WO2011001862A1 - 皮膜を有するステンレス鋼部材の製造方法 - Google Patents
皮膜を有するステンレス鋼部材の製造方法 Download PDFInfo
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- WO2011001862A1 WO2011001862A1 PCT/JP2010/060597 JP2010060597W WO2011001862A1 WO 2011001862 A1 WO2011001862 A1 WO 2011001862A1 JP 2010060597 W JP2010060597 W JP 2010060597W WO 2011001862 A1 WO2011001862 A1 WO 2011001862A1
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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
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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
- C25D13/20—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
Definitions
- the present invention relates to a method for producing a stainless steel member having a film excellent in film hardness, impact resistance, adhesion and finish.
- stainless steel uses the fact that chromium (Cr) in the composition combines with oxygen in the air to form a passive film on the surface, and as a highly corrosion-resistant material, it is used outdoors, in humid places, chemicals It is used in machinery and equipment, kitchen facilities, etc.
- Cr chromium
- the scratch resistance is improved by increasing the film hardness, but it is known that the impact resistance and adhesion are reduced by increasing the film hardness. It was difficult to form an electrodeposition coating film satisfying the scratch resistance, impact resistance and adhesion. Furthermore, the electronic device parts are also required to have excellent design properties, particularly finish properties.
- the chemical conversion coating is an aminosilane-based chemical conversion treatment.
- a chromate-free clear-coated stainless steel sheet comprising a coating film, a clear coating film comprising an acrylic resin having a glass transition point of 30 to 90 ° C. and a number average molecular weight of 3000 to 50000 and a blocked isocyanate compound. ing.
- an object of the present invention is to provide a method for producing a stainless steel member having a film excellent in film hardness, impact resistance, adhesion and finish.
- the present inventors are a method for producing a stainless steel member having a film, wherein the stainless steel member is made of an amino group-containing silane coupling agent (A).
- a step of forming a first film on the stainless steel member by immersing in an aqueous solution bath and energizing the stainless steel member, a carboxyl group-containing resin (b1), an amino resin on the first film (B2), an electrodeposition paint (B) containing a hydroxyl group-containing epoxyphosphate compound (b3) and a coloring component (b4), wherein the amount of the hydroxyl group-containing epoxyphosphate compound (b3) is a carboxyl group-containing
- electrodeposition-coating a resin in the range of 0.1 to 10.0 parts by mass based on the total solid content of the resin (b1) and amino resin (b2) of 100 parts by mass It has been found that the above-mentioned problems can be solved by a method comprising the steps of forming
- a method for producing a stainless steel member having a coating Immersing the stainless steel member in an aqueous solution of an amino group-containing silane coupling agent (A) and energizing the stainless steel member to form a first film on the stainless steel member;
- An electrodeposition paint (B) comprising a carboxyl group-containing resin (b1), an amino resin (b2), a hydroxyl group-containing epoxyphosphate compound (b3), and a coloring component (b4) on the first film,
- the amount of the hydroxyl group-containing epoxy phosphate ester compound (b3) is in the range of 0.1 to 10.0 parts by mass based on 100 parts by mass of the total solid content of the carboxyl group-containing resin (b1) and the amino resin (b2).
- a method comprising the steps of:
- the amino group-containing silane coupling agent (A) is N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its Selected from the group consisting of partial hydrolysates, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolysates, and N-phenyl-3-aminopropyltrimethoxysilane The method of embodiment 1.
- a stainless steel member having a coating having a first coating on the stainless steel member and a second coating on the first coating The first film is a film formed by energizing a stainless steel member in an aqueous solution of an amino group-containing silane coupling agent (A), and the second film is stainless steel having the first film.
- the member is an electrodeposition paint (B) containing a carboxyl group-containing resin (b1), an amino resin (b2), a hydroxyl group-containing epoxy phosphate ester compound (b3), and a coloring component (b4), and the hydroxyl group-containing epoxy phosphorus
- the amount of the acid ester compound (b3) is in the range of 0.1 to 10.0 parts by mass based on the total solid content of 100 parts by mass of the carboxyl group-containing resin (b1) and the amino resin (b2) It is a film formed by electrodeposition coating, A stainless steel member having the above film.
- the method for producing a stainless steel member having a coating according to the present invention can form a coating having excellent coating hardness, impact resistance, adhesion and finish on a stainless steel member.
- the manufacturing method of the stainless steel member which has a film of the present invention is explained.
- the stainless steel member is immersed in a bath of an aqueous solution of an amino group-containing silane coupling agent (A), and the stainless steel member is energized to form a first film on the stainless steel member (hereinafter referred to as “the first film”).
- the first film which may be referred to as “step for forming the first film”.
- the stainless steel member used in the present invention is formed from conventionally known stainless steels such as ferrite ( ⁇ ), martensite (M), austenite ( ⁇ ), and austenite / ferrite two-phase ( ⁇ + ⁇ ). A member can be mentioned.
- the stainless steel include, for example, austenitic stainless steel such as SUS304, SUS305, SUS310, SUS316, and SUSMX7; philite stainless steel such as SUS430, martensitic stainless steel such as SUS403, SUS410, SUS416, and SUS420; SUS631 Or a precipitation hardening stainless steel.
- austenitic stainless steel such as SUS304, SUS305, SUS310, SUS316, and SUSMX7
- philite stainless steel such as SUS430, martensitic stainless steel such as SUS403, SUS410, SUS416, and SUS420
- SUS631 Or a precipitation hardening stainless steel.
- the said stainless steel can use the thing which carried out the degreasing process suitably as needed.
- the stainless steel may or may not be subjected to a chemical conversion treatment on the surface, and is preferably not subjected to chemical conversion treatment.
- an aqueous solution of an amino group-containing silane coupling agent (A) (hereinafter referred to as an aqueous solution (A)
- the first film is formed by immersing in a bath (which may be abbreviated as “)” and energizing at least once.
- a plurality of amino group-containing silane coupling agents (A) can be used in combination.
- an aqueous bath of the silane coupling agent (A 1 ) and a silane coupling agent (A 2 ) Prepare an aqueous solution bath, immerse the stainless steel member in the silane coupling agent (A 1 ) bath, energize, and then immerse the stainless steel member in the silane coupling agent (A 2 ) bath.
- the first film can be formed.
- amino group-containing silane coupling agent (A) examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N 2- (Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propyl Examples thereof include amines and partial hydrolysates thereof, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and partial hydrolysates thereof, N-phenyl-3-aminopropyltrimethoxysilane, and the like.
