CN1179800C - Metallic plate material having excellent propoerties such as: corrosion-resistant, coating, anti-finger printing and processing, and mfg. process therefor - Google Patents
Metallic plate material having excellent propoerties such as: corrosion-resistant, coating, anti-finger printing and processing, and mfg. process therefor Download PDFInfo
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- CN1179800C CN1179800C CNB011109076A CN01110907A CN1179800C CN 1179800 C CN1179800 C CN 1179800C CN B011109076 A CNB011109076 A CN B011109076A CN 01110907 A CN01110907 A CN 01110907A CN 1179800 C CN1179800 C CN 1179800C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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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
- 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
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
Abstract
A metal article whose surface is coated with a coating composition composed of (A) a silane coupling agent component, (B) a polymer component having a specific chemical structure, and (C) a wax component provides a chromium-free surface treated metal material with superior corrosion resistance, paintability, fingerprint resistance, and workability.
Description
Technical field
The present invention is relevant a kind of invention that household electrical appliances, building material made etc. have the metallic sheet material of excellent corrosion resistance, coating, anti-finger printing and processibility that can be used for.
Background technology
Generally speaking, steel plate, Aludip, contain metallic sheet materials such as zinc steel plating plate or aluminium sheet and be widely used more in fields such as automobile, building materials and electrical home appliances.But, zinc or aluminium are many in atmosphere corrosion can to take place and generation corrosion product (i.e. " white rust "), except that can cause the metallic substance outward appearance not good, also can produce detrimentally affect to coating, when making goods through various steps again according to various different demands in addition, it is attached to it that often the process of handling because of operator makes greasy dirt such as fingerprint, and can exist cause the significantly reduced doubt of commodity value or, add the needs of removing after the wet goods moulding that needs man-hour to use in carrying out punching press etc. as lubricant.
So when going up the erosion resistance, coating, fingerprint of note metal material surface and processibility for improvement, the metallic sheet material that following method makes is used for punch process, described metallic sheet material generally carries out after chromic acid handles as the treatment solution of main body more than using on the metal material surface with chromic acid, dichromic acid or its esters, is had and contains not the metallic sheet material of coating agent gained of lubricated composition that can form the wax etc. of processibility because of wet goods in the polyolefin-based resins of carboxyl or the coated with resin coated with containing colloided silica and wax etc. thereon again.
But, surging gradually because of environmental consciousness in recent years, and the people is known from experience exert an adverse impact because of handling 6 valency chromium that the employed chromic acid treatment solution of metal material surface contained, so generally avoid using the chromic acid processing more.In addition, the waste water that contains 6 valency chromium need be handled especially according to the water prevention and cure of pollution law regulation, and this also has the doubt that causes whole cost to go up for all.Again, carry out the metallic substance that chromic acid is handled, will form the industrial waste that contains chromium and have the shortcoming of can't recirculation using, and can form society and go up great problem.
Surface preparation beyond chromic acid is handled, known general use contains the Weibull of multi-phenol carboxylic acid as surface treatment agent.When using the tannin aqueous acid that metallic substance is handled,, can form obstruct for the immersion of corrosive deposit, and the erosion resistance of note metallic substance promotes upwards before making because of the formed protection tunicle of the reaction of Weibull and metallic substance.
But, in recent years,, general many to require tunicle itself should have high corrosion resistance along with the demand of high-qualityization of goods.But Weibull is independent or also neither fully with its erosion resistance of tunicle of inorganic components gained, still belongs to the very thing of difficulty so will make it reach practicability at present.
Again, improve the treatment process of the erosion resistance of metallic substance, for example special opening promptly has the method that the aqueous solution that uses water-dispersible silica and Synolac and trialkoxy silane compound to constitute is coated the metallic surface that discloses among the clear 53-121034.
Again, the aqueous solution that uses the hydroxy pyrone compound to constitute, to give the surface treatment method that the metallic substance erosion resistance is a purpose, and the method that the water-soluble or aqueous dispersion polymers that uses the hydroxy styrenes compound is given erosion resistance to metallic substance then is disclosed in special public clear 57-44751 communique, opens in the flat 1-177380 communique with the spy.
But no matter any method all can't obtain the tunicle with excellent corrosion resistance of the chromic salt tunicle gained of alternative metal material surface, so in fact all fail to solve for preceding note problem.Therefore, still failing at present to obtain the Chrome-free that a kind of metallic substance with excellent corrosion resistance uses is surface treatment agent and surface treatment method.
Summary of the invention
The present invention be to solve the foregoing problems proposed invention, and is to be that surface-treated metal material is a purpose so that a kind of Chrome-free with excellent corrosion resistance, coating, anti-finger printing and processibility to be provided.
Present inventors are for solving the problem that conventional art produced, if results of the self-criticism are learnt in the surface-coated silane coupling agent composition that contains of metallic sheet material through going deep into, component of polymer with particular chemical structure, during with the composition of wax composition, can obtain having the metallic sheet material of excellent corrosion resistance, coating, anti-finger printing and processibility, and manufacture method, thereby finish the present invention.
