WO2007102544A1 - Tôle de métal revêtue de résine et composition de traitement de surface servant à produire celle-ci - Google Patents

Tôle de métal revêtue de résine et composition de traitement de surface servant à produire celle-ci Download PDF

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Publication number
WO2007102544A1
WO2007102544A1 PCT/JP2007/054441 JP2007054441W WO2007102544A1 WO 2007102544 A1 WO2007102544 A1 WO 2007102544A1 JP 2007054441 W JP2007054441 W JP 2007054441W WO 2007102544 A1 WO2007102544 A1 WO 2007102544A1
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Prior art keywords
mass
carboxylic acid
parts
unsaturated carboxylic
resin
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PCT/JP2007/054441
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English (en)
Japanese (ja)
Inventor
Tadashige Nakamoto
Yoshiaki Shinohara
Tatsuhiko Iwa
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Kabushiki Kaisha Kobe Seiko Sho
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Priority to CN2007800080786A priority Critical patent/CN101395302B/zh
Publication of WO2007102544A1 publication Critical patent/WO2007102544A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0869—Acids or derivatives thereof
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09D5/08—Anti-corrosive paints

Definitions

  • the present invention relates to a resin-coated metal plate provided with a resin film used for automobiles, home appliances, building materials, and the like, and a surface treatment composition for producing the same, and more particularly to corrosion resistance, resin film and other coatings.
  • Excellent adhesion to the film may be abbreviated as “coat film adhesion”
  • adhesion between the resin film and the metal plate may be abbreviated as “resin film adhesion”
  • the present invention relates to a resin-coated metal plate and a surface treatment composition for producing the same. Background art
  • Patent Document 1 As a means for improving corrosion resistance in place of such chromate treatment, for example, Patent Document 1
  • Patent Document 2 proposes a surface treatment agent containing a carboxyl group-containing resin and an inorganic silicate, and a surface-treated steel sheet obtained therefrom.
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-220237
  • Patent Document 2 JP 2000-282254 A
  • an object of the present invention is to provide a resin-coated metal plate having excellent corrosion resistance.
  • the resin-coated metal plate of the present invention that has achieved the above object is a resin-coated metal plate provided with a resin film obtained from a surface treatment composition
  • the surface treatment composition contains 55 95 parts by mass of olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer and ⁇ , ⁇ -unsaturated carboxylic acid polymer, and
  • colloidal silica (however, the total of olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer, a, unsaturated carboxylic acid polymer and colloidal silica is 100 parts by mass),
  • silane coupling agent 7 In addition to 100 parts by mass of a total of 100 parts by mass of olefin fin j3-unsaturated carboxylic acid copolymer, ⁇ , unsaturated carboxylic acid polymer and colloidal silica, 30 parts by mass of silane coupling agent 7
  • the content ratio of the olefin-unsaturated carboxylic acid copolymer to the ⁇ , ⁇ -unsaturated carboxylic acid polymer is 1,000: 1 to 10: 1 by mass ratio.
  • colloidal silica has a surface area average particle size of S4 to 20 nm, and / or ( 3) Silane coupling agent power A glycidyl group-containing silane coupling agent is preferred.
  • the surface treatment composition further comprises a vanadium compound with respect to a total of 100 parts by mass of (a) olefin, j3-unsaturated carboxylic acid copolymer, cis, ⁇ -unsaturated carboxylic acid polymer and colloidal silica. 0.56 containing 6 parts by mass, and when the total of ⁇ or (b) olefin- ⁇ , ⁇ monounsaturated carboxylic acid copolymer and ⁇ , ⁇ monounsaturated carboxylic acid polymer is 100 parts by mass, It is also a preferred embodiment of the present invention to contain a carpositimide group-containing compound at a ratio of 0.:!30 parts by mass with respect to 100 parts by mass.
  • the amount of the resin film attached is preferably 0.23 g / m 2 in terms of dry mass.
  • the present invention provides a total of 55 95 parts by mass of olefin ⁇ , ⁇ unsaturated carboxylic acid copolymer and ⁇ , ⁇ -unsaturated carboxylic acid polymer, and 5 45 parts by mass of colloidal silica (provided that Unsaturated carboxylic acid copolymer, ct,; 3-unsaturated carbo The total of the acid polymer and colloidal silica is 100 parts by mass.
  • the content ratio force S of the olefin and ⁇ -unsaturated carboxylic acid copolymer and O, ⁇ -unsaturated carboxylic acid polymer is S, and the mass ratio is 1,000 ::! To 10: 1.
  • a featured surface treatment composition is also provided.
  • the surface treatment composition may further comprise a vanadium compound 0.5 to 100 parts by mass in total of olefin 1,3_unsaturated carboxylic acid copolymer, hi, j3-unsaturated carboxylic acid polymer and colloidal silica. 6 to 10 parts by mass, and / or 1 to 9 parts by mass of an oxazoline-containing polymer, and / or 0.5 to 5 parts by mass of spherical polyethylene wax particles having an average particle diameter of 0.6 to 4 zm may be contained.
  • a vanadium compound 0.5 to 100 parts by mass in total of olefin 1,3_unsaturated carboxylic acid copolymer, hi, j3-unsaturated carboxylic acid polymer and colloidal silica. 6 to 10 parts by mass, and / or 1 to 9 parts by mass of an oxazoline-containing polymer, and / or 0.5 to 5 parts by mass of spherical polyethylene wax particles having an average particle diameter of 0.6
  • the combination of the olefin ⁇ , ⁇ unsaturated carboxylic acid copolymer and the ⁇ , ⁇ unsaturated carboxylic acid polymer can significantly enhance the corrosion resistance of the resin-coated metal sheet.
  • the surface treatment composition is an olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer (hereinafter sometimes referred to as “olefin monoacid copolymer”). And a combination of an ⁇ , ⁇ -unsaturated carboxylic acid polymer (hereinafter sometimes abbreviated as “carboxylic acid polymer”).
  • olefin monoacid copolymer a combination of an ⁇ , ⁇ -unsaturated carboxylic acid polymer (hereinafter sometimes abbreviated as “carboxylic acid polymer”).
