CN101547977B - Surface-modified (effect) pigments - Google Patents

Surface-modified (effect) pigments Download PDF

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Publication number
CN101547977B
CN101547977B CN200780044932.4A CN200780044932A CN101547977B CN 101547977 B CN101547977 B CN 101547977B CN 200780044932 A CN200780044932 A CN 200780044932A CN 101547977 B CN101547977 B CN 101547977B
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pigment
acid ester
phosphoric acid
oxide
coating
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CN101547977A (en
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K·伊瓦萨
M·哈恩
P·巴格农
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BASF Schweiz AG
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Ciba SC Holding AG
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Priority claimed from PCT/EP2007/062780 external-priority patent/WO2008068152A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention relates to pigment based on (multiple) coated platelet-shaped substrates comprising an outer layer which is obtained by treatment with a metal oxide/hydroxide and then a phosphate ester, or phosphonate, or a salt thereof, with the proviso that the phosphate ester, or phosphonate do not contain fluorine, to a method for producing said pigments and the use thereof. The outer layer provides a very good photo-stabilisation of the TiO2coated platelet-shaped substrates, such as mica, combined with a good water resistance and an anti-yellowing performance.

Description

Surface-modified (synergy) pigment
The present invention relates to the pigment of the platelet-shaped substrate applying based on (multilayer), prepare method of described pigment and uses thereof, wherein said pigment comprises that condition is that described phosphoric acid ester or phosphonic acid ester are not fluorine-containing by using metal oxide/oxyhydroxide and phosphoric acid ester afterwards or phosphonic acid ester or its salt to process the skin obtaining.
The known titanium dioxide granule existing as pigment composition in coating causes polymkeric substance in the time being exposed under ultraviolet ray and moisture oxygenolysis to occur, and this is called and brightens.In order to suppress this effect of titanium dioxide, proposed with the compound titanium dioxide coating of chromium, silicon, aluminium, zinc, phosphorus or zirconium or with its doping.
In EP0268918, described a kind of weathering resistance pearly pigment on the pigment of titanium dioxide basis with aqua oxidation zirconium coating, this coating obtains by being hydrolyzed zirconates under existing at hypophosphite.
In EP0342533, described a kind of on the pigment of titanium dioxide basis, the have top layer that is made up of hydrous zirconium oxide and the weathering resistance pearly pigment of hydrated metal oxide, wherein said hydrous zirconium oxide obtains by being hydrolyzed under existing at hypophosphite.Described metal oxide can be cobalt oxide, manganese oxide or cerium oxide.
Modified pearlite pigment has enough dispersivenesses and weathering resistance in nonaqueous coating system.But it causes forming micro bubble in coated membrane, described bubble significantly improves scattering of light and therefore gloss and color is had to disadvantageous effect, thereby it is not suitable for being used in water-dilutable (water-thinable) coating system.In addition, the sharpness of image (DOI) significantly reduces and the regenerative power of coated membrane is damaged.
Platelet-shaped transparent substrate based on having applied nonferrous metal oxides or metal hydroxides has been described in US4435220, the transparent colored pigment of for example mica, talcum or glass, the alkaline earth metal compound that wherein said metal oxide or hydroxide layer contain 0.1-5% weight, dispersiveness, gloss, color powder and the stability to heat and weather and filling and the cohesiveness improved in order to give pigment.
In US3650790, describe and demonstrated the oyster white of strong interference color, reduction and the nacre pigment of gloss firmly, its be by deposition of titanium oxide thin layer on mica sheet, under the pH of 7-11.5 in the water-soluble serous middle pigments, mica of titanium dioxide-coated of processing gained with soluble silicate, the pigment of and the silicate of calcining gained-processed makes; And the pigment of gained.In US3650790, disclosed pigment is stable not under UV light.
EP0446986 relates to light and pigments, mica moisture stable, that applied metal oxide with enhancing, and described pigment has aluminum hydrous oxide coating on particle surface.
EP0632109 relates to the pearly pigment that comprises the strip substrate that has applied metal oxide layer and top metal oxide skin, top layer, wherein said top layer is by silicon-dioxide, at least one other metal hydroxides or metal oxide hydrate, and at least one organic coupler composition.Other described metal hydroxides or metal oxide hydrate are oxyhydroxide or oxygenate or its mixtures of cerium, aluminium and zirconium.Coupler used is the ester of silane, zirconium aluminate or the metal acid of functional organic.According to EP0888410, be no more than 60% added coupler and can be bonded in surface of pigments, result must correspondingly increase material used.Described non-coupling part is retained in reaction medium and damages the filterableness of pigment.
In EP0888410, disclose the modified pearlite pigment for aqueous coating system, it is based on having applied the tabular substrate of metal oxide and being positioned at the tectum on top metal oxide skin.Described tectum is made by being selected from silicon-dioxide, aluminum oxide, cerium oxide, titanium oxide and zirconic at least two oxide compounds, hopcalite and/or mixed oxide, or is made up of water base oligomeric silane system.
EP1084198 relates to a kind of synergy pigment that has applied surface-modifying agent, and wherein initial pigment comprises the layer with at least one reactive surfaces properties-correcting agent.Described surface-modifying agent is to be bonded on initial pigment by least two functional groups that differ from one another and separated by spacer groups.Due to surface modification, the pigment of describing in EP1084198 has the pigment bounding force of improvement in basic enamelled coating.But, the unexposed pearly pigment that there is weathering resistance and there is stability with respect to UV light in EP1084198.
WO2006021388 relates to the laminar substrate that comprises containing metal oxide and the pearly pigment of protective layer, and the compound of wherein said metal oxygen has the specific refractory power that is greater than 1.8.Described protective layer is by the SiO of organic-chemical surface-modification 2layer composition, described organic-chemical surface modification is applied to described SiO 2layer.
US4209430 relates to a kind of by directly adding or add the polyenoid of phosphorylation to suppress to contain phenol antioxidant and TiO as the coating of pigment in polyolefine 2the method of the TPO yellowing of pigment.Described phosphorylation polyenoid is the reaction product of phosphorylation agent and polyenoid (unsaturated compound of polyenoid class).
In EP0644242, disclose and comprised (a) polyolefine; (b) antioxidant; (c) composition of mica particles, its surface-coated the first layer-titanium dioxide, and the second layer-silicon-dioxide subsequently and the calcining coating of aluminum oxide, its polyolefin compositions yellowing for preventing from containing antioxidant.
WO9858017 (US5951750) relates to one and comprises polyolefine; Antioxidant; With the composition of the pearly pigment that comprises mica particles, wherein said mica particles has the first layer-coating of titanium dioxide in its surface, and the second layer thereon-be selected from oxide compound and phosphorus compound and the doping ZrO of Mg, Ca, Ce, Zn, Y 2the metallic compound of calcining, wherein said doping agent is Y, Ca or Ce.The upper coating of described calcining prevents the yellowing of described composition.Described phosphorus compound is preferably phosphoric acid salt, but can be also phosphite.
EP0505086 discloses a kind of method of processing lamelliform or thin flaky pigment or supplement, it comprises by step and a) on the particle surface of material, forms phosphoric acid zinc coating, a) by 50-100 DEG C, make material and pH be 11 or the sodium hydroxide of higher zinc salt or potassium hydroxide solution contact and apply the particle of described material with zinc oxide or zinc hydroxide, thereby on the surface of described particle, form zinc oxide or hydroxide deposits thing; B) by having applied the material of zinc oxide or zinc hydroxide and zinc oxide or zinc hydroxide be converted into zinc phosphate with acid phosphatase salts solution or phosphoric acid processing.
US4482389 relates to pearly pigment weather to the stability of improvement, its mica sheet based on having applied the second coating containing chromium metal oxide, that have stabilization, the combination that described the second coating comprises metal-salt.In order to form the described second layer, iron and/or manganese are deposited on initial pigment with oxyhydroxide, carbonate or phos-phate forms, by chromium using oxyhydroxide, carbonate or phosphatic form or be deposited on initial pigment as methacrylic acid-chromium chloride.
