JP4105043B2 - Aluminum alloy material for lithographic printing plate and method for producing the same - Google Patents
Aluminum alloy material for lithographic printing plate and method for producing the same Download PDFInfo
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- JP4105043B2 JP4105043B2 JP2003168246A JP2003168246A JP4105043B2 JP 4105043 B2 JP4105043 B2 JP 4105043B2 JP 2003168246 A JP2003168246 A JP 2003168246A JP 2003168246 A JP2003168246 A JP 2003168246A JP 4105043 B2 JP4105043 B2 JP 4105043B2
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- 229910000838 Al alloy Inorganic materials 0.000 title claims description 58
- 239000000956 alloy Substances 0.000 title claims description 47
- 238000007639 printing Methods 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000002245 particle Substances 0.000 claims description 97
- 229910000765 intermetallic Inorganic materials 0.000 claims description 85
- 239000000463 material Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052745 lead Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 3
- 238000000866 electrolytic etching Methods 0.000 description 36
- 238000005530 etching Methods 0.000 description 34
- 239000010410 layer Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 10
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- 238000000265 homogenisation Methods 0.000 description 9
- 238000005098 hot rolling Methods 0.000 description 8
- 238000007788 roughening Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000005097 cold rolling Methods 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000001226 reprecipitation Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- 241000252254 Catostomidae Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
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Landscapes
- Printing Plates And Materials Therefor (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、感光層が形成されて印刷用に用いられる平版印刷版用のアルミニウム合金材料とその製造方法に関し、特に電解エッチングによる粗面の均一性と版切れ性、耐刷性、取り扱い性、耐傷性等に優れた印刷版用のアルミニウム合金板を提供可能な技術に関する。
【０００２】
【従来の技術】
平版印刷は、アルミニウム合金板とジアゾ化合物等を感光物とする感光体とからなるＰＳ版（Ｐｒｅｓｅｎｓｉｔｉｚｅｄ Ｐｌａｔｅ）に、画像露光、現像等の製版処理を行って画像部を形成した版を印刷機の円筒状版胴に巻き付け、非画像部に付着した湿し水の存在のもとにインキを画像部に付着させてこのインキをゴム製ブランケットに転写し、紙面に印刷するものである。
前述のＰＳ版の支持体として、一般には、電解エッチングによる粗面化処理（砂目立て）、陽極酸化処理などの表面処理を施したアルミニウム合金板が用いられている。この種の用途に用いられるアルミニウム合金としては、当初、ＪｌＳ１０５０（純度９９.５％以上の純Ａｌ系）、ＪｌＳ１１００（Ａｌ−０.０５〜０.２０％Ｃｕ合金）、ＪｌＳ３００３（Ａｌ−０.０５〜０.２０％Ｃｕ−１.５％Ｍｎ合金）が主に用いられてきた。
【０００３】
この種の平版印刷版用アルミニウム合金板においては、一般に、
（１）電解エッチングによる粗面が均一であること。
（２）感光剤の密着性が良好であること。
（３）印刷中に画像部に汚れが生じないこと。
（４）印刷機の円筒状版胴に巻き付ける際の強度がある程度必要で、巻き付け時に部分的に折れたり、切れたりしないこと。
（５）大量の印刷を行っても画像部に汚れを生じることがなく、耐印刷性に優れること。等の種々の特性が要求されている。
しかし、ＪＩＳに規定されているＪＩＳ１０５０、ＪＩＳ１１００、ＪＩＳ３００３の合金そのものでは以上の各要求を十分に満足させることができない。例えばＪＩＳ３０００系のアルミニウム合金材料では材料強度が高く、版を印刷機の版胴に取り付ける際に変形し難く、かつ、硬いために、傷が付き難いという取り扱い性の面で優れ、仮に印刷版が大判化しても版切れし難いという利点を有する。
しかしながら、ＪＩＳ３０００系のアルミニウム材料は電解エッチング性が劣っており、一般的には機械研磨により粗面化されるが、機械研磨により得られる粗面は電解エッチング処理により得られる粗面に比べて粗いので、感光層の密着性が悪く、耐刷性が低くなってしまう問題がある。このため、この種のアルミニウム合金材料では合金組成と得られる表面状態について種々の改良が行われてきた。
【０００４】
例えば、粗面化処理はアルミニウム合金板表面に保水性を与えると共に、感光層の形成において印刷版に感光剤を密着させて固定するために行うものであり、この密着性は印刷版としての性能に影響する。
しかし、従来の粗面化処理では粗面化表面に未エッチング部が生じたり、粗面化により形成されるピットの分布が不均一であったりすることがあり、少なからず印刷版としての性能に悪影響が生じており、この粗面状態を改善することが求められている。
従来から上述の観点において材料面での改善が試みられており、その一方法として材料に特殊な元素を添加する方法が提案されている。例えば、以下の特許文献１では、所定量のＮｉを添加することによりピットの形成を促進してエッチング性を向上させる方法が開示されており、以下の特許文献２ではＳｎ、Ｉｎ、Ｇａを添加して微細ピットを形成してエッチング性を向上させる方法が開示されている。
しかし、前記のように特殊な元素を添加しても前記の要望を十分に満足するには至っておらず、また、特殊な元素の添加によって材料費のコストアップを招いたり、リサイクルの障害になるという問題がある。
また、アルミニウム合金材料中に析出する金属間化合物の大きさ、密度に着目しこれらを制御することによって特殊元素を添加することなくエッチング性を向上させる方法も提案されている。（特許文献３参照）
【０００５】
【特許文献１】
特開平１１−１１５３３３号公報
【特許文献２】
特開平５８−２１０１４４号公報
【特許文献３】
特開平１１−１５１８７０号公報
【０００６】
【発明が解決しようとする課題】
先の特許文献３に記載の方法では、該金属間化合物がエッチングの起点となって微細なピットが均一に形成されるものとしている。しかし、この方法によっても十分にエッチング性を向上させることはできず、前記の要望を満足させるには至っていない。
本発明者らの研究から、前記における金属間化合物の大きさ、密度の制御によって十分なエッチング性を得られないのは、該金属間化合物の化学溶解性が予想以上に大きく、電解液に溶解し、消失してしまうためにエッチングピットの起点として十分に機能していないためであることがわかった。そして、さらに研究を進めた結果、前記金属間化合物は安定相からなるのに対し、準安定相のＡｌＦｅ系金属間化合物粒子を適度に分散させるとエッチング性が大幅に向上し、前記した要望にも十分に応えられることが判明した。
