CN107299352B - Metal surface treating agent - Google Patents
Metal surface treating agent Download PDFInfo
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- CN107299352B CN107299352B CN201710241715.XA CN201710241715A CN107299352B CN 107299352 B CN107299352 B CN 107299352B CN 201710241715 A CN201710241715 A CN 201710241715A CN 107299352 B CN107299352 B CN 107299352B
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
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Abstract
The present invention relates to a metal surface treatment agent. The present invention provides non-chromate goldThe surface treating agent can impart excellent workability, adhesion and corrosion resistance to a metal surface when used as a pretreatment agent for a coating layer of paint or the like on the metal surface. A metal surface treating agent comprising a benzotriazole compound represented by the general formula (1) and a silane coupling agent. In the formula (1), R1Independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2R represents an alkylene group having 1 to 10 carbon atoms3And R4Independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group represented by the general formula (2), R3And R4At least one of (A) and (B) is a group represented by the general formula (2), wherein R in the formula (2)5Represents an alkylene group having 1 to 10 carbon atoms.
Description
Technical Field
The present invention relates to a metal surface treatment agent, and more particularly, to a chromium-free non-chromate metal surface treatment agent.
Background
Chromium-based surface treatment agents such as chromate and phosphoric acid chromate have been widely used as metal surface treatment agents.
However, in view of recent trends in environmental regulations, chromium may be used in the future only in a limited manner due to its toxicity, particularly carcinogenicity, and therefore development of a chromium-free (nonchromate) metal surface treatment agent having adhesion and corrosion resistance equivalent to those of chromate treatment agents is desired.
As a nonchromate metallic surface treating agent, for example, patent document 1 discloses a nonchromate rust preventive agent containing a water-soluble resin, a thiocarbonyl group-containing compound, phosphate ions and water-dispersible silica, which is excellent in corrosion resistance but insufficient in workability and adhesion to a substrate.
Patent document 2 discloses an acidic surface treatment agent containing 2 or more silane coupling agents, and this system is insufficient in corrosion resistance when high corrosion resistance and workability are required after metal surface treatment.
As a technique for solving these disadvantages, patent document 3 discloses a nonchromate metal surface treating agent containing a silane coupling agent, water-dispersible silica, and zirconium ion or titanium ion as essential components. Although this surface treatment agent improves corrosion resistance and workability, it is still insufficient in terms of coatability to a base material, adhesion strength to an upper layer coating film, and the like.
Patent document 4 discloses a surface treatment agent for a steel structure containing a silane coupling agent having a specific functional group that reacts with an aqueous emulsion, and in this case, the corrosion resistance required is only a relatively mild test such as a wetting test, but does not have such a corrosion resistance as to withstand a severe corrosion test.
Patent document 5 discloses a surface treatment agent using an organic silicon compound containing an imidazole group for metals and the like, and patent document 6 discloses a surface treatment agent using an organic silicon compound containing a benzotriazole group for metals and the like, but none of them has sufficient performance to satisfy requirements in corrosion resistance, deep drawability and the like.
Patent document 7 discloses a surface treatment agent for rust prevention, which contains an aqueous emulsion, a compound in which 2 molecules of a β -diketone and 2 molecules of water are present in a 3-valent transition metal ion, and a silane coupling agent. Although this surface treatment agent is characterized in that the 3-valent transition metal complex is converted into a sparingly soluble compound by drying and exhibits rust prevention ability and coating film adhesion ability, the required corrosion resistance is not able to withstand a severe environment, and there is still much room for improvement.
As described above, a metal surface treatment agent that exhibits various performances such as corrosion resistance, work adhesion, coatability, adhesive strength, and the like at high levels with a thin film has not been known so far, and development of a surface treatment agent having such performances has been desired.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-29724
Patent document 2: japanese laid-open patent publication No. 8-073775
Patent document 3: japanese laid-open patent publication No. 2001-316845
Patent document 4: japanese laid-open patent publication No. 10-60315
Patent document 5: japanese laid-open patent publication No. 2000-297093
Patent document 6: japanese laid-open patent publication No. 6-279463
Patent document 7: japanese laid-open patent publication No. 2007-297648
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a non-chromate metal surface treatment agent capable of imparting excellent workability, adhesion, and corrosion resistance to a metal surface when used as a pretreatment agent for a coating layer of paint or the like on the metal surface.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a composition containing a benzotriazole compound having an alcohol group and a silane coupling agent as essential components may form a coating film having excellent rust and corrosion resistance by integrating the benzotriazole layer and the siloxane layer through the reaction between the alcohol group and an alkoxysilyl group in the silane coupling agent, and thus is suitable as a metal surface treatment agent, and have completed the present invention.
