CN101138895B

CN101138895B - Surface-treated steel sheet

Info

Publication number: CN101138895B
Application number: CN2007101490737A
Authority: CN
Inventors: 藤林亘江; 松崎晃; 安藤聪; 野村修二; 洼田隆广; 诸星好一; 中野多佳士; 大久保崇; 阿久井润
Original assignee: Kansai Paint Co Ltd; NKK Corp
Current assignee: JFE Steel Corp; Kansai Paint Co Ltd; JFE Engineering Corp
Priority date: 2006-09-07
Filing date: 2007-09-07
Publication date: 2011-09-14
Anticipated expiration: 2027-09-07
Also published as: CN101138895A; JP2008063621A; SA07280482B1; JP4972240B2

Abstract

A surface-treated steel sheet is disclosed, including a zinc based plated steel sheet having thereon a surface-treated film containing titanium, nickel, aluminum and fluorine and having a film thickness of from 0.05 to 1.0 mum, the surface-treated film having a titanium deposition amount of from 0.01 to 0.5 g/m<2 >and containing from 0.01 to 5 parts by mass of nickel, from 0.1 to 25 parts by massof aluminum and from 1 to 500 parts by mass of fluorine relative to 100 parts by mass of titanium. This surface-treated steel sheet does not contain hexavalent chromium in the film thereof at all andhas excellent heat discoloration resistance, corrosion resistance and resistance to blackening.

Description

Surface treated steel plate

Technical field

The present invention relates to optimal surface treated steel plate in automobile, household electrical appliances, building materials purposes, particularly do not contain the environment-adaptive type surface treated steel plate of 6 valency chromium in the surface treatment capsule.

Background technology

In household electrical appliances steel plate, building materials steel plate, automotive sheet, be widely used in the surface of galvanized steel plate or aluminum type plated steel sheet all the time, to improve corrosion resistance (anti-white rust, anti-red rust) is purpose, uses with chromic acid, dichromic acid or its esters and implements the steel plate that chromate is handled as the treatment fluid of main component.This chromate is handled and can be made excellent corrosion resistance and implement easylier, is a kind of processing method of economy.

Chromate is handled and has been used public hazards restrictive substance 6 valency chromium, but this 6 valency chromium is handled in closed system in the treatment step, in addition, because the sealing function that the organic envelope that forms on the upper strata produces, stripping chromium also almost can be zero from the chromate tunicle, so does not cause the pollution of 6 valency chromium to human body or environment in fact.Yet, along with the concern to the earth environment problem in recent years constantly increases, singly not working environment and the rules and regulations of paying attention to all the time handled of draining, pay attention to the rules and regulations that carrying capacity of environment and environment be in harmonious proportion and also come into effect gradually.In addition, also there is the historical background of estimating the producer with the environment percentage contribution, reduces and use the trend of the heavy metal that contains 6 valency chromium to increase day by day.

Under such background, the multiple white rust inhibition technology (Chrome-free technology) of not using the galvanized steel plate of 6 valency chromium has been proposed.For example, in the patent documentation 1,2, proposed to contain the surface conditioning agent of Al, phosphate cpd, silica and water system organic resin emulsion, and the metal material that applies this surface conditioning agent.In addition, in patent documentation 3, propose the dihydric phosphate of coating polyvalent metal and the mixed aqueous solution of metal oxide sol, behind the dry formation noncrystalline tunicle, be formed with the galvanized steel plate of organic coat layer.In addition, also proposed to contain oxide fine particle and phosphoric acid and/or phosphate cpd in the patent documentation 4,5 and be selected among Mg, Mn, the Al more than a kind the composite oxides of metal by rete as lower floor, layer forms the steel plate of organic envelope thereon.

Patent documentation 1: Japanese kokai publication hei 11-350157 communique

Patent documentation 2: TOHKEMY 2000-26980 communique

Patent documentation 3: TOHKEMY 2000-129460 communique

Patent documentation 4: TOHKEMY 2002-53979 communique

Patent documentation 5: TOHKEMY 2002-53980 communique

In the purposes that galvanized steel plate is suitable for, there are the parts of much accepting heating in the temperature range more than the zinc fusing point (about 500～600 ℃).For example, in the heat exchanger in air-conditioner outdoor unit, when welding copper pipe and aluminum evaporimeter,, galvanized steel plate is placed between copper pipe and the evaporimeter, makes the flame of blowtorch directly not contact aluminium in order to prevent to use the fusion of gas arc lamp heating causing aluminium.In such purposes, if use the surface treated steel plate of above-mentioned prior art, then owing to be the tunicle of organic resin main body, the thermal decomposition variable color is yellow or brown, and the result produces bad order.Therefore may use the surface treated steel plate of prior art hardly.

In order to solve such problem, the Chrome-free technology of heat-resisting discolouration excellence has been proposed.For example, in the patent documentation 6,7, having proposed with dihydric phosphate and cataloid is the inorganic tunicle of main component.In addition, in the patent documentation 8, having proposed dihydric phosphate and cataloid is that the inorganic tunicle of main component is arranged at lower floor, and silicate coating and/or silicones are arranged at the double-deck tunicle on upper strata.

Patent documentation 6: TOHKEMY 2000-79370 communique

Patent documentation 7: TOHKEMY 2001-348672 communique

Patent documentation 8: TOHKEMY 2004-91826 communique

But, the tunicle that is rich in inorganic matter in the patent documentation 6,7, the corrosion resistance level is extremely low, is difficult to use as the substitute of chromate tunicle.On the other hand, though have the corrosion resistance level that can be suitable as chromate tunicle substitute, owing to used the silicate or the silicones of high price, there is the problem of cost aspect in the double-deck tunicle in the patent documentation 8.In addition, use the tunicle of these technology, owing to the phenomenon that is easy to generate blackening under moist environment (the black change), therefore application is very difficult in the heat exchanger of easy dewfall, and the preservation environment in the Product transport process also is restricted in addition, and is therefore impracticable.

Therefore, the objective of the invention is to solve such prior art problems, be provided at and do not contain 6 valency chromium in the surface treatment capsule, and obtain the surface treated steel plate of excellent heat-resisting discolouration, corrosion resistance and anti-blackening.

Summary of the invention

The present invention is a kind of surface treated steel plate, and it has the surface treatment capsule of titaniferous, nickel, aluminium and fluorine on the surface of galvanized steel plate, and this is 0.05～1.0 μ m by film thickness, and the titanium adhesion amount of this surface treatment capsule is 0.01～0.5g/m ², and for the titanium of 100 mass parts, contain the nickel of 0.01～5 mass parts, the aluminium of 0.1～25 mass parts, the fluorine of 1～500 mass parts.

In addition on this surface treated steel plate, described surface treatment capsule preferably for the described titanium of 100 mass parts, also contains at least a kind in the vanadium of phosphorus, 1～300 mass parts of the zirconium that is selected from 2～1000 mass parts, 1～300 mass parts.

In addition, the present invention is 0.1～2.0g/m for having the tunicle adhesion amount on the surface of galvanized steel plate or aluminum type plated steel sheet also ²The surface treated steel plate of surface treatment capsule, this surface treatment capsule is for containing the waterborne liquid of titaniferous by coating, and the nickel compound of solid constituent 100 mass parts 0.01～10 mass parts of the waterborne liquid of this titaniferous relatively, the surface treating composition of the fluorochemical of the aluminium compound of 1～100 mass parts and 1～800 mass parts, make it dry and form, the waterborne liquid of wherein said titaniferous is to be selected from water-disintegrable titanium compound, the low condensation product of water-disintegrable titanium compound, titanium hydroxide, at least a kind of waterborne liquid that titanium compound mixes to obtain with hydrogen peroxide in the low condensation product of titanium hydroxide.

In addition, in this surface treated steel plate, preferred described fluorochemical is at least a kind that is selected from ammonium zirconium fluoride and the hydrofluorination zirconium.

In addition, handle in the steel plate at above-mentioned arbitrary surfaces, described surface treating composition, more preferably for solid constituent 100 mass parts of the waterborne liquid of described titaniferous, also contain at least a kind in the zirconium carbonate compound that is selected from 1～400 mass parts organic phosphoric acid compound, 1～400 mass parts vanadic acid compound and 1～400 mass parts.

In addition, handle in the steel plate at above-mentioned arbitrary surfaces, described surface treating composition, more preferably solid constituent 100 mass parts of the waterborne liquid of described relatively titaniferous, also contain 30 mass parts following be selected from least a kind of resin in water-soluble organic resin and the water dispersible organic resin.

Description of drawings

Fig. 1 is as the water-fast figure that adheres to the model (photo) of discolouration metewand among the expression embodiment 1.

The specific embodiment

Mode 1

The inventor has carried out research and inquirement for the tunicle composition that can address the above problem, found that by on the galvanized steel plate surface, formation contains the surface treatment capsule of titanium, nickel, aluminium and fluorine, can obtain having the surface treated steel plate of excellent heat-resisting discolouration, corrosion resistance, working position corrosion resistance and anti-blackening.

Galvanized steel plate as surface treated steel board substrate of the present invention can use for example galvanized steel plain sheet, plating Zn-Ni alloy steel plate, plating zn-fe alloy steel plate (electroplating steel plate, alloy galvanized steel plate), plating Zn-Cr alloy-steel plate, plating Zn-Mn alloy-steel plate, plating Zn-Co alloy-steel plate, plating Zn-Co-Cr alloy-steel plate, plating Zn-Cr-Ni alloy-steel plate, plating Zn-Cr-Fe alloy-steel plate, plating Zn-Al alloy steel plate (for example, plating Zn-5 quality %Al alloy-steel plate, plating Zn-55 quality %Al alloy-steel plate), plating Zn-Mg alloy-steel plate, plating Zn-Al-Mg alloy-steel plate, also has dispersing metal oxides in the coating tunicle of these clad steel sheets, zinc-plated class clad steel plate (for example, the Zn-SiO of polymer etc. ₂Disperse clad steel sheet) etc.In addition, also can be in above-mentioned such coating, use the multilayer coating steel plate that is coated with two-layer above of the same race or different coating.

In addition, clad steel sheet can plate Ni etc. at surface of steel plate in advance on a small quantity, carries out various as mentioned above coating thereon again.