  • a resin-coated metal plate obtained by applying and drying a surface treatment composition containing both of these on a metal plate is a surface treatment composition containing only one of these. Compared to the resin-coated metal plate obtained from
  • the “olefin ⁇ , ⁇ unsaturated carboxylic acid copolymer” or “olefinic acid copolymer” in the present invention is a copolymer of olefin and ⁇ , ⁇ unsaturated carboxylic acid.
  • a structural unit force derived from olefins means that the copolymer contains 50% by mass or more (that is, the structural unit derived from ⁇ , ⁇ -unsaturated carboxylic acid is 50% by mass or less), “ct,; 3-
  • saturated carboxylic acid polymer” or “carboxylic acid polymer” refers to a polymer obtained using ⁇ , —unsaturated carboxylic acid as a monomer.
  • the conventional structural unit is 90% by mass or more in the polymer.
  • ethylene-acrylic acid copolymer was used as the “olefin-acid copolymer”
  • polymaleic acid or “polyacrylic acid” was used as the “strong rubonic acid polymer”.
  • the olefin monoacid copolymer used in the present invention can be produced by copolymerizing olefin and ⁇ , unsaturated carboxylic acid by a known method, and is commercially available. In the present invention, one or more olefin monoacid copolymers can be used.
  • the olefin that can be used for the production of the olefin-acid copolymer is not particularly limited, but ethylene and propylene are preferred, and ethylene is more preferred.
  • ethylene and propylene are preferred, and ethylene is more preferred.
  • the olefinic acid copolymer any of those derived from only one olefin having a unit strength of olefin, or one derived from two or more olefins can be used.
  • the ⁇ , ⁇ unsaturated carboxylic acid that can be used in the production of the olefinic acid copolymer is not particularly limited.
  • monostrength rubonic acid maleic acid such as acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid.
  • dicarboxylic acids such as fumaric acid and itaconic acid.
  • acrylic acid is preferable.
  • the structural unit of ⁇ , ⁇ -unsaturated carboxylic acid is derived from only one type of ⁇ , ⁇ unsaturated carboxylic acid, or from two or more types of ⁇ , ⁇ unsaturated carboxylic acid. You can use any of the things you do.
  • the olefin-acid copolymer used in the present invention may have a structural unit derived from another monomer within a range that does not adversely affect the corrosion resistance and the like that are the effects of the present invention.
  • the amount of structural units derived from other monomers is preferably 10% by mass or less, more preferably 5% by mass or less, and the most preferred olefin-acid copolymer is It consists only of olefin, and ⁇ -unsaturated carboxylic acid.
  • ethylene monoacrylic acid copolymer The body is mentioned.
  • the structural unit of ⁇ , ⁇ unsaturated carboxylic acid in the olefinic acid copolymer improves the adhesion between the resin film and the metal plate, and secures the amount of the carboxyl group serving as a reactive group for crosslinking.
  • the constituent unit amount of ⁇ , ⁇ -unsaturated carboxylic acid in the copolymer is preferably 5% by mass or more, more preferably 10% by mass or more. However, if the ⁇ monounsaturated carboxylic acid unit is excessive, the corrosion resistance and alkali resistance may be lowered. Therefore, the amount of the constituent unit is preferably 30% by mass or less, more preferably 25% by mass or less. .
  • the weight-average molecular weight of the olefinic monoacid copolymer used in the present invention is preferably 1,000 to 100,000, more preferably 3,000 to 70,000, and still more preferably 5,000 to 30,000. This weight average molecular weight can be measured by GPC using styrene as a standard.
  • carboxylic acid polymer a homopolymer or copolymer of one or two or more kinds of j3_unsaturated carboxylic acids, or a copolymer obtained by copolymerizing another monomer. You can use any of them.
  • carboxylic acid polymers can be produced by known methods and are commercially available. In the present invention, one or more carboxylic acid polymers can be used.
  • the ⁇ , ⁇ unsaturated carboxylic acid that can be used for the production of the carboxylic acid polymer is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid, maleic acid, and fumaric acid. Examples thereof include dicarboxylic acids such as acid and itaconic acid. Of these, acrylic acid and maleic acid are preferred, and maleic acid is more preferred.
  • Carboxylic acid polymers may contain constituent units derived from monomers other than ⁇ , unsaturated carboxylic acids, but the amount of constituent units derived from other monomers is A carboxylic acid polymer composed of only a, j3-unsaturated carboxylic acid is more preferable, and the content is 10% by mass or less, preferably 5% by mass or less in the polymer.
  • Preferred examples of the carboxylic acid polymer include polyacrylic acid, polymethacrylic acid, acrylic acid-maleic acid copolymer, polymaleic acid and the like. Among these, coating film adhesion, resin film adhesion, and corrosion resistance From the viewpoint, polymaleic acid is more preferable. The exact mechanism by which the corrosion resistance is improved by using polymaleic acid is unknown. It is considered that the adhesion between the resin film and the metal plate is improved, and the corrosion resistance is improved accordingly. However, the present invention is not limited to this estimation.
  • the weight average molecular weight of the carboxylic acid polymer used in the present invention is preferably 500 to 30,000, more preferably 800 to 10000, more preferably 900 to 3,000, and most preferably 1,000 to 3,000. 2,000. This weight average molecular weight can be measured by GPC using styrene as a standard.
  • the content ratio of the olefinic monoacid copolymer to the carboxylic acid polymer in the surface treatment composition is 1,000 ::! ⁇ 10: 1, prefer ⁇ 200 ::! ⁇ 20: 1, more preferred ⁇ 100: 1 ⁇ : 100: 3. If the content ratio of the rubonic acid polymer is too low, the combined effect of the olefinic monoacid copolymer and the carboxylic acid polymer is not sufficiently exerted, and conversely, the content ratio of the carboxylic acid polymer is excessive. This is because the olefinic monoacid copolymer and the carboxylic acid polymer are phase-separated in the surface treatment composition, so that a uniform resin film may not be formed and the alkali resistance may be lowered.
  • One of the characteristics of the surface treatment composition of the present invention is that it contains colloidal silica.
  • the silica When colloidal silica is present in the resin film, the silica is eluted in a corrosive environment, so that the dissolution and elution of the metal plate is suppressed, and the corrosion resistance is improved.
