JPH0849034A - Aluminum alloy supporting body for planographic printing plate - Google Patents
Aluminum alloy supporting body for planographic printing plateInfo
- Publication number
- JPH0849034A JPH0849034A JP6184900A JP18490094A JPH0849034A JP H0849034 A JPH0849034 A JP H0849034A JP 6184900 A JP6184900 A JP 6184900A JP 18490094 A JP18490094 A JP 18490094A JP H0849034 A JPH0849034 A JP H0849034A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- aluminum
- printing plate
- aluminum alloy
- support
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007639 printing Methods 0.000 title claims description 40
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 26
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 abstract description 36
- 238000007788 roughening Methods 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000009749 continuous casting Methods 0.000 abstract description 15
- 238000005097 cold rolling Methods 0.000 abstract description 14
- 229910045601 alloy Inorganic materials 0.000 abstract description 13
- 239000000956 alloy Substances 0.000 abstract description 13
- 238000005098 hot rolling Methods 0.000 abstract description 10
- 238000005266 casting Methods 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 238000002791 soaking Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 3
- 238000007670 refining Methods 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 39
- 239000002994 raw material Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000000866 electrolytic etching Methods 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Printing Plates And Materials Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は平版印刷版に使用される
アルミニウム合金支持体及びその製造方法に関する、特
に電気化学的粗面化処理に適した平版印刷版用アルミニ
ウム合金支持体及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum alloy support used for a lithographic printing plate and a method for producing the same, and particularly to an aluminum alloy support for a lithographic printing plate suitable for electrochemical graining treatment and a method for producing the same. It is about.
【０００２】[0002]
【従来の技術】印刷版用アルミニウム支持体、特にオフ
セット印刷版用支持体としてはアルミニウム板（アルミ
ニウム合金板を含む）が用いられている。一般にアルミ
ニウム板をオフセット印刷版用支持体として使用するた
めには、感光材料との適度な接着性と保水性を有してい
ることが必要である。このためにはアルミニウム板の表
面を均一かつ緻密な砂目を有するように粗面化しなけれ
ばならない。この粗面化処理は製版後実際にオフセット
印刷を行ったときに版材の印刷性能や耐刷力に著しい影
響をおよぼすので、その良否は版材製造上重要な要素と
なっている。印刷版用アルミニウム支持体の粗面化方法
としては、交流電解エッチング法が一般的に採用されて
おり、電流としては、普通の正弦波交流電流、矩形波な
どの特殊交番波形電流が用いられている。そして、黒鉛
等の適当な電極を対極として交流電流によりアルミニウ
ム板の粗面化処理を行うもので、通常一回の処理で行わ
れているが、そこで得られるピット深さは全体的に浅
く、耐刷性能に劣るものであった。このため、その直径
に比べて深さの深いピットが均一かつ緻密に存在する砂
目を有する印刷版用支持体として好適なアルミニウム板
が得られるように、数々の方法が提案されている。その
方法としては、特殊電解電源波形を使った粗面化方法
（特開昭５３−６７５０７号公報）、交流を使った電解
粗面化時の陽極時と陰極時の電気量の比率（特開昭５４
−６５６０７号公報）、電源波形（特開昭５５−２５３
８１号公報）、単位面積あたりの通電量の組合わせ（特
開昭５６−２９６９９号公報）などが知られている。ま
た、機械的な粗面化と組みあわせた（特開昭５５−１４
２６９５号公報）なども知られている。2. Description of the Related Art Aluminum plates (including aluminum alloy plates) are used as aluminum supports for printing plates, especially as supports for offset printing plates. Generally, in order to use an aluminum plate as a support for an offset printing plate, it is necessary to have appropriate adhesiveness to a photosensitive material and water retention. For this purpose, the surface of the aluminum plate must be roughened so as to have uniform and fine grain. This roughening treatment has a significant influence on the printing performance and printing durability of the plate material when offset printing is actually carried out after plate making, and therefore its quality is an important factor in the plate material production. As a roughening method for the aluminum support for printing plates, an alternating current electrolytic etching method is generally adopted, and as the current, a normal sinusoidal alternating current, a special alternating waveform current such as a rectangular wave is used. There is. Then, the surface of the aluminum plate is roughened by an alternating current using an appropriate electrode such as graphite as a counter electrode, which is usually performed in a single treatment, but the pit depth obtained there is generally shallow. The printing durability was inferior. Therefore, various methods have been proposed in order to obtain an aluminum plate suitable as a printing plate support having a grain in which pits having a depth deeper than its diameter are present uniformly and densely. As a method thereof, a surface roughening method using a special electrolysis power source waveform (Japanese Patent Laid-Open No. 53-67507), a ratio of an electric quantity at the time of an anode and a cathode at the time of electrolytic surface roughening using an alternating current (Japanese Patent Laid-Open No. A54
-65607), power supply waveform (JP-A-55-253)
No. 81), a combination of energization amount per unit area (Japanese Patent Laid-Open No. 56-29699) and the like are known. Also, in combination with mechanical surface roughening (Japanese Patent Laid-Open No. 55-14
2695) is also known.
【０００３】一方、アルミニウム支持体の製造方法とし
ては、アルミニウムのインゴットを溶解保持してスラブ
（厚さ４００〜６００ｍｍ、幅１０００〜２０００ｍ
ｍ、長さ２０００〜６０００ｍｍ）を鋳造し、スラブ表
面の不純物組織部分を面削機にかけて３〜１０ｍｍづつ
切削する面削工程を経た後、スラブ内部の応力の除去と
組織の均一化の為、均熱炉において４８０〜５４０℃、
６〜１２時間保持する均熱化処理工程を行い、しかる後
に熱間圧延を４８０〜５４０℃で行う。熱間圧延で５〜
４０ｍｍの厚みに圧延した後、室温で所定の厚みに冷間
圧延を行う。またその後組織の均一化のため焼鈍を行い
圧延組織等を均質化した後、規定の厚みに冷間圧延を行
い、平坦度の良い板にするため矯正する。この様にして
作られたアルミニウム支持体を平版印刷版用支持体とし
ていた。しかしながら、電解粗面化処理の場合は特に対
象となるアルミニウム支持体の影響を受けやすく、アル
ミニウム支持体を溶解保持→鋳造→面削→均熱という工
程を通して製造する場合、加熱、冷却をくり返し、面削
という表面層を削り取る工程があったとしても、表面層
に金属合金成分などのばらつきを生じて平版印刷版とし
ては得率低下の原因となっていた。On the other hand, as a method of manufacturing an aluminum support, an aluminum ingot is melted and held to form a slab (thickness 400 to 600 mm, width 1000 to 2000 m).
m, a length of 2000 to 6000 mm) and subjected to a chamfering step of cutting the impurity textured portion of the slab surface by a chamfering machine in increments of 3 to 10 mm, for removing stress inside the slab and homogenizing the texture, 480-540 ° C in a soaking furnace,
A soaking treatment step of holding for 6 to 12 hours is performed, and then hot rolling is performed at 480 to 540 ° C. 5 by hot rolling
After rolling to a thickness of 40 mm, cold rolling is performed to a predetermined thickness at room temperature. Further, after that, annealing is performed to homogenize the structure to homogenize the rolled structure and the like, and then cold rolling is performed to a prescribed thickness to correct the plate so as to have a good flatness. The aluminum support thus prepared was used as a support for a lithographic printing plate. However, in the case of electrolytic surface roughening treatment, it is particularly susceptible to the target aluminum support, and when the aluminum support is manufactured through the steps of melting and holding → casting → chamfering → soaking, heating and cooling are repeated, Even if there is a step of scraping off the surface layer called surface grinding, variations in metal alloy components and the like occur in the surface layer, which causes a reduction in the yield as a lithographic printing plate.