Can adopt any means that to implement in electrolysis (electrolysis in the aqueous solution or the electrolysis in the nonaqueous solvents), fusion method, the vapor phase method as method of coating.

In addition, when coating tunicle surface forms surface treatment capsule, in order not produce tunicle defective or inequality, can carry out alkali degreasing, solvent degreasing, surface adjustment processing processing such as (the surface adjustment of alkalescence are handled or acid surface adjustment processing) in case of necessity in advance on the tunicle surface.

In addition, in order to prevent the black change (coating surface oxidative phenomena a kind of) under environment for use, also can use the acidity or the alkaline aqueous solution that contain iron group metal ion (in Ni ion, Co ion, the Fe ion more than a kind) in case of necessity, carry out surface adjustment at coating surface in advance and handle.

In addition, when plated steel sheet uses as base steel sheet,, can in electroplate liquid, add iron group metal ion (in Ni ion, Co ion, the Fe ion more than a kind), make in the plating tunicle and contain more than these metals 1 quality ppm in order to prevent black the change.At this moment, be not particularly limited for the upper limit of electroplating iron group metal concentration in the tunicle.

In the surface treated steel plate of the present invention, the surface treatment capsule that forms on the surface of galvanized steel plate is for containing the tunicle of quantitative titanium, nickel, aluminium and fluorine.This surface treatment capsule does not contain 6 valency chromium.

By after containing the waterborne liquid of titanium compound in coating on the clad steel sheet, carry out drying or low-temperature heat is handled, can make and contain above-mentioned titanium in the tunicle.Use the waterborne liquid of such titanium-containing compound, the tunicle that contains titanium dioxide that can form densification, adaptation excellence and have corrosion resistance, shielding.In addition, the heat treated temperature behind the waterborne liquid of coating titanium-containing compound is below 200 ℃, and is preferred especially below 150 ℃.

Titanium adhesion amount in the surface treatment capsule is 0.01～0.5g/m ², be preferably 0.03～0.3g/m ²As the not enough 0.01g/m of titanium adhesion amount ²The time, being difficult to apply whole clad steel sheets surface densely, the corrosion resistance of corrosion resistance, particularly working position is inferior.On the other hand, surpass 0.5g/m when the titanium adhesion amount ²The time, because the tunicle internal stress, cause that easily steel plate adds the man-hour tunicle and peels off.

Above-mentioned nickel is the active ingredient that improves anti-blackening, by add nickel compound in the above-mentioned waterborne liquid that contains titanium compound, can make and contain nickel in the tunicle.

The content of nickel in the surface treatment capsule is 0.01～5 mass parts for the titanium of 100 mass parts, is preferably 0.05～1.5 mass parts.During less than 0.01 mass parts, nickel content can't fully improve the black effect that becomes for the titanium of 100 mass parts.On the other hand, when surpassing 5 mass parts, though substantially improved black change, corrosion resistance significantly worsens.

Above-mentioned aluminium is the active ingredient that improves corrosion resistance, by add aluminium compound in the waterborne liquid of above-mentioned titanium-containing compound, can make and contain aluminium in the tunicle.

The content of aluminium in the surface treatment capsule is 0.1～25 mass parts for the titanium of 100 mass parts, is preferably 0.5～10 mass parts.During less than 0.1 mass parts, corrosion resistance improves insufficiently aluminium content for the titanium of 100 mass parts.On the other hand, when surpassing 25 mass parts, unnecessary addition worsens corrosion resistance, can think that this is owing to can not suitably form the cause of the shielding tunicle that is produced by titanium dioxide.

In addition, particularly from making the viewpoint of anti-blackening and corrosion resistance coexistence, the mass ratio that is desirably in the nickel that contains in the surface treatment capsule and aluminium is 1: 1～1: 50 scope, preferably 1: 5～1: 25 scope.

Above-mentioned fluorine is corrosion resistance and the water-fast active ingredient of adhering to discolouration etc. that improves corrosion resistance, particularly working position, by add fluorochemical in the above-mentioned waterborne liquid that contains titanium compound, can make and contain fluorine in the tunicle.

The content of fluorine in the surface treatment capsule is 1～500 mass parts for the titanium of 100 mass parts, is preferably 10～400 mass parts.Fluorine content during less than 1 mass parts, is not seen the raising effect of corrosion resistance for the titanium of 100 mass parts.On the other hand, when surpassing 500 mass parts, not only the raising effect of corrosion resistance is saturated, and hinders the effect of the nickel that exists for anti-blackening.

Can also make contain in the surface treatment capsule in zirconium, phosphorus, the vanadium etc. more than a kind.

Above-mentioned zirconium is the active ingredient that improves the corrosion resistance behind the alkali degreasing, by add zirconium compounds in the above-mentioned waterborne liquid that contains titanium compound, can make and contain zirconium in the tunicle.

The content of zirconium in the surface treatment capsule is 2～1000 mass parts for the titanium of 100 mass parts, is preferably 30～1000 mass parts.Zirconium content during less than 2 mass parts, can't fully obtain by adding the effect that zirconium produced for the titanium of 100 mass parts.On the other hand, when surpassing 1000 mass parts, because superfluous addition, not only the raising effect of corrosion resistance is saturated behind the alkali degreasing, and has hindered the effect of titanium.

Above-mentioned phosphorus is the active ingredient that improves the storage stability of the waterborne liquid that contains above-mentioned titanium compound, by add phosphorus-containing compound in identical waterborne liquid, can make and contain phosphorus in the tunicle.

The content of phosphorus in the surface treatment capsule is 1～300 mass parts for the titanium of 100 mass parts, and preferred 10～200 mass parts are advisable.Phosphorus content during less than 1 mass parts, can't fully obtain adding the effect that phosphorus produces for the titanium of 100 mass parts.On the other hand, when adding the amount that surpasses the such surplus of 300 mass parts, not only the effect of phosphorus is saturated, and has hindered the effect of titanium.

Though above-mentioned vanadium worsens heat-resisting discolouration slightly, for improving water-fast active ingredient of adhering to discolouration,, can make and contain vanadium in the tunicle by in the above-mentioned waterborne liquid that contains titanium compound, adding vfanadium compound.

The content of vanadium in the surface treatment capsule is 1～300 mass parts for the titanium of 100 mass parts, and preferred 5～300 mass parts are advisable.Content of vanadium during less than 1 mass parts, can't fully obtain adding the effect that vanadium produces for the titanium of 100 mass parts.On the other hand, when adding the amount that surpasses the such surplus of 300 mass parts, not only the effect of vanadium is saturated, and has hindered the effect of titanium.

The constituent analysis of aforesaid surface treatment capsule can be undertaken by for example following method.At first, known by the surface of the surface treated steel plate of membrane area, the coating concentrated sulfuric acid dissolves coating together, with distilled water flushing, be collected in the kieldahl flask, carry out acid and decompose, add concentrated hydrochloric acid in addition and make not that dissolved matter all dissolves, can analyze titanium, zirconium, phosphorus, vanadium, nickel by the calibration curve method that uses the ICP spectroscopy apparatus.Can use the fluorescent x-ray analyzer of wavelength dispersion type, the calibration curve of being made by the fluorine compounds of concentration known carries out quantitatively fluorine.For aluminium, with the aforesaid difference of icp analysis value of acid decomposition liquid that makes the acid decomposition liquid that coating dissolves together and only make the coating dissolving as the amount of aluminium in the tunicle.

Aforesaid surface treatment capsule of the present invention obtains by be coated with aqueous treating fluid (surface treating composition), drying or heat-agglomerating on the clad steel sheet surface, and preferably each is supplied with by treatment fluid composition shown below by film component.Mix the waterborne liquid (A) of the titaniferous that obtains by at least a kind of titanium compound in the low condensation product of the low condensation product that is selected from water-disintegrable titanium compound, water-disintegrable titanium compound, titanium hydroxide, titanium hydroxide and hydrogen peroxide, supply with titanium.

The said hydrolyzed titanium compound is the titanium compound with the hydrolization group that directly combines with titanium, by with reaction of moisture such as water, water vapour, generate titanium hydroxide.In addition, water-disintegrable titanium compound can be that the group that combines with titanium all is a hydrolization group, and the group that also can combine with a titanium part is hydrolization group.

The said hydrolyzed group is if generate titanium hydroxide by aforesaid with reaction of moisture, then there is no particular limitation, can enumerate lower alkoxy for example or form group halogen atom, hydrogen atom, sulfate ions etc. such as (for example) chlorine etc. of salt with titanium.

Contain water-disintegrable titanium compound, be preferably general formula Ti (OR) especially as the lower alkoxy of hydrolization group ₄Four alkoxytitaniums of (R represents that identical or different carbon number is 1～5 alkyl in the formula) expression.As carbon number is that 1～5 alkyl can be enumerated, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group etc.

Contain with titanium and form the water-disintegrable titanium compound of the group of salt, can enumerate titanium chloride, titanium sulfate etc. as representative as hydrolization group.

In addition, the low condensation product of water-disintegrable titanium compound is the low condensation product between the said hydrolyzed titanium compound.The group that combines with titanium in this low condensation product can all be a hydrolization group, and the group that combines with titanium also can a part be hydrolization group.

About hydrolization group be with titanium form salt group water-disintegrable titanium compound (for example, titanium chloride, titanium sulfate etc.), the ortho-titanic acid (titanic hydroxide gel) that the aqueous solution by water-disintegrable titanium compound and the reaction of alkaline solutions such as ammonia or NaOH obtain also can be used as low condensation product and uses.

As the low condensation product of water-disintegrable titanium compound and the low condensation product of titanium hydroxide, can use condensation degree is 2～30 compound, and especially preferably using condensation degree is 2～10 compound.When condensation degree surpasses 30, generate white precipitate when mixing with hydrogen peroxide, can not obtain the waterborne liquid of stable titaniferous.

The low condensation product of the low condensation product of the water-disintegrable titanium compound of more than enumerating, water-disintegrable titanium compound, titanium hydroxide, titanium hydroxide, can use more than a kind or 2 kinds, but four alkoxytitaniums of the water-disintegrable titanium compound of conduct that wherein preferred especially above-mentioned general formula is represented.

The waterborne liquid of titaniferous (A) does not then have special restriction if mix the waterborne liquid of the titaniferous that obtains by above-mentioned titanium compound and hydrogen peroxide, can use existing knownly, specifically can be listed below.