That is, the invention provides a kind of metallic sheet material with excellent corrosion resistance, coating, anti-finger printing and processibility, it is characterized by, the metal material surface lining contains the coating composition of note composition down:
(A) by containing the silane coupling agent composition that at least 1 silane coupled compound that is selected from the reactive functional group of the amino, epoxy group(ing), vinyl, sulfydryl and the methacryloxy that contain active hydrogen constitutes more than a kind,
(B) contain the component of polymer more than a kind that mean polymerisation degree more than a kind is a monomer component shown in 2 to 50 the following note formula (1),
(wherein, with phenyl ring bonded X, for the aryl of the hydroxyalkyl of the alkyl of hydrogen atom, hydroxyl, C1 to C5, C1 to C5, C6 to C12, benzyl, benzylidene, can form the unsaturated alkyl of naphthalene nucleus or be the base shown in the note formula (2) down with preceding note phenyl ring condensation:
In the formula (2), R1 and R2 can be mutually each other hydrogen atom, hydroxyl,
The alkyl of C1 to C5 or the hydroxyalkyl of C1 to C10; In formula (1) and the formula (2), can with phenyl ring bonded Y1 and Y2, can be independent separately be hydrogen atom, or the Z base shown in time note formula (3), (4):
R3, R4, R5, R6 and R7 in preceding note formula (3) and (4) can separately be the alkyl of hydrogen atom, C1 to C10 or the hydroxyalkyl of C1 to C10, with each phenyl ring bonded X in the preceding note polymer molecule, Y1, Y2 and with X, Y1, the Y2 of other phenyl ring bond can be identical or different each other mutually, and in the preceding note polymer molecule in each phenyl ring before the replacement of note Z base to count mean value be 0.2 to 1.0) and
(C) wax composition.
Preceding note silane coupling agent composition (A) is good to the weight ratio (A)/(B) of component of polymer (B) with 1/10 to 10/1.
Preceding note silane coupling agent composition (A) preferably contains
(a) silane coupling agent that constitutes by the silane coupled compound of the amino that contains 1 above active hydrogen more than a kind with
(b) silane coupling agent that constitutes by the silane coupled compound that contains 1 above epoxy group(ing) more than a kind.
Before the contained equivalence ratio that contains epoxy group(ing) in the contained amino that contains active hydrogen and the preceding note silane coupling agent (b) in note silane coupling agent (a), be good with 3: 1～1: 3 scope.
Before the note silane coupling agent (a) and the total amount of preceding note silane coupling agent (b), being good with 1: 5～5: 1 scope to the weight ratio ((a)+(b))/(B) of preceding note component of polymer (B).
Before note wax composition (C) be good to weight ratio (C)/((A)+(B)) of the total weight of silane coupling agent composition (A) and this component of polymer (B) with 1/100～2/1 scope.
The fusing point of preceding note wax is good with 40 to 120 ℃ scope.
Below will do detailed explanation to the present invention.
The coating composition that is used for metallic sheet material of the present invention, contain, have silane coupling agent composition (A) that specific reactivity functional group's silane coupled compound more than a kind forms with, polymerization composition (B) that constitutes by the resol based polymer that contains special amino more than a kind and, wax composition (C).
Contained silane coupled compound in the silane coupling agent composition used in the present invention (A), if in 1 molecule, contain when being selected from the amino that contains active hydrogen, epoxy group(ing), vinyl, sulfydryl and methacryloxy compound as at least one of reactive functional group, then special qualification do not arranged in textural, particularly, for example can use and have down 1.～5. compound of component content of note.
1. has amino person
N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-(aminoethyl) 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane
2. has epoxy group(ing) person
3-glycidoxy (glycidoxy) propyl trimethoxy silicane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane
3. the person that has the vinyl
Vinyltriethoxysilane
4. the person that has the sulfydryl
3-sulfydryl propyl trimethoxy silicane
5. the person that has the methacryloxy
3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane
Silane coupling agent composition used in the present invention (A) preferably contains
The silane coupling agent (a) that constitutes by the silane coupled compound of the amino that contains 1 above active hydrogen more than a kind with
The silane coupling agent (b) that constitutes by the silane coupled compound that contains 1 above epoxy group(ing) more than a kind.
Again, silane coupling agent composition used in the present invention (A) is if when the silane coupling agent (a) that is made of the silane coupled compound of the amino that contains active hydrogen is constituted with the silane coupling agent (b) that contains epoxy group(ing), the contained amino that contains active hydrogen in the silane coupling agent, its equivalence ratio to epoxy group(ing) was good with 3: 1～1: 3.If surpass at 3: 1 o'clock, the film-forming properties of coating composition will worsen and erosion resistance, coating or the processibility of prepared metallic sheet material are worsened this amino that contains active hydrogen to the equivalence ratio of epoxy group(ing).Again, if be lower than at 1: 3 o'clock, coated metallic sheet material, its erosion resistance, coating, anti-finger printing or processibility will be state of saturation.
Again, component of polymer used in the present invention (B) is the oligopolymer or the polymkeric substance of polymerized unit shown in the note formula (1) before containing, and the mean polymerisation degree of formula (1) polymerized unit (following represent with n) is 2 to 50.
In the formula (1), with phenyl ring bonded X, be hydroxyl, the alkyl of C1 to C5 is methyl, ethyl, propyl group etc. for example, and the hydroxyalkyl of C1 to C5 is methylol, hydroxyethyl, hydroxypropyl etc. for example, and the aryl of C6 to C12 is phenyl, naphthyl etc. for example, benzyl, benzylidene, the unsaturated alkyl that can form naphthalene nucleus with preceding note phenyl ring condensation for example-CH=CH-CH=CH-or=CH-CH=CH-CH=, or be the base shown in the preceding note formula (2).
