CN1340635A - Surface treatment of aquo-metal containing no sexavalence chromium and its treated metal plate for surface treatment - Google Patents

Surface treatment of aquo-metal containing no sexavalence chromium and its treated metal plate for surface treatment Download PDF

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Publication number
CN1340635A
CN1340635A CN 01124079 CN01124079A CN1340635A CN 1340635 A CN1340635 A CN 1340635A CN 01124079 CN01124079 CN 01124079 CN 01124079 A CN01124079 A CN 01124079A CN 1340635 A CN1340635 A CN 1340635A
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metal
composition
water
resin
treating agent
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CN 01124079
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CN1182274C (en
Inventor
木下康弘
小崎匠
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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Abstract

Provided is an aqueous agent for metal surface treatment without including hexa-valent chromium which form a superior film in corrosion resistance, electroconductivity and fingerprint resistance on a surface of a metal material and to provide a metal plate treated with the treatment agent. The aqueous agent for metal surface treatment without including hexa-valent chromium comprises (A) a trivalent chromium compound, (B) a metal nitrate (C) water-dispersible silica and water, and besides, comprises that the weight ratio of a metal in the component (A) to a metal in the component (B) is in the range of 5/95-95/5. The aqueous agent preferably includes aqueous resins such as an acryl resin, a urthane resin and an epoxy resin, phosphate compounds, and lubricants as additional components. Water class resin such as acryl resin, urethane resin and epoxy resin, phosphate compounds and a lubricant are preferably included as additional components. A film of 0.1-5 g/m2 by dry coating weight is formed by means of applying the above aqueous agent for metal surface treatment on at least one side of the surface of the metal and drying it.

Description

Not chromyl water-based metal-surface-treating agent and handled surface-treated metal plate thereof
Technical field
The present invention relates to a kind of water-based metal-surface-treating agent, particularly a kind of not chromyl water-based metal-surface-treating agent can form all superior epithelium of an erosion resistance, electroconductibility, anti-finger printing at metal material surface.The invention still further relates to the handled surface-treated metal plate of this treatment agent.
Background technology
General known household electrical appliance goods all are to make chromate treating on the gold-plated steel plate of sub-lead series, to improve its erosion resistance with steel plate and material of construction steel plate.Yet, but contain in this type of chromate treating environment and all deleterious sexavalent chrome of human body, therefore, in recent years for the not requirement of chromyl synthetic processing, more very the person is that not contain the expectation of synthetic processing of chromium more strong.And, requiring after these synthetic processing, performances such as erosion resistance, electroconductibility, anti-finger printing, application adherence still must have same effect with known synthetic processing.
Relevant this type of synthetic known technology of handling is opened the 2000-054157 communique and the spy opens in the 2000-000519 communique on the books the spy.
Open in the 2000-054157 communique the spy, a kind of metal and trivalent chromic ions such as phosphorus, molybdenum of containing are disclosed, and do not contain the synthetic surface treatment agent of sexavalent chrome and fluorochemical, this treatment agent is applied in the known synthetic processing, when chromate treating for reaching temporary rust prevention (chromium adhesion amount 10mg/m 2The time, brine spray 72 hours, white rust generation area occupation ratio is less than 10%) effect, the epithelium amount maintains 1g/m 2More than be necessary, yet the anti-finger printing of the epithelium that obtains still can't be satisfactory.
In addition; open in the 2000-000519 communique the spy; disclose a kind of plate sub-lead series or the surface of steel plate that is of aluminizing on; to contain chela in water-dispersed resin and/or water soluble resin and the high polymer binder and to form basic polymer chela and agent is main component, forms the surface treated steel plate and the surface preparation thereof of protection epithelium.Because this method is a main component with water-dispersed resin and/or water soluble resin, though anti-finger printing is good, electroconductibility is relatively poor.
Metal conditioner of the present invention does not contain sexavalent chrome fully, and forms all superior surface-treated metal plate of erosion resistance, electroconductibility and anti-finger printing of epithelium, still can not obtain in the prior art.
