JP5231738B2 - Metal material processed using metal surface treatment composition - Google Patents
Metal material processed using metal surface treatment composition Download PDFInfo
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- 239000007769 metal material Substances 0.000 title claims description 67
- 229910052751 metal Inorganic materials 0.000 title claims description 56
- 239000002184 metal Substances 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 title claims description 35
- 238000004381 surface treatment Methods 0.000 title claims description 35
- 239000011347 resin Substances 0.000 claims description 124
- 229920005989 resin Polymers 0.000 claims description 124
- 239000000126 substance Substances 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910000838 Al alloy Inorganic materials 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 239000002335 surface treatment layer Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000005001 laminate film Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 20
- 238000005260 corrosion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000003755 zirconium compounds Chemical class 0.000 description 6
- 229920000083 poly(allylamine) Polymers 0.000 description 5
- -1 zirconium ions Chemical class 0.000 description 5
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
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- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 108010039918 Polylysine Proteins 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920000656 polylysine Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KATAXDCYPGGJNJ-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethoxy)propan-2-ol Chemical compound C1OC1COCC(O)COCC1CO1 KATAXDCYPGGJNJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- ABXXWVKOBZHNNF-UHFFFAOYSA-N chromium(3+);dioxido(dioxo)chromium Chemical compound [Cr+3].[Cr+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O ABXXWVKOBZHNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Description
本発明は、金属素材の表面に施され、ラミネートフィルムと金属素材との密着性を向上させるための金属表面処理組成物を用いて処理されてなる金属材料に関する。 The present invention relates to a metal material which is applied to the surface of a metal material and processed using a metal surface treatment composition for improving the adhesion between a laminate film and the metal material.
従来から、金属材料表面を保護し、意匠を施すために、金属表面にラミネート加工を施すことが行われている。ラミネートフィルムは、成型加工性、耐食性、及び内容物のバリア性等に優れ、また塗料と異なり金属材料への塗布工程において有機溶剤等の揮発がなく、生産環境面で好ましいことから、食品缶、意匠缶、コンデンサーケース、電池材等、コイルやシート状でプレコートされる包装用の金属材料の表面保護材として、多く用いられている。 2. Description of the Related Art Conventionally, in order to protect a metal material surface and apply a design, the metal surface is laminated. Laminate film is excellent in molding processability, corrosion resistance, content barrier properties, etc., and unlike coating, there is no volatilization of organic solvents etc. in the application process to metal materials, which is preferable in terms of production environment. It is often used as a surface protective material for metal materials for packaging such as design cans, capacitor cases, battery materials, etc., which are pre-coated in coils or sheets.
ところで、ラミネートフィルムは、上述のような優れた特性を有する一方で、ラミネート加工を施した金属材料においては、金属素材とラミネートフィルムとの密着性が十分でないために、金属材料に包装材としての高度な加工を施したり、加工後の包装材に内容物を加えて加熱処理を施したりする際に、金属素材からラミネートフィルムが剥離することがあった。このような、金属素材からのラミネートフィルムの剥離は、金属材料の美観を損ね、耐食性を低下させる大きな原因となっていた。 By the way, the laminate film has the excellent characteristics as described above. On the other hand, in the laminated metal material, since the adhesion between the metal material and the laminate film is not sufficient, the metal material is used as a packaging material. When performing advanced processing or adding a content to the processed packaging material and subjecting it to heat treatment, the laminate film may peel off from the metal material. Such peeling of the laminate film from the metal material is a major cause of deteriorating the aesthetic appearance of the metal material and lowering the corrosion resistance.
したがってラミネート加工が施された金属材料における、このような問題を解決するため、ラミネート加工に先立って、金属素材の表面に金属表面処理組成物による表面処理層を形成し、ラミネートフィルムと金属素材との密着性を向上させることが行われている。 Therefore, in order to solve such a problem in the metal material subjected to lamination, a surface treatment layer is formed by a metal surface treatment composition on the surface of the metal material prior to lamination, and the laminate film and the metal material are formed. It has been carried out to improve the adhesion.
例えば、特許文献１には、アミノ化フェノール重合体と、Ｔｉ、Ｚｒ、Ｈｆ、Ｍｏ、Ｗ、Ｓｅ、Ｃｅ、Ｆｅ、Ｃｕ、Ｚｎ、Ｖ及び３価Ｃｒから選ばれる少なくとも１種の金属化合物とを含有し、ｐＨが１．５〜６．０の範囲であることを特徴とする接着下地用の金属表面処理薬剤が開示されている。この金属表面処理薬剤によれば、アミノ化フェノール重合体に含まれる水酸基、アミノ基等の官能基が金属化合物と金属架橋することで、バリア性を向上するために耐食性と耐溶剤性が得られ、更に残存した水酸基により金属材料の表面と強く接着するとされている。このため、ラミネートフィルムや塗膜との層間密着性を向上させることができるとされている。 For example, Patent Document 1 discloses an aminated phenol polymer and at least one metal compound selected from Ti, Zr, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V, and trivalent Cr. And a metal surface treatment agent for an adhesive base, characterized in that the pH is in the range of 1.5 to 6.0. According to this metal surface treatment agent, a functional group such as a hydroxyl group and an amino group contained in the aminated phenol polymer is metal-crosslinked with the metal compound, so that corrosion resistance and solvent resistance can be obtained in order to improve barrier properties. Furthermore, it is said that the remaining hydroxyl group strongly adheres to the surface of the metal material. For this reason, it is supposed that the interlayer adhesiveness with a laminate film or a coating film can be improved.
また、特許文献２には、ビス（２−オキサゾリン）化合物（ａ）と芳香族ポリアミン（ｂ）、必要に応じてビス（２−オキサゾリン）化合物と反応する（ｂ）以外の化合物（ｃ）及び／又は芳香族ポリアミンと反応する（ａ）以外の化合物（ｄ）からなる組成物を反応させて得られる樹脂液に、熱潜在性触媒であるスルホン酸とアルカノールアミンの反応物を加えることにより得られる架橋樹脂原液が開示されている。
しかしながら、特許文献１に記載の金属表面処理薬剤では、ラミネートフィルムを接着させた金属材料の、多くの用途において要求される、金属素材とラミネートフィルムとの高い密着性を満足することはできなかった。このため、ラミネートフィルムを接着させた状態で、十分な密着性と耐食性を示す、金属表面処理組成物、及び当該表面処理組成物により処理されてなる金属材料の開発が望まれていた。 However, the metal surface treatment agent described in Patent Document 1 cannot satisfy the high adhesion between the metal material and the laminate film, which is required in many applications of the metal material to which the laminate film is bonded. . For this reason, there has been a demand for the development of a metal surface treatment composition that exhibits sufficient adhesion and corrosion resistance in a state in which the laminate film is adhered, and a metal material that has been treated with the surface treatment composition.
なお、特許文献２に記載の架橋樹脂原液は、高強度、高靭性、低吸水性で耐熱性に優れる架橋樹脂を与えるとするが、もともと架橋性樹脂成型物を得るためのものであり、金属素材に適用するラミネート接着剤としての適用性については開示も示唆もしていない。 The cross-linked resin undiluted solution described in Patent Document 2 is intended to give a cross-linked resin having high strength, high toughness, low water absorption and excellent heat resistance. It does not disclose or suggest applicability as a laminate adhesive applied to the material.
