CN1240468A - Metal surface treatment composition containing acrylic resin, method for treatment, and treated metal materials - Google Patents
Metal surface treatment composition containing acrylic resin, method for treatment, and treated metal materials Download PDFInfo
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- CN1240468A CN1240468A CN 97180762 CN97180762A CN1240468A CN 1240468 A CN1240468 A CN 1240468A CN 97180762 CN97180762 CN 97180762 CN 97180762 A CN97180762 A CN 97180762A CN 1240468 A CN1240468 A CN 1240468A
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Abstract
A metal surface treatment composition which can improve the corrosion resistance and the tight adhesion to coating films and impart slipperiness. The composition is an aqueous solution, dispersion or emulsion characterized by containing both an acrylic resin having amino and/or ammonium groups, hydroxyl groups and hydrophobic groups and a heavy metal or a salt thereof. The amino or ammonium groups have at least one structure selected from among those represented by general formulae (I) (wherein R1, R2: hydrogen, hydroxyl, substituted or unsubstituted, linear or branched C1-C5 alkyl, or substituted or unsubstituted, linear or branched C1-C5 hydroxyalkyl) and (II) (wherein R3, R4, R5: hydrogen, hydroxyl, substituted or unsubstituted, linear or branched C1-C5 alkyl, or substituted or unsubstituted, linear or branched C1-C5 hydroxyalkyl).
Description
Technical field
The present invention relates to contain the metal surface treating composition, treatment process of acrylic resin and handle eventually after metallic substance, particularly improved erosion resistance, the metal surface treating composition that contains acrylic resin, the treatment process of the binding property of filming or sliding (also claiming " oilness ") and handle eventually after metallic substance.
Background technology
The surface treatment of metallic substance such as canned food box, body of a motor car, steel plate coiled material coating, building materials is carried out with phosphatizing, chromate treating or non-chromate processing etc. on the prior art.For example, when organic epitheliums such as the coating that is coated with metallic surfaces such as iron, zinc, aluminium, tackiness agent,, on the metallic surface, form phosphate coating earlier by phosphatizing as pre-treatment.Then, by organic epitheliums such as coating compositions on it, just can improve erosion resistance, the binding property of filming.Yet, the metal surface treating composition in the phosphatizing method that has earlier etc., for requirement in recent years, its erosion resistance, the binding property of filming or sliding are not necessarily satisfactory.
Therefore, in order to attempt further to improve erosion resistance, adopt usually and after phosphatizing, be coated with base paint, and then the method for coating process is carried out.Yet if coating prime lacquer, although the erosion resistance and the binding property of filming have improved, the application step has increased, and makes operation become numerous and diverse, has also had painting cost to improve such problem simultaneously.
Therefore, as being the metal conditioner of purpose to give high corrosion resistance with film binding property and omission primer painting, the someone has proposed to open such as the spy scheme of " composite film forms and uses metal conditioner " of flat 5-117869 communique.The metal conditioner of above-mentioned patent gazette according to disclosing, being to be made up of a kind of Bonderisation liquid, wherein contains a kind of cationic organic high molecular compound or its salt that contains cationic nitrogen-atoms more than 1, molecular weight 1,000～1,000,000.
In addition, the spy opens in " surface preparation of aluminium and alloy thereof " of clear 51-73938 communique, disclose carry out the surface-treated metal be defined in aluminium etc., to give erosion resistance and the binding property of filming is the metal finishing method of purpose.This metal finishing method, according to record, what use is a kind ofly to form material and the water-soluble titanium compound treatment solution as principal constituent with the organic polymer epithelium that contains water soluble resin such as vinyl-acetic ester, vinylidene chloride, vinylformic acid or emulsion resin.
Yet above-mentioned metal conditioner or facture have improved erosion resistance and the binding property of filming although compare with the prior art metal conditioner, do not reach the level that requires in recent years as yet.
Particularly, making with aluminium or its alloy under the situation of canned food box, above-mentioned metal conditioner etc. have and can not prevent to block, and oilness is short of such problem when the steel plate coiled material be coated with.
Disclosure of the Invention
The objective of the invention is to provide to contain and to improve erosion resistance or the binding property of filming can further be given metal surface treating composition, treatment process and the metallic substance after treatment of the acrylic resin of oilness again.
