CN101087854A - Highly anti-corrosive thin platelet-like metal pigments, preparing method of the same, and colored interference pigments having metallic luster based on the same - Google Patents

Abstract

The present invention provides a highly anti-corrosive thin platelet-like metal pigments which have high corrosion resistance and good dispersibility even in a strong alkaline atmosphere thereby maintaining the inherent metallic luster of thin platelet-like metal substrates. The highly anti-corrosive thin platelet-like metal pigments in which the surface of thin platelet-like metal substrates are treated with phosphoric acid compounds and/or boric acid compounds, and further coated with a layer containing hydrated tin oxide.

Description

Highly anti-corrosive thin platelet-like metallic pigment, its preparation method and based on the colored interference pigments with metalluster of this pigment

Technical field

The present invention relates to novel highly anti-corrosive thin platelet-like (thin platelet-like) metallic pigment, its preparation method and based on the colored interference pigments with metalluster of this pigment, and the purposes of this pigment.

Background technology

Commercially available pearly pigment is known, and this pigment uses and is coated with the laminar mica base material of highly refrangible metal oxide (hereinafter referred to as " interference chromatograph ") as titanium oxide etc., to show the color by interfering.Yet because mica is translucent, its reflectivity is low; Therefore, the interference color expression by interference effect fully is not achieved.Therefore, such colored interference pigments has appearred, wherein with opaque and metal with high optical reflectivity as laminar base material, and will interfere chromatograph (as titanium oxide etc.) to be coated on its surface (referring to for example, patent documentation 1).In these colored interference pigments, this interference chromatograph directly applies by the so-called sol-gel method of avoiding aqueous treatment, because laminar metal base has following shortcoming: they can easily react with water and be oxidized easily.

In addition, known angle heterochromia pigment (multicoloured colored interference pigments) also, wherein on the surface of laminar metal base, by so-called sol-gel method or vapour phase processes, utilize material, for example hydrated SiO 2 with low refractive index, form first coating, apply another kind of metal oxide thereon by vapour-phase reaction then, repeat this process to produce the tonal variation (color moves effect) (for example, patent documentation 2) relevant with the visual angle with high refractive index.

In addition, in order to obtain highly corrosion layer (passivation layer), be known that, the product (for example patent documentation 3) that useful phosphoric acid salt etc. are handled, product (for example patent documentation 4) with the organophosphate processing, only use the product (patent documentation 5) of silica treatment, product (patent documentation 6) of handling with volatility P contained compound and the nitrogenous silicoorganic compound of volatility by vapour phase processes etc.

Yet, in these ordinary methods, there is such shortcoming: must use expensive starting material, or the intrinsic smoothness on the surface of laminar metal base is not held, but by deterioration, perhaps the particulate dispersiveness is not enough, causes irregular reflection, thereby can not make full use of the reflected light on the foil surfaces.Therefore, even further apply the top thereon when interfering chromatograph, also can not realize the expression of interference color fully.

On the other hand, as the metallic pigment that can in water-based system, handle, in the described system aspect equipment the low and processing ease of cost, the laminar metallic pigment (patent documentation 7) that acidic aqueous solution had improved erosion resistance aspect are disclosed.According to this etch-proof metallic pigment, might take such method, neutralizing hydrolysis that wherein will be by using water-soluble metal salt and alkali or the hydrated metal oxide that obtains by the thermal hydrolysis of water-soluble metal salt in water-based system apply, filter, dry and, if necessary, calcination (following in comprising the whole specification sheets of claim general definition be " wet treatment (wet-process) method "); Yet these metallic pigment still can not provide enough erosion resistancies under alkaline condition.

Patent documentation 1:JP, A, 01-110568

Patent documentation 2:JP, A, 07-258579

Patent documentation 3:DE19836810.0

Patent documentation 4:JP, A, 03-74472

Patent documentation 5:JP, A, 08-209025

Patent documentation 6:JP, A, 07-292279

Patent documentation 7:JP, A, 2003-41150

Summary of the invention

The technical problem to be solved in the present invention

The purpose of this invention is to provide the highly anti-corrosive thin platelet-like metallic pigment,, thereby keep the intrinsic metalluster of this laminar metal base even this pigment also has high erosion resistance and good dispersiveness in strong alkaline atmosphere.Another object of the present invention provide have metalluster, highly interfere colour developing and color to move the colored interference pigments of effect, wherein might take so-called wet processing methods (even in alkaline aqueous solution) in order to auxiliary water metal oxide-coated to the surface of highly anti-corrosive thin platelet-like metallic pigment.

In order to address the above problem, the present inventor has in depth carried out research and has found, by handle the surface of laminar metal base with phosphate cpd and/or boronic acid compounds, and further apply the layer that comprises aqua oxidation tin thereon afterwards and the highly anti-corrosive thin platelet-like metallic pigment that form can address the above problem, therefore finished the present invention.

Therefore, the present invention relates to the highly anti-corrosive thin platelet-like metallic pigment, on the surface of laminar metal base, comprise by handling the layer that described surface forms with phosphate cpd and/or boronic acid compounds and comprising aqua oxidation tin as outermost layer.

The invention further relates to the highly anti-corrosive thin platelet-like metallic pigment, wherein on the surface of this laminar metal base, be formed with subsequently: by handle the layer that described surface forms with phosphate cpd and/or boronic acid compounds; By the hydrated metal oxide layer that one or more metals form, this metal is selected from silicon, aluminium, zirconium, titanium and tin; And the layer that comprises aqua oxidation tin.

The invention further relates to above-mentioned highly anti-corrosive thin platelet-like metallic pigment, it is characterized in that this laminar metal base is the metallic pigment with metalluster.

The invention further relates to above-mentioned highly anti-corrosive thin platelet-like metallic pigment, it is characterized in that these metallic pigment with metalluster are any in aluminum slice, titanium thin slice, golden thin slice, silver-colored thin slice, copper-zinc alloy thin slice, nickel-base alloy thin slice, stainless steel thin slice or the bronze flakes.

The invention further relates to above-mentioned highly anti-corrosive thin platelet-like metallic pigment, wherein this hydrated metal oxide is a hydrated SiO 2.

The invention further relates to above-mentioned highly anti-corrosive thin platelet-like metallic pigment, it is characterized in that the amount of employed phosphate cpd and/or boronic acid compounds, with the per unit surface-area (m of this laminar metal base ²) P ₂O ₅And/or B ₂O ₃Meter is equivalent to 0.0001g-0.1g; Be used to prepare the amount of the metallic compound of the layer that applies by hydrated metal oxide, with the per unit surface-area (m of this laminar metal base ²) the metal oxide meter, be equivalent to 0.01g-1.0g; Be used to prepare the amount of the tin compound of aqua oxidation tin layer, with the per unit surface-area (m of this laminar metal base ²) stannic oxide (SnO ₂) meter, be equivalent to 0.0008g-1.0g.

The invention further relates to the method that is used to prepare the highly anti-corrosive thin platelet-like metallic pigment, it comprises: the laminar metal base that will be coated with hydrated metal oxide layer disperses (suspension) Yu Shuizhong; And simultaneously tin salt aqueous solution and alkaline aqueous solution are added in the described dispersion (suspension), keep the pH value constant simultaneously on the surface of the described laminar metal base that is coated with hydrated metal oxide layer, to form aqua oxidation tin layer.

The invention still further relates to the colored interference pigments with metalluster, the surface that it is characterized in that above-mentioned highly anti-corrosive thin platelet-like metallic pigment further is coated with and comprises one or more layers auxiliary hydrated metal oxide layer.

The invention further relates to above-mentioned colored interference pigments with metalluster, it is characterized in that should auxiliary hydrated metal oxide layer by wet processing methods, chemical vapor deposition method or physical vapor deposition preparation.

The invention further relates to above-mentioned colored interference pigments with metalluster, it is characterized in that this auxiliary hydrated metal oxide layer is the layer that comprises one or more hydrated metal oxides of one or more metals, this metal is selected from titanium, aluminium, zirconium, tin, zinc, iron, chromium, cobalt, silicon and boron.

The invention still further relates to above-mentioned colored interference pigments, it is characterized in that this auxiliary hydrated metal oxide layer is the multiple coat that contains different hydrated metal oxides with metalluster.

The invention further relates to above-mentioned colored interference pigments, it is characterized in that this auxiliary hydrated metal oxide layer is by alternately applying the multiple coat that hydrated metal oxide layer with high refractive index and the hydrated metal oxide layer with low refractive index form with metalluster.

The invention still further relates to above-mentioned highly anti-corrosive thin platelet-like metallic pigment and/or above-mentioned colored interference pigments with metalluster at lacquer, powder coating and film, the purposes in printing ink, safety printing ink and printed matter, plastics, pellet and moulded goods and the makeup.

