CN103717686A - Aqueous composition for metal surface treatment, method for metal surface treatment using composition, and method for producing metal material having film, as well as metal surface treatment film using same - Google Patents
Aqueous composition for metal surface treatment, method for metal surface treatment using composition, and method for producing metal material having film, as well as metal surface treatment film using same Download PDFInfo
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- CN103717686A CN103717686A CN201280033230.7A CN201280033230A CN103717686A CN 103717686 A CN103717686 A CN 103717686A CN 201280033230 A CN201280033230 A CN 201280033230A CN 103717686 A CN103717686 A CN 103717686A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
Abstract
[Problem] To provide means for dramatically improving Bi precipitation and preventing deterioration of metal film appearance in the form of fisheyes, dimples, and the like. [Solution] An aqueous composition for metal surface treatment is characterized in being an aqueous composition for metal surface treatment containing a cationic resin emulsion, wherein the dispersoid of the cationic resin emulsion comprises an amino compound of a modified epoxy resin, a block polyisocyanate, and a tin compound represented by formula 1 (1) (where in formula 1, m is 4 or greater and n is between 0 and 10), and the dispersion medium of the cationic resin emulsion contains Bi ions.
Description
Technical field
The present invention relates to can for metallic substance, particularly complex-shaped metal constituting body form the epithelium that can give excellent erosion resistance and appearance of film metal finishing use composition, used its metal surface treating method and with the manufacture method of the metallic substance of epithelium and the metal finishing epithelium that has used them.
Background technology
In the past, as for various metallic substance, particularly complex-shaped metal constituting body being given to the method for excellent erosion resistance, general what use was to have high all electrodeposition-coatings of plating property.But therefore, if the electrodeposition coating that just utilizes electrodeposition-coating to obtain often cannot obtain required erosion resistance, in previous stage of electrodeposition-coating, as the way of standard, be that application zinc phosphate system changes into process and waits the coated surface of the type that changes into process.
Electrodeposition-coating can be divided into haply by coated article being carried out to the negatively charged ion electrodeposition-coating that anode electrolysis makes to film and separates out in the water-borne coatings containing anionic property resin emulsion, by coated article being carried out to the catholyte cationic electrodeposition of separating out that makes to film in the water-borne coatings containing resin cation (R.C.) emulsion, apply, yet for the erosion resistance that improves Ferrious material material, favourable way is not worry that in electrolysis treatment matrix metal applies to the cationic electrodeposition of stripping in coating, for belonging to, take the car body of ferrous material as main metal constituting body, trolley part, family's electrical article, material of construction etc. are applied widely cationic electrodeposition and are applied.
Cationic electrodeposition is coated in a long history in market, in the past by coordinating chromium cpd or lead compound to guarantee rust-preventing characteristic.But, even if rust-preventing characteristic is also abundant not like this, therefore must carries out zinc phosphate system and change into the surface treatments such as processing.ELV standard because of environmental standard, particularly Europe can not re-use chromium cpd, lead compound in fact now, is therefore studying alternative composition, finds that bismuth compound is effective, discloses specifically the patent documentation of enumerating below.
Patent documentation 1(Japanese kokai publication hei 5-32919) in, disclose a kind of electrocoating paint resin combination, it is characterized in that, contained at least a kind of pigment that applies bismuth compound.
Patent documentation 2(WO99/31187) in, disclose a kind of cation electric deposition paint composition, it is characterized in that, comprised the aqueous dispersion paste that has coordinated the aqueous liquid dispersion that modified with organic acids bismuth compound exists with non-water-soluble form.
Patent documentation 3(TOHKEMY 2004-137367) in, disclose a kind of cation electrodeposition coating, it is characterized in that the resin combination that comprises colloidal bismuth metal and there is sulfonium base and propargyl.
Patent documentation 4(TOHKEMY 2007-197688) in, a kind of electrocoating paint was disclosed, it is the electrocoating paint that contains the particle that is selected from least a kind of metallic compound in bismuth hydroxide, zirconium compounds and tungsten compound, it is characterized in that, this metallic compound is 1～1000nm.
Patent documentation 5(Japanese kokai publication hei 11-80621) in, disclose a kind of cation electric deposition paint composition, it is characterized in that, contained aliphatics alkoxyl group bismuth carboxylate salt brine solution.
Patent documentation 6(Japanese kokai publication hei 11-80622) in, a kind of cation electric deposition paint composition was disclosed, it is the aqueous solution of organic acid bismuth salt of more than two kinds, it is characterized in that, containing at least a kind of this organic acid is the organic acid bismuth salt brine solution of aliphatic hydroxyl carboxylic acid.
Patent documentation 7(Japanese kokai publication hei 11-100533) in, disclose a kind of cation electric deposition paint composition, it is characterized in that, contained the bismuth lactate that uses the lactic acid of the L body in the middle of the optical isomer comprise more than 80% to form.
Patent documentation 8(Japanese kokai publication hei 11-106687) in, a kind of cation electric deposition paint composition was disclosed, it is the aqueous solution of organic acid bismuth salt of more than two kinds, it is characterized in that, containing at least a kind of this organic acid is the organic acid bismuth salt brine solution of aliphatics alkoxyl group carboxylic acid.
These patent documentations can be divided into patent documentation 1～4 and patent documentation 5～8 haply.; patent documentation 1～4 is characterised in that; being dispersed with respect to water-borne coatings is insoluble bismuth compound or bismuth metal; patent documentation 5～8 is characterised in that; to major general's bismuth compound, be dissolved into the residual degree that there is no solids component, adding in coating after namely making the state of Bi ion.
But the bismuth compound in these patent documentations is to play a role as the alternative of chromium cpd or lead compound all the time, cannot be to change in the surface-treated such as processing situation to obtain sufficient erosion resistance not carrying out zinc phosphate.In fact, in these patent documentations, only disclose to change into the embodiment that is combined as prerequisite of processing with zinc phosphate system.
And on the other hand, recently studying following technology, that is, utilize bismuth compound method in addition further to improve erosion resistance, even if do not implement zinc phosphate system, change into the surface treatments such as processing, also can utilize 1 layer of coating to guarantee enough erosion resistances.
For example, at patent documentation 9(TOHKEMY 2008-274392) in, a kind of formation method of surface treatment epithelium was disclosed, it is to apply by the multistep step mode with at least 2 stages on metal base the method that epithelium forming agent forms epithelium, it is characterized in that, (i) epithelium forming agent contains to add up to amount of metal (mass conversion) to count 30～20, the zirconium compounds of 000ppm and as required containing of use are selected from titanium, cobalt, vanadium, tungsten, molybdenum, copper, zinc, indium, aluminium, bismuth, yttrium, lanthanide series metal, the compound of the metal of at least a kind (a) in alkalies and alkaline earth, resinous principle with 1～40 quality %, (ii) by usining metal base, as negative electrode, in the lower energising of the voltage (V1) of 1～50V, within 10～360 seconds, carry out the coating of first stage, then by usining metal base, as negative electrode, in the lower energising of the voltage (V2) of 50～400V, within 60～600 seconds, carry out the later coating of subordinate phase, also have (iii) voltage (V2) to be at least 10V with the difference of voltage (V1).
