CN102227517A - Chromate-free surface-treated metal material - Google Patents

Chromate-free surface-treated metal material Download PDF

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CN102227517A
CN102227517A CN2009801476116A CN200980147611A CN102227517A CN 102227517 A CN102227517 A CN 102227517A CN 2009801476116 A CN2009801476116 A CN 2009801476116A CN 200980147611 A CN200980147611 A CN 200980147611A CN 102227517 A CN102227517 A CN 102227517A
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metal material
treated metal
methyl
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compound
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CN102227517B (en
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森下敦司
菊池郁夫
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Nippon Steel Corp
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Nippon Steel Corp
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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
    • C23C22/34—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 fluorides or complex fluorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C09D5/4415—Copolymers wherein one of the monomers is based on an epoxy resin
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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

Disclosed is a surface-treated metal material which does not contain hexavalent chromium that has a high environmental load, can be produced relatively readily, and has excellent stain-proof properties, solvent resistance, alkali resistance and corrosion resistance. Specifically disclosed is a chromate-free surface-treated metal material characterized by having a coating film formed thereon, wherein the coating film is produced by applying an aqueous treatment solution on the surface of a metal material and drying the aqueous treatment solution, wherein the aqueous treatment solution comprises an organosilicon compound (A) containing an alkylene group, a siloxane bond and a cross-linkable functional group represented by the formula -SiR1R2R3 (wherein R1, R2 and R3 independently represent an alkoxy group or a hydroxy group and at least one of R1, R2 and R3 may be substituted by a methyl group) and an organofluorine compound (B) containing a perfluoroalkyl group.

Description

The non-chromate surface-treated metal material
Technical field
The present invention relates to not contain the high sexavalent chrome of carrying capacity of environment, make than being easier to and hydrophobic-oleophobic property, stain resistance, solvent resistance, alkali resistance, the erosion resistance non-chromate surface-treated metal material of excellence extremely.In addition, relate to and to satisfy hydrophobic-oleophobic property and close-burning non-chromate surface-treated metal material simultaneously.
Background technology
In the every profession and trade of electrical article, automobile, material of construction etc. of being in, be purpose to give erosion resistance etc., usually using zinc is that Coated Steel and aluminium are the technology that the metallic substance of Coated Steel etc. has implemented to use the chromate treating of chromic salt etc.Chromate treating only is coated on by the aqueous solution that will contain chromic acid and makes its drying just finish processing on the metallic substance, therefore handles as the chemical transformation that can make with comparalive ease and is used on a large scale.Yet, rise to background with environmental problem in recent years, wish to get rid of high chromic activeization of trend of carrying capacity of environment from supplying with material, the industry of abolish is also arranged.Recently, under non-chromate is handled prerequisite, improving guaranteeing the requirement that erosion resistance has the metallic substance of various value addeds again concurrently.
As one of such value added, can enumerate hydrophobic-oleophobic property and stain resistance.Stain resistance among so-called the present invention, mean: the pollution etc. of polluting (adhering to of outdoor airborne dust, carbon etc.), food contamination (adhering to of food, edible oil, seasonings, refreshment drink etc.), other (cigarette foxy old hand, fingerprint, work oil, oiliness China inks etc.) with respect to raindrop is difficult to contaminated, even performance perhaps contaminated but that also remove pollutent easily by washing.Metallic substance, before being processed to end article, the processing that usually is formed, and via the washing procedure that has used organic solvent and/or alkali degreasing liquid.Even importantly also keep stain resistance, require to tolerate the weather resistance of repetitive scrubbing according to purposes through such washing procedure.
Up to now, many technical schemes of not using chromic chromate-free had once been proposed.For example, as non-chromate treatment technology based on inorganic components, patent documentation 1 discloses the chemical transformation of the complex chemical compound that contains manganese and titanium and has handled epithelium, and patent documentation 2 discloses the metal conditioner that contains at least a metallic compound in vanadium compound and selected among zirconium, titanium, molybdenum, tungsten, manganese and the cerium.As non-chromate treatment technology based on resinous principle, patent documentation 3 discloses and has used the surface treated steel plate that contains the surface treatment agent of specific resin compound, cationic urethane resin, silane coupling agent, Ti compound and oxygen compound with specific ratio, and patent documentation 4 discloses the resin-coated metal sheet with the resin involucra that is obtained by the emulsion compositions that with specific ethene-copolymers of unsaturated carboxylic acids is principal constituent.
Non-chromate treatment technology shown in these patent documentations 1～4 does not carry out the research about hydrophobic-oleophobic property and stain resistance fully, does not have the stain resistance of realization to the height of all pollution substances.In addition, also exist solvent resistance and/or alkali resistance low, in the problem that with an organic solvent reduces with washing such as neutralizing treatment liquid back stain resistance.
On the other hand, as the technology of the stain resistance that has height under the chromate-free prerequisite, it is the varnish coated stainless steel plate of fluorine that thermosetting resin obtains that patent documentation 5 discloses by the organic solvent that contains specific fluoro-resin, blocked isocyanate resin and aminoresin.Yet, not only do not carry out the research of relevant erosion resistance fully, and since in the solvent with an organic solvent, therefore, in safety and sanitation, have the problem can not use chromic salt coating apparatus in the past to make.In addition, must carry out high bake, also to have problem from the viewpoint of productivity and energy efficiency for resin involucra is solidified.
Like this, present situation is the non-chromate surface-treated metal material that never provides hydrophobic-oleophobic property, stain resistance, solvent resistance, alkali resistance, erosion resistance all excellent.
The prior art document
Patent documentation 1: TOHKEMY 2002-30459 communique
Patent documentation 2: TOHKEMY 2002-30460 communique
Patent documentation 3: TOHKEMY 2003-105562 communique
Patent documentation 4: TOHKEMY 2005-246953 communique
Patent documentation 5: TOHKEMY 2007-118291 communique
Summary of the invention
The present invention is in view of above-mentioned present situation, and its purpose is to provide and does not contain the high sexavalent chrome of carrying capacity of environment, manufacturing than the surface-treated metal material that is easier to and has concurrently extremely excellent hydrophobic-oleophobic property, stain resistance, solvent resistance, alkali resistance, erosion resistance.And its purpose also is to provide and can satisfies hydrophobic-oleophobic property and close-burning non-chromate surface-treated metal material simultaneously.
What present inventors concentrated on studies repeatedly in order to address these problems found that: by forming at metal material surface: to contain alkylidene group, siloxane bond and by formula-SiR 1R 2R 3(in the formula, R 1, R 2And R 3Represent alkoxyl group or hydroxyl independently of each other, R 1, R 2And R 3Any one can be by methyl substituted) silicoorganic compound (A) of the bridging property functional group of expression are binder constituents, and to the wherein compound epithelium that contains the organofluorine compound (B) of perfluoroalkyl, can obtain all extremely excellent non-chromate surface-treated metal material of hydrophobic-oleophobic property, stain resistance, solvent resistance, alkali resistance, erosion resistance, thereby finish the present invention.
That is, purport of the present invention is as follows:
(1) a kind of non-chromate surface-treated metal material, it is characterized in that, has epithelium, described epithelium is by being coated with aqueous treatment agent at metal material surface, and carry out drying or baking forms, described aqueous treatment agent contain have alkylidene group, siloxane bond and by the silicoorganic compound (A) of the bridging property functional group of following general formula [X] expression with have the organofluorine compound (B) of perfluoroalkyl
-SiR 1R 2R 3 [X]
In the formula, R 1, R 2And R 3Represent alkoxyl group or hydroxyl independently of each other.(comprise R 1, R 2And R 3Any one by methyl substituted situation)).
According to (1) described non-chromate surface-treated metal material, it is characterized in that (2) above-mentioned silicoorganic compound (A) are 4～200 with the solids component mass ratio [(A)/(B)] of above-mentioned organofluorine compound (B).
(3) according to (1) or (2) described non-chromate surface-treated metal material, it is characterized in that above-mentioned silicoorganic compound (A) have at least a bridging property functional group that is selected from amino, epoxy group(ing) and the hydroxyl (group of opening respectively with the group that can be contained in the above-mentioned general formula [X]).
(4), according to any one described non-chromate surface-treated metal materials of (1)～(3), it is characterized in that above-mentioned silicoorganic compound (A) are the hydrolytic condensate of silane coupling agent.
(5) any one described non-chromate surface-treated metal material of basis (1)～4, it is characterized in that above-mentioned silicoorganic compound (A) are to obtain with the reaction with silane coupling agent (A2) of epoxy group(ing) by having amino silane coupling agent (A1).
According to (5) described non-chromate surface-treated metal material, it is characterized in that (6) above-mentioned silane coupling agent (A1) with amino is 0.5～2.5 with above-mentioned mol ratio [(A1)/(A2)] with silane coupling agent (A2) of epoxy group(ing).
(7) according to any one described non-chromate surface-treated metal material of (1)～(6), it is characterized in that the number-average molecular weight of above-mentioned silicoorganic compound (A) is 1000～10000.
(8) according to any one described non-chromate surface-treated metal material of (1)～(7), it is characterized in that the carbonatoms of contained perfluoroalkyl is below 6 in the above-mentioned organofluorine compound (B).
(9) according to any one described non-chromate surface-treated metal material of (1)～(8), it is characterized in that above-mentioned organofluorine compound (B) is the polymkeric substance that contains based on the polymerized unit of (methyl) acrylate (B1) with perfluoroalkyl.
(10) according to (9) described non-chromate surface-treated metal material, it is characterized in that above-mentioned (methyl) acrylate (B1) with perfluoroalkyl is by following general formula [B-1] expression,
CH 2＝C(R 4)COO(CH 2) nR 5 [B-1]
In the formula, R 4Expression H or CH 3, R 5The expression perfluoroalkyl, n is 0～4 integer.
(11) according to any one described non-chromate surface-treated metal material of (1)～(10), it is characterized in that above-mentioned organofluorine compound (B) has bridging property functional group (b).
(12) any one described non-chromate surface-treated metal material of basis (9)～(11), it is characterized in that above-mentioned organofluorine compound (B) is the polymkeric substance that contains based on the polymerized unit of (methyl) acrylate (B2) with bridging property functional group (b).
(13) according to (11) or (12) described non-chromate surface-treated metal material, it is characterized in that, above-mentioned bridging property functional group (b) is selected from amino, isocyanate group, epoxy group(ing), at least a by in the functional group of following general formula [Y] expression and the hydroxyl (group of opening respectively with the group that can be contained in the following general formula [Y])
-SiR 6R 7R 8 [Y]
In the formula, R 6, R 7And R 8Represent alkoxyl group or hydroxyl independently of each other.(comprise R 6, R 7And R 8Any one by methyl substituted situation)).