(i) in gel that contains titanium hydroxide or colloidal sol, add the titanium oxide ion hydrogen peroxide complex thing or metatitanic acid (titanium peroxide water and the thing) aqueous solution (with reference to Japanese kokai publication sho 63-35419 communique, Japanese kokai publication hei 1-224220 communique) that hydrogen peroxide obtains.

(ii) the titanic hydroxide gel of being made by the aqueous solution and the alkaline solution of titanium chloride or titanium sulfate synthesizes the liquid that is used to form titanium dioxide film (with reference to Japanese kokai publication hei 9-71418 communique, Japanese kokai publication hei 10-67516 communique) that obtains with the hydrogen peroxide effect.

When obtaining this and being used to form titanium dioxide film liquid, by making alkaline solutions reactions such as titanium chloride or titanium sulfate aqueous solution and ammonia or NaOH, can make the titanic hydroxide gel precipitation that is called as ortho-titanic acid.Afterwards, repeat the separation and the washing of titanic hydroxide gel, add hydrogen peroxide again, remove unnecessary hydrogen peroxide, can obtain the viscous liquid of yellow transparent through decomposing by decant.

The above-mentioned ortho-titanic acid of precipitation be by OH polymerization or the producing high-molecular gel state that produces of hydrogen bond each other, can not be directly as the waterborne liquid use of titaniferous.As in this gel, adding hydrogen peroxide, the part of OH promptly becomes the peroxidating state, dissolve as the titanium peroxide acid ion, perhaps macromolecular chain is cut off and makes its degraded a kind of like this collosol state, unnecessary hydrogen peroxide decomposes is water and oxygen, can be used as the waterborne liquid that forms the titaniferous that inoranic membrane uses and uses.

Because this colloidal sol only contains oxygen atom and hydrogen atom except titanium atom, so when becoming titanium dioxide by dry or calcining, only produce water and oxygen, therefore need not in the thermal decomposition of sol-gal process or sulfate etc., remove necessary carbon component or halogenic ingredient, also can form density at low temperatures than higher titanium dioxide film.

(iii) in the inorganic titanium compound aqueous solution of titanium chloride or titanium sulfate, adding hydrogen peroxide generates after titanium peroxide water and the thing, the solution that the interpolation alkaline matter obtains is by placing or heating, generate titanium peroxide water and the polymeric sediment of thing, afterwards, remove at least from behind the solvent components outside the water in the titaniferous materials solution solution that is used to form titanium oxide (with reference to TOHKEMY 2000-247638 communique, TOHKEMY 2000-247639 communique) that obtains with the hydrogen peroxide effect.

Use water-disintegrable titanium compound and/or its low condensation product (following be called for convenience of description " water-disintegrable titanium compound a ") waterborne liquid (A) as the titaniferous of titanium compound, can react acquisition in about 10 minutes～20 minutes by making water-disintegrable titanium compound a and hydrogen peroxide under 1～70 ℃ of reaction temperature.

Think the waterborne liquid (A) of the titaniferous that uses this water-disintegrable titanium compound a, be by making the reaction of water-disintegrable titanium compound a and hydrogen peroxide, water-disintegrable titanium compound a is hydrolyzed in water, generation contains the titanium compound of hydroxyl, afterwards, the hydrogen peroxide titanium compound coordination of hydroxyl therewith forms, and this hydrolysis and almost taken place simultaneously to obtain by the coordination that hydrogen peroxide causes generates stable high, the chelate liquid that can long preservation of room temperature range.The titanic hydroxide gel that uses in the existing method for making, because Ti-O-Ti key part three-dimensional, gel and hydrogen peroxide react the waterborne liquid (A) of the titaniferous that obtains therewith, all have essence different on composition and stability.

In addition, use the waterborne liquid (A) of the titaniferous of water-disintegrable titanium compound a to handle, can obtain containing the ultramicronized titanium oxide dispersion of titanium dioxide of crystallization through heat treated or autoclaving more than 80 ℃.Above-mentioned heat treated or autoclaving are handled when being lower than 80 ℃, and the crystallization of titanium dioxide carries out insufficient.In the titanium oxide dispersion that expectation is made like this, the ultramicronized average grain diameter of titanium dioxide is below the 10nm, preferably is about 1～6nm.If the ultramicronized average grain diameter of titanium dioxide, is then made film reduction (as the dry tunicle in coating back time, more than the thickness 1 μ m, crack) greater than 10nm, and is therefore not preferred.The outward appearance of this titanium oxide dispersion is translucent.The waterborne liquid (A) that such titanium oxide dispersion also can be used as titaniferous uses.

The aqueous treating fluid (being also referred to as surface treating composition) of the waterborne liquid (A) by will comprising the titaniferous that has used water-disintegrable titanium compound a, coating on the clad steel sheet surface, drying are (for example, the low-temperature heat drying), himself can form the tack excellence densification contain titanium dioxide tunicle (surface treatment capsule).

As the heating-up temperature behind the coating aqueous treating fluid, for example be below 200 ℃, preferred especially below 150 ℃.By heat drying under such temperature, what can form the noncrystalline (amorphous) that contains some hydroxyls contains the titanium dioxide tunicle.

In addition, through heat treated more than 80 ℃ or autoclaving are handled as mentioned above, when the titanium oxide dispersion that obtains uses as the waterborne liquid (A) of titaniferous, therefore only be coated with aqueous treating fluid and also can form the crystalline titanium dioxide tunicle that contains, the coating material as material that can not heat treated is useful.

In addition, as the waterborne liquid (A) of titaniferous, in the presence of TiO 2 sol, also can use water-disintegrable titanium compound a and hydrogen peroxide to react the waterborne liquid (Al) of the titaniferous that obtains.

Above-mentioned TiO 2 sol is that the amorphous titania particulate is or/and the colloidal sol that the anatase titanium dioxide particulate disperses in water (as required, can add for example aqueous organic solvent such as alcohols, pure ethers).This TiO 2 sol can use existing known, for example the titanium dioxide condensation product that titaniferous solutions such as (i) hydrolysis titanium sulfate or titanyl sulfate are obtained, (ii) the titanium dioxide condensation product that obtains of organic titanic compound such as hydrolysis alkoxytitanium, (iii) hydrolysis or in and the titanium dioxide condensation products such as titanium dioxide condensation product that obtain of halogenated titanium solution such as titanium tetrachloride be scattered in the water, the amorphous titania colloidal sol that obtains, perhaps calcining above-mentioned titanium dioxide condensation product becomes Detitanium-ore-type titanium particulate, and it is dispersed in colloidal sol in the water.

In the calcining of above-mentioned amorphous titania, at least under the temperature more than the anatase crystallization temperature, for example during the temperature lower calcination more than 400～500 ℃, can make amorphous titania be converted to anatase titanium dioxide.The aqueous sol of this titanium dioxide can be enumerated as, TKS-201 (trade name for example, テイカ corporate system, Detitanium-ore-type crystallization shape, average grain diameter 6nm), TA-15 (trade name, daily output chemical company system, Detitanium-ore-type crystallization shape), STS-11 (trade name, the former industry corporate system of stone, Detitanium-ore-type crystallization shape) etc.

In the waterborne liquid (Al) of titaniferous, the mass ratio x/y of above-mentioned TiO 2 sol x and titanium hydroperoxidation thing y (product of water-disintegrable titanium compound a and hydrogen peroxide) is 1/99～99/1, and about 10/90～90/10 the scope of being preferably is more suitable.When mass ratio x/y less than 1/99, there is not fully to obtain the effect of interpolation TiO 2 sol at aspects such as stability, photoreactivities, on the other hand, it is poor to make film when surpassing 99/1, therefore not preferred.

By in the presence of TiO 2 sol, water-disintegrable titanium compound a and hydrogen peroxide were reacted about 10 minutes～20 minutes down for 1～70 ℃ in reaction temperature, can obtain the waterborne liquid (Al) of titaniferous.

The generating mode of the waterborne liquid of titaniferous (Al) and its characteristic, identical with the waterborne liquid (A) of the titaniferous of the water-disintegrable titanium compound a of described use before, but cause a part of condensation reaction when synthetic especially owing to used TiO 2 sol, suppress thickening.Think that it is former because the condensation reaction thing is adsorbed in the TiO 2 sol surface, suppressed the producing high-molecular of solution state.

In addition, when the waterborne liquid of titaniferous (Al) is handled at heat treated or autoclaving more than 80 ℃, obtain containing the ultramicronized titanium oxide dispersion of titanium dioxide of crystallization.Be the ultramicronized particle diameter of titanium dioxide of the temperature conditions that obtains this titanium oxide dispersion, crystallization, dispersion liquid outward appearance etc., also the waterborne liquid (A) with the titaniferous of the water-disintegrable titanium compound a of described use before is identical.The waterborne liquid (Al) that such titanium oxide dispersion also can be used as titaniferous uses.

Identical with the waterborne liquid (A) of the titaniferous of the water-disintegrable titanium compound a of described use before, the aqueous treating fluid (surface treating composition) that comprises the waterborne liquid (Al) of titaniferous, by coating on the clad steel sheet surface, drying (for example, the low-temperature heat drying), himself can form the tack excellence densification contain titanium dioxide tunicle (surface treatment capsule).

As the heating-up temperature behind the coating aqueous treating fluid, for example be below 200 ℃, preferred especially below 150 ℃.By heat drying under such temperature, can form the Detitanium-ore-type that contains some hydroxyls and contain the titanium dioxide tunicle.

As mentioned above in the waterborne liquid (A) of titaniferous, the waterborne liquid (A) of the titaniferous of water-disintegrable titanium compound a or the waterborne liquid (Al) of titaniferous have been used, owing to have excellent performance such as storage stability, corrosion resistance, especially preferably use these in the present invention.

Be selected from the low condensation product of low condensation product, titanium hydroxide, titanium hydroxide of water-disintegrable titanium compound, water-disintegrable titanium compound at least a kind titanium compound relatively, the cooperation ratio of hydrogen peroxide, for the titanium compound of 10 mass parts, be scaled 0.1～100 mass parts, be preferably 1～20 mass parts into expectation with hydrogen peroxide.The cooperation ratio of hydrogen peroxide is during with hydrogen peroxide conversion less than 0.1 mass parts, because that chelate forms is insufficient, generates the precipitation of white casse.On the other hand, when surpassing 100 mass parts, unreacted hydrogen peroxide is remaining easily, emits dangerous active oxygen in the storage, and is therefore not preferred.