In addition, patent documentation 10(TOHKEMY 2008-538383) in, a kind of method of forming layered coating film was disclosed, comprise: dipping process, in following water-based paint compositions, flood coated article,, be to contain (A) rare earth compound, (B) to have the matrix resin of cation radical and (C) water-based paint compositions of solidifying agent, in this water-based paint compositions, with respect to coating solids component, to be scaled rare earth metal be 0.05～10 % by weight to the amount of contained (A) rare earth compound; Pretreatment procedure, in this water-based paint compositions, the coated article of usining applies the voltage of not enough 50V as negative electrode; And electrodeposition-coating operation, in this water-based paint compositions, the coated article of usining applies the voltage of 50～450V as negative electrode.
Patent documentation 11(TOHKEMY 2010-24471) in, a kind of method of forming layered coating film was disclosed, to impregnating metal base material in the aqueous solution of the organic acid salt that contains bismuth or inorganic acid salt, as the first operation, by usining this metal base, as negative electrode, carry out electrolysis and form bismuth compound tunicle, as the second operation, on this tunicle, utilize cationic electrodeposition to apply and form electrodeposition coating.
What the zinc phosphate system recording in these patent documentations 1～8 changed into record in the treatment solution composition that applies in the processings surface treatment of etc.ing, patent documentation 9～11 can be change into the surface treatments such as processing and guarantee in the treatment solution composition of sufficient erosion resistance not carrying out zinc phosphate, as common technology, containing the catalyzer that is useful on the cross-linking and curing reaction that promotes aqueous resin, contribute to the raising of cross-linking density, the reduction of solidification value etc.
As catalyzer, generally use lead compound, tin compound.Wherein, in recent years due to the toxicity of lead compound, generally use tin compound, also can be as the present invention or patent documentation 9, and with the compound that can expect catalytic effect.
Contained tin compound can be divided into 2 kinds haply.
The use of the tin compound of solid state has been shown in the embodiment of patent documentation 1,4,9,11, patent documentation 12～14.
In the embodiment of patent documentation 5～8, patent documentation 15～17, provided the use of liquid tin compound.
As the tin compound of solid state, can enumerate the use of Dibutyltin oxide, dioctyl tin oxide, Mono-n-butyltin, single octyl group stannic oxide etc.
As liquid tin compound, can enumerate the use of the aromatic carboxylic acid esters, tin alkyl soap, tin alkyl (alkyl sulfhydryl) etc. of dibutyltin diacetate, tin alkyl.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 5-32919 communique
Patent documentation 2:WO99/31187 communique
Patent documentation 3: TOHKEMY 2004-137367 communique
Patent documentation 4: TOHKEMY 2007-197688 communique
Patent documentation 5: Japanese kokai publication hei 11-80621 communique
Patent documentation 6: Japanese kokai publication hei 11-80622 communique
Patent documentation 7: Japanese kokai publication hei 11-100533 communique
Patent documentation 8: Japanese kokai publication hei 11-106687 communique
Patent documentation 9: TOHKEMY 2008-274392 communique
Patent documentation 10: TOHKEMY 2008-538383 communique
Patent documentation 11: TOHKEMY 2010-24471 communique
Patent documentation 12: Japanese kokai publication hei 5-65438 communique
Patent documentation 13: TOHKEMY 2008-231142 communique
Patent documentation 14: TOHKEMY 2004-269582 communique
Patent documentation 15: Japanese Patent Publication 61-9986 communique
Patent documentation 16: Japanese kokai publication hei 5-65439 communique
Patent documentation 17: TOHKEMY 2004-123942 communique
Summary of the invention
Invent problem to be solved
The inventor etc. have carried out various research to these conventional arts, result is reached following conclusion,, in order to be to be coated on metallic substance and to form the epithelium of giving sufficient erosion resistance with 1 layer in the situation that of changing into the pre-treatments such as epithelium not carrying out zinc phosphate, the most effective way remains application Bi.In addition the action effect for Bi has carried out research again.
In addition, what as the action effect of Bi, paid close attention to is the function of curing catalysts and the corrosion-resisting function of matrix metal as resin in the past, and in conventional art, although can expect the function as curing catalysts to a certain extent, yet very insufficient for the corrosion-resisting function of matrix metal, only have and bring into play to greatest extent this effect, the solution that just can bring problem, has advanced research accordingly.
Corrosion-resisting function for matrix metal, Bi must be present in the face with metallic contact, must be present in the interface of base metal surface and epithelium, yet Bi composition is scattered in epithelium equably in conventional art, infers in base metal surface and be not pre-existing in the Bi that is enough to bring into play erosion resistance.
In addition, the inventor etc. have confirmed that following reaction mechanism is most suitable, that is, utilize low voltage catholyte that Bi reduction is separated out in same body lotion, then utilize high-voltage catholyte that the diffusion of Bi ion is become the inadequate stage, this pH raises and causes cationic resin to be separated out.
Specifically, the epithelium obtaining thus has the curing catalytic capability of the resin that Bi has certainly, and confirms the Bi because existing with greater concn in base metal surface, can also improve fully the erosion resistance of matrix metal.
But, in previous methods, there is following problem.As previously mentioned, in this law (multistep electrolysis mode), adopt and first utilize low voltage catholyte to make Bi reduction separate out, then separate out the operation of cationic resin.Here, improve the Bi property separated out and can cause the Bi amount of separating out that obtains being in advance enough to obtain essential erosion resistance, the short period of time that can realize like this low voltage treated state, the i.e. reduction of productive raising or cost.Thus, the first object of the present invention is, a kind of method that improves significantly the property separated out of Bi is provided.In addition,, in this law (multistep electrolysis mode), according to differences such as conditions, have the situation that the appearance of films such as shrinkage cavity or seediness worsen.So the second object of the present invention is, a kind of method that prevents that the appearance of films such as shrinkage cavity or seediness from worsening is provided.
For the method for dealing with problems
The inventor etc. check various cationic resins, solidifying agent and curing catalysts, for the combination that can reach above-mentioned the first object and the second object, check.Consequently, the discoveries such as the inventor, by adopting cationic emulsion as composition, and when there is bismuth ion in making the dispersion agent of emulsion, as the dispersate of emulsion, become the combination of the specific cationic resin curing agent of component selections curing catalysts, just can reach described object, thereby complete the present invention.Specifically, be following invention (1)～(10).
The present invention (1) provides a kind of metal finishing use composition, it contains cationic resin emulsion, it is characterized in that, the dispersate of cationic resin emulsion contains the tin compound shown in the amides of modified epoxy (particularly preferably bisphenol type), blocked polyisocyanates and formula 1:
Here, in formula 1, m is more than 4, and n is that more than 0 and below 10, the dispersion agent of cationic resin emulsion contains Bi ion.And, also can contain as required pigment particles.In addition, the dispersate of emulsion also can contain resin beyond the amides of modified epoxy (such as other cationic resin or nonionic resin etc.).
The present invention (2) provides the metal finishing use composition of following described invention (1), it is characterized in that, the m in formula 1 is more than 7.