【０００７】
本発明は、電解エッチングによる粗面化処理の均一性を向上させるとともに、版切れ性と取り扱い性と耐傷つき性にも優れさせた平版印刷版用アルミニウム合金材料とその製造方法の提供を目的とする。
【０００８】
【課題を解決するための手段】
本発明者は前記課題を解決すべくＰＳ版用アルミニウム合金支持体の電解エッチングの均一性について検討を行ったところ、アルミニウムマトリクス中に晶出又は析出するＡｌ−Ｆｅ系の金属間化合物が、電解エッチング中にカソード点として作用し、ＰＳ版用アルミニウム合金支持体の溶解性を支配していることが判明した。
このような観点からアルミニウムに対する添加元素の検討を行い、添加元素の作用を調査したところ、Ｓｉ、Ｃｕ、Ｔｉなどの添加成分は、添加量を増加するとカソード溶解性を低下させることが判明した。
一方、Ｆｅはカソード溶解性を向上させる。
また、この系の組成において金属間化合物の状態が重要であり、特定の粒径のものの含有量及び個数が重要であることが判明し、これらの知見に鑑みて本願発明に到達した。
【０００９】
本発明のアルミニウム合金材料は、重量％で、Ｆｅ：０．１０〜１．００％、Ｓｉ：０．０１〜０．５０％、Ｃｕ：０．００１〜０．０５％、Ｔｉ：０．００５〜０．０３％、Ｍｎ：０．０５〜０．８０％、残部がＡｌ及び不可避的不純物からなり、金属組織中に複数の金属間化合物粒子を有し、粒径が円相当径で０．１μｍ以上で、ＡｌとＦｅの原子量の比をＦｅ／Ａｌ≦０．６０とした準安定相を有する金属間化合物粒子が、材料表面に３０個／ｍｍ２以上分散されてなるとともに、粒径が円相当径で０．１〜３．０μｍで、Ｍｎを有するＡｌＭｎ系の金属間化合物粒子が、材料表面に６０個／ｍｍ２以上分散されてなることを特徴とする。
本発明は前記組成に加え、Ｐｂ、Ｂ、Ｖ、Ｇａ、Ｚｒ、Ｃｒ、Ｎｉのうちの１種以上を０．０００１０〜０．１０％の範囲で含有していても良い。
本発明において前記準安定相を有する金属間化合物粒子が、材料表面に３０個／ｍｍ ２ 以上、３０００個／ｍｍ ２ 以下の範囲で分散され、前記ＡｌＭｎ系の金属間化合物粒子が、材料表面に６０個／ｍｍ ２ 以上、６０００個／ｍｍ ２ 以下の範囲で分散されていても良い。
【００１０】
本発明の製造方法は、重量％で、Ｆｅ：０．１０〜１．００％、Ｓｉ：０．０１〜０．５０％、Ｃｕ：０．００１〜０．０５％、Ｔｉ：０．００５〜０．０３％、Ｍｎ：０．０５〜０．８０％、残部がＡｌ及び不可避的不純物からなる組成を有し、金属組織中に複数の金属間化合物粒子を有し、粒径が０．１μｍ以上でＡｌとＦｅの原子量の比をＦｅ／Ａｌ≦０．６０とした準安定相を有する金属間化合物粒子が材料表面に３０個／ｍｍ２以上分散されてなるとともに、粒径が円相当径で０．１〜３．０μｍで、Ｍｎを有するＡｌＭｎ系の金属間化合物が、材料表面に６０個／ｍｍ２以上分散されてなるとともに、粒径が円相当径で０．１〜３．０μｍで、Ｍｎを有するＡｌＭｎ系の金属間化合物粒子が、材料表面に６０個／ｍｍ２以上分散されてなることを特徴とする平版印刷版用アルミニウム合金材料を製造するにあたり、前記組成の合金鋳塊を均質化処理を施すことなく均熱処理を施して熱間圧延するか、前記組成の合金鋳塊を５５０℃以下の温度で均質化処理して熱間圧延することを特徴とする。
本発明の製造方法において、前記組成に加え、Ｎｉを０．００１〜０．２％の範囲で含有してなるアルミニウム合金材料を用いることができる。
本発明の製造方法において、前記組成に加え、Ｐｂ、Ｂ、Ｖ、Ｇａ、Ｚｒ、Ｃｒ、Ｎｉのうちの１種以上を０．０００１０〜０．１０％の範囲で含有してなる組成の平版印刷版用アルミニウム合金材料を用いても良い。
本発明の製造方法において、前記準安定相を有する金属間化合物粒子が、材料表面に３０個／ｍｍ ２ 以上、３０００個／ｍｍ ２ 以下の範囲で分散され、前記ＡｌＭｎ系の金属間化合物粒子が、材料表面に６０個／ｍｍ ２ 以上、６０００個／ｍｍ ２ 以下の範囲で分散されていても良い。
【００１１】
【発明の実施の形態】
以下に本発明の実施の形態について説明するが、本発明が以下の実施の形態に限定されるものではないのは勿論である。
先に説明した本発明者が得た知見から、本実施の形態では、重量％で、Ｆｅ：０.１０〜１.００％、Ｓｉ：０.０１〜０.５０％、Ｃｕ：０.００１〜０.０５％、Ｔｉ：０.００５〜０.０３％、Ｍｎ：０.０５〜０.８０％、残部がＡｌ及び不可避的不純物からなり、金属組織中に複数の金属間化合物粒子を有し、粒径が０.１μｍ以上で、ＡｌとＦｅの含有量の比をＦｅ／Ａｌ≦０.６０とする準安定相を有する金属間化合物を材料表面に３０個／ｍｍ２以上分散させてなるとともに、粒径が円相当径で０.１〜３.０μｍで、Ｍｎを有するＡｌＭｎ系の金属間化合物が、材料表面に６０個／ｍｍ２以上分散されてなる平板印刷版用アルミニウム合金材料がこの種の目的のために好ましいとした。
【００１２】
更に本発明者の研究の結果、この種のアルミニウム合金材料には、金属間化合物（ＡｌＦｅ系、ＡｌＦｅＳｉ系、Ｓｉ系、Ｔｉ系）粒子が複数含有されているが、これらの金属間化合物粒子が微細に分散している程、カソード反応性が増すことが判明した。
その条件は、先に記載の金属間化合物粒子において円相当径で粒径１.０μｍ以上の金属間化合物粒子の数が３０個／ｍｍ２以上分散するとともに、
粒径が円相当径で０.１〜３.０μｍで、Ｍｎを有するＡｌＭｎ系の金属間化合物が、材料表面に６０個／ｍｍ２以上分散されてなることである。
更にＡｌＦｅ系の金属間化合物は、安定相（Ａｌ３Ｆｅ）よりも準安定相の方が好ましく、金属間化合物の組成において、Ｆｅ／Ａｌの比率が０.６０以下の準安定相を有する金属間化合物粒子が材料表面に３０個／ｍｍ２以上分散しているものが好ましい。
このアルミニウム合金材料において、少なくとも表層部が準安定相のＡｌＦｅ系金属間化合物粒子を分散させた準安定分散層からなるものに本発明を適用することができる。
更に金属間化合物粒子が分散されている表面層部分については、電解エッチング処理に寄与する最表層から５０μｍ程度の深さの領域までの範囲で差し支えないと考えられる。
【００１３】
以下に本発明で規定したアルミニウム合金材料に対する合金成分の限定理由を述べる。また、本願明細書において含有量の上限値と下限値の間の範囲を「〜」で示す場合、特に指定しない限り、以上、以下を意味する。よって特に指定しない限り０.１０〜１.００重量％は、０.１０重量％以上、１.００重量％以下の範囲を意味するものとする。
「Ｆｅ」：０.１０〜１.００重量％
ＦｅはＡｌＦｅ系の準安定相を含む金属間化合物を形成し、電解エッチング均一性を向上させる元素である。Ｆｅ含有量が０.１０重量％未満では、カソード反応性が不足し、電解エッチング均一性の効果が得られない。また、Ｆｅ含有量が１.００重量％を超えると粗大な金属間化合物を生成し易くなり、カソード溶解性は低下する。更に好ましいＦｅ含有量の範囲は０.２〜０.６０重量％である。
「Ｓｉ」：０.０１〜０.５０重量％
Ｓｉはアルミニウム素地中に析出して結晶粒の微細化に寄与する元素である。即ち、ＡｌＦｅＳｉ系の金属間化合物を形成し、熱間圧延時の再結晶粒を微細化する効果を奏する。Ｓｉ含有量が０.０１％未満ではこのような効果が不足となり、逆にＳｉ含有量が０.５０％を超えると粗大な金属間化合物が生成し、電解エッチング均一性が低下する。更に、Ｓｉ含有量を０.０１重量％未満とするためには、高純度の地金を使用する必要が生じ、コストが大幅に増大する。また、更に好ましいＳｉ含有量の範囲は０.０５〜０.２０重量％である。
【００１４】
「Ｃｕ」：０.００１〜０.０５重量％
Ｃｕはエッチングピットの形成にとって大きく影響する元素である。Ｃｕ含有量が０.００１重量％未満ではカソード溶解性が不足し、エッチングピット形成が促進されなくなる。また、Ｃｕ含有量が０.０５％を越えると粗大ピットの生成が増加してしまう。また、更に好ましいＣｕ含有量の範囲は０.００２〜０.０２重量％である。
「Ｔｉ」：０.００５〜０.０３重量％
Ｔｉは結晶粒を微細化する元素であるが、Ｔｉ含有量が０.００５重量％未満ではこの微細化効果が得られない。また、Ｔｉ含有量が０.０３重量％を越えると粗大な金属間化合物が増加して電解エッチング均一性を低下させ、Ｔｉ含有量が０.００５％未満となると、結晶粒微細化の効果が不足するようになる。また、更に好ましいＴｉ含有量の範囲は０.００６〜０.０２重量％である。
【００１５】
「Ｍｎ」：０.０５〜０.８０重量％
Ｍｎは強度を向上させる効果があるが、その含有量が０.０５重量％未満ではその効果が少なく、０.８０重量％を超える含有量では電解エッチングピットが粗大化する問題を有する。
更に好ましいＭｎ含有量は、０.１０〜０.６０重量％の範囲である。
「Ｐｂ、Ｖ、Ｂ、Ｇａ、Ｚｒ、Ｎｉ、Ｃｒの１種以上の合計」：０.０００１０〜０.１０重量％
