CN103572298B - Metal conditioner, surface treated steel product and its surface treatment method and coated steel and its manufacture method - Google Patents
Metal conditioner, surface treated steel product and its surface treatment method and coated steel and its manufacture method Download PDFInfo
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- CN103572298B CN103572298B CN201310339849.7A CN201310339849A CN103572298B CN 103572298 B CN103572298 B CN 103572298B CN 201310339849 A CN201310339849 A CN 201310339849A CN 103572298 B CN103572298 B CN 103572298B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The present invention relates to metal conditioner, surface treated steel product and its surface treatment method and coated steel and its manufacture method.A kind of chromate-free metal conditioner is provided, it is most suitable as metal envelope steel use, is used as the pretreatment of the coatings such as coating, it is possible to provide excellent processability, adaptation, corrosion resistance.Organo-silicon compound shown in the metal conditioner using following formulas (1) are used as essential component：R is hydrolization group in formula (1), and R ' is the alkyl of carbon number 1~4, and A is the alkylidene of the carbon number 1~8 of straight-chain or branched, and X is oxygen atom, sulphur atom, any, R of nitrogen-atoms1、R2Hydrogen atom, the alkyl of carbon number 1~20, the fluoroalkyl of carbon number 1~20, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10, or the substituent shown in following formulas (2) are separately represented, m is 1~3 integer,
Description
Technical field
The present invention relates to a kind of metal conditioner, the surface treated steel product being surface-treated by the inorganic agent
And its surface treatment method and thereon have upper strata envelope coated steel and its manufacture method, the Treatment of Metal Surface
Agent is applied to cold rolling steel, hot-strip, stainless steel steel and electrogalvanizing steel, molten zinc plating steel, plating Zn-Al alloy
Class steel, plating zinc-iron alloys class steel, zinc-plated-magnesium alloy class steel, zinc-plated-aluminium-magnesium alloy class steel, class of aluminizing steel, plating
The coated steels such as aluminium-silicon alloys class steel, tin plating class steel, lead-tin alloy plating alloy type steel, plating chromium class steel, plating nickel class steel
Deng.
Background technology
In the past, as metallic surface inorganic agent, using the chromium class surface conditioning agent such as chromate or phosphoric acid chromate, now
Still it is widely used.However, the trend limited according to nearest environment, due to the toxicity that chromium has, particularly carcinogenicity, therefore
In the future limitation is possible to use.Therefore, it is desirable to develop it is a kind of without chromium and with the adaptation equal with chromic acid salt treatment agent and
The metal conditioner of corrosion resistance.
In Unexamined Patent 11-29724 publications (patent document 1), it is proposed that one kind contains in water-soluble resin
The anti-rust agent for treatment of the compound and phosphate anion of thiocarbonyl and the Chrome-free of water-dispersible silica.However, the body
System is mainly focused on the improvement of naked corrosion resistance (rust-preventing characteristic), the processability of process film and is not filled with the adaptation of base material
Point, in addition, though the finishing coat adaptation of the item for disposal is good, but corrosion resistance may not be satisfactory after application.
In addition, in Unexamined Patent 8-073775 publications (patent document 2), disclosing a kind of even containing two or more silane
Join the acidic surface inorganic agent of agent, the system is requiring highly corrosion resistant and processing after being handled with metal conditioner
Property in the case of, corrosion resistance is not enough.
It is related to this, in JP 2001-316845 publications (patent document 3), disclose it is a kind of with silane coupler,
Water-dispersible silica, zirconium or titanium ion are improved corrosion-resistant as the chromate-free metal conditioner of essential component
Property and processability, but it is insufficient in terms of the dhering strength to the screening characteristics of base material and with upper strata envelope.
In Unexamined Patent 10-60315 publications (patent document 4), disclose it is a kind of contain have and water serial emulsion reacts
Particular functional group silane coupler steel structure surface conditioning agent, now, it is desirable to corrosion resistance only relate to as resistance to
The naked corrosion resistance (resistance to white rust) of comparatively gentle experiment as wet test, it is tolerable harsh with as the present invention
The metal conditioner of corrosion resistance test is compared, and corrosion resistance is not enough.
Recorded the organo-silicon compound containing imidazole radicals in JP 2000-297093 publications (patent document 5)
For the surface conditioning agent of metal etc., but as improving the bonding of the resins such as the metal materials such as aluminium alloy plate and epoxy resin
The material of property (adhesive strength) is suggested, not of great satisfaction as the corrosion resistance or deep drawability of application product etc..
In JP 2007-297648 publications (patent document 6), disclose a kind of containing water serial emulsion, trivalent transition gold
Belong to ion, the compound of 2 molecule beta-diketons and the coordination of 2 molecular waters, the antirust of silane coupler surface conditioning agent (chemistry
Conversion treating solution), although show antirust energy as insoluble chemical compound by drying in trivalent transition metal complex
It is that unique but required corrosion resistance can not be resistant to harsh ring as the present invention in terms of the closely sealed ability of power, film
Border, with the leeway that should be improved enough.
As discussed above, it is desired to develop a kind of film and show the processability after application at a high level, it is adaptation, corrosion-resistant
The metal conditioners as all performances such as property.
Prior art literature
Patent document
The Unexamined Patent 11-29724 publications of patent document 1
The Unexamined Patent 8-073775 publications of patent document 2
The JP 2001-316845 publications of patent document 3
The Unexamined Patent 10-60315 publications of patent document 4
The JP 2000-297093 publications of patent document 5
The JP 2007-297648 publications of patent document 6
The content of the invention
Invent problem to be solved
The present invention is to complete in view of the foregoing, and its object is to there is provided a kind of processing of non-chromate metal surface
Agent, the surface treated steel product and its surface treatment method being surface-treated by the inorganic agent and thereon have upper strata
The coated steel and its manufacture method of envelope, the non-chromate metal surface treatment agent are most suitable for metal, particularly metal quilt
Film steel are used, and without chromium, as the pretreatment of the coatings such as coating, can assign excellent processability, adaptation, corrosion resistance.
Means for solving the problems
There is provided following metal conditioners, surface treated steel product and its surface to achieve these goals by the present invention
Processing method, and coated steel and its manufacture method.
