CN102666921A - Surface-treating composition, and surface-treated steel sheet - Google Patents

Abstract

Disclosed is a surface-treating composition having excellent corrosion resistance, thermal discoloration resistance, blackening resistance, scratch resistance, post-processing adhesion to an organic resin layer that is formed thereon, and adhesion under high-temperature high-humidity environments. The surface-treating composition comprises (A) an aqueous titanium-containing solution produced by mixing at least one titanium compound selected from a hydrolysable titanium compound, a low-condensed product of a hydrolysable titanium compound, titanium hydroxide and a low-condensed product of titanium hydroxide with aqueous hydrogen peroxide, (B) a zirconium carbonate compound, (C) an organic phosphoric acid compound, (D) a metal phosphate salt, (E) silicon oxide, (F) a water-soluble organic resin and/or a water-dispersible organic resin, and (G) a silane coupling agent at a specified proportion.

Description

Surface treating composition and surface treated steel plate

Technical field

The present invention relates to be fit to the surface treating composition and the surface treated steel plate of automobile, household electrical appliances, building materials purposes, and the surface treated steel plate that relates to not chromyl fully environment-adaptive type surface treating composition in compsn or the tunicle and use this surface treating composition.

Background technology

All the time; The steel plate that household electrical appliances are widely used and obtain as follows with steel plate, automotive sheet with steel plate, building materials: to improve erosion resistance (anti-white rust property, anti-red rust property) be purpose, and utilizing with chromic acid, dichromic acid or its esters is that the treatment solution of staple is to zinc-based metal plated steel sheet or to aluminize be the surface enforcement chromate treating of steel plate.This chromate treating is to make excellent corrosion resistance and the treatment process of the economy that can carry out more simply.

Chromate treating uses the sexavalent chrome as the public hazards restrictive substance; But because this sexavalent chrome is processed in closed system in treatment process; Perhaps; The sealing function of organic envelope that can be through being formed on the upper strata makes the chromium of stripping from the chromic salt tunicle almost nil, therefore, can not polluted owing to sexavalent chrome makes human body and environment in fact.But, to the raising of the concern of global environment problem, except the legal provisions that existing attention operating environment and draining are handled, also begin to formulate the legal provisions of paying attention to carrying capacity of environment and environment harmony along with in recent years.In addition, under the historical background of the mfr being estimated with the environment contribution degree, the trend that cut down the use of the heavy metal that comprises sexavalent chrome is also improving.

Under this background, proposed not use in a large number the white rust inhibition technology (chromate-free technology) of chromic zinc-based metal plated steel sheet.For example, the surface treatment agent of Al, phosphate cpd, silicon-dioxide and water system organic resin emulsion and the metallic substance that is coated with this treatment agent have been proposed to contain in the patent documentation 1,2.In addition, a kind of zinc-based metal plated steel sheet has been proposed in the patent documentation 3, wherein, at the mixed aqueous solution of dihydrogen phosphate and the metal oxide sol of coating polyvalent metal and dry and behind the formation amorphousness tunicle, form organic coating.And then; In the patent documentation 4,5 a kind of steel plate has been proposed; Wherein, with the composite oxides that contain oxide fine particle, phosphoric acid and/or phosphate cpd and be selected from more than one metals among Mg, Mn, the Al by rete as lower floor, and layer forms organic envelope above that.

In the purposes that zinc-based metal plated steel sheet was suitable for, there are the parts that are heated in a lot of TRs (about 500 ℃ ~ about 600 ℃) more than the fusing point of zinc.For example; In the heat exchanger in air-conditioner outdoor unit, when copper pipe and aluminum vaporizer are carried out soldering, in order to prevent to make al dissolution owing to the heating of using gas burner; Zinc-based metal plated steel sheet is configured between copper pipe and the vaporizer, so that the flame of burner does not directly contact with aluminium.When the surface treated steel plate of above-mentioned prior art is applied to this purposes, owing to be to be the tunicle of main body with the organic resin, therefore, and can be because of thermolysis variable color yellowly or brown, thus bad order produced.Therefore, possibly use the surface treated steel plate of prior art hardly.

In order to address the above problem, the good chromate-free technology of heat-resisting discolouration has been proposed.For example, having proposed in the patent documentation 6,7 with primary magnesium phosphate, colloidal silica and phosphinic acid compounds is the tunicle that is rich in inorganic components of staple.In addition, having proposed in the patent documentation 8 to be that the tunicle that is rich in inorganic components of staple is configured in lower floor and silicate coating and/or silicone resin is configured in the double-deck tunicle on upper strata with dihydrogen phosphate and colloidal silica.In addition, disclose in the patent documentation 9 to contain at least a titanium compound in the low condenses of the low condenses, titanium hydroxide and the titanium hydroxide that are selected from water-disintegrable titanium compound, water-disintegrable titanium compound has been mixed with aqueous hydrogen peroxide solution and the surface treating composition of the titaniferous aqueous solution that obtains, organic phosphoric acid, water-soluble or water dispersible organic resin, vanadic acid compound, Zirconium tetrafluoride compound and zirconium carbonate compound.

The prior art document

Patent documentation

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

Patent documentation 6: TOHKEMY 2000-79370 communique

Patent documentation 7: TOHKEMY 2001-348672 communique

Patent documentation 8: TOHKEMY 2004-91826 communique

Patent documentation 9: TOHKEMY 2006-9121 communique

Summary of the invention

Invent problem to be solved

But the tunicle erosion resistance level that is rich in inorganic components of patent documentation 6,7 is extremely low, is difficult to use as the surrogate of chromic salt tunicle.On the other hand, though the erosion resistance level that the double-deck tunicle of patent documentation 8 is used for the surrogate that can be used as the chromic salt tunicle, owing to use expensive silicate or silicone resin, therefore, existing problems aspect cost.In addition, the tunicle that utilizes above-mentioned technology to form is easy to generate the phenomenon (the black change) that variable color becomes black under moist environment, therefore; Be difficult in the heat exchanger of easy dewfall, use; In addition, also there is restriction for the preservation environment in the transportation of goods, thus impracticable.In addition,, have on the upper strata under the situation of thicker organic resin layer, can cause the reduction of adaptation though contained fluorochemical improves the erosion resistance behind water-fast tack and the alkali degreasing in the surface treating composition of patent documentation 9.

In addition; In organic resin coating steels such as coated steel plate, laminate steel; The adaptation of organic resin layer becomes important performance, is crystalline state owing to handling the resulting tunicle of phosphatizing in the past that carries out as matrix, therefore; Crystal can be destroyed because of severe cruel processing, and the adaptation of organic resin layer reduces easily.Particularly reach under the situation of coated steel plate or laminate steel more than the 100 μ m at the thickness of organic resin layer, steel plate is being added man-hour, phosphate coating is destroyed, and is that starting point is peeled off with this part easily thereby make organic resin layer.

To the problems referred to above; For example; In the patent documentation of more than enumerating 3 ~ 5; The insoluble phosphate film that forms as thin as a wafer through coating metal and the treatment solution reaction that makes on the substrate shows erosion resistance, coating adhesion etc., even but with this surface treated steel plate as under the situation of organic resin coating steel, the adaptation, the erosion resistance that add man-hour also reduce easily.Particularly have under the situation of organic resin coating steel that thickness reaches the organic resin layer more than the 100 μ m; Because it is high by film toughness; Therefore, during distortion strong shear action in organic resin layer and its matrix at the interface, thereby be easy to generate peeling off of organic resin layer.

In view of above prior art problems; Be willing to propose a kind of surface treating composition 2008-335387 number so that Japan is special before the applicant; It can access superior corrosion resistance, heat-resisting discolouration and anti-blackening; And can access adaptation good and the organic resin layer upper strata that is formed on surface treatment capsule, the thick organic resin layer that particularly has the above thickness of 100 μ m can access good adaptation when steel plate deformed.This surface treating composition contains with specific ratio: will be selected from that at least a titanium compound in the low condenses of low condenses, titanium hydroxide and titanium hydroxide of water-disintegrable titanium compound, water-disintegrable titanium compound mixes with aqueous hydrogen peroxide solution and the titaniferous aqueous solution, zirconium carbonate compound, organic phosphoric acid compound, metal phosphate and the silicon-dioxide that obtain.

But; Follow-up study according to the inventor carries out is found; Therefore the tunicle that is formed by above-mentioned surface treating composition has more crisp character, has following problem: utilizing prototype to make under the situation of surface treated steel plate, when tunicle forms back and metallic roll etc. and contacts; Tunicle can be scratched, and erosion resistance reduces easily.Find to exist following problem in addition: under the such harsh and unforgiving environments of high temperature moist environment, can not guarantee sufficient adaptation with aforesaid thick organic resin layer.

Therefore; The objective of the invention is to solve aforesaid problem, a kind of surface treating composition and surface treated steel plate are provided, said surface treating composition does not contain sexavalent chrome fully; Can access superior corrosion resistance, heat-resisting discolouration and anti-blackening; And the scratch resistance when surface treatment capsule forms the back and metallic roll etc. contacts is good, and can access adaptation good and the organic resin layer upper strata that is formed on surface treatment capsule, particularly; Even have the thick organic resin layer of the thickness more than the 100 μ m and apply the severe cruel man-hour that adds in formation; Also can access good adaptation, even and under the harsh like this environment of high temperature moist environment, also can access good and adaptation above-mentioned thick organic resin layer.

In addition, another object of the present invention is to, the organic resin coating steel that uses this surface treated steel plate is provided.