The present invention (3) provides following described invention (1) or the metal finishing use composition of (2), it is characterized in that, the m in formula 1 is 7.
The present invention (4) provides the metal finishing use composition of following described invention (3), it is characterized in that, the m in formula 1 be 7 and n be 0.
The present invention (5) provides the metal finishing use composition of any one in following described invention (1)～(4), it is characterized in that, all the content of the tin compound in compositions is 0.01～1 % by weight as Sn amount.
The present invention (6) provides the metal finishing use composition of any one in following described invention (1)～(5), it is characterized in that, it is the composition using in the multistep current flow method in same body lotion.
The present invention (7) provides a kind of metal surface treating method, it is characterized in that, by in the waterborne compositions of metal to be treated material soaking any one in described invention (1)～(6), utilize and to using metal to be treated material and as the electrolysis treatment operation of negative electrode, epithelium is separated out on metallic substance.
The present invention (8) provides the metal surface treating method of following described invention (7), it is characterized in that, electrolysis treatment operation has: the first operation, in surface is immersed in to described invention (1)～(6) by purifying metallic substance in the waterborne compositions of any one after, or in dipping, usingd this metallic substance as negative electrode, the following electrolysis of voltage 15V 10～120 seconds; The second operation is then implemented after described the first operation in same body lotion, and under voltage 50～400V, electrolysis is 30～300 seconds.
The present invention (9) provides a kind of manufacture method of the metallic substance with epithelium, it is characterized in that, has the electrolysis treatment operation of described invention (7) or (8).
The present invention (10) provides a kind of metal finishing epithelium, and it utilizes the manufacture method of described invention (9) to obtain, and it is characterized in that, as Bi in metal Bi and oxidation Bi, is attached with 20～250mg/m
2, total leather film thickness is 5～40 μ m, and the Bi adhesion amount with the metallic substance side of counting from the center of leather film thickness be B is that A is that the Bi of more than 55% (B/A>=55%) adheres to distribution with respect to total Bi adhesion amount.
Accompanying drawing explanation
Fig. 1 means the figure with the relation of application time about the Bi amount of the separating out waterborne compositions of embodiment and comparative example, while applying certain voltage.
The figure of the distribution of B/A when Fig. 2 means the waterborne compositions that uses embodiment 1.
Embodiment
< < metal surface treating method > >
(applicable object)
Metal finishing use composition of the present invention prevents that the object that various metals are corroded from being used.Metallic substance is not particularly limited, yet can enumerate the ferrous materials such as cold-rolled steel sheet, hot-rolled steel sheet, casting material, steel pipe, on these ferrous materials, implemented that electrogalvanized is processed and/or aluminium is that material, aluminium alloy plate, the aluminium of plating is that casting material, magnesium alloy plate, magnesium are casting material etc.Be specially adapted to complex-shaped metal constituting body, such as belonging to, take ferrous material and be in the car body, trolley part, family's electrical article, material of construction etc. of main metal constituting body.
(metal surface treating method)
Metal surface treating method of the present invention comprises following operation,, uses aforesaid metal finishing use composition that is, utilizes to using metal to be treated material and at metal material surface, separate out epithelium as the electrolysis treatment operation of negative electrode.More preferably metal surface treating method of the present invention comprises following operation, that is, in order to separate out epithelium on metallic substance, effects on surface is implemented electrolysis treatment operation and the washing of carrying out after electrolysis treatment operation and the roasting procedure of electrolysis treatment by purifying metallic substance.Below, distinctive electrolysis treatment operation and roasting procedure in present method are described in detail.
< electrolysis treatment operation >
This electrolysis treatment operation (catholyte) has: the first operation, is being immersed in described metallic substance under the state in metal finishing use composition, the following electrolysis of voltage 15V 10～120 seconds; The second operation, after described the first operation, then implement, described metallic substance is being immersed under the state in metal finishing use composition, under voltage 50～400V, electrolysis is 30～300 seconds, here, described the second operation is then in same body lotion, to implement after described the first operation.
Here, the first operation is mainly the operation of carrying out in order preferentially to adhere to Bi, and the second operation is mainly the operation of carrying out in order preferentially to separate out cationic resin.In order to obtain enough erosion resistances, need to have the Bi directly contacting with metallic substance, namely need to have the interface Bi at the interface that is present in metallic substance and epithelium, the order of the first operation and the second operation and condition are very important thus.
Preferably the voltage of the first operation is 15V following (lower value is not particularly limited, yet is for example 0.01V), electrolysis 10～120 seconds.At voltage, be that 0V is following in the situation that, usining metallic substance carry out electrolysis as anode in the situation that, metallic substance, to stripping in composition, not only reduces the stability of composition, and can not adhere to fully essential interface Bi for improving erosion resistance.In the situation that surpassing the upper limit, before Bi preferentially separates out to metallic surface, just started resin and separated out, therefore also still cannot obtain sufficient erosion resistance.
In the treatment time, be that lower limit can not separated out enough interface Bi following in the situation that yet, be the upper limit above in the situation that, the adhesion amount of interface Bi is too much, thereby has the situation of the adaptation of infringement epithelium.
Preferably the voltage of the second operation is 50～400V, electrolysis 30～300 seconds.At voltage, be lower limit following in the situation that, the quantitative change of separating out of resin involucra obtains insufficiently, being the upper limit above in the situation that, not only because separating out too much of resin involucra is unfavorable economically, but also has the situation of the outward appearance after infringement epithelium completes.
When carrying out the second operation after the first operation, not needing moment increases voltage, even if increase and also can not damage effect of the present invention lentamente.In addition, it is always constant that the first operation and the second operation do not need voltage.
< roasting procedure >
Below, roasting procedure is described.Baking method is not particularly limited, for example, can enumerate the method for toasting with baking oven.In addition, storing temperature is for example 100 ℃～200 ℃.In addition, although baking time also to determine according to the shape of metal to be treated material, size, material, yet be generally 10～30 minutes.
Below, metal finishing use composition of the present invention is described in detail.
< < metal finishing use composition > >
Metal finishing use composition of the present invention is the metal finishing use composition that contains cationic resin emulsion, it is characterized in that, the dispersate of cationic resin emulsion must contain as the amides of the modified epoxy of matrix resin, as the end-blocking polyisocyanates of solidifying agent and as the tin compound of (or as promotor) ad hoc structure of curing catalysts, and the dispersion agent of resin cation (R.C.) emulsion contains Bi ion (be for example equivalent to use as electrocoating paint F2 agent).Here, metal finishing use composition of the present invention for example also can at random coordinate pigment composition.Now, this pigment composition is for example equivalent to the F1 agent of using as electrocoating paint.Below, each composition is described in detail.
< composition constituent: the dispersate > of cationic resin emulsion
(composition constituent: dispersate/cationic resin of cationic resin emulsion)
※ composition
Matrix resin of the present invention must contain the amine resin of cationization in addition for the matrix resin of modified epoxy as cationic resin.Here, in the middle of the amides of modified epoxy, the modified epoxy of preferred bisphenol type, phenol aldehyde type, most preferably bisphenol type.And, use modification in addition the reasons are as follows of composition shown in.If conventionally only use the composition of these matrix resins, the performance of the epithelium of gained can be not satisfactory.Thus, adopt the compound of the addition structure different from matrix resin, the method for carrying out modification.As an example, if use the bisphenol A type epoxy resin that does not carry out modification, though be imbued with very much rigidity, flexibility lacked, cannot obtain enough performances.Specifically, by addition polyol compound (below describe in detail) etc., can obtain having concurrently the epithelium of hardness and flexibility.
