CN101547977A

CN101547977A - Surface-modified (effect) pigments

Info

Publication number: CN101547977A
Application number: CN200780044932.4A
Authority: CN
Inventors: K·伊瓦萨; M·哈恩; P·巴格农
Original assignee: Ciba SC Holding AG
Current assignee: BASF Schweiz AG
Priority date: 2006-12-05
Filing date: 2007-11-26
Publication date: 2009-09-30
Anticipated expiration: 2027-11-26
Also published as: CN101547977B

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 pigment based on the platelet-shaped substrate of (multilayer) coating, 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 handle the skin that obtains.

The known titanium dioxide granule that exists as pigment composition in coating causes polymkeric substance being exposed to ultraviolet ray and moisture generation of following time oxygenolysis, 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.

Described a kind of weathering resistance pearly pigment that has the aqua oxidation zirconium coating on the pigment of titanium dioxide basis among the EP0268918, this coating obtains by hydrolysis zirconates in the presence of hypophosphite.

Described a kind of have on the pigment of titanium dioxide the basis top layer be made up of hydrous zirconium oxide and the weathering resistance pearly pigment of hydrated metal oxide among the EP0342533, wherein said hydrous zirconium oxide obtains by hydrolysis in the presence of hypophosphite.Described metal oxide can be cobalt oxide, manganese oxide or cerium oxide.

Modified pearlite pigment has enough dispersivenesses and weathering resistance in the nonaqueous coating system.But it causes forming micro bubble in coated membrane, and described bubble significantly improves scattering of light and therefore gloss and color had 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.

Described among the US4435220 based on the platelet-shaped transparent substrate that has applied nonferrous metal oxides or metal hydroxides, the transparent colored pigment of mica, talcum or glass for example, wherein said metal oxide or hydroxide layer contain the alkaline earth metal compound of 0.1-5% weight, in order to give dispersiveness that pigment improves, gloss, color powder and to stability and the filling and the cohesiveness of heat and weather.

The oyster white that demonstrates intensive interference color, reduction and firm glossy nacre pigment have been described among the US3650790, it is by handling the pigments, mica of the titanium dioxide-coated of gained with soluble silicate in water-soluble serous under deposition of titanium oxide thin layer on the mica sheet, pH at 7-11.5, and the pigment of and the silicate of calcining gained-handled makes; And the pigment of gained.Disclosed pigment is stable inadequately under UV light among the US3650790.

EP0446986 relates to and has pigments, mica enhanced light and moisture stable, that applied metal oxide, 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 made up of silicon-dioxide, at least one other metal hydroxides or metal oxide hydrate and at least one organic coupler.Described other metal hydroxides or metal oxide hydrate are oxyhydroxide or oxygenate or its mixtures of cerium, aluminium and zirconium.Used coupler 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 on the surface of pigments, the result then must correspondingly increase used material.Described non-coupling partly is retained in the reaction medium and damages the filterableness of pigment.

Disclose the modified pearlite pigment that is used for aqueous coating system among the EP0888410, it is based on tabular substrate that has applied metal oxide and the tectum that is positioned on the top metal oxide skin.Described tectum is made by being selected from silicon-dioxide, aluminum oxide, cerium oxide, titanium oxide and zirconic two oxide compounds, hopcalite and/or mixed oxide at least, is perhaps made by 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 differ from one another and be bonded on the initial pigment by the functional group that spacer groups is separated by at least two.Because surface modification, the pigment of describing among the EP1084198 has the pigment bounding force of improvement in basic enamelled coating.But, the unexposed pearly pigment that has weathering resistance and have stability with respect to UV light among the EP1084198.

WO2006021388 relates to the laminar substrate that comprises the containing metal oxide compound and the pearly pigment of protective layer, and the change thing of wherein said metal oxygen has the specific refractory power greater than 1.8.Described protective layer is by the SiO of organic-chemical surface-modification ₂Layer is formed, described organic-chemical surface modification is applied to described SiO ₂Layer.

US4209430 relates to a kind of by directly adding in polyolefine or suppressing to contain phenol antioxidant and TiO as the polyenoid that the coating of pigment adds phosphorylation 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).

Disclose among the EP0644242 and comprised (a) polyolefine; (b) antioxidant; (c) composition of mica particles, its surface-coated the calcining coating of the first layer-titanium dioxide and the second layer-silicon-dioxide subsequently and aluminum oxide, it is used for preventing containing the polyolefin compositions yellowing of antioxidant.

WO9858017 (US5951750) relates to a kind of polyolefine that comprises; Antioxidant; With the composition of the pearly pigment that comprises mica particles, wherein said mica particles has the first layer-coating of titanium dioxide and the second layer thereon-be selected from oxide compound and phosphorus compound and the doping ZrO of Mg, Ca, Ce, Zn, Y in its surface ₂The incinerating metallic compound, wherein said doping agent is Y, Ca or Ce.Coating prevents the yellowing of described composition on the described incinerating.Described phosphorus compound is preferably phosphoric acid salt, but also can be phosphite.