(14) according to any one described non-chromate surface-treated metal material of (1)～(13), it is characterized in that above-mentioned organofluorine compound (B) has alkyl.
(15) according to any one described non-chromate surface-treated metal material of (9), (10), (12), it is characterized in that above-mentioned organofluorine compound (B) is the polymkeric substance that contains based on the polymerized unit of (methyl) acrylate (B3) with alkyl.
(16), it is characterized in that it is alkyl more than 16 that abovementioned alkyl has carbon number according to (14) or (15) described non-chromate surface-treated metal material.
(17) according to any one described non-chromate surface-treated metal material of (1)～(16), it is characterized in that above-mentioned organofluorine compound (B) has oxyalkylene group (alkylene oxide group).
(18) any one described non-chromate surface-treated metal material of basis (9), (10), (12), (15), it is characterized in that, above-mentioned organofluorine compound (B) is the polymkeric substance that contains based on the polymerized unit of (methyl) acrylate (B4) with oxyalkylene group.
(19) according to (18) described non-chromate surface-treated metal material, it is characterized in that above-mentioned (methyl) acrylate (B4) that contains oxyalkylene group is by following general formula (B-4) expression,
CH 2＝C(R 9)COO(CH 2) p-(R 10O) q-R 11 [B-4]
In the formula, R 9Be H or CH 3, R 10Be the alkylidene group of carbon number 2～4, R 11Be hydrogen atom, methyl or (methyl) acryl, p is 0～4, q is 1～15 integer.
(20) according to (19) described non-chromate surface-treated metal material, it is characterized in that, in formula by above-mentioned general formula (B-4) expression, R 9Be H or CH 3, R 10Be the alkylidene group of carbon number 2～4, R 11Be hydrogen atom or methyl, p is 0～4, q is 4～30 integer.
(21) according to any one described non-chromate surface-treated metal material of (1)～(20), it is characterized in that, in above-mentioned aqueous treatment agent, also contain organic acid.
(22) any one described non-chromate surface-treated metal material of basis (1)～(21), it is characterized in that, in above-mentioned aqueous treatment agent, also contain and be selected from least a in phosphate cpd, fluorine metal coordination compound, vanadium compound and the cobalt compound.
According to any one described non-chromate surface-treated metal material of (1)～(22), it is characterized in that (23) drying of above-mentioned aqueous treatment agent or storing temperature by arriving thermometer, are 60 ℃～150 ℃.
(24) according to any one described non-chromate surface-treated metal material of (1)～(23), it is characterized in that the adhesion amount of the epithelium of above-mentioned formation is 0.2～20g/m 2
(25) according to any one described non-chromate surface-treated metal materials of (1)～(24), it is characterized in that, is more than 100 ° under 20 ℃ and contact angle water.
(26) according to any one described non-chromate surface-treated metal materials of (1)～(25), it is characterized in that, is more than 55 ° under 20 ℃ and contact angle n-hexadecane.
(27) according to any one described non-chromate surface-treated metal material of (1)～(26), it is characterized in that above-mentioned metallic substance is that zinc is that Coated Steel or aluminium are Coated Steel.
Non-chromate surface-treated metal material of the present invention does not contain the high sexavalent chrome of carrying capacity of environment, makes than being easier to and the equal excellence extremely of hydrophobic-oleophobic property, stain resistance, solvent resistance, alkali resistance, erosion resistance.In addition, also can satisfy hydrophobic-oleophobic property and cohesiveness simultaneously.Therefore be hopeful very much the corresponding section bar material of conduct high additive value environment from now on, very big to the contribution of each industrial field.
Embodiment
Detailed content of the present invention below is described and limits reason.
Non-chromate surface-treated metal material of the present invention, it is characterized in that, has epithelium, described epithelium is by being coated with aqueous treatment agent at metal material surface, and carry out drying and form, described aqueous treatment agent contain have alkylidene group, siloxane bond and by the silicoorganic compound (A) of the bridging property functional group of following general formula [X] expression with have the organofluorine compound (B) of perfluoroalkyl
-SiR 1R 2R 3 [X]
In the formula, R 1, R 2And R 3Represent alkoxyl group or hydroxyl independently of each other, R 1, R 2And R 3Any one also can be by methyl substituted.
Being used to form the treatment agent of above-mentioned epithelium, is the aqueous treatment agent that contains silicoorganic compound (A) and organofluorine compound (B) in the aqueous medium that is principal constituent with water.So-called " is principal constituent with water " means: water surpasses 50 quality % for the total mass of aqueous medium.This aqueous medium can contain organic solvent, but the organic solvent amount that contains in the aqueous medium, preferably the total mass with respect to aqueous medium is below the 15 quality %.Aqueous treatment agent of the present invention can only form epithelium by it being coated on the metal material surface and carrying out drying, therefore can similarly make with comparalive ease with chromate treating in the past.
The above-mentioned epithelium of Xing Chenging in this wise is to be binder constituents with silicoorganic compound (A), and to its compound epithelium of organofluorine compound (B).Contained alkylidene group in the silicoorganic compound (A) is undertaken the effect of epithelium being made the barrier etc. of film, flexibility, water tolerance, alkali resistance, corrosion factor, and siloxane bond is undertaken the effect that epithelium is given obdurability, weather resistance, solvent resistance.And, contained in the silicoorganic compound (A) by above-mentioned formula-SiR 1R 2R 3The bridging property functional group of expression, has self-crosslinking, the formation stage at epithelium can form siloxane bond each other by this bridging property functional group on three-dimensional, the cross-linking density of epithelium is improved, and undertakes and gives compactness, obdurability, weather resistance, solvent-proof effect to epithelium.In addition, this bridging property functional group also undertake improve with the adhering effect of base metal material, improve the effect of the epithelium retentivity that carries out compound organofluorine compound (B), to the additional wetting ability of silicoorganic compound (A), make the dissolving in hydrotropisms's medium or disperse to be easy to effect.Can think R in this bridging property functional group 1, R 2, R 3, in aqueous medium, preferentially generating the hydroxyl (silanol group) that the hydrolysis by alkoxyl group generates respectively, this is favourable on the self-crosslinking that improves this bridging property functional group, is well suited on above-mentioned all effects obtaining.Promptly, the aqueous treatment agent that contains the silicoorganic compound (A) that side by side contain alkylidene group, siloxane bond and this bridging property functional group by use, make the film excellence, have flexibility and obdurability, densification concurrently and can guarantee the barrier (erosion resistance) of water tolerance, alkali resistance, solvent resistance, corrosion factor chronically, form and the adhesivity excellence of base metal material, the also high tackiness agent epithelium of epithelium retentivity of compound organofluorine compound (B).
By the compound organofluorine compound (B) that contains perfluoroalkyl, can give hydrophobic-oleophobic property, the stain resistance of height to this tackiness agent epithelium.This is owing to contain the organofluorine compound (B) of the perfluoroalkyl that is made of the C-F key, can form to result from the cause on the low low free energy surface of the polarizability of C-F key.In addition, by forming epithelium as the aqueous treatment agent of solvent by the aqueous medium that will be principal constituent with water, and in the binder constituents of epithelium, use silicoorganic compound (A), can make perfluoroalkyl preferentially at the epithelium surface orientation, therefore can reduce the surface free energy of epithelium expeditiously.In this wise by perfluoroalkyl lining surface, epithelium that surface free energy is low hydrophobic-the oleophobic property excellence, and be difficult to adhere to all pollution substances, present extremely excellent stain resistance.In addition, utilize composite effect with silicoorganic compound (A), form stain resistance and continue chronically, have with an organic solvent and/or washing such as neutralizing treatment liquid afterwards hydrophobic-the high hydrophobic-oleophobic property anti-pollution type epithelium of the resisting power that oleophobic property and stain resistance also do not reduce.
That is, by side by side to contain alkylidene group, siloxane bond and by above-mentioned formula-SiR 1R 2R 3The silicoorganic compound (A) of the bridging property functional group of expression are binder constituents, and, can form hydrophobic-oleophobic property, stain resistance, solvent resistance, alkali resistance, all extremely excellent chromate-free epithelium of erosion resistance (also comprising the processing back that is shaped) to its compound organofluorine compound (B) that contains perfluoroalkyl.
The solids component mass ratio [(A)/(B)] of silicoorganic compound (A) and organofluorine compound (B) is preferably 4～200, and more preferably 10～100.Solids component mass ratio [(A)/(B)] is less than 4 o'clock, not only since make film reduction and sometimes erosion resistance reduce, and also unfavorable economically.Greater than 200 o'clock, hydrophobic sometimes-oleophobic property and/or stain resistance reduced.
Silicoorganic compound (A) are so long as the bridging property functional group of containing alkylidene group, siloxane bond and being represented by following general formula [X], can with water the silicoorganic compound that stably exist in the aqueous medium of principal constituent, then have no particular limits, but at the epithelium that forms the higher densification of cross-linking density, improve and preferably also contain at least a bridging property functional group that is selected from the amino, epoxy group(ing), hydroxyl (group of opening respectively with the group that can be contained in the above-mentioned general formula [X]) on the epithelium retentivity of organofluorine compound (B).That is, can further improve stain resistance, solvent resistance, alkali resistance, erosion resistance.In addition, these bridging property functional groups show wetting ability, and are therefore also favourable on the stability of raising silicoorganic compound (A) in aqueous medium.The stability of what is called in this specification sheets in aqueous medium, expression by through the time be difficult in aqueous medium condensation product and/or sediment take place, be difficult to cause the phenomenon of tackify and/or gelation.
-SiR 1R 2R 3 [X]
(in the formula, R 1, R 2And R 3Represent alkoxyl group or hydroxyl independently of each other.R 1, R 2And R 3Any one also can be by methyl substituted).
As these silicoorganic compound (A), can exemplify the hydrolytic condensate of silane coupling agent etc.Example as concrete silane coupling agent, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, N-2 (amino-ethyl) 3-TSL 8330, N-2 (amino-ethyl) 3-aminopropyltriethoxywerene werene, N-2 (amino-ethyl) 3-aminopropyl methyl dimethoxysilane, two (trimethoxy-silylpropyl) amine, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-phenyl-3-TSL 8330,3-urea groups propyl-triethoxysilicane, 3-mercapto propyl group methyl dimethoxysilane, the 3-mercaptopropyl trimethoxysilane, the 3-mercaptopropyltriethoxysilane, 3-isocyanic ester propyl-triethoxysilicane, two (trimethoxysilyl) hexane etc.Above-mentioned silane coupling agent can use separately, also can will also use more than 2 kinds.
