JP5183586B2 - Water-based paint surface treatment agent also used as a primer, surface-treated metal material, and pre-coated metal material - Google Patents
Water-based paint surface treatment agent also used as a primer, surface-treated metal material, and pre-coated metal material Download PDFInfo
- Publication number
- JP5183586B2 JP5183586B2 JP2009162095A JP2009162095A JP5183586B2 JP 5183586 B2 JP5183586 B2 JP 5183586B2 JP 2009162095 A JP2009162095 A JP 2009162095A JP 2009162095 A JP2009162095 A JP 2009162095A JP 5183586 B2 JP5183586 B2 JP 5183586B2
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- Prior art keywords
- film
- glycidyl
- water
- group
- coating
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- 239000007769 metal material Substances 0.000 title claims description 54
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- 150000002334 glycols Chemical class 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- BQWORYKVVNTRAW-UHFFFAOYSA-N heptane-3,5-diol Chemical compound CCC(O)CC(O)CC BQWORYKVVNTRAW-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XGFPOHQJFNFBKA-UHFFFAOYSA-B tetraaluminum;phosphonato phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O XGFPOHQJFNFBKA-UHFFFAOYSA-B 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical class [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Description
本発明は、建材や家電製品、自動車部品などに使用されるプレコート金属材料の分野において、金属材料に、プライマーを介さずとも優れた塗膜の加工密着性、耐食性、耐薬品性、耐コインスクラッチ性を付与することができるプレコート金属材料用プライマー兼用水系塗装下地処理剤、並びにそれを用いて得られる表面処理金属材料及びその処理表面に上層皮膜を形成させて得られるプレコート金属材料に関する。 In the field of pre-coated metal materials used for building materials, home appliances, automobile parts, etc., the present invention provides excellent coating adhesion, corrosion resistance, chemical resistance, and coin scratch resistance to metal materials without using a primer. TECHNICAL FIELD The present invention relates to a primer / water-based paint base treatment agent for a precoat metal material that can be imparted with properties, a surface-treated metal material obtained by using the primer, and a precoat metal material obtained by forming an upper film on the treated surface.
プレコート金属材料としては、塗膜の加工密着性、耐食性、耐薬品性、耐コインスクラッチ性、意匠性など多くの性能が要求されるために、下地処理を施した金属板上に、プライマーと呼ばれる下塗り塗膜を施し、さらに着色した上塗り塗膜を施した２コート型のものが幅広く使用されている。この種のプレコート金属材料では、下地処理を施すことで金属板との密着性を確保し、樹脂及び防錆顔料などを含有するプライマーを上塗り塗膜との間に存在させることで加工密着性、耐食性、耐コインスクラッチ性などを付与している。 The pre-coated metal material is called a primer on the metal plate that has undergone the base treatment because it requires many performances such as coating adhesion, corrosion resistance, chemical resistance, coin scratch resistance, and design properties. A two-coat type having a base coat and a colored top coat is widely used. In this type of pre-coated metal material, the adhesion with the metal plate is ensured by applying a base treatment, and the processing adhesion by having a primer containing a resin and an anti-rust pigment etc. between the top coat film, Corrosion resistance, coin scratch resistance, etc. are added.
プレコート金属材料における下地処理としては、従来、金属材料表面との密着性に優れ、金属材料表面に優れた耐食性を付与するクロム酸、重クロム酸もしくはそれらの塩とを主成分として含有する処理液によるクロメート処理が用いられ、プライマーにも、優れた耐食性が得られるクロム系の防錆顔料を含有した塗料が幅広く使用されてきた。しかし、近年の環境への配慮から、現在はクロムを他の架橋性金属へ代替したクロムフリーの技術が実用に供されている。 Conventionally, as a base treatment in a pre-coated metal material, a treatment liquid containing, as a main component, chromic acid, dichromic acid, or a salt thereof that has excellent adhesion to the metal material surface and imparts excellent corrosion resistance to the metal material surface. Chromate treatment is used, and paints containing chromium-based anticorrosive pigments that provide excellent corrosion resistance have been widely used as primers. However, in recent years, due to environmental considerations, a chromium-free technique in which chromium is replaced with another crosslinkable metal is now in practical use.
また、従来の溶剤型塗料を用いた２コートでは、塗料の焼付け工程において揮発性成分が多く発生する上、塗装や焼付けの際の工程数も多くかかるなど、環境への負荷が大きい。このため、有機溶剤使用量の低減、塗料の水系化が望まれているほか、省資源化、低コスト化を目的に塗膜の薄膜化や工程短縮（１コート化）なども望まれている。 In addition, the conventional two-coat using a solvent-based paint has a large environmental load, for example, a large amount of volatile components are generated in the paint baking process, and the number of processes during painting and baking is also large. For this reason, reduction of the amount of organic solvent used and water-based coatings are desired, as well as reduction of the coating film and shortening of the process (single coating) for the purpose of resource saving and cost reduction. .
特許文献１には、化成処理を施した亜鉛めっき鋼板上に、ポリエステル樹脂、メラミン樹脂硬化剤、防錆顔料、有機高分子微粒子などを配合した塗料組成物を塗装することにより、優れた加工性、耐食性、密着性、耐衝撃性、耐スクラッチ性を有する１コート型プレコート鋼板の製造方法が開示されている。しかし、この塗料組成物に含まれる防錆顔料が塗膜の見栄えを低下させ、かつプレコート鋼板に多種多様の意匠を施すことができなくなるという問題がある。また、この塗料組成物はクロメート処理した鋼板に塗布するものであり、時代の要請から外れている。 Patent Document 1 shows excellent workability by coating a coating composition containing a polyester resin, a melamine resin curing agent, a rust preventive pigment, organic polymer fine particles, and the like on a galvanized steel sheet subjected to chemical conversion treatment. A method for producing a one-coat type pre-coated steel sheet having corrosion resistance, adhesion, impact resistance and scratch resistance is disclosed. However, there is a problem that the rust preventive pigment contained in the coating composition deteriorates the appearance of the coating film and a variety of designs cannot be applied to the precoated steel sheet. In addition, this coating composition is applied to a chromate-treated steel plate, and is not satisfying the needs of the times.
特許文献２には、化成処理が施された亜鉛系めっき鋼板の表面に、ポリエステル樹脂、エポキシ樹脂、ブロック化ポリイソシアネート化合物、メラミン樹脂硬化剤などを特定の割合で配合した溶剤型塗料組成物を塗装することによって、成形加工性に優れた１コートプレコート鋼板の製造方法が開示されている。しかし、この塗料組成物もクロメート処理した鋼板に塗布するものであり、時代の要請から外れていると共に、クロメート処理を含む従来の化成処理を施した鋼板に上記塗料組成物を塗装した場合、形成される有機皮膜が防錆剤を含有しないものであるため、耐食性が不十分となる。 Patent Document 2 discloses a solvent-type coating composition in which a polyester resin, an epoxy resin, a blocked polyisocyanate compound, a melamine resin curing agent, and the like are blended at a specific ratio on the surface of a zinc-based plated steel sheet that has been subjected to chemical conversion treatment. A method for producing a 1-coated precoated steel sheet that is excellent in forming processability by coating is disclosed. However, this coating composition is also applied to a chromate-treated steel sheet, which is not in line with the demands of the times, and is formed when the above coating composition is applied to a steel sheet that has undergone conventional chemical conversion treatment including chromate treatment. Since the organic film formed does not contain a rust inhibitor, the corrosion resistance becomes insufficient.
特許文献３には、樹脂、シランカップリング剤、平均粒径が１μｍ以下の微粒子などを特定の割合で配合した水系塗装下地処理剤が開示されている。しかし、この下地処理剤は２コート型プレコート鋼板のためのものであり、プライマーを省略すると、皮膜量が少ない場合は耐食性が不十分となり、皮膜量が多い場合は塗膜の加工密着性が得られなくなる。 Patent Document 3 discloses a water-based coating base treatment agent in which a resin, a silane coupling agent, fine particles having an average particle diameter of 1 μm or less, and the like are blended at a specific ratio. However, this surface treatment agent is for a two-coat type precoated steel sheet. If the primer is omitted, the corrosion resistance is insufficient when the coating amount is small, and the processing adhesion of the coating film is obtained when the coating amount is large. It becomes impossible.
特許文献４には、シランカップリング剤、水分散性シリカ、並びにジルコニム化合物及び／又はチタン化合物を必須成分として含み、更にチオカルボニル基含有化合物及び／又は水溶性アクリル樹脂を含んでいてもよい金属表面処理剤が開示されている。しかし、この表面処理剤は１コートで耐食性が得られるように皮膜設計されておらず、このため１コートでは十分な耐食性が得られない。 Patent Document 4 includes a silane coupling agent, water-dispersible silica, a zirconium compound and / or a titanium compound as essential components, and further a thiocarbonyl group-containing compound and / or a water-soluble acrylic resin. A surface treatment agent is disclosed. However, this surface-treating agent is not designed so that the corrosion resistance can be obtained with one coat. For this reason, sufficient corrosion resistance cannot be obtained with one coat.
特許文献５には、水性樹脂、架橋剤、無機防錆剤、有機防錆剤などを含む金属表面処理剤により形成された、耐食性、耐アルカリ性、耐溶剤性、耐傷付性、密着性の全てを満足させる皮膜を有する有機被覆処理金属板が開示されている。しかし、この表面処理剤はプレコート鋼板用下地処理剤としては設計されておらず、仮にプレコート鋼板用塗装下地処理として転用してもプレコート鋼板に要求されるレベルの塗膜の加工密着性を達成できない。 Patent Document 5 includes all of corrosion resistance, alkali resistance, solvent resistance, scratch resistance, and adhesion formed by a metal surface treatment agent containing an aqueous resin, a crosslinking agent, an inorganic rust inhibitor, an organic rust inhibitor, and the like. An organic coating-treated metal plate having a film satisfying the above has been disclosed. However, this surface treating agent is not designed as a pretreatment agent for pre-coated steel sheets, and even if it is diverted as a pre-treatment for pre-coated steel sheets, it does not achieve the required level of processing adhesion to the pre-coated steel sheet. .
特許文献６には、水系有機樹脂成分、縮合リン酸カルシウム、トリポリリン酸アルミニウム、金属酸素酸塩、並びにリン酸もしくは水溶性リン酸塩を含有するプレコート金属材料用水系プライマー兼下地処理剤が開示されており、クロメート系防錆顔料を使用しなくとも耐食性、加工性に優れた塗膜が得られる旨記載されている。しかし、この処理剤からの皮膜は緻密さ、強靭性が足りないために耐コインスクラッチ性、耐薬品性が不十分である。 Patent Document 6 discloses a water-based primer / base treatment agent for a pre-coated metal material containing a water-based organic resin component, condensed calcium phosphate, aluminum tripolyphosphate, metal oxyacid salt, and phosphoric acid or a water-soluble phosphate. In addition, it is described that a coating film excellent in corrosion resistance and workability can be obtained without using a chromate rust preventive pigment. However, the coating film from this treatment agent is insufficient in denseness and toughness, so that the coin scratch resistance and chemical resistance are insufficient.
特許文献７には、化成処理を施さない金属基材に、アクリル化エポキシ樹脂、防錆顔料を含有する水性塗料組成物を塗装することを特徴とする、化成処理皮膜を有する塗膜と同等の優れた密着性を有する塗膜を形成することができる塗装方法が開示されている。しかし、この塗料組成物ではプレコート鋼板に要求されるレベルの塗膜の加工密着性を達成できず、また、耐薬品性も不十分である。 In Patent Document 7, a metal substrate not subjected to chemical conversion treatment is coated with an aqueous coating composition containing an acrylated epoxy resin and a rust preventive pigment, and is equivalent to a coating film having a chemical conversion treatment film. A coating method capable of forming a coating film having excellent adhesion is disclosed. However, this coating composition cannot achieve the level of processing adhesion of the coating film required for the precoated steel sheet, and also has insufficient chemical resistance.
特許文献８には、ウレタン樹脂、特定の有機化合物、ジルコニウム化合物を含有する金属表面処理剤及びそれにより形成された、優れた耐食性、成形加工性、耐薬品性、耐湿性を有する金属材料が開示されている。しかし、この表面処理剤は無塗装で用いられる金属材料の防錆目的で用いられるものであり、塗装下地皮膜に転用してもプレコート鋼板に要求されるレベルの塗膜の加工密着性、耐コインスクラッチ性を達成できない。 Patent Document 8 discloses a metal surface treatment agent containing a urethane resin, a specific organic compound, and a zirconium compound, and a metal material formed thereby and having excellent corrosion resistance, molding processability, chemical resistance, and moisture resistance. Has been. However, this surface treatment agent is used for the purpose of rust prevention of metal materials used without coating, and even when it is diverted to a coating base film, the coating adhesion of the coating film at the level required for pre-coated steel sheets, and coin resistance The scratch property cannot be achieved.
プレコート鋼板には、曲げ加工、絞り加工のような厳しい後加工に耐え得る塗膜の加工密着性が求められるため、通常、鋼板上に下地処理が施される。下地処理皮膜は、十分な密着性が得られ難い金属表面と上層（プライマーおよび上塗り塗膜）とを結びつけることで、優れた塗膜の加工密着性を付与する役割を担っている。なお、プレコート鋼板の加工密着性の評価には、極めて厳しい試験として折り曲げ試験が行われている。 Since the pre-coated steel sheet is required to have a work adhesion of a coating film that can withstand severe post-processing such as bending and drawing, a base treatment is usually applied on the steel sheet. The ground treatment coating plays a role of imparting excellent processing adhesion of the coating film by combining the metal surface and the upper layer (primer and top coating film), for which sufficient adhesion is difficult to obtain. In addition, the bending test is performed as an extremely severe test for evaluating the work adhesion of the precoated steel sheet.
また、プレコート鋼板には、長期間の暴露に耐え得る耐食性が求められる。プレコート鋼板での腐食は主に、傷部や端面部でのアノード溶解、及び傷部からやや離れた塗膜下で生じるカソード反応に起因するブリスターの発生である。２コート型プレコート鋼板の場合、下地処理に起因する耐食性は、皮膜の耐酸性、耐アルカリ性が強いことによって発揮され、プライマーに起因する耐食性は、塗膜の低い透水性などの環境遮断能と、皮膜中に豊富に含まれる防錆顔料によるインヒビター効果によって発揮される。また、プライマー層の硬質な皮膜による良好な耐傷付き性（耐コインスクラッチ性）も、腐食の起点を作り難くするという点で重要な特性である。上塗り塗膜に起因する耐食性は、耐汚染性に強い樹脂を用いた皮膜、厚い膜厚による環境遮断能によって発揮される。 Further, the precoated steel sheet is required to have corrosion resistance that can withstand long-term exposure. Corrosion in the pre-coated steel sheet is mainly the generation of blisters due to anodic dissolution at the flaws and end faces and cathodic reaction that occurs under the coating film slightly away from the flaws. In the case of a two-coat type pre-coated steel sheet, the corrosion resistance due to the base treatment is exhibited by the strong acid resistance and alkali resistance of the film, and the corrosion resistance due to the primer has an environmental barrier ability such as low water permeability of the coating film, It is exhibited by the inhibitor effect of the anticorrosive pigments abundantly contained in the film. Also, good scratch resistance (coin scratch resistance) due to the hard coating of the primer layer is an important characteristic in that it is difficult to make a starting point of corrosion. Corrosion resistance due to the top coat film is exhibited by a film using a resin having a high resistance to contamination and an environmental barrier ability due to a thick film thickness.
さらに、プレコート鋼板には多種多様な意匠性が要求される。光沢のある美しい外観、光沢の低いつや消しなど、目的に応じた上塗り塗装が施される。 Furthermore, a wide variety of design properties are required for precoated steel sheets. A top coat is applied according to the purpose, such as a beautiful appearance with gloss and a matte finish with low gloss.