EP0757085 discloses pearly pigment, and it comprises sheet substrate, is coated in its lip-deep titanium oxide and phosphate metal compound, or is coated in phosphate metal compound and metal oxide on the particle surface that is coated with titanium oxide.The discoloration-resistant of described pigment and with avidity (dispersiveness) excellence of resin." phosphate metal compound " and " phosphate metal compound and metal oxide " means final state, the i.e. hydrolysate of phosphoric acid or phosphate compounds and various metal-salts.
EP1479731 relates to a kind of new synergy pigment, the substrate of described pigment based on comprising at least one layer being made up of coloured cooperation phosphate system, preparation of these pigment and uses thereof.Described cooperation phosphate system has formula A pb qp xo y, wherein 1,2 of A=ammonium, periodictable, the metal of 11 and/or 12 families, the element of B=periodictable 3-15 family, group of the lanthanides and/or actinium series, p=1,2 ... .r, q=1,2 ... .s, x=1,2....n, and y=2 ... .m.
EP1479730 relates to a kind of new synergy pigment, and described pigment is based on comprising at least one substrate by the layer of binary phosphate composing system, preparation of these pigment and uses thereof.Described binary phosphate system has formula A xp yo z, the wherein element of A=periodictable 1-14 family, group of the lanthanides or actinium series, x=1,2....n, y=1,2 ... .m, its by many-or pyrophosphate salt structure define, z defines by valency and the cationic valency of A-of phosphorus.
It is of fine quality different that WO02064682 relates to a kind of separability, and between granules of pigments and coating (resin), there is excellent fusible flaky pigment, wherein said coating is by with coupler with have the organic compound of perfluoro alkyl group, and the phosphoric acid ester coated platelet surface of pigments for example with perfluoro alkyl group obtains.The example with the phosphoric acid ester of perfluoro alkyl group is following formula: compound: [Rf (C nh 2no) m] ypO (OM) 3-y, wherein Rf represents straight or branched C 6-C 21perfluoro alkyl group or perfluoro alkoxy group, M represents the ammonium of hydrogen, basic metal, ammonium and replacement, and n is 1-4, and m is 0-10, and y is 1-3; (RfSO 2nRC nh 2no) ypO (OM) 3-y, wherein Rf represents straight or branched C 6-C 21perfluoroalkyl or perfluoro alkoxy, M represents the ammonium of hydrogen, basic metal, ammonium or replacement.Described coupler is preferably one or more materials that are selected from silane coupling agent, titanium-Ji coupler and zirconium-Ji coupler.
EP1090963 relates to the flaky pigment of the excellent high orientation of a kind of planar orientation (peeling off effect), wherein by general formula (RfC nh 2no) mpO (OM) 3-mand (RfSO (A) 2nRC nh 2no) mpO (OM) 3-m(B) or hydrated metal oxide and one or more fluorine-containing phosphoric acid ester of the representative of its salt cover on the flaky pigment surface with pearly-lustre, wherein Rf is identical or different, represents straight or branched C 3-C 21perfluoro alkyl group or perfluor oxygen base alkyl group, n is 1-12, and m is 1-3, and M represents the ammonium group of hydrogen, basic metal, ammonium group or replacement, and R represents hydrogen or C 1-C 3alkyl group.
WO9830637 relates to the use substrate (S) that is made up of tinting material and substrate and the composite pigment of tinting material (C), described substrate and tinting material are coated with ion and the ionizable compound of the electric charge with equidirectional rotation separately, and if wish also to comprise that the ion of the other electric charge with equidirectional rotation or ionizable compound are as layer material (L), the wherein electric charge symbol of (I) coating S, or the symbol of the electric charge of coating S and the electric charge of L is contrary with the electric charge symbol of coating C, the electric charge of its floating coat S is identical with the symbol of the electric charge of L, or (II) the electric charge symbol of coating S and C is identical, and contrary with the electric charge symbol of L.In the preferred embodiment of WO9830637, first use HO-SiMe 2-(CH 2) 3-P (O) (OH) 2scatter coated the pigments, mica of titanium dioxide, formerly use afterwards Zr 4+process, use afterwards inorganic phosphate processing again, conventionally at room temperature add subsequently PAH solution, described like this substrate just has positively charged surface.After applying, filter and wash the substrate through applying how to obtain.Conventionally join in the aqueous dispersion of coated substrate thering is electronegative surperficial coating tinting material afterwards, described coated substrate be preferably applied zirconium phosphate and, if wished, replaced by alkyl or aryl in 3-and 6-position 1,4-diketone 2,5-pyrrolin also-[3,4-c] pyrroles (" DPP ").
In WO0242381, disclose and comprised by Organic Alcohol and P 2o 5or the pigment of the pigment substrate of the product processing of phosphatase reaction gained, the wherein weighing scale based on described pigment substrate, the amount of described product is about 0.01%-approximately 5%.The example of pigment substrate comprises titanium dioxide, kaolin, talcum, mica and calcium carbonate.Described pigment substrate titanium dioxide can be by other metal oxide, and for example aluminum oxide, silicon-dioxide, zirconium white are further processed.
The object of this invention is to provide and applied flaky pigment metal oxide, that there is effective protective layer.Especially, described protective layer should play effective provide protection and make its photocatalytic activity that avoids the pigment that produces ultraviolet induction, does not also affect the optical property of described pigment simultaneously.In addition, described pigment should have the jaundice effect of the TPO that excellent weathering stability and inhibition contain phenol antioxidant.
Described object realizes by the pigment of the platelet-shaped substrate based on (multilayer) coating, wherein said pigment comprises that condition is that described phosphoric acid ester or phosphonic acid ester are not fluorine-containing by processing with metal oxide/oxyhydroxide and phosphoric acid ester afterwards or phosphonic acid ester or its salt the skin obtaining.
Described skin is to TiO 2the platelet-shaped substrate applying, for example mica provides extraordinary light stability, and make it combine good water tolerance and anti-yellowing performance, thereby make the described product can be in high-grade plastics (anti-yellowing effect) and high-grade coating (automobile).
In preferred embodiments, described pigment comprises
(A) small pieces-shape substrate;
(B) titanium dioxide layer;
(C) at the skin at layer (B) top, it obtains by using metal oxide/oxyhydroxide and phosphoric acid ester or phosphonic acid ester or its salt to process.
The example of the salt of phosphoric acid ester or phosphonic acid ester is the salt that itself and basic metal, ammonia, amine, alkanolamine or quaternary ammonium compound form.
Suitable small pieces-shape substrate is transparent, partly reflection or reflection.Its example is mica shape ferric oxide (for example, described in EP-A 0068311), mica (biotite, vermiculite, sericite, white mica, phlogopite, fluorophlogopite, kaolinite or the related substances of natural mica shape ferric oxide (for example, described in WO 99/48634), synthetic and doping, or any synthetic mica, for example synthetic fluorophlogopite), basic lead white, laminar barium sulfate, MoS 2, SiO 2, Al 2o 3, TiO 2, glass, ZnO, ZrO 2, SnO 2, BiOCl, chromic oxide, BN, MgO thin slice, Si 3n 4, and graphite.Especially preferred substrate is mica, SiO 2thin slice, Al 2o 3thin slice, TiO 2thin slice and glass flake.
Another preferred embodiment is the flat metallic particles purposes as core.The example of suitable metallic particles is Ag, Al, Au, Cu, Cr, Fe, Ge, Mo, Ni, Si, Ti or its alloy, the thin slice of for example brass or steel, preferably Al thin slice.Depend on material, can in surface of metal particles, form natural non-optical interference oxide skin.Preferably to vertically falling into, it is lip-deep for the core of part reflection, light within the scope of 380-800nm has at least 35% reflectivity.