- Examples of commercially available amino group-containing silane coupling agents include KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBM-9103, KBM-573, KBM-575 and KBM-6123 ( As mentioned above, the product name of Shin-Etsu Silicone Co., Ltd. is mentioned.
- amino group-containing silane coupling agent (A) in particular, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane are This is preferable from the viewpoint of adhesion to a second film formed by electrodeposition coating of an anionic electrodeposition coating material (B) described later.
- the concentration of the aqueous solution of the amino group-containing silane coupling agent (A) is not particularly limited, but from the viewpoint of bath stability, formed impact resistance, and adhesion,
- the content is preferably 0.1 to 20% by mass, more preferably 0.5 to 5% by mass, and still more preferably 1 to 3% by mass.
- the stainless steel member is immersed in an aqueous solution of an amino group-containing silane coupling agent (A) and the liquid temperature is adjusted to 10 to 40 ° C. It is preferable to energize according to a normal electrodeposition coating method using as a positive electrode.
- the current density during the conduction is not particularly limited, but preferably 0.001A / cm 2 ⁇ 0.1A / cm 2, more preferably at 0.005A / dm 2 ⁇ 0.05A / cm 2, and energizing
- the time is preferably 10 seconds to 300 seconds, more preferably 30 seconds to 200 seconds.
- the energization may be repeated a plurality of times.
- the plurality of aqueous solution (A) baths are the same type of aqueous solution (A) baths.
- the stainless steel member is immersed in one bath and energized, it is not washed with water, and the stainless steel member is subsequently immersed in another bath and energized.
- the plurality of aqueous solution (A) baths are different types of aqueous solution (A) baths, the stainless steel member is immersed in a certain bath and energized, then washed with water and adhered to the surface. After removing the unprecipitated metal salt, it can be immersed in a separate bath and energized.
- the method of the present invention may further include, after the step of forming the first film, optionally drying at room temperature, or heating and drying at 40 to 80 ° C. for 1 to 60 minutes.
- the first film preferably has a dry film thickness of 0.01 to 3 ⁇ m, more preferably 0.1 to 1.0 ⁇ m, considering impact resistance, adhesion, and finish.
- step of forming the second film by electrodeposition-coating the anionic electrodeposition paint (B) on the first film (hereinafter referred to as “step of forming the second film”).
- step of forming the second film Exist).
- the anionic electrodeposition paint (B) used in the step of forming the second film comprises a carboxyl group-containing resin (b1), an amino resin (b2), a hydroxyl group-containing epoxyphosphate compound (b3), and a coloring component (b4). ), And the amount of the hydroxyl group-containing epoxy phosphate ester compound (b3) is based on a total solid content of 100 parts by mass of the carboxyl group-containing resin (b1) and the amino resin (b2). In the range of 0.1 to 10.0 parts by mass.
- the carboxyl group-containing resin (b1) is a resin having at least one carboxyl group in one molecule.
- the carboxyl group-containing resin (b1) is preferably a resin further having at least one hydroxyl group.
- Specific examples of the carboxyl group-containing resin (b1) include resins such as an acrylic resin, a polyester resin, a polyether resin, a polycarbonate resin, and a urethane resin.
- An acrylic resin is preferable in terms of film hardness and finish. is there.
- the acrylic resin is produced by copolymerizing a carboxyl group-containing radical polymerizable unsaturated monomer, a desired hydroxyl group-containing radical polymerizable unsaturated monomer, and other radical polymerizable unsaturated monomers. be able to.
- Examples of the carboxyl group-containing radical polymerizable unsaturated monomer include monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.
- Examples of the hydroxyl group-containing radical polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate,
- Plaxel FM1, Plaxel FM2, Plaxel FM3, Plaxel FA1, Plaxel FA2, Plaxel FA3 (manufactured by Daicel Chemical Industries, trade name, caprolactone-modified (meth) acrylic acid hydroxy ester).
- Examples of the other radical polymerizable unsaturated monomer include ⁇ - (meth) acryloyloxypropyltrimethoxysilane, ⁇ - (meth) acryloyloxypropylmethyldimethoxysilane, and ⁇ - (meth) acryloyloxypropyltriethoxy.
- Alkoxysilyl group-containing unsaturated monomers such as silane and vinyltrimethoxysilane; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl ( C1-C18 alkyl or cycloalkyl esters of (meth) acrylates such as (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate, and styrene Aromatic vinyl monomers; (meth) acrylic acid amide, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N
- the acrylic resin is generally a polymerization containing the carboxyl group-containing radically polymerizable unsaturated monomer, the desired hydroxyl group-containing radically polymerizable unsaturated monomer, and other radically polymerizable unsaturated monomers.
- the solution can be obtained by radical polymerization in a solvent using a polymerization initiator.
- the radical polymerization the polymerization solution contains 1 to 20% by mass, preferably 4 to 10% by mass of the carboxyl group-containing polymerizable unsaturated monomer, based on the total amount of monomers, and the hydroxyl group-containing radical polymerizable monomer.
- a saturated monomer may be contained in an amount of 0 to 40% by mass, preferably 5 to 30% by mass, and other radical polymerizable unsaturated monomer in an amount of 40 to 99% by mass, preferably 60 to 91% by mass. preferable.
- the polymerization solution contains 0.1 to 30 (meth) acrylamide monomers as other radical polymerizable unsaturated monomers based on the total amount of monomers. It is preferable to contain in the range of mass%.
- the solvent examples include alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, and isobutyl alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, 2-methoxyethanol, and 2-ethoxy.
- the solvent examples include aromatics such as xylene and toluene; ketones such as acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone, isophorone, and cyclohexanone; methyl acetate, ethyl acetate, pentyl acetate, 3- Esters such as methoxybutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl propionate, and ethyl propionate can be further included.
- aromatics such as xylene and toluene
- ketones such as acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone, isophorone, and cyclohexanone
- radical polymerization initiators used for radical polymerization include benzoyl peroxide, di-t-butyl hydroperoxide, t-butyl hydroperoxide, cumyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, t -Peroxides such as butylperoxybenzoate, lauryl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, ⁇ , ⁇ '-azobisisobutyronitrile, azobisdimethylvaleronitrile, Examples include azo compounds such as azobiscyclohexanecarbonitrile.
- the acrylic resin has a weight average molecular weight of preferably 5,000 to 150,000, more preferably 20,000 to 100,000.
- the weight average molecular weight is 40 ° C. using four TSK gel2000HXL, TSK gel2500HXL, TSK gel3000HXL, and TSK gel4000HXL (above, manufactured by Tosoh Corporation) according to JIS K 0124-83.