このように、プレコート鋼板における塗膜の各層には役割分担がされており、従来の技術において１コートを検討する場合、プライマーだけでは意匠性、耐汚染性が不十分となり、上塗り塗膜だけでは加工密着性、耐食性が不十分となる。従って、プレコート鋼板に求められる特性を全て満足し、前記した環境上の課題をも同時に改善するプレコート鋼板における１コート化を達成するには、加工密着性、耐食性、耐コインスクラッチ性などのプライマーの機能をも兼ね備えた下地処理皮膜が必要となるが、そのような皮膜を形成できる水系塗装下地処理剤は開発されていないのが現状である。
本発明は、従来技術の有する前記課題点を解決して、プライマーを介さずとも優れた塗膜の加工密着性、耐食性、耐薬品性、耐コインスクラッチ性を付与することができるプレコート金属材料用プライマー兼用水系塗装下地処理剤、並びにそれからの皮膜を表面に有する金属材料及びプレコート金属材料を提供することを目的とする。 The present invention solves the above-mentioned problems of the prior art, and for pre-coated metal materials that can provide excellent coating adhesion, corrosion resistance, chemical resistance, and coin scratch resistance without using a primer It is an object of the present invention to provide a primer combined water-based coating surface treatment agent, and a metal material and a pre-coated metal material having a film formed thereon.
本発明者らは、前記目的を達成するべく鋭意検討を重ねた結果、水性ポリウレタン樹脂と水性エポキシ樹脂とグリシジル基を有する有機化合物とチタン元素もしくはジルコニウム元素を含有する架橋剤とを含有する水系塗装下地処理剤を用いることで、優れた塗膜の加工密着性、意匠性、耐食性、耐薬品性、耐コインスクラッチ性を有する１コート型プレコート金属材料が得られることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have made an aqueous coating containing an aqueous polyurethane resin, an aqueous epoxy resin, an organic compound having a glycidyl group, and a crosslinking agent containing titanium element or zirconium element. The present invention has been completed by finding that a 1-coat type pre-coated metal material having excellent coating adhesion, design, corrosion resistance, chemical resistance, and coin scratch resistance can be obtained by using a base treatment agent. .
すなわち、本発明は、ウレタン基濃度が１．０〜４．０ｍｍｏｌ／ｇで、酸価が１０〜６０ｍｇＫＯＨ／ｇであって、カルボキシル基を含有する水性ポリウレタン樹脂（Ａ）、重量平均分子量が１，０００〜３０，０００である水性エポキシ樹脂（Ｂ）、グリシジル基を有する有機化合物（Ｃ）、及びチタン元素もしくはジルコニウム元素を含有する架橋剤（Ｄ）を含有し、各成分間の固形分質量比として、（Ｂ）／（Ａ）が１／５０〜１０／１、（Ｃ）／［（Ａ）＋（Ｂ）］が１／３００〜１／１、（Ｄ）／［（Ａ）＋（Ｂ）］が１／３００〜１／１であるプレコート金属材料用プライマー兼用水系塗装下地処理剤であって、該処理剤の全固形分に対する［（Ａ）＋（Ｂ）］の固形分割合が４５〜９５質量％である該処理剤に関する。 That is, in the present invention, the urethane group concentration is 1.0 to 4.0 mmol / g, the acid value is 10 to 60 mgKOH / g, and the aqueous polyurethane resin (A) containing a carboxyl group has a weight average molecular weight of 1. 30,000 to 30,000 aqueous epoxy resin (B), organic compound (C) having a glycidyl group, and a crosslinking agent (D) containing titanium element or zirconium element, and the solid content mass between each component As a ratio, (B) / (A) is 1/50 to 10/1, (C) / [(A) + (B)] is 1/300 to 1/1, (D) / [(A) + (B)] is a primer for water-based pre-coating material for precoat metal material having a ratio of 1/300 to 1/1, and the solid content ratio of [(A) + (B)] to the total solid content of the treatment agent Is related to the treatment agent.
水性ポリウレタン樹脂（Ａ）は、上記物性に加え、ガラス転移温度が３０〜１８０℃であることが好ましく、また、その皮膜物性としての抗張力が３０〜８０ＭＰａであることが好ましい。
有機化合物（Ｃ）は、重量平均分子量が８００以下である水性エポキシ樹脂、ポリグリシジルエーテル化合物、ポリグリシジルエステル化合物及びグリシジル基含有シラン化合物よりなる群から選ばれる少なくとも１種であることが好ましい。
本発明の処理剤は、コロイダルシリカ、気相シリカ、アルミナゾル、リン酸系防錆顔料、モリブデン酸系防錆顔料及びバナジウム系防錆顔料よりなる群から選ばれる少なくとも１種の平均粒径が０．０１〜５μｍである微粒子（Ｅ）を、固形分質量比として、（Ｅ）／［（Ａ）＋（Ｂ）］が１／１００〜１／１となるように含有することができ、含有する方が好ましい。
In addition to the above physical properties, the aqueous polyurethane resin (A) preferably has a glass transition temperature of 30 to 180 ° C., and preferably has a tensile strength as a film physical property of 30 to 80 MPa.
The organic compound (C) is preferably at least one selected from the group consisting of an aqueous epoxy resin having a weight average molecular weight of 800 or less, a polyglycidyl ether compound, a polyglycidyl ester compound, and a glycidyl group-containing silane compound.
The treatment agent of the present invention has an average particle size of at least one selected from the group consisting of colloidal silica, gas phase silica, alumina sol, phosphoric acid rust preventive pigment, molybdate rust preventive pigment and vanadium rust preventive pigment. Fine particles (E) having a diameter of 0.01 to 5 μm can be contained such that (E) / [(A) + (B)] is 1/100 to 1/1 as a solid content mass ratio. Is preferred.
本発明は、また、上記処理剤からの乾燥皮膜であって、０．５〜５ｇ／ｍ２の乾燥皮膜を表面に有する金属材料、及び該金属材料の乾燥皮膜を有する表面に、さらに、クロムを含まない上層皮膜を形成させて得られるプレコート金属材料に関する。 The present invention also provides a dry film from the above-mentioned treatment agent, the metal material having a dry film of 0.5 to 5 g / m 2 on the surface, and a chromium film on the surface having the dry film of the metal material. It is related with the precoat metal material obtained by forming the upper layer film | membrane which does not contain.
本発明のプレコート金属材料用プライマー兼用水系塗装下地処理剤は、プライマーを介さずとも、プライマーを有する場合の皮膜と同程度の塗膜の加工密着性、耐食性、耐薬品性及び耐コインスクラッチ性を有する皮膜を形成することができ、換言すれば、塗膜物性を低下させることなく塗装工程を削減した１コート型プレコート金属材料の製造を行うことができる。すなわち、本発明の下地処理剤を用いる１コートでは、従来の２コートに比べ、環境への負荷を軽減しつつ、省資源化、低コスト化を達成できる。したがって、本発明は極めて大きな工業的価値を有する。
なお、本発明の水系塗装下地処理剤はノンクロム処理剤であり、本発明のプレコート金属材料上に形成された皮膜（下地皮膜及び上層皮膜）もクロムフリーである。
The primer-based water-based coating surface treatment agent for pre-coated metal materials of the present invention has the same coating adhesion, corrosion resistance, chemical resistance and coin scratch resistance as the film with a primer without using a primer. In other words, it is possible to manufacture a one-coat type pre-coated metal material with a reduced coating process without deteriorating the physical properties of the coating film. That is, in one coat using the ground treatment agent of the present invention, resource saving and cost reduction can be achieved while reducing the burden on the environment as compared with the conventional two coats. Therefore, the present invention has extremely great industrial value.
In addition, the aqueous | water-based coating ground-treating agent of this invention is a non-chromium treating agent, and the film | membrane (undercoat and upper film) formed on the precoat metal material of this invention is also chromium free.
以下に、本発明を詳細に説明する。本発明のプレコート金属材料用プライマー兼用塗装下地処理剤は、水性ポリウレタン樹脂（Ａ）、水性エポキシ樹脂（Ｂ）、グリシジル基を有する有機化合物（Ｃ）及びチタン元素もしくはジルコニウム元素を含有する架橋剤（Ｄ）を含有する必要がある。上記（Ａ）や（Ｂ）に言う「水性」は水溶性又は水分散性を意味する。
本発明の水系塗装下地処理剤の必須成分である水性ポリウレタン樹脂（Ａ）は主として密着性向上に寄与するが、下記に記載する如くそれだけに止まるものではない。密着性は金属材料表面との密着性及び上塗り塗膜との密着性の両方を含む。
水性ポリウレタン樹脂（Ａ）は、カルボキシル基を含有し、かつ、特定のウレタン基濃度、酸価及びガラス転移温度を有することが必要である。水性ポリウレタン樹脂（Ａ）
の骨格中に含まれるカルボキシル基は、その極性により金属表面に配向するため、皮膜と基材との密着性向上に効果的に作用する。さらに、架橋性官能基としての役割も持っており、皮膜形成時に水性エポキシ樹脂（Ｂ）、有機化合物（Ｃ）及び／又は架橋剤（Ｄ）と反応して結合を作るために、強靭で緻密な皮膜の形成に寄与する。その結果、密着性、耐食性、耐薬品性などが向上する。また、未反応のカルボキシル基が存在する場合、上層（上塗り塗膜）形成時に、上層に含まれる架橋性官能基との反応により強固な結合を作るため、塗膜の加工密着性の向上にも効果的に作用する。水性ポリウレタン樹脂（Ａ）中のカルボキシル基の量は下記に述べる酸価によって調節する。
The present invention is described in detail below. The primer and coating base treatment agent for precoat metal material of the present invention includes an aqueous polyurethane resin (A), an aqueous epoxy resin (B), an organic compound (C) having a glycidyl group, and a crosslinking agent containing a titanium element or a zirconium element ( D) must be contained. “Aqueous” in the above (A) and (B) means water-soluble or water-dispersible.
The aqueous polyurethane resin (A), which is an essential component of the water-based paint base treatment agent of the present invention, mainly contributes to the improvement of adhesion, but does not stop there as described below. The adhesion includes both adhesion to the metal material surface and adhesion to the top coat film.
The aqueous polyurethane resin (A) needs to contain a carboxyl group and have a specific urethane group concentration, acid value, and glass transition temperature. Aqueous polyurethane resin (A)
Since the carboxyl group contained in the skeleton is oriented on the metal surface depending on its polarity, it effectively acts to improve the adhesion between the film and the substrate. Furthermore, it also has a role as a crosslinkable functional group, and is strong and dense because it reacts with the aqueous epoxy resin (B), the organic compound (C) and / or the crosslinker (D) to form a bond at the time of film formation. Contributes to the formation of a strong film. As a result, adhesion, corrosion resistance, chemical resistance and the like are improved. In addition, when an unreacted carboxyl group is present, a strong bond is formed by reaction with the crosslinkable functional group contained in the upper layer when forming the upper layer (top coating film), which also improves the processing adhesion of the coating film. Acts effectively. The amount of the carboxyl group in the aqueous polyurethane resin (A) is adjusted by the acid value described below.
水性ポリウレタン樹脂（Ａ）のウレタン基濃度は、１．０〜４．０ｍｍｏｌ／ｇである必要があり、２．０〜３．０ｍｍｏｌ／ｇであることが好ましく、２．３〜２．８ｍｍｏｌ／ｇであることがより好ましい。ウレタン基は極性基であるため、金属基材との密着性向上に寄与する。また、ウレタン基同士の水素結合による分子間の相互作用が、皮膜に高い強靭性を付与することから、ウレタン基濃度は形成皮膜の物性に著しく影響する。水性ポリウレタン樹脂（Ａ）のウレタン基濃度が上記範囲内である場合、ウレタン分子の凝集力が好適となり、良好な加工密着性、耐食性、耐薬品性を併せ持った皮膜を形成できる。ウレタン基濃度が１．０ｍｍｏｌ／ｇ未満であると、皮膜に高い強靭性を付与できないため、十分な加工密着性、耐食性、耐薬品性が得られ難くなる。一方、ウレタン基濃度が４．０ ｍｍｏｌ／ｇを超えると高い皮膜硬度、抗張力は得られるものの、伸びや弾性が低下するため、加工密着性が著しく低下する傾向となる。
上記ウレタン基濃度の算出方法については後述する。
The urethane group concentration of the aqueous polyurethane resin (A) needs to be 1.0 to 4.0 mmol / g, preferably 2.0 to 3.0 mmol / g, and 2.3 to 2.8 mmol / g. More preferably, it is g. Since the urethane group is a polar group, it contributes to improving the adhesion to the metal substrate. Moreover, since the interaction between molecules due to hydrogen bonding between urethane groups imparts high toughness to the film, the concentration of urethane groups significantly affects the physical properties of the formed film. When the urethane group concentration of the aqueous polyurethane resin (A) is within the above range, the cohesive force of urethane molecules is suitable, and a film having good process adhesion, corrosion resistance, and chemical resistance can be formed. When the urethane group concentration is less than 1.0 mmol / g, high toughness cannot be imparted to the film, and it becomes difficult to obtain sufficient work adhesion, corrosion resistance, and chemical resistance. On the other hand, when the urethane group concentration exceeds 4.0 mmol / g, high film hardness and tensile strength can be obtained, but elongation and elasticity are lowered, so that work adhesion tends to be remarkably lowered.
The method for calculating the urethane group concentration will be described later.
水性ポリウレタン樹脂（Ａ）の酸価は、１０〜６０ｍｇＫＯＨ／ｇであることが必要であり、１５〜４０ｍｇＫＯＨ／ｇであることが好ましい。酸価が上記範囲である場合には、樹脂の水溶性もしくは水分散性が良好になるほか、加工密着性、耐食性及び耐薬品性に優れた皮膜を形成できる。酸価が１０ｍｇＫＯＨ／ｇ未満であると十分な下降密着性が得られにくくなり、また樹脂の水溶性、水分散性が低下するために薬剤の安定性が低下する傾向になる。酸価が６０ｍｇＫＯＨ／ｇを超えると皮膜の耐水性及び耐アルカリ性が低下する傾向になる。 The acid value of the aqueous polyurethane resin (A) needs to be 10 to 60 mgKOH / g, and preferably 15 to 40 mgKOH / g. When the acid value is within the above range, the water solubility or water dispersibility of the resin is improved, and a film excellent in processing adhesion, corrosion resistance and chemical resistance can be formed. If the acid value is less than 10 mg KOH / g, sufficient downward adhesion becomes difficult to obtain, and the water solubility and water dispersibility of the resin decrease, and the stability of the drug tends to decrease. When the acid value exceeds 60 mgKOH / g, the water resistance and alkali resistance of the film tend to decrease.
水性ポリウレタン樹脂（Ａ）のガラス転移温度（Ｔｇ）は３０〜１８０℃であることが好ましく、４０〜１６０℃であることがより好ましい。ガラス転移温度が上記範囲である場合には、得られる皮膜が強靭性を有し、耐食性及び耐薬品性がより向上する。 The glass transition temperature (Tg) of the aqueous polyurethane resin (A) is preferably 30 to 180 ° C, and more preferably 40 to 160 ° C. When the glass transition temperature is in the above range, the resulting film has toughness, and the corrosion resistance and chemical resistance are further improved.
水性ポリウレタン樹脂（Ａ）の皮膜物性としては、抗張力が３０〜８０ＭＰａであることが好ましく、４０〜７０ＭＰａであることがより好ましい。抗張力が上記範囲である場合には、加工密着性がより向上する。 As film properties of the aqueous polyurethane resin (A), the tensile strength is preferably 30 to 80 MPa, and more preferably 40 to 70 MPa. When the tensile strength is within the above range, the work adhesion is further improved.