In the formula (2), R1 and R2 can separately be hydrogen atom, hydroxyl, and the alkyl of C1 to C10 is methyl, ethyl, propyl group etc. for example, and the hydroxyalkyl of C1 to C10 is methylol, hydroxyethyl, hydroxypropyl etc. for example.
In formula (1) and the formula (2), can with phenyl ring bonded Y1 and Y2, be hydrogen atom independently separately mutually, or the Z base shown in time note formula (3), (4).Again, R3, R4, R5, R6 and the R7 in formula (3) and (4) is separate to be alkyl for example methyl, ethyl, the propyl group etc. of C1 to C10, and the hydroxyalkyl of C1 to C5 is methylol, hydroxyethyl, hydroxypropyl etc. for example.
Can with Y2 in X, Y1 and the formula (2) in each phenyl ring bonded formula (1) in the preceding note polymer molecule, reach with other phenyl ring bonded X, Y1, Y2 can be identical or different each other mutually.Again, the mean value of the replacement number of the preceding note Z base of each phenyl ring is 0.2 to 1.0 in the preceding note polymer molecule.
The mean value of the replacement number of Z base, be in the polymer molecule all phenyl ring import the mean value of the number of Z base separately.For example in formula (1), n=10, and X is when containing phenyl ring basic in the formula (2), per 1 molecule phenyl ring number of this polymkeric substance is 20, if when importing 1 Z base separately on 10 phenyl ring in this polymkeric substance 1 molecule, it is ((1 * 10)+(0 * 10))/20=0.5 that the Z base of this polymer molecule replaces mean value.
The mean value that this Z base replaces number is lower than at 0.2 o'clock, can cause resulting polymers to the adaptation deterioration of metallic substance coating to be worsened.If surpass at 1.0 o'clock, then the wetting ability of resulting polymers will increase, and makes the erosion resistance of gained metallic sheet material insufficient again.
Shown in formula (3) and the formula (4) in the Z base, R3～R7 respectively the do for oneself alkyl of C1 to C10, the hydroxyalkyl of C1 to C10.If when this carbon number 11 is above, will the film-forming properties of formed coating composition be reduced, and make erosion resistance, coating, anti-finger printing or processibility not good.
Wax composition used in the present invention (C) does not have special qualification, is that 40～120 ℃ of persons are for good with fusing point.Use the metallic sheet material that surpasses the outer wax composition gained of this melting range, its processibility is insufficient.
Among the present invention, the lining weight on metallic sheet material surface is with 0.01～3.0g/m
2For good.This lining weighs less than 0.01g/m
2The time, will reduce erosion resistance, anti-finger printing and the processibility etc. of gained metallic sheet material.Surpass 3.0g/m again,
2The time, can cause coating, particularly adaptation deterioration.
In the employed coating composition, preceding note silane coupling agent composition (A) was good to the weight ratio (A)/(B) of preceding note water-soluble polymers composition (B) with 1: 10 to 10: 1, was more preferred from 1: 1 to 5: 1 in the manufacture method of the present invention.This weight ratio is lower than at 1: 10 o'clock, and promptly the ratio of silane coupling agent composition (A) is crossed when low, and the clinging power of itself and matrix surface will reduce, and causes the not good situation of erosion resistance, coating.Again, its ratio is if surpass at 10: 1 o'clock, when promptly the ratio of silane coupling agent composition (A) is too high, because of the film-forming properties of coating composition reduces, so the erosion resistance of gained metallic sheet material, coating are insufficient.
In the manufacture method of the present invention in the employed coating composition, before the content of note wax composition (C) special qualification is not arranged, being preferably weight ratio (C)/((A)+(B)) of the total weight of silane coupling agent composition (A) and component of polymer (B) is good with 1/100～2/1 scope.Wax composition (C) is lower than at 1/100 o'clock, and its anti-finger printing, processibility are not good, surpasses at 2/1 o'clock, because of the film-forming properties of coating composition reduces, so the erosion resistance of gained metallic sheet material, coating are insufficient.
Below will describe manufacture method of the present invention.In the manufacture method of the present invention, be that the waterborne compositions that contains coating composition that the pH value is adjusted to 2.0～6.5 scopes is coated on the metallic sheet material surface, making it be dried to dry back lining weight subsequently is 0.01～3.0g/m
2, be preferably 0.05～1.5g/m
2Degree.Type of heating is good with the metallic sheet material heat drying that will be coated with waterborne compositions.
Again, in the manufacture method of the present invention, waterborne compositions is that preceding note coating composition is with the water-based medium, water is diluted, or under undiluted, modulate, in this situation, the pH value for example can use phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, fluoro complex (wrong Off ッization thing) the pH value to be adjusted to 2.0～6.5 scope with organic acid.
The employed waterborne compositions pH of manufacture method of the present invention value adjustment mode is good to use phosphoric acid, superphosphate, fluorochemical, fluoro complex.Better pH value is 3.0～5.0 scope.The pH value is lower than at 2.0 o'clock, because of the excessive reactivity of coating composition and matrix surface in the gained waterborne compositions, so the bad situation of lining takes place easily.Again, the pH value surpasses at 6.5 o'clock, because of water-soluble polymers composition (B) itself is very easily separated out by precipitation in the waterborne compositions, and can make the lost of life of waterborne compositions.