- Means a value obtained from a chromatograph obtained with an RI refractometer and a calibration curve of polystyrene using a flow rate of 1.0 ml / min and tetrahydrofuran for GPC as an eluent.
- amino resin (b2) As the amino resin (b2), conventionally known compounds can be used.
- the amino resin (b2) can be obtained by reacting an amino component such as melamine resin, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the aldehyde. Examples include methylolated amino resins and alkyl etherified products of the above methylolated amino resins.
- a methylolated melamine resin is suitable, and a part or all of the methylol group of the methylolated melamine resin is 1 such as methanol, ethanol, propanol, butanol, octyl alcohol, 2-ethylhexyl alcohol or the like. Mention may be made of melamine resins modified with seeds or two or more monohydric alcohols.
- melamine resins Commercially available products of the melamine resin include, for example, Uban 20SE-60, Uban 225 (all are trade names manufactured by Mitsui Chemicals, Inc.), Super Becamine G840, Super Becamine G821 (All are Dai Nippon Ink Chemical Co., Ltd.) Butyl etherified melamine resins such as trade name, manufactured by Kogyo Co., Ltd .; Sumimar M-100, Sumimar M-40S, Sumimar M-55 (all of which are trade names manufactured by Sumitomo Chemical Co., Ltd.), Cymel 232, Cymel 303, Cymel 325 , Cymel 327, Cymel 350, Cymel 370 (all of which are manufactured by Nihon Cytec Industries, Inc., trade name), Nicarak MS17, Nicarak MX15, Nicarak MX430, Nicarak MX600 (all of which are manufactured by Sanwa Chemical Co., Ltd., trade name) Resimin 741 (Mon Methyl
- the mixing ratio of the carboxyl group-containing resin (b1) and the amino resin (b2) is based on the total solid content of 100 parts by mass of the carboxyl group-containing resin (b1) and the amino resin (b2).
- b1) 50 to 75 parts by mass, preferably 50 to 65 parts by mass, amino resin (b2) 25 to 50 parts by mass, preferably 35 to 50 parts by mass, the film hardness, impact resistance, adhesion and finish From the viewpoint of sex.
- the anionic electrodeposition paint (B) used in the step of forming the second film can further contain a blocked polyisocyanate compound in addition to the amino resin (b2).
- polyisocyanate compound examples include (o-, m-, p-) tolylene diisocyanate, (o-, m-, p-) xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,2'-diisocyanate, diphenylmethane- Aromatics such as 2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate An aliphatic or alicyclic polyisocyanate compound; a cyclized polymer or biuret of these polyisocyanate compounds; or a combination thereof. Can.
- oxime compounds such as methyl ethyl ketoxime, methyl amyl ketoxime and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol and cresol; n-butanol, 2- Aliphatic alcohols such as ethyl hexanol; Aromatic alkyl alcohols such as phenyl carbinol and methyl phenyl carbinol; Ether alcohol compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; ⁇ -caprolactam, ⁇ -butyrolactam, etc. And lactam compounds.
- block polyisocyanate compounds include, for example, Barnock D-750, Barnock D-800, Barnock DN-950, Barnock DN-970 or Barnock DN-15-455, (manufactured by Dainippon Ink & Chemicals, Inc.
- Death Module L Death Module N
- Death Module HL Death Module IL or Death Module N3390 (above, manufactured by Bayer Products), Takenate D-102, Takenate D-202, Takenate D-110N or Takenate D -123N (manufactured by Takeda Pharmaceutical Company Limited, trade name), Coronate L, Coronate HL, Coronate EH or Coronate 203 (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name) or Duranate 24A-90CX (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) Cited That.
- the hydroxyl group-containing epoxy phosphate ester compound (b3) is a compound obtained by adding a phosphate compound to an epoxy resin, and the hydroxyl group and phosphate residue in the hydroxyl group-containing epoxy phosphate ester compound (b3) are: While improving adhesiveness with a 1st membrane
- the epoxy resin examples include bisphenol-type epoxy resins, novolac-type epoxy resins, and modified epoxy resins obtained by reacting an epoxy group or a hydroxyl group in these epoxy resins with a modifier.
- the bisphenol-type epoxy resin is, for example, a resin produced by condensing epichlorohydrin and bisphenol to a high molecular weight in the presence of a catalyst such as an alkali catalyst, if desired, and epichlorohydrin and bisphenol, if desired, such as an alkali catalyst. It can be a resin obtained by condensing in the presence of a catalyst and synthesizing with a low molecular weight epoxy resin, and then polyadding the low molecular weight epoxy resin and bisphenol.
- the epoxy equivalent of the epoxy resin is preferably 172 to 4,000, more preferably 175 to 1,000.
- bisphenol examples include bis (4-hydroxyphenyl) methane [bisphenol F], 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxyphenyl) butane [bisphenol B], bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-tert-butyl-phenyl) -2,2-propane, Examples thereof include p- (4-hydroxyphenyl) phenol, oxybis (4-hydroxyphenyl), sulfonylbis (4-hydroxyphenyl), 4,4′-dihydroxybenzophenone, and bis (2-hydroxynaphthyl) methane.
- the bisphenols may be used alone or as a mixture of two or more.
- novolak type epoxy resin examples include a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and a phenol glyoxal type epoxy resin having a plurality of epoxy groups in the molecule.
- the hydroxyl group-containing epoxy phosphate ester compound (b3) is prepared by adding a phosphate compound to an epoxy resin and, for example, at a reaction temperature of 70 to 150 ° C., preferably 110 to 130 ° C. in the presence of a catalyst such as imidazoles and phosphonium salts. The reaction time is 1 to 8 hours, preferably 3 to 6 hours.
- the reaction is preferably performed in such an amount as follows.
- the acid value of the hydroxyl group-containing epoxy phosphate ester compound (b3) is preferably 5 to 70 mgKOH / g, more preferably 28 to 60 mgKOH / g, and still more preferably 35 to 57 mgKOH / g, from the viewpoint of improving adhesion. is there.
- the hydroxyl group-containing epoxy phosphate ester compound (b3) is 0.1 to 10.0 parts by mass, preferably 0, based on 100 parts by mass in total of the solid content of the carboxyl group-containing resin (b1) and the amino resin (b2). It is contained in the anionic electrodeposition coating material (B) in an amount in the range of 0.5 to 8.0 parts by mass, more preferably 1.0 to 6.0 parts by mass.