本発明は、以上のような課題に鑑みてなされたものであり、ラミネートフィルムを接着させた金属材料に、ラミネートフィルムと金属素材との間の十分な密着性と耐食性を付与することができる、金属表面処理組成物により処理されてなる金属材料を提供することを目的とする。 The present invention has been made in view of the above problems, and can impart sufficient adhesion and corrosion resistance between the laminate film and the metal material to the metal material to which the laminate film is bonded. It aims at providing the metal material processed by the metal surface treatment composition.
本発明者らは、金属素材の表面に、多価金属を含む化成処理剤で化成処理を施して、化成皮膜を形成させた後、オキサゾリン基含有樹脂、及び１級アミノ基含有樹脂を含有する金属表面処理組成物を接触させて表面処理を行ったとき、ラミネートフィルムと金属素材とを、高い密着性を持って密着させることができることを見出し、本発明を完成するに至った。 The present inventors include a oxazoline group-containing resin and a primary amino group-containing resin after a chemical conversion treatment is performed on the surface of a metal material with a chemical conversion treatment agent containing a polyvalent metal to form a chemical conversion film. When the surface treatment was carried out by bringing the metal surface treatment composition into contact, it was found that the laminate film and the metal material can be brought into close contact with high adhesion, and the present invention has been completed.
具体的には、本発明は以下のものを提供する。 Specifically, the present invention provides the following.
（１） 金属素材の表面に、多価金属を含む化成処理剤を接触させて、化成皮膜を形成させた後、オキサゾリン基含有樹脂及び１級アミノ基含有樹脂を含有する金属表面処理組成物を接触させて、表面処理層を形成させることにより製造される金属材料。 (1) After a chemical conversion treatment agent containing a polyvalent metal is brought into contact with the surface of a metal material to form a chemical conversion film, a metal surface treatment composition containing an oxazoline group-containing resin and a primary amino group-containing resin is prepared. A metal material produced by bringing it into contact and forming a surface treatment layer.
（２） 樹脂固形分の総量に対する前記オキサゾリン基含有樹脂の含有量は、１０質量％以上９０質量％以下であり、樹脂固形分の総量に対する前記１級アミノ基含有樹脂の含有量は、１０質量％以上９０質量％以下である（１）に記載の金属材料。 (2) The content of the oxazoline group-containing resin with respect to the total amount of resin solids is 10% by mass to 90% by mass, and the content of the primary amino group-containing resin with respect to the total amount of resin solids is 10% by mass. % To 90% by mass of the metal material according to (1).
（３） 前記金属表面処理組成物は、グリシジル基含有樹脂、フェノール性水酸基含有樹脂、カルボキシル基含有樹脂、及びブロックイソシアネート基含有樹脂、からなる群より選ばれる少なくとも１種を更に含有する（１）又は（２）に記載の金属材料。 (3) The metal surface treatment composition further contains at least one selected from the group consisting of a glycidyl group-containing resin, a phenolic hydroxyl group-containing resin, a carboxyl group-containing resin, and a blocked isocyanate group-containing resin (1). Or the metal material as described in (2).
（４） 前記オキサゾリン基含有樹脂は、主鎖がアクリル骨格のオキサゾリン基含有樹脂である、（１）から（３）いずれかに記載の金属材料。 (4) The metal material according to any one of (1) to (3), wherein the oxazoline group-containing resin is an oxazoline group-containing resin having an acrylic skeleton as a main chain.
（５） 前記１級アミノ基含有樹脂は、アリルアミン系重合体である（１）から（４）いずれかに記載の金属材料。 (5) The metal material according to any one of (1) to (4), wherein the primary amino group-containing resin is an allylamine polymer.
ここで、「アリルアミン系重合体」とは、化学式（１）で示される構造単位を有する樹脂をいう。
（６） 前記表面処理層の全有機炭素換算の乾燥皮膜量は、５ｍｇ／ｍ２から１０００ｍｇ／ｍ２である（１）から（５）いずれかに記載の金属材料。 (6) The metal material according to any one of (1) to (5), wherein a dry film amount in terms of total organic carbon of the surface treatment layer is from 5 mg / m 2 to 1000 mg / m 2 .
ここで、「全有機炭素換算の乾燥皮膜量」とは、当該乾燥皮膜中に含まれる全有機炭素量を意味する。なお、全有機炭素量は市販の全有機炭素自動分析装置等を用いて測定することができる。 Here, “the amount of dry film in terms of total organic carbon” means the total amount of organic carbon contained in the dry film. The total organic carbon amount can be measured using a commercially available total organic carbon automatic analyzer or the like.
（７） 前記化成処理剤に含まれる前記多価金属は、ジルコニウム、チタン、及びクロムよりなる群から選ばれる少なくとも１種である（１）から（６）いずれかに記載の金属材料。 (7) The metal material according to any one of (1) to (6), wherein the polyvalent metal contained in the chemical conversion treatment agent is at least one selected from the group consisting of zirconium, titanium, and chromium.
（８） 前記化成皮膜の乾燥重量は、金属元素換算の合計含有量で５ｍｇ／ｍ２から１００ｍｇ／ｍ２である、（１）から（７）いずれかに記載の金属材料。 (8) The metal material according to any one of (1) to (7), wherein the dry weight of the chemical conversion film is 5 mg / m 2 to 100 mg / m 2 in terms of the total content in terms of metal elements.
ここで、「金属元素換算」とは、金属化合物の含有量に金属元素換算係数（金属化合物量を金属得元素量に換算するための係数であり、具体的には、金属化合物中の金属元素の原子量を、金属化合物の分子量で除算した値を意味する）を積算することにより、目的の金属元素量を求めることである。例えば、錯イオンＺｒＦ６ ２−（分子量２０５）１００ｐｐｍのジルコニウムの金属元素換算濃度は１００×（９１／２０５）の計算により４４ｐｐｍと算出される。 Here, the “metal element conversion” is a metal element conversion coefficient (a coefficient for converting a metal compound amount into a metal-derived element amount to a metal compound content, specifically, a metal element in a metal compound. Is the value obtained by dividing the atomic weight by the molecular weight of the metal compound) to obtain the target metal element amount. For example, the metal element equivalent concentration of zirconium of complex ion ZrF 6 2− (molecular weight 205) 100 ppm is calculated to be 44 ppm by calculation of 100 × (91/205).
また、「合計含有量」とは、金属表面処理組成物に含有される当該化合物、当該元素及び当該イオン全ての固形分の含有量の合計質量を指し、当該化合物のうち、いずれかの含有量が０である場合を含むものとする。 The “total content” refers to the total mass of the solid content of the compound, the element, and the ions contained in the metal surface treatment composition, and the content of any of the compounds Including the case where is 0.
（９） 前記金属素材は、アルミニウム及び／又はアルミニウム合金である（１）から（８）いずれかに記載の金属材料。 (9) The metal material according to any one of (1) to (8), wherein the metal material is aluminum and / or an aluminum alloy.
本発明によれば、ラミネートフィルムと金属素材とを、高い密着性を持って接着させることができる金属表面処理組成物を用いて金属素材を表面処理するため、表面処理を行った金属素材にラミネートフィルムを接着させた場合、密着性、耐食性に優れた金属材料を得ることができる。 According to the present invention, since the metal material is surface-treated using the metal surface treatment composition capable of bonding the laminate film and the metal material with high adhesion, the laminate is laminated on the surface-treated metal material. When the film is adhered, a metal material having excellent adhesion and corrosion resistance can be obtained.
