CN1694928A - Non-flak coated colouring pigment and method for the production and use thereof - Google Patents
Non-flak coated colouring pigment and method for the production and use thereof Download PDFInfo
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- CN1694928A CN1694928A CN 03824923 CN03824923A CN1694928A CN 1694928 A CN1694928 A CN 1694928A CN 03824923 CN03824923 CN 03824923 CN 03824923 A CN03824923 A CN 03824923A CN 1694928 A CN1694928 A CN 1694928A
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Abstract
The invention relates to a non-flak coated colouring pigment consisted of organic or inorganic, amorphous or partially crystalline material provided at least with one coating. Each layer contains at least cured melamine-formaldehyde resin or consists thereof. The inventive pigment is successfully used for producing cosmetic products and confers a pleasurable sensation to the user thereof.
Description
The present invention relates to a kind of non-flak coated colouring pigment, and relate to its production method and purposes.The invention still further relates to the composition that comprises described pigment.
Makeup comprise pigment usually so that give their coloured appearances.Some above-mentioned pigment make the user's of makeup pachylosis, drying, and therefore produce sensation beastly.Particularly especially true under the situation of employing based on the pigment of six sour iron of cyanogen iron (II) (III) (also being called Prussian blue) or chromic oxide (III).
The purpose of this invention is to provide especially for makeup and the tinting pigment that imposes on the other products on the skin, described tinting pigment gives skin pleasant sensation.
Astoundingly, found that above-mentioned purpose can obtain by adopting curing melamine-formaldehyde resin coating tinting pigment.
Coating color is known in principle.Therefore, EP-A-0 601 378 has described the thin slice pigments, mica that coating has melamine resin.These pigment are as the effect pigment in the Vehicular metal coating, and described coating has the effect of the surface property of the stability in storage of improving coating and resulting paint film.
DE-A-197 10 619 discloses the solid particulate that coating has melamine resin, and above-mentioned solid particulate joined the solution of the solvent impregnated resin that is used for the productive zone stampings so that improve the wear resistance that coating has the wooden materials of laminated product.The core of coating solid particulate comprises quartz, nitride, carbide.These all are not tinting pigments.
The invention provides non-flak coated colouring pigment, it is characterized in that described pigment is made of the material inorganic or organic, amorphous or partial crystallization with at least one coating, wherein, each coating comprises at least a curing melamine-formaldehyde resin or is made of a kind of described resin.Comprise according to tinting pigment of the present invention as fruit cosmetic and the other products that is applied on the skin, then they give user's skin pleasant sensation.
Pigment is six sour iron of cyanogen iron (II) (III) or chromic oxide (III) advantageously.But, can also identical mode adopt other pigment of curing melamine-formaldehyde resin coating.These pigment are, the oxide compound of titanium oxide (IV), zirconium white (IV) and iron for example is as magnetite and rhombohedral iron ore.
Under the situation of crosslinked melamine-formaldehyde resin, the part melamine molecules also can be substituted by other crosslinkable molecule, as phenols, guanamines or urea.Melamine-formaldehyde resin can be the melamine-formaldehyde adducts of etherificate or etherificate not, as has C
1-C
6-alkoxyl group is as the alkoxyl group methylol melamine and the precondensate of methoxyl group or n-butoxy.As an example, unetherified resin is Madurit MW 909, or the resin of etherificate is Madurit SMW 818 (two kinds of products all available from Solutia, Wiesbaden, Germany).The part melamine-formaldehyde resin also can be substituted by other crosslinked organic polymer.What be fit to particularly has those of high refractive index herein equally, and the specific refractory power that more particularly has is higher than those of specific refractory power of the pigment of coating not.
Do not add dyestuff owing to adopt melamine-formaldehyde coating color, the inherent colour of pigment also changes according to coat-thickness.Along with the increase of coat-thickness, color effects changes on more shallow and lighter color direction.But skin is more pleasant feels under the necessary coat-thickness that illumination effect is that eyes almost be can't see giving.
Luminously be not suitable for leuco-pigment certainly, as titanium oxide (IV) or zirconium white (IV).
Opposite with flaky pigment, when adopting melamine-formaldehyde coating, form the interference color that can regulate by coat-thickness.Such reason is the very uneven surface of containing non-flaky pigment basically, and this has suppressed to be used to form the uniform layer thickness of interference.
If any organic and inorganic dyestuff and suitable colourless UV absorption agent all can join in the melamine-formaldehyde resin.Only be its solubleness in the medium that carries out coating reaction for the determinative that joins in the polymeric matrix herein.Even also can being embedded in the polymeric matrix, water-soluble dye,, fluoroscein red as dawn or Victoria Pure Blue BO can not ooze out subsequently.Under the situation of oleophylic dyestuff, if add the general solubility promoter of those of ordinary skills, then coating reaction can be carried out in water-bearing media equally.The solubility promoter that can mention example is a 1-Methyl-2-Pyrrolidone herein.
In order to obtain color shades, can utilize additive color blended conventional principles.Herein, can be by dyestuff being mixed in advance and it is joined polymer layer together, or by two-layer or multilayer dye-polymer layer being imposed in succession on the inorganic substrates so that distinct colors stacked adding, regulated color and luster.
Basically also can be with changing color resulting from acid (Acidochromic) dyestuff, promptly its color depends on the dyestuff of pH, joins in the melamine-formaldehyde resin, keeps color and luster and color transition point simultaneously.The example that can provide is phenolphthalein, dibromothymolsulfonphthalein, xylene bromide indigo plant (bromo xylene blue) and thymolphthalein herein.
Except the above fluoroscein that has mentioned, also other fluorescence dye, white dyes or other UV extinction dyestuff can be joined in the polymeric matrix.
Especially, can be to add two or more dyestuffs, wherein at least a dyestuff is a fluorescence dye.Particularly advantageous is to add at least two kinds of fluorescence dyes, and second kind of fluorescence dye adds with much smaller consumption.As a result, can obtain the pigment that its final fluorescence color obviously is different from the fluorescence color of raw material.Like this, simply mode is synthesized the pigment of a large amount of different fluorescence.Type by changing fluorescence dye and changing with much smaller second kind of dyestuff (about type and concentration) that consumption was added can produce the fluorescence color of big bandwidth.Usually, because the dyestuff of the decision color of low levels, these pigment have very difficult to perceive and lighter effect in visible light.Except the primary colours red, green and blue, can realize surpassing the clear different fluorescence color of distinguishing of the available eye of kind more than 100 well.
Deposit on the polymer layer that comprises the dyestuff that applies in advance by the polymer layer that will comprise one or more fluorescence dyes, can obviously improve the lightness and the brightness of pigment.In addition, can be by absorbing the bleaching that ultraviolet ray suppresses bottom.Described UV protection also can obtain by the UV absorption agent is joined in the polymer layer that itself contains dyestuff.
In principle, the UV absorption agent of Shi Heing is all UV lightscreening agents.Particularly preferably be and prove UV lightscreening agent acceptable on the physiology.For the UV-A lightscreening agent and for the UV-B lightscreening agent, exist many by the known material of having tested and having tested in the technical literature.Example is the benzylidene camphor derivative herein; as 3-(4 '-methyl benzylidene)-dl-camphor; the 3-benzylidene camphor; N-{ (2 and 4)-[(2-oxo inferior borneol-3-yl) methyl] benzyl } polymkeric substance of acrylamide; N; N; N-trimethylammonium-4-(the inferior borneol of 2-oxo-3-ylmethyl) puratized agricultural spray Methylsulfate or α-(the inferior borneol of 2-oxo-3-yl) toluene-4-sulfonic acid; benzoyl methane or phenyl phenacyl ketone; as 1-(4-tert-butyl-phenyl)-3-(4-p-methoxy-phenyl) propane-1; 3-diketone or 4-isopropyl diphenyl formyl radical methane; benzophenone; as 2-hydroxyl-4-methoxy benzophenone or 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid and sodium salt thereof; the Methoxycinnamate class; as octyl methoxycinnamate; 4-methoxy cinnamic acid isopentyl ester and isomer mixture thereof; salicylic acid ester derivative; as Whitfield's ointment (2-ethylhexyl) ester; Whitfield's ointment (4-isopropyl benzyl) ester or Whitfield's ointment (3; 3; the 5-trimethylcyclohexyl) ester; 4-benzaminic acid and derivative thereof; 4-subcutin as 4-(dimethylamino) phenylformic acid (2-ethylhexyl) ester or ethoxylation; with other material; as 2-cyano group-3; 3-diphenylacrylate (2-ethylhexyl) ester; 2-Phenylbenzimidazole-5-sulfonic acid and sylvite thereof; sodium salt and triethanolamine salt; 3; 3-(1; 4-phenylene dimethylene) two (7; 7-dimethyl-2-oxo dicyclo [2.2.1] heptan-1-base methylsulfonic acid and salt and 2; 4; 6-triphen amido (right-carbon-2 '-ethylhexyl-1 '-the oxygen base)-1; 3, the 5-triazine.
