CN102713021A - Method for producing stainless steel member having coating film - Google Patents
Method for producing stainless steel member having coating film Download PDFInfo
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- CN102713021A CN102713021A CN2010800289350A CN201080028935A CN102713021A CN 102713021 A CN102713021 A CN 102713021A CN 2010800289350 A CN2010800289350 A CN 2010800289350A CN 201080028935 A CN201080028935 A CN 201080028935A CN 102713021 A CN102713021 A CN 102713021A
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- Prior art keywords
- tunicle
- stainless steel
- steel component
- resin
- hydroxyl
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Classifications
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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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
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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
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
Abstract
Disclosed is a method for producing a stainless steel member having a coating film that has excellent coating film hardness, impact resistance, adhesion properties and finish appearance. Specifically disclosed is a method for producing a stainless steel member having a coating film, which is characterized by comprising: a step wherein a stainless steel member is immersed in a bath of an aqueous solution of a silane coupling agent (A) that contains an amino group and an electric current is passed through the stainless steel member, thereby forming a first coating film on the stainless steel member; a step wherein an electrodeposition coating material (B) that contains a carboxyl group-containing resin (b1), an amino resin (b2), a hydroxy group-containing epoxy phosphate ester compound (b3) and a coloring component (b4) is coated on the first coating film by electrodeposition, thereby forming a second coating film; and a step wherein at least the second coating film is baked.
Description
Technical field
The present invention relates to have method of manufacture by the stainless steel component of the tunicle of film hardness, shock-resistance, adaptation and excellent in workability.
Background technology
Before this, utilize the chromium (Cr) in the stainless steel composition to combine, form the phenomenon of passivity tunicle in the surface,, can in some outdoor and moist place, the mechanical implement that uses pharmaceutical chemicals, galley equipment etc., use as the high corrosion resistance material with airborne oxygen.
Recently, in electronic instrument parts such as mobile phone, consider, use stainless steel component was implemented the exterior member that electrophoresis is filmed from the requirement of lightweight and high design property.Yet these parts and clothes friction, or come off, and when being trampled, electrophoresis is filmed impaired phenomenon such as are peeled off and are happened occasionally.
On stainless steel component, adopt the exterior member of anaphoresis coating; Known passing through improved by film hardness, can improve scuff resistance, but when being improved by film hardness; Shock-resistance and adaptation reduce, and are difficult to form the electrophoresis that satisfies scuff resistance, shock-resistance and adaptation and film.In addition, in above-mentioned electronic instrument part, also require design property, particularly excellent in workability.
In order to solve above-mentioned problem; For example; Patent documentation 1 and patent documentation 2 disclose the stainless steel plate that a kind of light of chromate-free is filmed, and it is characterized in that, have as the chemical treatment of lower floor film with the stainless steel plate of filming as the light on upper strata in; It is that chemical treatment is filmed and constituted that chemical treatment is filmed by aminosilane, and to contain second-order transition temperature be that 30～90 ℃, number-average molecular weight are 3000～50000 vinyl resin and block isocyanate compound and light is filmed.
The prior art document
Patent documentation
Patent documentation 1 spy opens the 2005-313630 communique
Patent documentation 2 spies open the 2007-98883 communique
Summary of the invention
The problem that invention will solve
Yet, in the invention of patent documentation 1 and patent documentation 2 records, can not get having and satisfy by the stainless steel component of the tunicle of film toughness, shock-resistance and adaptation and processibility.
Therefore, the purpose of this invention is to provide the method for manufacture that has by the stainless steel component of the tunicle of film toughness, shock-resistance and adaptation and excellent in workability.
Be used to solve the means of problem
The inventor etc. concentrate one's attention on the result of research and find in order to solve above-mentioned problem; Method of manufacture with stainless steel component of tunicle; It is characterized in that; This method comprises: be immersed in above-mentioned stainless steel component in the water-soluble bath of liquid that contains amino silane coupling agent (A), through to this stainless steel component energising, on this stainless steel component, form the step of the 1st tunicle then; And, on the 1st tunicle, coating is implemented electrophoretic painting, form the step of the 2nd tunicle; Said coating is the epoxy phosphate ester cpds (b3) of carboxylic resin (b1), aminoresin (b2), hydroxyl and the electrophoretic paint (B) of coloring components (b4); The carboxylic relatively resin of amount (b1) of the epoxy phosphate ester cpds (b3) of hydroxyl adds up to 100 mass parts with the solids component of aminoresin (b2); Be in the scope of 0.1～10.0 mass parts; Then, at least the 2nd tunicle is carried out the agglomerating step.Can solve above-mentioned problem, accomplish the present invention.
Specifically the present invention relates to following scheme:
[scheme 1]
Have the method for manufacture of the stainless steel component of tunicle, it is characterized in that, this method comprises:
This stainless steel component is immersed in the water-soluble bath of liquid that contains amino silane coupling agent (A), through to this stainless steel component energising, on this stainless steel component, forms the step of the 1st tunicle then;
On the 1st tunicle, coating is implemented electrophoretic painting, form the step of the 2nd tunicle; Said coating is the epoxy phosphate ester cpds (b3) of carboxylic resin (b1), aminoresin (b2), hydroxyl and the electrophoretic paint (B) of coloring components (b4); The carboxylic relatively resin of amount (b1) of the epoxy phosphate ester cpds (b3) of hydroxyl adds up to 100 mass parts to be in the scope of 0.1～10.0 mass parts with the solids component of aminoresin (b2); And
At least the 2nd tunicle is carried out the agglomerating step.
[scheme 2]
Method according to record in the scheme 1; Wherein, Containing amino silane coupling agent (A) is selected from: N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-3-aminopropyltriethoxywerene werene, 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-triethoxysilyl-N-(1; 3-dimethyl--butylidene) group of propylamine and partial hydrolystate thereof, 3-trimethoxysilyl-N-(1,3-dimethyl--butylidene) propylamine and partial hydrolystate thereof and N-phenyl-3-TSL 8330 formation.
[scheme 3]
Stainless steel component has tunicle, and above-mentioned tunicle has the 1st tunicle and the 2nd tunicle on the 1st tunicle on the stainless steel component, it is characterized in that:
The 1st tunicle is through in the aqueous solution that contains amino silane coupling agent (A), the tunicle that forms to this stainless steel component energising, and
The 2nd tunicle is the stainless steel component with the 1st tunicle to be implemented electrophoretic painting and the tunicle that forms with coating; Said coating is the epoxy phosphate ester cpds (b3) of carboxylic resin (b1), aminoresin (b2), hydroxyl and the electrophoretic paint (B) of coloring components (b4), and the carboxylic relatively resin of amount (b1) of the epoxy phosphate ester cpds (b3) of hydroxyl adds up to 100 mass parts to be in the scope of 0.1～10.0 mass parts with the solids component of aminoresin (b2).
