JP2008184557A - Metal surface-treating composition and metal surface-treating method using the composition - Google Patents
Metal surface-treating composition and metal surface-treating method using the composition Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 27
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 67
- 238000004381 surface treatment Methods 0.000 claims abstract description 58
- 239000007769 metal material Substances 0.000 claims abstract description 49
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000011282 treatment Methods 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 38
- 125000002091 cationic group Chemical group 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000002335 surface treatment layer Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 108010039918 Polylysine Proteins 0.000 claims description 7
- 229920000656 polylysine Polymers 0.000 claims description 7
- 229920000083 poly(allylamine) Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 239000005001 laminate film Substances 0.000 abstract description 24
- 239000000853 adhesive Substances 0.000 abstract description 14
- 230000001070 adhesive effect Effects 0.000 abstract description 14
- 238000012360 testing method Methods 0.000 abstract description 11
- 150000002739 metals Chemical class 0.000 abstract 1
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- 239000010408 film Substances 0.000 description 11
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- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
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- 239000011651 chromium Substances 0.000 description 3
- 239000012787 coverlay film Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical group NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- 229920002873 Polyethylenimine Polymers 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
- 239000002253 acid Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical group O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 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
- 238000003672 processing method Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 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
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
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、及びこれを用いた金属表面処理方法に関する。 The present invention relates to a metal surface treatment composition that is applied to the surface of a metal material and improves the adhesion between a laminate film and the metal material, and a metal surface treatment method using the same.
従来から、金属材料表面を保護し、意匠を施すために、金属素材の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ることから、食品缶等に用いられる包装用の金属材料の表面保護剤として、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 surface of the metal material is laminated. Laminate films are often used as surface protective agents for metal materials for packaging used in food cans and the like because of their excellent moldability, corrosion resistance, and barrier properties of contents.
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、金属材料の美観及び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 has been a major cause of reducing the aesthetics and corrosion resistance of the metal material.
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 problems in the laminated metal material, prior to laminating, a surface treatment layer by a metal surface treatment composition is formed on the surface of the metal material, and the laminate film and the metal material Improvement of the adhesion is performed.
例えば、特許文献１には、ドライラミネーション法に適した水性接着剤であって、イソシアネート基を有するカルボキシル基含有ウレタンプレポリマーの中和物、及びビニルモノマーを含む分散液中のビニルモノマーを重合した水性分散液、エポキシ樹脂、並びにヒダントイン骨格を有する酸ヒドラジド又はイミダゾール系化合物を含有する水性接着剤が開示されている。この水性接着剤によれば、ウレタン成分の有する接着性をより向上させ、かつ、耐水性も向上させることができるとされている。更に、耐白化性を有するとされている。 For example, Patent Document 1 discloses a water-based adhesive suitable for a dry lamination method, wherein a neutralized product of a carboxyl group-containing urethane prepolymer having an isocyanate group and a vinyl monomer in a dispersion containing a vinyl monomer are polymerized. An aqueous adhesive containing an aqueous dispersion, an epoxy resin, and an acid hydrazide or imidazole compound having a hydantoin skeleton is disclosed. According to this water-based adhesive, it is said that the adhesiveness of the urethane component can be further improved and the water resistance can be improved. Furthermore, it is supposed to have whitening resistance.
また、特許文献２には、フェノキシ樹脂及びレゾール型フェノールホルムアルデヒド樹脂を含有することを特徴とするプラスチックフィルム被覆金属板用接着剤が開示されている。このプラスチックフィルム被覆金属板用接着剤によれば、接着部が水、熱水及び水蒸気に接触する条件下でも経時劣化することがないとされている。 Further, Patent Document 2 discloses an adhesive for plastic film-covered metal plates, which contains a phenoxy resin and a resol type phenol formaldehyde resin. According to this adhesive for plastic film-covered metal plates, it is said that the adhesive portion does not deteriorate with time even under conditions in which the bonded portion is in contact with water, hot water and water vapor.
更に、特許文献３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。 Further, Patent Document 3 discloses a compound (c) other than (b) which reacts with a bis (2-oxazoline) compound (a), an aromatic polyamine (b), and optionally a bis (2-oxazoline) compound. It is obtained by adding a reaction product of a sulfonic acid and an alkanolamine, which are thermal latent catalysts, to a resin liquid obtained by reacting a composition comprising a compound (d) other than (a) that reacts with an aromatic polyamine. A cross-linked resin stock solution is disclosed.