(1) a kind of metal conditioner, it is characterised in that contain：
(A) organo-silicon compound shown in following formulas (1),
[changing 1]
In formula (1), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and A is the carbon of straight-chain or branched
The alkylidene of atomicity 1~8, X is oxygen atom, sulphur atom, any, R of nitrogen-atoms1、R2It is separately hydrogen atom, carbon
Alkyl, the fluoroalkyl of carbon number 1~20, the aryl of carbon number 6~10, the alkene of carbon number 2~10 of atomicity 1~20
Substituent shown in base or following formulas (2), m is 1~3 integer,
[changing 2]
In formula (2), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and B is the carbon of straight-chain or branched
The alkylidene of atomicity 1~8, m is 1~3 integer；
(B) water and/or organic solvent.
(2) metal conditioner as described in (1), it is characterised in that above-mentioned organo-silicon compound are following formulas
(3),
[changing 3]
In formula (3), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and A is the carbon of straight-chain or branched
The alkylidene of atomicity 1~8, R1~R3It is separately hydrogen atom, the alkyl of carbon number 1~20, carbon number 1~20
Fluoroalkyl, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10 or following formulas (4) shown in substituent, m is
1~3 integer,
[changing 4]
In formula (4), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and B is the carbon of straight-chain or branched
The alkylidene of atomicity 1~8, m is 1~3 integer.
(3) metal conditioner as described in (2), it is characterised in that above-mentioned organo-silicon compound are following formulas
(5),
[changing 5]
In formula (5), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, R1For hydrogen atom, carbon number 1~
20 alkyl, the fluoroalkyl of carbon number 1~20, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10 or following
Substituent shown in formula (6), m is 1~3 integer,
[changing 6]
In formula (6), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and m is 1~3 integer.
(4) metal conditioner as described in any one of (1)~(3), it is characterised in that also containing following formulas (7)
Shown alkoxy silane or part thereof hydrolytic condensate,
R4 XSi(OR5)4-X (7)
In formula (7), R4Represent the monovalent hydrocarbon of the non-substituted of carbon number 1~20 or substitution, R5Represent carbon number 1
~8 non-substituted or substitution monovalent hydrocarbon, x is 0~3 integer.
(5) metal conditioner as described in any one of (1)~(4), it is characterised in that also contain organic titanate.
(6) metal conditioner as described in any one of (1)~(5), it is characterised in that also containing water dispersible dioxy
SiClx or organic solvent dispersion silica.
(7) metal conditioner as described in any one of (1)~(6), it is characterised in that also containing selected from Fe, Zr,
The compound of more than a kind of metal in Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn.
(8) metal conditioner as described in any one of (1)~(7), it is characterised in that also comprising containing thiocarbonyl
Compound.
(9) metal conditioner as described in any one of (1)~(8), it is characterised in that also containing water-soluble resin or
Water-dispersed resin.
(10) metal conditioner as described in any one of (1)~(9), it is characterised in that also contain phosphate anion.
(11) a kind of surface treatment method of steel, it is characterised in that with the metal surface described in any one of (1)~(10)
Inorganic agent is surface-treated to the surface of steel.
(12) surface treatment method as described in (11), wherein, steel are coating metal steel.
(13) a kind of surface treated steel product, it is obtained by the surface treatment method described in (11) or (12).
(14) a kind of manufacture method of coated steel, it is characterised in that with the metal surface described in any one of (1)~(10)
After inorganic agent is handled steel, upper strata is further set by film layer.
(15) a kind of coated steel, it is obtained by the manufacture method of the coated steel described in (14).
Invention effect
The present invention metal conditioner using the silane coupler with thioamides base as essential component, comprising
In the case of processed steel and other metals (ion) composition, the thioamides that the surface conditioning agent passes through the silane coupler
Polymerization of olefin using catalyst combines and formed the complex compound of slightly solubility, good antirust ability is shown, by hydrolyzable silyl group, with steel
And the processing excellent adhesion in the organic and inorganic resin coating layer on upper strata is arranged as required to, therefore, adhesive strength is uprised,
As a result, the antirust corrosion-proof of obtained coated steel is emerged from a high level.
Embodiment
Hereinafter, the present invention is specifically illustrated.
The metal conditioner of the present invention is made with the organo-silicon compound (silane coupler) with thioamides base
For essential component, the in the mixed solvent for being dissolved in water, organic solvent or water and organic solvent is formed.
[organo-silicon compound]
The organo-silicon compound used in the present invention are represented by following formulas (1).
[changing 7]
In formula (1), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and A is the carbon of straight-chain or branched
The alkylidene of atomicity 1~8, X is oxygen atom, sulphur atom, any, R of nitrogen-atoms1、R2It is separately hydrogen atom, carbon
Atomicity 1~20, preferably 1~8 alkyl, carbon number 1~20, preferably 1~8 fluoroalkyl, the virtue of carbon number 6~10
Substituent shown in base, the alkenyl of carbon number 2~10 or following formulas (2), m is 1~3 integer.
[changing 8]
In formula (2), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and B is the carbon of straight-chain or branched
The alkylidene of atomicity 1~8, m is 1~3 integer.
More preferably represented by following formulas (3).
[changing 9]
In formula (3), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and A is the carbon of straight-chain or branched
The alkylidene of atomicity 1~8, R1~R3It is separately hydrogen atom, carbon number 1~20, preferably 1~8 alkyl, carbon original
Subnumber 1~20, preferably 1~8 fluoroalkyl, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10 or following formulas
(4) substituent shown in, m is 1~3 integer.
[changing 10]
In formula (4), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and B is the carbon of straight-chain or branched
The alkylidene of atomicity 1~8, m is 1~3 integer.
Further preferably represented by following formulas (5).
[changing 11]
In formula (5), R is hydrolization group, and R ' is the alkane assistant officer of carbon number 1~4, R1For hydrogen atom, carbon number 1~
20 alkyl, the fluoroalkyl of carbon number 1~20, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10 or following
Substituent shown in formula (6), m is 1~3 integer.
[changing 12]
In formula (6), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and m is 1~3 integer.