The special silicoorganic compound that preferably obtain of silicoorganic compound (A) by silane coupling agent (A1) that contains amino and the reaction that contains the silane coupling agent (A2) of epoxy group(ing).By reaction and alkoxysilyl that contains separately or the mutual reaction of its partial hydrolysis resultant amino and epoxy group(ing), the epithelium of the high densification of cross-linking density can be formed, stain resistance, solvent resistance, alkali resistance, erosion resistance can be further improved.As containing amino silane coupling agent (A1), can exemplify the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, N-2 (amino-ethyl) 3-TSL 8330, N-2 (amino-ethyl) 3-aminopropyltriethoxywerene werene, N-2 (amino-ethyl) 3-aminopropyl methyl dimethoxysilane, two (trimethoxy-silylpropyl) amine, as the silane coupling agent that contains epoxy group(ing) (A2), can exemplify the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane.
Contain amino silane coupling agent (A1) and be preferably 0.5～2.5, more preferably 0.7～1.6 with the mol ratio [(A1)/(A2)] that contains the silane coupling agent (A2) of epoxy group(ing).Mol ratio [(A1)/(A2)] was made the film reduction sometimes less than 0.5 o'clock, and stain resistance reduces.Greater than 2.5 o'clock, water tolerance reduction sometimes, alkali resistance and erosion resistance reduced.
The number-average molecular weight of silicoorganic compound (A) is preferably 1000～10000, and more preferably 2000～10000.There is no particular limitation at the measuring method of this said molecular weight, can adopt the direct mensuration of TOF-MS method and any method that chromatographic conversion is measured.Number-average molecular weight was less than 1000 o'clock, and the water tolerance of formed epithelium reduces sometimes, and alkali resistance and/or erosion resistance reduce.Number-average molecular weight was difficult to make above-mentioned silicoorganic compound (A) dissolving stably or dispersion in the aqueous medium that with water is principal constituent greater than 10000 o'clock, and storage stability reduces sometimes.
The manufacture method of silicoorganic compound (A) has no particular limits, and for example can enumerate silane coupling agent dissolving or is dispersed in the water, stirs the specified time under the temperature of regulation, obtains the method for the water-based liquid of hydrolytic condensate; With the silicoorganic compound dissolving of silane coupling agent hydrolytic condensate etc. or be dispersed in the method that obtains water-based liquid in the water; Or the like.In the occasion of using silane coupling agent and/or its hydrolytic condensate, in order to make its dissolving or dispersion, also can suitably add acid, alkali, organic solvent, tensio-active agent etc., consider especially preferably to add organic acid pH regulator to 3～6 from the viewpoint of storage stability.The solid component concentration of the water-based liquid of silicoorganic compound (A) is preferably below the 25 quality %.When surpassing 25 quality %, the storage stability of aqueous treatment agent reduces sometimes.
Organofluorine compound (B) can be that the organofluorine compound that stably exists in the aqueous medium of principal constituent then has no particular limits with water so long as contain perfluoroalkyl at intramolecularly, but the carbonatoms of preferred perfluoroalkyl is below 6.Carbonatoms is for a long time easily at the epithelium surface orientation, reduce surface free energy, the effect that improves stain resistance is big, but contain the occasion that carbonatoms is the organofluorine compound of the perfluoroalkyl more than 8 in use, because as the impurity from raw material is the carrying capacity of environment material, worry conditional perfluorooctane sulfonate or derivatives thereof, Perfluorocaprylic Acid or derivatives thereof in a part is used remain in the epithelium, thereby not preferred.Carbonatoms was less than 2 o'clock, and hydrophobic sometimes-oleophobic property and/or stain resistance are insufficient, if also consider the load reduction of environment, being easy to get property, low cost etc., carbonatoms is preferred 2～6, and more preferably 4～6.
Organofluorine compound (B) preferably contains the polymkeric substance based on the polymerized unit of (methyl) acrylate (B1) that contains perfluoroalkyl.In this manual, so-called (methyl) acrylate means acrylate or methacrylic ester.Therefore (methyl) acrylate is with respect to the solvability excellence of all kinds of SOLVENTS, and emulsion polymerization is easy, uses (methyl) acrylate (B1) that contains perfluoroalkyl as monomer, and is very suitable aspect the synthetic organofluorine compound (B) that contains perfluoroalkyl.So the stability of the polymkeric substance that obtains in the aqueous solvent that with water is principal constituent is also excellent.Because to carry out copolymerization also easy with (methyl) esters of acrylic acid that does not contain perfluoroalkyl, vinyl ethers, vinyl ester etc., therefore also has the big advantage of design freedom of polymkeric substance.
(methyl) acrylate (B1) that contains perfluoroalkyl is more preferably the structure of being represented by following general formula [B-1].
CH 2＝C(R 4)COO(CH 2) nR 5 [B-1]
In the formula [B-1], R 4Expression H or CH 3, R 5The expression perfluoroalkyl, n represents 0～4 integer.Structure by above-mentioned general formula [B-1] expression, make perfluoroalkyl preferentially effective especially aspect the epithelium surface orientation, and also high with the affinity as the silicoorganic compound (A) of the binder constituents of epithelium, so the epithelium retentivity of organofluorine compound (B) is also high.Promptly, stain resistance and hydrophobic-oleophobic property and the stain resistance that can obtain height continue chronically, even can be had with an organic solvent, washing such as neutralizing treatment liquid is afterwards hydrophobic-the high hydrophobic-oleophobic property anti-pollution type epithelium of the resisting power that oleophobic property and stain resistance also do not reduce.
As (methyl) acrylate (B1) that contains perfluoroalkyl that has by the structure of following general formula [B-1] expression, for example, can enumerate CH 2=CHCOOC 2H 4C 4F 9, CH 2=C (CH 3) COO C 2H 4C 4F 9, CH 2=CHCOOC 2H 4C 6F 13, CH 2=C (CH 3) COOC 2H 4C 6F 13, CH 2=C (CH 3) COOC 3H 6C 6F 13, CH 2=CHCOOC 2H 4C 8F 17, CH 2=C (CH 3) COOC 2H 4C 8F 17, CH 2=C (CH 3) COOC 8F 17CH is preferably arranged 2=CHCOOC 2H 4C 4F 9, CH 2=C (CH 3) COOC 2H 4C 4F 9, CH 2=CHCOOC 2H 4C 6F 13, CH 2=C (CH 3) COOC 2H 4C 6F 13, CH 2=C (CH 3) COOC 3H 6C 6F 13These materials can use separately, also can will also use more than 2 kinds.
Organofluorine compound (B) preferably contains polymerized unit 60～98 quality % based on (methyl) acrylate (B1) that contains perfluoroalkyl.During less than 60 quality %, stain resistance reduces sometimes.When surpassing 98 quality %, the epithelium retentivity of organofluorine compound (B) reduces, and the weather resistance of hydrophobic sometimes-oleophobic property and/or stain resistance reduces.And also the stability of organofluorine compound (B) in the aqueous medium that with water is principal constituent reduces sometimes.
Preferred organofluorine compound (B) contains bridging property functional group (b) at intramolecularly.Can think that bridging property functional group (b) forms crosslinking structure with the bridging property functional group chemistry bonding that is contained in the silicon compound (A) as binder constituents in the forming process of epithelium, can improve cross-linking density, and improve the epithelium retentivity of organofluorine compound (B).That is the stain resistance that, can have resisting power.And bridging property functional group (b) shows wetting ability, therefore also can improve the stability of organofluorine compound (B) in the aqueous medium that with water is principal constituent.
At organofluorine compound (B) is the occasion that contains based on the polymkeric substance of the polymerized unit of (methyl) acrylate (B1) that contains perfluoroalkyl, is more preferably the polymkeric substance that also contains based on the polymerized unit of (methyl) acrylate (B2) that contains bridging property functional group (b).This polymkeric substance can be made with comparalive ease by (methyl) acrylate (B1) that contains perfluoroalkyl and the copolymerization that contains (methyl) acrylate (B2) of crosslinked functionality base (b).The multipolymer that obtains in this wise demonstrates the stability of the excellence in the aqueous medium that with water is principal constituent, and the epithelium that obtains shows hydrophobic-oleophobic property, the stain resistance of the excellence that has resisting power.
Above-mentioned bridging property functional group (b) so long as functional group that can crosslinking reaction then have no particular limits, for example, can enumerate amino, isocyanate group, alkoxysilyl, silanol group (silanol group), alkoxyl-methyl amide group, ammonium, amide group, epoxy group(ing), hydroxyl,
Figure BDA0000064394780000121
Azoles quinoline base, carboxyl, alkenyl (alkenyl), sulfonic group etc.Wherein, consider from the viewpoint of the weather resistance of the stability the aqueous solvent that with water is principal constituent, hydrophobic-oleophobic property, stain resistance, especially preferably be selected from least a in the amino, isocyanate group, epoxy group(ing), functional group, hydroxyl (group of opening respectively with the group that can be contained in the following general formula [Y]) by following general formula [Y] expression.
-SiR 6R 7R 8 [Y]
In the formula [Y], R 6, R 7And R 8Represent alkoxyl group or hydroxyl independently of each other, R 6, R 7And R 8Any one also can be by methyl substituted.Isocyanate group also comprises the blocked isocyanate base.
As (methyl) acrylate (B2) that contains bridging property functional group (b), have no particular limits, for example, can enumerate 2-isocyanate group ethyl (methyl) acrylate, 3-isocyanate group propyl group (methyl) acrylate, 4-isocyanate group butyl (methyl) acrylate, the 2-butanone oxime affixture of 2-isocyanate group ethyl (methyl) acrylate, the pyrazoles affixture of 2-isocyanate group ethyl (methyl) acrylate, 3 of 2-isocyanate group ethyl (methyl) acrylate, 5-dimethyl pyrazole affixture, the 3-methylpyrazole affixture of 2-isocyanate group ethyl (methyl) acrylate, the ε-Ji Neixianan affixture of 2-isocyanate group ethyl (methyl) acrylate, the 2-butanone oxime affixture of 3-isocyanate group propyl group (methyl) acrylate, the pyrazoles affixture of 3-isocyanate group propyl group (methyl) acrylate, 3 of 3-isocyanate group propyl group (methyl) acrylate, 5-dimethyl pyrazole affixture, the 3-methylpyrazole affixture of 3-isocyanate group propyl group (methyl) acrylate, the ε-Ji Neixianan affixture of 3-isocyanate group propyl group (methyl) acrylate, the 2-butanone oxime affixture of 4-isocyanate group butyl (methyl) acrylate, the pyrazoles affixture of 4-isocyanate group butyl (methyl) acrylate, the 3 affixture of 4-isocyanate group butyl (methyl) acrylate, the 3-methylpyrazole affixture of 4-isocyanate group butyl (methyl) acrylate, the acrylic acid ε-Ji Neixianan affixture of 4-isocyanate group butyl (methyl), 3-methacryloxypropyl methyl dimethoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane, (methyl) vinylformic acid dimethyl aminoethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid dimethylaminopropyl ester, (methyl) vinylformic acid diethylamino propyl diester, (methyl) vinylformic acid diisopropylaminoethyl ethyl ester, (methyl) glycidyl acrylate, polyoxyalkylene diols monoglycidyl ether (methyl) acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, single (methyl) acrylate of polyoxyalkylene diols, (methyl) allyl acrylate.These materials can use separately, also can will also use more than 2 kinds.