同様に、特許文献４には、（ａ）カルボキシル基含有アクリルゴム１００重量部、（ｂ）フェノール樹脂５〜５０重量部、（ｃ）エポキシ樹脂１０〜９０重量部、（ｄ）硬化剤０．１〜１０重量部、に対し、アクリルゴム架橋剤として、（ｅ）ビス−オキサゾリンを０．０１〜５．０重量部添加することを特徴とするカバーレイフィルム用接着剤組成物が開示されている。
しかしながら、特許文献１に記載の水性接着剤は、複雑な製造工程を経て製造されるものであり、長期間の保存により性質が変わりやすいという問題点を有する。更に、例えば熱水中１２０℃、３０分のような過酷な条件における接着強度は十分ではない。 However, the water-based adhesive described in Patent Document 1 is produced through a complicated production process, and has a problem that its properties are easily changed by long-term storage. Furthermore, the adhesive strength under severe conditions such as 120 ° C. for 30 minutes in hot water is not sufficient.
また、特許文献２に記載のプラスチックフィルム被覆金属板用接着剤は、接着後に高度の加工を加え、その後レトルト処理した場合、凝集力不足に起因する接着破壊が発生する等の問題点があった。 Further, the adhesive for plastic film-covered metal plate described in Patent Document 2 has a problem such as adhesion failure caused by insufficient cohesive force when a high degree of processing is applied after adhesion and then retort treatment is performed. .
特許文献３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 3 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 to be applied.
特許文献４に記載のカバーレイフィルム用接着剤組成物は、フレキシブルプリント回路基板用カバーレイフィルムの製造を目的としており、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 adhesive composition for coverlay film described in Patent Document 4 is intended for the production of a coverlay film for a flexible printed circuit board, and discloses and suggests applicability as a laminate adhesive applied to a metal material. Absent.
本発明は、このような課題に鑑みてなされたものであり、水系のラミネート接着剤であって、耐水試験後のラミネートフィルムと金属素材との密着性を高く維持するための、金属表面処理組成物を提供することを目的とする。 The present invention has been made in view of such problems, and is a water-based laminating adhesive, which is a metal surface treatment composition for maintaining high adhesion between a laminate film after a water resistance test and a metal material. The purpose is to provide goods.
本発明者らは、オキサゾリン基含有樹脂、フェノール性水酸基含有樹脂、及びカチオン性基含有樹脂を含む金属表面処理組成物を用いたときに、ラミネートフィルムと金属素材との密着性を高く保てることを見出し、本発明を完成するに至った。 When the metal surface treatment composition containing the oxazoline group-containing resin, the phenolic hydroxyl group-containing resin, and the cationic group-containing resin is used, the present inventors can maintain high adhesion between the laminate film and the metal material. The headline and the present invention were completed.
（１） 金属の表面処理に用いられる金属表面処理組成物であって、金属表面処理組成物固形分中、少なくとも２つのオキサゾリン基を含有するオキサゾリン基含有アクリル樹脂を５質量％以上９０質量％以下と、少なくとも２つのフェノール性水酸基を含有するフェノール性水酸基含有樹脂を５質量％以上９０質量％以下と、カチオン性基含有樹脂を５質量％以上９０質量％以下とを含み、前記カチオン性基含有樹脂が、樹脂固形分中、５．０ｍｅｑ／ｇ以上の１級アミノ基を含有するカチオン性基含有樹脂である、金属表面処理組成物。 (1) A metal surface treatment composition used for metal surface treatment, wherein the oxazoline group-containing acrylic resin containing at least two oxazoline groups in the solid content of the metal surface treatment composition is 5% by mass or more and 90% by mass or less. And 5% to 90% by mass of a phenolic hydroxyl group-containing resin containing at least two phenolic hydroxyl groups, and 5% to 90% by mass of a cationic group-containing resin. A metal surface treatment composition, wherein the resin is a cationic group-containing resin containing a primary amino group of 5.0 meq / g or more in the resin solid content.
本発明における、「カチオン性基」は、具体的には、アミノ基、イミノ基、グアニジン基、及びビグアニド基からなる群から選択される少なくとも１種を意味する。 In the present invention, the “cationic group” specifically means at least one selected from the group consisting of an amino group, an imino group, a guanidine group, and a biguanide group.