水性ポリウレタン樹脂（Ａ）の分子量としては特に制限はないが、重量平均分子量として５，０００〜１，０００，０００であることが好ましく、１０，０００〜５００，０００であることがより好ましい。 Although there is no restriction | limiting in particular as molecular weight of water-based polyurethane resin (A), It is preferable that it is 5,000-1,000,000 as a weight average molecular weight, and it is more preferable that it is 10,000-500,000.
水性ポリウレタン樹脂（Ａ）は従来公知の製造方法により得ることができ、例えば、限定的に解釈されるべきではないが、いずれもポリウレタン樹脂の製造に通常用いられるポリオール、ポリイソシアネート、及び２個以上のヒドロキシル基もしくはアミノ基と１個以上のカルボキシル基を有する化合物を、従来公知の方法により重合させて得られたウレタンポリマーに、アンモニア、ポリアミンなどの塩基性化合物を加えて水中に分散させることによって得ることができる。製造されるポリウレタン樹脂は単独でもしくは２種以上を組み合わせて用いることができる。 The aqueous polyurethane resin (A) can be obtained by a conventionally known production method. For example, it should not be construed in a limited manner, but any of polyols, polyisocyanates, and two or more usually used in the production of polyurethane resins. By adding a basic compound such as ammonia or polyamine to a urethane polymer obtained by polymerizing a compound having a hydroxyl group or amino group and at least one carboxyl group by a conventionally known method and dispersing the compound in water. Can be obtained. The polyurethane resin produced can be used alone or in combination of two or more.
前記ポリオールとしては、 ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオールなどを単独でもしくは２種以上組み合わせてすることができる。 As said polyol, polyester polyol, polyether polyol, polycarbonate polyol etc. can be used individually or in combination of 2 or more types.
ポリエステルポリオールとしては、低分子量のポリオールと多価カルボン酸又はそのエステル、無水物、ハライドなどのエステル形成性誘導体との直接エステル化反応及び／又はエステル交換反応により得られるもの；ラクトン類もしくはその加水分解開環して得られるヒドロキシカルボン酸化合物の縮重合によって得られるものなどが挙げられる。 Polyester polyols are those obtained by direct esterification and / or transesterification of low molecular weight polyols with polycarboxylic acids or ester-forming derivatives such as esters, anhydrides and halides thereof; lactones or their hydrolysis Examples thereof include those obtained by condensation polymerization of hydroxycarboxylic acid compounds obtained by ring decomposition.
ポリエステルポリオールの製造に用いる低分子量のポリオールとしては、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、ネオペンチルグリコール、１，２−ブチレングリコール、１，３−ブチレングリコール、１，４−ブチレングリコール、ヘキサメチレングリコール、ビスフェノールＡ、水添ビスフェノールＡ、トリメチロールプロパン、１，２−プロパンジオール、１，３−プロパンジオール、２−メチル−１，３−プロパンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、１，４−ブタンジオール、ネオペンチルグリコール、３−メチル−２，４−ペンタンジオール、２，４−ペンタンジオール、１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、２−メチル−２，４−ペンタンジオール、２，４−ジエチル−１，，５−ペンタンジオール、１，６−ヘキサンジオール、１，７−ヘプタンジオール、３，５−ヘプタンジオール、１，８−オクタンジオール、２−メチル−１，８−オクタンジオール、１，９−ノナンジオール、１，１０−デカンジオールなどの脂肪族ジオール；トリメチロールエタン、トリメチロールプロパン、ヘキシトール類、ペンチトール類、グリセリン、ジグリセリン、ポリグリセリン、ペンタエリスリトール、ジペンタエリスリトール、テトラメチロールプロパンなどの３価以上の脂肪族又は脂環式アルコールなどが挙げられる。 Examples of the low molecular weight polyol used in the production of the polyester polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1, 3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3- Propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5 -Pentange , 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,, 5-pentanediol, 1,6-hexanediol, 1,7- Aliphatic diols such as heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol; trimethylolethane , Trimethylolpropane, hexitols, pentitols, glycerin, diglycerin, polyglycerin, pentaerythritol, dipentaerythritol, tetramethylolpropane and the like trivalent or higher aliphatic or alicyclic alcohols.
ポリエステルポリオールの製造に用いる多価カルボン酸としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、２−メチルコハク酸、２−メチルアジピン酸、３−メチルアジピン酸、３−メチルペンタン二酸、２−メチルオクタン二酸、３，８−ジメチルデカン二酸、３，７−ジメチルデカン二酸、ダイマー酸、水添ダイマー酸などの脂肪族ジカルボン酸類；シクロヘキサンジカルボン酸などの脂環式ジカルボン酸；フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸；トリメリット酸、トリメシン酸、ひまし油脂肪酸の３量体などのトリカルボン酸類；ピロメリット酸などのテトラカルボン酸以上のポリカルボン酸が挙げられる。多価カルボン酸のエステル形成性誘導体としては、これらの多価カルボン酸の酸無水物、ハライド（クロライド、ブロマイドなど）、低級脂肪族アルコールとのエステル（メチルエステル、エチルエステル、プロピルエステル、イソプロピルエステル、ブチルエステル、イソブチルエステル、アミルエステルなど）などが挙げられる。 Examples of the polyvalent carboxylic acid used for producing the polyester polyol include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 2-methylsuccinic acid. 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, dimer acid, hydrogenated Aliphatic dicarboxylic acids such as dimer acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid; trimellitic acid, trimesic acid, castor oil fatty acid 3 Tricarboxylic acids such as isomers; polymers higher than tetracarboxylic acids such as pyromellitic acid And a carboxylate. Examples of ester-forming derivatives of polycarboxylic acids include acid anhydrides, halides (chlorides, bromides, etc.) of these polycarboxylic acids, and esters with lower aliphatic alcohols (methyl esters, ethyl esters, propyl esters, isopropyl esters). Butyl ester, isobutyl ester, amyl ester, etc.).
ポリエステルポリオールの製造に用いるラクトン類としては、γ−カプロラクトン、δ−カプロラクトン、ε−カプロラクトン、γ−バレロラクトン、δ−バレロラクトンなどが挙げられる。 Examples of the lactones used for producing the polyester polyol include γ-caprolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, and δ-valerolactone.
前記ポリエーテルポリオールとしては、例えばエチレングリコール、ジエチレングリコ−ル、トリエチレングリコールなどのエチレンオキサイド付加物、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコールなどのプロピレンオキサイド付加物、上記のポリオールのエチレンオキサイド及び／又はプロピレンオキサイド付加物、ポリテトラメチレングリコールなどが挙げられる。 Examples of the polyether polyol include ethylene oxide adducts such as ethylene glycol, diethylene glycol and triethylene glycol, propylene oxide adducts such as propylene glycol, dipropylene glycol and tripropylene glycol, ethylene oxides of the above polyols and / or Or a propylene oxide adduct, polytetramethylene glycol, etc. are mentioned.
前記ポリカーボネートポリオールとしては、例えば１，４−ブタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、シクロヘキサンジメタノールなどのグリコールと、シフェニルカルボネート、ホスゲンなどとを反応させることにより得られるものが挙げられる。 Examples of the polycarbonate polyol include those obtained by reacting glycols such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanedimethanol with siphenyl carbonate, phosgene, and the like. .
前記ポリイソシアネートとしては、例えばテトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネートエステル、水添キシリレンジイソシアネート、１，４−シクロヘキシレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、２，４’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、３，３’−ジメトキシ−４，４’−ビフェニレンジイソシアネート、１，５−ナフタレンジイソシアネート、１，５−テトラヒドロナフタレンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、フェニレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネートなどが挙げられる。これらの中で、より好ましいものとして、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネートエステル、水添キシリレンジイソシアネート、１，４−シクロヘキシレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、２，４’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネートなどが挙げられる。 Examples of the polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 2,4′-dicyclohexylmethane diisocyanate. , Isophorone diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, phenylene diisocyanate, Siri diisocyanate, tetramethyl xylylene diisocyanate. Among these, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'- Examples include dicyclohexylmethane diisocyanate and isophorone diisocyanate.
前記２個以上のヒドロキシル基もしくはアミノ基と１個以上のカルボキシル基を有する化合物としては、例えば２，２−ジメチロールプロピオン酸、２，２−ジメチロールブタン酸、２，２ジメチロールペンタン酸、２，２−ジメチロールプロピオン酸、２，２−ジメチロール酪酸などのジヒドロキシカルボン酸や、リジン、アルギニンなどのジアミノカルボン酸が挙げられる。また、上記ジヒドロキシカルボン酸と多価カルボン酸とを反応させて得られるカルボキシル基含有ポリエステルポリオールも使用することができる。 Examples of the compound having two or more hydroxyl groups or amino groups and one or more carboxyl groups include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2 dimethylolpentanoic acid, Examples include dihydroxycarboxylic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutyric acid, and diaminocarboxylic acids such as lysine and arginine. Moreover, the carboxyl group-containing polyester polyol obtained by making the said dihydroxycarboxylic acid and polyhydric carboxylic acid react can also be used.
前記ウレタン基濃度は、ポリウレタン樹脂を合成する際の原料成分の仕込み量から算出する樹脂固形分中のイソシアナト基の量で示すことができる。以下に計算式を示す。
［（ａ２の質量）／〔（ａ１の質量）＋（ａ２の質量）＋（ａ３の質量）〕］／（ａ２の分子量）×ｎ×１０３ ＝ ウレタン基濃度（ｍｍｏｌ／ｇ）
（式中、ａ１はポリオール、ａ２はポリイソシアネート、ａ３は２個以上のヒドロキシル基もしくはアミノ基と１個以上のカルボキシル基を有する化合物を表し、ｎは１分子のａ２に含まれるイソシアナト基の数を表す）。
The urethane group concentration can be represented by the amount of isocyanato groups in the resin solid content calculated from the charged amount of raw material components when the polyurethane resin is synthesized. The calculation formula is shown below.
[(Mass of a2) / [(mass of a1) + (mass of a2) + (mass of a3)]] / (molecular weight of a2) × n × 10 3 = urethane group concentration (mmol / g)
(In the formula, a1 is a polyol, a2 is a polyisocyanate, a3 is a compound having two or more hydroxyl groups or amino groups and one or more carboxyl groups, and n is the number of isocyanate groups contained in one molecule of a2. Represents).
本発明の水系塗装下地処理剤の必須成分である水性エポキシ樹脂（Ｂ）は主として耐コインスクラッチ性の向上に寄与するが、それだけに止まるものではない。
水性エポキシ樹脂（Ｂ）の重量平均分子量は、１，０００〜３０，０００である必要があり、１，５００〜２０，０００であることが好ましく、１，５００〜１０，０００であることがより好ましい。重量平均分子量が上記範囲を満足する場合、耐コインスクラッチ性に極めて優れた皮膜を形成できる。重量平均分子量が１，０００未満であると強靭な皮膜を形成できず、耐薬品性及び耐コインスクラッチ性が低下する傾向になる。一方、重量平均分子量が３０，０００を超えると、当該エポキシ樹脂を安定に水溶化もしくは水分散化することが困難になるため、多量の乳化剤及び親水基が必要となり、耐薬品性が低下する傾向になる。
尚、水性エポキシ樹脂（Ｂ）の場合に限らず、本発明における重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）によって測定される値（ポリスチレン換算）である。
The aqueous epoxy resin (B), which is an essential component of the water-based paint base treatment agent of the present invention, mainly contributes to the improvement of the coin scratch resistance, but does not stop there.
The weight average molecular weight of the water-based epoxy resin (B) needs to be 1,000 to 30,000, preferably 1,500 to 20,000, and more preferably 1,500 to 10,000. preferable. When the weight average molecular weight satisfies the above range, a film having excellent coin scratch resistance can be formed. When the weight average molecular weight is less than 1,000, a tough film cannot be formed, and the chemical resistance and the coin scratch resistance tend to be lowered. On the other hand, if the weight average molecular weight exceeds 30,000, it becomes difficult to stably dissolve or disperse the epoxy resin in water, so a large amount of emulsifiers and hydrophilic groups are required, and chemical resistance tends to decrease. become.
In addition, not only in the case of water-based epoxy resin (B), the weight average molecular weight in this invention is a value (polystyrene conversion) measured by GPC (gel permeation chromatography).
本発明で使用する水性エポキシ樹脂（Ｂ）は従来公知の製造方法により得ることができ、例えば、限定的に解釈されるべきではないが、いずれも水性エポキシ樹脂の製造に通常用いられるビスフェノールＡ、ビスフェノールＦ、ノボラック樹脂などと、エピクロルヒドリンなどのエピハロヒドリン類又はグリシジル基を２個以上有するエポキシ化合物との付加反応及び縮合反応の繰返し又は付加反応の繰返しにより得られるエポキシ樹脂を水分散化することにより得ることができる。上記エポキシ化合物としては、例えば後述の有機化合物（Ｃ）に包含されるポリグリシジルエーテル化合物と同様のものを用いることができる。本発明では、特に、水性エポキシ樹脂がビスフェノールＡ由来の構造を有する場合、耐薬品性に優れた皮膜が形成できるため好ましい。 The aqueous epoxy resin (B) used in the present invention can be obtained by a conventionally known production method. For example, it should not be construed in a limited manner, but both are bisphenol A commonly used in the production of aqueous epoxy resins, Obtained by water-dispersing an epoxy resin obtained by repeating addition reaction and condensation reaction of bisphenol F, novolak resin, etc. with an epihalohydrin such as epichlorohydrin or an epoxy compound having two or more glycidyl groups, or by repeating the addition reaction. be able to. As said epoxy compound, the thing similar to the polyglycidyl ether compound included by the below-mentioned organic compound (C) can be used, for example. In the present invention, in particular, when the aqueous epoxy resin has a structure derived from bisphenol A, it is preferable because a film excellent in chemical resistance can be formed.
水性エポキシ樹脂（Ｂ）は、樹脂中のエポキシ基又は水酸基に変性剤を反応させて得られるものであってもよく、例えば、不飽和脂肪酸を反応させたエポキシエステル樹脂、（メタ）アクリル酸又はそのエステルを反応させたアクリル変性エポキシ樹脂、イソシアネート化合物を反応させたウレタン変性エポキシ樹脂、シランカップリング剤を反応させたシラン変性エポキシ樹脂、リン酸類もしくはそのエステルを反応させたリン酸変性エポキシ樹脂などが挙げられる。
上記の如き変性エポキシ樹脂を包含する水性エポキシ樹脂（Ｂ）は各単独で又は２種以上組み合わせて用いることができる。
The aqueous epoxy resin (B) may be obtained by reacting an epoxy group or a hydroxyl group in the resin with a modifier, for example, an epoxy ester resin obtained by reacting an unsaturated fatty acid, (meth) acrylic acid or Acrylic modified epoxy resin reacted with ester, urethane modified epoxy resin reacted with isocyanate compound, silane modified epoxy resin reacted with silane coupling agent, phosphoric acid modified epoxy resin reacted with phosphoric acid or its ester, etc. Is mentioned.
The aqueous epoxy resin (B) including the modified epoxy resin as described above can be used alone or in combination of two or more.
水性ポリウレタン樹脂（Ａ）及び水性エポキシ樹脂（Ｂ）は、本発明の処理剤の安定性の観点から、水溶性又は水分散性であることを要する。水溶性又は水分散性の付与は、樹脂の分子構造中にカルボキシル基、水酸基などの親水基を導入したり、界面活性剤を用いて水に可溶化又は強制分散させることにより達成できる。しかしながら、界面活性剤を使用すると、金属材料への密着性や耐水性に悪影響を及ぼす可能性があるため、界面活性剤を使用しないか、その使用量を極力抑えることが好ましい。 The aqueous polyurethane resin (A) and the aqueous epoxy resin (B) are required to be water-soluble or water-dispersible from the viewpoint of the stability of the treatment agent of the present invention. Providing water solubility or water dispersibility can be achieved by introducing hydrophilic groups such as carboxyl groups and hydroxyl groups into the molecular structure of the resin, or by solubilizing or forcibly dispersing in water using a surfactant. However, since the use of a surfactant may adversely affect the adhesion to a metal material and water resistance, it is preferable not to use a surfactant or to suppress its use amount as much as possible.
