CN102086518A - Composition for metallic surface treatment and metallic base material with surface treatment envelope - Google Patents
Composition for metallic surface treatment and metallic base material with surface treatment envelope Download PDFInfo
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- CN102086518A CN102086518A CN2010105776909A CN201010577690A CN102086518A CN 102086518 A CN102086518 A CN 102086518A CN 2010105776909 A CN2010105776909 A CN 2010105776909A CN 201010577690 A CN201010577690 A CN 201010577690A CN 102086518 A CN102086518 A CN 102086518A
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- Prior art keywords
- composition
- surface treatment
- metal finishing
- aqueous solution
- mass parts
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention provides a composition for metallic surface treatment which is characterized by comprising following components (A) to (C): (A) an aqueous solution obtained by mixing at least one titanium compound selecting from water weakened titanium compound, the condensate of water weakened titanium compound, titanium hydroxide and the condensate of titanium hydroxide with hydrogen peroxide solution(A2), or vanadate peroxide solution (A2); (B) organic phosphate compound; and (C) condensation product of amino silane (c1) and multi-silyl-functional silanes (c2). The composition for metallic surface treatment can form surface treatment envelope which is excellent for storage and has excellent corrosion resistance performance. The adhesive property of a film subjected to a post coating process is good.
Description
Technical field
The present invention relates to metal finishing with composition and have the metal base of surface treatment capsule.
Background technology
In the past, in order to improve the solidity to corrosion of metallic surface,, generally carry out chromate treating and phosphatizing as surface treatment.But in recent years, the toxicity of chromium is just becoming social concern.There are the following problems to use the surface treatment method of chromic salt: the problem that the chromic acid salt fog vapour (chromate fume) in treatment process disperses, drainage treatment equipment need a lot of expenses and chromic acid from changing into the caused problem of stripping etc. of handling the tunicle.In addition, 6 valency chromium cpds are extremely harmful material by the carcinogens that a plurality of official missions that with IARC (International Agency for Research on Cancer Review) are representative are appointed as human body.
In addition,, carry out phosphatizing, for example the surface treatment of zinc phosphate system, tertiary iron phosphate system in order to improve the solidity to corrosion of metallic surface.In phosphate-based surface treatment, utilize phosphatizing after, in order to give solidity to corrosion, utilize the flushing of chromic acid to handle usually.Therefore, in the problem that exists chromium to handle, the draining processing, metal ion that also has reaction promotor in the phosphatizing agent, a metal ion etc. stripping and sludge conditioning problems such as (Sludge treatment) of causing from metal to be treated.
As the surface treatment method beyond chromate treating and the phosphatizing, know the surface treatment agent (with reference to patent documentation 1～5 etc.) of zirconium system and titanium system, mainly be useful for the material of aluminium system.But the problem that these treatment agents exist is, treatment agent stable insufficient, and in addition, about metal bases such as zinc steel plates, to compare solidity to corrosion poor with existing chromate treating.
Except the surface treatment agent of zirconium system and titanium system, be surface treatment agent also at the research vanadium, for example, patent documentation 6 discloses vanadic salts that comprises vanadate and/or mineral acid and the organic acid metal finishing electrolysis chemical synthesis treatment liquid with reducing power.In the invention of patent documentation 6 records, change into processing by carrying out negative electrode, even Zinc material also can form the tunicle of corrosion resistance excellent.But there is the limit in the treatment process that electrolysis changes into processing and so on, and comparing cost with the processing of only material being flooded in treatment solution or be coated with also increases, and therefore, has the limited problem of purposes.
Because the corrosion resistance excellent of vanadium, therefore can ammonium meta-vanadate etc. the state of vanadate as rust-preventive agent.But, because therefore the poor stability of vanadium compound in water need make it be dispersed in the water with above-mentioned water-based organic resin with specific water-based organic resin mixing and add.But, in these class methods, can not improve vanadium concentration, the not too big raising of the solidity to corrosion of metallic surface.
In addition, studying and to be added in the surface treatment agent by the peroxide vanadic acid that vanadium compound and hydroperoxidation are generated.For example, patent documentation 7 discloses the surface treatment agent that comprised oxometallate (peroxo metal oxysalt), example vanadium as above-mentioned metal.But the peroxide vanadic acid is compared the excellent in stability in water with described vanadate, but insufficient as the ability of surface treatment agent.
The applicant in patent documentation 8 motion comprise peroxide vanadic acid and organic phospho acid metal finishing with composition as surface treatment capsule that not only can form corrosion resistance excellent but also the also excellent treatment agent of storage stability.
But, though the storage stability excellence of above-mentioned composition, can form the surface treatment capsule of corrosion resistance excellent,, there is inadequate situation sometimes in its adhesivity of filming that forms with painting process by the back because of the kind of coating is different.
The prior art document
Patent documentation
[patent documentation 1] Japanese Patent Publication 48-24618 number
[patent documentation 2] Japanese kokai publication sho 54-24232 number
[patent documentation 3] Japanese kokai publication sho 54-160527 number
[patent documentation 4] Japanese kokai publication hei 9-20984 number
[patent documentation 5] Japanese kokai publication hei 9-143752 number
[patent documentation 6] Japanese kokai publication hei 9-95796 number
[patent documentation 7] Japanese kokai publication sho 54-147141 number
[patent documentation 8] TOHKEMY 2009-174050 number
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide metal finishing with composition and have the metal base of surface treatment capsule, described metal finishing is with the storage excellence of composition, and the also excellent surface treatment capsule of the adhesivity of filming that can form corrosion resistance excellent and form with painting process by the back.
Be used to solve the means of problem
The inventor etc. concentrate on studies to achieve these goals, found that, utilize metal finishing can realize above-mentioned purpose with composition (D), thereby finished the present invention, wherein, described metal finishing is characterized in that comprising following composition (A)～composition (C) with composition (D): (A) at least a titanium compound and the aquae hydrogenii dioxidi in the group that constitutes of the condenses of condenses, titanium hydroxide and the titanium hydroxide by will being selected from water-disintegrable titanium compound, water-disintegrable titanium compound mixes the titaniferous aqueous solution (A that obtains
1); (B) organic phosphoric acid compound; And (C) the condensation resultant of aminosilane (c1) and multi-silyl functional silane (c2).
The inventor etc. concentrate on studies to achieve these goals, the result also finds, utilize metal finishing also can realize above-mentioned purpose with composition (E), thereby finished the present invention, wherein, described metal finishing is characterized in that comprising following composition (A)～composition (C): (A) the peroxide vanadic acid aqueous solution (A with composition (E)
2); (B) organic phosphoric acid compound; And (C) the condensation resultant of aminosilane (c1) and multi-silyl functional silane (c2).
