JP3893031B2 - Aluminum alloy plate for printing plate and method for producing the same - Google Patents
Aluminum alloy plate for printing plate and method for producing the same Download PDFInfo
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- 238000007639 printing Methods 0.000 title claims description 15
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- 239000002245 particle Substances 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 13
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- 238000000265 homogenisation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
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- 229910018084 Al-Fe Inorganic materials 0.000 description 2
- 229910018192 Al—Fe Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 229910018191 Al—Fe—Si Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は平版印刷版用アルミニウム合金板及びその製造方法に関し、より少ない電気量で均一な電解粗面化面を形成することができる印刷版用アルミニウム合金板及びその製造方法に関するものである。
【０００２】
【従来の技術】
印刷用アルミニウム合金板は、一般的に塩酸又は硝酸の希釈液中で通電を行うことにより、表面を粗面化して使用される。このとき、少ない電気量でかつ均一な粗面を形成するアルミニウム合金が求められる。
【０００３】
電解粗面化時に、反応性が高く且つ均一な粗面が得られるアルミニウム合金板の製造技術として、２種類の技術が提案されている。先ず、添加元素を調整することにより電解粗面の均一化を図った方法として、例えば、特開平１１−９９７６０号公報に記載されたものが挙げられる。また、アルミニウム合金中の添加元素の金属間化合物を調整することにより電解粗面の均一化を図った方法として、例えば、特開平１１−１１５３３３号公報に記載されたものが挙げられる。
【０００４】
【発明が解決しようとする課題】
しかしながら、近時、高生産性の要求のもとに、特開平１１−１８８９７３号公報に記載されているように、電解処理条件が１２０Ａ／ｄｍ２にて３秒間、８５Ａ／ｄｍ２にて６秒間のように、高電流密度及び短時間での電解粗面化が提案されるようになった。
【０００５】
また、感光膜の技術の向上により、より細かいピットを形成すること、換言すれば、均一に分散したピットを形成することができるアルミニウム合金板が求められている。
【０００６】
しかし、前述の従来の電解粗面の均一化技術では、高電流密度及び短時間での電解処理において、反応性、ピットの細かさ、及び粗面の均一性がいずれも不十分なものであり、近時の印刷版及びその製造方法に要求される特性を満足するアルミニウム合金板の開発が要望されている。
【０００７】
本発明はかかる問題点に鑑みてなされたものであって、高電流密度及び短時間での電解粗面化処理において、電解効率が高く、反応性、ピットの細かさ及び粗面の均一性を向上させることができる印刷版用アルミニウム合金板及びその製造方法を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明に係る印刷版用アルミニウム合金板は、Ｆｅ：０.２５乃至０.４５質量％、Ｓｉ：０.０２乃至０.０８質量％、Ｃｕ：０.０４質量％以下を含有し、残部がＡｌ及び不可避的不純物からなり、不可避的不純物におけるＮｉを０.００５質量％以下に規制した組成を有し、粒径が１μｍ以下のＦｅ金属間化合物が０.０２質量％以上であることを特徴とする。