（２） 前記カチオン性基含有樹脂が、ポリリジン及び／又はポリアリルアミンである、（１）に記載の金属表面処理組成物。 (2) The metal surface treatment composition according to (1), wherein the cationic group-containing resin is polylysine and / or polyallylamine.
（３） （１）又は（２）に記載の金属表面処理組成物を、金属素材の表面に接触させて、前記金属素材の表面に表面処理層を形成させる表面処理工程を含む金属表面処理方法。 (3) A metal surface treatment method comprising a surface treatment step of bringing the metal surface treatment composition according to (1) or (2) into contact with the surface of a metal material to form a surface treatment layer on the surface of the metal material. .
（４） 前記金属素材が、アルミニウム及び／又はアルミニウム合金である、（３）記載の金属表面処理方法。 (4) The metal surface treatment method according to (3), wherein the metal material is aluminum and / or an aluminum alloy.
（５） 前記表面処理工程に先立って、前記金属素材の表面に、化成皮膜を形成させる化成処理工程を含む、（３）又は（４）に記載の金属表面処理方法。 (5) The metal surface treatment method according to (3) or (4), including a chemical conversion treatment step of forming a chemical conversion film on the surface of the metal material prior to the surface treatment step.
（６） （３）から（５）のいずれかに記載の金属表面処理方法により処理されてなる金属材料であって、前記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以下である金属材料。 (6) It is a metal material processed by the metal surface treatment method according to any one of (3) to (5), and the dry film amount in terms of total organic carbon of the surface treatment layer is 5 mg / m 2. A metal material of 1000 mg / m 2 or less.
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.
本発明の金属表面処理組成物によれば、耐水試験後であっても金属素材表面にラミネートフィルムを接着させたときに、ラミネートフィルムと金属素材との密着性を高く保つことができる According to the metal surface treatment composition of the present invention, even when the laminate film is adhered to the surface of the metal material even after the water resistance test, the adhesion between the laminate film and the metal material can be kept high.
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.
＜金属表面処理方法＞
本実施形態に係る金属表面処理方法は、金属素材の表面に、金属表面処理組成物を接触させる表面処理工程を含む。好ましくは、この表面処理工程に先立って、金属素材の表面に、必要に応じて化成処理剤による化成処理を施す化成処理工程を含む。
<Metal surface treatment method>
The metal surface treatment method according to the present embodiment includes a surface treatment step of bringing the metal surface treatment composition into contact with the surface of the metal material. Preferably, prior to the surface treatment step, a chemical conversion treatment step is performed on the surface of the metal material, if necessary, with a chemical conversion treatment with a chemical conversion treatment agent.
［化成処理工程］
本実施形態に係る金属表面処理方法の化成処理工程では、後述する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酸洗、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 process]
In the chemical conversion treatment step of the metal surface treatment method according to the present embodiment, a chemical conversion treatment is performed on the surface of the metal material using a chemical conversion treatment agent described later. 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, pickling, or etching treatment as necessary.
［表面処理工程］
本実施形態に係る金属表面処理方法の表面処理工程では、化成処理が施された、又は化成処理が施されていない金属素材の表面に、後述する金属表面処理組成物を接触させる。金属表面処理組成物を接触させる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。金属表面処理組成物を金属素材の表面に接触させた後は、４０℃から１５０℃において、１０秒から６０秒加熱して、金属表面処理組成物を乾燥させる。
[Surface treatment process]
In the surface treatment step of the metal surface treatment method according to the present embodiment, a metal surface treatment composition described later is brought into contact with the surface of a metal material that has been subjected to chemical conversion treatment or not subjected to chemical conversion treatment. The method for bringing the metal surface treatment composition into contact is not particularly limited, and examples thereof include a spray treatment method, an immersion treatment method, and the like. After the metal surface treatment composition is brought into contact with the surface of the metal material, the metal surface treatment composition is dried by heating at 40 to 150 ° C. for 10 to 60 seconds.