Ｐｂ、Ｖ、Ｂ、Ｇａ、Ｚｒ、Ｎｉ、Ｃｒは電解エッチング中に一旦溶出するが電解エッチング面に再析出し、電解エッチングピットの核となる。これら元素の合計の添加量が０.０００１０％未満ではこの作用が不足する。逆に添加量が０.１０％を超えると再析出の量が多くなり過ぎて局部的な電解エッチングになり、電解エッチング均一性は低下する。更に好ましいこれら元素の含有量は０.００１〜０.０５重量％の範囲である。
「その他の元素」
本願発明に係るアルミニウム合金板に対して含有されていても良い不純物としてＹ、Ｓｎ、Ｉｎ等を例示することができる。これらの不純物の含有量は、個々に０.０３重量％以下に抑えることが好ましい。また、その他の元素としてＭｇを０.０５重量％以下の範囲で含有していても差し支えない。
【００１６】
「金属間化合物粒子」
準安定相を有する金属間化合物粒子は、エッチングピットの起点になることから、前記した分散層における該粒子の大きさは、その後に成長するピットの性状に影響する。この粒子径が小さくて（円相当径０.１μｍ未満）、粒子が微細すぎるとエッチングピットの起点として十分に作用せず、一方、粒子径が大きすぎる（円相当径１.０μｍ超）とピットの均一性を低下させる。従って、ピットの形成に好適に影響を与える金属間化合物粒子径は円相当径０.１μｍ〜１.０μｍのものである。
従ってアルミニウム合金材料の表面の面方向において、金属間化合物粒子の中でこの大きさの範囲にある粒子の比率が高いほど良好なエッチング性が得られる。面方向とは、分散層の任意の深さ位置での材料表面と平行する面方向を意味する。なお、０.１μｍ未満の金属間化合物粒子は、ピットの起点という観点からは殆ど無視できる存在であるから、０.１μｍ以上の金属間化合物粒子のみに着目して、前記範囲内の粒子の比率を規定することができる。
【００１７】
次に、金属間化合物粒子においてＡｌとＦｅの比をＦｅ／Ａｌ≦０.６０としてなる準安定相からなる金属間化合物粒子あるいは該準安定相を含む金属間化合物粒子が、材料表面において３０個／ｍｍ２以上分散していることが好ましい。このような準安定相は電解エッチングの核として有効に作用する。Ｆｅ／Ａｌが０.６０を超えると安定相になり、電解エッチングの核としての作用が低下する。ＡｌとＦｅの比の下限は０.２５程度である。準安定相の金属間化合物粒子が３０個／ｍｍ２未満の分散状態では電解エッチングの核として作用が不足する。準安定相の金属間化合物粒子の分布数は８０個／ｍｍ２以上が好ましく、上限は３０００個／ｍｍ２程度である。これ以上の個数の金属間化合物を分散させるには、後述する製造方法における熱間圧延の温度を低下させる必要があるなど、コスト増の要因が大きくなる。
更に金属間化合物粒子において、粒径が円相当径で０.１〜３.０μｍで、Ｍｎを有するＡｌＭｎ系の金属間化合物が、材料表面に６０個／ｍｍ２以上分散されてなることが好ましい。ＡｌＭｎ系の金属間化合物粒子の数が６０個／ｍｍ２未満では核としての作用が不足し、逆に６０００個／ｍｍ２以上の個数を分散しても電解エッチング性の向上効果は少ない。
【００１８】
「準安定相分散層」
従来、平版印刷版用アルミニウム合金板では、安定相のＡｌＦｅ系金属間化合物（Ａｌ３Ｆｅ）粒子が分散しており、準安定相の分散層は見られない。本発明では従来の安定相の金属間化合物が析出したものと異なり、表層部に準安定相のＡｌＦｅ系金属間化合物粒子が分散した分散層を有している。この準安定相は、量比でＡｌ４Ｆｅ、Ａｌ５Ｆｅ、Ａｌ６ＦｅまたはＡｌｍＦｅ（４＜ｍ＜６）で示される。これらは単独または安定相との混相として存在する。また、準安定相粒子は、通常は、この準安定相の金属間化合物のみで構成されるが、安定相の金属間化合物が一部混ざったものであっても良い。
上述した準安定相の金属間化合物粒子は、安定相の金属間化合物粒子に比してピットの起点となり易く、ピットの分散性を高めて未エッチング部の発生を効果的に防止する。また、量比で示すＡｌｍＦｅの場合のｍは６に近い方が効果的である。
【００１９】
「分散層深さ」
前記分散層は、表面から２〜５０μｍに至る深さまで形成されているのが望ましい。これは、平板印刷用アルミニウム合金坂の製造において、圧延後、電解エッチング前に、苛性洗浄による脱脂、酸エッチングや機械研磨等により表面層除去が行われており、一般的に、化学的前処理では０.１〜２μｍ程度、機械研磨では０.１〜５μｍ程度が除去されることから、分散層の深さは、表層除去前、圧延後の状態を示している。一方、分散層の深さは５０μｍを越えても電解エッチングの改善には殆ど関与しないので、分散層の深さは５０μｍ程度あれば十分であると考える。
「準安定相と安定相の比率（分散層における）」
分散層では、ピットの起点として優れている準安定相の金属間化合物粒子が、ある程度の比率以上で分散しているものが望ましい。
【００２０】
また、金属間化合物が準安定相であるか安定相であるかは、粒子中のＦｅ含有量とＡｌ含有量との比率を調査することにより判明する。なお、金属間化合物粒子では、安定相と準安定相の結晶が接して存在する場合もあるが、この場合には準安定相単独粒子と同様にピットの起点として十分に機能し得ることから、準安定相のものと同列に扱うことができる。
前記の比率は各粒子におけるＦｅ量／Ａｌ量で示すことができ、これが０.６０を超えるもの（Ｆｅ量／Ａｌ量＞０.６０）を安定相粒子とみなすことができ、０.６０以下のもの（Ｆｅ量／Ａｌ量≦０.６０）を本発明では準安定相とみなす。
【００２１】
「アルミニウム合金材料の製造方法」
前記組成を有し、前記金属間化合物粒子が表面層において分散されているアルミニウム合金材料は、常法または公知の製造方法を組み合わせる方法においてその一部を特別な条件に変更することにより製造することが可能である。
アルミニウム合金材料の通常の製造方法では、目的組成の合金を溶製した後、成分の偏析等をなくする目的で均質化処理を行っており、この均質化処理の段階で既に準安定相は殆ど存在しなくなっている。また、熱間圧延前の加熱処理（均熱処理）の過程で十分に加熱されることがあっても、そこで僅かに残存している準安定相が消失してしまう。従って、製造工程において以下に説明する適正な熱管理を行うことで、準安定相粒子が十分に分散した状態のアルミニウム合金材料を得ることができる。
【００２２】
以下に、本実施形態に係るアルミニウム合金材料からなる板材の一例を製造するための過程について説明する。
まず、本実施形態に係るアルミニウム合金材料は、常法により溶製することができるが、例えば、目的の組成比となるように原料を混合して成分調整し、鋳造することで鋳塊を得ることができる。その後、常法では５５０℃を超える温度で鋳塊に均質化処理を行って成分の均質化を図るが、本実施形態においては、準安定相を得るために、鋳塊に対する均質化処理を省略するか、均質化処理を施すとしても、５５０℃以下の温度、より好ましくは５００℃以下の温度で行い、その後に熱間圧延工程においても５００℃以下の温度となるように圧延し、更に、冷間圧延して目的の板厚のアルミニウム合金板を得る。なお、冷間圧延工程においては適宜焼鈍工程を施しても差し支えない。
このように得られたアルミニウム合金材料からなる板材では、感光剤の塗布に先だって苛性ソーダを用いた苛性処理等により表面洗浄がなされる。
【００２３】
表面が洗浄されたアルミニウム合金材料の板材は、表面を粗面化するための粗面化処理が施され、この粗面化処理は電解エッチングによりなされる。この電解エッチング処理においては、例えばロールでアルミニウム合金板を送りながら、ロールに交流電圧を印加することで電解処理することで得ることができる。
以上の製造工程により得られた準安定相の金属間化合物を有するアルミニウム合金材料であるならば、後述する実施例の試験結果から立証されるように、電解エッチングの均一性に優れ、円筒状の版胴に巻き付けた際に部分的に切れることがなく、版切れ性に優れるとともに、耐曲がり性と耐傷つき性にも優れたアルミニウム合金板材を得ることができる。
【００２４】
【実施例】
以下本発明を実施例に基づき説明するが、本発明が以下の実施例のみに制限されるものではないことは明らかである。
「アルミニウム合金板の製作」
目的の組成比になるように原料を調合し鋳造して得たスラブに対し、面削後、均質化処理を後述する表２、４に示す如く４７０〜５５０℃の範囲の温度で行い、次いで熱間圧延により厚さ７.０ｍｍの板材とし、次いで冷間圧延により厚さ１.０ｍｍの板材とした。この後、４５０℃で１５秒の中間焼鈍を行い、更に冷間圧延により厚さ０.３ｍｍの板材とした。
一方、先の工程において均質化処理を施さずに他の熱間圧延、冷間圧延、中間焼鈍、冷間圧延は同じ条件で施して厚さ０.３ｍｍの板材を得た。
これらのアルミニウム合金の板材に対して電解エッチング処理と陽極酸化処理を施し、以下の試験に供するアルミニウム合金板材試料を得た。
試料についてはＮｏ.１〜２６の試料を本発明範囲の試料として、以下に説明する各評価の試験に供し、後述する表１、表２にその結果を示した。また、本発明範囲から外れる条件の試料Ｎｏ.５１〜６３については、以下に説明する各評価の試験に供し、後述する表３、表４にその結果を示した。
