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CN1325926A - Metal surface treating agents, methods and materials thereof - Google Patents

Metal surface treating agents, methods and materials thereof Download PDF

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Publication number
CN1325926A
CN1325926A CN01110505A CN01110505A CN1325926A CN 1325926 A CN1325926 A CN 1325926A CN 01110505 A CN01110505 A CN 01110505A CN 01110505 A CN01110505 A CN 01110505A CN 1325926 A CN1325926 A CN 1325926A
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hydrogen atom
alkyl
metal
compound
carbon number
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Inventor
迫良辅
上野圭一
本田匠
山本真由美
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NIPPON BACALAIJINGU CO Ltd
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NIPPON BACALAIJINGU CO Ltd
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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • 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
    • 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
    • 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
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a chromium-free metallic surface treating agent imparting excellent corrosion resistance, a coating adhesion and fingerprint resistance to a metallic material or the like. This metallic surface treating agent contains a polymer of the following general formula(I)or(II)and a compound of metals selected from V, Zr, Ti, Mo, W, Mn and Ce: the formula(I) wherein R1 to R6 are H; V<1> and V<2> are Ar, alkoxymethyl or a phosphorus-containing group; V<3> is H or a phosphorus-containing group; and X is a group formed in such a manner that, in a compound having an ethylenic double bond, the double bond of the compound is opened, and the formula(II) wherein W<1> to W<3> are H, alkoxymethyl, a phosphorus-containing group or the like; W<4> is H or a phosphorus-containing group; at least one among W<1> to W<4> is a phosphorus-containing group; and Y is a group formed in such a manner that, from an aromatic compound capable of additionally condensed with formaldehyde, a hydrogen atom bonded to a carbon atom composing the aromatic ring is lost are used.

Description

Metal conditioner, metal surface treating method and surface-treated metal material
The present invention is relevant, and to be the car body, automobile spare part, building materials, household electrical appliances of former material with steel plating plates such as zinc-based metal plated steel sheet, steel plate can invest solidity to corrosion, anti-finger printing, scoring resistance, processibility, coating tack with the moulding goods of spare part etc., casting product, coiled sheet etc., form the non-chromate tunicle do not contain chromium and the single coating shaped metal surface treatment agent of usefulness, surface treatment method and surface-treated metal material.
Zinc-based metal plated steel sheet, metallic substance such as steel plate are subjected to ion contained in the oxygen, moisture, moisture in the atmosphere etc. and oxidation, corrosion.As for preventing these corroding method, treatment solution that metal material surface and chromic acid chromium Plessy's green etc. contain chromium is contacted and make the method that forms the chromic salt tunicle, the treatment solution that will contain chromium coats the metallic surface after heat drying and make the method that forms tunicle.
Yet, these inorganic be the chromic salt tunicle independent aspect, under relatively mild environment, though but the performance rust-preventing characteristic of short-term, solidity to corrosion is not enough under long-term or strict environment.The coiled sheet that will apply the chromic salt individual curing again cuts out, and give being shaped and add man-hour, then through give formation by membranous hard and crisp and lack oilness, not only undermine outward appearance so tunicle comes off, fail to process fully, can generate be full of cracks on the former material and generate the crack improper.Again moreover, even operator's fingerprint can adhere to and gives cleaning by degreasing during operation, its vestige is also remaining, it is improper also to undermine outward appearance.Therefore usually, for satisfying all properties such as high anti-corrosion, anti-finger printing, scoring resistance, oilness, coating tack, on metal material surface, form the chromic salt tunicle, on the chromic salt tunicle that Yu Jingyu forms, two layers of processing of resin coating are set again, again except that the chromic salt tunicle on performance and deficiency, owing to contain deleterious sexavalent chrome in its treatment solution, so it is more numerous and diverse or expend cost during wastewater treatment, also in handling formed tunicle, contain sexavalent chrome in addition, so from environmental protection, security standpoint, this is to be excluded use.
Handle the trial that to satisfy all performances as for desiring to make with one deck, have and make resin chromic salt that chromic salt and resin coating once forming through giving self-criticism, in the special fair 4-2672 communique of Japan, announcement has on the zinc surface of steel plate of aluminizing, coating has cooperated the treatment process of the chromic resin combination of specific aqueous dispersion or water soluble resin and specified quantitative, in the special fair 7-6070 communique of Japan, announcement has hexavalent chromium or hexavalent chromium and the trivalent chromic ion that contains mineral compound, reaches the metal finishing constituent of polymeric acrylic ester emulsion under specific emulsion polymerization condition.Yet, though the sexavalent chrome that is contained in the tunicle is a trace as before, have the character of stripping slowly, in environmental protection, secure context is problematic.
As for adopting the non-chromate treatment solution method that does not contain chromium, disclosing in Japanese kokai publication hei 7-278410 communique has the particular configuration of containing phenol resins based polymer and acidic cpd metal material surface with polymer composition and surface treatment method, disclose the superior metal conditioner and the treatment processs such as anti-finger printing of silica coupler more than two kinds of reactive functional group that the particular configuration with not of the same race mutually and mutually reactive is arranged in the Japanese kokai publication hei 8-73775 communique, disclose the metal conditioner and the treatment process of the phenol resins based polymer that the silica coupler that contains particular configuration and particular configuration are arranged in the Japanese kokai publication hei 9-241576 communique, disclose in the Japanese kokai publication hei 10-1789 communique Resins, epoxy that contains at least one nitrogen-atoms is arranged, the acrylic ester resin, organic polymer and specific polybasic anionic metal conditioners such as amine ester resin, treatment process and processing metallic substance.Disclose in the Japanese kokai publication hei 10-60233 communique to have and contain (1) to contain the bisphenol-A epoxy of particular configuration be the rust-preventive agent that phenol resin and specific resin such as polyester are in addition mixed in resin rust-preventive agent, (2), adopt (1) and (2) treatment process and handle metallic substance.
Yet in the above-mentioned metal conditioner situation that does not contain chromium, do not contain chromic advantage though have, opposite solidity to corrosion is also not enough, especially at pars affecta, add the solidity to corrosion of the Ministry of worker, compare inferior with the chromic salt tunicle, anti-finger printing again, scoring resistance and oilness are also not enough.
Therefore, form on metal material surface under present situation and can invest superior solidity to corrosion simultaneously, the non-chromate of the tunicle of coating tack and anti-finger printing is that metal conditioner is unavailable.
The purpose of this invention is to provide metallic substance is invested superior solidity to corrosion, coating tack and anti-finger printing and the metal conditioner that does not contain chromium of usefulness, metal surface treating method and surface-treated metal material.
It is the treatment agent processing metal material surface of necessary composition that the present invention adopts with polymkeric substance with particular configuration and specific metallic compound, can have the tunicle of superior solidity to corrosion, coating tack and anti-finger printing, so that finish the present invention.