Preferably: organic fluoride (B) contains polymerized unit 1～30 quality % based on (methyl) acrylate (B2) that contains bridging property functional group (b).During less than 1 quality %, in the raising of the weather resistance of hydrophobic-oleophobic property, stain resistance, can not obtain effect sometimes.When surpassing 30 quality %, the stability of organofluorine compound (B) in the aqueous medium that with water is principal constituent reduces sometimes.
Preferred organofluorine compound (B) contains alkyl at intramolecularly.By contain alkyl can make surge-oleophobic property, stain resistance further improve.More preferably to contain carbon number at intramolecularly be alkyl more than 16 to organofluorine compound (B).The chain alkyl of carbon number more than 16, with perfluoroalkyl similarly easily at the epithelium surface orientation, the free energy on surface is reduced, therefore hydrophobic-oleophobic property, stain resistance are further improved.
At organofluorine compound (B) is the occasion that contains based on the polymkeric substance of the polymerized unit of (methyl) acrylate (B1) that contains perfluoroalkyl, further preferably also contains the polymkeric substance based on the polymerized unit of (methyl) acrylate (B3) that contains alkyl.This polymkeric substance can be made with comparalive ease by (methyl) acrylate (B1) that contains perfluoroalkyl and the copolymerization that contains (methyl) acrylate (B3) of alkyl.By the epithelium that the multipolymer that obtains in this wise obtains, show hydrophobic-oleophobic property, the stain resistance of the excellence that has resisting power.In addition, at organofluorine compound (B) is the occasion that contains based on the polymkeric substance of the polymerized unit of (methyl) acrylate (B1) that contains perfluoroalkyl, also can except containing polymerized unit, also contain polymerized unit based on (methyl) acrylate (B2) that contains bridging property functional group (b) based on (methyl) acrylate (B3) that contains alkyl.
As (methyl) acrylate (B3) that contains alkyl, have no particular limits, for example, can enumerate methyl acrylate, ethyl propenoate, propyl acrylate, butyl methacrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid cetyl, (methyl) stearyl acrylate acyl ester, (methyl) vinylformic acid Shan Yu ester.These materials can use separately, also can will also use more than 2 kinds.Consider from the viewpoint of stain resistance, preferably contain at least a, (methyl) vinylformic acid cetyl, (methyl) stearyl acrylate acyl ester, (methyl) vinylformic acid Shan Yu ester of carbon number more than 16.(methyl) acrylate that contains the alkyl of carbon number more than 16 can make hydrophobic-oleophobic property, stain resistance improve as described above, but have the possibility of making the film reduction that makes epithelium.On the other hand, contain (methyl) acrylate of the alkyl of carbon number below 6, have the effect of making the film raising that makes epithelium.Therefore by (methyl) acrylate that will contain the alkyl of carbon number more than 16 and (methyl) acrylate that contains the alkyl of carbon number below 6 and usefulness, can improve and make film and improve hydrophobic-oleophobic property, anti-pollution, therefore can have more hydrophobic-oleophobic property, the stain resistance of weather resistance, thereby more preferably.
Preferred organofluorine compound (B) contains polymerized unit 1～25 quality % based on (methyl) acrylate (B3) that contains alkyl.During less than 1 quality %, can not obtain the raising effect of hydrophobic-oleophobic property, stain resistance sometimes, when surpassing 25 quality %, the stability of organofluorine compound (B) in the aqueous medium that with water is principal constituent reduces sometimes.
Need close-burning occasion at surface-treated metal material of the present invention, preferably the intramolecularly at organofluorine compound (B) contains oxyalkylene group.Oxyalkylene group shows excellent cohesiveness, therefore by with perfluoroalkyl and usefulness, can satisfy hydrophobic-oleophobic property and cohesiveness simultaneously.Especially, the alkylidene chain of oxyalkylene group is short more, the repeating unit of oxyalkylene group is many more, then as the flexual functional group of high polar, at sticky object (binding agent and tackiness agent etc.) when contacting with surface-treated metal material, in the easy more preferentially orientation of sticky object side, can guarantee excellent cohesiveness.And oxyalkylene group also has: by the effect that shows the stability of raising organofluorine compound (B) in aqueous medium that wetting ability is brought, improve the effect of the epithelium retentivity of organofluorine compound (B).
At organofluorine compound (B) is the occasion that contains based on the polymkeric substance of the polymerized unit of (methyl) acrylate (B1) that contains perfluoroalkyl, for above-mentioned reason, further preferably also contain polymkeric substance based on the polymerized unit of (methyl) acrylate (B4) that contains oxyalkylene group.(methyl) acrylate (B4) that contains oxyalkylene group is more preferably the structure of being represented by following general formula [B-4].
CH 2＝C(R 9)COO(CH 2) P-(R 10O) q-R 11 [B-4]
In the formula [B-4], R 9Be H or CH 3, R 10Be the alkylidene group of carbon number 2～4, R 11Be hydrogen atom, methyl, (methyl) acryl, p is 0～4, q is 1～30 integer.And then, improving on the cohesiveness, in the formula (B-4), preferred R 9Be H or CH 3, R 10Be alkylidene group, the R of carbon number 2～3 11Be hydrogen atom, methyl, p is 0～4, q is 4～30 integer.Moreover, at organofluorine compound (B) is the occasion that contains based on the polymkeric substance of the polymerized unit of (methyl) acrylate (B1) that contains perfluoroalkyl, also can be except containing polymerized unit based on (methyl) acrylate (B4) that contains oxyalkylene group, also contain based on the polymerized unit of (methyl) acrylate (B3) that contains alkyl with based at least one side of the polymerized unit of (methyl) acrylate (B2) that contains bridging property functional group (b).
By the structure of above-mentioned general formula [B-4] expression, on epithelium retentivity that improves organofluorine compound (B) and contaminative, be the most effective, also be the most effective on based on the stability in the aqueous medium of water improving organofluorine compound (B).Especially R 11Be the occasion of (methyl) acryl, organofluorine compound (B) dimensional topography easily becomes crosslinking structure, therefore can access hydrophobic-oleophobic property, the stain resistance with weather resistance.More preferably with R 11Compound and R for (methyl) acryl 11Compound and usefulness for hydrogen atom or methyl.
As (methyl) acrylate (B4) that contains oxyalkylene group, have no particular limits, for example, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, polyoxyethylene glycol list (methyl) acrylate, single (methyl) propylene ester of polyoxypropylene diols, methoxy polyoxyethylene glycol (methyl) acrylate, three oxygen ethylene glycol two (methyl) acrylate, four oxygen ethylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, acryloxy polyoxyethylene glycol (methyl) acrylate, 2-hydroxyl-3-acryloxy propyl group (methyl) acrylate, poly-(oxypropylene-oxygen butylene) glycol two (methyl) acrylate, poly-(oxygen ethene-oxypropylene) glycol two (methyl) acrylate, poly-(oxygen ethene-oxygen butylene) glycol two (methyl) acrylate etc.These materials can use separately, also can will also use more than 2 kinds.
Preferred organofluorine compound (B) contains polymerized unit 1～20 quality % based on (methyl) acrylate (B4) that contains oxyalkylene group.During less than 1 quality %, in the weather resistance of hydrophobic-oleophobic property, stain resistance, close-burning raising, can not obtain effect sometimes.When surpassing 20 quality %, hydrophobic sometimes-oleophobic property, stain resistance reduces.
In the present invention, in order to improve the weather resistance of stain resistance, also can in organofluorine compound (B), also contain other monomer.Containing other monomeric occasion, be preferably below the 30 quality % based on the ratio of other monomeric polymerized units, more preferably below the 15 quality %.
As other monomer, for example, can enumerate ethene, vinylidene chloride, vinylchlorid, vinylidene fluoride, vinyl-acetic ester, vinyl propionate base ester, the isopropylformic acid vinyl ester, isodecyl acid vinyl ester, vinyl stearate base ester, the hexadecyl vinyl ether, dodecyl vinyl, IVE, ethyl vinyl ether, 2-chloroethyl vinyl ether, vinylbenzene, alpha-methyl styrene, p-methylstyrene, (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, two acetone (methyl) acrylamide, methylolation two acetone (methyl) acrylamide, the vinyl alkyl ketone, divinyl, isoprene, chloroprene, (methyl) benzyl acrylate, (methyl) acrylate with polysiloxane, allyl acetate, the N-vinylcarbazole, maleimide, N-methyl maleimide etc.Wherein, as other monomer, preferred vinylchlorid, vinyl-acetic ester, vinyl propionate base ester, vinylidene chloride, the excellent in te pins of durability of hydrophobic-oleophobic property, contaminative.
The manufacture method of organofluorine compound (B) has no particular limits, for example, can enumerate: after employing makes in organic solvent and comprises the monomeric various monomer copolymerizations that contain perfluoroalkyl, in the aqueous medium that with water is principal constituent, carry out emulsification dispersive method, in the aqueous medium that with water is principal constituent, will comprise the monomeric various monomers that contain perfluoroalkyl and carry out the method that dispersion and emulsion polymeric method waits the water-based liquid of making organofluorine compound (B).The solution that obtains, dispersion liquid, emulsion can directly use on former state ground, also can dilute with water and use.In addition, can also distill to remove and be contained in the organic solvent in the solvent and use.