Other example of strip substrate is strip pigment dyestuff, for example quinacridone, phthalocyanine pigment, fluorine rubine (fluororubine), Hong perylene or diketopyrrolo-pyrrole.Apply the strip particle of metal oxide layer and be well known in the art as the purposes of synergy pigment, for example, can derive from DE 1467468, EP 0045851, DE 3237264, DE 3617430, EP 0298604, EP 0388932 and EP 0402943.
Described skin (protective layer) is applicable to having applied metal oxide, and the platelet-shaped substrate that has especially applied titanium dioxide carries out stabilization.Its example is that pearl pigment (comprises that those react the material that forms nitride, oxynitride under fluidized-bed condition, or form the material of suboxide etc. by reduction) (for example EP-A-9739066, EP-A-0948571, WO99/61529, EP-A-1028146, EP-A-0763573, US-A-5,858,078, WO98/53012, WO97/43348, US-B-6,165,260, DE-A-1519116, WO97/46624, EP-A-0509352); Pearl multi-layer pigments (for example EP-A-0948572, EP-A-0882099, US-A-5,958,125,6,139,613), especially can be with title Iriodin (E.Merck, Darmstadt), Flonac (Kemira Oy, Finland), Mearlin (Mearl Corporation, New York/USA) and Infinite Color (Shisheido, Japan) and commercially available coating the mica small pieces of metal oxide, and the sheet metal applying, for example, applied the sheet metal of titanium dioxide.The granularity of described slug particle itself is not strict with, and it can be adapted to specific purposes.Conventionally, described particle has the length of about 1-200 μ m, especially about 5-100 μ m, and the thickness of about 0.05-5 μ m, preferred 0.1-2 μ m.The particle with similar platelet morphology is understood to have two substantially flat and parallel surfaces, and slenderness ratio is approximately 2: 1-approximately 1000: 1, long-width ratio is 3: 1-1: 1 particle.
The preferably transparent substrate based on thering is low-refraction, especially natural or synthetic mica, another kind of layered silicate, glass, Al 2o 3, SiO z, especially SiO 2, SiO 2/ SiO x/ SiO 2(0.03≤x≤0.95), SiO 1.40-2.0/ SiO 0.70-0.99/ SiO 1.40-2.0or Si/SiO zstrip particle (wherein 0.70≤z≤2.0, especially 1.40≤z≤2.0), there is titanium oxide layer on described substrate top.By at TiO 2the metal oxide of layer applied on top low-refraction, for example SiO 2, Al 2o 3, AlOOH, B 2o 3or its mixture, preferably SiO 2, and further use TiO on rear layer top 2layer and obtain the stronger and more transparent pigment (EP-A-892832, EP-A-753545, WO93/08237, WO98/53011, WO9812266, WO9838254, WO99/20695, WO00/42111 and EP-A-1213330) of color.Can make outmost titanium oxide layer stabilization by skin of the present invention (protective layer).
The pigment with following layer structure is particularly preferred:
TRASUB TiO 2
TRASUB TiO 2/Fe 2O 3
TRASUB Fe 2TiO 5
TRASUB TiO 2 SiO 2 TiO 2
TRASUB TiO 2 SiO 2 TiO 2/Fe 2O 3
TRASUB (Sn，Sb)O 2 SiO 2 TiO 2
TRASUB TiO 2/Fe 2O 3 SiO 2 TiO 2/Fe 2O 3
TRASUB Cr 2O 3 SiO 2 TiO 2
TRASUB Fe 2O 3 SiO 2 TiO 2
TRASUB TiO suboxide SiO 2 TiO suboxide
TRASUB TiO 2 SiO 2 TiO 2+SiO 2+TiO 2
TRASUB TiO 2+SiO 2+TiO 2 SiO 2 TiO 2+SiO 2+TiO 2
TRASUB TiO 2 Al 2O 3 TiO 2
TRASUB Fe 2TiO 5 SiO 2 TiO 2
TRASUB TiO 2 SiO 2 Fe 2TiO 5/TiO 2
TRASUB STL TiO 2
Wherein TRASUB is the transparent or semitransparent substrate with low-refraction, especially natural or synthetic mica, another kind of layered silicate, glass, Al 2o 3, SiO z, especially SiO 2, SiO 2/ SiO x/ SiO 2(0.03≤x≤0.95), SiO 1.40-2.0/ SiO 0.70-0.99/ SiO 1.40-2.0, or Si/SiO z, wherein 0.70≤z≤2.0, are especially 1.40≤z≤2.0, and
STL is semitransparent layer, for example translucent Cu, Ag, Cr or Sn metal level, or translucent carbon-coating.
Outer field metal oxide/oxyhydroxide is preferably selected from oxide/hydroxide and the combination thereof of silicon (silicon oxide, silicon oxide hydrate), aluminium, zirconium, magnesium, calcium, iron (III), yttrium, cerium, zinc.
The weighing scale of the platelet-shaped substrate applying based on described (multilayer), the amount of described metal oxide/oxyhydroxide is 0.1-10 % by weight, preferably 0.8-4 % by weight.
In a preferred embodiment of the invention, the oxide/hydroxide that described metal oxide/oxyhydroxide is following substances: aluminium (aluminum oxide, hydrated alumina), zirconium ((hydration) zirconium dioxide) or its mixture.Aluminum oxide/aluminium hydroxide is preferably used as color and stabilization; Zirconium white/zirconium hydroxide is preferred for stabilization, and best is by for stabilization with as its combination of color.
Zirconium white, aluminum oxide and zinc oxide, or zirconium white, aluminum oxide and magnesian tertiary mixture also demonstrate excellent result.
If be used in combination, can or add successively two or more salt corresponding to metal oxide/oxyhydroxide to prepare described metal oxide/hydroxide layer by the while.
The example of described phosphoric acid ester is polyoxyethylene alkyl ether phosphate, for example poly-C 2-C 4the poly-C of aklylene glycol monoether and/or carboxylic acid 2-C 4the phosphoric acid ester (ester of phosphoric acid) of aklylene glycol monoesters.
For example, it is with reference to the polyoxyethylenated alkyl phosphate of following formula: or its salt, wherein R 1can be identical or different while appearance at every turn, represent straight or branched alkyl, especially the straight or branched alkyl of 1-20 carbon atom; Phenyl; Alkylaryl, more particularly alkyl phenyl, described alkyl is the alkyl chain of 8-12 carbon atom especially; Arylalkyl, more particularly phenyl aryl; N can be the numerical value of ethylene oxide, and it is for example 2-12, and m is 1,2 or 3.In particular, R 1can be hexyl, octyl group, decyl, dodecyl, oil base or nonyl phenyl.Most preferably wherein n is 6,7 or 8, R 1for methyl and m are 1 or 2 compound.
Other example of this compounds that can mention is the Lubrophos that the material of selling with following trade name: Rhodia sells and Rhodafac , especially following products: polyoxyethylene (C 8-C 10) alkyl ether phosphate Rhodafac rA 600, polyoxyethylene tridecyl ether phosphate Rhodafac rS 710 or RS 410, polyoxyethylene oil cetyl ether phosphoric acid ester Rhodafac pA35, polyoxyethylene nonylplenyl ether phosphoric acid ester Rhodafac pA 17, polyoxyethylene (side chain) nonyl ethers phosphoric acid ester Rhodafac rE 610.
In addition any material that, phosphoric acid ester is following general formula: or or its salt, wherein R 2and R 2' be C 6-20the alkyl of alkyl or ethoxylation.Preferably R 2and R 2' be the group of following general formula: alkyl-(OCH 2cH 2) y, wherein said alkyl substituent is C 12-C 18, Y is 0-approximately 4.Most preferably the alkyl substituent of this general formula is C 12-C 18, Y is about 2-approximately 4.Should be appreciated that, that described formula represents is single-and two-ester, and commercially available phosphoric acid ester generally includes single-and the mixture of two-ester, and three esters of some ratios.