Namely, the present invention provides:
1. a metal surface treating agent characterized by containing a benzotriazole compound represented by the following general formula (1) and a silane coupling agent,
[ CHEM 1]
[ in the formula, R1Independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2R represents an alkylene group having 1 to 10 carbon atoms3And R4Independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group represented by the following general formula (2), R3And R4At least one of (a) and (b) is a group represented by the following general formula (2).
[ CHEM 2]
-R5-OH (2)
(in the formula, R5Represents an alkylene group having 1 to 10 carbon atoms. )]
2.1 the metal surface treating agent, wherein R is2Is methylene, R3And R4Are all groups represented by the above general formula (2), and the above R5Is an ethylene group, and is characterized in that,
3.1 or 2, wherein the silane coupling agent is a silane coupling agent having an amino group,
4.1 or 2, wherein the silane coupling agent is a silane coupling agent having an epoxy group,
5.1 to 4, which comprises an organic titanate,
6.1 to 5, which comprises a water-dispersible silica or an organic solvent-dispersible silica,
7.1 to 6, which comprises a compound of 1 or more metals selected from the group consisting of Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn,
8.1 to 7, which comprises a thiocarbonyl group-containing compound,
9.1 to 8, which comprises a water-soluble resin or a water-dispersible resin,
10.1 to 9, which contains a phosphate ion.
ADVANTAGEOUS EFFECTS OF INVENTION
Since the metal surface treatment agent of the present invention contains a benzotriazole compound having an alcohol group and a silane coupling agent as essential components, it is considered that an ester exchange reaction occurs between the alcohol group in the benzotriazole compound and the alkoxysilyl group in the silane coupling agent in the coating solution or in the treated coating film, and the benzotriazole group and the siloxane layer are integrated.
Therefore, the coated steel sheet treated with the metal surface treatment agent of the present invention can exhibit high rust and corrosion resistance.
Detailed Description
The present invention will be specifically described below.
The metal surface treatment agent according to the present invention contains a benzotriazole compound represented by the following general formula (1) and a silane coupling agent.
[ CHEM 3]
In the formula (1), R1Independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2R represents an alkylene group having 1 to 10 carbon atoms3And R4Independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group represented by the following general formula (2), R3And R4At least one of (a) and (b) is a group represented by the following general formula (2).
[ CHEM 4]
-R5-OH (2)
(in the formula, R5Represents an alkylene group having 1 to 10 carbon atoms. )]
The alkyl group having 1 to 10 carbon atoms may be any of a straight chain, cyclic and branched, and specific examples thereof include a straight chain or branched alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group and a n-decyl group, and a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propylene, isopropylene, tetramethylene, isobutylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene.
Wherein, as R1The alkyl group is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group or an n-propyl group, still more preferably a hydrogen atom or a methyl group, and yet more preferably R1Is methyl, most preferably R1Any of (a) is a methyl group, and the remainder is a hydrogen atom.
As R2The alkylene group having 1 to 5 carbon atoms is preferable, and methylene, ethylene and trimethylene are more preferable, and methylene is further preferable.
As R3And R4Preferably, both are represented by the above formula (2).
As R5Preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, an ethylene group,Trimethylene, and ethylene are more preferable.
Preferred examples of the benzotriazole compound represented by the formula (1) include compounds represented by the following general formula (3).
[ CHEM 5 ]
(in the formula, R1The same meanings as described above are indicated. )
In particular, 2 ' - [ [ (4-methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol (formula (4)), 2 ' - [ [ (5-methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol (formula (5)), 2 ' - [ [ (1H-benzotriazol-1-yl) methyl ] imino ] diethanol (formula (6)), and the like can be preferably used.
[ CHEM 6 ]
Further, 2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol (manufactured by Tokyo chemical industry Co., Ltd., TT-LYK), which is represented by the following formula (7) and in which the position of the methyl group on the benzotriazole ring is not limited, is already marketed, and this compound can also be preferably used in the present invention.
[ CHEM 7]
On the other hand, the silane coupling agent is not particularly limited, and can be suitably selected from known silane coupling agents, and specific examples thereof include silane coupling agents having an alkyl group, silane coupling agents having an aryl group, silane coupling agents having a vinyl group, silane coupling agents having an amino group, silane coupling agents having an epoxy group, silane coupling agents having a (meth) acryloyl group, silane coupling agents having a mercapto group, and the like, and 1 of these may be used alone, or 2 or more of these may be used in combination.