Again, use the method on this waterborne compositions coated metal material surface that special qualification is not arranged, for example can use pickling process, spray method, and mode such as rolling method be coated with.Again, the metallic substance through coating carries out drying for good with type of heating.It is good that Heating temperature then arrives 50～180 ℃ scope with the temperature of metallic sheet material.
Again, in the manufacture method of the present invention, when waterborne compositions contacts with metallic substance, will form complex compound with water-soluble polymers composition (B), produce sedimentary situation and take place and have by the metal ion of stripping in the metallic substance.Can add the metal shadowing agent this moment in surface treatment composition.Metal shadowing agent for example EDTA, Cy-DTA, trolamine, glyconic acid, seven glyconic acids, oxalic acid, tartrate, oxysuccinic acid and organic phospho acid etc. is good.
In the employed waterborne compositions of manufacture method of the present invention, when promoting coating, desire can add tensio-active agent again.Anion surfactant, polyethylene glycol type nonionogenic tenside, polyol-based non-ionic surfactant, amine cation tensio-active agents etc. such as for example commercially available carboxylic acid type of tensio-active agent, sulfuric acid type, sulfonate type, phosphate ester salt type.
Employed metallic substance among the present invention for example can be by steel plate, steel plate galvanized, to aluminize be selected persons such as steel plate, aluminium alloy plate, stainless steel plate, copper coin.
Use the metallic sheet material of the employed waterborne compositions lining of manufacture method of the present invention can have excellent corrosion resistance, anti-finger printing, processibility etc., it is fully clear that its mechanism of action is still failed, but present inventors think that its mechanism of action should be down note mechanism.Produce etching because of the sour composition in the waterborne compositions makes the metallic surface, and the pH value at interface is risen, via the reaction of the metal ion and the water-soluble polymers composition of stripping, and in the tunicle of interface formation insoluble.The barriering effect of having been given play to through this insoluble tunicle, and improve its erosion resistance.But, if only as this moment, the adaptation of metallic substance and tunicle will be lower, so and if during with the silane coupling agent composition, can form oxyethane (ォ キ サ Application) key with metal material surface because of hydrolysis makes the functional group's (OR yl) in the silane coupling agent, in addition, another reactive functional group partly then produces reaction with the water-soluble polymers composition in the silane coupling agent, and then promotes the adaptation of metallic substance and water-soluble polymers composition and application.Again, the wax composition that contains simultaneously should be the factor that causes anti-finger printing and processibility to promote.
Embodiment
Following embodiment will make specific description to the present invention, but scope of the present invention is not subjected to any qualification of these a little embodiment.
1, test materials
Thickness of slab 0.6mm hot-dip galvanized steel sheet (GI material)
Thickness of slab 0.6mm electrogalvanizing steel plate (EG material)
Thickness of slab 0.8mm contains the steel plate galvanized (GF) of 5% aluminium
Thickness of slab 0.8mm contains the steel plate galvanized (GL) of 55% aluminium
Thickness of slab 0.6mm aluminium alloy plate (AL) JIS A5052
2, the cleaning method of steel plate
The surface of last note metallic substance is used the alkali cleaner (trade mark: fragrant purification agent 4336 of drug concentration: 20g/ liter, Japan's Parker printing ink corporate system), in treatment temp: 60 ℃, treatment time: the processing of spraying under 20 seconds the condition, the filthy or oil of surface attachment is removed.The alkali composition that will remain in the surface subsequently is fully clean with tap water, cleans so that the surface of test materials reaches.
3, waterborne compositions example
(waterborne compositions A)
Will as the 3-sulfydryl propyl trimethoxy silicane of silane coupling agent composition (A) with, n=5, X=hydrogen, Y1=Z=-CH
2N (CH
3)
2, the Z base water-soluble polymers composition (B) that replaces mean value=1 of number mixes, and makes (A): (B)=1: 8.Use H subsequently
2SiFe adjusts pH value to 3.0, and again with (C): the ratio of ((A)+(B))=1: 5 is sneaked into the dispersion liquid as the carnauba wax of fusing point=82 of wax composition (C) ℃, after the deionized water dilution, and solids component that must 10 weight %.
(waterborne compositions B)
Will as N-(2-aminoethyl)-3-aminopropyl trimethoxysilane of silane coupling agent composition (A) with, n=5, X=-CH
2-C
6H
4-OH, Y1=Z=-CH
2N (CH
3)
2, the Z base water-soluble polymers composition (B) that replaces mean value=0.50 of number mixes, and makes (A): (B)=5: 1.Use HF to adjust pH value to 4.0 subsequently, again with (C): the ratio of ((A)+(B))=1: 100 is sneaked into the dispersion liquid as the polyethylene wax of fusing point=104 of wax composition (C) ℃, after the deionized water dilution, and solids component that must 10 weight %.
(waterborne compositions C)
Will as the 3-aminopropyl triethoxysilane+3-glycidoxy propyl group methyl dimethoxysilane of silane coupling agent composition (A) (active hydrogen in the amino: epoxide equivalent is than=1: 2) with, n=5, X=-CH
2-C
6H
4-OH, Y1=Z=-CH
2N (CH
3)
2, the Z base water-soluble polymers composition (B) that replaces mean value=0.75 of number mixes, and makes (A): (B)=1: 1.Use H subsequently
2TiF
6Adjust pH value to 4.0, again with (C): the ratio of ((A)+(B))=2: 1 is sneaked into the dispersion liquid as brown matchmaker's wax of fusing point=79 of wax composition (C) ℃, after the deionized water dilution, and solids component that must 10 weight %.