The concentration of hydrogen peroxide of hydrogen peroxide is not particularly limited, from the suitable angle of solid component concentration of handling easiness, generation liquid that painting operation is relevant, preferably be about 3～30 quality %.

In the waterborne liquid of titaniferous (A), the colloidal sol or the pigment that also can add other as required make its dispersion.For example, can enumerate commercially available TiO 2 sol or titania powder, mica, talcum powder, silica, barium monoxide, clay etc. as additive, can add in these more than a kind.

The content of the waterborne liquid (A) of the titaniferous in the aqueous treating fluid (surface treating composition) from the viewpoints such as stability of treatment fluid, is preferably counted 1～100g/L with solid constituent, preferred 5～50g/L.

By in aqueous treating fluid, add in for example nickel acetate, nickel nitrate, the nickelous sulfate etc. more than a kind or 2 kinds, can make and contain nickel in the tunicle.Wherein from the viewpoint of anti-blackening, nickel acetate is very suitable.

By in aqueous treating fluid, add in for example aluminum nitrate, aluminum acetate, aluminum sulfate, aluminium oxide, aluminium acetylacetonate, the aluminate etc. more than a kind or 2 kinds, can make and contain aluminium in the tunicle.

By in aqueous treating fluid, add in for example ammonium zirconium fluoride, potassium zirconium fluoride, hydrofluorination zirconium, titanium fluoride ammonium, hydrofluoric acid, the hydrofluoric acid ammonium etc. more than a kind or 2 kinds, can make and contain fluorine in the tunicle.Very suitable more than a kind in ammonium zirconium fluoride, the hydrofluorination zirconium wherein, that is, and the corrosion resistance of ammonium zirconium fluoride behind the alkali degreasing, water-fast viewpoint of adhering to discolouration and preferred, the viewpoint of the corrosion resistance of hydrofluorination zirconium behind the alkali degreasing and preferred.

Preferably adding organic phosphate cpd in aqueous treating fluid makes and contains phosphorus in the tunicle.The organic phosphoric acid compound can be enumerated, 1-hydroxyl methane-1 for example, and 1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxy propane-1,1-di 2 ethylhexyl phosphonic acid etc. contains the organic phosphorous acid of hydroxyl; 2-hydroxyl phosphoryl acetate, 2-phosphoryl butane-1,2,4-tricarboxylic acids etc. contain the organic phosphorous acid of carboxyl and salt thereof etc. as suitable compounds, can use in these more than a kind or 2 kinds.Wherein with 1-hydroxyl ethane-1, the effect of 1-di 2 ethylhexyl phosphonic acid is remarkable, and is preferred especially.

By in aqueous treating fluid, add in for example lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, the anhydrous vanadic acid etc. more than a kind or 2 kinds, can make and contain vanadium in the tunicle.Wherein from the water-fast viewpoint such as discolouration of adhering to, preferred ammonium metavanadate.

In the salt such as the sodium by in aqueous treating fluid, adding zirconium carbonate, potassium, lithium, ammonium more than a kind or 2 kinds, can make and contain zirconium in the tunicle.Wherein from the water-fast viewpoint such as discolouration of adhering to, preferred zirconium carbonate ammonium.

In addition, also can make and contain the organic resin composition that improves corrosion resistance in the surface treatment capsule of the present invention.To contain the organic resin composition in the tunicle in order making, can in aqueous treating fluid, to add water-soluble organic resin or/and the water dispersible organic resin.

Above-mentioned water-soluble organic resin is or/and the water dispersible organic resin is the organic resin that can dissolve or disperse in water, and the method as making the water-soluble or aqueous dispersion of organic resin can adopt existing known method.Particularly, organic resin can use the organic resin that contains functional group's (for example, hydroxyl, polyoxy alkylidene, carboxyl, ammonia (imido) base, sulfenyl, phosphino-etc.) of can be water-soluble separately or can disperseing in water; And as required, when being acidic resins when (containing the organic resin of carboxyl etc.), with amines such as monoethanolamine, triethylamines, ammoniacal liquor, the hydroxide of alkalinous metals such as lithium hydroxide, NaOH, potassium hydroxide part or all organic resin that obtains in these functional groups that neutralizes; And when for basic resin (contain amino organic resin etc.), with aliphatic acid such as acetic acid, lactic acid, inorganic acids such as phosphoric acid part or all organic resin that obtains in these functional groups etc. that neutralizes.

Water-soluble or water dispersible organic resin can be enumerated, for example, epoxylite, phenolic resinoid, acrylic resin, urethane esters resin, alkene-carboxylic acids resin, nylon-based resin, resin, polyvinyl alcohol, polyglycerol, carboxymethyl cellulose, CMC, hydroxyethylcellulose etc. with polyoxy alkylidene chain, can use in these more than a kind or 2 kinds.

According to further needs, can contain heavy metal compound beyond silane coupling agent for example, resin particle, the composition of the present invention, thickener, surfactant, lubricant (Tissuemat E, fluorine wax, Brazil wax etc.), antirust agent, coloring pigment, extender pigment, rust resisting pigment, dyestuff etc. in the surface treatment capsule (perhaps being used to form the aqueous treating fluid of tunicle).Surface treatment capsule be 0.05～1.0 μ m by film thickness, preferred 0.10～0.70 μ m, more preferably 0.15～0.50 μ m.When by film thickness less than 0.05 μ m, corrosion resistance variation behind corrosion resistance, working position corrosion resistance and the alkali degreasing, on the other hand, corrosion resistance and the water-fast discolouration variation of adhering to behind heat-resisting discolouration, corrosion resistance, working position corrosion resistance, the alkali degreasing when surpassing 1.0 μ m.

When making surface treated steel plate of the present invention, can be behind described aqueous treating fluid before the coating of galvanized steel plate surface, drying or heat-agglomerating.

The coating process of aqueous treating fluid can be any, for example spraying+edging, roller rubbing method etc.In addition, also can be any about the drying mode after the coating, for example hot blast is done mode, induction heating mode, electric furnace mode etc.

The baking temperature (steel billet temperature) of coating aqueous treating fluid preferably is about 60～200 ℃.Baking temperature is during less than 60 ℃, and tunicle forms insufficient, becomes inferior tunicles such as corrosion resistance.On the other hand, even surpassing drying under 200 ℃ the plate temperature, the situation that corrosion resistance descends appears in effect that the corrosion resistance that does not also obtain conforming to baking temperature improves on the contrary.Can think that this is because heat makes on the tunicle and cracks.

Embodiment 1

The waterborne liquid (A) of employed titaniferous and composition (B)～(G) are as follows in being used to form the aqueous treating fluid of tunicle (surface treating composition).

[manufacturing of the waterborne liquid of titaniferous (A)]

Production Example 1 (the waterborne liquid T1 of titaniferous)

In the 500cc solution that 60 quality % titanium tetrachloride solution 5cc adding distil waters are mixed with, dropping ammonia (1: 9) makes the titanium hydroxide precipitation.After cleaning with distilled water, add the hydrogen peroxide solution 10cc of 30 quality %, mixing obtains the waterborne liquid T1 of yellow translucent, the titaniferous with viscosity of titaniferous.

Production Example 2 (the waterborne liquid T2 of titaniferous)

Under 20 ℃ in the mixture of 30 quality % hydrogen peroxide 10 mass parts and deionized water 100 mass parts, the mixture that dripped tetraisopropoxy titanium 10 mass parts and isopropyl alcohol 10 mass parts through a hour stirs simultaneously.25 ℃ of following slakings 2 hours, obtain the slightly waterborne liquid T2 of the titaniferous of toughness of yellow transparent afterwards.

[nickel compound (B)]

B1: nickel acetate

B2: nickel nitrate

[aluminium compound (C)]

C1: aluminum nitrate

C2: aluminum acetate

[fluorochemical (D)]

D1: ammonium zirconium fluoride

D2: hydrofluoric acid

[organic phosphoric acid compound (E)]

E1:1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid

[vanadic acid compound (F)]

F1: ammonium metavanadate

F2: sodium metavanadate

[zirconium carbonate compound (G)]

G1: zirconium carbonate ammonium

G2: sodium zirconium carbonate

As the matrix steel plate of surface treated steel plate, use clad steel sheet as shown in table 1.

On the clad steel sheet surface, the suitable waterborne liquid (A) of above-mentioned titaniferous and the aqueous treating fluid (surface treating composition) of composition (B)～(G) of cooperating of coating makes peak metal temperature reach 100 ℃ of dryings after 3 seconds, as supplying the examination material., carry out as follows for the examination material about these by the analysis of film component and performance evaluation (corrosion resistance, anti-blackening, the water-fast discolouration that adheres to behind heat-resisting discolouration, corrosion resistance, working position corrosion resistance, the alkali degreasing).

Its result and each are for the tunicle composition of examination material and the adding ingredient of aqueous treating fluid etc., all by shown in table 2～table 5.

[tunicle analytical method]

The constituent analysis of surface treatment capsule, following carrying out.

About titanium, zirconium, phosphorus, vanadium, nickel, be by the surface of the surface treated steel plate of membrane area known, the coating concentrated sulfuric acid dissolves coating together, with distilled water flushing, be collected in the kieldahl flask, carry out acid and decompose, add concentrated hydrochloric acid in addition and make not that dissolved matter all dissolves, analyze by the calibration curve method that uses the ICP spectroscopy apparatus.About fluorine, use the fluorescent x-ray analyzer of wavelength dispersion type, quantitative by the calibration curve that the fluorine compounds of concentration known are made.In addition about aluminium, with the difference of the aforesaid icp analysis value that makes acid decomposition liquid that coating dissolves together and the acid decomposition liquid that only makes the coating dissolving amount as aluminium in the tunicle.

[method of evaluating performance]

(1) heat-resisting discolouration

Kept after 30 seconds to 500 ℃ of plate temperature in 30 seconds for the heating in infrared ray image furnace (Line イメ-ジ stove outside red, infrared imagefurnace) of examination material, the appearance when perusal naturally cools to room temperature, its metewand is as follows.