[scheme 4]
Electronic instrument part wherein comprises in employing scheme 1 or 2 stainless steel component with tunicle of the method manufacturing of record.
The invention effect
Method of manufacture with stainless steel component of tunicle of the present invention can form by the tunicle of film toughness, shock-resistance and adaptation and excellent in workability on stainless steel component.
Embodiment
The method of manufacture of facing the stainless steel component with tunicle of the present invention is down explained.
At first, be immersed in stainless steel component in the water-soluble bath of liquid that contains amino silane coupling agent (A), then through switching on to this stainless steel component, the step (be called sometimes and form the 1st tunicle step) that on stainless steel component, forms the 1st tunicle is explained.
[stainless steel component]
As the stainless steel component that uses among the present invention, can enumerate by ferrite (α) be, martensite (M), austenite (γ) are, (γ+α) such as is at the member that known before this stainless steel forms to the two-phase of austenitic iron oxysome.
As above-mentioned stainless steel, concretely, for example, can use austenite stainless steels such as SUS 304, SUS 305, SUS 310, SUS 315 and SUS MX7; SUS 430 ferrites such as grade are martensitic stainless steels such as stainless steel, SUS 403, SUS 410, SUS 416 and SUS 420; It is stainless steel etc. that SUS 631 grades are separated out curing.
Also have, above-mentioned stainless steel can adopt the stainless steel through suitable skimming treatment as required.
In addition, above-mentioned stainless steel both can adopt the surface through chemically treated stainless steel, also can adopt the surface not pass through chemically treated stainless steel, but preferably not pass through chemically treated stainless steel.
[containing amino silane coupling agent (A)]
In the step that forms the 1st tunicle; Make anode with above-mentioned stainless steel component; Be immersed in the bath of the aqueous solution that contains amino silane coupling agent (A) (following abbreviate the aqueous solution that contains amino silane coupling agent (A) as " aqueous solution (A) " sometimes), switch at least 1 time, form the 1st tunicle whereby.
In addition, in the step that forms the 1st tunicle, can be also with the multiple silane coupling agent (A) that contains amino.Concrete is, as silane coupling agent (A
1) and silane coupling agent (A
2) and the time spent, prepare silane coupling agent (A respectively
1) water-soluble bath of liquid and silane coupling agent (A
2) water-soluble bath of liquid, be immersed in silane coupling agent (A to stainless steel component
1) water-soluble bath of liquid in switch on, be immersed in silane coupling agent (A to stainless steel component then
2) water-soluble bath of liquid in switch on, form the 1st tunicle whereby.
As the object lesson that contains amino silane coupling agent (A); Can enumerate N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-3-aminopropyltriethoxywerene werene, 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-triethoxysilyl-N-(1; 3-dimethyl--butylidene) propylamine and partial hydrolystate thereof, 3-trimethoxysilyl-N-(1,3-dimethyl--butylidene) propylamine and partial hydrolystate and N-phenyl-3-TSL 8330.
Also have, so-called " partial hydrolystate " that contains amino silane coupling agent (A) is meant the hydrolyzate that is hydrolyzed into the OH base at least with 1 of Siliciumatom bonded alkoxyl group in this specification sheets.
The amino silane coupling agent that contains as market sale; For example; Can enumerate KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBM-9103, KBM-573, KBM-575 and KBM-6123 (more than be the シ リ コ of SHIN-ETSU HANTOTAI-Application society make trade(brand)name).
In containing amino silane coupling agent (A); Particularly N-2-(amino-ethyl)-3-aminopropyltriethoxywerene werene, 3-TSL 8330, and 3-aminopropyltriethoxywerene werene, from after the anion electrophoresis coating (B) stated adopt the tack aspect of the 2nd tunicle that the electrophoretic painting method forms to consider it is preferred.
As an example, be immersed in stainless steel component when switching in the aqueous solution of " 3-aminopropyltriethoxywerene werene ", on stainless steel component, form the 1st tunicle of " silica gel ".The 1st tunicle of this silica gel helps to improve the adaptation of the 2nd tunicle that stainless steel component and anion electrophoresis coating (B) form through electrophoretic painting.
Also have; In the step that forms the 1st tunicle; The concentration of aqueous solution that contains amino silane coupling agent (A); Do special the qualification, but consider, preferred 0.1～20 quality %, more preferably 0.5～5 quality %, especially preferred 1～3 quality % from the stability of bathing, the shock-resistance that forms thing, adaptation aspect.
In addition, in order to form the 1st tunicle, be immersed in stainless steel component in the water-soluble bath of liquid that contains amino silane coupling agent (A), solution temperature is adjusted to 10～40 ℃, makes anode with stainless steel component, and it is preferred switching on according to common electrophoretic painting method.Current density during energising is not done special qualification, but preferred 0.001A/cm
2～0.1A/cm
2, more preferably 0.005A/dm
2～0.05A/cm
2, and preferred 10 seconds～300 seconds, more preferably 30 seconds～200 seconds conduction time.
In the step that forms the 1st tunicle, above-mentioned energising also can be carried out several repeatedly.
Be immersed in stainless steel component in the bath of a plurality of aqueous solution (A); Energising then; Form in the instance of the 1st tunicle, when the bath of a plurality of aqueous solution (A) is the bath of the aqueous solution of the same race (A), in certain is bathed the dipping stainless steel component and switch on after; Do not wash, then in other is bathed, flood the stainless steel component processing of switching on then.On the other hand, when the bath of a plurality of aqueous solution (A) is the bath of the aqueous solution not of the same race (A), in certain is bathed, after dipping stainless steel component and the energising, wash, remove the undecomposed metal-salt that adheres on the surface after, be immersed in during other bathes, switch on then.
Method of the present invention after the step that forms the 1st tunicle, can also can comprise as required and carry out Air drying, or in 40～80 ℃, 1 minute～60 minutes step of heat drying.When the shock-resistance of considering the 1st tunicle, adaptation and processibility, preferably have 0.01～3 μ m, more preferably have the dry film thickness of 0.1～1.0 μ m.
Secondly, on the 1st tunicle, anion electrophoresis coating (B) being carried out electrophoretic painting, the step (following the 2nd tunicle of claiming sometimes forms step) that forms the 2nd tunicle is explained.
[anion electrophoresis coating (B)]
Form the anion electrophoresis coating (B) that uses in the step of the 2nd tunicle; Can enumerate the epoxy phosphate ester cpds (b3) of carboxylic resin (b1), aminoresin (b2), hydroxyl and the electrophoretic paint (B) of coloring components (b4), wherein the carboxylic relatively resin of amount (b1) of the epoxy phosphate ester cpds (b3) of hydroxyl adds up to 100 mass parts to be in the scope of 0.1～10.0 mass parts with the solids component of aminoresin (b2).
[carboxylic resin (b1)]
Carboxylic resin (b1) is the resin that has at least 1 carboxyl in 1 molecule.The resin that carboxylic resin (b1) also has at least 1 hydroxyl is preferred.As carboxylic resin (b1), concrete can enumerate resins such as vinyl resin, vibrin, polyether resin, polycarbonate resin, urethane resin, from being considered that by film hardness and processibility aspect vinyl resin is fit to.