Metal conditioner of the present invention contains polymkeric substance (a) that following general formula I or general formula II represent, and the metal conditioner of the metallic compound (b) of at least a metal selected of the colony that is formed by vanadium, zirconium, titanium, molybdenum, tungsten and cerium.
Figure A0111050500071
(in the formula, R 1～R 6Be separate hydrogen atom or carbon number 1～5 alkyl, V 1And V 2For separately independently hydrogen atom ,-CH 2OR 7,-Z ,-OZ ,-R 8Z or-OR 8Z, R 7Be carbon number 1～5 alkyl, R 8For carbon number 1～5 is stretched alkyl, Z is a general expression
Figure A0111050500072
Or
Figure A0111050500073
(in the formula, T 1～T 4System is the base represented of hydrogen atom or carbon number 1-5 alkyl independently separately,
V 3For hydrogen atom or-Z (Z and above-mentioned synonym),
X is the two openable bases of key key of ethene of the compound with ethene two key bonds different with the compound of the tectonic unit that gives the tectonic unit of drawing together with n and draw together with m,
N is 2～50 integers, and m is 0 or 1～50 integer, and P is 0 or 1～20 integer, 0.1≤n (n+m+p)≤1.0,0≤m/ (n+m+p)≤0.9,0≤p/ (n+m+p)≤0.6)
Figure A0111050500081
(in the formula, W 1～W 3Be separate hydrogen atom ,-CH 2OR a,-Z ,-OZ ,-R bZ ,-OR cZ or general expression (ⅰ)
Figure A0111050500082
The base of expression, R a, R dAnd R eBe separate hydrogen atom or carbon number 1～5 alkyl, R 6And R CStretch the Z synonym of alkyl, Z system and general formula I for separate carbon number 1～5, the base that can become general expression (ⅰ) expression is W only 1～W 3In one,
W 4For hydrogen atom or-Z (Z system with above-mentioned synonym),
W 1～W 4At least one be functional group with Z,
But Y serves as reasons and loses the different divalent radical of fragrant cyclic group in the structure that bond to the hydrogen atom of the carbon atom that constitutes this aromatic nucleus draws together with S with the aromatics of formaldehyde addition condensation, or two amidos of trimeric cyanamide, guanamine or urea respectively lose the base of the divalence of a hydrogen atom
S represents 2～30 integers, and t represents 0 or 1～20 integer).
Relevant metal conditioner of the present invention is the solidity to corrosion further raising again of tunicle, the anti-finger printing of tunicle, and the raising of alkali resistance, solvent resistance etc. more is preferably and contains anionic property or nonionic organic polymer (C).
The present invention is again about after metal material surface is handled with aforesaid metal conditioner, heat drying to the temperature of previous materials becomes 50～250 ℃ of surface treatment methods for the metallic substance of feature, and has the metal materials that adopts this surface treatment method and give formation.
Polymkeric substance (a) to the necessary composition of treatment agent of the present invention, two terminal bases to general formula I, can adopt AIBN (azobis isobutyronitrile), BPO (benzoyl peroxide), persulphates etc. are as polymerization starter, though by and have the different possibility of terminal constructions two terminal bases not give special the qualification, can enumerate hydrogen atom, phenyl ,-((CH 3) 2(CN)), benzene first acyloxy grp etc.
General formula I polymkeric substance (a), comprise the polymkeric substance that only forms by the tectonic unit of drawing together with n, the multipolymer that is formed by the tectonic unit of drawing together with n and the tectonic unit of drawing together with m is by tectonic unit of drawing together with n and the multipolymer that forms with p tectonic unit of drawing together and the tectonic unit of drawing together with p.The multipolymer that the tectonic unit of drawing together by the tectonic unit of drawing together with n and with m and the tectonic unit of drawing together with p form.The tectonic unit of drawing together with n and with mutual which kind of arranges person arranged side by side with also can of m tectonic unit of drawing together and the system of tectonic unit of drawing together with p, therefore side by side order is that any one of n → m → p, n → p → m, m → n → p, m → p → n, p → n → m, p → m → n, n → m, n → p, m → n, p → n also can, moreover each tectonic unit can the block bond, also can with the mutual bond of other tectonic units, also can be fully random bond.Formula I system comprises these whole persons.
Each tectonic unit again, for example each tectonic unit in the tectonic unit of drawing together with n is not only identical, also can be different.
As for R 1～R 7Carbon number 1～5 alkyl can have been enumerated: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group etc.
As for R 8Carbon number 1～5 is stretched alkyl, can enumerate methylene radical, stretches ethyl, stretches propyl group, differently stretches propyl group, stretches butyl, stretch amyl group etc.
As for T 1～T 4Carbon number 1～5 alkyl can have been enumerated methyl, ethyl, propyl group, sec.-propyl, butyl amyl group etc.
Do not give special restriction as for X definition so-called " compound " with ethene pair key bonds different with the compound of the structure of giving the tectonic unit of drawing together and drawing together with m with n, can enumerate: ethene unsaturated carboxylic acid ((methyl) vinylformic acid, maleic acid, FUMARIC ACID TECH GRADE, Ba Dousuan, Yi Kang acid etc.), (methyl) olefin(e) acid alkyl (carbon number 1～8) ester ((methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate (methyl) vinylformic acid 2-b hexyl etc.), (methyl) acrylamide based compound ((methyl) acrylamide, N-methylol (methyl) acrylamide, N-methyl (methyl) acrylamide, N-J oxygen ylmethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamides etc.), other contain the compound (vinyl acetate of the two key bonds of ethene, vinylbenzene, vinyl toluene, propylene is fine, Vinyl toluene, vinylchlorid etc.).
In general formula I, n was less than 2 o'clock, and the weather resistance when being tunicle with metal conditioner of the present invention is inferior, n or m if surpass at 500 o'clock then viscosity become too highly, the stability in water lacks, so not good.P then fails to obtain enough solidity to corrosions, coating tack if surpass at 20 o'clock, and unsuitable.
Again, R 1～R 7The carbon number of alkyl is if surpass at 5 o'clock, hydrophobicity grow then, and the stability in water reduces, and unsuitable.R 8Stretch alkyl or T 3～T 4The carbon number of alkyl if surpass at 5 o'clock, the then same stability in water reduces, and unsuitable.
About the polymkeric substance (a) of the necessary composition of treatment agent of the present invention, two terminal base system methylols of general formula II, alkoxy methyl (the alkoxyl group carbon number is 1～5), W 1, W 2, W 3And any of hydrogen atom.
With the polymkeric substance that general formula II is represented, be relevant repeating unit of drawing together with s and t, no matter the block-wise structure same with general formula I situation, or the structure of mutual bond, or the structure of random bond also can.