Here, as the hydrolization group of R in above-mentioned formula, the halogen atoms such as chlorine, bromine, methoxyl group, ethyoxyl can be enumerated
Deng the alkoxy of carbon number 1~4, preferably alkoxy, particularly preferred methoxyl group.R ' is used as, methyl, ethyl, third can be enumerated
The alkyl such as base, preferably methyl.A can enumerate methylene, ethylidene, propylidene etc., be used as branched as the group of straight-chain
Group, the alkylidene of methylallyl, isopropylidene etc., the preferably straight-chain of carbon number 1~3 can be enumerated, it is especially excellent
Select propylidene.B can enumerate methylene, ethylidene, propylidene etc. as the group of straight-chain, can as the group of branched
To enumerate the alkylidene of methylallyl, isopropylidene etc., the preferably straight-chain of carbon number 1~3, particularly preferred propylidene.
As X, oxygen atom, sulphur atom, nitrogen-atoms can be enumerated, wherein it is preferred that nitrogen-atoms.If X is nitrogen-atoms, for Thiourea Type, it is believed that
Improved with the coordination power of metal, corrosion resistance is improved.It is used as R1、R2、R3, can enumerate hydrogen atom, methyl, ethyl, propyl group,
The alkyl such as isopropyl, butyl, isobutyl group, some or all fluothane replaced with fluorine atom by the hydrogen atom of these groups
The alkenyls such as the aryl such as base, phenyl, tolyl, vinyl, cyclobutenyl, pentenyl.M be 1~3 integer, preferably 2 or 3, especially
Preferably 3.
As the concrete structure of organo-silicon compound, structure as described below can be enumerated, but be not limited to these illustrations
Structure.
[changing 13]
Above-mentioned organo-silicon compound are for example to make the different sulphur cyanogen of silane compound and alkyl with amino and hydrolization group
Obtained from acid esters is reacted, or make the silane compound with isothiocyanate group and hydrolization group in catalyst
In the presence of reacted with ammonia, primary amine or secondary amine obtained from.
Above-mentioned organo-silicon compound (silane coupler) can with metal (ion) formation such as following formula (15) or
(16) stable coordinate bond as.
[changing 14]
In formula, X represents oxygen atom, sulphur atom or nitrogen-atoms, and M represents metal (ion).R1、R2As described above.
As the residual components of the metal conditioner of the present invention, water can be enumerated, above-mentioned organo-silicon compound are dissolved
Organic solvent or water and the organic solvent mixed solvent, as the organic solvent, can enumerate：The alcohols such as methanol, ethanol
Solvent, the amide solvent, acetone, methyl second such as formamide, DMF, pyrrolidones, 1-METHYLPYRROLIDONE
The ketones solvents such as base ketone, methyl iso-butyl ketone (MIBK), the saturated hydrocarbons solvent such as pentane, hexane, heptane, the aromatics such as benzene,toluene,xylene
Varsol etc., wherein, particularly preferred methanol and/or ethanol, but it is not limited to composition listed herein.
In addition, the organo-silicon compound of above-mentioned formula (1)~(6) preferably the present invention metal conditioner in 0.01
~200g/L, particularly 0.05~100g/L concentration contain, if content is very few, and the effect of the present invention is insufficient, if excessively,
The then liquid stability reduction of coating.
Beyond the metal conditioner of the present invention is preferably also containing the organo-silicon compound shown in above-mentioned formula (1)~(6)
Organo-silicon compound.As the organo-silicon compound, as long as beyond for the organo-silicon compound shown in above-mentioned formula (1)~(6)
The compound with hydrolyzable silyl group be just not particularly limited, but shown in preferably following formulas (7) have hydrolysis
The organo-silicon compound of property silicyl or part thereof hydrolytic condensate.
R4 XSi(OR5)4-X (7)
In formula (7), R4Represent carbon number 1~20, particularly 1~15 it is non-substituted (preferably methyl, ethyl, propyl group,
Vinyl, phenyl) or substitution (preferably comprise epoxy radicals, (methyl) acryloxy, sulfydryl, amino, aminoalkyl amino, alkane
Base amino, NCO, polyether-based, halogen-substituted alkyl, perfluoroalkyl, holo-fluorine polyester) monovalent hydrocarbon, R5Represent carbon
Non-substituted or substitution the monovalent hydrocarbon of atomicity 1~8, particularly 1~6, preferably methyl, ethyl.X is 0~3 integer,
Particularly preferably 0~2.
Specifically, it can enumerate：Tetramethoxy-silicane, tetraethoxysilane, MTMS, the second of methyl three
TMOS, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylmethoxysilane, front three base oxethyl
Silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl methyl dimethoxysilane, phenyl methyl diethoxy
Silane, pheiiyldimetliyl methoxy silane, phenyldimethylethoxysilane, dimethoxydiphenylsilane, diphenyl diethyl
TMOS, vinyltrimethoxy silane, VTES, vinyl methyl dimethoxysilane, vinyl
Methyldiethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxysilane,
γ-glycidoxypropyl dimethoxysilane, γ-glycidoxypropyl diethoxy silane, γ-(methyl)
Acryloxypropyl trimethoxy silane, γ-(methyl) acryloxypropyl triethoxysilane, γ-(methyl) propylene
Methyl dimethoxysilane, γ-(methyl) acryloxypropyl diethoxy silane, 3- mercaptopropyis
Trimethoxy silane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyis methyl dimethoxysilane, 3- mercaptopropyi methyl
Diethoxy silane, 3- TSL 8330s, APTES, 3- amino propyl methyl diformazans
TMOS, 3-amino propyl methyl diethoxy silane, N- amino-ethyls-gamma-amino propyl trimethoxy silicane, N- amino
Ethyl-γ aminopropyltriethoxy silane, N- amino-ethyls-gamma-amino hydroxypropyl methyl dimethoxysilane, N- amino second
Base-gamma-amino hydroxypropyl methyl diethoxy silane, γ-isocyanates propyl trimethoxy silicane, γ-isocyanates propyl group three
Ethoxysilane, γ-isocyanates hydroxypropyl methyl dimethoxysilane, γ-isocyanates hydroxypropyl methyl diethoxy silane, 3-
R-chloropropyl trimethoxyl silane, 3- chloropropyl triethoxysilanes, 3- chloropropylmethyldimethoxysilanes, 3- chloropropyls
Diethoxy silane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, the ethoxy of 2- (3,4- epoxycyclohexyl) ethyl three
Base silane, 2- (3,4- epoxycyclohexyl) ethyl-methyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl-methyl diethyl
TMOS etc..