以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜金属素材＞
本実施形態に係る金属材料を提供するために用いる金属素材としては、特に限定されないが、例えば、鉄、亜鉛、アルミニウム、又はアルミニウム合金を好適に用いることができる。この中でも特に、加工性に富むこと、耐食性に優れること等の点から、アルミニウム及び／又はアルミニウム合金を用いることが好ましい。
<Metal material>
Although it does not specifically limit as a metal raw material used in order to provide the metal material which concerns on this embodiment, For example, iron, zinc, aluminum, or an aluminum alloy can be used suitably. Among these, it is particularly preferable to use aluminum and / or an aluminum alloy from the viewpoints of excellent workability and excellent corrosion resistance.
＜化成処理剤＞
本実施形態に係る化成処理剤は、多価金属イオンを含む化成処理剤を用いることができる。化成処理剤としては特に限定されないが、クロムイオンを含むリン酸クロメート系化成処理剤であってもよいし、ジルコニウムイオン、又はチタンイオンを含むノンクロム化成処理剤、即ち、ジルコニウム系化成処理剤、又はチタン系化成処理剤であってもよい。これらの化成処理剤としては、市販のものを用いることができる。
<Chemical conversion treatment agent>
As the chemical conversion treatment agent according to the present embodiment, a chemical conversion treatment agent containing a polyvalent metal ion can be used. The chemical conversion treatment agent is not particularly limited, but may be a chromium chromate chemical conversion treatment agent containing chromium ions, a non-chromium chemical conversion treatment agent containing zirconium ions or titanium ions, that is, a zirconium chemical conversion treatment agent, or A titanium chemical conversion treatment agent may be used. As these chemical conversion treatment agents, commercially available products can be used.
化成処理剤による化成皮膜の形成は、当業者に知られた方法で行うことができる。このようにして得られる化成皮膜の乾燥重量は、金属元素換算の合計含有量で５ｍｇ／ｍ２から１００ｍｇ／ｍ２である Formation of the chemical conversion film by the chemical conversion treatment agent can be performed by a method known to those skilled in the art. The dry weight of the chemical conversion film thus obtained is 5 mg / m 2 to 100 mg / m 2 in terms of the total content in terms of metal elements.
＜金属表面処理組成物＞
本実施形態においては、化成処理剤による処理を施した後、金属表面処理組成物を用いて表面処理層を形成させる。金属表面処理組成物は、オキサゾリン基含有樹脂と、１級アミノ基含有樹脂と、を含み、更に、必要に応じて、グリシジル基含有樹脂、フェノール性水酸基含有樹脂、カルボキシル基含有樹脂、及びブロックイソシアネート基含有樹脂からなる群より選ばれる少なくとも一種を含む。
<Metal surface treatment composition>
In the present embodiment, after the treatment with the chemical conversion treatment agent, the surface treatment layer is formed using the metal surface treatment composition. The metal surface treatment composition includes an oxazoline group-containing resin and a primary amino group-containing resin, and, if necessary, a glycidyl group-containing resin, a phenolic hydroxyl group-containing resin, a carboxyl group-containing resin, and a blocked isocyanate. It contains at least one selected from the group consisting of group-containing resins.
［オキサゾリン基含有樹脂］
本実施形態において用いることができる、オキサゾリン基含有樹脂としては、オキサゾリン基を有しているものであれば、特に限定されない。即ち、オキサゾリン基含有樹脂は、主鎖がアクリル骨格のオキサゾリン基含有樹脂、主鎖がスチレン／アクリル骨格のオキサゾリン基含有樹脂、主鎖がスチレン骨格のオキサゾリン基含有樹脂、及び主鎖がアクリロニトリル／スチレン骨格のオキサゾリン基含有樹脂等を用いることができる。本実施形態においては、水溶媒中での安定性に優れ、塗装後の外観が無色透明であるという点から、主鎖がアクリル骨格のオキサゾリン基含有樹脂を用いることが好ましい。オキサゾリン基含有アクリル樹脂としては、市販のものを用いることができ、例えば、「エポクロスＷＳ５００」（商品名、日本触媒社製）、「エポクロスＷＳ７００」（商品名、日本触媒社製）、及び「ＮＫ Ｌｉｎｋｅｒ ＦＸ」（商品名、新中村化学工業社製）を用いることができる。オキサゾリン基含有樹脂のオキサゾリン価は、２００〜２４０であることが好ましい。
[Oxazoline group-containing resin]
The oxazoline group-containing resin that can be used in the present embodiment is not particularly limited as long as it has an oxazoline group. That is, the oxazoline group-containing resin is an oxazoline group-containing resin having an acrylic skeleton as the main chain, an oxazoline group-containing resin having a styrene / acryl skeleton as the main chain, an oxazoline group-containing resin having a styrene skeleton as the main chain, and an acrylonitrile / styrene as the main chain. A skeleton oxazoline group-containing resin or the like can be used. In the present embodiment, it is preferable to use an oxazoline group-containing resin having an acrylic skeleton as the main chain because it is excellent in stability in an aqueous solvent and the appearance after coating is colorless and transparent. As the oxazoline group-containing acrylic resin, commercially available products can be used. For example, “Epocross WS500” (trade name, manufactured by Nippon Shokubai Co., Ltd.), “Epocross WS700” (trade name, manufactured by Nippon Shokubai Co., Ltd.), and “NK” Linker FX "(trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) can be used. The oxazoline value of the oxazoline group-containing resin is preferably 200 to 240.
本実施形態に係る金属表面処理組成物におけるオキサゾリン基含有樹脂の含有量は、樹脂固形分当たり１０質量％以上９０質量％以下であることが好ましく、２０質量％以上６０質量％以下であることが更に好ましい。オキサゾリン基含有樹脂の含有量が１０質量％未満では、オキサゾリン基の含有量が十分でないため、ラミネートフィルムと金属素材との密着性が低下し、９０質量％を超えると、他の構成成分の好ましい含有量を確保することができない。 The content of the oxazoline group-containing resin in the metal surface treatment composition according to the present embodiment is preferably 10% by mass or more and 90% by mass or less, and preferably 20% by mass or more and 60% by mass or less per resin solid content. Further preferred. If the content of the oxazoline group-containing resin is less than 10% by mass, the content of the oxazoline group is not sufficient, so that the adhesion between the laminate film and the metal material is reduced, and if it exceeds 90% by mass, the other constituent components are preferable. Content cannot be secured.
［１級アミノ基含有樹脂］
本実施形態において用いることができる、１級アミノ基含有樹脂としては、１級アミノ基を含有しているものであれば、特に限定されないが、例えば、ポリアリルアミン、ポリリジン、及びポリビニルアミン等を挙げることができる。１級アミノ基含有樹脂としては、市販のものを用いることができ、例えば、ポリアリルアミンとして「ＰＡＡ−００１」（商品名、日東紡績社製）、ポリリジンとして「ポリリジン」（商品名、チッソ社製）、ポリビニルアミンとして、「ＰＶＡＭ−０５９５」（商品名、三菱化学社製）を用いることができる。なお、本実施形態においては、多価金属皮膜との反応性が高く、密着性に優れることから、１級アミン含有樹脂としては、ポリアリルアミンを用いることが好ましい。
[Primary amino group-containing resin]
The primary amino group-containing resin that can be used in this embodiment is not particularly limited as long as it contains a primary amino group, and examples thereof include polyallylamine, polylysine, and polyvinylamine. be able to. As the primary amino group-containing resin, commercially available resins can be used. For example, “PAA-001” (trade name, manufactured by Nitto Boseki Co., Ltd.) as polyallylamine, and “polylysine” (trade name, manufactured by Chisso Corporation) as polylysine. ), “PVAM-0595” (trade name, manufactured by Mitsubishi Chemical Corporation) can be used as the polyvinylamine. In the present embodiment, polyallylamine is preferably used as the primary amine-containing resin because of its high reactivity with the polyvalent metal film and excellent adhesion.