The method that is used to deal with problems

The inventor studies the tunicle composition that can address the above problem; The result finds; Through surface at metallic substance (preferred zinc-based metal plated steel sheet or aluminize be steel plate); Be utilized in the specific titaniferous aqueous solution and form surface treatment capsule with the predetermined compound surface treating composition that is added with zirconium carbonate compound, organic phosphoric acid compound, metal phosphate, silicon-dioxide, water-soluble organic resin and/or water dispersible organic resin and silane coupling agent of ratio; Can access superior corrosion resistance, heat-resisting discolouration and anti-blackening; And the scratch resistance when surface treatment capsule forms the back and metallic roll etc. contacts is good; Even form organic resin layer on the upper strata of surface treatment capsule, particularly have a thick organic resin layer of the thickness more than the 100 μ m and apply the severe cruel man-hour that adds; Also can access good adaptation, even and under the harsh like this environment of high temperature moist environment, also can access good and adaptation above-mentioned thick organic resin layer.

The present invention is based on above-mentioned discovery and accomplish, is purport with following technical scheme.

[1] a kind of surface treating composition; It is characterized in that; Contain at least a titanium compound in the low condenses of low condenses, titanium hydroxide and titanium hydroxide through will being selected from water-disintegrable titanium compound, water-disintegrable titanium compound and mix the titaniferous aqueous solution (A) that obtains with aqueous hydrogen peroxide solution, be the zirconium carbonate compound (B) of 10 ~ 300 mass parts and be the organic phosphoric acid compound (C) of 50 ~ 200 mass parts, and contain the silane coupling agent (G) of counting the metal phosphate (D) of 2 ~ 20 quality %, counting the silicon-dioxide (E) of 20 ~ 40 quality %, count water-soluble organic resin and/or the water dispersible organic resin (F) of 2 ~ 10 quality % and count 0.5 ~ 20 quality % with the ratio in the total solids composition of surface treating composition with the ratio in the total solids composition of surface treating composition with the ratio in the total solids composition of surface treating composition with the ratio in the total solids composition of surface treating composition with respect to solids component 100 mass parts of titaniferous aqueous solution (A) with respect to solids component 100 mass parts of titaniferous aqueous solution (A).

Like above-mentioned [1] described surface treating composition, it is characterized in that [2] silicon-dioxide (E) is the aerosil that utilizes drying process to make.

Like above-mentioned [2] described surface treating composition, it is characterized in that [3] tap density of aerosil is below the 40g/L.

Like each described surface treating composition in above-mentioned [1] ~ [3], it is characterized in that [4] silane coupling agent (G) has glycidyl.

Like each described surface treating composition in above-mentioned [1] ~ [4], it is characterized in that [5] pH is 7 ~ 12.

[6] a kind of surface treated steel plate is characterized in that, having the tunicle adhesion amount is 0.03 ~ 0.5g/m ²Surface treatment capsule, said surface treatment capsule is on the surface of steel plate and makes its dry formation through each described surface treating composition in above-mentioned [1] ~ [5] being applied to zinc-based metal plated steel sheet or aluminizing.

[7] a kind of organic resin coating steel is characterized in that, on the surface treatment capsule of the surface treated steel plate of above-mentioned [6], has organic resin layer.

The invention effect

The surface treatment capsule that forms by surface treating composition of the present invention; Owing to constitute barrier by specific inorganic components with height; Therefore; Have the superior corrosion resistance and the anti-blackening that can compare favourably with the chromic salt tunicle, but also have the good heat-resisting discolouration that is difficult for producing colour developing or variable color because of heating.And then; Scratch resistance when surface treatment capsule forms the back and metallic roll etc. contacts is good; Even form organic resin layer on the upper strata of surface treatment capsule, particularly have a thick organic resin layer of the thickness more than the 100 μ m and apply the severe cruel man-hour that adds; Also can access good adaptation, even and under the harsh like this environment of high temperature moist environment, also can access good and adaptation above-mentioned thick organic resin layer.

In addition; The erosion resistance of surface treated steel plate of the present invention and organic resin coating steel, anti-blackening, heat-resisting discolouration and scratch resistance are good; And the adaptation of organic resin layer, particularly to have an adaptation of thick organic resin layer of the above thickness of 100 μ m good; And the adaptation under the harsh like this environment of high temperature moist environment is also good.

Embodiment

Surface treating composition of the present invention contains titaniferous aqueous solution (A), zirconium carbonate compound (B), organic phosphoric acid compound (C), metal phosphate (D), silicon-dioxide (E), water-soluble organic resin and/or water dispersible organic resin (F) and silane coupling agent (G).This surface treating composition does not contain sexavalent chrome (still, as the sexavalent chrome of unavoidable impurities except).

Above-mentioned titaniferous aqueous solution (A) is that at least a titanium compound in the low condenses of the low condenses, titanium hydroxide and the titanium hydroxide that are selected from water-disintegrable titanium compound, water-disintegrable titanium compound is mixed with aqueous hydrogen peroxide solution and the titaniferous aqueous solution that obtains.

Said hydrolyzed property titanium compound is the titanium compound that has with the direct bonded hydrolization group of titanium, through generating titanium hydroxide with reaction of moisture such as water, water vapors.In addition, water-disintegrable titanium compound can be all to be the water-disintegrable titanium compound of hydrolization group with titanium bonded group, also can be with titanium bonded part group be the water-disintegrable titanium compound of hydrolization group.

As said hydrolyzed property group; So long as the then not special restriction of group through generating titanium hydroxide with reaction of moisture as stated; For example can enumerate lower alkoxy, with the salifiable group of titanium shape halogen atom, Wasserstoffatoms, sulfate ions etc. such as (for example) chlorine etc.

As containing the water-disintegrable titanium compound of lower alkoxy, especially preferably by general formula Ti (OR) as hydrolization group ₄Four titan-alkoxides of (in the formula, R representes the alkyl of identical or different carbonatoms 1 ~ 5) expression.As the alkyl of carbonatoms 1 ~ 5, for example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl etc.

As having and the water-disintegrable titanium compound of the salifiable group of titanium shape, can enumerate titanium chloride, titanium sulfate etc. as representational compound as hydrolization group.

In addition, the low condenses of water-disintegrable titanium compound is the low condenses between the said hydrolyzed property titanium compound.Should low condenses can be all to be the low condenses of hydrolization group with titanium bonded group, also can be with titanium bonded part group be the low condenses of hydrolization group.

For hydrolization group be with the water-disintegrable titanium compound of the salifiable group of titanium shape (for example; Titanium chloride, titanium sulfate etc.), the titanic hydroxide (titanic hydroxide gel) that the reaction of basic solns such as the aqueous solution through this water-disintegrable titanium compound and ammonia or sodium hydroxide obtains also can be used as low condenses and uses.

As the low condenses of water-disintegrable titanium compound and the low condenses of titanium hydroxide, can use condensation degree is 2 ~ 30 compound, and especially preferably using condensation degree is 2 ~ 10 compound.Condensation degree is 30 when following, through mixing with hydrogen peroxide, can access stable titaniferous aqueous solution.

The low condenses of low condenses, titanium hydroxide and the titanium hydroxide of the water-disintegrable titanium compound of more than enumerating, water-disintegrable titanium compound; Can use one or more; Wherein, preferred especially four titan-alkoxides as the water-disintegrable titanium compound of representing by above-mentioned general formula.Its reason is that the alcohol that generates during four titan-alkoxide hydrolysis volatilizees in making surface treating composition exsiccant process, therefore, erosion resistance etc. is not exerted an influence by film properties, can access good in especially film properties.

As titaniferous aqueous solution (A), so long as, then can especially restrictedly not use existing known titaniferous aqueous solution through above-mentioned titanium compound is mixed the titaniferous aqueous solution that obtains with aqueous hydrogen peroxide solution.Particularly, can enumerate following titaniferous aqueous solution.

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

(ii) through making aqueous hydrogen peroxide solution and forming with liquid (with reference to japanese kokai publication hei 9-71418 communique, japanese kokai publication hei 10-67516 communique) by the aqueous solution and the titanic hydroxide gel effect of basic soln manufacturing, the titanium dioxide film that is synthesized into of titanium chloride or titanium sulfate.

Form when use liquid obtaining this titanium dioxide film, react with basic solns such as ammonia or sodium hydroxide, the titanic hydroxide gel that is called titanic hydroxide is precipitated through making to have with the titanium chloride of the salifiable group of titanium shape or the aqueous solution of titanium sulfate.Then, isolate titanic hydroxide gel through the decant that makes water, and fully washing, further add aqueous hydrogen peroxide solution, unnecessary hydrogen peroxide decomposition is removed, can access the yellow transparent viscous liquid thus.

The above-mentioned titanic hydroxide that is settled out is the gel state of high molecular through polymerization between the OH or hydrogen bond, can not directly use as titaniferous aqueous solution.When in this gel, adding aqueous hydrogen peroxide solution; The part of OH reaches the peroxo-state; Formation is blocked into low molecular a kind of collosol state with the form dissolving or the macromolecular chain of titanium peroxide acid ion; Unnecessary hydrogen peroxide decomposition Cheng Shui and oxygen, thus can use as the titaniferous aqueous solution that mineral membrane form usefulness.

This colloidal sol is except containing titanium atom; Only contain Sauerstoffatom and Wasserstoffatoms, therefore, becoming under the situation of titanium oxide through dry or calcining; Only produce water and oxygen; Therefore, need not remove the required carbon component or the halogenic ingredient of thermolysis of sol-gel method, vitriol etc., even can form the higher titanium dioxide film of density at low temperatures yet.

The titanium oxide that (iii) obtains as follows forms and use solution: adding hydrogen peroxide in the inorganic titanium compound aqueous solution of titanium chloride or titanium sulfate and generate the titanium peroxide hydrate; Add alkaline matter then; The solution that obtains is placed or heating; Generate the throw out of titanium peroxide hydrate polymer thus, then, the solvent components in addition that dewaters that derives from titaniferous materials solution is at least removed; Then, make itself and hydrogen peroxide effect (with reference to TOHKEMY 2000-247638 communique, TOHKEMY 2000-247639 communique).