In the case where coordinating above-mentioned organo-silicon compound, preferably with 0.05~100g/L's in metal conditioner
Concentration contains, and is particularly preferably contained with 0.5~60g/L concentration.Content is less than 0.05g/L, and corrosion resistance is not enough sometimes, if super
100g/L is crossed, then corrosion resistance saturation, productivity ratio is reduced sometimes.
The metal conditioner of the present invention preferably also contains organic titanate class.The organic titanate class can also be used
Commercially available product, structure etc. is not particularly limited, but as organic titanate class, specifically, can enumerate tetraethyl titanate, metatitanic acid
Four isopropyl esters, tetra-n-butyl titanate, butyltitanate dimer, four (2- ethylhexyls) titanate esters and their polymer, also may be used
To use acetyl metatitanic acid titanium (ト of チ タ Application ア セ チ Le チ タ ネ mono-), poly- acetyl acetone titanium (Port リ チ sunset Application ア セ チ Le ア
The ト of セ ト ネ mono-), the titanium chelate compound such as octyl group glycine titanium, lactic acid titanium, titanium lactate ethyl ester, titanium triethanolamine, these can be single
Solely using a kind or and with using two or more.
In the case where coordinating above-mentioned organic titanate class, preferably with 0.05~100g/L's in metal conditioner
Concentration contains, and is particularly preferably contained with 0.5~60g/L concentration.Content is less than 0.05g/L, and corrosion resistance is insufficient sometimes, if
More than 100g/L, then corrosion resistance saturation, on the contrary, the bath stability reduction of metal conditioner sometimes.
The metal conditioner of the present invention preferably also contains water dispersible or organic solvent dispersion silica.As
The water dispersible or organic solvent dispersion silica, are not particularly limited, but preferably the impurity such as sodium is few and weak base class
Spherical silicon dioxide, chain silica, aluminium improved silica.As spherical silicon dioxide, " the テ Star of ス ノ mono- can be enumerated
Network ス N ", " silica colloidal or " the ア エ ロ such as テ Star Network ス UP " (being Nissan Chemical Ind Ltd's system) of ス ノ mono-
The aerosils such as ジ Le " (Japanese ア エ ロ ジ Le Co. Ltd. system), as chain silica, can use " ス ノ
The silica gel such as one テ Star Network ス PS " (Nissan Chemical Ind Ltd's system), and then, as aluminium improved silica, it can use
" the commercially available silica gel such as ア デ ラ ィ ト AT-20A " (Asahi Denka Co., Ltd.'s system).
In addition, as organic solvent, the alcohol such as methanol, ethanol, isopropanol, propylene glycol monomethyl ether, tetrahydrofuran can be illustrated
Deng ether compound.
In the case where coordinating above-mentioned water dispersible or organic solvent dispersion silica, preferably in Treatment of Metal Surface
0.05~100g/L is calculated as with solid constituent in agent, particularly 0.5~60g/L concentration contains.Water or organic solvent dispersion
The content of silica be less than 0.05g/L, corrosion resistance is not enough sometimes, if more than 100g/L, not finding that corrosion resistance is carried
High effect, on the contrary, the bath stability reduction of metal conditioner sometimes.
The present invention metal conditioner preferably also contain selected from Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho,
The compound of metal more than any of Bi, La, Ce and Zn.Specifically, it can enumerate：The carbonate of above-mentioned metal,
Oxide, hydroxide, nitrate, sulfate, phosphate, fluoride, fluoracid (Off Le オ ロ acid) or its salt, oxyacid
Salt, acylate etc..More specifically, as the example of zirconium (zr) compound, it can enumerate：Zirconium carbonate ammonium, fluorine zirconic acid, fluorine zirconium
Sour ammonium, potassium fluorozirconate, sodium fluozirconate, acetylacetone,2,4-pentanedione zirconium, butanol zirconium n-butyl alcohol solution, zirconium-n-propylate etc..In addition, being used as titanium (Ti)
The example of compound, can be enumerated：Fluotitanic acid, ammonium titanium fluoride, titanium potassium oxalate, titanium isopropoxide, isopropyl titanate, titanium ethanolate,
2- ethyl -1- hexanols titanium, tetraisopropyl titanate, tetra-n-butyl titanate, potassium fluotitanate, titanium sodium fluoride etc..In addition, being used as vanadium (V)
The example of compound, can be enumerated：Vanadic anhydride (V), vanadium trioxide (III), vanadium dioxide (IV), vanadium hydroxide
(II), vanadium hydroxide (III), vanadic sulfate (II), vanadic sulfate (III), vanadic sulfate (IV), vanadium fluoride (III), vanadium fluoride
(IV), vanadium fluoride (V), vanadium oxytrichloride VOCl3, vanadium trichloride VCl3, hexafluoro vanadic acid (III) or its salt (sylvite, ammonium salt etc.),
Metavanadic acid (V) or its salt (sodium salt, ammonium salt etc.), oxidation diacetyl acetone close vanadium (IV) VO (OC (=CH2)CH2COCH3)2, acetyl
Acetone vanadium (III) V (OC (=CH2)CH2COCH3)3, phosphovanadomolybdic acid H15-X[PV12-XMoO40]·nH20(6 ＜ X ＜ 12, n ＜ 30)
Deng.In addition, as the example of tungsten (W) compound, tungsten oxide (IV), tungsten oxide (V), tungsten oxide (VI), tungsten fluoride can be enumerated
(IV), tungsten fluoride (VI), wolframic acid (VI) H2WO4Or its salt (ammonium salt, sodium salt etc.), metatungstic acid (VI) H6[H2W12O40] or its salt (ammonium
Salt, sodium salt etc.), para-tungstic acid (VI) H10[H10W12O46] or its salt (ammonium salt, sodium salt etc.) etc..In addition, being used as molybdenum (Mo) compound
Example, can be enumerated：Phosphovanadomolybdic acid H15-X[PV12-XMoO40]·nH20(6 ＜ X ＜ 12, n ＜ 30), molybdenum oxide, molybdic acid H2MoO4、
Ammonium molybdate, ammonium paramolybdate, sodium molybdate, phosphomolybdic acid compound are (for example, ammonium phosphomolybdate (NH4)3[PO4Mo12O36]·3H2O, phosphomolybdic acid
Sodium Na3[PO4MO12O36]·nH2O etc.) etc..In addition, as the example of aluminium (Al) compound, can enumerate：Aluminum nitrate, sulfuric acid
Aluminium, alum, aluminum sodium sulfate, alum, aluminum phosphate, aluminium carbonate, aluminum oxide, aluminium hydroxide etc..In addition, being used as tin (sn)
The example of compound, can be enumerated：Tin oxide (IV), sodium stannate Na2snO3, stannic chloride (II), stannic chloride (IV), nitric acid tin
(II), nitric acid tin (IV), hexafluoro stannic acid ammonium (NH4)2SnF6Deng.In addition, as the example of niobium (Nb) compound, can enumerate：Five
Aoxidize two niobium (Nb2O5), sodium niobate (NaNbO3), fluorination niobium (NbF5), hexafluoro niobic acid ammonium (NH4)NbF6Deng.In addition, being used as hafnium
(Hf）Compound, yttrium (Y) compound, holmium (Ho) compound, bismuth (Bi) compound, the example of lanthanum (La) compound, can be enumerated：
Hafnium oxide, hexafluoro hafnium acid, yittrium oxide, acetylacetone,2,4-pentanedione yttrium, holimium oxide, bismuth oxide, lanthana etc..In addition, being used as cerium (Ce) chemical combination
The example of thing, can be enumerated：Cerium oxide, cerous acetate Ce (CH3CO2)3, cerous nitrate (III) or (IV), ammonium ceric nitrate, cerous sulfate,
Cerium chloride etc..In addition, as the example of zinc (zn) compound, can enumerate：Zinc oxide, zinc hydroxide, zinc acetate, zinc nitrate,
Zinc sulfate, zinc chloride, sodium zincate etc..Above-claimed cpd can be used alone or two or more kinds may be used.