Summary of the invention
The present invention is to be purpose with the problem that solves in the above-mentioned known technology, and provide a kind of sexavalent chrome that do not contain, certainly has erosion resistance in the metallic surface, form the water-based metal-surface-treating agent of all superior epithelium of electroconductibility and anti-finger printing simultaneously, and the handled surface-treated metal plate of this water-based metal-surface-treating agent.
Be devoted to solve problem in the known technology the present inventor, research is repeatedly used when containing the water-based metal-surface-treating agent of 3 valency chromium cpds, nitric acid metal-salt, water dispersible silica, finds that it can solve the above problems, so propose the present invention.
The present invention is valency chromium cpd, (B) nitric acid metal-salt, (C) water-dispersible silicas and the not chromyl water-based metal-surface-treating agent of water of a kind of containing (A) 3, and it is characterized by: metal and the weight ratio (A)/(B) of the middle metal of composition (B) are in 5/95～95/5 scope in the composition (A).
In above-mentioned water-based metal-surface-treating agent, the metal in composition (B) the nitric acid metal-salt is that at least a metal of selecting in the formed metal group of alkaline-earth metal, cobalt, nickel, iron, zirconium and titanium is an ideal.In addition, with respect to the total amount that the solid formation of composition (A), composition (B) and composition (C) divides, the solid shape components in proportions of composition (C) is comparatively desirable between 10～90 weight %.In the above-mentioned water-based metal-surface-treating agent, if it is then comparatively desirable to comprise (D) aqueous resin that is considered as appending composition, this aqueous resin is a comparatively ideal of at least a aqueous resin selected among the group who is formed by acrylic resin, urethane resin and Resins, epoxy.If it then is comparatively ideal comprising (E) phosphate compounds that is considered as appending composition.If it then is comparatively ideal comprising (F) lubricant that is considered as appending composition.
Moreover the present invention is the above-mentioned water-based metal-surface-treating agent of local coating in the metallic surface, makes its drying again, and will form a dry epithelium weight is 0.1～5g/m 2The surface metal disposable plates of epithelium.
The specific embodiment
Water system metal conditioner of the present invention contains composition (A) trivalent chromium compound, but Do not contain hexavalent chromium compound, the trivalent chromium compound is not particularly limited, chromium sulfate (III), nitric acid Chromium (III), heavy chromium phosphate (III), charomic fluoride (III), hafnium halide (III) etc. all are, even use The trivalent chromium that Cr VI reduces does not fully have obstruction yet. Water system metal conditioner of the present invention In the use level of relevant composition (A) there is no particular restriction.
Composition used in the present invention (B) though the metal in the nitric acid slaine be not particularly limited, With the alkaline-earth metals such as magnesium, calcium, barium, and cobalt, nickel, iron, zirconium and titanium form among the group selected At least a metal that goes out is than suitable; Have in the water system metal conditioner of the present invention There is no particular restriction for the use level of pass composition (B).
As mentioned above, relevant composition (A) and composition in the water system metal conditioner of the present invention (B) though use level be not particularly limited the weight of metal and the middle metal of composition (B) in the composition (A) Amount must maintain than (A)/(B) in 5/95～95/5 the scope. Should (A)/(B) 15/85～During 85/15 scope than in 10/90～90/10 scope ideal, but when the ratio of (A)/(B) be Less than 5/95 or surpass at 95/5 o'clock, its corrosion resistance degree is not good, is undesirable situation.
Composition used herein (C) aqueous dispersion silica comprises cataloid, gas Aerosil, and this cataloid is not particularly limited, and can list SNOWTAX C, SNOWTAXO, SNOWTAXN, SNOWTAXS, SNOWTAXUP, SNOWTAXPS-M, SNOWTAXPS-L, SNOWTAX20, SNOWTAX30, SNOWTAX40 etc. (trade (brand) name is all Nissan Chemical Industries Ltd.'s system) should Aerosil also is not particularly limited, can list AEROJIL50, AEROJIL130, AEROJIL200, AEROJIL300, AEROJIL380, AEROJIL TT600, (trade (brand) name is all the chemical worker of daily output for AEROJIL MOX80, AEROJIL MOX170 etc. Industry limited company system).