The invention further relates to and comprise above-mentioned highly anti-corrosive thin platelet-like metallic pigment and/or above-mentioned colored interference pigments, and one or more are selected from the composition of other pigment of pigment dyestuff, mineral dye, effect pigment, filler and functional pigment with metalluster.

Finished the present invention based on following novel concepts: the laminar metallic pigment that have erosion resistance in strong alkaline condition can be applied to the environment-friendly type lacquer of wide region, as water-miscible paint.

Highly anti-corrosive thin platelet-like metallic pigment of the present invention provide good erosion resistance, and don't can destroy the smoothness on the surface of this laminar metal base, and can be applied to the environment-friendly type aqueous lacquer in wide ph range, because they are at water-based system and even seldom produce hydrogen in alkaline aqueous solution.In addition, the coating that is used for the auxiliary hydrated metal oxide layer that interference color manifest by the wet processing methods possibility that also becomes.

As for these highly anti-corrosive thin platelet-like metallic pigment, though may not be clearly by the mechanism of the performance variation that causes with the processing of phosphate cpd and/or boronic acid compounds and combining of the coating that comprises aqua oxidation tin; Yet, because above-mentioned combination, for the highly anti-corrosive thin platelet-like metallic pigment, not only may obtain Corrosion Protection under the alkaline condition by passivation, but also may obtain, and further may realize good dispersiveness by irrealizable surface compact of conventional anti-corrosive treatment and smoothness level.Therefore, when highly anti-corrosive thin platelet-like metallic pigment according to the present invention are used as the base material of colored interference pigments, might realize the coating of fine and close and homogeneous, and obtain to have the colored interference pigments of metalluster and favorable dispersity, because because the surface compact of this pigment, they have good affinity to the auxiliary hydrated metal oxide layer that applies thereon.Gained pigment has because the metal due to the high-reflectivity on the surface of laminar metal base intrinsic painted, with the good interference color due to the interference of coated hydrated metal oxide layer, thereby produce the tonal variation (color moves effect) that occurs along with the visual angle that changes.Therefore, realize having the new type colorful coated interference pigment of metalluster, its colour developing (colourity) is improved astoundingly.

Hereinafter, will explain the present invention in more detail in conjunction with the preparation method.

The laminar metal base that uses among the present invention is the so-called metallic pigment that comprise laminar metal and metal alloy.

The laminar metal base that uses among the present invention preferably has the median size of 2-100 μ m and the mean thickness of 0.05-5 μ m, more preferably they have the median size of 5-50 μ m and the mean thickness of 0.1-2 μ m, even more preferably they have the median size of 5-30 μ m and the mean thickness of 0.1-2 μ m.

Their specific examples (for example comprises aluminum slice (flake), titanium thin slice, golden thin slice, silver-colored thin slice, copper-zinc alloy thin slice, iron thin slice, bronze flakes, stainless steel thin slice, xantal thin slice, various aluminum alloy flake, various titanium alloy thin slice, nickelalloy thin slice, at JP, A is described among the 2004-292758 etc.) etc.Preferred thin slice comprises kaolin, titanium thin slice, golden thin slice, silver-colored thin slice, copper-zinc alloy thin slice, stainless steel thin slice, bronze flakes etc.; Even preferred thin slice comprises that the bright gold of extensive sale belongs to pigment such as aluminum slice (for example derives from Silberline; ShowaAluminum Co., Ltd.; Toyo Aluminum Co., Ltd.; Asahi Kasei MetalsCo., Ltd.; Eckart-Werke; Deng), titanium thin slice, stainless steel thin slice etc., these pigment can be stablized supply and buy; Aluminum slice most preferably.

Among these, can use various states, commercially available laminar metal base, for example: be suspended in the organic solvent to prevent by those base materials (for example being suspended in pigment paste in the mineral turpentine (mineral spirit) etc.) that are included in the oxidation corrosion that airborne moisture causes; For buoyant purpose or dispersed, those base materials in the organic solvent had been handled and be suspended in with dissimilar surface treatment agents for improving; And those base materials that are applied with oxygen-proof film (passive film, for example thin film layer of surface oxidation) in its surface in advance.About purpose of the present invention, oxidized as long as the surface does not have basically, then its effect especially by have highly corrosive sheet metal brought; Therefore its use is preferred.

For example, those base materials with high corrosion, for example available on the market, before handling, be in the aluminum slice under the suspension state in the organic solvent, and handled those base materials that also have been suspended in the organic solvent with different surface treatment agents, recommend to be used for the present invention especially.

When utilizing when passing through laminar metal base that protection against corrosion (passivation) handles or laminar alloy base material in advance, need not to handle and give erosion resistance simply based on the present invention; Yet, except the purpose of above-mentioned anti-corrosive treatment, not only effectively improve the protection against corrosion weather resistance according to corrosion-resistant coating of the present invention, and to after form auxiliary hydrated metal oxide smooth, homogeneous and fine and close layer also be effective.

Next, with the polar organic solvent prepare suspension that wherein is dispersed with these laminar metal bases.According to the present invention, the suspension of polar organic solvent is defined as the material that can be prepared as follows:

(1) the laminar metal base that will be suspended in the organic solvent in statu quo is suspended in the polar organic solvent to obtain to have the suspension of desired concn;

(2) to reclaiming by the filtration and the centrifugation of organic solvent in advance, be suspended in then in the polar organic solvent to obtain to have the suspension of desired concn as the laminar metal base of solid part (thin slice is not exclusively dry to be contacted with air and the direct of moisture preventing so that keep some solvents that adhere to);

(3) if this laminar metal base handle with surface treatment agent, use the polar organic solvent washing and remove this surface treatment agent, and after filtering, utilize polar organic solvent to suspend this base material once more to obtain to have the suspension of desired concn;

(4), then in statu quo it is suspended in the polar organic solvent to obtain to have the suspension of desired concn if laminar metal base is commercially available with the state of the powder that passes through Passivation Treatment.

The example that is used for polar organic solvent of the present invention comprises ketone for example acetone, methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK) etc.; Alcohol with the alkyl that contains 1-10 carbon atom; Tetrahydrofuran (THF) (THF); Dimethyl formamide (DMF); Methyl-sulphoxide (DMSO); Two  alkane; Glycol, polyvalent alcohol and its ether and cellosolve.Among these, can select to be at normal temperatures liquid alcohol; The example comprises for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, enanthol, octanol, isooctyl alcohol, nonyl alcohol, decyl alcohol and their isomer.The example of preferred alcohol comprises ethanol, Virahol, butanols, isopropylcarbinol, because they cheaply and at normal temperatures are easy to handle.Especially use Virahol and ethanol etc., this is because their low volatility and low cost.The example of two pure and mild its ethers comprises ethylene glycol (EG), propylene glycol (PG), glycol ether (DEG), diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol list ether etc.In addition, also these solvents suitably can be mixed.

In addition, if use the metal alkoxide thing to form the layer that hydrated metal oxide applies, the alcohol of then selecting to have high-compatibility with the metal alkoxide thing is used for the polar organic solvent that the present invention uses.Nature also need be made suitable selection under the condition of considering with the consistency of employed phosphate cpd and boronic acid compounds.From economic angle,, use identical polar organic solvent to wish for the processing (being defined herein as " fs processing ") of phosphate cpd and/or boronic acid compounds with for aqua oxidation tin applies elementary reaction; Yet, when considering the reaction effect and during with the consistency of the reagent that uses in step of reaction separately, also may using different solvents to be used to deal with separately and the coating stage.In addition, consider the consistency of itself and surface treatment agent, suitably be chosen in polar organic solvent that is used to remove this surface treatment agent of describing in above-mentioned (3).

According to the density of employed those metal bases, the serviceability of agitator and the viscosity of solvent, can suitably change the concentration of suspension of the polar solvent of the laminar metal base that wherein suspended.

The highly anti-corrosive thin platelet-like metallic pigment that obtained are parts of the present invention (claim 1-6) and have good corrosion resistance, good brightness and good dispersiveness, even also almost do not have particle agglomeration in highly basic atmosphere.

In the present invention, fs handles or the formation of aqua oxidation tin coat all can not realize purpose of the present invention individually, and it will give the erosion resistance under the highly basic condition and obtain homogeneous and fine and close hydrated metal oxide coating by the wet processing methods that carries out thereafter.

Therefore, highly anti-corrosive thin platelet-like metallic pigment of the present invention can be constituted as to have at the lip-deep fs processing layer of laminar metal base with as the outermost coat that comprises aqua oxidation tin, and also can constitute between this fs processing layer and this aqua oxidation tin coat (third step layer), have another the layer (second step layer).