Coordinate above-claimed cpd in the case of, preferably in metal conditioner with the gauge of metal ion respectively with
0.01~50g/L, particularly 0.05~5g/L concentration contain.Have if the content of above-claimed cpd is respectively lower than 0.01g/L
When corrosion resistance it is insufficient, if more than 50g/L, not finding to process the raising effect of closely sealed performance, on the contrary, bath stability sometimes
Reduction.
The metal conditioner of the present invention preferably also includes the compound containing thiocarbonyl.As containing thiocarbonyl
Compound, thiocarbamide, dimethyl sulfourea, 1,3- dimethyl sulfoureas, dipropyl thiocarbamide, dibutyl thiourea, 1,3- bis- can be illustrated
Phenyl -2- thiocarbamides, 2,2- bis- (tolyl) thiocarbamide, thioacetamide, SDD, a vulcanization tetramethyl
Thiuram, tetrabutylthiuram disulfide, N- ethyl, N-phenyls zinc dithiocarbamate, dimethyl dithiocarbamic acid
Zinc, pentamethylene aminodithioformic acid piperidinium salt, zinc diethyl dithiocarbamate, diethyldithiocar bamic acid
Sodium, zinc isopropyl xanthate, ethylene thiourea, dimethyl sulfide xanthic acid, dithiooxamide, Polydithiocarbamate or
The compound containing at least one thiocarbonyl such as its salt.Above-claimed cpd can be used alone, and can also use two or more.
In the case where coordinating the above-mentioned compound containing thiocarbonyl, preferably in the metal conditioner of the present invention
Contained with 0.01~100g/L, particularly 0.1~10g/L concentration.If the content of above-claimed cpd is less than 0.01g/L, have
When corrosion resistance it is insufficient, if more than 100g/L, corrosion resistance saturation becomes uneconomical sometimes.
The metal conditioner of the present invention is preferably also containing water-soluble or water-dispersed resin.As water-soluble or
Water-dispersed resin, can be enumerated：Acrylic resin, epoxylite, polyurethane based resin, ethylene, propylene acids copolymerization
Thing, phenolic resinoid, polyester resin, polyolefin resin, alkyd based resin, polycarbonate resin etc..These resins can
To be used alone, and two or more can also be used, copolymerization can also be carried out to use.Specifically, for example as water soluble propene
Acid resin, can be illustrated：The copolymer of main component, i.e. methyl acrylate, third are used as using acrylic acid and/or methacrylic acid
Olefin(e) acid ethyl ester, methyl methacrylate, EMA etc., can also use they derivative or with other propylene
The copolymer of acrylic monomer.The ratio of acrylic acid and/or methacrylic acid monomer in particularly preferred copolymer is 70 mass %
More than.
In addition, in order to improve its film forming when using resin, formed evenly and smooth film, can also used
Machine solvent.And then, surfactant, levelling agent, wettability improving agent, defoamer can be used.
Polystyrene of the molecular weight of water-soluble or water-dispersed resin preferably to be obtained by gel permeation chromatography
The weight average molecular weight of conversion is calculated as more than 10,000.More preferably 300,000~2,000,000.Less than 10,000, effect sometimes of the invention, especially
It is that the raising effect of the deep drawability of film can not give full play to.In addition, if more than 2,000,000, viscosity is uprised, operation sometimes is made
Industry efficiency is reduced.
In the case where coordinating above-mentioned water-soluble or water-dispersed resin, preferably with 0.1 in metal conditioner
~100g/L, particularly 5~80g/L concentration contain.The concentration of resin is less than 0.1g/L, and bending adaptation and depth are improved sometimes
The effect of drawability is insufficient, if more than 100g/L, the raising effect saturation of bending adaptation and deep drawability becomes sometimes
It is uneconomical.
The metal conditioner of the present invention preferably also contains phosphate anion.By adding phosphate anion, one can be entered
Step improves corrosion resistance.The addition of the phosphate anion can form the compound of phosphate anion by addition in water
Come carry out.As such compound, it can enumerate：Phosphoric acid, Na3PO4、Na2HPO4、NaH2PO4Deng phosphoric acid salt, condensation phosphorus
The phosphoric acid of the condensations such as acid, polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid or their salt.These can be used alone, and can also use 2
More than kind.
It is the dense of 0.01~100g/L to coordinate addition during above-mentioned phosphate anion preferably in metal conditioner
Degree, more preferably 0.1~10g/L concentration.If addition is less than 0.01g/L, the improvement of corrosion resistance is not filled sometimes
Point, if more than 100g/L, producing excessive etching on zinc-plated class steel, causing performance to reduce, or make containing water-base resin
In the case of for other compositions, gelation is caused sometimes.