Organic UV lightscreening agent of Shi Heing is in addition, 2-(2H-benzotriazole-2-yl)-4-methyl-6-(2-methyl-3-(1 for example, 3,3,3-tetramethyl--1-(trimethyl silyl oxygen base) sily oxide base) phenol propyl group), 4,4 '-[(6-[4-((1, the 1-dimethyl ethyl) phenyl amino aminocarboxyl)]-1,3,5-triazine-2,4-two bases) diimino] dibenzoic acid two (2-ethylhexyl) ester, α-(trimethyl silyl)-ω-[trimethyl silyl) oxygen base] is poly-, and [[[2-[is to [2 with about 6% methyl for oxygen base (dimethyl), 2-two (di ethoxy carbonyl] vinyl] phenoxy group]-1-methylene radical ethyl] and about 1.5% methyl [3-[is to [2,2-two (di ethoxy carbonyl) vinyl) propenyl phenoxy group)) and 0.1-0.4% (methyl hydrogen] silylene]] (n ≈ 60) (CAS numbers 207574-74-1), 2,2-methylene radical two (6-(2H-benzotriazole-2-yl)-4-(1,1,3,3,-tetramethyl butyl) phenol), 2,2 '-(1, the 4-phenylene) two (1H-benzoglyoxaline-4,6-disulfonic acid, single sodium salt) and 2,4-two { [4-(2-ethyl hexyl oxy)-2-hydroxyl] phenyl }-6-(4-p-methoxy-phenyl)-1,3,5-triazines.
Preferred compound with UV absorptive character is 3-(4 '-methyl benzylidene)-dl-camphor, 1-(4-tert-butyl-phenyl)-3-(4-p-methoxy-phenyl) propane-1; 3-diketone, 4-isopropyl diphenyl formyl radical methane, 2-hydroxyl-4-methoxy benzophenone, octyl methoxycinnamate, Whitfield's ointment (3; 3; the 5-trimethylcyclohexyl) ester, 4-(dimethylamino) phenylformic acid (2-ethylhexyl) ester, 2-cyano group-3,3-diphenylacrylate (2-ethylhexyl) ester, 2-Phenylbenzimidazole-5-sulfonic acid and sylvite, sodium salt and triethanolamine salt.
By with two or more UV lightscreening agent combinations, can make the protection best resultsization of opposing UV radiating harmful effect.
The coating tinting pigment can solidify by also making their on the pigment that crosslinked melamine-formaldehyde resin is deposited to suspension subsequently, even the crosslinked production of melamine-formaldehyde resin.
According to the present invention, the method for producing the tinting pigment with one or more coatings comprises, under the situation of single coating,
The first step, wherein tinting pigment is suspended in the alkaline aqueous medium that comprises melamine and formaldehyde and/or methylol melamine (optional can with its alkoxylate) and
Second step wherein caused the crosslinked of organic component by pH being reduced to acid range,
With under the situation of a plurality of coatings,
Adopt the product of aforementioned coating operation to repeat the first step and second step.
Found that particularly advantageous is by adding hydrogen peroxide, reducing pH by making excessive or unreacted oxidation of formaldehyde from the first step produce formic acid in second step.Because formaldehyde has problem in cosmetic applications, therefore no free formaldehyde molecule can be provided and thereby be the acceptable pigment of makeup.This also works to adopting methylol melamine, because in most of the cases methylol melamine also comprises the free formaldehyde of q.s.
In the method according to the invention, the corsslinking molecular that the part melamine can be selected from " guanamines class, phenols and ureas " by other is substituted, and/or the part methylol melamine can be substituted by the analogue of corresponding guanamines, phenol or urea.
Inorganic or organic dye and/or inorganic or organic UV absorption agent can add before crosslinking reaction begins or during crosslinking reaction.
If the incomplete water-soluble medium of dyestuff or UV absorption agent then can use solubility promoter to cause dissolving fully.This is particularly suitable when using oleophilic substance.
The bed thickness of coating can be by the concentration control of melamine-formaldehyde resin.For example, under high density, than under lower concentration, obtaining bigger bed thickness.PH also is the method that is fit to of control bed thickness.Low pH value causes thin coating.In addition, DE 1595386 has described by adding protective colloid control bed thickness.
Preferred total bed thickness with substrate of one or more coatings is preferably 0.2 μ m-4 μ m.
By using excessive melamine-formaldehyde resin, can be on the outermost layer coating with melamine-formaldehyde resin particle deposition extra and that be circle basically, described resin particle can also comprise the UV absorption agent except organic dye, or does not have dyestuff or UV absorption agent fully.
According to reaction method, can control number, sphere diameter and the sphere diameter distribution (dispersiveness) of each tinting pigment particulate spheroid.Particularly for makeup, the spheroid of certain content helps improving the sensation of skin.
But too high-load spheroid has reduced the lightness and the outward appearance of pigment.If the content of dyestuff is enough, then extra spheroid has the color that matches with tinting pigment.
Can significantly improve the space-time yield of relevant cost efficient by the polymkeric substance that adding has a strong acid group, as for example described in the EP 0415273.
For some application,,, can advantageously also in the outermost condensation product of polymkeric substance, introduce the functional group that is different from specified strong acid group for example for its tackiness agent consistency and dispersion behavior for it is improved.The outermost layer of the crosslinked organic polymer with functional group can also be provided by the reaction of melamine-formaldehyde resin subsequently.DD 224602 has described the whole bag of tricks that makes resin functionalized.
For the present invention, functional group can be that any is hydrophilic or hydrophobic, acidity or basic group, therefore for example comprises or even the pure hydrophobic inert group that is to a great extent, as alicyclic radical.
According to the method described in the DD 224602, introduce functional group by the polycondensation of in the presence of amino-functional compounds, carrying out melamine-formaldehyde resin to the polymer beads surface, wherein amino-functional compounds also has other functional group except amino.Amino-functional compounds is with the amount based on used methylol melamine, and the consumption of preferred 2-20mol% adds, and is attached in melamine-formaldehyde network by amino.Therefore, for example can when using amino acid, introduce carboxyl, or under the situation of sultaine or aminophosphonic acid, introduce sulfo group or phosphonyl group to particle surface to particle surface.And this type of-COOH ,-SO
3H and-PO
2The H group can react with other compound.For example, acidic group can be converted into corresponding acyl chlorides by reacting with thionyl chloride, and acyl chlorides for example can form corresponding ester or acid amides with alcohol or amine reaction.The method of this surface modification is characterised in that simply, only is the method for condensing that changes a little because adopt, the functionalized direct generation of melamine-resin surface.But issuable disadvantageous effect is, because condensation course, also corresponding functionality can be incorporated in the polymkeric substance volume and therefore to the tackiness of following layer, or under the situation of single layer structure, reduce the tackiness to substrate.But, on the other hand, suitably selecting under the situation of some system, because surface-modifying agent, improve the consistency of surrounding medium and give following layer and the adhesive group of substrate if introduce, then can improve tackiness to following layer or substrate.But, in this method,, need relatively large functionalisation of surfaces reagent owing to be incorporated in melamine-formaldehyde network.And, during polycondensation, only can obtain more complicated chemical functional group by simple adding difficultly.
Therefore by the melamine-formaldehyde surface beginning of polycondensation, described melamine-formaldehyde surface has vacant, uncrosslinked methylol amine (NH-CH to the another kind of method of functionalisation of surfaces
2OH) or amino.These groups can for example react in simple mode with acyl chlorides.Therefore, for example under the situation of using the long-chain acyl chlorides, can obtain the hydrophobicity of pigment.Adopt the perfluorination acyl chlorides,, can obtain the surface of not only hydrophobic but also oleophobic as Perfluorocaprylic Acid.Can contain for example compound acyl chlorides of strong UV extinction group by using, the function of other acquisition also can be contained in melamine-formaldehyde surface, protects as UV.
Advantageous embodiment of the present invention produces from the additional claims of institute.
The invention still further relates to and comprise composition and the cosmetic formulations of one or more non-thin slice coated carrier materials as tinting pigment.
In composition or preparation, also can make up certainly with the cosmetic material and the auxiliary agent of any type according to non-flak coated colouring pigment of the present invention.Wherein, especially, these materials comprise oil, fat, wax, membrane-forming agent, sanitas and determine the auxiliary agent of application performance usually, as thickening material and auxiliary rheological agents, as wilkinite, hectorite, silicon-dioxide, Calucium Silicate powder, gelatin, high molecular carbohydrate and/or surfactivity auxiliary agent or the like.