１級アミノ基含有樹脂が、ポリアリルアミンである場合、その平均分子量は、１０００以上６００００以下であることが好ましい。これらの範囲外では、目的とする効果が得られないおそれがある。上記平均分子量は１０００以上１５０００以下であることが更に好ましい。 When the primary amino group-containing resin is polyallylamine, the average molecular weight is preferably 1000 or more and 60000 or less. Outside these ranges, the intended effect may not be obtained. The average molecular weight is more preferably 1000 or more and 15000 or less.
本実施形態に係る金属表面処理組成物における１級アミノ基含有樹脂の含有量は、樹脂固形分当たり１０質量％以上９０質量％以下であることが好ましく、２０質量％以上６０質量％以下であることが更に好ましい。１級アミノ基含有樹脂の含有量が１０質量％未満では、１級アミノ基の含有量が十分でないため、ラミネートフィルムと金属素材との密着性が低下し、９０質量％を超えると、他の構成成分の好ましい含有量を確保することができない。 The content of the primary amino group-containing resin in the metal surface treatment composition according to the present embodiment is preferably 10% by mass or more and 90% by mass or less, and 20% by mass or more and 60% by mass or less per resin solid content. More preferably. If the content of the primary amino group-containing resin is less than 10% by mass, the content of the primary amino group is not sufficient, so that the adhesion between the laminate film and the metal material is reduced, and when the content exceeds 90% by mass, The preferable content of the constituent components cannot be ensured.
［グリシジル基含有樹脂］
本実施形態において用いることができる、グリシジル基含有樹脂としては、複数個のグリシジル基を含有しているものであれば、特に限定されないが、一般に、水溶性・水分散性のエポキシ化合物を用いることができ、例えば、ポリグリセロ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、及びグリセロールポリグリシジルエーテル等を用いることができる。グリシジル基含有樹脂は、加熱により、オキサゾリン基、及びアミノ基と架橋構造を形成し、安定な３次元網目構造の形成に寄与することができる。
[Glycidyl group-containing resin]
The glycidyl group-containing resin that can be used in the present embodiment is not particularly limited as long as it contains a plurality of glycidyl groups. Generally, a water-soluble / water-dispersible epoxy compound is used. For example, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, and the like can be used. The glycidyl group-containing resin forms a crosslinked structure with an oxazoline group and an amino group by heating, and can contribute to the formation of a stable three-dimensional network structure.
グリシジル基含有樹脂としては、市販のものを用いることができ、ポリグリセロールポリグリシジルエーテルとして「デナコールＥＸ−５１２」（商品名、ナガセ化成工業社製）、ジグリセロールポリグリシジルエーテルとして「デナコールＥＸ−４２１」（商品名、ナガセ化成工業社製）、グリセロールポリグリシジルエーテルとして「デナコールＥＸ−３１３」（商品名、ナガセ化成工業社製）を用いることができる。グリシジル基含有樹脂は、例えば、カルボキシル基、アミノ基、アルコール性水酸基、及びフェノール性水酸基等と架橋構造を形成し、金属表面処理組成物を硬化させることができる。グリシジル基含有樹脂のエポキシ当量は、１２０〜１４０であることが好ましい。この範囲外では、目的とする効果が得られない。 As the glycidyl group-containing resin, commercially available resins can be used, and “Denacol EX-512” (trade name, manufactured by Nagase Kasei Kogyo Co., Ltd.) as the polyglycerol polyglycidyl ether, “Denacol EX-421” as the diglycerol polyglycidyl ether. (Trade name, manufactured by Nagase Kasei Kogyo Co., Ltd.) and “Denacol EX-313” (trade name, manufactured by Nagase Kasei Kogyo Co., Ltd.) can be used as the glycerol polyglycidyl ether. The glycidyl group-containing resin can form a crosslinked structure with, for example, a carboxyl group, an amino group, an alcoholic hydroxyl group, and a phenolic hydroxyl group, and can cure the metal surface treatment composition. The epoxy equivalent of the glycidyl group-containing resin is preferably 120 to 140. Outside this range, the intended effect cannot be obtained.
本実施形態に係る金属表面処理組成物におけるグリシジル基含有樹脂の含有量は、樹脂固形分当たり５質量％以上４０質量％以下であることが好ましく、１０質量％以上２０質量％以下であることが更に好ましい。グリシジル基含有樹脂の含有量が５質量％未満では、グリシジル基の含有量が十分ではないため、架橋剤としての効果を十分に得られず、耐水性向上効果が得られない。一方、グリシジル基含有樹脂の含有量が４０質量％を超えると、密着性に寄与するオキサゾリン基含有樹脂、及び１級アミノ基含有樹脂の含有量が低減し、ラミネートフィルムと金属材料との密着性が低下する。 The content of the glycidyl group-containing resin in the metal surface treatment composition according to this embodiment is preferably 5% by mass or more and 40% by mass or less, and preferably 10% by mass or more and 20% by mass or less per resin solid content. Further preferred. If the content of the glycidyl group-containing resin is less than 5% by mass, the content of the glycidyl group is not sufficient, so that the effect as a crosslinking agent cannot be sufficiently obtained, and the water resistance improvement effect cannot be obtained. On the other hand, when the content of the glycidyl group-containing resin exceeds 40% by mass, the content of the oxazoline group-containing resin and the primary amino group-containing resin contributing to adhesion decreases, and the adhesion between the laminate film and the metal material. Decreases.
［フェノール性水酸基含有樹脂］
本実施形態において用いることができる、フェノール性水酸基含有樹脂としては、特に限定されないが、例えば、レゾール型フェノール樹脂を用いることができる。レゾール型フェノール樹脂を用いた場合には、レゾール樹脂に含まれるフェノール性水酸基と、オキサゾリン基含有樹脂に含まれるオキサゾリン基とが、加熱により架橋構造を形成し、強固な３次元の網目構造が形成される。レゾール型フェノール樹脂としては、市販のものを用いることができ、例えば、「ＢＲＬ１４１Ｂ」（商品名、昭和高分子社製）、「ＢＲＬ２８５４」（商品名、昭和高分子社製）、及び「ＢＲＬ１２０Ｚ」（商品名、昭和高分子社製）を用いることができる。
[Phenolic hydroxyl group-containing resin]
Although it does not specifically limit as phenolic hydroxyl group containing resin which can be used in this embodiment, For example, a resol type phenol resin can be used. When a resol type phenol resin is used, the phenolic hydroxyl group contained in the resole resin and the oxazoline group contained in the oxazoline group-containing resin form a crosslinked structure by heating, forming a strong three-dimensional network structure. Is done. As the resol type phenolic resin, commercially available products can be used. For example, “BRL141B” (trade name, manufactured by Showa Polymer Co., Ltd.), “BRL2854” (trade name, manufactured by Showa Polymer Co., Ltd.), and “BRL120Z”. (Trade name, manufactured by Showa Polymer Co., Ltd.) can be used.