An embodiment of these highly anti-corrosive thin platelet-like metallic pigment can obtain by the following method: handle the surface (fs processing) of laminar metal base and apply aqua oxidation tin layer thereafter with phosphate cpd and/or boronic acid compounds.

In addition, another embodiment of the invention can obtain by the following method: form hydrated metal oxide coat (second step layer) and further apply aqua oxidation tin layer (third step layer) thereon on the surface of handling with the fs.

Hereinafter, will handle the fs and describe.

Carry out with the processing of phosphate cpd and/or boronic acid compounds is following: phosphate cpd and/or boronic acid compounds are added in the suspension of polar organic solvent of the laminar metal base that wherein suspended.

Consider good corrosion resistance, dispersiveness and economic factors, the amount of employed phosphate cpd and/or boronic acid compounds is preferred, with the per unit surface-area (m of this laminar metal base ²) P ₂O ₅And/or B ₂O ₃Count, be equivalent to the amount of 0.0001g-0.1g, more preferably be equivalent to the amount of 0.0002g-0.08g, more preferably be equivalent to the amount of 0.0005g-0.05g again.Therefore, the consumption that is used for this processing considers that naturally the per surface area of this laminar metal base measures; That is, the amount that needs when particle diameter is big is few, and if particle diameter is little, the amount that needs is many.

When in the aqueous solution, using phosphate cpd and boronic acid compounds, the preferred water yield of measuring, so that can not become excessive in the consumption (amount that is consumed) in considering subsequent process, and make the raw-material surfaceness of this laminar metal base not increase.In addition, also may use these solvents of phosphate cpd and boronic acid compounds and the water of mentioning before, they are dissolved in as a kind of solvent with the polar organic solvent of the suspension that is used to prepare laminar metal base subsequently.Under any circumstance, in the affinity and consistency of consideration and laminar metal base and phosphate cpd and boronic acid compounds, suitably select employed polar organic solvent.

The example of the phosphate cpd that uses among the present invention comprises phosphoric acid, ortho-phosphoric acid, metaphosphoric acid, tripolyphosphate, Hypophosporous Acid, 50, phosphorous acid, their various polyphosphoric acids, their various phosphoric acid ester (salt) with at least one OH base, the organic acidity phosphoric acid ester (for example, the acid methyl orthophosphoric acid, acid butyl phosphate, dibutyl acid phosphate, the acid monobutyl phosphate, acid phosphoric acid 2-ethylhexyl, the acid di-phosphoric acid, acid phosphoric acid isodecyl ester, acid di(2-ethylhexyl)phosphate isodecyl ester etc.), organic acidity phosphorous acid ester (for example, hydrogen phosphite dibutyl ester etc.), acid phosphoric acid 2-methacryloxy ethyl ester, hydroxyl ethane di 2 ethylhexyl phosphonic acid { CH ₃C (OH) (PO ₃H ₂) ₂, two [2-(the N-propyl group perfluoro octyl group sulfuryl amino) ethyl] esters of phosphoric acid, perfluoroalkyl ethyl phosphonic acid ester (for example, (RfCH ₂CH ₂O) P (O) (OH) ₂, (RfCH ₂CH ₂O) ₂P (O) (OH), wherein Rf represents CF ₃(CF ₂) _6-17Perfluoroalkyl).In above-mentioned phosphate cpd, term " acidity " and " acid " are meant the such phosphate cpd with at least one OH group.In addition, by selecting the keyed jointing group of suitable organic ester group, might improve affinity with the polar organic solvent that in subsequent reaction, uses as this phosphate cpd.

The example that is used for boronic acid compounds of the present invention comprises boric acid, ammonium borate, metaboric acid, lithium metaborate, ammonium metaborate, hypoboric acid, hypoboric acid ammonium etc.

The processing of highly anti-corrosive thin platelet-like metallic pigment of the present invention can be undertaken by phosphate cpd, boronic acid compounds or phosphoric acid and boronic acid compounds etc., as long as realize purpose of the present invention.

After finishing processing, when on the surface of handling this laminar metal base that obtains by the fs, forming aqua oxidation tin layer, can in statu quo or after use suspension, to be transferred to the reaction that forms aqua oxidation tin layer by the filtered and recycled solid part.

Hereinafter,, will the reaction that form aqua oxidation tin coat be described, in this case, on the surface of handling the laminar metal base that obtains by the fs, form aqua oxidation tin layer at this situation.

Do not have enough erosion resistancies because handle the laminar metal base that obtains, preferably in polar organic solvent, carry out the coating of aqua oxidation tin by sol-gel method by the fs; Especially, preferably use the tin alcoxylates as the method for the treatment of the tin compound of hydrolysis.

The specific examples of the tin alcoxylates that uses among the present invention comprises tetrem alkoxyl group tin, the four different third alkoxyl group tin etc.

Can in statu quo use the suspension of handling acquisition by the fs, perhaps can be used as by the solid part form of filtered and recycled and use, can be scattered in once more in the polar organic solvent with prepare suspension, what this polar organic solvent can be with the fs processing reaction is the sort of identical or different.Carry out the formation of aqua oxidation tin coat by adding the required predetermined water yield of metallic compound and hydrolysis, it needs the existence of catalyzer.Might use an acidic catalyst to be used for hydrolysis; Yet, in order to form homogeneous and fine and close coat, be preferred based on the basic catalyst of ammonium compound and/or aminocompound.Using basic catalyst is characteristics of the present invention.

Consider erosion resistance and economic factors, preferably be equivalent to per unit surface-area (m according to the amount of metal alkoxide thing used in the present invention or other metallic compound (calculating) as the metal oxide form ²) laminar metal base be the amount of 0.01g-1.0g, even more preferably be equivalent to the amount of 0.02g-0.8g, more preferably be equivalent to the amount of 0.05g-0.5g again.

As the polar organic solvent that in the reaction that forms aqua oxidation tin coat, uses, the preferred alcohol that constitutes the tin alcoxylates that uses.

The ammonium compound and/or the aminocompound that are used as basic catalyst in the reaction that is used to form aqua oxidation tin coat not only can also influence the formation of homogeneous with the coat of densification of aqua oxidation tin as by the catalyzer of sol-gel method with the hydrolysis of tin alcoxylates.

The ammonium compound that uses among the present invention and/or the specific examples of amine compound comprise, for example, and as the ammonia of ammonium compound, volatile salt, bicarbonate of ammonia, ammonium phosphate, ammonium formiate, ammonium acetate, ammonium oxalate, urea etc.; Comprise with the specific examples of aminocompound, for example, gamma-amino propyl-triethoxysilicane acid esters, trolamine, diethanolamine and their salt.Among these, gamma-amino propyl-triethoxysilicane acid esters etc. combines two kinds of functional groups of above-mentioned silicon alcoxylates and amino group in same molecule, so they are suitably selected to obtain desired properties.

Aspects such as amount from speed of response, corrosion resistance and hydrated metal oxide to be coated, these basic catalysts, the amount that is ammonium and/or aminocompound preferably is equivalent to, count the amount of 0.01-100 mole with every mole of tin alkoxylate compounds, especially preferably be equivalent to the amount of 0.1-30 mole.

Can adopt following any method to be used for adding water in described sol-gel method:

(1) before adding tin alcoxylates solution, the water of hydrolysis aequum is added into by the fs handles in the suspension that obtains,

(2) separately and side by side Jiang Shui and Xi alcoxylates be added into by the fs handle in the suspension that obtains and

(3) before adding water, the tin alcoxylates is added in the suspension that obtains by the fs processing.

Or rather, after the fs processing, can adopt following method for suspension:

A. add the water and the catalyzer of predetermined amount, add the tin alcoxylates solution in the polar organic solvent of being dissolved in of preparation separately then,

B. separately and add simultaneously the aqueous solution of water of the catalyzer of preparation separately and predetermined amount and another kind of preparation separately be dissolved in the polar organic solvent tin alcoxylates solution and

C. before the water that the catalyzer separately provide and predetermined amount are provided, add the tin alcoxylates of predetermined amount.

Among these methods, when the speed of hydrolysis reaction was high, the method for wherein separately adding water and tin alcoxylates solution simultaneously was preferred, because can avoid the state of excessive water during hydrolysis reaction like this.

Preferred high temperature of reaction is to improve the speed of hydrolysis reaction; Yet, consider the boiling point of employed polar organic solvent etc., suitably determine temperature of reaction.When under temperature, operating near boiling point, can be by using condenser etc. that this solution is cooled off and refluxing.