The preparaton that comprises according to tinting pigment of the present invention can belong to oleophylic, hydrophilic or hydrophobic type.Under situation with discontinuous water and nonaqueous phase, according to tinting pigment of the present invention can exist only in all cases biphase one mutually in, or be dispersed in the two-phase.
The pH value of preparaton can be 1-14, preferred 2-11, and preferred especially 5-8.
In preparaton, do not limit according to the concentration of tinting pigment of the present invention.According to applicable cases, this concentration is 0.001 (the flushing product is used gel as bathing)-100% (the sparkle effect goods that are used for special applications).
In addition, also can make up according to tinting pigment of the present invention with cosmetic active ingredient.The activeconstituents that is fit to is, for example wormer, UV A/BC protective lightscreening agent (as OMC, B3, MBC), anti-aging activeconstituents, VITAMIN and derivative (as vitamin A, C, E or the like) thereof, self-tanning agent (as DHA, erytrolose or the like) and other cosmetic active ingredient are as Hydagen B, LPO, ectoin, emblica, wallantoin, Vitamin P complex and derivative thereof.
Herein, preparation is generally the preparation that can local apply, as cosmetic formulations or dermatological formulations.In this case, preparation comprises carrier and the optional composition that is fit in addition that depends on needed performance profile that is fit on makeup or the dermatology.
As mentioned above, particularly preferred preparation preferably comprises UV-A and UV-A-I lightscreening agent according to the present invention.In principle, all UV lightscreening agents all are suitable for and tinting pigment combination according to the present invention.Those UV lightscreening agents of its physiology acceptability have especially preferably been proved.For UVA and UVB lightscreening agent, exist many by the known material of having tested and having tested of technical literature, as
The benzylidene camphor derivative, as 3-(4 '-methyl benzylidene)-dl-camphor (as Eusolex 6300), 3-benzylidene camphor (as Mexoryl SD), N-{ (2 and 4)-[(the inferior borneol of 2-oxo-3-yl) methyl] benzyl } polymkeric substance (as Mexoryl SW), the N of acrylamide, N, N-trimethylammonium-4-(the inferior borneol of 2-oxo-3-ylmethyl) puratized agricultural spray Methylsulfate (as Mexoryl SK) or (the inferior borneol of 2-oxo-3-yl) toluene-4-sulfonic acid (as Mexoryl SL)
Benzoyl methane or phenyl phenacyl ketone, as 1-(4-tert-butyl-phenyl)-3-(4-p-methoxy-phenyl) propane-1,3-diketone (as Eusolex 9020) or 4-isopropyl diphenyl formyl radical methane (as Eusolex 8020),
Benzophenone, as 2-hydroxyl-4-methoxy benzophenone (as Eusolex 4360) or 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid and sodium salt (as Uvinul MS-40) thereof,
The Methoxycinnamate class, as octyl methoxycinnamate (as Eusolex 2292), 4-methoxy cinnamic acid isopentyl ester, as isomer mixture (as Neo Heliopan E 1000),
Salicylic acid ester derivative, as Whitfield's ointment (2-ethylhexyl) ester (as Eusolex OS), Whitfield's ointment (4-isopropyl benzyl) ester (as Megasol ) or Whitfield's ointment (3,3, the 5-trimethylcyclohexyl) ester (as Eusolex HMS),
4-benzaminic acid and derivative thereof, as the 4-subcutin (as Uvinul P25) of 4-benzaminic acid, 4-(dimethylamino) phenylformic acid (2-ethylhexyl) ester (as Eusolex 6007) or ethoxylation,
The Phenylbenzimidazolesulfonic acid class, as 2-Phenylbenzimidazole-5-sulfonic acid and sylvite, sodium salt and triethanolamine salt (as Eusolex 232), 2,2-(1, the 4-phenylene) bisbenzimidazole-4,6-disulfonic acid and salt thereof (as Neoheliopan AP) and 2,2-(1, the 4-phenylene) bisbenzimidazole-6-sulfonic acid;
With other materials, as
-2-cyano group-3,3-diphenylacrylate (2-ethylhexyl) ester (as Eusolex OCR),
-3,3 '-(1,4-phenylene dimethylene) two (7,7-dimethyl-2-oxo dicyclo [2.2.1] heptan-1-base methylsulfonic acid and salt (as Mexoryl SX) thereof and
-2,4,6-triphen amido (right-carbon-2 '-ethylhexyl-1 '-the oxygen base)-1,3,5-triazines (as Uvinul T150)
-2-(4-diethylamino-2-hydroxy benzoyl) hexyl-benzoate is (as Uvinul UVA Plus, BASF).
Cited compound should only be looked at as example.Certainly can also use other UV lightscreening agent.
These organic UV lightscreening agents are usually with 0.5-10 weight %, and the amount of preferred 1-8 weight % joins in the cosmetic formulations.
Organic UV lightscreening agent of Shi Heing is in addition, for example
-2-(2H-benzotriazole-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl--1-(trimethyl silyl oxygen base) sily oxide base) propyl group) phenol (as Silatrizole ),
-4,4 '-[(6-[4-((1, the 1-dimethyl ethyl) aminocarboxyl) phenyl amino]-1,3,5-triazines-2,4-two bases) diimino] dibenzoic acid two (2-ethylhexyl) ester (Uvasorb HEB),
-α-(trimethyl silyl)-ω-[trimethyl silyl) oxygen base] is poly-, and [[[2-[is to [2 with about 6% methyl for oxygen base (dimethyl), 2-two (ethoxy carbonyl] vinyl] phenoxy group]-1-methylene radical ethyl] and about 1.5% methyl [3-[is to [2,2-two (ethoxy carbonyl) vinyl) propenyl phenoxy group)) and (methyl hydrogen) silylene of 0.1-0.4%]] (n ≈ 60) (CAS numbers 207574-74-1)
-2,2 '-methylene radical two (6-(2H-benzotriazole-2-yl)-4-(1,1,3,3 ,-tetramethyl butyl) phenol) (CAS numbers 103597-45-1),
-2,2 '-(1, the 4-phenylene) two (1H-benzoglyoxaline-4,6-disulfonic acid, single sodium salt) (CAS numbers 180898-37-7) and
-2,4-two { [4-(2-ethyl hexyl oxy)-2-hydroxyl] phenyl }-6-(4-p-methoxy-phenyl)-1,3,5-triazines (CAS numbers 103597-45-, 187393-00-6),
-4,4 '-[(6-[4-((1, the 1-dimethyl ethyl) aminocarboxyl) phenyl amino]-1,3,5-triazines-2,4-two bases) diimino] dibenzoic acid two (2-ethylhexyl) ester (as Uvasorb HEB).
Organic UV lightscreening agent usually can 0.5-20 weight %, and the amount of preferred 1-15 weight % joins in the cosmetic formulations.
Possible inorganic UV lightscreening agent is for being selected from titanium dioxide, as those of coating titanium dioxide (as Eusole T-200, Eusolex T-AQUA), zinc oxide (as Sachtotec ), ferric oxide and oxide-cerium oxide.These inorganic UV lightscreening agents usually can 0.5-20 weight %, and the amount of preferred 2-10 weight % joins in the cosmetic formulations.
Preferred compound with UV optical filtering is 3-(4 '-methyl benzylidene)-dl-camphor, 1-(4-tert-butyl-phenyl)-3-(4-p-methoxy-phenyl) propane-1; 3-diketone, 4-isopropyl diphenyl formyl radical methane, 2-hydroxyl-4-methoxy benzophenone, octyl methoxycinnamate, Whitfield's ointment (3; 3; the 5-trimethylcyclohexyl) ester, 4-(dimethylamino) phenylformic acid (2-ethylhexyl) ester, 2-cyano group-3,3-diphenylacrylate (2-ethylhexyl) ester, 2-Phenylbenzimidazole-5-sulfonic acid and sylvite, sodium salt and triethanolamine salt.
The best group compound can comprise, for example organic UV lightscreening agent 4 '-methoxyl group-6-flavonol and 1-(4-tert-butyl-phenyl)-3-(4-p-methoxy-phenyl) propane-1, the combination of 3-diketone and 3-(4 '-methyl benzylidene)-dl-camphor.The protection of this combination results broadband, the protection of described broadband can replenish by adding inorganic UV lightscreening agent such as titanium dioxide fine particles in addition.
All UV lightscreening agents of enumerating can also capsule form use.Specifically, advantageously use organic UV lightscreening agent of capsule form.Especially, produce following advantage:
-can not consider the solubleness of UV lightscreening agent and the wetting ability of regulating capsule wall.Therefore, even for example hydrophobic UV lightscreening agent also can join in the pure aqueous compositions.In addition, when applying the hydrophobic preparations that comprises the UV lightscreening agent, suppressed to be commonly referred to be the sensation of oil beastly.