The invention effect
Metal finishing of the present invention is with the storage excellence of composition (D), and the also excellent surface treatment capsule of the adhesivity of filming of utilizing various coating that can form corrosion resistance excellent and form with painting process by the back.
Metal finishing of the present invention is with the storage excellence of composition (E), and the also excellent surface treatment capsule of the adhesivity of filming of utilizing various coating that can form corrosion resistance excellent and form with painting process by the back.
Embodiment
＜metal finishing composition (D) 〉
Metal finishing of the present invention is with in the composition (D), as mixing and the titaniferous aqueous solution (A that obtains as at least a titanium compound in the condenses of the condenses that is selected from water-disintegrable titanium compound, water-disintegrable titanium compound, titanium hydroxide and the titanium hydroxide of composition (A) and aquae hydrogenii dioxidi
1) (following " titaniferous aqueous solution (the A that only is called sometimes
1) "), can enumerate known titaniferous aqueous solution (A
1).
The said hydrolyzed titanium compound is the titanium compound with the hydrolization group that is bonded directly to titanium atom, by generating titanium hydroxide with reaction of moisture such as water, water vapour.In addition, in the said hydrolyzed titanium compound, the part of hydrolization group also can be hydrolyzed, and becomes hydroxyl.
As the said hydrolyzed group,, for example can enumerate: lower alkoxy, with the salifiable group of titanium atom shape etc. so long as, just be not particularly limited by generating the group of hydroxyl with reaction of moisture.As with the salifiable group of titanium atom shape, for example can enumerate: halogen atom (chlorine etc.), hydrogen atom, sulfate ion etc.
As containing the water-disintegrable titanium compound that lower alkoxy is used as hydrolization group, for example can enumerate four titan-alkoxides.
As having the water-disintegrable titanium compound that is used as hydrolization group with the salifiable group of titanium shape, can enumerating with titanium chloride, titanium sulfate etc. is the water-disintegrable titanium compound of representative.
The condenses of water-disintegrable titanium compound is a said hydrolyzed titanium compound condenses each other.In above-mentioned condenses, a part that is bonded to the hydrolization group of titanium atom also can be hydrolyzed, and becomes hydroxyl.
As the condenses of titanium hydroxide, the aqueous solution and the alkaline aqueous solutions such as ammonia, sodium hydroxide that for example can enumerate by titanium chloride, titanium sulfate etc. react positive metatitanic acid (the orthotitanic acid that obtains; Titanic hydroxide gel) etc.
Condensation degree in the condenses of said hydrolyzed titanium compound or the condenses of titanium hydroxide is preferably in about scope of 2～about 30, and in more preferably about scope of 2～about 10.
As titaniferous aqueous solution (A
1), especially preferably by water-disintegrable titanium compound and/or its condenses and aquae hydrogenii dioxidi are mixed the pertitanic acid aqueous solution (a that obtains
1).
As above-mentioned titanium compound, four titan-alkoxides of preferred especially following general formula (1) expression.
Ti(OR)
4 (1)
(in the formula, R represents that identical or different carbonatomss is 1～5 alkyl.)
As R, for example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc.
In addition, as the condenses of above-mentioned titanium compound, be preferably that to carry out the condensation degree that condensation reaction generates mutually by the compound that makes general formula (1) be about condenses of 2～about 30, more preferably condensation degree is about condenses of 2～about 10.
In order to obtain titaniferous aqueous solution (A
1), for with the water-disintegrable titanium compound of general formula (1) and/or its condenses (following sometimes " the water-disintegrable titanium compound of general formula (1) and/or its condenses " only is called " water-disintegrable titanium compound (T) ") and aquae hydrogenii dioxidi blended ratio, with respect to water-disintegrable titanium compound (T) 10 mass parts, hydrogen peroxide is preferably the ratio of about 0.1～about 100 mass parts, and is preferably the ratio of about 1～about 20 mass parts especially.When hydrogen peroxide water converts when being lower than about 0.1 mass parts in hydrogen peroxide, the generation of pertitanic acid is insufficient and produce the gonorrhoea precipitation sometimes.On the other hand, when hydrogen peroxide water convert to surpass about 100 mass parts in hydrogen peroxide, unreacted hydrogen peroxide was residual easily, discharge dangerous active oxygen in storage sometimes.
The concentration of the hydrogen peroxide in the aquae hydrogenii dioxidi is not particularly limited, and considers from the easy to handle viewpoint, is preferably in the scope of about 3～about 40 quality %.
In addition, the pertitanic acid aqueous solution (a
1) usually can by with water-disintegrable titanium compound (T) in about 1～about 70 ℃ scope, under agitation mix with aquae hydrogenii dioxidi and prepared in about 10 minutes～about 20 hours.During mixing, can add for example water-soluble solvents such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether as requested, the pertitanic acid aqueous solution (a
1), except water, also can comprise water-soluble solvent.
Can infer the pertitanic acid aqueous solution (a
1) be by water-disintegrable titanium compound (T) and aquae hydrogenii dioxidi are mixed, water-disintegrable titanium compound (T) is hydrolyzed and generates the hydroxyl titanium compound, and then the direct coordination of hydrogen peroxide forms pertitanic acid on this hydroxyl titanium compound.The pertitanic acid aqueous solution (a
1) high in the stability of room temperature region, can stand prolonged preservation.
Metal finishing of the present invention is with in the composition (D), organic phosphoric acid compound as composition (B) is the storage stability of raising metal finishing with composition (D), and the corrosion proof composition of the surface treatment capsule of raising formation, for example can enumerate: the organic phospho acid that comprises the hydroxyl organic group, 1-hydroxyl methane-1 for example, the 1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid, 1-hydroxy propane-1, the 1-di 2 ethylhexyl phosphonic acid, inferior amino (amino) trimethylene phosphonic, inferior amino (amino) triethylene phosphonic acids, inferior amino (amino) Sanya propyl phosphonous acid, ethylenediamine tetramethylene phosphonic acid, ethylenediamine tetraacetic ethylidene phosphonic acids, ethylenediamine tetraacetic propylidene phosphonic acids, N, two (2-phosphonoethyl) azanols of N-, N, two (2-phosphoryl methyl) azanols of N-, the hydrolyzate of 2-hydroxyethyl phosphonic acids dimethyl ether; Phosphonic acids with carboxylic organic group, for example 2-HPAA, 2-phosphinylidyne butane-1,2, the salt of 4-tricarboxylic acid and these organic phosphoric acid compounds etc.Consider with the corrosion proof viewpoint of the surface treatment capsule of the storage stability of composition (D) and formation from improving metal finishing, as composition (B), be preferably 1-hydroxyl methane-1,1-di 2 ethylhexyl phosphonic acid and 1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid, and be preferably 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid especially.