EP0505086 discloses a kind of method of handling lamelliform or thin flaky pigment or supplement, it comprises by step a) form phosphoric acid zinc coating on the particle surface of material, a) by under 50-100 ℃, making material and pH is 11 or the sodium hydroxide of higher zinc salt or potassium hydroxide solution contacts and apply the particle of described material with zinc oxide or zinc hydroxide, thereby forms zinc oxide or hydroxide deposits thing on described particulate surface; 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 the pearly pigment that weather is had the stability of improvement, and it is based on the mica sheet that has applied second coating that contains chromium metal oxide, that have stabilization, and described second coating comprises the combination of metal-salt.In order to form the described second layer, iron and/or manganese are deposited on the initial pigment with oxyhydroxide, carbonate or phos-phate forms, chromium is deposited on the initial pigment with oxyhydroxide, carbonate or phosphatic form or 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, described pigment based on comprise at least one by coloured cooperation phosphate system form the layer substrate, 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, described pigment based on comprise at least one by the binary phosphate system form the layer substrate, preparation of these pigment and uses thereof.Described binary phosphate system has formula A _xP _yO _z, the element of A=periodictable 1-14 family, group of the lanthanides or actinium series wherein, x=1,2....n, y=1,2 ... .m, its by many-or the pyrophosphate salt structure define, z defines by the 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), has excellent fusible flaky pigment, wherein said coating is by with coupler and have the organic compound of perfluoro alkyl group, and the phosphoric acid ester coated platelet surface of pigments that for example has perfluoro alkyl group obtains.Example with phosphoric acid ester of perfluoro alkyl group is a following formula: compound: [R _f(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 are represented 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 with general formula (RfC _nH _2nO) _mPO (OM) _3-m(A) and (RfSO 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) be made up of tinting material and substrate and the composite pigment of tinting material (C), described substrate and tinting material are coated with the ion and the ionizable compound of the electric charge with equidirectional rotation separately, if and wish also to comprise that the ion of the other electric charge with equidirectional rotation or ionizable compound are as layer material (L), the electric charge symbol of (I) coating S wherein, the perhaps electric charge opposite in sign of the symbol of the electric charge of the electric charge of coating S and L and coating C, the electric charge of its floating coat S is identical with the symbol of the electric charge of L, perhaps the electric charge symbol of (II) coating S and C is identical, and with the electric charge opposite in sign of L.In the preferred embodiment of WO9830637, at first use HO-SiMe ₂-(CH ₂) ₃-P (O) (OH) ₂Scatter coated the pigments, mica of titanium dioxide, formerly use Zr afterwards ⁴⁺Handle, handle with inorganic phosphate more afterwards, at room temperature add PAH hydrochloride solution subsequently usually, described like this substrate just has positively charged surface.Filter and wash the substrate how to obtain after applying through applying.The coating tinting material that will have electronegative surface afterwards usually joins in the aqueous dispersion of coated substrate, described coated substrate be preferably applied zirconium phosphate and, if wished in 3-and 6-position by alkyl or aryl replace 1,4-diketone 2, the 5-pyrrolin also-[3,4-c] pyrroles (" DPP ").

Disclose among the WO0242381 and comprised by organic alcohol and P ₂O ₅Or the pigment of the pigment substrate of the product of phosphatase reaction gained processing, wherein based on the weight meter of described pigment substrate, the amount of described product is about 0.01%-about 5%.The example of pigment substrate comprises titanium dioxide, kaolin, talcum, mica and lime carbonate.Described pigment substrate titanium dioxide can be by other metal oxide, and for example aluminum oxide, silicon-dioxide, zirconium white are further handled.

The purpose of this invention is to provide and applied flaky pigment metal oxide, that have effective protective layer.Especially, described protective layer should play effective provide protection and make its photocatalytic activity that avoids producing the pigment of ultraviolet induction, does not also influence the optical property of described pigment simultaneously.In addition, described pigment should have the weathering stability of excellence and the jaundice effect that inhibition contains the TPO of phenol antioxidant.

Described purpose realizes by the pigment of the platelet-shaped substrate that applies based on (multilayer), wherein said pigment comprises that condition is that described phosphoric acid ester or phosphonic acid ester are not fluorine-containing by handling the skin that obtains with metal oxide/oxyhydroxide and phosphoric acid ester afterwards or phosphonic acid ester or its salt.

Described skin is given TiO ₂The platelet-shaped substrate that applies, for example mica provides extraordinary light stability, and make it combine excellent water tolerance and anti--yellowing performance, thereby make described product can be used for 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 handle.

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, partial reflection or reflection.Its example is natural mica shape ferric oxide (for example described in WO 99/48634), synthetic and adulterated mica shape ferric oxide (for example described in EP-A 0 068 311), mica (biotite, vermiculite, sericite, white mica, phlogopite, fluorophlogopite, kaolinite or related substances, perhaps 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 embodiment preferred is the flat metallic particles purposes as core.Proper metal particulate example is Ag, Al, Au, Cu, Cr, Fe, Ge, Mo, Ni, Si, Ti or its alloy, for example the thin slice of brass or steel, preferably Al thin slice.Depend on material, can on surface of metal particles, form natural non-optical interference oxide skin.Preferably it is lip-deep to vertically falling into for the core of partial reflection, the light in the 380-800nm scope has at least 35% reflectivity.

Other example of strip substrate is the strip pigment dyestuff, for example quinacridone, phthalocyanine pigment, fluorine rubine (fluororubine), Hong perylene or diketopyrrolo-pyrrole.Applied the strip particle of metal oxide layer and be well known in the art, for example can derive from DE 14 67 468, EP 0 045 851, DE 32 37 264, DE 36 17 430, EP 0 298604, EP 0 388 932 and EP 0 402 943 as the purposes of synergy pigment.

Described skin (protective layer) is applicable to that to having applied metal oxide 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 the fluidized-bed condition, perhaps form the material etc. of suboxide 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 (E.Merck, Darmstadt), (Kemira Oy, Finland),

(Mearl Corporation, New York/USA) and Infinite

(Shisheido, Japan) and commercially available coating the mica small pieces of metal oxide and the sheet metal that applies, for example applied the sheet metal of titanium dioxide.Granularity itself to described slug particle is not strict with, and it can be adapted to specific purposes.Usually, 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.Particle with similar platelet morphology is understood that to have two flat substantially and parallel surfaces, and slenderness ratio is the about 1000:1 of about 2:1-, and long-width ratio is the particle of 3:1-1:1.