-some UV lightscreening agent, particularly phenyl phenacyl ketone derivative only demonstrates the light stability of minimizing in cosmetic formulations.By with the compound of described lightscreening agent with the light stability of the described lightscreening agent of infringement, be wrapped in the capsule as cinnamic acid derivative, can improve the light stability of whole preparation.
-in the literature, organic UV lightscreening agent skin permeation and relevant therewith potential stimulus when repeatedly discussing on the skin that directly imposes on the people.Be wrapped in the capsule by respective substance, suppressed above-mentioned influence view mentioned herein.
-usually,,, can avoid the formulation problems that produces owing to independent preparation interaction between component, as crystallisation process, precipitation and reunion owing to having suppressed interaction by independent UV lightscreening agent or other composition are wrapped in the capsule.
The capsule that is fit to can have by wall inorganic or that organic polymer is made.For example, US6,242,099B1 has described the capsular preparation that is fit to wall of being made by chitin, chitin derivative or polyhydroxylated polyamine.The capsule that especially preferably uses according to the present invention has the wall that can obtain by the sol-gel method described in application WO 00/09652, WO 00/72806 and WO 00/71084.And preferred herein its wall is by silica gel (silicon-dioxide; Undefined silicon oxide oxyhydroxide) capsule of Gou Chenging.Producing corresponding capsule is known to those skilled in the art, and as being known by the patent application of being quoted, the content of above-mentioned patent application also belongs to the application's theme.
Herein, capsule preferably is present in according in the preparation of the present invention with the consumption that above-mentioned consumption is present in the preparation with capsulated UV lightscreening agent guaranteeing.
If preparation comprises one or more oxidation inhibitor, can obtain to resist the protection effect of oxidation and the influence of opposing free radical.
Exist many by the known material that can be used as oxidation inhibitor of having tested and having tested of technical literature; as amino acid (as glycine; Histidine; tyrosine; tryptophane) and derivative; imidazoles (as urocanic acid) and derivative thereof; peptide; as D; the L-carnosine; the D-carnosine; L-carnosine and derivative thereof (as anserine); carotenoid; carotene is (as alpha-carotene; β-Hu Luobusu; Lyeopene) and derivative; chlorogenic acid and derivative thereof; Thioctic Acid and derivative thereof (as Thioctic acid, dihydro-); gold thioglucose; propylthiouracil and other mercaptan are (as Trx; gsh; halfcystine; Gelucystine; cystamine and glycosyl thereof; the N-ethanoyl; methyl; ethyl; propyl group; amyl group; butyl and lauryl; palmitoyl; oleyl; γ-Ya oleoyl; cholest-and glyceryl ester) and salt; Tyox B; distearylthiodi-propionate; thio-2 acid and derivative (ester thereof; ether; peptide; lipoid; Nucleotide; nucleosides and salt); with with the sulfo group oxime compound of very low acceptable emergency dose (as pmol-μ mol/kg) (as fourth thionine sulfo group oxime; homocysteine sulfo group oxime; fourth thionine sulfone; penta thionine sulfo group oxime; own thionine sulfo group oxime; heptan thionine sulfo group oxime), and (metal) intercalating agent is (as alpha-hydroxy fatty acid; palmitinic acid; phytinic acid; lactoferrin); alpha-hydroxy acid is (as citric acid; lactic acid; oxysuccinic acid); humic acid; bile acide; bile extract; bilirubin; uteroverdine; EDTA; EGTA and derivative thereof; unsaturated fatty acids and derivative thereof; vitamins C and derivative thereof are (as Quicifal; magnesium ascorbyl phosphate; the xitix acetic ester); tocopherol and derivative thereof (as Vitamin E acetate); the coniferyl benzoate of vitamin A and derivative thereof (as Vitamin A Palmitate 1.7 M.I.U/Gram) and bitter almond oil camphor resin; rutinic acid and derivative thereof; the alpha-glycosyl violaguercitrin; forulic acid; the furfurylidene glucitol; carnosine; butylhydroxy toluene; butylated hydroxy anisole; guaiaconic acid (nordohydroguaiaretic acid); THBP 2,4,5 trihydroxybutyrophenone; essence; uric acid and derivative thereof; seminose and derivative thereof; zinc and derivative thereof are (as ZnO; ZnSO4); selenium and derivative thereof (selenomethionine); stilbene and derivative thereof are (as the oxidation stilbene; anti-oxidation stilbene).
According to the present invention, the mixture of oxidation inhibitor is suitable for being used in the cosmetic formulations equally.Known and commercially available mixture is, as contain Yelkin TTS as activeconstituents, the mixture of L-(+)-Quicifal and citric acid (as Oxynex AP), natural tocopherol, L-(+)-Quicifal, the mixture of L-(+)-xitix and citric acid (as Oxynex KLIQUID), tocopherol extract from natural origin, L-(+)-Quicifal, the mixture of L-(+)-xitix and citric acid (as Oxynex L LIQUID), the DL-alpha-tocopherol, L-(+)-Quicifal, mixture of citric acid and Yelkin TTS (as Oxynex LM) or butylhydroxy toluene, (BHT), L-(+)-Quicifal and citric acid) mixture (as Oxynex 2004.In described composition, described oxidation inhibitor can with tinting pigment according to the present invention usually with 1000: 1-1: 1000 ratio, preferably with 100: 1-1: 100 consumption uses together.
As other composition, can comprise VITAMIN according to preparation of the present invention.Preferably in cosmetic formulations according to the present invention, exist and be selected from vitamin A, vitamin A propionic ester, Vitamin A Palmitate 1.7 M.I.U/Gram,, Vogan-Neu, vitamins B, thiamine chloride hydrochloride (vitamins B
1), riboflavin (vitamins B
2), niacinamide, vitamins C (xitix), vitamins D, ergocalciferol (vitamins D
2), vitamin-E, DL-alpha-tocopherol, tocopherol E acetic ester, tocopherol hydrogen succinate ester, vitamin K
1, Vitamin C2 (vitamin P activeconstituents), VitB1 (vitamins B
1), nicotinic acid (nicotinic acid), pyridoxol, pyridoxal, Pyridoxylamine (vitamins B
6), pantothenic acid, vitamin H, folic acid and cobalami (vitamins B
12) VITAMIN and vitamin derivative, special preferred vitamin A cetylate, vitamins C, DL-alpha-tocopherol, tocopherol E acetic ester, nicotinic acid, pantothenic acid and vitamin H.Herein VITAMIN with according to tinting pigment of the present invention usually with 1000: 1-1: 1000 ratio, preferably with 100: 1-1: 100 consumption uses together.
In addition, can comprise other general activeconstituents or skin care activity composition according to preparation of the present invention to the skin gentleness.These activeconstituentss can be all activeconstituentss well known by persons skilled in the art in principle.
Particularly preferred activeconstituents is pyrimidine carboxylic and/or aryl oxime.
Pyrimidine carboxylic is present in the halophilic microorganism and plays a role (E.A.Galinski etc., Eur.J. Biochem., 149 (1985) 135-139 pages or leaves) in the osmotic pressure of these organisms is regulated.Herein, in pyrimidine carboxylic, what mention especially is ectoin ((S)-1,4,5,6-tetrahydrochysene-2-methyl-4-pyrimidine carboxylic) and hydroxyectoin ((S, S)-1,4,5,6-tetrahydrochysene-5-hydroxy-2-methyl-4-pyrimidine carboxylic) and derivative thereof.These compounds make enzyme and other biomolecules stable in the aqueous solution and organic solvent.In addition, they make enzyme at particularly sex change condition, and are stable as salt, extreme pH value, tensio-active agent, urea, chlorination guanidinesalt and other compound.
Can be used for medicament as hydroxyectoin advantageously with ectoin and ectoin derivative.Specifically, hydroxyectoin can be used for production for treating cutaneous disorder with medicament.Use the other field of hydroxyectoin and other ectoin derivative typically to be used as in the field of additive at for example trehalose.Therefore, can be with the ectoin derivative, as hydroxyectoin as the protective agent in dry yeast and the bacterial cell.Also can adopt ectoin or derivatives thereof protection medicinal product, as effective peptide of nonglycosylated pharmacy and protein, as t-PA.
In cosmetic applications, mentioned that especially ectoin and ectoin derivative are used to nurse the purposes of the skin of aging, drying or irriate.Therefore, European patent application EP-A-0671161 has described especially ectoin and hydroxyectoin has been used for cosmetic formulations, as powder, soap, the cleaning product that contains tensio-active agent, lipstick, kermes, makeup, protective skin cream and sun-screening agent.