  • colloidal silica is commercially available, and general commercial products can be used. Examples of colloidal power include the Snowtex series “ST-40”, “ST-XS”, “ST-N”, “ST-SS”, “ST- ⁇ ” manufactured by Nissan Chemical Industries, Ltd. .
  • colloidal power include the Snowtex series “ST-40”, “ST-XS”, “ST-N”, “ST-SS”, “ST- ⁇ ” manufactured by Nissan Chemical Industries, Ltd. .
  • the surface treatment composition used for forming the resin film is aqueous, it is preferable to select the type of colloidal silica according to the pH of the surface treatment composition in order to disperse the colloidal silica well.
  • the total amount of olefinic monoacid copolymer and carboxylic acid polymer (hereinafter sometimes abbreviated as “resin component”) is 55 to 95 parts by mass,
  • the amount of dull silica is 5 to 45 parts by mass (provided that the total of the resin component and colloidal silica is 100 parts by mass).
  • the amounts of the resin component and colloidal silica specified in the present invention are values converted into solid contents.
  • the amount of colloidal silica exceeds 45 parts by mass, the resin component is reduced and the surface treatment is performed. The film forming property of the chemical composition is lowered, cracks are generated in the resin film, and the corrosion resistance and other properties are lowered.
  • the amount of colloidal silica is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less from the viewpoint of spot weldability (however, the total of the resin component and colloidal silica force is 100 parts by mass). When the amount of colloidal silica is 25 parts by mass or less, accumulation of silica on the electrode is effectively suppressed by spot welding.
  • the amount of colloidal silica is less than 5 parts by mass, the effect of improving the corrosion resistance of colloidal silica is not sufficiently exhibited, and the alkali resistance is also lowered.
  • the amount of colloidal silica is preferably 10 parts by mass or more, more preferably 15 parts by mass or more (provided that the total of the resin component and the colloidal silica is 100 parts by mass).
  • the surface area average particle diameter of colloidanol silica is preferably 4 to 20 nm. “The surface area average particle diameter of silica can be measured by the Sears method when the average particle diameter is about 1 to:! Onm, and by the BET method when it is about 10 to: OOnm.
  • the surface treatment composition of the present invention contains a silane coupling agent.
  • a silane coupling agent By using a silane coupling agent, the adhesion between the metal and the resin film is improved, and accordingly the corrosion resistance is also improved. Therefore, the surface treatment composition does not need to contain an acidic compound (for example, a phosphoric acid compound, a nitric acid compound, and a fluorine compound) for the purpose of etching the surface of the metal plate. This is because the adhesion of the resin film can be improved by the silane coupling agent without etching the surface of the metal plate.
  • a surface treatment composition that does not contain an acid compound for etching purposes has improved stability and can form a good resin film.
  • the amount of the silane coupling agent in the surface treatment composition is 7 parts by mass or more, preferably 9 parts by mass with respect to 100 parts by mass in total of the olefin-acid copolymer, carboxylic acid polymer and colloidal silica. Part or more, more preferably 11 parts by weight or more, preferably 30 parts by weight or less, preferably 25 parts by mass or less. If the amount is less than parts by mass, the adhesion and corrosion resistance of the resin film will be reduced, and if it exceeds 30 parts by mass, the stability of the surface treatment composition will be reduced, leading to adhesion and corrosion resistance. Decreases.
  • Silane coupling agents are commercially available, and general commercial products can be used in the present invention.
  • One or more silane coupling agents can be used.
  • Examples of silane coupling agents include butyltrimethoxysilane, butyltriethoxysilane, butyltris (monomethoxyethoxy) silane, ⁇ -chloropropylmethoxysilane, ⁇ -aminopropyltriethoxysilane, N- (j3-amino Ethyl) 1 ⁇ -aminopropyltrimethoxysilane, ⁇ — (j3
  • silane coupling agents preferred is a glycidyl group-containing silane coupling agent.
  • Glycidyl group-containing silane coupling agents are highly reactive, so they have a significant effect on improving corrosion resistance and alkali resistance.
  • Examples of the glycidinole group-containing silane coupling agent include silane.
  • the surface treatment composition of the present invention may contain a vanadium compound.
  • vanadium compounds also have the effect of suppressing the dissolution and dissolution of the metal plate and enhancing the corrosion resistance.
  • the vanadium compound improves the corrosion resistance, particularly the corrosion resistance of the buttock, of the molten zinc-plated steel sheet and the electrogalvanized steel sheet.
  • vanadium compounds examples include vanadium pentoxide (V O) and ammonium metavanadate.
  • Nium (NH VO), sodium metavanadate (NaV0), potassium metavanadate (KV)
  • V (C H O) vanadium acetylylacetonate
  • the surface treatment composition of the present invention is water-based, a vanadium compound having high solubility in water, "Vanadinic acid solution (IV)” manufactured by Shinsei Chemical Industry Co., Ltd. (VO is tetravalent with oxalic acid).
  • VO is tetravalent with oxalic acid.
  • an aqueous solution containing the original one If the aqueous surface treatment composition is neutral or alkaline, it is desirable to neutralize the vanadic acid solution with a base (preferably aqueous ammonia) to a pH of 5-7, The pH of the “vanadic acid solution (IV)” is about 3.) However, if the pH of the vanadic acid solution exceeds 7, fine suspension of vanadium hydroxide may be formed.
  • the amount of the vanadium compound in the surface treatment composition is preferably 0.5 to 6 parts by mass, more preferably 1 to 100 parts by mass in total of the olefinic monoacid copolymer, the carboxylic acid polymer and the colloidal silica. ⁇ 3 parts by mass. If the vanadium compound is less than 0.5 parts by mass, the effect of improving the corrosion resistance cannot be exhibited sufficiently. On the other hand, even if the amount exceeds 6 parts by mass, the effect of improving the corrosion resistance is saturated, and the coating film adhesion and the resin film adhesion may be deteriorated.
  • the vanadium compound amount specified in the present invention is the V O amount calculated from the V 2 O equivalent concentration (manufacturer indication) of the “vanadic acid solution”.
  • the surface treatment composition of the present invention may further contain a carpositimide group-containing compound.