Preferably based on transparent substrate with low-refraction, especially natural or synthetic mica, another kind of layered silicate, glass, Al ₂O ₃, SiO _z, SiO especially 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), that on described substrate top, have titanium oxide layer.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, preferred SiO ₂, and on back layer top, further use TiO 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).

Pigment with following layer structure is particularly preferred:

TRASUB	TiO ₂
TRASUB	TiO ₂			TRASUB	TiO ₂/Fe ₂O ₃
TRASUB	Fe ₂TiO ₅			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	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	(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	Cr ₂O ₃	SiO ₂	TiO ₂
TRASUB	Fe ₂O ₃	SiO ₂	TiO ₂	TRASUB	The TiO suboxide	SiO ₂	The TiO suboxide
TRASUB	TiO ₂	SiO ₂	TiO ₂+SiO ₂+TiO ₂	TRASUB	The TiO suboxide	SiO ₂	The 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	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	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, SiO especially 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, 0.70≤z≤2.0 wherein, especially be 1.40≤z≤2.0 and

STL is a 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 the oxide/hydroxide and the combination thereof of silicon (silicon oxide, silicon oxide hydrate), aluminium, zirconium, magnesium, calcium, iron (III), yttrium, cerium, zinc.

The weight meter of the platelet-shaped substrate that applies based on described (multilayer), the amount of described metal oxide/oxyhydroxide is 0.1-10 weight %, preferred 0.8-4 weight %.

In a preferred embodiment of the invention, described metal oxide/oxyhydroxide is the oxide/hydroxide of 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 its combination that will be used for stabilization and be used as color.

Zirconium white, aluminum oxide and zinc oxide, perhaps zirconium white, aluminum oxide and magnesian tertiary mixture also demonstrate excellent result.

If be used in combination, then can or add two or more salt successively and prepare described metal oxide/hydroxide layer by the while corresponding to metal oxide/oxyhydroxide.

The example of described phosphoric acid ester is the 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 of aklylene glycol monoesters (ester of phosphoric acid).

For example, it is with reference to the polyoxyethylenated alkyl phosphate of following formula:

Or its salt, wherein R ¹Can be identical or different when occurring at every turn, represent the straight or branched alkyl, especially the straight or branched alkyl of 1-20 carbon atom; Phenyl; Alkylaryl, alkyl phenyl more particularly, 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 for example is 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 ¹It for methyl and m 1 or 2 compound.

The material of other example of this compounds that can mention for selling with following trade name: Rhodia sells

With

Especially following products: polyoxyethylene (C ₈-C ₁₀) alkyl ether phosphate

RA 600, polyoxyethylene tridecyl ether phosphate

RS 710 or RS 410, polyoxyethylene oil cetyl ether phosphoric acid ester

PA35, polyoxyethylene nonylplenyl ether phosphoric acid ester

PA 17, polyoxyethylene (side chain) nonyl ethers phosphoric acid ester

RE 610.

In addition, phosphoric acid ester is any material of following general formula:

Or

Or its salt, wherein R ²And R ²' be C _6-20The alkyl of alkyl or ethoxylation.Preferred 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-about 4.Most preferably the alkyl substituent of this general formula is C ₁₂-C ₁₈, Y is about 2-about 4.Should be appreciated that that described formula is represented 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 be 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), The alkyl ether phosphate of PA23 (deriving from Rhodia), polyethyleneization and

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 PA15, perhaps poly-aryl polyether phosphate, for example

PR221T (deriving from Akzo Nobel), perhaps alkyl phosphonic acid, for example

ASI 80 (deriving from Rhodia), perhaps polyvinyl-methyl phospho acid polymkeric substance, especially polyvinyl-phosphonic acids polymkeric substance comprises vinyl phosphonate and/or vinyl methyl phospho acid and other monomer, the multipolymer of vinylformic acid, acrylamide and vinyl acetate for example, for example

CP30 (deriving from Rhodia).

Usually, the weight meter of the platelet-shaped substrate that applies based on (multilayer), the amount of described metal oxide/oxyhydroxide is 0.1-10 weight %, preferred 0.8-4 weight %.Usually, the weight meter of the platelet-shaped substrate that applies based on (multilayer), described phosphoric acid ester, or the amount of phosphonic acid ester is 0.1-10 weight %, preferred 1-6 weight %.

In addition, the present invention relates to a kind of method for preparing pigment of the present invention, it is characterized in that

(a) with thin slice (pearly-lustre) pigment suspension in water, with the pH regulator of suspension to about 3, the aqueous solution that will be selected from one or more metal-salts of silicon, aluminium, zinc, calcium, magnesium, zirconium, iron (III), yttrium and cerium afterwards joins in the described suspension, with alkaline aqueous solution pH is kept constant simultaneously, after this adds, with its pH regulator to about 7-8.5 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 dry.

By the aqueous solution or its corresponding metal salt that makes these (hydration) metal oxides, for example muriate, vitriol, nitrate, halogenide and oxyhalogenation thing can be with 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 among the present invention is enough to make it can form the individual layer hydrated metal oxide on the surface of flaky pigment.Therefore,, then need a large amount of metal-salts if the specific surface area of described thin slice pearly pigment is very big, and for little specific surface area, a spot of just enough.In addition, preferably do not adopt a large amount of metal-salts,, and granules of pigments is reunited easily because this can cause the tone (color, colourity, gloss) of described thin slice pearly pigment to change.Usually, 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 weight %.

Entire method is carried out under preferred 60-90 ℃ the temperature at 10-90 ℃.

Preferably aluminium is used to give color and stabilization; Zirconium is preferred for stabilization; Best is that its combination is used for stabilization and gives 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 in the combination successively two kinds of salt whiles.