Consider with the corrosion proof viewpoint of the surface treatment capsule of the storage stability of composition (D) and formation from improving metal finishing, with respect to titaniferous aqueous solution (A
1) in the TiO of conversion
2Amount 100 mass parts, the containing ratio of wishing composition (B) is about 1～about 400 mass parts, is preferably in the scope of about 10～about 200 mass parts.
Need to prove, in this manual, " the TiO of conversion
2Amount " or " TiO of conversion
2Concentration " be meant: based at preparation titaniferous aqueous solution (A
1) time the above-mentioned titanium compound that adds form afterwards with TiO at the tunicle that utilizes metal finishing with composition (D)
2The hypothesis that exists of form, the TiO that obtains by calculating by the titanium amount in the above-mentioned titanium compound
2Amount or TiO
2Concentration.
Use in the composition (D) in metal finishing of the present invention, (C) the condensation resultant of aminosilane (c1) and multi-silyl functional silane (c2) (below be sometimes referred to as " composition (C) ") for the solidity to corrosion of the surface treatment capsule that is used to improve formation, improve and utilize the composition that the adhesivity of filming that the painting process of back forms etc. comprises, usually by aminosilane (c1) and multi-silyl functional silane (c2) are obtained in water, alcohol, the medium hydrolysis of acidic aqueous solution and condensation.In hydrolysis, use under the situation of acid, can use for example hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid etc.
As aminosilane (c1), for example can enumerate: 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-aminopropyl methyldiethoxysilane, N-phenyl-3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyltriethoxywerene werene etc.
Multi-silyl functional silane (c 2) preferably has the structure of following general formula (I) expression.
(X
1)
3-a-b(R
1)
a(R
2)
bSi-Y-Si(R
3)
c(R
4)
d(x
2)
3-c-d ...(I)
(in the formula, R
1, R
2, R
3And R
4Represent that independently hydrogen atom or carbonatoms are 1～30 1 valency organic group, Y represents the organic group or the imino-of divalent, X
1And X
2Represent hydrolization group independently, a and b are 0,1 or 2 independently, 0≤a+b≤2 wherein, and c and d are 0,1 or 2 independently, wherein 0≤c+d≤2.)
As R
1, R
2, R
3And R
4In the organic group of 1 valency, can enumerate: alkyl such as alkyl, thiazolinyl, cycloalkyl, aryl; Bonding has the group of functional groups such as hydroxyl, epoxy group(ing), amino etc. on hydrocarbon skeleton, low alkyl groups such as special preferable methyl, ethyl.
As the organic group of the divalent among the Y, preferred carbonatoms be 2～30 and also more preferably carbonatoms be the combination of 2～12 alkylidene group, alkylene oxide group and alkylene sulfenyl and these groups.
As X
1And X
2In hydrolization group, can enumerate carbonatoms and be 1～4 alkoxyl group, preferred especially methoxyl group, oxyethyl group.In addition, a+b and c+d all are preferably 0 or 1.
Concrete example as multi-silyl functional silane (c2), for example can enumerate: two (trimethoxysilyl) methane, two (trimethoxysilyl) ethane, 1, two (triethoxysilyl) ethane of 2-, 1, two (trimethoxysilyl) ethane of 2-, two (triethoxysilyl) hexane, two (trimethoxysilyl) hexane, 1, two (triethoxysilyl) nonanes of 9-, 1, two (trimethoxysilyl) nonanes of 9-, 1, two (triethoxysilyl) octanes of 8-, two (trimethoxysilyl) amine, two (triethoxysilyl) amine, two (triethoxysilyl methyl) amine, two (triethoxysilylpropyltetrasulfide) amine etc., from improving the security on handling, the solidity to corrosion of the surface treatment capsule that forms and improve the adhering viewpoint consideration of filming that forms with the painting process that utilizes the back, be preferably 1, two (triethoxysilyl) ethane of 2-.
For composition (C), prevent that the viewpoint of gelation, the solidity to corrosion that improves the surface treatment capsule that forms and economy from considering when making, preferably by make aminosilane (c1) and multi-silyl functional silane (c2) with about 50/50～about 99/1, preferred about 70/30～about 99/1 so that the mol ratio condensation of preferred about scope of 80/20～about 95/5 generate.
In the generation of composition (C), except aminosilane (c1) and multi-silyl functional silane (c2), can also add aminosilane (c1) and multi-silyl functional silane (c2) organosilane (c3) in addition as requested, generate the composition (C) of the condensation resultant that comprises aminosilane (c1), multi-silyl functional silane (c2) and organosilane (c3).
As organosilane (c3), for example can enumerate: methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, to the styryl Trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane, the 3-r-chloropropyl trimethoxyl silane, 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.
For organosilane (c3), in order to control separating out of composition (C), can in the scope that the solvent solubility that does not make composition (C) descends, add, total molar weight with respect to aminosilane (c1) and multi-silyl functional silane (c2), be generally about 100 moles below the %, be preferably about 50 moles below the %.
, consider from the corrosion proof viewpoint that improves adhesivity of filming that forms with the painting process that utilizes the back and the surface treatment capsule that improves formation, with making up in (D) in metal finishing of the present invention with respect to titaniferous aqueous solution (A
1) in the TiO of conversion
2Amount 100 mass parts, the containing ratio of preferred component (C) is in the scope of about 1～about 400 mass parts, preferred about 5～about 200 mass parts.
Metal finishing of the present invention comprises titaniferous aqueous solution (A with composition (D)
1), composition (B) and composition (C), for metal finishing for composition (D), from the solidity to corrosion that improves the surface treatment capsule that forms, the viewpoints such as adhesivity of the filming consideration that improves and utilize the painting process formation of back, can contain water-soluble as requested or the water dispersible organic resin.As above-mentioned water-soluble or water dispersible organic resin, for example can enumerate: Resins, epoxy, acrylic resin, vibrin, PAH resin, polyvinylamine resin, polybutadiene, urethane resin, polyvinyl alcohol, ethylene-vinyl acetate resin etc.In addition, for composition (D), can comprise melamine resin, benzoguanamine resin, urea resin, (block) polyisocyanates, resol etc. for metal finishing of the present invention as water-soluble or water dispersible organic resin.
When metal finishing of the present invention comprises the above-mentioned aqueous solution or water dispersible organic resin with composition (D), consider from improving the viewpoints such as adhesivity of filming that form with the painting process that utilizes the back, with respect to titaniferous aqueous solution (A
1) 100 mass parts, its amount be preferably about 1～about 20000 mass parts, more preferably about 5～about 10000 mass parts, more preferably about 20～about 5000 mass parts, be preferably about 500～about 2500 mass parts especially.