The polymkeric substance (a) that contains in metal conditioner of the present invention is relevant with making, general formula II W 1～W 3Definition in, as for R a, R d, R eCarbon number 1～5 alkyl of expression, can enumerate: methyl, ethyl, propyl group, sec.-propyl, butyl, amyl group etc., as for R b, R cThe carbon number 1～5 of expression is stretched alkyl, can enumerate: methylene radical, stretch ethyl, stretch propyl group, stretch sec.-propyl, stretch butyl, stretch amyl group etc.
In general formula II, Y as described above, but lose the different divalent radical of fragrant cyclic group in the structure that bond to the hydrogen atom of the carbon atom that constitutes this aromatic nucleus draws together with s by aromatics with the formaldehyde addition condensation, but as for the aromatics of above-mentioned formaldehyde addition condensation, do not give special restriction, for example can enumerate phenol sulfonic acid, stretch the alkyl diol phenyl ether (as for stretching alkyl, can enumerate carbon number 2～10 and stretch alkyl, for example stretch ethyl, stretch propyl group etc.), 2-Naphthol, naphthene sulfonic acid, toluene, dimethylbenzene, aniline, ethylbenzene amine, the thiophenol thiophene, alditol, aromatics such as furfuryl alcohol.
In general formula II, s is less than 2 situation, and solidity to corrosion is inferior when making tunicle, if surpass at 50 o'clock, then viscosity becomes too highly, and so the security in water lacks not good.T fails to obtain enough solidity to corrosions, coating tack if surpass 20 situation.In R a, R d, R e, T 1, T 2, T 3And T 4, if the alkyl carbon number surpasses at 5 o'clock, hydrophobicity grow then, the security in water reduces and is unsuitable.Again to R bAnd R CStretch alkyl, if carbon number surpasses at 5 o'clock, the then same stability in water reduces, so also unsuitable.
Polymkeric substance so that general formula I is represented produces with V 1=V 2=V 3The polymkeric substance that the general formula I of=H is represented is then by the suitable V of conversion earlier 1, V 2, V 3, made, but the present invention is subjected to this to make method to restrain.With V 1=V 2=V 3The polymkeric substance that the general formula I of=H is represented, by the suitable common method of utilizing, make can invest with the tectonic unit that n was drawn together monomer and if the monomer that invests the tectonic unit of drawing together when existing with m with can make if invest the equal polymerization of monomer of the tectonic unit of drawing together or copolymerization when existing with p.
The polymkeric substance of representing with general formula II is usually at W 1=W 2=W 3=W 4=H or W 1=W 2=W 4=H makes W 3For the phenol of general formula I is monomer and the monomer and the formaldehyde reaction that become the source of Y, produce polymkeric substance Hou, by suitable conversion W 1, W 2, W 3And W 4Can give manufacturing, but the present invention is subjected to this to make method to restrain.
Secondly, in each the substituent importing of general formula I if get final product according to common method.In brief ,-CH 2OR 7Base system is by making formaldehyde and pure effect can be directed in the polymkeric substance with phenol hydroxyl, for example in the polycarboxylated styrene.
Phosphonate group (P (=O) (OH) 2) direct importing aromatic nucleus, make trialkyl phosphite (R-P (=O) (OR) 2) effect examines halogenated polymkeric substance with phenol hydroxy to for example having, and for example examines in the halogenation polycarboxylated styrene and carries out the dehalogenation alkyl, then adding water decomposition can carry out.Phosphonate group (P (=O) (OH) 2) directly import and make aromatic nucleus, make oxygen base phosphorus chloride (POCl 3) and lewis' acid (AlCl for example 3) between the P+OCl that generates of reaction 2Effect is to the polymkeric substance with phenol hydroxyl, for example in the polycarboxylated styrene and make dehydrohalogenation, then can add water decomposition.Again, phosphonate group (P (=O) (OH) 2) directly import aromatic nucleus, for example make phosphorus trichloride and lewis' acid (AlCl for example 3) between the P+ClO that generates of reaction 2Effect is to the polymkeric substance with phenol hydroxyl, for example in the polycarboxylated styrene and make dehydrohalogenation, then adds water decomposition and can give and carrying out.Again by phosphonous acid base (P (=O) (OH) 2) alkyl imports aromatic nucleus, for example makes chlorine alkyl methyl ether (chloromethyl methyl ether (CH for example 3OCH 2Cl)) effect is to the polymkeric substance that for example has the phenol hydroxyl, for example in the polycarboxylated styrene and nuclear chlorine alkylation body in make and phosphonous acid (HP (OH) 2) effect gives dehydrochlorination and can give and carrying out.
Import aromatic nucleus by the Sauerstoffatom of phosphonate group, make the phosphorus pentachloride effect, for example in the polycarboxylated styrene and the phenol hydroxy is converted to-O-PCL to the polymkeric substance that for example has the phenol hydroxy 4, then add water decomposition and can give and carrying out.Import aromatic nucleus by the Sauerstoffatom of phosphonate group, make the phosphorus trichloride effect, for example carry out dehydrochlorination in the polycarboxylated styrene, then add water decomposition and can give and carrying out to the polymkeric substance that for example has the phenol hydroxy.
Get final product according to common method in each the substituent importing of general formula II.Usually if with when each the substituent importing of above-mentioned general formula I is carried out with method, get final product.
The necessary composition of this treatment agent contains the metallic compound (b) of at least a metal that the colony that formed by vanadium, zirconium, titanium, molybdenum, tungsten, manganese and cerium selects, above-mentioned metal oxide, oxyhydroxide, complex compound, salt between mineral acid or organic acid etc., and the good person of intermiscibility between aforementioned polymer (a) is advisable.
As for metallic compound (b), particularly can enumerate: Vanadium Pentoxide in FLAKES V 2O 5, three vanadium oxide VO 3, vanadium dioxide VO 2, metavanadic acid HVO 3, ammonium meta-vanadate, sodium metavanadate, oxygen base Vanadosulfuric acid VOSO 4, oxygen base acetyl group acetic acid ketone ester vanadium VO (OC (CH 3)=CHCOCH 3)) 2, vanadium acetyl group methylacetal acid esters V (OC (CH 3)=CHCOCH 3) 3, oxygen base vanadium trichloride VOCL 3, vanadium trichloride VCL 3, zirconium nitrate ZrO (NO 3) 2, zirconyl sulfate, zirconyl acetate, ammonium zirconyl carbonate (NH 4) 2[Zr (CO 3) 2(OH) 2], fluorine zirconic acid H 2ZrF 6, titanyl sulfate TiOSO 4, the two acetyl group acetone (C of diisopropoxy titanium 5H 7O 2) 2Ti[OCH (CH 3) 2] 2, lactic acid and alkyl dioxide reactant, hydrofluotitanic acid H 2TiF 6, lactic acid titanium Ti (OH) 2(C 3H 5O 3) 2, molybdic acid H 2MoO 4, ammonium molybdate, Sodium orthomolybdate, molybdophosphate compound (for example, ammonium phosphomolybdate (NH 4) 3[PO 4Mo 12O 36] .3H 2O, molybdophosphate sodium Na 3(PO 4.12MoO 3) .nH 2O etc.), metatungstic acid H 6(H 2W 12O 40), ammonium metawolframate (NH 4) 6[H 2W 12O 40], metatungstic acid sodium, to wolframic acid H 10(W 12O 46H 10), to ammonium tungstate, to sodium wolframate, cross mangaic acid HMnO 4, potassium permanganate, sodium permanganate, phosphate dihydrogen manganese Mn (H 2PO 4) 2, manganous nitrate Mn (NO 3) 2, manganous sulfate, manganous fluoride, manganous carbonate, manganese acetate, cerous acetate Ce (CH 3CO 2) 3, cerous nitrate, Cerium II Chloride etc.