本実施形態の金属表面処理組成物においては、フェノール性水酸基含有樹脂は、樹脂固形分当たり５質量％以上４０質量％以下含まれていることが好ましく、１０質量％以上２０質量％以下含まれていることが更に好ましい。フェノール性水酸基含有樹脂の含有量が５質量％未満では、フェノール性水酸基の含有量が十分でないため、架橋剤としての効果が十分に得られず、ラミネートフィルムと金属素材との密着性、及び耐水性の向上効果が得られない。一方、フェノール性水酸基含有樹脂の含有量が４０質量％を超えると、フェノール性水酸基含有樹脂の自己架橋が進行し、ラミネートフィルムと金属材料との密着性が低下する。 In the metal surface treatment composition of the present embodiment, the phenolic hydroxyl group-containing resin is preferably contained in an amount of 5% by mass to 40% by mass and preferably 10% by mass to 20% by mass per resin solid content. More preferably. If the content of the phenolic hydroxyl group-containing resin is less than 5% by mass, the content of the phenolic hydroxyl group is not sufficient, so that the effect as a crosslinking agent cannot be obtained sufficiently, the adhesion between the laminate film and the metal material, and water resistance The effect of improving the property cannot be obtained. On the other hand, when the content of the phenolic hydroxyl group-containing resin exceeds 40% by mass, the self-crosslinking of the phenolic hydroxyl group-containing resin proceeds, and the adhesion between the laminate film and the metal material decreases.
［カルボキシル基含有樹脂］
本実施形態において用いることができる、カルボキシル基含有樹脂としては、特に限定されないが、例えば、水溶性・水分散性アクリル樹脂、及び水溶性・水分散性ポリエステル樹脂等を用いることができる。カルボキシル基含有樹脂に含まれるカルボキシル基と、オキサゾリン基含有樹脂に含まれるオキサゾリン基とが、加熱により架橋構造を形成し、強固な３次元の網目構造が形成される。カルボキシル基含有樹脂としては、市販のものを用いることができ、水溶性・水分散性アクリル樹脂として「ジュリマーＡＣ−１０Ｌ」（商品名、日本純薬社製）、水溶性・水分散性ポリエステル樹脂として「バイロナールＭＤ−１４００」（商品名、東洋紡績社製）を用いることができる。カルボキシル基含有樹脂の分子量は、２０００〜１０００００であることが好ましく、樹脂溶液の酸価が３〜５０ＫＯＨｍｇ／ｇであることが好ましい。これらの範囲外では、目的とする効果が得られないおそれがある。
[Carboxyl group-containing resin]
Although it does not specifically limit as carboxyl group-containing resin which can be used in this embodiment, For example, water-soluble and water-dispersible acrylic resin, water-soluble and water-dispersible polyester resin, etc. can be used. The carboxyl group contained in the carboxyl group-containing resin and the oxazoline group contained in the oxazoline group-containing resin form a crosslinked structure by heating to form a strong three-dimensional network structure. As the carboxyl group-containing resin, commercially available resins can be used. As a water-soluble / water-dispersible acrylic resin, “Jurimer AC-10L” (trade name, manufactured by Nippon Pure Chemical Co., Ltd.), a water-soluble / water-dispersible polyester resin. “Vitalnal MD-1400” (trade name, manufactured by Toyobo Co., Ltd.) can be used. The molecular weight of the carboxyl group-containing resin is preferably 2000 to 100,000, and the acid value of the resin solution is preferably 3 to 50 KOHmg / g. Outside these ranges, the intended effect may not be obtained.
本実施形態の金属表面処理組成物においては、カルボキシル基含有樹脂は、樹脂固形分当たり５質量％以上４０質量％以下含まれていることが好ましく、１０質量％以上２０質量％以下含まれていることが更に好ましい。カルボキシル基含有樹脂の含有量が５質量％未満では、カルボキシル基の含有量が十分でないため、架橋剤としての効果が十分ではなく、耐水性向上効果が得られない。一方、カルボキシル基含有樹脂の含有量が、４０質量％を超えると、密着性に寄与するオキサゾリン基含有樹脂、１級アミノ基含有樹脂、及びグリシジル基含有樹脂の含有量が低減し、ラミネートフィルムと金属材料との密着性が低下する。 In the metal surface treatment composition of the present embodiment, the carboxyl group-containing resin is preferably contained in an amount of 5% by mass or more and 40% by mass or less per resin solid content, and is contained in an amount of 10% by mass or more and 20% by mass or less. More preferably. If the content of the carboxyl group-containing resin is less than 5% by mass, the content of the carboxyl group is not sufficient, so that the effect as a crosslinking agent is not sufficient, and the water resistance improvement effect cannot be obtained. On the other hand, when the content of the carboxyl group-containing resin exceeds 40% by mass, the content of the oxazoline group-containing resin, the primary amino group-containing resin, and the glycidyl group-containing resin contributing to adhesion decreases, and the laminate film Adhesion with metal materials is reduced.
［ブロックイソシアネート基含有樹脂］
本実施形態において用いることができる、ブロックイソシアネート基含有樹脂としては、特に限定されないが、例えば、水溶性・水分散性ウレタン樹脂等を用いることができる。ブロックイソシアネート基含有樹脂は、加熱により、１級アミノ基含有樹脂のアミノ基や、フェノール性水酸基含有樹脂のフェノール性水酸基と、架橋構造を形成し、３次元網目構造を形成することができる。ブロックイソシアネート基含有樹脂としては、市販のものを用いることができ、水溶性・水分散性ウレタン樹脂として「エラストロンＢＮ−６９」（商品名、第一工業製薬社製）、及び「エラストロンＢＮ−３１」（商品名、第一工業製薬社製）を用いることができる。
[Block isocyanate group-containing resin]
Although it does not specifically limit as blocked isocyanate group containing resin which can be used in this embodiment, For example, water-soluble and water-dispersible urethane resin etc. can be used. The blocked isocyanate group-containing resin can form a three-dimensional network structure by forming a crosslinked structure with the amino group of the primary amino group-containing resin or the phenolic hydroxyl group of the phenolic hydroxyl group-containing resin by heating. As the blocked isocyanate group-containing resin, a commercially available resin can be used. As a water-soluble / water-dispersible urethane resin, “Elastolon BN-69” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and “Elastolon BN-31” are used. (Trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
本実施形態の金属表面処理組成物においては、ブロックイソシアネート基含有樹脂は、樹脂固形分当たり５質量％以上４０質量％以下含まれていることが好ましく、１０質量％以上２０質量％以下含まれていることが更に好ましい。ブロックイソシアネート基含有樹脂の含有量が５質量％未満では、ブロックイソシアネート基の含有量が十分でないため、架橋剤としての効果が十分ではなく、ラミネートフィルムと金属素材との密着性、及び耐水性の向上効果が得られない。一方、ブロックイソシアネート基含有樹脂の含有量が、４０％を超えると、密着性に寄与するオキサゾリン基含有樹脂、１級アミノ基含有樹脂、及びグリシジル基含有樹脂の含有量が低減し、ラミネートフィルムと金属材料との密着性が低下する。 In the metal surface treatment composition of the present embodiment, the blocked isocyanate group-containing resin is preferably contained in an amount of 5% by mass or more and 40% by mass or less per resin solid content, and is contained in an amount of 10% by mass or more and 20% by mass or less. More preferably. If the content of the blocked isocyanate group-containing resin is less than 5% by mass, the content of the blocked isocyanate group is not sufficient, so the effect as a crosslinking agent is not sufficient, the adhesion between the laminate film and the metal material, and water resistance Improvement effect cannot be obtained. On the other hand, if the content of the blocked isocyanate group-containing resin exceeds 40%, the content of the oxazoline group-containing resin, primary amino group-containing resin, and glycidyl group-containing resin contributing to adhesion decreases, and the laminate film Adhesion with metal materials is reduced.