For composition (D),, can contain the above metal ion of divalents such as Al, Ca, V, Mn, Co, Fe, Cu, Zn, Zr, Nb, Mo, Ta, W as requested for metal finishing of the present invention in order to improve the acid resistance of filming, alkali resistance etc.
And metal finishing of the present invention can contain alkaline neutralisers such as ammonia, organic basic compound, alkali metal hydroxide, alkaline earth metal hydroxides as requested with composition (D).As above-mentioned organic basic compound, for example can enumerate: thanomin, triethylamine, and as alkali metal hydroxide, for example can enumerate: lithium hydroxide, sodium hydroxide, potassium hydroxide etc.
And then metal finishing of the present invention can contain various additives as requested with composition (D).As above-mentioned additive, for example can enumerate: thickening material, anti-microbial inoculum, rust-preventive agent, titanium oxide sol, titanium dioxide powder, filler pigment, rust-stabilising pigment, tinting pigment, tensio-active agent etc.As above-mentioned rust-preventive agent, for example can enumerate: tannic acid, phytic acid, benzotriazole, ammonium meta-vanadate, zirconium carbonate ammonium etc.As above-mentioned filler pigment, for example can enumerate: mica, talcum, silicon-dioxide, fine silica powder, barium oxide, clay etc.
Metal finishing of the present invention is not particularly limited with the manufacture method of composition (D), and for example, metal finishing of the present invention can be by mixing titaniferous aqueous solution (A with composition (D)
1), composition (B) and composition (C) and other composition as requested, adjust concentration so that its be preferably about 0.1～about 50 quality %, more preferably about 0.5～about 40 quality % make.
Need to prove that in this manual, metal finishing is meant the TiO of conversion with the concentration of composition (D)
2The relative metal finishing of amount of solids component of amount, composition (B) with the total amount of the solids component of composition (C) with the ratio of the total amount of composition (D).
Metal base with surperficial tunicle of the present invention has the surface treatment capsule that is formed with composition (D) by metal finishing.Particularly, have above-mentioned surface treatment capsule metal base can by with metal finishing of the present invention with composition (D) clad metal base material, the metal base that coats with composition (D) with metal finishing carried out drying form.
As above-mentioned metal base, so long as metal just is not particularly limited, for example can enumerate: the alloy of iron, copper, aluminium, tin, zinc and these metals and utilize above-mentioned metal and the steel of alloy plating and utilize above-mentioned metal and the goods of alloy evaporation etc., for the corrosion proof raising effect of the surface treatment capsule that makes formation is remarkable, preferably utilize the steel of zinc or zinc alloy plating, particularly steel plate galvanized or galvanized alloy steel plate.
In this manual, steel comprise piece, forming composition, board-like material, club-shaped material of iron and iron containing alloy etc., and steel plate is meant the board-like material of iron and iron containing alloy.
With composition (D), can on above-mentioned metal base, utilize known treatment process, for example dip coated, injection coating, roll coating etc. to be coated with for metal finishing.
Generally, the metal base that coats with composition (D) with metal finishing is under about 60～about 250 ℃ condition dry about 2 seconds～about 30 seconds in the top temperature of metal base, thereby can form the metal base with surface treatment capsule.
Cross when thin when above-mentioned surface treatment capsule, performances such as solidity to corrosion, water tolerance reduce, and on the other hand, when blocked up, can break, problem such as processibility reduction, therefore, preferably have about 0.001～about 10g/m
2The basic weight (basis weight) of scope, and, more preferably have about 0.05～about 3g/m
2The basic weight of scope.
For the metal base with surface treatment capsule of the present invention, use in the purposes that has the surface treatment plates now with, jar usefulness, pre-coated steel plate etc. with, automobile with, household electrical appliances at building materials, can use, as requested painting bottom coating coating, last coated coating etc. with being not particularly limited.Above-mentioned bottom coating, go up the coating process of coated coating etc., can wait selected, for example can enumerate: spray coating, hairbrush coating, electrophoresis coating, roll coating, the curtain formula coating etc. of flowing according to the shape of purposes, coated article.Also stacked film replacement coating on the metal base of surface treatment capsule can be had.
For metal base, can form and be coated with rete by being coated with present known coating, or can between it, form organic resin-coated layer by the clamping bond layer with above-mentioned surface treatment capsule.As above-mentioned present known coating, be not particularly limited, for example can enumerate: organic solvent diluting type coating, water-borne coatings, powder coating etc.
＜metal finishing composition (E) 〉
Use in the composition (E), in metal finishing of the present invention as the peroxide vanadic acid aqueous solution (A of composition (A)
2) can make by vanadium compound and aquae hydrogenii dioxidi are reacted easily.
As above-mentioned vanadium compound, for example can enumerate: vanadium oxides such as three vanadium oxides, vanadium pentoxide; Halo such as vanadium oxydichloride, vanadylic chloride vanadium oxide; Halogenation vanadium such as vanadium trichloride; Ammonium meta-vanadate, sodium metavanadate, sodium vanadate, vanadylic sulfate, sodium pyrovanadate etc. are considered from viewpoints such as easy manufacturings, preferred vanadium pentoxide and ammonium meta-vanadate.
For with above-mentioned vanadium compound and aquae hydrogenii dioxidi blended ratio, be preferably with respect to vanadium compound 100 mass parts, hydrogen peroxide is the ratio of about 10～about 5000 mass parts.
In addition, generally, in aquae hydrogenii dioxidi, add above-mentioned vanadium compound, keep or heated about 15～about 120 minutes at about 20～about 100 ℃, thereby generate the peroxide vanadic acid aqueous solution (A
2).
Metal finishing is not particularly limited with the concentration of the vanadium in the composition (E), changes according to embodiment, for example, is preferably about 0.01～about 100g/L, and more preferably about 0.1～about 30g/L.When the concentration of vanadium is lower than 0.01g/L, there is the inadequate tendency of solidity to corrosion of the surface treatment capsule that forms, when surpassing about 100g/L, there be the tendency of metal finishing with the storage stability difference of composition (E).
Need to prove that in this manual, " concentration of vanadium " or " amount of vanadium " is meant the peroxide vanadic acid aqueous solution (A
2) in the concentration or the amount of vanadium atom, for example, at the preparation peroxide vanadic acid aqueous solution (A
2) time, can calculate by the amount of the vanadium compound that is used as raw material.
Use in the composition (E) in metal finishing of the present invention, organic phosphoric acid compound as composition (B) is the storage stability of raising metal finishing with composition (E), and the corrosion proof composition of the surface treatment capsule of raising formation, can enumerate the organic phosphoric acid compound of example in the part of metal finishing usefulness composition (D), consider from the corrosion proof viewpoint of the surface treatment capsule that improves storage stability and formation, the organic phospho acid that preferably comprises the hydroxyl organic group, more preferably 1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl methane-1, the 1-di 2 ethylhexyl phosphonic acid.