◎: not variable color

Zero: variable color slightly

△: become faint yellow

*: become yellow～brown

(2) corrosion resistance

According to the neutral brine spray testing method of JIS-Z-2371-2000, to sealed the end and the back side (50mm * 150mm) carries out salt spraytest, and measuring and producing the white rust area ratio is 5% test period, and its metewand is as follows for the examination material.

◎: more than 120 hours

More than zero: 96 hour and less than 120 hours

△: more than 48 hours and less than 96 hours

*: less than 48 hours

(3) working position corrosion resistance

For sealed the end and the back side for examination material (50mm * 100mm), behind crooked 180 degree in outside 2.5mmR place, neutral brine spray testing method according to JIS-Z-2371-2000, to carrying out salt spraytest for examination face, in the width 50mm at curved apex position length, mensuration white rust generation rate is 5% test period, and its metewand is as follows.

◎: more than 96 hours

More than zero: 48 hour and less than 96 hours

△: more than 24 hours and less than 48 hours

*: less than 24 hours

(4) corrosion resistance behind the alkali degreasing

Alkali cleaner [CLN-364S] (the rapids smart Co., Ltd of Japanese handkerchief card system) concentration with 2 quality % in pure water is dissolved, be heated to 60 ℃, it is being supplied examination material (50mm * 150mm) go up spraying after 2 minutes, the hermetic terminal and the back side, neutral brine spray testing method according to JIS-Z-2371-2000, carry out salt spraytest, mensuration white rust generation area ratio is 5% test period, and its metewand is as follows.

◎: more than 96 hours

More than zero: 48 hour and less than 96 hours

△: more than 24 hours and less than 48 hours

*: less than 24 hours

(5) anti-blackening

To rest on the control temperature for the examination material is that 80 ℃, relative humidity are in 95% the Constant Temperature and Humidity Chambers 24 hours, and (△ L: the test back L value-preceding L value of test), its metewand is as follows to calculate the variation of whiteness this moment (L value).

○：△L≥-5.0

△：-5.0>△L≥-10.0

×：-10.0>△L

(6) the water-fast discolouration that adheres to

For the examination material (on the 50mm * 50mm) roughly same point drip 10 ion exchange waters, in being heated to 100 ℃ baking oven dry 10 minutes, after the drying at once naked eyes judge its outward appearance, its metewand is as follows.Fig. 1 has shown the model photo as " △ " and " * " standard.

Zero: not variable color

△: variable color slightly

*: variable color

Mode 2

The inventor has carried out research and inquirement for the tunicle composition that can address the above problem, found that by on galvanized steel plate or aluminum type plated steel sheet surface, use the waterborne liquid of specific relatively titaniferous, with the compound interpolation nickel compound of regulation ratio, aluminium compound and fluorochemical, according to the organic phosphate cpd of an amount of interpolation of further needs, the vanadic acid compound, the zirconium carbonate compound, the surface treating composition of water-based organic resin, form surface treatment capsule, obtain having excellent anticorrosive, the surface treated steel plate of heat-resisting discolouration and anti-blackening.

Surface treated steel plate of the present invention has by the surface treatment capsule at galvanized steel plate or the regulation tunicle adhesion amount that the aluminum type plated steel sheet surface is coated with, desiccated surface treatment compositions (I) back forms.The water-based liquid that has cooperated titaniferous in the described surface treating composition (I), and with respect to this with the regulation ratio mixed Ni compound (B), aluminium compound (C) and fluorochemical (D), the waterborne liquid of wherein said titaniferous, be to be selected from water-disintegrable titanium compound, the low condensation product of water-disintegrable titanium compound, titanium hydroxide, the waterborne liquid of the titaniferous that at least a kind of titanium compound in the low condensation product of titanium hydroxide mixes to obtain with hydrogen peroxide has cooperated with the regulation ratio according to further needs to be selected from organic phosphoric acid compound (E), vanadic acid compound (F), zirconium carbonate compound (G), in water-soluble organic resin (H) and the water dispersible organic resin (H) at least a kind.This surface treatment capsule does not contain 6 valency chromium.

Galvanized steel plate as surface treated steel board substrate of the present invention, can use for example galvanized steel plain sheet, plating Zn-Ni alloy steel plate, plating zn-fe alloy steel plate (electroplating steel plate, alloy galvanized steel plate), plating Zn-Cr alloy-steel plate, plating Zn-Mn alloy-steel plate, plating Zn-Co alloy-steel plate, plating Zn-Co-Cr alloy-steel plate, plating Zn-Cr-Ni alloy-steel plate, plating Zn-Cr-Fe alloy-steel plate, plating Zn-Al alloy steel plate (for example, plating Zn-5 quality %Al alloy-steel plate, plating Zn-55 quality %Al alloy-steel plate), plating Zn-Mg alloy-steel plate, plating Zn-Al-Mg alloy-steel plate, also has dispersing metal oxides in the coating tunicle of these clad steel sheets, zinc-plated class clad steel plate (for example, the Zn-SiO of polymer etc. ₂Disperse clad steel sheet) etc.In addition, also can be in above-mentioned such coating, use the multilayer coating steel plate that is coated with two-layer above of the same race or different coating.

In addition, the aluminum type plated steel sheet of surface treated steel board substrate of the present invention can use aludip, plating Al-Si alloy-steel plate etc.

In addition, clad steel sheet can plate small amount of N i etc. at surface of steel plate in advance, also can carry out various as mentioned above coating on it.Can adopt any means that to implement in electrolysis (electrolysis in the aqueous solution or the electrolysis in the nonaqueous solvents), fusion method, the vapor phase method as method of coating.

In addition, in order to prevent the black change (coating surface oxidative phenomena a kind of) under environment for use, also can use the acidity or the alkaline aqueous solution that contain iron group metal ion (in Ni ion, Co ion, the Fe ion more than a kind) in case of necessity, implement surface adjustment at coating surface in advance and handle.

In addition, when plated steel sheet uses as base steel sheet,, can in electroplate liquid, add iron group metal ion (in Ni ion, Co ion, the Fe ion more than a kind), make in the plating tunicle and contain more than these metals 1ppm in order to prevent black the change.At this moment, be not particularly limited for the upper limit of electroplating iron group metal concentration in the tunicle.

In surface treated steel plate of the present invention, the surface treatment capsule that on the surface of galvanized steel plate or aluminum type plated steel sheet, forms, be by coating with waterborne liquid (A), nickel compound (B), aluminium compound (C) and the fluorochemical (D) of titaniferous serve as must composition surface treating composition (I), make its dry formation.

The waterborne liquid of above-mentioned titaniferous (A) is the waterborne liquid of the titaniferous that at least a kind titanium compound mixes to obtain with hydrogen peroxide in the low condensation product of the low condensation product that is selected from water-disintegrable titanium compound, water-disintegrable titanium compound, titanium hydroxide, titanium hydroxide.

Contain water-disintegrable titanium compound, be preferably general formula Ti (OR) especially as the lower alkoxy of hydrolization group ₄Four alkoxytitaniums of (R represents that identical or different carbon number is 1～5 alkyl in the formula) expression.As carbon number is that 1～5 alkyl can be enumerated, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group etc.Contain as water-disintegrable titanium compound hydrolization group and group titanium formation salt, can enumerate titanium chloride, titanium sulfate etc. as representative.

About hydrolization group be with titanium form salt group water-disintegrable titanium compound (for example, titanium chloride, titanium sulfate etc.), the ortho-titanic acid (titanic hydroxide gel) that the aqueous solution by this water-disintegrable titanium compound and the reaction of alkaline solutions such as ammonia or NaOH obtain also can be used as low condensation product and uses.

The waterborne liquid of titaniferous (A) does not then have special restriction if mix the waterborne liquid of the titaniferous that obtains by above-mentioned titanium compound and hydrogen peroxide, can use existing known.Specifically can be listed below.

When obtaining this and being used to form titanium dioxide film liquid, have titanium chloride or the alkaline solutions reactions such as titanium sulfate aqueous solution and ammonia or NaOH that form the group of salt with titanium, can make the titanic hydroxide gel precipitation that is called as ortho-titanic acid by making.Afterwards, by water decant separation of hydrogen titanium oxide gel, fully washing adds hydrogen peroxide again, removes unnecessary hydrogen peroxide through decomposing, and can obtain the viscous liquid of yellow transparent.

The above-mentioned ortho-titanic acid of precipitation be by OH polymerization or the producing high-molecular gel state that produces of hydrogen bond each other, can not be directly as the waterborne liquid use of titaniferous.In this gel, add hydrogen peroxide, the part of OH promptly becomes the peroxidating state, dissolve as the titanium peroxide acid ion, perhaps becoming macromolecular chain is cut off and makes its degraded a kind of like this collosol state, unnecessary hydrogen peroxide decomposes is water and oxygen, promptly can use as the waterborne liquid that forms the titaniferous that inoranic membrane uses.

The surface treating composition (being also referred to as aqueous treating fluid) of the waterborne liquid (A) by will comprising the titaniferous that has used water-disintegrable titanium compound a (I), coating on the clad steel sheet surface, drying are (for example, the low-temperature heat drying), himself can form the tack excellence densification contain titanium dioxide tunicle (surface treatment capsule).

As the heating-up temperature after the coating surface treatment compositions (I), for example be below 200 ℃, preferred especially below 150 ℃.By heat drying under such temperature, what can form the noncrystalline (amorphous) that contains some hydroxyls contains the titanium dioxide tunicle.

In addition, handle through aforesaid heat treated or autoclaving more than 80 ℃, when the titanium oxide dispersion that obtains uses as the waterborne liquid (A) of titaniferous, coating surface treatment compositions (I) also can form the crystalline titanium dioxide tunicle that contains, and therefore the coating material as the processing material that can not heat is useful.

Above-mentioned TiO 2 sol is that the amorphous titania particulate is or/and the colloidal sol that the anatase titanium dioxide particulate disperses in water (as required, can add for example aqueous organic solvent such as alcohols, pure ethers).This TiO 2 sol can use existing known, for example the titanium dioxide condensation product that titaniferous solutions such as (i) hydrolysis titanium sulfate or titanyl sulfate are obtained, (ii) the titanium dioxide condensation product that obtains of organic titanic compound such as hydrolysis alkoxytitanium, (iii) hydrolysis or in and the titanium dioxide condensation products such as titanium dioxide condensation product that obtain of halogenated titanium solution such as titanium tetrachloride be scattered in water, obtain amorphous titania colloidal sol, perhaps calcining above-mentioned titanium dioxide condensation product becomes Detitanium-ore-type titanium particulate, and it is dispersed in colloidal sol in the water.