As the solvent that in organic solvent, carries out using under the occasion of polyreaction, have no particular limits, for example, can use ketone (acetone, methylethylketone, methyl iso-butyl ketone (MIBK) etc.), alcohol (Virahol etc.), ester (ethyl acetate, butylacetate etc.), ether (diisopropyl ether etc.), aliphatic hydrocarbon or aromatic hydrocarbons, halohydrocarbon (tetrachloroethylene, three chloro-1,1,1-ethane, Refrigerant R 113, dichloro pentafluoropropane etc.), dimethyl formamide, N-methyl-pyrrolidone-2, butyryl acetone (butyroacetone), DMSO (dimethyl sulfoxide (DMSO)), glycol ether and derivative etc. thereof.
If consider operation, the organic solvent that then preferred boiling point is lower or form the organic solvent of azeotropic mixture, preferred acetone, 2-propyl alcohol, methyl iso-butyl ketone (MIBK), methylethylketone, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or their mixed solvent with water.In the polyreaction that obtains organofluorine compound (B), the total of the monomeric concentration in the organic solvent is preferably 5～60 quality %, more preferably 10～40 quality %.
In the polyreaction that obtains organofluorine compound (B), preferably use polymerization starter.As polymerization starter, the superoxide of preferred benzoyl peroxide, lauroyl peroxide, succinyl peroxide, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester (tert-butyl perpivalate) etc., azo-compound, azo amidine compound etc.Initiator concentration in the solvent is preferably 0.1～1.5 quality % with respect to monomeric total amount.
As polymerization starter, in above-mentioned polymerization starter, following polymerization starter is because polymerizability excellence, excellent in safety and preferred.
Polymerization starter: being azo-compound or azo amidine compound, is that for more than the 1000mg/kg, 10 hours half life temperatures are the compound more than 30 ℃ to acute oral toxicity this compound or its resolvent, big white mouse or mouse (below be designated as LD50).
Concrete example as such polymerization starter, preferably: 2,2 '-azo two-2-methylbutyronitrile (LD50:1316mg/kg, 10 hours half life temperatures: 67 ℃), dimethyl-2,2 '-azo-bis-isobutyrate (LD50:2369mg/kg, 10 hours half life temperatures: 65 ℃), 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] is (more than the LD50:2000mg/kg, 10 hours half life temperatures: 61 ℃), 2,2 '-azo two (4-methoxyl group-2, the 4-methyl pentane nitrile) (LD50:2900mg/kg, 10 hours half life temperatures: 30 ℃), 1,1 '-azo two (2-hexanaphthene-1-nitrile) is (more than the LD50:11800mg/kg, 10 hours half life temperatures: 88 ℃), 2,2 '-azo two (2, the 4-methyl pentane nitrile) (LD50:6000mg/kg, 10 hours half life temperatures: 51 ℃), 1,1-azo two (1-acetoxyl group-1-diphenylphosphino ethane) is (more than the LD50:5000mg/kg, 10 hours half life temperatures: 61 ℃), the dimethyl azo-bis-isobutyrate is (more than the LD50:2000mg/kg, 10 hours half life temperatures: 68 ℃) etc., more preferably dimethyl-2,2 '-azo-bis-isobutyrate, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl)] propane.
For the polymerization degree (molecular weight) of regulating organofluorine compound (B), preferably in polyreaction, use chain-transfer agent.As chain-transfer agent, preferably enumerate alkyl sulfhydryl, ethylamine mercaptan, the mercaptoethanol, 2 of uncle's lauryl mercaptan, n-dodecyl mercaptan, stearyl mercaptan etc., 4-phenylbenzene-4-methyl-1-pentene, tetracol phenixin etc.The usage quantity of chain-transfer agent is preferably 0.05～1 quality % with respect to the monomeric total amount in the polyreaction.
Temperature of reaction in the polyreaction is preferably the scope of the boiling point from normal temperature to the reaction mixture, considers from the viewpoint of using polymerization starter expeditiously, is preferably more than the half life temperature of polymerization starter more preferably 30～90 ℃.
The monomer of synthetic organofluorine compound (B) or organofluorine compound (B) will be used for when being dispersed in aqueous medium, also tensio-active agent can be used.As tensio-active agent, can use the tensio-active agent of hydrocarbon system or fluorine system, can use anionic property, nonionic, cationic or amphoteric tensio-active agent.Consider from the viewpoint of dispersion stabilization, preferred nonionic surfactant, preferred especially nonionic surfactant and other ionic surfactant also use.As carrying out and the tensio-active agent of usefulness preferred cationic surfacant or amphoterics.Preferred especially nonionic surfactant and cationic surfactant are also used.Consider from the viewpoint of hydrophobic-oleophobic property, stain resistance, more preferably with nonionogenic tenside and cationic surfactant and usefulness.
As nonionic surfactant, be preferably selected from more than one the nonionic surfactant in the following tensio-active agent (a)～(f).
Tensio-active agent (a): polyoxyalkylene monoalky lether, polyoxyalkylene mono-alkenyl ether, polyoxyalkylene strand polyene-based ether or polyoxyalkylene list gather fluoroalkyl ether.
Tensio-active agent (b): by the nonionic surfactant of the compound formation that has more than one CC triple bond ((C ≡ C)) and more than one hydroxyl in the molecule.
Tensio-active agent (c): by the continuous polyoxyethylene chain (hereinafter referred to as POE) that connects of the oxyethylene group more than 2, with the carbon number more than 2 is that the chain that the oxyalkylene group more than 3 is connected continuously connects, and two ends are the nonionic surfactant of the compound formation of hydroxyl.
Tensio-active agent (d): the nonionic surfactant that in molecule, has the amine oxide part.
Tensio-active agent (e): the nonionic surfactant that forms by the condenses or polyoxyethylene list (substituted-phenyl) ether of polyoxyethylene list (substituted-phenyl) ether.
Tensio-active agent (f): the nonionic surfactant that forms by the fatty acid ester of polyvalent alcohol.
Contain the occasion of cationic surfactant (g) at tensio-active agent, preferably use the cationic surfactant of substituted ammonium salt type.As the cationic surfactant of substituted ammonium salt type, preferred: with nitrogen-atoms bonded hydrogen atom be the ammonium salt of POA (polyoxyalkylenes) replacement of hydroxyl by alkyl, alkenyl or end more than 1.Contain the occasion of amphoterics (h) at tensio-active agent, preferred: the amphoterics of L-Ala class, imidazoles betaines, amido betaine class or acetate trimethyl-glycine etc.
The amount of tensio-active agent, with respect to 100 quality % of organofluorine compound (B), preferred 1～10 quality %, preferred especially 3～8 quality %.The amount of tensio-active agent when this scope, organofluorine compound (B) having good stability in the aqueous medium that with water is principal constituent, the excellent in te pins of durability of hydrophobic-oleophobic property, stain resistance and preferred.Use the occasion of cationic surfactant (g) and/or amphoterics (h) as tensio-active agent, preferred also with nonionic surfactant (a)～(f), the amount of cationic surfactant (g) and/or amphoterics (h) is with respect to preferred 0.1～2 quality % of 100 quality % difference of organofluorine compound (B).
Organofluorine compound (B) dissolves or is dispersed in water is in the aqueous medium of principal constituent.Under the dispersed situation of organofluorine compound (B), below the preferred 300nm of its number average bead diameter, more preferably below the 100nm, most preferably below the 30nm.Number average bead diameter is 300nm when following, and the homogeneity in epithelium increases, and can access more excellent stain resistance.At this, number average bead diameter can be used the particle size determination device that adopts dynamic light scattering method, for example FPAR-1000 (Da mound electronics corporation system) measure.
As this aqueous medium, consider from the viewpoint of operation, safety and sanitation, can make water or be principal constituent and trace has added the mixture of aqueous organic solvent with water.As aqueous organic solvent, preferred propylene glycol monomethyl ether, dipropylene glycol monomethyl ether.
Be used to form the aqueous treatment agent of the epithelium among the present invention, as long as contain above-mentioned silicoorganic compound (A) and above-mentioned organofluorine compound (B) then has no particular limits, but in above-mentioned silicoorganic compound (A) and/or organofluorine compound (B), contain amino occasion, preferably contain organic acid.By amino carry out amine saltization, the storage stability of aqueous treatment agent improves.Amine saltization is preferably used acid etc., especially preferably uses organic acid.There is no particular limitation for organic acid, can enumerate formic acid, acetate, butyric acid, oxalic acid, succsinic acid, lactic acid, xitix, tartrate, citric acid, oxysuccinic acid, propanedioic acid, toxilic acid, phthalandione etc.Wherein, consider that more preferably acetate, lactic acid etc. has volatile organic acid from the viewpoint that is difficult to remain in the epithelium, does not reduce the erosion resistance of epithelium and weather resistance.Organic acid also can add in the stage of making each silicoorganic compound (A) water-based liquid and/or organofluorine compound (B) water-based liquid.
Be used to form the aqueous treatment agent of the epithelium among the present invention, in order to improve at least a corrosion inhibitor that erosion resistance also preferably contains phosphate cpd, fluorine metal coordination compound, vanadium compound, cobalt compound.These corrosion inhibitors mainly improve erosion resistance by forming the passive state epithelium with the base metal surfaces reaction.On the other hand, the organofluorine compound (B) that is contained in the epithelium has the raising epithelium to the barrier of corrosion factor, the effect that erosion resistance is improved.By corrosion inhibitor and organofluorine compound (B) with these difference in functionalitys are co-existed in the epithelium, erosion resistance improves by leaps and bounds.Epithelium among the present invention is only handled the erosion resistance that just has excellence by one deck on metallic substance, therefore also have the advantage that does not need base treatment and primary coat etc.Consider from the viewpoint that erosion resistance improves, more preferably with phosphate cpd and fluorine metal coordination compound or phosphate cpd and vanadium compound and usefulness, especially preferably with phosphate cpd, fluorine metal coordination compound and vanadium compound and usefulness.Cobalt compound also has the effect of the anti-blackening that improves metallic substance and coated metal material surface except improving corrosion resistant effect.
At least a occasion in containing phosphate cpd, fluorine metal coordination compound, vanadium compound, cobalt compound, 1～15 quality % in the preferably formed epithelium solids component of its amount.During less than 1 quality %, can not obtain the effect of improving of erosion resistance sometimes, when surpassing 5 quality %, stain resistance reduces sometimes.