In addition, the metal conditioner of the present invention can further coordinate known additive as Treatment of Metal Surface
Agent.For example, tannic acid or its salt, phytic acid or its salt etc. can be illustrated.
The metal conditioner of the present invention can be used as cold rolling steel, hot-strip, stainless steel steel and electrolytic zinc-coated steel sheet
Material, molten zinc plating steel, plating Zn-Al alloy class steel, plating zinc-iron alloys class steel, zinc-plated-magnesium alloy class steel, it is zinc-plated-
Aluminium-magnesium alloy class steel, class of aluminizing steel, aluminize-silicon alloys steel, tin plating class steel, lead-tin alloy plating alloy type steel, plating
Chromium class steel, plating nickel class steel etc. the surface conditioning agent of metal steel, imitate especially for coating metal steel (plating steel)
Fruit is significantly.
Can be that above-mentioned gold is coated with coated article as the application method of the surface conditioning agent, i.e. surface treatment method
Metal surface inorganic agent, the method for after coating drying coated article, or coated article is heated in advance, is then coated with above-mentioned
The metal conditioner of the present invention, makes the method that it is dried using waste heat.
Above-mentioned drying condition can be all set at room temperature~250 DEG C 2 seconds~1 hour in the case of any, preferably be set
For 5 seconds~20 minutes at 40~180 DEG C.If more than 250 DEG C, it is likely that produce the performance such as adaptation and corrosion resistance bad
Change.
In above-mentioned surface treatment method, the coating weight of the metal conditioner of the invention described above is preferably dried
It is 0.1mg/m by film quality2More than.0.1mg/m is less than by film quality2, rust-preventing characteristic is not enough sometimes.On the other hand, if adhesion amount mistake
It is many, then uneconomical with pretreating agent as application, more preferably 0.5~500mg/m2, more preferably 1~250mg/m2。
In above-mentioned surface treatment method, the coating method of metal conditioner is not particularly limited, can be by logical
Roller coat, showering, spraying, dipping, brushing for often using etc. are coated.In addition, the steel as process object are above-mentioned gold
Belong to steel, be particularly suitable for the processing of various plating steel.
The manufacture method of the coated steel of the present invention is following method：With above-mentioned metal conditioner to above-mentioned metallic steel
Material is surface-treated and dried, and is then coated with upper strata by film layer.As above-mentioned by film layer, it can enumerate：As needed in nothing
After the coating of chromate subbing is dried, further refer to using the finishing system formation for being coated with finishing coat by film layer or with resistance to
Functional coating of the function such as line and lubricity etc..Above-mentioned manufacture method is not limited to precoat steel, and steel are applied after can also be applied to,
Coated steel in the present invention includes these steel.In addition, the steel in the present invention are to include the concept of steel plate.
As above-mentioned chromate-free subbing workable in the present invention, chromium is not used in the cooperation of subbing
The subbing of Barbiturates rust resisting pigment can be used.As such subbing, preferably use vanadic acid class rust resisting pigment and
The subbing (V/P pigment subbing) of phosphoric acid class rust resisting pigment or the subbing using calcium silicates class rust resisting pigment.
The coating film thickness of above-mentioned subbing is preferably calculated as 1~20 μm with dry film thickness.Less than 1 μm, corrosion resistance sometimes
Deficiency, if more than 20 μm, adaptation reduction is processed sometimes.
The sintering and drying condition of above-mentioned chromate-free subbing can be set to for example to be calculated as 150 with metallic surface temperature~
250 DEG C, the time is set to 10 seconds~5 minutes.
It is not particularly limited as above-mentioned top coat, common application top coat can be used.In addition, being used as function
Coating is not particularly limited, and coating being applied to now on chromate pretreatment envelope etc. can be used.It is above-mentioned without chromic acid
The coating method of salt subbing and top coat and functional coating is not particularly limited, it is possible to use usually used roller coat, drench
Painting, aerial spraying, airless spraying, impregnating.
[embodiment]
Hereinafter, synthesis example, embodiment and comparative example is enumerated to illustrate the present invention in further detail, but the present invention is simultaneously
It is not limited to these embodiments.In addition, part represents mass parts in the following examples, Me represents methyl, and Et represents ethyl, and Ph is represented
Phenyl, IR is the abbreviation of infrared measure.
[synthesis example 1：The autofrettage of organo-silicon compound (8) (following formula (8))]
3- aminopropans are added in the 1L separate type flasks for possess mixer, reflux condenser, dropping funel and thermometer
Simultaneously different sulphur cyanogen is added dropwise in base trimethoxy silane (Shin-Etsu Chemial Co., Ltd's system, KBM-903) 358.6g (2mol) wherein
Sour methyl esters 146.2g (2mol), is stirred at room temperature 1 hour.Then, determined by IR and confirm the isothiocyanates from raw material
The absworption peak of base is wholly absent, and is set to reaction and is terminated.Obtained product is brown liquid, passes through gel permeation chromatography
(GPC) analyze, reaction product is single product.
[changing 15]
[synthesis example 2：The autofrettage of organo-silicon compound (9) (following formula (9))]
3- aminopropans are added in the 1L separate type flasks for possess mixer, reflux condenser, dropping funel and thermometer
Simultaneously different sulphur cyanogen is added dropwise in base trimethoxy silane (Shin-Etsu Chemial Co., Ltd's system, KBM-903) 358.6g (2mol) wherein
Acetoacetic ester 174.3g (2mol), is stirred at room temperature 1 hour.Then, determined by IR and confirm the isothiocyanates from raw material
The absworption peak of base is wholly absent, and is set to reaction and is terminated.Obtained product is brown liquid, passes through gel permeation chromatography
(GPC) analyze, reaction product is single product.
[changing 16]
[synthesis example 3：The autofrettage of organo-silicon compound (10) (following formula (10))]
3- aminopropans are added in the IL separate type flasks for possess mixer, reflux condenser, dropping funel and thermometer
Simultaneously different sulphur cyanogen is added dropwise in base trimethoxy silane (Shin-Etsu Chemial Co., Ltd's system, KBM-903) 358.6g (2mol) wherein
Acid phenenyl ester 270.4g (2mol), is stirred at room temperature 1 hour.Then, determined by IR and confirm the isothiocyanates from raw material
The absworption peak of base is wholly absent, and is set to reaction and is terminated.Obtained product is brown liquid, passes through gel permeation chromatography
(GPC) analyze, reaction product is single product.