表面処理層が形成された金属素材の表面と、ラミネートフィルムとを接触させ、２００℃から３００℃において、５秒から６０秒加熱する。この加熱により、表面処理層中の高分子化合物の間に、オキサゾリン基とフェノール性水酸基との反応による架橋構造が形成され、表面処理層が硬化するとともに、表面処理層中のカチオン性基含有樹脂の効果により、ラミネート皮膜−表面処理層間、金属素材−表面処理層間にも水素結合や配位結合等の結合が形成されて、金属素材とラミネートフィルムとの密着性を向上させるものと考えられている。表面処理層に生じる凝集力は、また、金属素材とラミネートフィルムとの密着性に寄与するものと考えられる。 The surface of the metal material on which the surface treatment layer is formed is brought into contact with the laminate film, and heated at 200 to 300 ° C. for 5 to 60 seconds. By this heating, a crosslinked structure is formed between the polymer compounds in the surface treatment layer by the reaction of the oxazoline group and the phenolic hydroxyl group, the surface treatment layer is cured, and the cationic group-containing resin in the surface treatment layer It is considered that bonds such as hydrogen bonds and coordination bonds are formed between the laminate film and the surface treatment layer, and between the metal material and the surface treatment layer, thereby improving the adhesion between the metal material and the laminate film. Yes. It is considered that the cohesive force generated in the surface treatment layer also contributes to the adhesion between the metal material and the laminate film.
＜金属素材＞
本実施形態に係る金属表面処理方法に用いる金属素材としては、特に限定されないが、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。食品缶に用いる場合には、この中でも、アルミニウム及び／又はアルミニウム合金を特に好適に用いることができる。
<Metal material>
Although it does not specifically limit as a metal raw material used for the metal surface treatment method concerning this embodiment, Iron, zinc, aluminum, or an aluminum alloy can be used conveniently. Among them, aluminum and / or an aluminum alloy can be particularly preferably used when used for food cans.
＜化成処理剤＞
本実施形態に係る化成処理剤は、一般的に用いられているどのような化成処理剤でも用いることができる。例えば、化成処理剤は、リン酸クロメート系化成処理剤であってもよいし、ノンクロム化成処理剤であってもよい。また、本実施形態においては、金属素材の表面に、化成処理剤による化成処理を施さず、直接、後述する接着性の樹脂組成物を塗布してもよい。
<Chemical conversion treatment agent>
As the chemical conversion treatment agent according to the present embodiment, any chemical conversion treatment agent that is generally used can be used. For example, the chemical conversion treatment agent may be a phosphate chromate chemical conversion treatment agent or a non-chromium chemical conversion treatment agent. Moreover, in this embodiment, the adhesive resin composition mentioned later may be directly apply | coated to the surface of a metal raw material, without performing the chemical conversion treatment with a chemical conversion treatment agent.
［リン酸クロメート系化成処理剤］
本実施形態において用いることができる、リン酸クロメート系化成処理剤としては、特に限定されない。リン酸クロメート系化成処理剤は、市販されているものを用いることができ、例えば、「アルサーフ４０８」（商品名、日本ペイント社製）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）を用いることができる。
[Phosphate chromate conversion treatment agent]
It does not specifically limit as a phosphoric acid chromate type | system | group chemical conversion treatment agent which can be used in this embodiment. Commercially available phosphate chromate conversion treatment agents can be used such as “Alsurf 408” (trade name, manufactured by Nippon Paint Co., Ltd.) and “Alsurf 48” (trade name, which is a reaction accelerator). Nippon Paint Co., Ltd.) can be used.
［ノンクロム化成処理剤］
本実施形態に係るノンクロム化成処理剤としては、特に限定されないが、例えば、ジルコニウム系化成処理剤、及びチタン系化成処理剤を用いることができる。ジルコニウム系化成処理剤を用いる場合には、市販されているものを用いることができ、例えば、「アルサーフ４０２」（商品名、日本ペイント社製）及び「アルサーフ４１３０」（商品名、日本ペイント社製）を用いることができる。また、チタニウム系化成処理剤を用いる場合には、市販されているものとして、例えば、「アルサーフＬＸ−３４０」（商品名、日本ペイント社製）を用いることができる。
[Non-chromium chemical conversion treatment agent]
Although it does not specifically limit as a non-chrome chemical conversion treatment agent which concerns on this embodiment, For example, a zirconium type chemical conversion treatment agent and a titanium type chemical conversion treatment agent can be used. In the case of using a zirconium-based chemical conversion treatment agent, commercially available products can be used, for example, “Alsurf 402” (trade name, manufactured by Nippon Paint Co., Ltd.) and “Alsurf 4130” (trade name, manufactured by Nippon Paint Co., Ltd.). ) Can be used. Moreover, when using a titanium type | system | group chemical conversion treatment agent, "Alsurf LX-340" (a brand name, the Nippon Paint company make) can be used as what is marketed, for example.