If when using these metallic compounds (b) more than two kinds, be more effective aspect the performance raising of solidity to corrosion, alkali resistance etc. then, more producing effect aspect the raising of above-mentioned performance with its at least a vanadium compound that is required to be, be the vanadium compound that contains Oxidation Number trivalent or tetravalence vanadium with relevant vanadium compound aspect the above-mentioned performance raising for the most suitable.
As for making the method that in this treatment agent, contains trivalent or tetravalent vanadium compound, except that adopting aforesaid trivalent or tetravalent vanadium compound, can adopt prior employing reductive agent to make pentavalent vanadium compound be reduced into trivalent or tetravalence person.Used reductive agent be inorganic system, organic system any all can, be preferably and have, by hydroxyl, carbonyl, carboxyl, phosphate (OP (=O) OH by organic system 2), at least a functional group's that selects of the colony that forms of phosphonate group, 1～3 grade of amido and vinegar amido organic compound (e), especially with water-soluble organic compounds for more suitable.
Have by hydroxyl, carbonyl, carboxyl, phosphate (OPO as for this kind reductive agent 3H 2), phosphonate group (PO 3H 2), at least a functional group's that selects of the colony that forms of 1～3 grade of amido and vinegar amido organic compound (e), can enumerate: alcohols such as methyl alcohol, ethanol, Virahol, ethylene glycol; Formaldehyde, acetaldehyde, alditol, oxalic dialdehyde etc. aldehyde cpd; The carbonyl compound of acetyl group acetone, acetoacetic ester, two trimethylammonium acetyl group methane, 3-methylpentane diketone etc.; The organic acid of formic acid, acetate, propionic acid, tartrate, xitix, glyconic acid, citric acid, oxysuccinic acid etc.; The amine compound of triethylamine, trolamine, quadrol, pyridine, imidazoles, pyrroles, morpholine, hexahydropyridine etc., the sour vinegar amine compound of Dimethyl formamide, ethanamide, the third vinegar amine, N-methyl-prop vinegar amine etc.; Amido acids such as glycine, Beta Alanine, pyrroline, paddy ammonia vinegar amino acid; Monoses such as glucose, sweet pears sugar, semi-lactosi; Natural polysaecharides such as maltose, sucrose, starch, Mierocrystalline cellulose; Amido three (medronic acid) 1-hydroxy ethylene-1,1 '-di 2 ethylhexyl phosphonic acid, stretch the organic phosphoric acid of ethylenediamine tetraacetic (medronic acid), phytic acid etc.; Gallic acid, Weibull, humic acids, natural polymers such as lignin sulfonic acid, poly-phenol; Polyvinyl alcohol, polyoxyethylene glycol, polyacrylic acid, polypropylene vinegar amine, the poly-synthetic macromolecules such as ethyliminum, water-soluble nylon of stretching; Amido carboxylic acids such as EDTA etc.
In this treatment agent, by make contain anionic property or nonionic organic polymer (c) as moreover the composition that forms, can make solidity to corrosion, the anti-finger printing of tunicle, raisings such as alkali resistance, solvent resistance again.As for aforementioned organic polymer (c) is to wait other compositions that intermiscibility is arranged with polymers (a), metallic compound (b), is dissolved in the water medium or even and stabile dispersion or can even and stabile dispersion person be advisable in the presence of interfacial agent class emulsifying agent.
Polymkeric substance (a) ties up to and is anionic property in the water, thus if during the coexistence of the organic polymer of cationic, then lose electric charge and be destabilization, so can adopt anionic property or nonionic.
Organic polymer (c) anionic property by have the anionic property functional group, nonionic is reached by having the nonionic functional group, do not give special qualification as for the anionic property functional group, as for carboxyl, sulfonic group, phosphate, phosphonate group, thiol group, silanol base etc. and these acidic groups salt, as for the nonionic functional group, though do not give special qualification, but can enumerate hydroxyl, vinegar amido, polyethylene oxide chain etc.Organic polymer (c) is one or two or more kinds of functional group that can have these.
Do not give special qualification as for organic polymer (c) resin construction, for example can enumerate the resin (acrylic resin, ethenoid resin system etc.) that gets by monomeric (being total to) polymerization, amine ester resin system with the two key bonds of ethene, epoxy resin, vibrin system, polyamide resin system etc.
As for the organic polymer (c) that gets by monomeric (being total to) polymerization with the two key bonds of ethene, for example can enumerate: have (methyl) vinylformic acid, maleic acid, Ba Dousuan, Yi Kang acid, FUMARIC ACID TECH GRADE, vinyl sulfonic acid, methacrylic acid sulfonic acid, styrene sulfonic acid, phosphonate group oxygen ylmethyl (methyl) acrylate, phosphonate group oxygen base ethyl (methyl) acrylate, vinyl phosphonate, vinyl mercaptan, 2-hydroxyethyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, (methyl) acrylamide, N-methylol (methyl) acrylamide, anionic properties such as polyoxyethylene glycol (methyl) acrylate or nonionic functional group's monomeric homopolymer or multipolymer, or these monomer and alkyl (for example C=1～8) acrylate, ethene, vinylbenzene, the multipolymer of the fine grade of propylene.
As for amine ester resin system organic polymer (c), the bunching compound between polyvalent alcohol such as polyester polyol, polyether glycol, polycarbonate polyol and polymeric polyisocyanate for example, the polyvalent alcohol that employing has anionic property or nonionic functional group is that raw material is a kind of, water-soluble isocyanic ester performed polymer.
As for epoxy resin organic polymer (c), for example can enumerate: with glycidyl through giving the residual Resins, epoxy upgrading that has and importing anionic property or nonionic functional group person.
As for vibrin is organic polymer (c), for example can enumerate: adopting polyvalent alcohol or two base acid to import anionic property or nonionic functional group is raw material.