In addition, when forming another layer, for example, during hydrated metal oxide coat (second step layer) between fs processing layer and the aqua oxidation tin coat, can preferably carry out the coating of aqua oxidation tin coat (third step layer) by wet processing methods.

When the layer of handling with phosphate cpd and/or boronic acid compounds (fs processings) and comprise when applying hydrated metal oxide layer (second step layer) between layer (the third step layer) of aqua oxidation tin, can apply and comprise the hydrated metal oxide that one or more are selected from the metal of silicon, aluminium, zirconium, titanium and tin.

These hydrated metal oxides can be the hydrated metal oxides that is made of a kind of metal, or comprise the compound hydrated metal oxide of two or more metals; Consider its high transparency, low reflectivity and low material cost, hydrated SiO 2 is especially preferred.

In addition, also may form multiwalled and comprise one or more hydrated metal oxide coat in these hydrated metal oxides.The raw-material example of the metal that uses in this comprises the metal alkoxide thing of those metals and the organic acid salt of those metals in stage.

The specific examples of the silicon alcoxylates that uses among the present invention comprises, for example, tetramethoxy silicon ester, tetraethoxy silicon ester, tetrapropoxy-silicane acid esters, tetraisopropoxide silicon ester, four butoxy silicon ester, four pentyloxy silicon ester, four hexyloxy silicon ester, so-called silane coupling agent (for example, contain alkyl the alkoxyl silicone acid esters, contain aminoalkyl the alkoxyl silicone acid esters, contain the alkoxyl silicone acid esters of glycidyl alkyl etc.).Can be individually or be used in combination in them each.When using silane coupling agent, can design the surface modification of hope.

The specific examples of aluminium alcoxylates for example comprises: aluminum ethylate, aluminium isopropoxide, tri sec-butoxy aluminum, ethyl acetic acid diisopropoxy aluminium etc.

The specific examples of zirconium alcoxylates for example comprises: tetraethoxy zirconium, four n-propoxyzirconium, zirconium tetraisopropoxide, four n-butoxy zirconiums etc.

The specific examples of titanium alcoxylates comprises purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide etc.

The specific examples of tin alcoxylates for example comprises: tin tetraethoxide, four isobutoxy tin etc.

Coating method that can be by above-mentioned aqua oxidation tin, i.e. sol-gel method in polar organic solvent forms the coating of hydrated metal oxide.The amount of metallic compound that is used to form this hydrated metal oxide coat (second step layer) is preferred, with the per unit surface-area (m of this laminar metal base ²) the metal oxide meter, be equivalent to the amount of 0.01g-1.0g, more preferably 0.02g-0.8g, very preferably 0.05g-0.5g.

The amount of the light of the laminar metal base of the transparency of the highly anti-corrosive thin platelet-like metallic pigment that consideration will obtain, arrival processing layer below, the amount that relies on this reflection of light light, required tinctorial property etc. determine that the fs handles and the combination of the kind of the hydrated metal oxide of formation hydrated metal oxide coat (second step layer); In those, preferably on the surface that will stand the laminar metal base that the fs handles, form by the silicon alcoxylates layer (second step layer) that the hydrated SiO 2 that produces applies that is hydrolyzed.

Next, with the aqua oxidation tin coat of describing under the following situation (third step layer), wherein, stand after the fs processing, the surface of this laminar metal base is coated with hydrated metal oxide layer (second step layer) by sol-gel method, and its skin further is coated with the layer (third step layer) that comprises aqua oxidation tin.

In the present invention, though this aqua oxidation tin coat (third step layer) can form by vapour phase processes or sol-gel method, but more preferably adopt wet processing methods, compare with sol-gel method with vapor-phase process, wet processing methods has less restriction to starting material and production unit, and this method obtains the coat of homogeneous easily, and owing to its simple technology and for all operations easily of multiple application.

Temperature is remained on 60-90 ℃ so that the coat of control homogeneous, and add to tin salt aqueous solution and alkaline aqueous solution in the suspension simultaneously, keep the pH value constant simultaneously, thereby aqua oxidation tin layer (third step layer) is coated on the metal base of highly corrosion.The pH value is preferably below 3.0.More preferably adopt the value of 1.0-2.5.

Be used for above-mentionedly handling the back or handling and the amount of the aqua oxidation tin coating on subsequently the second layer surface after applying need be enough amounts so that ground below being positioned at (layer of handling at non-aqueous system) is come out in the fs in the fs.That is, this amount must surpass the required amount of formation individual layer.In this case, the per unit surface-area (m of laminar metal base ²) the amount of aqua oxidation tin with SnO ₂Meter suitably is no less than 0.0008g.

Especially, the amount of employed aqua oxidation tin needs to carry out suitable adjusting according to kind, particle size, the size-grade distribution of this laminar metal base.Certainly, when particle size is big, should measure reduction, otherwise, when particle size hour needs improve this amount.

Consider erosion resistance enough under the highly basic condition, enough adhesivityes of auxiliary hydrated metal oxide layer as described below and improved compactness, and the control of the tone of interference color are with the per unit surface-area (m of this laminar metal base ²) stannic oxide (SnO ₂) meter, preferably the amount with aqua oxidation tin is adjusted to 0.0008g-1.0g, more preferably 0.0009g-0.9g, very preferably 0.001g-0.8g.For example, (specific surface area is 3.01m when the base material that uses metallic aluminium wherein as the highly corrosion of this laminar metal ²/ g (at JP, A is among the 2003-411150 described in the table 3)) time, appropriate vol is per unit area (m ²) laminar metal base be 0.001g-0.8g.

Employed tin salt aqueous solution is water-soluble tin (II) salt or tin (IV) salt.For example, tin (II) salt, tin chloride (IV), tin sulphate (II), tin acetate (II), tin oxalate (II) etc. are preferred.

Wherein hydrate and the stannic oxide of hydroxyl bonding and the compound that other bonding state exists as the integral body (inclusive whole) in all being included in of stannic oxide, stannic oxide represented in the term that uses in this specification sheets " aqua oxidation tin ".Similarly, comprise term " hydrated metal oxide " expression used in this specification sheets of claim by dry and, if necessary, the metal-salt of calcination hydrolysis and metallic compound be the compound that obtained such as metal alkoxide thing for example, and wherein the metal oxide of the hydrate of metal oxide, metal oxide and hydroxyl bonding and other bonding state as the compound of the global existence in all being included in.

Even highly anti-corrosive thin platelet-like metallic pigment of the present invention also have high erosion resistance and produce hydrogen hardly in the pH value that is the highly basic condition is 11 the NaOH aqueous solution.

Highly anti-corrosive thin platelet-like metallic pigment of the present invention can especially have the pigment of brightness mainly as having metalluster, are used for lacquer, printing ink, plastics etc.Because they can use in water-based system or powder systems, therefore consider the environment aspect and for the improvement of Working environment, and as being included in water-miscible paint under the alkaline condition and printing ink and as powder coating, they are particularly preferred.Intended purpose according to them is decided, these highly anti-corrosive thin platelet-like metallic pigment can be used to carry out for example using required photostabilization as automobile finish, water tolerance and weatherability treatment are (for example, according to JP, A, 63-130673, JP, A, 01-292067 etc.), for example, the processing that is used for the high planar orientation performance (floating) that needs at japanning and print field (for example, according to JP, A, 2001-106937, Japanese patent application No.11-347084 etc.), the aqueous treatment that is used for water-miscible paint or printing ink (for example, according to JP, A, 08-283604 etc.), being used for improving dispersed silicon handles and is used to improve and be used for hydrophobicity that cosmetic field uses and the hydrogen polysiloxanes of oleophobic property is handled, when the surface treatment that is used to prevent weld bond (weld-line) when the resin (for example, according to JP, A, 03-100068), and variously be used to improve dispersed processing.

Highly anti-corrosive thin platelet-like metallic pigment among the present invention be absolutely necessary for the base-material with new type colorful coated interference pigment of metalluster according to the present invention as described below and needs its as base-material; And processing with phosphate cpd and/or boronic acid compounds, the surface that not only is used to give this laminar metal base with the coating processing of aqua oxidation tin is with high corrosion resistance, and they are to obtaining subsequently layer thereon and go up the densification that forms and the hydrated metal oxide layer of homogeneous also being important.Promptly, only by forming the highly corrosion layer that obtains by above-mentioned processing, just may carry out with satisfying condition subsequently pass through hydrated metal oxide coating procedure that wet processing methods carries out and easily on the upper strata of this corrosion-resistant coating coating assist hydrated metal oxide.