In the calcining of above-mentioned amorphous titania, at least under the temperature more than the anatase crystallization temperature, for example during the temperature lower calcination more than 400～500 ℃, can make amorphous titania be converted to anatase titanium dioxide.The aqueous sol of this titanium dioxide can be enumerated as, TKS-201 (trade name for example, テイカ corporate system, Detitanium-ore-type crystallization shape, average grain diameter 6nm), TA-15 (trade name, daily output chemical company system, Detitanium-ore-type crystallization shape), STS-11 (trade name, the former industry corporate system of stone, Detitanium-ore-type crystallization shape) etc.In the waterborne liquid (Al) of titaniferous, the mass ratio x/y of above-mentioned TiO 2 sol x and titanium hydroperoxidation thing y (product of water-disintegrable titanium compound a and hydrogen peroxide) is 1/99～99/1, and about 10/90～90/10 the scope of being preferably is more suitable.During mass ratio x/y less than 1/99, do not have fully to obtain the effect of interpolation TiO 2 sol at aspects such as stability, photoreactivities, on the other hand, it is poor to make film when surpassing 99/1, therefore not preferred.

Identical with the waterborne liquid (A) of the titaniferous of the water-disintegrable titanium compound a of described use before, the surface treating composition (I) that comprises the waterborne liquid (Al) of titaniferous, by coating on the clad steel sheet surface, drying (for example, the low-temperature heat drying), himself can form the tack excellence densification contain titanium dioxide tunicle (surface treatment capsule).

As the heating-up temperature after the coating surface treatment compositions (I), for example be below 200 ℃, preferred especially below 150 ℃.By heat drying under such temperature, can form the Detitanium-ore-type that contains some hydroxyls and contain the titanium dioxide tunicle.

Even as mentioned above in the waterborne liquid (A) of titaniferous, use the waterborne liquid (A) of the titaniferous of water-disintegrable titanium compound a or the waterborne liquid (Al) of titaniferous, owing to have excellent performance such as storage stability, corrosion resistance, especially preferably use these in the present invention.

The concentration of hydrogen peroxide of hydrogen peroxide is not particularly limited, from the suitable angle of solid component concentration of handling easiness, generation liquid that painting operation is relevant, preferably be about 3～30 quality %.。

The content of the waterborne liquid (A) of the titaniferous in the surface treating composition (I) from the viewpoints such as stability of treatment fluid, is preferably counted 1～100g/L with solid constituent, preferred 5～50g/L.

The surface treating composition that uses among the present invention (I) for compound interpolation nickel compound (B), aluminium compound (C) and fluorochemical (D) in the waterborne liquid (A) of titaniferous, obtains following such effect.That is, if add fluorochemical (D) in the waterborne liquid (A) of titaniferous, then corrosion resistance and storage stability improve, but anti-blackening variation.On the other hand, when adding nickel compound (B), then anti-blackening improves, but the corrosion resistance variation.Therefore to add the deterioration that aluminium compound (C) suppresses corrosion resistance.Therefore think that by in the waterborne liquid (A) of titaniferous, compound interpolation nickel compound (B), aluminium compound (C) and fluorochemical (D) make corrosion resistance, storage stability, anti-blackening all reach good.

In order to improve anti-blackening, cooperate above-mentioned nickel compound (B), nickel compound (B) can be enumerated, for example nickel acetate, nickel nitrate, nickelous sulfate etc., can use in these more than a kind or 2 kinds.Wherein, nickel acetate is very suitable from improving anti-blackening viewpoint.

The use level of nickel compound (B) for solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, is 0.01～10 mass parts, is preferably 0.1～2 mass parts.Relative solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous when use level less than 0.01 mass parts of nickel compound (B), then can not substantially improve anti-blackening, on the other hand, when surpassing 10 mass parts, the corrosion resistance variation.

Above-mentioned aluminium compound (C) cooperates in order to improve corrosion resistance, and aluminium compound (C) can be enumerated for example aluminum nitrate, aluminum acetate, aluminum sulfate, aluminium oxide, aluminium acetylacetonate, aluminate etc., can use in these more than a kind or 2 kinds.Wherein, aluminum nitrate water-soluble good, very suitable from improving the corrosion resistance viewpoint.

The use level of aluminium compound (C) for solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, is 1～100 mass parts, is preferably 5～30 mass parts.Relative solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous when use level less than 1 mass parts of aluminium compound (C), then can not substantially improve corrosion resistance, on the other hand, when surpassing 100 mass parts, anti-blackening variation.

Among the present invention, from the viewpoint of anti-blackening and corrosion resistance coexistence, the match ratio B/C that expectation makes nickel compound (B) and aluminium compound (C) counts 1/1～1/100 with the mass ratio of solid constituent, preferred 1/5～1/50 especially.

In order to make raisings such as storage stability, corrosion resistance, water-fast tack, cooperate above-mentioned fluorochemical (D).Fluorochemical (D) can be enumerated for example ammonium zirconium fluoride, potassium zirconium fluoride, hydrofluorination zirconium, titanium fluoride ammonium, hydrofluoric acid, hydrofluoric acid ammonium etc., can use in these more than a kind or 2 kinds.Wherein, preferably use at least a kind that is selected from ammonium zirconium fluoride, the hydrofluorination zirconium.Corrosion resistance, water-fast tack viewpoint behind the alkali degreasing, ammonium zirconium fluoride is suitable especially, the corrosion resistance viewpoint behind the alkali degreasing, the hydrofluorination zirconium is suitable especially.

The use level of fluorochemical (D) for solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, is 1～800 mass parts, is preferably 50～500 mass parts.For solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, use level less than 1 mass parts of fluorochemical (D) then can not substantially improve storage stability, corrosion resistance, water-fast tack etc., on the other hand, when surpassing 800 mass parts, anti-blackening variation.

The surface treating composition that uses among the present invention (I) must comprise the waterborne liquid (A) and the composition (B)～(D) of above-described titaniferous, as required, can also contain at least a kind that is selected from organic phosphoric acid compound (E), vanadic acid compound (F), zirconium carbonate compound (G), water-soluble organic resin (H) and the water dispersible organic resin (H).

Above-mentioned organic phosphoric acid compound (E) can be enumerated for example 1-hydroxyl methane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl ethane-1, and 1-di 2 ethylhexyl phosphonic acid, 1-hydroxy propane-1,1-di 2 ethylhexyl phosphonic acid etc. contains the organic phosphorous acid of hydroxyl; 2-hydroxyl phosphoryl acetate, 2-phosphoryl butane-1,2,4-tricarboxylic acids etc. contain suitable compound as a comparison such as the organic phosphorous acid of carboxyl and salt thereof, can use in these more than a kind or 2 kinds.

Organic phosphoric acid compound (E) has the effect of the storage stability raising of the waterborne liquid (A) that makes titaniferous, and wherein owing to 1-hydroxyl ethane-1, therefore this particular significant effect of 1-di 2 ethylhexyl phosphonic acid especially preferably uses these.

The use level of organic phosphoric acid compound (E) for solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, is 1～400 mass parts, from viewpoints such as water-fast tacks, is preferably 20～300 mass parts especially.For solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, when the use level of organic phosphate cpd (E) surpasses 400 mass parts, water-fast tack variation, therefore not preferred.

Above-mentioned vanadic acid compound (F) can be enumerated for example lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, anhydrous vanadic acid etc., can use in these more than a kind or 2 kinds.Wherein, from viewpoints such as water-fast tacks, preferred ammonium metavanadate.

The use level of vanadic acid compound (F) for solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, is 1～400 mass parts, and the viewpoints such as corrosion resistance behind the tunicle alkali degreasing are preferably 10～400 mass parts especially.For solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, when the use level of vanadic acid compound (F) surpasses 400 mass parts, the corrosion-resistant behind the alkali degreasing, therefore not preferred.

Above-mentioned zirconium carbonate compound (G) can be enumerated the salt such as sodium, potassium, lithium, ammonium of zirconium carbonate for example, can use in these more than a kind or 2 kinds.Wherein, from viewpoints such as water-fast tacks, preferred zirconium carbonate ammonium.

The use level of zirconium carbonate compound (G) for solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, is 1～400 mass parts, and the viewpoints such as corrosion resistance behind the tunicle alkali degreasing are preferably 10～400 mass parts especially.For solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, when the use level of zirconium carbonate compound (G) surpasses 400 mass parts, the corrosion-resistant behind the alkali degreasing, therefore not preferred.

Above-mentioned water-soluble organic resin is or/and water dispersible organic resin (H) is the organic resin that can dissolve or disperse in water.The method of using organic resin to dissolve in water or disperse can adopt existing known method.Particularly, organic resin can use the organic resin that contains functional group's (for example, hydroxyl, polyoxy alkylidene, carboxyl, ammonia (imido) base, sulfydryl, phosphino-etc.) of can be water-soluble separately or can disperseing in water; And as required, when being acidic resins when (containing the organic resin of carboxyl etc.), with amines such as monoethanolamine, triethylamines, ammoniacal liquor, the hydroxide of alkalinous metals such as lithium hydroxide, NaOH, potassium hydroxide part or all organic resin that obtains in these functional groups that neutralizes; And when for basic resin (contain amino organic resin etc.), with aliphatic acid such as acetic acid, lactic acid, inorganic acids such as phosphoric acid part or all organic resin that obtains in these functional groups etc. that neutralizes.

Water-soluble or water dispersible organic resin, for example can enumerate, epoxylite, phenolic resinoid, acrylic resin, urethane esters resin, alkene-carboxylic acids resin, nylon-based resin, the resin with polyoxy alkylidene chain, polyvinyl alcohol, polyglycerol, carboxymethyl cellulose, CMC, hydroxyethylcellulose etc., above-mentioned resin can use more than a kind or 2 kinds.Wherein, from the storage stability viewpoint of surface treating composition, the preferred especially at least a kind of organic resin that uses in acrylic resin, urethane esters resin and the epoxylite that is selected from water-soluble or water dispersible.In addition, from the storage stability of surface treating composition and the balanced viewpoint of film performance, especially preferably use acrylic resin to be main component with water-soluble or water dispersible.