Especially suitable phosphoric acid ester is EFKA-5066, EFKA-5070, EFKA-5207, EFKA-5244, EFKA-6220, EFKA-6225, EFKA-6230, EFKA-8503, EFKA-8510, EFKA-8511, EFKA-8512, EFKA-8530, EFKA-8531, EFKA-8532 (Ciba Speciality Chemicals), Rhodafac the alkyl ether phosphate of PA23 (deriving from Rhodia), polyethylene, and Phospholan pE 169 (AKZO-NOBEL).
In a further preferred embodiment, described phosphoric acid ester or phosphonic acid ester are alkyl or alkylaryl phosphonic acid ester, for example Rhodafac pA15, or poly-aryl polyether phosphate, for example Phospholan pR221T (deriving from Akzo Nobel), or alkyl phosphonic acid, for example Rhodafac aSI 80 (deriving from Rhodia), or polyvinyl-methyl-phosphinic acid polymkeric substance, especially polyvinyl-phosphonic acids polymkeric substance, comprise vinyl phosphonate and/or vinyl methyl-phosphinic acid and other monomer, the for example multipolymer of vinylformic acid, acrylamide and vinyl acetate, for example Albritect cP30 (deriving from Rhodia).
Conventionally, the weighing scale of the platelet-shaped substrate applying based on (multilayer), the amount of described metal oxide/oxyhydroxide is 0.1-10 % by weight, preferably 0.8-4 % by weight.Conventionally, the weighing scale of platelet-shaped substrate applying based on (multilayer), described phosphoric acid ester, or the amount of phosphonic acid ester is 0.1-10 % by weight, preferably 1-6 % by weight.
In addition, the present invention relates to a kind of method of preparing pigment of the present invention, it is characterized in that
(a) by thin slice (pearly-lustre) pigment suspension in water, by the pH regulator of suspension to approximately 3, afterwards the aqueous solution of one or more metal-salts that are selected from silicon, aluminium, zinc, calcium, magnesium, zirconium, iron (III), yttrium and cerium is joined in described suspension, with alkaline aqueous solution, pH is kept to constant simultaneously, after this adds, by extremely about 7-8.5 of its pH regulator, and
(b) under agitation the aqueous solution of described phosphoric acid ester or phosphonic acid ester or its salt is joined in the suspension of gained, after this adds, filter its suspension, wash with water and be dried.
By making the aqueous solution or its corresponding metal-salt of these (hydration) metal oxides, for example muriate, vitriol, nitrate, halogenide and oxyhalogenation thing, can be by these metal oxide-coated on thin slice (pearly-lustre) pigment as raw material generation alkaline hydrolysis.
The amount that forms the metal-salt of hydrated metal oxide used in the present invention is enough to make it can on the surface of flaky pigment, form individual layer hydrated metal oxide.Therefore,, if the specific surface area of described thin slice pearly pigment is very large, need a large amount of metal-salts, and for little specific surface area, a small amount of is just enough.In addition, preferably do not adopt a large amount of metal-salts, because this can cause the tone (color, colourity, gloss) of described thin slice pearly pigment to change, and make further granules of pigments easily reunite.Conventionally, depend on the specific surface area of described thin slice pearly pigment, the amount of described metal-salt can change, and for the weight of described thin slice pearly pigment, this amount can be defined as 0.1-10 % by weight.
Whole method, at 10-90 DEG C, is preferably carried out at the temperature of 60-90 DEG C.
Preferably aluminium is used for giving color and stabilization; Zirconium is preferred for stabilization; Best is combined for stabilization and is given color.
The preferred precursor of aluminum oxide or aluminium hydroxide is muriate, nitrate or the vitriol of aluminium.The preferred precursor of zirconium white or zirconium hydroxide is oxychlorination thing, nitrate or the vitriol of chlorine.Can or join successively in combination two kinds of salt whiles.
Best pH is that pH is 3, after adding metal-salt its to become pH be 7 or larger.
Be changed to and after 8.5, add phosphoric acid ester (ester of phosphoric acid) or phosphonic acid ester by 7 at pH.Preferably phosphoric acid ester.
Now, describe the preparation method of the flaky pigment for the preparation of high orientation of the present invention in detail.
First prepare the waterborne suspension of described thin slice (pearly-lustre) pigment, and use acidic aqueous solution or alkaline aqueous solution by the pH regulator of described suspension to the predetermined pH value that is about 3.Depend on the type of metal-salt used in the present invention, also different for the pH value of this hydrolysis.Under agitation, to the salts solution that adds independent preparation in described suspension, make during this period the pH of suspension keep constant.After this adds, described pH becomes neutrality from 3.
By the solution of described phosphoric acid ester or phosphonic acid ester or its salt drop to step a) in obtain product in.In this coating processing process, the pH of described solution and temperature are adjusted to and are suitable for each pending material, thereby and stir each material described pigment is evenly applied.After this coating processing, filter described pigment, wash with water and be dried according to common mode, for example dry at 100 DEG C-150 DEG C in baking oven, obtain desired pigment.
(synergy) of the present invention pigment can be for all conventional objects, for example, for giving a large amount of dying polymers, (comprising synergy final lacquer as coating, comprise the final lacquer for trolley part), and printing-ink (comprising offset printing, intaglio, copper powder and flexographic printing), and for example for makeup, spray ink Printing, for textile dyeing, pottery and glass glazing, and the laser labelling of paper and plastics.This application can be known from document works, for example " IndustrielleOrganische Pigmente " (W.Herbst and K.Hunger, VCH VerlagsgesellschaftmbH, Weinheim/ New York, the 2nd edition, revised edition completely, 1995).
In the time that pigment of the present invention is coated interference pigment (synergy pigment), it is the heterochromatic also generation in angle becomes clear, HI SA highly saturated (glossiness) color.Therefore it is especially applicable to and conventional transparent pigment, for example pigment dyestuff, and as combinations such as diketopyrrolo-pyrrole, quinoline Azone, dioxazine, perylene, isoindolinones, it may be as having the transparent pigment of similar color with synergy pigment.But, in the time of the color of transparent pigment and the complementary colors of synergy pigment, according to having obtained interesting especially combined effect with for example EP-A-388932 or the similar mode of EP-A-402943.
Pigment of the present invention has excellent result when dyeing to high molecular weight organic materials.
Can use the high molecular weight organic materials that pigment of the present invention or color compositions dye to it can be natural or synthetic source.High molecular weight organic materials has approximately 10 conventionally 3-10 8g/mol or even larger molecular weight.It can be for example natural resin, dry oil, rubber or casein; or by its derivative crude substance; the for example Synolac of chlorinated rubber, oily modification, viscose, ether of cellulose or ester; for example ethyl cellulose, cellulose acetate, cellulose propionate, ethanoyl cellulose butyrate or Nitrocellulose, but especially as the complete synthesis organic polymer (thermoset(ting)plastic and thermoplastics) obtaining by polymerization, polycondensation or polyaddition.The especially polyolefine that can mention in polymer resin class, for example polyethylene, polypropylene or polyisobutene, and the polyolefine replacing, the for example polymerisate of vinylchlorid, vinyl acetate, vinylbenzene, vinyl cyanide, acrylate, methacrylic ester or divinyl, and the copolymerization product of described monomer, for example especially ABS or EVA.
What in polyaddition resin and condensation resin, can mention is for example the polycondensation product of formaldehyde and phenol, so-called phenoplast, condensation product with formaldehyde and urea, thiocarbamide or trimeric cyanamide, so-called aminoplastics, with the saturated polyester as top coat resin, for example Synolac, or unsaturated polyester, for example maleic ester resin; And linear polyesters and polymeric amide, urethane or silicone.
Described high-molecular weight compounds can be with the form of plastic body or melts separately or mix and exist.It can also be using monomer whose form or as phragmoplast or for the binder of coating or printing-ink, be present under polymerization state Toenol 1140, Nitrocellulose, Synolac, melamine resin and the urea-formaldehyde resins or the acrylic resin that for example boil with solubilized form.
