CN102822290B - Surface treating composition - Google Patents

Surface treating composition Download PDF

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Publication number
CN102822290B
CN102822290B CN201180014567.9A CN201180014567A CN102822290B CN 102822290 B CN102822290 B CN 102822290B CN 201180014567 A CN201180014567 A CN 201180014567A CN 102822290 B CN102822290 B CN 102822290B
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mass parts
surface treatment
rust
agent
water
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CN102822290A (en
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竹山和宏
大久保崇
诸星好一
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • 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
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C23C22/73—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 characterised by the process
    • C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

Abstract

The invention provides the surface treatment plate that a kind of workability, erosion resistance, Anti-dew/whitening resistance etc. are excellent.Surface treatment agent provided by the invention comprises: water-dispersible polyurethane resin (A); Rust-preventive agent (B); Use the colloidal silica (C) of silane coupling agent process; And subsilicate (D), wherein, relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, the content of rust-preventive agent (B) is 5 ~ 50 mass parts, the content using the colloidal silica (C) of silane coupling agent process is 10 ~ 150 mass parts, the content of subsilicate (D) is 30 ~ 110 mass parts, rust-preventive agent (B) comprises titanium compound (b1) and organic phosphoric acid compound (b2), and comprises the compound that at least one is selected from vanadium compound (b3) and zirconium compounds (b4) further.

Description

Surface treating composition
Technical field
The present invention relates to the surface treating composition obtaining the excellent film such as workability, erosion resistance and Anti-dew/whitening resistance and the surface-treated metal plate that can obtain by using this surface treating composition.
Background technology
All the time, there are the following problems for the surface treatment method of use chromic salt, that is, the problem that the chromic salt smog in treatment process disperses, sewage treatment equipment need the problem of high expense and the chromic acid chemically problem etc. that causes of conversion processing film stripping.In addition, with IARC(InternationalAgencyforResearchonCancerReview: international cancer research institution) for 6 valency chromium cpds are appointed as human carcinogen's property material by numerous public organizations of representative, be the material be very harmful to.Therefore, be strongly required to develop to possess the surface treated steel plate not comprising the film of harmful chromium that one deck has workability and erosion resistance concurrently.
Chromium is not contained and the composition having the film of workability and erosion resistance concurrently as being formed, such as, Patent Document 1 discloses a kind of composition, it can form the film comprising water soluble resin and/or water-dispersed resin, lubricant, silicon dioxide granule and vanadium compound.In addition, Patent Document 2 discloses a kind of metal surface treating composition, it comprises the fluorine cpd that water-soluble or water-dispersible polyurethane resin, silicon dioxide granule, silane coupling agent, vanadic acid compound and at least one are selected from hydrofluoric acid metal and hydrofluoric acid metal-salt.These cooperation compositions described in patent documentation 1 and 2, although can obtain workability, film that erosion resistance is excellent, have problems in Anti-dew/whitening resistance.
When Anti-dew/whitening resistance is poor, uses the coil of strip after surface treatment agent process to soak into from its end due to moisture thus the phenomenon of albefaction occurs on the surface of steel plate, thus affect the use of user to steel plate.The albefaction occurred to prevent this coil of strip and the content of the silicon dioxide granule reduced in surface treatment agent or vanadium compound time, erosion resistance can be caused to reduce.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-183587 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-298837 publication
Summary of the invention
Inventing problem to be solved is, provides the surface treatment agent that can form the excellent surface-treated metal plate such as workability, erosion resistance, Anti-dew/whitening resistance and the steel plate being coated with this surface treatment agent.
The present inventor finds, by the solution using following surface treatment agent can realize above-mentioned problem, thus completes the present invention.Described surface treatment agent comprises: water-dispersible polyurethane resin (A); Rust-preventive agent (B); Use the colloidal silica (C) of silane coupling agent process; And subsilicate (D), wherein, relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, the content of rust-preventive agent (B) is 5 ~ 50 mass parts, the content using the colloidal silica (C) of silane coupling agent process is 10 ~ 150 mass parts, the content of subsilicate (D) is 30 ~ 110 mass parts, and, rust-preventive agent (B) comprises titanium compound (b1) and organic phosphoric acid compound (b2), and comprises the compound that at least one is selected from vanadium compound (b3) and zirconium compounds (b4) further.
That is, the present invention relates to following item:
Item 1. surface treatment agents, comprise: water-dispersible polyurethane resin (A); Rust-preventive agent (B); Use the colloidal silica (C) of silane coupling agent process; And subsilicate (D), wherein, relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, the content of rust-preventive agent (B) is 5 ~ 50 mass parts, the content using the colloidal silica (C) of silane coupling agent process is 10 ~ 150 mass parts, the content of subsilicate (D) is 30 ~ 110 mass parts, and
Rust-preventive agent (B) comprises titanium compound (b1) and organic phosphoric acid compound (b2), and comprises the compound that at least one is selected from vanadium compound (b3) and zirconium compounds (b4) further.