In the water system metal conditioner of the present invention, reach with respect to composition (A), composition (B) The solid composition total amount of composition (C), the ratio of the solid composition of composition (C), just relative In 100 % by weight of whole solid compositions of composition (A)～(C), the solid composition of composition (C) Ratio is desirable with 10～90 % by weight; 20～80 % by weight are then more desirable; But If this ratio is in less than 10 % by weight the time, the corrosion resistance of the epithelium that obtains and anti-finger printing are all Lower, be undesirable; On the contrary, if when this ratio surpassed 90 % by weight, it had anti-The absolute magnitude of the composition of corrosive effect (A) and composition (B) then reduces, and corrosion resistance also lowers, Undesirable.
Water system metal conditioner of the present invention is to improve corrosion resistance as purpose, to join Close (D) aqueous resin water-soluble and/or the aqueous dispersion resin and use this water as appending composition Be resin be allyl resin, urethane resin, epoxy resin, mylar, phenolic resins, Jealous woman acid vinylite, salinization ethenylidene resin etc., from allyl resin, urethane resin, At least a aqueous resin of selecting among the formed group of epoxy resin is comparatively desirable.
The water system allyl resin is not particularly limited, (partially) acrylic acid, (partially) acrylate, (partially) The propylene such as acrylic amine are monomer, and with it possible vinyl compound of polymerization is arranged (for example: Styrene, acrylonitrile etc.) polymer be desirable, if when polymerization, can be used reactivity Emulsifying agent is then even more ideal. For example: PRIMAL K-3 (trade (brand) name, Loam﹠Hearth public affairs Department's system).
This water system urethane resin is not particularly limited, but uses the self-emulsifying type (need not use emulsification Then self-dispersing type of water is met in agent) comparatively desirable, this kind of resin for example can list: Super Flex110, Super flex 150, Super flex 300, Super flex 420 (trade (brand) name, all Be the first industrial Pharmacy stock Co., Ltd system), Adecabontiter-HUX-232, (trade (brand) name is all rising sun electrochemical industry for Adecabontiter-HUX-, Adecabontiter-HUX-Limited company's system).
Water system epoxy resin among the present invention is not particularly limited, but uses bis-phenol type epoxy Resin, phenol novolac type epoxy resin, orthochromatism cresols novolac type The amination upgrading thing of epoxy resin etc. is comparatively desirable. For example: can list AdecareginEPE-0436B (trade (brand) name is all by rising sun electrochemical industry limited company system).
With respect to 100 % by weight of whole solid compositions of composition (A)～(D), composition (D) consolidates The shape component ratio is comparatively desirable with 10～90 % by weight, and even more ideal with 20～85 % by weight, But this ratio is less than 10% the time, and corrosion resistance can't improve; When surpassing 90%, can make to have The absolute magnitude of the composition of corrosion resistance effect (A)～(C) reduces, and also is undesirable.
If cooperate as (E) phosphate cpd that appends composition, might improve then that it is corrosion-resistant The property. Wherein phosphate cpd is not particularly limited, and for example can list: ammonium dihydrogen phosphate (ADP), Diammonium hydrogen phosphate, tricresyl phosphate hydrogen ammonium, sodium dihydrogen phosphate, sodium hydrogen phosphate, tertiary sodium phosphate, Potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, magnesium monohydrogen phosphate, magnesium phosphate, phosphoric acid hydrogen Calcium, calcium phosphate, tripolyphosphate ammonium, sodium phosphate trimer, PTPP, tripolyphosphate magnesium, Tripolyphosphate calcium, ammonium pyrophosphate, sodium pyrophosphate, potassium pyrophosphate, magnesium pyrophosphate, pyrophosphoric acid Calcium etc.
With respect to whole solid composition 100 % by weight of composition (A)～(E), the solid of composition (E) Component ratio is take 0.1～10 % by weight as desirable, and even more ideal with 0.2～5 % by weight, phase For whole solid composition 100 % by weight of composition (A)～(E), the solid composition ratio of composition (E) During example less than 0.1 % by weight, corrosion resistance can't improve; When surpassing 10%, then can make anti-Corrosivity improves effect and reaches capacity, and does not have economy.
