CN107002246B - Surface treating agent for galvanized steel sheet - Google Patents
Surface treating agent for galvanized steel sheet Download PDFInfo
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- CN107002246B CN107002246B CN201580063709.9A CN201580063709A CN107002246B CN 107002246 B CN107002246 B CN 107002246B CN 201580063709 A CN201580063709 A CN 201580063709A CN 107002246 B CN107002246 B CN 107002246B
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/18—Homopolymers or copolymers of nitriles
- C09D133/20—Homopolymers or copolymers of acrylonitrile
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/47—Levelling agents
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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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Abstract
A kind of corrosion resistance, the surface treating agent with the adaptation of top coat, anti-blackening and the zinc-based metal plated steel sheet satisfied with the cementability of structure bonding agent are provided.A kind of water system surface treating agent of zinc-based metal plated steel sheet, allotment have carbonic acid zirconium compounds, specific acrylic resin, vfanadium compound, phosphorus compound and cobalt compound.
Description
Technical field
The present invention relates to corrosion resistance, with the adaptation of top coat, anti-blackening and bonding with structure bonding agent
The processing on the excellent zinc-based metal plated steel sheet surface of property.
Background technique
Zinc-based metal plated steel sheet is applied to the extensive purposes such as building materials, automobile, family's electrical article.
The technology that overlay film assigns corrosion resistance etc. is set on zinc-based metal plated steel sheet surface usually as by surface treating agent,
Known following method: implement chromic acid salt treatment by making treatment fluid as main component containing chromic acid, dichromic acid or these salt
Method, implement parkerized method, the method for implementing inorganic metal coating processing, implement the processing of organic resin coating
Method etc., and it is practical.
As long as being listed in patent document 1 comprising vfanadium compound and as the technology using inorganic constituents containing being selected from
The metal conditioner of the metallic compound of at least one kind of metal in zirconium, titanium, molybdenum, tungsten, manganese and cerium.In addition, patent document 2
In list using containing alkaline zirconium compounds, the place containing vanadium oxide compound, phosphate cpd, cobalt compound, organic acid and water
The compound film laminating for managing liquid handles the steel of plating containing zinc.
As the main technology for using organic resin coating processing, patent document 3, which is disclosed, dissipates tree in anionic water
Include the surface treating agent for metallic materials of silicic acid alkali metal salt in rouge, discloses in patent document 4 comprising zirconium carbonate ammonium, 4 valences
Vfanadium compound, organic phospho acid, anionic water dissipate property acrylic resin surface treating agent.
In addition, being mentioned as overlay film is arranged by surface treating agent on the Zn-Al alloy plated steel sheet of excellent corrosion resistance
The technology of high corrosion-resistant etc. is disclosed in patent document 5 and is provided on Zn-Al-Mg-Si alloy layer comprising zirconium chemical combination
Object, vfanadium compound overlay film Zn-Al alloy plated steel sheet, patent document 6 discloses a kind of Zn-Al alloy plated steel sheet,
It includes vfanadium compound, phosphate cpd, metal component, the propylene being made of specific monomer ingredient on zn-al alloy coating
Acid resin.
But for these technologies, planar portions corrosion resistance, processing department corrosion resistance, with the adaptation of top coat, resistance to
Blackening is poor, is especially unsatisfied with in terms of the cementability of structure bonding agent, there are problems in functionization.Therefore, it wants strongly
Seek the surface treating agent for developing the zinc-based metal plated steel sheet that can synthetically meet extensive use.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2002-30460 bulletin
Patent document 2:WO2007/123276
Patent document 3:WO2007/069783
Patent document 4:WO2009/004684
Patent document 5: Japanese Unexamined Patent Publication 2003-55777 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2005-097733 bulletin
Summary of the invention
Subject to be solved by the invention
It is an object of the present invention to solve the above subject present in the prior art, a kind of corrosion resistance and top coating are provided
The surface treating agent of the adaptation of coating, anti-blackening and the zinc-based metal plated steel sheet satisfied with the cementability of structure bonding agent.
Solution for solving the problem
In order to realize the purpose, the present inventors further progress research, as a result, it has been found that, by using containing zirconium carbonate
Compound, specific acrylic resin, vfanadium compound, phosphorus compound and cobalt compound water system surface treating agent and be coated on plating
On zinc system surface of steel plate, surface treated steel plate obtained by heat drying, above-mentioned purpose may be implemented, until complete the present invention.
That is, the present invention provides following scheme.
(1) a kind of zinc-based metal plated steel sheet inorganic agent, allotment have carbonic acid zirconium compounds (A), acrylic resin (B), 2~
Vfanadium compound (C), phosphorus compound (D), cobalt compound (E) and the water of 4 valences, pH are 8~11, and the acrylic resin (B) is
Make the monomer at least containing styrene (b1), (methyl) acrylic acid (b2), (methyl) alkyl acrylate (b3), acrylonitrile (b4)
Ingredient copolymerization obtains resin, wherein on the basis of the solid state component quality of whole monomer components of the resin, acrylonitrile (b4)
Amount be 20~38 mass %, and be glass transition temperature be -12~15 DEG C of water-soluble resin and water serial emulsion resin.