Because the poor stability of composition (A) in water, therefore, preferred added ingredients (B) immediately after making the peroxide vanadic acid.
Consider from the viewpoint of storage stability, with respect to the peroxide vanadic acid aqueous solution (A
2) in amount 100 mass parts of vanadium, the containing ratio of composition (B) is preferably about 1～about 400 mass parts, more preferably about 5～about 300 mass parts, and more preferably about 10～about 200 mass parts.
Use in the composition (E) in metal finishing of the present invention, the condensation resultant (C) of aminosilane (c1) and multi-silyl functional silane (c2) is the composition that comprises for the solidity to corrosion that improves adhesivity of filming that forms with the painting process that utilizes the back or the surface treatment capsule that improves formation, for metal finishing of the present invention for composition (E), as composition (C), comprise aminosilane (c1) and multi-silyl functional silane (c2), can be included in the material of enumerating in the part of metal finishing with composition (D).
Metal finishing of the present invention with composition (E) in, from improve the adhesivity of filming that forms with the painting process that utilizes the back, and the corrosion proof viewpoint that improves the surface treatment capsule that forms consider, with respect to the peroxide vanadic acid aqueous solution (A
2) in amount 100 mass parts of vanadium, the containing ratio of composition (C) is preferably about 1～about 400 mass parts, and in the scope of more preferably about 5～about 200 mass parts.
In the generation of composition (C), except aminosilane (c1) and multi-silyl functional silane (c2), can also add aminosilane (c1) and multi-silyl functional silane (c2) organosilane (c3) in addition as requested, generate the composition (C) of the condensation resultant that comprises aminosilane (c1), multi-silyl functional silane (c2) and organosilane (c3).
For organosilane (c3), in order to control separating out of composition (C), can in the scope that the solvent solubility that does not make composition (C) reduces, add,, for composition (E), can comprise and organosilane (c3) the identical organosilane (c3) of metal finishing with the ratio of in the part of metal finishing, putting down in writing as requested for metal finishing of the present invention with record in the composition (D) with composition (D).
From the solidity to corrosion of the surface treatment capsule that improve to form, improve the adhering viewpoint of filming that forms with the painting process that utilizes the back and consider, metal finishing of the present invention with composition (E) can comprise as requested with metal finishing with middle put down in writing water-soluble of composition (D) or water-soluble or water dispersible organic resin that the water dispersible organic resin is identical.
When metallic surface of the present invention comprises above-mentioned water-soluble or water dispersible organic resin with composition (E), consider from improving the adhering viewpoint of filming that forms with the painting process that utilizes the back, with respect to the peroxide vanadic acid aqueous solution (A
2) 100 mass parts, its amount is preferably about 1～about 20000 mass parts, more preferably about 5～about 10000 mass parts, and more preferably about 20～about 5000 mass parts, and be preferably about 500～about 2500 mass parts especially.
Metal finishing of the present invention can comprise metallic compounds such as vanadic acid compound beyond the peroxide vanadic acid, Zirconium tetrafluoride compound, zirconium carbonate compound, titanium fluoride compound as requested with composition (E).
As above-mentioned vanadic acid compound, for example can enumerate: partially alum acid lithium, potassium metavanadate, sodium vanadate, alum acid ammonium, anhydrous vanadic acid etc. partially partially, consider preferred ammonium meta-vanadate from the viewpoints such as solidity to corrosion of the surface treatment capsule that forms.
As above-mentioned Zirconium tetrafluoride compound, for example can enumerate the salt of zirconic acid hydrofluoro (zirconium hydrofluoride) and zirconic acid hydrofluoro etc., for example sodium salt, sylvite, lithium salts, ammonium salt etc. are considered preferred zirconic acid hydrofluoro ammonium and zirconic acid hydrofluoro from the viewpoints such as solidity to corrosion of the surface treatment capsule that forms.
As above-mentioned zirconium carbonate compound, for example can enumerate the sodium salt, sylvite, lithium salts, ammonium salt of zirconium carbonate etc., consider preferred zirconium carbonate ammonium from the viewpoints such as solidity to corrosion of the surface treatment capsule that forms.
As above-mentioned titanium fluoride compound, for example can enumerate the sodium salt, sylvite, lithium salts, ammonium salt of fluotitanic acid (titanium hydrofluoride) etc., consider preferred fluotitanic acid ammonium from the viewpoints such as solidity to corrosion of the surface treatment capsule that forms.
Consider that from the viewpoints such as solidity to corrosion of the surface treatment capsule that forms metal finishing of the present invention can comprise above-mentioned metallic compound as requested with composition (E), with respect to the peroxide vanadic acid aqueous solution (A
2) in amount 100 mass parts of vanadium, the amount of above-mentioned metallic compound be preferably about 2000 mass parts following, more preferably about 1～about 2000 mass parts, more preferably about 10～about 1500 mass parts, be preferably about 20～about 800 mass parts and most preferably be the scope of about 50～about 300 mass parts especially.
Metal finishing of the present invention can comprise organic fine particles and/or inorganic particles as requested with composition (E).By comprising above-mentioned particulate, therefore the rainbow spot (interference color) that the transparency that can suppress to film descends, is easy to generate in film, can be preferred for paying attention to the purposes of outward appearance to metal finishing of the present invention with composition (E).
For the particle diameter of above-mentioned particulate, consider preferably have the interior median size of scope of about 3～about 1000nm, particularly about 3～about 500nm from the corrosion proof viewpoint of the surface treatment capsule of the sedimentation stability of particle and formation.
Need to prove that in this manual, " median size " is meant that the aggregate-value by size distribution (quality) shows 50% the defined median particle diameter of particle diameter (D50).
As above-mentioned organic fine particles, for example can enumerate: particulates such as vinylformic acid, urethane, nylon, polyoxyethylene glycol.In addition,, for example can enumerate as above-mentioned inorganic particles: particulates such as silicon-dioxide, titanium dioxide, barium sulfate, lime carbonate, consider preferred silicon-dioxide, titanium dioxide, barium sulfate etc. from viewpoints such as costs.
Consider from the viewpoints such as solidity to corrosion of the surface treatment capsule that forms, metal finishing of the present invention with composition (E) can be preferably below about 30 quality % in the solids component conversion, more preferably the scope of about 1～about 30 quality % and more preferably about 1～about 20 quality % contains above-mentioned organic fine particles and/or inorganic particles.