- the amount of the hydroxyl group-containing epoxy phosphate ester compound (b3) is less than 0.1 parts by mass, the second film tends not to adhere sufficiently to the first film and the stainless steel member, and the hydroxyl group
- the amount of the contained epoxyphosphate compound (b3) exceeds 10.0 parts by mass, the coating stability and the weather resistance tend to decrease.
- the anion electrodeposition coating material (B) can contain a coloring component (b4) for the purpose of improving design properties.
- a coloring component (b4) include titanium oxide, zinc oxide, carbon black, iron black, aniline black, Hansa yellow, benzidine yellow, tartrazine lake, permanent yellow toner, cadmium yellow, benzidine orange, chrome vermillion, cadmium.
- a processed pigment in which a pigment is dispersed with a dispersant is preferable from the viewpoint of paint stability and design, and Unisperse Yellow 10GN-S, Unisperse DPP Orange RA-S, Unisper Red 2G -S, Unisparse Violet BS, Unispers Blue BS, Unispers Green GS, Unispers Black CS (manufactured by Ciba Specialty Chemicals Co., Ltd.), Koranil Yellow 10G130, Koranil Red FGRG130, Koranyl Carmine FB130, Koranil Violet RL130, Koranil Blue A2R200, Koranil Blue A2R130, Koranil Blue B2G130, Koranil Green GG131, Koranil Black PR130, Koranil Oxai Blue CD100, Coranyl Oxide Green G131, Host Fine Blue B2G, Coranil Yellow HR, Collanil Black T (made by Clariant), EMF Color Yellow 3G, EMF Orange O,
- the anionic electrodeposition paint (B) can contain two or more coloring components (b4), and the amount of the coloring component (b4) varies depending on the purpose of use, but the weather resistance, impact resistance and design properties are different. From the viewpoint, based on the total solid content of 100 parts by mass of the carboxyl group-containing resin (b1) and the amino resin (b2), preferably 0.01 to 40 parts by mass, more preferably 0.01 to 25 parts by mass, More preferably, it is in the range of 0.01 to 10 parts by mass.
- the aqueous dispersion of carboxyl group-containing resin (b1) was prepared by adding amino resin (b2), hydroxyl group-containing epoxyphosphate compound (b3), and optionally blocked polyisocyanate compound to carboxyl group-containing resin (b1).
- an acid catalyst, a basic compound and deionized water are further added and stirred with a disper or the like.
- the acid catalyst examples include n-butylbenzenesulfonic acid, n-aminobenzenesulfonic acid, n-octylsulfonic acid, n-octylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid, n-octadecylbenzenesulfonic acid, n-dibutylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, pentadecylbenzenesulfonic acid, cumenesulfonic acid, methanesulfone Examples include acids, ethanesulfonic acid, trifluo
- the amount of the acid catalyst is preferably 0.01 to 5 parts by mass based on the total solid content of 100 parts by mass of the carboxyl group-containing resin (b1) and the amino resin (b2) from the viewpoints of curability and finish. More preferably, it is in the range of 0.02 to 1.0 part by mass, and still more preferably 0.03 to 0.2 part by mass.
- Examples of the basic compound include primary amines such as ethylamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentanolamine, 2-aminopropanol, and 3-aminopropanol; diethylamidiethanolamine, di-n- Or secondary monoamines such as diisopropanolamine, N-methylethanolamine, N-ethylethanolamine; tertiary monoamines such as dimethylethanolamine, trimethylamine, triethylamine, triisopropylamine, methyldiethanolamine, dimethylaminoethanol; diethylenetriamine, Polyamines such as hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine and the like can be mentioned.
- the amount of the basic compound is preferably such that the neutralization equivalent is 0.1 to 1.2 equivalents.
- the stainless steel member is immersed in the aqueous solution (A), preferably 0.01 to 3.0 ⁇ m, and more preferably 0.1 to 1.0 ⁇ m.
- an anion electrodeposition coating material (B) is dried to a thickness of preferably 30 ⁇ m or less, more preferably 5 to 20 ⁇ m, and even more preferably 8 to 17 ⁇ m. It is carried out by electrodeposition coating so that a second film having a thickness is formed.
- the stainless steel member having the second film can be washed with water or set at room temperature and dried by heating. Heat drying is usually carried out at a temperature of 130 to 200 ° C., preferably 150 to 190 ° C., for 20 to 50 minutes, preferably 25 to 40 minutes.
- Parts and % indicate “parts by mass” and “% by mass” unless otherwise specified.
- Emulsion No. 2 ⁇ No. Production of No. 8 Emulsion No. 8 having a solid content of 40% was prepared in the same manner as in Production Example 7 except that the composition was changed to the composition shown in Table 1. 2 ⁇ No. 8 was obtained.
- Emulsion No. 9 ⁇ No. Production of No. 15 Emulsion No. 15 having a solid content of 40% was prepared in the same manner as in Production Example 7 except that the composition was changed to the composition shown in Table 2. 9 ⁇ No. 15 was obtained.
- Pigment dispersion paste No. Production Example 1 1 60% amine-neutralized acrylic resin pigment dispersion resin (weight average molecular weight 36,000, hydroxyl value 70 mg KOH / g, acid value 56 mg KOH / g) 9.6 parts (solid content 5.8 parts), CR- 97 (Note 10) 10.0 parts, 0.5 parts of triethylamine, and 11.5 parts of deionized water were mixed, and then dispersed for 20 hours by a ball mill to obtain a pigment dispersion paste No. 40 having a solid content of 40%. 1 was obtained.
- Pigment dispersion paste No. 2 ⁇ No. Production Example 6 A pigment dispersion paste No. 6 having a solid content of 40% was prepared in the same manner as in Production Example 15 except that the composition was changed to the composition shown in Table 3. 2 ⁇ No. 6 was obtained.
- Anionic electrodeposition paint No. 14 ⁇ No. Production of No. 20 Anion electrodeposition paint No. 20 was prepared in the same manner as in Production Example 21 except that the composition was changed to the composition shown in Table 6. 14 ⁇ No. 20 was obtained.
- No. 1 is a stainless steel plate No. 1 having a first film. Electric current was applied at 150 V for 2 minutes so that 1 became an anode, and electrodeposition was applied. Subsequently, it heat-dried at 180 degreeC for 20 minute (s), and has the 1st membrane
- Example 2 to 16 Stainless steel member No. 2 ⁇ No. 16 In the same manner as in Example 1 except that the stainless steel member having the first film and the electrodeposition paint shown in Table 7 were used, the stainless steel member No. 2 ⁇ No. 16 was obtained. Stainless steel member No. 1-No. 16 was evaluated for the coating film performance with respect to the following items. The results are shown in Table 7.