(2) the zinc-based metal plated steel sheet surface treating agent according to above-mentioned (1), wherein above-mentioned acrylic resin (B)
Blending amount is 20~60 mass % relative to whole solid state components of surface treating agent,
Quality when above-mentioned vfanadium compound (C) is scaled V and matter when above-mentioned carbonic acid zirconium compounds (A) to be scaled to Zr
The mass ratio ((V)/(Zr)) of amount is 0.07~0.69,
Quality when above-mentioned phosphorus compound (D) is scaled P and matter when above-mentioned carbonic acid zirconium compounds (A) to be scaled to Zr
The mass ratio ((P)/(Zr)) of amount is 0.04~0.58,
Quality when above-mentioned cobalt compound (E) is scaled Co with when above-mentioned carbonic acid zirconium compounds (A) is scaled Zr
The mass ratio ((Co)/(Zr)) of quality is 0.005~0.08.
(3) the zinc-based metal plated steel sheet surface treating agent according to above-mentioned (1) or (2), wherein about above-mentioned acrylic compounds
The amount of each monomer component of resin (B), on the basis of the solid state component quality of whole monomer components of the resin, styrene (b1)
For 15~25 mass %, (methyl) acrylic acid (b2) be 1~10 mass %, (methyl) alkyl acrylate (b3) is 40~58 matter
Measure %.
(4) the zinc-based metal plated steel sheet surface treating agent according to above-mentioned (1)~(3), wherein above-mentioned zinc-based metal plated steel sheet
Zinc-plated system's layer is following composition: other than zinc and inevitable impurity, can also contain 60 mass % Al below, 10 matter
Measure one or more of % Mg below, 2 mass % Si below.
(5) surface treating agent according to above-mentioned (1)~(4), wherein at least part of phosphorus compound (D) is nothing
Machine phosphoric acid and/or its salt.
The effect of invention
The present invention is corrosion resistance, adaptation, anti-blackening and the cementability with structure bonding agent with top coat
The surface treating agent of the zinc-based metal plated steel sheet of full up meaning.
Specific embodiment
The present invention is specifically described below.
Water system surface treating agent used in the present invention is by carbonic acid zirconium compounds (A) as one of raw material.With regard to zirconium carbonate
For closing object (A), when forming overlay film, carbanion is detached from, zirconium combination, molecular weight via oxygen each other, to cover
The barrier raising of film.It is reacted in addition, carbonic acid zirconium compounds is crosslinked with acrylic resin (B), can be improved overlay film
It is barrier.The type of carbonic acid zirconium compounds (A) is not particularly limited, can be enumerated for example: zirconium carbonate, zirconium carbonate ammonium, carbonic acid
Zirconium potassium, sodium zirconium carbonate etc., can be used one or more of these.Wherein, in terms of excellent corrosion resistance and it is preferred that zirconium carbonate and carbon
Sour zirconium ammonium.
Water system surface treating agent used in the present invention is by acrylic resin (B) as one of raw material.It is believed that third
Olefin(e) acid resinoid by with above-mentioned zirconium carbonate (A) it is regularly arranged and molecular weight, assign organic system to the zirconium overlay film of slightly solubility
The usually possessed characteristic of overlay film.In particular, being had been assigned by the overlay film of regularly arranged molecular weight from composition third
The characteristic of the monomer component of olefin(e) acid resinoid, it becomes able to show and performance necessary to the cementability of structure bonding agent.
It is suitable that the content of acrylic resin (B), which is 20~60 mass % relative to whole solid state components of surface treating agent,.More
Preferably 20~40 mass %.When less than 20 mass %, adaptation decline, when more than 60 mass %, corrosion resistance decline.
Acrylic resin (B) is to make at least to contain styrene (b1), (methyl) acrylic acid (b2), (methyl) alkyl acrylate
The monomer component of base ester (b3) and acrylonitrile (d4) copolymerization obtained from resin, with the solid-state of whole monomer components of the resin at
On the basis of sub-prime amount, the amount of acrylonitrile (b4) is 20~38 mass %, and is the water that glass transition temperature is -12~15 DEG C
Soluble resin and water serial emulsion resin.Here, with regard to the monomer component (composition) in addition to acrylonitrile (b4), as raw material
For, the gross mass relative to the whole monomer component contains 15~25 mass % of styrene (b1), (methyl) acrylic acid (b2) 1
~10 mass %, 40~58 mass % of (methyl) alkyl acrylate (b3) are suitable.
In order to have the effect of improving corrosion resistance and adaptation, the styrene (b1) of 15~25 mass % is preferably comprised, more
Preferably 17~23 mass %.When less than 15 mass %, corrosion resistance and adaptation decline, when more than 25 mass %, overlay film is hardened,
The decline of processing department corrosion resistance.
(methyl) acrylic acid (b2) has the adaptation improvement effect for the overlay film for improving resin and steel plate, preferably comprise 1~
10 mass %, more preferably 2~6 mass %.When less than 1 mass %, adaptation decline, when more than 10 mass %, corrosion resistance and
Water resistance decline.