  • the carpositimide group in the compound reacts with the carboxyl group in the olefinic acid copolymer and the carboxylic acid polymer. Therefore, the use of a carpositimide group-containing compound can reduce the amount of carboxyl groups in the resin film and improve the alkali resistance.
  • one kind or two or more kinds of carpositimide group-containing compounds can be used.
  • Carpositimide group-containing compounds include isocyanates such as hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H XDI), 4, 4-diphenyl. It can be produced by heating enylmethane diisocyanate (MDI) or tolylene diisocyanate (TDI) in the presence of a calpositimidization catalyst, and it can also be modified by aqueous (water-soluble, water-emulsifiable) Or water dispersibility). When the surface treatment composition is water-based, an aqueous carpositimide group-containing compound is preferable.
  • isocyanates such as hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H XDI), 4, 4-diphenyl. It can be produced by heating enylmethane
  • a compound containing a plurality of carposimide groups in one molecule is preferable.
  • the corrosion resistance and the like can be further improved by a crosslinking reaction with a carboxyl group in the resin component.
  • Examples of commercially available polycarbodiimide compounds include N, N dicyclohexyl carbonyl levodiimide, N, N diisopropyl carbodiimide, and "Polycarbodiimide” (polymer having a plurality of carbodiimide groups in one molecule).
  • polycarbodiimide having a plurality of carboxyl groups is preferable.
  • the amount of the compound in the surface treatment composition is as described above when the total of the olefinic monoacid copolymer and the carboxylic acid polymer is 100 parts by mass.
  • the amount is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 8 parts by mass or more with respect to 100 parts by mass.
  • the amount of the compound containing the carpositimide group is excessive, the effect of the combination of olefinic monoacid copolymer and carboxylic acid polymer is reduced.
  • the amount of the carpositimide group-containing compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 16 parts by mass or less with respect to 100 parts by mass.
  • the surface treatment composition of the present invention may contain a resin and / or a wax other than the olefinic acid copolymer and the carboxylic acid polymer as long as the effects of the present invention are not impaired.
  • the amount of other resin and wax in the surface treatment composition is preferably 10 parts by mass or less with respect to 100 parts by mass when the total amount of olefinic acid copolymer and carboxylic acid polymer is 100 parts by mass. More preferably, it is 5 parts by mass or less.
  • the surface treatment composition is a cross-linking agent, diluent, anti-skinning agent, surfactant, emulsifier, dispersant, leveling agent, antifoaming agent, penetrating agent, structure, and the like as long as the effects of the present invention are not impaired. It can also contain film aids, dyes, pigments, thickeners, lubricants and the like.
  • the surface treatment composition of the present invention further comprises an oxazoline-containing polymer with respect to a total of 100 parts by mass of an olefin, j3-unsaturated carboxylic acid copolymer, a ⁇ -unsaturated carboxylic acid polymer, and colloidal silica. You may contain 1-9 mass parts.
  • the oxazoline-containing polymer can be dried at a low temperature, does not deteriorate the fluidity (viscosity) and wettability of the surface treatment composition, and has good mechanical stability.
  • Oxazoline-containing polymers include “Epocross ⁇ Series” manufactured by Nippon Shokubai Co., Ltd., “K-2010E”, “K_2020E”, “K_2030E” of styrene / acryl main chain emulsion.
  • the oxazoline-containing polymer is less than 1 part by mass with respect to 100 parts by mass of the total of olefin, / 3--unsaturated carboxylic acid copolymer, H, / 3-unsaturated carboxylic acid polymer and colloidal silica,
  • the film is rolled and broken due to contact with the roll during roll forming, resulting in film peeling.
  • the coating is 9 parts by mass or more with respect to 100 parts by mass of the total of olefin, j3—unsaturated carboxylic acid copolymer, 3 / 3-unsaturated carboxylic acid polymer and colloidal silica, the coating The improvement cannot be obtained, and the coating film adhesion is significantly deteriorated.
  • it is 2-6 mass parts, More preferably, it is 3-4 mass parts.
  • the surface treatment composition of the present invention further has an average particle size of 0. 100 parts by mass in total of olefin 1a, monounsaturated carboxylic acid copolymer, ⁇ , ⁇ monounsaturated carboxylic acid polymer and colloidal silica. 0.5 to 5 parts by mass of spherical polyethylene wax particles of 6 to 4 ⁇ may be contained.
  • Spherical polyethylene wax particles include Chemipearl (Polyolefin Water Dispersion) “W-100”, “W-400”, “W-500”, “W-700”, “W-900” from Mitsui Chemicals, Inc. Or the like.
  • a roll and resin-coated metal are used to gradually form a resin-coated metal sheet with multi-stage rolls while flowing a normal coolant liquid (water-based emulsion liquid in which water is added and dispersed).
  • a normal coolant liquid water-based emulsion liquid in which water is added and dispersed.
  • the average particle diameter of the spherical polyethylene wax is 0.6 / m or less, the protrusions of the wax particles covered with the film are not formed on the surface of the film, and the contact resistance with the roll cannot be reduced during roll forming.
  • the average particle size is 4 zm or more, it becomes difficult to cover the wax particles with a film, which causes deterioration of the adhesion of the paint film after painting when it is repainted.
  • the surface treatment composition of the present invention may be either a solvent-based composition or an aqueous composition that can be applied to the surface of a metal plate, but is an aqueous composition because of environmental problems. Is preferred.
  • Organic solvent in the case of solvent-based composition
  • water preferably deionized water (in the case of aqueous composition)
  • olefinic acid copolymer carboxylic acid
  • a surface treatment composition can be prepared by blending a predetermined amount of a polymer, colloidal silica and a silane coupling agent, and if necessary, a vanadium compound, a carpositimide group-containing compound and / or other components and stirring.
  • the olefinic acid copolymer which is the main component of the resin.
  • the olephinic acid copolymer can be emulsified by using an emulsifier and / or by neutralizing a carboxyl group in the copolymer.
  • an emulsifier is used, the average particle diameter of the aqueous emulsion of the olefin monoacid copolymer can be reduced, and the film-forming property and thereby the density of the resin film can be improved.