【０００４】これに対して、本出願人は先にアルミニウ
ム支持体の材質のバラツキを少くし、電解粗面化処理の
得率を向上させることによって品質の優れた得率のよい
平版印刷版を作れる方法として、アルミニウム溶湯から
鋳造、熱間圧延を連続して行い、薄板の熱間圧延コイル
を形成させた後、冷間圧延、熱処理、矯正を行ったアル
ミニウム支持体を粗面化処理することを特徴とする平版
印刷版用支持体の製造方法を提案した（特開平３−７９
７９８号公報）。それに加えて、特開平６−４８０５８
号公報では良好な電解粗面化性を得るため、Ｆｅ：０．
４〜０．２％、Ｓｉ：０．２〜０．０５％、Ｃｕ：０．
０２％以下、アルミニウム９９．５％以上で連続鋳造を
行ない、Ｆｅの含有量の内２０〜９０％が結晶粒界に存
在していることを提案している。また、支持体の合金成
分を規定した発明としては、特開昭６２−１４６６９４
号、特開昭６０−２３０９５１号、特開昭６０−２１５
７２５号、特開昭６１−２６７４６号、特公昭５８−６
６３５号各公報が開示されている。On the other hand, the applicant of the present invention reduced the variation in the material of the aluminum support and improved the efficiency of the electrolytic surface roughening treatment to obtain a lithographic printing plate of excellent quality and good efficiency. As a method that can be made, after casting from an aluminum melt and hot rolling continuously to form a thin plate hot rolling coil, cold rolling, heat treatment, straightening the aluminum support to roughen it A method for producing a support for a lithographic printing plate characterized by the following is proposed (JP-A-3-79).
798 publication). In addition to that, JP-A-6-48058
In the publication, in order to obtain a good electrolytic surface roughening property, Fe: 0.
4 to 0.2%, Si: 0.2 to 0.05%, Cu: 0.
It is proposed that continuous casting is performed with 02% or less and aluminum 99.5% or more, and 20 to 90% of the Fe content is present in the grain boundaries. Further, as an invention which defines the alloy component of the support, Japanese Patent Laid-Open No. 62-146694
No. 60-230951, JP-A-60-215
725, JP-A-61-26746, JP-B-58-6.
Japanese Patent No. 635 is disclosed.
【０００５】また、本出願人らは、原材料をシンプル化
して、平版印刷版用支持体の製造を低コストで行う方法
として、特願平５−２４９６９９号、特願平６−７１２
６４号各明細書に記載の方法を提案している。それに加
えて特願平５−３０７１０８号明細書では、良好な電解
砂目形状を得るためにアルミニウム溶湯から直接板状に
連続鋳造圧延し、冷間圧延、熱処理、矯正を適宜行なう
アルミニウム合金基材において、金属間化合物の個数、
サイズを所定の範囲内におさめることを特徴とする平版
印刷版用アルミ合金基材を提案している。Further, the present applicants have proposed, as a method for simplifying raw materials and producing a support for a lithographic printing plate at low cost, Japanese Patent Application Nos. 5-249699 and 6-712.
No. 64 proposes the method described in each specification. In addition to that, Japanese Patent Application No. 5-307108 discloses an aluminum alloy base material which is directly cast and rolled directly from a molten aluminum into a plate shape in order to obtain a good electrolytic grain shape, and is subjected to cold rolling, heat treatment and straightening as appropriate. Where, the number of intermetallic compounds,
We have proposed an aluminum alloy base material for a lithographic printing plate which is characterized in that its size is kept within a predetermined range.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら先に提案
した特開平６−４８０５８号公報に記載の製造方法につ
いても、アルミニウム支持体の成分によって電解粗面化
処理の得率及び粗面化適正のばらつきがあった。本発明
の目的はアルミニウム合金支持体の材質のバラツキを少
くし、電解粗面化処理の得率を向上させると共に、低コ
スト平版印刷版が作れる粗面化適性の優れた平版印刷版
用アルミニウム合金支持体及びその製造方法を提供する
ことにある。However, also in the manufacturing method described in Japanese Patent Laid-Open No. 6-48058, which has been previously proposed, the yield of electrolytic surface roughening treatment and variations in the appropriateness of surface roughening depend on the components of the aluminum support. was there. The object of the present invention is to reduce the variation in the material of the aluminum alloy support, improve the yield of the electrolytic surface roughening treatment, and make a low-cost lithographic printing plate. It is to provide a support and a method for manufacturing the same.
【０００７】[0007]
【課題を解決するための手段及び作用】本発明者らはア
ルミニウム支持体と電解粗面化処理の関係を鋭意研究し
た結果、粗面化がばらつく原因が、Ｆｅ、Ｓｉ、Ｃｕ、
Ｔｉ等微量合金成分分布のばらつきであり、特に金属間
化合物の形で存在する微量合金成分の分布ばらつきが、
粗面化を不均一にする原因であることをつきとめ本発明
を見出したものである。即ち、本発明の上記目的は、下
記平版印刷版用アルミニウム合金支持体によって達成さ
れた。 ０＜Ｆｅ≦０．２０重量％、０≦Ｓｉ≦０．１３重
量％、Ａｌ≧９９．７重量％、残部が不可避不純物元素
からなるアルミニウム合金板であって、板表面から１０
μｍ以内の任意の厚み方向深さにおいて金属間化合物の
数が１００〜３０００個／ｍｍ2、平均粒子サイズが
０．５〜８μｍ、粒子サイズ１０μｍ以上のものの数の
割合が２％以下であることを特徴とする平版印刷版用ア
ルミニウム合金支持体。 前記アルミニウム合金支持体の成分が、０≦Ｔｉ＜
０．０５重量％、０≦Ｃｕ＜０．０５重量％を含むこと
を特徴とする前記記載の平版印刷版用アルミニウム合
金支持体。Means and Actions for Solving the Problems As a result of intensive studies on the relationship between the aluminum support and the electrolytic surface roughening treatment, the present inventors have found that the causes of uneven surface roughening are Fe, Si, Cu,
This is the variation in the distribution of trace alloy components such as Ti, and in particular, the variation in the distribution of trace alloy components existing in the form of intermetallic compounds,
The inventors have found the present invention by finding out that it is the cause of making the roughening uneven. That is, the above object of the present invention was achieved by the following aluminum alloy support for lithographic printing plates. An aluminum alloy plate having 0 <Fe ≦ 0.20% by weight, 0 ≦ Si ≦ 0.13% by weight, Al ≧ 99.7% by weight, and the balance being an unavoidable impurity element.