In order to achieve the above object, the metal surface treating composition that contains acrylic resin involved in the present invention is any among these of water miscible, water dispersible or emulsion, and contain a kind of acrylic resin that contains any hydroxyl again and hydrophobic group in amino or the ammonium at least, and heavy metal or its salt.
Therefore, the inorganic epithelium of being made up of heavy metal or its salt can suppress water-permeable, thereby has improved erosion resistance.And, because amino or ammonium and (weight) metal-complexing in the acrylic resin, thereby above-mentioned inorganic epithelium is by the mutual banded of acrylic resin.Therefore, the cohesion that can prevent inorganic epithelium destroys, also can form the almost application end liner epithelium of homogeneous on the metallic surface.Therefore, also improved the application end liner with epithelium and on the binding property of filming.Application end liner epithelium among the present invention means the epithelium that the above-mentioned inorganic epithelium of acrylic resin banded is formed that passes through that forms on the metallic surface.And then, because the aforesaid propylene acid resin is present in the application end liner almost evenly with on the epithelium surface, thereby can reduce friction resistance, thereby can improve oilness.
Be more preferably, the metal surface treating composition that contains acrylic resin that the present invention relates to, be amino in the described acrylic resin or ammonium have at least following chemical formula (I) or (II) shown in structure person:
(in the formula, R
1, R
2Be hydrogen, hydroxyl, the straight chain that the having of 1～5 carbon replaces or do not have replacement or the alkyl of branch chain, or 1～5 carbon has the straight chain that replaces or do not have replacement or a hydroxyalkyl of branch chain),
(in the formula, R
3, R
4, R
5Be hydrogen, hydroxyl, the straight chain that the having of 1～5 carbon replaces or do not have replacement or the alkyl of branch chain, or 1～5 carbon has the straight chain that replaces or do not have replacement or a hydroxyalkyl of branch chain).
In addition, the molecular weight of acrylic resin is 500～100 among the present invention, 000, be preferably 1,000～20,000.Under the situation of molecular weight less than 500, erosion resistance descends.On the other hand, if molecular weight surpasses 100,000, then wetting ability descends.
And in the present invention, for metal surface treating composition, the content of acrylic resin is 0.01～10g/l, be preferably 0.1～5g/l.Under the situation of the not enough 0.01g/l of acrylic acid content, can not bring into play the binding agent effect, thereby the application end liner is reduced with the physical durability of epithelium.On the other hand, if acrylic resin content surpasses 10g/l, then the application end liner reduces with the binding property of epithelium and metallic surface.
And then the metal surface treating composition that contains acrylic resin that the present invention relates to is that per 1000 molecular weight of described acrylic resin contain 1～10 amino and/or ammonium, 1～10 hydroxyl and 1～5 hydrophobic group person.Under per 1000 molecular weight contain situation less than 1 amino and/or ammonium, wetting ability and the tack of metal reduced; On the other hand, if contained amino and/or the ammonium of per 1000 molecular weight surpasses 10, then erosion resistance descends.
And under per 1000 molecular weight contained situation less than 1 hydroxyl, the wetting ability and the binding property of filming descended.On the other hand, surpass under 10 the situation at the contained hydroxyl of per 1000 molecules, erosion resistance descends.And then the contained hydrophobic group of per 1000 molecular weight is less than under 1 the situation, and erosion resistance and oilness descend.On the other hand, surpass under 5 the situation at the contained hydrophobic group of per 1000 molecular weight, the wetting ability and the binding property of filming descend.
In addition, contain in the metal surface treating composition of acrylic resin, in the described acrylic resin contained amino or ammonium be by make following at least chemical formula (III) or (IV) shown in the monomer copolymerization of structure introduce:
(in the formula, R
6Be hydrogen or methyl,
R
7, R
8Be hydrogen, hydroxyl, the straight chain that the having of 1～5 carbon replaces or do not have replacement or the alkyl of branch chain, or 1～5 carbon has the straight chain that replaces or do not have replacement or a hydroxyalkyl of branch chain,
R
9Be the alkylidene group of 1～5 carbon),
(in the formula, R
10Be hydrogen or methyl,
R
11, R
12Be hydrogen, hydroxyl, the straight chain that the having of 1～5 carbon replaces or do not have replacement or the alkyl of branch chain, or 1～5 carbon has the straight chain that replaces or do not have replacement or a hydroxyalkyl of branch chain,
R
13Be the alkylidene group of 1～5 carbon).