Best pH is that pH is 3, after adding metal-salt its to become pH be 7 or bigger.

Be changed to by 7 at pH and add phosphoric acid ester (ester of phosphoric acid) or phosphonic acid ester after 8.5.The preferably phosphoric acid ester.

Now, describe the preparation method who is used to prepare the flaky pigment of high orientation of the present invention in detail.

The waterborne suspension that at first prepares described thin slice (pearly-lustre) pigment, and use acidic aqueous solution or alkaline aqueous solution with the pH regulator of described suspension to the predetermined pH value that is about 3.The type that depends on metal-salt used among the present invention, the pH value that is used for this hydrolysis is also different.Under agitation in described suspension, add the salts solution of preparation separately, make the pH of suspension keep constant during this period.Described pH becomes neutrality by 3 after this adds.

The drips of solution of described phosphoric acid ester or phosphonic acid ester or its salt is added in the product that obtains in the step a).In this coating processing process, with the pH of described solution and temperature regulation to being suitable for each pending material, thereby and stir each material described pigment evenly applied.After this coating processing, filter described pigment, wash with water and according to common mode drying, for example in baking oven in 100 ℃-150 ℃ dry down, obtain desired pigment.

(synergy) of the present invention pigment can be used for all purposes commonly used, for example be used for to a large amount of dying polymers, (comprise the synergy final lacquer as coating, comprise the final lacquer that is used for trolley part), and printing-ink (comprising offset printing, intaglio, copper powder and flexographic printing), and for example be used for makeup, spray ink Printing, be used for textile dyeing, pottery and glass glazing, and the laser labelling of paper and plastics.This application can be known from the document works, for example " IndustrielleOrganische Pigmente " (W.Herbst and K.Hunger, VCH VerlagsgesellschaftmbH, Weinheim/ New York, the 2nd edition, complete revised edition, 1995).

When pigment of the present invention was coated interference pigment (synergy pigment), it was heterochromatic and generation is bright, HI SA highly saturated (glossiness) color in angle.Therefore it especially is fit to and conventional transparent pigment, pigment dyestuff for example, and as combinations such as diketopyrrolo-pyrrole, quinoline a word used for translation ketone, dioxazine, perylene, isoindolinones, it may be as the transparent pigment that has similar color with synergy pigment.But, when the complementary colors of the color of transparent pigment and synergy pigment, according to having obtained interesting especially combined effect with for example EP-A-388 932 or EP-A-402 943 similar modes.

Pigment of the present invention is used for having excellent result when dyeing to high molecular weight organic materials.

Can use pigment of the present invention or color compositions that it is carried out painted high molecular weight organic materials and can be natural or synthetic source.High molecular weight organic materials has about 10 usually ³-10 ⁸G/mol or even bigger molecular weight.It can for example be natural resin, dry oil, rubber or casein; perhaps by its deutero-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) that obtains by polymerization, polycondensation or polyaddition.The especially polyolefine that in the polymer resin class, can mention, for example polyethylene, polypropylene or polyisobutene, and the polyolefine that replaces, the polymerisate of vinylchlorid, vinyl acetate, vinylbenzene, vinyl cyanide, acrylate, methacrylic ester or divinyl for example, and described monomeric copolymerization product, for example especially ABS or EVA.

What can mention in polyaddition resin and condensation resin for example is the polycondensation product of formaldehyde and phenol, so-called phenoplast, condensation product with formaldehyde and urea, thiocarbamide or trimeric cyanamide, so-called aminoplastics, with saturated polyester as the 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 with the monomer whose form or as phragmoplast or be used for coating or the connection material of printing-ink, be present under the polymerization state Toenol 1140 that for example boils, Nitrocellulose, Synolac, melamine resin and urea-formaldehyde resins or acrylic resin with solubilized form.

The purpose that depends on intention has confirmed to use synergy pigment of the present invention or synergy color compositions as toner or to use its dosage form be favourable.The purpose that depends on control method or intention, adding a certain amount of fabric activator before or after the regulate process in synergy pigment is favourable, condition be its to synergy pigment at high molecular weight organic materials, particularly the application in the polyethylene color does not have disadvantageous effect.Suitable reagent is especially for containing the lipid acid of at least 18 carbon atoms, for example stearic acid or mountain Yu 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, stearyl alcohol for example perhaps contains the aliphatics 1 of 8-22 carbon atom, the 2-dihydroxy compound, for example 1,2-dodecanediol, and the rosin maleic ester resin of modification or fumaric acid Gum Rosin.Based on the end product meter, the add-on of described fabric improving agent is preferably 0.1-30 weight %, particularly 2-15 weight %.

Can (effect) of the present invention pigment be joined in the high molecular weight organic materials of waiting to dye with the significant quantity that dyes arbitrarily.Advantageously comprise high molecular weight organic materials and based on the coloring material composition of the pigment of the present invention of the 0.01-80 weight % of high molecular weight organic materials meter, preferred 0.1-30 weight %.In fact usually can use 1-20 weight %, the particularly concentration of about 10 weight %.

High density, for example the concentration greater than 30 weight % is generally enriched material form (" masterbatch "), it can be used as tinting material and is used to make the coloring material with low relatively pigment content, and 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 synergy pigment of the present invention separately.But, in order to realize different colors or color effects, except synergy pigment of the present invention, can also in high-molecular-weight organic material matter, add other colouration composition of any desired amount, for example white, colour, black or synergy pigment.When coloured pigment mixed use with synergy pigment of the present invention, total amount was preferably the 0.1-10 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 10 ° measured angular, use the color and luster that described synergy pigment obtains and use heterochromia (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 the same medium with synergy pigment of the present invention, perhaps is present in the contiguous medium.The example that synergy pigment and coloured pigment advantageously are present in the configuration in the contiguous medium is the 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, extrude, apply, pour into or injection moulding makes the described material that is colored become the final form of hope.Can be with any additives of convention amount before or after in conjunction with pigment with routine in the plastics industry, for example softening agent, filler or stablizer join in the polymkeric substance.Especially, for the goods of making non-rigid shape or in order to reduce its fragility, wish in moulding forward direction high-molecular weight compounds, to add softening agent, for example the ester of phosphoric acid, phthalic acid or sebacic acid.