As for polyamide resin system organic polymer (c), for example how to enumerate: after giving methylolation with part or all of the H of the NHCO-bases that wait the polyamide resins more, partial oxidation also becomes carboxyl, and the diamines with polyethylene oxide chain is the polyamide resin of raw material etc.
In surface treatment agent of the present invention, by making the composition that contains fluorine cpd (N) conduct moreover form, the tack that can make solidity to corrosion reach coating improves.This be in when coating and when dry the former material of etching with due to the evolution reaction that promotes tunicle.
This kind fluorine cpd (d) are to comprise the hydrofluoric acid class, metal fluoride, and fluorine misfit thing particularly can be enumerated hydrofluoric acid, boron hydrofluoric acid, silicon hydrofluoric acid, chromium hydrofluoric acid, titanium hydrofluoric acid, Tin tetrafluoride., ferrous fluoride, ferric fluoride etc.
The mass ratio of surface treatment agent constituent of the present invention, be preferably metallic compound (b) (mould calculation metal)/polymkeric substance (a)=0.005～2.0, be preferably 0.01～1.0, if this mass ratio is when low than 0.005, then solidity to corrosion is also not enough, if surpass at 2.0 o'clock, tunicle become fragile fail the performance expected.
Be suitable for the situation of organic polymer (c), be preferably mass ratio=0.05～2.0 of organic polymer (c)/polymkeric substance (a), be preferably 0.1～10.No matter this mass ratio makes when low than 0.05, or surpass 20 and also fail to bring into play enough solidity to corrosions.
Fluorine cpd (d) are that the concentration among the treatment solution 1L is preferably 0.1～100g/L in F, are preferably 0.2～50g/L.
In surface treatment agent of the present invention, for improving the solidity to corrosion of formed tunicle, solvent resistance, resistance to chemical reagents, can make the polymkeric substance (a) that contains the composition of can be crosslinked moreover forming and/or the organic crosslinking agent or the inorganic crosslinking agent of organic polymer (c), as for organic crosslinking agent, can adopt epoxy system, trimeric cyanamide system, aldehyde system, isocyanate-based.As for inorganic crosslinking agent, except that this specific metallic compound, can enumerate metallic compounds such as iron, cobalt, nickel, niobium, molybdenum, zinc.
Aforementioned linking agent usage quantity is preferably 0.05～30 quality branch to whole non-volatility composition 100 quality branches, is preferably 0.1～20 quality branch.During less than 0.05 quality, the effect of being expected is also not enough, surpasses the then stability reduction of treatment agent of 30 quality timesharing.
And mean with 110 ℃ of these surface treatment agents of heat drying remaining composition after 2 hours at the whole non-volatility compositions of the present invention.
In surface treatment agent of the present invention, for the solidity to corrosion that makes tunicle more improves, adjust tunicle rerum naturas such as tensile strength, can make and contain water-dispersible silica colloidal sol and/or alumina sol, conduct of metal-sols such as zirconia sol moreover the composition that forms, the addition of relevant composition is that the 5-40 quality % of whole nonvolatile component is advisable, and 10～30 quality % are for more suitable.
In surface treatment agent of the present invention, for improving the oilness of tunicle, the processibility scoring resistance can make and contain polyethylene wax, ethylene series waxes such as Poly Propylene Wax, esters such as carnauba wax, rice wax, gama wax, lanolin are that hydrogen such as hydrocarbon system wax such as wax, micro-crystallization wax are the wax that wax is selected.The addition of relevant composition is 0.5～30 quality % of whole non-volatile contents, more is preferably 1～20 quality %.
In surface treatment agent of the present invention, in the scope that does not undermine the object of the invention, can make lubrication prescription or matting agents such as resin particle powder such as containing methyl methacrylate, polystyrene, trimeric cyanamide.
The used solvent of surface treatment of the present invention is based on water, and also not hinder alcohol, ketone, ethoxy ethanol in case of necessity be that the merging of water-miscible organic solvent is used but the improvement of the drying property of tunicle etc. are looked.
This is external not to undermine the object of the invention or can be added interfacial agent, defoamer, all spreader, fungi-proofing mould inhibitor, tinting material etc. in the scope of film properties.
Next illustrates surface preparation of the present invention.
Do not give special restriction as for step before of the present invention, usually carry out this processinging before for removing the oil content that has been attached on former resisting, dirt is with alkaline defatting agent or acid degreasing agent cleaning or carry out hot water wash, solvent cleaning.Its backsight carries out being adjusted by surfaces such as acid, alkali in case of necessity.Cleaning aspect in former material surface does not remain on the former material surface sanitising agent being preferably after the cleaning to be washed to as far as possible.
As for this treatment process, surface treatment agent of the present invention coated metal material surface after, if can get final product at 50～250 ℃ of heat dryings, as for coating process, drying means etc. then do not give special restriction.
Usually on former material surface, adopt the rolling method that makes the transfer printing of treatment agent roller coat and give coating, or the method for utilizing showering Hou such as sprinkle mode to press dry, the raw-material method of dipping in handling, the method for spray cloth treating agent to the former material with running roller.The temperature of treatment solution is not given special restriction, but the solvent of this treatment agent is based on water, so treatment temp is preferably 0～60 ℃, is preferably 5～40 ℃.
The pH that handles, adopt mineral acid, organic acid, ammonia, amine etc., the welcome stable pH territory that is adjusted to the treatment agent composition, if when considering running reduction (influence of the former material metal of dissolved in the treatment solution) that the excessive erosion agent by former material metal causes, then be preferably 2～11, be preferably 3～10, be preferably 4～9 especially.
Drying step need not promote polymkeric substance (a) and/or organic polymer (d) to solidify, only remove the situation of attached water, not necessarily need heat, or also can with physical removal such as air-dry or air blowings, but promote polymkeric substance (a) and/or organic polymer (d) to solidify, or improve necessity by the softening lining effect heat drying that causes.The temperature of this situation is preferably 50～250 ℃, is preferably 60～220 ℃.
The adhesion amount of formed tunicle is all to be preferably 30～5000mg/m by film quality 2, be preferably 50～3,000mg/m 2Less than 30mg/m 2Shi Ze fails to obtain enough solidity to corrosions, and on tack between being coated with.If be worth when above at this, then generate be full of cracks etc. on the tunicle, the tack of tunicle itself can reduce.
Treatment agent of the present invention is coated former material metal and is given the exsiccant step through giving, and can be considered with the reaction of former material metallic surface and form the good tunicle of tack, makes the resinous principle film forming simultaneously, and former material is invested superior solidity to corrosion, coating tack person.