(methyl) alkyl acrylate (b3) has the processability improvement effect of resin coating, preferably comprises 40~58 matter
Measure %, more preferably 40~55 mass %.When less than 40 mass %, the decline of processing department corrosion resistance, when more than 58 mass %, plane
The decline of portion's corrosion resistance.The type of (methyl) alkyl acrylate (b3) is not limited, can be enumerated for example: (methyl) acrylic acid
Methyl esters, (methyl) ethyl acrylate, (methyl) butyl acrylate, the own ester of acrylic acid 2- methyl and these isomers etc., can be with
Use one or more of these.Wherein, in terms of excellent corrosion resistance and it is preferred that ethyl acrylate and butyl acrylate.
Acrylonitrile (b4) has the effect of the cementability of raising and structure bonding agent, contains 20~38 mass %, preferably
For 20~35 mass %.By being set as 20 mass % or more, cementability can be improved.It is resistance to when on the other hand, more than 38 mass %
Aqueous decline, corrosion resistance decline.
The glass transition temperature of acrylic resin (B) being calculated is -12~15 DEG C.Glass transition temperature
When being -12 DEG C or more, corrosion resistance can be improved.When on the other hand, more than 15 DEG C, cementability decline.It should be noted that glass
Glass transition temperature is calculated by the following formula, and in formula, the integer that i is 1 or more, Wi indicates the mass fraction of i homopolymer, Tgi
Indicate the Tg (K) of i homopolymer.
(formula 1)
1/Tg (K)=∑ (Wi/Tgi) (1)
Acrylic resin (B) is as long as at least make styrene (b1), (methyl) acrylic acid (b2), (methyl) acrylic acid alkyl
Other vinyl-containing monomers also can be used as starting monomer with amount appropriate copolymerization in ester (b3) and acrylonitrile (b4).
It as the vinyl-containing monomers, is not particularly limited, can enumerate for example: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl)
Acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) propylene
Sour 4- hydroxybutyl, ethyoxyl-diethylene glycol (methyl) acrylate, 2- hydroxyethyl (methyl) allyl ether, 3- hydroxyl
Base propyl (methyl) allyl ether, 4- hydroxybutyl (methyl) allyl ether, acrylic acid 2- dimethylamino ethyl ester, acryloyl
Amine, allyl alcohol, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, vinyl trimethoxy
Silane, vinyltriethoxysilane, allyl glycidyl ether, (methyl) glycidyl acrylate, acrylic acid 2-
(1- '-aziridino) ethyl ester, methacrylic acid imidohydrine (イ ミ ノ ー Le) ester, acryloyl morpholine, vinyl formate, acetic acid
Vinyl acetate, vinyl butyrate, vinyl acrylate, vinyltoluene, cinnamonitrile, (methyl) acryloyl-oxyethyl phosphate and
Double-(methyl) acryloyl-oxyethyl phosphate etc., can be used one or more of these.In these, from the stabilization of lotion
From the perspective of property is excellent, preferably acrylic acid 2- hydroxy methacrylate, acrylic acid 4- hydroxybutyl, ethyoxyl-diethylene glycol propylene
Acid esters and acrylamide.
The polymerization of polymer used in the present invention is not particularly limited, suspension polymerisation can be enumerated, lotion is gathered
Conjunction and solution polymerization process.In addition, solvent and polymerization initiator can also be used when copolymerization.As polymerization initiator, without special
It limits, the radical polymerization initiators such as azo compound, peroxide based compound, the whole relative to resin can be used
Solid state component is, it is preferable to use 0.1~10 mass %.Reaction temperature is usually room temperature to 200 DEG C, and preferably 40~150 DEG C, reaction
Time is 30 minutes~8 hours, and preferably 2~4 hours or so are suitable.
Water system surface treating agent used in the present invention is by the vfanadium compound (C) of 2~4 valences as one of raw material.Vanadium chemical combination
Object includes the vfanadium compound of 2~5 valences.Vfanadium compound preferentially dissolves out in a corrosive environment, inhibits pH caused by the dissolution of plating ingredient
Rise, therefore effective in terms of corrosion resistance raising.For the oxidation number of vanadium, when any oxidation number it is same effectively, but 5 valences
Vanadium dissolubility it is high, it is therefore desirable to use the vfanadium compound of 2~4 valences.
For the vfanadium compound (C) of these 2~4 valences, carbonic acid zirconium compounds (A) is being scaled Zr, by vfanadium compound
(C) mass ratio ((V)/(Zr)) when being scaled V is 0.07~0.69, preferably 0.14~0.56.((V)/(Zr)) is 0.07
When above, processing department corrosion resistance can be improved.On the other hand, when ((V)/(Zr)) is more than 0.69, the decline of top coating coating, because
This is not preferred.
The type of the vfanadium compound (C) of 2~4 valences is not particularly limited, can be enumerated for example: by vanadium pentoxide (V2O5)、
Metavanadic acid (HVO3), ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride (VOCl3) etc. the vfanadium compound of 5 valences be reduced to 2 by reducing agent
The substance of~4 valences, three vanadium oxide (V2O3), vanadium dioxide (VO2), vanadic sulfate (VOSO4), vanadyl oxalate [VO (COO)2], (second
Ethyl acetoacetic acid vanadyl [VO (OC (CH3)=CHCOCH3))2], acetoacetate vanadium [V (OC (CH3)=CHCOCH3))3], vanadium trichloride
(VCl3), phosphovanadomolybdic acid { H15-X[PV12-xMoxO40]·nH2O (6 < x < 12, n < 30) }, vanadic sulfate (VSO4·8H2O), two
Vanadium chloride (VCl2), the vfanadium compound of 4~divalent of oxidation numbers such as vanadium oxide (VO) etc..