As phosphate cpd, have no particular limits, for example, can enumerate ammonium salt, metal-salt, amino three (methylene phosphonic acids), the 1-hydroxy ethylene-1 of the phosphoric acid class, triammonium phosphate, Secondary ammonium phosphate etc. of ortho-phosphoric acid, metaphosphoric acid, tetra-sodium, triphosphoric acid, four phosphoric acid etc., the organophosphorus acids of the phosphonic acid based of 1-di 2 ethylhexyl phosphonic acid, ethylenediamine tetraacetic (methylene phosphonic acid), Diethylenetriamine five (methylene phosphonic acid) etc. and their salt, phytic acid etc. and their salt etc. with Na, Mg, Al, K, Ca, Mn, Ni, Zn, Fe etc.These materials can use separately, also can will also use more than 2 kinds.
As the fluorine metal coordination compound, have no particular limits, for example, can enumerate phosphofluoric acid, hexafluoro metatitanic acid, hexafluoro zirconate, hexafluorosilicic acid, hexafluoro niobic acid, hexafluoro-antimonic acid and their ammonium salt, sylvite, sodium salt, calcium salt, magnesium salts etc.These materials can use separately, also can will also use more than 2 kinds.
Have no particular limits as vanadium compound, for example, can exemplify Vanadium Pentoxide in FLAKES, metavanadic acid, ammonium meta-vanadate, sodium metavanadate, vanadium oxytrichloride, three vanadium oxides, vanadium dioxide, alkali formula Vanadosulfuric acid, oxygen vanadium acetylacetonate, vanadium acetylacetonate, vanadium trichloride, phosphovanadomolybdic acid etc.Can also use: utilize to have the organic compound that is selected from least a functional group in hydroxyl, carbonyl, carboxyl, primary～uncle amino, amide group, phosphate and the phosphonate group, the vanadium compound of 5 valencys is reduced into the vanadium compound of 4 valencys～divalent gained.These materials can use separately, also can will also use more than 2 kinds.
As cobalt compound, have no particular limits, for example, can enumerate rose vitriol, the sour cobalt of pin and cobaltous carbonate and their ammonium salt, sylvite, sodium salt, calcium salt, magnesium salts etc.These materials can use separately, also can will also use more than 2 kinds.
Be used to form the aqueous treatment agent of the epithelium among the present invention, in the scope of not damaging effect of the present invention, can use flow agent, water-soluble solvent, stabilized metal agent, etching inhibitor and the pH regulator agent etc. that are used to improve coating.As flow agent, can enumerate: as polyethylene oxide or the poly(propylene oxide) affixture and the acetylenediol compound etc. of nonionic or cationic tensio-active agent, as the ketone of ester class, acetone, methylethylketone and the methyl iso-butyl ketone (MIBK) etc. of the cellosolve class of the alcohols of ethanol, Virahol, the trimethyl carbinol and the propylene glycol etc. of water-soluble solvent, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether etc., ethyl acetate, butylacetate etc.As the stabilized metal agent, can enumerate the chelate compound of EDTA (ethylenediamine tetraacetic acid (EDTA)), DTPA (diethylene triaminepentaacetic acid(DTPA)) etc., as the etching inhibitor, can enumerate the amine compound class of quadrol, triethylene five amine, guanidine and pyrimidine etc.Particularly have the compound of the amino more than 2, thereby also have effect more preferably as the stabilized metal agent at 1 intramolecularly.As the pH regulator agent, can enumerate inorganic acids, ammonium salt and the amine etc. of the organic acid, hydrofluoric acid etc. of acetate and lactic acid etc.
Be used to form the manufacture method of the aqueous treatment agent of the epithelium among the present invention, have no particular limits, for example, can enumerate water-based liquid that in accordance with regulations ratio will contain above-mentioned silicoorganic compound (A), contain the water-based liquid of above-mentioned organofluorine compound (B), additive mixes stirring method successively arbitrarily.Also dilution such as the aqueous medium of water etc. and using as required.Above-mentioned silicoorganic compound (A) are preferably 5～25 quality % with the total of the solids component of above-mentioned organofluorine compound (B).During less than 5 quality %, the epithelium adhesion amount that can not obtain stipulating sometimes, when surpassing 25 quality %, the storage stability of aqueous treatment agent reduces sometimes.
Be used to form the amount of the organic solvent that is contained in the aqueous treatment agent of the epithelium among the present invention, be preferably below the 15 quality % with respect to the total mass of aqueous medium.In aqueous medium, contain occasion greater than the organic solvent of 15 quality %, exist to hinder the self-crosslinking of the above-mentioned bridging property functional group that is contained in the silicoorganic compound (A), perhaps hinder the perfluoroalkyl that is contained in the organofluorine compound (B) possibility in the lip-deep orientation of epithelium.In addition, in the occasion that contains the organic solvent with boiling point higher than water, also have the possibility of organic solvent residual in epithelium behind dry epithelium, epithelium makes the film reduction sometimes.In addition, the viewpoint from the safety and sanitation is considered, the amount of contained organic solvent in the aqueous treatment agent is preferably below the 5 quality % with respect to the total mass of aqueous treatment agent.
Surface-treated metal material of the present invention has by being coated with above-mentioned aqueous treatment agent at metal material surface and carrying out drying or epithelium that baking forms.The coating process of above-mentioned aqueous treatment agent has no particular limits, and can use suitably that known roller coat, spraying, rod are coated with, dipping, electrostatic applications etc.Drying or baking method have no particular limits, heating of metal material in advance, or at coating post-heating metallic substance.Heating means have no particular limits, and hot blast, induction heating, near infrared ray, straight fire etc. can be used singly or in combination.Relevant drying or storing temperature by arriving thermometer, are preferably 60 ℃～150 ℃, more preferably 70 ℃～150 ℃, most preferably are 100 ℃～150 ℃.When the arrival temperature was lower than 60 ℃, stain resistance reduced sometimes.Even when surpassing 150 ℃, can not expect that further performance improves, it is unfavorable to consider from the viewpoint of productivity and energy efficiency.
The adhesion amount of the epithelium that forms is preferably 0.2～2.0g/m 2, 0.3～1.0g/m more preferably 2, most preferably be 0.3～0.7g/m 2, the epithelium quality is less than 0.1g/m 2The time, the surface of this metallic substance that can not be covered, erosion resistance and stain resistance reduce sometimes.Surpass 2.0g/m 2The time, make film reduction, stain resistance reduction sometimes.
Being preferably more than 100 ° of formed epithelium at 20 ℃ of following contact angles with water.During less than 100 °, can not obtain sufficient stain resistance sometimes.Being preferably more than 55 ° with contact angle n-hexadecane of formed epithelium under 20 ℃.Becoming the index of expression and the wettability of various oiliness things with the contact angle of n-hexadecane, therefore improved the epithelium design with the contact angle of n-hexadecane, is very effective on the stain resistance that improves the oiliness pollutent.During less than 55 °, inabundant especially to the stain resistance of oiliness pollution sometimes.Moreover there is no particular limitation about the higher limit at the higher limit of under 20 ℃ and contact angle water and under 20 ℃ and contact angle n-hexadecane.But, as the upper limit of the effect that under the effect of chemistry, obtains, be about 120 ° in the higher limits with contact angle water under 20 ℃ in fact, be (with reference to embodiment described later) about 75 ° in the higher limits with contact angle n-hexadecane under 20 ℃.
As the metallic substance that uses among the present invention, there is no particular limitation, for example, can use the material (ethyls such as sheet material, tubing, wire rod, section bar with their shaping-joints after material) of the various metal or alloy systems of steel, aluminum, copper, titanium system etc. and they have been implemented the metallic substance etc. of the metal or alloy arbitrarily of zinc-plated, aluminium, nickel, chromium, copper, cobalt, silicon, iron, magnesium, calcium, manganese etc.Wherein, as the metallic substance that uses among the present invention preferably steel plate, Coated Steel, aluminium sheet, stainless steel plate, consider that from the equilibrated viewpoint of erosion resistance and cost more preferably zinc is that Coated Steel, aluminium are Coated Steel.
As zinc is Coated Steel, comprise: steel plate galvanized, the steel plate of zinc-plated-nickel, the steel plate of zinc-plated-iron, the steel plate of zinc-plated-chromium, the steel plate of zinc-plated-aluminium, the steel plate of zinc-plated-titanium, the steel plate of zinc-plated-magnesium, the steel plate of zinc-plated-manganese, the steel plate of zinc-plated-aluminium-magnesium, the zinc of the steel plate of zinc-plated-Al-Si-Mg etc. is Coated Steel, is included in addition to contain a spot of dissimilar metal element in their coating or as the cobalt of impurity, molybdenum, tungsten, nickel, titanium, chromium, aluminium, manganese, iron, magnesium, plumbous, bismuth, antimony, tin, copper, cadmium, the steel plate of arsenic etc., in their coating, be dispersed with silicon-dioxide, aluminum oxide, the steel plate of the inorganics of titanium dioxide etc.
As aluminium is Coated Steel, can enumerate Aludip or the plating steel plate by at least a alloy that forms of aluminium and silicon, zinc, magnesium, for example aluminize-steel plate of silicon, aluminize-steel plate of zinc, aluminize-steel plate of silicon-magnesium etc.And then, for the coating of above coating and other kinds for example the multiple layer coating that is formed by combining of iron plating, iron-phosphorus coating, nickel coating, cobalt coating also can use.There is no particular limitation for solution and coating method, can be the arbitrary method of known electrochemical plating, hot dip process method, evaporation plating method, dispersion plating method, vacuum plating method etc.
Embodiment
Below embodiments of the invention are described.But the present invention is not limited to these embodiment.
[manufacturing of silicoorganic compound (A) (Production Example 1)]
Silicoorganic compound shown in the table 1, organic acid are added in the water, stir at normal temperatures, obtaining solid component concentration is the silicoorganic compound water-based liquid of 10 quality %.
[manufacturing of organofluorine compound (B) (Production Example 2)]
Monomer shown in the table 2, polymerization starter, organic solvent are mixed, carry out the nitrogen displacement after, carried out polyreaction in 16 hours while stir down at 65 ℃, obtain the polymers soln that solid component concentration is 20 quality %.In the polymers soln that obtains, add water, acetate, stirred 15 minutes, carry out emulsification and disperse.Under reduced pressure, after organic solvent is removed in 65 ℃ of distillations, add water and make solid component concentration become 20 quality %, obtain the organofluorine compound aqueous dispersions.The following meaning is represented in abbreviation in the table 2.