【０００９】
本発明に係る印刷版用アルミニウム合金板の製造方法は、Ｆｅ：０.２５乃至０.４５質量％、Ｓｉ：０.０２乃至０.０８質量％、Ｃｕ：０.０４質量％以下を含有し、残部がＡｌ及び不可避的不純物からなり、不可避的不純物におけるＮｉを０.００５質量％以下に規制した組成を有するアルミニウム合金鋳塊を、５５０℃以上の温度で均質化処理する工程と、開始温度を４００乃至４５０℃として熱間圧延する工程と、その後、少なくとも１回、平均昇温速度１０乃至６０℃／時で昇温させて４５０乃至５００℃に１乃至２０時間保持する焼鈍処理を行う工程とを有し、粒径が１μｍ以下のＦｅ金属間化合物が０.０２質量％以上であるアルミニウム合金板を製造することを特徴とする。
【００１０】
【発明の実施の形態】
以下、本発明について更に詳細に説明する。本願発明者等は、アルミニウム合金板中のＦｅ金属間化合物の影響について鋭意研究した。即ち、従来技術では、Ｆｅ含有量の殆どが、主に鋳造工程で発生する粒径１μｍ超の晶出物となり、僅かの残部Ｆｅがアルミニウム合金中に固溶しており、粒径１μｍ以下の析出物（Ｆｅ金属間化合物）の存在量は極めて少ない状態であった。上述した粒径１μｍ超の晶出物である金属間化合物だけでは適度の存在密度（面密度）とならない。そこで、本発明では粒径１μｍ以下のＦｅ金属間化合物に注目し、均質化処理及び焼鈍処理で粒径１μｍ以下の金属間化合物を析出させることにより、その分布を調整して、反応性と粗面の均一性について試験を行った。
【００１１】
その結果、粒径１μｍ以下のＦｅ金属間化合物がピット形成核となり、ピットが多数発生することによって、少ない電気量でかつ均一な粗面を形成できることを見出した。本発明はこの知見に基づき完成されたものである。
【００１２】
即ち、アルミニウム合金板中の粒径が１μｍ以下の微細なＦｅ金属間化合物のアルミニウム合金中の含有量を０.０２質量％以上に調整することにより、ピット発生のための起点が多数となり、少ない電気量で均一に分散した細かいピットを形成することができる。
【００１３】
この場合に、このような微細なＦｅ金属間化合物を所定量以上生成するためには、Ｆｅの固溶度が可能な限り高い値を示す条件で鋳造を行うことが望ましい。また、鋳造工程で生成した粒径が１μｍを超えるＦｅ金属間化合物は、均質化処理により、アルミニウム合金中に一旦固溶させた後、中間焼鈍で粒径が１μｍ以下のＦｅ金属間化合物として析出させることが可能である。即ち、均質化処理では、アルミニウム合金板をＦｅ金属間化合物が固溶する５５０℃以上の温度に加熱して、Ｆｅ系晶出物を微細化させ、アルミニウム合金中のＦｅ固溶量を増加させる。そして、熱間圧延終了後に、焼鈍を行うことにより、固溶しているＦｅを析出させ、粒径が１μｍ以下のＦｅ金属間化合物に変化させる。
【００１４】
熱間圧延を行い、その後、少なくとも１回、焼鈍処理する。この焼鈍処理条件は、平均昇温速度が１０乃至６０℃／時で昇温させ、４５０乃至５００℃に１乃至２０時間保持して加熱するものである。これにより、粒径が１μｍ以下のＦｅ金属間化合物のアルミニウム合金中の含有量を０.０２質量％以上とすることができる。
【００１５】
次に、本発明の製造方法における数値限定理由について説明する。
【００１６】
［均質化処理温度：５５０℃以上］
均質化処理温度が５５０℃未満であると、鋳造工程で発生した晶出物を充分に微細化することができず、Ｆｅ固溶量を増加させることができない。従って、粒径が１μｍ未満のＦｅ金属間化合物が少なくなる。
【００１７】
［熱間圧延開始温度：４００乃至５５０℃］
熱間圧延の開始温度が５５０℃を超えると、結晶粒が過剰に成長する。これにより、粗面が不均一となるので、熱間圧延の開始温度は５５０℃以下とする。また、熱間圧延の開始温度が４００℃未満では、圧延中の動的再結晶が不十分であり、同様に粗面の均一性が損なわれる。このため、熱間圧延開始温度は４００乃至５５０℃とする。
【００１８】
［平均昇温速度：１０乃至６０℃／時］
平均昇温速度が１０℃／時未満であると、スループットが長くなりすぎ、製造コストが上昇する。一方、昇温速度が６０℃／時を超えると、昇温速度が速すぎて充分に析出が進行せず、所望の微細なＦｅ金属間化合物を生成できない。