Herein, the preferred use according to pyrimidine carboxylic with following formula I,
R wherein
1Be group H or C1-8-alkyl, R
2Be group H or C1-4-alkyl, and R
3, R
4, R
5And R
6Independently of one another in all cases, for being selected from H, OH, NH
2Group with the C1-4-alkyl.Preferably use wherein R
2Be methyl or ethyl, and R
1Or R
5And R
6Pyrimidine carboxylic for H.Especially preferably use pyrimidine carboxylic ectoin ((S)-1,4,5,6-tetrahydrochysene-2-methyl-4-pyrimidine carboxylic) and hydroxyectoin ((S, S)-1,4,5,6-tetrahydrochysene-5-hydroxy-2-methyl-4-pyrimidine carboxylic).Herein, preparation according to the present invention comprises the pyrimidine carboxylic that consumption is up to the above-mentioned type of 15 weight %.Preferably herein pyrimidine carboxylic being 100 with respect to tinting pigment ratio according to the present invention: 1-1: 100 use, and preferred especially this ratio is 1: 10-1: 10.
In aryl oxime, preferably use 2-hydroxy-5-methyl base laurophenone oxime, it also is called HMLO, LPO or F5.Its suitability that is used for make-up composition is known, is for example known by German prospectus DE-A-4116123.Therefore, the preparation that comprises 2-hydroxy-5-methyl base bay ketoxime is suitable for treating the cutaneous disorder that comprises inflammation.Known described preparation can be used for, and for example treats psoriasis, various forms of eczema, pungency and contact dermatitis, UV dermatitis and other skin and the supersensitivity and/or the inflammatory imbalance of cutaneous appendage.Preparation according to the present invention demonstrates surprising anti-inflammatory suitability, and described preparation comprises aryl oxime in addition except tinting pigment according to the present invention, preferred 2-hydroxy-5-methyl base laurophenone oxime.Herein, said preparation preferably comprises the aryl oxime of 0.01-10 weight %, and special preferred formulation comprises the aryl oxime of 0.05-5 weight %.
In preparation operable all compounds or composition be known or commercially available maybe can be synthetic by currently known methods.
Can join in the cosmetic formulations in a usual manner according to tinting pigment of the present invention.The external preparation that for example is on the sprayed to skin of form of frost, lotion, gel or solution is fit to.For interior usefulness, be fit to such as the form of medication of capsule, coated tablet, powder, sheet agent solution.
The example according to the administration form of composition of the present invention or preparation that can mention is: solution, suspension, emulsion, PIT emulsion, paste, cream, gel, frost, lotion, powder, soap, the cleaning formulation that contains tensio-active agent, oil, aerosol and spraying.Other administration form is, for example club, shampoo and body lotion.Can in preparation, add any conventional carrier substance, auxiliary agent and optional other activeconstituents.
Preferred auxiliary agent derives from sanitas, oxidation inhibitor, stablizer, solubility promoter, VITAMIN, tinting material, odor improvers.
Cream, paste, frost and gel can comprise conventional carrier substance, as the mixture of animal tallow and vegetation fat, wax, paraffin, starch, tragacanth, derivatived cellulose, polyoxyethylene glycol, siloxanes, wilkinite, silicon-dioxide, talcum and zinc oxide or these materials.
Powder and spraying can comprise conventional carrier substance, as the mixture of lactose, talcum, silicon oxide, aluminium hydroxide, Calucium Silicate powder and polyamide powder or these materials.Spraying can also comprise conventional propellant, for example Chlorofluorocarbons (CFCs), propane/butane or dme.。
Solution and emulsion can comprise conventional carrier substance, as solvent, solubility promoter and emulsifying agent, as water, ethanol, Virahol, ethyl-carbonate, vinyl acetic monomer, benzylalcohol, peruscabin, propylene glycol, 1, the fatty acid ester of 3-butyleneglycol, oil, particularly Oleum Gossypii semen, peanut oil, Semen Maydis oil, sweet oil, Viscotrol C and sesame oil, glycerol fatty acid ester, polyoxyethylene glycol and sorbitanic or the mixture of these materials.
Suspension can comprise conventional carrier substance, liquid diluent for example, as water, ethanol or propylene glycol, suspension agent is as isooctadecanol, polyoxyethylene sorbitan ester and the polyoxyethylene sorbitol acid anhydride ester of ethoxylation, Microcrystalline Cellulose, the mixture of aluminium hydroxide, wilkinite, agar agar and tragacanth or these materials partially.
Soap can comprise conventional carrier substance, as the mixture of salt, fatty acid protein matter hydrolysate, different thiosulphate, lanolin, Fatty Alcohol(C12-C14 and C12-C18), vegetables oil, plant milk extract, glycerine, sugar or these materials of an alkali metal salt of lipid acid, fatty acid half ester.
The cleaning product that contains tensio-active agent can comprise conventional carrier substance, as salt, fatty alcohol ether sulfate, sulfo-succinic acid half ester, fatty acid protein matter hydrolysate, different thiosulphate, imidazoline salt derivative, methyl taurate, sarcosinate, fatty acid acyl amidogen ether sulfuric ester, alkylamidoalkyl trimethyl-glycine, Fatty Alcohol(C12-C14 and C12-C18), glycerin fatty acid ester, fatty diglycollic amide, vegetables oil and synthetic oil, lanolin derivative, the glycerol fatty acid ester of ethoxylation or the mixture of these materials of fatty alcohol sulfate.
Facial and health can comprise for example synthetic oil of conventional carrier substance with oil, as fatty acid ester, Fatty Alcohol(C12-C14 and C12-C18), silicone oil, natural oil, as the mixture of vegetables oil and oil plant extract, paraffin oil, lanolin oil or these materials.
Typical makeup application form in addition still is lipstick, lipstick, mascara, eyeliner, eye shadow cream, kermes, powder, emulsion and wax system makeup and sun-screening agent, solarization is preceding and shine the back preparation.
Specifically, preferred formulation form according to the present invention comprises emulsion.
Emulsion according to the present invention is favourable and comprises, for example cited fat, oil, wax and other lipoid material, and water and emulsifying agent, and it is generally used for the preparation of described type.
Advantageously oil phase can be selected from following material:
-mineral oil, mineral wax
-oil is as capric acid or sad tri-glyceride and natural oil, as Viscotrol C;
-fat, wax and other natural and synthetic fat class material, the alcohol of preferred fatty acid and low carbon number, for example with the ester of Virahol, propylene glycol or glycerine, or the paraffinic acid of Fatty Alcohol(C12-C14 and C12-C18) and low carbon number or with the ester of lipid acid;
-silicone oil is as dimethyl polysiloxane, diethyl polysiloxane, phenylbenzene polysiloxane and mixed form thereof.
For the present invention, the oil phase of emulsion, oleogel and water dispersion or fat dispersion advantageously be selected from the alcohol of saturated and/or unsaturated, branching that the alkanoic acid of saturated and/or unsaturated, branching that chain length is a 3-30 carbon atom and/or non-branching and chain length are 3-30 carbon atom and/or non-branching ester, be selected from the ester of the alcohol of saturated and/or unsaturated, branching that aromatic carboxylic acid and chain length are 3-30 carbon atom and/or non-branching.Then described ester oil can advantageously be selected from synthetic, semi-synthetic and natural mixture, for example the jojoba oil of the just own ester of Isopropyl myristate, Wickenol 111, isopropyl stearate, acid isopropyl, n-butyl stearate, lauric acid, oleic acid ester in the positive last of the ten Heavenly stems, the different monooctyl ester of stearic acid, stearic acid ester in the different ninth of the ten Heavenly Stems, isononyl isononanoate, palmitinic acid (2-hexyl decyl) ester, palmitinic acid (2-octyl group dodecyl) ester, oleic oil alkene ester, erucic acid oil alkene ester, oleic acid mustard alkene ester, erucic acid mustard alkene ester and above-mentioned ester.
In addition, oil phase can advantageously be selected from the hydrocarbon of branching or non-branching and chloroflo, silicone oil, dialkyl ether, be selected from the pure and mild fatty acid triglyceride of saturated or unsaturated, branching or non-branching, be that chain length is 8-24, the Witepsol W-S 55 of the alkanoic acid of saturated and/or unsaturated, the branching of 12-18 carbon atom and/or non-branching particularly.Fatty acid triglyceride can, for example advantageously be selected from synthetic, semi-synthetic and natural oil, as sweet oil, sunflower oil, soya-bean oil, peanut oil, rapeseed oil, Prunus amygdalus oil, plam oil, Oleum Cocois, palm-kernel oil or the like.
For the present invention, also can advantageously use any mixture of described oil and wax composition.In some cases, advantageously also can use wax, as cetin, as the independent lipid component of oil phase.
Advantageously, oil phase is selected from Unimac 5680 (2-ethylhexyl) ester, Standamul G, different n-nonanoic acid isotridecyl ester, different petrosilane, coconut acid (2-ethylhexyl) ester, phenylformic acid (C
12-15-alkyl) ester, sad-the capric acid tri-glyceride, didecyl ether.