水性ポリウレタン樹脂（Ａ）と水性エポキシ樹脂（Ｂ）の配合割合については、樹脂（Ａ）と樹脂（Ｂ）との固形分質量比（Ｂ）／（Ａ）が１／５０〜１０／１であることが必要であり、１／１０〜５／１であることが好ましく、１／５〜５／１であることがより好ましい。前記固形分質量比（Ｂ）／（Ａ）が１／５０未満であるとエポキシ樹脂の添加効果が発現されず、十分な耐コインスクラッチ性が得られ難くなり、逆に１０を超えるとポリウレタン樹脂の添加効果が発現されず、十分な塗膜の加工密着性が得られ難くなる。
また、水性ポリウレタン樹脂（Ａ）と水性エポキシ樹脂（Ｂ）の固形分の合計〔（Ａ）＋（Ｂ）〕が本発明の処理剤の全固形分に対して４５〜９５質量％であることが必要であり、６０〜９０質量％であることが好ましい。前記固形分の合計〔（Ａ）＋（Ｂ）〕が全固形分に対して４５質量％未満であると、樹脂（Ａ）及び樹脂（Ｂ）の特性が発現されず、塗膜の加工密着性、耐薬品性及び耐コインスクラッチ性が低下する傾向となり、逆に９５％を超えると有機化合物（Ｃ）及び架橋剤（Ｄ）の含有率が小さくなるため、本発明の目的に適う塗膜の加工密着性及び耐食性が得られ難くなる。
About the compounding ratio of water-based polyurethane resin (A) and water-based epoxy resin (B), solid content mass ratio (B) / (A) of resin (A) and resin (B) is 1 / 50-10 / 1. It is necessary to be 1/10 to 5/1, more preferably 1/5 to 5/1. When the solid content mass ratio (B) / (A) is less than 1/50, the addition effect of the epoxy resin is not expressed, and it becomes difficult to obtain sufficient coin scratch resistance. Thus, it is difficult to obtain sufficient processing adhesion of the coating film.
Moreover, the sum total [(A) + (B)] of solid content of water-based polyurethane resin (A) and water-based epoxy resin (B) is 45-95 mass% with respect to the total solid of the processing agent of this invention. Is necessary, and it is preferable that it is 60-90 mass%. When the total solid content [(A) + (B)] is less than 45% by mass with respect to the total solid content, the characteristics of the resin (A) and the resin (B) are not expressed, and the processing adhesion of the coating film , Chemical resistance and coin scratch resistance tend to decrease. On the contrary, if it exceeds 95%, the content of the organic compound (C) and the crosslinking agent (D) decreases, so that the coating film meets the purpose of the present invention. It becomes difficult to obtain the processing adhesion and corrosion resistance.
本発明の水系塗装下地処理剤の必須成分であるグリシジル基を有する有機化合物（Ｃ）は主として密着性の向上に寄与するが、後述する如く、それだけに止まるものではない。
有機化合物（Ｃ）としては、重量平均分子量が８００以下のエポキシ樹脂、ポリグリシジルエーテル化合物、グリシジルエステル化合物、グリシジル基含有シラン化合物などを用いることができる。これらは各単独でもしくは２種以上組み合わせて用いることができる。
有機化合物（Ｃ）である重量平均分子量が８００以下のエポキシ樹脂としては、分子量を異にする以外は、水性エポキシ樹脂（Ｂ）と同様のものを用いることができる。有機化合物（Ｃ）であるエポキシ樹脂の重量平均分子量を８００以下とするのはグリシジル基の反応容易性を確保するためであり、同じ観点から、該重量平均分子量は２００〜８００であるのが好ましく、２００〜５００であるのがより好ましい。
ポリグリシジルエーテル化合物としては、特に限定するものではないが、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、トリメチルプロパンポリグリシジルエーテル、ネオペンチルグリコールグリシジルエーテル、エチレングリコールグリシジルエーテル、ポリエチレングリコールグリシジルエーテル、プロピレングリコールグリシジルエーテル、ポリプロピレングリコールグリシジルエーテル、ビスフェノールＡグリシジルエーテルなどが挙げられる。
The organic compound (C) having a glycidyl group, which is an essential component of the water-based paint base treatment agent of the present invention, mainly contributes to the improvement of adhesion, but does not stop there as described later.
As the organic compound (C), an epoxy resin having a weight average molecular weight of 800 or less, a polyglycidyl ether compound, a glycidyl ester compound, a glycidyl group-containing silane compound, and the like can be used. These can be used alone or in combination of two or more.
As an epoxy resin having a weight average molecular weight of 800 or less that is an organic compound (C), the same epoxy resin as the aqueous epoxy resin (B) can be used except that the molecular weight is different. The reason why the weight average molecular weight of the epoxy resin that is the organic compound (C) is 800 or less is to ensure the ease of reaction of the glycidyl group. From the same viewpoint, the weight average molecular weight is preferably 200 to 800. 200 to 500 is more preferable.
The polyglycidyl ether compound is not particularly limited, but sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylpropane polyglycidyl ether, neodymium Examples include pentyl glycol glycidyl ether, ethylene glycol glycidyl ether, polyethylene glycol glycidyl ether, propylene glycol glycidyl ether, polypropylene glycol glycidyl ether, and bisphenol A glycidyl ether.
グリシジルエステル化合物としては、特に限定するものではないが、アジピン酸グリシジルエステル、フタル酸グリシジルエステル、テレフタル酸グリシジルエステルなどが挙げられる。
グリシジル基含有シラン化合物としては、特に限定するものではないが、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルメチルジエトキシシランなどのグリシジル基含有シラン化合物などが挙げられる。
The glycidyl ester compound is not particularly limited, and examples thereof include adipic acid glycidyl ester, phthalic acid glycidyl ester, and terephthalic acid glycidyl ester.
The glycidyl group-containing silane compound is not particularly limited, but glycidyl such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Examples thereof include group-containing silane compounds.
有機化合物（Ｃ）の配合割合については、樹脂（Ａ）と樹脂（Ｂ）の固形分の合計〔（Ａ）＋（Ｂ）〕と有機化合物（Ｃ）の固形分質量比（Ｃ）／〔（Ａ）＋（Ｂ）〕が１／３００〜１／１であることが必要であり、１／２００〜１／２であることが好ましく、１／１００〜１／３であることがより好ましい。（Ｃ）／〔（Ａ）＋（Ｂ）〕が１／３００未満の場合は、有機化合物（Ｃ）の効果が発現されず、十分な塗膜の加工密着性が得られにくくなり、１を超える場合は、形成される皮膜の強靭性が低下し、塗膜の加工密着性が低下する傾向となる。 About the compounding ratio of the organic compound (C), the total solid content of the resin (A) and the resin (B) [(A) + (B)] and the solid content mass ratio of the organic compound (C) (C) / [ (A) + (B)] is required to be 1/300 to 1/1, preferably 1/200 to 1/2, and more preferably 1/100 to 1/3. . When (C) / [(A) + (B)] is less than 1/300, the effect of the organic compound (C) is not expressed, and it is difficult to obtain sufficient processing adhesion of the coating film. When exceeding, the toughness of the film formed is lowered, and the processing adhesion of the coating film tends to be lowered.
本発明の水系塗装下地処理剤の必須成分であるチタン元素もしくはジルコニウム元素を含有する架橋剤（Ｄ）は主として耐薬品性及び耐食性の向上に寄与する。架橋剤（Ｄ）は、チタン化合物及びジルコニウム化合物よりなる群から選ばれる少なくとも１つであることが好ましい。
チタン化合物としては、特に限定するものではないが、チタンアルコキシド、チタン原子を含むキレート錯体などの有機チタン化合物が好ましく、具体的には、テトライソプロピルチタネート、テトラｎ−ブチルチタネート、テトラオクチルチタネート、チタンアセチルアセトネート、チタンオクチレングリコレート、チタンラクテート、チタンラクテートエチルエステル、チタントリエタノールアミネートなどが挙げられる。
ジルコニウム化合物としては、特に限定するものではないが、ジルコニウムの炭酸塩、塩化物、硝酸塩、硫酸塩などの無機酸塩；ジルコニウム酸化物；及びジルコニウムの有機酸塩、ジルコニウムアルコキシド、ジルコニウム原子を含むキレート錯体などの有機ジルコニウム化合物を使用できる。具体的には、炭酸ジルコニウムアンモニウム、オキシ塩化ジルコニウム、硝酸ジルコニウム、硫酸ジルコニウム、乳酸ジルコニウム、テトラプロポキシジルコニウム、テトラブトキシジルコニウム、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシアセチルアセトネートなどが挙げられる。
The crosslinking agent (D) containing a titanium element or a zirconium element, which is an essential component of the water-based paint base treatment agent of the present invention, mainly contributes to improvement of chemical resistance and corrosion resistance. The cross-linking agent (D) is preferably at least one selected from the group consisting of a titanium compound and a zirconium compound.
Although it does not specifically limit as a titanium compound, Organic titanium compounds, such as a titanium alkoxide and a chelate complex containing a titanium atom, are preferable, and specifically, tetraisopropyl titanate, tetra n-butyl titanate, tetraoctyl titanate, titanium Examples thereof include acetylacetonate, titanium octylene glycolate, titanium lactate, titanium lactate ethyl ester, and titanium triethanolamate.
Zirconium compounds include, but are not limited to, inorganic acid salts such as zirconium carbonates, chlorides, nitrates and sulfates; zirconium oxides; and organic acid salts of zirconium, zirconium alkoxides and chelates containing zirconium atoms. Organic zirconium compounds such as complexes can be used. Specific examples include ammonium zirconium carbonate, zirconium oxychloride, zirconium nitrate, zirconium sulfate, zirconium lactate, tetrapropoxyzirconium, tetrabutoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate and the like.
架橋剤（Ｄ）の配合割合については、前記樹脂（Ａ）と樹脂（Ｂ）の固形分の合計〔（Ａ）＋（Ｂ）〕と架橋剤（Ｄ）の固形分質量比（Ｄ）／〔（Ａ）＋（Ｂ）〕が１／３００〜１／１であることが必要であり、１／２００〜１／２であることが好ましく、１／１００〜１／３であることがより好ましい。（Ｄ）／〔（Ａ）＋（Ｂ）〕が１／３００未満の場合は、十分な耐食性、耐薬品性が得られ難くなり、１を超える場合は、形成される皮膜が硬く脆くなり、塗膜の加工密着性が低下する傾向になる。 As for the blending ratio of the crosslinking agent (D), the total solid content of the resin (A) and the resin (B) [(A) + (B)] and the solid content mass ratio of the crosslinking agent (D) (D) / [(A) + (B)] is required to be 1/300 to 1/1, preferably 1/200 to 1/2, and more preferably 1/100 to 1/3. preferable. When (D) / [(A) + (B)] is less than 1/300, it is difficult to obtain sufficient corrosion resistance and chemical resistance. When it exceeds 1, the formed film becomes hard and brittle. The processing adhesion of the coating film tends to decrease.
本発明の水系塗装下地処理剤は、さらに特定の微粒子（Ｅ）を含有することが好ましい。微粒子（Ｅ）は耐食性及び耐コインスクラッチ性の向上に寄与する。微粒子（Ｅ）はコロイダルシリカ、気相シリカ、アルミナゾル、リン酸系防錆顔料、モリブデン酸系防錆顔料及びバナジウム系防錆顔料よりなる群から選ばれる少なくとも１種である。
より具体的には、コロイダルシリカとしては日産化学工業（株）製のスノーテックスＯ、スノーテックスＮ、スノーテックスＣ、スノーテックスＵＰ、スノーテックスＰＳ−Ｍ、スノーテックスＸＬ、スノーテックスＺＬなど；気相シリカとしては日本アエロジル（株）製のアエロジル２００など；アルミナゾルとしては日産化学工業（株）製のアルミナゾル−２００、アルミナゾル−５２０、など；リン酸系防錆顔料としてはリン酸亜鉛、リン酸アルミニウム亜鉛、リン酸アルミニウム、リン酸カルシウム亜鉛、リン酸カルシウム、ピロリン酸アルミニウム、ピロリン酸カルシウム、リン酸鉄、トリポリリン酸２水素アルミニウム、メタリン酸アルミニウム、メタリン酸カルシウムなど；モリブデン酸系防錆顔料としてはモリブデン酸カルシウム、モリブデン酸アルミニウム、モリブデン酸バリウムなど；及びバナジウム系防錆顔料としては酸化バナジウムなどが挙げられる。これらは各単独で又は２種以上組み合わせてを使用することができる。
It is preferable that the water-based coating surface treatment agent of the present invention further contains specific fine particles (E). The fine particles (E) contribute to the improvement of corrosion resistance and coin scratch resistance. The fine particles (E) are at least one selected from the group consisting of colloidal silica, vapor phase silica, alumina sol, phosphoric acid rust preventive pigment, molybdate rust preventive pigment and vanadium rust preventive pigment.
More specifically, examples of colloidal silica include Snowtex O, Snowtex N, Snowtex C, Snowtex UP, Snowtex PS-M, Snowtex XL, Snowtex ZL, etc., manufactured by Nissan Chemical Industries, Ltd .; As phase silica, Aerosil 200 manufactured by Nippon Aerosil Co., Ltd .; As alumina sol, Alumina Sol-200, Alumina Sol-520, manufactured by Nissan Chemical Industries, Ltd .; As phosphate-based anticorrosive pigments, zinc phosphate, phosphoric acid, etc. Aluminum zinc, aluminum phosphate, calcium zinc phosphate, calcium phosphate, aluminum pyrophosphate, calcium pyrophosphate, iron phosphate, aluminum dihydrogen triphosphate, aluminum metaphosphate, calcium metaphosphate, etc .; Like vanadium oxide as and vanadium anticorrosive pigments; um, aluminum molybdate, barium molybdate. These can be used alone or in combination of two or more.
微粒子（Ｅ）の平均粒径は、０．０１〜５μｍであることが好ましく、０．０１〜３μｍであることがより好ましく、０．０１〜２μｍであることがより一層好ましい。平均粒径が０．０１μｍより小さい場合には、粒子同士の凝集力が強すぎるため水中に安定に分散させることが困難になる。一方、平均粒径が５μｍより大きい場合には、粒子が皮膜表面より突き出した状態となり皮膜の連続性が阻害されるため、塗膜の加工密着性及び耐食性が低下する傾向となる。 The average particle diameter of the fine particles (E) is preferably 0.01 to 5 μm, more preferably 0.01 to 3 μm, and still more preferably 0.01 to 2 μm. When the average particle size is smaller than 0.01 μm, the cohesive force between the particles is too strong, making it difficult to stably disperse in water. On the other hand, when the average particle size is larger than 5 μm, the particles protrude from the surface of the film, and the continuity of the film is hindered, so that the work adhesion and corrosion resistance of the coating film tend to decrease.