The aforesaid propylene acid resin is carboxylic free-radical polymerised unsaturated monomer, makes through copolymerization according to free-radical polymerised unsaturated monomer and other free-radical polymerised unsaturated monomers of the hydroxyl of hope.
As above-mentioned carboxylic free-radical polymerised unsaturated monomer, for example, can enumerate monomers such as vinylformic acid, methylacrylic acid, butenoic acid, methylene-succinic acid, toxilic acid, fumaric acid.Free-radical polymerised unsaturated monomer as above-mentioned hydroxyl; For example; Can enumerate 2-hydroxyethyl (methyl) propenoate, 2-hydroxypropyl (methyl) propenoate, 3-hydroxypropyl (methyl) propenoate, hydroxyl butyl (methyl) propenoate and can enumerate in addition プ ラ Network セ Le FM1, プ ラ Network セ Le FM2, プ ラ Network セ Le FM3, プ ラ Network セ Le FA1, プ ラ Network セ Le FA2, プ ラ Network セ Le FA3 (more than be ダ ィ セ Le chemistry society and make; Trade(brand)name, caprolactone modification (methyl) crylic acid hydroxy ester class) etc.
As above-mentioned other free-radical polymerised unsaturated monomers; For example, can enumerate γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl-triethoxysilicane, vinyltrimethoxy silane etc. and contain alkoxyl group base unsaturated monomer; Aromatic vinyl monomer classes such as the acrylic acid C1 of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) Bing Xisuandingzhi, (methyl) NSC 11786, (methyl) Octyl acrylate, (methyl) lauryl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate etc. (methyl)～C18 alkyl or cycloalkyl ester class, vinylbenzene; (methyl) acrylic amide, N-methylol (methyl) acrylic amide, N; N-dihydroxymethyl (methyl) acrylic amide, N-methoxymethyl (methyl) acrylic amide, N-ethoxyl methyl (methyl) acrylic amide, N-isopropoxy methyl (methyl) acrylic amide, N-n-butoxy methyl (methyl) acrylic amide, the positive hexyloxy methyl of N-(methyl) acrylic amide, N; N-dimethoxy-methyl (methyl) acrylic amide, N, N-two n-butoxy methyl (methyl) acrylic amides, N-methoxymethyl-(methyl) acrylamide monomers such as N-methylol (methyl) acrylic amide.
The aforesaid propylene acid resin; Generally contain carboxylic free-radical polymerised unsaturated monomer, according to the free-radical polymerised unsaturated monomer of the hydroxyl of hope and the polymeric solution of other free-radical polymerised unsaturated monomers, in solvent, adopt polymerization starter to obtain through radical polymerization.In above-mentioned radical polymerization; Above-mentioned polymeric solution is a benchmark with the monomer gross weight; Hope that carboxylic free-radical polymerised unsaturated monomer is 1～20 quality %, preferred 4～10 quality %; The free-radical polymerised unsaturated monomer of hydroxyl is 0～40 quality %, preferred 5～30 quality %, and the scope that other free-radical polymerised unsaturated monomers are 40～99 quality %, preferred 60～91 quality %.
Particularly consider that from improving by the viewpoint of film hardness above-mentioned polymeric solution is a benchmark with the monomer total amount, it is preferred containing in 0.1～30 quality % scope as (methyl) acrylamide monomers of other free-radical polymerised unsaturated monomers.
As above-mentioned solvent; For example; Use alcohols such as n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, isopropylcarbinol, ethers such as ethylene glycol monobutyl ether, Ucar 35 monomethyl ether, 2-methyl cellosolve, cellosolvo, 2-isopropoxide ethanol, butoxy ethanol, glycol ether, diethylene glycol monomethyl ether, ethyl carbitol, DEGMBE, triglycol monomethyl ether, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, dipropylene glycol monomethyl ether etc. are suitable.
Above-mentioned solvent can also contain the for example fragrant same clan such as YLENE, toluene; Acetone, methylethylketone, 2 pentanone, 2-be ketones such as ketone, mibk, isophorone, pimelinketone; Ester classes such as methyl acetate, ETHYLE ACETATE, pentyl acetate, 3-methoxyl group butylacetic acid ester, 2-ethylhexyl acetic ester, jasmal, hexalin acetate, methyl propionate, ethyl propionate.
The radical polymerization initiator that uses in the radical polymerization; For example; Can enumerate superoxide such as Lucidol, two-tert-butyl hydroperoxide, tert-butyl hydroperoxide, cumyl peroxide, cumene hydroperoxide, diisopropylbenzene(DIPB) hydroperoxide, tert butyl peroxy benzoate, lauryl peroxide, acetyl peroxide, tert-butyl hydroperoxide-2-ethylhexanoate; α, azo cpds such as α '-Diisopropyl azodicarboxylate, the two methyl pentane nitriles of azo, azo dicyclohexyl nitrile.
The weight-average molecular weight of aforesaid propylene acid resin, preferred 5000～150000, more preferably 20000～100000 scope.
Also have; In this manual; Weight-average molecular weight is meant the 0124-83 according to JIS K, and separator column adopts 4 posts (more than be eastern ソ-society make) of TSK ge1 2000HXL, TSK ge1 2500HXL, TSK ge1 3000HXL, TSK ge1 4000HXL, at 40 ℃, flow velocity 1.0ml/ minute; Elutriant is that GPC uses THF, the value that color atlas that obtains from the RI index meter and polystyrene standard curve are obtained.
[aminoresin (b2)]
Aminoresin (b2); Can use known before this compound; For example, can enumerate the methylolation aminoresin that amino components such as melamine resin, urea, benzo guanamine, acetyl guanamine, purine guanamine, spiral shell guanamine, dicyan diamide and aldehyde reaction obtain, the alkyl etherate of this methylolation aminoresin.
As above-mentioned methylolation aminoresin; The methylolation melamine resin is fit to, and can also enumerate the methylol part of methylolation melamine resin or all use the melamine resin of the monohydroxy-alcohol modifications more than a kind or 2 kinds such as methyl alcohol, ethanol, propyl alcohol, butanols, octanol, 2-Ethylhexyl Alcohol.