The surface treatment agent of item 2. as described in item 1, wherein, it also comprises the total solids level of the water-dispersible polyurethane resin (A) relative to 100 mass parts, the colloidal silica (E) not using silane coupling agent process of 0.1 ~ 160 mass parts.
3. films, it is included in and steel plate applies item 1 or the surface treatment agent described in item 2 to form dry film weight for 0.1 ~ 3.0g/m 2film.
According to surface treatment agent of the present invention, the surface treated steel plate that workability, erosion resistance, Anti-dew/whitening resistance etc. are excellent can be obtained.
Embodiment
Surface treatment agent of the present invention, is characterized in that, comprises: water-dispersible polyurethane resin (A); Specific rust-preventive agent (B); Use the colloidal silica (C) of silane coupling agent process; And subsilicate (D), wherein, relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, the content of rust-preventive agent (B) is 5 ~ 50 mass parts, the content using the colloidal silica (C) of silane coupling agent process is 10 ~ 150 mass parts, and the content of subsilicate (D) is 30 ~ 110 mass parts.Below, be described in detail.
water-dispersible polyurethane resin (A):
Surface treatment agent of the present invention, is coated with the tack between film and workability, uses urethane resin from the view point of the top on gained film.Water-dispersible polyurethane resin is, as required glycol, diamines etc. such there is the low-molecular weight compound of plural active hydrogen and the existence of chainextender under, make the urethane generation chain extension formed by the polyvalent alcohol such as polyester polyol, polyether glycol and vulcabond, thus the material stably dispersed or dissolved in water, known material can be widely used.
Method in water is stably dispersed or dissolved in as making urethane resin, such as following method can be utilized: (1) by importing hydroxyl at the side chain of polyether polyols with reduced unsaturation or end, amino, carboxyl isoiony group give wetting ability, by self-emulsifying thus the method be dispersed or dissolved in water; (2) method using emulsifying agent and mechanical shear stress to be dispersed in water with making following polymer enforced, wherein, described polymkeric substance comprise reaction terminate after polymkeric substance or by utilizing the block agent such as oxime, alcohol, phenol, mercaptan, amine, sodium bisulfite to make the polymkeric substance after terminal isocyanate group block; (3) by the carbamate prepolymer with terminal isocyanate group and water, emulsifying agent and extend agent and mix, use mechanical shear stress to carry out method that is decentralized and high molecular simultaneously; (4) water-soluble polyol using polyoxyethylene glycol such as the polyvalent alcohol of urethane main raw material, and then is dispersed or dissolved in the method etc. in water with the form of water-soluble urethane.In addition, the molecular weight of urethane resin is not particularly limited, and weight-average molecular weight is preferably 10, and 000 ~ 1,000,000, be more preferably 50,000 ~ 500,000.
As the commercially available product of above-mentioned urethane resin, such as, can enumerate: HYDRANHW-330, HYDRANHW-340, HYDRANHW-350(are large Japanese ink chemical industrial company system), SUPERFLEX100, SUPERFLEX130, SUPERFLEX150, SUPERFLEX170(be the first industrial pharmaceutical Inc.), ADECABONTIGHTERHUX-206, ADECABONTIGHTERHUX-232, ADECABONTIGHTERHUX-360, ADECABONTIGHTERHUX-540(be Chinese mugwort Dicon A/S system) etc.
rust-preventive agent (B):
Surface treatment agent of the present invention, by comprising rust-preventive agent (B), thus can obtain the excellent film of erosion resistance.Above-mentioned rust-preventive agent (B) comprises titanium compound (b1) and organic phosphoric acid compound (b2), also comprises the salt that at least one is selected from the metal of vanadium compound (b3) and zirconium compounds (b4).Below, each composition comprised rust-preventive agent (B) carries out describing.
titanium compound (b1)
As above-mentioned titanium compound (b1), such as, can enumerate: the salt, titanium oxide, titanium fluoride etc. of ammonium titanium fluoride, phosphoric acid-oxygen-titanium, titanium chloride, titanium sulfate, titanyl sulfate, Titanium Nitrate, titanyl nitrate, hydrofluotitanic acid, hydrofluotitanic acid.Be preferably ammonium titanium fluoride, hydrofluotitanic acid, phosphoric acid-oxygen-titanium etc.
From the view point of rust-preventing characteristic, stability etc., with the total solids level of the rust-preventive agent of 100 mass parts (B) for benchmark, the content of titanium compound (b1) is preferably 10 ~ 50 mass parts, is particularly preferably 20 ~ 40 mass parts.These titanium compounds (b1) can be used alone one, also can mix two or more use.
organic phosphoric acid compound (b2)
As organic phosphoric acid compound (b2), such as, can enumerate: 1-hydroxy methane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxy propane-1,1-di 2 ethylhexyl phosphonic acid etc., 2-hydroxyphosphono acetic acid, 2-phosphinylidyne butane-1,2,4-tricarboxylic acid and their salt etc.In the present invention, phosphoric acid-oxygen-titanium is not use as organic phosphoric acid compound, but uses as titanium compound.