Hereinafter to based on highly anti-corrosive thin platelet-like metallic pigment of the present invention and comprise the colored interference pigments (claim 8-12) with metalluster of the present invention that one or more layers auxiliary hydrated metal oxide layer obtains by further coating and be described.In the present invention, the coating of the auxiliary hydrated metal oxide layer on this etch-proof laminar metallic surface can also be passed through vapor-phase process (chemical vapor deposition (CVD) and physical vapor deposition (PVD)) or sol-gel method formation; Yet, preferably using wet processing methods, it is opposite with vapour phase and sol-gel method, without limits, and all is easy to simply handle concerning multiple application aspect starting material and production unit.

Main characteristic of the present invention is, in this stage, because excellent corrosion resistance can adopt so-called wet processing methods.

The metal that is used to produce this auxiliary hydrated metal oxide layer of formation of interference color not only comprises titanium, aluminium, zirconium, tin, zinc, iron, chromium and cobalt, also comprises silicon, boron etc.Suitably select the hydrated metal oxide of hydrated metal oxide with transparent titanium, zirconium, tin, zinc, silicon, boron etc. and iron, chromium, cobalt etc. for use with colourful transparent.In these, consider the refractive index that it is high, titanium is preferred, and considers the generation of the interference color with its inherent colour, and iron is preferred.

Colored interference pigments with metalluster of the present invention can use water-soluble metal salt itself by adopting wet processing methods, or with the compound coating that adopts combination (promptly, as the hydration complex metal oxides) obtain, wherein in the laminated coating of this compound coating, each layer by kinds of materials (for example is, press the sequential scheduling of hydrous titanium oxide-hydrous iron oxide), or (representative of this class is a hydrous titanium oxide for example to have the hydrated metal oxide layer of high refractive index in the laminated coating of compound coating, hydrous zirconium oxide etc.) with (hydrated aluminum oxide for example of the hydrated metal oxide layer with low refractive index, hydrated silica, aqua oxidation boron etc.) replace etc.

Though the wet processing methods that uses among the present invention is described before, or rather, this method comprises: in water-based system, and

(1) under the situation of neutralizing hydrolysis, selects the aqueous solution of required water-soluble metal salt (for example, nitrate, vitriol, muriate, acetate etc.) with the preparation predetermined amount, prepare basic solution simultaneously separately, they are splashed in the suspension (it is the base-material that obtains in advance) of highly anti-corrosive thin platelet-like metallic pigment, keep predetermined pH value simultaneously, to form hydrolysis layer, and afterwards, with its washing, filter, dry and, if necessary, calcination;

(2) under the situation of thermal hydrolysis, in the suspension (it is the base-material that obtains in advance) of highly anti-corrosive thin platelet-like metallic pigment, add the required water-soluble metal salt of predetermined amount, heat this mixture to form hydrolysis layer, and afterwards with its washing, filter, dry and, if necessary, calcination.

In addition,, can also mention, replace alkaline aqueous solution and use the ethanamide by adding thermogenesis basicity and the method (so-called " precipitation from homogeneous solution method ") of urea as variant by neutralizing hydrolysis (1) method.Therefore, can be by selecting randomly water miscible metal-salt, separately or be used in combination them, and they are introduced the time of this suspension by changing, obtain to have the colored interference pigments of metalluster, described pigment is target of the present invention.

More particularly, colored interference pigments with metalluster of the present invention can be prepared as follows: under the situation of individual layer hydrated metal oxide coating, by selecting a kind of water-soluble metal salt, this metal is titanium, zirconium, tin, zinc, iron, chromium, cobalt etc. for example, is used for applying hydrated metal oxide by the neutralizing hydrolysis under the alkaline condition or by thermal hydrolysis; Under the situation of the coating of composition metal, be used for applying this hydration complex metal oxides by neutralizing hydrolysis or by thermal hydrolysis by mixing multiple metal-salt; Or, under the situation of laminated coating, by sequentially adding the successive layers that different metal-salts is used to apply hydrated metal oxide; With by after with they washings, filter, dry and, if necessary, calcination.When formed according to the present invention when having the laminated coating of alternating layer, the aqueous solution that alternately will be used to form in the same way than the metal-salt of high refractive index layer (mentioning) and low refractive index layer (mentioning) before before splashes into base-material, promptly, in the suspension of highly anti-corrosive thin platelet-like metallic pigment, thereby sequentially apply its hydrolysate (hydrolate).When the reflection of light/transmission of the boundary of each layer alternately controlled a plurality of layers of optical thickness alternately coating repeats the time, by the accumulation of interfering, improved colourity (details is referring to WO98/53011) by the colored interference pigments that forms the acquisition of alternate multiple coating with metalluster.Have high colourity by forming the colored interference pigments with metalluster that the alternative laminated coating obtains, this colourity can not obtain by the single hydrated metal oxide coating of using single metal, having a high refractive index.

In the present invention, if hydrous titanium oxide is included in the component of this interference chromatograph, may it be changed into rutile-type by using tin compound or other rutile crystallizing agent, to improve this hydrous titanium oxide crystalline refractive index.Improved tinctorial property by changing into Titanium Dioxide (Rutile) Top grade.

The colored interference pigments with metalluster that obtains by the present invention produces so-called color and moves effect (it is characterized in that observed color varies by angle of view), its inherent colour with metal (mass-tone) and interference color combine, because corrosion-resistant coating is a homogeneous and fine and close and be coated in its lip-deep hydrated metal oxide with high refractive index and have high homogeneity and compactness.

In these interfere chromatographs, can comprise known coloured or the blacking up inorganic and pigment dyestuff of ultra-fine grain, have the colored interference pigments of metalluster with generation, this pigment has kept these pigment inherent colours (mass-tone) when producing interference color.This just just becomes possibility by adapting to maneuverable wet processing methods, and this method makes and these pigment to be extended to various colour gamuts and the broadened application scope becomes possibility.

By using according to JP, A, 62-101662, JP, A, 62-101664, and JP, A, the method of 05-214257, the dye granule that can use compact grained (organic and inorganic) pigment and/or be made of particle it being coated to the corrosion resistant laminar metallic pigment of height according to the present invention and having on the surface of colored interference pigments of metalluster, thereby provides the pigment of all even firm coatings.The pigment dyestuff that can use in these methods comprises azo lake pigment, phthalocyanine pigment, indigo pigment, perylene dye, quinophthalone pigment, two  piperazine pigment, quinacridone pigment, isoindolinone and metal complex pigments; Mineral dye comprises chrome yellow, Zh 1, iron oxide red, titanium dioxide, carbon black, Prussian blue and ultramarine blue.

Can be by known wet chemistry methods, by reducing inorganic or organometallic compound and will the corrosion resistant laminar metallic pigment of height according to the present invention and have a surface metallization layer of the colored interference pigments of metalluster.In addition, can pass through CVD (chemical vapor deposition) method, for example gas-phase decomposition of metal carbonyl, or PVD (physical vapor deposition) method, for example the sputter of metal or gas deposition precipitate metal level.For metal level, preferred metal has strong especially reflecting properties.This preferred metals is drawn together aluminium, titanium, chromium, nickel, silver, zinc, molybdenum, tantalum, tungsten, palladium, copper, gold, platinum and their alloy, for example haas troy alloy (hastelloy).Especially preferred is aluminium and silver.This metal layer thickness is arranged in the translucent scope of maintenance, i.e. 2-100nm, more preferably 5-50nm.

Handle by carrying out dissimilar additional surfaces, the colored interference pigments with metalluster that obtains according to the present invention satisfies for the needed quality of application of using these processing.For example, might carry out using needed photostabilization as automobile finish, the processing of water tolerance and weathering resistance (for example, according to JP, A, 63-130673, JP, A, 01-29206 7 etc.), for example, the required processing of giving the many orientation characteristics of height (floating) in japanning and print field (for example, according to JP, A, 2001-106937, Japanese patent application No. 11-347084 etc.), be used for the aqueous treatment of water-miscible paint or printing ink (for example, according to JP, A, 08-283604 etc.), be used for improving dispersed silicon and handle and be used to improve the hydrogen polysiloxanes of the hydrophobic and oleophobic performance that cosmetic field uses and handle, the surface treatment that is used to prevent weld bond when as resin (for example, according to JP, A 03-100068), improves dispersed processing with different being used to.

Hereinafter, with describe by the present invention's preparation the highly anti-corrosive thin platelet-like metallic pigment and used as the purposes of the colored interference pigments with metalluster of base-material.The highly anti-corrosive thin platelet-like metallic pigment that obtain according to the present invention can be used for various application with the colored interference pigments with metalluster, for example coating, printing-ink, the ink that is used for writing implement, resin combination, laser labelling, artificial marble, makeup etc.Its concrete example will provide following.Though not special the description, what be used for following examples comprises above-mentioned pigment and the product prepared therefrom by carrying out above-mentioned various processing according to highly anti-corrosive thin platelet-like metallic pigment of the present invention and the colored interference pigments with metalluster.