And then in the metal surface treating composition that contains acrylic resin involved in the present invention, contained hydroxyl is to introduce by the monomer copolymerization that makes structure shown in the following at least chemical formula V in the described acrylic resin:
(in the formula, R
14Be the alkylidene group of 1～4 carbon,
R
15Be hydrogen or methyl).
Moreover in the metal surface treating composition that contains acrylic resin involved in the present invention, contained hydrophobic group is to introduce by the monomer copolymerization that makes structure shown in the following at least chemical formula (VI) in the described acrylic resin:
(in the formula, R
16Be straight chain, branch chain or cyclic alkyl, the R of 4～18 carbon
17Be hydrogen or methyl).
Contain the acrylic resin in the metal surface treating composition of acrylic resin among the present invention, be preferably monomeric multipolymer shown below.Promptly, (1) as the Acrylic Acid Monomer that contains amino (ammonium), can enumerate (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) acrylamide, N, N-DMAA, N hydroxymethyl acrylamide, N-methylamino propyl group (methyl) acrylamide, N, N dimethylamine base propyl group (methyl) acrylamide, N-ethylamino-propyl group (methyl) acrylamide, N, N dimethylamine base propyl group (methyl) acrylamide and these chloride salt etc.
In addition, (2) can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2,3-dihydroxyl propyl ester etc. as the Acrylic Acid Monomer that contains hydroxyl.
(3) as the monomer that contains hydrophobic group, can enumerate (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, vinylbenzene, to t-butyl styrene, Vinyl toluene, vinylphenol, (methyl) benzyl acrylate etc.
(4) in addition,, can enumerate vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, vinyl cyanide etc. as the monomer that can further add.
The copolymerization ratio of the multipolymer that above-mentioned monomer is formed is: the Acrylic Acid Monomer that contains amino (ammonium) is 5～60% (weight), the Acrylic Acid Monomer that contains hydroxyl is 20～80% (weight), the monomer that contains hydrophobic group is 5～50% (weight), and other monomer is 0～30% (weight).Be preferably, the Acrylic Acid Monomer that contains amino (ammonium) is 20～40% (weight), and the Acrylic Acid Monomer that contains hydroxyl is 30～60% (weight), and the monomer that contains hydrophobic group is 20～40% (weight).
In the above-mentioned multipolymer, contain under the situation of copolymerization ratio less than 5% (weight) of Acrylic Acid Monomer of amino (ammonium), wetting ability descends, and the connectivity decline between the inorganic epithelium formed of acrylic resin and heavy metal or its salt.On the other hand, the copolymerization ratio of Acrylic Acid Monomer that contains amino (ammonium) in the above-mentioned multipolymer is if surpass 60% (weight), and then erosion resistance descends.
In addition, contain in the above-mentioned multipolymer under the situation of copolymerization ratio less than 20% (weight) of Acrylic Acid Monomer of hydroxyl, the wetting ability and the binding property of filming descend.On the other hand, the copolymerization ratio that contains the Acrylic Acid Monomer of hydroxyl in the above-mentioned multipolymer surpasses under the situation of 80% (weight), and erosion resistance descends.
And then, containing in the above-mentioned multipolymer under the situation of monomeric copolymerization ratio less than 5% (weight) of hydrophobic group, oilness and erosion resistance descend.On the other hand, the monomeric copolymerization ratio that contains hydrophobic group in the above-mentioned multipolymer surpasses under the situation of 50% (weight), and the wetting ability and the binding property of filming descend.
Heavy metal
In addition, in the metal surface treating composition that contains acrylic resin that the present invention relates to, described heavy metal is at least a kind in zirconium (Zr), molybdenum (Mo), tungsten (W), niobium (Nb), nickel (Ni), cobalt (Co), manganese (Mn), the tantalum (Ta).The supply source of above-mentioned heavy metal is preferably the cooperation fluorochemical of above-mentioned heavy metal, in addition, also can enumerate nitrate, phosphoric acid salt.
For the metal surface treating composition that contains acrylic resin that the present invention relates to, heavy metal cooperates the content of fluorochemical to be preferably 0.01～10g/l.Heavy metal cooperates under the situation that contains quantity not sufficient 0.01g/l of fluorochemical, and erosion resistance descends.On the other hand, heavy metal cooperates the content of fluorochemical to surpass under the situation of 10g/l, and erosion resistance also can descend.