In order to give the dyeing of coating and printing-ink, 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 the solvent mixture, can be with dissolving or the dispersion separately of single component, perhaps a plurality of components are dissolved together or disperse, and only again all components is mixed after this.

Preferably under the condition that only produces weak relatively shearing force, treating synergy colo(u)rant dispersion of the present invention in the painted high molecular weight organic materials and processing color compositions of the present invention that described like this synergy pigment can not be broken into less part.

Plastics comprise the pigment of the present invention of 0.1-50 weight %, especially 0.5-7 weight %.In the coating part, the consumption of pigment of the present invention is 0.1-10 weight %.Be used for painting or the dyeing of the connection material system of printing-ink, wherein said paint or printing-ink for example are used for intaglio printing, offset printing or silk screen printing, described pigment with 0.1-50 weight %, preferred 5-30 weight % and in particular the amount of 8-15 weight % introduce in the 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, the purity of color of particularly high saturation ratio, outstanding stability, height and the angle heterochromia of height.

When treating that painted high molecular weight material is coating, it is a tailor-(made) coating especially, and it is the automobile final lacquer very especially.

Synergy pigment of the present invention also is applicable to lip or skin makeup and is used for to hair or nail colouring.

Therefore, the invention still further relates to a kind of cosmetic formulations or prescription, based on total restatement of cosmetic formulations or prescription, it comprises the pigment of the present invention of 0.0001-90 weight %, especially the solid support material that is applicable to makeup of 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 with other pigment and/or tinting material, for example be used in combination in the manner described above or according to known mode in the cosmetic formulations.

Cosmetic formulations of the present invention and formula optimization contain the pigment of the present invention based on the 0.005-50 weight % of total formulation weight.

The appropriate carriers material that is used for cosmetic formulations of the present invention and prescription comprises the material that this composition is commonly used.

Cosmetic formulations of the present invention and prescription 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 a stripe shape; lipstick for example; eye shadow; kermes or foundation cream; then the major part of described preparation is made up of lipid fraction; it can be made up of one or more wax; ceresine for example; 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 down its fatty ester of solid at 25 ℃; silicone wax; for example methyl octadecane-oxygen polysiloxane and poly-(dimethylsilane oxygen base) stearoyl keto radical siloxane; the stearic acid monoethanolamine; rosin and derivative thereof, for example sylvic acid glycol ester and rosin triglyceride; be the solid winterized stearin down at 25 ℃; sugar glyceryl ester and calcium; magnesium; the oleate of zirconium and aluminium; myristate; the lanolin hydrochlorate; stearate and dihydroxystearic acid salt.

Described lipid fraction can also be made up of the mixture of at least a wax and at least a oil; for example following in this case oil is suitable: paraffin oil; purcelline oil; perhydrosqualene; sweet almond oil; Lipoval A; U.S. coral oil; Viscotrol C; sesame oil; the California Oil of jojoba; boiling point is about 310-410 ℃ a mineral oil; silicone oil; dimethyl polysiloxane for example; inferior oleyl alcohol; linolenyl alcohol; oleyl alcohol; Cereals oil; Wheat germ oils for example; isopropyl lanolate; Wickenol 111; Isopropyl myristate; butyl myristate; cetyl myristate; the stearic acid cetyl ester; butyl stearate; decyl oleate; ethanoyl glyceryl ester; pure and mild polyvalent alcohol; the for example octanoate of ethylene glycol and glycerine and decylate; pure and mild polyvalent alcohol, for example hexadecanol; the ricinoleate of isooctadecanol; the different cetyl of lanoceric acid; the hexanodioic acid isopropyl ester; lauric acid hexyl ester and Standamul G.

Lipid fraction in the preparation of this bar form can constitute usually total formulation weight up to 99.91 weight %.

Cosmetic formulations of the present invention and prescription can comprise further composition extraly, for example ethylene glycol, polyoxyethylene glycol, polypropylene glycol, monoalkylol amide, the non-staining polymeric is inorganic or organic filler, sanitas, UV filtering medium or other are usually used in auxiliary agent and additive in the makeup, two of for example natural or synthetic or partial synthesis-or Three-glycerol ester, mineral oil, silicone oil, wax, Fatty Alcohol(C12-C14 and C12-C18), 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 for allowing to be used for skin or partial composition or constituents mixt.Can mention following material by the mode of example:

-skin surface and hair are had an activeconstituents of cleaning action; These materials comprise all substances that are used for cleaning skin, for example oil, perfumed soap, synthetic detergent and solid matter;

-have 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, the reodorant of triclosan, Hexachlorophene for example, pure and mild cationic substance, for example quaternary ammonium salt, and deodorant agent, for example

(combinations of zinc ricinoleate and various additives) or triethyl citrate (randomly with antioxidant, for example butylhydroxy toluene combination) or ion exchange resin;

-activeconstituents (UV filtering medium) of the provide protection of anti-daylight is provided: suitable activeconstituents is for absorbing the UV radiation and being translated into hot medium (opalizer) from daylight; 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 in about 280-315nm scope, the bright protective agent of the light of 315-400nm (UV-A scope) for example, and only absorb longer wavelength, the radiating bright protective agent (UV-A absorption agent) in the UV-A scope 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 the inorganic little pigment of micaceous;