If cooperate as the use of appending (F) lubricant of composition, might improve that it is corrosion-resistant The property, also can expect by being used of lubricant, processability is improved. Lubricant wherein Be not particularly limited, can list Tissuemat E, polypropylene wax, alkane wax, microwax, The aqueous dispersion such as Carnauba wax, polytetrafluoroethylene (PTFE). The side that these lubricants utilize water to disperse Method also is not particularly limited, but with interfacial agent, that acidifying wax carries out aqueous dispersion is more satisfactory, For example: (trade (brand) name is all by Mitsui Chemicals for ChemipearlW900, ChemipearlWP250 Limited company's system).
With respect to whole solid composition 100 % by weight of composition (A)～(F), the solid of composition (F) Component ratio is take 1～20 % by weight as desirable, and even more ideal with 2～15 % by weight, relatively In whole solid composition 100 % by weight of composition (A)～(F), the solid component ratio of composition (F) During less than 1 % by weight, corrosion resistance can't improve; When surpassing 20%, then can make corrosion-resistant Property raising effect reaches capacity, and does not have economy.
Then, be described for surface-treated metal plate of the present invention. Surface of the present invention Processing metallic plate, is the water system metal conditioner with the invention described above, at metal material At least the one side on surface is coated with, and makes its drying again, forms a dry epithelium weight 0.1～5g/m2Epithelium. If should drying epithelium weight less than 0.1g/m2The time, its corrosion resistance Deficiency is undesirable; Dry epithelium weight surpasses 5g/m2The time, its corrosion resistance improves effect Fruit reaches capacity, and does not have economy.
Metallic plate in the surface-treated metal plate of the present invention can list plating sub-lead series steel plate (for example: plate electric inferior leaded steel plate, plating dissolves inferior leaded steel plate, alloy plating dissolves inferior leaded steel plate Deng), plating contains the inferior leaded steel plate of aluminium (plating contains that aluminium 5% dissolves inferior leaded steel plate, plating contains aluminium 55% and dissolves the Asia Leaded steel plate etc.), the inferior plumbous nickel alloy steel plate of aludip, plating etc., with these metal material surfaces Carry out the cleaning step of degreasing, pickling with alkali after, with water system Treatment of Metal Surface of the present invention Agent is coated with, and makes it dry for desirable again.
The coating process of relevant water system metal conditioner is not particularly limited, roller method, Infusion process, electrostatic applications method etc. all can be used, and the drying after the coating is to arrive plate temperature 60～200 ℃, make it dry for desirable.
In addition, with the handled surface-treated metal plate of water system metal conditioner of the present invention, for making corrosion resistance stronger, coating forms a resin involucra, this resin involucra is not particularly limited, but the surface conditioning agent take allyl resin, urethane resin, epoxy resin, mylar etc. as main component be coated with the former of institute for desirable, and the dry weight of this resin involucra weight is at 0.5～10g/m2Be desirable in the scope.
Below, with embodiment and comparative example the present invention is done one and specify. These embodiment Only as explanation of the present invention, and non-limiting use thing of the present invention.
Experiment material is made:
(1): experiment material
Use as equipment with following commercially available material.
Plate electric inferior leaded steel plate (EG) thickness of slab 0.8mm and electroplate adhesion amount 20/20 (g/m2)
Plating dissolves inferior leaded steel plate (GI) thickness of slab 0.8mm and electroplates adhesion amount 60/60 (g/m2)
Plating contains aluminium 5% inferior leaded steel plate (GF) thickness of slab 0.8mm and electroplates adhesion amount 90/90 (g/m2)
Plating contains aluminium 55% and dissolves inferior leaded steel plate (GL) thickness of slab 0.8mm plating adhesion amount 90/90 (g/m2)
(2): ungrease treatment
Above-mentioned each experiment material is with the Finecleaner4336 (login of silicate alkali cleaner Trade mark: Nippon Bacalaijingu Co.,Ltd.'s system), carry out ungrease treatment (concentration 20g/L, Temperature 60 C, spraying was processed 20 seconds) after, clean with running water.
The modulation of water system metal conditioner:
Be used in the trivalent of the modulation of the water system metal conditioner in embodiment and the comparative example Chromium compound such as table 1, nitric acid slaine such as table 2, aqueous dispersion silica such as table 3, water Be resin such as table 4, phosphate compounds such as table 5, lubricant is as shown in table 6.