[changing 17]
[synthesis example 4：The autofrettage of organo-silicon compound (13) (following formula (13))]
The different sulphur cyanogen of 3- is added in the IL separate type flasks for possess mixer, reflux condenser, dropping funel and thermometer
The sour tin 1g of propyl propionate base trimethoxy silane 221.4g (lmol), hexane 500g, two (2- ethyl hexanes), is heated to 60 DEG C.To
Ammonia is wherein blown into, is determined by IR, stops being blown into when the absworption peak of the isothiocyanate group from raw material is wholly absent.So
Afterwards, product obtained from removing solvent is yellow liquid, is analyzed by gel permeation chromatography (GPC), and reaction product is
Single product.
[changing 18]
[embodiment 1]
Organo-silicon compound (8) are obtained as not in methanol 990g, water 10g in the mixed solvent addition 10g synthesis examples 1
Volatile ingredient, is stirred at room temperature 5 minutes, thus obtains metal conditioner.With scraping strip coating machine No.20 with dry film thickness
As 10 μm of modes degreaser drying commercially available hot-dip galvanized steel sheet (Japanese テ ス ト パ ネ Le society system；70×150×
Obtained metal conditioner is coated with 0.4mm), is dried 10 minutes at 105 DEG C of metallic surface temperature.Then, scraping article is used
Coating machine No.16 is coated with the chromate-free subbing containing V/P pigment in the way of dry film thickness turns into 5 μm, in metal watch
Dried 5 minutes at 215 DEG C of face temperature.And then, as top coat, 15 μm are turned into dry film thickness with scraping strip coating machine No.36
Mode is coated with the ト 1060 (ペ ィ Application ト societies of polyesters investment precoat Japan system) of Off レ キ Us one, is done at 230 DEG C of metallic surface temperature
It is dry, obtain breadboard.According to following evaluation methods to bending adaptation, deep drawability, the corrosion resistance of obtained breadboard
Evaluated, its result is recorded in table 1.
[embodiment 2~4]
In embodiment 1, except the compound for being changed to obtain in synthesis example 2~4 by the compound obtained in synthesis example 1
(9), beyond (10), (13), metal conditioner is prepared similarly to Example 1.Using these metal conditioners, with
Embodiment 1 similarly makes breadboard, carries out their evaluation.Obtained result is recorded in table 1.
[embodiment 5~12]
In embodiment 1, except by the species and concentration of silane compound, organic titanate, water-dispersible silica, zirconium
Ion, the compound containing thiocarbonyl, the concentration of water-soluble resin and phosphate anion are carried out like that as shown in table 1 respectively
Beyond cooperation, metal conditioner is prepared similarly to Example 1.It is same with embodiment 1 using these metal conditioners
Make breadboard sample, carry out their evaluation.Obtained result is recorded in table 1.
[comparative example 1,2]
In embodiment 1, without using the compound obtained in synthesis example, by the species and concentration of silane compound, organic
Titanate esters, water-dispersible silica, zirconium ion, the compound containing thiocarbonyl, water-soluble resin and phosphate anion
Concentration coordinated like that as shown in table 1 respectively, in addition, metal conditioner is prepared similarly to Example 1.Make
These metal conditioners are used, breadboard is made similarly to Example 1, their evaluation is carried out.By obtained result note
It is loaded in table 1.
[comparative example 3]
In embodiment 1, instead of metal conditioner, by commercially available application type chromic acid salt treatment agent (resinous type) with
Chromium adhesion amount turns into 20mg/m2Mode be coated, dry, and (contain strontium chromate pigment using the subbing containing chromium
Subbing), in addition, make breadboard and evaluate similarly to Example 1, obtained result is recorded in table 1.
In addition, in table 1 below, as silane compound, organic titanate, water-dispersible silica, formed zirconium from
Compound, the compound containing thiocarbonyl, water-soluble resin, the compound for forming phosphate anion of son, using following
Commercially available product.
[silane compound]
A：KBM-903 (gamma-amino propyl trimethoxy silicanes；Shin-Etsu Chemial Co., Ltd's system)
B：KBM-403 (γ-glycidoxypropyltrime,hoxysilane；Shin-Etsu Chemial Co., Ltd's system)
[organic titanate]
Tetraisopropoxy titanium
[water-dispersible silica]
Methanol silicon dioxide gel (Nissan Chemical Ind Ltd's system)
[the red compound into zirconium ion]
Le AC-7 (the zirconium carbonate ammoniums of ジ Le Us ゾ mono-；N. E. Chemcat Corp.'s system)
[compound containing thiocarbonyl]
Thiocarbamide
[water-soluble resin]
Polyacrylic acid (weight average molecular weight 1,000,000)
[compound for forming phosphate anion]
Phosphoric acid
[evaluation method]
Bending adaptation, deep drawability in above-described embodiment 1~12 and comparative example 1~3, the evaluation of corrosion resistance are based on
Following method, metewand are carried out.
(1) adaptation is bent
Clamped in the environment of 20 DEG C using flow mandrel testerPad to breadboard carry out 180 ° it is curved
Qu Jiagong, 3 adhesive tapes are carried out to bending machining portion and are peeled off, and with 20 times of amplification sem observation extent of exfoliation, are carried out with following benchmark
Evaluate.
A：Free from flaw
B：There is crack before processing department
C：Peels off area is less than the 20% of processing department
D：Peels off area for processing department more than 20%~be less than 80%
E：Peels off area is more than the 80% of processing department
(2) deep drawability
In drawing ratio in the environment of 20 DEG C：2.3rd, wrinkle resistant pressure：2t, punching R：5mm, die orifice R：5mm, the bar without oiling
The cup drawing experiment of the breadboard of the cross that enters to pass through under part cutting.Then, determine and apply from the cross cutting part in cylinder side wall portion
The stripping width of film, is evaluated with following benchmark.
A：Peel off width and be less than 1mm
B：Stripping width be more than 1mm~be less than 2mm
C：Stripping width be more than 2mm~be less than 3mm
D：Stripping width be more than 3mm~be less than 5mm
E：Stripping width is more than 5mm
(3) corrosion resistance
(cutting part)
Proceed to the cross cutting up to zinc coat to breadboard, carry out the brine spray based on JIS z2371 of 500 hours
After experiment, the unilateral protuberance width of cross cutting part (cutting part) is determined, is evaluated with following benchmark.