According to existing known method, for example emulsion polymerization, outstanding turbid polymerization, polymerisation in solution contain the condensate of hydrophilic radical, and synthesizing water-solubility or water dispersible acrylic resin can pass through acquisitions such as neutralization, water-borne modification method as required.

The condensate of above-mentioned possess hydrophilic property group, can for example have by polymerization the unsaturated monomer of hydrophilic radicals such as carboxyl, amino, hydroxyl, polyoxy alkylidene and as required other unsaturated monomer obtain.

The acrylic resin of water-soluble or water dispersible, from viewpoints such as corrosion resistances, the optimization styrene copolymerization forms.Styrene amount in all unsaturated monomers is 10～60 quality %, preferred especially 15～50 quality %.In addition, the Tg of the acrylic resin that copolymerization obtains (glass transition point) is 30～80 ℃, and the viewpoints such as obdurability from the tunicle that obtains are preferably 40～70 ℃ especially.

Above-mentioned carboxylic unsaturated monomer can be enumerated acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid, itaconic acid etc.

The above-mentioned nitrogenous unsaturated monomers such as unsaturated monomer that contain amino, can enumerate (methyl) acrylate-N, N-dimethylaminoethyl, (methyl) acrylic acid-N, N-lignocaine ethyl ester, (methyl) acrylic acid-nitrogenous Arrcostabs of (methyl) acrylic acid such as uncle's N-fourth amino ethyl ester; Acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxy (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, N, polymerizable amide classes such as N-dimethylaminoethyl (methyl) acrylamide; Aromatic series nitrogen containing monomers such as 2-vinylpyridine, l-vinyl-2-pyrrolidone, 4-vinylpridine; Allylamine etc.

The above-mentioned unsaturated monomer that contains hydroxyl, can enumerate (methyl) acrylic acid-2-hydroxyl ethyl ester, hydroxypropyl (methyl) acrylate, (methyl) acrylic acid-2, the mono-esterification thing of polyalcohol such as 3-two hydroxy butyl esters, (methyl) acrylic acid-4-hydroxy butyl ester, list (methyl) polyalkylene glycol acrylate ester, list (methyl) acrylic acid polypropylene glycol ester and acrylic or methacrylic acid; On the mono-esterification thing of above-mentioned polyalcohol and acrylic or methacrylic acid, carry out compound that the ring-opening polymerisation of ε-own lactones obtains etc.

Other unsaturated monomers can be enumerated carbon numbers such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, acrylic acid-2-ethyl caproite, (methyl) acrylic acid n-octyl, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid isostearate and be (methyl) alkyl acrylate of 1～24; Vinyl acetate etc.

More than cited unsaturated monomer, can use more than a kind or 2 kinds.In addition, in the application's the record, " (methyl) acrylate " expression " acrylate or methacrylate ".

Above-mentioned urethane esters resin, can suit to use and have glycol as required, the such chain elongation agent of the low molecular weight compound of 2 above reactive hydrogens such as diamines exists down, prolong PEPA, the polyurethane chain that polyalcohol such as PPG and vulcabond are formed, make its stable dispersion or be dissolved in the water, can be extensive use of existing known resin (for example with reference to Japanese Patent Publication 42-24192 communique, Japanese Patent Publication 42-24194 communique, Japanese Patent Publication 42-5118 communique, Japanese Patent Publication 49-986 communique, Japanese Patent Publication 49-33104 communique, Japanese Patent Publication 50-15027 communique, Japanese Patent Publication 53-29175 communique).

As the method that makes polyurethane resin stable dispersion or dissolving in water, can utilize for example following method.

(1) by at the side chain of polyurethane or terminal hydroxyl, amino, the carboxyl plasma type group introduced, gives hydrophily, the method that in water, disperses or dissolves by self-emulsifying.

(2) reaction after finishing polyether polyols with reduced unsaturation or with the polyether polyols with reduced unsaturation of end-capping reagent closed end NCOs such as oxime, ethanol, phenol, mercaptan, amine, sodium hydrogensulfite, use the shear strength of emulsifying agent and machinery, force the method for in water, disperseing.In addition, have the urethane ester polymer of terminal isocyanate group, mix,, disperse the method that quantizes with macromolecule simultaneously by the shear strength of machinery with water, emulsifying agent and chain elongation agent.

(3) use as water-soluble polyols such as polyethylene glycol, as the polyalcohol of polyurethane primary raw material, the method that in water, disperses or dissolves as water-soluble polyurethane.

In addition, the polyurethanes resin also can mix use with the above-mentioned resin that disperses or dissolves diverse ways preparation in the method.

At the resinoid vulcabond that can use in synthetic of above-mentioned polyurethane, can enumerate aromatic series, alicyclic or aliphatic vulcabond.Particularly, can enumerate hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate, the terephthaldehyde supports vulcabond, between xylylene diisocyanate, 1,3-(two isocyanic acid methyl) cyclohexanone, 1,4-(two isocyanic acid methyl) cyclohexanone, 4,4 '-two cyclic isocyanate hexanones, 4,4 '-methylene bis (cyclohexyl isocyanate), IPDI, 2, the 4-toluene di-isocyanate(TDI), 2, the 6-toluene di-isocyanate(TDI), PPDI, two phenylene diisocyanates, m-benzene diisocyanate, 2, the 4-naphthalene diisocyanate, 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, 4,4 '-biphenyl diisocyanate etc.Wherein, preferred especially 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), hexamethylene diisocyanate, IPDI.

The resinoid commercially available product of polyurethane, can enumerate Ha イ De ラ Application HW-330, Ha イ De ラ Application HW-340, Ha イ De ラ Application HW-350 (is trade name, big Japanese イ Application キ chemical industrial company system), ス-パ-Off レ Star Network ス 100, ス-パ-Off レ Star Network ス 150, ス-パ-Off レ Star Network ス E-2500, ス-パ-Off レ Star Network ス F-3438D (being trade name, the first industrial drugmaker system) etc.

Above-mentioned epoxylite can suit to use the cationic epoxy resin that additional amine obtains on epoxy resin; Modified epoxy such as acrylic acid modified, urethane-modified etc.Cationic epoxy resin for example can be enumerated, the addition compound product (for example, with reference to No. 3984299 specification of United States Patent (USP)) of the mixture of epoxide and unary primary amine or poly-primary amine, monobasic secondary amine or polynary secondary amine, polynary primary amine, polynary secondary amine etc.; Epoxide with have the monobasic of ketimide primary amino radical or an addition compound product of polynary secondary amine (for example, with reference to No. 4017438 specification of United States Patent (USP)); Epoxide and etherification reaction product (for example, with reference to Japanese kokai publication sho 59-43013 communique) etc. with hydroxy compounds of ketimide primary amino radical.

The epoxylite number-average molecular weight is preferably 400～4000, and is preferred especially 800～2000, and epoxide equivalent is preferably 190～2000, and preferred especially 400～1000.Such epoxylite for example, can obtain by the reaction of polyphenolic substance and chloropropylene oxide.Polyphenolic substance can be enumerated for example two (4-hydroxy phenyls)-2,2-propane, 4,4-dihydroxy benaophenonel, two (4-hydroxy phenyl)-1,1-ethane, two (4-hydroxy phenyl)-1,1-iso-butane, two (4-hydroxyl-tert-butyl-phenyl)-2,2-propane, two (2 hydroxy naphthalene base) methane, 1,5-dihydroxy naphthlene, two (2, the 4-dihydroxy phenyl) methane, four (4-hydroxy phenyl)-1,1,2,2-ethane, 4,4-dihydroxydiphenylsulisomer, phenolic resins, cresol resin etc.

Water-soluble organic resin is or/and the use level of water dispersible organic resin (H), from viewpoints such as resulting tunicle homogeneity, for solid constituent 100 mass parts of the waterborne liquid (A) of titaniferous, be below 30 mass parts preferably, preferred especially 5～20 mass parts.Or/and the use level of water dispersible organic resin (H) when surpassing 30 parts, heat-resisting discolouration reduces easily when water-soluble organic resin.

In surface treating composition (I), as required, can also contain heavy metal compound beyond etchants such as silane coupling agent, resin particle, inorganic phosphate compound for example, the predetermined component of the present invention, thickener, surfactant, lubricant (Tissuemat E, fluorine wax, Brazil wax etc.), antirust agent, coloring pigment, extender pigment, rust resisting pigment, dyestuff etc.

In addition, as required, surface treating composition (I) can use hydrophilic solvent dilution backs such as methyl alcohol, ethanol, isopropyl alcohol, glycol solvent, propandiols solvent to use.The adhesion amount of the surface treatment capsule that is formed by surface treating composition (I) is 0.1～2.0g/m ², be preferably 0.2～1.5g/m ²As the not enough 0.1g/m of tunicle adhesion amount ²The time, corrosion-resistant, on the other hand, when surpassing 2.0g/m ²The time, tunicle easily breaks, and corrosion resistance reduces.

When making surface treated steel plate of the present invention, on galvanized steel plate or aluminum type plated steel sheet surface, coating is a main component with waterborne liquid (A), nickel compound (B), aluminium compound (C) and the fluorochemical (D) of above-mentioned titaniferous, as required, also contain organic phosphoric acid compound (E), vanadic acid compound (F), zirconium carbonate compound (G), water-soluble organic resin or/and behind the surface treating composition more than a kind (I) (treatment fluid) in the water dispersible organic resin (H), do not wash convection drying with water.

In addition, as required, can also make the waterborne liquid (A) of titaniferous or surface treating composition (I) contain above other cited adding ingredients.

The coating process of surface treating composition (treatment fluid) can be any, and for example spraying+roller squeezes, roller rubbing method etc.In addition, also can be any about the drying mode after the coating, for example hot blast is done mode, induction heating mode, electric furnace mode etc.

The baking temperature of the surface treating composition (treatment fluid) of coating preferably is about 60～200 ℃.Baking temperature is during less than 60 ℃, and tunicle forms insufficient, becomes inferior tunicles such as corrosion resistance.On the other hand, even surpassing drying under 200 ℃ the plate temperature, the situation that corrosion resistance descends appears in effect that the corrosion resistance that does not also obtain conforming to baking temperature improves on the contrary.Think that this is because heat makes on the tunicle and cracks.