- Pencil hardness In accordance with “scratch hardness (pencil method)” defined in JIS K 5600-5-4 (1999), the hardness of the stainless steel member having the film was evaluated.
- Impact resistance Evaluated according to the DuPont type of “weight drop resistance” defined in JIS K 5600-5-3 (1999). Specifically, a stainless steel member having a coating is placed in a constant temperature and humidity chamber at a temperature of 20 ° C. ⁇ 1 and a humidity of 75 ⁇ 2% for 24 hours, and then a shooting mold defined in JIS K 5600-5-3 is used. A cradle is attached, the surface of the stainless steel member having the film is turned upward, and sandwiched between them. Next, a 500 g weight is dropped on the mold, and cracking or peeling occurs on the film (surface) due to the impact. The drop height (cm) was measured.
- Adhesion Evaluated according to adhesion (cross-cut method) defined in JIS K 5600-5-6 (1999). Specifically, on the coating surface of the stainless steel member having the coating, 11 crosscuts are made in each of the vertical and horizontal sides at intervals of about 1 mm so as to reach the substrate using a knife, Form. Subsequently, a vinyl adhesive tape was stuck on a total of 100 (10 ⁇ 10) lattices in the grid, and the film after the tape was rapidly peeled was evaluated according to the following criteria.
- a stainless steel member having a coating obtained by the method of the present invention is an exterior of an electronic device (for example, for a digital camera or a mobile phone) that is supposed to be rubbed, dropped, or stepped on clothes. Very useful as a part.
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Abstract
Description
従って、本発明は、皮膜硬度、耐衝撃性、密着性及び仕上り性に優れる皮膜を有するステンレス鋼部材の製造方法を提供することを目的とする。
[態様1]
皮膜を有するステンレス鋼部材の製造方法であって、
上記ステンレス鋼部材を、アミノ基含有シランカップリング剤(A)の水溶液の浴に浸漬し、そして上記ステンレス鋼部材に通電することにより、上記ステンレス鋼部材上に第1の皮膜を形成するステップ、
第1の皮膜上に、カルボキシル基含有樹脂(b1)、アミノ樹脂(b2)、水酸基含有エポキシリン酸エステル化合物(b3)、及び着色成分(b4)を含む電着塗料(B)であって、水酸基含有エポキシリン酸エステル化合物(b3)の量が、カルボキシル基含有樹脂(b1)とアミノ樹脂(b2)との固形分合計100質量部に基づいて0.1~10.0質量部の範囲にあるものを電着塗装することにより、第2の皮膜を形成するステップ、そして
少なくとも第2の皮膜を焼き付けるステップ、
を含むことを特徴とする方法。
アミノ基含有シランカップリング剤(A)が、N−2−(アミノエチル)−3−アミノプロピルメチルジメトキシシラン、N−2−(アミノエチル)−3−アミノプロピルトリメトキシシラン、N−2−(アミノエチル)−3−アミノプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−トリエトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン及びその部分加水分解物、3−トリメトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン及びその部分加水分解物、並びにN−フェニル−3−アミノプロピルトリメトキシシランから成る群から選択される、態様1に記載の方法。
ステンレス鋼部材の上の第1の皮膜と、当該第1の皮膜上の第2の皮膜とを有する、皮膜を有するステンレス鋼部材であって、
第1の皮膜が、アミノ基含有シランカップリング剤(A)の水溶液内でステンレス鋼部材に通電することにより形成された皮膜であり、そして
第2の皮膜が、第1の皮膜を有するステンレス鋼部材を、カルボキシル基含有樹脂(b1)、アミノ樹脂(b2)、水酸基含有エポキシリン酸エステル化合物(b3)、及び着色成分(b4)を含む電着塗料(B)であって、水酸基含有エポキシリン酸エステル化合物(b3)の量が、カルボキシル基含有樹脂(b1)とアミノ樹脂(b2)との固形分合計100質量部に基づいて0.1~10.0質量部の範囲にあるものの中で電着塗装することにより形成された皮膜であることを特徴とする、
上記皮膜を有するステンレス鋼部材。
態様1又は2に記載の方法により製造された皮膜を有するステンレス鋼部材を含む電子機器部品。
はじめに、ステンレス鋼部材を、アミノ基含有シランカップリング剤(A)の水溶液の浴に浸漬し、そしてステンレス鋼部材に通電することにより、ステンレス鋼部材上に第1の皮膜を形成するステップ(以下、「第1の皮膜を形成するステップ」と称する場合がある)について説明する。
本発明に用いられるステンレス鋼部材としては、フェライト(α)系、マルテンサイト(M)、オーステナイト(γ)系、オーステナイト・フェライト二相(γ+α)系等の従来から公知のステンレス鋼から形成される部材を挙げることができる。
なお、上記ステンレス鋼は、必要に応じて適宜、脱脂処理なされたものを用いることができる。
さらに、上記ステンレス鋼は、表面に化成処理がなされていても、又はなされていなくともよく、そして化成処理がなされていないことが好ましい。