The activeconstituents of-anti-insect (wormer) prevents insect contact skin and brings into play active reagent at this place for being intended to; It drives away insect and slowly evaporation; The most frequently used wormer is diethyl toluamide (DEET); Other wormer commonly used can find the 161st page of for example " Pflegekosmetik " (W.Raab and U.Kindl, Gustav-Fischer-Verlag Stuttgart/New York, 1991);

-being used to shield to avoid the activeconstituents of chemistry and mechanical influence: these materials are included in and form all substances that intercept between skin and the outside objectionable impurities, for example be used to protect paraffin oil, silicone oil, vegetables oil, PCL product and the lanolin of aqueous solution, be used to protect the membrane-forming agent of the effect of organic solvent, for example sodiun alginate, alginic acid trolamine, polyacrylic ester, polyvinyl alcohol or ether of cellulose, perhaps based on the material as mineral oil, vegetables oil or the silicone oil of " lubricant ", it is used to protect 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;

-have an 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 the 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: comprise vitamin A, C, E, B especially ₁, B ₂, B ₆, B ₁₂, folic acid and vitamin H, amino acid and enzyme and trace elements magnesium, silicon, phosphorus, calcium, manganese, iron or copper the active ingredient compositions of compound;

-skin repair title complex: the passivation and the disintegration culture that can derive from bifid family bacterium;

-plant and plant extract: for example arnica oil, aloe, must the shape lichens, ivy, stinging nettle, genseng, 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, the California simmondsia oil, the 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 a certain amount of water in some cases, but it is no more than 40 weight % of cosmetic formulations gross weight usually.

If cosmetic formulations of the present invention and prescription are the forms of semi-solid product, that is to say that it is ointment or newborn white form, then it can also be for anhydrous or water-based.This preparation and Formulation Example are as being mascara, informer, foundation cream, kermes, eye shadow or being used to handle the composition of the circle of portion now.

On the other hand, if this ointment or breast frost are water-based, then it is in particular for also comprising the water-in-oil-type or the emulsion oil-in-water of 1-98.8 weight % fat phase, 1-98.8 weight % water and 0.2-30 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 a powder type, then it is basically by mineral or inorganic or organic filler, for example talcum, kaolin, starch, polyethylene powders or polyamide powder and form such as the auxiliary agent of tackiness agent, tinting material etc.

This preparation can comprise the various auxiliary agents that are usually used in the makeup, for example spices, antioxidant, sanitas etc. equally.

If cosmetic formulations of the present invention and prescription are nail varnish, then it mainly is made up of Nitrocellulose and the natural or synthetic polymer that is dissolved in the solution form in the 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 weight %.

Cosmetic formulations of the present invention and prescription can also be used for to hair-dyeing, in this case its shampoo, newborn frost or gel form of being made up of substrate commonly used in the cosmetic industry and pigment of the present invention that adopts.

Prepare cosmetic formulations of the present invention and prescription in a usual manner, for example in optionally heating so that under the mixture fused situation each component is mixed or is stirred in together.

In the following example to each feature of the present invention and aspect be further described.Though provide these embodiment to show how within the scope of the invention operation to affiliated field those of skill in the art, as the demonstration to scope of the present invention, scope of the present invention is not only defined by claim for it.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 centigrade, and pressure is normal atmosphere or near normal atmosphere.

Embodiment

Embodiment 1

With 50g TiO ₂Mica-CIBA the XYMARA that applies ^TMSilver Pearl S03 (deriving from CIBA SC)-be dispersed in the 500ml water.Described suspension is heated to 75 ℃.With the speed adding 1.96g AlCl of volume pump with 4ml/min ₃Be dissolved in the solution of gained in the 200ml water.PH by adding NaOH (1%) solution compensation pH with described suspension remains on 3.Making described suspension is to keep 30 minutes under 3 the condition at pH.With 1% NaOH solution the pH of described suspension is increased to 7 afterwards.Making described suspension is to keep 30 minutes under 7 the condition at pH.Add the 0.5g CIBA EFKA 8512 (100% active substance) that is dissolved in the 50ml water.Making described suspension afterwards is to keep 60 minutes under 7 the condition at pH.Filter described suspension; Reclaim described pigment, wash with water and in baking oven in 120 ℃ of following dried overnight.

Embodiment 2

With 50g TiO ₂Mica-CIBA the XYMARA that applies ^TMSilver Pearl S03 (deriving from CIBA SC)-be dispersed in the 500ml water.Described suspension is heated to 75 ℃.With the speed adding 5.76g ZrOCl of volume pump with 4ml/min ₂8H ₂O AlCl ₃Be dissolved in the solution of gained in the 290ml water.PH by adding NaOH (1%) solution compensation pH with described suspension remains on 3.Making described suspension is to keep 30 minutes under 3 the condition at pH.With 1%NaOH solution the pH of described suspension is increased to 7 afterwards.Making described suspension is to keep 30 minutes under 7 the condition at pH.Add the 0.5g CIBA EFKA 8512 (100% active substance) that is dissolved in the 50ml water.Making described suspension afterwards is to keep 60 minutes under 7 the condition at pH.Filter described suspension; Reclaim described pigment, wash with water and in baking oven in 120 ℃ of following dried overnight.