Here, in order to give cationic to resin, in typical situation, can adopt the method (, with regard to epoxy resin, being for example, the method that glycidyl addition endways contains amino compound) that amino is imported to (particularly end) in resin matrix.And, for this point, will describe in detail in the back.
Below, to being particularly suitable for, as the amides of modified epoxy cationic resin, bisphenol type, describe in detail.Here, the amides of the modified epoxy of specially suitable bisphenol A-type is by using epoxy resin, the compound that contains uncle and/or secondary amino group that modified resin, epoxy equivalent (weight) are 180～2500 as raw material or also using dihydroxyphenyl propane and make their react the amides of the modified epoxy obtaining.Below, each composition is described.
* the raw material of the modified epoxy of bisphenol A-type
First, as modified resin, conventionally use polyol compound.To be plasticities etc. of improving epoxy resin use for object for they.Specifically, can enumerate the polyol resins such as polyester polyol, polyether glycol, polyurethane polyol, acrylic polyol, addition phenol there is aromatic condensation compound of hydroxyl etc. endways.More particularly, can enumerate polycaprolactone glycol, polyoxyethylene glycol, polypropylene glycol, there is the xylene formaldehyde resin of phenol hydroxyl etc.Utilizing way that these compounds carry out modification because the hydroxyl that these compounds have can easily react with the glycidyl ether portion of epoxy resin, is therefore the technology of using till today.In modified epoxy, these modified resin that contain 5～30 % by weight.
Secondly, the epoxy resin that is 180～2500 as epoxy equivalent (weight), considers the epoxy resin that particularly preferably utilizes polyphenol compound to obtain with reacting of epihalohydrin, for example Epicholorohydrin from the viewpoints such as non-corrosibility of filming.Wherein, most suitable is the dihydroxyphenyl propane diglycidyl ether of utilizing dihydroxyphenyl propane to obtain with reacting of Epicholorohydrin.In addition, using dihydroxyphenyl propane as basic structure polymerization and epoxy resin also demonstrate identical effect, optimal is to be 180～2500, to be preferably 180～2000, more preferably 180～1500 resin as epoxy equivalent (weight).In modified epoxy, these epoxy resin that contain 5～30 % by weight.
In addition, dihydroxyphenyl propane is used for the molecule of the skeleton amount of gate ring epoxy resins.Utilize this content (addition), can control epoxy equivalent (weight).In modified epoxy, the dihydroxyphenyl propane that contains 5～30 % by weight.
In addition, contain uncle and/or the compound of secondary amino group be amino for importing to epoxy resin-base, by this epoxy resin in addition the cationic of cationization give composition.Here the amine that used is used is to contain at least 1 amine with the active hydrogen of epoxy reaction.As the amino compound that contains using with this kind of object, such as enumerating list or the dialkylamines such as monomethyl amine, dimethyl amine, MEA, diethylamide, single isopropylamine, diisopropylamine, monobutyl amine, dibutylamine; Monoethanolamine, diethanolamine, list (2-hydroxypropyl) amine, two (2-hydroxypropyl) amine, monomethyl monoethanolamine, the alkanolamine such as single ethyl amido alcohol; The ketoimine compound of the alkylene polyamines such as quadrol, propylene diamine, butanediamine, hexanediamine, tetren, penten, diethylamino propyl group amine, diethylenetriamine, Triethylenetetramine (TETA) and these polyamines; The alkylene imine such as ethylenimine, propylidene imines; The cyclic amine such as piperazine, morpholine etc.In modified epoxy, the compound that contains uncle and/or secondary amino group that contains 0.5～20 % by weight.
* the manufacture method of the amides of the modified epoxy of bisphenol A-type
First, the modified resin of specified amount, epoxy resin are mixed, carry out heated and stirred.Heating temperature is preferably 70～100 ℃.After each material dissolution, add catalyzer, improve Heating temperature, synthesize.Catalyzer is used the tertiary amine of dimethyl benzyl amine and so on conventionally.Synthesis temperature general control is at 120 ℃～170 ℃.
By adjusting synthesis temperature and time, can synthesize the modified epoxy of the epoxy equivalent (weight) with regulation.Utilize the epoxy equivalent (weight) of stipulating in JIS K7236 to measure and calculate epoxy equivalent (weight).Epoxy equivalent (weight) is now preferably 800～10000, and more preferably 800～5000, most preferably be 800～3000.Epoxy equivalent (weight) is larger, and emulsification when emulsion is made is just more difficult.
Then the compound that on the modified epoxy, synthesizing to this, addition contains uncle and/or secondary amino group.By modified epoxy being remained in 60 ℃～110 ℃, add the compound that contains uncle and/or secondary amino group, carry out synthesizing for 1～3 hour, just can obtain the amides of modified epoxy.
* the cationization of modified epoxy
In the amides of the modified epoxy synthesizing, add neutralizing acid, after being uniformly mixed, dilute with water, makes the resin emulsion of normality.Neutralizing acid can be used formic acid, acetic acid, lactic acid, thionamic acid etc.
Now, preferably before adding neutralizing acid, first add solidifying agent or curing catalysts, organic solvent etc.By adding like this in advance, just can obtain uniform emulsion.
The content of the cationic resin in ※ dispersate
For the content of the cationic resin in the dispersate of emulsion (the particularly amides of modified epoxy), the gross weight (gross weight that also comprises organic solvent) of dispersate of take is benchmark, is preferably 30～80 % by weight.
(composition constituent: the dispersate/solidifying agent of cationic resin emulsion)
※ composition
In the dispersate of cationic resin emulsion of the present invention, contained solidifying agent is blocked polyisocyanates.Blocked polyisocyanates is the addition reaction product under the roughly stoichiometry of polyisocyanate compound and isocyanate-terminated dose.As the polyisocyanate compound that used here, for example can enumerate tolylene diisocyanate, Xylene Diisocyanate, phenylene vulcabond, ditan-2,4'-vulcabond, ditan-4, aromatic series, aliphatics or the alicyclic polyisocyanate compounds such as 4'-vulcabond (being commonly referred to as " MDI "), thick MDI, two (isocyanic ester methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate; The cyclized polymer of these polyisocyanate compounds, isocyanic ester biuret material; Compound that ethylene glycol, propylene glycol, TriMethylolPropane(TMP), hexanetriol, castor-oil plant wet goods contain low molecular activity hydrogen is reacted with excessive these isocyanate compounds and the compound that contains terminal isocyanate etc.They can use separately respectively or combine two or more ground and use.
On the other hand, described isocyanate-terminated dose is on adding to the isocyanate group of polyisocyanate compound and carry out the material of end-blocking, in addition wish: the blocked polyisocyanates compound generating by addition is stable at normal temperatures, and when being heated to the storing temperature of filming (approximately 100～approximately 200 ℃ conventionally), end-capping reagent can dissociate and regenerate go on a tour from isocyanate group.