Above-mentioned organic phosphoric acid compound (b2) has the effect that the storage stability of rust-preventive agent (B) is improved, wherein, and particularly preferably 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid.From the view point of rust-preventing characteristic, stability etc., with the total solids level of the rust-preventive agent of 100 mass parts (B) for benchmark, the content of organic phosphoric acid compound (b2) is preferably 20 ~ 70 mass parts, is particularly preferably 40 ~ 60 mass parts.These organic phosphoric acid compounds (b2) can be used alone one, also can mix two or more use.
vanadium compound (b3)
As vanadium compound (b3), such as, can enumerate: lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium meta-vanadate etc., wherein, particularly from the view point of stability, erosion resistance, preferred ammonium meta-vanadate.
From the view point of erosion resistance etc., with the total solids level of the rust-preventive agent of 100 mass parts (B) for benchmark, the content of vanadium compound (b3) is preferably 0 ~ 30 mass parts, is particularly preferably 5 ~ 25 mass parts.These vanadium compound (b3) can be used alone one, also can mix two or more use.
zirconium compounds (b4)
As zirconium compounds (b4), such as, can enumerate: the salt such as sodium salt, sylvite, lithium salts, ammonium salt, zirconium nitrate, zirconium hydroxide, zirconium carbonate ammonium of fluorine zirconic acid, wherein, from the view point of erosion resistance etc., ammonium fluozirconate is preferably, and in Storage etc., zirconium carbonate ammonium is preferred.
From the view point of erosion resistance etc., with the total solids level of the rust-preventive agent of 100 mass parts (B) for benchmark, the content of zirconium compounds (b4) is preferably 0 ~ 30 mass parts, is particularly preferably 5 ~ 25 mass parts.
In addition, from the view point of stability and the erosion resistance of surface treatment agent, with the total solids level of the rust-preventive agent of 100 mass parts (B) for benchmark, the total content of vanadium compound (b3) and zirconium compounds (b4) is preferably 5 ~ 60 mass parts, is particularly preferably 10 ~ 50 mass parts.These zirconium compoundss (b4) can be used alone one, also can mix two or more use.
In the preparation of rust-preventive agent (B), the temperature mixed each composition is 10 DEG C ~ 100 DEG C, and be preferably 30 DEG C ~ 90 DEG C, the time mixed each composition is 1 minute ~ 180 minutes, is preferably 10 minutes ~ 60 minutes.From the aspect making each component dissolves in water, preferably heat.
In addition, in order to improve the stability of surface treatment agent, and in order to improve workability, erosion resistance and Anti-dew/whitening resistance, relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, in surface treatment agent of the present invention, the ratio of rust-preventive agent (B) is 5 ~ 50 mass parts, be preferably 6 ~ 35 mass parts, more preferably 7 ~ 25 mass parts.
use the colloidal silica (C) of silane coupling agent process:
Surface treatment agent of the present invention comprises the colloidal silica (C) (following, sometimes referred to as " (C) composition ") using silane coupling agent process.The colloidal silica (C) of use silane coupling agent process can by the solids content relative to the colloidal silica of the starting material of 100 mass parts, add 1 ~ 50 mass parts, be preferably the silane coupling agent of 3 ~ 30 mass parts, more preferably 5 ~ 20 mass parts, and make it react and obtain.
When carrying out above-mentioned reaction, the mutual condensation of silane coupling agent be avoided or cause viscosity to rise with colloidal silica vigorous reaction or gelation occurs.Temperature of reaction is 10 DEG C ~ 100 DEG C, and be preferably 40 DEG C ~ 90 DEG C, the reaction times is 1 minute ~ 180 minutes, is preferably 10 minutes ~ 60 minutes.In order to the hydroxyl and silane coupling agent that make colloidal silica react efficiently, also preferably heat.
In addition, when silane coupling agent and colloidal silica pasc reaction, metallic compound, water soluble resin, tensio-active agent etc. can also be added as required.
As above-mentioned silane coupling agent, such as, can enumerate: vinyl methoxy silane, vinylethoxysilane, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, β-(3,4 expoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl diethoxy silane, γ-glycidoxypropyl group triethoxyl silane, N-β (amino-ethyl) gamma-amino hydroxypropyl methyl dimethoxysilane, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloyloxypropyl methyl diethoxy silane, γ-methacryloxypropyl, γ-mercaptopropyi methyl dimethoxysilane, γ mercaptopropyitrimethoxy silane, p-styryl Trimethoxy silane, γ-acryloxypropyl Trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-ureidopropyltriethoxysilane, γ-r-chloropropyl trimethoxyl silane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, γ-isocyanic ester propyl-triethoxysilicane, γ-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-(vinyl benzyl amine)-beta-aminoethyl-gamma-amino propyl trimethoxy silicane etc., these compounds can be used alone one, also can mix two or more use.