(waterborne compositions D)
Will as N-(2-aminoethyl)-3-aminopropyl trimethoxysilane+3-glycidoxy propyl group methyl dimethoxysilane of silane coupling agent composition (A) (active hydrogen in the amino: epoxide equivalent is than=1: 2) with, n=5, X=-CH
2-C
6H
4-OH, Y1=Z=-CH
2N (CH
3)
2, the Z base water-soluble polymers composition (B) that replaces mean value=0.75 of number mixes, and makes (A): (B)=1: 1.Use phosphoric acid to adjust pH value to 3.0 subsequently, again with (C): the ratio of ((A)+(B))=2: 1 is sneaked into the dispersion liquid as the paraffin of fusing point=40 of wax composition (C) ℃, after the deionized water dilution, and solids component that must 10 weight %.
(waterborne compositions E)
Will as N-(2-aminoethyl)-3-aminopropyl trimethoxysilane+3-glycidoxy propyl group methyl dimethoxysilane of silane coupling agent composition (A) (active hydrogen in the amino: epoxide equivalent is than=1: 1) with, n=5, X=hydrogen, Y1=Z=-CH
2N (CH
3)
2, the Z base water-soluble polymers composition (B) that replaces mean value=0.3 of number mixes, and makes (A): (B)=1: 1.Use H subsequently
2TiF
6Adjust pH value to 4.0, again with (C): the ratio of ((A)+(B))=1: 50 is sneaked into the dispersion liquid as the polyethylene wax of fusing point=120 of wax composition (C) ℃, after the deionized water dilution, and solids component that must 10 weight %.
(waterborne compositions F)
Will as N-(2-aminoethyl)-3-aminopropyl trimethoxysilane of silane coupling agent composition (A) with, n=5, X=-CH
2-C
6H
4-OH, Y1=Z=-CH
2N (CH
3)
2, the Z base water-soluble polymers composition (B) that replaces mean value=0.50 of number mixes, and makes (A): (B)=5: 1.Use HF to adjust pH value to 4.0 subsequently, again with (C): the ratio of ((A)+(B))=1: 20 is sneaked into the dispersion liquid as the lanolin of fusing point=34 of wax composition (C) ℃, after the deionized water dilution, and solids component that must 10 weight %.
(waterborne compositions G)
Will as the 3-aminopropyl triethoxysilane+3-glycidoxy propyl group methyl dimethoxysilane of silane coupling agent composition (A) (active hydrogen in the amino: epoxide equivalent is than=1: 2) with, n=5, X=-CH
2-C
6H
4-OH, Y1=Z=-CH
2N (CH
3)
2, the Z base water-soluble polymers composition (B) that replaces mean value=0.75 of number mixes, and makes (A): (B)=1: 1.Use H subsequently
2TiF
6Adjust pH value to 4.0, after the deionized water dilution, get the solids component of 10 weight % again.
(waterborne compositions H)
Will as N-(2-aminoethyl)-3-aminopropyl trimethoxysilane+3-glycidoxy propyl group methyl dimethoxysilane of silane coupling agent composition (A) (active hydrogen in the amino: epoxide equivalent is than=1: 2) with, n=5, X=-CH
2-C
6H
4-OH, Y1=Z=-CH
2N (CH
3)
2, the Z base water-soluble polymers composition (B) that replaces mean value=0.75 of number mixes, and makes (A): (B)=1: 1.Use phosphoric acid to adjust pH value to 3.0 subsequently, again with (C): the ratio of ((A)+(B))=3: 1 is sneaked into the dispersion liquid as the polyethylene wax of fusing point=120 of wax composition (C) ℃, after the deionized water dilution, and solids component that must 10 weight %.
Embodiment 1
On the hot-dip galvanized steel sheet (GI) that the method according to (preceding paragraph 2) cleans in advance, use rolling method lining waterborne compositions A, being applied to lining weight is 1.0g/m
2Degree, and reach 80 ℃ mode drying with plate temperature.
Embodiment 2
On the aluminium sheet (AL) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions B, drying, and to be applied to lining weight be 0.01g/m
2Degree, and reach 150 ℃ mode drying with plate temperature.
Embodiment 3
On the hot-dip galvanized steel sheet (GI) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions B, drying, and to be applied to lining weight be 0.6g/m
2Degree, and reach 100 ℃ mode drying with plate temperature.
Embodiment 4
On the electrogalvanizing steel plate (EG) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions C, drying, and to be applied to lining weight be 1.5g/m
2Degree, and reach 180 ℃ mode drying with plate temperature.
Embodiment 5
On the electrogalvanizing steel plate (EG) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions D, drying, and to be applied to lining weight be 3.0g/m
2Degree, and reach 80 ℃ mode drying with plate temperature.
Embodiment 6
On the hot-dip galvanized steel sheet (GI) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions E, drying, and to be applied to lining weight be 0.06g/m
2Degree, and reach 80 ℃ mode drying with plate temperature.