Embodiment 3

With 50g TiO ₂(SnO ₂) mica-CIBA XYMARA of applying ^TMDual Pearl D25 (deriving from CIBA SC)-be dispersed in the 500ml water.Described suspension is heated to 75 ℃.With the speed adding 5.76g ZrOCl of volume pump with 4ml/min ₂8H ₂O AlCl ₃Be dissolved in the solution of gained in the 300ml water.PH by adding NaOH (1%) solution compensation pH with described suspension remains on 3.Making described suspension is to keep 30 minutes under 3 the condition at pH.With 1%NaOH solution the pH of described suspension is increased to 7 afterwards.Making described suspension is to keep 30 minutes under 7 the condition at pH.Add the 0.5g CIBA EFKA8512 (100% active substance) that is dissolved in the 50ml water.Making described suspension afterwards is to keep 60 minutes under 7 the condition at pH.Filter described suspension; Reclaim described pigment, wash with water and in baking oven in 120 ℃ of following dried overnight.

Embodiment 4

With 50g TiO ₂Mica-CIBA the XYMARA that applies ^TMSilver Pearl S23 (deriving from CIBA SC)-be dispersed in the 500ml water.Described suspension is heated to 75 ℃.With the speed adding 1.96g AlCl of volume pump with 4ml/min ₃Be dissolved in the solution of gained in the 200ml water.PH by adding NaOH (1%) solution compensation pH with described suspension remains on 3.Making described suspension is to keep 30 minutes under 3 the condition at pH.With 1% NaOH solution the pH of described suspension is increased to 7 afterwards.Making described suspension is to keep 30 minutes under 7 the condition at pH.Add the 0.5g CIBA EFKA 8512 (100% active substance) that is dissolved in the 50ml water.Making described suspension afterwards is to keep 60 minutes under 7 the condition at pH.Filter described suspension; Reclaim described pigment, wash with water and in baking oven in 120 ℃ of following dried overnight.

Embodiment 5 (vinyl phosphonate acrylic copolymer)

With 50g TiO ₂Mica-the XYMARA that applies ^TMSilver Pearl S03 (deriving from CIBASC)-be dispersed in the 500ml water.Described suspension is heated to 75 ℃.With the speed adding 0.98g AlCl of volume pump with 4ml/min ₃Be dissolved in the solution of gained in the 200ml water.PH by adding NaOH (1%) solution compensation pH with described suspension remains on 3.Making described suspension is to keep 30 minutes under 3 the condition at pH.In 1.2h, use volume pump to add 2.88g ZrOCl with the speed of 4ml/min ₂.8H ₂O AlCl ₃Be dissolved in the solution of gained in the 300ml water, the pH by adding NaOH (1%) solution compensation pH with described suspension remains on 3.Making described suspension is to keep 30 minutes under 3 the condition at pH again.With 1%NaOH solution the pH of described suspension is increased to 7 afterwards.Making described suspension is to keep 30 minutes under 7 the condition at pH.Add 2.5g Albritect CP30 (20% active substance) (the deriving from Rhodia) solution that is dissolved in the 200ml water.PH reduces to 5.4, and described suspension was kept 30 minutes under this pH.Filter described suspension; Reclaim described pigment, wash with water and in baking oven in 120 ℃ of following dried overnight.

Embodiment 6-8 and 9-11

Use following material replaced C IBA EFKA 8512 to come repetition embodiment 1 and 2:

-octyl phosphonic acid

0.5g 0.8% in 50ml water

ASI 80 (deriving from Rhodia) (80% active substance)

-based on the list of the ethoxylated alcohol of sour form-and two-phosphate mixture

10g 5% in 200ml water

PR221T (deriving from AKZO-NOBEL) (25% active substance)

-alcohol ethoxy phosphoric acid ester

2.5g 5% in 200ml water

PE 169 (deriving from AKZO-NOBEL) (100% active substance)

Embodiment 12

Test is from the light stability of all samples of embodiment 1-11 in methylenum coeruleum experiment, immersion experiment and anti-yellowing experiment, and all samples all demonstrate improvement with respect to untreated product.

Embodiment 13

With 50g TiO ₂Mica-CIBA the XYMARA that applies ^TMSilver Pearl S19 (deriving from CIBA SC)-be dispersed in the 500ml water.Described suspension is heated to 75 ℃.With the speed adding 2.61g ZrOCl of volume pump with 4ml/min ₂Be dissolved in 1% solution of gained in the water.Similarly, with the speed adding 1.30g AlCl of volume pump with 4ml/min ₃Be dissolved in the solution of gained in the 130ml water.Afterwards with the speed adding 0.42g ZnCl of volume pump with 4ml/min ₂1% solution of gained soluble in water.PH by adding NaOH (1%) solution compensation pH with described suspension remains on 3 consistently.With 1% NaOH solution the pH of described suspension is increased to 7 afterwards.Making described suspension is to keep 30 minutes under 7 the condition at pH.Add 0.5gCIBA EFKA 8512 (100% active substance) solution that is dissolved in the 50ml water.Making described suspension is to keep 60 minutes under 7 the condition at this pH.

Filter described suspension; Reclaim described pigment, wash with water and in baking oven in 120 ℃ of following dried overnight.

Embodiment 14

With 50g TiO ₂Mica-CIBA the XYMARA that applies ^TMSilver Pearl S19 (deriving from CIBA SC)-be dispersed in the 500ml water.Described suspension is heated to 75 ℃.With the speed adding 2.61g ZrOCl of volume pump with 4ml/min ₂Be dissolved in 1% solution of gained in the water.Similarly, with the speed adding 1.30g AlCl of volume pump with 4ml/min ₃Be dissolved in the solution of gained in the 130ml water.Afterwards with the speed adding 2.10g MgCl of volume pump with 4ml/min ₂.6H ₂1% solution of O gained soluble in water.PH by adding NaOH (1%) solution compensation pH with described suspension remains on 3 consistently.Making described suspension is to keep 30 minutes under 3 the condition at pH.With 1% NaOH solution the pH of described suspension is increased to 7 afterwards.Making described suspension is to keep 30 minutes under 7 the condition at pH.Add 0.5g CIBA EFKA 8512 (100% active substance) solution that is dissolved in the 50ml water.Making described suspension is to keep 60 minutes under 7 the condition at this pH.