Among these, silane coupling agents having an amino group and silane coupling agents having an epoxy group are preferable.
Specific examples of the silane coupling agent having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (. beta. -aminoethyl) -gamma-aminopropyltrimethoxysilane, n- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane and the like.
Specific examples of the silane coupling agent having an epoxy group include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.
In the surface treatment agent of the present invention, the amount of the silane coupling agent to be used is preferably 0.1 to 100 times, more preferably 1 to 50 times, and still more preferably about 5 to 30 times, in terms of a mass ratio, relative to the benzotriazole compound.
The metal surface treatment agent of the present invention can exhibit high rust and corrosion resistance by using the benzotriazole compound having a hydroxyl group together with a silane coupling agent as described above.
The reason for this is presumed to be that the hydroxyl group of the benzotriazole group and the hydrolyzable group of the silane coupling agent are integrated by transesterification in the composition or the coating film, and thus the benzotriazole group forms a complex on the metal surface and a siloxane layer is formed on the upper layer.
The metal surface treatment agent of the present invention preferably contains a solvent in addition to the above-mentioned essential components.
Examples of the solvent include water, an organic solvent in which the benzotriazole compound and the silane coupling agent as essential components are dissolved, and a mixed solvent of the organic solvent and water.
Specific examples of the organic solvent include alcohol solvents such as methanol and ethanol; amide solvents such as formamide, N-dimethylformamide, pyrrolidone, and N-methylpyrrolidone; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; saturated hydrocarbon solvents such as pentane, hexane, and heptane; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and among these, methanol and ethanol are preferable.
In a metal surface treating agent comprising a benzotriazole compound, a silane coupling agent and a solvent, the benzotriazole compound is preferably contained in a concentration of 0.01 to 100g/L, more preferably 0.05 to 50g/L, in view of the rust and corrosion preventing effect obtained and the liquid stability of the coating material.
On the other hand, in view of the rust and corrosion preventing effect and the liquid stability of the coating material, the silane coupling agent is preferably contained in the metal surface treatment agent at a concentration of 0.01 to 200g/L, and more preferably at a concentration of 0.05 to 100 g/L.
The metal surface treatment agent of the present invention preferably further comprises an organic titanate.
The organic titanate may be a commercially available one, and the structure and the like thereof are not particularly limited, and specific examples thereof include tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, and polymers thereof, and titanium chelate compounds such as titanium acetyltitanate, titanium polyacetylacetonate, titanium octylglycinate, titanium lactate, titanium ethyl lactate, and titanium triethanolamine.
These can be used alone in 1 kind, or can be used in combination of more than 2 kinds.
When the organic titanates are used, the amount of the organic titanates is preferably 0.05 to 100g/L, more preferably 0.5 to 60g/L, in the metal surface treatment agent, in view of the effect of improving corrosion resistance and bath stability of the metal surface treatment agent.
The metal surface treatment agent of the present invention preferably further comprises water-dispersible silica or organic solvent-dispersible silica. In this case, specific examples of the organic solvent include alcohols such as methanol, ethanol, and isopropyl alcohol; and ethers such as propylene glycol monomethyl ether and tetrahydrofuran.
The water-or organic solvent-dispersible silica is not particularly limited, and is preferably a weak alkali-based spherical silica, a chain silica, or an aluminum-modified silica containing a small amount of impurities such as sodium.
As the spherical silica, various commercially available products such as colloidal silica such as "SNOTEX N" and "SNOTEX UP" (both manufactured by Nissan chemical industry Co., Ltd.), vapor-phase silica such as "AEROSIL" (manufactured by Nippon AEROSIL (Co., Ltd.)), silica gel such as "SNOTEX PS" (manufactured by Nissan chemical industry Co., Ltd.) as a chain silica, and "ADELITE AT-20A" (manufactured by ADEKA) as an aluminum-modified silica can be used.
When the above-mentioned water-or organic solvent-dispersible silica is used, the amount of the silica to be added is preferably 0.05 to 100g/L, more preferably 0.5 to 60g/L, as a solid content in the metal surface treatment agent, in view of the corrosion resistance-improving effect and bath stability of the metal surface treatment agent.
The metal surface treatment agent of the present invention preferably further contains a compound of any one or more metals selected from Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn.
Examples of the compound of the metal include carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, fluorides, fluoroacids or salts thereof, oxyacids, organic acid salts, and the like of the metal.