Water system surface treating agent used in the present invention is by phosphorus compound (D) as one of raw material.It is believed that phosphatization is closed
Zinc-aluminium-magnesium alloy plating overlay film is partially dissolve to form phosphate by object (D).The phosphate mainly in the form of trbasic zinc phosphate and
It is formed, makes excellent corrosion resistance due to making the surface passivation of plating overlay film, and improve adaptation.In particular, from structure
From the perspective of being improved with the cementability of bonding agent, preferably at least part of phosphorus compound (D) be inorganic phosphate and/or its
Salt.It should be noted that as that cation, can be enumerated for example in salt (also including following documented salt): alkali metal,
Alkaline-earth metal, ammonium.
For phosphorus compound (D), when carbonic acid zirconium compounds (A) to be scaled Zr, phosphorus compound (D) be scaled P
Mass ratio ((P)/(Zr)) be 0.04~0.58, preferably 0.07~0.29.When ((P)/(Zr)) is 0.04 or more, Ke Yiti
High processing department corrosion resistance.On the other hand, when ((P)/(Zr)) is more than 0.58, anti-blackening decline, therefore not preferably.
For the phosphorus compound (D) used in the present invention, for example, as the inorganic acid yin with phosphorous acidic group from
Son, can enumerate for example: former phosphoric acid, metaphosphoric acid, condensed phosphoric acid, pyrophosphoric acid, tripolyphosphate, tetraphosphate, hexa metaphosphoric acid etc. are inorganic
Inorganic anion and these salt after at least one hydrogen of sour zhong is free, as the organic acid with phosphorous acidic group
Anion can be enumerated for example: 1- hydroxy methane -1,1- di 2 ethylhexyl phosphonic acid, 1- hydroxyl ethane -1,1- di 2 ethylhexyl phosphonic acid, 1- hydroxyl
Propane -1,1- di 2 ethylhexyl phosphonic acid, 1- hydroxy vinyl -1,1- di 2 ethylhexyl phosphonic acid, 2- hydroxyphosphonoacetic acid, (the methylene phosphine of amino three
Acid), ethylenediamine-N, N, N ', N '-four (methylene phosphonic acid), hexamethylene diamine-N, N, N ', (the methylene phosphine of N '-four
Acid), Diethylenetriamine-N, N, N ', N ", N "-five (methylene phosphonic acid), 2- phosphonobutane -1,2,4- tricarboxylic acid, inositol six
Organic anion and these salt after at least one hydrogen of the organic phospho acids such as phosphonic acids, phytic acid, organic phosphoric acid etc. is free.
Water system surface treating agent used in the present invention is by cobalt compound (E) as one of raw material.In general, with regard to zinc-aluminium-
For magnesium alloy plating overlay film, in a corrosive environment, aluminium and magnesium show to sacrifice corrosion protection result, therefore the zinc in plating overlay film can
Observe the blacking phenomenon aoxidized under oxygen lack state.This is the phenomenon that readily occurring in the soluble part of plating overlay film,
It is believed that displacement precipitation is carried out in the part by cobalt compound, so as to assign excellent anti-blackening.
For cobalt compound (E), when carbonic acid zirconium compounds (A) to be scaled Zr, cobalt compound (E) be scaled Co
Mass ratio ((Co)/(Zr)) be 0.005~0.08, preferably 0.009~0.038.When ((Co)/(Zr)) is 0.005 or more,
Processing department corrosion resistance and anti-blackening can be improved.On the other hand, when ((Co)/(Zr)) is more than 0.08, corrosion resistance decline.To cobalt
The type of compound (E) is not particularly limited, and can enumerate: cobaltous sulfate, cobalt nitrate and cobalt carbonate etc..
The pH of water system surface treating agent used in the present invention is 8~11.More preferably 8.5~10.In addition, the survey to pH
Determine method not limit, for example, can be with DKK-TOACORPORATION system (HM-30R) in 25 DEG C of measuring temperature surveys of getting off
It is fixed.It when pH is less than 8, can not steadily dissolve carbonic acid zirconium compounds (A), corrosion resistance decline.When on the other hand, more than 11, plating
Overlay film sharply dissolves, corrosion resistance decline.Also, pH in the range when, it helps the stability of said preparation.Adjusting to pH
Agent is not particularly limited, and can enumerate: ammonia, guanidine carbonate, carbonic acid, acetic acid, hydrofluoric acid etc..
In addition, in water system surface treating agent used in the present invention, in order to improve scratch resistance, lubricant can be added
(F).It is suitable that the blending amount of lubricant (F), which is 1~8 mass % relative to whole solid state components of surface treating agent,.Lubrication
When the blending amount of agent (F) is less than 1 mass %, it cannot get the raising of scratch resistance.In addition, having coating closely sealed when more than 8 mass %
Property decline anxiety, therefore not preferably.