As commercially available product, KBM-403, KBM-502, KBM-503, KBM-603, KBE-903, KBM-603, KBE-602, KBE-603(of Silicone Inc. of SHIN-ETSU HANTOTAI are trade(brand)name) etc.
On the other hand, colloidal silica preferably uses, and makes silicon-dioxide (SiO by sodium, ammonium etc. 2) ultramicron stabilization after colloidal silica.Silicon-dioxide (SiO 2) ultramicron be preferably, carry out polymer by siloxane bond and to quantize and its surface can have the spherical silicon-dioxide of hydroxyl.In addition, preferably the size of this particulate in the scope of 1 ~ 50nm, particularly 5 ~ 20nm.
Be somebody's turn to do the spendable colloidal silica of (C) composition, can obtain in the mode of commercially available product, such as, can enumerate: SNOWTEXS, SNOWTEXNXS, SNOWTEXC(are Nissan Chemical Ind Ltd's system, trade(brand)name), ADELITEAT-20A, ADELITEAT-2045(Asahi Denka Co., Ltd. system, trade(brand)name) etc.
In addition, as the described metallic compound that can add when reacting, such as, can enumerate: the metallic compound of zirconium, titanium, zinc, aluminium etc.Specifically, zirconium compounds can be enumerated: the salt, zirconium white, bromination oxygen zirconium, zirconyl acetate, zirconyl carbonate, Zirconium tetrafluoride etc. of zirconium chloride, zirconyl chloride, zirconium sulfate, zirconyl sulfate, zirconium nitrate, Zircosol ZN, hydrofluoric acid zirconium, fluorine zirconic acid.
As titanium compound, can enumerate: the salt, titanium oxide, titanium fluoride etc. of titanium chloride, titanium sulfate, titanyl sulfate, Titanium Nitrate, titanyl nitrate, hydrofluoric acid titanium, hydrofluotitanic acid.
As zn cpds, such as, can enumerate: zinc acetate, zinc lactate, zinc oxide, zinc nitrate etc.Ammonium compound can enumerate ammonium nitrate.
Above-mentioned water soluble resin is the resin beyond above-mentioned carbamate resins, such as, can enumerate: the water dispersion of acrylic resin, poly-(N-vinyl acetamide), polyvinylpyrrolidone, polyacrylamide, polyoxyethylene glycol, water-soluble nylon, Sumstar 190 etc.
Above-mentioned tensio-active agent can be any one in non-ionic species tensio-active agent, anionic based surfactants, cationic based surfactants and zwitterionic classes tensio-active agent.Nonionic class tensio-active agent such as can be enumerated: Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene compound, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine, alkylalkanol acid amides etc.Anionic based surfactants such as can be enumerated: soap, alkyl sodium sulfate ester salt, alkylbenzene sulfonate, alkylphosphonic etc.As cationic based surfactants, such as, can enumerate: alkylamine salt, quaternary ammonium salt etc.Zwitterionics such as can enumerate alkyl betaine.
In addition, in surface treatment agent of the present invention, relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, the content of the colloidal silica (C) of silane coupling agent process is used to be 10 ~ 150 mass parts, to be preferably 12 ~ 100 mass parts, more preferably 15 ~ 80 mass parts, to realize good erosion resistance and Anti-dew/whitening resistance.
subsilicate (D):
Containing subsilicate (D) in surface treatment agent of the present invention.As subsilicate (D), such as, can enumerate: water glass, potassium silicate, lithium silicate, ammonium silicate etc.Wherein, from the view point of raising Anti-dew/whitening resistance, preferred water glass.
In addition, from the stability of surface treatment agent and the aspect of erosion resistance, relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, the content of subsilicate (D) is 30 ~ 110 mass parts, be preferably 35 ~ 105 mass parts, more preferably 40 ~ 100 mass parts.
do not utilize the colloidal silica (E) that silane coupling agent carries out processing:
In surface treatment agent of the present invention, according to required performance, can also containing the colloidal silica (E) (hereinafter referred to as " untreated colloidal silica (E) ") not utilizing silane coupling agent to carry out processing.Specifically, preferably can use the colloidal silica of starting material illustrated in the project of above-mentioned (C) composition, can enumerate: SNOWTEXNXS, SNOWTEXXS(are Nissan Chemical Ind Ltd's system, trade(brand)name), ADELITEAT-20A(ends Dicon A/S's system) etc.
Relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, the content of untreated colloidal silica (E) is 0.1 ~ 160 mass parts, be preferably 50 ~ 150 mass parts, more preferably 90 ~ 145 mass parts, to realize good erosion resistance.