Specific examples of the zirconium (Zr) compound include ammonium zirconyl carbonate, zirconium hydrofluoric acid, ammonium zirconium fluoride, potassium zirconium fluoride, sodium zirconium fluoride, zirconium acetylacetonate, zirconium 1-butanol butylate solution, zirconium n-propoxide, and the like.
Specific examples of the titanium (Ti) compound include titanium hydrofluoric acid, ammonium titanium fluoride, potassium titanium oxalate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, titanium 2-ethyl-1-hexanoate, tetraisopropyl titanate, tetra-n-butyl titanate, potassium titanium fluoride, and sodium titanium fluoride.
Specific examples of the vanadium (V) compound include vanadium pentoxide (V), vanadium trioxide (III), vanadium dioxide (IV), vanadium hydroxide (II), vanadium hydroxide (III), vanadium sulfate (II), vanadium sulfate (III), vanadyl sulfate (IV), vanadium fluoride (III), vanadium fluoride (IV), vanadium fluoride (V), vanadyl trichloride VOCl3Vanadium trichloride VCl3Hexafluorovanadic acid (III) or a salt thereof (potassium salt, ammonium salt, etc.), metavanadic acid (V) or a salt thereof (sodium salt, ammonium salt, etc.), vanadyl (IV) acetylacetonate VO (OC (═ CH)2)CH2COCH3)2Vanadium (III) acetylacetonate V (OC (═ CH)2)CH2COCH3)3Phosphovanadomolybdic acid H15-X[PV12-XMoO40]·nH2O(6 < X < 12, n < 30), etc.
Specific examples of the tungsten (W) compound include tungsten (IV) oxide, tungsten (V) oxide, tungsten (VI) oxide, tungsten (IV) fluoride, tungsten (VI) fluoride, tungstic acid (VI) H2WO4Or salts thereof (ammonium salt, sodium salt, etc.), metatungstic acid (VI) H6[H2W12O40]Or salts thereof (ammonium salt, sodium salt, etc.), paratungstic acid (VI) H10[H10W12O46]Or salts thereof (ammonium salts, sodium salts, etc.), and the like.
Specific examples of the molybdenum (Mo) compound include phosphovanadomolybdic acid H15-X[PV12-XMoO40]·nH2O(6 < X < 12, n < 30), molybdenum oxide, molybdic acid H2MoO4Ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compounds (e.g., ammonium molybdophosphate (NH)4)3[PO4Mo12O36]·3H2O, molybdenum sodium phosphate Na3[PO4Mo12O36]·nH2O, etc.) and the like.
Specific examples of the aluminum (Al) compound include aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate, ammonium aluminum sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, and aluminum hydroxide.
Specific examples of the tin (Sn) compound include tin (IV) oxide and sodium stannate Na2SnO3Tin (II) chloride, tin (IV) chloride, tin (II) nitrate, tin (IV) nitrate, ammonium hexafluorostannate (NH)4)2SnF6And the like.
Specific examples of the niobium (Nb) compound include niobium pentoxide (Nb)2O5) Sodium niobate (NaNbO)3) Niobium fluoride (NbF)5) Ammonium hexafluoroniobate (NH)4)NbF6And the like.
Specific examples of the hafnium (Hf) compound, the yttrium (Y) compound, the holmium (Ho) compound, the bismuth (Bi) compound, and the lanthanum (La) compound include hafnium oxide, hexafluorohafnate, yttrium oxide, yttrium acetylacetonate, holmium oxide, bismuth oxide, lanthanum oxide, and the like.
Specific examples of the cerium (Ce) compound include cerium oxide and cerium acetate Ce (CH)3CO2)3Cerium (III) or (IV) nitrate, ammonium cerium nitrate, cerium sulfate, cerium chloride, and the like.
Specific examples of the zinc (Zn) compound include zinc oxide, zinc hydroxide, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, sodium zincate, and the like.
Further, each of the above metal compounds may be used alone, or 2 or more species of the same species may be used in combination, or 2 or more species of different species may be used in combination.
When the metal compound is used, the amount of the metal compound is preferably 0.01 to 50g/L, more preferably 0.05 to 5g/L, in terms of the amount of the metal ion in the metal surface treatment agent, in consideration of the effect of improving corrosion resistance, the effect of improving crosslinking adhesion, bath stability of the metal surface treatment agent, and the like.
The metal surface treatment agent of the present invention preferably further comprises a thiocarbonyl group-containing compound.