【００１９】
［加熱保持温度：４５０乃至５００℃］
加熱保持温度が４５０℃未満であると、析出の進行速度が遅く、析出が不十分である。また、加熱保持温度が５００℃を超えると、逆に固溶が進行して析出物が減少する。
【００２０】
次に、本発明の印刷版用アルミニウム合金板の成分添加理由及び組成限定理由について説明する。
【００２１】
［Ｆｅ：０．２５乃至０．４５質量％］
ＦｅはＡｌ−Ｆｅ系金属間化合物を形成し、再結晶粒の微細化及び組織の均一化による機械的強度維持に効果を有する。このＦｅ系金属間化合物は、電解粗面化時のイニシャルピットの開始点として作用する。しかし、Ｆｅ含有量が０.２５質量％未満では、アルミニウム合金中に含有される全てのＦｅを金属間化合物として析出させても、電解処理における反応性が不十分であり、均一なピットを形成することができず、また、強度が低いため、印刷版としての用途に適さない。一方、Ｆｅ含有量が０.４５質量％を超えると、均質化処理の条件に拘わらず、粒径が１μｍを超える金属間化合物、即ち晶出物が十分に減少しない。このため、このような粗大晶出物が、粗大なピットを発生させる起点となる。従って、Ｆｅ含有量は、０．２５乃至０．４５質量％とする。
【００２２】
［Ｓｉ：０．０２乃至０．０８質量％］
ＳｉはＡｌ−Ｆｅ−Ｓｉ系金属間化合物を形成し、熱間圧延時における各パス間での再結晶の核として作用するので、熱間圧延時の再結晶を微細化する効果を有する。更に、イニシャルピットの形成を促進し、ピットの均一性を向上させる効果を奏する。しかし、Ｓｉ含有量が０.０２質量％未満では電解処理における反応性が低く、逆にＳｉ含有量が０.０８質量％を超えると電解処理における反応性が過剰となり、不均一なピットが形成される。
【００２３】
［Ｃｕ：０．０４質量％以下］
Ｃｕは電解粗面化の均一性に影響するが、Ｃｕ含有量が０.０４質量％を超えると、均一に分散したピットを形成できない。このため、Ｃｕ含有量は０．０４質量％以下とする。
【００２４】
積極添加元素については上述のとおりであるが、不可避的不純物であるＮｉの含有量を規制する理由は、以下のとおりである。
【００２５】
［Ｎｉ：０．００５質量％以下］
Ｎｉは電解粗面化のエッチング性を向上させるものの、Ｎｉ含有量が０.００５質量％を超えると、電解粗面化時のエッチング性が過剰となり、腐食されやすくなって印刷汚れを生じる。このため、Ｎｉ含有量は０．００５質量％以下に規制する。
【００２６】
なお、不可避的不純物であるＭｎはアルミニウム合金のエッチング性を低下させて印刷汚れの原因となりうるので、その含有量は０．０５質量％以下に規制することが好ましい。
【００２７】
【実施例】
以下、本発明の実施例について、本発明の範囲から外れる比較例と比較して本発明の効果について説明する。下記表１は使用したアルミニウム合金板の組成と、その製造条件を示す。先ず、この表１に示す組成のアルミニウム合金の溶湯を４００ｍｍ厚さの鋳塊に鋳造した。次に、表１に記載の温度で６時間加熱することによりこのアルミニウム合金板を均質化処理し、開始温度を４５０℃として熱間圧延を開始した。また、アルミニウム合金板の厚さが３ｍｍになったときに熱間圧延を終了した。その後、厚さが１.５ｍｍになるまで冷間圧延し、その後、表１に記載の条件で中間焼鈍した。中間焼鈍後に、アルミニウム合金板を厚さが０.２４ｍｍになるまで冷間圧延した。なお、表１におけるＦｅ金属間化合物の量は粒径１μｍ以下のＦｅ系金属間化合物がアルミニウム合金全体に占める質量割合である。
【００２８】
【表１】
次に、上述の条件で製造されたアルミニウム合金板の試験方法について説明する。
【００３０】
［Ｆｅ金属間化合物の析出量の測定方法］
約２ｇのアルミニウム合金板を１８０℃に加熱したフェノールに溶解させた。そして、残渣を１μｍ孔のミクロフィルターで濾過した。この濾液をさらに０.１μｍ孔のミクロフィルターで濾過した。得られた残渣はＡｌ−Ｆｅ系化合物と単体金属Ｓｉである。更に、この残渣を塩酸で溶解し、浴中のＦｅ量をＩＣＰ−ＭＳ（原子吸光分析法）により測定し、この測定値から１μｍ以下のＦｅ金属間化合物量を算出した。
【００３１】
［電解効率の測定方法］