Depend on the object of intention, confirmed to use synergy pigment of the present invention or synergy color compositions as toner or to use its dosage form be favourable.Depend on the object of control method or intention, before or after regulate process, be favourable to adding a certain amount of fabric activator in synergy pigment, condition be its to synergy pigment at high molecular weight organic materials, particularly the application in polyethylene color does not have disadvantageous effect.Suitable reagent is the lipid acid for containing at least 18 carbon atoms especially, for example stearic acid or behenic acid, or its acid amides or metal-salt, particularly magnesium salts, and softening agent, wax, resinous acid, for example sylvic acid, rosined soap, alkylphenol or fatty alcohol, for example stearyl alcohol, or the aliphatics 1 that contains 8-22 carbon atom, 2-dihydroxy compound, for example 1,2-dodecanediol, and the rosin maleic ester resin of modification or fumaric acid Gum Rosin.Based on end product meter, the add-on of described fabric improving agent is preferably 0.1-30 % by weight, particularly 2-15 % by weight.
Can (effect) of the present invention pigment be joined in high molecular weight organic materials to be dyeed with the significant quantity that dyes arbitrarily.Advantageously comprise the coloring material composition of the pigment of the present invention of high molecular weight organic materials and the 0.01-80 % by weight based on high molecular weight organic materials meter, preferred 0.1-30 % by weight.In fact conventionally can use 1-20 % by weight, the particularly concentration of approximately 10 % by weight.
High density, the concentration that is for example greater than 30 % by weight is generally enriched material form (" masterbatch "), it can be used as tinting material for the manufacture of the coloring material with relatively low pigment content, the conventional formulation of pigment of the present invention has especially low viscosity, therefore still can be processed well.
In order to give organic materials painted, can use separately synergy pigment of the present invention.But, in order to realize different colors or color effects, can also be to other colouration composition that adds any desired amount in high-molecular-weight organic material matter except synergy pigment of the present invention, for example white, colored, black or synergy pigment.When coloured pigment mixes use with synergy pigment of the present invention, total amount is preferably the 0.1-10 % by weight of high molecular weight organic materials.The preferably combination of the colored pigment of synergy pigment of the present invention and another kind of color, especially complementary colors provides extra high angle heterochromia, wherein under the measured angular of 10 °, use the color and luster that described synergy pigment obtains and use heterochromia (the Δ H between the color and luster that described colored pigment obtains *) be 20-340, especially 150-210.
Preferably, synergy pigment of the present invention is combined with transparent coloured pigment, described transparent color pigment can be present in same medium with synergy pigment of the present invention, or is present in contiguous medium.The example that synergy pigment and coloured pigment are advantageously present in the configuration in contiguous medium is multi-layer effect coating.
For example with pigment of the present invention, high-molecular-weight organic material matter is dyeed in the following manner: use roll-in or mixing or milling device that this pigment of suitable master batch form is mixed with substrate.The known method of use afterwards itself, for example calendering, compression molding, extrudes, applies, pours into or material that injection moulding is colored described in making becomes the final form of hope.Can be before or after in conjunction with pigment with convention amount by any additive conventional in plastics industry, for example softening agent, filler or stablizer join in polymkeric substance.Especially, for example, in order to manufacture the goods of non-rigid shape or in order to reduce its fragility, to wish to add softening agent in moulding forward direction high-molecular weight compounds, the ester of phosphoric acid, phthalic acid or sebacic acid.
In order to give coating and printing-ink dyeing, to suitably combine conventional additives, the for example high molecular weight organic materials of filler, other pigment, siccative or softening agent and synergy pigment fine dispersion or be dissolved in same organic solvent or solvent mixture, single component can be dissolved separately or disperseed, or multiple components are dissolved together or disperseed, and only again all components is mixed after this.
Preferably under the condition that only produces relatively weak shearing force by synergy colo(u)rant dispersion of the present invention in high molecular weight organic materials to be dyeed and process color compositions of the present invention, described like this synergy pigment can not be broken into less part.
Plastic packets is containing the pigment of the present invention of 0.1-50 % by weight, especially 0.5-7 % by weight.In coating part, the consumption of pigment of the present invention is 0.1-10 % by weight.For painting or the dyeing of the binder system of printing-ink, wherein said paint or printing-ink be for example for intaglio printing, offset printing or silk screen printing, described pigment with 0.1-50 % by weight, preferably 5-30 % by weight and in particular the amount of 8-15 % by weight introduce in printing-ink.
Gained, for example plastics, coating or printing-ink, particularly coating or printing-ink, more particularly the painted difference of coating is excellent character, particularly high saturation ratio, outstanding stability, purity of color and the angle heterochromia highly of height.
When in the time that the high molecular weight material dyeing is coating, it is tailor-(made) coating especially, and it is automobile final lacquer very especially.
Synergy pigment of the present invention is also applicable to lip or skin makeup with for to hair or nail colouring.
Therefore, the invention still further relates to a kind of cosmetic formulations or formula, based on total restatement of cosmetic formulations or formula, the pigment of the present invention that it comprises 0.0001-90 % by weight, the solid support material that is applicable to makeup of especially synergy pigment, and 10-99.9999%.
This cosmetic formulations or Formulation Example are as being lipstick, kermes, foundation cream, nail varnish and shampoo.
Described pigment can use separately or with form of mixtures.In addition, pigment of the present invention can also be used together with other pigment and/or tinting material, for example, be used in combination in the manner described above or according to mode known in cosmetic formulations.
The pigment of the present invention that cosmetic formulations of the present invention and formula optimization contain the 0.005-50 % by weight based on total formulation weight.
Suitable carrier substance for cosmetic formulations of the present invention and formula comprises the material that this composition is conventional.
Cosmetic formulations of the present invention and formula can be for example bar, ointment, breast frost, emulsion, suspension, dispersion, powder or solution form.It is for example lipstick, mascara preparations, kermes, eye shadow, foundation cream, informer, powder or nail varnish.
If described preparation is stripe shape, for example lipstick, eye shadow, kermes or foundation cream, the major part of described preparation is made up of lipid fraction, it can be made up of one or more wax, for example ceresine, lanolin, lanosterol, hydrogenated lanolin, Modulan, wool wax, beeswax, gama wax, Microcrystalline Wax, brazil wax, hexadecanol, stearyl alcohol, theobroma oil, lanolin fatty acid, vaseline, vaseline oil, single-, two-or Three-glycerol ester or be its fatty ester of solid at 25 DEG C, silicone wax, for example methyl octadecane-oxygen polysiloxane and poly-(dimethylsilane oxygen base) stearoyl keto radical siloxane, stearic acid monoethanolamine, rosin and derivative thereof, for example sylvic acid glycol ester and rosin triglyceride, it at 25 DEG C, is the winterized stearin of solid, sugar glyceryl ester and calcium, magnesium, the oleate of zirconium and aluminium, myristate, lanolin hydrochlorate, stearate and dihydroxystearic acid salt.
Described lipid fraction can also be by least one wax and at least one oily compositions of mixtures, for example following oil is suitable in this case: paraffin oil, purcelline oil, perhydrosqualene, sweet almond oil, Lipoval A, U.S. coral oil, Viscotrol C, sesame oil, California Oil of jojoba, boiling point is the mineral oil of about 310-410 DEG C, silicone oil, for example dimethyl polysiloxane, sub-oleyl alcohol, linolenyl alcohol, oleyl alcohol, Cereals oil, for example Wheat germ oils, isopropyl lanolate, Wickenol 111, Isopropyl myristate, butyl myristate, cetyl myristate, stearic acid cetyl ester, butyl stearate, decyl oleate, ethanoyl glyceryl ester, alcohol and polyvalent alcohol, the octanoate of for example ethylene glycol and glycerine and decylate, alcohol and polyvalent alcohol, for example hexadecanol, the ricinoleate of isooctadecanol, the different cetyl of lanoceric acid, hexanodioic acid isopropyl ester, lauric acid hexyl ester and Standamul G.