In addition, in surface treatment agent of the present invention, except mentioned component, can also comprise: such as, lubricant, tackifier, anti-shrinking medium, defoamer, tensio-active agent, oxygenant, antiseptic-germicide, rust-preventive agent (tannic acid, phytic acid, benzotriazole etc.), tinting pigment, pigment extender, rust-stabilising pigment, conductive pigment etc.In addition, can also add as required: such as, the hydrophilic solvents such as methyl alcohol, ethanol, Virahol, glycol solvent.
the manufacture of surface-treated metal plate
Surface treatment agent of the present invention can omit existing chromic salt treatment process, by directly applying on the plated steel sheet such as untreated cold-rolled steel sheet, aluminium sheet etc., untreated steel plate galvanized, Aludip and making it dry, thus the excellent metal sheet of workability, erosion resistance and Anti-dew/whitening resistance can be obtained.
As above-mentioned steel plate galvanized, can enumerate: electrogalvanizing steel plate, hot-dip galvanizing sheet steel, nickel-zinc alloy electropalting steel plate, zinc-plated-aluminium alloy steel plate etc.As zinc-plated-aluminium steel plate, when using zinc as the metal sheet of coating principal constituent, can enumerate: 5%Al-Zn steel plate, 8%Al-Zn steel plate, 15%Al-Zn steel plate etc., in addition, for using aluminium as the metal sheet of coating principal constituent, can enumerate: 55%Al-Zn steel plate, 75%Al-Zn steel plate etc.In addition, also can be applicable to, with the addition of in Al-Zn alloy Mg, Mn, Si, Ti, Ni, Co, Pb, Sn, Cr and rare metal (La, Ce, Y, Nb etc.) etc., composite deposite steel plate using aluminum and zinc as principal constituent.
Surface treatment agent of the present invention is coated on above-mentioned metal sheet and uses, and its coating amount is preferably 0.1 ~ 3.0g/m in dry film weight 2, be more preferably 0.5 ~ 3.0g/m 2.
When surface treatment agent of the present invention is coated in film forming on steel plate, after by thinners such as water the viscosity of surface treatment agent being suitably adjusted to 5 ~ 30mPas according to coating amount, applied by the known method of such as roller coat coating, spray application, dip coating, to reach predetermined film weight.Afterwards, at atmosphere temperature be under the condition of 150 DEG C ~ 250 DEG C dry 10 ~ 40 seconds.Preferably metal sheet now be up to Da Wendu (PMT) in the scope of 90 DEG C ~ 160 DEG C.Coated surfaces treatment agent make it dry in the above described manner, manufactures the metal sheet that workability, erosion resistance and Anti-dew/whitening resistance etc. are excellent thus.
embodiment
Below, by preparation example, embodiment and comparative example, the present invention is described in detail further, but the present invention is not limited to these examples.Each example " part " represents mass parts, and " % " represents quality %.
the preparation example of preparation example 1 rust-preventive agent No.1
In the beaker of glass, to deionized water 400 parts, ammonium titanium fluoride 24 parts, 1-hydroxy methane-1,1-di 2 ethylhexyl phosphonic acid 46 parts, ammonium meta-vanadate 12 parts, ammonium fluozirconate 8 parts, zirconium carbonate ammonium 10 parts stir, make simultaneously they mixed be incorporated in 80 DEG C at heating two hours, let cool afterwards, obtain rust-preventive agent No.1 thus.
preparation example 2 ~ 8
Except adopting the formula of table 1, by the method identical with preparation example 1, obtain rust-preventive agent No.2 ~ No.8 that solids content is 20%.
Table 1
Content represents solid masses part
use the preparation of the colloidal silica (C) of silane coupling agent process
The preparation example of preparation example 9 improved silica No.1
SNOWTEXNXS(particle diameter is about 5nm, SiO 2concentration is 15% mass ratio, Nissan Chemical Ind Ltd's system) 667 parts (solids contents 100 parts) to put into internal volume be possessing in the glass reaction vessel of stirrer of 1L.Add by organosilicon Inc. of mixing KBM-403(SHIN-ETSU HANTOTAI wherein, trade(brand)name, 3-glycidoxypropyltrime,hoxysilane) mixture of gained after 20 parts (solids content) and ethanol 30 parts, after stirring, mixture be heated to 95 DEG C and stir 2 hours, obtaining the colloidal silica and the improved silica No.1 that use silane coupling agent process.
the preparation example of preparation example 10 improved silica No.2
SNOWTEXNXS(particle diameter is about 5nm, SiO 2concentration is 15% mass ratio, Nissan Chemical Ind Ltd's system) 667 parts (solids contents 100 parts) to put into internal volume be possessing in the glass reaction vessel of stirrer of 1L.Add by organosilicon Inc. of mixing KBM-503(SHIN-ETSU HANTOTAI wherein, trade(brand)name, 3-methacryloxypropyl trimethoxy silane) mixture that obtains after 10 parts (solids content) and ethanol 30 parts, after stirring, mixture be heated to 95 DEG C and stir 2 hours, obtaining the colloidal silica and the improved silica No.2 that use silane coupling agent process.