アルミニウム合金板を２質量％−ＨＣｌ水溶液中に浸漬し、このＨＣｌ水溶液の温度を２５℃に調整し、電流密度が８０Ａ/ｄｍ２、通電時間が１１秒間の条件で通電し、電解粗面化を行った。アルミニウム合金板の通電前後の質量を測定し、これらの差を溶解減量とした。この場合に、通電された電気量は８８０Ｃ／ｄｍ２であるから、ファラデーの法則から理論溶解量は０.０８２１ｇ／ｄｍ２と算出される。従って、電解効率は下記数式１により算出できる。
【００３２】
【数１】
電解効率［％］＝溶解減量［ｇ／ｄｍ２］／０.０８２１［ｇ／ｄｍ２］×１００［％］
【００３３】
［粗面の観察］
上述の電解効率の測定で電解粗面化を行ったアルミニウム合金板の表面を走査型電子顕微鏡で観察した。そして、粗面を走査型電子顕微鏡で１０００倍にて観察し、約７乃至１０μｍのピットがほぼ全面に均一に分散して存在する場合を○、３μｍ以下の小さなピット又は１５μｍ以上の粗大なピットが混在する場合を×とした。
【００３４】
表１に、粒径１μｍ未満のＦｅ金属間化合物の割合、電解効率及び粗面の均一性を記載した。その結果、実施例１乃至７は組成及びＦｅ金属間化合物の割合が本発明の請求項１を満足するものであり、電解効率及び粗面の均一性のいずれも優れたものであった。また、実施例１乃至７は本発明の請求項２に記載の製造条件を満足するものであり、Ｆｅ金属間化合物の量が充分に多いものであった。
【００３５】
一方、比較例１は、平均昇温速度が速すぎ、また中間焼鈍の保持時間が短すぎて、微細なＦｅ金属間化合物の生成が不十分であった。比較例２は、中間焼鈍の保持温度が高すぎて、微細なＦｅ金属間化合物の量が少なかった。比較例３は、中間焼鈍の保持温度が低すぎて、微細なＦｅ金属間化合物の量が少なかった。比較例４は、中間焼鈍の保持温度が高すぎ、保持時間が長すぎたため、微細なＦｅ金属間化合物の量が不十分であった。比較例８は均質化温度が低すぎたため、鋳造時に発生した粒径１μｍ以上のＦｅ金属間化合物が充分に固溶せず、このため、後工程で微細なＦｅ金属間化合物が充分に析出しなかった。更に、比較例５はＦｅ含有量が少ないと共に、平均昇温速度が速すぎ、また中間焼鈍時間が短すぎたため、Ｆｅ金属間化合物の割合が少なかった。このため、比較例１乃至５、８はいずれも電解効率が低く、粗面の均一性も劣るものであった。
【００３６】
比較例６はＦｅ含有量が少ないため、電解効率が低く、反応性が不十分で、粗面の均一性が悪いものであった。比較例７はＦｅ含有量が過剰であるため、反応性が過大であり、粗面が不均一であった。比較例９はＣｕ含有量が多すぎたため、均一なピットが形成されず、粗面の均一性が劣るものであった。比較例１０は不可避的不純物のＮｉ含有量が多すぎるため、反応性が過剰となり、粗面の均一性が劣るものであった。
【００３７】
【発明の効果】
以上説明したように、本発明によれば、高電流密度及び短時間での電解粗面化処理において、電解効率が高く、反応性が優れており、ピットが細かく均一に分散されており、粗面の均一性が優れた印刷版用アルミニウム合金板を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aluminum alloy plate for a lithographic printing plate and a method for producing the same, and relates to an aluminum alloy plate for a printing plate capable of forming a uniform electrolytic roughened surface with a smaller amount of electricity and a method for producing the same.
[0002]
[Prior art]
The aluminum alloy plate for printing is generally used by roughening the surface by energizing in a dilute solution of hydrochloric acid or nitric acid. At this time, an aluminum alloy that forms a uniform rough surface with a small amount of electricity is required.