The number of intermetallic compounds is 100 to 3000 / mm 2 , the average particle size is 0.5 to 8 μm, and the ratio of the number of particles having a particle size of 10 μm or more is 2% or less at an arbitrary depth within μm. An aluminum alloy support for a lithographic printing plate. The composition of the aluminum alloy support is 0 ≦ Ti <
The aluminum alloy support for a lithographic printing plate as described above, which contains 0.05% by weight and 0 ≦ Cu <0.05% by weight.
【０００８】本発明において、アルミニウム溶湯から、
例えば固定鋳型を用いてアルミ鋳塊を製造する方法とし
ては、ＤＣ法などの鋳造技術が実用化されている。ま
た、駆動鋳型を用いる連続鋳造方法としては、ハズレー
法などの冷却ベルトを用いる方法と、ハンター法、３Ｃ
法などの冷却ロールを用いる方法を用いることが出来
る。また、特開昭６０−２３８００１号公報、特開昭６
０−２４０３６０号公報などには薄板のコイルを作成す
る方法が開示されている。In the present invention, from the molten aluminum,
For example, as a method of manufacturing an aluminum ingot using a fixed mold, a casting technique such as a DC method has been put into practical use. Further, as a continuous casting method using a driving mold, a method using a cooling belt such as a Hazley method, a Hunter method, and 3C
A method using a cooling roll such as a method can be used. Further, JP-A-60-238001 and JP-A-6-238001
No. 0-240360 discloses a method of forming a thin plate coil.
【０００９】本発明は平版印刷版用アルミニウム合金支
持体として優れた特性を得るため、前記のような合金成
分組織範囲と、それら合金成分について、金属間化合物
の形で存在するものの、単位面積あたりの個数、平均粒
子サイズ、及び粒子サイズが１０μｍ以上のものの数の
割合を選び、なおかつ原材料のシンプル化を実現するも
のである。アルミニウム合金中の金属間化合物の解析方
法としては、電子プローブ微量分析（ＥＰＭＡ）を用い
て面分析をする方法や熱フェノールを用いて抽出分離す
る方法がある。アルミニウム合金中の合金成分の重量％
を定量的に求める方法としては、発光分析法が用いられ
る。In order to obtain excellent properties as an aluminum alloy support for a lithographic printing plate, the present invention provides a range of alloy component structures as described above and the alloy components in the form of intermetallic compounds, but per unit area. , The average particle size, and the ratio of the number of particles having a particle size of 10 μm or more, and simplification of the raw material is realized. As a method of analyzing the intermetallic compound in the aluminum alloy, there are a method of surface analysis using electron probe microanalysis (EPMA) and a method of extraction separation using hot phenol. Weight% of alloy components in aluminum alloy
As a method for quantitatively obtaining, an emission analysis method is used.
【００１０】本発明において、Ｆｅ成分としては、０＜
Ｆｅ≦０．２０重量％であり、好ましくは０．０５≦Ｆ
ｅ≦０．１９重量％であり、特に好ましくは０．０８≦
Ｆｅ≦０．１８重量％である。本発明において、Ｓｉの
成分として０≦Ｓｉ≦０．１３重量％であり、好ましく
は０．０２≦Ｓｉ≦０．１２重量％であり、特に好まし
くは０．０２５≦Ｓｉ≦０．１０重量％である。本発明
において、板表面から１０μｍ以内の任意の厚み方向深
さにおいて金属間化合物の数は、１００〜３０００個／
ｍｍ2であり、好ましくは、３００〜２０００個／ｍ
ｍ2、特に好ましくは５００〜１５００個／ｍｍ2であ
る。金属間化合物の粒子サイズとしては、平均０．５〜
８μｍ、好ましくは０．５〜５μｍである。また、金属
間化合物の粒子サイズ１０μｍ以上のものの数の割合は
２％以下、好ましくは１％以下である。なお、金属間化
合物とは、アルミニウム中の合金成分の中で、アルミニ
ウム中に固溶しないものが化合物（例えば、Ａｌ3Ｆ
ｅ、Ａｌ6Ｆｅ、α−ＡｌＦｅＳｉ、単体Ｓｉ等）とし
て、アルミニウム合金中に共晶の形で晶出したものをい
う。（「アルミニウム材料の基礎と工業技術」，社団法
人軽金属協会発行、３２頁等より）In the present invention, the Fe component is 0 <
Fe ≦ 0.20% by weight, preferably 0.05 ≦ F
e ≦ 0.19% by weight, particularly preferably 0.08 ≦
Fe ≦ 0.18% by weight. In the present invention, the Si component is 0 ≦ Si ≦ 0.13% by weight, preferably 0.02 ≦ Si ≦ 0.12% by weight, and particularly preferably 0.025 ≦ Si ≦ 0.10% by weight. Is. In the present invention, the number of intermetallic compounds is 100 to 3000 / at any depth in the thickness direction within 10 μm from the plate surface.
mm 2 , preferably 300 to 2000 pieces / m
m 2 , particularly preferably 500 to 1500 pieces / mm 2 . The average particle size of the intermetallic compound is 0.5 to
It is 8 μm, preferably 0.5 to 5 μm. The ratio of the number of intermetallic compounds having a particle size of 10 μm or more is 2% or less, preferably 1% or less. The intermetallic compound is a compound (for example, Al 3 F) that does not form a solid solution in aluminum among alloy components in aluminum.
e, Al 6 Fe, α-AlFeSi, simple substance Si, etc.), which are crystallized in a eutectic form in an aluminum alloy. (From "Fundamental and Industrial Technology of Aluminum Materials", Published by Japan Light Metal Association, page 32, etc.)
【００１１】本発明において、Ｃｕ成分としては０≦Ｃ
ｕ＜０．０５重量％、好ましくは、０．００１≦Ｃｕ＜
０．００８重量％であり、Ｔｉ成分としては０≦Ｔｉ＜
０．０５重量％、好ましくは、０≦Ｔｉ＜０．０３重量
％である。なお、一般に、Ｔｉは結晶粒微細化剤として
添加するものであり、またＣｕは砂目ピット形状をコン
トロールするために添加するものである。In the present invention, as the Cu component, 0 ≦ C
u <0.05% by weight, preferably 0.001 ≦ Cu <
0.008% by weight, and as a Ti component, 0 ≦ Ti <
0.05% by weight, preferably 0 ≦ Ti <0.03% by weight. In general, Ti is added as a grain refiner, and Cu is added to control the grain pit shape.