The purposes that is used to coat with lacquer

The example that uses in lacquer is those of organic solvent type lacquer, NAD lacquer, water-miscible paint, emulsion paint, colloid lacquer and powder coating.Pigment of the present invention can 1-100 weight part/100 weight parts as the lacquer of solid part mixed with resin.The ratio of 1-70 weight part is preferred.The ratio of 1-20 weight part is especially preferred.In order to improve dispersiveness, can handle the surface of the pigment among the present invention with silane coupling agent and titanium coupling agent.The example of resin Composition that is used for the present invention's lacquer is acrylate resin, Synolac, unsaturated polyester resin, aminoresin, melamine resin, urethane resin, Resins, epoxy, polyamide resin, phenol resins, celluosic resin, Vinylite, silicone resin, fluoro-resin etc.These resins can use or being used in combination with two or more individually.

In water-miscible paint, what can exemplify has emulsion resin that comprises by the crosslinked cross-linked resin of acrylate melamine resin etc.

Pigment of the present invention can be used for lacquer, particularly is used for lacquer with one or more other pigment combinations that are selected from pigment dyestuff, mineral dye, effect pigment, filler and functional pigment.The example of mixture and blend comprises combination pigment as mentioned below, pigment dyestuff, mineral dye, anti-sagging agent, viscosity modifier, anti-sedimentation agent, crosslinking accelerator, solidifying agent, flow agent, defoamer, softening agent, sanitas, anti-mycotic agent, ultra-violet stabilizer, filler etc.The example of combination pigment is a titanium dioxide, lime carbonate, clay, talcum, barium sulfate, white carbon black, chromic oxide, zinc oxide, zinc sulphide, zinc powder, metallic powdery pigment (for example, aluminum slice, painted aluminum slice, the stainless steel thin slice, titanium thin slice etc.), iron black, Zh 1, red iron oxide, chrome yellow, carbon black, molybdate orange, Prussian blue, ultramarine blue, cadmium type pigment, high-visibility pigment, the solubility azoic dyestuff, insoluble azo dye, the azoic dyestuff of condensation, phthalocyanine pigment, many rings pigment of condensation, complex oxide pigment, graphite, mica (for example, white mica, phlogopite, synthetic mica, fluorine four silicon micas etc.), the mica of metal oxide-coated (for example, the mica that titanium oxide applies, the mica of titanium dioxide-coated, the mica of (hydration) iron oxide-coated, mica with ferric oxide and titanium oxide coating, mica with the coating of low order titanium oxide), the graphite of metal oxide-coated (for example, the graphite of titanium dioxide-coated etc.), flake aluminum oxide, the flake aluminum oxide of metal oxide-coated (for example, the flake aluminum oxide of titanium dioxide-coated, the flake aluminum oxide of iron oxide-coated, Fe ₂O ₃The flake aluminum oxide, the Fe that apply ₃O ₄The flake aluminum oxide that applies, the flake aluminum oxide of interference color metal oxide-coated etc.), MIO (iron mica), the MIO of metal oxide-coated, the silicon-dioxide thin slice of metal oxide-coated, the aluminum oxide of metal oxide-coated, the glass flake that is called the metal oxide-coated of optical effect pigment, photochromic pigment, thermochromism pigment, be called the holographic pigment of functional pigment etc.By in conjunction with these pigment and other pigment, produce new tone and can improve colourity.These lacquers can be applied to timber, plastics, metal sheet, glass, pottery, paper, diaphragm, thin slice, be used for the semitransparent thin film etc. of the reverberator of LCD.The example of the purposes that is used to coat with lacquer comprises automobile, buildings, boats and ships, household electrical appliance, canned commodity, industrial equipments, traffic sign, plastics, household goods etc.

The example of structure of filming for example has: successively with undercoat, inter coat, comprise the layer of pigment of the present invention and film that transparent layer applies and have undercoat successively, comprise the inter coat of pigment of the present invention and the structure of transparent layer etc.; Yet the structure of filming is not limited thereto.

The example that is used to form the method for filming comprises primary coating/once baking, twice coating/once baking, twice coating/twice baking, applies for three times/once baking, applies/twice baking for three times, applies/three bakings for three times.The example of coating method comprises electrostatic coating, spraying, no air coating, roller coat, dip-coating etc.

The purposes that is used for printing ink and printing-ink

Pigment of the present invention can be used for printing ink and printing-ink, particularly combines with other pigment that is selected from pigment dyestuff, mineral dye, effect pigment, filler and functional pigment to be used for printing ink and printing-ink.The example that is used for printing ink and printing-ink comprises burr printing-ink, planographic ink, gravure printing ink, the printing ink that is used for metal sheet, radiation curable ink, UV printing ink, EB printing ink, multi-functional printing ink, silk-screen ink, flexographic ink, rotogravure printing ink etc., with and water color ink etc.Pigment of the present invention with 1-100 weight part/100 weight parts in printing ink as the mixed of the resin of solid part.The ratio of 1-70 weight part is preferred.The ratio of 1-20 weight part is especially preferred.In addition, the surface of the pigment among the present invention can be handled with silane coupling agent and titanium coupling agent etc.The example of resin Composition for example comprises, rosin maleic acid resin, maleic acid resin, Synolac, polyamide resin, phenol resins, petroleum resin, urethane resin, Resins, epoxy, acrylate resin, butyral resin, melamine resin, Resins, epoxy, vinyl chloride resin, vinylidene resin, celluosic resin, Vinylite, unsaturated polyester resin, celluosic resin etc.These resins can use or being used in combination with two or more individually.

The example of mixture and blend comprises combination pigment, pigment dyestuff, mineral dye and additive as described below, for example varnish, reductive agent, compounding agent, super varnish, jelling agent, dry promotor, antioxidant, prevent that printing ink is passed to the reagent of backing, lubricant, tensio-active agent etc.Other example comprises anti-sagging agent, viscosity modifier, anti-sedimentation agent, linking agent, solidifying agent, flow agent, defoamer, softening agent, sanitas, anti-mycotic agent, ultra-violet stabilizer, filler etc.

The example of combination pigment comprises extender pigment; Process white; Precipitated chalk; White lake; Magnesiumcarbonate and white carbon black; White pigment is titanium dioxide, zinc oxide etc. for example; Black pigment is carbon black for example; Yellow ultramarine is chrome yellow, dual-azo yellow, organic yellow for example; Red pigment is brilliant carmine 6B, Lake red C, permanent red F5R, rhodamine color lake etc. for example; Blue pigments is phthalocyanine blue, victoria blue color lake, Prussian blue for example; Orange pigments is chrome vermilion, tetrazo orange for example; Veridian is phthalocyanine green etc. for example; Violet pigment is methyl violet color lake, two  piperazine purples etc. for example; Other pigment is isoindolinone, benzimidazoline, condensation azo, quinacridine (quinacdrine) etc. for example; Complex oxide pigment; Graphite; Mica (for example, white mica, phlogopite, synthetic mica, fluorine tetravalence silicon mica etc.); The mica of metal oxide-coated (for example, the mica of the mica of the mica of titanium dioxide-coated, titanium dioxide-coated, (hydration) iron oxide-coated, mica, the mica of using the low order titanium oxide to apply) with ferric oxide and titanium oxide coating; The graphite of metal oxide-coated (for example, graphite of titanium dioxide-coated etc.); Flake aluminum oxide; The flake aluminum oxide of metal oxide-coated (for example, the flake aluminum oxide of the flake aluminum oxide of titanium dioxide-coated, iron oxide-coated, Fe ₂O ₃The flake aluminum oxide, the Fe that apply ₃O ₄The flake aluminum oxide that applies, the flake aluminum oxide of interference color metal oxide-coated etc.); MIO; The MIO of metal oxide-coated; The silicon-dioxide thin slice of metal oxide-coated; The glass flake that is called the metal oxide-coated of optical effect pigment; Photochromic pigment; Thermochromism pigment; The holographic pigment that is called functional pigment; Deng.These printing ink can be printed in timber, plastics, metal sheet, glass, pottery, paper, corrugated cardboard, film, sheet material, canned commodity, be used for the semitransparent thin film etc. of the reflection of LCD.When pigment of the present invention combines with these pigment, can find new color harmony color.Pigment according to the present invention is particularly suitable for preventing the forgery of security, bill, tour coupon, passenger ticket etc., and this is because their color moves effect (tone changes with visual angle change).Therefore, they can be advantageously used in safety printing ink and printed matter.