And then metal finishing of the present invention can comprise heavy metal compound beyond the etching agents such as inorganic phosphate compound, etching acid, composition of the present invention, thickening material, tensio-active agent, lubricated imparting agent (polyethylene wax, fluorine are wax, carnauba wax), rust-preventive agent, tinting pigment, filler pigment, rust-stabilising pigment, dyestuff etc. as requested with composition (E).
As above-mentioned inorganic phosphate compound, for example can enumerate: ortho-phosphoric acid, metaphosphoric acid, phosphorous acid, metaphosphorous acid, Hypophosporous Acid, 50, ortho phosphorous acid, tetra-sodium, tripolyphosphate, four phosphoric acid, six phosphoric acid, three metaphosphoric acids, pyrophosphorous acid and phosphoric acid derivatives, and and the salt of basic cpd and these combination etc.As above-mentioned basic cpd, for example can enumerate organic basic compound or the inorganic alkaline compound that comprises lithium, sodium, potassium, ammonium etc.As the inorganic phosphate compound, be preferably and have water miscible inorganic phosphate compound.
As above-mentioned heavy metal compound, for example can enumerate the salt of metals such as Co, Fe, Ni, In; Molybdic acid, wolframic acid and these salt.
As above-mentioned rust-preventive agent, for example can enumerate; Polyphenol compounds such as Weibull; The compound of sulfur atom-containing such as thio-alcohol, thiono base class; The compound of nitrogen atoms such as triazole species; The compound of thiazoles, thiadiazole, thiurams sulfur atom-containing such as (thiurams) and nitrogen-atoms; Calcium ion-exchanged silicon-dioxide etc. contains the compound of calcium atom; Boric acid, metaboric acid etc.
In addition, with composition (E), in order to dilute, can contain hydrophilic solvent, for example methyl alcohol, ethanol, Virahol, glycol solvent, propandiols solvent etc. for metal finishing of the present invention.
Metal finishing of the present invention is not particularly limited with the manufacture method of composition (E), for example, metal finishing of the present invention can be passed through mixing element (A)～composition (C) and other composition as requested with composition (E), adjusts concentration and makes to be about 0.1～about 50 quality % (preferred about 0.5～about 40 quality %).
Need to prove, in this manual, metal finishing is meant that with the concentration of composition (E) the relative metal finishing with the total amount of the amount of the solids component of composition (C) of amount of solids component of amount, composition (B) of vanadium is with the ratio of the total amount of composition (E).
Metal base with surface treatment capsule of the present invention has the surface treatment capsule that is obtained with composition (E) by metal finishing.Particularly, have above-mentioned surface treatment capsule metal base can by with metal finishing of the present invention with composition (E) clad metal base material, the metal base that coats with composition for treating (E) carried out drying form.
As above-mentioned metal base, can enumerate the metal base of in the part of metal finishing, putting down in writing with composition (D).
, can on above-mentioned metal base, be coated with composition (E) for surface treatment with known treatment process, for example dip coated, injection coating, roll coating etc.
Generally, the metal base that has coated with composition (E) with metal finishing is under about 60～about 250 ℃ condition dry about 2 seconds～about 30 seconds in the top temperature of metal base, thereby can form the metal base with surface treatment capsule.
Cross when thin when above-mentioned surface treatment capsule, performances such as solidity to corrosion, water tolerance reduce, and on the other hand, when blocked up, can break, problem such as processibility reduction, therefore, preferably have about 0.001～about 10g/m
2The basic weight of scope, and, more preferably have about 0.05～about 3g/m
2The basic weight of scope.
For the metal base with surface treatment capsule of the present invention, use in the purposes that has the surface treatment plates now with, jar usefulness, pre-coated steel plate etc. with, automobile with, household electrical appliances at building materials, can use, as requested painting bottom coating coating, last coated coating etc. with being not particularly limited.Above-mentioned bottom coating, go up the coating process of coated coating etc., can wait selected, for example can enumerate: spray coating, hairbrush coating, electrophoresis coating, roll coating, the curtain formula coating etc. of flowing according to the shape of purposes, coated article.Also can replace coating in metal base upper laminate film with surface treatment capsule.
For metal base, can form and be coated with rete by being coated with present known coating, or can between it, form organic resin-coated layer by the clamping bond layer with above-mentioned surface treatment capsule.As above-mentioned present known coating, be not particularly limited, for example can enumerate: organic solvent diluting type coating, water-borne coatings, powder coating etc.
Embodiment
Below, enumerate embodiment the present invention is described in further detail.Need to prove that " part " reaches " % " and represents that respectively " mass parts " reaches " quality % ".
＜metal finishing the example of composition (D) 〉
[titaniferous aqueous solution (A
1) preparation]
[preparation example D-1]
In the mixture of 100 parts of 10 parts of 30% aquae hydrogenii dioxidis and deionized waters, while under 20 ℃, with stirring the mixture that drips 10 parts of 10 parts of tetraisopropoxy titaniums and Virahols in 1 hour.Then, 25 ℃ of slakings 2 hours, obtain zona pellucida, little yellowy and also have slightly viscosity as the pertitanic acid aqueous solution (a
1) titaniferous aqueous solution (A
1-1).Titaniferous aqueous solution (A
1The TiO of the conversion-1)
2Concentration be 2%.
[preparation example D-2]
Except four titanium n-butoxide of using equivalent replaced tetraisopropoxy titanium, D-1 operated equally with preparation example, obtains titaniferous aqueous solution (A
1-2).Titaniferous aqueous solution (A
1The TiO of the conversion-2)
2Concentration be 2%.
[preparation example D-3]
Except the trimer of the tetraisopropoxy titanium that uses equivalent replaced tetraisopropoxy titanium, D-1 operated equally with preparation example, obtains titaniferous aqueous solution (A
1-3).Titaniferous aqueous solution (A
1The TiO of the conversion-3)
2Concentration be 2%.
[manufacturing of composition (C)]
[Production Example D-1]
In the round-bottomed flask of the 1L that reflux exchanger, thermometer, nitrogen ingress pipe and agitator are installed, pack into Virahol 200g and deionized water 200g begin to stir.In gas phase, be blown into nitrogen, while stir disposable input 3-TSL 8330 90g and two (triethoxysilyl) ethane 10g.Stirred at normal temperatures 1 hour, 60 ℃ of down reactions 6 hours, remove cut after, on one side with propylene glycol monomethyl ether displacement Virahol and water, being warming up to boiling point reaches 120 ℃ on one side.After being cooled to 60 ℃, concentrate, obtain condensation resultant (C as composition (C) with underpressure distillation
1) solution 120g.Condensation resultant (C
1) the solids component of solution be 40%, be water white heavy-gravity liquid.Need to prove that above-mentioned solids component is for passing through condensation resultant (C
1) solution 130 ℃ of down heating 1 hour and values of trying to achieve.