【００１２】Ａｌ≧９９．７重量％について、Ａｌ≧９
９．７重量％とすることで、一般市場に安価で流通して
いるＡｌ≧９９．７重量％インゴット材を使用すること
が出来、原材料のコスト低減に効果がある。また、砂目
形状がくずれることを防止するため、上限は望ましくは
９９．９９重量％未満であるのが良い。その他、不可避
不純物（例えば、Ｍｇ、Ｍｎ、Ｃｒ、Ｚｒ、Ｖ、Ｚｎ、
Ｂｅ等）は含有量が少ないので、表面処理性、汚れ性、
バーニング性に特に悪影響を及ぼさない。For Al ≧ 99.7% by weight, Al ≧ 9
By setting it as 9.7% by weight, it is possible to use an Al ≧ 99.7% by weight ingot material that is inexpensively distributed in the general market, and it is effective in reducing the cost of raw materials. In addition, the upper limit is preferably less than 99.99% by weight in order to prevent the grain shape from breaking. In addition, inevitable impurities (for example, Mg, Mn, Cr, Zr, V, Zn,
(Be, etc.) has a small content, so surface treatment, stain resistance,
No particular adverse effect on the burning property.
【００１３】Ｆｅ成分の原料としては市販のＦｅ含有量
５０％のＡｌ−Ｆｅ母合金を用いることができ、Ｓｉ成
分の原料としては市販のＳｉ含有量２５％のＡｌ−Ｓｉ
母合金を用いることができ、Ｃｕ成分の原料としては市
販のＣｕ含有量５０％のＡｌ−Ｃｕ母合金を用いること
ができ、また、Ｔｉ成分の原料としては市販のＴｉ含有
量５％のＡｌ−Ｔｉ母合金または線状になったＡｌ−Ｔ
ｉ−Ｂ合金を用いることができる。Ｆｅ、Ｓｉ、Ｃｕ、
Ｔｉの各成分は、Ａｌ≧９９．７重量％インゴット材の
溶解時に上記各原料を目的とする重量範囲となるように
添加して使用される。尚、Ｆｅ及びＳｉについては９
９．７％Ａｌインゴット材に微量含まれる場合があり、
この量を考慮してＦｅとＴｉ成分の原料は添加される。
また、Ｃｕ及びＴｉについては９９．７％Ａｌインゴッ
ト材にごく微量含まれる場合と含まれない場合とがあ
り、Ｃｕ及びＴｉにおいてもこの量を考慮して各原料は
添加される。A commercially available Al--Fe mother alloy having a Fe content of 50% can be used as the raw material of the Fe component, and a commercially available Al--Si alloy having a Si content of 25% can be used as the raw material of the Si component.
A mother alloy can be used, a commercially available Al-Cu mother alloy having a Cu content of 50% can be used as a raw material of the Cu component, and a commercially available Al content of 5% Al can be used as a raw material of the Ti component. -Ti master alloy or linear Al-T
An i-B alloy can be used. Fe, Si, Cu,
Each component of Ti is used by adding each of the above raw materials so as to be in a target weight range when Al ≧ 99.7% by weight of the ingot material is melted. For Fe and Si, 9
A small amount of 9.7% Al ingot material may be contained,
The raw materials for the Fe and Ti components are added in consideration of this amount.
Further, Cu and Ti may or may not be contained in a very small amount in the 99.7% Al ingot material, and in Cu and Ti, the respective raw materials are added in consideration of these amounts.
【００１４】次に上記のような本発明の平版印刷版用ア
ルミニウム合金支持体を、低コストでかつ、安定した粗
面化適性を持たせて、金属間化合物の個数、サイズを制
御して製造するための方法は以下の如くである。図１〜
図４の工程概念図を用いて本発明に用いるアルミニウム
合金支持体の製造方法の実施態様の１例について更に具
体的に説明する。図示せぬ溶解保持炉にて、０＜Ｆｅ≦
０．２０重量％、０≦Ｓｉ≦０．１３重量％になるよう
にＡｌ原材料を溶解・調整し、図１に示すように水冷鋳
型１を通して鋳塊受け台２に溶湯供給ノズル３より溶湯
を供給し、鋳塊４を作る。この場合鋳塊に面削を行い、
２８０℃以上６５０℃以下の温度、好ましくは４００℃
以上６３０℃以下で、特に好ましくは５００℃以上６０
０℃以下であり、時間としては２時間〜１５時間、好ま
しくは４時間〜１２時間であり、特に好ましくは６時間
〜１１時間均熱処理を施した後、次に図３に示すように
冷間圧延機８によって０．５ｍｍ〜０．１ｍｍに圧延し
て、さらに図４に示すように矯正装置９によって矯正を
行ってアルミニウム支持体を作る。圧延は熱間圧延機
（図無し）によって行なってもよいし、熱間圧延機と冷
間圧延機を組合せて行なってもよい。又、図２に示すよ
うに溶解保持炉５で０＜Ｆｅ≦０．２０重量％、０≦Ｓ
ｉ≦０．１３重量％になるようにＡｌ原材料を溶解・調
整し、双ロール連続鋳造機６によって２〜３０ｍｍの板
を作っても良い。次に図３に示すように冷間圧延機８に
かけて冷間圧延を行い、０．５〜０．１ｍｍに圧延した
後、さらに図４に示すように矯正装置９にかけて矯正を
行ってアルミニウム支持体を作る。又、溶解保持炉で０
＜Ｆｅ≦０．２０重量％、０≦Ｓｉ≦０．１３重量％に
なるようにＡｌ原材料を溶解調整し、双ベルト連続鋳造
機によって約４〜３０ｍｍの板を作る場合は、その後、
次に図３に示すように冷間圧延機８によって冷間圧延を
行い、図４に示すような矯正装置９によって矯正を行な
った支持体を作る。双ベルト連続鋳造機を用いる場合
は、連続鋳造機の直後に熱間圧延を行なってもよい。Next, the aluminum alloy support for a lithographic printing plate of the present invention as described above is produced at a low cost and with a stable surface roughening suitability by controlling the number and size of intermetallic compounds. The method for doing this is as follows. Figure 1
An example of the embodiment of the method for producing an aluminum alloy support used in the present invention will be described more specifically with reference to the process conceptual diagram of FIG. In a melting and holding furnace (not shown), 0 <Fe ≦
The Al raw material is melted and adjusted so that 0.20% by weight and 0 ≦ Si ≦ 0.13% by weight, and the molten metal is supplied from the molten metal supply nozzle 3 to the ingot pedestal 2 through the water-cooled mold 1 as shown in FIG. It is supplied and the ingot 4 is made. In this case, the ingot is chamfered,
A temperature of 280 ° C or higher and 650 ° C or lower, preferably 400 ° C
Or more and 630 ° C. or less, particularly preferably 500 ° C. or more 60
The temperature is 0 ° C. or lower, the time is 2 hours to 15 hours, preferably 4 hours to 12 hours, and particularly preferably 6 hours to 11 hours. After soaking, it is then cooled as shown in FIG. The aluminum support is made by rolling to a thickness of 0.5 mm to 0.1 mm by a rolling mill 8 and then straightening it by a straightening device 9 as shown in FIG. Rolling may be performed by a hot rolling mill (not shown), or may be performed by combining a hot rolling mill and a cold rolling mill. Further, as shown in FIG. 2, in the melting and holding furnace 5, 0 <Fe ≦ 0.20% by weight, 0 ≦ S
The Al raw material may be melted and adjusted so that i ≦ 0.13% by weight, and a plate of 2 to 30 mm may be produced by the twin roll continuous casting machine 6. Next, as shown in FIG. 3, a cold rolling mill 8 is used to perform cold rolling, and after rolling to 0.5 to 0.1 mm, a straightening device 9 is further used to perform straightening as shown in FIG. make. Also, 0 in the melting and holding furnace
When the Al raw material is melt-adjusted so that <Fe ≦ 0.20% by weight and 0 ≦ Si ≦ 0.13% by weight, and a plate of about 4 to 30 mm is produced by a twin belt continuous casting machine, then,
Next, as shown in FIG. 3, cold rolling is carried out by a cold rolling mill 8 and a support body straightened by a straightening device 9 as shown in FIG. 4 is produced. When a twin-belt continuous casting machine is used, hot rolling may be performed immediately after the continuous casting machine.