【００２５】
「電解エッチング評価」
前記のアルミニウム合金板材試料を２００×３００ｍｍ２の面積に切断し、２％塩酸浴にて、浴温２５℃、電流密度１００Ａ／ｄｍ２、周波数５０Ｈｚ、処理時間１５秒の条件で電解エッチング処理を施した。得られた試料の表面のエッチング状態とピットの形態を観察し、以下の基準で評価した。
（エッチング均一性）
未エッチング部分を全く確認できない試料を◎印、未エッチング部分の面積率が５％未満の試料を〇印、未エッチング部分の面積率が５％以上のものを×印で示した。
（ピットの形態）
１０μｍを超える粗大ピットの面積率が１％未満のものを◎印、１％以上、３％未満の試料を〇印、３％以上のものを×印で示した。
（版切れ性）
前記のアルミニウム合金板材試料の裏面を樹脂板で遮蔽し、表側に１０％硫酸浴中で陽極酸化処理し、３ｇ／ｍ２の陽極酸化皮膜を形成した。この板材を幅６００ｍｍ、長さ７３０ｍｍに切断し、長手方向の両端を６ｍｍずつ裏面側に向けて９０゜折り曲げた。また、この板材を２００ｍｍφの円筒に巻き付けて両端の先の折曲部をチャッキングした後、板材が０.１５％伸びるまで引張り、２４時間放置した。その後、板材を円筒から取り外して前述のチャッキング部分を観察した。
このような試験を２０枚の板材に対して行い、僅かでも切断が見られた場合、後述の表２、４に×印、切断の見られない場合を〇印で示した。
【００２６】
「取り扱い性」
（耐曲がり性試験）
得られたアルミニウム合金板試料を幅７００ｍｍ、長さ１３００ｍｍに切断し、７０ｍｍφのエアー吸引可能な吸盤を２個使用して、板の中央部を吸着して積み替えを行い、Ｌ反りの変形量の変化を測定した。試料１０００枚測定し、元の合金板試料から各反りが２ｍｍ以上変化したものの枚数を数えた。
ここで、Ｌ反りとは、２個の吸盤のうち、１個の吸盤を板の長手方向中央、かつ、幅方向１／４の位置に、残り１個の吸盤を板の長手方向中央、かつ、幅方向３／４の位置にそれぞれ吸着させて板を吊り下げ、板の長手方向両端が重力で下方に垂れ下がった長さを示す。
試験結果は、全く変化しないものを後述の表１に〇印、変化した版が１〜２０枚のものを△印、変化した版が２０枚を超えるものを×印で示した。
（耐傷付き性）
上述のアルミニウム合金板試料の裏面を２Ｈの鉛筆で引っ掻いて、傷が付かないものを〇印、傷がつくものを×印で後述の表２、４に示した。
【００２７】
【表１】
【表２】
【表３】
【表４】
表１、表２のＮｏ.１〜Ｎｏ.２６の試料は本発明の範囲内の試料であるが、ＰＳ版として必要な強度を有し、未エッチング領域がほとんど見られずエッチング均一性に優れ、粗大ピットの発生が少ないかほとんど無く、版切れ性と耐刷性の面で良好であり、反りが少なく取り扱い性に優れ、傷も付き難い特徴を有している。なお、Ｎｏ.２３の試料は請求項１に係る実施例である。
【００３２】
表３、表４のＮｏ.５１の試料はＦｅの含有量を０.０９重量％にした例であるが、Ｆｅの含有量が少ないので、エッチング均一性に劣り、耐刷性、版切れ性、耐傷性にも劣る結果となり、Ｎｏ.５２の試料はＦｅの含有量を１.１０重量％にした例であるが、Ｆｅの含有量が多いので版切れ性と耐傷性が良好となった反面粗大ピットが多くなり、エッチング均一性と耐刷性にも問題を生じた。
表３、４のＮｏ.５３の試料はＳｉの含有量を０.００４重量％にした例であるが、エッチング均一性とピットと耐刷性は良好であるものの、Ｓｉ量が少ないので熱間圧延時の再結晶粒の微細化が不充分で版切れ性、耐傷性に劣る結果となり、Ｎｏ.５４の試料はＳｉの含有量を０.５２重量％にした例であるが、Ｓｉの含有量が多いので粗大な金属間化合物の析出が増加してエッチング均一性と粗大ピットが多くなり、エッチング均一性と耐刷性に問題を生じた。
表３、４のＮｏ.５５の試料はＣｕの含有量を０.０００４重量％にした例であるが、Ｃｕが少ない場合にエッチング均一性のみが劣る結果となり、Ｎｏ.５６の試料はＣｕの含有量を０.０６重量％にした例であるが、Ｃｕの含有量が多いので粗大な金属間化合物の析出が増加してエッチング均一性とピットと耐刷性に問題を生じた。
【００３３】
表３、４のＮｏ.５７の試料はＴｉの含有量を０.００４重量％にした例であるが、エッチング均一性とピットと耐刷性は良好であるものの、Ｔｉ量が少ないので結晶粒の微細化が不充分で版切れ性、耐傷性に劣る結果となり、Ｎｏ.５８の試料はＴｉの含有量を０.０４重量％にした例であるが、Ｔｉ量が多いので粗大な金属間化合物の析出が増加してエッチング均一性と粗大ピットが多くなり、エッチング均一性とピットと耐刷性に問題を生じた。
表３、４のＮｏ.５９の試料はＭｎの含有量を０.０４重量％にした例であるが、エッチング均一性とピットと耐刷性は良好であるものの、Ｍｎ量が少ないので強度が不足になり、版切れ性、取り扱い性、耐傷性に劣る結果となり、Ｎｏ.６０の試料はＭｎの含有量を０.９０重量％にした例であるが、Ｍｎの含有量が多いので電解エッチングのピットが粗大化し、エッチング均一性とピットと耐刷性が悪くなる問題を生じた。
表３、４のＮｏ.６１の試料はＢ＋Ｇａ量が上限を超えた例であるが、Ｂ＋Ｇａ量が本発明から外れているのでエッチング均一性と耐刷性とピットに問題を生じた。
【００３４】
表３、４のＮｏ.６２の試料はＦｅとＳｉとＣｕとＴｉとＭｎの含有量を好ましい範囲としたが、金属間化合物Ａの数と金属間化合物Ｂの数をいずれも少なくした例であるが、これが原因となってエッチング均一性とピットと耐刷性が悪化した試料である。Ｎｏ.６３の試料はＰｂ＋Ｃｒを０.１５重量％含有させた試料であるが、Ｐｂ＋Ｃｒの量が多すぎて再析出の量が多くなり過ぎ、局部的な電解エッチングになってエッチング均一性とピットと耐刷性がいずれも悪化した試料である。
【００３５】
【発明の効果】
以上説明のように本発明は、ＦｅとＳｉとＣｕとＴｉとＭｎを規定量含有し、残部Ａｌ及び不可避的不純物からなり、ＡｌとＦｅの原子量の比をＦｅ／Ａｌ≦０．６０とした準安定相を有する金属間化合物で粒径を０．１μｍ以上としたものを材料表面に３０個／ｍｍ２以上、ＡｌＭｎ系の金属間化合物を材料表面に６０個／ｍｍ２以上分散してなるので、エッチング時の反応の起点となり得る金属間化合物粒子の粒径の揃ったものを均一に分散させることができ、準安定相の金属間化合物としていることで電解エッチングした場合にアノード部位とカソード部位の双方をバランス良く反応できる結果、エッチング均一性に優れ、粗大ピットをほとんど有しないものであって、耐刷性と版切れ性と取り扱い性と耐傷性に優れた平版印刷版用アルミニウム合金材料を得ることができる。
【００３６】
更に本発明の製造方法によれば、前記の合金組成を有し、前記金属間化合物粒子の特徴を備えたアルミニウム合金材料を製造するにあたり、前記組成の合金鋳塊を５５０℃以下の温度で均質化処理するか、あるいは、均質化処理を施すことなく熱間圧延するので、準安定相である金属間化合物粒子を消失させることなく確実に析出させた状態のアルミニウム合金材料を得ることができる。
【００３７】
更に前記組成に加え、Ｐｂ、Ｂ、Ｖ、Ｇａ、Ｚｒ、Ｃｒ、Ｎｉのうちの１種以上を０．０００１０〜０．１０％の範囲で含有させてなる組成を適用することで、電解エッチング面に再析出して電解エッチングのピットの核を生成させることができる。
前記準安定相を有する金属間化合物粒子が、材料表面に３０個／ｍｍ ２ 以上、３０００個／ｍｍ ２ 以下の範囲で分散され、前記ＡｌＭｎ系の金属間化合物粒子が、材料表面に６０個／ｍｍ ２ 以上、６０００個／ｍｍ ２ 以下の範囲で分散されていても良い。
準安定相を有する金属間化合物粒子数がこの範囲であると、熱間圧延の温度を低下させる必要が無く、コスト面で不利になり難く、電解エッチングの核としての作用を確実に得ることができるとともに、ＡｌＭｎ系の金属間化合物粒子がこの範囲であると、電解エッチングの核としての作用が確実に得られる。 [0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aluminum alloy material for a lithographic printing plate used for printing with a photosensitive layer formed thereon and a method for producing the same, and in particular, uniformity of rough surface by electroetching and plate cutting property, printing durability, handling property, The present invention relates to a technology capable of providing an aluminum alloy plate for a printing plate having excellent scratch resistance and the like.