Use water-disintegrable titanium compound and/or its low condenses (below; Be called " water-disintegrable titanium compound a " for ease of explanation) as the titaniferous aqueous solution (A) of titanium compound, can obtain in about 10 minutes ~ about 20 hours through water-disintegrable titanium compound a and aqueous hydrogen peroxide solution are reacted under 1 ~ 70 ℃ temperature of reaction.

Use the titaniferous aqueous solution (A) of this water-disintegrable titanium compound a to obtain as follows: through making the reaction of water-disintegrable titanium compound a and aqueous hydrogen peroxide solution; Make water-disintegrable titanium compound a because of the water hydrolysis; Thereby generate the titanium compound of hydroxyl; Then, the titanium compound generation coordination of hydrogen peroxide and this hydroxyl, and this hydrolysis reaction and almost generation simultaneously of hydrogen peroxide coordination.This titaniferous aqueous solution (A) stable high in room temperature range, generation can be stood the chelating liquid of prolonged preservation.The titanic hydroxide gel that uses in the method for manufacture in the past utilizes the Ti-O-Ti key and three dimensional stress partly, compares with the titaniferous aqueous solution (A) that aqueous hydrogen peroxide solution is obtained with this gel reaction, forms and stability has the difference of essence.

In addition, more than 80 ℃ the titaniferous aqueous solution (A) that uses water-disintegrable titanium compound a is carried out heat treated or autoclave when handling, can access the titanium oxide dispersion of the ultramicron of the titanium oxide that contains crystallization.When carrying out the processing of above-mentioned heat treated or autoclave more than 80 ℃, can carry out the crystallization of titanium oxide fully.Preferably making the median size of the titanium oxide ultramicron of the titanium oxide dispersion of as above making is below the 10nm, is preferably about 1nm ~ about 6nm.The median size that makes the titanium oxide ultramicron is 10nm when following, film-forming properties good (coating after drying and when forming tunicle, thickness are that 1 μ m can not crack when above), therefore preferably.In addition, the median size of titanium oxide ultramicron is 1nm when above, can make surface treating composition maintain the state that viscosity does not increase, and is therefore preferred.The outward appearance of this titanium oxide dispersion is translucent.This titanium oxide dispersion also can be used as titaniferous aqueous solution (A) and uses.

Be applied on the surface of plated steel sheet through the surface treating composition (H) that will contain the titaniferous aqueous solution (A) that uses water-disintegrable titanium compound a and (for example carry out drying; Heat drying at low temperatures), can the tack of formation own good densification contain titanium oxide tunicle (surface treatment capsule).

Heating temperature as the steel plate after the coating surface treatment compositions (H); For example be below 200 ℃; Be preferably especially below 150 ℃, contain the titanium oxide tunicle through the non-crystalline state (amorphous) of under said temperature, carrying out heat drying, can form containing small amount of hydroxyl groups.

In addition; Under the situation of titanium oxide dispersion of using above-mentioned heat treated more than 80 ℃ of process or autoclave to handle and obtaining as titaniferous aqueous solution (A); Only just can form the crystalline titanium oxide tunicle that contains through coating surface treatment compositions (H); Therefore, be useful as the coating material that can not carry out the material of heat treated.

In addition, as titaniferous aqueous solution (A), also can use water-disintegrable titanium compound a and aqueous hydrogen peroxide solution in the presence of TiO 2 sol, to react and the titaniferous aqueous solution (A1) that obtains.

Above-mentioned TiO 2 sol is to make amorphous titania particulate and/or anatase titanium dioxide microparticulate in water (also can add for example aqueous organic solvent such as alcohols, pure ethers as required) and the colloidal sol that forms.As this TiO 2 sol; Can use existing known TiO 2 sol; For example; The amorphous titania colloidal sol that can use the titanium oxide condensation prod to be dispersed in the water and form, said titanium oxide condensation prod is: the titanium oxide condensation prod that titaniferous solution hydrolysis such as titanium sulfate or titanyl sulfate are obtained; The titanium oxide condensation prod that (ii) makes organic titanic compound hydrolysis such as titan-alkoxide and obtain; The titanium oxide condensation prod that (iii) makes halogenated titanium solution hydrolysis such as titanium tetrachloride or neutralization and obtain; Deng, perhaps, can use above-mentioned titanium oxide condensation prod is calcined and processed anatase titanium dioxide titanium particulate and it is dispersed in the water and the colloidal sol that forms.

In the calcining of above-mentioned amorphous titania, when calcining under the temperature of the temperature more than the crystallized temperature at sharp titanium at least, for example 400 ℃ ~ more than 500 ℃, can make amorphous titania be converted into anatase titanium dioxide.As the aqueous sol of this titanium oxide, for example can enumerate: TKS-201 (trade(brand)name, テ イ カ manufactured; The anatase titanium dioxide crystal formation; Median size 6nm), TA-15 (trade(brand)name, daily output chemical company makes the anatase titanium dioxide crystal formation), STS-11 (trade(brand)name; The former industry manufactured of stone, the anatase titanium dioxide crystal formation) etc.

In the titaniferous aqueous solution (A1), the quality ratio x/y of above-mentioned TiO 2 sol x and titanium hydroperoxidation thing y (reaction product of water-disintegrable titanium compound a and aqueous hydrogen peroxide solution) is suitable 1/99 ~ 99/1, in preferred about scope of 10/90 ~ about 90/10.Quality ratio x/y is 1/99 when above, at aspects such as stability, photoreactivities, can obtain fully adding TiO 2 sol and the effect brought, and on the other hand, quality ratio x/y is 99/1 when following, can access good film-forming properties, and is therefore preferred.

Titaniferous aqueous solution (A1) can obtain through water-disintegrable titanium compound a and aqueous hydrogen peroxide solution are reacted under 1 ~ 70 ℃ temperature of reaction in about 10 minutes ~ about 20 hours.

The generation form of titaniferous aqueous solution (A1) and characteristic thereof are identical with the titaniferous aqueous solution (A) of the water-disintegrable titanium compound a of the use of above explanation, particularly through using TiO 2 sol, the part condensation reaction take place and thickening in the time of can suppressing synthetic.Think that its reason is, condensation reaction products is adsorbed onto the surface of TiO 2 sol, thereby suppresses the high molecular under the solution state.

In addition, more than 80 ℃ titaniferous aqueous solution (A1) is carried out heat treated or autoclave when handling, can access the titanium oxide dispersion of the ultramicron of the titanium oxide that contains crystallization.Also the titaniferous aqueous solution (A) with the water-disintegrable titanium compound a of the use of above explanation is identical to be used to obtain the particle diameter, the outward appearance of dispersion liquid etc. of titanium oxide ultramicron of temperature condition, crystallization of this titanium oxide dispersion.This titanium oxide dispersion also can be used as titaniferous aqueous solution (A1) and uses.

Same with the titaniferous aqueous solution (A) of the water-disintegrable titanium compound a of the use of above explanation; Be applied to the surface of plated steel sheet and (for example carry out drying through the surface treating composition (H) that will contain titaniferous aqueous solution (A1); Heat drying at low temperatures), can the tack of formation own good densification contain titanium oxide tunicle (surface treatment capsule).

As the Heating temperature of the steel plate after the coating surface treatment compositions (H), for example be below 200 ℃, be preferably especially below 150 ℃, contain the titanium oxide tunicle through the anatase titanium dioxide that under said temperature, carries out heat drying, can form containing small amount of hydroxyl groups.

As stated; In the titaniferous aqueous solution (A), use the titaniferous aqueous solution (A) of water-disintegrable titanium compound a and titaniferous aqueous solution (A1) to have good performances such as stability in storage, erosion resistance, therefore; In the present invention, especially preferably use these titaniferous aqueous solutions.

With regard to aqueous hydrogen peroxide solution with respect to regard to the cooperation ratio of at least a titanium compound in the low condenses of the low condenses, titanium hydroxide and the titanium hydroxide that are selected from water-disintegrable titanium compound, water-disintegrable titanium compound; Preferably convert with hydrogen peroxide and count 0.1 ~ 100 mass parts, be preferably 1 ~ 20 mass parts with respect to 10 mass parts titanium compounds.The cooperation ratio of aqueous hydrogen peroxide solution converts with hydrogen peroxide and counts 0.1 mass parts when above, and the formation of inner complex is abundant, therefore; Can not produce the gonorrhoea deposition; On the other hand, the cooperation ratio of aqueous hydrogen peroxide solution converts with hydrogen peroxide and counts 100 mass parts when following, hydrogen peroxide that can remained unreacted; Thereby can activated oxygen released in storage, therefore preferred.

The concentration of hydrogen peroxide of aqueous hydrogen peroxide solution is not special to be limited, and the aspect consideration from the solids component of the easy degree handled, the Generation Liquid relevant with the application operability is preferably about 3 quality % ~ about 30 quality %.

Can also in titaniferous aqueous solution (A), add other colloidal sols or pigment as required and make its dispersion.For example,, commercially available TiO 2 sol or titania powder, mica, talcum, barium oxide, clay etc. can be enumerated, in them more than one can be added as additive.

From the aspects such as stability of treatment solution, the preferred content of titaniferous aqueous solution (A) in surface treating composition is counted 1 ~ 100g/L with solids component, is preferably 5 ~ 50g/L.