More particularly, contain metal ion and the reaction of former material metallic surface in the acidic group metallizing thing (b) of phosphorus in the polymkeric substance (a), form insoluble salt or insoluble compound and separate out and be bonded on the surface.Again in drying step, polymkeric substance (a) carries out condensation and crosslinked voluntarily or be that linking agent forms fine and close three-D structure and film forming with metallic compound (b) intermolecular.
The superior solidity to corrosion of formed tunicle, remove the superior tack of the former material that causes by polymkeric substance (a) phosphorated acidic group, outside the metallic surface barrier performance of formed tunicle causes, can be considered following reason, the specific polymkeric substance (a) of the present invention has the compound of the resonance stabilization of resonance configuration, specific therewith transistion metal compound (b) has the effect that the electronics that utilizes the ψ track to be generated by corrosion gives delocalization, true thus, can be considered surface potential keeps evenly through giving, can invest superior solidity to corrosion (not only planar portions, the end face pars affecta also).Again especially vanadium, tungsten, molybdenum and chromium same have an oxidisability, having with the electronics that utilizes the corrosion reaction anode water to generate is the effect of going back primary electron and giving consumption, can be considered to have the effect that the solidity to corrosion of making improves.
By the formed tunicle of treatment agent of the present invention, because of being principal constituent with the organic resin, can be considered in processibility, oilness aspect etc. also has superior characteristic.
Embodiment:
1. former material
A: galvanizing steel plate (thickness of slab: 0.8mm)
B: hot-dip galvanized steel sheet (skin depth: 0.8mm)
Steel plate galvanized (the thickness of slab: 0.5mm) of C:55% aluminium
D:Al-Mn is alloy A-3004 a material (thickness of slab: 0.5mm)
2. treatment agent
(1) treatment agent composition
The polymkeric substance that has used (a) is contained in the general formula I a1～a5 shown in the following table 1, and is contained in the general formula II a6～a12 shown in the following table 2.
Table 1
Table 2
???W 4 ????????W 1 ???W 2 ???W 3 ?S The source of Y
??a6 ?PO 3H 2 ????????H ???H ???H ?12 ????---
???H ????????H ???H ???H ?18
??a7 ?PO 3H 2 ??????CH 2OH ???H ???H ?4 ????---
???H ?????CH 2OC 3H 7 ???H ???H ?16
??a8 ???H ???C(CH 3) 2C 3H 5OH ?PO 3H 2 ?CH 2OH ?15 ????---
???H ??????CH 2OH ???H ???H ?5
??a9 ???H ??????OPO 3H 2 ?CH 2OH ???H ?2 Sulphonated phenol (sulphur heart rate: t=10 40%)
???H ????????H ???H ???H ?18
?a10 ???H ????(CH 2) 2PO 3H 2 ???H ???H ?3 Alditol t=2
?a11 ?PO 3H 2 ????????H ???H ???H ?10 Toluene t=3
?a12 ?PO 3H 2 ???C(CH 3) 2C 6H 5OH ?CH 2OH ???H ?30 Aniline t=20
(b) is as described below for the metallic compound that has used.B1:(NH 4) VO 3B2:V 2O 5Tartrate reduzate b3:(NH 4) VO 3Glucose reduzate b4:VO (C 5H 7O 2) 2B5:(NH 4) 6Mo 7O 244H 2Ob6:3 (NH 4) 2O.12WO 3NH 2Ob7:(NH 4) 2[Zr (CO 3) 2(OH) 2] b8:H 2TiF 6B9:MnCO 3
In b2, mix V with mass ratio 5/1 2O 5And tartrate, adding distil water and about 50 ℃ of heating two hours to becoming solid shape to divide 2 quality %.
In b3, mix (NH with mass ratio 1/1 4) VO 3And D-glucose, adding distil water and about 70 ℃ of heating 2 hours to becoming solid shape to divide 10 quality %.
(C) is as described below for the organic polymer that has used, C1: the acrylic ester emulsion (make by clear and polymer (thigh), Polysol Ap6530) C2: ((thigh) Japan touches the coal manufacturing to the acrylic ester emulsion, Acryset SC-548) C3: negatively charged ion upgrading Resins, epoxy (make by rising sun electrochemical industry (thigh), Adecaresin EM-0433) C4: water system polyurethane (the first industry system industry (thigh) is made SUPER flex 150)
The fluorine cpd that used (d) are as described below.d1:HFd2:H 2ZrF 6d3:H 2TiF 6d4:H 2SiF 6
Other compositions that embodiment has used are as described below.E1: daily output chemistry (thigh) is made, Colloidalsilica Snow Tex Ne2: Mitsui Chemicals (thigh) is made, water system wax, Chemipearl W700
(2) preparation of treatment agent
10～20% aqueous solution of mixed polymer (a), metallic compound (c) and fluorine cpd (d) then add 20～40% aqueous solution of organic polymer (c) and other compositions (e), are adjusted to prescribed concentration with deionized water
3. (20g/L just throws stoste to the alkaline defatting agent Parclean364S that 1. makes with Japanese Parkerizing limited-liability company of treatment process (1) degreasing, 60 ℃ of spray 10 seconds of cloth, spray cloth pressure 50kPa) former material is given degreasing after, spray cloth and washed for 10 seconds.2. after the alkaline defatting agent Finecleaner 315 that makes with Japanese Parkerizing limited-liability company (30g/L just throws liquid, 60 ℃ dipping 40 seconds) gives degreasing with former material, carry out sprinkle and washed for 30 seconds.(2) coating and dry I: with the modulated treatment solution that is made into concentration 16 quality %, be coated with the device rod with rod and be applied to dry film thickness, in 80 ℃ of (PMT) dryings into about 1/um.II: with the modulated treatment solution that is made into concentration 16 quality %, be coated with the device rod with rod and be applied to dry film thickness, in 150 ℃ of (PMT) dryings into about 1/um.
4. appraisal procedure
(1) solidity to corrosion
The processing test portion of having made for embodiment, comparative example, do not carry out the chessboard grid and be cut to the person's (chessboard grid cutting part) that reaches the base material and solidity to corrosion is carried out in Erischen7mm extrusion processing (processing) recognize and test there being processing (planar portions) with the NT cutter, appraisal procedure is as follows.
(planar portions) is to be as the criterion according to JIS-Z-2371 salt spray testing method, asks for and carries out the white rust generation area of brine spray after 72 hours, and give assessment.
The assessment benchmark: to rust take place area ◎ less than more than 10%, 0 10% less than 30%, △ more than 30% less than 60%, * more than 60%.
(chessboard grid cutting part) is to be as the criterion according to the JIS-Z-2371 salt spray testing, carried out 72 hours white rust situation occurred of brine spray with visual assessment,
The assessment benchmark: white rust situation occurred ◎ gets rusty hardly, zero only have a little rust, △ be considered to get rusty, * significantly get rusty
(adding the Ministry of worker) is as the criterion according to the JIS-Z-2371 salt spray testing, carried out salt spray testing with visual assessment and has been as the criterion, and carried out the white rust situation occurred of 72 hours Hous of brine spray with visual assessment.