Table 1
Chromium compound The solid constituent concentration
A1 A2 A3 Charomic fluoride aqueous solution chromic acid 100% reducing solution Cr VI 30% reducing solution     10％     10％     10％
Table 2
The nitric acid slaine The solid constituent concentration
 B1  B2  B3 The inferior lead water solution of cobalt nitrate aqueous solution calcium nitrate aqueous solution nitric acid     10％     10％     10％
Table 3
Aqueous dispersion silica Manufacturing company The solid constituent concentration
 C1  C2 SNOWTAXO AEROJIL 200 aqueous dispersion liquid Daily output chemical industry Japan AEROJIL     20％     10％
Table 4
Aqueous resin Manufacturing company The solid constituent concentration
 D1  D2  D3  Adecabontiter HUX-670     Primal K-3  Adecaregin EPE-043 6B The electrochemical industry of the rising sun electrochemical industry Loam﹠Hearth rising sun     30％     46％     25％
Table 5
Phosphate compounds The solid constituent concentration
E1 E2 The ammonium dihydrogen phosphate aqueous solution calcium monohydrogen phosphate aqueous solution     10％     10％
Table 6
Lubricant Manufacturing company The solid constituent concentration
F1 F2  ChemipearlW900  ChemipearlWP250 The Mitsui Chemicals Mitsui Chemicals     40％     50％
At room temperature, with trivalent chromium compound, the nitric acid slaine of table 2, the table 3 of table 1 Aqueous dispersion silica, the aqueous resin of table 4, the phosphate compounds of table 5, table 6 lubricant according to the proportion of composing shown in table 7 and the table 8, is put into distilled water in regular turn, Mix with screw mixer, be modulated into the water system metal conditioner, reality is finished in modulation The water system metal conditioner of executing example forms as shown in table 7. The water system metal watch of comparative example The composition of face inorganic agent is as shown in table 8, the metal conditioner of water system shown in table 7 and the table 8 The solid constituent concentration be all 10 % by weight.
Table 7
Embodiment The solid of water system metal conditioner becomes to be grouped into*1 (A)/(B)   * 2
The trivalent chromium compound The nitric acid slaine Aqueous dispersion silica Aqueous resin Append composition*3
  1 A1(60) B1(30)   C1(10) Do not have Do not have 66/34
  2 A2(40) B1(20)   C1(40) Do not have Do not have 76/24
  3 A1(50) B2(25)   C1(25) Do not have Do not have 72/28
  4 A1(60) B3(30)   C1(20) Do not have Do not have 64/36
  5 A1(40) B1(20)   C2(40) Do not have Do not have 66/34
  6 A1(30) B1(20)   C1(20)   D1(30) Do not have 59/41
  7 A1(30) B1(20)   C1(20)   D2(30) Do not have 59/41
  8 A1(30) B1(20)   C1(20)   D3(30) Do not have 59/41
  9 A1(30) B1(20)   C1(20)   D1(28)     E1(2) 59/41
  10 A1(30) B1(20)   C1(20)   D1(28)     E2(2) 59/41
  11 A1(72) B1(8)   C1(20) Do not have Do not have 90/10
  12 A1(6) B1(54)   C1(40) Do not have Do not have 10/90
  13 A1(50) B1(25)   C1(25) Do not have Do not have 66/34
  14 A1(10) B1(10)   C1(80) Do not have Do not have 49/51
  15 A1(60) B1(30)   C1(10) Do not have Do not have 66/34
  16 A1(40) B1(18)   C1(40) Do not have   E1(2) 68/32
  17 A1(40) B1(18)   C1(40) Do not have   E2(2) 68/32
  18 A1(40) B1(18)   C1(30) Do not have   F1(12) 68/32
  19 A1(40) B1(18)   C1(30) Do not have   F2(12) 68/32
*In the numeric representation water system metal conditioner in 1:() with respect to the solid composition % by weight of whole solid composition 100 % by weight,*2: the weight ratio of metal in metal ingredient and the composition (B) in the composition (A),*3: composition (E) and composition (F).