第1の皮膜を形成するステップでは、上記ステンレス鋼部材を陽極として、アミノ基含有シランカップリング剤(A)の水溶液(以下、アミノ基含有シランカップリング剤(A)の水溶液を「水溶液(A)」と略することがある)の浴に浸漬して、少なくとも1回通電することにより、第1の皮膜が形成される。
なお、本明細書において、アミノ基含有シランカップリング剤(A)の「部分加水分解物」とは、ケイ素原子と結合するアルコキシ基の少なくとも1つがOH基に加水分解されているものを意味する。
アミノ基含有シランカップリング剤(A)の中でも、特に、N−2−(アミノエチル)−3−アミノプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシラン、及び3−アミノプロピルトリエトキシシランが、後述のアニオン電着塗料(B)を電着塗装することにより形成される第2の皮膜との付着性の面から好ましい。
なお、第1の皮膜を形成するステップにおいて、アミノ基含有シランカップリング剤(A)の水溶液の濃度は、特に制限されないが、浴安定性、形成された耐衝撃性、密着性の面から、好ましくは0.1~20質量%、より好ましくは0.5~5質量%、さらに好ましくは1~3質量%である。
第1の皮膜を形成するステップにおいて、上記通電は、複数回繰り返されてもよい。
第2の皮膜を形成するステップに用いられるアニオン電着塗料(B)は、カルボキシル基含有樹脂(b1)、アミノ樹脂(b2)、水酸基含有エポキシリン酸エステル化合物(b3)、及び着色成分(b4)を含む電着塗料(B)であって、水酸基含有エポキシリン酸エステル化合物(b3)の量が、カルボキシル基含有樹脂(b1)とアミノ樹脂(b2)との固形分合計100質量部に基づいて0.1~10.0質量部の範囲にある。
カルボキシル基含有樹脂(b1)は、1分子中に少なくとも1個のカルボキシル基を有する樹脂である。カルボキシル基含有樹脂(b1)は、少なくとも1個の水酸基をさらに有する樹脂であることが好ましい。カルボキシル基含有樹脂(b1)としては、具体的には、アクリル樹脂、ポリエステル樹脂、ポリエーテル樹脂、ポリカーボネート樹脂、ウレタン樹脂等の樹脂が挙げられ、皮膜硬度及び仕上り性の面からアクリル樹脂が好適である。
特に、皮膜硬度向上の点から、上記重合溶液が、単量体の総量を基準にとして、その他のラジカル重合性不飽和単量体としての(メタ)アクリルアミド系単量体を0.1~30質量%の範囲で含むことが好ましい。
なお、本明細書において、重量平均分子量は、JIS K 0124−83に準じ、分離カラムに、TSK gel2000HXL、TSK gel2500HXL、TSK gel3000HXL、TSK gel4000HXLの4本(以上、東ソー社製)を用いて40℃で流速1.0ml/分、溶離液にGPC用テトラヒドロフランを用いて、RI屈折計で得られたクロマトグラフとポリスチレンの検量線から求めた値を意味する。
アミノ樹脂(b2)は、従来から公知の化合物を使用することができ、例えば、メラミン樹脂、尿素、ベンゾグアナミン、アセトグアナミン、ステログアナミン、スピログアナミン、ジシアンジアミド等のアミノ成分とアルデヒドとの反応によって得られるメチロール化アミノ樹脂、上記メチロール化アミノ樹脂のアルキルエーテル化物が挙げられる。
上記メチロール化アミノ樹脂としては、メチロール化メラミン樹脂が好適であり、そしてメチロール化メラミン樹脂のメチロール基の一部又は全部が、メタノール、エタノール、プロパノール、ブタノール、オクチルアルコール、2−エチルヘキシルアルコール等の1種又は2種以上の1価アルコールで変性されたメラミン樹脂を挙げることができる。
第2の皮膜を形成するステップにおいて用いられるアニオン電着塗料(B)は、アミノ樹脂(b2)に加えて、ブロック化ポリイソシアネート化合物をさらに含むことができる。
水酸基含有エポキシリン酸エステル化合物(b3)は、エポキシ樹脂にリン酸化合物を付加することにより得られる化合物であり、水酸基含有エポキシリン酸エステル化合物(b3)中の水酸基とリン酸残基とが、第1の皮膜及びステンレス鋼部材との密着性を向上させると共に、仕上り性及び安定性に寄与する。
アニオン電着塗料(B)は、意匠性向上を目的として、着色成分(b4)を含むことができる。
着色成分(b4)としては、例えば、酸化チタン、酸化亜鉛、カーボンブラック、鉄黒、アニリンブラック、ハンザイエロー、ベンジジンイエロー、タートラジンレーキ、パーマネントイエロートナー、カドミウムイエロー、ベンジジンオレンジ、クロムバーミリオン、カドミウムオレンジ、パーマネントオレンジGTR、ファーストオレンジレーキ、レーキレッドC、弁柄、ワッチングレッド、ブリリアントカーミン6B、パーマネントレッドF5R、パーマネントレッド2B、パーマネントレッドFRLL、カーマインレーキ、キナクリドンレッド、メチルバイオレットレーキ、ファーストバイオレットB、キナクリドンバイオレット、インダスレンバイオレット、フタロシアニンブルー、ファーストスカイブルー、紺青、群青、ビクトリアブルーレーキ、フタロシアニングリーン、マーカライトグリーンレーキ、ピグメントグリーンB、ビリジアン、シェンナー、アンバー、アルミニウム粉末、ブロンズ粉末等、有機顔料、無機顔料及び金属粉顔料、染料、顔料等を樹脂粉体と組み合わせた着色加工粉体、及び蛍光顔料、天然マイカの表面を金属酸化物で被覆したもの、合成マイカの表面を金属酸化物で被覆したパール顔料等を挙げることができる。
本発明の皮膜を有するステンレス鋼部材の製造方法は、ステンレス鋼部材を、水溶液(A)中に浸漬して、好ましくは0.01~3.0μm、そしてより好ましくは0.1~1.0μmの膜厚を有する第1の皮膜が形成するように通電し、次いで、アニオン電着塗料(B)を、好ましくは30μm以下、より好ましくは5~20μm、そしてさらに好ましくは8~17μmの乾燥膜厚を有する第2の皮膜が形成するように電着塗装することにより実施される。
SUS304(150mm×70mm×0.5mm、オーステナイト系ステンレス鋼板)を、25℃、100g/Lの硫酸水溶液に5分間浸漬することにより脱脂し、2質量%のKBE−903(注1)水溶液中にSUS304を浸漬し、SUS304を陽極として0.01A/cm2の定電流密度で60秒間通電し、水洗し、そして膜厚0.3μmの第1の皮膜を有するステンレス鋼部材No.1を作成した。
(注1)KBE−903:信越シリコーン株式会社製、商品名、3−アミノプロピルトリエトキシシラン
SUS430(150mm×70mm×0.5mm、フェライト系ステンレス鋼板)を、25℃で100g/Lの硫酸水溶液に5分間浸漬することにより脱脂し、2質量%のKBM−903(注2)水溶液にSUS430を浸漬し、SUS430を陽極として0.01A/cm2の定電流密度で40秒間通電し、水洗し、そして膜厚0.5μmの第1の皮膜を有するステンレス鋼部材No.2を作成した。
(注2)KBM−903:信越シリコーン株式会社製、商品名、3−アミノプロピルトリメトキシシラン
SUS430(150mm×70mm×0.5mm、フェライト系ステンレス鋼板)を、25℃で100g/Lの硫酸水溶液に5分間浸漬することにより脱脂し、2質量%のKBM−603(注3)水溶液中にSUS430を浸漬し、SUS430を陽極として0.01A/cm2の定電流密度で40秒間通電し、水洗し、そして膜厚0.6μmの第1の皮膜を有するステンレス鋼部材No.3を作成した。
(注3)KBM−603:信越シリコーン株式会社製、商品名、N−2−(アミノエチル)−3−アミノプロピルトリエトキシシラン