［乾燥皮膜量］
上述の金属表面処理組成物により形成される表面処理層の全有機炭素換算の乾燥皮膜量は、５ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下であることが好ましい。乾燥皮膜量が５ｍｇ／ｍ２より少ない場合には、樹脂量（官能基量）が少ないため密着性が低下する。１０００ｍｇ／ｍ２より多い場合には、膜厚が厚くなり、金属表面処理組成物の凝集破壊により密着性が低下する。
[Dry film amount]
The amount of the dry film in terms of total organic carbon of the surface treatment layer formed by the above-described metal surface treatment composition is preferably 5 mg / m 2 or more and 1000 mg / m 2 or less. When the dry film amount is less than 5 mg / m 2 , the adhesiveness decreases because the resin amount (functional group amount) is small. When the amount is more than 1000 mg / m 2 , the film thickness becomes thick, and the adhesiveness decreases due to cohesive failure of the metal surface treatment composition.
＜ラミネートフィルム＞
本実施形態において用いることができる、ラミネートフィルムの貼り付け方法としては、ドライラミネート法、押出ラミネート法を挙げることができるが、特に限定されない。また、ラミネートフィルムの素材としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリプロピレン（ＰＰ）、ポリカーボネート（ＰＣ）、トリアセチルセルロース（ＴＡＣ）、ポリ塩化ビニル（ＰＶＣ）、ポリエステル、ポリオレフィン、アクリル等の熱可塑性の樹脂を挙げることができる。
<Laminated film>
Examples of the method for attaching a laminate film that can be used in the present embodiment include a dry lamination method and an extrusion lamination method, but are not particularly limited. In addition, as the material of the laminate film, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polycarbonate (PC), triacetyl cellulose (TAC), polyvinyl chloride (PVC), polyester, polyolefin, Mention may be made of thermoplastic resins such as acrylic.
＜金属材料＞
本実施形態に係る金属材料は、金属素材の表面を化成処理剤で化成処理し、次いで、金属表面処理組成物を塗布して、表面処理層を形成させる。そして、形成された表面処理層の上からラミネートフィルムを接着させ、ラミネート構造を形成させた金属材料を得る。
<Metal material>
In the metal material according to the present embodiment, the surface of the metal material is subjected to a chemical conversion treatment with a chemical conversion treatment agent, and then a metal surface treatment composition is applied to form a surface treatment layer. Then, a laminate film is adhered on the formed surface treatment layer to obtain a metal material on which a laminate structure is formed.
［化成処理］
本実施形態においては、化成処理剤を用いて金属素材の表面に化成処理を施す。化成処理を施す方法は特に限定されず、例えばスプレー処理、浸漬処理等による方法が挙げられる。化成処理に先立って、必要に応じて脱脂処理やエッチング処理を施した後に、化成処理剤を適用してもよい。
[Chemical conversion treatment]
In this embodiment, a chemical conversion treatment is performed on the surface of a metal material using a chemical conversion treatment agent. A method for performing the chemical conversion treatment is not particularly limited, and examples thereof include a spray treatment, a dipping treatment, and the like. Prior to the chemical conversion treatment, the chemical conversion treatment agent may be applied after performing a degreasing treatment or an etching treatment as necessary.
［表面処理層の形成］
本実施形態においては、化成処理が施された金属素材の表面に、後述する金属表面処理組成物を塗布する。金属表面処理組成物を塗布する方法は特に限定されず、例えば、ロールコート法、バーコート法、スプレー処理法、浸漬処理法等による方法が挙げられる。金属表面処理組成物を金属素材の表面に塗布した後は、４０℃から１６０℃において、２秒から６０秒加熱して、金属表面処理組成物を乾燥させる。
[Formation of surface treatment layer]
In the present embodiment, a metal surface treatment composition to be described later is applied to the surface of a metal material that has been subjected to chemical conversion treatment. The method for applying the metal surface treatment composition is not particularly limited, and examples thereof include a roll coating method, a bar coating method, a spray treatment method, and a dipping treatment method. After apply | coating the metal surface treatment composition to the surface of a metal raw material, it heats at 40 to 160 degreeC for 2 to 60 second, and dries a metal surface treatment composition.
＜化成皮膜１の形成（Ｚｒ皮膜）＞
厚さ０．２８ｍｍのアルミニウム合金３００４板材を、「サーフクリーナーＥＣ７１０」（商品名、日本ペイント社製）の２％希釈水溶液を用いて、６０℃で６秒間、スプレー処理した。これを、水道水を用いて、６秒間、スプレー処理により洗浄した。次に、ジルコニウム化合物系化成処理剤である「アルサーフ４０２」（商品名、日本ペイント社製）の２％希釈水溶液を用いて、５０℃で４秒間スプレー処理を行い、ジルコニウム量で１０ｍｇ／ｍ２のジルコニウム皮膜を形成させた。ジルコニウム皮膜を形成させたアルミニウム合金は、水道水を用いて６秒間、スプレー処理により洗浄した。余剰の水分をゴムロールで除いた後、コンベア式オーブンを用いて、５０℃にて１０秒間乾燥した。
<Formation of chemical conversion film 1 (Zr film)>
An aluminum alloy 3004 plate having a thickness of 0.28 mm was spray-treated at 60 ° C. for 6 seconds using a 2% diluted aqueous solution of “Surf Cleaner EC710” (trade name, manufactured by Nippon Paint Co., Ltd.). This was washed by spraying with tap water for 6 seconds. Next, spray treatment was performed at 50 ° C. for 4 seconds using a 2% diluted aqueous solution of “Alsurf 402” (trade name, manufactured by Nippon Paint Co., Ltd.), which is a zirconium compound-based chemical conversion treatment agent, and the amount of zirconium was 10 mg / m 2. A zirconium film was formed. The aluminum alloy on which the zirconium film was formed was cleaned by spraying for 6 seconds using tap water. After excess water was removed with a rubber roll, it was dried at 50 ° C. for 10 seconds using a conveyor oven.
＜化成皮膜２の形成（Ｚｒ／Ｐ皮膜）＞
化成皮膜１の形成方法において、ジルコニウム化合物系化成処理剤「アルサーフ４０２」の代わりに、ジルコニウム化合物・リン酸系化成処理剤である「アルサーフ４１３０」（商品名、日本ペイント社製）の２％希釈水溶液を用い、４５℃で３秒間スプレー処理を行った。これ以外は、化成皮膜１の形成方法と同様の方法により、ジルコニウム量で５ｍｇ／ｍ２のリン酸ジルコニウム皮膜を形成させた。更に、「アルサーフ４１３０」の２％希釈水溶液による処理温度を上昇させ、処理時間を延長させて、ジルコニウム量で１０、２０、５０、１００ｍｇ／ｍ２のリン酸ジルコニウム皮膜を形成させた。
<Formation of chemical conversion film 2 (Zr / P film)>
In the formation method of the chemical conversion film 1, 2% dilution of “Alsurf 4130” (trade name, manufactured by Nippon Paint Co., Ltd.), which is a zirconium compound / phosphoric acid-based chemical conversion treatment agent, instead of the zirconium compound-based chemical conversion treatment agent “Alsurf 402” Spray treatment was performed at 45 ° C. for 3 seconds using an aqueous solution. Except for this, a zirconium phosphate film having a zirconium amount of 5 mg / m 2 was formed by the same method as the chemical film 1. Furthermore, the treatment temperature with a 2% diluted aqueous solution of “Alsurf 4130” was increased, and the treatment time was extended to form zirconium phosphate coatings with 10, 20, 50, and 100 mg / m 2 of zirconium.