In addition, as lubricant (F), the lubricant that 0.1~5.0 μm of preferred mass average grain diameter.In addition, to weight average
The measuring method of grain warp does not limit, for example, can pass through (the laser diffraction and scattering formula size distribution survey of Nikkiso Company Limited's system
Determine device MICROTRAC HRA-X100) it measures.When mass median diameter is less than 0.1 μm, it is easy agglutination, stability is poor, because
This is not preferred.In addition, when mass median diameter is more than 5.0 μm, dispersion stabilization decline, therefore not preferably.
In water system surface treating agent used in the present invention, as long as not damaging effect of the invention, use can also be added
In the surfactant and tackifier, the conduction for improving weldability of the referred to as wetability enhancer for obtaining uniform overlay film
Property substance, the coloring pigment for improving design, extinction material, for improving the solvent etc. for making film property.
Water system surface treating agent is by the way that mentioned component to be obtained by mixing in the water such as deionized water, distilled water.Water system table
The solid state component ratio of surface treatment liquid can be selected suitably.In addition, can also be added as needed in water system surface treating agent
Alcohol, ketone, cellosolve system water-soluble solvent, surfactant, defoaming agent, levelling agent, fungi-proofing mould inhibitor etc..By adding these,
Drying property, coating appearance, workability, the design of surface treating agent improve.It is important that these are not damage and pass through this
What the degree for the quality that invention obtains was added, additive amount is up to relative to whole solid state components of water system surface treatment liquid
5 mass %.
Then, the processing method of water system surface treating agent of the invention is illustrated.
In the present invention, by being coated with water system surface treating agent and heat drying, on the surface of zinc-based metal plated steel sheet to have
The Zr adhesion amount for having every one side is 8~700mg/m2Surface treatment overlay film be suitable.Zr adhesion amount is 8mg/m2When above,
Corrosion resistance can be improved.On the other hand, more than 700mg/m2When, the performances such as corrosion resistance saturation.More preferably 50~350mg/m2。
As the method for coating water system surface treating agent, can enumerate: rolling method, stick coating method, infusion process, spraying coating method
Deng according to the suitable best approach of the selections such as handled shape.More specifically, for example, if shape is sheet, Ke Yixuan
Select rolling method, stick coating method or spraying coating method.Spraying coating method be water system surface treating agent is carried out it is spraying, by roller drawing or
High pressure blows gas come the method for adjusting coating weight.When molded product is made, selection be immersed in surface treatment liquid and pick up, root
The method etc. for compressed air blowing extra water system surface treating agent off according to situation to adjust coating weight.
Heating temperature (highest reaches plate temperature, PMT) when by water system surface treating agent heat drying is usually 60~200
DEG C, more preferable 80~180 DEG C.It, will not moisture of the remaining as main solvent in overlay film if heating temperature is 60 DEG C or more；Separately
Outside, if heating temperature be 200 DEG C hereinafter, if will not cause resin decomposition, therefore will not generate corrosion resistance decline the problems such as.Separately
Outside, heating time selects suitable optimum condition according to used shape etc..It should be noted that from viewpoints such as productivities
It sets out, preferably 0.1~60 second, more preferably 1~30 second.
It is applied with the zinc-based metal plated steel sheet that surface treating agent of the invention forms surface treatment overlay film in corrosion resistance, with top coating
Adaptation, anti-blackening and the cementability aspect all satisfaction with structure bonding agent of material.The reason is presumed as follows, but this hair
It is bright not constrained by the supposition.Pass through zirconium carbonate chemical combination using the overlay film that water-based metal-surface-treating agent used in the present invention is formed
Object and anionic property acrylic resin and form barrier overlay film.Carbonic acid zirconium compounds vapors away carbonic acid in the drying process, remains
Remaining zirconium producing high-molecular and the overlay film for forming slightly solubility.It is presumed that in this process, a part (- Zr-OH base) of zirconium with
Metal surface forms Zr-O-M key (M: zinc-plated system), so that the adaptation with plating is excellent, plays significant screen effect.Separately
The outer arrangement being believed that through zirconium and anionic property acrylic resin rule, thus molecular weight, to the zirconium of slightly solubility
Overlay film assigns organic based coating usually possessed characteristic.
In particular, assigning to by the overlay film after regularly arranged molecular weight from the list for constituting acrylic resin
The characteristic of body ingredient can especially be shown and performance necessary to the cementability of structure bonding agent.On the other hand, vanadium
Closing object is considered as the inhibitor ingredient for dissolving out, working in a corrosive environment.It dissolves out, delay in a corrosive environment that is, having
The effect that the pH of plating overlay film rises.By the process, zinc-plated system can be by forming the sacrifice corrosion protection result, long-term of oxidation film
Ground maintains excellent corrosion resistance.In addition, when phosphorus compound and metal surface contact, by metal etch, and with the gold that gradually dissolves
Belong to the metal salt for forming slightly solubility.It is believed that or when metal erosion occurs, captures metal ion and form metal salt,
Inhibit further corrosion.In turn, cobalt compound exists in the form of an ion in treatment fluid, when contacting with metal, in metal watch
Face occurs displacement and is precipitated.Although blacking phenomenon caused by oxygen lack not yet illustrates, may be by as caused by cobalt compound
The modification of metal surface and show excellent blackening.