the preparation example of preparation example 11 improved silica No.3
SNOWTEXNXS(particle diameter is about 5nm, SiO 2concentration is 15% mass ratio, Nissan Chemical Ind Ltd's system) 667 parts (solids contents 100 parts) to put into internal volume be possessing in the glass reaction vessel of stirrer of 1L.Add by organosilicon Inc. of mixing KBE-903(SHIN-ETSU HANTOTAI wherein, trade(brand)name, APTES) mixture that obtains after 5 parts (solids content) and ethanol 7.5 parts, after stirring, mixture be heated to 95 DEG C and stir 2 hours, obtaining the colloidal silica and the improved silica No.3 that use silane coupling agent process.
the preparation example of preparation example 12 improved silica No.4
SNOWTEXNXS(particle diameter is about 5nm, SiO 2concentration is 15% mass ratio, Nissan Chemical Ind Ltd's system) 667 parts (solids contents 100 parts) to put into internal volume be possessing in the glass reaction vessel of stirrer of 1L.Add by organosilicon Inc. of mixing KBM-403(SHIN-ETSU HANTOTAI wherein, trade(brand)name, 3-glycidoxypropyltrime,hoxysilane) mixture that obtains after 5 parts (solids content) and ethanol 30 parts, after stirring, add ammonium meta-vanadate 5 parts (solids content) wherein, stir, mixture be heated to 95 DEG C and stir 2 hours, obtain the colloidal silica and the improved silica No.4 that use silane coupling agent process.
the preparation example of preparation example 13 improved silica No.5
SNOWTEXNXS(particle diameter is about 5nm, SiO 2concentration 15% mass ratio, Nissan Chemical Ind Ltd's system) 667 parts (solids contents 100 parts) to put into internal volume be possessing in the glass reaction vessel of stirrer of 1L.Add by organosilicon Inc. of mixing KBM-403(SHIN-ETSU HANTOTAI wherein, trade(brand)name, 3-glycidoxypropyltrime,hoxysilane) mixture that obtains after 10 parts (solids content) and ethanol 70 parts, after stirring, add ammonium meta-vanadate 5 parts (solids content), zirconium carbonate ammonium 5 parts (solids content), be heated to 95 DEG C and stir 2 hours, obtaining the colloidal silica and the improved silica No.5 that use silane coupling agent process.
The formula of improved silica No.1 ~ No.5 shown in following table 2.
Table 2
Content represents solid masses part
the preparation of surface treatment agent
embodiment 1 ~ 18
According to the formula shown in following table 3 and table 4, by stirrer, each composition is mixed fully, add deionized water adjustment solids content, thus make surface treatment agent No.1 ~ No.18 that solids content is 20%.
Table 3
Content represents solid masses part
Table 4 (continued 3)
Content represents solid masses part
(note 1) ADEKABONTIGHTERHUX-206: Chinese mugwort Dicon A/S system, trade(brand)name, water-dispersible polyurethane resin
(note 2) ADEKABONTIGHTERHUX-540: Chinese mugwort Dicon A/S system, trade(brand)name, water-dispersible polyurethane resin
(note 3) SUPERFLEX150: the first industrial pharmaceutical Inc., trade(brand)name, water-dispersible polyurethane resin
(note 4) SUPERFLEX500: the first industrial pharmaceutical Inc., trade(brand)name, water-dispersible polyurethane resin
(note 5) SNOWTEXNXS: Nissan Chemical Industries Inc., trade(brand)name, colloidal silica, particle diameter 5mm
(note 6) ADELITEAT-2045: Chinese mugwort Dicon A/S system, trade(brand)name, colloidal silica, median size 5nm.
comparative example 1 ~ 8
By stirrer, each composition shown in following table 5 fully mixed, add deionized water adjustment solids content, thus make the substrate treating agent No.19 ~ No.26 of solids content 20%.
Table 5
Content represents solid masses part
making and performance evaluation of surface treatment plate
embodiment 19
Utilize roller coating machine at hot-dip galvanizing sheet steel (thickness of slab 0.6mm, coating adhesion amount 100g/m 2) upper coated surfaces treatment agent No.1, reach 0.5g/m to make dry film 2, be dry 10 seconds at atmosphere temperature under the condition of 230 DEG C, thus make surface treatment plate No.1.
embodiment 20 ~ 36
Except use surface treatment agent No.2 ~ No.18, operate similarly to Example 1, obtain surface treatment plate No.2 ~ No.18.According to aftermentioned test method, the surface treatment plate of gained is tested.The results are shown in table 6 ~ table 7.
Table 6
Table 7
comparative example 9 ~ 16
Except using surface treatment agent No.19 ~ No.26, operate similarly to Example 1, obtain surface treatment plate No.19 ~ No.26.According to aftermentioned test method, the surface treatment plate of gained is tested.The results are shown in table 8.
Table 8
test method
(note 7) film outward appearance: about each surface treatment plate, film outward appearance is evaluated according to following standard by visual:
B represents, film is level and smooth continuous film and transparent;
C represents, film is level and smooth continuous film, there is obvious gonorrhoea, or exists significantly painted;
D represents, does not become level and smooth continuous print film.