【００１５】本発明における平版印刷版用支持体の粗面
化の方法は機械的粗面化、化学的粗面化、電気化学的粗
面化及びそれらの組合わせ等各種用いることが出来る。
機械的な砂目立て法としては、例えばボールグレイン、
ワイヤーグレイン、ブラッシグレイン、液体ホーニング
法などがある。また電気化学的砂目立て方法としては、
交流電解エッチング法が一般的に採用されており、電流
としては、普通の正弦波交流電流あるいは矩形波など、
特殊交番電流が用いられている。またこの電気化学的砂
目立ての前処理として、苛性ソーダなどでエッチング処
理をしても良い。Various methods such as mechanical surface roughening, chemical surface roughening, electrochemical surface roughening, and combinations thereof can be used for the method of surface roughening of the lithographic printing plate support of the present invention.
As a mechanical graining method, for example, ball grain,
Wire grain, brush grain, liquid honing method, etc. Also, as an electrochemical graining method,
The AC electrolytic etching method is generally adopted, and as the current, a normal sine wave AC current or a rectangular wave,
Special alternating current is used. Further, as a pretreatment for this electrochemical graining, etching treatment with caustic soda may be performed.
【００１６】また電気化学的粗面化を行う場合、塩酸ま
たは硝酸主体の水溶液で交番電流によって粗面化される
のが良い。以下詳細に説明する。先ず、アルミニウム支
持体は、まずアルカリエッチングされる。好ましいアル
カリ剤は、苛性ソーダ、苛性カリ、メタ珪酸ソーダ、炭
酸ソーダ、アルミン酸ソーダ、グルコン酸ソーダ等であ
る。濃度０．０１〜２０％、温度は２０〜９０℃、時間
は５ｓｅｃ〜５ｍｉｎ間の範囲から選択されるのが適当
であり、好ましいエッチング量としては０．１〜５ｇ／
ｍ2である。特に不純物の多い支持体の場合、０．０１
〜１ｇ／ｍ2が適当である（特開平１−２３７１９７号
公報）。引き続き、アルカリエッチングしたアルミニウ
ム板の表面にアルカリに不溶な物質（スマット）が残存
するので、必要に応じてデスマット処理を行っても良
い。When performing electrochemical surface roughening, it is preferable that the surface is roughened by an alternating current with an aqueous solution mainly containing hydrochloric acid or nitric acid. This will be described in detail below. First, the aluminum support is first alkali etched. Preferred alkaline agents are caustic soda, caustic potash, sodium metasilicate, sodium carbonate, sodium aluminate, sodium gluconate and the like. It is suitable that the concentration is 0.01 to 20%, the temperature is 20 to 90 ° C., and the time is 5 sec to 5 min. The preferable etching amount is 0.1 to 5 g /
m 2 . Particularly in the case of a support containing a large amount of impurities, 0.01
-1 g / m 2 is suitable (JP-A-1-237197). Subsequently, an alkali-insoluble substance (smut) remains on the surface of the alkali-etched aluminum plate, and therefore a desmut treatment may be performed if necessary.
【００１７】前処理は上記の通りであるが、引き続き、
本発明として塩酸、または硝酸を主体とする電解液中で
交流電解エッチングされる。交流電解電流の周波数とし
ては、０．１〜１００Ｈｚ、より好ましくは０．１〜
１．０又は１０〜６０Ｈｚである。液濃度としては、３
〜１５０ｇ／リットル、より好ましくは５〜５０ｇ／リ
ットル、溶内のアルミニウムの溶解量としては５０ｇ／
リットル以下が適当であり、より好ましくは２〜２０ｇ
／リットルである。必要によって添加物を入れても良い
が、大量生産をする場合は、液濃度制御などが難しくな
る。また、電流密度は、５〜１００Ａ／ｄｍ2 が適当で
あるが、１０〜８０Ａ／ｄｍ2がより好ましい。また、
電源波形としては、求める品質、使用されるアルミニウ
ム支持体の成分によって適時選択されるが、特公昭５６
−１９２８０号、特公昭５５−１９１９１号各公報に記
載の特殊交番波形を用いるのがより好ましい。この様な
波形、液条件は、電気量とともに求める品質、使用され
るアルミニウム支持体の成分などによって適宜選択され
る。The pretreatment is as described above, but
In the present invention, AC electrolytic etching is performed in an electrolytic solution containing hydrochloric acid or nitric acid as a main component. The frequency of the alternating electrolysis current is 0.1 to 100 Hz, more preferably 0.1 to 100 Hz.
It is 1.0 or 10 to 60 Hz. The liquid concentration is 3
~ 150 g / liter, more preferably 5 to 50 g / liter, and the amount of aluminum dissolved in the melt is 50 g / liter.
It is suitable to be less than 1 liter, more preferably 2 to 20 g.
/ Liter. If necessary, additives may be added, but in the case of mass production, it becomes difficult to control the liquid concentration. A current density of 5 to 100 A / dm 2 is suitable, but 10 to 80 A / dm 2 is more preferable. Also,
The power waveform is appropriately selected according to the required quality and the components of the aluminum support used.