Commodity as the market sale of above-mentioned melamine resin; For example; Can enumerate ュ-パ Application 20SE-60, ュ-パ Application 225 (more than any Mitsui Chemicals society that is make; Trade(brand)name), butyl ether melamine resins such as ス-パ-ベ Star カ ミ Application G840, ス-パ-ベ Star カ ミ Application G821 (more than any big Japanese ィ Application キ chemical industry society that is make trade(brand)name); ス ミ マ-Le M-100, ス ミ マ-Le M-40S, ス ミ マ-Le M-55 (more than any Sumitomo Chemical society that is make; Trade(brand)name), サ ィ メ Le 232, サ ィ メ Le 303, サ ィ メ Le 325, サ ィ メ Le 327, サ ィ メ Le 350, サ ィ メ Le 370 (more than any Japanese サ ィ テ Star Network ィ Application ダ ス ト リ-ズ society that is make; Trade(brand)name), ニ カ ラ Star Network MS 17, ニ カ ラ Star Network MX 15, ニ カ ラ Star Network MX 430, ニ カ ラ Star Network MX 600 (more than anyly be three and make with ケ ミ カ Le society; Trade(brand)name), レ ジ ミ Application 741 methyl-etherified melamine resins such as (モ Application サ Application ト society make, trade(brand)name); サ ィ メ Le 235, サ ィ メ Le 202, サ ィ メ Le 232S, サ ィ メ Le 238, サ ィ メ Le 254, サ ィ メ Le 272, サ ィ メ Le 1130 (more than any Japanese サ ィ テ Star Network ィ Application ダ ス ト リ-ズ society that is make; Trade(brand)name), the complex etherified melamine resin of ス マ ミ-Le M66B methyl-etherifieds such as (Sumitomo Chemical society make, trade(brand)name) and isobutyl; サ ィ メ Le XV 805 (Mitsui サ ィ テ Star Network society make, trade(brand)name), ニ カ ラ Star Network MS 95 (three make trade(brand)name with ケ ミ カ Le society) etc. methylate with the complex etherified melamine resin of normal-butylization etc.
The ratio that cooperates of carboxylic resin (b1) and aminoresin (b2); Adding up to 100 mass parts with the solids component of carboxylic resin (b1) and aminoresin (b2) is benchmark; Carboxylic resin (b1) is 50～75 mass parts, preferred 50～65 mass parts; Aminoresin (b2) is the scope of 25～50 mass parts, preferred 35～50 mass parts, from being considered it is preferred by film hardness, shock-resistance, adaptation and processibility aspect.
The anion electrophoresis coating (B) that in the step that forms the 2nd tunicle, uses except that aminoresin (b2), can also contain the block polyisocyanate compounds.
As polyisocyanate compounds; For example, can enumerate (adjacent-,-; Right-) first phenylene vulcabond, (adjacent-; Between-, right-) diformazan phenylene vulcabond, phenylene vulcabond, ditan-2,2 '-vulcabond, ditan-2; 4 '-vulcabond, ditan-4,4 '-aromatic series, aliphatics or alicyclic polymeric isocyanate compound such as vulcabond, Network Le-De MDI [polymethylene polyphenyl isocyanate], two (isocyanic ester methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate; The cyclopolymerization body of these polyisocyanate compounds or the disome that contracts; Or these condenses.
On the other hand, as the block agent of polyisocyanate compounds being carried out blockization, can enumerate oxime compounds such as methyl ethyl ketone oxime, methyl amyl ketoxime, OxiKhim-Styrol; Phenol, to phenolic cpds such as tert-butyl phenol, cresols; Aliphatics such as propyl carbinol, 2-Ethylhexyl Alcohol alcohols; Aromatic series alkyl alcohols such as phenyl Trivalin SF, aminomethyl phenyl Trivalin SF; Ether alcohol such as ethylene glycol monobutyl ether, DEGMBE based compound; Lactan such as ε-Ji Neixianan, butyrolactam based compound.
Commodity as the market sale of block polyisocyanate compound; For example; Can enumerate バ-ノ Star Network D-750, バ-ノ Star Network D-800, バ-ノ Star Network DN-950, バ-ノ Star Network DN-970 or バ-ノ Star Network DN-15-455 (more than be big Japanese ink chemical industry society and make; Trade(brand)name), デ ス モ ジ ュ-Le L, デ ス モ ジ ュ-Le N, デ ス モ ジ ュ-Le HL, デ ス モ ジ ュ-Le IL or デ ス モ ジ ュ-Le N 3390 (more than be バ ィ エ Le society and make; Trade(brand)name), (military field pharmaceutical industries society makes for タ ケ ネ-ト D-102, タ ケ ネ-ト D-202, タ ケ ネ-ト D-110N or タ ケ ネ-ト D-123N; Trade(brand)name), (the industrial society of Japanese Port リ ゥ レ タ Application makes for コ ロ ネ-ト L, コ ロ ネ-ト HL, コ ロ ネ-ト EH or コ ロ ネ-ト 203; Trade(brand)name) or デ ュ ラ ネ-ト 24A-90CX (Asahi Chemical Industry industry society makes, trade(brand)name) etc.
[the epoxy phosphate ester cpds (b3) of hydroxyl]
The epoxy phosphate ester cpds (b3) of hydroxyl is the compound that the addition phosphate cpd obtains on epoxy resin; Hydroxyl and phosphoric acid residue in the epoxy phosphate ester cpds (b3) of hydroxyl; In the adaptation of raising and the 1st tunicle and stainless steel component, help processibility and stability.
Above-mentioned epoxy resin for example, can be enumerated bisphenol-type epoxy resin, lacquer react generation with the epoxy group(ing) in type epoxy resin, these epoxy resin or hydroxyl and properties-correcting agent modified epoxy etc.Above-mentioned bisphenol-type epoxy resin for example, can be enumerated Epicholorohydrin and bis-phenol; As required in the presence of catalyzer such as alkaline catalysts, through being condensed into the resin that HMW is made, Epicholorohydrin and bis-phenol; In the presence of catalyzer such as alkaline catalysts,, synthesize as required with low-molecular-weight epoxy resin through condensation; Then, this low-molecular-weight epoxy resin and bis-phenol obtain resin through the condensation polyaddition.The epoxy equivalent (weight) of above-mentioned epoxy resin preferred 172～4000, more preferably 175～1000.
As bis-phenol, for example, can enumerate two (4-hydroxy phenyl) methane [Bisphenol F], 1; Two (4-hydroxy phenyl) ethane, 2 of 1-; Two (4-hydroxy phenyl) propane [dihydroxyphenyl propane], 2 of 2-, two (4-hydroxy phenyl) butane [bisphenol b] of 2-, two (4-hydroxy phenyl)-1,1-Trimethylmethane, two (4-hydroxyl-tertiary butyl-phenyl)-2; 2-propane, right-(4-hydroxy phenyl) phenol, hydroxyl two (4-hydroxy phenyl), sulphonyl two (4-hydroxy phenyl), 4,4 '-dihydroxy benaophenonel, two (2 hydroxy naphthalene base) methane.Above-mentioned bisphenols can use separately or as the mixture more than 2 kinds.
Use type epoxy resin as above-mentioned lacquer, for example, can enumerate bis-phenol lacquer and coat with lacquer the phenol acetaldehyde type epoxy resin etc. that a plurality of epoxy group(ing) are arranged with type epoxy resin, intramolecularly with type epoxy resin, cresols.