[0003]
Two types of techniques have been proposed as a technique for producing an aluminum alloy plate that has a high reactivity and a uniform rough surface during electrolytic roughening. First, as a method for making the electrolytic rough surface uniform by adjusting the additive element, for example, the method described in JP-A-11-99760 can be mentioned. Moreover, as a method of making the electrolytic rough surface uniform by adjusting the intermetallic compound of the additive element in the aluminum alloy, for example, the method described in JP-A-11-115333 can be mentioned.
[0004]
[Problems to be solved by the invention]
However, recently, under the demand for high productivity, as described in Japanese Patent Application Laid-Open No. 11-1881973, the electrolytic treatment conditions are 6 seconds at 120 A / dm 2 for 3 seconds and 85 A / dm 2 . As in seconds, high current density and short-time electrolytic surface roughening have been proposed.
[0005]
Further, there is a demand for an aluminum alloy plate capable of forming finer pits, in other words, forming uniformly distributed pits, by improving the technology of the photosensitive film.
[0006]
However, the conventional electrolytic roughened surface homogenization technique described above has insufficient reactivity, pit fineness, and rough surface uniformity in high current density and short time electrolytic treatment. There has been a demand for the development of an aluminum alloy plate that satisfies the properties required for recent printing plates and methods for producing the same.
[0007]
The present invention has been made in view of such problems, and in high-current density and short-time electrolytic surface roughening treatment, the electrolytic efficiency is high, and the reactivity, fineness of pits and uniformity of the rough surface are improved. An object of the present invention is to provide an aluminum alloy plate for a printing plate that can be improved and a method for producing the same.
[0008]
[Means for Solving the Problems]
The aluminum alloy plate for a printing plate according to the present invention contains Fe: 0.25 to 0.45% by mass, Si: 0.02 to 0.08% by mass, Cu: 0.04% by mass or less, and the balance being It is composed of Al and inevitable impurities, has a composition in which Ni in the inevitable impurities is regulated to 0.005 mass% or less, and Fe intermetallic compound having a particle diameter of 1 μm or less is 0.02 mass% or more. And
[0009]
The method for producing an aluminum alloy plate for a printing plate according to the present invention contains Fe: 0.25 to 0.45% by mass, Si: 0.02 to 0.08% by mass, and Cu: 0.04% by mass or less. A step of homogenizing an aluminum alloy ingot having a composition in which the balance is made of Al and unavoidable impurities and Ni in the unavoidable impurities is regulated to 0.005 mass% or less at a temperature of 550 ° C. or more, and a start temperature Hot-rolling at a temperature of 400 to 450 ° C., and then performing an annealing process of raising the temperature at an average temperature increase rate of 10 to 60 ° C./hour and holding at 450 to 500 ° C. for 1 to 20 hours at least once. And an aluminum alloy plate having a particle diameter of 1 μm or less and an Fe intermetallic compound of 0.02% by mass or more is manufactured.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail. The inventors of the present application conducted extensive research on the influence of Fe intermetallic compounds in the aluminum alloy sheet. That is, in the prior art, most of the Fe content is a crystallized product having a particle size exceeding 1 μm mainly generated in the casting process, and a small amount of remaining Fe is dissolved in the aluminum alloy, and the particle size is 1 μm or less. The amount of precipitates (Fe intermetallic compound) was extremely small. Only an intermetallic compound that is a crystallized substance having a particle diameter of more than 1 μm described above does not provide an appropriate density (area density). Therefore, in the present invention, attention is paid to Fe intermetallic compounds having a particle size of 1 μm or less, and the distribution is adjusted by precipitating intermetallic compounds having a particle size of 1 μm or less by homogenization treatment and annealing treatment, thereby reacting and roughening. The surface was tested for uniformity.
[0011]
As a result, it has been found that an Fe intermetallic compound having a particle size of 1 μm or less serves as pit formation nuclei and a large number of pits can form a uniform rough surface with a small amount of electricity. The present invention has been completed based on this finding.
[0012]
That is, by adjusting the content in the aluminum alloy of fine Fe intermetallic compound having a particle size of 1 μm or less in the aluminum alloy plate to 0.02 mass% or more, the number of starting points for pit generation becomes large and small. It is possible to form fine pits that are uniformly dispersed by the amount of electricity.