Embodiment 7
On the hot-dip galvanized steel sheet (GI) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions E, drying, and to be applied to lining weight be 2.5g/m
2Degree, and reach 80 ℃ mode drying with plate temperature.
Embodiment 8
On the steel plate galvanized that contains 5% aluminium (GF) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions A, drying, and to be applied to lining weight be 0.5g/m
2Degree, and reach 80 ℃ mode drying with plate temperature.
Embodiment 9
On the steel plate galvanized that contains 55% aluminium (GL) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions A, drying, and to be applied to lining weight be 1.5g/m
2Degree, and reach 60 ℃ mode drying with plate temperature.
Comparative example 1
On the hot-dip galvanized steel sheet (GI) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions C, drying, and to be applied to lining weight be 0.006g/m
2Degree, and reach 80 ℃ mode drying with plate temperature.
Comparative example 2
On the electrogalvanizing steel plate (EG) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions A, drying, and to be applied to lining weight be 4.0g/m
2Degree, and reach 80 ℃ mode drying with plate temperature.
Comparative example 3
On the aluminium alloy plate (AL) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions F, drying, and to be applied to lining weight be 1.5g/m
2Degree, and reach 180 ℃ mode drying with plate temperature.
Comparative example 4
On the electrogalvanizing steel plate (EG) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions G, drying, and to be applied to lining weight be 2.0g/m
2Degree, and reach 180 ℃ mode drying with plate temperature.
Comparative example 5
On the hot-dip galvanized steel sheet (GI) that cleans in advance according to the method for (preceding paragraph 2), use rolling method lining waterborne compositions H, drying, and to be applied to lining weight be 1.0g/m
2Degree, and reach 80 ℃ mode drying with plate temperature.
3, appraisal procedure
Assess according to following method, its result is as shown in table 1.
3.1, corrosion resistance test
To the metallic sheet material of test, implement 240 hours salt spray testing according to the JIS-Z2371 regulation.Anti-white rust use visual type is measured, and is assessed.The assessment benchmark is as follows.
◎: the white rust incidence is lower than 5%
Zero: the white rust incidence is more than 5%, less than 10%
△: the white rust incidence is more than 10%, less than 50%
*: the white rust incidence is more than 50%
3.2, the application fitness test
Each metallic sheet material carries out application with as test materials according to following note condition, and the fitness test of filming.
(application condition)
Coating: Northwest paint company system Ah rice clarke #1000 (trade mark) (whitewash)
Finishing: spread coating
Baking vanish condition: 140 ℃, 20 minutes, thickness 25 μ m
(fitness test)
To filming, cut with the NT blade with 1mm four directions, 100 chessboard hole purpose modes, this test materials uses the extruding of Erichsen test device as behind the 5mm, and the jut that extruding is produced uses adhesive tape to carry out stripping test, and the number of peeling off to film is as evaluation object.The benchmark of assessment is as follows.
◎: peel off situation and produce
Zero: peel off number 1～10
△: peel off number 11～50
*: white rust incidence 51～100
3.3, the erosion resistance after the application
Use the blade incision to film and reach the degree of steel plate materials, to its salt spray testing of implementing 240 hours, with adhesive tape cutting part is peeled off after finishing, and the width of peeling off is assessed according to the JIS-Z2371 regulation.The benchmark system of judging measures the width of being peeled off to filming by cutting part (mm).
◎: be lower than 3mm
Zero: more than the 3mm, be lower than 5mm
△: more than the 5mm, be lower than 10mm
*: more than the 10mm
3.4, anti-finger printing test
For each metal sheet test materials, after the use colour-difference meter is measured L, a, b value earlier, be coated with Vaseline again, use the gauze wiping subsequently, re-use colour-difference meter and measure its a, b value, and try to achieve Δ E value.
◎: Δ E is lower than 0.2
Zero: Δ E more than 0.2, is lower than 2.0
△: Δ E more than 2.0, is lower than 3.0
*: Δ E is more than 3.0
3.5, workability test
For each metal sheet test materials, use Bao Dingshi (バ ゥ デ Application formula) frictional dissipation machine to measure initial stage frictional coefficient and the μ value of wiping after moving 10 times in the mode of loading 1kg.
◎: the μ value is lower than 0.1
Zero: the μ value is more than 0.1, to be lower than 0.2
△: the μ value is more than 0.2, to be lower than 0.3
*: the μ value is more than 0.3
Table 1 evaluation test result
| No. | Material | Erosion resistance | The application adaptation | Erosion resistance after the application | Anti-finger printing (Δ E) | Frictional coefficient (μ value) | ||
| Initial stage | After 10 times | |||||||
| Embodiment | 1 | GI | ○ | ◎ | ○ | ◎ | ◎ | ○ |
| 2 | AL | ○ | ◎ | ○ | ○ | ○ | ○ | |
| 3 | GI | ○ | ◎ | ○ | ○ | ◎ | ○ | |
| 4 | EG | ○ | ◎ | ○ | ○ | ◎ | ○ | |
| 5 | EG | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | |
| 6 | GI | ○ | ◎ | ○ | ○ | ○ | ○ | |
| 7 | GI | ◎ | ◎ | ○ | ○ | ◎ | ◎ | |
| 8 | GF | ◎ | ◎ | ◎ | ○ | ◎ | ○ | |
| 9 | GI | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | |
| Comparative example | 1 | GI | × | ◎ | △ | × | △ | × |
| 2 | EG | ◎ | × | × | ○ | ◎ | ◎ | |
| 3 | AL | ○ | × | × | × | × | × | |
| 4 | EG | ◎ | ◎ | ◎ | × | × | × | |
| 5 | GI | × | × | × | × | ◎ | ○ | |
Can obtain following result by table 1 content.