Surface treating composition of the present invention is through adding zirconium carbonate compound (B) in titaniferous aqueous solution (A); Erosion resistance is further improved, and make by elementary antirust before organic resin layer (organic resin layer that forms through lamination or the application) lining with by the erosion resistance after the organic resin layer lining and improve tremendously.In addition, organic phosphoric acid compound (C) thus the reactivity that improves with steel plate improves erosion resistance, and make the stability in storage of surface treating composition good.And then; Through adding metal phosphate (D) and silicon-dioxide (E); The thick organic resin layer that make the organic resin layer that is formed on the upper strata, particularly has the above thickness of 100 μ m (for example; The organic resin layer that forms through lamination) adaptation when steel plate deformed improves, and through adding silane coupling agent (G), the adaptation (with the adaptation of aforesaid thick organic resin layer) under the harsh like this environment of high temperature moist environment is also improved.And then, through adding water-soluble organic resin and/or water dispersible organic resin (F), improve the scratch resistance of surface treatment capsule, thereby, also can show superior corrosion resistance even form under the situation of back generation roller contact at surface treatment capsule.

As zirconium carbonate compound (B), preferred zirconium carbonate ammonium, zirconyl carbonate etc. through using in them more than one, can be realized the raising of erosion resistance.The use level of zirconium carbonate compound (B) is 10 ~ 300 mass parts with respect to solids component 100 mass parts of titaniferous aqueous solution (A), is preferably 50 ~ 100 mass parts.When the use level of zirconium carbonate compound (B) was lower than 10 mass parts with respect to solids component 100 mass parts of titaniferous aqueous solution (A), the effect that improves erosion resistance was low, on the other hand, when surpassing 300 mass parts, had the tendency of adaptation variation.

As organic phosphoric acid compound (C), for example can enumerate: 1-hydroxyl methane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxy propane-1, the organic phosphorous acid of hydroxyls such as 1-di 2 ethylhexyl phosphonic acid; 2-HPAA, 2-phosphonic acid butane-1,2, conduct such as the organic phosphorous acid of hydroxyls such as 4-tricarboxylic acid and their salt is the organic phosphoric acid compound preferably, can use in them one or more.

Organic phosphoric acid compound (C) has the effect of the stability in storage that improves erosion resistance and titaniferous aqueous solution (A), wherein, 1-hydroxyl ethane-1, this effect of 1-di 2 ethylhexyl phosphonic acid is strong especially, therefore, especially preferably uses 1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid.

The use level of organic phosphoric acid compound (C) is 50 ~ 200 mass parts with respect to solids component 100 mass parts of titaniferous aqueous solution (A), from aspects such as water-fast tacks, is preferably 70 ~ 150 mass parts especially.When the use level of organic phosphoric acid compound (C) is lower than 50 mass parts with respect to solids component 100 mass parts of titaniferous aqueous solution (A), the poor storage stability of surface treating composition, and the reduction that can bring erosion resistance.On the other hand, when surpassing 200 mass parts, water-fast tack is poor.

Metal phosphate (D) and silicon-dioxide (E) are to cooperate in order to improve with the adaptation that is formed on the organic resin layer on upper strata through lamination etc., particularly have a thick organic resin layer of the thickness more than the 100 μ m.As silicon-dioxide (E), for example can enumerate: utilize the liquid phase silica of liquid phase reaction manufactured, the amorphous silicas such as aerosil that utilize drying process to make, can use in them one or more.Particularly; As liquid phase silica; Can use ス ノ one テ Star Network ス (registered trademark) O that Nissan Chemical Ind Ltd makes, ス ノ one テ Star Network ス N, ス ノ one テ Star Network ス 20, ス ノ one テ Star Network ス 30, ス ノ one テ Star Network ス 40, ス ノ one テ Star Network ス C, ス ノ one テ Star Network ス S; As aerosil, can use AEROSIL (registered trademark) 130 that Japanese ア エ ロ ジ Le Co., Ltd. makes, AEROSIL 200, AEROSIL 200V, AEROSIL 200CF, AEROSIL300, AEROSIL 300CF etc.

Wherein, from the aspect of the adaptation of organic resin layer, very preferably aerosil can access good performance.

In addition, the not special restriction of the kind of metal phosphate (D), wherein, aluminium salt, magnesium salts, manganese salt are effective.Particularly under the situation of aluminium salt, phosphatic solvability reduces, and has the advantage that the effect under moist environment continues.Above-mentioned metal phosphate can use one or more.In addition, as metal phosphate (D), the preferred use in advance phosphoric acid/metallic cation composition than being set at the excessive commercial aqueous solutions of phosphoric acid, so that it can exist with the form of the aqueous solution.

When in surface treating composition, adding (cooperation) metal phosphate (D) and silicon-dioxide (E), preferably in advance metal phosphate (D) is mixed with silicon-dioxide (E), and add with the form of its mixture.Compare with the situation of adding respectively, the method for under the state that is pre-mixed, adding can access better adaptation and erosion resistance.Its reason is not clear and definite as yet, but thinks because make the cohesive force enhancing of the tunicle that is obtained by surface treating composition owing to the effect of phosphate compsn.In addition, the stability in storage of utilizing this method to mix can to make surface treating composition improves.

In addition; Utilize in use under the situation of silicon-dioxide (aerosil) as silicon-dioxide (E) of drying process manufacturing; Through in the metal tripolyphosphate salt brine solution, adding aerosil and carrying out vigorous stirring; Make making aerosil be dispersed in the silica dispersions in the metal tripolyphosphate salt brine solution in advance, and it is mixed with other compositions get final product.Perhaps, also can aerosil and metal tripolyphosphate salt brine solution be carried out vigorous stirring together with other gradation compositions and water and make surface treating composition.

In addition, utilizing sand mill etc. that aerosil is dispersed under the situation in the surface treating composition, in about one thoughtful several weeks, cohesion is taking place and generate throw out.Detailed mechanism is still indeterminate, but finds, improves stability in storage (liquid medicine stability) thereby will make this cohesion be difficult to produce, and it is effective using the low aerosil of tap density.Particularly, preferably use tap density to be the aerosil below the 40g/L.The tap density of aerosil can utilize the degassing condition after the drying process manufacturing to regulate through control, thus, can access the low aerosil of tap density.

Make with the adaptation of organic resin layer through complexed metal phosphoric acid salt (D) and silicon-dioxide (E) and to improve; Think this be because; Through cooperating silicon-dioxide and metal phosphate, the surface polarity of surface treatment capsule changes, thereby adaptation is produced favourable effect.Because silicon-dioxide improves polarity, therefore, when directly being coated with organic resin layer on the upper strata or organic resin tunicle and upper strata being connected airtight, has the effect of the adhesive power of raising and resin layer or adhesive layer by tackiness agent.On the other hand,, then under moist environment, absorb moisture easily if polarity is too high, thus unfavorable to expanding.To this,, can realize to take into account the surface polarity of the appropriateness of adaptation and the stability when moistening through cooperating nonpolar phosphoric acid (metal phosphate).In addition, silicon-dioxide forms the concave-convex surface of submicron order through secondary aggregation, and the formation of this concave-convex surface increases the useful area that connects airtight at the interface, therefore thinks adaptation is produced effective function.Complexed metal phosphoric acid salt is very not clear and definite as yet to the influence of texture, thinks that it works and texture is exerted an influence through the secondary aggregation to silicon-dioxide.

The use level of metal phosphate (D) is counted 2 ~ 20 quality % with the ratio in the total solids composition of surface treating composition; Be preferably 2 ~ 8 quality %, the use level of silicon-dioxide (E) is counted 20 ~ 40 quality % with the ratio in the total solids composition of surface treating composition.

When the use level of metal phosphate (D) is lower than 2 quality % with the proportional meter in the total solids composition of surface treating composition, can not bring into play its effect, insufficient with the adaptation of steel plate.On the other hand, surpass 20 quality % and during excessive interpolation, become the reason of the degradations such as black change when before organic resin layer is covered, preserving.In addition, when the use level of metal phosphate (D) surpasses 8 quality %, the tendency that exists the stability of solution when preserving to reduce.

When the use level of silicon-dioxide (E) was lower than 20 quality % with the proportional meter in the total solids composition of surface treating composition, the concavo-convex formation of submicron order was insufficient, can't obtain the sufficient adaptation with the organic resin layer on upper strata man-hour in severe cruel adding.On the other hand, when surpassing 40 quality %, though can access good adaptation, surface treatment capsule becomes fragile, and therefore, because roller contact etc. scratch tunicle, naked erosion resistance reduces, and after the organic resin lining, is that starting point is corroded with scuffing portion.

Above-mentioned water-soluble organic resin and/or water dispersible organic resin (F) are to dissolve or to be dispersed in the organic resin in the water, as making organic resin water-solubleization or decentralized method in water, can use existing known method.Particularly; As organic resin; Can use contain can independent water-solubleization or the functional group of water-dispersionization (for example; Hydroxyl, polyoxyalkylene, carboxyl, ammonia (imido) base, thioether group, phosphino-etc.) organic resin and as required above-mentioned part or all of functional group is neutralized and organic resin of obtaining etc., that is, if acidic resins (carboxylic resin etc.); The organic resin that can use alkali metal hydroxides such as amine compound such as utilizing thanomin, triethylamine, ammoniacal liquor, Lithium Hydroxide MonoHydrate, sodium hydroxide, Pottasium Hydroxide that above-mentioned part or all of functional group is neutralized and obtain; In addition, (contain amino resin etc.) if basic resin, can use mineral acids such as lipid acid such as utilizing acetic acid, lactic acid, phosphoric acid that above-mentioned part or all of functional group is neutralized and the organic resin that obtains.

As water-soluble or water dispersible organic resin, for example can enumerate: redix, phenolic resinoid, acrylics, polyurethanes resin, alkene-carboxylic-acid resin, nylon-based resin, resin, Z 150PH, poly-glycerol, CMC 99.5, Walocel MT 20.000PV, Natvosol etc. with polyoxyalkylene chain.Above-mentioned organic resin can use one or more.

Wherein, Aspect from the stability in storage of surface treating composition; The preferred especially at least a organic resin that uses in acrylics, polyurethanes resin and the redix that is selected from water-soluble or water dispersible; In addition, from the stability in storage of surface treating composition and the equilibrated aspect between the film performance, preferred especially acrylics that uses water-soluble or water dispersible or polyurethanes resin are as staple.