[0013]
In this case, in order to produce a predetermined amount or more of such a fine Fe intermetallic compound, it is desirable to perform casting under conditions where the solid solubility of Fe is as high as possible. In addition, the Fe intermetallic compound having a particle size exceeding 1 μm generated in the casting process is once dissolved in an aluminum alloy by homogenization, and then precipitated as an Fe intermetallic compound having a particle size of 1 μm or less by intermediate annealing. It is possible to make it. That is, in the homogenization treatment, the aluminum alloy plate is heated to a temperature of 550 ° C. or higher at which the Fe intermetallic compound is dissolved, thereby making the Fe-based crystallized finer and increasing the amount of Fe solid solution in the aluminum alloy. . Then, after the hot rolling is finished, annealing is performed to precipitate Fe that is in solid solution, and the Fe particle is changed to an Fe intermetallic compound having a particle size of 1 μm or less.
[0014]
Hot rolling is performed, and then annealing is performed at least once. In this annealing treatment condition, the temperature is raised at an average temperature rise rate of 10 to 60 ° C./hour, and heated at 450 to 500 ° C. for 1 to 20 hours for heating. Thereby, content in the aluminum alloy of the Fe intermetallic compound whose particle size is 1 micrometer or less can be 0.02 mass% or more.
[0015]
Next, the reason for the numerical limitation in the manufacturing method of the present invention will be described.
[0016]
[Homogenization temperature: 550 ° C or higher]
If the homogenization temperature is less than 550 ° C., the crystallization product generated in the casting process cannot be sufficiently refined, and the amount of Fe solid solution cannot be increased. Therefore, Fe intermetallic compounds having a particle size of less than 1 μm are reduced.
[0017]
[Hot rolling start temperature: 400 to 550 ° C.]
When the hot rolling start temperature exceeds 550 ° C., crystal grains grow excessively. Thereby, since a rough surface becomes non-uniform | heterogenous, the start temperature of hot rolling shall be 550 degrees C or less. Moreover, if the starting temperature of hot rolling is less than 400 degreeC, the dynamic recrystallization in rolling will be inadequate and the uniformity of a rough surface will be impaired similarly. For this reason, the hot rolling start temperature is set to 400 to 550 ° C.
[0018]
[ Average heating rate: 10 to 60 ° C./hour]
If the average rate of temperature rise is less than 10 ° C./hour, the throughput becomes too long and the production cost increases. On the other hand, if the rate of temperature rise exceeds 60 ° C./hour, the rate of temperature rise is too fast and the precipitation does not proceed sufficiently, and the desired fine Fe intermetallic compound cannot be produced.
[0019]
[Heat holding temperature: 450 to 500 ° C.]
When the heating and holding temperature is less than 450 ° C., the progress of precipitation is slow and the precipitation is insufficient. On the other hand, when the heating and holding temperature exceeds 500 ° C., solid solution progresses conversely and precipitates decrease.
[0020]
Next, the reason for adding components and the reason for limiting the composition of the aluminum alloy plate for printing plates of the present invention will be described.
[0021]
[Fe: 0.25 to 0.45 mass%]
Fe forms an Al—Fe-based intermetallic compound, and is effective in maintaining mechanical strength by recrystallizing grains and making the structure uniform. This Fe-based intermetallic compound acts as a starting point of initial pits during electrolytic surface roughening. However, if the Fe content is less than 0.25% by mass, even if all the Fe contained in the aluminum alloy is precipitated as an intermetallic compound, the reactivity in the electrolytic treatment is insufficient and uniform pits are formed. In addition, since the strength is low, it is not suitable for use as a printing plate. On the other hand, when the Fe content exceeds 0.45% by mass, intermetallic compounds having a particle diameter exceeding 1 μm, that is, crystallized substances, are not sufficiently reduced regardless of the conditions of the homogenization treatment. For this reason, such a coarse crystallized product becomes a starting point for generating coarse pits. Therefore, the Fe content is 0.25 to 0.45 mass%.