C 4FMA：CH 2＝C(CH 3)COOC 2H 4C 4F 9
C 6FMA：CH 2＝C(CH 3)COOC 2H 4C 6F 13
DEAEMA:N, N-diethyllaminoethyl methacrylic ester
DMAEMA:N, N-dimethylaminoethyl methacrylic ester
MAEO8:CH 2=C (CH 3) COO (C 2H 4O) nH (mean value of n is 8)
2MAEO8:CH 2=C (CH 3) COO (C 2H 4O) nCOC (CH 3)=CH 2(mean value of n is 8)
HEMA:2-hydroxyethyl methacrylic ester
MAEO9:CH 2=C (CH 3) COO (C 2H 4O) nCH 3(mean value of n is 9)
The TMSiMA:3-methacryloxypropyl trimethoxy silane
2MAEO14:CH 2=C (CH 3) COO (C 2H 4O) nCOC (CH 3)=CH 2(mean value of n is 14)
2AEE：CH 2＝CHCOOCH 2CH(OH)CH 2OCH 2CH(OH)OCH 2CH(OH)CH 2OCOCH＝CH 2
IEO12M:CH2=C (CH 3) COOC 2H 4NHCOO (C 2H 4O) nCH 3(mean value of n is 12)
2MAE04:CH 2=C (CH 3) COO (C 2H 4O) nCOC (CH 3)=CH 2(mean value of n is 4)
2MEO3:CH 2=C (CH 3) COO (C 2H 4O) nCOC (CH 3)=CH 2(mean value of n is 3)
The 3 affixture of 135DP:2-isocyanic ester ethyl-methyl acrylate
AEO2:CH 2=CHCOO (C 2H 4O) nH (mean value of n is 2)
MAEO4:CH 2=C (CH 3) COO (C 2H 4O) nH (mean value of n is 4)
AEO10:CH 2=CHCOO (C 2H 4O) nH (mean value of n is 10)
MAEO14:CH 2=C (CH 3) COO (C 2H 4O) nCH 3(mean value of n is 14)
MAEO23:CH 2=C (CH 3) COO (C 2H 4O) nCH 3(mean value of n is 23)
MAEO30:CH 2=C (CH 3) COO (C 2H 4O) nCH 3(mean value of n is 30)
MAPO9:CH 2=C (CH 3) COO (C 3H 6O) nH (mean value of n is 9)
MABO9:CH 2=C (CH 3) COO (C 4H 8O) nH (mean value of n is 9)
[manufacturing of organofluorine compound (B) (Production Example 3)]
Monomer shown in the table 3, emulsifying agent (polyoxyl 10 oleyl ether, polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer, stearyl trimethyl ammonium chloride), dipropylene glycol, n-dodecane mercaptan are mixed in the water, stirred 30 minutes down at 56 ℃, obtain mixed solution.With the mixed solution that obtains while remain on 50 ℃ under 40MPa high pressure stir, obtain emulsion.After being cooled to the emulsion that obtains below 30 ℃, carry out the nitrogen displacement, add polymerization starter 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], acetate, carry out 12 hours polyreactions while stirring under 55 ℃, obtaining solid component concentration is the organofluorine compound water-based liquid of 20 quality %.The following meaning is represented in abbreviation in the table 3.
C 6FMA：CH 2＝C(CH 3)COOC 2H 4C 6F 13
C 6FA：CH 2＝CHCOOC 2H 4C 6F 13
C 8FA：CH 2＝CHCOOC 2H 4C 8F 17
C 6FPMA：CH 2＝C(CH 3)COOC 3H 6C 6F 13
The 3 affixture of 135DP:2-isocyanic ester ethyl-methyl acrylate
The 2-butanone oxime affixture of BOBI:2-isocyanic ester ethyl-methyl acrylate
GMA: glycidyl methacrylate
DEAEMA:N, N-diethyllaminoethyl methacrylic ester
The TMSiMA:3-methacryloxypropyl trimethoxy silane
LuA: lauryl acrylate
StA: stearyl acrylate acyl ester
VA: vinylformic acid Shan Yu base ester
BA: butyl acrylate cores
VCM: vinylchlorid
[manufacturing of aqueous treatment agent (Production Example 4)]
Organofluorine compound water-based liquid, the commercially available organofluorine compound water-based liquid shown in the table 4 and other composition that silicoorganic compound water-based liquid, Production Example 2 or the Production Example of Production Example 1 being made by the cooperation shown in the table 53 made add in the water and mix, and obtain solid component concentration and be 10% aqueous treatment agent.The following meaning is represented in abbreviation in the table 5.
V1: alkali formula Vanadosulfuric acid
V2: Vanadium Pentoxide in FLAKES
V3: acetic oxide acetone vanadium
V4: vanadium acetylacetonate
[making of surface-treated metal material]
Be coated with the aqueous treatment agent of Production Examples 4 manufacturings and carry out drying at the thick various metal sheet surfaces of 0.8mm by using rod to be coated with device, form epithelium, obtain the surface-treated metal plate (test board) that evaluation test is used.Arrival temperature during with metal sheet kind, epithelium adhesion amount, drying is shown in table 6.The following meaning is represented in abbreviation in the table 6.
EG: electrogalvanizing steel plate (coating adhesion amount 20g/m 2)
GI: hot-dip galvanized steel sheet (coating adhesion amount 60g/m 2)
GA: alloyed hot-dip galvanized steel plate (coating adhesion amount 45g/m 2)
ZL: the steel plate of electro-galvanizing-12%Ni alloy (coating adhesion amount 20g/m 2)
The steel plate of SD: galvanizing-11%Al-3%Mg-0.2%Si (coating adhesion amount 60g/m 2)
AL: the steel plate of hot dip process Al-9%Si (coating adhesion amount 40g/m 2)
SUS: the ferrite-group stainless steel steel plate (composition of steel: C:0.008 quality %, Si:0.07 quality %, Mn:0.15 quality %, P:0.011 quality %, S:0.009 quality %, Al:0.067 quality %, Cr:17.3 quality %, Mo:1.51 quality %, N:0.0051 quality %, Ti:0.22 quality %, rest part is Fe and unavoidable impurities)
[evaluation test]
Estimate solvent resistance, alkali resistance, with the contact angle of water, with contact angle, the erosion resistance of n-hexadecane.And, estimate the black contaminative of anti-fingerprint contaminative, oil-proofness of solvent resistance test front and back and alkaline resistance test front and back, anti-mustard contaminative.For the surface-treated metal example of a part only estimated with the contact angle of water, with contact angle, the cohesiveness of n-hexadecane.It the results are shown in table 7, table 8 and table 9.Estimate and adopt following method to carry out.
[solvent resistance]
After on the frictional testing machines test board being set, will be impregnated with alcoholic acid absorbent cotton with 49kPa (0.5kgf/cm 2) load carry out 10 reciprocal wipings after, estimate the epithelium state by following metewand.
◎: do not have vestige fully at wiping surface
Zero: vestige (carefully seeing the level that can barely determine rub) is arranged slightly at wiping surface
△: have obvious marks (the instantaneous level that can determine rub) at wiping surface
*: disappear in the wiping surface epithelial membrane.
[alkali resistance]
Test board after 2 minutes, is estimated epithelium state by following metewand at 60 ℃ of dippings on one side in stirring in 50 ℃ alkali cleaner (Pal Clean N364S, Japanese parkerizing corporate system) the 2 quality % aqueous solution on one side.
◎: epithelium is not peeled off, and the epithelium outward appearance does not change yet
Zero: epithelium is not peeled off, but the epithelium outward appearance has tonal variation
△: the part of epithelium is peeled off
*: the epithelium disappearance that becomes
[with the contact angle of water]
Use contact angle meter (PG-X sells in Matsubo company), under 20 ℃ atmosphere, drip 3 μ l ion exchanged waters, measure the quiet contact angle after 60 seconds.
[with the contact angle of n-hexadecane]
Use contact angle meter (PG-X sells in Matsubo company), under 20 ℃ atmosphere, drip 3 μ l n-hexadecanes, measure the quiet contact angle after 60 seconds.
[anti-fingerprint contaminative]
Adhere to fingerprint by on test board, pushing finger, leave standstill 1 hour at normal temperatures after, use absorbent cotton wiping fingerprint, estimate the vestiges of fingerprint by following metewand.
◎: do not have fingerprint trace fully
Zero: residual slightly fingerprint trace (carefully seeing the level that can barely determine fingerprint trace)
△: residual fingerprint trace (instantaneously can determine fingerprint trace, but tone compare with the position that does not have fingerprint trace do not have obvious variation).
*: clearly residual fingerprint trace (instantaneous can determine fingerprint trace, tone is compared with the position that does not have fingerprint trace also obvious variation).
[oil-proofness China ink contaminative]
Use red oiliness China ink (the temple westernization Magic of industrial China ink (registered trademark) setting-out on test board.After leaving standstill 7 days at normal temperatures, use and flooded the wiping of alcoholic acid absorbent cotton.Estimate the residual look of China ink by following metewand.
◎: do not have residual look fully
Zero: residual look (carefully seeing the level that can determine residual look) is arranged slightly
△: residual look (the instantaneous level that can determine residual look) is arranged
*: (before using the absorbent cotton wiping and after the wiping, the color of China ink does not change basically) basically do not disappear
[anti-mustard contaminative]
On test board, be coated with S﹠amp; B food company system Japan mustard cream, leave standstill 7 days at normal temperatures after, use flowing water to wash, estimate the vestiges of mustard coating part by following metewand.
◎: do not have vestiges fully
Zero: vestiges (carefully seeing the level that can pick out vestiges) are arranged slightly
△: vestiges (instantaneous can pick out vestiges, but the slighter level of the variable color of test board) are arranged
*: vestiges serious (instantaneous can pick out vestiges, the level that the variable color of test board is also serious)
[erosion resistance]
Planar portions or Sven-Gan Eriksson (Erichsen) 7mm extrusion processing portion to test board, after the edge carried out rubber belt sealing, carry out 72 hours the salt spray testing according to JIS Z 2371 standards (SST), observe the white rust situation occurred, estimate by following metewand.
◎: area takes place less than 1% in rust
Zero: area takes place rust is more than 1% and less than 5%
△: area takes place rust is more than 5% and less than 1%
*: area takes place rust is more than 10%
[cohesiveness]
Attach the adhesive tape No.5000N (C) of day eastern electrician's corporate system of wide 20mm on test board, employing is peeled off method according to 180 degree of the tape test method of JIS Z 0237 standard, measures cohesive force, presses commentary valency benchmark and estimates.