As the end-capping reagent that meets this kind of condition, such as enumerating the lactan based compounds such as ε-caprolactam, butyrolactam; The oxime compound such as methyl ethyl ketoxime, cyclohexanone-oxime; The phenol based compounds such as phenol, p-tert-butylphenol, cresols; The aliphatics such as propyl carbinol, 2-Ethylhexyl Alcohol alcohols; The aromatic series alkyl alcohols such as phenyl Trivalin SF, aminomethyl phenyl Trivalin SF; The ether alcohol such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether based compound etc.These end-capping reagents can be used separately respectively or combine two or more ground and use.In addition, in order effectively to advance the dissociating of end-capping reagent, curing reaction etc., in addition, in order to generate required cured product, also can take in advance on the skeleton of modified epoxy a part for addition isocyanate group and the method with end-capping reagent end-blocking by remaining isocyanate group.
The content of the blocked polyisocyanates in ※ dispersate
Blocked polyisocyanates in the dispersate of emulsion be take the gross weight (gross weight that also comprises organic solvent) of dispersate and is preferably 5～40 % by weight as benchmark.
(composition constituent: the dispersate/tin compound of cationic resin emulsion)
※ composition
In the dispersate of cationic resin emulsion of the present invention, contained tin compound comprises the tin compound shown in formula 1.And, in the present invention, not must limit the tin compound shown in independent use formula 1, can be with the m of dibutyl tin compound and so on also tin compound below 3 or solid state tin compound, other curing catalysts and use.
The dispersate of resin emulsion comprises cationic resin or solidifying agent, curing catalysts, organic solvent etc. as previously mentioned, yet think that the hydrophobic/hydrophilic character of cationic resin composition in addition goes far towards to improve the property separated out of Bi, from this point, consider, the m shown in preferred formula 1 is more than 4 compound.More preferably the m that hydrophobicity is high is more than 7 tin compound, the dioctyl tin compound that the m that wherein most preferably catalytic capability is high is 7.And higher limit is for example 12.
In addition, n is that the intermiscibility of more than 11 compound and resin is poor, and the stability that has an emulsion is bad, solidified nature is not enough, the generation of shrinkage cavity or seediness, thereby improper.
Here, from improving the property separated out of Bi and preventing that the viewpoint of the generation of shrinkage cavity, seediness from considering, the combination of specially suitable m and n is more preferably 6≤m≤8 of 4≤m≤10() and 0≤n≤5(, 0≤n≤3 more preferably).In addition, the total number that further preferred combination is m and n is 7～10, most preferred combination be m and n add up to for example oxalic acid dialkyl tin of 7().For example, as shown in embodiment, comparative example, the situation of the dibutyltin diacetate low with having used hydrophobicity (m=3, n=0) is compared, in the situation that used the oxalic acid dioctyl tin that hydrophobicity is high (m=7, n=0), the Bi property separated out improves significantly.
※ mechanism of action
But, if investigated as mentioned above in the situation that use the property separated out of the tin compound Bi of aforesaid ad hoc structure to improve significantly and can prevent the mechanism of action of the generation of shrinkage cavity, seediness in specific system, can be presumed as follows.
In the situation that considered the formation of the dispersate composition in cationic resin emulsion, utilize the cationization ability of the amine moiety that the amides self of modified epoxy has, can obtain the affinity (emulsion) with water as medium.On the other hand, as the end-blocking polyisocyanates of solidifying agent or low with the affinity of water due to the feature of chemical structure as the tin compound of curing catalysts, be difficult to be present in dispersate surface, be easily present in dispersate inside.Can easily predict its be have take the amides of modified epoxy as shell, take the material of the core shell structure that end-blocking polyisocyanates or tin compound be core.
In this situation, due to the hydrophobic/hydrophilic character of core composition, the condition of surface of dispersate changes.The hydrophobicity of core composition is higher, is more difficult to be present in dispersate near surface, and is more easily present in core, and on the other hand, hydrophobicity is lower, also may reside in dispersate near surface.
Conventionally time (without electrolysis time), even if utilize the sufficient cationization of the amides of modified epoxy, realized stabilization emulsion state, also low with the affinity of water, but in the situation that the low composition of hydrophobicity is present in dispersate near surface, in the delicate variation of the cationization in the basal body interface when the first operation, the instability of emulsion increases.
Specifically, under low voltage electrolysis state (the first operation), emulsion is concentrated, and instability also increases, and according to circumstances, also has the situation about separating out causing as the resinous principle of dispersate.
In the present invention, when separating out resinous principle under low voltage electrolysis state, will hinder separating out of Bi, cause not good situation.By using the tin compound low with hydrophobicity to compare the high tin compound of hydrophobicity that more can be present in core, be difficult to hinder Bi and separate out conversely speaking.That is, the Bi property separated out improves.
For the hydrophobicity of tin compound, the value effect of the m in its structure, particularly formula 1 is very large.The value of this m is larger, and hydrophobicity is higher, is more easily present in core, that is, be difficult to hinder Bi and separate out, and the Bi property separated out improves.
Dialkyl tin di fatty acid ester shown in formula 1 is liquid at normal temperatures, excellent with the intermiscibility of resin.In addition, can not produce shrinkage cavity, the seediness being caused by them yet.
Preferred: utilizing electrolysis to make resin separate out, during by the dispersate unificationization of emulsion, be present in outmost tin compound and contact with moisture, and be now hydrolyzed with the dialkyl tin di fatty acid ester of contact with moisture, easily to become the form of dialkyltin.That is, be preferably the fatty acid radical of lipid acid position easily departs from and easily move to water afterwards in disengaging (high-hydrophilic).Like this, because moving to aqueous phase side, unnecessary composition contained in filming reduces, thereby realize, solidified nature improves, erosion resistance improves.From this viewpoint, consider that n is preferably below above-mentioned numerical value.On the other hand, because of during high-grade aliphatic ester portion etc. is difficult for being hydrolyzed, easily remains in and film, thereby have the situation that solidified nature reduces, erosion resistance reduces that causes.For example, when evaluate cure, the gauze that pushing has wet with acetone, make it after back and forth movement, while utilizing the outward appearance that Visual Confirmation films, in the situation that have, do not participate in curing composition, because this composition is dissolved in acetone, thereby in appearance of film, can see the vestige that peels off of filming.
The content of the tin compound in the dispersate of ※ emulsion
If the content of tin compound is too much, unfavorable economically.Moreover, the core segment of core shell structure can become the structure of expanding, and cannot keep and the balance with the shell part of newborn liquefying power.The core segment expanding is wrapped into and the shell of emulsion partly becomes not enough, thereby make emulsion easily condense, unify, cannot keep the state of resin emulsion.
Thus, also become important with the ratio that becomes the resinous principle of shell part.It is benchmark that tin compound amount in the dispersate of emulsion be take the gross weight (gross weight that also comprises organic solvent) of dispersate, as Sn amount, is preferably 0.05～3 % by weight, and more preferably 0.05～2 % by weight, most preferably is 0.05～1 % by weight.