[0002]
[Prior art]
In lithographic printing, a plate in which an image portion is formed by performing plate making processing such as image exposure and development on a PS plate (Presensitized Plate) composed of an aluminum alloy plate and a photoreceptor having a diazo compound or the like as a photosensitizer The ink is wound around a cylindrical plate cylinder, ink is attached to the image portion in the presence of dampening water attached to the non-image portion, the ink is transferred to a rubber blanket, and printed on a paper surface.
In general, an aluminum alloy plate subjected to surface treatment such as roughening treatment (graining) or anodizing treatment by electrolytic etching is used as a support for the PS plate. As an aluminum alloy used for this kind of application, initially, JlS1050 (pure Al type having a purity of 99.5% or more), JlS1100 (Al-0.05 to 0.20% Cu alloy), JlS3003 (Al-0. (05-0.20% Cu-1.5% Mn alloy) has been mainly used.
[0003]
In this type of lithographic printing plate aluminum alloy plate,
(1) The rough surface by electrolytic etching is uniform.
(2) Adhesiveness of the photosensitive agent is good.
(3) The image area is not smudged during printing.
(4) A certain degree of strength is required for winding around the cylindrical plate cylinder of the printing press, and it should not be partially broken or cut during winding.
(5) Even if a large amount of printing is performed, the image portion is not smudged and excellent in printing resistance. Various characteristics such as these are required.
However, the JIS 1050, JIS 1100, and JIS 3003 alloys themselves defined in JIS cannot sufficiently satisfy the above requirements. For example, a JIS 3000 series aluminum alloy material has high material strength, is difficult to be deformed when the plate is attached to a plate cylinder of a printing press, and is hard, so that it is difficult to be scratched. There is an advantage that it is difficult to cut the plate even if it is enlarged.
However, JIS 3000 series aluminum materials have poor electrolytic etching properties and are generally roughened by mechanical polishing. However, the rough surface obtained by mechanical polishing is rougher than the rough surface obtained by electrolytic etching. Therefore, there is a problem that the adhesion of the photosensitive layer is poor and the printing durability is lowered. For this reason, in this type of aluminum alloy material, various improvements have been made with respect to the alloy composition and the obtained surface condition.
[0004]
For example, the surface roughening treatment is performed to provide water retention to the surface of the aluminum alloy plate and to fix the photosensitive agent in close contact with the printing plate in the formation of the photosensitive layer, and this adhesion is a performance as a printing plate. Affects.
However, in the conventional roughening treatment, an unetched portion may occur on the roughened surface, or the distribution of pits formed by the roughening may be non-uniform. There is an adverse effect, and there is a need to improve this rough surface condition.
Conventionally, in terms of the above-mentioned viewpoints, attempts have been made to improve the material, and as one method there has been proposed a method of adding a special element to the material. For example, the following Patent Document 1 discloses a method of improving the etching property by promoting the formation of pits by adding a predetermined amount of Ni, and the following Patent Document 2 adding Sn, In, and Ga. Thus, a method for improving etching properties by forming fine pits is disclosed.
However, even if a special element is added as described above, the above-mentioned demand has not been sufficiently satisfied, and addition of a special element causes an increase in material costs or becomes an obstacle to recycling. There is a problem.
In addition, a method for improving etching properties without adding a special element has been proposed by paying attention to the size and density of intermetallic compounds precipitated in the aluminum alloy material and controlling them. (See Patent Document 3)
[0005]
[Patent Document 1]
JP 11-115333 A
[Patent Document 2]
Japanese Patent Laid-Open No. 58-210144
[Patent Document 3]
Japanese Patent Laid-Open No. 11-151870
[0006]
[Problems to be solved by the invention]
In the method described in Patent Document 3, the intermetallic compound is used as a starting point for etching to form fine pits uniformly. However, this method cannot sufficiently improve the etching property, and does not satisfy the above-mentioned demand.
From the researches of the present inventors, the sufficient etching property cannot be obtained by controlling the size and density of the intermetallic compound described above, and the chemical solubility of the intermetallic compound is larger than expected, so that it can be dissolved in the electrolytic solution. It has been found that it is not sufficiently functioning as the starting point of the etching pit because it disappears. As a result of further research, the intermetallic compound is composed of a stable phase, whereas when the metastable phase AlFe-based intermetallic compound particles are appropriately dispersed, the etching property is greatly improved. Was found to be sufficient.
[0007]
An object of the present invention is to provide an aluminum alloy material for a lithographic printing plate that improves the uniformity of the roughening treatment by electrolytic etching, and also has excellent plate cutting properties, handling properties, and scratch resistance, and a method for producing the same. To do.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventor examined the uniformity of electrolytic etching of the aluminum alloy support for PS plate. As a result, the Al—Fe intermetallic compound crystallized or precipitated in the aluminum matrix was electrolyzed. It has been found that it acts as a cathode spot during etching and controls the solubility of the aluminum alloy support for PS plate.
From this point of view, the additive element with respect to aluminum was examined and the action of the additive element was investigated. As a result, it was found that additive components such as Si, Cu, and Ti decrease the cathode solubility when the additive amount is increased.
On the other hand, Fe improves cathode solubility.
Further, it has been found that the state of the intermetallic compound is important in the composition of this system, and the content and number of the particles having a specific particle size are important, and the present invention has been reached in view of these findings.
[0009]
The aluminum alloy material of the present invention is, by weight, Fe: 0.10 to 1.00%, Si: 0.01 to 0.50%, Cu: 0.001 to 0.05%, Ti: 0.005. -0.03%, Mn: 0.05-0.80%, the balance is made of Al and inevitable impurities, has a plurality of intermetallic compound particles in the metal structure, and the particle diameter is 0. 1 μm or more of Al and FeAtomic weightOf intermetallic compound particles having a metastable phase in which the ratio of Fe / Al ≦ 0.60 is 30 / mm on the material surface.2In addition to being dispersed, AlMn-based intermetallic compound particles having a particle diameter of 0.1 to 3.0 μm in equivalent circle diameter and having Mn are 60 / mm on the material surface.2It is characterized by being dispersed as described above.
In addition to the above composition, the present invention may contain one or more of Pb, B, V, Ga, Zr, Cr, and Ni in a range of 0.00010 to 0.10%.
In the present invention, the intermetallic compound particles having the metastable phase are 30 particles / mm on the material surface. 2 3000 / mm 2 The AlMn-based intermetallic compound particles dispersed in the following range are 60 particles / mm on the material surface. 2 Above, 6000 pieces / mm 2 It may be dispersed in the following range.
[0010]
In the production method of the present invention, Fe: 0.10 to 1.00%, Si: 0.01 to 0.50%, Cu: 0.001 to 0.05%, Ti: 0.005 to% by weight. 0.03%, Mn: 0.05 to 0.80%, the balance is composed of Al and inevitable impurities, has a plurality of intermetallic compound particles in the metal structure, and the particle size is 0.1 μm With the above, Al and FeAtomic weight30 / mm on the surface of the material having a metastable phase with a ratio of Fe / Al ≦ 0.602In addition to being dispersed, the AlMn-based intermetallic compound having a particle diameter of 0.1 to 3.0 μm in equivalent circle diameter and Mn is 60 / mm on the material surface.2In addition to being dispersed, AlMn-based intermetallic compound particles having a particle diameter of 0.1 to 3.0 μm in equivalent circle diameter and having Mn are 60 / mm on the material surface.2In producing an aluminum alloy material for a lithographic printing plate characterized by being dispersed as described above, the alloy ingot having the above composition is subjected to soaking treatment without subjecting it to homogenization treatment or hot rolling. The alloy ingot is homogenized at a temperature of 550 ° C. or lower and hot-rolled.