◎: cohesive force is more than the 15N/20mm
Zero: cohesive force is more than the 10N/20mm and less than 15N/20mm
△: cohesive force is more than the 5N/20mm and less than 10N/20mm
*: cohesive force is less than 5N/20mm
Embodiments of the invention in any evaluation test (except that cohesiveness), all show ◎ or zero excellence solvent resistance, alkali resistance, with the contact angle of water, contact angle, erosion resistance, solvent borne test with n-hexadecane before and after and anti-fingerprint contaminative, oil-proofness China ink contaminative, anti-mustard contaminative before and after the alkaline resistance test.Moreover, the aqueous treatment agent that uses in the embodiments of the invention is left standstill the result who investigates storage stability over 1 month at 40 ℃, gelation has taken place in w3, w13, w24, w34.That is, the molecular weight that does not contain organic acid aqueous treatment agent and silicoorganic compound (A) in the water-based liquid of silicoorganic compound (A) is 12000 aqueous treatment agent, and to compare storage stability poor slightly with other aqueous treatment agent.
On the other hand, as the surface-treated metal example 151 that does not contain organofluorine compound (B) of the comparative example that breaks away from the scope of the invention, various low contamination resistance.Do not contain the surface-treated metal example 152,153 of silicoorganic compound (A), all performances are all poor.Use the surface-treated metal example 154,155 of colloid silica replacement silicoorganic compound (A), the poor performance beyond the solvent resistance.Using silane is the surface-treated metal example 156 that the hydrophobic treatment agent replaces organofluorine compound (B), and the oil-proofness China ink contaminative before and after anti-fingerprint contaminative behind solvent and alkali test and solvent and the alkali test, anti-mustard contaminative are poor.Used the surface-treated metal example 157 of chromate treating liquid, various low contamination resistance.Having used inorganic is the surface-treated metal example 158 of non-chromate treatment solution, alkali resistance, adds Ministry of worker's erosion resistance, various low contamination resistance.Used the surface-treated metal example 159,160 of resin system non-chromate treatment solution, the epithelium adhesion amount is 0.5g/m 2The time anti-mustard contaminative before and after anti-fingerprint contaminative, oil-proofness China ink contaminative, solvent and the alkali test behind alkali resistance, erosion resistance, solvent and the alkali test poor, the epithelium adhesion amount is 2.0g/m 2The time anti-mustard contaminative behind oil-proofness China ink contaminative, solvent and the alkali test before and after anti-fingerprint contaminative, solvent and the alkali test behind alkali resistance, solvent resistance, the alkali test poor.
In addition, by table 9 (close-burning evaluation result) as can be known, contain the surface-treated metal example 44,49,161～169 of oxyalkylene group at the intramolecularly of organofluorine compound (B), compare, show excellent cohesiveness with the surface-treated metal example 29,58 that does not contain oxyalkylene group.And the alkylidene chain of oxyalkylene group is short more, the repeating unit of oxyalkylene group is many more, then shows excellent more cohesiveness.
Figure BDA0000064394780000311
Figure BDA0000064394780000321
Figure BDA0000064394780000331
Figure BDA0000064394780000341
Table 5-1 aqueous treatment agent (Production Example 4)
Figure BDA0000064394780000351
Table 5-2 aqueous treatment agent (Production Example 4)
Figure BDA0000064394780000361
Table 5-3 aqueous treatment agent (Production Example 4)
Figure BDA0000064394780000371
* 1: the system Snowtex 0*2:Toray-Dow corning of daily output chemical industrial company corporate system Dryseal S
Table 5-4 aqueous treatment agent (Production Example 4)
Figure BDA0000064394780000372
Table 6-1 surface-treated metal material is created conditions
Figure BDA0000064394780000381
Table 6-2 surface-treated metal material is created conditions
Figure BDA0000064394780000391
Table 6-3 surface-treated metal material is created conditions
Figure BDA0000064394780000401
Table 6-4 surface-treated metal material is created conditions
Figure BDA0000064394780000411
Table 7-1 evaluation result
Table 7-2 evaluation result
Figure BDA0000064394780000431
Table 7-3 evaluation result
Figure BDA0000064394780000441
Table 8-1 evaluation result
Figure BDA0000064394780000451
Table 8-2 evaluation result
Figure BDA0000064394780000461
Table 8-3 evaluation result
Figure BDA0000064394780000471
Table 9 evaluation result
Figure BDA0000064394780000481
More than preferred implementation of the present invention is illustrated, certainly the present invention is not limited to described example.So long as those skilled in the art just can expect various modifications or correction example in the scope of asking for protection that the application put down in writing,, will of course be appreciated that obviously to belonging to technical scope of the present invention for these modifications and correction example.

Claims (27)

1. non-chromate surface-treated metal material, it is characterized in that, has epithelium, described epithelium is by being coated with aqueous treatment agent at metal material surface, and carry out drying or baking forms, described aqueous treatment agent contain have alkylidene group, siloxane bond and by the silicoorganic compound (A) of the bridging property functional group of following general formula [X] expression with have the organofluorine compound (B) of perfluoroalkyl
-SiR 1R 2R 3 [X]
In the formula, R 1, R 2And R 3Represent alkoxyl group or hydroxyl independently of each other, comprise R 1, R 2And R 3Any one by methyl substituted situation.
2. non-chromate surface-treated metal material according to claim 1 is characterized in that, described silicoorganic compound (A) are 4～200 with the solids component mass ratio [(A)/(B)] of described organofluorine compound (B).
3. non-chromate surface-treated metal material according to claim 1 and 2, it is characterized in that described silicoorganic compound (A) have at least a bridging property functional group that is selected from amino, epoxy group(ing) and the hydroxyl (group of opening respectively with the group that can contain in the described general formula [X]).
4. according to any one described non-chromate surface-treated metal material of claim 1～3, it is characterized in that described silicoorganic compound (A) are the hydrolytic condensate of silane coupling agent.
5. according to any one described non-chromate surface-treated metal material of claim 1～4, it is characterized in that described silicoorganic compound (A) are to obtain with silane coupling agent (A2) reaction with epoxy group(ing) by having amino silane coupling agent (A1).
6. non-chromate surface-treated metal material according to claim 5 is characterized in that, described silane coupling agent (A1) with amino is 0.5～2.5 with described mol ratio (A1)/(A2) with silane coupling agent (A2) of epoxy group(ing).
7. according to any one described non-chromate surface-treated metal material of claim 1～6, it is characterized in that the number-average molecular weight of described silicoorganic compound (A) is 1000～10000.
8. according to any one described non-chromate surface-treated metal material of claim 1～7, it is characterized in that the carbonatoms of contained perfluoroalkyl is below 6 in the described organofluorine compound (B).
9. according to any one described non-chromate surface-treated metal material of claim 1～8, it is characterized in that described organofluorine compound (B) is the polymkeric substance that contains based on the polymerized unit of (methyl) acrylate (B1) with perfluoroalkyl.
10. non-chromate surface-treated metal material according to claim 9 is characterized in that, described (methyl) acrylate (B1) with perfluoroalkyl is by following general formula [B-1] expression,
CH 2＝C(R 4)COO(CH 2) nR 5 [B-1]
In the formula, R 4Expression H or CH 3, R 5The expression perfluoroalkyl, n is 0～4 integer.
11. any one the described non-chromate surface-treated metal material according to claim 1～10 is characterized in that described organofluorine compound (B) has bridging property functional group (b).
12. any one described non-chromate surface-treated metal material according to claim 9～11, it is characterized in that described organofluorine compound (B) is the polymkeric substance that contains based on the polymerized unit of (methyl) acrylate (B2) with bridging property functional group (b).
13. according to claim 11 or 12 described non-chromate surface-treated metal materials, it is characterized in that, described bridging property functional group (b) is selected from amino, isocyanate group, epoxy group(ing), at least a by in the functional group of following general formula [Y] expression and the hydroxyl (group of opening respectively with the group that can contain in the following general formula [Y])
-SiR 6R 7R 8 [Y]
In the formula, R 6, R 7And R 8Represent alkoxyl group or hydroxyl independently of each other, comprise R 6, R 7And R 8Any one by methyl substituted situation.
14. any one the described non-chromate surface-treated metal material according to claim 1～13 is characterized in that described organofluorine compound (B) has alkyl.
15., it is characterized in that described organofluorine compound (B) is the polymkeric substance that contains based on the polymerized unit of (methyl) acrylate (B3) with alkyl according to claim 9,10, any one described non-chromate surface-treated metal material of 12.
16., it is characterized in that it is alkyl more than 16 that described alkyl has carbon number according to claim 14 or 15 described non-chromate surface-treated metal materials.
17. any one the described non-chromate surface-treated metal material according to claim 1～16 is characterized in that described organofluorine compound (B) has oxyalkylene group.
18. according to claim 9,10,12, any one described non-chromate surface-treated metal material of 15, it is characterized in that described organofluorine compound (B) is the polymkeric substance that contains based on the polymerized unit of (methyl) acrylate (B4) with oxyalkylene group.
19. non-chromate surface-treated metal material according to claim 18 is characterized in that, described (methyl) acrylate (B4) that contains oxyalkylene group is by following general formula (B-4) expression,
CH 2＝C(R 9)COO(CH 2) p-(R 10O) q-R 11 [B-4]
In the formula, R 9Be H or CH 3, R 10Be the alkylidene group of carbon number 2～4, R 11Be hydrogen atom, methyl or (methyl) acryl, p is 0～4, q is 1～30 integer.
20. non-chromate surface-treated metal material according to claim 19 is characterized in that, in formula by described general formula (B-4) expression, and R 9Be H or CH 3, R 10Be the alkylidene group of carbon number 2～3, R 11Be hydrogen atom or methyl, p is 0～4, q is 4～30 integer.
21. any one the described non-chromate surface-treated metal material according to claim 1～20 is characterized in that, also contains organic acid in described aqueous treatment agent.
22. any one described non-chromate surface-treated metal material according to claim 1～21, it is characterized in that, in described aqueous treatment agent, also contain and be selected from least a in phosphate cpd, fluorine metal coordination compound, vanadium compound and the cobalt compound.
23. any one the described non-chromate surface-treated metal material according to claim 1～22 is characterized in that, the drying of described aqueous treatment agent or storing temperature by arriving thermometer, are 60 ℃～150 ℃.
24. any one the described non-chromate surface-treated metal material according to claim 1～23 is characterized in that the adhesion amount of the epithelium of described formation is 0.2～20g/m 2
25. any one the described non-chromate surface-treated metal material according to claim 1～24 is characterized in that, is more than 100 ° under 20 ℃ and contact angle water.
26. any one the described non-chromate surface-treated metal material according to claim 1～25 is characterized in that, is more than 55 ° under 20 ℃ and contact angle n-hexadecane.
27. any one the described non-chromate surface-treated metal material according to claim 1～26 is characterized in that, described metallic substance is that zinc is that Coated Steel or aluminium are Coated Steel.
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