(note 8) workability: metal sheet cup-drawing test instrument 142 type using Erichsen Inc., under the following conditions, deep-draw processing experiment is carried out to each surface treatment plate:
Test temperature is 20 DEG C and 80 DEG C
Sheet-holder pressure 1500Kg
Punch diameter 50mm
Blank diameter 110mm
Drawing is than 2.2
Process velocity 10mm/ second
Test board after processing is evaluated according to following standard by visual:
A: without dirt settling on punch die, does not find scratch on the surface of machined object;
B: dirt settling punch die having trace, finds small scratch on the surface of machined object;
C: punch die has slightly many dirt settlings, find more scratch on the surface of machined object;
D: punch die has a large amount of dirt settlings, finds significantly scratch on the whole surface of machined object.
(note 9) erosion resistance: implement salt spray testing according to JISZ-2371.Carry out the test of 360 hours to " flat board " before processing, test to above-mentioned " workability " test that the test portion obtained carries out 240 hours, the generation degree according to becoming rusty is evaluated according to following standard:
A represents, does not find the generation of becoming rusty completely;
B represents, the area being less than 5% finds the generation of becoming rusty;
C represents, more than 5%, the area being less than 20% finds the generation of becoming rusty;
D represents, the area more than 20% finds the generation of becoming rusty.
(note 10) Anti-dew/whitening resistance: the deionized water of the 1ml that dripped on each surface treatment plate by glass pipette, after at room temperature placing drying, evaluate according to following judgement criteria:
A represents, does not have vestige.
B represents, finds vestige slightly;
C represents, finds variable color slightly;
D represents, finds obvious variable color.
(note 11) treatment agent stability:
Be add each surface treatment agent of 500g in the Glass Containers of 1L and seal in inner capacities, preserve 14 days in the thermostatic chamber of 40 DEG C.Afterwards, return room temperature, by visual, state in container is observed, evaluate according to following standard.
A represents: do not find soft junction block or separation, for well;
B represents: although find soft junction block or separation, become even by the stirrings of less than 10 minutes;
C represents: find soft junction block or separation, by more than 10 minutes and the stirring being less than 60 minutes becomes even;
D represents: find scleroma block or separation, even if also cannot become even by the stirring more than 60 minutes.
(note 12) comprehensive evaluation:
In the surface-treated field belonging to the present invention, expect the film outward appearance of surface treatment plate, workability, erosion resistance and Anti-dew/whitening resistance and treatment agent stability all excellent.Therefore, comprehensive evaluation is carried out according to following standard:
A represents: film outward appearance, workability, erosion resistance, Anti-dew/whitening resistance and treatment agent stability are all that A evaluates or B evaluates, and A evaluation is at least one;
B represents: above-mentioned five is all that B evaluates;
C represents: above-mentioned five is all that A, B or C evaluate, and C evaluation is at least one;
D represents: the project that D evaluates is at least one.
industrial Availability
The steel plate that the excellent household electrical appliances such as workability, erosion resistance, Anti-dew/whitening resistance, automobile are used can be obtained.

Claims (3)

1. surface treatment agent, it comprises:
Water-dispersible polyurethane resin (A);
Rust-preventive agent (B);
Use the colloidal silica (C) of silane coupling agent process; And
Subsilicate (D),
Relative to the total solids level of the water-dispersible polyurethane resin (A) of 100 mass parts, the content of described rust-preventive agent (B) is 5 ~ 50 mass parts, the content of the colloidal silica (C) of described use silane coupling agent process is 10 ~ 150 mass parts, the content of described subsilicate (D) is 30 ~ 110 mass parts
Wherein, described rust-preventive agent (B) comprises titanium compound (b1) and organic phosphoric acid compound (b2), and comprises the compound that at least one is selected from vanadium compound (b3) and zirconium compounds (b4) further.
2. surface treatment agent as claimed in claim 1, it also comprises the total solids level of the water-dispersible polyurethane resin (A) relative to 100 mass parts, the colloidal silica (E) not using silane coupling agent process of 0.1 ~ 160 mass parts.
3. film, it is included in and steel plate applies surface treatment agent described in claim 1 or 2 to form dry film weight for 0.1 ~ 3.0g/m 2film.