And the tin compound amount in metal finishing use composition or dispersate can be grasped with the form of Sn amount.Under the condition of high temperature 600 ℃ of left and right, during long-time heating, the compositions such as resin will burn, and tin compound all becomes stannic oxide state.By the dissolvings such as hot concentrated sulfuric acid for stannic oxide of gained here, produce the aqueous solution, by it being carried out to ICP luminescence analysis or ICP mass analysis etc., can determine Sn amount.
< composition constituent: the dispersion agent > of cationic resin emulsion
(composition constituent: the dispersion agent/liquid medium of cationic resin emulsion)
As the liquid medium of metal finishing use composition of the present invention (as the liquid medium of the dispersion agent of cationic resin emulsion), be preferably aqueous medium, more preferably water.And, in the situation that liquid medium is water, as liquid medium, also can contain other the water solvent (for example water miscible alcohols) weight of whole liquid mediums (for example take as benchmark is below 10 % by weight) beyond water.
(composition constituent: the bismuth ion of dispersion agent/3 valency of cationic resin emulsion)
In the present invention, said Bi ion refers to, not solidification in composition is the Bi composition that utilizes the formation inner complexs such as aminopolycarboxylic described later, fully becomes dissolved state specifically.And this ion is present in the dispersion agent of emulsion.
As the supply source of Bi ion, so long as the bismuth compound of 3 valencys is just not particularly limited, yet such as enumerating the inorganic bismuth compounds such as Bismuth trinitrate, bismuth phosphate, bismuth sulfate, bismuth oxide, bismuth hydroxide; Fluoridize the halogenation bismuth compounds such as bismuth, bismuth chloride, bismuth bromide, bismuth iodide; The organic acid bismuth compounds such as bismuth acetate, formic acid bismuth, bismuth lactate, bismuth citrate.
In the present invention, also can contain aminopolycarboxylic.So-called aminopolycarboxylic is the general name in molecule with the sequestrant of amino and a plurality of carboxyls.Aminopolycarboxylic becomes the more stably state of water-solubleization by the Bi ion of 3 valencys in composition, therefore can contain aminopolycarboxylic.Specifically, what meet has an EDTA(ethylenediamine tetraacetic acid (EDTA)), HEDTA(Oxyethylethylenediaminetriacetic acid), NTA(complexon I), DTPA(diethylene triaminepentaacetic acid(DTPA)), TTHA(triethylenetetraaminehexaacetic acid) etc., yet from the viewpoint of the inner complex stability with Bi ion, consider more preferably EDTA, HEDTA, NTA.
< composition constituent: other composition >
In composition of the present invention, also can use as required normally used additive in the paint field such as pigment, organic solvent, pigment dispersing agent, tensio-active agent.As pigment, can enumerate the tinting pigments such as titanium white, carbon black; Clay, talcum, barium oxide equal-volume pigment; The rust-stabilising pigment such as aluminium triphosphate, zinc phosphate etc.And, although in above-mentioned, the composition (liquid medium, bismuth ion) of the composition of the dispersate of cationic resin emulsion (cationic resin, end-blocking polyisocyanates, tin compound) and dispersion agent is separately illustrated, yet mean that these compositions are substantially present in dispersate or dispersion agent, rather than mean and exist only in dispersate or exist only in dispersion agent.For example, though a part of oligodynamical of cationic resin in dispersion agent, also within the scope of the invention.
The composition > of < composition
Below, the composition of metal finishing use composition of the present invention is described.First, metal finishing use composition of the present invention can be by the material of high density dilute with water and be adjusted into required concentration suitably.Below, the preferred concentration of each composition in this waterborne compositions is described.
(the cationic resin in waterborne compositions)
Said composition be take the gross weight of composition as benchmark preferably contains the cationic resin of 5～30 % by weight (solids component), more preferably contains 5～20 % by weight, further preferably contains 5～15 % by weight.
(blocked isocyanate in waterborne compositions)
Said composition preferably be take the blocked isocyanate that the gross weight of composition contains 2～20 % by weight (solids component) as benchmark, more preferably contains 2～15 % by weight, further preferably contains 2～10 % by weight.
(tin compound in waterborne compositions)
The content of the tin compound in said composition is preferably 0.01～1 % by weight as Sn amount, and more preferably 0.01～0.5 % by weight, most preferably is 0.01～0.2 % by weight.If the content of tin compound is too low, the curing catalytic capability expected reduces, and can not meet solidified nature, when carrying out as previously mentioned the round test of acetone, can see the vestige that peels off of filming.
(the Bi ions of 3 valencys in waterborne compositions)
The Bi ion of 3 valencys that said composition contains 100～5000ppm.More preferably 500～4000ppm, most preferably is 1000～3000ppm.In the situation that Bi ionic concn is too low, unfavorable for the property separated out of Bi, if too high, the specific conductivity of composition is too high, epithelium is deteriorated to all platings that have on the metallic substance of complicated shape, and Bi adhesion amount is too much, likely damages epithelium adaptation.For the Bi ionic concn in composition, can utilize ultracentrifuge by composition solid-liquid separation, to liquid phase, use high-frequency inductive coupling plasma body emmission spectrometric analysis (ICP) or atom extinction spectrum to analyze (AA) and carry out quantitatively.
The physical property > of < metal finishing use composition
（pH）
The pH of metal finishing use composition of the present invention is not particularly limited, yet conventionally can be adjusted into 2.0～7.0, be preferably adjusted into 3.0～6.5 scope and use.
(temperature)
For the temperature of metal finishing use composition of the present invention also not special restriction, however when utilizing electrolysis treatment that epithelium is separated out, conventionally can 15～40 ℃, preferably in the scope of 20～35 ℃, use.
< < metal finishing epithelium > >
Metal finishing epithelium of the present invention can be used metal finishing use composition of the present invention, utilizes treatment process of the present invention to obtain.Here, being present in Bi in epithelium exists with the form of metal and oxide compound.Utilizing Bi that catholyte is separated out is the metal Bi that reduction is separated out substantially, and its part is especially oxidized in the roasting procedure of epithelium and become oxide compound.In addition, apply in high-tension situation in the second operation, due to the pH rising on epithelium surface, the stabilization of the Bi based on aminopolycarboxylic becomes insufficient, therefore especially in epithelium face side, also as oxidation Bi, separates out.
Bi adhesion amount is preferably 20～500mg/m
2, 30～400mg/m more preferably
2, most preferably be 50～300mg/m
2.If Bi adhesion amount is too low, cannot obtain sufficient erosion resistance, if too high, not only cannot expect the raising of erosion resistance, and have the situation of infringement epithelium adaptation.And Bi adhesion amount can utilize x-ray fluorescence analysis quantitative.And " the metal Bi adhesion amount " in the scope of the art of this patent scheme and this specification sheets and " oxidation Bi adhesion amount " adopt and utilize the quantitative value of this x-ray fluorescence analysis.And, although as other form, cannot negate also the existence of oxyhydroxide, yet in this measuring method quantitative as " metal Bi " or " oxidation Bi " in the situation that, its numerical value is regarded " metal Bi adhesion amount " or " oxidation Bi adhesion amount " as.