The bonding agent that good cementability is shown with the overlay film formed by surface treating agent of the invention is not limited especially
It is fixed, it can enumerate for example: silicon systems (including acrylic acid modified, epoxy-modified), epoxy, acrylic resin system, phenolic aldehyde system, ammonia
Carbamate system, vinyl acetate system, cyanoacrylate system, SBR styrene butadiene rubbers system etc..In addition, using various viscous
Agent is connect, be bonded material is carried out with the zinc-based metal plated steel sheet for being provided with overlay film via bonding agent and is not particularly limited, example can be enumerated
Such as: steel plate, mortar, float glass, pottery magnetic substance brick and MDF (medium density fibre board (MDF)).
The zinc-based metal plated steel sheet of application surface treating agent is not particularly limited, to be formed with by well known method for plating etc.
The steel plate of the overlay film of plating containing zinc.It as method for plating, can enumerate for example: melting plating, plating etc..As zinc-plated system's steel
Plate can be enumerated: zinc plating steel plate, electroplating zinc-nickel alloy plated steel sheet, hot-dip galvanized steel sheet, melting Zn-Al alloy plating
Apply steel plate, fused zinc-aluminium-magnesium alloy plated steel sheet, fused zinc-al-mg-si alloy plated steel sheet, hot dip alloyed plating
Apply steel plate etc..Coating adhesion amount is not particularly limited, can be determined according to use environment, purposes.Here, zinc-based metal plated steel sheet
Zinc-plated system layer be following composition: other than zinc and inevitable impurity, 60 mass % Al below, 10 can also be contained
One or more of quality % Mg below, 2 mass % Si below.Here, inevitably impurity refers to due to manufacturing process
Deng and inevitably mixed impurity, can enumerate for example: Pb, Cd, Sb, Cu, Fe, Ti, Ni, B, Zr, Hf, Sc, Sn, Be,
Co, Cr, Mn, Mo, P, Nb, V, Bi, and then the 3rd race's element etc. such as can also enumerate La, Ce, Y.These inevitable impurity members
Total preferably 0.5 mass % or so of element is following.
Embodiment
By the following examples and comparative example illustrates the present invention, but the present embodiment is only simple an example, not pair
The present invention is defined.The test film made in embodiment, comparative example evaluation method is as follows.
1. material
Used plating steel are described below.
M1: melting Zn plating (coating adhesion amount 90g/m2)
M2: melting 11%Al-3%Mg-0.2%Si-Zn plating
(coating adhesion amount 90g/m2)
M3: plating Zn (coating adhesion amount 20g/m2)
M4: plating 11%Ni-Zn (coating adhesion amount 20g/m2)
M5: melting 55%Al-1.6%Si-Zn plating
(coating adhesion amount 90g/m2)
2. inorganic agent
(1) inorganic agent ingredient
Used carbonic acid zirconium compounds (A) and other zirconium compounds are described below.
A1: potassium zirconium carbonate
A2: zirconium carbonate ammonium
A3: zircon ammonium fluoride (ジ Le U Application Off ッization ア Application モ ニ ウ system)
Styrene (b1), (methyl) acrylic acid (b2), (methyl) alkyl acrylate of abbreviation will be expressed as in table 1
(b3), acrylonitrile (b4) and can with these monomers be copolymerized unsaturated monomer (b5) according to ratio shown in table 2 come using,
Obtain the polymer of B1~B38 shown in table 3.The Tg of the right end of table 2 is the glass transition temperature of each polymer.It needs to illustrate
, unsaturated monomer (b5) is from acrylic acid 2- hydroxy methacrylate, acrylic acid 4- hydroxybutyl, ethyoxyl-diethylene glycol propylene
It is suitably selected in acid esters and acrylamide.
[table 1]
[table 2]
The vfanadium compound (C) of used 2~4 valence is described below.
C1: acetoacetate vanadium
C2: vanadyl oxalate
Used phosphorus compound (D) is described below.
D1: phosphoric acid
D2:1- hydroxyl ethane -1,1- di 2 ethylhexyl phosphonic acid
Used cobalt compound (E) is described below.
E1: cobalt carbonate
E2: cobalt nitrate
The preparation > of < inorganic agent
The composition of the treatment fluid of Examples and Comparative Examples is shown in table 3A and table 3B.Treatment fluid is prepared as follows: for
Pre-prepd a certain amount of deionized water stirs liquid with paddle stirrer on one side, successively adds each ingredient on one side, so that solid
State constituent concentration reaches 15 mass %.Regulator as pH uses carbonic acid and ammonia.It should be noted that and use D1 and D2 as
When phosphorus compound (D), prepared in the way of being D1:D2=85:15 by quality when being scaled P in treatment fluid.
3. processing method
(1) degreasing
With Nihon Parkerizing Co., Ltd. alkaline degreasing agent Fine Cleaner E6406, (20g/L builds bath, 60
DEG C, 10 seconds spraying, spraying pressure 50kPa) spraying washing in 10 seconds will be carried out after former material degreasing.