Particularly advantageous is phenylformic acid (C
12-15-alkyl) mixture, the phenylformic acid (C of ester and Unimac 5680 (2-ethylhexyl) ester
12-15-alkyl) mixture and the phenylformic acid (C of ester and different n-nonanoic acid isotridecyl ester
12-15-alkyl) mixture of ester, Unimac 5680 (2-ethylhexyl) ester and different n-nonanoic acid isotridecyl ester.
For the present invention, in hydrocarbon, advantageously use paraffin oil, squalane and squalene.
In addition, although except silicone oil, preferably use other oil-phase component of additional quantity, advantageously oil phase also can have the ring-type or the linear silicone oil of certain content or be made up of described oil fully.
Ring first silicone (Cyclomethicone) (octamethylcyclotetrasiloxane) is advantageously used for according to silicone oil used in the present invention.But, advantageously also can use other silicone oil for the present invention, for example hexamethyl cyclotrisiloxane, polydimethylsiloxane, poly-(methylphenyl siloxane).
Also particularly advantageous is the mixture of ring first silicone and different n-nonanoic acid isotridecyl ester and the mixture of ring first silicone and Unimac 5680 (2-ethylhexyl) ester.
According to the optional alcohol that advantageously comprises low carbon number of the water of preparation of the present invention, two pure and mild polyvalent alcohol and ethers thereof, preferred alcohol, Virahol, propylene glycol, glycerine, ethylene glycol, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether or propylene glycol monobutyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether and analogous products, and the alcohol of low carbon number, as ethanol, Virahol, 1, the 2-propylene glycol, glycerine and particularly one or more thickening materials, described thickening material advantageously is selected from silicon-dioxide, pure aluminium silicate, polysaccharide and derivative thereof, as hyaluronic acid, xanthan gum, HYDROXY PROPYL METHYLCELLULOSE, particularly advantageous is to be selected from polyacrylic ester, be preferably selected from the polyacrylic ester of so-called carbopol, as alone or in combination carbopol series 980 in all cases, 981,1382,2984,5984.
Specifically, use the mixture of above-mentioned solvent.Under the situation of alcoholic solvent, water can be other composition.
Emulsion according to the present invention is favourable and comprises that for example cited fat, oil, wax and other lipoid material, and water and emulsifying agent are as the preparaton that is generally used for described type.
In preferred embodiments, preparation according to the present invention comprises hydrophilic surfactant.
Hydrophilic surfactant is preferably selected from alkyl glucoside, acyl-lactate, trimethyl-glycine and cocounut oil both sexes acetate (cocoamphoacetate).
Alkyl glucoside advantageously is selected from by structural formula it
The alkyl glucoside that is characterized, wherein R has the branching of 4-24 carbon atom or the alkyl and the DP of non-branching is up to 2 average glucosylation degree.
Numerical value DP represents the glucosylation degree according to alkyl glucoside used in the present invention, and is defined as
Herein, p
1, p
2, p
3... and p
iExpression is single doubly, double, three times ... the mark of i times of glucosylation product, by weight percentage.According to the present invention, the product that has the glucosylation degree and be 1-2 advantageously is selected from, and particularly advantageously is selected from 1.1-1.5, more particularly advantageously is selected from 1.2-1.4, and especially 1.3.
Numerical value DP considers alkyl glucoside because this fact of mixture of its preparation ordinary representation list glucoside and oligomeric glucopyranoside.According to the present invention, single glucoside of high level advantageously, typically its order of magnitude is 40-70 weight %.
The alkyl glucoside that particularly advantageously uses according to the present invention is selected from octyl group glucose pyranoside, nonyl glucose pyranoside, decyl glucose pyranoside, undecyl glucose pyranoside, dodecyl glucose pyranoside, tetradecyl glucose pyranoside and hexadecyl glucose pyranoside.
Use natural also advantageously or synthesis material and auxiliary agent or by the mixture of the effective amount of actives used, as Plantaren 1200 (Henkel KGaA), Oramix NS 10 (Seppic) as feature according to the present invention.
Acyl-lactate advantageously is selected from by structural formula it
The material that is characterized, wherein R
1Be the branching with 1-30 carbon atom or the alkyl of non-branching, and M
+The ammonium ion that is selected from alkalimetal ion and replaces by one or more alkyl and/or one or more hydroxyalkyl, or corresponding to a seminormal alkaline-earth metal ions.
For example, iso stearyl Sodium.alpha.-hydroxypropionate advantageously is as the product P athionic ISL available from American IngredientsCompany.
Trimethyl-glycine advantageously is selected from by structural formula
The material that is characterized, wherein R
2Be the branching with 1-30 carbon atom or the alkyl of non-branching.
R
2Particularly advantageously for having the branching of 6-12 carbon atom or the alkyl of non-branching.
For example, caprinoyl amido CAB advantageously is as the product Tetgo Betaine 810 available from Th.Goldschmidt AG.
Selected favourable cocounut oil both sexes acetate is according to the present invention, cocounut oil both sexes sodium acetate for example, as title that can Miranol Ultra C32 available from Miranol Chemical Corp's.
Formulation characteristics advantageously according to the present invention is that hydrophilic surfactant is 0.01-20 weight % with concentration, preferred 0.05-10 weight %, and the consumption of preferred especially 0.1-5 weight % exists, in all cases all based on the total amount of composition.
For purposes, impose on skin and/or the hair with competent amount with the makeup usual manner according to makeup of the present invention and skin preparation.
Can take various forms according to makeup of the present invention and skin preparation.Therefore, for example they can be solution, anhydrous formulation, water-in-oil (W/O) type or oil-in-water (O/W) type emulsion or microemulsion, for example water-in-oil-in-water (W/O/W) type multiple emulsion, gel, solid stick thing, cream or aerosol.With capsule shape,, for example encapsulate, use ectoin also advantageously with the form of gelatin, wax-matrix or liposome encapsulation as Mierocrystalline cellulose as in collagen stroma and other conventional packaged material.Specifically, proved that the wax-matrix described in DE-A 4308282 is favourable.Preferred emulsion.Preferred especially O/W emulsion.Emulsion, W/O emulsion and O/W emulsion obtain with ordinary method.
Used emulsifying agent can be for example known W/O and O/W emulsifying agent.Advantageously in preferred O/W emulsion according to the present invention, use other conventional co-emulsifier.
According to the present invention, selected emulsifying agent advantageously, O/W emulsifying agent for example mainly is selected from the HLB value and is 11-16, more preferred HLB value is the material of 14.5-15.5, condition is that the O/W emulsifying agent has saturated radicals R and R '.If the O/W emulsifying agent has undersaturated radicals R and/or R ', if or have the iso-alkyl derivative, then the preferred HLB value of described emulsifying agent can also be lower or higher.
Advantageously from the stearyl alcohol of ethoxylation, hexadecanol, hexadecyl stearyl alcohol (cetostearyl alcohol), select fatty alcohol ethoxylate.Preferred especially: polyoxyethylene glycol (13) stearyl ether (steareth-13), polyoxyethylene glycol (14) stearyl ether (steareth-14), polyoxyethylene glycol (15) stearyl ether (steareth-15), polyoxyethylene glycol (16) stearyl ether (steareth-16), polyoxyethylene glycol (17) stearyl ether (steareth-17), polyoxyethylene glycol (18) stearyl ether (steareth-18), polyoxyethylene glycol (19) stearyl ether (steareth-19), polyoxyethylene glycol (20) stearyl ether (steareth-20), the different stearyl ether of polyoxyethylene glycol (12) (isosteareth-12), the different stearyl ether of polyoxyethylene glycol (13) (isosteareth-13), the different stearyl ether of polyoxyethylene glycol (14) (isosteareth-14), the different stearyl ether of polyoxyethylene glycol (15) (isosteareth-15), the different stearyl ether of polyoxyethylene glycol (16) (isosteareth-16), the different stearyl ether of polyoxyethylene glycol (17) (isosteareth-17), the different stearyl ether of polyoxyethylene glycol (18) (isosteareth-18), the different stearyl ether of polyoxyethylene glycol (19) (isosteareth-19), the different stearyl ether of polyoxyethylene glycol (20) (isosteareth-20), polyoxyethylene glycol (13) cetyl ether (ceteth-13), polyoxyethylene glycol (14) cetyl ether (ceteth-14), polyoxyethylene glycol (15) cetyl ether (ceteth-15), polyoxyethylene glycol (16) cetyl ether (ceteth-16), polyoxyethylene glycol (17) cetyl ether (ceteth-17), polyoxyethylene glycol (18) cetyl ether (ceteth-18), polyoxyethylene glycol (19) cetyl ether (ceteth-19), polyoxyethylene glycol (20) cetyl ether (ceteth-20), the different cetyl ether of polyoxyethylene glycol (13) (isoceteth-13), the different cetyl ether of polyoxyethylene glycol (14) (isoceteth-14), the different cetyl ether of polyoxyethylene glycol (15) (isoceteth-15), the different cetyl ether of polyoxyethylene glycol (16) (isoceteth-16), the different cetyl ether of polyoxyethylene glycol (17) (isoceteth-17), the different cetyl ether of polyoxyethylene glycol (18) (isoceteth-18), the different cetyl ether of polyoxyethylene glycol (19) (isoceteth-19), the different cetyl ether of polyoxyethylene glycol (20) (isoceteth-20), polyoxyethylene glycol (12) oleyl ether (oleth-12), polyoxyethylene glycol (13) oleyl ether (oleth-13), polyoxyethylene glycol (14) oleyl ether (oleth-14), polyoxyethylene glycol (15) oleyl ether (oleth-15), polyoxyethylene glycol (12) bay ether (laureth-12), the different bay ether of polyoxyethylene glycol (12) (isolaureth-12), polyoxyethylene glycol (13) hexadecyl stearyl ether (ceteareth-13), polyoxyethylene glycol (14) hexadecyl stearyl ether (ceteareth-14), polyoxyethylene glycol (15) hexadecyl stearyl ether (ceteareth-15), polyoxyethylene glycol (16) hexadecyl stearyl ether (ceteareth-16), polyoxyethylene glycol (17) hexadecyl stearyl ether (ceteareth-17), polyoxyethylene glycol (18) hexadecyl stearyl ether (ceteareth-18), polyoxyethylene glycol (19) hexadecyl stearyl ether (ceteareth-19), polyoxyethylene glycol (20) hexadecyl stearyl ether (ceteareth-20).