It is more preferable to use the special alternating waveform described in each of Japanese Patent Publication No. 19280 and Japanese Patent Publication No. 55-19191. Such waveforms and liquid conditions are appropriately selected depending on the quality required along with the quantity of electricity, the components of the aluminum support used, and the like.
【００１８】電解粗面化されたアルミニウムは、次にス
マット処理の一部としてアルカリ溶液に浸漬しスマット
を溶解する。アルカリ剤としては、苛性ソーダなど各種
あるが、ｐＨ１０以上、温度２５〜６０℃、浸漬時間１
〜１０ｓｅｃの極めて短時間で行うことが好ましい。次
に硫酸主体の液に浸漬する。硫酸の液条件としては、従
来より一段と低い濃度５０〜４００ｇ／リットル、温度
２５〜６５℃が好ましい。硫酸の濃度が４００ｇ／リッ
トルを超える、又は温度が６５℃を超えると処理槽など
の腐食が大きくなり、しかも、マンガン含有量の多い
（例えば、約０．３重量％以上の）アルミニウム合金で
は、電気化学的に粗面化された砂目が崩れてしまう。ま
た、アルミニウム素地の溶解量が０．２ｇ／ｍ2を超え
てエッチングされると、耐刷力が低下して来るので、
０．２ｇ／ｍ2以下にすることが好ましい。The electrolytically grained aluminum is then immersed in an alkaline solution as part of a smut treatment to dissolve the smut. There are various alkaline agents such as caustic soda, pH 10 or higher, temperature 25 to 60 ° C., immersion time 1
It is preferable to carry out in an extremely short time of 10 seconds. Next, it is dipped in a liquid containing mainly sulfuric acid. As a liquid condition of sulfuric acid, it is preferable that the concentration is 50 to 400 g / liter and the temperature is 25 to 65 ° C., which is much lower than the conventional one. When the concentration of sulfuric acid exceeds 400 g / liter or the temperature exceeds 65 ° C., corrosion of the treatment tank and the like becomes large, and the aluminum alloy having a high manganese content (for example, about 0.3% by weight or more), Electrochemically roughened grain will collapse. Further, when the amount of dissolution of the aluminum base material exceeds 0.2 g / m 2 and is etched, the printing durability decreases, so
It is preferably 0.2 g / m 2 or less.
【００１９】陽極酸化皮膜は、０．１〜１０ｇ／ｍ2、
より好ましくは０．３〜５ｇ／ｍ2を表面に形成するの
が良い。陽極酸化の処理条件は、使用される電解液によ
って種々変化するので一概には決定されないが、一般的
には電解液の濃度が１〜８０重量％、液温５〜７０℃、
電流密度０．５〜６０Ａ／ｃｍ2、電圧１〜１００Ｖ、
電解時間１秒〜５分の範囲が適当である。この様にして
得られた陽極酸化皮膜を持つ砂目のアルミニウム板はそ
れ自身安定で親水性に優れたものであるから、直ちに感
光性塗膜を上に設ける事も出来るが、必要により更に表
面処理を施す事が出来る。たとえば、アルカリ金属珪酸
塩によるシリケート層あるいは、親水性高分子化合物よ
りなる下塗層を設けることができる。下塗層の塗布量は
５〜１５０ｍｇ／ｍ2が好ましい。次に、このように処
理したアルミニウム支持体上に感光性塗膜を受け、画像
露光、現像して製版した後に、印刷機にセットし、印刷
を開始する。The anodic oxide film has a thickness of 0.1 to 10 g / m 2 ,
More preferably, 0.3 to 5 g / m 2 is formed on the surface. The treatment conditions for anodization are not generally determined because they vary depending on the electrolytic solution used, but generally the concentration of the electrolytic solution is 1 to 80% by weight, the liquid temperature is 5 to 70 ° C,
Current density 0.5 to 60 A / cm 2 , voltage 1 to 100 V,
A range of electrolysis time of 1 second to 5 minutes is suitable. The thus-obtained aluminum plate having an anodized film is itself stable and excellent in hydrophilicity, so that a photosensitive coating film can be immediately provided on the aluminum plate, but if necessary, the surface can be further improved. Can be processed. For example, a silicate layer made of an alkali metal silicate or an undercoat layer made of a hydrophilic polymer compound can be provided. The coating amount of the undercoat layer is preferably 5 to 150 mg / m 2 . Next, after receiving the photosensitive coating on the aluminum support thus treated, exposing it to light and developing it to make a plate, it is set in a printing machine and printing is started.
【００２０】[0020]
【実施例】 実施例１〜４、比較例１〜９ アルミニウム原材料等を溶解・調整し、図１の様に、水
冷固定鋳型を用いて注湯温度７４０℃の条件で鋳塊を作
成した。その鋳塊に面削を行ない約１３ｍｍ削除した
後、図示しない均質化加熱炉によって５５０℃で１０時
間の均質化処理を行なった。その後冷間圧延・熱処理の
何れか又は両方を１回以上行ない、最終的に板厚０．２
４ｍｍの厚さに仕上げた。溶解・調整の際、合金成分の
添加量を変えて本発明の実施例１〜４、及び比較例１〜
８を作成した。 尚、比較例９は特開平６−４８０８５号公報に記載の製
造方法に従ってサンプルを作成した。各サンプルについ
て、金属間化合物の個数、サイズを測定するため、電子
プロブマイクロアナライザ（略称ＥＰＭＡ、日本電子
（株）製ＪＸＡ−８８００Ｍ）を用い、加速電圧２０．
０ｋＶ、測定電流１．０×１０-6Ａで、板表層から１０
μｍまでの範囲について、元素分析の面分析を行なっ
た。サンプルの内訳を表１に示す。[Examples] Examples 1 to 4 and Comparative Examples 1 to 9 Aluminum raw materials and the like were melted and adjusted, and ingots were prepared using a water-cooled stationary mold at a pouring temperature of 740 ° C as shown in Fig. 1. The ingot was chamfered to remove about 13 mm, and then homogenized at 550 ° C. for 10 hours in a homogenizing heating furnace (not shown). After that, either or both of cold rolling and heat treatment are performed once or more, and finally the plate thickness is 0.2.
Finished to a thickness of 4 mm. At the time of melting and adjusting, the addition amount of the alloy component is changed, and Examples 1 to 4 of the present invention and Comparative Examples 1 to 1
8 was created. In Comparative Example 9, a sample was prepared according to the manufacturing method described in JP-A-6-48085. For each sample, in order to measure the number and size of intermetallic compounds, an electron probe microanalyzer (abbreviation EPMA, JXA-8800M manufactured by JEOL Ltd.) was used, and an acceleration voltage of 20.