The metal surface treating composition that contains acrylic resin that the present invention relates to also can further contain phosphoric acid or phosphoric acid salt.As phosphoric acid or phosphoric acid salt, can enumerate H
3PO
4, Na
3PO
4, Na
2HPO
4, NaH
2PO
4, (NH
4)
3PO
4Deng.For the above-mentioned metal surface treating composition that contains acrylic resin, phosphoric acid or phosphatic content are 0.01～20g/l, are preferably 0.05～0.1g/l.Under phosphoric acid or the phosphatic situation that contains quantity not sufficient 0.01g/l, erosion resistance descends.Phosphoric acid or phosphatic content are if surpass 20g/l, and the binding property of then filming descends.
The metal surface treating composition that contains acrylic resin that the present invention relates to can also contain following etching reagent or etching auxiliary agent in case of necessity.
Etching reagent
As etching reagent, can enumerate fluorochemical and salt thereof.And this etching reagent also can contain 0.005～0.5g/l for metal surface treating composition.Under the situation that contains quantity not sufficient 0.005g/1 of etching reagent, the etching deficiency, the application end liner forms on the metallic surface unsatisfactorily with epithelium.On the other hand, the content of etching reagent then can make etching excessive if surpass 0.5g/l.
The etching auxiliary agent
As the etching auxiliary agent, can enumerate hydrogen peroxide (H
2O
2), nitrous acid (HNO
3), HBF
4And salt.And hydrogen peroxide (H in this etching auxiliary agent
2O
2), nitrous acid (HNO
2) or its salt, for metal surface treating composition, also can contain 0.005～5g/l.Contain under the situation of quantity not sufficient 0.005g/l, erosion resistance descends.On the other hand, even content surpasses 5g/l, erosion resistance also can descend.In addition, HBF
4Or its salt is preferably and contains 0.003～0.2g/l for metal surface treating composition.Contain under the situation of quantity not sufficient 0.003g/l, erosion resistance descends.On the other hand, even content surpasses 0.2g/l, erosion resistance also can descend.
Treatment condition and treatment process
The metal surface treating method that the present invention relates to is that the above-mentioned metal surface treating composition that contains acrylic resin is contacted with the metallic surface, uses water rinse, drying then.In addition, the pH of above-mentioned metal surface treating composition is about 2.0～5.0, is preferably 2.5～3.5.At this moment, the adjustment of pH is carried out with NaOH, ammonia soln, nitric acid etc.The temperature that contacts of metal surface treating composition of the present invention and metallic substance is normal temperature (for example 20 ℃)～90 ℃, is preferably 35～65 ℃.In general, be that the high more person of contact temperature is short more the duration of contact of metallic substance and the metal surface treating composition that contains acrylic resin involved in the present invention.
Under the situation of coating that metallic substance is sprayed, general is contacts about 5 second～5 minute with composition of the present invention, be preferably for 10～60 seconds.Using under the situation of pickling process time that need be longer than above-mentioned duration of contact.In addition, also can use flow coat method, rolling method contact.
As mentioned above, implement the surface-treated metallic substance, just washed, entered drying step.When drying temperature was 150 ℃ of 150～240 ℃, drying temperature less than, erosion resistance descended.About described washing, be at metallic substance with after composition of the present invention contacts, the metallic substance after the surface treatment is washed, to remove the present composition that does not become the chemical conversion epithelium.According to the present invention, can obtain inorganic-organic transformation epithelium with a step treatment process.
And then the surface-treated metal material that the present invention relates to is to be feature to have carried out surface treatment with the above-mentioned metal surface treating composition that contains acrylic resin.
Optimal morphology is implemented in invention
Below enumerate embodiment and comparative example, specifically describe the present invention.
Embodiment 1～11 and comparative example 1～3
(1) object being treated
Al-Mn system (JIS-A3004) aluminium alloy plate carries out DI processing and waits the shaping can body that obtains.
(2) surface treatment epithelium evaluation method
A) anti-boiling water blackening
The boiling water blackening here, mean in the canned food box, when the boiling water treating of the tap water that carries out for sterilization etc., the not starting material of application part and the metal interaction in the water and become the phenomenon of black, anti-boiling water blackening is exactly the tolerance to this phenomenon.
Composition with present embodiment and comparative example has carried out the surface-treated metallic substance, and dipping carried out ocular estimate by following benchmark after 30 minutes in the boiling tap water.