  • emulsification it is one of preferred embodiments to neutralize carboxyl groups in the olefinic monoacid copolymer. Because by neutralizing and emulsifying carboxyl groups, the amount of emulsifier used can be reduced, or no emulsifier can be used, and the adverse effect of the emulsifier on the water resistance and corrosion resistance of the resin film can be reduced or eliminated. Because. Ole When neutralizing the carboxyl group in the phosphinic acid copolymer, a base of preferably about 0.5 to 0.95 equivalent, more preferably about 0.6 to 0.8 equivalent is used with respect to the carboxyl group. It is preferable to use it.
  • the degree of neutralization is too low, the emulsifying property will not improve much.
  • the degree of neutralization is too high, the amount of carboxyl groups reacting with the silane coupling agent will decrease, which will adversely affect corrosion resistance.
  • the viscosity of the composition containing the olefin-acid copolymer may become too high.
  • a base for neutralization for example, hydroxides of alkali metals and alkaline earth metals
  • Strong base, aqueous ammonia, or primary, secondary or tertiary amines preferably triethylamine. If a strong base such as NaOH is used, the emulsifying property is improved, but if it is too much, the corrosion resistance of the resin film may be lowered.
  • amines, especially those having a low boiling point, preferably those having a boiling point of 100 ° C. or less at atmospheric pressure eg, triethylenamine
  • the strong base and amine when neutralizing the carboxynole group of the olefinic acid copolymer and emulsifying, it is preferable to use a combination of the strong base and amine, preferably a combination of NaOH and triethylamine.
  • the amount of the strong base is preferably 0.01 to 0.3 equivalents, and the amine is preferable with respect to the amount of the carboxyleno group of the olephinic acid copolymer. Is 0.4 ⁇ 0.8 equivalents.
  • a small amount of an organic solvent may be added to reduce interfacial tension and improve wettability to a metal plate.
  • the organic solvent for this purpose include methanol, ethanol, isopropanol, butanols, hexanol, 2-ethino hexanol, ethylene glycol eno eno enoate, ethylene glycol butyl ether, diethylene glycol, propylene glycol and the like. it can.
  • the solid content of the surface treatment composition is not particularly limited, and can be adjusted according to the method for applying the surface treatment composition to the metal plate.
  • the solid content of the surface treatment composition is generally about 5 to 20% by mass.
  • the spray ringer method (the surface treatment composition is applied to the surface of the metal plate). In the case of application by spraying and then squeezing with a roll, it is preferably about 10 to 18 mass%.
  • the metal plate used in the present invention is not particularly limited, for example, a non-plated cold-rolled steel sheet, a molten zinc-plated steel sheet (GI), a molten alloyed zinc-plated steel sheet (GA), or an electrogalvanized steel sheet.
  • a non-plated cold-rolled steel sheet a molten zinc-plated steel sheet (GI), a molten alloyed zinc-plated steel sheet (GA), or an electrogalvanized steel sheet.
  • examples include steel plates (EG), aluminum plates and titanium plates. Of these, chromate treatment is used, and nale, galvanized steel sheets are preferred.
  • the method and conditions for forming a resin film on a metal plate are not particularly limited, and the surface treatment composition is applied to one or both surfaces of the metal plate surface by a known coating method, followed by heating.
  • a resin-coated metal plate can be produced by drying.
  • the method for applying the surface treatment composition include a curtain flow coater method, a roll coater method, a spray method, and a spray ringer method.
  • the spray ringer method is preferable from the viewpoint of cost and the like.
  • the heating and drying conditions there is no particular limitation on the heating and drying conditions, and the heating and drying temperature is about 50 to 120 ° C, preferably about 70 to 90 ° C. However, an excessively high heat drying temperature is not preferable because the resin film deteriorates.
  • the amount of the resin film deposited on the surface of the metal plate is preferably 0.2 to 3 g / m 2 , more preferably 0.7 to 2 g / m 2 in terms of dry mass.
  • the specimen was bar-coated with acrylic paint so that the coating thickness was 20 ⁇ m, and baked at 160 ° C for 20 minutes for post-coating. Subsequently, after immersing this test material in boiling water for 1 hour, taking it out and leaving it for 1 hour, 100 mm of the lmm square grid was cut with a cutter knife, and a tape peeling test was carried out on this.
  • the coating film adhesion was evaluated according to the following criteria based on the number of residual cells.
  • test material After immersing the test material in alkaline degreasing agent (CL_N364S, manufactured by Nihon Parker Rising Co., Ltd.) 20g / L, adjusted to a liquid temperature of 60 ° C for 2 minutes, lifting, washing and drying, the test material is Based on S Z2371, a salt spray test was conducted to measure the time until 10% white birch was generated.
  • alkaline degreasing agent (CL_N364S, manufactured by Nihon Parker Rising Co., Ltd.) 20g / L, adjusted to a liquid temperature of 60 ° C for 2 minutes, lifting, washing and drying, the test material is Based on S Z2371, a salt spray test was conducted to measure the time until 10% white birch was generated.
  • a filament tape (# 9510, manufactured by Sliontic) was applied to the surface of the specimen, and the temperature was 40 ° CX RH98. After storing for 168 hours in an atmosphere of / o , the filament tape was peeled off, and the ratio of the area where the resin film remained (remaining ratio) was measured. The resin film adhesion was evaluated based on the following criteria.
  • the surface of the resin-coated metal plate was slid with stainless steel (SUS) protrusions (line contact) using a roll formability evaluation apparatus, and the damage state of the film was visually observed.
  • the roll formability evaluation device consists of a flat plate die and a die with protrusions (both are made of SUS) and is pulled through a resin-coated metal plate between these dies while applying pressure. The test was carried out with the size of the resin-coated metal plate to be tested set to 40 X 300 mm, the drawing speed 300 mm / min, and the applied pressure 1960 N.
  • the resin-coated metal plate used in the examples was produced by applying a surface treatment composition to a metal plate and drying it.
  • This surface treatment composition is a composition containing an olefin-acid copolymer, a carboxylic acid polymer, and less than a specified amount of a silane coupling agent. (Referred to as “resin composition” in the Examples) was prepared, and this resin composition was prepared by adding colloidal silica and the remaining amount of a silane coupling agent. Then, the resin composition used for preparation of the surface treatment composition in an Example is demonstrated.