10kV from the surface of the plate at 0kV and a measuring current of 1.0 × 10 -6 A
Area analysis of elemental analysis was performed in the range up to μm. Table 1 shows the breakdown of the samples.
【００２１】[0021]
【表１】 [Table 1]
【００２２】このようにして出来たアルミニウム板を平
版印刷版用支持体として用い、１５％苛性ソーダ水溶液
でエッチング量が５ｇ／ｍ2 になる様に温度５０℃でエ
ッチングし、水洗後１５０ｇ／リットル、５０℃の硫酸
液中に１０ｓｅｃ浸漬してデスマットし、水洗した。更
に支持体を１６ｇ／リットル硝酸水溶液中で、特公昭５
５−１９１９１号公報に記載の交番波形電流を用いて、
電気化学的に粗面化した。電解条件としては、アノード
電圧ＶA＝１４ボルト、カソード電圧Ｖc＝１２ボルトと
して、陽極時電気量が、３５０クーロン／ｄｍ2となる
様にした。The aluminum plate thus produced was used as a support for a lithographic printing plate and etched with a 15% caustic soda aqueous solution at a temperature of 50 ° C. so that the etching amount was 5 g / m 2, and after washing with water 150 g / liter, It was immersed in a sulfuric acid solution at 50 ° C. for 10 seconds, desmutted, and washed with water. Further, the support is placed in a 16 g / liter nitric acid aqueous solution, and
Using the alternating waveform current described in JP-A-5-19191,
Electrochemically roughened. As electrolysis conditions, the anode voltage V A was 14 V and the cathode voltage V C was 12 V, and the amount of electricity at the anode was 350 coulomb / dm 2 .
【００２３】以上の如くして作成した基板に、感光液を
塗布することで感光性平版印刷版となるが、ここでは、
感光液塗布前の基板の表面面質の評価を行った。感光性
平版印刷版に、ネガフィルムまたはポジフィルムを通し
て露光を行った後、現像すると、（一部感光層が取
れ、）基板の表面自体が平版印刷版の非画像部または画
像部となるため、基板表面の面質自体が印刷性、印刷版
の視認性に大きな影響を与えるからである。また併わせ
て、原材料のコスト比較を行なった。表面の面質評価及
び原材料のコスト比較の結果を表２に示す。A photosensitive lithographic printing plate is obtained by applying a photosensitive solution to the substrate prepared as described above.
The surface quality of the substrate before applying the photosensitive solution was evaluated. Since the photosensitive lithographic printing plate is exposed through a negative film or a positive film and then developed (the photosensitive layer is partially removed), the surface of the substrate itself becomes a non-image part or an image part of the lithographic printing plate, This is because the surface quality of the substrate surface itself greatly affects the printability and the visibility of the printing plate. In addition, the costs of raw materials were compared. Table 2 shows the results of surface quality evaluation and cost comparison of raw materials.
【００２４】[0024]
【表２】 [Table 2]
【００２５】面質不良であった比較例１〜５の表面をＥ
ＰＭＡで観察したところ、比較例１〜４については、金
属間化合物の密集したところと粗なところがスジ状に分
布しており、その周辺に粗大な砂目が形成され、面質不
良の原因になっていることが確認できた。また、比較例
５については、Ｔｉ金属間化合物が引き伸ばされてお
り、その部分には砂目が均一に形成できておらず面質不
良の原因になっていることが確認できた。面質不良であ
った比較例６の表面を走査型電子顕微鏡（略称ＳＥＭ）
で観察したところ、粗大な砂目と、砂目がまったく形成
できない箇所が混在しており、面質不良の原因になって
いることが確認できた。比較例７の表面を同様にＳＥＭ
で観察したところ、極めて粗大でかつ形状が不揃いの砂
目が広範囲にわたって形成されており、面質不良の原因
になっていることが確認できた。これは金属間化合物が
少なすぎ、砂目製成の開始点が均一に分散できなかった
ためである。比較例８および９は面質に問題はないが、
原材料コストが大きいという欠点がある。The surfaces of Comparative Examples 1 to 5 which had poor surface quality were treated with E
As a result of observation with PMA, in Comparative Examples 1 to 4, dense areas and coarse areas of the intermetallic compound were distributed in a streak shape, and coarse grains were formed around the areas, which was a cause of poor surface quality. I was able to confirm that it has become. Further, in Comparative Example 5, the Ti intermetallic compound was stretched, and it was confirmed that the grain was not formed uniformly in that portion, which was a cause of poor surface quality. The surface of Comparative Example 6 having poor surface quality was scanned with a scanning electron microscope (abbreviated as SEM).
As a result of observation, it was confirmed that coarse grains and places where no grains were formed were mixed, which was a cause of poor surface quality. The surface of Comparative Example 7 was similarly subjected to SEM.
As a result of observation, it was confirmed that extremely coarse and irregularly shaped grains were formed over a wide range, which was a cause of poor surface quality. This is because the intermetallic compound was too small and the starting point of grain formation could not be uniformly dispersed. Comparative Examples 8 and 9 have no problem in surface quality,
It has the drawback of high raw material costs.
【００２６】上記のように、本発明による平版印刷版用
アルミニウム合金支持体は、０＜Ｆｅ≦０．２０重量
％、０≦Ｓｉ≦０．１３重量％、Ａｌ≧９９．７重量％
であり、板表面から１０μｍ以内の任意の厚み方向深さ
において金属間化合物の数が１００〜３０００個／ｍｍ
2、平均粒子サイズが０．５〜８μｍ、粒子サイズ１０
μｍ以上の金属間化合物の数の割合が２％以下であるも
のにおいて、良好な面質と低い原材料コストが得られ
た。As described above, the aluminum alloy support for a lithographic printing plate according to the present invention has 0 <Fe ≦ 0.20% by weight, 0 ≦ Si ≦ 0.13% by weight, Al ≧ 99.7% by weight.
And the number of intermetallic compounds is 100 to 3000 pieces / mm at any depth in the thickness direction within 10 μm from the plate surface.
2 , average particle size is 0.5 to 8 μm, particle size 10
When the ratio of the number of intermetallic compounds of μm or more was 2% or less, good surface quality and low raw material cost were obtained.