微粒子（Ｅ）の配合割合については、樹脂（Ａ）と樹脂（Ｂ）の固形分の合計〔（Ａ）＋（Ｂ）〕と前記微粒子（Ｅ）の固形分質量比（Ｅ）／〔（Ａ）＋（Ｂ）〕が１／１００〜１／１であることが好ましく、１／５０〜３／４であることがより好ましく、１／２０〜１／２であることがより一層好ましい。前記固形分質量比（Ｅ）／〔（Ａ）＋（Ｂ）〕が１／１００未満である場合には、微粒子（Ｅ）による耐食性及び耐コインスクラッチ性の向上効果が発現し難くなる。一方、（Ｅ）／〔（Ａ）＋（Ｂ）〕が１を超える場合には、微粒子（Ｅ）よる耐食性改善効果が飽和するだけでなく、皮膜の連続性が阻害され皮膜自体が脆くなり、塗膜の加工密着性が低下する傾向になる。 Regarding the blending ratio of the fine particles (E), the total solid content of the resin (A) and the resin (B) [(A) + (B)] and the solid content mass ratio (E) / [(( A) + (B)] is preferably 1/100 to 1/1, more preferably 1/50 to 3/4, and even more preferably 1/20 to 1/2. When the solid content mass ratio (E) / [(A) + (B)] is less than 1/100, the effect of improving the corrosion resistance and the coin scratch resistance by the fine particles (E) is hardly exhibited. On the other hand, when (E) / [(A) + (B)] exceeds 1, not only the corrosion resistance improving effect by the fine particles (E) is saturated, but also the continuity of the film is inhibited and the film itself becomes brittle. The processing adhesion of the coating film tends to decrease.
本発明の水系塗装下地処理剤中には、さらに任意成分として、より均一な塗膜を形成するために、造膜性の向上や皮膜の乾燥性を改善する有機溶剤、濡れ性を向上させる界面活性剤、皮膜量調整のための増粘剤、発泡を抑える消泡剤、溶接性向上のための導電性物質、意匠性向上のため着色顔料などを、処理剤の液安定性や本発明の効果を損なわない範囲で配合することができる。特に限定するものではないが、上記有機溶剤としては、アルコール系、ケトン系、エステル系、エーテル系などの親水性溶剤；界面活性剤としてはアルキルアリルエーテル系、アルキルエーテル系、アルキルエステル系、アルキルアミン系などのノニオン系界面活性剤、及び脂肪酸塩、アルキル硫酸エステル塩、脂肪族アミンの硫酸塩、二塩基性脂肪酸エステルのスルホン酸塩などのアニオン系界面活性剤；導電性物質としては導電性金属微粉末、炭素微粉末など；着色顔料としては、カーボンブラック、酸化チタンなどの無機顔料及びフタロシアニンなどの有機顔料が挙げられる。 In the aqueous coating surface treatment agent of the present invention, as an optional component, in order to form a more uniform coating film, an organic solvent for improving the film forming property and the drying property of the film, an interface for improving the wettability Activators, thickeners for adjusting the coating amount, antifoaming agents for suppressing foaming, conductive materials for improving weldability, colored pigments for improving design properties, liquid stability of treatment agents and the present invention It can mix | blend in the range which does not impair an effect. Although not particularly limited, the organic solvent includes hydrophilic solvents such as alcohols, ketones, esters, and ethers; surfactants include alkylallyl ethers, alkyl ethers, alkyl esters, and alkyls. Nonionic surfactants such as amines, and anionic surfactants such as fatty acid salts, alkyl sulfate esters, aliphatic amine sulfates, dibasic fatty acid sulfonates, etc .; Metal fine powder, carbon fine powder and the like; Examples of the coloring pigment include inorganic pigments such as carbon black and titanium oxide, and organic pigments such as phthalocyanine.
本発明の水系塗装下地処理剤のｐＨについては、本発明の効果を達成し得る限り特に制限はないが、ｐＨ５〜１１の範囲にあるのが好適である。
本発明の水系塗装下地処理剤の固形分濃度については、本発明の効果が達成し得る限り特に制限はないが、１〜４０質量％の範囲であることが好ましい。固形分濃度が１％未満の場合は目標とする皮膜量を得ることが難しくなり、一方、４０％を超える場合は当該プレコート金属材料用プライマー兼用塗装下地処理剤の安定性が保てなくなる傾向となる。
Although there is no restriction | limiting in particular as long as the effect of this invention can be achieved about the pH of the aqueous | water-based paint ground processing agent of this invention, It is suitable to exist in the range of pH5-11.
Although there is no restriction | limiting in particular as long as the solid content concentration of the water-system coating ground-treatment agent of this invention can achieve the effect of this invention, It is preferable that it is the range of 1-40 mass%. When the solid content concentration is less than 1%, it is difficult to obtain the target film amount, while when it exceeds 40%, the stability of the precoat metal material primer / coating undercoat treatment tends to be not maintained. Become.
本発明の水系塗装下地処理剤は、水性ポリウレタン樹脂（Ａ）、水性エポキシ樹脂（Ｂ）、有機化合物（Ｃ）及び架橋剤（Ｄ）、並びに、必要に応じてかつ好ましくは微粒子（Ｄ）、及び必要に応じてさらにその他の任意成分を、分散媒である水に添加し、撹拌することによって製造することができる。各成分の添加順序に特に制限はない。 The water-based paint base treatment agent of the present invention includes an aqueous polyurethane resin (A), an aqueous epoxy resin (B), an organic compound (C) and a crosslinking agent (D), and if necessary, preferably fine particles (D), In addition, if necessary, other optional components can be added to the dispersion medium water and stirred. There is no restriction | limiting in particular in the addition order of each component.
次に、本発明の水系塗装下地処理剤からの乾燥皮膜を表面に有する金属材料について述べる。
被処理物である金属材料としては、冷延鋼板、熱延鋼板、溶融亜鉛めっき鋼板、アルミニウム含有亜鉛めっき鋼板、電気亜鉛めっき鋼板、合金化亜鉛めっき鋼板、亜鉛ニッケルめっき鋼板、亜鉛コバルトめっき鋼板、蒸着亜鉛めっき鋼板、ニッケルめっき鋼板、スズめっき鋼板、ステンレス鋼板等の炭素鋼板、合金鋼板及びめっき鋼板；アルミニウム板、銅板、チタン板、マグネシウム板等の鋼板以外の金属板などの一般に公知の金属材料を用いることができる。特に好適な金属材料は溶融亜鉛めっき鋼板、アルミニウム含有亜鉛めっき鋼板、電気亜鉛めっき鋼板、合金化亜鉛めっき鋼板、亜鉛ニッケルめっき鋼板、亜鉛コバルトめっき鋼板、蒸着亜鉛めっき鋼板等の亜鉛系めっき鋼板である。
Next, a metal material having a dry film on the surface from the aqueous coating surface treatment agent of the present invention will be described.
Examples of metal materials to be processed include cold-rolled steel sheets, hot-rolled steel sheets, hot-dip galvanized steel sheets, aluminum-containing galvanized steel sheets, electrogalvanized steel sheets, galvannealed steel sheets, zinc-nickel-plated steel sheets, zinc-cobalt-plated steel sheets, Carbon steel plates such as vapor-deposited galvanized steel plates, nickel-plated steel plates, tin-plated steel plates, stainless steel plates, alloy steel plates and plated steel plates; generally known metal materials such as metal plates other than steel plates such as aluminum plates, copper plates, titanium plates and magnesium plates Can be used. Particularly suitable metal materials are galvanized steel sheets such as hot dip galvanized steel sheets, aluminum-containing galvanized steel sheets, electrogalvanized steel sheets, alloyed galvanized steel sheets, zinc nickel plated steel sheets, zinc cobalt plated steel sheets, and evaporated galvanized steel sheets. .
本発明の水系塗装下地処理剤による処理に先立って、必須ではないが通常、被処理金属材料に付着した油分、汚れを取り除くために、脱脂剤による洗浄、湯洗、酸洗、アルカリ洗、溶剤洗浄などを適宜組み合わせて行なう。また、通常不要であるが、本発明の処理剤による処理を行なう前に、金属材料の耐食性及び下地処理皮膜と金属材料との密着性をさらに向上させる目的で、表面調整を施すことができる。表面調整の方法については特に限定するものではないが、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｍｎ、Ｚｒ、Ｔｉ、Ｖ、などの金属を付着させる化成処理、リン酸塩化成処理などが挙げられる。金属材料表面の洗浄においては洗浄剤が金属材料表面に残留しないように洗浄後水洗することが好ましい。 Prior to the treatment with the water-based coating surface treatment agent of the present invention, it is not essential, but usually, in order to remove oil and dirt adhering to the metal material to be treated, washing with a degreasing agent, hot water washing, pickling, alkali washing, solvent Washing is performed in combination as appropriate. Moreover, although it is usually unnecessary, surface treatment can be performed for the purpose of further improving the corrosion resistance of the metal material and the adhesion between the base treatment film and the metal material before the treatment with the treatment agent of the present invention. The surface adjustment method is not particularly limited, and examples thereof include a chemical conversion treatment for attaching a metal such as Fe, Co, Ni, Cu, Zn, Mn, Zr, Ti, V, and a phosphate chemical conversion treatment. . In cleaning the surface of the metal material, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the surface of the metal material.
本発明の処理剤は金属材料へ塗布後乾燥させる。
金属材料への本発明の処理剤の塗布方法に関しては、特に制限はなく、例えば、ロールコーター法、浸漬法、スプレー法、バーコート法などが挙げられる。また、塗布時の処理剤温度については、特に制限はないが、１０〜６０℃が好ましく、１５〜４０℃がより好ましい。また、乾燥方法としては、特に制限はなく、風乾；エアーブローによる乾燥；熱風炉、誘導加熱炉、電気炉などを用いた加熱乾燥が挙げられるが、水性ポリウレタン樹脂（Ａ）、水性エポキシ樹脂（Ｂ）、有機化合物（Ｃ）及び架橋剤（Ｄ）の硬化及び架橋の促進による被覆効果を高めるためには、熱風炉、誘導加熱炉、電気炉などによる加熱乾燥が好ましい。また、乾燥時の到達金属材料温度については、特に制限はないが、５０〜２５０℃が好ましく、７０〜２２０℃がより好ましい。
The treatment agent of the present invention is applied to a metal material and then dried.
There is no restriction | limiting in particular about the coating method of the processing agent of this invention to a metal material, For example, a roll coater method, a dipping method, a spray method, a bar coating method etc. are mentioned. Moreover, there is no restriction | limiting in particular about the processing agent temperature at the time of application | coating, However, 10-60 degreeC is preferable and 15-40 degreeC is more preferable. Moreover, there is no restriction | limiting in particular as a drying method, Air drying; Drying by air blow; Heat drying using a hot air furnace, an induction heating furnace, an electric furnace, etc. are mentioned, However, Aqueous polyurethane resin (A), Aqueous epoxy resin ( B) In order to enhance the coating effect by promoting the curing and crosslinking of the organic compound (C) and the crosslinking agent (D), heat drying with a hot air furnace, an induction heating furnace, an electric furnace or the like is preferable. Moreover, there is no restriction | limiting in particular about the ultimate metal material temperature at the time of drying, However, 50-250 degreeC is preferable and 70-220 degreeC is more preferable.
本発明の処理剤からの乾燥皮膜の皮膜質量は、０．５〜５ｇ／ｍ２である必要があり、０．５〜４ｇ／ｍ２であることが好ましく、０．５〜３ｇ／ｍ２であることがより好ましい。皮膜質量が０．５ｇ／ｍ２未満であると十分な耐食性が得られ難くなり、５ｇ／ｍ２を超えると形成皮膜が凝集破壊を起こし易くなり、塗膜の加工密着性が低下する傾向になる。 Coating weight of the dry film from the processing agent of the present invention, should be 0.5 to 5 g / m 2, is preferably 0.5~4g / m 2, 0.5~3g / m 2 It is more preferable that When the coating mass is less than 0.5 g / m 2, it is difficult to obtain sufficient corrosion resistance. When the coating mass exceeds 5 g / m 2 , the formed coating tends to cause cohesive failure, and the processing adhesion of the coating tends to decrease. Become.
次に、１コート型プレコート金属材料である本発明のプレコート金属材料について述べる。本発明のプレコート金属材料は本発明の水系塗装下地処理剤からの乾燥皮膜を表面に有する金属材料の該乾燥皮膜上に上塗り塗料からの乾燥皮膜を形成させた金属材料である。上塗り塗料からの乾燥皮膜は主としてプレコート金属材料に意匠性を付与すること及び耐食性向上を目的として設ける。 Next, the precoat metal material of the present invention which is a one-coat type precoat metal material will be described. The precoat metal material of the present invention is a metal material in which a dry film from a top coat is formed on the dry film of a metal material having a dry film from the water-based coating surface treating agent of the present invention on the surface. The dry film from the top coat is provided mainly for the purpose of imparting design properties to the precoat metal material and improving the corrosion resistance.
上塗り塗料としては特に制限されず、下地処理した金属材料、例えば炭素鋼板、合金鋼板、めっき鋼板、鋼板以外の金属板等、特に亜鉛系めっき鋼板に対して通常使用される上塗り塗料（トップコート）のいずれをも使用することができ、例えばポリエステル樹脂系、エポキシ樹脂系、アクリル樹脂系、ウレタン樹脂系、メラミン樹脂系、フッ素樹脂系上塗り塗料などが挙げられ、これらの上塗り塗料は必要に応じて着色顔料や防錆顔料などを含有することができる。上塗り塗装の方法は特に制限されず、一般に使用されるロールコーター法、浸漬法、スプレー法、バーコート法などを使用することができる。焼き付け乾燥条件については、特に制限はなく、例えば、１３０〜２５０℃で１０秒〜５分とすることができる。上塗り塗膜の乾燥膜厚は、３〜５０μｍであることが好ましく、５〜３０μｍであるのがより好ましい。３μｍ未満では均一な着色外観を得ることが難しくなる上、耐食性が低下する傾向となる。また５０μｍを超えると皮膜自体が凝集破壊を起こしやすくなるため塗装密着性が低下する恐れがある。
通常使用される上塗り塗料は、通常、クロムを含まないが、含む場合には、かかる上塗り塗料の使用は差し控える。
The top coating is not particularly limited, and the top coating (top coat) usually used for ground metal materials such as carbon steel plates, alloy steel plates, plated steel plates, metal plates other than steel plates, especially zinc-based plated steel plates. Any of these can be used, and examples thereof include polyester resin-based, epoxy resin-based, acrylic resin-based, urethane resin-based, melamine resin-based, and fluororesin-based topcoat paints. A coloring pigment, an antirust pigment, etc. can be contained. The method of top coating is not particularly limited, and a commonly used roll coater method, dipping method, spray method, bar coating method and the like can be used. There is no restriction | limiting in particular about baking drying conditions, For example, it can be 10 seconds-5 minutes at 130-250 degreeC. The dry film thickness of the top coat film is preferably 3 to 50 μm, and more preferably 5 to 30 μm. If it is less than 3 μm, it is difficult to obtain a uniform colored appearance, and the corrosion resistance tends to decrease. On the other hand, if the thickness exceeds 50 μm, the coating itself tends to cause cohesive failure, which may reduce the coating adhesion.
Normally used top coats usually do not contain chromium, but if so, the use of such top coats is refrained.
