer 3.0
8. spices is an amount of
9. ethanol 5.0
10. the beauty treatment composition is an amount of
The surplus 11. purify waste water
(preparation method)
A: with composition 1～8 homomixer dispersing and mixing.
B: the mixed dissolution thing of added ingredients 9～11 in A, emulsification mixes, and promptly gets sun care preparations.
The gained sun care preparations has the effect of very strong antiultraviolet, but can't be white dazzling, use propertieies such as ductility are good.
The effect of invention
Surface-coated powder of the present invention, the hydrophobicity of its surface coated metal oxide-organopolysiloxane hybrid can be adjusted by the ratio that changes metal oxide and organopolysiloxane, by adjusting this hydrophobicity, even adhere to the hybrid of same amount at precursor powder, also can change the hydrophobicity of powder surface.
In addition, above-mentioned metal oxide-organopolysiloxane hybrid does not affect look and the flavor of precursor powder at the visible region highly transparent, and can form the controlled homogeneous overlay film of refractive index at powder surface, therefore can change the optical property of female powder.
And this metal oxide-organopolysiloxane hybrid has the flexibility from organopolysiloxane, can make the surface-coated powder with good use sense. Simultaneously, mixed the cosmetics of surface-coated powder of the present invention, sense of touch is good during coating, can reach the dressing effect of nature.
Claims (10)
1. surface-coated powder, it is coating by organopolysiloxane and metal oxide at powder surface and is carrying out compound metal oxide-organopolysiloxane hybrid at molecular level.
2. the described surface-coated powder of claim 1, it is characterized in that: the metal oxide of described metal oxide-organopolysiloxane hybrid is one or more metal oxides that are selected from titanium dioxide, zirconium white and silicon-dioxide.
3. claim 1 or 2 described surface-coated powders, the organopolysiloxane of wherein said metal oxide-organopolysiloxane hybrid are the residue of following general formula (1) expression,
In the formula, R is alkyl, the aryl or aralkyl of carbonatoms 1～22, can be the same or different separately; Y is-R ,-O-or-R
1-Si (O-)
3Shown in group (R wherein
1Alkylidene group for carbonatoms 1～5), can be the same or different, but have at least a Y for-O-or-R
1-Si (O-)
3In addition, n=1～100, m=0～5.
4. the described surface-coated powder of claim 3, the R of wherein said general formula (1) is a methyl.
5. the preparation method of the described surface-coated powder of claim 1, it is characterized in that: make end or side chain have the partial hydrolystate reaction of the organopolysiloxane and the metal alkoxide of active function groups, with the hybrid colloidal sol that obtains thus powder is carried out the surface and coat, dry then.
6. the organopolysiloxane that the described method of claim 5, wherein said end or side chain have active function groups is the organopolysiloxane derivative of following general formula (2) expression.
In the formula, R is alkyl, the aryl or aralkyl of carbonatoms 1～22, can be the same or different separately; X is-H ,-R or-R
1-Si (OR
2)
3Shown in group (R wherein
1Be the alkylidene group of carbonatoms 1～5, R
2Alkyl for hydrogen or carbonatoms 1～5), can be the same or different, but have at least an X be-H or-R
1-Si (OR
2)
3N=1～100, m=0～5.
7. the described method of claim 6, the R of wherein said general formula (2) is a methyl.
8. the described method of claim 6, the organopolysiloxane derivative of wherein said general formula (2) are the compounds of following general formula (3) expression.
In the formula, R
1Be the alkylidene group of carbonatoms 2～4, R
2Be-CH
3Or-C
2H
5, n=6～16.
9. the used for cosmetic powder of making by each described surface-coated powder of claim 1～4.
10. the makeup that contain the described used for cosmetic powder of claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003420377 | 2003-12-18 | ||
| JP420377/2003 | 2003-12-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1894312A true CN1894312A (en) | 2007-01-10 |
| CN100465213C CN100465213C (en) | 2009-03-04 |
Family
ID=34697248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200480037230XA Expired - Fee Related CN100465213C (en) | 2003-12-18 | 2004-12-15 | Surface-coated powder and cosmetic containing said powder |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4916174B2 (en) |
| KR (1) | KR101119534B1 (en) |
| CN (1) | CN100465213C (en) |
| HK (1) | HK1098775A1 (en) |
| TW (1) | TWI359164B (en) |
| WO (1) | WO2005059010A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039883A (en) * | 2012-01-16 | 2014-09-10 | 奥斯兰姆施尔凡尼亚公司 | Silicone-grafted core-shell particles, polymer matrix, and LED containing same |
| CN110934776A (en) * | 2019-12-17 | 2020-03-31 | 中南林业科技大学 | Titanium dioxide composite material coated with polytrifluoropropylmethylsiloxane and preparation method and application thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101256248B1 (en) * | 2005-03-23 | 2013-04-18 | 디에스엠 아이피 어셋츠 비.브이. | Polysiloxane coated metal oxide particles |