The assessment benchmark: white rust situation occurred ◎ gets rusty hardly, zero only have a little rust, △ be considered to get rusty, * significantly get rusty
(2) coating tack
With following condition be coated with for test plate (panel),, adopt the match Lopa Nationality to imitate adhesive tape and carry out belt stripping test (1 time adhere to) to filming with NT cutter 100 chessboard grid of cutting (the 1mm length of side) to reaching ground.Behind nicking chessboard grid, impregnated in the plank of boiling in the pure water to the same belt stripping test (secondary adheres to) that carries out again.The remaining number of film chessboard grid is assessed.◎: 100, zero: 80 above less than 100, △: more than 50 less than 80, *: less than 50
Coating process: be coated with Delicon#700 rod that device makes big Japanese coating limited-liability company with rod and be applied on the surface-treated metal plate, and gave drying in 20 minutes 140 ℃ of bakings to the about 25 μ m of dry film thickness.
(3) anti-finger printing
With nail extrusion process plate surface, and with visual inspection fingerprint trace state and give assessment.
Assessment benchmark: ◎ do not have fully vestige, zero little vestige, △ have vestige, * have clear and definite vestige remaining
The treatment solution content of embodiment and comparative example and treatment process system be shown in table 3 (use be contained in general formula I 2a1～a5 polymkeric substance a) and table 4 (use is contained in general formula II a6～a12 as polymkeric substance a), assessment result be shown in table 5 (use be contained in general formula I a1～a5 as polymkeric substance a) and table 6 (use is contained in general formula II a6～a12).
Can show and learn by table 3 and table 4, coat surface treatment agent of the present invention (embodiment 1～20) on the metal material surface and give the exsiccant tunicle, have superior solidity to corrosion, coating tack and anti-finger printing as can be known.
Do not have the organic macromolecule comparative example 1 and 6 of embodiment 1 and 11 (a) composition separately with respect to this, in solidity to corrosion, coating tack, anti-finger printing is all inferior.The comparative example 2 and 7 solidity to corrosions of metallic compound that do not contain embodiment 2 and 12 (b) composition separately are inferior.The comparative example 3 and 8 that does not contain embodiment 6 and 16 (a) composition separately is in solidity to corrosion, and the coating tack is inferior a little.Do not contain embodiment 5 and 15 (a) composition and (b) the two comparative example 4 and 9 inferior aspect solidity to corrosion of composition separately, do not contain the comparative example 5 of embodiment 8 and 18 (b) composition and any composition (c) composition and 10 inferior aspect solidity to corrosion separately.
Table 3
Embodiment or comparative example Material Degreasing Treatment agent composition (weight %) Treatment process
???(a) ??(b) ???(c) ??(d)** Other
Embodiment 1 ???A ?①① ?a1(88) ?b3(4) ?b7(8) ???--- ???--- ???--- ???Ⅰ
Embodiment 2 ???B ?①① ?a2(70) ?b2(16) ?b8(14) ???--- ???d1(2) ???--- ???Ⅱ
Embodiment 3 ???D ?②② ?a3(80) ?b2(20) ???--- ???d2(3) ???--- ???Ⅰ
Embodiment 4 ???A ?①① ?a1(40) ?b3(4) ?b7(8) ?c1(48) ???--- ???--- ???Ⅰ
Embodiment 5 ???B ?①① ?a2(30) ?b2(16) ?b8(14) ?c3(50) ???d1(2) ???--- ???Ⅱ
Embodiment 6 ???D ?②② ?a3(32) ?b2(20) ?c2(45) ???d2(3) ???--- ???Ⅰ
Embodiment 7 ???C ?①① ?a4(25) ?b4(15) ?b5(15) ?c3(30) ???d3(5) ?e1(10) ??e2(5) ???Ⅰ
Embodiment 8 ???C ?①① ?a1(20) ??b6(4) ?c4(70) ???d4(2) ??e2(6) ???Ⅰ
Embodiment 9 ???A ?①① ?a2(30) ??b1(4) ??b4(4) ?c1(62) ???d1(4) ???--- ???Ⅱ
Embodiment 10 ???B ?①① ?a3(10) ??b3(4) ??b7(6) ?c4(80) ???d2(1) ???--- ???Ⅱ
Comparative example 1 ???A ?①① What embodiment 1 does not use a composition ???Ⅰ
Comparative example 2 ???B ?①① What embodiment 2 does not use the b composition ???Ⅱ
Comparative example 3 ???D ?②② What embodiment 6 need not make a composition ???Ⅰ
Comparative example 4 ???B ?①① What embodiment 5 need not make a composition, b composition ???Ⅱ
Comparative example 5 ???C ?①① What embodiment 8 need not make b composition, c composition ???Ⅰ
* to the percentage (but 6 metals convert) of the summation of composition (a)+(b)+(c)+(e) nonvolatile component.Concentration in the * treatment agent (g/L)
Table 4
Embodiment or comparative example Material Degreasing Treatment agent composition (weight %) Treatment process
???(a) ????(b) ?????(c) ??(d)** He
Embodiment 11 ???A ?①① ?a6(90) ???b2(5) ???b8(5) ?????--- ????--- ???--- ???Ⅰ
Embodiment 12 ???B ?①① ?a7(80) ???b2(6) ???b7(14) ?????--- ???d1(2) ???--- ???Ⅱ
Embodiment 13 ???D ?②② ?a8(85) ???b3(15) ?????--- ???d2(3) ???--- ???Ⅰ
Embodiment 14 ???A ?①① ?a6(50) ???b2(5) ???b8(5) ???c1(40) ????--- ???--- ???Ⅰ
Embodiment 15 ???B ?①① ?a7(30) ???b2(6) ???b7(14) ???c3(50) ???d1(2) ???--- ???Ⅱ
Embodiment 16 ???D ?②② ?a8(35) ???b3(15) ???c2(50) ???d2(3) ???--- ???Ⅰ
Embodiment 17 ???C ?①① ?a9(50) ???b5(5) ???b8(5) ???c3(25) ???d3(5) ???e1(10) ???e2(5) ???Ⅰ
Embodiment 18 ???C ?①① ?a10(20) ???b6(4) ???c4(70) ???d4(2) ???e2(6) ???Ⅰ
Embodiment 19 ???A ?①① ?a11(30) ???b1(2) ???b4(2) ???c1(66) ???d1(4) ????--- ???Ⅱ
Embodiment 20 ???B ?①① ?a12(10) ???b2(2) ???b7(1) ???c4(87) ???d2(1) ????--- ???Ⅱ
Comparative example 6 ???A ?①① What embodiment 11 does not use a composition ???Ⅰ
Comparative example 7 ???B ?①① What embodiment 12 does not use the b composition ???Ⅱ
Comparative example 8 ???D ?②② What embodiment 16 need not make a composition ???Ⅰ