本発明のプライマー兼用水系塗装下地処理剤を用いることで、優れた塗膜の加工密着性、耐薬品性、耐食性、耐コインスクラッチ性及び意匠性を有する１コート型プレコート金属材料が得られる理由について以下に推定するが、かかる推定によって本発明及び本発明の効果が限定的に解釈されるべきではない。本発明の水系塗装下地処理剤では、加工密着性に特に優れるカルボキシル基含有ポリウレタン樹脂（Ａ）と、耐コインスクラッチ性に特に優れる高分子量のエポキシ樹脂（Ｂ）とを一定質量比で併用することで、塗膜の加工密着性、耐薬品性、耐食性及び耐コインスクラッチ性をバランス良く高水準で達成できる強靭なベース樹脂皮膜が得られる。一方、本発明の有機化合物（Ｃ）は、該有機化合物に含まれるグリシジル基及びその加水分解にて生じる水酸基が、金属表面に配向することで著しく基材との密着性を向上させるほか、上記ポリウレタン樹脂（Ａ）、エポキシ樹脂（Ｂ）、及び上層の樹脂皮膜中に存在する極性基と反応し、樹脂粒子間を結び付けることで、形成される皮膜の緻密化及び造膜性の向上に寄与している。その結果、塗膜の加工密着性、耐食性及び耐コインスクラッチ性の向上に効果的に作用する。架橋剤（Ｄ）もまた、該架橋剤に含まれる架橋性官能基が上記ポリウレタン樹脂（Ａ）、エポキシ樹脂（Ｂ）、及び有機化合物（Ｃ）中の水酸基、カルボキシル基、エポキシ基などの官能基と架橋反応することで、金属元素が皮膜骨格中に取り込まれ、形成される皮膜をさらに緻密化する。よって、耐薬品性及び耐食性の向上に効果的に作用する。以上のように、前記ポリウレタン樹脂（Ａ）、エポキシ樹脂（Ｂ）、有機化合物（Ｃ）及び架橋剤（Ｄ）は、互いに独立に効果を有するとともに相乗効果を発揮して、本発明の優れた効果を発現するものと推定される。 About the reason why a one-coat type pre-coated metal material having excellent processing adhesion of coating film, chemical resistance, corrosion resistance, coin scratch resistance and design property can be obtained by using the primer combined water-based coating surface treatment agent of the present invention. Although estimated below, the present invention and the effects of the present invention should not be interpreted in a limited manner by such estimation. In the aqueous coating base treatment agent of the present invention, a carboxyl group-containing polyurethane resin (A) that is particularly excellent in processing adhesion and a high molecular weight epoxy resin (B) that is particularly excellent in coin scratch resistance are used in a constant mass ratio. Thus, a tough base resin film that can achieve a high level of well-balanced processing adhesion, chemical resistance, corrosion resistance, and coin scratch resistance of the coating film can be obtained. On the other hand, the organic compound (C) of the present invention has a glycidyl group contained in the organic compound and a hydroxyl group produced by hydrolysis thereof, which remarkably improves the adhesion to the base material by being oriented on the metal surface. Reacts with the polar groups present in the polyurethane resin (A), the epoxy resin (B), and the upper resin film to connect the resin particles, thereby contributing to densification of the formed film and improvement of film formation doing. As a result, it effectively acts to improve the processing adhesion, corrosion resistance and coin scratch resistance of the coating film. In the crosslinking agent (D), the crosslinking functional group contained in the crosslinking agent is a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group in the polyurethane resin (A), the epoxy resin (B), and the organic compound (C). By cross-linking reaction with the group, the metal element is taken into the film skeleton and the formed film is further densified. Therefore, it works effectively for improving chemical resistance and corrosion resistance. As described above, the polyurethane resin (A), the epoxy resin (B), the organic compound (C), and the cross-linking agent (D) have an effect independently of each other and exhibit a synergistic effect. It is estimated that the effect is exhibited.
また、本発明の任意成分である微粒子（Ｅ）は、インヒビター（腐食抑制物質）として作用し、耐食性を向上させる効能を有する他、耐コインスクラッチ性の向上にも寄与する。ここで重要となるのは、微粒子（Ｅ）の粒径であり、微粒子の平均粒径が５μｍを超える場合は、分散状態が不均一になり易く、また粒子が皮膜表面から突出した状態となるため、耐食性、塗膜の加工密着性及び意匠性が低下する恐れがある。このような推定理由により、前記ポリウレタン樹脂（Ａ）、エポキシ樹脂（Ｂ）、有機化合物（Ｃ）、架橋剤（Ｄ）および必要に応じて微粒子（Ｅ）を含有するプライマー兼用水系塗装下地処理剤は、優れた塗膜の加工密着性、耐食性、耐薬品性、耐コインスクラッチ性を有する皮膜を形成し、さらに、該皮膜上には多種多様の意匠性の付与を目的とした上塗り塗装を行なうことが可能であるため、プライマーを介さない１コートであっても、求められる性能を全て満足できるプレコート金属材料を得ることができる。 The fine particles (E), which are optional components of the present invention, act as an inhibitor (corrosion-inhibiting substance), have the effect of improving corrosion resistance, and contribute to improving coin scratch resistance. What is important here is the particle size of the fine particles (E). When the average particle size of the fine particles exceeds 5 μm, the dispersion state tends to be non-uniform, and the particles protrude from the coating surface. For this reason, there is a risk that the corrosion resistance, the processing adhesion of the coating film, and the design properties are lowered. For such an estimation reason, the primer combined water-based coating surface treatment agent containing the polyurethane resin (A), the epoxy resin (B), the organic compound (C), the cross-linking agent (D) and, if necessary, the fine particles (E). Forms a film having excellent process adhesion, corrosion resistance, chemical resistance, and coin scratch resistance of the coating film, and further, overcoating is applied on the film for the purpose of imparting a variety of design properties. Therefore, it is possible to obtain a pre-coated metal material that can satisfy all of the required performance even with one coat without a primer.
以下に本発明の実施例及び比較例を挙げて、本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。
１．水系塗装下地処理剤の調製
１．１ 実施例１〜６９及び比較例１〜１５
表１〜３に示す組合せ及び割合にて、水性ポリウレタン樹脂（Ａ）もしくは比較例用水性ポリウレタン樹脂、水性エポキシ樹脂（Ｂ）もしくは比較例用水性ウレタン樹脂、有機化合物（Ｃ）、架橋剤（Ｄ）及び微粒子（Ｅ）をこの順序で混合し、脱イオン水により固形分濃度を２０質量％に調整することにより、水系塗装下地処理剤を調製した。
EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples of the present invention, but the present invention is not limited to these examples.
1. Preparation of water-based coating surface treatment agent 1.1 Examples 1 to 69 and Comparative Examples 1 to 15
In the combinations and proportions shown in Tables 1 to 3, the aqueous polyurethane resin (A) or the aqueous polyurethane resin for comparative examples, the aqueous epoxy resin (B) or the aqueous urethane resin for comparative examples, the organic compound (C), and the crosslinking agent (D ) And fine particles (E) were mixed in this order, and the solid content concentration was adjusted to 20% by mass with deionized water to prepare a water-based coating base treatment agent.
１．１．１ 水性ポリウレタン樹脂（Ａ）及び比較例用水性ポリウレタン樹脂
Ａ１（実施例用）：
テトラメチレングリコール及びアジピン酸から得られるポリエステルポリオール１５０質量部、４，４’−ジシクロヘキシルメタンジイソシアネート２５質量部及び２，２−ジメチロールプロピオン酸２０質量部をＮ−メチル−２−ピロリドン１００質量部中で反応させることにより得られるプレポリマーを、トリエチルアミンを用いて中和し、脱イオン水に分散させることにより、水性ポリウレタン樹脂を得た。
Ａ２〜Ａ１０及びＡ１５（実施例用）並びにＡ１１〜Ａ１４（比較例用）も同様にして製造した。Ａ１〜Ａ１５の水性ポリウレタン樹脂を表４に、下記の測定方法により測定したその物性を表５に示す。
1.1.1 Aqueous polyurethane resin (A) and Comparative example aqueous polyurethane resin A1 (for Examples):
In 100 parts by mass of N-methyl-2-pyrrolidone, 150 parts by mass of a polyester polyol obtained from tetramethylene glycol and adipic acid, 25 parts by mass of 4,4′-dicyclohexylmethane diisocyanate and 20 parts by mass of 2,2-dimethylolpropionic acid An aqueous polyurethane resin was obtained by neutralizing the prepolymer obtained by the reaction with triethylamine and dispersing it in deionized water.
A2 to A10 and A15 (for Examples) and A11 to A14 (for Comparative Examples) were produced in the same manner. Table 4 shows the water-based polyurethane resins A1 to A15, and Table 5 shows the physical properties measured by the following measuring methods.
（ウレタン基濃度）
水性ポリウレタン樹脂（Ａ）の説明のところで述べたウレタン基濃度の算出のための計算式にしたがって、算出した。
すなわち、ウレタン基濃度は、ポリウレタン樹脂を合成する際の原料成分の仕込み量から算出する樹脂固形分中のイソシアナト基の量で示すことができる。以下に計算式を示す。
［（ａ２の質量）／〔（ａ１の質量）＋（ａ２の質量）＋（ａ３の質量）〕］／（ａ２の分子量）×ｎ×１０３ ＝ ウレタン基濃度（ｍｍｏｌ／ｇ）
（式中、ａ１はポリオール、ａ２はポリイソシアネート、ａ３は２個以上のヒドロキシル基もしくはアミノ基と１個以上のカルボキシル基を有する化合物を表し、ｎは１分子のａ２に含まれるイソシアナト基の数を表す）。
（酸価の測定）
水性ポリウレタン樹脂（Ａ）及び比較水性ポリウレタン樹脂に含まれるカルボン酸を中和するのに、ウレタン樹脂の固形分１ｇ当たり必要となる水酸化カリウムの量（ｍｇ数）で表した。
(Urethane group concentration)
The calculation was performed according to the calculation formula for calculating the urethane group concentration described in the description of the aqueous polyurethane resin (A).
That is, the urethane group concentration can be represented by the amount of isocyanate group in the resin solid content calculated from the charged amount of raw material components when synthesizing the polyurethane resin. The calculation formula is shown below.
[(Mass of a2) / [(mass of a1) + (mass of a2) + (mass of a3)]] / (molecular weight of a2) × n × 10 3 = urethane group concentration (mmol / g)
(In the formula, a1 is a polyol, a2 is a polyisocyanate, a3 is a compound having two or more hydroxyl groups or amino groups and one or more carboxyl groups, and n is the number of isocyanate groups contained in one molecule of a2. Represents).
(Measurement of acid value)
Expressed in terms of the amount (mg) of potassium hydroxide required per 1 g of the solid content of the urethane resin to neutralize the carboxylic acid contained in the aqueous polyurethane resin (A) and the comparative aqueous polyurethane resin.
（ガラス転移温度（Ｔｇ）の測定）
水性ポリウレタン樹脂（Ａ）及び比較水性ポリウレタン樹脂のガラス転移温度（Ｔｇ）は、動的粘弾性測定装置（ＤＭＳ６１００ セイコーインスツルメント株式会社製）で測定したｔａｎδのピーク温度より求めた。
（抗張力の測定）
水性ポリウレタン樹脂（Ａ）及び比較水性ポリウレタン樹脂から樹脂フィルムを作製（製膜条件：常温乾燥２３℃×１２時間、ついで熱処理１２０℃×１時間、膜厚：１５０μｍ、膜サイズ：５０ｍｍ×２０ｍｍ）し、引張試験機（ＡＵＴＯＧＲＡＰＨ ＡＧＳ−１ＫＮＧ 島津製作所製）にて最大点の抗張力（ＭＰａ）を測定した。
(Measurement of glass transition temperature (Tg))
The glass transition temperature (Tg) of the aqueous polyurethane resin (A) and the comparative aqueous polyurethane resin was determined from the peak temperature of tan δ measured with a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.).
(Measurement of tensile strength)
A resin film is prepared from the aqueous polyurethane resin (A) and the comparative aqueous polyurethane resin (film forming conditions: room temperature drying 23 ° C. × 12 hours, then heat treatment 120 ° C. × 1 hour, film thickness: 150 μm, film size: 50 mm × 20 mm). The tensile strength (MPa) at the maximum point was measured with a tensile tester (AUTOGRAPH AGS-1KNG, manufactured by Shimadzu Corporation).
１．１．２ 水性エポキシ樹脂（Ｂ）及び比較水性エポキシ樹脂
Ｂ１〜３及びＢ６（実施例用）：
ビスフェノールＡとエピクロルヒドリンとを付加反応させることにより得られたエポキシ樹脂を、ポリオキシエチレン系乳化剤を含む水溶液中に攪拌機にて強制乳化させることで得た水性エポキシ樹脂。尚、ビスフェノールＡに対するエピクロルヒドリンの配合割合を変化させることで、重量平均分子量を調整した。
Ｂ４及びＢ５（実施例用）並びにＢ７（比較例用）：
ビスフェノールＡとエピクロルヒドリンとを付加反応させることにより得られたエポキシ樹脂と、高酸価のアクリル樹脂とを反応させた後、トリエタノールアミンで中和して水分散化させることで得た水性エポキシ樹脂。
下記測定方法により測定した水性エポキシ樹脂Ｂ１〜Ｂ７の重量平均分子量を表６に示す。
〈重量平均分子量の測定〉
水性エポキシ樹脂（Ｂ）及び比較例用水性エポキシ樹脂の重量平均分子量は、ＧＰＣによる測定装置（ＨＬＣ−８２２０ トーソー株式会社製）によりＲＩ（屈折率の差）を測定することにより決定した。なお、分子量の計算は、ポリスチレン換算で行なった。
1.1.2 Aqueous epoxy resin (B) and comparative aqueous epoxy resins B1-3 and B6 (for Examples):
An aqueous epoxy resin obtained by forcibly emulsifying an epoxy resin obtained by addition reaction of bisphenol A and epichlorohydrin with an agitator in an aqueous solution containing a polyoxyethylene emulsifier. In addition, the weight average molecular weight was adjusted by changing the blending ratio of epichlorohydrin to bisphenol A.
B4 and B5 (for examples) and B7 (for comparative examples):
An aqueous epoxy resin obtained by reacting an epoxy resin obtained by addition reaction of bisphenol A and epichlorohydrin with an acrylic resin having a high acid value, and then neutralizing with triethanolamine and dispersing in water. .
Table 6 shows the weight average molecular weights of the water-based epoxy resins B1 to B7 measured by the following measuring method.
<Measurement of weight average molecular weight>
The weight average molecular weights of the aqueous epoxy resin (B) and the comparative aqueous epoxy resin were determined by measuring RI (difference in refractive index) using a GPC measuring device (HLC-8220 manufactured by Tosoh Corporation). The molecular weight was calculated in terms of polystyrene.
１．１．３ グリシジル基を有する有機化合物（Ｃ）
Ｃ１：３−グリシジルオキシプロピルトリメトキシシラン（東京化成工業株式会社製）
Ｃ２：グリセロールポリグリシジルエーテル（デナコールＥＸ−３１３ ナガセケムテックス株式会社製）
Ｃ３：ビスフェノールＦとエピクロルヒドリンとを付加反応させることにより得られたエポキシ樹脂を、ポリオキシエチレン系乳化剤を含む水溶液中に攪拌機にて強制乳化させることで得た水性エポキシ樹脂。上記測定方法により測定した該水性エポキシ樹脂の重量平均分子量は６００であった。
1.1.3 Organic compound (C) having a glycidyl group
C1: 3-glycidyloxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
C2: Glycerol polyglycidyl ether (Denacol EX-313 manufactured by Nagase ChemteX Corporation)
C3: An aqueous epoxy resin obtained by forcibly emulsifying an epoxy resin obtained by addition reaction of bisphenol F and epichlorohydrin with an agitator in an aqueous solution containing a polyoxyethylene emulsifier. The weight average molecular weight of the water-based epoxy resin measured by the above measuring method was 600.
１．１．４ チタン元素もしくはジルコニウム元素を含有する架橋剤（Ｄ）
Ｄ１：炭酸ジルコニウムアンモニウム（ジルコゾールＡＣ−７ 第一稀元素化学工業株式会社製）
Ｄ２：チタントリエタノールアミネート（オルガチックスＴＣ―４００ 松本ファインケミカル株式会社製）
1.1.4 Crosslinking agent containing titanium element or zirconium element (D)
D1: Zirconium ammonium carbonate (Zircosol AC-7 manufactured by Daiichi Rare Element Chemical Co., Ltd.)
D2: Titanium triethanolamate (Orgatechs TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.)