A：Protuberance width is 0mm
B：Swell width be more than 0mm~be less than 1mm
C：Protuberance width be more than 1mm~be less than 3mm
D：Protuberance width be more than 3mm~be less than 5mm
E：Protuberance width is more than 5mm
(end face)
To breadboard carry out 500 hours salt spraytests based on JIS Z2371 after, with cutting part identical benchmark
Evaluate the protuberance width away from upper strata end face.
Table 1
Embodiment above and the result of comparative example confirm that the envelope of the metal conditioner formation using the present invention is carried
For good antirust ability and base material adaptation.
In addition, above, with embodiment, the present invention is described, but the present invention is not limited to implementation shown here
Mode, can in those skilled in the art such as other embodiments, addition, change, deletions it is conceivable that in the range of carry out
Change, in any mode, as long as the action effect of the present invention can be played, is then also contained in the scope of the present invention.
Claims (15)
1. a kind of metal conditioner, it is characterised in that contain the organo-silicon compound shown in (A) following formulas (1) and (B)
Water and/or organic solvent,
[changing 1]
In formula (1), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and A is the carbon atom of straight-chain or branched
The alkylidene of number 1~8, X is oxygen atom, sulphur atom, any, R of nitrogen-atoms1、R2It is separately hydrogen atom, carbon atom
The alkyl of number 1~20, the fluoroalkyl of carbon number 1~20, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10 or
Substituent shown in following formulas (2), m is 1~3 integer,
[changing 2]
In formula (2), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and B is the carbon atom of straight-chain or branched
The alkylidene of number 1~8, m is 1~3 integer,
R hydrolization group is selected from halogen atom, the alkoxy of carbon number 1~4 in above-mentioned formula (1) and formula (2).
2. the metal conditioner described in claim 1, it is characterised in that above-mentioned organo-silicon compound are following formulas (3),
[changing 3]
In formula (3), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and A is the carbon atom of straight-chain or branched
The alkylidene of number 1~8, R1~R3It is separately hydrogen atom, the alkyl of carbon number 1~20, the fluorine of carbon number 1~20
Substituent shown in alkyl, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10 or following formulas (4), m is 1~3
Integer,
[changing 4]
In formula (4), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and B is the carbon atom of straight-chain or branched
The alkylidene of number 1~8, m is 1~3 integer,
R hydrolization group is selected from halogen atom, the alkoxy of carbon number 1~4 in above-mentioned formula (3) and formula (4).
3. the metal conditioner described in claim 2, it is characterised in that above-mentioned organo-silicon compound are following formulas (5),
[changing 5]
In formula (5), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, R1For hydrogen atom, carbon number 1~20
Alkyl, the fluoroalkyl of carbon number 1~20, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10 or following formulas
(6) substituent shown in, m is 1~3 integer,
[changing 6]
In formula (6), R is hydrolization group, and R ' is the alkyl of carbon number 1~4, and m is 1~3 integer,
R hydrolization group is selected from halogen atom, the alkoxy of carbon number 1~4 in above-mentioned formula (5) and formula (6).
4. the metal conditioner described in any one of claims 1 to 3, it is characterised in that also containing following formulas (7) Suo Shi
Alkoxy silane or part thereof hydrolytic condensate,
R4 xSi(OR5)4-x (7)
In formula (7), R4Represent the monovalent hydrocarbon of the non-substituted of carbon number 1~20 or substitution, R5Represent carbon number 1~8
Non-substituted or substitution monovalent hydrocarbon, x is 0~3 integer.
5. the metal conditioner described in any one of claims 1 to 3, it is characterised in that also contain organic titanate.
6. the metal conditioner described in any one of claims 1 to 3, it is characterised in that also containing water dispersible titanium dioxide
Silicon or organic solvent dispersion silica.
7. the metal conditioner described in any one of claims 1 to 3, it is characterised in that also containing selected from Fe, Zr, Ti, V,
The compound of more than a kind of metal in W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn.
8. the metal conditioner described in any one of claims 1 to 3, it is characterised in that also comprising containing thiocarbonyl
Compound.
9. the metal conditioner described in any one of claims 1 to 3, it is characterised in that also containing water-soluble resin or water
Dispersion resin.
10. the metal conditioner described in any one of claims 1 to 3, it is characterised in that also contain phosphate anion.
11. a kind of surface treatment method of steel, it is characterised in that at the metal surface described in any one of claims 1 to 3
Reason agent is surface-treated to the surface of steel.
12. the surface treatment method described in claim 11, wherein, steel are coating metal steel.
13. a kind of surface treated steel product, it is obtained by the surface treatment method described in claim 11.
14. a kind of manufacture method of coated steel, it is characterised in that with the metal surface described in any one of claim 1~10
After inorganic agent is handled steel, upper strata is further set by film layer.
15. a kind of coated steel, it is obtained by the manufacture method of the coated steel described in claim 14.
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| US9222019B2 (en) * | 2013-10-29 | 2015-12-29 | Ecolab Usa Inc. | Use of niobate containing compounds as corrosion inhibitors |
| KR101614307B1 (en) | 2014-08-14 | 2016-04-22 | 대원강업주식회사 | Surface treatment system and its control method |
| JP6291442B2 (en) * | 2015-03-12 | 2018-03-14 | 京セラ株式会社 | Thermistor sensor casting resin composition and thermistor sensor |
| JP2017150012A (en) * | 2016-02-22 | 2017-08-31 | 日本ペイント・サーフケミカルズ株式会社 | Metal surface treatment agent |
| JP6561901B2 (en) * | 2016-04-15 | 2019-08-21 | 信越化学工業株式会社 | Metal surface treatment agent |
| JP6777492B2 (en) | 2016-10-06 | 2020-10-28 | 三菱重工業株式会社 | Surface treatment equipment and surface treatment method |
| CN106521473A (en) * | 2016-11-18 | 2017-03-22 | 安徽工业大学 | Copper and copper alloy surface anticorrosion liquid and preparation method thereof |
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| KR20140019236A (en) | 2014-02-14 |
| CN103572298A (en) | 2014-02-12 |
| TWI522493B (en) | 2016-02-21 |
| JP2014031556A (en) | 2014-02-20 |
| JP5712980B2 (en) | 2015-05-07 |
| KR102067841B1 (en) | 2020-01-17 |
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