| TWI519318B (en) * | 2010-02-25 | 2016-02-01 | Kose Corp | A powder dispersant containing a polysilicate phosphoric acid triester, a surface coating powder and a cosmetic |
| JP5584005B2 (en) * | 2010-03-31 | 2014-09-03 | 株式会社コーセー | Iron oxide / organopolysiloxane hybrid powder, method for producing the same, and cosmetics containing the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2966596B2 (en) * | 1991-09-05 | 1999-10-25 | 信越化学工業株式会社 | Polyorganosiloxane coated fine particles |
| JP4044210B2 (en) * | 1998-05-22 | 2008-02-06 | ポーラ化成工業株式会社 | Makeup cosmetic without whiteness |
| JP2000256133A (en) * | 1999-03-03 | 2000-09-19 | Daito Kasei Kogyo Kk | Pigment for cosmetic, production of its pigment and cosmetic |
| JP3843387B2 (en) * | 1999-08-30 | 2006-11-08 | 株式会社コーセー | Metal oxide / organopolysiloxane hybrid powder, method for producing the same, and cosmetic containing the same |
| TWI246924B (en) * | 2001-02-23 | 2006-01-11 | Kose Corp | Porous titanium oxide, organic polyorganosiloxane hybridized powder and titanium oxide, silicon oxide composite unit and matched cosmetic material thereof |
| JP4056722B2 (en) * | 2001-09-25 | 2008-03-05 | 住友大阪セメント株式会社 | Surface-coated metal oxide fine powder and cosmetic containing the same |
-
2004
- 2004-12-09 TW TW093138104A patent/TWI359164B/en not_active IP Right Cessation
- 2004-12-15 WO PCT/JP2004/019267 patent/WO2005059010A1/en active Application Filing
- 2004-12-15 KR KR1020067011973A patent/KR101119534B1/en not_active IP Right Cessation
- 2004-12-15 CN CNB200480037230XA patent/CN100465213C/en not_active Expired - Fee Related
- 2004-12-15 JP JP2005516390A patent/JP4916174B2/en not_active Expired - Fee Related
-
2007
- 2007-05-16 HK HK07105190.0A patent/HK1098775A1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039883A (en) * | 2012-01-16 | 2014-09-10 | 奥斯兰姆施尔凡尼亚公司 | Silicone-grafted core-shell particles, polymer matrix, and LED containing same |
| CN110934776A (en) * | 2019-12-17 | 2020-03-31 | 中南林业科技大学 | Titanium dioxide composite material coated with polytrifluoropropylmethylsiloxane and preparation method and application thereof |
| CN110934776B (en) * | 2019-12-17 | 2022-09-13 | 中南林业科技大学 | Titanium dioxide composite material coated with polytrifluoropropylmethylsiloxane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4916174B2 (en) | 2012-04-11 |
| KR20060109941A (en) | 2006-10-23 |
| CN100465213C (en) | 2009-03-04 |
| HK1098775A1 (en) | 2007-07-27 |
| JPWO2005059010A1 (en) | 2007-07-12 |
| KR101119534B1 (en) | 2012-03-13 |
| TW200521159A (en) | 2005-07-01 |
| TWI359164B (en) | 2012-03-01 |
| WO2005059010A1 (en) | 2005-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1856550A (en) | Black bright pigment, and cosmetic, coating composition, resin composition and ink composition comprising the same | |
| CN1281690C (en) | Titanium oxide compsn. having high brilliant color, compsn. comprising coating and cosmetic compsn. and method for their prepn. | |
| CN1158358C (en) | Pigment mixture having high light diffusion | |
| CN1317340C (en) | Highly anti-corrosive metal pigments | |
| CN1449736A (en) | Cosmetics composition | |
| CN1542059A (en) | Interference pigments having a mass tone | |
| CN1151768C (en) | Composition for external use | |
| CN100335413C (en) | Ultraviolet-screening zinc oxide excellent in transparency and composition containing the same | |
| CN1148419C (en) | Compounded powder, coloring composition and use method thereof | |
| CN1237956C (en) | Water in oil emulsion powdery cream | |
| CN1470569A (en) | Five-layer pigment | |
| CN1170517C (en) | Water-containing powder composition process for producing same and cosmetic preparation containing powder composition | |
| CN100346765C (en) | Emulsion composition | |
| CN1307970C (en) | Silica-coated mixed crystal oxide particle, production process thereof and cosmetic material using the same | |
| CN1942507A (en) | Silsesquioxane resin wax | |
| CN1340086A (en) | Comsmetic preparation, surface-hydrophobized silica-coated metal oxide particles, sol of silica-coated metal oxide, and processes for producing these | |
| CN1173321A (en) | Ester in application of powder-stuck composition and compact powdered anhydrous composition | |
| CN1679468A (en) | Compositions for application to the skin, to the lips, to the nails, and/or to hair | |
| CN101076313A (en) | Modified powder and cosmetic composition using same | |
| CN1241543C (en) | Film-forming cosmetic composition | |
| CN1346629A (en) | Makeup-removing prevention cosmetic composition contg. nonvolatile polysilicone compound, nonvolatile hydrocarbon contg. oil and inert particle phase | |
| CN1216515A (en) | Ultraviolet-screening composite particulate and process for the production thereof | |
| CN1638719A (en) | Composite powder, cosmetic containing the same and process for producing composite powder | |
| CN1226030C (en) | Oily solid cosmetics | |
| CN1441659A (en) | Cosmetic preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1098775 Country of ref document: HK |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1098775 Country of ref document: HK |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090304 Termination date: 20151215 |
|
| EXPY | Termination of patent right or utility model |