In the production method of the present invention, in addition to the above composition, an aluminum alloy material containing Ni in a range of 0.001 to 0.2% can be used.
In the production method of the present invention, in addition to the above composition, a lithographic plate having a composition containing at least one of Pb, B, V, Ga, Zr, Cr and Ni in a range of 0.00010 to 0.10% An aluminum alloy material for a printing plate may be used.
In the production method of the present invention, the intermetallic compound particles having the metastable phase are 30 particles / mm on the material surface. 2 3000 / mm 2 The AlMn-based intermetallic compound particles dispersed in the following range are 60 particles / mm on the material surface. 2 Above, 6000 pieces / mm 2 It may be dispersed in the following range.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below, but it is needless to say that the present invention is not limited to the following embodiments.
From the knowledge obtained by the present inventor described above, in the present embodiment, by weight percent, Fe: 0.10 to 1.00%, Si: 0.01 to 0.50%, Cu: 0.001 ~ 0.05%, Ti: 0.005 to 0.03%, Mn: 0.05 to 0.80%, the balance is made of Al and inevitable impurities, and has a plurality of intermetallic compound particles in the metal structure. 30 / mm on the surface of the material having a metastable phase having a particle size of 0.1 μm or more and a ratio of Al and Fe content of Fe / Al ≦ 0.60.2While being dispersed as described above, the AlMn-based intermetallic compound having a particle diameter of 0.1 to 3.0 μm in equivalent circle diameter and having Mn is 60 / mm on the material surface.2The aluminum alloy material for lithographic printing plates dispersed as described above is preferred for this type of purpose.
[0012]
Further, as a result of the inventor's research, this type of aluminum alloy material contains a plurality of intermetallic compound (AlFe, AlFeSi, Si, Ti) particles. It was found that the finer dispersion increases the cathode reactivity.
The condition is that the number of intermetallic compound particles having an equivalent circle diameter of 1.0 μm or more in the intermetallic compound particles described above is 30 / mm.2As well as being dispersed,
An AlMn-based intermetallic compound having a particle diameter of 0.1 to 3.0 μm in terms of a circle and having Mn is 60 / mm on the material surface.2That is, it is dispersed.
Furthermore, AlFe-based intermetallic compounds are stable phases (Al3The metastable phase is more preferable than Fe), and in the composition of the intermetallic compound, intermetallic compound particles having a metastable phase having a Fe / Al ratio of 0.60 or less are 30 / mm on the surface of the material.2Those dispersed as described above are preferable.
In this aluminum alloy material, the present invention can be applied to a material composed of a metastable dispersed layer in which at least the surface layer portion is dispersed with AlFe-based intermetallic compound particles having a metastable phase.
Furthermore, it is considered that the surface layer portion where the intermetallic compound particles are dispersed may be in a range from the outermost layer contributing to the electrolytic etching treatment to a region having a depth of about 50 μm.
[0013]
The reasons for limiting the alloy components for the aluminum alloy material defined in the present invention will be described below. Further, in the present specification, when the range between the upper limit value and the lower limit value of the content is indicated by “to”, the following means unless otherwise specified. Therefore, unless otherwise specified, 0.10 to 1.00% by weight means a range of 0.10% by weight or more and 1.00% by weight or less.
“Fe”: 0.10 to 1.00% by weight
Fe is an element that forms an intermetallic compound including an AlFe-based metastable phase and improves the uniformity of electrolytic etching. When the Fe content is less than 0.10% by weight, the cathode reactivity is insufficient and the effect of electrolytic etching uniformity cannot be obtained. On the other hand, if the Fe content exceeds 1.00% by weight, a coarse intermetallic compound is likely to be produced, and the cathode solubility is lowered. A more preferable range of Fe content is 0.2 to 0.60% by weight.
“Si”: 0.01 to 0.50% by weight
Si is an element that precipitates in the aluminum substrate and contributes to refinement of crystal grains. That is, the effect of forming an AlFeSi-based intermetallic compound and refining recrystallized grains during hot rolling is achieved. If the Si content is less than 0.01%, such an effect is insufficient. Conversely, if the Si content exceeds 0.50%, a coarse intermetallic compound is generated, and the electrolytic etching uniformity is lowered. Furthermore, in order to make the Si content less than 0.01% by weight, it is necessary to use a high-purity bare metal, which greatly increases the cost. Further, the more preferable range of the Si content is 0.05 to 0.20% by weight.
[0014]
“Cu”: 0.001 to 0.05% by weight
Cu is an element that greatly affects the formation of etching pits. If the Cu content is less than 0.001% by weight, the cathode solubility is insufficient and the formation of etching pits is not promoted. Further, when the Cu content exceeds 0.05%, the generation of coarse pits increases. Further, a more preferable range of Cu content is 0.002 to 0.02% by weight.
“Ti”: 0.005 to 0.03 wt%
Ti is an element for refining crystal grains. However, if the Ti content is less than 0.005% by weight, this refining effect cannot be obtained. Further, when the Ti content exceeds 0.03% by weight, coarse intermetallic compounds increase and the electrolytic etching uniformity decreases, and when the Ti content is less than 0.005%, the effect of crystal grain refinement is obtained. It becomes deficient. Further, a more preferable range of Ti content is 0.006 to 0.02% by weight.
[0015]
“Mn”: 0.05 to 0.80 wt%
Mn has an effect of improving the strength, but if the content is less than 0.05% by weight, the effect is small, and if the content exceeds 0.80% by weight, the electrolytic etching pits become coarse.
A more preferable Mn content is in the range of 0.10 to 0.60% by weight.
“Total of one or more of Pb, V, B, Ga, Zr, Ni and Cr”: 0.0010 to 0.10% by weight
Pb, V, B, Ga, Zr, Ni, and Cr are once eluted during the electrolytic etching, but re-deposited on the electrolytic etching surface and become the nucleus of the electrolytic etching pit. If the total amount of these elements is less than 0.00010%, this effect is insufficient. On the other hand, when the addition amount exceeds 0.10%, the amount of reprecipitation becomes too large, resulting in local electrolytic etching, and the electrolytic etching uniformity is lowered. A more preferable content of these elements is in the range of 0.001 to 0.05% by weight.
"Other elements"
Examples of impurities that may be contained in the aluminum alloy plate according to the present invention include Y, Sn, and In. The content of these impurities is preferably individually suppressed to 0.03% by weight or less. Further, Mg may be contained in the range of 0.05% by weight or less as another element.
[0016]
"Intermetallic compound particles"
Since intermetallic compound particles having a metastable phase serve as starting points of etching pits, the size of the particles in the dispersion layer affects the properties of pits that grow thereafter. If this particle size is small (equivalent circle diameter less than 0.1 μm) and the particle is too fine, it will not act sufficiently as a starting point for etching pits, while if the particle size is too large (equivalent circle diameter of more than 1.0 μm) Reduce the uniformity of. Therefore, the particle diameter of the intermetallic compound that favorably affects the formation of pits is a circle equivalent diameter of 0.1 μm to 1.0 μm.
Therefore, in the plane direction of the surface of the aluminum alloy material, the higher the ratio of particles in this size range among the intermetallic compound particles, the better the etchability. The plane direction means a plane direction parallel to the material surface at an arbitrary depth position of the dispersion layer. Since intermetallic compound particles of less than 0.1 μm are almost negligible from the viewpoint of the starting point of pits, the ratio of particles within the above range is focused on only intermetallic compound particles of 0.1 μm or more. Can be defined.
[0017]
Next, 30 intermetallic compound particles composed of a metastable phase in which the ratio of Al to Fe is Fe / Al ≦ 0.60 in the intermetallic compound particles or 30 intermetallic compound particles containing the metastable phase are present on the material surface. / Mm2It is preferable to be dispersed. Such a metastable phase effectively acts as a nucleus of electrolytic etching. When Fe / Al exceeds 0.60, a stable phase is obtained, and the action as a nucleus of electrolytic etching is lowered. The lower limit of the ratio of Al to Fe is about 0.25. Metastable phase intermetallic compound particles 30 / mm2If it is less than the dispersed state, the action as a nucleus of electrolytic etching is insufficient. The number of metastable phase intermetallic compound particles is 80 particles / mm.2Preferably, the upper limit is 3000 pieces / mm2Degree. In order to disperse a larger number of intermetallic compounds, it is necessary to lower the temperature of hot rolling in the production method described later, which increases the cost.
Further, in the intermetallic compound particles, the AlMn-based intermetallic compound having a particle diameter of 0.1 to 3.0 μm in equivalent circle diameter and having Mn is 60 / mm on the material surface.2It is preferable to be dispersed as described above. The number of AlMn-based intermetallic compound particles is 60 / mm2If it is less than 6000, the action as a nucleus is insufficient, conversely 6000 pieces / mm2Even if the above number is dispersed, the effect of improving the electrolytic etching property is small.