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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5480779B2 (en) * 2010-11-09 2014-04-23 株式会社神戸製鋼所 Pre-coated aluminum plate
JP5850526B2 (en) * 2011-10-04 2016-02-03 関西ペイント株式会社 Coating composition and coating film forming method
CN103360820B (en) * 2012-03-31 2015-11-25 攀钢集团攀枝花钢铁研究院有限公司 A kind of metal protection coating and uses thereof and hot-dip metal plated material
JP5457611B1 (en) * 2012-04-27 2014-04-02 日本パーカライジング株式会社 Surface-treated galvanized steel sheet excellent in scratch and end face corrosion resistance and method for producing the same
TWI493077B (en) * 2012-04-27 2015-07-21 China Steel Corp A water-based metal surface treatment agent and a metal surface treatment method using the same
IN2015DN01537A (en) 2012-08-29 2015-07-03 Ppg Ind Ohio Inc
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
TWI555881B (en) * 2012-11-16 2016-11-01 China Steel Corp A water-based metal surface treatment agent and a metal surface treatment method using the same
CN103214886B (en) * 2013-02-04 2016-08-10 安徽省繁昌县皖南阀门铸造有限公司 A kind of rust-proof oil containing butyl acrylate
JP6043663B2 (en) * 2013-03-21 2016-12-14 日本パーカライジング株式会社 Water-based hydrophilic coating composition that forms a film excellent in self-cleaning ability against adhering dirt and surface treatment material that forms a film excellent in self-cleaning ability against adhering dirt
CN104059489B (en) * 2013-05-03 2016-05-25 攀钢集团攀枝花钢铁研究院有限公司 A kind of metal surface chemical pretreatment solution and its production and use and hot-dip metal plated material
CN104059481B (en) * 2013-05-03 2016-06-08 攀钢集团攀枝花钢铁研究院有限公司 Application use paint and its production and use and coated metallic material
JP6315750B2 (en) * 2013-06-10 2018-04-25 関西ペイント株式会社 Aqueous metal surface treatment agent
WO2015019700A1 (en) * 2013-08-09 2015-02-12 Nok株式会社 (nitrile rubber)-metal-laminated gasket material
JP2015074743A (en) * 2013-10-10 2015-04-20 共栄社化学株式会社 Aqueous rust-removing paint
JP6366333B2 (en) * 2014-04-16 2018-08-01 新日鐵住金株式会社 Painted metal plate for automobiles with excellent resistance weldability, corrosion resistance, and formability
CN104099007B (en) * 2014-06-19 2016-07-06 锐展(铜陵)科技有限公司 A kind of many Dow metals surface conditioning agent
CN104099021B (en) * 2014-06-19 2016-07-06 锐展(铜陵)科技有限公司 A kind of anti-corrosive antibacterial Aluminum alloy surface treatment agent
CN104099017A (en) * 2014-06-19 2014-10-15 锐展(铜陵)科技有限公司 Rustless aluminium alloy surface treating agent
CN104929584B (en) * 2015-06-23 2017-11-10 重庆科技学院 Shaft in wall anti-corrosion method
JP2017087501A (en) * 2015-11-06 2017-05-25 新日鐵住金株式会社 Surface-treated steel plate
RU2729485C1 (en) 2016-08-24 2020-08-07 Ппг Индастриз Огайо, Инк. Iron-containing cleaner composition
JP6757220B2 (en) * 2016-09-27 2020-09-16 日本パーカライジング株式会社 Surface treatment agent for metal materials and its manufacturing method, and metal materials with surface treatment coating and its manufacturing method
JP6248270B1 (en) * 2016-12-22 2017-12-20 日本表面化学株式会社 Process for producing anti-rust film forming agent for metal to be processed and metal to be processed with anti-rust film.
CN107151518A (en) * 2017-05-23 2017-09-12 青岛辰达生物科技有限公司 It is a kind of for water paint of corrosive protection of aluminium alloy and its preparation method and application
CN107177295A (en) * 2017-05-25 2017-09-19 滕晓明 A kind of antirust paint
DE102018009153B4 (en) * 2017-11-22 2021-07-08 Mitsubishi Heavy Industries, Ltd. COATING PROCESS
CN112941499A (en) * 2021-01-29 2021-06-11 宁波百靓空间艺术工程有限公司 Surface treatment method of stainless steel product

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2992591B2 (en) * 1989-12-18 1999-12-20 ジーイー東芝シリコーン株式会社 Silica core-silicone shell, emulsion containing the same and method of producing emulsion
JPH04180921A (en) * 1990-11-16 1992-06-29 Toray Ind Inc Production of polyester
JP2975331B2 (en) * 1997-07-22 1999-11-10 関西ペイント株式会社 Metal surface treatment composition and galvanized steel sheet having a coating formed by the composition
JP2003183587A (en) * 2001-12-19 2003-07-03 Kansai Paint Co Ltd Composition for lubricating film and metal plate excellent in lubricity using the same
JP2004238638A (en) * 2002-12-09 2004-08-26 Kansai Paint Co Ltd Surface treatment composition and surface-treated metal strip
JP2005298837A (en) * 2004-04-06 2005-10-27 Kansai Paint Co Ltd Metal surface treatment composition and metal plate using the same
JP4575047B2 (en) * 2004-06-29 2010-11-04 関西ペイント株式会社 Metal surface treatment composition and metal surface treatment steel plate
JP4688715B2 (en) * 2006-03-31 2011-05-25 株式会社神戸製鋼所 Surface-treated metal plate with excellent corrosion resistance and surface properties

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