The methylenum coeruleum experiment

Light degradation by methylenum coeruleum is used for estimating the photocatalytic activity of sample: be dissolved in the 50mg synergy pigment among the 5g with magnetic stirrer and be exposed under the light in the presence of 1 methylene blue solution.The preparation control sample also stirs under the condition of getting rid of light simultaneously.Estimate the colour-change of sample with respect to duplicate every half an hour (4 *).

The anti-yellowing experiment

The mica of titanium dioxide-coated is incorporated in the classification small pieces that have antioxidant, Yoshinox BHT (BHT), described classification small pieces is exposed under the UV light in the QUV table, thereby determines yellowness index.Obtain yellowness index by on Hunter LabScan instrument, measuring, thus the yellowing situation that monitoring occurs.

The immersion experiment

Abrasive:

Product	％wt.
Product	％wt.	The 1-butanols	4.00
Baysilone?MA	0.035	The 1-butanols	4.00
Baysilone?MA	0.035	Buylglycolacetate	4.00
Setal?84XX-70	42.93	Buylglycolacetate	4.00
Setal?84XX-70	42.93	Hair amine US138BB70	16.66
Solvesso?100	32.36	Hair amine US138BB70	16.66
Solvesso?100	32.36	Amount to	99.99

Vehicle (Let Down):

Product	％wt.
Product	％wt.	The 1-butanols	5.14
Baysilone?MA	0.045	The 1-butanols	5.14

Buylglycolacetate	2.57
Buylglycolacetate	2.57	Setal?84XX-70	55.06
Hair amine US138BB70	21.39	Setal?84XX-70	55.06
Hair amine US138BB70	21.39	Solvesso?100	15.79
Amount to	100.00	Solvesso?100	15.79

According to the ratio 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 the 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 dodged in dodging dried cabinet did 30 minutes, afterwards in baking oven under 130 ℃ " baking " 30 minutes.

Before immersion, measure the initial value of color, gloss, turbidity and DOI.

Use the plate of view form.Draw the line apart from panel bottom side 5cm at its reverse side, this side will place under water.

Under 2 different conditions, experimentize:

1.60 ℃ following 16h

2.80 ℃ following 8h

The panel that described plate is held in place in the aluminum pot presss from both sides.Fill described pot until up to the line place (5cm is dark) of on panel, drawing with softening water afterwards; Fresh water is used in each experiment.Close described pot and, be set at 60 ℃ or 80 ℃ by placing thermostatted in the Kong Zaishui that opens on the lid.In case reach described temperature, then 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

1, a kind of pigment of the platelet-shaped substrate that applies based on (multilayer), it comprises

By using metal oxide/oxyhydroxide and phosphoric acid ester afterwards or phosphonic acid ester or its salt to handle the skin that obtains, condition is that described phosphoric acid ester or phosphonic acid ester are not fluorine-containing.

2, according to the pigment of claim 1, it comprises

(A) platelet-shaped substrate;

(B) titanium dioxide layer;

(C) at the skin at layer (B) top, it is to obtain by using metal oxide/oxyhydroxide and phosphoric acid ester afterwards or phosphonic acid ester or its salt to handle.

3, according to the pigment of claim 1 or 2, wherein said metal oxide/oxyhydroxide is selected from the oxide/hydroxide of following substances: silicon (silicon oxide, silicon oxide hydrate), aluminium, zirconium, magnesium, calcium, iron (III), yttrium, cerium, zinc and combination thereof.

4, according to the pigment of claim 3, wherein based on the platelet-shaped substrate meter of (multilayer) coating, the amount of described metal oxide/oxyhydroxide is 0.1-10 weight %, is preferably 0.8-4 weight %.

5, according to the pigment of claim 3, 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 (ester of phosphoric acid), for example 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 SpecialityChemicals), Rhodafac PA23 (deriving from Rhodia), polyoxyethylene alkyl ether phosphate and

PE 169 (AKZO-NOBEL).

6, according to the pigment of claim 1, wherein said phosphoric acid ester or phosphonic acid ester are alkyl or alkyl aryl phosphate ester, for example

PA15, or poly-aryl polyether phosphate, for example

PR221T (deriving from Akzo Nobel), or alkyl phosphonic acid, for example

ASI 80 (deriving from Rhodia), perhaps polyvinyl-methyl phospho acid polymkeric substance and especially polyvinyl-phosphonic acids polymkeric substance comprises vinyl phosphonate and/or vinyl methyl phospho acid and other monomer, the multipolymer of vinylformic acid, acrylamide and vinyl acetate for example, for example

CP30 (deriving from Rhodia).

7, a kind of preparation is characterized in that according to the method for the pigment of claim 1

(a) thin slice (pearly pigment) is suspended in the water, with the pH regulator of described suspension to about 3, the aqueous solution that will be selected from one or more metal-salts of silicon, aluminium, zinc, calcium, magnesium, zirconium, iron (III), yttrium and cerium afterwards joins in the described suspension, make its pH keep constant with alkaline aqueous solution simultaneously, after this adds with its pH regulator extremely about 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 drying.

8, strengthen purposes in characteristic at paint, varnish, printing-ink, powder coating, paper coating, plastics, makeup, printing ink, pottery and glass with the purposes in the decorative applications of glaze, food and medicine with in security according to each pigment among the claim 1-6.

9, comprise paint, varnish, printing-ink, powder coating, paper coating, plastics, makeup, printing ink, pottery and glass glaze according to each pigment among the claim 1-6.