Zero: the outward appearance no change
△: blackening a little
*: blackening
B) oilness on surface treatment epithelium surface
Carried out the surface-treated metallic substance with the method for present embodiment and on " HEIDON-14 type " trier, measured kinetic friction coefficient in 50g, stylus 300mm/ minute with 5mm steel ball, load.
Below zero: 0.6
△：0.6～0.8
*: surpass 0.8 situation
C) the outer binding property of filming
Be coated with device with rod and handling application BASF AG system coating (EB-70-001 N150mg/m on the metallic substance
2/ EB-69-002N 60mg/m
2).Then, the metallic substance of application carries out the wedge shape bending machining like this, and crooked position carries out band shape with Nichiban corporate system Sello-Tape machine to be peeled off, and carries out filming of this moment by following benchmark and peels off evaluation.
Zero: band is peeled off the not enough 15mm of width
△: band is peeled off width 15～20mm
*: band is peeled off width and is surpassed 20mm
(3) metal finishing condition
(embodiment 1)
Al-Mn system (JIS-A 3004) is shaped jar with the acid degreasing agent (" SurfCleaner NHC 250 ", Japanese Paint corporate system) of 30g/l concentration after degreasing under 75 ℃, the condition of spraying in 60 seconds, washing.Then, at zirconium phosphate is that treatment agent (" Alsurf440 " Japanese Paint corporate system) is diluted in the aqueous solution of 20g/l, water soluble acrylic resin 0.5g/l shown in the dissolving table 1 makes metal surface treating composition of the present invention, carries out spraying in 20 seconds with this composition at 50 ℃ and handles.Use the tap water rinsing then, carry out 2 minutes heat dryings at 190 ℃.Its evaluation result is listed in the table 3.
(embodiment 2～11 and comparative example 1～3)
Embodiment 2～11 and comparative example 1～3rd cooperate fluorochemical to make metal surface treating composition by the use level shown in the table 2 water soluble acrylic resin shown in the table 1 and heavy metal, carry out surface treatment with these compositions according to the foregoing description 1 again.Its evaluation result is listed in the table 3.Table 1
The water soluble acrylic resin
Copolymer kind copolymerization ratio (weight ratio) molecular weight (Mn) A-1 NVP/DMAPAA/NBA 60,/20,/20 3000 A-2 NVP/DMAEA/ST 50,/30,/20 6000 A-3 NVP/DMAPMA/EHA/HEA 30,/30,/30,/10 4000 A-4 VIZ/DMAAm/LMA 40,/30,/30 5000 A-5 VP/DMAAm/EHA 30,/40,/30 3000 B-1 HEA/NBA 80,/20 8000 B-2 HEMA/DMAPMA 80,/20 4000 notes) HEA: acrylic acid 2-hydroxy methacrylate HEMA: 2-hydroxyethyl methacrylate HBA: acrylic acid-4-hydroxyl butyl ester DMAEA: acrylic acid N; N-dimethylamino ethyl ester DMAEMA:methacrylic acid N; N-dimethylamino ethyl ester DMAPAA:N; TMSDMA N dimethylamine base propyl group acrylamide DMAPMA:N, TMSDMA N dimethylamine base propyl methyl acid amides NBA:n-butyl acrylate EHA:2-EHA CHMA:cyclohexyl methacrylate LMA:lauryl methacrylate SMA:methacrylic acid stearyl ester TBMA:Tert-butyl Methacrylate table 2
Water soluble acrylic resin's heavy metal compound
Kind content (g/l) kind content (g/l)
1 A-1,0.5 ALSURF, 440 20 real 2 A-2,0.1 ALSURF 440 20
3 A-3,1.0 ALSURF 440 20 execute 4 A-4,0.5 ALSURF 440 20
5 A-5,0.5 ALSURF, 440 20 examples, 6 A-1 0.5 (NH4) 2Z,rF6 1
7 A-1,5.0 ALSURF, 440 20 to 1 B-1,0.5 ALSURF 440 20 than 2 B-2,0.5 ALSURF, 440 20 examples 3--ALSURF 440 20 annotates: ALSURF 440: zirconium phosphate is treatment agent, Japanese Paint company tabulation 3
Evaluation result
The anti-boiling water blackening oilness binding property of filming outward
1 zero zero zero real 2 zero zero zero
3 zero zero zero execute 4 zero zero zero
5 zero zero zero examples 6 zero zero zero
7 zero zero zero to 1 * * * than 2 zero * △ example 3 zero * *
From these results as can be seen, according to metal finishing composition of the present invention, its anti-boiling water blackening, oilness, any performance of filming in the binding property is compared with prior art and is improved outward.