As above-mentioned phosphate cpd, for example, can enumerate ortho-phosphoric acid and tetra-sodium.The epoxy phosphate ester cpds (b3) of hydroxyl; Addition phosphate cpd on the epoxy resin; For example; In the presence of catalyzer such as imidazoles,
salt; In 70～150 ℃ of temperature of reaction, preferred 110～130 ℃, 1～8 hour reaction times, preferred 3～6 hours, obtain through reaction.Also have, the epoxy phosphate ester cpds (b3) of hydroxyl, 1 mole of the Oxyranyle of epoxy resin relatively, the H+ of phosphate cpd are that the amount of H+/Oxyranyle=0.5～3, preferred 1～3 scope reacts is preferred.The acid number of the epoxy phosphate ester cpds (b3) of hydroxyl is seen from the viewpoint that improves adaptation, preferred 5～70mgKOH/g, the more preferably scope of 28～60mgKOH/g, especially preferred 35～57mgKOH/g.
Also have; Commodity as the market sale of the epoxy phosphate ester cpds (b3) of hydroxyl; For example; Can enumerate XU-8096.07, XU-71899.00, XQ-82908.00, XQ-82919.00, DER620-PP50, DER621-EB50, DER621-PP50 (more than be ダ ゥ ケ ミ カ Le Japan society make trade(brand)name), エ Port ト-ト ZX1300, ZX1300-1 (more than be Dongdu change into society make trade(brand)name) etc.
The epoxy phosphate ester cpds (b3) of hydroxyl; Solids component with carboxylic relatively resin (b1) and aminoresin (b2) adds up to 100 mass parts; Reach 0.1～10.0 mass parts, preferred 0.5～8.0 mass parts, the more preferably amount of 1.0～6.0 mass parts scopes, be contained in the electrophoretic paint (B).When the amount of the epoxy phosphate ester cpds (b3) of hydroxyl during less than 0.1 mass parts; The 2nd tunicle and the 1st tunicle and stainless steel component have the tendency of insufficient driving fit; And; When the amount of the epoxy phosphate ester cpds (b3) of hydroxyl during greater than 10.0 mass parts, paint stability and weathering resistance have the tendency of decline.
[coloring components (b4)]
Anion electrophoresis coating (B) in order to improve design property, can contain coloring components (b4).
As coloring components (b4); For example; Can enumerate that titanium oxide, zinc oxide, carbon black, iron oxide black, nigrosine, organic yellow, diarylide yellow, tartrazine lake, permanent yellow toning agent, cadmium yellow, benzidine orange, chromium cinnabar, cadmium orange, winestone orange GTR, fast orange color lake, Lake red C, red iron oxide, red, the gorgeous carmine 6B of heart yarn, the red F5R of winestone, the red 2B of winestone, the red FRLL of winestone, Munich lake, quinoline a word used for translation ketone are red, pyoktanin blue color lake, Fast violet B, quinoline a word used for translation ketone purple, the red intellectual circle's purple of English, phthalocyanine blue, strong sun blue, blue lake, ultramarine, victoria blue color lake, phthalocyanine green, margarite green lake, pigment green B, dimension profit Dean pigment, Mei-Ge Er Shi dyestuff, amber, aluminium powder, copper bronze etc.; The painted processing powder of pigment dyestuff, mineral dye and metal powder pigment, dyestuff, pigment etc. and resin-oatmeal combination, and high-visibility pigment, natural mica surface with the pigment of MOX lining, synthetic mica surface with the pearl pigment of MOX lining etc.
As coloring components (b4); Consider from the viewpoint of paint stability and design property; It is preferred making the processed pigment of colo(u)rant dispersion with dispersion agent; And, can enumerate ュ ニ ス パ-ス-yellow 10GN-S, ュ ニ ス パ-ス DPP orange RA-S, the red 2G-S of ュ ニ ス パ-ス, the purple B-S of ュ ニ ス パ-ス, ュ ニ ス パ-ス indigo plant-B-S, the green G-S of ュ ニ ス パ-ス, the black C-S of ュ ニ ス パ-ス (more than be チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ (strain) make), the yellow 10G130 of コ ラ ニ one Le, the red FGRG130 of コ ラ ニ one Le, the carmine FB130 of コ ラ ニ one Le, the purple RL130 of コ ラ ニ one Le, the blue A2R200 of コ ラ ニ one Le, the blue A2R130 of コ ラ ニ one Le, the blue B2G130 of コ ラ ニ one Le, the green GG131 of コ ラ ニ one Le, the black PR130 of コ ラ ニ one Le, the blue CD100 of コ ラ ニ one Le ォ キ サ ィ De, the green G131 of コ ラ ニ one Le ォ キ サ ィ De, the blue B2G of ホ ス ト Off ァ ィ Application, the yellow HR of コ ラ ニ one Le, the black T of コ ラ ニ one Le (more than be Network ラ リ ァ Application ト make), the yellow 3G of EMF dyestuff, EMF orange O, the red HFB of EMF, the red HR of EMF, the blue HG of EMF, the purple HB of EMF (more than be Toyo Ink (strain) Zhi Zao), NKW2103, NKW2104, NKW2105, NKW2117, NKW2167, NKW2108 (more than be Japanese fluorescence (strain) Zhi Zao).
Anion electrophoresis coating (B); Can contain the coloring components (b4) more than 2 kinds; The amount of coloring components (b4) is according to application target and different; See that from the viewpoint of weathering resistance, shock-resistance and design property the solids component of carboxylic relatively resin (b1) and aminoresin (b2) adds up to 100 mass parts, preferred 0.01～40 mass parts, the more preferably scope of 0.01～25 mass parts, especially preferred 0.01～10 mass parts.
Also have; The water dispersion of carboxylic resin (b1); Be past carboxylic resin (b1) the middle interpolation aminoresin (b2) and the epoxy phosphate ester cpds (b3) of hydroxyl, block polyisocyanate compounds as required; Further add acid catalyst, basic cpd and deionized water, stir and obtain with stirrer etc.
As above-mentioned acid catalyst; For example, just can enumerate-butylbenzene-sulfonic acid, just-aniline sulfonic acid, just-octyl group sulfonic acid, just-octyl group Phenylsulfonic acid, just-dodecyl Phenylsulfonic acid, just-octadecyl Phenylsulfonic acid, just-dibutyl Phenylsulfonic acid, isopropyl naphthalene sulfonic acid, dodecyl naphthene sulfonic acid, dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, tosic acid, xylene monosulfonic acid, pentadecyl Phenylsulfonic acid, cumene sulfonic acid, methylsulfonic acid, ethyl sulfonic acid, trifluoromethanesulfonic acid, trichlorine methylsulfonic acid, trifluoroacetic acid and trichoroacetic acid(TCA) and these compound compositions.