Table 8
Comparative example The solid of water system metal conditioner becomes to be grouped into*1 Reason as a comparative example
The trivalent chromium compound The nitric acid slaine Aqueous dispersion silica Aqueous resin Append composition*3
20 A3(40) B1(20) C1(40) Do not have Do not have 6 valency chromium are arranged
21 A1(60) Do not have C1(40) Do not have Do not have No nitric acid slaine
22 Do not have B1(60) C1(40) Do not have Do not have There are not 3 valency chromium
23 A1(70) B1(30) Do not have Do not have Do not have No silica
24 A1(79) B1(1) C(20) Do not have Do not have (A)/(B) *4＝99/1
*In the value representation water system metal conditioner in 1:() with respect to the solid composition % by weight of whole solid composition 100 % by weight,*3: composition (E) and composition (F),*4: the weight ratio of metal in metal ingredient and the composition (B) in the composition (A).
Use the surface treatment of water system metal conditioner, the making of surface-treated metal plate:
With above-mentioned each water system metal conditioner of modulating, with the bar coating machine, coating On aforementioned each brassboard that has passed through ungrease treatment, make its drying with 240 ℃ temperature, Make the surface metal disposable plates. In addition, epithelium amount (g/m2) adjustment be with the water system metal surface The solid constituent concentration of inorganic agent is made an appropriateness and is adjusted, with resulting each surface treatment Metallic plate, as breadboard to make a service test.
The performance test of surface-treated metal plate:
(1): plane section corrosion resistance
According to the salt spraytest of JIS-Z-2371, be divided into the EG material and the GI material is carried out 72 hours brine spray, GF material and GL material are then carried out 144 hours brine spray, Observe again its white rust generation situation, take following as one assessment of benchmark do.
＜assessment benchmark 〉
◎: white rust generation area is less than 3% of gross area;
Zero: white rust generation area accounts for gross area more than 3%, less than 10%;
△: white rust generation area accounts for gross area more than 10%, less than 30%;
*: white rust generation area accounts for gross area more than 30%.
(2): electric conductivity
Electric conductivity analyzer Loresta MP MCP-with Mitsubishi Chemical limited company system T350 measures its resistance value, take following as one assessment of benchmark do.
＜assessment benchmark 〉
◎: resistance value is less than 10-3Ω；
Zero: resistance value is 10-3More than the Ω, less than 10-1Ω；
△: resistance value is 10-1More than the Ω, less than 101Ω；
*: the opposing value is 101More than the Ω.
(3): anti-finger printing
The tone of breadboard (L value, a value, b value), (Japanese electric look share is limited with colour difference meter The ZE-2000 processed of company) measure, then, on this breadboard, be coated with rear wiping with vaseline, Tone after the wiping is again with colorimeter measurement, and the difference (△ E) that this tone is measured is with following base Accurate do one assessment.
△E＝((L 2-L 1) 2+(a 2-a 1) 2+(b 2-b 1) 2) 0.5
In the formula, L1、a 1、b 1Before the vaseline coating, L2、a 2、b 2For vaseline is coated with Measured value behind the cloth.
＜assessment benchmark 〉
◎: △ E is less than 2;
Zero: more than the △ E2, less than 3;
△: more than the △ E3, less than 5;
*: more than the △ E5.
Performance test results:
Result of the test such as the table 9 of embodiment of the invention surface-treated metal plate, the comparative example surface The result of the test of processing metallic plate is as shown in table 10.
Table 9
Embodiment Material The water system metal conditioner Arrive plate temperature ℃ The epithelium performance
Kind*1 The epithelium amount*2g/m 2 Corrosion resistance Electric conductivity Anti-finger printing
1 EG 1 0.5 80 ○ ◎ ◎
2 GI 2 0.5 80 ○ ◎ ◎
3 GF 3 0.5 80 ○ ◎ ◎
4 EL 4 0.5 80 ○ ◎ ◎
5 EG 5 0.5 80 ○ ◎ ◎
6 GI 6 0.5 80 ◎ ○ ◎
7 GF 7 0.5 80 ◎ ○ ◎
8 GL 8 0.5 80 ◎ ○ ◎
9 EG 9 0.5 80 ◎ ○ ◎
10 GI 10 0.5 80 ◎ ○ ◎
11 GF 11 0.5 80 ○ ◎ ◎
12 GL 12 0.5 80 ○ ◎ ◎
13 EG 13 0.5 80 ○ ◎ ◎
14 GI 14 0.5 80 ○ ◎ ◎
15 GF 15 0.5 80 ○ ◎ ◎
16 GL 16 0.5 80 ◎ ◎ ◎
17 EG 17 0.5 80 ◎ ◎ ◎
18 GI 18 0.5 80 ◎ ◎ ◎
19 GF 19 0.5 80 ◎ ◎ ◎
20 GL 20 0.5 80 ○ ◎ ○
21 EG 21 0.5 80 ◎ ◎ ◎
22 GI 22 0.5 60 ○ ◎ ◎
23 GF 23 0.5 150 ◎ ◎ ◎
*1: water system metal conditioner embodiment sequence number,*2: dry epithelium weight.