  • An ethylene-acrylic acid copolymer (“Primacol 599 01” manufactured by Dow Chemical Co., Ltd., a structural unit derived from acrylic acid, with an autoclave equipped with a 1.0L emulsification facility equipped with a stirrer, thermometer and temperature controller : 20% by mass, weight average molecular weight: 20,000, melt index: 1300, acid value: 150) 20.0 g, polymaleic acid aqueous solution (“Non-Pole PMA_50W” manufactured by NOF Corporation, weight average molecular weight: about 1100, 50 mass% product) 8.0 g, triethylamine 35.5 g (0.63 equivalent to the carboxyl group of ethylene-acrylic acid copolymer), 4 8% NaOH aqueous solution 6.9 g (ethylene-acrylic acid copolymer) 0.15 equivalents to the carboxyl group of), tall oil fatty acid (Harima Kasei Co., Ltd.
  • silane coupling simultaneous lj (GE Toshiba Silicone “TSL8350”) 10.4 g, carbo Diimide group-containing compound (Nisshinbo “Polycarposimide SV-02”, solid content 40% by mass) 31.2 g and ion-exchanged water 72.8 g were added and stirred for 10 minutes to form an aqueous emulsion resin.
  • Composition 2 was prepared (solid content 20.1% by weight).
  • ethylene-acrylic acid copolymer ("Primacol 599 01" manufactured by Dow Chemical Co., Ltd.) 20.0g, polymaleic acid Aqueous solution (“Nonpol PMA_ 50W” manufactured by NOF Corporation), 50 mass 0 / o product) 16.0 g, 35.5 g of triethylenoleamine (0.63 equivalent to the carboxyl group of ethylene-acrylic acid copolymer) , 48% NaOH aqueous solution 6.9g (0.15 equivalents to the carboxyl group of ethylene-acrylic acid copolymer), tall oil fatty acid (Halima Kasei Co., Ltd.
  • ethylene-acrylic acid copolymer (Honeywell “AC5120”, allylic acid-derived structural unit: 15 mass) %, Weight average molecular weight: 5,000, acid value: 120) 20.0 g, polymaleic acid aqueous solution (“Nonpol PMA-50W”, 50% by mass, manufactured by NOF Corporation) 8.0 g, triethylamine 34.6 g (ethylene) —0.8 equivalent to the carboxyl group of acrylic acid copolymer), 5.4 g of 48% NaOH aqueous solution (0.15 equivalent to the carboxylate group of ethylene-acrylic acid copolymer), tall oil fatty acid ( Harima Chemical Co., Ltd.
  • ethylene acrylic acid copolymer (Primacol 599 01" manufactured by Dow Chemical Co., Ltd.) 20.0g, polymaleic acid aqueous solution (Non-Paul PMA-50W, 50% by mass, manufactured by NOF Corporation) 8.0 g, 35.5 g of triethylamine (0.63 equivalents relative to the carboxyl group of the ethylene acrylic acid copolymer), 48% NaOH Add 6.9 g of aqueous solution (0.15 equivalent to the carboxyl group of ethylene acrylic acid copolymer), add 788.
  • silane coupling agent GE Toshiba Silicone “TSL8350”
  • Carpositimide group-containing compound Nisshinbo “Polycarposimide SV-02”, solid content 40% by mass
  • ion-exchanged water 72.8 g was added and stirred for 10 minutes to prepare a resin composition 7 in the form of an aqueous emulsion (solid content: 20.2% by mass).
  • ethylene-acrylic acid copolymer (Primacol 599 01" manufactured by Dow Chemical Co., Ltd.) 20.0g, Triethylamine 35 5g (0 ⁇ 63 equivalents relative to the carboxyl group of the ethylene-acrylic acid copolymer), 48% NaOH7 solution 6.9g (0.15 equivalents relative to the carboxyl group of the ethylene acrylic acid copolymer), Toll Oil fatty acid (Hallima Kasei Co., Ltd. “Nool Toll FA3”) 3.5 g, ion-exchanged water 788.
  • silane cutlet Pulling agent GE Toshiba Silicone “TSL8350” 10.2 g, Carposiimide group-containing compound (Nisshinbo “Polycarpopositimide SV-02”, solid content 40% by mass) 30.6 g, ion-exchanged water 71. 4 g was added and stirred for 10 minutes to prepare a resin composition 9 (for comparison) in the form of an aqueous emulsion (solid content 19.1% by mass).
  • Resin composition 10 (for comparison): Polyacrylic acid aqueous solution instead of polymaleic acid in resin composition 1 (“AC — 10S” manufactured by Nippon Pure Chemical Industries, Ltd., weight average molecular weight: 5,000, solid content: 40.3 mass% )
  • Resin composition 11 (for comparison): Polymaleic acid aqueous solution in place of polymaleic acid in resin composition 1 (Non-Paul PMA_50W manufactured by NOF Corporation, solid content 50.1% by mass)
  • Resin composition 12 (for comparison): In place of polymaleic acid of resin composition 1, methyl vinyl ether-maleic anhydride copolymer aqueous solution (ISP Japan "AN_119", weight average molecular weight: 200,000, solid (15.3% by mass)
  • Resin composition 13 (for comparison): instead of the ethylene acrylic acid copolymer of resin composition 1, ethylene acrylic acid copolymer resin aqueous emulsion (“HYTEC”)
  • Resin composition 14 (for comparison): Polyallylamine aqueous solution (“PAA-01” manufactured by Nitto Boseki Co., Ltd., weight average molecular weight: 5,000, solid content 15.1% by mass) instead of triethylamine in resin composition 1
  • Colloidal silica (“ST_XS” manufactured by Nissan Chemical Industries, Ltd., surface area average particle diameter: 4 to 6 nm) 20 parts by mass is added to 80 parts by mass of the resin components 1 to 14 of the resin composition 1 to 100 in total. It was set as the mass part. Furthermore, 10 parts by mass of a silane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd., y-glycidoxypropyltrimethoxysilane) is added to 100 parts by mass in total, and water is added to adjust the solid content.
  • the surface treatment composition was prepared by diluting (solid content: 15 to 16.5% by mass) and stirring at room temperature.