As above-mentioned acid catalyst, dinonyl base naphthene sulfonic acid is from obtaining good being considered it is preferred by the film hardness aspect.The amount of above-mentioned acid catalyst; Consider from the viewpoint of solidified nature and processibility; The solids component of carboxylic relatively resin (b1) and aminoresin (b2) adds up to 100 mass parts, preferred 0.01～5 mass parts, the more preferably scope of 0.02～1.0 mass parts, especially preferred 0.03～0.2 mass parts.
As above-mentioned basic cpd, can enumerate uncle's monoamines such as ethamine, propylamine, butylamine, amylamine, Monoethanolamine MEA BASF, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol; Diethylamine diethylolamine, two-just-or secondary monoamine such as HSDB 338, N-Mono Methyl Ethanol Amine, N-ehtylethanolamine; Uncle's monoamines such as dimethylethanolamine, Trimethylamine 99, triethylamine, tri-isopropyl amine, methyldiethanolamine, dimethylaminoethanol; Polyamines such as NSC 446, hydroxyethyl aminoethyl, ethylamino ethamine, methylamino propylamine.The amount of above-mentioned basic cpd, it is preferred reaching 0.1～1.2 equivalent as neutralization equivalent.
[method of manufacture] with stainless steel component of tunicle
Method of manufacture with stainless steel component of tunicle of the present invention; Be that stainless steel component is immersed in the aqueous solution (A); Energising makes and forms preferred 0.01～3.0 μ m, more preferably the 1st tunicle of 0.1～1.0 μ m thickness; Then, adopt electrophoretic painting to carry out the coating of anion electrophoresis coating (B), make form have below the preferred 30 μ m, more preferably the 2nd tunicle of the dry film thickness of 5～20 μ m, especially preferred 8～17 μ m.
Secondly,, do not wash or wash, assemble under the room temperature, carry out heat drying then stainless steel component with the 2nd tunicle.Heat drying was implemented in 130～200 ℃, the heating of preferred 150～190 ℃ temperature usually in 20～50 minutes, preferred 25～40 minutes.
Embodiment
Enumerate embodiment below, illustrate in greater detail the present invention, but the present invention is not limited by it.Also have, " part " reaches " % ", and except that doing special record, all expression " mass parts " reaches " quality % ".
[making example 1] has the making of the stainless steel component No.1 of the 1st tunicle
SUS304 (150mm * 70mm * 0.5mm; The austenite stainless steel plate), dipping carried out degreasing in 5 minutes in 25 ℃, the aqueous sulfuric acid of 100g/L, in the KBE-903 of 2 quality % (the annotating 1) aqueous solution, flooded SUS304 then; As anode, use 0.01A/cm to SUS304
2The current density of deciding switched on for 60 seconds, wash, process the stainless steel component No.1 of the 1st tunicle with thickness 0.3 μ m.
(annotating 1) KBE-903: the シ リ コ of SHIN-ETSU HANTOTAI-Application Co., Ltd. makes, trade(brand)name, 3-aminopropyltriethoxywerene werene
[making example 2] has the making of the stainless steel component No.2 of the 1st tunicle
SUS430 (150mm * 70mm * 0.5mm; The austenite stainless steel plate), dipping carried out degreasing in 5 minutes in 25 ℃, the aqueous sulfuric acid of 100g/L, in the KBM-903 of 2 quality % (the annotating 2) aqueous solution, flooded SUS430 then; As anode, use 0.01A/cm to SUS430
2The current density of deciding switched on for 40 seconds, wash, process the stainless steel component No.2 of the 1st tunicle with thickness 0.5 μ m.
(annotating 2) KBM-903: the シ リ コ of SHIN-ETSU HANTOTAI-Application Co., Ltd. makes, trade(brand)name, 3-TSL 8330
[making example 3] has the making of the stainless steel component No.3 of the 1st tunicle
SUS430 (150mm * 70mm * 0.5mm; The austenite stainless steel plate), dipping carried out degreasing in 5 minutes in 25 ℃, the aqueous sulfuric acid of 100g/L, in the KBM-603 of 2 quality % (the annotating 3) aqueous solution, flooded SUS430 then; As anode, use 0.01A/cm to SUS430
2The current density of deciding switched on for 40 seconds, wash, process the stainless steel component No.3 of the 1st tunicle with thickness 0.6 μ m.
(annotating 3) KBM-603: the シ リ コ of SHIN-ETSU HANTOTAI-Application Co., Ltd. makes, trade(brand)name, N-2-(amino-ethyl)-3-aminopropyltriethoxywerene werene
The making of [making example 4] stainless steel component No.4
SUS430 (150mm * 70mm * 0.5mm, austenite stainless steel plate), dipping carried out degreasing in 5 minutes in 25 ℃, the aqueous sulfuric acid of 100g/L, obtained stainless steel component No.4.
The manufacturing example of [making example 5] acrylic resin soln No.1
Pack in the reactor drum 21 parts of mixed solvents (annotating 4); Remain on 85 ℃, spend 3 hours and drip following " mixture (A) ", then; Add 3 parts of the two methyl pentane nitriles of azo; After 85 ℃ of maintenances were reacted in 4 hours, regulate solids component with mixed solvent, process the acrylic resin soln No.1 of solids component 70 quality %.Acrylic resin soln No.1 has acid number 33.9mgKOH/g, hydroxyl value 52.0mgKOH/g and weight-average molecular weight 35000.
Mixture (A)
(annotate 4) mixed solvent: Ucar 35 monomethyl ether/Virahol/propyl carbinol/ethylene glycol monobutyl ether=42 part/42 parts/42 parts/84 parts
The manufacturing example of [making example 6] acrylic resin soln No.2
Pack in the reactor drum 21 parts of mixed solvents (annotating 4); Remain on 85 ℃, spend 3 hours and drip following " mixture (B) ", then; Add 3 parts of the two methyl pentane nitriles of azo; After 85 ℃ of maintenances were reacted in 4 hours, regulate solids component with mixed solvent (annotating 4), process the acrylic resin soln No.2 of solids component 70 quality %.Acrylic resin soln No.2 has acid number 63mgKOH/g, hydroxyl value 28mgKOH/g and weight-average molecular weight 35000.
Mixture (B)
The manufacturing of [making example 7] emulsion No.1
After mixing 120.4 parts of 92.9 parts (65 parts of the solids components), the サ ィ メ Le 232S that make the 70% acrylic resin soln No.1 that obtains in the example 5 (annotating 6) 35.0 parts of (35 parts of solids components), DER621-PP50 (annotating 7) 1.0 parts of (0.5 part of solids component), 0.05 part of dinonylnaphthalene sulfonic acid, 1.9 parts of triethylamines and deionized waters; Slowly drip deionized water while stirring toward this mixture; This mixture is disperseed; Regulate solids component, obtain 40% emulsion No.1.
The manufacturing of [making example 8～14] emulsion No.2～No.8
Except that changing to the composition shown in the table 1, operate equally with making example 7, obtain the emulsion No.2～No.8 of solids component 40%.
Table 1
[the numeral solids component in the system parantheses.