(1), be the embodiment 1 to 9 of metallic sheet material of the present invention, demonstrate have good anti-corrosion, erosion resistance, anti-finger printing, processibility after the application adaptation, application.
(2) but, amount of coating is lower than the comparative example 1 of the scope of the invention, its erosion resistance, anti-finger printing, processibility are neither good.
(3), again, amount of coating is higher than the comparative example 2 of the scope of the invention, and the erosion resistance after its application adaptation, the application is neither good.
(4), contain the comparative example 3 that fusing point is lower than the wax of the scope of the invention, erosion resistance, anti-finger printing, processibility after its application adaptation, the application are neither good.
(5), do not contain the comparative example 4 of the outer wax composition of the scope of the invention, though its erosion resistance, coating belong to fully, anti-finger printing, processibility are not good.
(6), wax content surpasses the comparative example 5 of the scope of the invention, though its processibility belongs to fully, the erosion resistance after erosion resistance, application adaptation, the application, anti-finger printing etc. are neither good.
According to the prepared metallic sheet material of manufacture method of the present invention, article more in the past still can have high corrosion resistance, coating, anti-finger printing, processibility etc. not using under the chromic acid.So for relevant from now on waste water control regulation, be a kind of splendid no chromaking manufacture method to industrial community.In addition, because of not selective for metallic substance, thus rust-preventing characteristic or coating are upwards promoted, and, also can process not using under the extruding wet goods oils, and save the degreasant step.
On the countermeasure to social concerns such as environment protection or recycles, has extremely effective and practical effect again.
Claims (5)
1. the metallic sheet material with excellent corrosion resistance, coating, anti-finger printing and processibility is characterized by, and metal material surface is coated with and contains the coating composition of note composition down:
(A) by containing the silane coupling agent composition that at least 1 silane coupled compound that is selected from the reactive functional group of the amino, epoxy group(ing) and the sulfydryl that contain active hydrogen constitutes more than a kind,
(B) contain the component of polymer more than a kind that mean polymerisation degree more than a kind is a monomer component shown in 2 to 50 the following note formula (1),
Wherein, be hydrogen atom with phenyl ring bonded X or be the following base shown in the note formula (2):
In the formula (2), R1 and R2 respectively the do for oneself alkyl of hydrogen atom, hydroxyl, C1 to C5 or the hydroxyalkyl of C1 to C10; In formula (1) and the formula (2), with phenyl ring bonded Y1 and Y2, independence is hydrogen atom mutually separately, or descends the Z base shown in note formula (3), (4):
Preceding note formula (3) is separate with R3, R4, R5, R6 and R7 in (4) to be hydrogen atom, methyl, ethyl, propyl group, methylol, hydroxyethyl or hydroxypropyl, with each phenyl ring bonded X in the preceding note polymer molecule, Y1, Y2 and with other phenyl ring bonded X, Y1, Y2 can be identical or different each other mutually, and the replacement of remembering the Z base in the preceding note polymer molecule before in each phenyl ring to count mean value be 0.2 to 1.0; With
(C) fusing point be 40～120 ℃ by at least a kind of wax composition selecting in polyethylene wax, montanin wax, the paraffin,
Wherein, preceding note silane coupling agent composition (A) is 1/8 to 5/1 to the weight ratio (A)/(B) of component of polymer (B), and preceding note wax composition (C) is 1/100～2/1 to weight ratio (C)/((A)+(B)) of the total weight of this silane coupling agent composition (A) and this component of polymer (B).
2. as the metallic sheet material of 1 of claim the, wherein, preceding note silane coupling agent composition (A) contains
(a) silane coupling agent that constitutes by a kind of silane coupled compound that contains the amino of 1 above active hydrogen, with
(b) silane coupling agent that constitutes by a kind of silane coupled compound that contains 1 above epoxy group(ing).
3. as the metallic sheet material of 2 of claims the, wherein, in the preceding note silane coupling agent (a) in contained amino that contains active hydrogen and the preceding note silane coupling agent (b) equivalence ratio of contained epoxy group(ing) be 1: 1～1: 3.
4. as claim the 2 or 3 s' metallic sheet material, wherein, the total amount of preceding note silane coupling agent (a) and preceding note silane coupling agent (b) is 1: 5～5: 1 to the weight ratio ((a)+(b))/(B) of preceding note component of polymer (B).