１．１．５ 微粒子（Ｅ）
Ｅ１：気相シリカ（ＣＡＢ−Ｏ−ＳＩＬ Ｍ５ ＣＡＢｏｔ社製）
Ｅ２：コロイダルシリカ（スノーテックスＮ 日産化学工業株式会社製）
Ｅ３：アルミナゾル（アルミナゾル２００ 日産化学工業株式会社製）
Ｅ４：リン酸系防錆顔料（ＬＦボウセイＤ−１ キクチカラー株式会社製）
Ｅ５：モリブデン酸系防錆顔料（ＬＦボウセイＭＣ−４００ＷＲ キクチカラー株式会社製）
1.1.5 Fine particles (E)
E1: Gas phase silica (CAB-O-SIL M5 manufactured by CABot)
E2: Colloidal silica (Snowtex N Nissan Chemical Industries, Ltd.)
E3: Alumina sol (Alumina sol 200 manufactured by Nissan Chemical Industries, Ltd.)
E4: Phosphoric acid-based anticorrosive pigment (LF Bowsei D-1 manufactured by Kikuchi Color Co., Ltd.)
E5: Molybdic acid rust preventive pigment (LF Bowsey MC-400WR manufactured by Kikuchi Color Co., Ltd.)
１．２ 比較例１６〜２１
特許文献３〜８を参考に下記の水系塗装下地処理剤を調製した。
比較例１６
水性ポリウレタン樹脂（アデカボンタイターＨＵＸ−２９０Ｈ 株式会社ＡＤＥＫＡ製）１００質量部、γ−グリシドキシプロピルトリエトキシシラン（東京化成工業株式会社製）３５質量部及びコロイダルシリカ（スノーテックスＮ 日産化学工業株式会社製）１５０質量部を混合し、脱イオン水により固形分濃度を２０質量％に調整することにより処理液を調製した。
比較例１７
γ−アミノプロピルトリエトキシシラン（東京化成工業株式会社製）２５質量部、コロイダルシリカ（スノーテックスＮ 日産化学工業株式会社製）１０質量部、炭酸ジルコニウムアンモニウム（ジルコゾールＡＣ−７ 第一稀元素化学工業株式会社製）１５０質量部、チオ尿素１０質量部及びリン酸アンモニウム２０質量部を混合し、脱イオン水により固形分濃度を２０質量％に調整することにより処理液を調製した。
比較例１８
水性ポリウレタン樹脂（アデカボンタイターＨＵＸ−２９０Ｈ 株式会社ＡＤＥＫＡ製）５５．７質量部、メラミン樹脂（サイメル３８５ サイテック社製）１５質量部、γ−グリシドキシプロピルトリエトキシシラン（東京化成工業株式会社製）２質量部、コロイダルシリカ（スノーテックスＮ 日産化学工業株式会社製）２２質量部、リン酸０．３質量部及び酸化ニオブゾル（多木化学株式会社製）５質量部を混合し、脱イオン水により固形分濃度を２０質量％に調整することにより処理液を調製した。
1.2 Comparative Examples 16-21
The following water-based coating surface treatment agent was prepared with reference to Patent Documents 3 to 8.
Comparative Example 16
100 parts by mass of an aqueous polyurethane resin (Adekabon titer HUX-290H manufactured by ADEKA Corporation), 35 parts by mass of γ-glycidoxypropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and colloidal silica (Snowtex N Nissan Chemical Co., Ltd.) 150 parts by mass) were mixed, and the treatment liquid was prepared by adjusting the solid content concentration to 20% by mass with deionized water.
Comparative Example 17
25 parts by mass of γ-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 10 parts by mass of colloidal silica (manufactured by Snowtex N Nissan Chemical Industries, Ltd.), ammonium zirconium carbonate (Zircozol AC-7, the first rare element chemical industry) 150 parts by mass, 10 parts by mass of thiourea and 20 parts by mass of ammonium phosphate were mixed, and the treatment liquid was prepared by adjusting the solid content concentration to 20% by mass with deionized water.
Comparative Example 18
Aqueous polyurethane resin (Adekabon titer HUX-290H manufactured by ADEKA Corporation) 55.7 parts by mass, melamine resin (Cymel 385 manufactured by Cytec Co., Ltd.) 15 parts by mass, γ-glycidoxypropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 parts by mass, 22 parts by mass of colloidal silica (Snowtex N Nissan Chemical Industries, Ltd.), 0.3 part by mass of phosphoric acid and 5 parts by mass of niobium oxide sol (manufactured by Taki Chemical Co., Ltd.) The treatment liquid was prepared by adjusting the solid content concentration to 20% by mass.
比較例１９
水性ポリウレタン樹脂（アデカボンタイターＨＵＸ−２９０Ｈ 株式会社ＡＤＥＫＡ製）６０質量部、縮合リン酸カルシウム（炭酸カルシウムとリン酸とをＣａ／Ｐ＝０．７５となる量比にて８０℃で３時間加熱後、２００℃の乾燥機で３０時間焼成して得たもの）１０質量部、トリポリリン酸アルミニウム（Ｋ−ホワイト８２ テイカ株式会社製）２０質量部、モリブデン酸ナトリウム５質量部及びリン酸５質量部を混合し、脱イオン水により固形分濃度を２０質量％に調整することにより処理液を調製した。
比較例２０
顔料分散剤（ＢＹＫ１９０ ビックケミー株式会社製）２質量部、酸化チタン（チタンＣＲ−９７ 石原産業株式会社製）４５質量部、トリポリリン酸二水素アルミニウム（Ｋ−１００Ｐ テイカ株式会社製）３０質量部及び脱イオン水２３質量部を混合して得たチタン分散ペースト１００質量部、水性エポキシ樹脂（ディックファインＥＮ−０２７４ 大日本インキ化学工業社製）及び３００質量部を混合し、脱イオン水により固形分濃度を２０質量％に調整することにより処理液を調製した。
比較例２１
テトラメチレングリコール及びアジピン酸から得られるポリエステルポリオール１７０質量部、１，６−ヘキサメチレンジイソシアネート３０質量部、２，２−ジメチロールプロピオン酸２５質量部及びＮ−メチル−２−ピロリドン１００質量部を反応させることにより得られるプレポリマーを、トリエチルアミンを用いて脱イオン水に分散させることにより得られたガラス転移温度が１００℃、かつ最低造膜温度が０℃以下である水性ウレタン樹脂１００質量部、メチロール化フェノール２質量部及び炭酸ジルコニウムアンモニウム（ジルコゾールＡＣ−７ 第一稀元素化学工業株式会社製）１質量部を混合し、脱イオン水により固形分濃度を２０質量％に調整することにより処理液を調整した。なお、最低造膜温度の測定として、最低造膜測定装置（三洋貿易株式会社製）を使用した。
Comparative Example 19
Aqueous polyurethane resin (Adekabon titer HUX-290H manufactured by ADEKA Corporation) 60 parts by mass, condensed calcium phosphate (calcium carbonate and phosphoric acid after heating at 80 ° C. for 3 hours at a ratio of Ca / P = 0.75, 10 parts by weight obtained by baking for 30 hours in a 200 ° C. dryer), 20 parts by weight of aluminum tripolyphosphate (K-White 82 manufactured by Teica Co., Ltd.), 5 parts by weight of sodium molybdate and 5 parts by weight of phosphoric acid Then, a treatment liquid was prepared by adjusting the solid content concentration to 20% by mass with deionized water.
Comparative Example 20
2 parts by mass of a pigment dispersant (BYK190 manufactured by Big Chemie Co., Ltd.), 45 parts by mass of titanium oxide (manufactured by Titanium CR-97 Ishihara Sangyo Co., Ltd.), 30 parts by mass of aluminum dihydrogen phosphate (manufactured by K-100P Taika Co., Ltd.) and desorption 100 parts by mass of titanium dispersion paste obtained by mixing 23 parts by mass of ionic water, aqueous epoxy resin (Dick Fine EN-0274 manufactured by Dainippon Ink & Chemicals, Inc.) and 300 parts by mass are mixed, and the solid content concentration is obtained with deionized water. Was adjusted to 20% by mass to prepare a treatment solution.
Comparative Example 21
Reaction of 170 parts by mass of a polyester polyol obtained from tetramethylene glycol and adipic acid, 30 parts by mass of 1,6-hexamethylene diisocyanate, 25 parts by mass of 2,2-dimethylolpropionic acid and 100 parts by mass of N-methyl-2-pyrrolidone 100 parts by mass of a water-based urethane resin having a glass transition temperature of 100 ° C. and a minimum film-forming temperature of 0 ° C. or lower obtained by dispersing the prepolymer obtained by dispersing in deionized water using triethylamine, methylol 2 parts by mass of chlorophenol and 1 part by mass of ammonium zirconium carbonate (Zircosol AC-7 manufactured by Daiichi Rare Element Chemical Co., Ltd.) are mixed, and the treatment liquid is adjusted to 20% by mass with deionized water. It was adjusted. In addition, as the measurement of the minimum film-forming temperature, a minimum film-forming measuring device (manufactured by Sanyo Trading Co., Ltd.) was used.
２．試験板の作製
２．１ 供試材
５５％アルミニウム−亜鉛合金めっき鋼板（ＧＬ）
板厚０．３５ｍｍ、めっき付着量片面当たり５０ｇ／ｍ２（両面めっき）
２．２ 前処理
供試材をアルカリ脱脂剤であるＣＬ―Ｎ３６４Ｓ（日本パーカライジング(株)製）を濃度２０ｇ／Ｌとし、温度６０℃の条件で３０秒間スプレー処理した。続いて、水道水で洗浄した後に、水切りロールで絞り、５０℃で３０秒間加熱乾燥した。
2. 2. Preparation of test plate 2.1 Test material 55% aluminum-zinc alloy plated steel plate (GL)
Plate thickness 0.35mm, plating coverage 50g / m 2 per side (double-sided plating)
2.2 Pretreatment The test material was spray-treated for 30 seconds at a temperature of 60 ° C. with CL-N364S (manufactured by Nihon Parkerizing Co., Ltd.) as an alkaline degreasing agent at a concentration of 20 g / L. Then, after wash | cleaning with a tap water, it squeezed with the draining roll and heat-dried at 50 degreeC for 30 second (s).
２．３ 表面処理
２．３．１ 実施例１〜６９及び比較例１〜２１
２．３．１．１ 下地処理
前処理後の供試材の表面（片面）に、表１〜３に示した組成の水系塗装下地処理剤を、それぞれ表７に示す乾燥皮膜量が得られるようにロールコーターを用いて塗布した。続いて、熱風乾燥炉にてそれぞれ表７に示す到達板温度となるように加熱乾燥した。
２．３．１．２ 上塗り塗装
ついで、上塗り塗料（ポリエステル樹脂６０質量部、ブチル化メラミン樹脂１５質量部、酸化チタン１０質量部及び着色顔料１５質量部）を塗布し、２２０℃の乾燥・焼付けを行い、乾燥膜厚１５μｍの上塗り塗膜を得た。
2.3 Surface Treatment 2.3.1 Examples 1 to 69 and Comparative Examples 1 to 21
2.3.1.1 Substrate treatment The surface of the specimen after pretreatment (one side) is obtained with the water-based paint base treatment agent having the composition shown in Tables 1 to 3 and the dry film amount shown in Table 7 respectively. It applied using a roll coater. Then, it heat-dried so that it might become the reach | attainment board temperature shown in Table 7, respectively with a hot-air drying furnace.
2.3.1.2 Top coating Next, top coating (60 parts by weight of polyester resin, 15 parts by weight of butylated melamine resin, 10 parts by weight of titanium oxide and 15 parts by weight of coloring pigment) is applied, and dried and baked at 220 ° C. And a top coat film having a dry film thickness of 15 μm was obtained.
２．３．２ 比較例２２
２．３．２．１ 下地処理（クロメート処理）
脱イオン水６００質量部に、三酸化クロム水溶液（濃度６０質量％）２００質量部及び気相シリカ（ＣＡＢ−Ｏ−ＳＩＬ Ｍ５ ＣＡＢｏｔ社製）１００質量部を混合して得た水系塗装下地処理剤を、０．１ｇ／ｍ２の乾燥皮膜量が得られるようにロールコーターを用いて塗布した。続いて、熱風乾燥炉にて到達板温度が１００℃となるように加熱乾燥した。
２．３．２．２ プライマー処理
プライマー（ポリエステル樹脂７０質量部、メラミン樹脂１０質量部、リン酸亜鉛系防錆顔料５質量部、リン酸マグネシウム系防錆顔料５質量部、トリポリリン酸２水素アルミニウム５質量部及び変性シリカ５質量部）を塗布し、２１０℃で乾燥及び焼付けを行い、乾燥膜厚５μｍのプライマー皮膜を下地処理皮膜の上に形成させた。
２．３．２．３ 上塗り塗装
上塗り塗料（ポリエステル樹脂６０質量部、ブチル化メラミン樹脂１５質量部、酸化チタン１０質量部及び着色顔料１５質量部）を塗布し、２２０℃で乾燥及び焼付けを行い、乾燥膜厚１５μｍの上塗り塗膜を形成させた。
2.3.2 Comparative Example 22
2.3.2.1 Ground treatment (chromate treatment)
A water-based coating surface treatment agent obtained by mixing 600 parts by mass of deionized water with 200 parts by mass of a chromium trioxide aqueous solution (concentration 60% by mass) and 100 parts by mass of vapor phase silica (CAB-O-SIL M5 manufactured by CABot). Was applied using a roll coater such that a dry film amount of 0.1 g / m 2 was obtained. Subsequently, it was heated and dried in a hot air drying furnace so that the ultimate plate temperature was 100 ° C.
2.3.2.2 Primer treatment Primer (70 parts by weight of polyester resin, 10 parts by weight of melamine resin, 5 parts by weight of zinc phosphate-based rust preventive pigment, 5 parts by weight of magnesium phosphate-based rust preventive pigment, aluminum dihydrogen tripolyphosphate 5 parts by mass and 5 parts by mass of modified silica) were applied, dried and baked at 210 ° C., and a primer film having a dry film thickness of 5 μm was formed on the base treatment film.
2.3.2.3 Top coat Apply top coat (60 parts by weight of polyester resin, 15 parts by weight of butylated melamine resin, 10 parts by weight of titanium oxide and 15 parts by weight of color pigment), and dry and bake at 220 ° C. A top coat film having a dry film thickness of 15 μm was formed.
３．評価試験
上記で作製した各塗装鋼板から試験片を切り出して試験板とし、以下に示す試験に供した。
３．１耐食性
３．１．１ 塩水噴霧試験
作製した各試験板の塗膜に、金属素地に達する傷をカッターで入れ、ＪＩＳ−Ｚ２３７１に規定された塩水噴霧試験を４８０時間実施した。評価はカット部からの塗膜膨れ幅（片側最大値）を測定することにより行った。また、端面耐食性は、端面からの塗膜膨れ幅（最大値）を測定した。
＜評価基準−カット部＞
◎：１ｍｍ未満
○：１ｍｍ以上２ｍｍ未満
△：２ｍｍ以上４ｍｍ未満
▲：４ｍｍ以上６ｍｍ未満
×：６ｍｍ以上
＜評価基準−端面＞
◎：３ｍｍ未満
○：３ｍｍ以上６ｍｍ未満
△：６ｍｍ以上１０ｍｍ未満
▲：１０ｍｍ以上１５ｍｍ未満
×：１５ｍｍ以上
3. Evaluation test A test piece was cut out from each of the coated steel plates produced above to obtain a test plate, which was subjected to the following tests.