The manufacturing of [relatively making example 1～7] emulsion No.9～No.15
Except that changing to the composition shown in the table 2, operate equally with making example 7, obtain the emulsion No.9～No.15 of solids component 40%.
Table 2
Numeral solids component in the parantheses.
(annotating 6) サ ィ メ Le 232S: Mitsui サ ィ テ Star Network society makes, trade(brand)name, methyl butyl complex etherified melamine resin, solids component 100%
(annotating 7) DER621-PP50: ダ ゥ ケ ミ カ Le society makes, trade(brand)name, epoxy phosphate ester cpds, acid number 45mgKOH/g, solids component 50.0%
(annotating 8) DER621-EB50: ダ ゥ ケ ミ カ Le society makes, trade(brand)name, epoxy phosphate ester cpds, acid number 35mgKOH/g, solids component 50.0%
(annotating 9) XU-7189.00: ダ ゥ ケ ミ カ Le society makes, trade(brand)name, epoxy phosphate ester cpds, acid number 9.8mgKOH/g, solids component 50.0%
The manufacturing example of [making example 15] colo(u)rant dispersion paste No.1
Mix for 11.5 parts with 10.0 parts of acrylic resin pigment dispersing resin (weight-average molecular weight 36000, hydroxyl value 70mgKOH/g, acid number 56mgKOH/g) 9.6 parts of (5.8 parts of solids components), CR-97 (annotating 10), 0.5 part of triethylamine and deionized water in 60% amine; Disperseed 20 hours with ball mill then, obtain the colo(u)rant dispersion paste No.1 of solids component 40%.
The manufacturing example of [making example 16～20] colo(u)rant dispersion paste No.2～No.6
Except that changing to the composition shown in the table 3, operate equally with making example 15, obtain the colo(u)rant dispersion paste No.2～No.6 of solids component 40%.
Table 3
Numeral solids component in the parantheses.
(annotating 10) CR-97: the former industry of stone society makes, trade(brand)name, titanium white
(annotating 11) carbon black MA-100: Mitsubishi Chemical society makes, trade(brand)name, carbon black
(annotating 12) メ タ シ-Application KM1000: Japan ァ Le ミ ニ ゥ system society makes, and trade(brand)name is given the AM aluminum metallization pigment of anchor, median size 11.1 μ m, particle thickness 0.025 μ m
(annotating 13) SF640: Toyo Ink is made society and is made, trade(brand)name, and キ Na Network リ De Application is a tinting pigment, solids component 36%, pigment composition 30%
(annotating 14) EMF BLUE 2R: Toyo Ink is made society and is made, and trade(brand)name, phthalocyanine blue are tinting pigment, solids component 40%, pigment composition 28%
(annotating 15) EMF YELLOW H2RN-2: Toyo Ink is made society and is made, trade(brand)name, and dual-azo yellow is a tinting pigment, solids component 40%, pigment composition 32%
The manufacturing of [making example 21] anion electrophoresis coating No.1
The emulsion No.1 of solids component 40% 251.2 parts (100.5 parts of solids components) 39.5 parts (15.8 parts of solids components) with the colo(u)rant dispersion paste No.1 of solids component 40%; Mix for 1163.1 parts with deionized water, obtain the anion electrophoresis coating No.1 of solids component 8%.
The manufacturing of [making example 22～33] anion electrophoresis coating No.2～No.13
Except that changing to the composition shown in table 4 and the table 5, operate equally with making example 21, obtain anion electrophoresis coating No.2～No.13.
Table 4
Numeral solids component in the parantheses.
Table 5
Numeral solids component in the parantheses.
The manufacturing of [relatively making example 8～14] anion electrophoresis coating No.14～No.20
Except that changing to the composition shown in the table 6, operate equally with making example 21, obtain anion electrophoresis coating No.14～No.20.
Table 6
Numeral solids component in the parantheses.
[embodiment 1] has the stainless steel component No.1 of tunicle
In the bath of anion electrophoresis coating No.1, dipping has the stainless steel plate No.1 of the 1st tunicle, as anode, in 150V energising 2 minutes, carries out electrophoretic painting to the stainless steel plate No.1 with the 1st tunicle.Secondly, in 180 ℃ of heat dryings 20 minutes, obtain having the stainless steel plate No.1 of tunicle, said tunicle has the 1st tunicle and the 2nd tunicle (dry film thickness 15 μ m).
[embodiment 2～16] have the stainless steel component No.2～No.16 of tunicle
Except that the stainless steel component shown in the employing table 7 and the electrophoretic paint with the 1st tunicle, operate equally with embodiment 1, obtain having the stainless steel component No.2～No.16 of tunicle.
Have the stainless steel component No.1～No.16 of tunicle, carry out the film performance evaluation by following items.The result is shown in table 7.
Table 7
Table 7 is continuous
[comparative example 1] has the stainless steel component No.17 of tunicle
In the bath of anion electrophoresis coating No.1, dipping stainless steel component No.4 as anode, in 150V energising 2 minutes, carries out electrophoretic painting to stainless steel component No.4.Secondly, in dry 20 minutes of 180 ℃ of sintering, obtain having the stainless steel component No.17 of tunicle, said tunicle has the tunicle from anion electrophoresis coating No.1 of dry film thickness 15 μ m.
[comparative example 2～15] has the stainless steel component No.18～No.31 of tunicle
Except that adopting the stainless steel component shown in the table 8 and the electrophoretic paint, operating equally, obtain coated panel No.18～No.31 with comparative example 1.
Have the stainless steel component No.18～No.31 of tunicle, carry out the film performance evaluation by following items.The result is shown in table 8.
Table 8
Table 8 is continuous
(annotate 16) pencil hardness: estimate according to " stroke hardness (the pencil method) " of regulation among the JIS K 5600-5-4 (1999) stainless steel component with tunicle by film hardness.
(annotating 17) shock-resistance: the デ ュ パ Application formula according to " the anti-counterweight whereabouts property " of regulation among the JIS K 5600-5-3 (1999) is estimated.Concrete is; Stainless steel component with tunicle is in the indoor placement of the fixed temperature and humidity of temperature 20 ℃ ± 1, humidity 75 ± 2% after 24 hours; Be installed in the impingement of stipulating among the JIS K 5600-5-3 and tried on the platform, the tunicle of the stainless steel component with tunicle is faced up, clamping betwixt; Make the 500g counterweight fall to impingement then and tried on the platform, measure the height of drop (cm) that on tunicle, cracks or peel off because of impacting.