Lipid fraction in the preparation of this bar form conventionally can form total formulation weight up to 99.91 % by weight.
Cosmetic formulations of the present invention and formula can comprise further composition extraly, the for example inorganic or organic filler of ethylene glycol, polyoxyethylene glycol, polypropylene glycol, monoalkylol amide, non-staining polymerization, sanitas, UV filtering medium or other are usually used in auxiliary agent and the additive in makeup, two of for example natural or synthetic or partial synthesis-or Three-glycerol ester, mineral oil, silicone oil, wax, fatty alcohol, Guerbet alcohol or its ester, lipophilic function cosmetic active ingredient, comprise anti-daylight filtering medium, or the mixture of this material.
The lipotropy function cosmetic active ingredient that is applicable to skin cosmetics, active ingredient compositions or activeconstituents extract is to be allowed for skin or local composition or constituents mixt.Can mention following material by the mode of example:
-to skin surface and the abstersive activeconstituents of hair tool; These materials comprise all substances for cleaning skin, for example oil, perfumed soap, synthetic detergent and solid matter;
-there is deodorizing and suppress the activeconstituents of perspire effect: the antiperspirant that it comprises based on aluminium salt or zinc salt, comprise sterilization or bacteriostasis, and deodorization material, for example reodorant of triclosan, Hexachlorophene, alcohol and cationic substance, for example quaternary ammonium salt, and deodorant agent, for example grillocin (combinations of zinc ricinoleate and various additives) or triethyl citrate (for example, optionally with antioxidant, butylhydroxy toluene combination) or ion exchange resin;
-activeconstituents (UV filtering medium) of the provide protection of anti-daylight is provided: suitable activeconstituents is can from daylight, absorb UV radiation and be translated into hot medium (opalizer); Depend on the effect of hope, following preventing light agent is preferred: selectivity absorbs causing tanned high energy UV radiation (UV-B absorption agent) and launching more long wavelength's scope within the scope of about 280-315nm, the bright protective agent of the light of for example 315-400nm (UV-A scope), and only absorb longer wavelength, the bright protective agent (UV-A absorption agent) of the radiation within the scope of the UV-A of 315-400nm;
Suitable bright protective agent is for example for being selected from following organic UV absorption agent: para-amino benzoic acid derivative, salicyclic acid derivatives, methanone derivatives, phenyl phenacyl ketone derivative, diphenylacrylate, benzofuran derivative, the polymerization UV absorption agent that comprises one or more organosilicon radicals, cinnamic acid derivative, camphor derivatives, triphenylamine also-s-pyrrolotriazine derivatives, Phenylbenzimidazolesulfonic acid and salt thereof, menthyl Aminobenzoate, benzotriazole derivatives, and/or be selected from aluminum oxide-or silicon-dioxide-coating TiO 2, zinc oxide or mica inorganic micro-pigment;
The activeconstituents (wormer) of-anti-insect is for being intended to prevent insect contact skin and bringing into play active reagent at this place; It drives away insect slow evaporation; The most frequently used wormer is diethyl toluamide (DEET); Other conventional wormer can find the 161st page of for example " Pflegekosmetik " (W.Raab and U.Kindl, Gustav-Fischer-Verlag Stuttgart/New York, 1991);
-for shielding to avoid the activeconstituents of chemistry and mechanical influence: these materials are included in all substances that form obstruct between skin and outside objectionable impurities, for example, for protecting paraffin oil, silicone oil, vegetables oil, PCL product and the lanolin of aqueous solution, be used for the membrane-forming agent of the effect of protecting organic solvent, for example sodiun alginate, alginic acid trolamine, polyacrylic ester, polyvinyl alcohol or ether of cellulose, or the material of mineral oil, vegetables oil or silicone oil based on as " lubricant ", it is for protecting the serious mechanical stress that puts on skin;
-wetting material: for example following material is used as moisture regulator (wetting agent): Sodium.alpha.-hydroxypropionate, urea, alcohol, Sorbitol Powder, glycerine, propylene glycol, collagen, elastin and hyaluronic acid;
-there is the activeconstituents of cutin moulding effect: benzoyl peroxide, vitamin A acid, sulfoid and Resorcinol;
-biocide, for example triclosan or quaternary ammonium compound;
-can be applied to oily or oil-soluble vitamine or the vitamin derivative of skin: for example vitamin A (Vogan-Neu of free acid or derivatives thereof form), panthenol, pantothenic acid, folic acid and combination thereof, vitamin-E (tocopherol), vitamin F; Indispensable fatty acid; Or niacinamide (niacin hydroxyacyl amine);
-VITAMIN-Ji placenta extract: particularly comprise vitamin A, C, E, B 1, B 2, B 6, B 12, folic acid and vitamin H, amino acid and enzyme and Determination of Trace Magnesium, silicon, phosphorus, calcium, manganese, iron or copper the active ingredient compositions of compound;
-skin repair title complex: passivation and the disintegration culture that can derive from bifid family bacterium;
-plant and plant extract: for example arnica oil, aloe, must shape lichens, ivy, stinging nettle, ginseng, Lawsonia inermis, camomile, Flower of Aztec Marigold, Rosmarinus officinalis, Salvia japonica Thunb., scouring rush or Thymus vulgaris;
-animal extract: for example, royal jelly, propolis, protein or thymus gland extract;
-can be applied to the greasepaint of skin: Miglyol 812 class neutral oils, Prunus amygdalus oil, Lipoval A, babassu oil, Oleum Gossypii semen, borage oil, Ji oil, peanut oil, gamma oryzanol, rose-seed oil, cannabis oil, hazelnut oil, blackcurrant seed oil, California simmondsia oil, cherry kernel oil, trout oil, Toenol 1140, Oleum Gossypii semen, Queensland nut oil, Prunus amygdalus oil, Oenothera oil, ermine oil, sweet oil, pecan oil, persic oil, pistachio oil, beet oil, rice seed oil, Viscotrol C, Thistle oil, sesame oil, soybean oil, Trisun Oil R 80, tea tree oil, raisin seed oil or Wheat germ oils.
The described preparation of bar shaped is preferably anhydrous, but can comprise in some cases a certain amount of water, but it is no more than 40 % by weight of cosmetic formulations gross weight conventionally.
If cosmetic formulations of the present invention and formula are the forms of semi-solid product, that is to say that it is ointment or newborn white form, it can also be anhydrous or water-based.This preparation and Formulation Example are as being mascara, informer, foundation cream, kermes, eye shadow or for the treatment of the composition of the circle of portion now.
On the other hand, if this ointment or breast frost are water-based, it in particular for also comprising water-in-oil-type or the emulsion oil-in-water of 1-98.8 % by weight fat phase, 1-98.8 % by weight water and 0.2-30 % by weight emulsifying agent except pigment.
This ointment and newborn frost can also comprise further conventional additives, for example perfume, antioxidant, sanitas, one-tenth gelifying agent, UV filtering medium, tinting material, pigment, pearling agent, non-staining polymkeric substance and inorganic or organic filler.
If described preparation is powder type, it is substantially by mineral or inorganic or organic filler, and such as talcum, kaolin, starch, polyethylene powders or polyamide powder and the auxiliary agent such as tackiness agent, tinting material etc. form.
This preparation can comprise the various auxiliary agents that are usually used in makeup, such as spices, antioxidant, sanitas etc. equally.
If cosmetic formulations of the present invention and formula are nail varnish, it is mainly made up of Nitrocellulose and the natural or synthetic polymer that is dissolved in the solution form in solvent system, and described solution can comprise other auxiliary agent, for example pearling agent.
In that embodiment, the amount of described colored polymeric is about 0.1-5 % by weight.
Cosmetic formulations of the present invention and formula can also be used for to hair-dyeing, its shampoo being made up of substrate conventional in cosmetic industry and pigment of the present invention, newborn frost or gel form adopting in this case.