＜金属表面処理組成物＞
本実施形態に係る金属表面処理方法の表面処理工程では、化成処理剤による処理を施した後、又は、化成処理剤による処理を施さずに、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、フェノール性水酸基含有樹脂とを含み、必要に応じてカチオン性基含有樹脂を含む。
<Metallic surface treatment composition>
In the surface treatment step of the metal surface treatment method according to the present embodiment, the surface treatment layer is formed using the metal surface treatment composition after the treatment with the chemical conversion treatment agent or without the treatment with the chemical conversion treatment agent. Let The metal surface treatment composition includes an oxazoline group-containing resin and a phenolic hydroxyl group-containing resin, and optionally includes a cationic group-containing resin.
［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、オキサゾリン基を複数個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、水溶媒中での相溶性、安定性に優れ、塗装後の外観が無色透明である点から、オキサゾリン基含有アクリル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。なお、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。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。
[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 a plurality of oxazoline groups. 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 this embodiment, it is preferable to use an oxazoline group-containing acrylic resin from the viewpoints of excellent compatibility and 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. Outside these ranges, the intended effect may not be obtained.
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、５質量％以上９０質量％以下であり、２５質量％以上８０質量％以下であることが好ましい。オキサゾリン基含有樹脂の含有量が５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材料との密着性が低下し、９０質量％を超えると、フェノール性水酸基含有樹脂の架橋効果が減少し、表面処理層の硬化度が低下して耐水性が低下する。このため、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 oxazoline group-containing resin in the metal surface treatment composition according to this embodiment is 5% by mass to 90% by mass and preferably 25% by mass to 80% by mass per resin solid content. If the content of the oxazoline group-containing resin is less than 5% 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. The crosslinking effect is reduced, the degree of curing of the surface treatment layer is lowered, and the water resistance is lowered. For this reason, the adhesiveness of a laminate film and a metal material falls.
［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。このため、金属表面処理組成物にフェノール性水酸基含有樹脂を添加することにより、ラミネートフィルムの貼り付け後の耐水性に優れた金属素材を提供することができる。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. Therefore, by adding a phenolic hydroxyl group-containing resin to the metal surface treatment composition, it is possible to provide a metal material having excellent water resistance after the laminate film is attached. 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９０質量％以下含まれており、１５質量％以上６０質量％以下含まれていることが好ましい。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、ラミネートフィルムと金属材料との密着性が低下し、９０質量％を超えると、オキサゾリン基含有樹脂の架橋効果が減少し、表面処理層の硬化度が低下して耐水性が低下する。このため、ラミネートフィルムと金属材料との密着性が低下する。なお、オキサゾリン基とフェノール性水酸基との当量比は、０．８〜１．２５の範囲に設定すること架橋構造を形成する観点からが好ましい。 In the metal surface treatment composition of the present embodiment, the phenolic hydroxyl group-containing resin is contained in an amount of 5% by mass to 90% by mass and 15% by mass to 60% by mass per resin solid content. Is preferred. 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 adhesiveness between the laminate film and the metal material is lowered, and if it exceeds 90% by mass, the oxazoline group-containing resin The cross-linking effect decreases, the degree of curing of the surface treatment layer decreases, and the water resistance decreases. For this reason, the adhesiveness of a laminate film and a metal material falls. The equivalent ratio of the oxazoline group and the phenolic hydroxyl group is preferably set in the range of 0.8 to 1.25 from the viewpoint of forming a crosslinked structure.
［カチオン性基含有樹脂］
本実施形態において用いることができるカチオン性基含有樹脂は、樹脂固形分中にカチオン性基を５．０ｍｅｑ／ｇ以上有するものであり、好ましくは、７．０ｍｅｑ／ｇ以上有するものである。カチオン性基が５ｍｅｑ／ｇより少ない場合には、接着効果が弱いため密着性が低下する。その平均分子量は、５００以上１００００００以下であることが好ましく、１０００以上７００００以下であることが更に好ましい。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。
[Cationic group-containing resin]
The cationic group-containing resin that can be used in this embodiment has a cationic group in the resin solid content of 5.0 meq / g or more, preferably 7.0 meq / g or more. When the number of cationic groups is less than 5 meq / g, the adhesion effect is weak and the adhesion is lowered. The average molecular weight is preferably 500 or more and 1000000 or less, and more preferably 1000 or more and 70000 or less. Outside these ranges, the intended effect may not be obtained.