SUS430(150mm×70mm×0.5mm、フェライト系ステンレス鋼板)を、25℃で100g/Lの硫酸水溶液に5分間浸漬することにより脱脂し、ステンレス鋼部材No.4を得た。
反応容器中に混合溶剤(注4)21部を仕込み、85℃に保持した中に、下記「混合物(A)」を3時間かけて滴下し、次いでアゾビスジメチルバレロニトリル3部を添加し、85℃で4時間保持して反応を行った後、混合溶剤にて固形分を調整し、固形分70質量%のアクリル樹脂溶液No.1を製造した。アクリル樹脂溶液No.1は、酸価33.9mgKOH/g、水酸基価52.0mgKOH/g、及び重量平均分子量35,000を有していた。
スチレン 5.0部
メチルメタクリレート 36.0部
エチルアクリレート 37.5部
2−エチルヘキシルメタクリレート 4.0部
アクリル酸 5.5部
2−ヒドロキシエチルメタクリレート 12.0部
アゾビスジメチルバレロニトリル 2.1部
反応容器中に混合溶剤(注4)21部を仕込み、85℃に保持した中に、下記「混合物(B)」を3時間かけて滴下し、次いでアゾビスジメチルバレロニトリル3部を添加し、85℃で4時間保持して反応を行った後、混合溶剤(注4)にて固形分を調整し、固形分70質量%のアクリル樹脂溶液No.2を製造した。アクリル樹脂溶液No.2は、酸価63mgKOH/g、水酸基価28mgKOH/g、及び重量平均分子量35,000を有していた。
スチレン 13.0部
メチルメタクリレート 48.5部
エチルアクリレート 5.0部
アクリル酸 5.5部
n−ブチルアクリレート 11.0部
2−ヒドロキシエチルメタクリレート 12.0部
N−n−ブトキシメチルアクリルアミド 5.0部
アゾビスジメチルバレロニトリル 2.1部
製造例5で得た70%のアクリル樹脂溶液No.1 92.9部(固形分65部)、サイメル232S(注6)35.0部(固形分35部)、DER621−PP50(注7)1.0部(固形分0.5部)、ジノニルナフタレンスルホン酸0.05部、トリエチルアミン1.9部、及び脱イオン水120.4部を混合した後、当該混合物に、攪拌しながら脱イオン水を徐々に滴下することにより、当該混合物を分散させ、固形分を調整して40%のエマルションNo.1を得た。
表1に示される組成に変更した以外は、製造例7と同様にして、固形分40%のエマルションNo.2~No.8を得た。
表2に示される組成に変更した以外は、製造例7と同様にして、固形分40%のエマルションNo.9~No.15を得た。
(注7)DER621−PP50:ダウケミカル社製、商品名、エポキシリン酸エステル化合物、酸価45mgKOH/g、固形分50.0%
(注8)DER621−EB50:ダウケミカル社製、商品名、エポキシリン酸エステル化合物、酸価35mgKOH/g、固形分50.0%
(注9)XU−7189.00:ダウケミカル社製、商品名、エポキシリン酸エステル化合物、酸価9.8mgKOH/g、固形分50.0%。
60%アミン中和アクリル樹脂系顔料分散樹脂(重量平均分子量36,000、水酸基価70mgKOH/g、酸価56mgKOH/g)9.6部(固形分5.8部)、CR−97(注10)10.0部、トリエチルアミン0.5部、及び脱イオン水11.5部を混合し、次いでボールミルで20時間分散して固形分40%の顔料分散ペーストNo.1を得た。
表3に示される組成に変更した以外は、製造例15と同様にして、固形分40%の顔料分散ペーストNo.2~No.6を得た。
(注11)カーボンブラックMA−100:三菱化学社製、商品名、カーボンブラック
(注12)メタシーンKM1000:東洋アルミニウム社製、商品名、リーフィング性を付与した蒸着アルミニウム顔料、平均粒子径11.1μm、粒子厚み0.025μm
(注13)SF640:東洋インキ製造社製、商品名、キナクリドン系の着色顔料、固形分36%、顔料分30%
(注14)EMF BLUE 2R:東洋インキ製造社製、商品名、フタロシアニンブルー系の着色顔料、固形分40%、顔料分28%
(注15)EMF YELLOW H2RN−2:東洋インキ製造社製、商品名、ジアゾイエロー系の着色顔料、固形分40%、顔料分32%
固形分40%のエマルションNo.1 251.2部(固形分100.5部)と、固形分40%の顔料分散ペーストNo.1 39.5部(固形分15.8部)とを、脱イオン水1163.1部と混合して、固形分8%のアニオン電着塗料No.1を得た。
表4及び表5に示される組成に変更した以外は、製造例21と同様にして、アニオン電着塗料No.2~No.13を得た。
表6に示される組成に変更した以外は、製造例21と同様にして、アニオン電着塗料No.14~No.20を得た。
アニオン電着塗料No.1の浴に、第1の皮膜を有するステンレス鋼板No.1を浸漬し、第1の皮膜を有するステンレス鋼板No.1が陽極となるように150Vで2分間通電し、電着塗装した。次いで、180℃で20分間加熱乾燥して、第1の皮膜及び第2の皮膜(乾燥膜厚15μm)を有する、皮膜を有するステンレス鋼部材No.1を得た。
表7に示される第1の皮膜を有するステンレス鋼部材及び電着塗料を用いた以外は実施例1と同様にして、皮膜を有するステンレス鋼部材No.2~No.16を得た。
皮膜を有するステンレス鋼部材No.1~No.16を、下記項目に関して塗膜性能を評価した。結果を表7に示す。
アニオン電着塗料No.1の浴に、ステンレス鋼部材No.4を浸漬し、ステンレス鋼部材No.4が陽極となるように150Vで2分間通電し、電着塗装した。次いで、180℃で20分間焼付け乾燥して、乾燥膜厚15μmのアニオン電着塗料No.1に由来する皮膜を有する、皮膜を有するステンレス鋼部材No.17を得た。
表8に示されるステンレス鋼部材及び電着塗料を用いた以外は、比較例1と同様にして、塗装板No.18~No.31を得た。
皮膜を有するステンレス鋼部材No.18~No.31を、下記項目に関して皮膜性能を評価した。結果を表8に示す。
(注17)耐衝撃性:JIS K 5600−5−3(1999)に規定される「耐おもり落下性」のデュポン式に準じて評価した。具体的には、皮膜を有するステンレス鋼部材を、温度20℃±1、湿度75±2%の恒温恒湿室に24時間置いた後、JIS K 5600−5−3に規定される撃ち型と受け台とを取り付け、皮膜を有するステンレス鋼部材の皮膜面を上向きにして、その間に挟み、次に500gのおもりを撃ち型の上に落とし、衝撃により皮膜(表面)にワレ又はハガレが発生する落下高さ(cm)を測定した。
G(Good):碁盤目内の100個の格子のうち、一部の端部に、わずかに剥離があった
F(Fair):計100個の格子のうち、1~20個が剥離した
P(Poor):計100個の格子のうち、21個以上が剥離した
VG(Very Good):皮膜に異常がなかった
G(Good):皮膜にラウンド感がややあるが、仕上がりに問題がなかった
F(Fair):ラウンド感又はツヤボケが観察された
P(Poor):著しいラウンド感又は著しいツヤボケが観察された
Claims (4)
- 皮膜を有するステンレス鋼部材の製造方法であって、
前記ステンレス鋼部材を、アミノ基含有シランカップリング剤(A)の水溶液の浴に浸漬し、そして前記ステンレス鋼部材に通電することにより、前記ステンレス鋼部材上に第1の皮膜を形成するステップ、