Water-soluble or water dispersible vinyl resin can through existing known method for example emulsion polymerization, suspension polymerization, utilize the polymkeric substance of the synthetic possess hydrophilic property group of solution polymerization and neutralize as required, the method for hydration etc. obtains.

The polymkeric substance of above-mentioned possess hydrophilic property group can obtain through making unsaturated monomer with hydrophilic radicals such as carboxyl, amino, hydroxyl, polyoxyalkylene for example and other unsaturated monomers that use as required carry out polymerization.

From aspects such as erosion resistances, water-soluble or water dispersible vinyl resin is preferably the styrene copolymerized resin that forms, and the amount of vinylbenzene in whole unsaturated monomers is preferably 10 ~ 60 quality %, is preferably 15 ~ 50 quality % especially.In addition, from the aspects such as obdurability of resulting tunicle, the Tg (second-order transition temperature) of the vinyl resin that obtains through copolymerization is preferably 30 ~ 80 ℃, is preferably 35 ~ 70 ℃ especially.

As above-mentioned carboxylic unsaturated monomer, can enumerate: vinylformic acid, methylacrylic acid, toxilic acid, maleic anhydride, Ba Dousuan, methylene-succinic acid etc.

As the above-mentioned nitrogenous unsaturated monomers such as unsaturated monomer that contain amino; Can enumerate: (methyl) vinylformic acid N; N-dimethylaminoethyl, (methyl) vinylformic acid N, the nitrogenous alkyl esters of (methyl) vinylformic acid such as N-lignocaine ethyl ester, (methyl) vinylformic acid uncle N-fourth amino ethyl ester; Acrylic amide, USAF RH-1, N-methyl (methyl) acrylic amide, N-ethyl (methyl) acrylic amide, N-methylol (methyl) acrylic amide, N-methoxymethyl (methyl) acrylic amide, N-butoxymethyl (methyl) acrylic amide, N; N-dimethyl-(methyl) acrylic amide, N; N-dimethylamino-propyl (methyl) acrylic amide, N, polymerizable amide classes such as N-dimethylaminoethyl (methyl) acrylic amide; Aromatic series nitrogen containing monomers such as 2-vinyl pyridine, l-vinyl-2-pyrrolidone, 4-vinylpridine; Allylamine etc.

Unsaturated monomer as above-mentioned hydroxyl; Can enumerate: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid 2, polyvalent alcohol and the sour mono-esterification things of acrylic or methacrylic such as 3-dihydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, polyethyleneglycol (methyl) propenoate, W 166 list (methyl) propenoate; Make compound that the 6-caprolactone ring-opening polymerization obtains in the mono-esterification thing of above-mentioned polyvalent alcohol and acrylic or methacrylic acid etc.

As other unsaturated monomers, can enumerate: (methyl) alkyl acrylate of carbonatomss 1 ~ 24 such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) NSC 20949, (methyl) tert-butyl acrylate, 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid isooctadecane base ester; Vinyl acetate etc.

The unsaturated monomer of more than enumerating can use one or more.Need to prove, in the application's record, " (methyl) propenoate " expression " propenoate or methacrylic ester ".

As above-mentioned polyurethanes resin; Thereby can preferably use make as required the urethane that constitutes by polyvalent alcohols such as polyester polyol, polyether glycol and vulcabond the low-molecular weight compound that glycol, diamines etc. have two above active hydrogens be chainextender in the presence of carry out chain extension and it stably be dispersed or dissolved in the water and the polyurethanes resin that forms; Existing known polyurethanes resin (for example, with reference to the special public clear 42-24192 communique of Japan, the special public clear 42-24194 communique of Japan, the special public clear 42-5118 communique of Japan, the special public clear 49-986 communique of Japan, the special public clear 49-33104 communique of Japan, the special public clear 50-15027 communique of Japan, the special public clear 53-29175 communique of Japan) can be widely used.

As making urethane resin stably be dispersed or dissolved in the method in the water, can utilize for example following method.

(1) gives wetting ability and be dispersed or dissolved in the method in the water through import hydroxyl, amino, carboxyl isoiony group to the side chain of polyether polyols with reduced unsaturation or terminal through self-emulsifying.

(2) use emulsifying agent and mechanical shear stress to make polyether polyols with reduced unsaturation after reaction finishes perhaps utilize encapsulants such as oxime, alcohol, phenol, mercaptan, amine, sodium sulfite anhy 96 that terminal isocyanate group is sealed and the polyether polyols with reduced unsaturation that obtains forcibly is dispersed in the method in the water.And the polyether polyols with reduced unsaturation that will have a terminal isocyanate group mixes with water, emulsifying agent and chainextender and uses mechanical shear stress to carry out method decentralized and that polymer quantizes simultaneously.

(3) use the water-soluble polyol as polyoxyethylene glycol to be dispersed or dissolved in the method in the water as the polyvalent alcohol of urethane main raw material and with the form of water-soluble urethane.

Need to prove, also can be with dispersing or dissolving the polyurethanes mixed with resin that diverse ways obtains in the method and use through above-mentioned.

As can be used in the resinoid synthetic vulcabond of above-mentioned urethane, can enumerate aromatic series, alicyclic or aliphatic vulcabond, particularly; Can enumerate: hexamethylene diisocyanate, 1,4-fourth vulcabond, 3; 3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate, terephthalylidene vulcabond, mphenylenedimethylim-vulcabond, 1,3-(two isocyanato-methyl) pimelinketone, 1; 4-(two isocyanato-methyl) pimelinketone, 4,4 '-two isocyanato-pimelinketone, 4,4 '-vulcabond dicyclohexyl methyl hydride, isophorone diisocyanate, 2; 4-tolylene diisocyanate, 2; 6-tolylene diisocyanate, PPDI, diphenylmethanediisocyanate, m-benzene diisocyanate, 2,4-naphthalene diisocyanate, 3,3 '-dimethyl--4; 4 '-biphenyl diisocyanate, 4,4 '-biphenyl diisocyanate etc.Wherein, preferred especially 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.

As the resinoid commercially available article of urethane; Can enumerate: Ha イ De ラ Application (registered trademark) HW-330, Ha イ De ラ Application HW-340, Ha イ De ラ Application HW-350 (are trade(brand)name; Big Japanese ink chemical industrial company makes), ス one パ one Off レ Star Network ス (registered trademark) 100, ス one パ one Off レ Star Network ス 150, ス one パ one Off レ Star Network ス E-2500, ス one パ one Off レ Star Network ス F-3438D (be trade(brand)name, the first industrial drugmaker makes) etc.

As above-mentioned redix, can preferably use amine and epoxy resin addition and the cationic epoxy resin that forms; Modified epoxy such as acrylic acid modified, polyurethane-modified etc.As cationic epoxy resin, for example can enumerate: the affixture (for example, with reference to No. 3984299 specification sheets of USP) that mixes polyamines etc. of epoxy compounds and uncle's monoamine or uncle's polyamines, secondary monoamine or secondary polyamine, primary amine and secondary amine; Epoxy compounds and the secondary monoamine with the primary amino after the ketoimineization or the affixture (for example, with reference to No. 4017438 specification sheets of USP) of secondary polyamine; The etherification reaction product (for example, with reference to japanese kokai publication sho 59-43013 communique) of epoxy compounds and oxy-compound etc. with the primary amino after the ketoimineization.

As redix, number-average molecular weight is preferably 400 ~ 4000, is preferably 800 ~ 2000 especially, and epoxy equivalent (weight) is preferably 190 ~ 2000, is preferably 400 ~ 1000 especially.This redix can obtain through the reaction of for example polyphenolic substance and Epicholorohydrin, as polyphenolic substance, for example can enumerate: two (4-hydroxy phenyls)-2; 2-propane, 4,4-dihydroxy benaophenonel, two (4-hydroxy phenyl)-1,1-ethane, two (4-hydroxy phenyl)-1; 1-Trimethylmethane, 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-dihydroxy diphenylsulphone, phenol phenolic aldehyde, cresols phenolic aldehyde etc.

The use level of water-soluble organic resin and/or water dispersible organic resin (F) is counted 2 ~ 10 quality % with the ratio in the total solids composition of surface treating composition.When the use level of water-soluble organic resin and/or water dispersible organic resin (F) is lower than 2 quality % with the proportional meter in the total solids composition of surface treating composition; Can't improve the fragility of surface treatment capsule; Because of the roller contact of surface treatment capsule after forming etc. scratches tunicle; Naked erosion resistance reduces, and organic resin lining back is that starting point is corroded with scuffing portion.On the other hand, when surpassing 10 quality %, heat-resisting discolouration and processing back adaptation reduce.

As silane coupling agent (G); For example can enumerate: vinyl methoxy silane, vinyl Ethoxysilane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, β-(3; 4 epoxycyclohexyls) ethyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl methyldiethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, N-β (aminoethyl) γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl) γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyldiethoxysilane, γ-methacryloxypropyl triethoxyl silane, γ-mercapto propyl group methyl dimethoxysilane, γ-mercaptopropyl trimethoxysilane, to styryl Trimethoxy silane, γ-acryloxy propyl trimethoxy silicane, N-phenyl-γ-An Bingjisanjiayangjiguiwan, γ-urea propyl-triethoxysilicane, γ-r-chloropropyl trimethoxyl silane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, γ-NCO propyl-triethoxysilicane, γ-triethoxysilyl-N-(1; 3-dimethyl--Ding fork) propylamine, N-(vinyl benzylamine)-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan etc. can use in them one or more.Wherein, From improving the aspect of erosion resistance; The silane coupling agent that especially preferably has glycidyl, i.e. γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl methyldiethoxysilane, γ-glycidoxypropyltrietandysilane andysilane.