本実施形態において用いることができるカチオン性基含有樹脂としては、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、ポリビニルアミン、及びポリエチレンイミン等が挙げられ、これらのうち、ポリアリルアミン、ポリリジンが好ましく用いられる。カチオン性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−０１」（商品名、日東紡績社製）、「ＰＡＡ−０５」（商品名、日東紡績社製）、及び「ＰＡＡ−１０Ｃ」（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）、並びに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。 The cationic group-containing resin that can be used in the present embodiment is not particularly limited, and examples thereof include polyallylamine, polylysine, polyvinylamine, and polyethyleneimine. Among these, polyallylamine and polylysine are preferably used. It is done. As the cationic group-containing resin, commercially available resins can be used. For example, as polyallylamine, “PAA-01” (trade name, manufactured by Nitto Boseki Co., Ltd.), “PAA-05” (trade name, manufactured by Nitto Boseki Co., Ltd.) ), And “PAA-10C” (trade name, manufactured by Nitto Boseki Co., Ltd.), “Polylysine” (trade name, manufactured by Chisso Corporation) as polylysine, and “PVAM-0595” (trade name, manufactured by Mitsubishi Chemical Corporation) as polyvinylamine. Can be used.
本実施形態に係る金属表面処理組成物におけるカチオン性基含有樹脂に含有されるカチオン性基としては、アミノ基、イミノ基、グアニジン基、及びビグアニド基を挙げることができる。カチオン性基含有樹脂の含有量は、樹脂固形分当たり、５質量％以上９０質量％以下であることが好ましい。カチオン性基含有樹脂の含有量が５質量％未満の場合には、カチオン性基含有樹脂の含有量が十分でないため、ラミネートフィルムと金属材料との密着性が低下し、９０質量％を超える場合には、オキサゾリン基含有樹脂、及びフェノール性水酸基含有樹脂の架橋効果が減少し、表面処理層の硬化度が低下して耐水性が低下する。このため、ラミネートフィルムと金属材料との密着性が低下する。なお、各樹脂の含有量を合計すると、樹脂固形分の１００質量％となる。 Examples of the cationic group contained in the cationic group-containing resin in the metal surface treatment composition according to this embodiment include an amino group, an imino group, a guanidine group, and a biguanide group. The content of the cationic group-containing resin is preferably 5% by mass or more and 90% by mass or less per resin solid content. When the content of the cationic group-containing resin is less than 5% by mass, since the content of the cationic group-containing resin is not sufficient, the adhesion between the laminate film and the metal material is reduced, and the content exceeds 90% by mass. The cross-linking effect of the oxazoline group-containing resin and the phenolic hydroxyl group-containing resin is reduced, the degree of curing of the surface treatment layer is lowered, and the water resistance is lowered. For this reason, the adhesiveness of a laminate film and a metal material falls. In addition, when content of each resin is totaled, it will be 100 mass% of resin solid content.
［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。前記乾燥皮膜量が５ｍｇ／ｍ２未満の場合には、樹脂量（官能基量）が少ないため密着性が低下する。１０００ｍｇ／ｍ２を超える場合には、膜厚が厚くな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 is lowered because the resin amount (functional group amount) is small. When it exceeds 1000 mg / m 2 , the film thickness becomes thick and the adhesiveness decreases.
＜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加工方法としては、一般にはドライラミネート法、押出ラミネート法を用いることができるが、特に限定されない。また、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、及び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>
As a processing method of the laminate film that can be used in the present embodiment, a dry lamination method and an extrusion lamination method can be generally used, but are not particularly limited. In addition, as the material of the film, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polycarbonate (PC), triacetyl cellulose (TAC), polyvinyl chloride (PVC), polyester, polyolefin, and Mention may be made of thermoplastic resins such as acrylic.
次に本発明を実施例及び比較例を挙げて具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited only to these Examples.