In addition, when being used for printing-ink, especially preferably the colored interference pigments with metalluster that obtains according to the present invention being carried out high planar orientation and handle (as indicated above).Standing this surface-treated pigment can mix with various printing-inks, and is used for offset printing, photogravure, silk screen printing, ultraviolet curing printing and burr and lithography.The application of pigment in printing ink that has stood high planar orientation processing especially improves the colour developing of interference color on the print surface, thereby the color that influences with visual angle change moves effect, and this effect is preferred for anti-counterfeit printing.

The purposes that is used for plastics

Pigment of the present invention can be used for plastics, particularly combines with other pigment that is selected from pigment dyestuff, mineral dye, effect pigment, filler and functional pigment to be used for plastics.

In the present invention, when introducing plastics, this pigment can be directly or make in advance pellet and then by extrusion molding, roll molding, blowing etc. make various moulded products after and mixed with resin.About resin Composition, can use based on polyolefinic thermoplastic resin and based on epoxy, based on polyester with based on the thermosetting resin of polymeric amide (nylon).A spot of pigment may be enough to produce effectively the color effects with colored interference pigments of metalluster of the present invention, and for example, when shaping laminated plastics bottle, by pigment is introduced in the outermost resin, the outward appearance of bottle can be manifested effectively.The pigment that carries out additional orientation plane treatment that obtains according to the present invention is especially preferred, because they have good tinctorial property.Certainly, can use the chromatic metallic gloss coated interference pigment related to the present invention that carries out weld bond protective treatment (for example, sealing etc.).The highly anti-corrosive thin platelet-like metallic pigment that obtain according to the present invention can also be used in combination with other pigment with the colored interference pigments with metalluster.The example of the pigment that can be used in combination with pigment of the present invention comprises titanium dioxide, lime carbonate, clay, talcum, barium sulfate, white carbon black, chromic oxide, zinc oxide, zinc sulphide, zinc powder, metallic powdery pigment, iron black, Zh 1, red iron oxide, chrome yellow, carbon black, molybdate orange, Prussian blue, ultramarine blue, cadmium type pigment, high-visibility pigment, the solubility azoic dyestuff, insoluble azo dye, the azoic dyestuff of condensation, phthalocyanine pigment, many rings pigment of condensation, complex oxide pigment, graphite, mica (for example, white mica, phlogopite, synthetic mica, fluorine tetravalence silicon mica etc.), the mica of metal oxide-coated (for example, the mica that titanium oxide applies, the mica of titanium dioxide-coated, the mica of (hydration) iron oxide-coated, mica with ferric oxide and titanium oxide coating, mica with the coating of low order titanium oxide), the graphite of metal oxide-coated (for example, the graphite of titanium dioxide-coated etc.), flake aluminum oxide, the flake aluminum oxide of metal oxide-coated (for example, the flake aluminum oxide of titanium dioxide-coated, the flake aluminum oxide of iron oxide-coated, Fe ₂O ₃The flake aluminum oxide, the Fe that apply ₃O ₄The flake aluminum oxide that applies, the flake aluminum oxide of interference color metal oxide-coated etc.), MIO, the MIO of metal oxide-coated, the silicon-dioxide thin slice of metal oxide-coated, the glass flake that is called the metal oxide-coated of optical effect pigment, photochromic pigment, thermochromism pigment, be called the holographic pigment of functional pigment etc.

The purposes that is used for makeup

Pigment of the present invention can be used for makeup, and particularly combining with other pigment that is selected from pigment dyestuff, mineral dye, effect pigment, filler and functional pigment is used for makeup.

The example of the application in makeup comprises makeup, hair products, beauty mask (cosmetic pack) etc.For example, this pigment can be used for gel, lipstick, foundation cream (comprising emulsion, liquid, oil type emulsion etc.), cheek kermes, mascara, nail varnish, eyebrow pencil, eye shadow cream, eyeliner, hair with product etc.They can use with the ratio of 1-90wt%.For example, can mention, be 1-50wt% for foundation cream, is 1-80wt% for eye shadow cream, is 1-40wt% for lipstick, is 0.1-20wt% for nail varnish.

The example of mixture and blend will provide below.The example of the pigment that can be used in combination with pigment of the present invention comprises titanium dioxide, lime carbonate, clay, talcum, barium sulfate, white carbon black, chromic oxide, zinc oxide, zinc sulphide, zinc powder, metallic powdery pigment, iron black, Zh 1, red iron oxide, chrome yellow, carbon black, molybdate orange, Prussian blue, ultramarine blue, cadmium type pigment, high-visibility pigment, the solubility azoic dyestuff, insoluble azo dye, the azoic dyestuff of condensation, phthalocyanine pigment, many rings pigment of condensation, complex oxide pigment, graphite, mica (for example, white mica, phlogopite, synthetic mica, fluorine tetravalence silicon mica etc.), the mica of metal oxide-coated (for example, the mica that titanium oxide applies, the mica of titanium dioxide-coated, the mica of (hydration) iron oxide-coated, mica with ferric oxide and titanium oxide coating, mica with the coating of low order titanium oxide), the graphite of metal oxide-coated (for example, the graphite of titanium dioxide-coated etc.), flake aluminum oxide, the flake aluminum oxide of metal oxide-coated (for example, the flake aluminum oxide of titanium dioxide-coated, the flake aluminum oxide of iron oxide-coated, Fe ₂O ₃The flake aluminum oxide, the Fe that apply ₃O ₄The flake aluminum oxide that applies, the flake aluminum oxide of interference color metal oxide-coated etc.), MIO, the MIO of metal oxide-coated, the silicon-dioxide thin slice of metal oxide-coated, the glass flake that is called the metal oxide-coated of optical effect pigment, photochromic pigment, thermochromism pigment, the holographic pigment that is called functional pigment, silk Muscovitum, magnesiumcarbonate, silicon-dioxide, zeolite, hydroxyapatite, chromic oxide, cobalt titanate, glass beads, the nylon bead, organosilicon bead etc.

It is red 2,3,102,104,105,106,201,202,203,204,205,206,207,208,213,214,215,218,219,220,221,223,225,226,227,228 that the example of pigment dyestuff comprises, 230-1,230-2,231,232,405; Huang 4,5,201,202-1,202-2,203,204,205,401,402,403,404,405,406,407; Green 3,201,202,204,205,401,402; Blue 1,2,201,202,203,204,205,403,404; Orange 201,203,204,205,206,207,401,402,403; Palm fibre 201; Purple 201,401; Black 401.

The example of natural earth pigment comprises salol Huang, famille rose, β-Hu Luobusu, rose of Sharon colorant, capsaicine, cochinilin, laccaic acid, gurcumin, riboflavin, Tokyo Violet etc.

In addition, the example of other component comprises organic solvent, antioxidant, sanitas, polyvalent alcohol, spices of the hydrocarbon, acetone, toluene, butylacetate, acetic ester etc. of grease, wax, tensio-active agent, oxidation retarder, UV absorption agent, VITAMIN, hormone, squalane, whiteruss, palmitinic acid, stearic acid, beeswax, Tetradecyl tetradecanoate etc. etc.By pigment of the present invention is combined with these pigment and component, can find novel effect color and function.

When being used for makeup, according to pigment of the present invention for example can be used for compacting cake, emulsifiable paste, lipstick etc. any; Yet when being used for the makeup that color wherein is even more important, they are especially effective.Nature might use the colored interference pigments with metalluster related to the present invention that carries out surface treatment (mentioning in front).

Other purposes

Pigment of the present invention can be used in combination with the color toner that is used for duplicating machine etc.For example, when it is used as the color toner of duplicating machine, realizes that color moves effect, thereby can realize false proof effect.

Embodiment

Hereinafter, describe the present invention in more detail, yet these embodiment are not intended to limit the present invention with reference to embodiment and Comparative Examples.

Embodiment 1

Highly anti-corrosive thin platelet-like metallic pigment (SnO ₂/ [SiO ₂/ Al (P)]) preparation

With its layer of 100 grams through antiseptic laminar metal base (according to JP, the A, [SiO of the embodiment 4-b acquisition in [0061] section of 2003-41150 ₂/ Al (P)], specific surface area: 3.01m ²/ g) be suspended in 2 premium on currency.Under agitation this suspension is heated to 75 ℃.SnCl with 372 milliliters ₄5H ₂O solution (concentration is 50g/l) splashes into this suspension, uses the aqueous sodium hydroxide solution of 32wt% that the pH value is remained on 1.8 simultaneously.The solid part washing that will filter out from this suspension afterwards, is also dry to obtain highly anti-corrosive thin platelet-like metallic pigment (SnO ₂/ [SiO ₂/ Al (P)]).Per unit surface-area (m with this laminar metal base (Al) ²) stannic oxide (SnO ₂) meter, the amount of the coating of aqua oxidation tin is the amount that is equivalent to 0.036g.