  • resin component means “olefin-acid copolymer and carboxylic acid polymer” in resin compositions 1 to 7, and “resin component” in resin compositions 8 and 9.
  • Acid resin ", and resin compositions 10 to 14 represent polymers contained in the respective resin compositions.
  • resin compositions 10 to 12 for comparison
  • colloidal silica instead of the colloidal silica “ST-XS”, acidic colloidal silica (“ST_0” manufactured by Nissan Chemical Industries, Ltd., surface area average
  • the surface treatment composition was prepared using a particle diameter of 10 to 20 nm.
  • an alkali degreased hot-dip galvanized steel plate (Zn adhesion amount 45 g / m 2 ) was used, and the surface treatment composition was applied to the surface of the steel plate with a bar coat (bar No. 3).
  • the plate was heated and dried at a plate temperature of 90 ° C. for about 12 seconds to produce a resin-coated metal plate with a coating amount of 1. Og / m 2 :! -14.
  • the characteristics of the obtained resin-coated metal sheet were evaluated. The results are shown in Table 1. As shown in Table 1 below, the resin-coated metal plates 1 to 7 obtained from the surface treatment composition containing a combination of an olefin monoacid copolymer and a carboxylic acid polymer have good corrosion resistance and coating film. Adhesion, alkali resistance and resin film adhesion.
  • colloidal silica (“ST-XS” manufactured by Nissan Chemical Industries, Ltd.) 5 to 45 parts by mass was added to 55 to 95 parts by mass of the resin component of the resin composition 1 to make a total of 100 parts by mass. Furthermore, silane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) 10 Add part by weight and dilute with water to adjust the solid content (solid content 16.5% by mass)
  • the surface treatment composition was prepared by stirring at room temperature.
  • Resin-coated metal plates 15 to 26 were produced in the same manner as in Example 1, and the characteristics thereof were evaluated.
  • the resin-coated metal plates 15 to 23 that satisfy the requirements of the resin component amount and colloidal silica amount specified in the present invention have good corrosion resistance, coating film adhesion, alkali resistance and resin. Has film adhesion.
  • Resin-coated metal plates 27 to 36 were produced in the same manner as in Example 1, and their characteristics were evaluated.
  • a white precipitate was generated in one week after the preparation of the surface treatment composition.
  • Resin-coated metal plates 37 to 40 were produced in the same manner as in Example 1, and their characteristics were evaluated.
  • the resin-coated metal plates 37 and 38 using colloidal silica having a preferred average particle size have good corrosion resistance, coating film adhesion, ano- ral resistance, and resin film adhesion.
  • the vanadium compound diluted aqueous solution is prepared by diluting “vanadic acid solution (IV)” manufactured by Shinsei Chemical Industry Co., Ltd. with pure water to a predetermined concentration, and then adjusting the pH to 6.5 using aqueous ammonia.
  • Resin-coated metal plates 41 to 51 were produced in the same manner as in Example 1, and the characteristics thereof were evaluated.
  • Colloidal silica (Nissan Chemical Industries) with respect to 80 parts by mass of the resin component of the resin composition 1 20 parts by mass of “ST-XS” manufactured by the company was added to make a total of 100 parts by mass. Furthermore, 10 parts by mass of a silane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by mass of the total, and further diluted with water to adjust the solid content (solid content 16.5 (Mass%) and stirring at room temperature to prepare a surface treatment composition.
  • KBM403 silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.
  • an alkaline degreased hot-dip galvanized steel plate (Zn adhesion amount 45 g / m 2 ) was used, and the surface treatment composition was applied to the surface of the steel plate with a bar coat (bar No. 3). Then, it was dried by heating at a plate temperature of 90 ° C. for about 12 seconds to produce resin-coated metal plates 52 to 62 with a resin film adhesion amount of 0.:! To 3.5 g / m 2 .
  • the properties of the obtained resin-coated metal sheet were evaluated. The results are shown in Table 6. As shown in Table 6 below, the resin-coated metal plates 52 to 59 provided with a resin film with a preferable resin adhesion amount have good corrosion resistance, coating film adhesion, alkali resistance, and resin film adhesion.
  • colloidal silica (“ST_XS” manufactured by Nissan Chemical Industries, Ltd.) was added to the resin component 70 of the resin composition 1 to make a total of 100 parts by mass. Furthermore, 7 parts by mass of a silane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the total of 100 parts by mass, and sodium metavanadate as a vanadium compound (“Sodium Metavanadate” manufactured by Shinsei Chemical Industry Co., Ltd.) was added so that the amount converted to VO was 2 parts by mass. In addition, it contains oxazoline
  • Styrene / acryl main chain oxazoline polymer (Nippon Shokubai Co., Ltd.) as polymer (crosslinking agent) “Epocross K 2030E”) is added to 0 to 15 parts by mass with respect to 100 parts by mass in total, and diluted with water to adjust the solid content (solid content concentration 16.5% by mass) at room temperature.
  • the surface treatment composition was prepared by stirring.
  • Resin-coated metal plates 63 to 76 were produced in the same manner as in Example 1 and their characteristics were evaluated. The results are shown in Table 7. As shown in the following metal plates 63 to 72 in Table 6, corrosion resistance and adhesion as well as roll formability are improved by the addition of the polymer containing oxazoline.
  • colloidal silica (“ST-XS” manufactured by Nissan Chemical Industries, Ltd.) was added to the resin component 70 of the resin composition 1 to make a total of 100 parts by mass. Furthermore, 7 parts by mass of a silane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the total of 100 parts by mass, and sodium metavanadate as a vanadium compound (“Sodium Metavanadate” manufactured by Shinsei Chemical Industry Co., Ltd.) was added so that the equivalent amount of V 0 was 2 parts by mass. In addition, it contains oxazoline
  • styrene / acryl main chain oxazoline polymer (Nippon Shokubai "Epocross K-2030E") is added to 100 parts by mass in total, and the average particle size is 0 3 ⁇ m spherical polyethylene wax particles (“Permarin KUE-17J” manufactured by Sanyo Chemical Industries, Ltd.) and spherical polyethylene wax particles with an average particle size of 0.6-7 ⁇ m (Mitsui "Chemical Pearl W900", “Chemical Pearl W700”, “Cheminole W500”, “Chemipe Norre W300J”, “Chemino Monore W400J” On the other hand, 0.5 to 5 parts by mass was added, and further diluted with water to adjust the solid content (solid content concentration: 16.5% by mass) and stirred at room temperature to prepare a surface treatment composition.