Advantageously also be selected from the fatty acid ethoxylate of following each group:
Polyoxyethylene glycol (20) stearate, polyoxyethylene glycol (21) stearate, polyoxyethylene glycol (22) stearate, polyoxyethylene glycol (23) stearate, polyoxyethylene glycol (24) stearate, polyoxyethylene glycol (25) stearate, polyoxyethylene glycol (12) isostearate, polyoxyethylene glycol (13) isostearate, polyoxyethylene glycol (14) isostearate, polyoxyethylene glycol (15) isostearate, polyoxyethylene glycol (16) isostearate, polyoxyethylene glycol (17) isostearate, polyoxyethylene glycol (18) isostearate, polyoxyethylene glycol (19) isostearate, polyoxyethylene glycol (20) isostearate, polyoxyethylene glycol (21) isostearate, polyoxyethylene glycol (22) isostearate, polyoxyethylene glycol (23) isostearate, polyoxyethylene glycol (24) isostearate, polyoxyethylene glycol (25) isostearate, polyoxyethylene glycol (12) oleic acid ester, polyoxyethylene glycol (13) oleic acid ester, polyoxyethylene glycol (14) oleic acid ester, polyoxyethylene glycol (15) oleic acid ester, polyoxyethylene glycol (16) oleic acid ester, polyoxyethylene glycol (17) oleic acid ester, polyoxyethylene glycol (18) oleic acid ester, polyoxyethylene glycol (19) oleic acid ester, polyoxyethylene glycol (20) oleic acid ester.
Also advantageously can be with alkyl ether carboxylic acid or its salt of laureth-11 carboxylic acid sodium as ethoxylation.As sulfated alkyl ether, advantageously can use laureth-14 sodium sulfate.Used ethoxylation cholesterol derivative is polyoxyethylene glycol (30) courage steroid ether advantageously.Polyoxyethylene glycol (25) soyasterol also proves useful.Spendable ethoxylated glycerol three acid esters are polyoxyethylene glycol (60) root of Redsepal Eveningprimrose glyceryl ester advantageously.
Select the polyethylene glycol glycerol fatty acid ester from polyoxyethylene glycol (20) glyceryl laurate, polyoxyethylene glycol (21) glyceryl laurate, polyoxyethylene glycol (22) glyceryl laurate, polyoxyethylene glycol (23) glyceryl laurate, polyoxyethylene glycol (6) glyceryl decylate, polyoxyethylene glycol (20) glyceryl oleic acid ester, polyoxyethylene glycol (18) glyceryl oleic acid ester (cocounut oil acid esters) (cocoate) also advantageously.
From polyoxyethylene glycol (20) sorbitanic mono-laurate, polyoxyethylene glycol (20) sorbitan monostearate, polyoxyethylene glycol (20) sorbitanic list isostearate, polyoxyethylene glycol (20) sorbitanic monopalmitate, polyoxyethylene glycol (20) sorbitanic monoleate, select sorbitan ester also advantageously.
Randomly, but operable in some cases favourable W/O emulsifying agent is according to the present invention:
Fatty Alcohol(C12-C14 and C12-C18) with 8-30 carbon atom, carbochain is 8-24, particularly 12-18 carbon atom is saturated and/or unsaturated, the direactive glyceride of the alkanoic acid of branching and/or non-branching, carbochain is 8-24, particularly 12-18 carbon atom is saturated and/or unsaturated, two glyceryl ester of the alkanoic acid of branching and/or non-branching, carbochain is 8-24, particularly 12-18 carbon atom is saturated and/or unsaturated, single glyceryl ether of the alcohol of branching and/or non-branching, carbochain is 8-24, particularly 12-18 carbon atom is saturated and/or unsaturated, two glyceryl ethers of the alcohol of branching and/or non-branching, carbochain is 8-24, particularly 12-18 carbon atom is saturated and/or unsaturated, the propylene glycol ester of the alkanoic acid of branching and/or non-branching and carbochain are 8-24, and particularly 12-18 carbon atom is saturated and/or unsaturated, the sorbitan ester of the alkanoic acid of branching and/or non-branching.
Particularly advantageous W/O emulsifying agent is a glyceryl monostearate, single Tegin ISO, single tetradecanoic acid glyceryl ester, XU 61518.10, Stearinsaeure two glyceryl ester, single Unimac 5680 two glyceryl ester, propylene glycolmonostearate, single Unimac 5680 propylene glycol ester, single sad propylene glycol ester, the mono laurate propylene glycol ester, single Unimac 5680 sorbitan ester, the mono laurate sorbitan ester, single sad sorbitan ester, single isooleic acid sorbitan ester, distearyl acid sucrose ester, hexadecanol, stearyl alcohol, n-Eicosanol behenyl alcohol Yi behenyl alcohol, selachyl alcohol, testriol, polyoxyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, single caprin, single caprylin.
Preferred preparation is specially adapted to protect people's skin aging and anti-oxidation to prevent according to the present invention, promptly prevents the damage by the free radical that for example passes through solar irradiation, heat and other influence generation.Therefore, they are the various administration forms that routine is used for above-mentioned application.Thereby they can be lotion or emulsion especially, as the form of frost or emulsion (O/W, W/O, O/W/O, W/O/W), be oil-containing-contain alcohol, oil-containing-moisture or moisture-contain alcogel or solution, be the form of solid stick thing or be mixed with aerosol.
Preparation can comprise the cosmetic additive that routine is used for the preparation of described type, as the conventional composition that uses in thickening material, tenderizer, wetting Agent for Printing Inks, tensio-active agent, emulsifying agent, sanitas, defoamer, spices, wax, lanolin, propelling agent, the dyestuff that makes composition itself or pigmenting of skin and/or pigment and other makeup.
Operable dispersion agent and/or solubilizing agent are oil, wax or other lipoid material, low-grade monobasic alcohol or lower polyol or its mixture.Particularly preferred monohydroxy-alcohol or polyvalent alcohol comprise ethanol, Virahol, propylene glycol, glycerine and sorbyl alcohol,
The preferred embodiments of the invention are emulsion; described emulsion is the form of protectiveness frost or emulsion; and except tinting pigment according to the present invention; in the presence of water, also comprise; for example Fatty Alcohol(C12-C14 and C12-C18), lipid acid, fatty acid ester; the tri-glyceride of lipid acid particularly, lanolin, natural and synthetic is oily or wax and emulsifying agent.
Embodiment preferred is oily and wax, lanolin, fatty acid ester based on natural or synthetic in addition, particularly the tri-glyceride of lipid acid contain oil-emulsion, based on lower alcohol, as ethanol, or glycerine, as propylene glycol, and/or polyvalent alcohol, as glycerine, with oil, wax and fatty acid ester, as the pure lotion of the oil-containing of the tri-glyceride of lipid acid-contain.
Also can be the form that contains alcogel according to preparation of the present invention, it comprises one or more lower alcohols or polyvalent alcohol, as ethanol, propylene glycol or glycerine, and thickening material, as diatomite.Oil-containing-contain alcogel also can comprise natural or synthetic is oily or wax.
The solid stick thing comprises natural or synthetic wax and oil, Fatty Alcohol(C12-C14 and C12-C18), lipid acid, fatty acid ester, lanolin and other lipoid material.