Comparative Examples 1

Laminar metal-like pigment [SiO ₂/ Al (P)] preparation

By obtaining laminar metallic pigment [SiO with embodiment 1 identical operations step ₂/ Al (P)], difference is to have omitted passes through SnCl ₄5H ₂O forms the process of aqua oxidation tin layer.

Alkali resistance test (measuring the amount of the hydrogen that is produced)

Each 1 gram of every kind of sample is distributed to the pH value is adjusted to by sodium hydroxide (NaOH) in 11 and 12 the warm water, and keep this dispersion 75 ℃ steady temperature.After the scheduled time slot, measure the hydrogen (H that produces by this dispersion ₂) amount.Measurement was carried out 60 minutes.The result is shown in Figure 1.

Fig. 1 shows when using (SnO ₂/ [SiO ₂/ Al (P)]) time hydrogen that produces.Highly anti-corrosive thin platelet-like metallic pigment (SnO of the present invention ₂/ [SiO ₂/ Al (P)]) to be presented at the pH value be almost not have hydrogen to produce in 11 the solution.Omitting SnO ₂[the SiO of layer ₂/ Al (P)] situation under, in the pH value is 11 solution, produced relatively large hydrogen.

In the pH value was 12 solution, embodiment and Comparative Examples all produced a large amount of hydrogen at short notice; Yet, (SnO ₂/ [SiO ₂/ Al (P)]) than [SiO ₂/ Al (P)] show than hydrogen in a small amount.Therefore, confirm (SnO ₂/ [SiO ₂/ Al (P)]) than wherein omitting SnO ₂[the SiO of layer ₂/ Al (P)] the higher alkali resistance of demonstration.

Embodiment 2: have erythroid colored interference pigments (Fe with metalluster ₂O ₃/ SnO ₂/ [SiO ₂/ Al (P)]) preparation

With the height corrosion resistant laminar metallic pigment (SnO of 50 grams from embodiment 1 acquisition ₂/ [SiO ₂/ Al (P)]) be suspended in one liter of (litter) water.Under agitation this suspension is heated to 75 ℃.Afterwards, use hydrochloric acid/aqueous sodium hydroxide solution that the pH value is adjusted to 3.0.In addition, splash into 1816 gram FeCl ₃(III) aqueous solution (concentration: 30 grams per liters),, use aqueous sodium hydroxide solution that the pH value is remained on 3.0 simultaneously up to obtaining required tone.Further washing/filtrations, this mixture of drying, and have erythroid colored interference pigments with acquisition with metalluster 350 ℃ of following calcination 30 minutes.

Embodiment 3: the colored interference pigments (TiO with metalluster ₂/ SnO ₂/ [SiO ₂/ Al (P)]) preparation

With the height corrosion resistant laminar metallic pigment (SnO of 50 grams from embodiment 1 acquisition ₂/ [SiO ₂/ Al (P)]) be suspended in the premium on currency.Under agitation this suspension is heated to 75 ℃.Afterwards, use hydrochloric acid/aqueous sodium hydroxide solution that the pH value is adjusted to 1.8.Then, with titanium tetrachloride solution (TiCl ₄, concentration: 448 grams per liters) splash into this suspension,, use the aqueous sodium hydroxide solution of 32wt% that the pH value is remained on 1.8 simultaneously, under green tone, finish reaction up to obtaining required tone.Further filter this mixture to remove solid part, washing, drying and calcination (following 30 minutes at 350 ℃) have the colored interference pigments (TiO with metalluster of little green with acquisition ₂/ SnO ₂/ [SiO ₂/ Al (P)]).

Industrial applicibility

The metallic pigments of highly corrosion of the present invention can be widely used in the ring under the wide region pH value Guarantor's type water paint. In addition, the invention enables and to apply the hydrated metal oxidation by the wet process method Thing, it is inadequate that this wet process method routine is regarded as for metal base.

Description of drawings

Fig. 1 shows and uses SnO ₂The result of the alkali resistance test of the aluminum slice of the highly corrosion that applies.

Claims (16)

1. highly anti-corrosive thin platelet-like metallic pigment, it comprises: on the surface of laminar metal base, the layer of form by handling described surface with phosphate cpd and/or boronic acid compounds; As the outermost layer that comprises aqua oxidation tin.

2. according to the highly anti-corrosive thin platelet-like metallic pigment of claim 1, wherein on the surface of this laminar metal base, follow-up being formed with: by handle the layer that described surface forms with phosphate cpd and/or boronic acid compounds with lower floor; By the hydrated metal oxide layer that one or more metals form, this metal is selected from silicon, aluminium, zirconium, titanium and tin; And the layer that comprises aqua oxidation tin.

3. according to the highly anti-corrosive thin platelet-like metallic pigment of claim 1 or 2, it is characterized in that this laminar metal base is the metallic pigment with metalluster.

4. according to the highly anti-corrosive thin platelet-like metallic pigment of claim 3, it is characterized in that these metallic pigment with metalluster are any in aluminum slice, titanium thin slice, golden thin slice, silver-colored thin slice, copper-zinc alloy thin slice, nickel-base alloy thin slice, stainless steel thin slice or the bronze flakes.

5. according to the highly anti-corrosive thin platelet-like metallic pigment of claim 2, wherein this hydrated metal oxide is a hydrated SiO 2.

6. according to each highly anti-corrosive thin platelet-like metallic pigment among the claim 2-5, it is characterized in that the amount of employed phosphate cpd and/or boronic acid compounds, with the per unit surface-area (m of this laminar metal base ²) P ₂O ₅And/or B ₂O ₃Meter is equivalent to 0.0001g-0.1g; Be used to prepare the amount of the metallic compound of hydrated metal oxide coat, with the per unit surface-area (m of this laminar metal base ²) metal oxide calculate, be equivalent to 0.01g-1.0g; Be used to prepare the amount of the tin compound of aqua oxidation tin layer, with the per unit surface-area (m of this laminar metal base ²) stannic oxide (SnO ₂) calculate, be equivalent to 0.0008g-1.0g.

7. according to each highly anti-corrosive thin platelet-like metallic pigment among the claim 1-6, wherein semi-transparent metal layer further is coated on the described layer that comprises aqua oxidation tin.

8. prepare the method for highly anti-corrosive thin platelet-like metallic pigment, it comprises: the laminar metal base that will be coated with hydrated metal oxide layer disperses (suspension) Yu Shuizhong; And simultaneously tin salt aqueous solution and alkaline aqueous solution are added in the described dispersion (suspension), keep the pH value constant simultaneously, on the surface of the described laminar metal base that is coated with hydrated metal oxide layer, to form aqua oxidation tin layer.

9. the colored interference pigments that has metalluster is characterized in that surface according to each highly anti-corrosive thin platelet-like metallic pigment among the claim 1-6 further is coated with and comprises one or more layers auxiliary hydrated metal oxide layer.

10. according to the colored interference pigments with metalluster of claim 9, it is characterized in that preparing this auxiliary hydrated metal oxide layer by wet processing methods, process for chemical vapor deposition of materials with via or physical vapor deposition methods.

11. colored interference pigments with metalluster according to claim 9 or 10, it is characterized in that this auxiliary hydrated metal oxide layer is the layer that comprises one or more hydrated metal oxides of one or more metals, this metal is selected from titanium, aluminium, zirconium, tin, zinc, iron, chromium, cobalt, silicon and boron.

12., it is characterized in that this auxiliary hydrated metal oxide layer is the multiple coat that contains different hydrated metal oxides according to each colored interference pigments among the claim 9-11 with metalluster.

13., it is characterized in that this auxiliary hydrated metal oxide layer is by alternately applying the multiple coat that hydrated metal oxide layer with high refractive index and the hydrated metal oxide layer with low refractive index form according to the colored interference pigments with metalluster of claim 12.

14. require among the 9-13 each colored interference pigments according to aforesaid right, wherein translucent metal level further be coated on the described auxiliary hydrated metal oxide layer.

15. according among the claim 1-7 each the highly anti-corrosive thin platelet-like metallic pigment and/or according to each colored interference pigments among the claim 9-14 with metalluster be used for coating with lacquer, powder coating and film, the purposes of printing ink, safety printing ink and printed matter, plastics, pellet and moulded goods and makeup.

16. comprise according among the claim 1-7 each the highly anti-corrosive thin platelet-like metallic pigment and/or according to each colored interference pigments among the claim 9-14 with metalluster, and one or more are selected from the composition of other pigment of pigment dyestuff, mineral dye, effect pigment, filler and functional pigment.

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