  • solid content concentration solid content concentration: 16.5% by mass
  • Resin-coated metal plates 77 to 94 were produced in the same manner as in Example 1 and their characteristics were evaluated. The results are shown in Table 8. As shown in the metal plates 77 to 81 and 85 to 90 in the following table, the roll formability was particularly improved by adding the polymer containing oxazoline and adding the spherical polyethylene wax.
  • colloidal silica (“ST_XS” manufactured by Nissan Chemical Industries, Ltd.) was added to the resin component 70 of the resin composition 1 to make a total of 100 parts by mass. Furthermore, 7 parts by mass of a silane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the total of 100 parts by mass, and sodium metavanadate as a vanadium compound (“Sodium Metavanadate” manufactured by Shinsei Chemical Industry Co., Ltd.) was added so that the equivalent amount of V 0 was 2 parts by mass. In addition, it contains oxazoline Styrene / acryl main chain oxazoline polymer (Nippon Shokubai Co., Ltd.) as polymer (crosslinking agent)
  • Epocross K-2030E 4 parts by mass of “Epocross K-2030E” is added to 100 parts by mass of the total, and an average particle size of 1.0 / m spherical polyethylene wax particles (“Chemical W700” manufactured by Mitsui Chemicals, Inc.) To 100 parts by mass, 2 parts by mass was added, and further diluted with water to adjust the solid content (solid content concentration: 16.5% by mass), and stirred at room temperature to prepare a surface treatment composition.
  • Metal plates 95-102 and 107-109 are steel plates with molten subgrowth
  • Metal plates 103 to 104 are galvanized steel plates
  • Metal plates 105 to 106 are electrogalvanized steel plates

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Abstract

L'invention concerne une tôle de métal revêtue de résine ayant une excellente résistance à la corrosion. L'invention concerne précisément une tôle de métal revêtue de résine ayant un film de revêtement de résine, lequel est obtenu à partir d'une composition de traitement de surface. La composition de traitement de surface contient 55-95 parties en masse du total d'un copolymère d'oléfine-acide carboxylique à insaturation en α,β et d'un polymère d'un acide carboxylique à insaturation en α,β et 5-45 parties en masse de silice colloïde (à condition que le total des polymères et de la silice soit de 100 parties en masse). La composition de traitement de surface contient en outre 7-30 parties en masse d'un agent de couplage de type silane pour 100 parties en masse du total des polymères et de la silice. Le rapport en masse entre la teneur du copolymère d'oléfine-acide carboxylique à insaturation en α,β et la teneur du polymère d'un acide carboxylique à insaturation en α,β va de 1000:1 à 10:1.
PCT/JP2007/054441 2006-03-07 2007-03-07 Tôle de métal revêtue de résine et composition de traitement de surface servant à produire celle-ci WO2007102544A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
JP2012178550A (ja) * 2011-02-04 2012-09-13 Kobe Steel Ltd 樹脂被覆金属板
JP2013222185A (ja) * 2012-04-19 2013-10-28 Konica Minolta Inc 箔接着用トナーおよび画像形成方法
WO2019116326A1 (fr) * 2017-12-15 2019-06-20 Ppg Industries Ohio, Inc. Durcissement de polyoxazoline pour compositions de revêtement d'emballage
DE102010030114B4 (de) 2009-08-11 2021-11-04 Evonik Operations Gmbh Wässriges Silansystem für den Blankkorrosionsschutz, Verfahren zu dessen Herstellung, dessen Verwendung sowie mit diesem behandelte Gegenstände und Korrosionsschutzschicht

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JP2013056441A (ja) * 2011-09-07 2013-03-28 Sumitomo Light Metal Ind Ltd 導電性プレコートアルミニウム合金板
JP2017155261A (ja) * 2016-02-29 2017-09-07 株式会社神戸製鋼所 外観に優れた表面処理亜鉛系めっき鋼板
JP6856451B2 (ja) * 2016-08-05 2021-04-07 株式会社神戸製鋼所 表面処理金属板、及び表面処理金属板の製造方法

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JP2005161562A (ja) * 2003-11-28 2005-06-23 Kobe Steel Ltd 潤滑性とアルカリ脱膜性に優れた樹脂膜積層金属板
JP2005281863A (ja) * 2004-03-04 2005-10-13 Nippon Steel Corp 表面処理金属板

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JP4398827B2 (ja) * 2004-02-06 2010-01-13 株式会社神戸製鋼所 樹脂塗装金属板

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JP2004143293A (ja) * 2002-10-24 2004-05-20 Du Pont Mitsui Polychem Co Ltd 水性分散体及びその用途
JP2005161562A (ja) * 2003-11-28 2005-06-23 Kobe Steel Ltd 潤滑性とアルカリ脱膜性に優れた樹脂膜積層金属板
JP2005281863A (ja) * 2004-03-04 2005-10-13 Nippon Steel Corp 表面処理金属板

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010030114B4 (de) 2009-08-11 2021-11-04 Evonik Operations Gmbh Wässriges Silansystem für den Blankkorrosionsschutz, Verfahren zu dessen Herstellung, dessen Verwendung sowie mit diesem behandelte Gegenstände und Korrosionsschutzschicht
JP2012178550A (ja) * 2011-02-04 2012-09-13 Kobe Steel Ltd 樹脂被覆金属板
JP2013222185A (ja) * 2012-04-19 2013-10-28 Konica Minolta Inc 箔接着用トナーおよび画像形成方法
WO2019116326A1 (fr) * 2017-12-15 2019-06-20 Ppg Industries Ohio, Inc. Durcissement de polyoxazoline pour compositions de revêtement d'emballage
US10836928B2 (en) 2017-12-15 2020-11-17 Ppg Industries Ohio, Inc. Polyoxazoline curing for packaging coating compositions

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CN101395302A (zh) 2009-03-25
TW200744835A (en) 2007-12-16

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