＜実施例１〜９、比較例１〜４＞
０．５ｃｍ×１０ｃｍに切断した２枚のアルミニウム材（３００４板材）に、２％の脱脂剤（「ＳＣＬ４２０Ｎ−２」、日本ペイント社製）を６５℃で７秒間スプレー塗布し、水洗により脱脂剤を洗い流して、水分をゴムロールによって搾り取った。次に、樹脂成分を表１の通り含有する金属表面処理組成物をナイロンバーで塗布し、８０℃で６０秒間乾燥させた。全有機炭素換算の乾燥皮膜量は、全有機炭素測定装置（製品名「ＲＣ−４１２」、ＬＥＣＯ社製）を用いて行った。
<Examples 1-9, Comparative Examples 1-4>
2% degreasing agent ("SCL420N-2", manufactured by Nippon Paint Co., Ltd.) is spray-applied at 65 ° C for 7 seconds on two pieces of aluminum material (3004 plate material) cut to 0.5 cm x 10 cm, and degreased by washing with water. The water was washed out and the water was squeezed out with a rubber roll. Next, a metal surface treatment composition containing a resin component as shown in Table 1 was applied with a nylon bar and dried at 80 ° C. for 60 seconds. The amount of dry film in terms of total organic carbon was measured using a total organic carbon measuring device (product name “RC-412”, manufactured by LECO).
なお、表面処理組成物の各成分の供給源としては、以下のものを用いた。
オキサゾリン基含有樹脂；「エポクロスＷＳ７００」（商品名、日本触媒社製、オキサゾリン価２２０）
フェノール性水酸基含有樹脂；「ＢＲＬ２８５４」（商品名、昭和高分子社製）
カチオン性基含有樹脂Ａ；「ＰＡＡ−１０Ｃ」（商品名、日東紡績社製、ポリアリルアミン、分子量１５０００）
カチオン性基含有樹脂Ｂ；「ポリリジン」（商品名、チッソ社製）
In addition, the following were used as a supply source of each component of a surface treatment composition.
Oxazoline group-containing resin; “Epocross WS700” (trade name, manufactured by Nippon Shokubai Co., Ltd., oxazoline number 220)
Phenolic hydroxyl group-containing resin; “BRL2854” (trade name, manufactured by Showa Polymer Co., Ltd.)
Cationic group-containing resin A; “PAA-10C” (trade name, manufactured by Nitto Boseki Co., Ltd., polyallylamine, molecular weight 15000)
Cationic group-containing resin B: “Polylysine” (trade name, manufactured by Chisso Corporation)
［Ｔピール試験］
これらのアルミニウム材２枚の間に、ＰＥＴフィルムを挟み、２３９℃、３０ｋｇｆ／ｍ２で１５秒間熱圧着した。この試験片に、なんらの処理も施さず（初期）、又は１１５℃で６０分間耐水試験を行い（耐水試験後）、「テンシロン試験機」（商品名、東洋ボールドウィン社製）にて剥離強度の測定を行った。剥離強度の測定の際の引き剥がし速度は４０ｍｍ／ｍｉｎであった。
[T peel test]
A PET film was sandwiched between these two aluminum materials, and thermocompression bonded at 239 ° C. and 30 kgf / m 2 for 15 seconds. This test piece was not subjected to any treatment (initial stage), or was subjected to a water resistance test at 115 ° C. for 60 minutes (after the water resistance test), and the peel strength of “Tensilon tester” (trade name, manufactured by Toyo Baldwin) was measured. Measurements were made. The peeling speed at the time of measuring the peel strength was 40 mm / min.
剥離強度の結果を表１に示した。
○；引っ張り強度１．５ｋｇｆ／５ｍｍ以上
△；引っ張り強度０．５ｋｇｆ／５ｍｍ以上１．５ｋｇｆ／５ｍｍ未満
×；引っ張り強度０．５ｋｇｆ／５ｍｍ未満
The results of peel strength are shown in Table 1.
○: Tensile strength 1.5 kgf / 5 mm or more Δ: Tensile strength 0.5 kgf / 5 mm or more and less than 1.5 kgf / 5 mm ×: Tensile strength less than 0.5 kgf / 5 mm
＜実施例１０〜１３＞
０．５ｃｍ×１０ｃｍに切断した２枚のアルミニウム材（３００４板材）に、２％の脱脂剤「ＳＣＬ４２０Ｎ−２」（商品名、日本ペイント社製）を６５℃で７秒間スプレー処理し、２％の硫酸を５０℃で３秒間スプレー塗布した。これを水洗により洗浄し、表１に示す、各化成処理剤により５０℃で４秒間スプレー塗布した。水洗により化成処理剤を洗い流して、水分をゴムロールで搾り取り、樹脂成分を表１の通り含有する金属表面処理組成物をナイロンバーで塗布して、８０℃で６０秒間乾燥させた。
<Examples 10 to 13>
2% degreasing agent “SCL420N-2” (trade name, manufactured by Nippon Paint Co., Ltd.) was sprayed at 65 ° C. for 7 seconds on 2 pieces of aluminum material (3004 plate material) cut to 0.5 cm × 10 cm, 2% Of sulfuric acid was sprayed at 50 ° C. for 3 seconds. This was washed with water and spray-coated at 50 ° C. for 4 seconds with each chemical conversion treatment agent shown in Table 1. The chemical conversion treatment agent was washed away by washing with water, the water was squeezed out with a rubber roll, a metal surface treatment composition containing the resin component as shown in Table 1 was applied with a nylon bar, and dried at 80 ° C. for 60 seconds.