Specific examples of the thiocarbonyl group-containing compound include compounds containing at least one thiocarbonyl group such as thiourea, dimethylthiourea, 1, 3-dimethylthiourea, dipropylthiourea, dibutylthiourea, 1, 3-diphenyl-2-thiourea, 2-ditolylthiourea, thioacetamide, sodium dimethyldithiocarbamate, tetramethylthiuram monosulfide, tetrabutylthiuram disulfide, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate, piperidine salt of pentamethylenedithiocarbamate, zinc diethyldithiocarbamate, sodium diethyldithiocarbamate, zinc isopropylxanthate, ethylenethiourea, dimethylxanthate sulfide, dithiooxamide, polydithiocarbamic acid or a salt thereof, these may be used alone, or 2 or more of them may be used in combination.
When the above-mentioned thiocarbonyl group-containing compound is used, the amount thereof is preferably 0.01 to 100g/L, more preferably 0.1 to 10g/L, in the metal surface treatment agent, in view of the balance between the effect of improving corrosion resistance and the economical efficiency.
The metal surface treatment agent of the present invention preferably further comprises a water-soluble resin or a water-dispersible resin.
Specific examples of the water-soluble or water-dispersible resin include acrylic resins, epoxy resins, polyurethane resins, ethylene acrylic copolymers, phenolic resins, polyester resins, polyolefin resins, alkyd resins, polycarbonate resins, and the like, and these may be used alone, or 2 or more thereof may be used in combination, or they may be copolymerized and used.
Examples of the water-soluble acrylic resin include copolymers containing acrylic acid and/or methacrylic acid derivatives as a main component. Examples of the derivatives include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, and copolymers of these with other acrylic monomers can also be used.
In particular, the acrylic acid and/or methacrylic acid monomer ratio in the copolymer is preferably 70% by mass or more.
The molecular weight of the water-soluble or water-dispersible resin is preferably 1 ten thousand, more preferably 30 to 200 ten thousand, based on the weight-average molecular weight in terms of polystyrene by Gel Permeation Chromatography (GPC), in view of sufficiently exhibiting the effect of improving the deep drawability of the coating film and making the viscosity within an appropriate range to improve the handling property.
When the water-soluble or water-dispersible resin is used, the amount of the resin is preferably 0.1 to 100g/L, more preferably 5 to 80g/L, in the metal surface treatment agent, in view of the effects of improving the bending adhesion and the deep drawability and the economy.
When a resin is used, an organic solvent, a surfactant, a leveling agent, a wettability improver, and an antifoaming agent may be used to improve the film forming property and to form a more uniform and smooth coating film.
The metal surface treatment agent of the present invention preferably further contains phosphate ions, and the corrosion resistance can be further improved by adding phosphate ions.
The addition of the phosphate ions can be performed by adding a compound that generates phosphate ions in water.
Examples of such a compound include phosphoric acid and Na3PO4、Na2HPO4、NaH2PO4And phosphates, condensed phosphoric acids such as condensed phosphoric acid, polyphosphoric acid, metaphosphoric acid, and diphosphoric acid, or salts thereof, and they may be used alone or in combination of 2 or more.
When the phosphate ion is used, the amount of the phosphate ion is preferably 0.01 to 100g/L, more preferably 0.1 to 10g/L, in the metal surface treatment agent. If the amount is less than 0.01g/L, the effect of improving corrosion resistance may be insufficient, and if it exceeds 100g/L, excessive etching may be caused to the zinc-based plated steel material to degrade the performance, or gelling may be caused when an aqueous resin is contained as another component.
Furthermore, the metal surface treatment agent of the present invention may be blended with various known additives for metal surface treatment agents such as tannic acid or a salt thereof, phytic acid or a salt thereof, and the like.
The metal surface-treated with the metal surface-treating agent of the present invention is not particularly limited, and known general metals can be used, and among them, copper, nickel, silver, zinc, iron, aluminum, or an alloy thereof is preferable, aluminum, copper, and a copper alloy are more preferable, and various plated steel materials can be preferably used.
The surface treatment method using the metal surface treatment agent of the present invention may be a method of applying the metal surface treatment agent to a metal surface to be coated and drying the coated object after the application, or a method of heating the coated object in advance, applying the metal surface treatment agent, and drying the coated object by using residual heat.
The coating method is not particularly limited, and generally used roll coating, curtain coating, spray coating, dipping, brush coating, and the like can be employed.