[Production Example D-2～D-12]
Except making raw material consists of shown in the table 1, D-1 operates equally with Production Example, obtains the condensation resultant (C as composition (C)
2)～(C
8) solution and the silane condensation resultant (C '
1)～(C '
4) solution.
[embodiment D-1～D-8 and Comparative Example D-1～D-4]
[metal finishing preparation of compositions]
According to the cooperation shown in the table 2, preparation metal finishing composition.Utilize deionized water prepare each metal finishing with composition so that concentration is 5%.
Need to prove that in table 2, composition (B) is the 1-hydroxyl ethane-1 of solids component 60%, the 1-di 2 ethylhexyl phosphonic acid.
[surface treatment]
As metal base, (the plating basic weight of EG steel plate, the manufacturing of Japanese Testpanel company, 70mm * 150mm * 0.8mm, single face is 20g/m with commercially available electrogalvanizing steel plate
2) (below be sometimes referred to as " EG steel plate ") and 5000 be that (Japanese Testpanel company makes aluminium, 70mm * 150mm * 0.8mm) (below be sometimes referred to as " 5000AL ") carries out surface treatment by operation shown below.
(1), then, washes with tap water and to handle 30 seconds by above-mentioned metal base dipping in being adjusted into 40 ℃ commercially available degreasing fluid was carried out degreasing in 2 minutes.
(2) on the metal base after the washing, the metal finishing composition of coating embodiment D-1～D-8 and Comparative Example D-1～D-4, it was 0.5g/m that formation has basic weight so that the top temperature of metal base reaches 150 ℃ in dry 20 seconds
2The metal base of surface treatment capsule.
[making of test board (1)]
On the metal base of the surface treatment capsule that the metal finishing that has by embodiment D-1～D-8 and Comparative Example D-1～D-4 forms with composition, " MAGICRON 1000# " (Northwest paint company manufacturing, vinylformic acid/melamine resin are organic solvent diluting type coating) carried out the air spray coating so that dry film thickness is 30 μ m, 160 ℃ of dryings 30 minutes, make test board.The test board that obtains according to following evaluation assessment evaluation.The results are shown in table 3.
[making of test board (2)]
On the metal base of the surface treatment capsule that the metal finishing that has by embodiment D-1～D-8 and Comparative Example D-1～D-4 forms with composition, " AMYLAC 1000# " (Northwest paint company manufacturing, alkyd/melamine resin are organic solvent diluting type coating) carried out the air spray coating so that dry film thickness is 30 μ m, 130 ℃ of dryings 30 minutes, make test board.Estimate according to following evaluation assessment.The result is shown in table 3 simultaneously.
[making of test board (3)]
On the metal base of the surface treatment capsule that the metal finishing that has by embodiment D-1～D-8 and Comparative Example D-1～D-4 forms with composition, " ASIME " (Northwest paint company manufacturing, polyester/melamine resin are organic solvent diluting type coating) carried out the air spray coating so that dry film thickness is 30 μ m, 140 ℃ of dryings 30 minutes, make test board.Estimate according to following evaluation assessment.The result is shown in table 3 simultaneously.
[Comparative Example D-5]
Commercially available to be metal finishing with zinc phosphate carried out the surface-treated steel plate (base material: SPCC-SD, Japanese Testpanel company make) with composition except using, operate equally with embodiment D-1, make test board (1)～(3), estimate according to following evaluation assessment, the result is shown in table 3 simultaneously.
[Comparative Example D-6]
Commercially available carried out the surface-treated aluminium sheet (base material: 5000 is that aluminium, Japanese Testpanel company make) with composition except using with the chromate metal finishing, operate equally with embodiment D-1, make test board (1)～(3), estimate according to following evaluation assessment, the result is shown in table 3 simultaneously.
[evaluation assessment]
(* 1) solidity to corrosion 1: for the metal base with the surface treatment capsule that forms with composition by the metal finishing of embodiment D-1～D-8 and Comparative Example D-1～D-4 and with Comparative Example D-5 with zinc phosphate be metal finishing with composition carried out the surface-treated steel plate and with Comparative Example D-6 carried out the surface-treated aluminium sheet with the chromate metal finishing with composition, the brine spray corrosion test of implementing 120 hours is (according to SST:JIS Z-2371.35 ℃ of brine temps), the production that becomes rusty according to following benchmark visual assessment.
VG (Very Good): be lower than 5% of area and get rusty
G (Good): area more than 5% and be lower than 20% scope and get rusty
F (Fair): area more than 20% and be lower than 30% scope and get rusty
P (Poor): the scope more than 30% at area is got rusty
(* 2) solidity to corrosion 2: on test board (1)～(3) of embodiment D-1～D-8 and Comparative Example D-1～D-6 making, so that reach the damage that the mode of metal base is given the X font deeply, the brine spray corrosion test of implementing 240 hours is (according to SST:JIS Z-2371 with cutters.35 ℃ of brine temps), then, paste scotch tape, observe the state of peeling off of filming of damaged portion when peeling off scotch tape fast, estimate with following benchmark in damaged portion.
VG (Very Good): film and do not peel off
G (Good): the width of peeling off of filming is lower than 3mm
F (Fair): the width of peeling off of filming is that 3mm is above and be lower than 5mm
P (Poor): the width of peeling off of filming is more than the 5mm
(* 3) adhesivity: will be immersed in the warm water (40 ℃) 240 hours by test board (1)～(3) that embodiment D-1～D-8 and Comparative Example D-1～D-6 makes.After pulling out, draw lattice adhesive tape test method according to JISK-54008.5.2 (1990) immediately, in the film coated surface of test board with cutters so that the mode that reaches metal base deeply marks straight each parallel straight line of 11 in length and breadth with the interval of 1mm, make the grid of 100 1mm * 1mm, on above-mentioned grid, paste scotch tape, then, peel off scotch tape fast, observe the extent of exfoliation of grid, estimate according to following standard.
VG (Very Good): do not have grid to peel off
G (Good): the grid of peeling off is below 5
F (Fair): the grid of peeling off is 6～10
P (Poor): the grid of peeling off is more than 11
＜metal finishing the example of composition (E) 〉
[the peroxide vanadic acid aqueous solution (A
2) preparation]
[preparation example E-1]
Deionized water 100 mass parts are put into container, add 30% aquae hydrogenii dioxidi, 30 mass parts in said vesse, fully stir, adjusting the liquid temperature is 25 ℃.Then, in said vesse, add ammonium meta-vanadate 15 mass parts, stirred 30 minutes, thereby obtain the peroxide vanadic acid aqueous solution (A
2-1).The peroxide vanadic acid aqueous solution (A
2The concentration of the vanadium-1) converts according to the amount of the ammonium meta-vanadate that adds, and is about 4.5 quality %.