Total leather film thickness of the epithelium of gained is preferably 5～40 μ m, and more preferably 5～30 μ m, most preferably are 7～25 μ m.If cross thinly, cannot obtain sufficient erosion resistance, if blocked up, not only unfavorable but also have a situation that all plating property reduces economically.For leather film thickness, if matrix metal is magneticmetal, can utilize induction film thickness gauge to measure, if matrix metal is non-magnetic metal, can utilize eddy current type film thickness gauge to measure.
Compared with epithelium surface, the Bi in epithelium need to be present in matrix metal side more.Specifically, the Bi adhesion amount that preferably has a metallic substance side of counting from the center of leather film thickness is B is that A is that the Bi of more than 55% (B/A >=55%) adheres to distribution with respect to total Bi adhesion amount.More preferably more than 58%, most preferably be more than 60%.If too low, cannot obtain sufficient erosion resistance.And if surpass 90%, the Bi concentration of epithelium face side is extremely low, loses the function as curing catalysts that Bi has, therefore not preferred.
For the Bi in epithelium, adhere to distribution, can measure by epithelium section being carried out to line analysis with EPMA.Utilize the backscattered electron image, of simultaneously taking to understand fully the interface of matrix metal and epithelium and the position on epithelium surface, the integrated value of obtaining the Bi intensity in the epithelium based on EPMA line analysis is A and to count the only integrated value of matrix metal side from the center of leather film thickness be B, just can calculate B/A.
Embodiment
the making of end-blocking isocyanic ester
To Cosmonate M200(Mitsui Chemicals, Inc system) add methyl iso-butyl ketone (MIBK) 115.6g in 678.4g, be warmed up to after 70 ℃, drip at leisure diethylene glycol monoethyl ether 706.0g, after dripping and finishing, be warmed up to 90 ℃.Under the condition of 90 ℃, react 12 hours, obtain end-blocking isocyanic ester.Carry out infrared absorption spectrometry, consequently, can't see the absorption that comes from unreacted isocyanate group, can confirm that isocyanic ester is by end-blocking fully.
The making of 30% quaternary salt type epoxy resin
To adding epoxy resin jER#828(Mitsubishi chemical Co., Ltd system, epoxy equivalent (weight) in the separable flask of the 1000ml that possesses thermometer, condenser, stirrer: 180) 134.9g, dihydroxyphenyl propane 80.94g, dimethyl benzylamine 0.1g, at 130 ℃, react, until reach epoxy equivalent (weight) 1200.Reaction adds ethylene glycol butyl ether 71.7g after finishing, then adds dimethylaminoethanol 13.16g, 90% lactic acid 14.79g and at 90 ℃, carry out reaction in 1 hour.After reaction, intensely agitated, with approximately 1 hour, drip deionized water 613.36g simultaneously, produce solids component and be 30% quaternary salt type epoxy resin.
the making of cationic resin emulsion
Production Example 1
To adding epoxy resin jER#828(Mitsubishi chemical Co., Ltd system, epoxy equivalent (weight) in the separable flask of the 1000ml that possesses thermometer, condenser, stirrer: 180) 114.0g, as the polycaprolactone glycol PLACCEL208(Daicel KCC system of modified resin) 41.5g, dihydroxyphenyl propane 45.6g, dimethyl benzylamine 0.1g, at 130 ℃, react, until epoxy equivalent (weight) reaches 1000.After reaction finishes, add ethylene glycol butyl ether 55.5g, then add the ketoimine compound 8.0g of diethanolamine 12.6g, diethylenetriamine, at 90 ℃, carry out reaction in 2 hours.Add wherein end-blocking isocyanic ester 105.5g, oxalic acid dioctyl tin (day east changes into the NEOSTANN U820 processed of Industrial Co., Ltd) 3.2g, acetic acid 5.4g, after being stirred to evenly, intensely agitated, with approximately 1 hour, drip deionized water 578.1g simultaneously, obtain solid component concentration and be 33% cationic resin emulsion (A1).
Production Example 2
In Production Example 1, by replacing oxalic acid dioctyl tin, and use oxalic acid dioctyl tin 1.6g, dibutyltin diacetate (day east changes into the NEOSTANN U200 processed of Industrial Co., Ltd) 1.6g, and carry out identical reaction, obtain cationic resin emulsion (A2).
Production Example 3
In Production Example 1, by replacing oxalic acid dioctyl tin, and use two dioctyltin laurate (day east changes into the NEOSTANN U810 processed of Industrial Co., Ltd) 3.2g, carry out identical reaction, obtain cationic resin emulsion (A3).
Production Example 4
In Production Example 1, by replacing oxalic acid dioctyl tin, and use dibutyltin diacetate (day east changes into the NEOSTANN U200 processed of Industrial Co., Ltd) 3.2g, carry out identical reaction, obtain cationic resin emulsion (A4).
Production Example 5
In Production Example 1, by replacing oxalic acid dioctyl tin, and use distearyl acid dioctyl tin (day east changes into the NEOSTANN U500 processed of Industrial Co., Ltd) 3.2g, carry out identical reaction, obtain cationic resin emulsion (A5).
the making of colo(u)rant dispersion paste
Production Example 6
16.6 parts of quaternary salt type epoxy resin with respect to 30%, add 7.0 parts of refining clays, 0.3 part of carbon black, 3.0 parts of zinc phosphates and deionized water, with ball mill, disperse 20 hours, and obtaining solids component is the colo(u)rant dispersion paste of 50 % by weight.
the making of Bi ionic liquid
In distilled water 500g, dissolve HEDTA13.3g, be heated to after 60 ℃, add Bismuth trinitrate pentahydrate 23.2g and be stirred to solids component and dissolve completely.So that the mode that final total amount is 1.0L adds distilled water again, produce Bi deionized water solution.
embodiment 1～3 and comparative example 1～2
the making of composition
To reaching of the combination shown in table 1, in the resin emulsion of amount that solids component is 16.0 % by weight, coordinating inoganic solids composition is colo(u)rant dispersion paste and the Bi deionized water solution of the amount of 4.0 % by weight, produces composition (the Bi concentration in composition: 1000ppm of embodiment 1～3 and comparative example 1～2; PH:6.0; Cationic resin in dispersate: 58 % by weight; Blocked isocyanate in dispersate: 27 % by weight).And, use deionized water dilution to adjust concentration separately.
electrolytic condition
As electrowinning process (1), electrolysis under 8V, after 90 seconds, is carried out the electrolysis treatment of 180 seconds as electrowinning process (2) immediately under 180V.
the making of test board
As test board, use cold-rolled steel sheet: SPCC(JIS3141) 70 * 150 * 0.8mm(is designated hereinafter simply as SPC), by the spraying of using Japanese Pa Kalaijing company's highly basic grease-removing agent processed " FC-E2001 " to carry out 120 seconds to its surface in advance, process and carry out skimming treatment.After skimming treatment, carry out the spraying washing of 30 seconds, be immersed in the composition shown in embodiment and comparative example, under the electrolytic condition shown in embodiment and comparative example, implemented catholyte processing.Test board after electrolysis finishes carries out the spraying washing of 30 seconds immediately with deionized water, carry out baking in 20 minutes in electric oven at 180 ℃.
the tune Check of epithelium characteristic
Utilize following method to investigate the epithelium characteristic of the epithelium of separating out on test board.