(2) coating and drying for the treatment of fluid
Spreader is applied come coating process liquid, with hot air circulation type oven drying with stick.According to reaching target Zr adhesion amount
Mode, to adjust the concentration and selection rod coaters model appropriate for the treatment of fluid.It should be noted that Zr adhesion amount passes through fluorescence X
Ray analysis device ZSX-PrimusII (Co., Ltd.'s rigaku system) is measured.
Assessment item described below and test method.In addition, showing the results of the evaluation table 4A and table 4B.
Corrosion resistance
For treadmill test piece and the test film highly processed for the Sven-Gan Eriksson (エ リ Network セ Application) of 7mm is implemented, is implemented
Salt spraytest based on JIS Z 2371 is to the stipulated time.Corrosion resistance is based on the white rust occurring area after salt spraytest
Rate determines.
Corrosion proof evaluation criteria is as shown below.
Treadmill test piece (after salt spraytest 240 hours)
◎: white rust 0%
Zero: white rust is more than 0%, 5% or less
Zero-: white rust is more than 5%, 15% or less
△: white rust is more than 15%, 30% or less
×: white rust is more than 30%
Sven-Gan Eriksson processing experiment piece (after salt spraytest 72 hours)
◎: white rust 0%
Zero: white rust is more than 0%, 15% or less
Zero-: white rust is more than 15%, 30% or less
△: white rust is more than 30%, 50% or less
×: white rust is more than 50%
Anti-blackening
After standing test film 144 hours under the atmosphere of 70 DEG C × RH85% using constant temperature and moisture test machine, visually observe
Appearance.
The evaluation criteria of anti-blackening is shown in following.
◎: absolutely not change
Zero: being hardly visible variation
Zero-: several discolorations can be seen in end
△: it can be seen that several discolorations
×: it can be seen that apparent discoloration
Coating adaptation
It is white (Northwest ペ イ Application ト corporation) that ア ミ ラ ッ Network 1000 is coated on test film using rod coaters, is heated at 125 DEG C
It is 20 minutes dry, obtain 20 μm of dry film thickness.Then, it impregnates 30 minutes, is placed naturally after taking-up 24 hours in boiling water.So
Afterwards, the gridiron pattern processing for implementing 1mm, 100 lattice with knife, finds out film extant number by belt stripping test.
The evaluation criteria of coating adaptation is shown in following.
◎: extant number 100
Zero: extant number 98 or more, 100 are less than
△: extant number 50 or more, 98 are less than
×: extant number is less than 50
The stability > of < inorganic agent
Inorganic agent is placed 3 months in 40 DEG C of temperature of thermostat, observes liquid appearance.
Evaluation criteria is shown in following.
◎: it has almost no change
Zero: having several muddinesses
△: there is precipitating
×: gelation has more precipitating
Cementability evaluation
Using various bonding agents, by evaluation method 1~4, implement zinc-based metal plated steel sheet each other or zinc-based metal plated steel sheet with it is other
The cementability of material.Other former material test films used in bonding agent and evaluation method 2 are shown in following.
A: epoxy (U ニ シ system, E2300J)
Other former material test films: mortar test piece
B: acrylic acid series (electrochemically industry, ハ ー De ロ ッ Network 8)
Other former material test films: mortar test piece
C: silicon systems (Dong Li Dow Corning Corporation system, PV8303)
Other former material test films: float glass
D: silicon systems (Shi Min beats hard corporation, PM210)
Other former material test films: pottery magnetic substance brick, float glass
E: silicon systems (Shi Min beats hard corporation, ス ー パ ー X No.8008)
Other former material test films；Float glass
F: phenolic aldehyde system (Shi Min beats hard corporation, 110)
Other former material test films: nothing
G: carbamate system (Shi Min beats hard corporation, UM700)
Other former material test films: MDF (medium density fibre board (MDF))
H: vinyl acetate base system (U ニ シ system, CH18)
Other former material test films: MDF (medium density fibre board (MDF))
I: chloroprene rubber system (Shi Min beats hard corporation, 575F)
Other former material test films: MDF (medium density fibre board (MDF))
Evaluation method 1: bonding portion is made with bonding agent in 2 test films (25 ± 0.5mm × 100 ± × 1.6mm is thick)
For the lap shear test body of (25 ± 0.5mm × 12.5 ± 0.5mm), after the health stipulated time, 1 cementability is evaluated.
Evaluation method 2: by test film (25 ± 0.5mm × 100 ± 0.5mm × 1.6mm is thick) and other former material test films (25
± 0.5mm × 100 ± 0.5mm × any thick) bonding portion is made with bonding agent is (25 ± 0.5mm × 12.5 ± 0.5mm)
Lap shear test body after the health stipulated time, evaluates 1 cementability.
Evaluation method 3: after the test body health of evaluation method 1, under 50 DEG C, 85% after the stipulated time, evaluation 2
Secondary cementability.
Evaluation method 4: after the test body health of evaluation method 1, under 85 DEG C, 85% after the stipulated time, evaluation 2
Secondary cementability.