＜化成皮膜３の形成（Ｔｉ／Ｐ皮膜）＞
化成皮膜１の形成方法において、ジルコニウム化合物系化成処理剤「アルサーフ４０２」の代わりに、チタン化合物・リン酸系化成処理剤である「アルサーフＬＸ−３４０」（商品名、日本ペイント社製）の２％希釈溶液を用いた。これ以外は、化成皮膜１の形成方法と同様の方法により、チタン量で１０ｍｇ／ｍ２のリン酸チタン皮膜を形成させた。
<Formation of chemical conversion film 3 (Ti / P film)>
In the formation method of the chemical conversion coating 1, in place of the zirconium compound-based chemical conversion treatment agent “Alsurf 402”, “Alsurf LX-340” (trade name, manufactured by Nippon Paint Co., Ltd.), which is a titanium compound / phosphate-based chemical conversion treatment agent, is used. % Diluted solution was used. Except for this, a titanium phosphate film having a titanium content of 10 mg / m 2 was formed by the same method as the method for forming the chemical conversion film 1.
＜化成皮膜４の形成（Ｚｒ／Ｔｉ／Ｐ皮膜）＞
化成皮膜１の形成方法において、ジルコニウム化合物系化成処理剤「アルサーフ４０２」の代わりに、「アルサーフ４１３０」（商品名、日本ペイント社製）と「アルサーフＬＸ−３０４」との各１％混合水溶液を用い、５０℃で４秒間スプレー処理を行った。これ以外は、化成皮膜１の形成方法と同様の方法により、ジルコニウム量とチタン量の和が１０ｍｇ／ｍ２となるように、リン酸ジルコニウム・リン酸チタン皮膜を形成させた。
<Formation of chemical conversion film 4 (Zr / Ti / P film)>
In the formation method of the chemical conversion film 1, instead of the zirconium compound-based chemical conversion treatment agent “Alsurf 402”, each 1% mixed aqueous solution of “Alsurf 4130” (trade name, manufactured by Nippon Paint Co., Ltd.) and “Alsurf LX-304” was used. And sprayed at 50 ° C. for 4 seconds. Except for this, a zirconium phosphate / titanium phosphate coating was formed by a method similar to the method of forming the chemical conversion coating 1 such that the sum of the zirconium content and the titanium content was 10 mg / m 2 .
＜化成皮膜５の形成（Ｃｒ／Ｐ皮膜）＞
化成皮膜１の形成方法において、ジルコニウム化合物系化成処理剤「アルサーフ４０２」の代わりに、クロム化合物・リン酸系化成処理剤である「アルサーフ４０８」（商品名、日本ペイント社製）１．５％と、反応促進剤である「アルサーフ４８」（商品名、日本ペイント社製）０．５％との混合水溶液を用い、４０℃で３秒間スプレー処理を行った。これ以外は、化成皮膜１の形成方法と同様の方法により、クロム量で１０ｍｇ／ｍ２のリン酸クロム皮膜を形成させた。
<Formation of chemical conversion film 5 (Cr / P film)>
In the formation method of the chemical conversion film 1, “Alsurf 408” (trade name, manufactured by Nippon Paint Co., Ltd.) 1.5%, which is a chromium compound / phosphoric acid-based chemical conversion treatment agent, is used instead of the zirconium compound-based chemical conversion treatment agent “Alsurf 402”. Then, spray treatment was performed at 40 ° C. for 3 seconds using a mixed aqueous solution of 0.5% of “Alsurf 48” (trade name, manufactured by Nippon Paint Co., Ltd.) which is a reaction accelerator. Except for this, a chromium phosphate film having a chromium content of 10 mg / m 2 was formed by the same method as the method for forming the chemical conversion film 1.
＜実施例１〜１７＞
オキサゾリン基含有樹脂として「エポクロスＷＳ−７００」（商品名、日本触媒社製、オキサゾリン価２２０）と、１級アミノ基含有樹脂として「ＰＡＡ−０５」（商品名、日東紡績社製、ポリアリルアミン、分子量１５０００）とを、表１に記載する有効成分重量比で混合した。これを、リバースロールコーターを用いて、化成皮膜１から化成皮膜５のいずれかの化成皮膜を形成させたアルミニウム合金に、皮膜量が片面当たり、表１に記載の皮膜量となるように塗布し、コンベア式オーブンを用いて８０℃で、２０秒間乾燥させた。
<Examples 1 to 17>
“Epocross WS-700” (trade name, manufactured by Nippon Shokubai Co., Ltd., oxazoline number 220) as the oxazoline group-containing resin, and “PAA-05” (trade name, manufactured by Nitto Boseki Co., Ltd., polyallylamine, (Molecular weight 15000) were mixed at the active ingredient weight ratio described in Table 1. Using a reverse roll coater, this was applied to the aluminum alloy on which any one of the conversion coatings 1 to 5 was formed so that the coating amount per side was the coating amount shown in Table 1. It was dried at 80 ° C. for 20 seconds using a conveyor type oven.
＜実施例１８〜３０＞
実施例１から実施例１７で用いた、各種樹脂に加えて、更にグリシジル基含有樹脂として、「デナコールＥＸ５１２」（商品名、ナガセケムテックス社製、エポキシ当量１８３）、カルボキシル基含有樹脂として、「ＥＭＡ１０１２」（商品名、日本ペイント社製、樹脂溶液としての酸価３０ｍｇ／ＫＯＨ）、フェノール性水酸基含有樹脂として、「ショーノールＢＲＬ−１４１Ｂ」（商品名、昭和高分子社製）、及びブロックイソシアネート基含有樹脂として、「エラストロンＢＮ−４４」（商品名、第一工業製薬社製）を表１に示す量で混合して金属表面処理組成物を調整し、実施例１から実施例１７と同様にアルミニウム合金に塗布し、乾燥させた。
<Examples 18 to 30>
In addition to various resins used in Example 1 to Example 17, as a glycidyl group-containing resin, “Denacol EX512” (trade name, manufactured by Nagase ChemteX Corporation, epoxy equivalent 183), as a carboxyl group-containing resin, “ “EMA1012” (trade name, manufactured by Nippon Paint Co., Ltd., acid value 30 mg / KOH as a resin solution), “Shonol BRL-141B” (trade name, manufactured by Showa Polymer Co., Ltd.), and blocked isocyanate as a phenolic hydroxyl group-containing resin As a group-containing resin, “Elastolon BN-44” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was mixed in the amount shown in Table 1 to prepare a metal surface treatment composition, and the same as in Examples 1 to 17 Was applied to an aluminum alloy and dried.
＜比較例１＞
化成皮膜の形成を行わずに、表２に示された組成のアルミニウム合金に金属表面処理組成物を塗布し、乾燥させた。
<Comparative Example 1>
Without forming the chemical conversion film, the metal surface treatment composition was applied to an aluminum alloy having the composition shown in Table 2 and dried.