The result of inventor's research finds; From the viewpoint of the scratch resistance of surface treatment capsule, the concentration of silicon-dioxide (E) is restricted, therefore; Only pass through the composite effect of metal phosphate (D) and silicon-dioxide (E); Can not obtain fully in the following adaptation of the harsh like this environment of high temperature moist environment the adaptation of thick organic resin layer (particularly with), in order to address this problem and to improve the adaptation under the high temperature moist environment, the interpolation silane coupling agent is effective.In this discovery; With silane coupling agent and organic resin and silicon-dioxide and time spent; Though the stability of solution when preserving has the tendency of reduction; But, can not produce the problems referred to above and not damage the adaptation that improves under the situation of the severe adaptation that extremely adds man-hour under the high temperature moist environment adaptation of thick organic resin layer (particularly with) through the concentration of control metal phosphate (D).

The use level of silane coupling agent (G) is counted 0.5 ~ 20 quality % with the ratio in the total solids composition of surface treating composition, is preferably 0.5 ~ 10 quality %.When the use level of silane coupling agent (G) is lower than 0.5 quality % with the proportional meter in the total solids composition of surface treating composition; Can't substantially improve the adaptation under the high temperature moist environment, on the other hand, when surpassing 20 quality %; Stability of solution reduces, and causes cost to increase.

The pH of surface treating composition preferably is adjusted to 7 ~ 12.PH is less than 7 with greater than 12 o'clock, and surface treating composition passes through in time and produces cohesion, thereby can not form tunicle.

In the surface treating composition of the present invention, can for example further contain as required: the heavy metal compound beyond etching reagents such as resin particle, inorganic phosphate compound, the composition given to this invention, thickening material, tensio-active agent, oilness imparting agent (polyethylene wax, fluorocarbon wax (Off Star ソ is ワ Star Network ス), POLISHING WAX-103 etc.), rust-preventive agent, tinting pigment, pigment extender, rust-stabilising pigment, dyestuff etc.

In addition, surface treating composition of the present invention can use with hydrophilic solvents such as for example methyl alcohol, ethanol, Virahol, glycol solvent, propandiols solvent dilution back as required.

Viewpoints such as stability during from stability in storage and application, the solid component content of preferred surface treating composition of the present invention are about 2 quality % ~ about 10 quality %.

The surface treatment agent that surface treating composition of the present invention can be used as various metallic substance uses, especially preferably as after state zinc-based metal plated steel sheet, to aluminize be the surface treatment agent of steel plate.

Surface treated steel plate of the present invention has the surface treatment capsule of predetermined tunicle adhesion amount, and said surface treatment capsule is applied to zinc-based metal plated steel sheet through the surface treating composition that aforesaid surface treating composition is promptly contained titaniferous aqueous solution (A), zirconium carbonate compound (B), organic phosphoric acid compound (C), metal phosphate (D), silicon-dioxide (E), water-soluble organic resin and/or water dispersible organic resin (F) and silane coupling agent (G) or aluminizes to be on the surface of steel plate and to make its dry formation.This surface treatment capsule does not contain sexavalent chrome (still, as the sexavalent chrome of unavoidable impurities except).

In addition, can further contain above other added ingredientss of enumerating as required in titaniferous aqueous solution (A) and the surface treating composition.

Zinc-based metal plated steel sheet as the matrix that forms surface treated steel plate of the present invention; For example can use: steel plate galvanized, Zn-Ni alloy plated steel sheet, zn-fe alloy plated steel sheet (electroplating steel plate, alloyed hot-dip galvanized steel sheet), Zn-Cr alloy plated steel sheet, Zn-Mn alloy plated steel sheet, Zn-Co alloy plated steel sheet, Zn-Co-Cr alloy plated steel sheet, Zn-Cr-Ni alloy plated steel sheet, Zn-Cr-Fe alloy plated steel sheet, Zn-Al alloy plated steel sheet are (for example; Zn-5 quality %Al alloy plated steel sheet, Zn-55 quality %Al alloy plated steel sheet), Zn-Mg alloy plated steel sheet, Zn-Al-Mg alloy plated steel sheet and MOX, polymkeric substance etc. are dispersed in the plating tunicle of these plated steel sheets and the compound zinc-based metal plated steel sheet that forms (for example, is dispersed with SiO ₂Steel plate galvanized) etc.In addition, also can use plating that the multilayer plated steel sheet of two-layer above coating identical or different in the above-mentioned coating is arranged.

In addition, be steel plate as the aluminizing of matrix that forms surface treated steel plate of the present invention, can use Aludip, Al-Si alloy plated steel sheet etc.

In addition, as plated steel sheet, can be on surface of steel plate, to apply the thin unit adhesion amount coating of Ni etc. in advance, apply aforesaid various coating above that and the plated steel sheet that obtains then.

As method for plating, can adopt any one method that to implement in electrolytic process (electrolysis or electrolysis in non-aqueous solvent in the aqueous solution), method of fusion, the vapor phase process.

In addition; When plating tunicle surface forms surface treatment capsule; In order not produce tunicle defective and inhomogeneous, can implement alkali degreasing, solvent degreasing, surperficial adjustment processing processing such as (the surface adjustment processing of alkalescence or tart surface are adjusted and handled) to plating tunicle surface in advance as required.

In addition; In advance coating surface being implemented the surface adjustment for the acidity that prevents the black change (oxidative phenomena of coating surface a kind of) under environment for use, can also utilize as required to contain iron family metal ion (more than one in Ni ion, Co ion, the Fe ion) or alkaline aqueous solution handles.

In addition; Using under the situation of electrogalvanizing steel plate as the matrix steel plate; In order to prevent black the change, can in plating bath, add iron family metal ion (more than one in Ni ion, Co ion, the Fe ion) in advance and make the above-mentioned metal that contains in the plating tunicle more than the 1 quality ppm.In this case, the upper limit of the iron family metal concentration in the plating tunicle is not special limits.

The adhesion amount of the surface treatment capsule that is formed by surface treating composition is set at 0.03 ~ 0.5g/m ²The tunicle adhesion amount is lower than 0.03g/m ²The time, corrosion-resistant on the other hand, surpasses 0.5g/m ²The time, tunicle splits easily, carries out the severe adaptation that extremely adds man-hour after the organic resin lining and reduces.

When making surface treated steel plate of the present invention; The surface treating composition (treatment solution) that aforesaid surface treating composition is promptly contained titaniferous aqueous solution (A), zirconium carbonate compound (B), organic phosphoric acid compound (C), metal phosphate (D), silicon-dioxide (E), water-soluble organic resin and/or water dispersible organic resin (F) and silane coupling agent (G) is applied to zinc-based metal plated steel sheet or aluminizes is on the surface of steel plate; Then, under the situation of not washing, carry out drying.

In addition, can further contain above other added ingredientss of enumerating as required in titaniferous aqueous solution (A) and the surface treating composition.

The coating process of surface treating composition (treatment solution) is arbitrarily, for example draws for spraying+roller, roller coat etc., and in addition, the drying mode after the coating also is arbitrarily, for example is hot blast mode, induction heating mode, electric furnace mode etc.

The drying temperature (steel billet temperature) of the surface treating composition after the coating (treatment solution) is preferably set to about 60 ℃ ~ about 200 ℃.If drying temperature is more than 60 ℃, then tunicle forms fully, obtains good tunicles such as erosion resistance.On the other hand,, then can not crack, therefore, can access the effect of sufficient raising erosion resistance because of heat makes tunicle if drying temperature is below 200 ℃.In addition, preferred drying temperature is 60 ~ 140 ℃, further is preferably 60 ~ 100 ℃.

In addition, organic resin coating steel of the present invention obtains through on the surface treatment capsule of aforesaid surface treated steel plate, forming organic resin layer.The formation method of this organic resin layer is arbitrarily, for example can use: the coating composition compsn also makes its exsiccant method, organic resin film is carried out laminated method etc.

In addition, the surface treatment capsule of the present invention particularly adaptation with the thick organic resin layer with the thickness more than the 100 μ m is good, and therefore, organic resin coating steel of the present invention is particularly useful under the situation more than the 100 μ m at the thickness of organic resin layer.

In addition, can in organic resin layer, cooperate with non-chromium rust-inhibiting additive, solid lubricant, tinting pigment etc. be the various additives of representative.

Embodiment

The titaniferous aqueous solution (A) and the composition (B) ~ (G) that use in the surface treating composition below are shown.

[manufacturing of titaniferous aqueous solution (A)]

Make example 1 (titaniferous aqueous solution T1)

5ml 60 quality % titanium tetrachloride solutions are adjusted to 500ml with zero(ppm) water, and dropping ammonia in gained solution (ammonia: the mass ratio of water is 1: 9) precipitates the low condenses of titanium hydroxide.After utilizing zero(ppm) water to clean, add 30 quality % aqueous hydrogen peroxide solutions and the stirring of 10ml, obtain the titaniferous aqueous solution T1 that titaniferous yellow is translucent, have viscosity.

Make example 2 (titaniferous aqueous solution T2)

20 ℃ down cost 1 hour the mixture of the Virahol of the tetraisopropoxy titanium of 10 mass parts and 10 mass parts is added drop-wise to while stirring in the mixture of deionized water of 30 quality % aqueous hydrogen peroxide solutions and 100 mass parts of 10 mass parts.Then, 25 ℃ of following slakings 2 hours, obtain yellow transparent, have a titaniferous aqueous solution T2 of viscosity a little.

Make example 3 (titaniferous aqueous solution T3)

Use four titanium n-butoxide to replace making the tetraisopropoxy titanium that uses in the example 2, in addition, under create conditions same, obtain titaniferous aqueous solution T3 with making example 2.