About cementability, tensile shear load and cohesional failure rate are had rated.Tensile shear load is in tensile speed:
100mm/min, room temperature: carrying out at 25 DEG C, with the tensile shear load ratio (tensile shear of test material with non-treated test film
Load/non-treated material tensile shear load) it evaluates.The evaluation criteria of tensile shear load is shown in following.
◎: 1.1 or more
Zero: more than 1.0 and less than 1.1
△: 1.0 (same with non-treated test film)
×: less than 1.0
In addition, by the remaining area (cohesional failure rate) and nothing of the bonding agent of the zinc-based metal plated steel sheet side after tensile shear(ing) test
Processing material is compared, evaluates.The evaluation criteria of cohesional failure rate is shown in following.
◎: the remaining area of bonding agent obviously increases
Zero: the remaining area of bonding agent increases
△: same with non-treated material
×: the remaining area decline of bonding agent
[table 3A]
[table 3B]
[table 4A]
[table 4B]
Claims (5)
1. a kind of zinc-based metal plated steel sheet surface treating agent, allotment has carbonic acid zirconium compounds (A), acrylic resin (B), 2~4
Vfanadium compound (C), phosphorus compound (D), cobalt compound (E) and the water of valence, pH are 8~11,
The acrylic resin (B) is to make at least to contain styrene (b1), (methyl) acrylic acid (b2), (methyl) alkyl acrylate
The resin that the monomer component of base ester (b3) and acrylonitrile (b4) is copolymerized, wherein with consolidating for whole monomer components of the resin
On the basis of state composition quality, the amount of acrylonitrile (b4) is the 20 mass % of mass %~38, and be glass transition temperature is -12 DEG C
~15 DEG C of water-soluble resin and water serial emulsion resin.
2. zinc-based metal plated steel sheet surface treating agent according to claim 1, wherein the tune of the acrylic resin (B)
Dosage is the 20 mass % of mass %~60 relative to whole solid state components of the surface treating agent,
The quality when vfanadium compound (C) is scaled V and the quality when carbonic acid zirconium compounds (A) to be scaled to Zr
Mass ratio (V)/(Zr) is 0.07~0.69,
The quality when phosphorus compound (D) is scaled P and the quality when carbonic acid zirconium compounds (A) to be scaled to Zr
Mass ratio (P)/(Zr) is 0.04~0.58,
The quality when cobalt compound (E) is scaled Co and the quality when carbonic acid zirconium compounds (A) to be scaled to Zr
Mass ratio (Co)/(Zr) be 0.005~0.08.
3. zinc-based metal plated steel sheet surface treating agent according to claim 1 or 2, wherein the acrylic resin (B)
In the amount of each monomer component, on the basis of the solid state component quality of whole monomer components of the resin, styrene (b1) is 15 matter
The mass % of %~25 is measured, (methyl) acrylic acid (b2) is the 1 mass % of mass %~10, and (methyl) alkyl acrylate (b3) is 40
The mass of quality %~58 %.
4. zinc-based metal plated steel sheet surface treating agent according to claim 1 or 2, wherein the zinc-based metal plated steel sheet it is zinc-plated
It is layer for following composition: below containing 60 mass % Al below, 10 mass % other than zinc and inevitable impurity
One or more of Mg, 2 mass % Si below.
5. zinc-based metal plated steel sheet surface treating agent according to claim 1 or 2, wherein at least one of phosphorus compound (D)
It is divided into inorganic phosphate and/or its salt.
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| PCT/JP2015/084575 WO2016093286A1 (en) | 2014-12-10 | 2015-12-09 | Surface treatment agent for zinc-plated steel sheets |
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| KR102075214B1 (en) * | 2017-12-22 | 2020-02-07 | 주식회사 포스코 | Coating composition for hot dip galvanized steel sheet having excellent corrosion-resistance and blackening-resistance the surface treated hot dip galvanized steel sheet prepared by using the coating composition and method for preparing the surface treated hot dip galvanized steel sheet |
| CN111733410B (en) * | 2020-07-07 | 2022-08-02 | 奎克化学（中国）有限公司 | Chromium-free passivation solution for zinc-aluminum-magnesium steel plate and preparation method thereof |
| CN112226754A (en) * | 2020-10-19 | 2021-01-15 | 武汉科润表面新材料有限公司 | Non-washing acrylic acid chromium-free passivator suitable for aluminum profile |
| EP4273283A1 (en) | 2021-03-01 | 2023-11-08 | Nippon Steel Corporation | Battery unit |
| EP4343928A1 (en) | 2021-05-20 | 2024-03-27 | Nippon Steel Corporation | Cooling structure, battery unit, and manufacturing method for cooling structure |
| CN117321835A (en) | 2021-05-20 | 2023-12-29 | 日本制铁株式会社 | Cooling structure, battery cell, and method for manufacturing cooling structure |
| CN114592223B (en) * | 2022-03-23 | 2023-12-26 | 中磁科技股份有限公司 | Neodymium-iron-boron magnet galvanization and surface lubrication process |
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| MY184050A (en) | 2021-03-17 |
| JPWO2016093286A1 (en) | 2017-08-03 |
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| JP6263278B2 (en) | 2018-01-17 |
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