Prepare in a usual manner cosmetic formulations of the present invention and formula, for example in optionally heating so that each component is mixed or is stirred in together mixture melting in the situation that.
In the following example to each feature of the present invention and aspect be further described.Although provide these embodiment to show how within the scope of the invention operation to affiliated field those of skill in the art, it is not as the demonstration to scope of the present invention, scope of the present invention is only defined by claim.Unless otherwise indicated, otherwise in other place at the following example and specification sheets and claims, described umber and percentage ratio are weight part, and temperature be degree Celsius, and pressure is normal atmosphere or near normal atmosphere.
Embodiment
Embodiment 1
By 50g TiO 2mica-CIBA the XYMARA applying tMsilver Pearl S03 (deriving from CIBA SC)-be dispersed in 500ml water.Described suspension is heated to 75 DEG C.Add 1.96g AlCl with the speed of 4ml/min with volume pump 3be dissolved in the solution of gained in 200ml water.By adding NaOH (1%) solution compensation pH, the pH of described suspension is remained on to 3.Under the condition that makes described suspension be 3 at pH, keep 30 minutes.With 1%NaOH solution, the pH of described suspension is increased to 7 afterwards.Under the condition that makes described suspension be 7 at pH, keep 30 minutes.Add the 0.5g CIBA EFKA 8512 (100% active substance) being dissolved in 50ml water.Under the condition that makes afterwards described suspension be 7 at pH, keep 60 minutes.Filter described suspension; Reclaim described pigment, wash with water and in baking oven at 120 DEG C dried overnight.
Embodiment 2
By 50g TiO 2mica-CIBA the XYMARA applying tMsilver Pearl S03 (deriving from CIBA SC)-be dispersed in 500ml water.Described suspension is heated to 75 DEG C.Add 5.76g ZrOCl with the speed of 4ml/min with volume pump 28H 2o AlCl 3be dissolved in the solution of gained in 290ml water.By adding NaOH (1%) solution compensation pH, the pH of described suspension is remained on to 3.Under the condition that makes described suspension be 3 at pH, keep 30 minutes.With 1%NaOH solution, the pH of described suspension is increased to 7 afterwards.Under the condition that makes described suspension be 7 at pH, keep 30 minutes.Add the 0.5g CIBA EFKA 8512 (100% active substance) being dissolved in 50ml water.Under the condition that makes afterwards described suspension be 7 at pH, keep 60 minutes.Filter described suspension; Reclaim described pigment, wash with water and in baking oven at 120 DEG C dried overnight.
Embodiment 3
By 50g TiO 2(SnO 2) apply mica-CIBA XYMARA tMdual Pearl D25 (deriving from CIBA SC)-be dispersed in 500ml water.Described suspension is heated to 75 DEG C.Add 5.76g ZrOCl with the speed of 4ml/min with volume pump 28H 2o AlCl 3be dissolved in the solution of gained in 300ml water.By adding NaOH (1%) solution compensation pH, the pH of described suspension is remained on to 3.Under the condition that makes described suspension be 3 at pH, keep 30 minutes.With 1%NaOH solution, the pH of described suspension is increased to 7 afterwards.Under the condition that makes described suspension be 7 at pH, keep 30 minutes.Add the 0.5g CIBA EFKA 8512 (100% active substance) being dissolved in 50ml water.Under the condition that makes afterwards described suspension be 7 at pH, keep 60 minutes.Filter described suspension; Reclaim described pigment, wash with water and in baking oven at 120 DEG C dried overnight.
Embodiment 4
By 50g TiO 2mica-CIBA the XYMARA applying tMsilver Pearl S23 (deriving from CIBA SC)-be dispersed in 500ml water.Described suspension is heated to 75 DEG C.Add 1.96g AlCl with the speed of 4ml/min with volume pump 3be dissolved in the solution of gained in 200ml water.By adding NaOH (1%) solution compensation pH, the pH of described suspension is remained on to 3.Under the condition that makes described suspension be 3 at pH, keep 30 minutes.With 1%NaOH solution, the pH of described suspension is increased to 7 afterwards.Under the condition that makes described suspension be 7 at pH, keep 30 minutes.Add the 0.5g CIBA EFKA 8512 (100% active substance) being dissolved in 50ml water.Under the condition that makes afterwards described suspension be 7 at pH, keep 60 minutes.Filter described suspension; Reclaim described pigment, wash with water and in baking oven at 120 DEG C dried overnight.
Embodiment 5 (vinyl phosphonate acrylic copolymer)
By 50g TiO 2mica-the XYMARA applying tMsilver Pearl S03 (deriving from CIBASC)-be dispersed in 500ml water.Described suspension is heated to 75 DEG C.Add 0.98g AlCl with the speed of 4ml/min with volume pump 3be dissolved in the solution of gained in 200ml water.By adding NaOH (1%) solution compensation pH, the pH of described suspension is remained on to 3.Under the condition that makes described suspension be 3 at pH, keep 30 minutes.In 1.2h, add 2.88g ZrOCl with volume pump with the speed of 4ml/min 28H 2o AlCl 3be dissolved in the solution of gained in 300ml water, by adding NaOH (1%) solution compensation pH, the pH of described suspension remained on to 3.Under the condition that makes described suspension be 3 at pH, keep again 30 minutes.With 1%NaOH solution, the pH of described suspension is increased to 7 afterwards.Under the condition that makes described suspension be 7 at pH, keep 30 minutes.Add 2.5g Albritect CP30 (20% active substance) (the deriving from Rhodia) solution being dissolved in 200ml water.PH is down to 5.4, and described suspension is kept 30 minutes under this pH.Filter described suspension; Reclaim described pigment, wash with water and in baking oven at 120 DEG C dried overnight.
Embodiment 6-8 and 9-11
Replace CIBA EFKA 8512 to carry out repetition embodiment 1 and 2 with following material:
-octyl phosphonic acid
0.5g 0.8%RHODAFAC in 50ml water aSI 80 (deriving from Rhodia) (80% active substance)
-list of ethoxylated alcohol based on sour form-and two-phosphate mixture
10g 5%Phospholan in 200ml water pR221T (deriving from AKZO-NOBEL) (25% active substance)
-ol ethoxylated phosphate esters
2.5g 5%Phospholan in 200ml water pE 169 (deriving from AKZO-NOBEL) (100% active substance)
Embodiment 12
In methylenum coeruleum experiment, immersion test and anti-yellowing experiment, test is from the light stability of all samples of embodiment 1-11, and all samples all demonstrate improvement with respect to untreated product.
Embodiment 13
By 50g TiO 2mica-CIBA the XYMARA applying tMsilver Pearl S19 (deriving from CIBA SC)-be dispersed in 500ml water.Described suspension is heated to 75 DEG C.Add 2.61g ZrOCl with the speed of 4ml/min with volume pump 2be dissolved in 1% solution of gained in water.Similarly, add 1.30g AlCl with volume pump with the speed of 4ml/min 3be dissolved in the solution of gained in 130ml water.Add 0.42g ZnCl with volume pump with the speed of 4ml/min afterwards 21% solution of gained soluble in water.By adding NaOH (1%) solution compensation pH, the pH of described suspension is remained on to 3 consistently.With 1%NaOH solution, the pH of described suspension is increased to 7 afterwards.Under the condition that makes described suspension be 7 at pH, keep 30 minutes.Add 0.5gCIBA EFKA 8512 (100% active substance) solution being dissolved in 50ml water.Under the condition that makes described suspension be 7 at this pH, keep 60 minutes.
Filter described suspension; Reclaim described pigment, wash with water and in baking oven at 120 DEG C dried overnight.