[manufacturing of composition (C)]
[Production Example E-1～E-12]
Operate equally with the Production Example D-1 in the example of composition (D)～D-12 with metal finishing, obtain condensation resultant (C as composition (C)
1)～(C
8) solution and the silane condensation resultant (C '
1)～(C '
4) solution.Condensation resultant (C
1)～(C
8) solution and the condensation resultant (C '
1)～(C '
4) the cooperation of solution as shown in table 1.
[embodiment E-1～E-8 and Comparative Example E-1～E-4]
[metal finishing preparation of compositions]
According to the cooperation shown in the table 4, preparation metal finishing composition.To make concentration with composition be 5% to prepare each metal finishing to utilize deionized water.Need to prove that in table 4, composition (B) is the 1-hydroxyl ethane-1 of solids component 60%, the 1-di 2 ethylhexyl phosphonic acid.
Table 4
1)The amount of expression vanadium
2)The amount of expression solids component
[surface treatment]
As metal base, with commercially available electrogalvanizing steel plate (the plating basic weight 20g/m of EG steel plate, the manufacturing of Japanese Testpanel company, 70mm * 150mm * 0.8mm, single face
2) (below be sometimes referred to as " EG steel plate ") and 5000 be that (Japanese Testpanel company makes aluminium, 70mm * 150mm * 0.8mm) (below be sometimes referred to as " 5000AL ") equally carries out surface treatment with composition and metal finishing with the example of composition (D) with the metal finishing of embodiment E-1～E-8 and Comparative Example E-1～E-4.
[making of test board (1)～(3)]
Make test board (1)～(3) with metal finishing equally with the example of composition (D), estimate according to following evaluation assessment.The results are shown in table 5.
[Comparative Example E-5]
Commercially available to be metal finishing with zinc phosphate carried out the surface-treated steel plate (base material: SPCC-SD, Japanese Testpanel company make) with composition except using, operate equally with the Comparative Example D-5 of the case history of composition (D) with metal finishing, make test board (1)～(3), estimate according to following evaluation assessment, the result is shown in table 5 simultaneously.
[Comparative Example E-6]
Use and commercially available carried out surface-treated aluminium sheet (base material: 5000 is that aluminium, Japanese Testpanel company make) with composition with the chromate metal finishing, operate equally with the Comparative Example D-6 of the case history of composition (D) with metal finishing, make test board (1)～(3), estimate according to following evaluation assessment, the result is shown in table 5 simultaneously.
[evaluation assessment]
Identical with metal finishing with solidity to corrosion 1, solidity to corrosion 2 and the adhering evaluation assessment of the case history of composition (D).
Claims (9)
1. metal finishing composition is characterized in that comprising following composition (A)～composition (C): (A) at least a titanium compound and the aquae hydrogenii dioxidi in the group that constitutes of the condenses of condenses, titanium hydroxide and the titanium hydroxide by will being selected from water-disintegrable titanium compound, water-disintegrable titanium compound mixes the titaniferous aqueous solution (A that obtains
1) or the peroxide vanadic acid aqueous solution (A
2); (B) organic phosphoric acid compound; And (C) the condensation resultant of aminosilane (c1) and multi-silyl functional silane (c2).
2. metal finishing composition as claimed in claim 1, wherein, described composition (B) is for having the organic phospho acid of hydroxyl organic group.
3. metal surface treating composition as claimed in claim 1 or 2, wherein, described composition (B) is a 1-hydroxyl methane-1,1-di 2 ethylhexyl phosphonic acid and/or 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid.
4. as each described metal finishing composition in the claim 1～3, wherein, with respect to titaniferous aqueous solution (A
1) in the TiO of conversion
2Amount 100 mass parts or the peroxide vanadic acid aqueous solution (A
2) in amount 100 mass parts of vanadium, the containing ratio of composition (B) is in the scope of 1～400 mass parts.
5. as each described metal finishing composition in the claim 1～4, wherein, multi-silyl functional silane (c2) is by following general formula (I) expression,
(X
1)
3-a-b(R
1)
a(R
2)
bSi-Y-Si(R
3)
c(R
4)
d(x
2)
3-c-d ...(I)
In the formula, R
1, R
2, R
3And R
4Represent that independently hydrogen atom or carbonatoms are 1～30 1 valency organic group, Y represents the organic group or the imino-of divalent, X
1And X
2Represent hydrolization group independently, a and b are 0,1 or 2 independently, 0≤a+b≤2 wherein, and c and d are 0,1 or 2 independently, wherein 0≤c+d≤2.
6. as each described metal finishing composition in the claim 1～5, wherein, composition (C) is by aminosilane (c1) and multi-silyl functional silane (c2) are generated with 50/50～99/1 mol ratio condensation.
7. as each described metal finishing composition in the claim 1～6, wherein, with respect to titaniferous aqueous solution (A
1) in the TiO of conversion
2Amount 100 mass parts or the peroxide vanadic acid aqueous solution (A
2) in amount 100 mass parts of vanadium, the containing ratio of composition (C) is in the scope of 1～400 mass parts.
8. the metal base that has surface treatment capsule, its by with each described metal finishing in the claim 1～7 with composition clad metal base material, then carry out drying and form.
9. the metal base with surface treatment capsule as claimed in claim 8, wherein, the basic weight of described surface treatment capsule is at 0.001～10g/m
2Scope in.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-276929 | 2009-12-04 | ||
| JP2009-276928 | 2009-12-04 | ||
| JP2009276929 | 2009-12-04 | ||
| JP2009276928 | 2009-12-04 |
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|---|---|
| CN102086518A true CN102086518A (en) | 2011-06-08 |
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|---|---|---|---|
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| TW (1) | TW201129717A (en) |
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| CN103540920A (en) * | 2013-09-27 | 2014-01-29 | 宁波英科特精工机械股份有限公司 | Metal surface anti-corrosion treatment agent |
| CN103820794A (en) * | 2014-02-24 | 2014-05-28 | 深圳市宝骏环保涂料有限公司 | Aqueous existing rust removal and rust prevention agent and production method thereof |
| CN104233243A (en) * | 2013-06-10 | 2014-12-24 | 关西涂料株式会社 | Aqueous metal surface treatment agent |
| TWI554647B (en) * | 2011-07-15 | 2016-10-21 | Nihon Parkerizing | An aqueous metal surface treatment agent and a metal material treated with the treatment agent |
| CN106521473A (en) * | 2016-11-18 | 2017-03-22 | 安徽工业大学 | Copper and copper alloy surface anticorrosion liquid and preparation method thereof |
| CN110923687A (en) * | 2019-12-25 | 2020-03-27 | 无锡伊佩克科技有限公司 | Chromium-free passivator and preparation method thereof |
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