Make example 4 (titaniferous aqueous solution T4)

Use the tripolymer (the low condenses of tetraisopropoxy titanium) of tetraisopropoxy titanium to replace making the tetraisopropoxy titanium that uses in the example 2, in addition, under create conditions same, obtain titaniferous aqueous solution T4 with making example 2.

Make example 5 (titaniferous aqueous solution T5)

Use is the aqueous hydrogen peroxide solution of 3 times of amounts with respect to making example 2,50 ℃ down cost dripped in 1 hour, again 60 ℃ of following slakings 3 hours, in addition, under create conditions same, obtain titaniferous aqueous solution T5 with making example 2.

Make example 6 (titaniferous aqueous solution T6)

With make the heat treated that the titaniferous aqueous solution T3 that makes in the example 3 further carried out 6 hours under 95 ℃, thus, obtain the translucent titaniferous aqueous solution of white xanchromatic T6.

Make example 7 (titaniferous aqueous solution T7)

10 ℃ down cost 1 hour the mixture of the Virahol of the tetraisopropoxy titanium of 10 mass parts and 10 mass parts is added drop-wise to while stirring " TKS-203 " (trade(brand)names of 5 mass parts; テ イ カ manufactured, TiO 2 sol) in the mixture of the deionized water of 30 quality % aqueous hydrogen peroxide solutions of (solids component), 10 mass parts and 100 mass parts.Then, 10 ℃ of following slakings 24 hours, obtain yellow transparent, have a titaniferous aqueous solution T7 of viscosity a little.

[zirconium compounds (B)]

B1: zirconium carbonate ammonium

B2: zirconyl carbonate

B3: ammonium fluozirconate

[organic phosphoric acid compound (C)]

C1:1-hydroxyl methane-1, the 1-di 2 ethylhexyl phosphonic acid

C2:1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid

[mixture of metal phosphate (D) and silicon-dioxide (E)]

Cooperate ratio in the aqueous solution of metal phosphate (D), to add silicon-dioxide (E) and vigorous stirring in the solids component shown in table 3, table 5, table 7, table 9, the table 11, obtain in the metal tripolyphosphate salt brine solution, being dispersed with the mixture of silicon-dioxide.Need to prove that the comparative example of the No.92 of table 9 and table 10 only contains silicon-dioxide E4.

Metal phosphate (D)

D1: aluminium dihydrogen phosphate

D2: primary magnesium phosphate

D3: phosphate dihydrogen manganese

Silicon-dioxide (E)

E1: (trade(brand)name, Japanese ア エ ロ ジ Le Co., Ltd. makes ア エ ロ ジ Le 300, aerosil, tap density: 50g/L)

E2: (trade(brand)name, Japanese ア エ ロ ジ Le Co., Ltd. makes ア エ ロ ジ Le 200, aerosil, tap density: 35g/L)

E3: ス ノ one テ Star Network ス O (trade(brand)name, Nissan Chemical Ind Ltd makes, colloidal silica)

E4: (trade(brand)name, Japanese ア エ ロ ジ Le Co., Ltd. makes ア エ ロ ジ Le 300CF, aerosil, tap density: 35g/L)

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

In the water-soluble or water dispersible organic resin, the water dispersible vinyl resin of F1 ~ F5 is made according to the manufacturing example 8 ~ 12 shown in following, and F6 ~ F13 uses commercially available article.Need to prove that following " part " and " % " of making example is a quality criteria.

Make example 8 (water dispersible vinyl resin F1)

To the capacity that possesses reflux exchanger, whisking appliance, TM, tap funnel is 5% (28.9 parts) that add 665 parts of deionized waters, 9 parts of ア Network ア ロ Application RN-50 (annotating 1), 87 parts of ア Network ア ロ Application RN-2025 (annotating 2) in 2 liters the four-hole boiling flask, make the pre-emulsion that monomer mixed solution 1 (fs) forced emulsification of following composition obtains, and carries out heating up behind the nitrogen replacement.

< monomer mixed solution 1 >

After reaching more than 55 ℃; Add 5 parts of パ, one Block チ Le H (annotating 3) to be dissolved in 83.5 parts of deionized waters and 5% (4.43 parts) of the aqueous oxidizing agent solution that forms and 2.5 parts of rongalites are dissolved in 83.5 parts of deionized waters and 5% (4.3 parts) of the reductive agent aqueous solution that forms, the back of further heating up keeps under 60 ℃ temperature.From adding beginning after 15 minutes, spend 1.5 hours and drip remaining pre-emulsion, spend the 3.5 hours dropping oxidizing agent aqueous solution, spend the 3.5 hours dropping reductive agent aqueous solution.Continue the dropping oxidizing agent aqueous solution and the reductive agent aqueous solution during in, finish 1 hour since the dropping of fs pre-emulsion after, spend the monomer mixed solution 2 (subordinate phase) that dripped following composition in 1 hour.

< monomer mixed solution 2 >

When whole droppings finish, further under 60 ℃ temperature, kept 1 hour, then; Temperature is reduced to below 40 ℃; Add 3.35 part of 25% ammoniacal liquor, 0.35 part of ス ラ オ Off EX (annotating 4), 83.5 part 2,2,4-trimethylammonium-1; The 3-pentanediol mono isobutyrate obtains pH and is 8.0, nonvolatile component is 31% water dispersible vinyl resin F1.

(annotating 1) ア Network ア ロ Application RN-50: trade(brand)name, Di-ichi Kogyo Seiyaku Co., Ltd. makes, nonionic emulsifier, solids component 60%

(annotating 2) ア Network ア ロ Application RN-2025: trade(brand)name, Di-ichi Kogyo Seiyaku Co., Ltd. makes, nonionic emulsifier, solids component 25%

(annotating 3) パ one Block チ Le H: trade(brand)name, NOF Corp makes, tertbutyl peroxide, effective constituent 69%

(annotate 4) ス ラ オ Off EX: trade(brand)name, Japanese エ Application パ イ ロ ケ ミ カ Le ズ Co., Ltd. makes sanitas

Manufacturing example 9 ~ 12 (water dispersible vinyl resin F2 ~ F5)

The monomer of making fs, subordinate phase in the example 8 formed be set at the proportioning shown in the table 2, in addition, the method through same with making example 8 obtains water dispersible vinyl resin F2 ~ F5.

The characteristic value of each water dispersible vinyl resin is shown in Table 2 in the lump.

F6: ス one パ one Off レ Star Network ス E-2500 (trade(brand)name, Di-ichi Kogyo Seiyaku Co., Ltd. makes, waterborne polyurethane resin)

F7: ス one パ one Off レ Star Network ス 150 (trade(brand)name, Di-ichi Kogyo Seiyaku Co., Ltd. makes, waterborne polyurethane resin)

F8: ス one パ one Off レ Star Network ス 420 (trade(brand)name, Di-ichi Kogyo Seiyaku Co., Ltd. makes, waterborne polyurethane resin)

F9: ス one パ one Off レ Star Network ス 300 (trade(brand)name, Di-ichi Kogyo Seiyaku Co., Ltd. makes, waterborne polyurethane resin)

F10: バ イ ロ Na one Le MD-1100 (trade(brand)name, Toyo Boseki K.K makes, aqueous polyester resin)

F11: ア デ カ レ ジ Application EM-0718 (trade(brand)name, Asahi Denka Co., Ltd. makes, the water-base epoxy resinoid)

F12: モ デ ピ Network ス 303 (trade(brand)name, Arakawa Chemical Industries, Ltd. makes, the water-base epoxy resinoid)

F13: ウ オ one タ one ゾ one Le S-370 (trade(brand)name, Dainippon Ink. & Chemicals Inc makes, the water-base epoxy resinoid)

[silane coupling agent (G)]

G1:KBM-403 (trade(brand)name, Shin-Etsu Chemial Co., Ltd makes, and contains the Racemic glycidol fundamental mode)

G2:KBE-403 (trade(brand)name, Shin-Etsu Chemial Co., Ltd makes, and contains the Racemic glycidol fundamental mode)

G3:KBE-402 (trade(brand)name, Shin-Etsu Chemial Co., Ltd makes, and contains the Racemic glycidol fundamental mode)

G4:KBM-303 (trade(brand)name, Shin-Etsu Chemial Co., Ltd makes, and contains the Racemic glycidol fundamental mode)

G5:KBE-903 (trade(brand)name, Shin-Etsu Chemial Co., Ltd makes, and contains amino-type)

G6:KBM-803 (trade(brand)name, Shin-Etsu Chemial Co., Ltd makes, and contains the sulfydryl type)

G7:KBE-585 (trade(brand)name, Shin-Etsu Chemial Co., Ltd makes, and contains the urea groups type)

G8:KBM-1003 (trade(brand)name, Shin-Etsu Chemial Co., Ltd makes, and contains vinyl-type)

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

Suitably gradation composition (B) ~ (G) and zero(ppm) water and mix in above-mentioned titaniferous aqueous solution (A); Solid component content is adjusted to 2 ~ 10 quality %; With pH regulator to 8; The surface treating composition of gained is applied on the plated steel sheet surface, carries out drying, make surface treated steel plate with the mode that reaches predetermined drying temperature (be up to and reach the plate temperature) after 5 seconds.For the surface treated steel plate that obtains like this; Copy paper is wrapped in rubber rollers (on the 48mm φ * 205mm); The surperficial scuffing of the tunicle that under the situation that does not make the roller rotation under the load (own wt that comprises roller) of 690g, once rubs is handled, as supplying examination material 1.Need to prove that the comparative example of the No.58 of record does not carry out above-mentioned scuffing processing in table 5 and the table 6.

TP through following (1) ~ (4) is estimated heat-resisting discolouration, water-fast tack, erosion resistance and the anti-blackening of above-mentioned confession examination material 1.