The possibility of using on the industry
According to the metal surface treating composition that the present invention relates to, because heavy metal or its salt composition Inorganic epithelium can suppress water penetration, thereby has improved corrosion resistance. In addition, in the acrylic resin Amino (ammonium) since with (weight) metal-complexing, thereby make above-mentioned inorganic epithelium pass through propylene Acid resin links mutually. Therefore, can prevent that the cohesion of inorganic epithelium from destroying, again can be at metal watch Form almost uniform application end liner epithelium on the face. Therefore, also improved application end liner epithelium With the cohesive of filming outward. Here, the application end liner means with epithelium and forms in the metal surface The epithelium that the above-mentioned inorganic epithelium that links by acrylic resin forms. In addition, because aforesaid propylene Acid resin is present in almost evenly the application end liner and uses the epithelium surface, thereby can make under the frictional resistance Fall, and lubricity is improved.
Therefore, according to the metal surface treating composition that the present invention relates to, compare with prior art, Can significantly improve corrosion resistance or the cohesive of filming, also can further give lubricity. In addition, According to metal surface treating composition of the present invention, making Tinned food container with aluminium or its alloy In the situation, can prevent from blocking (jamming), and when coiled material is coated with, can give lubricity.
And metal surface treating composition of the present invention can be used for Tinned food container, automobile The Treatment of Metal Surface of vehicle body, steel plate coiled material coating, building materials etc.
Claims (27)
1. the metal surface treating composition that contains acrylic resin, it is characterized in that be water miscible, water dispersible or emulsion in any, and contain a kind of acrylic resin that contains any hydroxyl again and hydrophobic group in amino or the ammonium at least, and heavy metal or its salt.
2. the metal surface treating composition that contains acrylic resin, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 record, amino in the described acrylic resin or ammonium have at least following chemical formula (I) or (II) shown in structure
(in the formula, R
1, R
2Be hydrogen, hydroxyl, the straight chain that the having of 1～5 carbon replaces or do not have replacement or the alkyl of branch chain, or 1～5 carbon has the straight chain that replaces or do not have replacement or a hydroxyalkyl of branch chain),
(in the formula, R
3, R
4, R
5Be hydrogen, hydroxyl, the straight chain that the having of 1～5 carbon replaces or do not have replacement or the alkyl of branch chain, or 1～5 carbon has the straight chain that replaces or do not have replacement or a hydroxyalkyl of branch chain).
3. the metal surface treating composition that contains acrylic resin, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 or claim 2 record, per 1000 molecular weight of described acrylic resin contain 1～10 at least a kind of selecting from amino and ammonium, 1～10 hydroxyl and 1～5 hydrophobic group.
4. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 or claim 2 record, the molecular weight of acrylic resin is 500～100,000.
5. metal surface treating composition, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 or claim 2 record, for described metal surface treating composition, the content of acrylic resin is 0.01～10g/l.
6. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 or claim 2 record, for described metal surface treating composition, the content of acrylic resin is 0.1～5g/l.
7. the metal surface treating composition that contains acrylic resin, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 record, in the described acrylic resin contained amino or ammonium be by make following at least chemical formula (III) or (IV) shown in the monomer copolymerization of structure introduce
(in the formula, R
6Be hydrogen or methyl,
R
7, R
8Be hydrogen, hydroxyl, the straight chain that the having of 1～5 carbon replaces or do not have replacement or the alkyl of branch chain, or 1～5 carbon has the straight chain that replaces or do not have replacement or a hydroxyalkyl of branch chain,
R
9Be the alkylidene group of 1～5 carbon),
(in the formula, R
10Be hydrogen or methyl,
R
11, R
12Be hydrogen, hydroxyl, the straight chain that the having of 1～5 carbon replaces or do not have replacement or the alkyl of branch chain, or 1～5 carbon has the straight chain that replaces or do not have replacement or a hydroxyalkyl of branch chain,
R
13Be the alkylidene group of 1～5 carbon).
8. the metal surface treating composition that contains acrylic resin, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 record, at least one is to introduce by the monomer copolymerization that makes structure shown in the following chemical formula V in the contained hydroxyl in the described acrylic resin
(in the formula, R
14Be the alkylidene group of 1～4 carbon,
R
15Be hydrogen or methyl).