Table 10
Comparative example Material The water system metal conditioner Arrive plate temperature ℃ The epithelium performance
Kind*1 The epithelium amount*2g/m 2 Corrosion resistance Electric conductivity Anti-finger printing
1  EG     20     0.5     80   ◎   ◎   ◎
2  GI     21     0.5     80   ×   ◎   ◎
3  GF     22     0.5     80   ×   ◎   ◎
4  EL     23     0.5     80   ×   ◎   ×
5  EG     24     0.5     80   ×   ◎   ◎
*1: water system metal conditioner comparative example sequence number,*2: dry epithelium weight.
Use the resultant embodiment of water system metal conditioner of the embodiment of the invention 1～19 1～23 surface-treated metal plate, at plane section corrosion resistance, electric conductivity, anti-finger printing all Well. On the other hand, use the water system metal watch of water system metal conditioner comparative example 20 The face inorganic agent, the surface-treated metal plate of resulting comparative example 1 is though demonstrate good As a result, but because it contains the Cr VI all harmful to human body and environment, with purport of the present invention Different; Use the water system metal conditioner of the outer comparative example 21～24 of the scope of the invention, The surface-treated metal plate of the comparative example 2～5 of gained is although electric conductivity and anti-finger printing are all good Good, but the plane section corrosion resistance of its most important performance is comparatively inferior.
As described above, coat metal material with water system metal conditioner of the present invention Its dry rear formed epithelium is treated, not only at corrosion resistance, electric conductivity and anti-finger in the surface All superior on the line, and do not contain human body and the harmful Cr VI of environment, industrially have non-Normal big value.

Claims (8)

1. water-based metal-surface-treating agent that contains (A) 3 valency chromium cpds, (B) nitric acid metal-salt, (C) water-dispersible silica and water, wherein, the not chromyl water-based metal-surface-treating agent of weight ratio (A)/(B) in 5/95～95/5 scope of the middle metal of metal and composition (B) in the composition (A).
2. water-based metal-surface-treating agent according to claim 1, the metal in composition (B) the nitric acid metal-salt are to form at least a metal of selecting among the group from alkaline-earth metal, cobalt, nickel, iron, zirconium and titanium.
3. water-based metal-surface-treating agent according to claim 1 and 2 is characterized in that: with respect to the solid formation deciliter metering of composition (A), composition (B) and composition (C), the solid shape components in proportions of composition (C) is between 10～90 weight %.
4. according to the described water-based metal-surface-treating agent of claim 1 to 3, it is characterized in that: contain (D) aqueous resin that appends composition.
5. water-based metal-surface-treating agent according to claim 4 is characterized in that: aqueous resin is an at least a aqueous resin selected in acrylic resin, urethane resin and Resins, epoxy group.
6. according to the described water-based metal-surface-treating agent of claim 1 to 5, it is characterized in that: contain (E) phosphate cpd that appends composition.
7. according to the described water-based metal-surface-treating agent of claim 1 to 6, it is characterized in that: contain (F) lubricant that appends composition.
8. according to the described water-based metal-surface-treating agent of claim 1 to 7, coat the one side at least of metallic surface, make its drying, and form dry epithelium weight a 0.1～5g/m 2The surface-treated metal plate of epithelium.
CNB011240792A 2000-08-28 2001-08-13 Surface treatment of aquo-metal containing no sexavalence chromium and its treated metal plate for surface treatment Expired - Fee Related CN1182274C (en)

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