And then, common vinyl chloride film is sticked with glue agent be applied to and supply to make its dry film thickness reach 3 μ m on the examination material 1, then; Temperature is to heat in 100 ℃ the process furnace in stove; Then, utilize roller with the vinyl chloride film of thickness 250 μ m to the pressed that supplies the examination material, and make steel billet temperature reach 230 ℃ and carry out thermo-compressed; Make vinyl chloride film (organic resin layer) gluing thus, thereby make organic resin-coated steel sheet (with it as " supply examination material 2 ").TP through following (5) ~ (7) to the processing of the confession examination material 2 of such making after adaptation, boiling water adaptation and erosion resistance estimate.

And then, through the TP of following (8), (9) stability in storage of surface treating composition is estimated.

Above result is shown in table 3 ~ table 12 together with the composition and the application condition thereof of the surface treating composition that uses in each confession examination material.

(1) heat-resisting discolouration

Utilizing the infrared rays image furnace will supply examination material 1 to use to be heated to the plate temperature 30 seconds is 500 ℃, keeps naturally cooling to room temperature after 30 seconds, and appearance is at this moment carried out visual observation.Its metewand is following.

Zero: do not have variable color

△: variable color becomes faint yellow

*: variable color yellowly ~ dark brown

(2) water-fast tack

Supplying to drip the 1mL pure water on the examination material 1, utilizing 100 ℃ oven drying 10 minutes, the appearance of this moment is being carried out visual observation.Its metewand is following.

◎: do not change

Zero: almost do not change

△: the profile of only observing dropping portion

*: the whole generation variable color of dropping portion

(3) erosion resistance

Use with the end and the sealing backside of this test film, is carried out the salt spray testing of JIS-Z-2371-2000 from the test film of the 50mm * 100mm of confession examination material 1 cutting-out, measures the area occupation ratio that produces white rust and reaches 5% o'clock required test period.Its metewand is following.

◎: more than 36 hours

More than zero: 24 hour and be lower than 36 hours

△: more than 12 hours and be lower than 24 hours

*: be lower than 12 hours

(4) anti-blackening

With supplying examination material 1 in atmosphere is controlled to be the constant temperature and humidity machine of 80 ℃ of temperature, relative humidity 95%, to leave standstill 24 hours, calculate whiteness (L value) variation at this moment with the form of Δ L (the L value before the L value-test after the test).Its metewand is following.

○：ΔL≥-5.0

△：-5.0＞ΔL≥-10.0

×：-10.0＞ΔL

(5) processing back adaptation (processing back stripping strength)

Use is from the test film of the 30mm * 120mm of confession examination material 2 cutting-outs; Substantial middle portion at the length direction of this test film; Mark two lines perpendicular to length direction with the interval of 50mm; The two ends that utilize the chuck of tensile testing machine to clamp the length direction of test film stretch on the single shaft direction, reach 60mm up to the interval of above-mentioned two lines.Test film after this is stretched is as sample, on the organic resin layer between two lines that broaden is that the mode of 20mm is provided with the otch that reaches steel plate deeply with the width.This end that is provided with the organic resin layer of otch is forcibly peeled off; The end of the organic resin layer after utilizing a chuck of tensile testing machine to clamp this to peel off; Utilizing another chuck of tensile testing machine to clamp steel plate, is to carry out stripping test under 50mm/ minute the condition at peeling rate.In this stripping test, organic resin layer is peeled off the maximum strength (=stripping strength) when measuring this and peeling off from surface of steel plate with the direction (reverse direction) of 180 degree.This stripping strength is big more, and organic resin layer is difficult to peel off from metal sheet more, and the adaptation after bending machining or the pull and stretch processing is good more.Based on the stripping strength of being measured, utilize following benchmark to estimate to processing the back adaptation.

4 (scorings): stripping strength is more than the 50N/20mm width

3 (scorings): stripping strength is more than the 40N/20mm width and is lower than the 50N/20mm width

2 (scorings): stripping strength is more than the 30N/20mm width and is lower than the 40N/20mm width

1 (scoring): stripping strength is lower than the 30N/20mm width

(6) boiling water adaptation (stripping strength after the Hot water immersion)

Use is from the test film of 30mm * 120mm of supplying examination material 2 and downcutting, this test film flooded lift up after 5 hours in boiling water.For this test film,, measure the stripping strength that organic resin layer is peeled off from steel plate through the method same with the test of above-mentioned (5).This stripping strength is big more, and the adaptation after the Hot water immersion is that the adaptation under the high temperature moist environment is good more.Based on the stripping strength of being measured, utilize following benchmark that the boiling water adaptation is estimated.

4 (scorings): stripping strength is more than the 50N/20mm width

3 (scorings): stripping strength is more than the 40N/20mm width and is lower than the 50N/20mm width

2 (scorings): stripping strength is more than the 30N/20mm width and is lower than the 40N/20mm width

1 (scoring): stripping strength is lower than the 30N/20mm width

(7) erosion resistance (scratch resistance)

Use marks the intersection otch from the test film of the 50mm * 100mm of confession examination material 2 cutting-outs on this test film surface, carry out 1000 hours salt spray testing according to the regulation of JIS-Z-2371-2000.Measure apart from the one-sided corrosion width of intersection otch.Its metewand is following.

◎: apart from the average corrosion width of notch less than 5mm

Zero: the average corrosion width apart from notch is more than the 5mm and less than 10mm

*: the average corrosion width apart from notch is more than the 10mm

If it is poor to be formed on the scratch resistance of lip-deep tunicle of surface treated steel plate, then tunicle is scraped off and is formed the scuffing of a plurality of arrival coating surfaces.Because there is not tunicle in this scuffing portion, therefore, make the water capacity be prone to invade with the adaptation difference of organic resin layer.The salt solution of therefore, invading from the intersection notch is penetrated into this scuffing portion and corrodes.As a result, under the situation of scratch resistance difference, apart from the corrosion width increase of intersection notch.Therefore, will be apart from intersecting the evaluation of one-sided average corrosion width of otch as the evaluation of scratch resistance.

(8) stability in storage (I)

Make solids component be the surface treating composition of 8 quality % under 40 ℃ through two weeks, estimate through visual deposition state and viscosity solids component.Its metewand is following.

◎: do not have the deposition of solids component and viscosity not to change

Zero: deposition or little viscosity change that the solids component of trace is arranged

△: the variation many or viscosity of the deposition of solids component is big

*: the deposition of solids component is many and variation viscosity is big

(9) stability in storage (II)

With solids component is that the surface treating composition of 8 quality % remains on 30 ℃, estimates through visual deposition state to solids component weekly.Its metewand is following.

◎: also do not precipitate after 4 weeks

Zero: 4 week back generation deposition

△: 2 week ~ 3 week back generation deposition

*: 1 week back generation deposition

Table 1

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

Table 2

※ unit: quality %

In table 3, table 5, table 7, table 9, table 11, the content below * 1 ~ * 10 expressions.

* the plated steel sheet No.1 ~ No.9 that puts down in writing in 1 table 1

* the titaniferous aqueous solution T1 ~ T7 that puts down in writing in the 2 specification sheets texts

* the zirconium compounds B1 ~ B3 that puts down in writing in the 3 specification sheets texts

* the organic phosphoric acid Compound C 1, the C2 that put down in writing in the 4 specification sheets texts

* the metal phosphate D1 ~ D3 that puts down in writing in the 5 specification sheets texts

* the silicon-dioxide E1 ~ E4 that puts down in writing in the 6 specification sheets texts

* the water-soluble or water dispersible organic resin F1 ~ F13 that puts down in writing in the 7 specification sheets texts

* the silane coupling agent G1 ~ G8 that puts down in writing in the 8 specification sheets texts

* the solids component quality (g) in 91 liters of surface treating compositions (aqueous treating fluid)

* the ratio (quality %) of 10 surface treating compositions (aqueous treating fluid) in the total solids composition

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Claims (7)

1. surface treating composition; It is characterized in that; Contain at least a titanium compound in the low condenses of low condenses, titanium hydroxide and titanium hydroxide through will being selected from water-disintegrable titanium compound, water-disintegrable titanium compound and mix the titaniferous aqueous solution (A) that obtains with aqueous hydrogen peroxide solution, be the zirconium carbonate compound (B) of 10 ~ 300 mass parts and be the organic phosphoric acid compound (C) of 50 ~ 200 mass parts, and contain the silane coupling agent (G) of counting the metal phosphate (D) of 2 ~ 20 quality %, counting the silicon-dioxide (E) of 20 ~ 40 quality %, count water-soluble organic resin and/or the water dispersible organic resin (F) of 2 ~ 10 quality % and count 0.5 ~ 20 quality % with the ratio in the total solids composition of surface treating composition with the ratio in the total solids composition of surface treating composition with the ratio in the total solids composition of surface treating composition with the ratio in the total solids composition of surface treating composition with respect to solids component 100 mass parts of titaniferous aqueous solution (A) with respect to solids component 100 mass parts of titaniferous aqueous solution (A).

2. surface treating composition as claimed in claim 1 is characterized in that, silicon-dioxide (E) is the aerosil that utilizes drying process to make.

3. surface treating composition as claimed in claim 2 is characterized in that, the tap density of aerosil is below the 40g/L.

4. like each described surface treating composition in the claim 1 ~ 3, it is characterized in that silane coupling agent (G) has glycidyl.

5. like each described surface treating composition in the claim 1 ~ 4, it is characterized in that pH is 7 ~ 12.

6. a surface treated steel plate is characterized in that, having the tunicle adhesion amount is 0.03 ~ 0.5g/m ²Surface treatment capsule, said surface treatment capsule is on the surface of steel plate and makes its dry formation through each described surface treating composition in the claim 1 ~ 5 being applied to zinc-based metal plated steel sheet or aluminizing.

7. an organic resin coating steel is characterized in that, on the surface treatment capsule of the described surface treated steel plate of claim 6, has organic resin layer.