Embodiment 14
By 50g TiO 2mica-CIBA the XYMARA applying tMsilver Pearl S19 (deriving from CIBA SC)-be dispersed in 500ml water.Described suspension is heated to 75 DEG C.Add 2.61g ZrOCl with the speed of 4ml/min with volume pump 2be dissolved in 1% solution of gained in water.Similarly, add 1.30g AlCl with volume pump with the speed of 4ml/min 3be dissolved in the solution of gained in 130ml water.Add 2.10g MgCl with volume pump with the speed of 4ml/min afterwards 26H 21% solution of O gained soluble in water.By adding NaOH (1%) solution compensation pH, the pH of described suspension is remained on to 3 consistently.Under the condition that makes described suspension be 3 at pH, keep 30 minutes.With 1%NaOH solution, the pH of described suspension is increased to 7 afterwards.Under the condition that makes described suspension be 7 at pH, keep 30 minutes.Add 0.5g CIBA EFKA 8512 (100% active substance) solution being dissolved in 50ml water.Under the condition that makes described suspension be 7 at this pH, keep 60 minutes.
Filter described suspension; Reclaim described pigment, wash with water and in baking oven at 120 DEG C dried overnight.
Methylenum coeruleum experiment
Be used for evaluating the photocatalytic activity of sample by the light degradation of methylenum coeruleum: under 1 methylene blue solution exists, be dissolved in the 50mg synergy pigment in 5g by magnetic stirrer and be exposed under light.Preparation control sample also stirs simultaneously under the condition of getting rid of light.Evaluate the colour-change of sample with respect to duplicate every half an hour (4 ×).
Anti-yellowing experiment
The mica of titanium dioxide-coated is incorporated in the classification small pieces with antioxidant, Yoshinox BHT (BHT), described classification small pieces are exposed under the UV light in QUV table, thereby determine yellowness index.By measuring and obtain yellowness index on Hunter LabScan instrument, thus the yellowing situation that monitoring occurs.
Immersion test
Abrasive:
Product ％wt.
N-butyl alcohol 4.00
Baysilone MA 0.035
Buylglycolacetate 4.00
Setal 84XX-70 42.93
Hair amine US138BB70 16.66
Solvesso 100 32.36
Amount to 99.99
Vehicle (Let Down):
Product ％wt.
N-butyl alcohol 5.14
Baysilone MA 0.045
Buylglycolacetate 2.57
Setal 84XX-70 55.06
Hair amine US138BB70 21.39
Solvesso 100 15.79
Amount to 100.00
According to the ratios of 30: 70 mixed grinding material and vehicle well.The mica of continuously stirring 0.2g titanium dioxide-coated and 9.8g mixture on magnetic stirring apparatus.Use wet film applicator that resin/pigment dispersion is coated on the Leneta black and white recording paper (panel) that derives from Leneta company.Described film is dodged dry 30 minutes dodging in dry cabinet, afterwards in baking oven at 130 DEG C " baking " 30 minutes.
Before immersion, measure the initial value of color, gloss, turbidity and DOI.
Use the plate of view form.Draw a line apart from panel bottom side 5cm at its reverse side, this side will be placed under water.
Under 2 different conditions, test:
16h at 1.60 DEG C
8h at 2.80 DEG C
Described plate is held in place on the panel folder in aluminum pot.Fill described pot until up to the line place (5cm is dark) of drawing with softening water on panel afterwards; Each experiment is used fresh water.Close described pot and by placing thermostatted in the Kong Shui opening on lid, be set as 60 DEG C or 80 DEG C.Once reach described temperature, the time arrives.
After finishing experimental period, stopping device also shifts out described panel from water-bath.Wipe water droplet, before measuring color, gloss, turbidity and the DOI that soaks side, make panel at room temperature keep 2h.

Claims (13)

1. a pigment for the platelet-shaped substrate based on multiple coating, it comprises
(A) platelet-shaped substrate;
(B) titanium dioxide layer;
(C) at the skin at layer (B) top, it is by with a) metal oxide and/or metal hydroxides with b), phosphoric acid ester afterwards or phosphonic acid ester or its salt are processed and obtained, wherein said metal oxide and/or metal hydroxides are selected from oxide compound and/or the metal hydroxides of following substances: silicon, aluminium, zirconium, magnesium, calcium, iron (III), yttrium, cerium, zinc and combination thereof, condition is that described phosphoric acid ester or phosphonic acid ester are not fluorine-containing.
2. according to the pigment of claim 1, wherein the metal oxide of silicon and/or metal hydroxides are selected from silicon oxide, silicon oxide hydrate and combination thereof.
3. according to the pigment of claim 1, the wherein platelet-shaped substrate meter based on multiple coating, the amount of described metal oxide and/or metal hydroxides is 0.1-10 % by weight.
4. according to the pigment of claim 3, the wherein platelet-shaped substrate meter based on multiple coating, the amount of described metal oxide and/or metal hydroxides is 0.8-4 % by weight.
5. according to the pigment of claim 1, wherein said phosphoric acid ester is poly-C 2-C 4the poly-C of aklylene glycol monoether and/or carboxylic acid 2-C 4the phosphoric acid ester of aklylene glycol monoesters.
6. according to the pigment of claim 1, wherein said phosphoric acid ester is purchased from the EFKA-8510 of Qi Ba fine chemistry company, EFKA-8511 or EFKA-8512; Purchased from the Rhodafac PA23 of Rhodia or purchased from Aksu-Nobel company pE169.
7. according to the pigment of claim 1, wherein said phosphoric acid ester is alkyl or alkyl aryl phosphate ester or poly-aryl polyether phosphate, and wherein said phosphonic acid ester is phosphonate ester or polyvinyl-phosphonic acids polymkeric substance.
8. according to the pigment of claim 7, wherein said polyvinyl-phosphonic acids polymkeric substance is the multipolymer of vinyl phosphonate and vinyl methyl-phosphinic acid and other monomer.
9. pigment according to Claim 8, wherein said other monomers are selected from vinylformic acid, acrylamide and vinyl acetate.
10. according to the pigment of claim 1, wherein said phosphoric acid ester is pA15 or purchased from Aksu-Nobel company pR221T, and wherein said phosphonic acid ester is purchased from Rhodia aSI80 or purchased from Rhodia cP30.
Prepare according to the method for the pigment of claim 1, it is characterized in that for 11. 1 kinds
(a) by TiO 2the platelet-shaped substrate applying is suspended in water, by the pH regulator to 3 of described suspension, afterwards the aqueous solution of one or more metal-salts that are selected from silicon, aluminium, zinc, calcium, magnesium, zirconium, iron (III), yttrium and cerium is joined in described suspension, make its pH keep constant with alkaline aqueous solution simultaneously, through this add after by its pH regulator to 7-8.5, and
(b) under agitation the aqueous solution of phosphoric acid ester or phosphonic acid ester or its salt is joined in the suspension of gained, after this adds, filter its suspension, wash with water and be dried.
12. according to the pigment of any one in claim 1-10 in paint, varnish, powder coating, paper coating, plastics, makeup, ink, pottery and the purposes in the decorative applications of glaze, food and medicine and strengthen the purposes in characteristic in security for glass.
13. comprise according to the paint of the pigment of any one in claim 1-10, varnish, powder coating, paper coating, plastics, makeup, ink, pottery and glass glaze.
CN200780044932.4A 2006-12-05 2007-11-26 Surface-modified (effect) pigments Expired - Fee Related CN101547977B (en)

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US10973743B2 (en) * 2014-12-22 2021-04-13 Rohm And Haas Company Skin care formulations containing copolymers and inorganic metal oxide particles
EP3478755A1 (en) * 2016-06-30 2019-05-08 Dow Global Technologies, LLC Phosphonate modified metal oxide particle
CN107384001A (en) * 2017-08-08 2017-11-24 海泉风雷新能源发电股份有限公司 Ester modified ink of UV radiation of a kind of macromolecular chain alkyl phosphoric acid and preparation method thereof
CN109705624A (en) * 2019-02-25 2019-05-03 华东理工大学 A kind of preparation method of the double-colored illusion-colour pearlescent pigment of Blue Curacao
CN114437566A (en) * 2022-03-03 2022-05-06 河南凌宝新材料科技有限公司 Anti-yellowing pearlescent pigment and preparation method thereof
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