第1の皮膜上に、カルボキシル基含有樹脂(b1)、アミノ樹脂(b2)、水酸基含有エポキシリン酸エステル化合物(b3)、及び着色成分(b4)を含む電着塗料(B)であって、水酸基含有エポキシリン酸エステル化合物(b3)の量が、カルボキシル基含有樹脂(b1)とアミノ樹脂(b2)との固形分合計100質量部に基づいて0.1~10.0質量部の範囲にあるものを電着塗装することにより、第2の皮膜を形成するステップ、そして
少なくとも第2の皮膜を焼き付けるステップ、
を含むことを特徴とする方法。 - アミノ基含有シランカップリング剤(A)が、N−2−(アミノエチル)−3−アミノプロピルメチルジメトキシシラン、N−2−(アミノエチル)−3−アミノプロピルトリメトキシシラン、N−2−(アミノエチル)−3−アミノプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−トリエトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン及びその部分加水分解物、3−トリメトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン及びその部分加水分解物、並びにN−フェニル−3−アミノプロピルトリメトキシシランから成る群から選択される、請求項1に記載の方法。
- ステンレス鋼部材の上の第1の皮膜と、当該第1の皮膜上の第2の皮膜とを有する、皮膜を有するステンレス鋼部材であって、
第1の皮膜が、アミノ基含有シランカップリング剤(A)の水溶液内でステンレス鋼部材に通電することにより形成された皮膜であり、そして
第2の皮膜が、第1の皮膜を有するステンレス鋼部材を、カルボキシル基含有樹脂(b1)、アミノ樹脂(b2)、水酸基含有エポキシリン酸エステル化合物(b3)、及び着色成分(b4)を含む電着塗料(B)であって、水酸基含有エポキシリン酸エステル化合物(b3)の量が、カルボキシル基含有樹脂(b1)とアミノ樹脂(b2)との固形分合計100質量部に基づいて0.1~10.0質量部の範囲にあるものの中で電着塗装することにより形成された皮膜であることを特徴とする、
前記皮膜を有するステンレス鋼部材。 - 請求項1又は2に記載の方法により製造された皮膜を有するステンレス鋼部材を含む電子機器部品。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150034487A1 (en) * | 2012-03-22 | 2015-02-05 | Nanogate Ag | Treatment of an anodically oxidized surface |
JP2019516002A (ja) * | 2017-04-17 | 2019-06-13 | Dic株式会社 | 水性樹脂組成物、水性塗料及び該水性塗料の硬化塗膜を有する物品 |
JP7272706B1 (ja) | 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 | ポリマーとステンレス鋼の接合体のためのステンレス鋼の表面処理方法 |
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TWI638907B (zh) | 2017-08-03 | 2018-10-21 | 國立高雄大學 | 具金屬防腐蝕能力的自組裝溶液及其製備方法 |
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JPS585377A (ja) * | 1981-07-01 | 1983-01-12 | Kansai Paint Co Ltd | アニオン型電着塗料 |
JPS62265369A (ja) * | 1986-04-03 | 1987-11-18 | ザ バルスパー コーポレーション | 熱硬化性、水性、アニオン性電着塗装用組成物 |
JPH02305993A (ja) * | 1989-05-17 | 1990-12-19 | Takasago Tekko Kk | 塗料密着性に優れたステンレス鋼の表面処理方法 |
JPH05179177A (ja) * | 1991-12-27 | 1993-07-20 | Kansai Paint Co Ltd | 低温硬化性電着塗料組成物 |
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US4957952A (en) * | 1986-04-03 | 1990-09-18 | Desoto, Inc. | Anionic electrocoat compositions containing epoxy phosphates |
CN1216736C (zh) * | 2000-04-12 | 2005-08-31 | 三菱树脂株式会社 | 被覆树脂的金属板及其制造方法 |
-
2010
- 2010-06-16 CN CN2010800289350A patent/CN102713021A/zh active Pending
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- 2010-06-16 WO PCT/JP2010/060597 patent/WO2011001862A1/ja active Application Filing
Patent Citations (4)
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JPS585377A (ja) * | 1981-07-01 | 1983-01-12 | Kansai Paint Co Ltd | アニオン型電着塗料 |
JPS62265369A (ja) * | 1986-04-03 | 1987-11-18 | ザ バルスパー コーポレーション | 熱硬化性、水性、アニオン性電着塗装用組成物 |
JPH02305993A (ja) * | 1989-05-17 | 1990-12-19 | Takasago Tekko Kk | 塗料密着性に優れたステンレス鋼の表面処理方法 |
JPH05179177A (ja) * | 1991-12-27 | 1993-07-20 | Kansai Paint Co Ltd | 低温硬化性電着塗料組成物 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150034487A1 (en) * | 2012-03-22 | 2015-02-05 | Nanogate Ag | Treatment of an anodically oxidized surface |
JP2019516002A (ja) * | 2017-04-17 | 2019-06-13 | Dic株式会社 | 水性樹脂組成物、水性塗料及び該水性塗料の硬化塗膜を有する物品 |
JP7272706B1 (ja) | 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 | ポリマーとステンレス鋼の接合体のためのステンレス鋼の表面処理方法 |
JP2023098504A (ja) * | 2021-12-28 | 2023-07-10 | 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 | ポリマーとステンレス鋼の接合体のためのステンレス鋼の表面処理方法 |
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