[0018]
`` Metastable phase dispersion layer ''
Conventionally, in an aluminum alloy plate for a lithographic printing plate, an AlFe intermetallic compound (Al3Fe) particles are dispersed and a metastable phase dispersion layer is not observed. In the present invention, unlike the conventional case where a stable phase intermetallic compound is precipitated, the surface layer portion has a dispersed layer in which metastable phase AlFe-based intermetallic compound particles are dispersed. This metastable phase is Al4Fe, Al5Fe, Al6Fe or AlmFe (4 <m <6). These exist as a single phase or as a mixed phase with a stable phase. The metastable phase particles are usually composed of only the metastable phase intermetallic compound, but may be a mixture of a part of the stable phase intermetallic compound.
The metastable phase intermetallic compound particles described above are more likely to be the starting point of pits than the stable phase intermetallic compound particles, and the dispersibility of the pits is enhanced to effectively prevent the generation of unetched portions. Moreover, Al shown in quantitative ratiomIt is more effective that m in the case of Fe is close to 6.
[0019]
"Dispersed layer depth"
The dispersion layer is preferably formed to a depth of 2 to 50 μm from the surface. In the production of aluminum alloy hills for flat printing, the surface layer is removed by degreasing by caustic cleaning, acid etching, mechanical polishing, etc. after rolling and before electrolytic etching. In this case, about 0.1 to 2 μm is removed and about 0.1 to 5 μm is removed by mechanical polishing. Therefore, the depth of the dispersion layer indicates the state before the surface layer removal and after the rolling. On the other hand, even if the depth of the dispersion layer exceeds 50 μm, it hardly contributes to the improvement of the electrolytic etching. Therefore, it is considered sufficient that the depth of the dispersion layer is about 50 μm.
"Ratio of metastable phase to stable phase (in dispersed layer)"
In the dispersion layer, it is desirable that the metastable phase intermetallic compound particles, which are excellent as pit starting points, are dispersed at a certain ratio or more.
[0020]
Whether the intermetallic compound is a metastable phase or a stable phase can be determined by examining the ratio of Fe content to Al content in the particles. In addition, in the intermetallic compound particles, there are cases where crystals of the stable phase and the metastable phase are in contact, but in this case, it can sufficiently function as the starting point of the pits as well as the metastable phase single particles, It can be handled in the same row as that of the metastable phase.
The above ratio can be expressed as Fe amount / Al amount in each particle, and those exceeding 0.60 (Fe amount / Al amount> 0.60) can be regarded as stable phase particles, and not more than 0.60. (Fe content / Al content ≦ 0.60) is regarded as a metastable phase in the present invention.
[0021]
"Production method of aluminum alloy material"
The aluminum alloy material having the above composition and in which the intermetallic compound particles are dispersed in the surface layer is manufactured by changing a part thereof to a special condition in a conventional method or a method combining known manufacturing methods. Is possible.
In the usual production method of aluminum alloy materials, after melting an alloy of the target composition, homogenization is performed for the purpose of eliminating segregation of components, etc., and almost no metastable phase is already present at this stage of homogenization. It no longer exists. Further, even if the material is sufficiently heated in the process of heat treatment (soaking) before hot rolling, the metastable phase that remains slightly disappears there. Therefore, an aluminum alloy material in which metastable phase particles are sufficiently dispersed can be obtained by performing appropriate thermal management described below in the manufacturing process.
[0022]
Below, the process for manufacturing an example of the board | plate material which consists of aluminum alloy material which concerns on this embodiment is demonstrated.
First, the aluminum alloy material according to the present embodiment can be melted by a conventional method. For example, raw materials are mixed to adjust the components so as to obtain a target composition ratio, and an ingot is obtained by casting. be able to. Thereafter, in the ordinary method, the ingot is homogenized at a temperature exceeding 550 ° C. to homogenize the components, but in this embodiment, in order to obtain a metastable phase, the homogenization processing for the ingot is omitted. Or, even if a homogenization treatment is performed, it is performed at a temperature of 550 ° C. or less, more preferably at a temperature of 500 ° C. or less, and after that, in the hot rolling process, it is rolled to a temperature of 500 ° C. or less, Cold rolling to obtain an aluminum alloy plate having a desired thickness. In the cold rolling process, an annealing process may be appropriately performed.
The plate material made of the aluminum alloy material thus obtained is subjected to surface cleaning by caustic treatment using caustic soda before application of the photosensitive agent.
[0023]
The aluminum alloy material plate whose surface has been cleaned is subjected to a roughening treatment for roughening the surface, and the roughening treatment is performed by electrolytic etching. In this electrolytic etching process, it can obtain by carrying out an electrolytic process by applying an alternating voltage to a roll, for example, sending an aluminum alloy plate with a roll.
If it is an aluminum alloy material having a metastable phase intermetallic compound obtained by the above manufacturing process, it is excellent in the uniformity of electrolytic etching, as shown in the test results of Examples described later, It is possible to obtain an aluminum alloy sheet material that is not partially cut when wound around a plate cylinder, has excellent plate cutting properties, and is also excellent in bending resistance and scratch resistance.
[0024]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, it is clear that this invention is not restrict | limited only to a following example.
"Production of aluminum alloy sheets"
For the slab obtained by blending and casting the raw materials so as to have the desired composition ratio, after chamfering, homogenization treatment is performed at a temperature in the range of 470 to 550 ° C. as shown in Tables 2 and 4 to be described later. A plate material having a thickness of 7.0 mm was formed by hot rolling, and then a plate material having a thickness of 1.0 mm was formed by cold rolling. Thereafter, intermediate annealing was performed at 450 ° C. for 15 seconds, and further, a plate material having a thickness of 0.3 mm was formed by cold rolling.
On the other hand, other hot rolling, cold rolling, intermediate annealing, and cold rolling were performed under the same conditions without performing homogenization in the previous step, and a 0.3 mm thick plate was obtained.
These aluminum alloy plate materials were subjected to electrolytic etching treatment and anodizing treatment to obtain aluminum alloy plate material samples used for the following tests.
Samples Nos. 1 to 26 were used as samples within the scope of the present invention and subjected to tests for each evaluation described below, and the results are shown in Tables 1 and 2 described later. Moreover, about sample No. 51-63 of the conditions remove | deviated from this invention range, it used for the test of each evaluation demonstrated below, and the result was shown in Table 3 and Table 4 mentioned later.
[0025]
"Electrolytic etching evaluation"
The aluminum alloy sheet material sample is 200 × 300 mm22% hydrochloric acid bath, bath temperature 25 ° C., current density 100 A / dm2The electrolytic etching process was performed under the conditions of a frequency of 50 Hz and a processing time of 15 seconds. The etching state of the surface of the obtained sample and the form of pits were observed and evaluated according to the following criteria.
(Etching uniformity)
Samples in which no unetched portion was confirmed were marked with ◎, samples with an unetched portion area ratio of less than 5% were marked with ○, and those with an unetched portion area ratio of 5% or more were marked with x.
(Pit form)
Samples with an area ratio of coarse pits exceeding 10 μm of less than 1% are indicated by ◎, samples of 1% or more and less than 3% are indicated by ○, and those by 3% or more are indicated by ×.
(Cutting property)
The back surface of the aluminum alloy plate material sample is shielded with a resin plate, and the front side is anodized in a 10% sulfuric acid bath, and 3 g / m.2An anodic oxide film was formed. This plate material was cut into a width of 600 mm and a length of 730 mm, and bent at 90 ° so that both ends in the longitudinal direction were 6 mm toward the back side. Further, this plate material was wound around a 200 mmφ cylinder to chuck the bent portions at both ends, and then pulled until the plate material was extended by 0.15% and left for 24 hours. Thereafter, the plate material was removed from the cylinder, and the above-mentioned chucking portion was observed.
When such a test was performed on 20 sheets of material, and even a slight cut was observed, in Tables 2 and 4 to be described later, an x mark was given, and a case where no cut was seen was marked by a circle mark.
[0026]
"Handability"
(Bend resistance test)
The obtained aluminum alloy plate sample was cut into a width of 700 mm and a length of 1300 mm, and two suction suckers with a diameter of 70 mmφ were used to adsorb the central part of the plate and transship, and the deformation amount of the L warp Changes were measured. 1000 samples were measured, and the number of sheets whose warpage was changed by 2 mm or more from the original alloy plate sample was counted.
Here, the L warp is one of the two suction cups, the one suction cup at the center in the longitudinal direction of the plate, and the other one suction cup at the center in the longitudinal direction of the plate, and The length of the plate is suspended by being adsorbed to each of the positions in the width direction 3/4 and both ends in the longitudinal direction of the plate are hung downward by gravity.