In any case, the drying conditions are preferably 2 seconds to 1 hour at room temperature to 250 ℃, and more preferably 5 seconds to 20 minutes at 40 to 180 ℃. If the temperature exceeds 250 ℃, deterioration of the properties such as adhesion and corrosion resistance may occur.
In the surface treatment method, the coating amount of the metal surface treatment agent is preferably 0.1mg/m in mass of the coating film after drying, in consideration of the rust prevention and economic efficiency to be exhibited2More preferably 0.5 to 500mg/m2More preferably 1 to 250mg/m2。
A coated steel material can be obtained by surface-treating a metal steel material with the metal surface-treating agent of the present invention, drying the surface-treated metal steel material, and then coating an upper coating film layer thereon. The metallic steel material may be a precoated steel material or a post-coated steel material. In the present invention, the steel material is a concept including a steel plate.
Examples of the coating layer include a coating system in which a non-chromate primer is applied and dried, and then a top coat is further applied, and a functional coating layer having functions such as fingerprint resistance and lubricity.
As the non-chromate primer, all primers not using a chromate type rust preventive pigment in the blending of the primer can be used.
As such a primer, a primer using a vanadate-based rust preventive pigment and a phosphate-based rust preventive pigment (V/P pigment primer) and a primer using a calcium silicate-based rust preventive pigment are preferable.
The coating thickness of the primer is preferably 1 to 20 μm in terms of dry film thickness in consideration of the balance between corrosion resistance and processing adhesion.
The non-chromate primer can be fired under drying conditions for 10 seconds to 5 minutes at a metal surface temperature of 150 to 250 ℃.
The topcoat is not particularly limited, and all ordinary topcoats for coating can be used.
The functional coating is not particularly limited, and any coating that is currently applied to chromate-based pretreatment films can be used.
The coating method of the non-chromate primer, top coat and functional coat is not particularly limited, and generally used roll coating, flow coating, air spraying, airless spraying, dipping and the like can be used.
The thickness of the top coat layer can be appropriately selected, and can be a normal coating film thickness according to the type thereof.
Examples
The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples.
In the following, the following commercially available products were used as the benzotriazole compound, silane coupling agent, organic titanate, water-dispersible silica, zirconium ion-generating compound, thiocarbonyl group-containing compound, water-soluble resin, and phosphate ion-generating compound.
[ benzotriazole Compound ]
A: TT-LYK (2, 2' - [ [ (methyl-1H-benzotriazole-1-yl) methyl ] imino ] diethanol, manufactured by Tokyo chemical industry Co., Ltd.)
B: BT-120 (benzotriazole, manufactured by Tokyo chemical industry Co., Ltd.)
[ silane coupling agent ]
A: KBE-903 (gamma-aminopropyltriethoxysilane; manufactured by shin-Etsu chemical Co., Ltd.)
B: KBM-403 (gamma-glycidoxypropyltrimethoxysilane; available from shin-Etsu chemical Co., Ltd.)
C: KBM-603(N- (. beta. -aminoethyl) -. gamma. -aminopropyltrimethoxysilane; manufactured by shin-Etsu chemical Co., Ltd.)
[ organic titanate ]
Titanium tetraisopropoxide (manufactured by Tokyo chemical industry Co., Ltd.)
[ Water-dispersible silica ]
Methanol silica sol (manufactured by Nissan chemical industry Co., Ltd.)
[ Compound Forming zirconium ion ]
ジルコノゾール AC-7 (ammonium zirconyl carbonate; manufactured by first Dilute elements chemical industry Co., Ltd.)
[ Compound containing a Thiocarbonyl group ]
Thiourea (manufactured by Tokyo chemical industry Co., Ltd.)
[ Water-soluble resin ]
Polyacrylic acid (weight average molecular weight 100 ten thousand) (manufactured by Tokyo chemical industry Co., Ltd.)
[ Compound generating phosphate ion ]
Phosphoric acid (manufactured by Tokyo chemical industry Co., Ltd.)
[ example 1]
0.5g of benzotriazole compound A and 9.5g of silane coupling agent A were added to a mixed solvent of 500g of methanol and 500g of water, and the mixture was stirred at room temperature for 5 minutes to obtain a metal surface treatment agent.
The obtained metal surface treatment agent was applied to a degreased and dried commercial aluminum plate (manufactured by Tokyo テストピース; 70X 150X 0.4mm) with a bar coater No.20 so that the dry film thickness became 10 μm, and dried at a metal surface temperature of 105 ℃ for 10 minutes.