5. the manufacture method with metallic sheet material of excellent corrosion resistance, coating, anti-finger printing and processibility is characterized by, and contains water-based medium and institute's dissolved wherein down that the composition of note composition mixes,
(A) by containing the silane coupling agent composition that at least 1 silane coupled compound that is selected from the reactive functional group of the amino, epoxy group(ing) and the sulfydryl that contain active hydrogen constitutes more than a kind,
(B) contain the component of polymer more than a kind that mean polymerisation degree more than a kind is a monomer component shown in 2 to 50 the following note formula (1),
Wherein, be hydrogen atom with phenyl ring bonded X or be the following base shown in the note formula (2):
In the formula (2), R1 and R2 respectively the do for oneself alkyl of hydrogen atom, hydroxyl, C1 to C5 or the hydroxyalkyl of C1 to C10; In formula (1) and the formula (2),, can mutual separately independence be hydrogen atom, or descend the Z base shown in note formula (3), (4) with phenyl ring bonded Y1 and Y2:
Preceding note formula (3) is separate with R3, R4, R5, R6 and R7 in (4) to be hydrogen atom, methyl, ethyl, propyl group, methylol, hydroxyethyl or hydroxypropyl, with each phenyl ring bonded X in the preceding note polymer molecule, Y1, Y2 and with other phenyl ring bonded X, Y1, Y2 can be identical or different each other mutually, and the replacement of remembering the Z base in the preceding note polymer molecule before in each phenyl ring to count mean value be 0.2 to 1.0; With
(C) fusing point is 40～120 ℃ the dispersion liquid by at least a kind of wax selecting in polyethylene wax, montanin wax, the paraffin,
Wherein, preceding note silane coupling agent composition (A) is 1/8 to 5/1 to the weight ratio (A)/(B) of component of polymer (B), preceding note wax composition (C) is 1/100～2/1 to weight ratio (C)/((A)+(B)) of the total weight of this silane coupling agent composition (A) and this component of polymer (B)
And to adjust its pH value be 2.0 to 6.5 to make waterborne compositions, subsequently so that the lining weight after the metallic sheet material surface drying is 0.01 to 3.0g/m
2Mode be coated with, the method for dry, lining.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50415/2000 | 2000-02-28 | ||
| JP2000050415A JP3993729B2 (en) | 2000-02-28 | 2000-02-28 | Metal plate material excellent in corrosion resistance, paintability, fingerprint resistance and workability, and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1311063A CN1311063A (en) | 2001-09-05 |
| CN1179800C true CN1179800C (en) | 2004-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011109076A Expired - Lifetime CN1179800C (en) | 2000-02-28 | 2001-02-28 | Metallic plate material having excellent propoerties such as: corrosion-resistant, coating, anti-finger printing and processing, and mfg. process therefor |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1261435A4 (en) |
| JP (1) | JP3993729B2 (en) |
| KR (1) | KR20010085362A (en) |
| CN (1) | CN1179800C (en) |
| CA (1) | CA2401130A1 (en) |
| MX (1) | MXPA02008216A (en) |
| WO (1) | WO2001064356A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003052005A1 (en) * | 2001-12-17 | 2003-06-26 | Henkel Kommanditgesellschaft Auf Aktien | Agent for producing a primer on metallic surfaces and method for treatment |
| CA2492936C (en) | 2002-07-24 | 2011-02-15 | University Of Cincinnati | Superprimer |
| JP2006316342A (en) * | 2005-04-15 | 2006-11-24 | Nippon Steel Corp | Metal member, rustproofing agent, and rustproofing method |
| DE102009008868B4 (en) | 2009-02-13 | 2013-11-14 | Daimler Ag | Motor vehicle trim part with handle protection coating and method for coating a motor vehicle trim part |
| JP5563274B2 (en) * | 2009-10-23 | 2014-07-30 | 関西ペイント株式会社 | Coating composition for aluminum alloy |
| CN101914344B (en) * | 2010-09-09 | 2012-12-19 | 上海丰野表面处理剂有限公司 | Non-chrome water-based organic fingerprint-resistant coating and preparation method thereof |
| ES2883105T3 (en) * | 2017-03-30 | 2021-12-07 | Tata Steel Ijmuiden Bv | Aqueous acid composition for treating metal surfaces, treatment method using this composition and use of a treated metal surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907613A (en) * | 1973-03-20 | 1975-09-23 | Zbrojovka Brno Np | Protective coatings on metals and on their alloys |
| JP4007627B2 (en) * | 1996-03-11 | 2007-11-14 | 日本パーカライジング株式会社 | Surface treatment agent composition for metal material and treatment method |
| JP3898302B2 (en) * | 1997-10-03 | 2007-03-28 | 日本パーカライジング株式会社 | Surface treatment agent composition for metal material and treatment method |
-
2000
- 2000-02-28 JP JP2000050415A patent/JP3993729B2/en not_active Expired - Fee Related
-
2001
- 2001-02-10 KR KR1020010006594A patent/KR20010085362A/en not_active Application Discontinuation
- 2001-02-28 MX MXPA02008216A patent/MXPA02008216A/en unknown
- 2001-02-28 CA CA002401130A patent/CA2401130A1/en not_active Abandoned
- 2001-02-28 EP EP01916269A patent/EP1261435A4/en not_active Withdrawn
- 2001-02-28 WO PCT/US2001/006267 patent/WO2001064356A1/en active Application Filing
- 2001-02-28 CN CNB011109076A patent/CN1179800C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2401130A1 (en) | 2001-09-07 |
| KR20010085362A (en) | 2001-09-07 |
| WO2001064356A1 (en) | 2001-09-07 |
| JP2001234350A (en) | 2001-08-31 |
| EP1261435A4 (en) | 2005-06-15 |
| JP3993729B2 (en) | 2007-10-17 |
| EP1261435A1 (en) | 2002-12-04 |
| MXPA02008216A (en) | 2004-04-05 |
| CN1311063A (en) | 2001-09-05 |
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