＜比較例２〜６＞
化成皮膜１から化成皮膜５のいずれかの化成皮膜を形成させた後、金属表面処理組成物を塗布していないアルミニウム合金を用意した。
<Comparative Examples 2-6>
After forming any chemical conversion film from chemical conversion film 1 to chemical conversion film 5, an aluminum alloy not coated with the metal surface treatment composition was prepared.
＜比較例７〜１１＞
化成皮膜１から化成皮膜５のいずれかの化成皮膜を形成させた後、アルミニウム合金に、オキサゾリン基含有樹脂、１級アミノ基含有樹脂、グリシジル基含有樹脂、カルボキシル基含有樹脂、及びフェノール性水酸基含有樹脂のそれぞれを単独で塗布、乾燥させた。
<Comparative Examples 7-11>
After forming any one of the chemical conversion films 1 to 5, the aluminum alloy is subjected to oxazoline group-containing resin, primary amino group-containing resin, glycidyl group-containing resin, carboxyl group-containing resin, and phenolic hydroxyl group-containing. Each of the resins was applied and dried alone.
＜ラミネート板の形成＞
実施例１から実施例３０、比較例１から比較例１１で表面処理を施したアルミニウム合金板に、加熱ローラーを用いて、「メリネックス８５０」（商品名、アイシーアイジャパン社製、フィルム厚１５μｍ）を１５０℃、ロール速度３０ｍ／ｍｉｎで圧着した。このフィルム貼り付け板を、コンベア式オーブンを用いて２４０℃で２０秒間再加熱し、オーブンから取り出した直後に水冷した。
<Formation of laminate plate>
Using the heating roller on the aluminum alloy plate subjected to the surface treatment in Examples 1 to 30 and Comparative Examples 1 to 11, "Melenex 850" (trade name, manufactured by IC Corporation Japan, film thickness 15 µm) Was pressure-bonded at 150 ° C. and a roll speed of 30 m / min. The film pasting plate was reheated at 240 ° C. for 20 seconds using a conveyor oven, and water-cooled immediately after removal from the oven.
＜密着力の評価＞
フィルム貼り付け板を１５０ｍｍ×５０ｍｍの金属板２枚に切断した。この金属板をフィルム面同士で重ね、ホットプレスを用いて、２４０℃、７ｋｇｆ／ｃｍ２で６０秒間圧着した。この操作により、フィルム同士は完全に溶融し、接着した。圧着した金属板を１５０ｍｍ×５ｍｍに切り出し、試験片とした。試験片をオートクレーブに入れ、１２５℃の加圧蒸気中で３０分間加熱処理した（レトルト処理）。レトルト処理を行った試験片を、「テンシロン引張り試験機」（商品名、東洋ボールドウィン社製）を用いて、フィルム面を引き剥がす際に係る剥離強度（ｋｇｆ／５ｍｍ幅）を測定した。剥離強度が１．５（ｋｇｆ／５ｍｍ幅）以上を以って、合格とした。
<Evaluation of adhesion>
The film sticking plate was cut into two 150 mm × 50 mm metal plates. This metal plate was piled up between the film surfaces, and pressure-bonded at 240 ° C. and 7 kgf / cm 2 for 60 seconds using a hot press. By this operation, the films were completely melted and bonded. The pressed metal plate was cut out to 150 mm × 5 mm, and used as a test piece. The test piece was placed in an autoclave and heat-treated in a pressurized steam at 125 ° C. for 30 minutes (retort treatment). Using a “Tensilon tensile tester” (trade name, manufactured by Toyo Baldwin Co., Ltd.), the peel strength (kgf / 5 mm width) when the film surface was peeled off was measured on the test piece subjected to the retort treatment. A peel strength of 1.5 (kgf / 5 mm width) or more was regarded as acceptable.
＜耐食性の評価＞
フィルム貼り付け板のフィルム面が外側になるように、カップ加工を行った後、カップ側面にカッターにより円周状に切れ込みを入れた。このカップを５０℃に保持した０．５％クエン酸、０．５％塩化ナトリウム混合溶液に７２時間浸漬し、側面の切れ込みからの腐食部分の先端までの長さ（腐食長さ）を以下の基準で評価した。４又は５を以って合格とした。
５；腐食長さ １ｍｍ未満
４；腐食長さ １ｍｍ以上、２ｍｍ未満
３；腐食長さ ２ｍｍ以上、３ｍｍ未満
２；腐食長さ ３ｍｍ以上、５ｍｍ未満
１；腐食長さ ５ｍｍ以上
<Evaluation of corrosion resistance>
After performing cup processing so that the film surface of the film sticking plate was on the outside, a cut was made in a circumferential shape with a cutter on the side surface of the cup. This cup is immersed in a 0.5% citric acid and 0.5% sodium chloride mixed solution maintained at 50 ° C. for 72 hours, and the length from the side cut to the tip of the corroded portion (corrosion length) is as follows: Evaluated by criteria. A score of 4 or 5 was accepted.
5; Corrosion length 1 mm or less 4; Corrosion length 1 mm or more and less than 2 mm 3; Corrosion length 2 mm or more and less than 3 mm 2; Corrosion length 3 mm or more and less than 5 mm 1; Corrosion length 5 mm or more
Claims (8)
前記化成処理剤に含まれる前記多価金属は、ジルコニウム、チタン、及びクロムよりなる群から選ばれる少なくとも１種である金属材料。 After a chemical conversion treatment agent containing a polyvalent metal is brought into contact with the surface of the metal material to form a chemical conversion film, a metal surface treatment composition containing an oxazoline group-containing resin and a primary amino group-containing resin is contacted. A metal material produced by forming a surface treatment layer ,
The said polyvalent metal contained in the said chemical conversion treatment agent is a metal material which is at least 1 sort (s) chosen from the group which consists of a zirconium, titanium, and chromium .
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| JP5077651B2 (en) * | 2007-05-31 | 2012-11-21 | 東洋製罐株式会社 | Resin-coated metal plate and molded body using the same |
| JP5229131B2 (en) * | 2009-06-26 | 2013-07-03 | 株式会社豊田中央研究所 | Corrosion-resistant conductive film, corrosion-resistant conductive material, polymer electrolyte fuel cell and separator thereof, and method for producing corrosion-resistant conductive material |
| US8613807B2 (en) | 2009-02-06 | 2013-12-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Conductive film, corrosion-resistant conduction film, corrosion-resistant conduction material and process for producing the same |
| JP5577653B2 (en) * | 2009-09-03 | 2014-08-27 | 凸版印刷株式会社 | Battery packaging material, method for producing the same, and secondary battery |
| JP5845563B2 (en) | 2010-09-15 | 2016-01-20 | Ｊｆｅスチール株式会社 | Manufacturing method of steel plate for containers |
| JP5720026B2 (en) * | 2011-02-08 | 2015-05-20 | 日新製鋼株式会社 | Battery exterior laminate and secondary battery |
| JP6146954B2 (en) * | 2012-03-09 | 2017-06-14 | 日本ペイント・サーフケミカルズ株式会社 | Chemical conversion treatment agent and chemical conversion treatment film |
| JP2014080637A (en) | 2012-10-12 | 2014-05-08 | Nippon Paint Co Ltd | Surface treating agent, and surface treating method |
| JP6055085B2 (en) | 2013-04-03 | 2016-12-27 | 日本ペイント・サーフケミカルズ株式会社 | Chemical conversion treatment agent and metal surface treatment method |
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