Then, a non-chromate primer containing a V/P pigment (manufactured by Japan ペイント Co., Ltd.) was applied using a bar coater No.16 so that the dry film thickness became 5 μm, and dried at a metal surface temperature of 215 ℃ for 5 minutes. Further, フレキコート 1060 (polyester top-coat paint; manufactured by Japan ペイント, Inc.) was applied as a top coat by a bar coater No.36 so that the dry film thickness became 15 μm, and the metal surface was dried at 230 ℃ to obtain a test plate.
[ example 2]
A metal surface treatment agent was prepared in the same manner as in example 1 except that the silane coupling agent a was changed to the silane coupling agent B, and a test plate was produced in the same manner as in example 1.
[ examples 3 to 10]
A metal surface treatment agent was prepared in the same manner as in example 1 except that a benzotriazole compound, a silane coupling agent, an organic titanate, water-dispersible silica, zirconium ions, a thiocarbonyl group-containing compound, a water-soluble resin, and phosphate ions were each blended at the concentrations shown in table 1, and a test plate was produced in the same manner as in example 1.
Comparative examples 1 and 2
A metal surface treatment agent was prepared in the same manner as in example 1 except that no silane coupling agent was used and the components shown in table 1 were mixed at the concentrations shown in table 1, and further a test plate was produced in the same manner as in example 1.
Comparative examples 3 to 7
A metal surface treatment agent was prepared in the same manner as in example 1 except that the benzotriazole compound B was used and the components shown in table 1 were mixed at the concentrations shown in table 1, and further a test plate was produced in the same manner as in example 1.
Comparative example 8
In addition to replacing the metal surface treatment agent, a commercially available coating-type chromate treatment agent (manufactured by Nippon ペイント Co., Ltd.) was used so that the amount of chromium deposited was 20mg/m2Test panels were produced in the same manner as in example 4, except that the coating and drying were carried out and a chromium-containing primer (manufactured by japan ペイント, ltd.) was used.
[ TABLE 1]
The test plates obtained in the examples and comparative examples were evaluated for curl adhesion, deep drawability, and corrosion resistance according to the following evaluation methods and evaluation criteria. The results are shown in table 2.
[ evaluation method ]
(1) Adhesion to bending
The test plate was subjected to 180 ° bending processing by holding a spacer of 2mm Φ between the test plate and a conical mandrel tester in an environment of 20 ℃, the tape was peeled off from the bent portion 3 times, and the degree of peeling was observed with a 20-fold magnifying glass, and evaluated according to the following criteria.
A: has no cracks
B: cracks are generated on the whole surface of the processing part
C: the peeling area is less than 20% of the processed part
D: the peeling area is more than 20% and less than 80% of the processed part
E: the stripping area is more than 80% of the processed part
(2) Deep drawability
Drawing ratio under an environment of 20 ℃: 2.3, wrinkle control pressure: 2t, punch R: 5mm, die shoulder R: a cylinder drawing test was conducted under the condition of 5mm without oiling. Then, the peeling width of the coating film was measured by the cross cut portion and evaluated by the following criteria.
A: expansion width of less than 1mm
B: the expansion width is more than 1mm and less than 2mm
C: the expansion width is more than 2mm and less than 3mm
D: the expansion width is more than 3mm and less than 5mm
E: the expansion width is more than 5mm
(3) Corrosion resistance
(cutting part)
The test plate was cross-cut, subjected to a salt water spray test for 500 hours in accordance with JIS Z2371, and then the expansion width on the cut portion side was measured and evaluated by the following criteria.
A: the expansion width is 0mm
B: the expansion width exceeds 0mm and is less than 1mm
C: the expansion width is more than 1mm and less than 3mm
D: the expansion width is more than 3mm and less than 5mm
E: the expansion width is more than 5mm
(end faces)
The test plate was subjected to a salt spray test for 500 hours in accordance with JIS Z2371, and then the width of expansion from the upper burr end face was evaluated by the same standard as that of the cut portion.
[ TABLE 2]
As shown in Table 2, it was found that the coating films formed by using the metal surface treatment agents of examples 1 to 10 exhibited excellent rust inhibitive ability and substrate adhesion.
[ example 11]
0.1g of benzotriazole compound A and 9.9g of silane coupling agent A were added to a mixed solvent of 500g of methanol and 500g of water, and the mixture was stirred at room temperature for 5 minutes to obtain a metal surface treatment agent.