(annotating 18) adaptation: the tack (cross-section method) according to regulation among the JIS K 5600-5-6 (1999) is estimated.Concrete is, tunicate stainless steel component by face on, use pocket knife, laterally respectively cut 11 crosscuts vertically reaching respectively with the interval of about 1mm, make to reach on the base material formation checker point-like.Then, the ethene splicing tape is pasted in amounting on 100 (10 * 10) grid in this chessboard lattice point, estimates splicing tape by the tunicle after peeling off rapidly according to standards:
VG (very good): 100 grid in the chessboard lattice point are peeled off
G (good): peel off slightly a part of end in 100 grid in the chessboard lattice point
F (qualified): peel off for 1～20 in 100 grid
P (defective): peel off more than 21 in 100 grid
(annotating 19) processibility: the surface of the tunicate stainless steel component of visual inspection, estimate by following standard:
VG (very good): tunicle is no abnormal
G (good): tunicle has spherical sense slightly, but the processing no problem
F (qualified): observe spherical sense or tarnish
P (defective): observe significant spherical sense or tarnish
The possibility of utilizing on the industry
The stainless steel component with tunicle according to method of the present invention obtains as easy and clothes friction, or comes off, or is stepped on the exterior member of the electronic machine of stepping on (for example digital camera, mobile phone), is very useful.
Claims (4)
1. the method for manufacture that has the stainless steel component of tunicle; It is characterized in that; This method comprises: be immersed in said stainless steel component in the water-soluble bath of liquid that contains amino silane coupling agent (A), then to said stainless steel component energising, on this stainless steel component, form the step of the 1st tunicle thus;
On the 1st tunicle, coating is implemented electrophoretic painting, form the step of the 2nd tunicle; Said coating is the epoxy phosphate ester cpds (b3) of carboxylic resin (b1), aminoresin (b2), hydroxyl and the electrophoretic paint (B) of coloring components (b4); The carboxylic relatively resin of amount (b1) of the epoxy phosphate ester cpds (b3) of hydroxyl adds up to 100 mass parts to be in the scope of 0.1～10.0 mass parts with the solids component of aminoresin (b2); And
At least the 2nd tunicle is carried out the agglomerating step.
2. according to the described method of claim 1; Wherein, Containing amino silane coupling agent (A) is selected from: N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-3-aminopropyltriethoxywerene werene, 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-triethoxysilyl-N-(1; 3-dimethyl--butylidene) group of propylamine and partial hydrolystate thereof, 3-trimethoxysilyl-N-(1,3-dimethyl--butylidene) propylamine and partial hydrolystate thereof and N-phenyl-3-TSL 8330 formation.
3. the stainless steel component that has tunicle, the 1st tunicle and the 2nd tunicle on the 1st tunicle that it has on the stainless steel component is characterized in that:
The 1st tunicle is through in the aqueous solution that contains amino silane coupling agent (A), the tunicle that forms to this stainless steel component energising; And
The 2nd tunicle is the stainless steel component with the 1st tunicle to be implemented electrophoretic painting and the tunicle that forms with coating; Said coating is the epoxy phosphate ester cpds (b3) of carboxylic resin (b1), aminoresin (b2), hydroxyl and the electrophoretic paint (B) of coloring components (b4), and the amount of the epoxy phosphate ester cpds (b3) of hydroxyl adds up to 100 mass parts to be in the scope of 0.1～10.0 mass parts to the solids component of carboxylic resin (b1) and aminoresin (b2).
4. electronic instrument part wherein comprises the stainless steel component of the tunicle that the method that adopts record in the claim 1 or 2 makes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-156283 | 2009-06-30 | ||
| JP2009156283 | 2009-06-30 | ||
| PCT/JP2010/060597 WO2011001862A1 (en) | 2009-06-30 | 2010-06-16 | Method for producing stainless steel member having coating film |
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|---|---|
| CN102713021A true CN102713021A (en) | 2012-10-03 |
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| CN2010800289350A Pending CN102713021A (en) | 2009-06-30 | 2010-06-16 | Method for producing stainless steel member having coating film |
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|---|---|
| JP (1) | JPWO2011001862A1 (en) |
| KR (1) | KR20120023140A (en) |
| CN (1) | CN102713021A (en) |
| WO (1) | WO2011001862A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI638907B (en) | 2017-08-03 | 2018-10-21 | 國立高雄大學 | Self-assembly solution having anti-corrosion ability and its manufacturing method |
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| DE102012204636A1 (en) * | 2012-03-22 | 2013-09-26 | Nanogate Ag | Treatment of anodized surface |
| WO2018191841A1 (en) * | 2017-04-17 | 2018-10-25 | Dic Corporation | Aqueous resin composition, aqueous coating material and article having cured coating film of the aqueous coating material |
| JP7272706B1 (en) | 2021-12-28 | 2023-05-12 | ドングァン ディーエスピー テクノロジー カンパニー リミテッド | Stainless steel surface treatment method for polymer-stainless steel joints |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS585377A (en) * | 1981-07-01 | 1983-01-12 | Kansai Paint Co Ltd | Anionic electrodeposition paint |
| US4957952A (en) * | 1986-04-03 | 1990-09-18 | Desoto, Inc. | Anionic electrocoat compositions containing epoxy phosphates |
| JPH02305993A (en) * | 1989-05-17 | 1990-12-19 | Takasago Tekko Kk | Surface treatment of metallic material with superior adhesion of coating |
| JPH05179177A (en) * | 1991-12-27 | 1993-07-20 | Kansai Paint Co Ltd | Low-temperature curable electrodeposition coating composition |
| CN1436122A (en) * | 2000-04-12 | 2003-08-13 | 三菱树脂株式会社 | Metal sheet coated with resin and method for its production |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0240876A3 (en) * | 1986-04-03 | 1988-08-31 | DeSoto, Inc. | Thermosetting aqueous anionic electrocoating composition containing epoxy phosphates |
-
2010
- 2010-06-16 KR KR1020117031260A patent/KR20120023140A/en active IP Right Grant
- 2010-06-16 WO PCT/JP2010/060597 patent/WO2011001862A1/en active Application Filing
- 2010-06-16 CN CN2010800289350A patent/CN102713021A/en active Pending
- 2010-06-16 JP JP2011520871A patent/JPWO2011001862A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS585377A (en) * | 1981-07-01 | 1983-01-12 | Kansai Paint Co Ltd | Anionic electrodeposition paint |
| US4957952A (en) * | 1986-04-03 | 1990-09-18 | Desoto, Inc. | Anionic electrocoat compositions containing epoxy phosphates |
| JPH02305993A (en) * | 1989-05-17 | 1990-12-19 | Takasago Tekko Kk | Surface treatment of metallic material with superior adhesion of coating |
| JPH05179177A (en) * | 1991-12-27 | 1993-07-20 | Kansai Paint Co Ltd | Low-temperature curable electrodeposition coating composition |
| CN1436122A (en) * | 2000-04-12 | 2003-08-13 | 三菱树脂株式会社 | Metal sheet coated with resin and method for its production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI638907B (en) | 2017-08-03 | 2018-10-21 | 國立高雄大學 | Self-assembly solution having anti-corrosion ability and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011001862A1 (en) | 2012-12-13 |
| KR20120023140A (en) | 2012-03-12 |
| WO2011001862A1 (en) | 2011-01-06 |
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