Embodiment 2

Waterborne liquid of the titaniferous that uses in surface treating composition (A) and composition (B)～(H) are as follows.

[manufacturing of the waterborne liquid of titaniferous (A)]

Production Example 1 (the waterborne liquid T1 of titaniferous)

In the 500cc solution that 60% titanium tetrachloride solution 5cc adding distil water is mixed with, dropping ammonia (1: 9) makes the titanium hydroxide precipitation.After cleaning with distilled water, add 30% hydrogen peroxide solution 10cc, mixing obtains the yellow translucent waterborne liquid T1 with titaniferous of viscosity of titaniferous.

Production Example 2 (the waterborne liquid T2 of titaniferous)

Under 20 ℃ in the mixture of 30% hydrogen peroxide 10 mass parts and deionized water 100 mass parts, the mixture that dripped tetraisopropoxy titanium 10 mass parts and isopropyl alcohol 10 mass parts through a hour stirs simultaneously.25 ℃ of following slakings 2 hours, obtain the slightly waterborne liquid T2 of the titaniferous of toughness of yellow transparent afterwards.

Production Example 3 (the waterborne liquid T3 of titaniferous)

Except using the tetraisopropoxy titanium that four titanium n-butoxide replace using in the Production Example 2, with Production Example 2 identical creating conditions down, obtain the waterborne liquid T3 of titaniferous.

Production Example 4 (the waterborne liquid T4 of titaniferous)

Except the tetraisopropoxy titanium that the tripolymer that uses tetraisopropoxy titanium replaces using in the Production Example 2, with Production Example 2 identical creating conditions down, obtain the waterborne liquid T4 of titaniferous.

Production Example 5 (the waterborne liquid T5 of titaniferous)

With respect to Production Example 2, except using the hydrogen peroxide of 3 times of amounts, dripped 1 hour down at 50 ℃, outside 60 ℃ of following slakings 3 hours,, obtain the waterborne liquid T5 of titaniferous again with Production Example 2 identical creating conditions down.

Production Example 6 (the waterborne liquid T6 of titaniferous)

The waterborne liquid T3 of the titaniferous that Production Example 3 is made, heat treated 6 hours again under 95 ℃ obtains the waterborne liquid T6 of the translucent titaniferous of yellow-white.

Production Example 7 (the waterborne liquid T7 of titaniferous)

Under 10 ℃ to " TKS-203 " (trade name, テイカ corporate system, TiO 2 sol) in the mixture of 5 mass parts (solid constituent), 30% hydrogen peroxide 10 mass parts and deionized water 100 mass parts, the mixture that dripped tetraisopropoxy titanium 10 mass parts and isopropyl alcohol 10 mass parts through 1 hour stirs simultaneously.10 ℃ of following slakings 24 hours, obtain the slightly waterborne liquid T7 of the titaniferous of toughness of yellow transparent afterwards.

[nickel compound (B)]

B1: nickel acetate

B2: nickel nitrate

B3: nickelous sulfate

[aluminium compound (C)]

C1: aluminum nitrate

C2: aluminum acetate

C3: aluminium acetylacetonate

[fluorochemical (D)]

D1: ammonium zirconium fluoride

D2: hydrofluorination zirconium

D3: zirconium fluoride sodium

D4: potassium zirconium fluoride

[organic phosphoric acid compound (E)]

E1:1-hydroxyl methane-1, the 1-di 2 ethylhexyl phosphonic acid

E2:1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid

[vanadic acid compound (F)]

F1: ammonium metavanadate

F2: sodium metavanadate

[zirconium carbonate compound (G)]

G1: zirconium carbonate ammonium

G2: sodium zirconium carbonate

[water-soluble or water dispersible organic resin (H)]

H1: ス-パ-Off レ Star Network E-2500 (trade name, the first industrial drugmaker system, waterborne polyurethane resin)

H2: バイロ Na-Le MD-1100 (trade name, Japan's corporate system of twisting flax fibers and weaving, aqueous polyester resin)

H3: アデカレジ Application EM-0718 (trade name, Asahi Electro-Chemical Co. Ltd's system, aqueous epoxy resins)

Matrix steel plate as surface treated steel plate can use clad steel sheet as shown in table 6.

To suit to cooperate the surface treating composition of above-mentioned titaniferous Generation Liquid (A) and composition (B)～(H), be coated on the clad steel sheet surface, with 5 seconds of baking temperature drying of regulation, as supplying the examination material.For the examination material,, estimate heat-resisting discolouration, corrosion resistance and anti-blackening about these by following test method.Its result be useful in each for composition of the surface treating composition of examination on material with and the application condition, shown in table 7～table 10.

(1) heat-resisting discolouration

In the infrared ray image furnace, heat 30 seconds to 500 ℃ of plate temperature for the examination material, keep after 30 seconds, the appearance when perusal naturally cools to room temperature, its metewand is as follows.

Zero: not variable color

△: become faint yellow

*: become yellow～brown

(2) corrosion resistance

To rubber belt sealing end and the back side carry out the salt spraytest of JIS-Z-2371 for the examination material, measuring and producing the white rust area ratio is 5% test period, its metewand is as follows.

◎: more than 120 hours

More than zero: 96 hour and less than 120 hours

△: more than 48 hours and less than 96 hours

*: less than 48 hours

(3) anti-blackening

To rest on the control temperature for the examination material is that 80 ℃, relative humidity are in the Constant Temperature and Humidity Chambers of 95%RH atmosphere 24 hours, calculates the variation △ L (test back L value one is tested preceding L value) of whiteness this moment (L value), and its metewand is as follows.

○：△L≥-5.0

△：-5.0>△L≥-10.0

×：-10.0>△L

Table 6

No.	Clad steel sheet	Single-face plating adhesion amount (g/m ²)
			1	Plated steel sheet	50
2	Hot-dip galvanized steel sheet	60
			3	Alloy galvanized steel plate (Fe:10 quality %)	45
4	Plating Zn-Ni alloy steel plate (Ni:12 quality %)	20
			5	Fusion plating Zn-Al alloy steel plate (Al:55 quality %)	90
6	Fusion plating Zn-5 quality %Al-0.5 quality %Mg alloy-steel plate	90
			7	Fusion aludip (Al-Si alloy, Si:6 quality %)	60
8	Plating Zn-Al-Mg alloy-steel plate (Al:6 quality %, Mg:3 quality %)	120
			9	Fusion plating Zn-Mg alloy-steel plate (Mg:0.5 quality %)	150

In table 7 and table 9, the following content of * 1～* 10 expressions.

* in 1 table 6 record clad steel sheet No.1～9

* the waterborne liquid T1～T7 of the titaniferous of putting down in writing in the 2 specification texts

* the nickel compound B1～B3 that puts down in writing in the 3 specification texts

* the aluminium compound C1～C3 that puts down in writing in the 4 specification texts

* the fluorochemical D1～D4 that puts down in writing in the 5 specification texts

* organic phosphoric acid compd E 1, the E2 that puts down in writing in the 6 specification texts

* vanadic acid compound F 17-hydroxy-corticosterone 1, the F2 that puts down in writing in the 7 specification texts

* zirconium carbonate compound G1, the G2 that puts down in writing in the 8 specification texts

* the water-soluble or water dispersible organic resin H1～H3 that puts down in writing in the 9 specification texts

* the solid constituent quality (g) in 101 liters the surface treating composition (aqueous treating fluid)

Table 8

Table 10

The possibility of industrial utilization

Surface treated steel plate of the present invention, because surface treatment capsule is can not produce the inorganic constituents of color or variable color as main body because of heating, therefore in heat-resisting discolouration excellence, because its inorganic constituents has the shielding of height, has excellent anticorrosive and the anti-blackening identical with the surface treated steel plate that contains the chromate tunicle.

Claims

1. surface treated steel plate, it has the surface treatment capsule of titaniferous, nickel, aluminium and fluorine on the surface of galvanized steel plate, and this is 0.05～1.0 μ m by film thickness, and the titanium adhesion amount of this surface treatment capsule is 0.01～0.5g/m ², and for the titanium of 100 mass parts, contain the nickel of 0.01～5 mass parts, the aluminium of 0.1～25 mass parts, the fluorine of 1～500 mass parts.

2. surface treated steel plate as claimed in claim 1, wherein, described surface treatment capsule also contains at least a kind in the vanadium of phosphorus, 1～300 mass parts of the zirconium that is selected from 2～1000 mass parts, 1～300 mass parts for the described titanium of 100 mass parts.

3. surface treated steel plate, it is 0.1～2.0g/m that its surface at galvanized steel plate or aluminum type plated steel sheet has the tunicle adhesion amount ²Surface treatment capsule, this surface treatment capsule is for containing the waterborne liquid of titaniferous by coating, and the nickel compound of solid constituent 100 mass parts 0.01～10 mass parts of the waterborne liquid of this titaniferous relatively, the surface treating composition of the fluorochemical of the aluminium compound of 1～100 mass parts and 1～800 mass parts, make it dry and form, the waterborne liquid of wherein said titaniferous is to be selected from water-disintegrable titanium compound, the low condensation product of water-disintegrable titanium compound, titanium hydroxide, the waterborne liquid of the titaniferous that at least a kind of titanium compound in the low condensation product of titanium hydroxide mixes to obtain with hydrogen peroxide.

4. surface treated steel plate as claimed in claim 3, wherein, described fluorochemical is at least a kind that is selected from ammonium zirconium fluoride and the hydrofluorination zirconium.

5. surface treated steel plate as claimed in claim 3, wherein, described surface treating composition also contains at least a kind in the zirconium carbonate compound of the vanadic acid compound of the organic phosphoric acid compound that is selected from 1～400 mass parts, 1～400 mass parts and 1～400 mass parts for solid constituent 100 mass parts of the waterborne liquid of described titaniferous.

6. as any described surface treated steel plate in the claim 3～5, wherein, described surface treating composition for solid constituent 100 mass parts of the waterborne liquid of described titaniferous, also contain 30 mass parts following be selected from least a kind of resin in water-soluble organic resin and the water dispersible organic resin.