[0022]
[Si: 0.02 to 0.08 mass%]
Since Si forms an Al—Fe—Si intermetallic compound and acts as a recrystallization nucleus between passes during hot rolling, it has the effect of refining recrystallization during hot rolling. Furthermore, the formation of initial pits is promoted, and the effect of improving pit uniformity is achieved. However, if the Si content is less than 0.02% by mass, the reactivity in the electrolytic treatment is low. Conversely, if the Si content exceeds 0.08% by mass, the reactivity in the electrolytic treatment becomes excessive and non-uniform pits are formed. Is done.
[0023]
[Cu: 0.04 mass% or less]
Cu affects the uniformity of electrolytic surface roughening, but when the Cu content exceeds 0.04 mass%, uniformly distributed pits cannot be formed. For this reason, Cu content shall be 0.04 mass% or less.
[0024]
Although the positively added elements are as described above, the reason for restricting the content of Ni, which is an unavoidable impurity, is as follows.
[0025]
[Ni: 0.005% by mass or less]
Although Ni improves the etching property of the electrolytic surface roughening, if the Ni content exceeds 0.005 mass%, the etching property at the time of electrolytic roughening becomes excessive and is easily corroded, resulting in printing stains. For this reason, Ni content is controlled to 0.005 mass% or less.
[0026]
In addition, Mn, which is an unavoidable impurity, can reduce the etching property of the aluminum alloy and cause printing stains. Therefore, the content is preferably regulated to 0.05% by mass or less.
[0027]
【Example】
Hereinafter, the effects of the present invention will be described with respect to examples of the present invention compared with comparative examples that are out of the scope of the present invention. Table 1 below shows the composition of the aluminum alloy plate used and the production conditions. First, a molten aluminum alloy having the composition shown in Table 1 was cast into an ingot having a thickness of 400 mm. Next, the aluminum alloy sheet was homogenized by heating at the temperature shown in Table 1 for 6 hours, and hot rolling was started at a start temperature of 450 ° C. Further, the hot rolling was finished when the thickness of the aluminum alloy plate became 3 mm. Then, it cold-rolled until thickness became 1.5 mm, and intermediate-annealed on the conditions of Table 1 after that. After the intermediate annealing, the aluminum alloy plate was cold-rolled until the thickness became 0.24 mm. In addition, the quantity of the Fe intermetallic compound in Table 1 is the mass ratio which the Fe type intermetallic compound with a particle size of 1 micrometer or less occupies for the whole aluminum alloy.
[0028]
[Table 1]
Next, a test method for an aluminum alloy plate manufactured under the above conditions will be described.
[0030]
[Measurement method of precipitation amount of Fe intermetallic compound]
About 2 g of aluminum alloy plate was dissolved in phenol heated to 180 ° C. The residue was filtered through a 1 μm pore microfilter. The filtrate was further filtered through a micro filter having a pore size of 0.1 μm. The obtained residue is an Al—Fe-based compound and elemental metal Si. Furthermore, this residue was dissolved with hydrochloric acid, the amount of Fe in the bath was measured by ICP-MS (atomic absorption analysis), and the amount of Fe intermetallic compound of 1 μm or less was calculated from this measured value.
[0031]
[Method of measuring electrolytic efficiency]
An aluminum alloy plate is immersed in a 2% by mass-HCl aqueous solution, the temperature of this HCl aqueous solution is adjusted to 25 ° C., and the current density is 80 A / dm 2 , and the energization time is 11 seconds. Went. The mass of the aluminum alloy plate before and after energization was measured, and the difference between them was taken as dissolution loss. In this case, since the amount of electricity supplied is 880 C / dm 2 , the theoretical dissolution amount is calculated as 0.0821 g / dm 2 from Faraday's law. Therefore, the electrolytic efficiency can be calculated by the following formula 1.
[0032]
[Expression 1]
Electrolytic efficiency [%] = Dissolution weight loss [g / dm 2 ] /0.0821 [g / dm 2 ] × 100 [%]
[0033]
[Observation of rough surface]
The surface of the aluminum alloy plate subjected to electrolytic surface roughening by the above-described measurement of electrolytic efficiency was observed with a scanning electron microscope. When the rough surface is observed with a scanning electron microscope at a magnification of 1000 times, when pits of about 7 to 10 μm are uniformly distributed over the entire surface, a small pit of 3 μm or less or a rough pit of 15 μm or more A case where x is mixed is indicated as x.