Comparative example 9 ???B ?①① What embodiment 15 need not make a composition, b composition ???Ⅱ
Comparative example 10 ???C ?①① What embodiment 18 need not make b composition, c composition ???Ⅰ
* to the percentage (but 6 metals convert) of the summation of composition (a)+(b)+(c)+(e) nonvolatile component.Concentration in the * treatment agent (g/L)
Table 5
Embodiment or comparative example Solidity to corrosion Tu adorns adherence Anti-finger printing
Flat part The cutting of chessboard grid Add the Ministry of worker 1 time 2 times
Embodiment 1 ???○ ??????○ ???○ ???◎ ???○ ????○
Embodiment 2 ???○ ??????○ ???○ ???◎ ???○ ????○
Embodiment 3 ???◎ ??????○ ???○ ???◎ ???◎ ????○
Embodiment 4 ???◎ ??????○ ???◎ ???◎ ???◎ ????◎
Embodiment 5 ???◎ ??????◎ ???◎ ???◎ ???◎ ????◎
Embodiment 6 ???◎ ??????◎ ???◎ ???◎ ???◎ ????◎
Embodiment 7 ???◎ ??????○ ???○ ???◎ ???◎ ????◎
Embodiment 8 ???◎ ??????○ ???○ ???◎ ???◎ ????◎
Embodiment 9 ???◎ ??????◎ ???◎ ???◎ ???◎ ????◎
Embodiment 10 ???◎ ??????◎ ???◎ ???◎ ???◎ ????◎
Comparative example 1 ???△ ??????× ???× ???△ ???× ????×
Comparative example 2 ???△ ??????△ ???× ???○ ???△ ????×
Comparative example 3 ???△ ??????△ ???△ ???△ ???△ ????○
Comparative example 4 ???× ??????× ???× ???△ ???△ ????○
Comparative example 5 ???△ ??????× ???× ???○ ???○ ????△
Table 6
Embodiment or comparative example Solidity to corrosion Tu cloth tack Anti-finger printing
Flat part The cutting of chessboard grid Add the Ministry of worker 1 time 2 times
Embodiment 11 ???○ ??????○ ???○ ???◎ ???○ ????○
Embodiment 12 ???○ ??????○ ???○ ???◎ ???○ ????○
Embodiment 13 ???◎ ??????○ ???○ ???◎ ???◎ ????○
Embodiment 14 ???◎ ??????○ ???◎ ???◎ ???◎ ????◎
Embodiment 15 ???◎ ??????◎ ???◎ ???◎ ???◎ ????◎
Embodiment 16 ???◎ ??????◎ ???◎ ???◎ ???◎ ????◎
Embodiment 17 ???◎ ??????○ ???○ ???◎ ???◎ ????◎
Embodiment 18 ???◎ ??????○ ???○ ???◎ ???◎ ????◎
Embodiment 19 ???◎ ??????◎ ???◎ ???◎ ???◎ ????◎
Embodiment 20 ???◎ ??????◎ ???◎ ???◎ ???◎ ????◎
Comparative example 6 ???△ ??????× ???× ???△ ???× ????×
Comparative example 7 ???△ ??????△ ???× ???○ ???△ ????×
Comparative example 8 ???△ ??????△ ???△ ???△ ???△ ????○
Comparative example 9 ???× ??????× ???× ???△ ???△ ????○
Comparative example 10 ???△ ??????× ???× ???○ ???○ ????△
Surface treatment agent of the present invention is not for containing the non-chromium type of deleterious chromium cpd, has superior solidity to corrosion by the formed tunicle of this surface treatment agent, coating tack and anti-finger printing, treatment agent of the present invention, treatment process and processing metallic substance have great utility value on industry.

Claims (4)

1. a metal conditioner, metal surface treating method and surface-treated metal material
1, a kind of metal conditioner is characterized in that containing following general formula I
Figure A0111050500021
(in the formula, R 1～R 6Be separate hydrogen atom or carbon number 1～5 alkyl, V 1And V 2Be hydrogen atom independently separately ,-CH 2OR 7,-Z ,-OZ ,-R 8Z or-OR 8Z, R 7Be carbon number 1～5 alkyl, R 8For carbon number 1～5 is stretched alkyl, Z is a general expression
Figure A0111050500022
Or
Figure A0111050500023
(in the formula, T 1～T 4Be independently hydrogen atom or carbon number 1～5 alkyl separately) base of expression,
V 3For hydrogen atom or-Z (Z and above-mentioned synonym)
X is the two openable bases of key bond of ethene of the compound with ethene two key bonds different with the compound of the tectonic unit that gives the tectonic unit of drawing together with n and draw together with m,
N is 2～50 integers, and m is 0 or 1～50 integer, and P is 0 or 1～20 integer, 0.1≤n/ (n+m+p)≤1.0,0≤m/ (n+m+p)≤0.9,0≤p/ (n+m+p)≤0.6) or general formula II
Figure A0111050500031
(in the formula, W 1～W 3Be separate hydrogen atom ,-CH 2OR a,-Z ,-OZ ,-R bZ ,-OR cZ or general expression (ⅰ)
The base of expression, R a, R dAnd R eBe separate hydrogen atom or carbon number 1～5 alkyl, R 6And R CStretch the Z synonym of alkyl, Z and general formula I for separate carbon number 1～5, the base system that can become general expression (ⅰ) expression is W only 1～W 3In a kind of.
W 4For hydrogen atom or-Z (Z and above-mentioned synonym)
W 1～W 4One for having the Z functional group
But Y serves as reasons and loses the different divalent radical of fragrant cyclic group in the structure that bond to the hydrogen atom of the carbon atom that constitutes this aromatic nucleus draws together with s with the aromatics of formaldehyde addition condensation, or trimeric cyanamide, guanamine or two amidos of urea respectively lose the divalent radical of a hydrogen atom, S represents 2～50 integers, t represents 0 or 1～20 integer) polymkeric substance (a) of expression, and the metallic compound (b) of at least a metal selected of the colony that formed by vanadium, zirconium, titanium, molybdenum, tungsten and cerium forms.
2. metal conditioner as claimed in claim 1 is characterized in that containing anionic property or nonionic organic polymer (c).
3. a metallic material surface treating method is characterized in that heat drying to the temperature of previous materials becomes 50～250 ℃ with after metal material surface usefulness claim 1 or the 2 described metal conditioners processing.
4. a metallic substance is characterized in that handling formed tunicle with the described metallic material surface treating method of claim 3.
CN01110505A 2000-05-31 2001-04-06 Metal surface treating agents, methods and materials thereof Pending CN1325926A (en)

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