3.1 Corrosion resistance 3.1.1 Salt spray test The wound which reaches a metal base was put into the coating film of each produced test board with the cutter, and the salt spray test prescribed | regulated to JIS-Z2371 was implemented for 480 hours. The evaluation was performed by measuring the swollen width (maximum value on one side) from the cut part. Moreover, the end surface corrosion resistance measured the coating film swelling width (maximum value) from the end surface.
<Evaluation criteria-Cut part>
◎: Less than 1 mm ○: 1 mm or more and less than 2 mm △: 2 mm or more and less than 4 mm ▲: 4 mm or more and less than 6 mm x: 6 mm or more <Evaluation criteria—End face>
◎: Less than 3 mm ○: 3 mm or more and less than 6 mm Δ: 6 mm or more and less than 10 mm ▲: 10 mm or more and less than 15 mm x: 15 mm or more
３．１．１ 複合サイクル試験
作製した各試験板の塗膜に、金属素地に達する傷をカッターで入れ、ＪＩＳ−Ｈ８５０２（ＪＡＳＯ Ｍ６０９−９１）に規定された複合サイクル試験を２００サイクル実施した。判定基準はカット部からの塗膜膨れ幅（片側最大値）を測定した。また、端面耐食性は、端面からの塗膜膨れ幅（最大値）を測定した。
＜評価基準−カット部＞
◎：１ｍｍ未満
○：１ｍｍ以上２ｍｍ未満
△：２ｍｍ以上４ｍｍ未満
▲：４ｍｍ以上６ｍｍ未満
×：６ｍｍ以上
＜評価基準−端面＞
◎：３ｍｍ未満
○：３ｍｍ以上６ｍｍ未満
△：６ｍｍ以上１０ｍｍ未満
▲：１０ｍｍ以上１５ｍｍ未満
×：１５ｍｍ以上
3.1.1 Combined cycle test The wound which reaches a metal base was put into the coating film of each produced test board with the cutter, and the combined cycle test prescribed | regulated to JIS-H8502 (JASO M609-91) was implemented 200 cycles. The criterion for determination was the film swelling width (maximum value on one side) from the cut part. Moreover, the end surface corrosion resistance measured the coating film swelling width (maximum value) from the end surface.
<Evaluation criteria-Cut part>
◎: Less than 1 mm ○: 1 mm or more and less than 2 mm △: 2 mm or more and less than 4 mm ▲: 4 mm or more and less than 6 mm x: 6 mm or more <Evaluation Criteria—End Face>
◎: Less than 3 mm ○: 3 mm or more and less than 6 mm Δ: 6 mm or more and less than 10 mm ▲: 10 mm or more and less than 15 mm x: 15 mm or more
３．２ 折曲げ塗装密着性試験
３．２．１ 一次折曲げ密着性
ＪＩＳ−Ｇ３３１２の試験法に準じて各試験板に対し、内側間隔板を挟まない０Ｔ折曲げ試験を２０℃で行い、テープ剥離後の塗膜剥離状態を肉眼で観察し、下記の判定基準に準じて評価を行った。
＜評価基準＞
◎：剥離なし
○：剥離面積１０％未満
△：剥離面積１０％以上５０％未満
▲：剥離面積５０％以上８０％未満
×：剥離面積８０％以上
３．２．２ 二次折曲げ密着性
試験板を沸水中に２時間浸漬した後、１日放置し一次折曲げ密着性試験と同様の試験を行った。判定基準は以下の通りである。
＜評価基準＞
◎：剥離なし
○：剥離面積１０％未満
△：剥離面積１０％以上５０％未満
▲：剥離面積５０％以上８０％未満
×：剥離面積８０％以上
3.2 Folding coating adhesion test 3.2.1 Primary bending adhesion A 0T bending test is performed at 20 ° C. with no inner spacing plate on each test plate in accordance with the test method of JIS-G3312. The state of coating film peeling after tape peeling was observed with the naked eye, and evaluated according to the following criteria.
<Evaluation criteria>
◎: No peeling ○: Peeling area less than 10% △: Peeling area 10% or more and less than 50% ▲: Peeling area 50% or more and less than 80% X: Peeling area 80% or more 3.2.2 Secondary bending adhesion test After immersing the plate in boiling water for 2 hours, the plate was left to stand for 1 day, and a test similar to the primary bending adhesion test was performed. Judgment criteria are as follows.
<Evaluation criteria>
A: No peeling B: Peeling area less than 10% B: Peeling area 10% or more and less than 50% B: Peeling area 50% or more and less than 80% X: Peeling area 80% or more
３．３ 耐コインスクラッチ性
１０円硬貨を各試験板に対して４５°の角度に設置し、塗膜を２ｋｇの荷重、一定速度でこすり、塗膜の傷つき度を肉眼で観察し、下記判定基準に従って耐コインスクラッチ性の評価を行った。
＜評価基準＞
◎：剥離面積１０％未満
○：剥離面積１０％以上２０％未満
△：剥離面積２０％以上５０％未満
▲：剥離面積５０％以上８０％未満
×：剥離面積８０％以上
3.3 Coin scratch resistance A 10-yen coin is placed at an angle of 45 ° with respect to each test plate, the coating film is rubbed at a constant speed with a load of 2 kg, and the degree of damage to the coating film is observed with the naked eye, and the following judgment is made. Coin scratch resistance was evaluated according to the standard.
<Evaluation criteria>
A: Peeling area less than 10% B: Peeling area 10% or more and less than 20% B: Peeling area 20% or more and less than 50% B: Peeling area 50% or more and less than 80% X: Peeling area 80% or more
３．４ 耐薬品性
３．４．１ 耐アルカリ性
試験板を５質量％の水酸化ナトリウム水溶液に室温で２４時間浸漬した後、ブリスターの大きさと発生密度の評価を肉眼で観察し、下記の判定基準に従って耐アルカリ性の評価を行った。
＜評価基準＞
◎：ブリスターなし。
○：１つのブリスターが１．５ｍｍ未満で、かつ発生密度がＦである。
△：１つのブリスターが１．５ｍｍ以上〜２ｍｍ未満で、かつ発生密度がＦである。もしくは、１つのブリスターの大きさが１．５ｍｍ未満で、かつ発生密度がＭである。
▲：１つのブリスターの大きさが２ｍｍ以上で、かつ発生密度がＦである。もしくは、１つのブリスターの大きさが１．５ｍｍ以上２ｍｍ未満で、かつ発生密度がＭである。もしくは、１つのブリスターの大きさが１．５ｍｍ未満で、かつ発生密度がＭＤである。
×：１つのブリスターの大きさが２ｍｍ以上で、かつ発生密度がＭである。もしくは、１つのブリスターの大きさが１．５ｍｍ以上２ｍｍ未満で、かつ発生密度がＭＤである。もしくは、ブリスターの大きさに関わらず発生密度がＤである。
３．４．２ 耐酸性
試験板を５質量％の硫酸水溶液に室温で２４時間浸漬した後、ブリスターの発生数と発生密度の評価を行った。評価基準は３．４．１と同様である。
3.4 Chemical resistance 3.4.1 Alkali resistance After immersing the test plate in a 5% by weight aqueous sodium hydroxide solution at room temperature for 24 hours, the blister size and generation density were evaluated with the naked eye, and the following judgment was made. The alkali resistance was evaluated according to the standard.
<Evaluation criteria>
A: No blister.
A: One blister is less than 1.5 mm, and the generation density is F.
(Triangle | delta): One blister is 1.5 mm or more and less than 2 mm, and the generation density is F. Alternatively, the size of one blister is less than 1.5 mm and the generation density is M.
B: The size of one blister is 2 mm or more and the generation density is F. Alternatively, the size of one blister is 1.5 mm or more and less than 2 mm, and the generation density is M. Alternatively, the size of one blister is less than 1.5 mm and the generation density is MD.
X: The size of one blister is 2 mm or more and the generation density is M. Alternatively, the size of one blister is 1.5 mm or more and less than 2 mm, and the generation density is MD. Alternatively, the generation density is D regardless of the size of the blister.
3.4.2 Acid resistance After the test plate was immersed in a 5% by mass sulfuric acid aqueous solution at room temperature for 24 hours, the number of blisters generated and the generation density were evaluated. The evaluation criteria are the same as 3.4.1.
４．評価結果
試験の評価結果を表８〜１０に示す。表８〜１０より、本発明の水系塗装下地処理剤を用いて形成された皮膜を有するＧＬプレコート鋼板である実施例１〜６９は、一次塗装密着性、二次塗装密着性、耐食性（×カット部及び端面部）、耐薬品性（アルカリ及び酸）及び耐コインスクラッチ性のすべての性能において優れた結果を示した。中でも微粒子（Ｅ）を併用した実施例４７〜６４ではより優れた性能バランスが取れており、２コート型である比較例２２と同程度であった。
一方、水性ポリウレタン樹脂（Ａ）、水性エポキシ樹脂（Ｂ）、有機化合物（Ｃ）及び架橋剤（Ｄ）のうち何れかの成分を含まない比較例１〜４、水性ポリウレタン樹脂の物性が本発明で特定した範囲外となる比較例５〜８、水性エポキシ樹脂の分子量が本発明で特定した範囲外となる比較例９、これらの成分の含有割合が本発明で特定した範囲外となる比較例１０〜１５、並びに従来技術となる特許文献を参考にした比較例１６〜２１では、加工密着性、耐食性、耐薬品性及び耐コインスクラッチ性のうち少なくとも１つの性能が劣っていた。
4). Evaluation results The evaluation results of the tests are shown in Tables 8-10. From Tables 8-10, Examples 1-69 which are GL precoat steel plates which have the film | membrane formed using the aqueous | water-based coating ground-treatment agent of this invention are primary coating adhesiveness, secondary coating adhesiveness, and corrosion resistance (x cut). Part and end face part), chemical resistance (alkali and acid) and coin scratch resistance were all excellent. Among them, Examples 47 to 64 using the fine particles (E) in combination had a better performance balance and were comparable to those of Comparative Example 22 which was a two-coat type.
On the other hand, the physical properties of Comparative Examples 1 to 4, which do not contain any component of the aqueous polyurethane resin (A), the aqueous epoxy resin (B), the organic compound (C) and the crosslinking agent (D), are the present invention. Comparative Examples 5 to 8 outside the range specified in the above, Comparative Example 9 in which the molecular weight of the aqueous epoxy resin is outside the range specified in the present invention, and Comparative Examples in which the content ratio of these components is outside the range specified in the present invention In Comparative Examples 16 to 21 with reference to 10 to 15 and the patent document as the prior art, at least one of the processing adhesion, corrosion resistance, chemical resistance and coin scratch resistance was inferior.
Claims (6)
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| KR101248610B1 (en) * | 2010-03-17 | 2013-03-29 | 박정득 | The rust clearance primer using natural resin and the method thereof |
| JP6094353B2 (en) * | 2013-04-17 | 2017-03-15 | Jsr株式会社 | Protective film forming composition, protective film forming method, protective film and protective film removing method |
| JP6080670B2 (en) * | 2013-04-22 | 2017-02-15 | 日本パーカライジング株式会社 | Ground treatment composition for coated steel sheet, plated steel sheet subjected to ground treatment and method for producing the same, painted steel sheet and method for producing the same |
| CN103509430B (en) * | 2013-09-27 | 2015-09-16 | 无锡阳工机械制造有限公司 | A kind of anticorrosive metal paint and preparation method thereof |
| JP5543004B1 (en) * | 2013-09-30 | 2014-07-09 | 日新製鋼株式会社 | Painted metal profile |
| CN103709807B (en) * | 2013-12-19 | 2016-03-02 | 常熟市加腾电子设备厂（普通合伙） | Corrosion-resistant dampproof cabinet |
| CN103694837B (en) * | 2013-12-19 | 2016-03-02 | 常熟市加腾电子设备厂（普通合伙） | Corrosion-resistant nitrogen cabinet |
| CN103666224B (en) * | 2013-12-19 | 2016-03-16 | 常熟市加腾电子设备厂（普通合伙） | Electric storage cabinet |
| WO2015126370A1 (en) * | 2014-02-18 | 2015-08-27 | Hewlett-Packard Development Company, L.P. | Finishing method for a metal surface |
| JP6455855B2 (en) * | 2015-04-20 | 2019-01-23 | 関西ペイント株式会社 | Aqueous metal surface treatment agent |
| JP6559085B2 (en) * | 2016-03-24 | 2019-08-14 | 第一工業製薬株式会社 | Aqueous composition and coating agent |
| JP6810528B2 (en) * | 2016-03-29 | 2021-01-06 | スリーエム イノベイティブ プロパティズ カンパニー | Graphic film for license plate and license plate, and their manufacturing method |
| US10370545B2 (en) * | 2017-09-19 | 2019-08-06 | Ppg Industries Ohio, Inc. | Low VOC anionic electrodepositable coating composition |
| JP6936706B2 (en) * | 2017-11-13 | 2021-09-22 | 日本ペイント・サーフケミカルズ株式会社 | Method for manufacturing water-based resin composition for rust-preventive coating, water-based resin composition for rust-preventive coating, rust-preventive treatment method and rust-preventive metal material |
| WO2019124521A1 (en) * | 2017-12-20 | 2019-06-27 | 日本製鉄株式会社 | Pre-coated steel sheet |
| CN108515002A (en) * | 2018-03-09 | 2018-09-11 | 安徽墙煌彩铝科技有限公司 | Two-sided decoration color coated aluminum plate preparation process |
| JP2021073104A (en) * | 2020-12-11 | 2021-05-13 | スリーエム イノベイティブ プロパティズ カンパニー | Graphic film for license plate, license plate and manufacturing method therefor |
| CN114989709B (en) * | 2022-06-17 | 2023-10-24 | 中车株洲车辆有限公司 | Water-based precoating primer, coating and product with coating |
| WO2024011502A1 (en) * | 2022-07-14 | 2024-01-18 | Henkel Ag & Co. Kgaa | Protection coating composition, treating method using the same and article thereof |
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| EP0512710A3 (en) * | 1991-05-08 | 1993-01-27 | Ici Americas Inc. | Aqueous coating compositions |
| JPH0517682A (en) * | 1991-07-09 | 1993-01-26 | Toyobo Co Ltd | Aqueous dispersion and aqueous coating resin composition prepared therefrom |
| JPH06228498A (en) * | 1993-02-08 | 1994-08-16 | Nippon Paint Co Ltd | Water-based coating composition |
| JPH07242833A (en) * | 1994-03-08 | 1995-09-19 | Nippon Parkerizing Co Ltd | Aqueous coating composition excellent in corrosion resistance and solvent resistance |
| JP2000234179A (en) * | 1999-02-12 | 2000-08-29 | Nisshin Steel Co Ltd | Zinc-aluminum alloy plated rectangular steel tube excellent in adhesive joining durability with wood and its production |
| JP2001081392A (en) * | 1999-09-13 | 2001-03-27 | Nippon Parkerizing Co Ltd | Treating agent for water-based coating substrate having excellent adhesion, production of metal material and metal material |
| JP4078044B2 (en) * | 2001-06-26 | 2008-04-23 | 日本パーカライジング株式会社 | Metal surface treatment agent, surface treatment method of metal material, and surface treatment metal material |
| JP4546884B2 (en) * | 2004-07-07 | 2010-09-22 | 新日本製鐵株式会社 | Surface treated galvanized steel sheet with excellent corrosion resistance |
| JP2006328445A (en) * | 2005-05-23 | 2006-12-07 | Nippon Parkerizing Co Ltd | Water-based surface treating agent for precoat metal material, surface treating method and method for manufacturing precoat metal material |
| JP3872493B1 (en) * | 2005-08-17 | 2007-01-24 | 日本パーカライジング株式会社 | Water-based surface treatment agent for metal material and surface-coated metal material |
| JP2008000910A (en) * | 2006-06-20 | 2008-01-10 | Jfe Steel Kk | Highly anticorrosive surface treated steel sheet and its manufacturing method |
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