In the test results, those that did not change at all were indicated by ◯ in Table 1 to be described later, those with 1 to 20 changed plates were indicated by Δ, and those with more than 20 changed plates were indicated by ×.
(Scratch resistance)
The back surface of the above-mentioned aluminum alloy plate sample is scratched with a 2H pencil, and those that are not scratched are indicated by ○ and those that are scratched are indicated by Tables 2 and 4 below.
[0027]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
The samples No. 1 to No. 26 in Tables 1 and 2 are samples within the scope of the present invention, but have the necessary strength as a PS plate and are excellent in etching uniformity with almost no unetched area being seen. There is little or almost no generation of coarse pits, it is good in terms of plate cutting and printing durability, has low warpage, excellent handleability, and is hardly damaged. The sample No. 23 is an example according to claim 1.
[0032]
The samples of No. 51 in Tables 3 and 4 are examples in which the Fe content is 0.09% by weight. However, since the Fe content is small, the etching uniformity is inferior, the printing durability, and the plate cutting property. As a result, the sample of No. 52 is an example in which the Fe content is 1.10% by weight. However, since the Fe content is large, the plate cutting property and the scratch resistance are improved. On the other hand, there were many coarse pits, which caused problems in etching uniformity and printing durability.
The sample No. 53 in Tables 3 and 4 is an example in which the Si content is 0.004% by weight, but the etching uniformity, pits and printing durability are good, but the amount of Si is small and hot. The result is inadequate refinement of recrystallized grains during rolling and inferior plate cutting and scratch resistance, and the sample No. 54 is an example in which the Si content is 0.52% by weight. Since the amount was large, precipitation of coarse intermetallic compounds increased, resulting in an increase in etching uniformity and coarse pits, resulting in problems in etching uniformity and printing durability.
The samples of No. 55 in Tables 3 and 4 are examples in which the Cu content is set to 0.0004 wt%. However, when the amount of Cu is small, only the etching uniformity is inferior. In this example, the content was set to 0.06% by weight. However, since the Cu content was large, precipitation of coarse intermetallic compounds increased, resulting in problems in etching uniformity, pits, and printing durability.
[0033]
The sample No. 57 in Tables 3 and 4 is an example in which the Ti content is 0.004% by weight, but the etching uniformity, pits and printing durability are good, but since the Ti amount is small, the crystal grains No. 58 sample is an example in which the content of Ti is 0.04 wt%, but since the amount of Ti is large, there is a large amount of coarse intermetallics. Compound precipitation increased and etching uniformity and coarse pits increased, causing problems in etching uniformity, pits and printing durability.
The sample No. 59 in Tables 3 and 4 is an example in which the Mn content is 0.04% by weight, but the etching uniformity, pits and printing durability are good, but the strength is low because of the small amount of Mn. Insufficient plate cutting performance, handleability, and scratch resistance, the sample No. 60 is an example in which the Mn content is 0.90% by weight. As a result, the pits became coarse and the etching uniformity and pit and printing durability deteriorated.
The sample No. 61 in Tables 3 and 4 is an example in which the amount of B + Ga exceeded the upper limit. However, since the amount of B + Ga was out of the present invention, problems occurred in etching uniformity, printing durability, and pits.
[0034]
Samples No. 62 in Tables 3 and 4 are examples in which the contents of Fe, Si, Cu, Ti, and Mn are within a preferable range, but the number of intermetallic compounds A and the number of intermetallic compounds B are both reduced. However, this is a sample whose etching uniformity, pits and printing durability deteriorated. The sample No. 63 is a sample containing 0.15% by weight of Pb + Cr, but the amount of Pb + Cr is too much and the amount of reprecipitation becomes too large, resulting in local electrolytic etching and etching uniformity and pits. And the printing durability were both deteriorated.
[0035]
【The invention's effect】
As described above, the present invention contains a specified amount of Fe, Si, Cu, Ti, and Mn, and the balance is Al and inevitable impurities.Atomic weightAn intermetallic compound having a metastable phase with a ratio of Fe / Al ≦ 0.60 and having a particle size of 0.1 μm or more is 30 / mm on the material surface.2As mentioned above, 60 / mm AlMn-based intermetallic compound on the material surface2Because it is dispersed above, it is possible to uniformly disperse particles of intermetallic compound particles that can be the starting point of the reaction at the time of etching, and when electroetching because it is a metastable phase intermetallic compound As a result, both the anode part and the cathode part can react in a well-balanced manner, resulting in excellent etching uniformity, almost no coarse pits, and lithographic printing with excellent printing durability, plate cutting ability, handleability and scratch resistance. An aluminum alloy material for a plate can be obtained.
[0036]
Furthermore, according to the production method of the present invention, in producing an aluminum alloy material having the above alloy composition and having the characteristics of the intermetallic compound particles, the alloy ingot having the above composition is homogeneous at a temperature of 550 ° C. or less. Since it is hot-rolled without subjecting it to a homogenization treatment or a homogenization treatment, it is possible to obtain an aluminum alloy material in a state of being surely precipitated without losing intermetallic compound particles that are metastable phases.
[0037]
Furthermore, in addition to the above composition, by applying a composition containing at least one of Pb, B, V, Ga, Zr, Cr, and Ni in a range of 0.00010 to 0.10%, electrolytic etching is performed. It can be re-deposited on the surface to generate pit nuclei for electrolytic etching.
The intermetallic compound particles having the metastable phase are 30 particles / mm on the material surface. 2 3000 / mm 2 The AlMn-based intermetallic compound particles dispersed in the following range are 60 particles / mm on the material surface. 2 Above, 6000 pieces / mm 2 It may be dispersed in the following range.
When the number of intermetallic compound particles having a metastable phase is in this range, it is not necessary to reduce the temperature of hot rolling, it is difficult to be disadvantageous in terms of cost, and it is possible to reliably obtain an action as a nucleus of electrolytic etching. In addition, when the AlMn-based intermetallic compound particles are in this range, the action as a nucleus of electrolytic etching can be reliably obtained.
Claims (6)
金属組織中に複数の金属間化合物粒子を有し、粒径が円相当径で０．１μｍ以上で、ＡｌとＦｅの原子量の比をＦｅ／Ａｌ≦０．６０とした準安定相を有する金属間化合物粒子が、材料表面に３０個／ｍｍ２以上分散されてなるとともに、粒径が円相当径で０．１〜３．０μｍで、Ｍｎを有するＡｌＭｎ系の金属間化合物粒子が、材料表面に６０個／ｍｍ２以上分散されてなることを特徴とする平版印刷版用アルミニウム合金材料。By weight, Fe: 0.10 to 1.00%, Si: 0.01 to 0.50%, Cu: 0.001 to 0.05%, Ti: 0.005 to 0.03%, Mn: 0.05-0.80%, the balance consists of Al and inevitable impurities,
A metal having a metastable phase having a plurality of intermetallic compound particles in a metal structure, a particle diameter of 0.1 μm or more in an equivalent circle diameter, and an atomic weight ratio of Al to Fe of Fe / Al ≦ 0.60 Intermetallic particles are dispersed at 30 particles / mm 2 or more on the material surface, and AlMn-based intermetallic compound particles having a Mn-equivalent particle diameter of 0.1 to 3.0 μm are equivalent to the material surface. An aluminum alloy material for a lithographic printing plate, characterized by being dispersed at a rate of 60 pieces / mm 2 or more.
前記組成の合金鋳塊を均質化処理を施すことなく均熱処理を施して熱間圧延するか、あるいは、前記組成の合金鋳塊を５５０℃以下の温度で均質化処理して熱間圧延することを特徴とする平版印刷版用アルミニウム合金板の製造方法。By weight, Fe: 0.10 to 1.00%, Si: 0.01 to 0.50%, Cu: 0.001 to 0.05%, Ti: 0.005 to 0.03%, Mn: 0.05 to 0.80%, the balance is composed of Al and inevitable impurities, has a plurality of intermetallic compound particles in the metal structure, and has an atomic weight of Al and Fe with a particle size of 0.1 μm or more And intermetallic compound particles having a metastable phase with a ratio of Fe / Al ≦ 0.60 are dispersed on the surface of the material by 30 particles / mm 2 or more, and the particle diameter is 0.1-3. In producing an aluminum alloy material for a lithographic printing plate characterized in that AlMn-based intermetallic compound particles having Mn at 0 μm are dispersed on the surface of the material by 60 particles / mm 2 or more.
The alloy ingot having the above composition is subjected to soaking treatment without being homogenized and hot rolled, or the alloy ingot having the above composition is homogenized at a temperature of 550 ° C. or less and hot rolled. A method for producing an aluminum alloy plate for a lithographic printing plate.
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