If preparation is mixed with aerosol, then use conventional propellant usually, as alkane, fluoroalkane, chlorofluoro-alkane.
Cosmetic formulations also can be used for protecting hair with photochemistry infringement, decolouring or the mechanicalness infringement of opposing in order to suppress the shade of color change.In this case, preparaton is suitable for being shampoo, lotion, gel or the flushing form with emulsion, and specific formulation is before or after the hair washing, before or after the painted or bleaching or use before or after the hair-waving.Can also select to be typing or treatment with the preparation of the form of lotion, be scrub or the having one's hair waved wave with the preparation of the form of lotion or gel, be bright agent, perm composition, composition for hair dying or make the preparation of hair decolorizing composition form.
Except tinting pigment according to the present invention; preparation with light-protection energy also comprises the various auxiliary agents that use in described type of composition, as interfacial agent, thickening material, polymkeric substance, tenderizer, sanitas, suds-stabilizing agent, ionogen, organic solvent, silicone derivative, oil, wax, grease-proof agent, the dyestuff that makes composition itself or hair coloring and/or pigment or other composition that is generally used for taking care of hair.
The present invention provides a kind of method of producing preparation in addition, it is characterized in that the carrier that will be suitable at least a tinting pigment according to the present invention and makeup or the dermatology mixes.Can use technology production well known in the art according to preparation of the present invention herein.
With reference to following examples the present invention that explains.
Embodiment:
In the erlenmeyer flask of 100ml, with 2,4 of 0.631g, 6-triamino-2,4,6-triazine (melamine) under agitation is dissolved in the deionized water of 50mi and 0.5mi concentration under 70 ℃ be in 2.5% the tetramethyl ammonium hydroxide solution, and to add 0.22ml concentration be 37% formaldehyde solution.Clear soln is stirred 15 minutes so that guarantee to form methylol melamine.Adding 29 is Prussian blue in solution then.Immediately be 30% H with 0.3ml concentration
2O
2Join in the suspension that just is blue with beginning coating (polycondensation).The pigment that water and acetone clean to be formed by whizzer, and be dried and to its evaluation.
With untreated Prussian blue comparing, coating has the material of melamine to demonstrate obviously more pleasant " similar fat-cream " sensation on skin.
Claims (19)
1. non-flak coated colouring pigment, it is characterized in that described pigment is made of the material inorganic or organic, amorphous or partial crystallization that is provided with at least one coating, wherein under every layer of coating comprise at least a curing melamine-formaldehyde resin or constitute by a kind of described resin.
2. the tinting pigment of claim 1 is characterized in that described pigment is made of six sour iron of cyanogen iron (II) (III) or chromic oxide (III).
3. claim 1 or 2 tinting pigment is characterized in that solidifying melamine-formaldehyde resin and comprise one or more inorganic or organic dye and/or one or more inorganic or organic UV absorption agents, and described dye soluble is in pigment is applied in the used medium.
4. the tinting pigment of claim 3 it is characterized in that described dyestuff is present in one or more layers internal layer that comprises melamine-formaldehyde resin, and the UV absorption agent is present in one or more layers skin that comprises melamine-formaldehyde resin.
5. one of claim 1-4 or multinomial tinting pigment, it is characterized in that the curing melamine-formaldehyde resin particle that will be essentially circular in addition imposes in the outermost layer coating, described particle comprises one or more dyestuffs and/or one or more UV absorption agents or does not contain dyestuff and/or the UV absorption agent.
6. one of claim 1-5 or multinomial tinting pigment is characterized in that outermost curing melamine-formaldehyde resin adopts functional group modification.
7. the tinting pigment of claim 6, it is characterized in that the described functional group of outermost layer modification that makes is through also having the amino-functional compounds introducing of one or more other functional groups except amino, polycondensation between this amino-functional compounds participation melamine and the formaldehyde and its are attached in melamine-formaldehyde network through amido functional group, and wherein so impose on the optional further modification of functional group on surface.
8. the tinting pigment of claim 6 is characterized in that methylol amine or amino employing and hydroxyl and/or amino react compound modified of outermost curing melamine-formaldehyde resin through existing therein, makes functionalisation of surfaces.
9. according to or the multinomial tinting pigment of claim 3-8, wherein the dyestuff of Cun Zaiing is at least a fluorescence dye and a kind of optional in addition fluorescence dye, it is present in the melamine-formaldehyde resin, and wherein other dyestuff exists with the consumption of not giving pigment color or fluorescence when using this dyestuff separately basically.
10. produce the method for non-thin slice tinting pigment, it is characterized in that with one or more layers coating
Under the situation of single coating,
In the first step, tinting pigment is suspended in the alkaline aqueous medium that comprises melamine and formaldehyde and/or can choose oxyalkylated methylol melamine wantonly and
In second step, cause the crosslinked of organic component by pH being reduced to acid range,
With under the situation of a plurality of coatings,
Adopt the product of aforementioned coating reaction to repeat the first step and second step.
11. the method for claim 10 it is characterized in that the part melamine is substituted by the corsslinking molecular that other is selected from " guanamines class, phenols and ureas ", and/or the part methylol melamine is alternative by the analogue of corresponding guanamines, phenol or urea.
12. the method for claim 10 or 11 is characterized in that inorganic or organic dye and/or inorganic or organic UV absorption agent add before crosslinking reaction begins or during crosslinking reaction.
13. the method for claim 12 is characterized in that the dyestuff that is added is at least a fluorescence dye and optional in addition fluorescence dye, wherein other dyestuff adds with the consumption of not giving pigment color or fluorescence when adding this dyestuff separately basically.
14. one or the multinomial method of claim 10-13, it is characterized in that pH is reduced in the acid range by the formaldehyde that makes excessive formaldehyde and/or unreacted formaldehyde and/or be present in the methylol melamine takes place with the oxidation of hydrogen peroxide.
15. one or the multinomial method of claim 10-14, it is characterized in that in last coating step, except melamine and formaldehyde and/or methylol melamine, the amino-functional compounds that also has one or more functional groups except amino is participated in the polycondensation, described amino-functional compounds is attached in melamine-formaldehyde network through amido functional group, and so imposes on the optional further modification of functional group on surface.
16. one or the multinomial method of claim 10-14 is characterized in that outermost curing melamine-formaldehyde resin is by being present in its lip-deep methylol amine or amino reacting with the compound that also has with hydroxyl and/or the amino group that reacts except one or more other functional groups.
17. the purposes of the non-flak coated colouring pigment of one or more claims 1-9 is as cosmetic formulations and/or be used for imposing on the effect pigment of the other products on the skin.
18. comprise the composition of the non-thin slice coated carrier material of one or more claims 1-9 as tinting pigment.
19. the non-thin slice coated carrier material that comprises one or more claims 1-9 of claim 18 is characterized in that as the composition of tinting pigment described composition is a cosmetic formulations.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02022553 | 2002-10-08 | ||
| EPEP02022553.8 | 2002-10-08 | ||
| EPEP02024370.5 | 2002-11-02 |
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| CN1694928A true CN1694928A (en) | 2005-11-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03824923 Pending CN1694928A (en) | 2002-10-08 | 2003-09-23 | Non-flak coated colouring pigment and method for the production and use thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102933661A (en) * | 2010-05-28 | 2013-02-13 | Omya发展股份公司 | Process for the preparation of surface treated mineral filler products and uses of same |
| CN113795555A (en) * | 2019-05-09 | 2021-12-14 | 莱雅公司 | UV screening multilayer material, composition comprising same, method for treating keratin materials using same, and method for producing said material |
-
2003
- 2003-09-23 CN CN 03824923 patent/CN1694928A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102933661A (en) * | 2010-05-28 | 2013-02-13 | Omya发展股份公司 | Process for the preparation of surface treated mineral filler products and uses of same |
| CN102933661B (en) * | 2010-05-28 | 2014-10-08 | Omya国际股份公司 | Process for the preparation of surface treated mineral filler products and uses of same |
| US9139735B2 (en) | 2010-05-28 | 2015-09-22 | Omya International Ag | Process for the preparation of surface treated mineral filler products and uses of same |
| US9139734B2 (en) | 2010-05-28 | 2015-09-22 | Omya International Ag | Process for the preparation of surface treated mineral filler products and uses of same |
| US9212283B2 (en) | 2010-05-28 | 2015-12-15 | Omya International Ag | Process for the preparation of surface treated mineral filler products and uses of same |
| US9212284B2 (en) | 2010-05-28 | 2015-12-15 | Omya International Ag | Process for the preparation of surface treated mineral filler products and uses of same |
| CN113795555A (en) * | 2019-05-09 | 2021-12-14 | 莱雅公司 | UV screening multilayer material, composition comprising same, method for treating keratin materials using same, and method for producing said material |
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