9. the metal surface treating composition that contains acrylic resin, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 record, at least one is to introduce by the monomer copolymerization that makes structure shown in the following chemical formula (VI) in the contained hydrophobic group in the described acrylic resin
(in the formula, R
16Be the straight chain of 4～18 carbon, branch chain or cyclic alkyl, R
17Be hydrogen or methyl).
10. the metal surface treating composition that contains acrylic resin, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 record, the monomer copolymerization ratio that constitutes the acrylic resin multipolymer of described acrylic resin is, the Acrylic Acid Monomer that contains amino and/or ammonium is 5～60% (weight), the Acrylic Acid Monomer that contains hydroxyl is 20～80% (weight), and the monomer that contains hydrophobic group is 5～50% (weight), and other monomer is 0～30% (weight).
11. contain the metal surface treating composition of acrylic resin, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 record, constituting the Acrylic Acid Monomer that contains amino and/or ammonium in the acrylic resin multipolymer of described acrylic resin is 20～40% (weight), the Acrylic Acid Monomer that contains hydroxyl is 30～60% (weight), and the monomer that contains hydrophobic group is 20～40% (weight).
12. contain the metal surface treating composition of acrylic resin, it is characterized in that in the metal surface treating composition that contains acrylic resin of claim 1 record, described heavy metal is in zirconium, molybdenum, tungsten, niobium, nickel, cobalt, manganese, the tantalum at least a kind.
13. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 1 record, heavy metal is at least a in zirconium, niobium, manganese, the tantalum.
14. metal surface treating composition, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 12 or claim 13 record, the source of supply of heavy metal is at least a in the cooperation fluorochemical, nitrate, phosphoric acid salt of respectively this heavy metal.
15. metal surface treating composition, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 12 or claim 13 record, for described metal surface treating composition, it is 0.01～10g/l that heavy metal cooperates the content of fluorochemical.
16. metal surface treating composition is characterized in that, in claim 1～claim 15 in the metal surface treating composition that contains acrylic resin of any one record, further contains at least in phosphoric acid or the phosphoric acid salt any.
17. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 16 record, described phosphoric acid or phosphoric acid salt are H
3PO
4, Na
3PO
4, Na
2HPO
4, NaH
2PO
4, (NH
4)
3PO
4Deng.
18. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 16 record, for described metal surface treating composition, phosphoric acid or phosphatic content are 0.01～20g/l.
19. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of any one record, further contains etching reagent in claim 1～claim 15.
20. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 19 record, described etching reagent is any in hydrogen fluoride or its salt at least.
21. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 19 record, the content of described etching reagent for metal surface treating composition of the present invention, is 0.005～5g/l.
22. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of any one record, further contains the etching auxiliary agent in claim 1～claim 15.
23. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 22 record, described etching auxiliary agent is hydrogen peroxide, nitrous acid, HBF at least
4And it is any in the salt.
24. metal surface treating composition, it is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 23 record, the content of described hydrogen peroxide, nitrous acid or its salt is 0.005～5g/l for described metal surface treating composition.
25. metal surface treating composition is characterized in that, in the metal surface treating composition that contains acrylic resin of claim 23 record, and described HBF
4Or the content of its salt is 0.003～0.2g/l for metal surface treating composition of the present invention.
26. metal surface treating method is characterized in that, the metal surface treating composition that contains acrylic resin of any one record contacts with the metallic surface in claim 1～claim 25, with after washing, drying.
27. the metallic substance after surface treatment is characterized in that, has carried out surface treatment with the metal surface treating composition that contains acrylic resin of any one record in claim 1～claim 25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180762 CN1240468A (en) | 1996-10-21 | 1997-10-13 | Metal surface treatment composition containing acrylic resin, method for treatment, and treated metal materials |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP278366/1996 | 1996-10-21 | ||
| JP265552/1997 | 1997-09-30 | ||
| CN 97180762 CN1240468A (en) | 1996-10-21 | 1997-10-13 | Metal surface treatment composition containing acrylic resin, method for treatment, and treated metal materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1240468A true CN1240468A (en) | 2000-01-05 |
Family
ID=5177854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97180762 Pending CN1240468A (en) | 1996-10-21 | 1997-10-13 | Metal surface treatment composition containing acrylic resin, method for treatment, and treated metal materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1240468A (en) |
-
1997
- 1997-10-13 CN CN 97180762 patent/CN1240468A/en active Pending
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