Leather film thickness is measured: use induction film thickness gauge to measure.
Bi adhesion amount: utilize fluorescent X-ray spectrometry to come quantitatively.
Bi adheres to distribution: utilize the line analysis of EPMA to analyze sample section.Concrete method is with reference to following.
Bi adhesion amount measure of spread in epithelium is analyzed with EPMA.Metallic substance after epithelium is processed utilizes sealing resin to fix, and grinds section, from matrix metal direction, at the line analysis of separating out epithelium surface direction and obtain Bi, distributes.So-called line analysis distributes, be take map analysis data as basis at the one-dimensional square of analysis area to calculate the figure of the mean value of characteristic X-ray intensity with width arbitrarily, can be understood as the line analysis with width.Condition determination is as follows.
Measure machine: Shimadzu Seisakusho Ltd.'s EPMA-1610 type processed
Electron beam gun: CeB6 cathode type
Beam current: 50nA, beam voltage: 15kV, beam diameter: below 1 μ m φ
Cumulative number: 1 time, sample time of every bit: 100ms
Spectrum crystal: PET(Bi M α)
Utilize the backscattered electron image of simultaneously taking to understand fully the interface of matrix metal and epithelium and the position on epithelium surface, the integrated value of obtaining the Bi intensity in epithelium is A and to count the only integrated value of matrix metal side from the center of leather film thickness be B, calculates B/A.And, for reference is shown in the analytical results of the epithelium of gained in embodiment 1 in Fig. 2 as representational distribution table.
The Bi property separated out: as the Bi property separated out, according to through time fluorescent X-ray spectrometry result, evaluated the Bi amount of separating out and reached 50mg/m
2time.Metewand is set to: in 45 seconds: ◎, 45～60 seconds: zero, more than 60 seconds: *.The results are shown in Table 1, the passing of the amount of separating out is shown in Fig. 1.And the Bi property separated out test is electrolysis 30,60,90 seconds under 8V, with after deionized water washing, air-dry.
Curing of coating: to the gauze that utilizes resin-coating plate pushing that catholyte process to be made to wet with acetone, make it after back and forth movement 30 times, by Visual Confirmation the outward appearance of filming.Metewand is made as does not have vestige: ◎, have vestige: zero, even to the state that can see matrix: *.The results are shown in Table 1.
Resin is separated out the time (the resin property separated out): under 15V, carry out the electrolysis treatment of 90 seconds, the time point that can see the reduction of current value is judged as the time point that manifests film electric resistance, there is the time point that resin is separated out, will separate out the time until the treatment time before this time point is made as resin.The results are shown in Table 1.
Shrinkage cavity, seediness: by Visual Confirmation have or not.
Adaptation: cut the wide checker of 100 lattice 1mm on filming, this part is extruded with Erichsen test device.After extruding, carry out tape stripping, count the lattice number of unstripped and residual part.Extrude distance: the residual number 80～100 of 4mm: ◎, 80～60: zero, 60～20: △, 20～0: *.
From table 1, can be clear that, the composition of embodiment can be realized preventing of the property the separated out raising of Bi and the deterioration of the appearance of film such as shrinkage cavity, seediness, has confirmed to give more excellent curing of coating and adaptation.Confirm, the composition of embodiment can form epithelium in same body lotion, and can form the epithelium that meets important character as epithelium.Known on the other hand, any character of the composition of comparative example is significance difference all, cannot use as utility.
[table 1]
* vestige slightly: zero has vestige: △
* has shrinkage cavity: * nothing: zero
Claims (10)
1. a metal finishing use composition, it contains cationic resin emulsion, it is characterized in that, and the dispersate of cationic resin emulsion contains the tin compound shown in the amides of modified epoxy, blocked polyisocyanates and formula 1:
Here, in formula 1, m is more than 4, and n is more than 0 and below 10,
The dispersion agent of cationic resin emulsion contains Bi ion.
2. metal finishing use composition according to claim 1, is characterized in that,
M in formula 1 is more than 7.
3. metal finishing use composition according to claim 1 and 2, is characterized in that,
M in formula 1 is 7.
4. metal finishing use composition according to claim 3, is characterized in that,
M in formula 1 be 7 and n be 0.
5. according to the metal finishing use composition described in any one in claim 1～4, it is characterized in that,
All the content of the tin compound in composition is counted 0.01～1 % by weight as Sn amount.
6. according to the metal finishing use composition described in any one in claim 1～5, it is characterized in that,
It is the composition using in the multistep current flow method in same body lotion.
7. a metal surface treating method, is characterized in that,
Metal to be treated material soaking in claim 1～6 in the waterborne compositions described in any one, is utilized and usings metal to be treated material and make to separate out epithelium as the electrolysis treatment operation of negative electrode on metallic substance.
8. metal surface treating method according to claim 7, is characterized in that,
Electrolysis treatment operation has: the first operation, after surface is immersed in claim 1～6 in the waterborne compositions described in any one by purifying metallic substance or in dipping, usingd this metallic substance as negative electrode, the following electrolysis of voltage 15V 10～120 seconds; The second operation is then implemented under voltage 50～400V electrolysis 30～300 seconds after described the first operation in same body lotion.
9. with a manufacture method for the metallic substance of epithelium, it is characterized in that,
There is the electrolysis treatment operation described in claim 7 or 8.
10. a metal finishing epithelium, it utilizes the manufacture method described in claim 9 to obtain, it is characterized in that,
As Bi in metal Bi and oxidation Bi, be attached with 20～250mg/m
2, total leather film thickness is 5～40 μ m, and has the Bi that the Bi adhesion amount B of the metallic substance side of counting from the center of leather film thickness is more than 55% (B/A>=55%) with respect to total Bi adhesion amount A and adhere to distribution.
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| JP2011-157635 | 2011-07-19 | ||
| JP2011157635A JP5718753B2 (en) | 2011-07-19 | 2011-07-19 | Aqueous composition for metal surface treatment, metal surface treatment method using the same, method for producing metal material with film, and metal surface treatment film using these |
| PCT/JP2012/065663 WO2013011790A1 (en) | 2011-07-19 | 2012-06-19 | Aqueous composition for metal surface treatment, method for metal surface treatment using composition, and method for producing metal material having film, as well as metal surface treatment film using same |
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| JP6406848B2 (en) * | 2014-03-26 | 2018-10-17 | 日本ペイント・オートモーティブコーティングス株式会社 | Electrodeposition coating composition |
| JP6367622B2 (en) * | 2014-06-30 | 2018-08-01 | 株式会社ブリヂストン | Composition for conductive member |
| CN115261866B (en) * | 2022-08-02 | 2023-12-19 | 黄山学院 | Long-acting thick film water-based antirust agent and preparation method thereof |
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| JP5718753B2 (en) | 2015-05-13 |
| WO2013011790A1 (en) | 2013-01-24 |
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