[0034]
Table 1 shows the proportion of Fe intermetallic compounds having a particle size of less than 1 μm, electrolysis efficiency and roughness of the rough surface. As a result, in Examples 1 to 7, the composition and the ratio of the Fe intermetallic compound satisfied Claim 1 of the present invention, and both the electrolytic efficiency and the uniformity of the rough surface were excellent. Examples 1 to 7 satisfied the production conditions described in claim 2 of the present invention, and the amount of Fe intermetallic compound was sufficiently large.
[0035]
On the other hand, in Comparative Example 1, the average temperature rising rate was too fast, and the holding time of the intermediate annealing was too short, and the production of fine Fe intermetallic compounds was insufficient. In Comparative Example 2, the holding temperature of the intermediate annealing was too high, and the amount of fine Fe intermetallic compound was small. In Comparative Example 3, the holding temperature of the intermediate annealing was too low, and the amount of fine Fe intermetallic compound was small. In Comparative Example 4, since the holding temperature of the intermediate annealing was too high and the holding time was too long, the amount of fine Fe intermetallic compound was insufficient. In Comparative Example 8, since the homogenization temperature was too low, the Fe intermetallic compound having a particle size of 1 μm or more generated during casting did not sufficiently dissolve, so that fine Fe intermetallic compound was sufficiently precipitated in the subsequent process. There wasn't. Furthermore, in Comparative Example 5, the Fe content was low, the average heating rate was too fast, and the intermediate annealing time was too short, so the proportion of Fe intermetallic compounds was small. For this reason, all of Comparative Examples 1 to 5 and 8 have low electrolysis efficiency and poor uniformity of the rough surface.
[0036]
Since Comparative Example 6 had a low Fe content, the electrolysis efficiency was low, the reactivity was insufficient, and the uniformity of the rough surface was poor. In Comparative Example 7, since the Fe content was excessive, the reactivity was excessive and the rough surface was non-uniform. Since the comparative example 9 had too much Cu content, uniform pits were not formed, and the uniformity of the rough surface was inferior. In Comparative Example 10, since the Ni content of the inevitable impurities was too large, the reactivity was excessive and the uniformity of the rough surface was poor.
[0037]
【The invention's effect】
As described above, according to the present invention, in the electrolytic surface roughening treatment at a high current density and in a short time, the electrolytic efficiency is high, the reactivity is excellent, the pits are finely and uniformly dispersed, An aluminum alloy plate for a printing plate having excellent surface uniformity can be obtained.
Claims (2)
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| JP5116267B2 (en) * | 2005-08-30 | 2013-01-09 | 富士フイルム株式会社 | Method for producing aluminum alloy plate for lithographic printing plate |
| US20090252642A1 (en) * | 2005-08-30 | 2009-10-08 | Akio Uesugi | Aluminum alloy sheet for lithographic printing plate and method of producing the same |
| JP2007070674A (en) * | 2005-09-06 | 2007-03-22 | Fujifilm Holdings Corp | Aluminum alloy sheet for planographic printing plate, and manufacturing method therefor |
| JP4925246B2 (en) * | 2005-08-30 | 2012-04-25 | 富士フイルム株式会社 | Aluminum alloy plate for lithographic printing plate and method for producing the same |
| JP4925248B2 (en) * | 2005-08-30 | 2012-04-25 | 富士フイルム株式会社 | Aluminum alloy plate for lithographic printing plate and method for producing the same |
| JP4925247B2 (en) * | 2005-08-30 | 2012-04-25 | 富士フイルム株式会社 | Aluminum alloy plate for lithographic printing plate and method for producing the same |
| US20090260531A1 (en) * | 2008-04-18 | 2009-10-22 | Fujifilm Corporation | Aluminum alloy plate for lithographic printing plate, lithographic printing plate support, presensitized plate, method of manufacturing aluminum alloy plate for lithographic printing plate and method of manufacturing lithographic printing plate support |
| JP5265955B2 (en) * | 2008-04-18 | 2013-08-14 | 富士フイルム株式会社 | Plane printing plate aluminum alloy plate, planographic printing plate support, planographic printing plate precursor, and method for producing planographic printing plate aluminum alloy plate |
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