A copper plate (manufactured by テストピース, Inc.; 70X 150X 0.4mm) cleaned with sulfuric acid was immersed in the obtained metal surface treatment agent for 1 minute, and dried at a metal surface temperature of 105 ℃ for 10 minutes to obtain a test plate.
[ example 12]
A metal surface treatment agent was prepared in the same manner as in example 11, except that the silane coupling agent a was changed to the silane coupling agent B, and a test plate was produced in the same manner as in example 11.
[ example 13]
A metal surface treatment agent was prepared in the same manner as in example 11, except that the silane coupling agent a was changed to the silane coupling agent C, and a test plate was produced in the same manner as in example 11.
[ examples 14 to 22]
A metal surface treatment agent was prepared in the same manner as in example 11 except that the type and the amount of the benzotriazole compound and the silane coupling agent were changed as shown in table 3, and further, a test plate was produced in the same manner as in example 11.
Comparative examples 9 and 10
A metal surface treatment agent was prepared in the same manner as in example 11 except that no silane coupling agent was used and the amount of benzotriazole compound was changed to the concentration shown in table 3, and further, a test plate was produced in the same manner as in example 11.
[ comparative examples 11 to 14]
A metal surface treatment agent was prepared in the same manner as in example 11 except that the type and the amount of the benzotriazole compound and the silane coupling agent were changed as shown in table 3, and further, a test plate was produced in the same manner as in example 11.
[ TABLE 3]
The test plates obtained in examples 11 to 22 and comparative examples 9 to 14 were evaluated for heat resistance and corrosion resistance according to the following evaluation methods and evaluation criteria. The results are shown in table 4.
(1) Heat resistance
The test piece was placed in a thermostatic machine at 150 ℃ and the appearance after 1 hour and the appearance after 5 hours were evaluated by the following criteria.
A: has no change
B: hardly changed
C: reddening with yellow
D: turned red violently
E: whitening
(2) Corrosion resistance
The test panels were subjected to salt spray tests for 24 hours and 72 hours in accordance with JIS Z2371, and then evaluated for appearance in accordance with the following criteria.
A: no rust generation
B: rust in 5-20% of the area
C: rust in 20-50% of the area
D: rust is generated in 50-90% of the area
E: rust is generated in 90-100% area
[ TABLE 4]
As shown in Table 4, it is understood that the coating films formed by using the metal surface treatment agents of examples 11 to 22 exhibit excellent heat resistance and rust inhibitive ability.
Claims (10)
1. A metal surface treatment agent characterized by containing a benzotriazole compound represented by the following general formula (1):
in the formula, R1Independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2R represents an alkylene group having 1 to 10 carbon atoms3And R4Independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group represented by the following general formula (2), R3And R4At least one of (a) and (b) is a group represented by the following general formula (2),
-R5-OH (2)
in the formula, R5Represents an alkylene group having 1 to 10 carbon atoms.
2. The metal surface treatment agent according to claim 1, wherein R is2Is methylene, R3And R4Are all groups represented by the above general formula (2), and the above R5Is an ethylene group.
3. The metal surface treatment agent according to claim 1 or 2, wherein the silane coupling agent is a silane coupling agent having an amino group.
4. The metal surface treatment agent according to claim 1 or 2, wherein the silane coupling agent is a silane coupling agent having an epoxy group.
5. The metal surface treatment agent according to claim 1 or 2, comprising an organic titanate.
6. The metal surface treatment agent according to claim 1 or 2, comprising a water-dispersible silica or an organic solvent-dispersible silica.
7. The metal surface treatment agent according to claim 1 or 2, comprising a compound of 1 or more metals selected from the group consisting of Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce, and Zn.
8. The metal surface treatment agent according to claim 1 or 2, comprising a thiocarbonyl group-containing compound.
9. The metal surface treatment agent according to claim 1 or 2, which comprises a water-soluble resin or a water-dispersible resin.
10. The metal surface treatment agent according to claim 1 or 2, which comprises phosphate ions.
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| CN108676387A (en) * | 2018-04-27 | 2018-10-19 | 江苏恒加机械工程有限公司 | A kind of metal surface treating liquid |
| CN108914105A (en) * | 2018-07-19 | 2018-11-30 | 苏州瑞沁精密机械有限公司 | A kind of die surface treatment fluid |
| CN111321414A (en) * | 2018-12-14 | 2020-06-23 | 日本帕卡濑精株式会社 | Surface treatment agent and use thereof |
| CN114164423A (en) * | 2021-11-30 | 2022-03-11 | 广东达志化学科技有限公司 | Chromium-free passivation solution and preparation method and application thereof |
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