また、化成処理は以下の化成処理剤で行った。
リン酸Ｃｒ；「アルサーフ４０８／４８」（商品名、日本ペイント社製）
Ｚｒ系；「アルサーフ４０２」（商品名、日本ペイント社製）
Ｔｉ系；「アルサーフＬＸ−３０４」（商品名、日本ペイント社製）
Moreover, the chemical conversion treatment was performed with the following chemical conversion treatment agent.
Cr phosphate; “Alsurf 408/48” (trade name, manufactured by Nippon Paint)
Zr system; “Alsurf 402” (trade name, manufactured by Nippon Paint)
Ti-based: “Alsurf LX-304” (trade name, manufactured by Nippon Paint Co., Ltd.)
［Ｔピール試験］
これらのアルミニウム材２枚の間に、ＰＥＴフィルムを挟み、２３９℃、３０ｋｇｆ／ｍ２で１５秒間熱圧着した。この試験片に、なんらの処理も施さず（初期）、又は１１５℃で６０分間耐水試験を行い（耐水試験後）、「テンシロン試験機」（商品名、東洋ボールドウィン社製）にて剥離強度の測定を行った。剥離強度の測定の際の引き剥がし速度は４０ｍｍ／ｍｉｎであった。
[T peel test]
A PET film was sandwiched between these two aluminum materials, and thermocompression bonded at 239 ° C. and 30 kgf / m 2 for 15 seconds. This test piece was not subjected to any treatment (initial stage), or was subjected to a water resistance test at 115 ° C. for 60 minutes (after the water resistance test), and the peel strength of “Tensilon tester” (trade name, manufactured by Toyo Baldwin) Measurements were made. The peeling speed at the time of measuring the peel strength was 40 mm / min.
剥離強度の結果を表１に示した。
○；引っ張り強度１．５ｋｇｆ／５ｍｍ以上
△；引っ張り強度０．５ｋｇｆ／５ｍｍ以上１．５ｋｇｆ／５ｍｍ未満
×；引っ張り強度０．５ｋｇｆ／５ｍｍ未満
The results of peel strength are shown in Table 1.
○: Tensile strength 1.5 kgf / 5 mm or more Δ: Tensile strength 0.5 kgf / 5 mm or more and less than 1.5 kgf / 5 mm ×: Tensile strength less than 0.5 kgf / 5 mm
Claims (6)
金属表面処理組成物固形分中、少なくとも２つのオキサゾリン基を含有するオキサゾリン基含有アクリル樹脂を５質量％以上９０質量％以下と、少なくとも２つのフェノール性水酸基を含有するフェノール性水酸基含有樹脂を５質量％以上９０質量％以下と、カチオン性基含有樹脂を５質量％以上９０質量％以下とを含み、
前記カチオン性基含有樹脂が、樹脂固形分中、５．０ｍｅｑ／ｇ以上の１級アミノ基を含有するカチオン性基含有樹脂である、金属表面処理組成物。 A metal surface treatment composition used for metal surface treatment,
5 mass% to 90 mass% of oxazoline group-containing acrylic resin containing at least two oxazoline groups and 5 mass of phenolic hydroxyl group-containing resin containing at least two phenolic hydroxyl groups in the solid content of the metal surface treatment composition % To 90% by mass, and 5% to 90% by mass of the cationic group-containing resin,
The metal surface treatment composition, wherein the cationic group-containing resin is a cationic group-containing resin containing a primary amino group of 5.0 meq / g or more in the resin solid content.
前記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以下である金属材料。 A metal material processed by the metal surface treatment method according to claim 3,
The amount of dry film in terms of total organic carbon of the surface treatment layer is a metal material that is 5 mg / m 2 or more and 1000 mg / m 2 or less.
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