【００２７】実施例５、６、比較例１０ アルミニウム原材料等を溶解し、実施例１〜４と同様の
方法で、実施例５及び比較例１０のサンプルを作成し
た。また、図２に示す双ロール連続鋳造装置を用いて、
溶解保持炉５にてアルミニウム原材料を溶解し、双ロー
ル連続鋳造機６にて厚さ７．５ｍｍの連続鋳造板を作成
し、コイラ７で巻き取った。引き続き、図３に示す冷間
圧延機を用い、最終的に板厚０．２４ｍｍの厚さに仕上
げ、実施例６のサンプルを作成した。各サンプルについ
て、表面から厚み方向の深さにおいて金属間化合物の個
数がどのように変化するかを調べた。厚み方向の深さに
おける金属間化合物を測定する方法としては、各サンプ
ルをアルカリエッチングして所定量表層部を除去し、表
面のスマットを酸で取り除いた後に、実施例１と同様
に、電子プロブマイクロアナライザを用いて面分析を行
なった。各サンプルの内訳および表面から厚み方向の深
さにおける金属間化合物の個数を表３に示す。Examples 5 and 6, Comparative Example 10 Aluminum raw materials and the like were melted, and samples of Example 5 and Comparative Example 10 were prepared in the same manner as in Examples 1 to 4. Further, using the twin roll continuous casting device shown in FIG.
The aluminum raw material was melted in the melting and holding furnace 5, and a twin-roll continuous casting machine 6 was used to prepare a continuously cast plate having a thickness of 7.5 mm, which was wound by the coiler 7. Subsequently, the cold rolling mill shown in FIG. 3 was used to finally finish the sheet to a thickness of 0.24 mm to prepare a sample of Example 6. For each sample, it was examined how the number of intermetallic compounds changed from the surface to the depth in the thickness direction. As a method for measuring the intermetallic compound at the depth in the thickness direction, each sample was alkali-etched to remove a predetermined amount of the surface layer portion, and smut on the surface was removed with an acid. Surface analysis was performed using a microanalyzer. Table 3 shows the breakdown of each sample and the number of intermetallic compounds at the depth from the surface in the thickness direction.
【００２８】[0028]
【表３】 [Table 3]
【００２９】これらのサンプルについて実施例１と同じ
方法で、表面の粗面化を行い、面質評価を行った。評価
結果を表４に示す。The surface of each of these samples was roughened and the surface quality was evaluated by the same method as in Example 1. Table 4 shows the evaluation results.
【００３０】[0030]
【表４】 [Table 4]
【００３１】上記のように、実施例５、６は表層から１
０μｍ以内における金属間化合物の数が１００〜３００
０個／ｍｍ2の範囲であり、良好な面質が得られた。As described above, in Examples 5 and 6, from the surface layer to 1
The number of intermetallic compounds within 0 μm is 100 to 300
The number was 0 / mm 2 , and good surface quality was obtained.
【００３２】[0032]
【発明の効果】本発明の平版印刷版用アルミニウム合金
支持体により、従来のものに比べ、低コストでかつ電解
粗面化性の優れた平版印刷版用アルミニウム合金支持体
が得られた。なお、実施例では固定式の水冷鋳型を用い
る鋳造方法と双ロール連続鋳造を用いる方法について示
したが、本発明はこれに限定されず、図５に示すような
双ベルト連続鋳造、その他薄板を連続的に鋳造する方法
を用いてもよい。双ロール連続鋳造や双ベルト連続鋳造
を用いると製造コストはさらに削減可能となる。EFFECTS OF THE INVENTION The aluminum alloy support for lithographic printing plates of the present invention can provide an aluminum alloy support for lithographic printing plates which is lower in cost and superior in electrolytic graining property than conventional ones. In addition, although the casting method using a fixed water-cooled mold and the method using twin roll continuous casting were shown in the examples, the present invention is not limited to this, and twin belt continuous casting as shown in FIG. A method of continuously casting may be used. If twin roll continuous casting or twin belt continuous casting is used, the manufacturing cost can be further reduced.
【図１】本発明の平版印刷版用支持体を製造する方法の
鋳造工程の一実施例の概念図。FIG. 1 is a conceptual diagram of an example of a casting step of a method for producing a lithographic printing plate support of the present invention.
【図２】本発明の平版印刷版用支持体を製造する方法の
鋳造工程のもう一つの実施例の概念図。FIG. 2 is a conceptual diagram of another embodiment of the casting step of the method for producing a lithographic printing plate support of the present invention.
【図３】本発明の平版印刷版用支持体を製造する方法の
冷間圧延工程の一実施例の概念図。FIG. 3 is a conceptual diagram of an example of a cold rolling step of the method for producing a lithographic printing plate support of the present invention.
【図４】本発明の平版印刷版用支持体を製造する方法の
矯正工程の一実施例の概念図。FIG. 4 is a conceptual diagram of an example of a straightening step of the method for producing a lithographic printing plate support of the present invention.
【図５】本発明の平版印刷版用支持体を製造する方法の
鋳造工程のもう一つの実施例の概念図。FIG. 5 is a conceptual diagram of another embodiment of the casting step of the method for producing a lithographic printing plate support of the present invention.
１ 水冷鋳型 ２ 鋳塊受け台 ３ 溶湯供給ノズル ４ 鋳塊 ５ 溶解保持炉 ６ 双ロール連続鋳造機 ７ コイラ ８ 冷間圧延機 ９ 矯正装置 １０ 双ベルト連続鋳造装置 １１ 熱間圧延機 DESCRIPTION OF SYMBOLS 1 Water-cooled mold 2 Ingot cradle 3 Molten metal supply nozzle 4 Ingot 5 Melt holding furnace 6 Twin roll continuous casting machine 7 Coiler 8 Cold rolling mill 9 Straightening device 10 Twin belt continuous casting device 11 Hot rolling mill
───────────────────────────────────────────────────── フロントページの続き (72)発明者 上杉 彰男 静岡県榛原郡吉田町川尻4000番地 富士写 真フイルム株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Uesugi 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Sha Shin Film Co., Ltd.
Claims (2)
０．１３重量％、Ａｌ≧９９．７重量％、残部が不可避
不純物元素からなるアルミニウム合金板であって、板表
面から１０μｍ以内の任意の厚み方向深さにおいて金属
間化合物の数が１００〜３０００個／ｍｍ2、金属間化
合物の平均粒子サイズが０．５〜８μｍ、粒子サイズ１
０μｍ以上の金属間化合物の数の割合が２％以下である
ことを特徴とする平版印刷版用アルミニウム合金支持
体。1. 0 <Fe ≦ 0.20% by weight, 0 ≦ Si ≦
An aluminum alloy plate having 0.13% by weight, Al ≧ 99.7% by weight, and the balance being unavoidable impurity elements, wherein the number of intermetallic compounds is 100 to 3000 at an arbitrary depth direction within 10 μm from the plate surface. Particles / mm 2 , average particle size of intermetallic compound is 0.5 to 8 μm, particle size 1
An aluminum alloy support for a lithographic printing plate, characterized in that the proportion of the number of intermetallic compounds of 0 μm or more is 2% or less.
０≦Ｔｉ＜０．０５重量％、０≦Ｃｕ＜０．０５重量％
を含むことを特徴とする請求項１記載の平版印刷版用ア
ルミニウム合金支持体。2. The component of the aluminum alloy support is
0 ≦ Ti <0.05% by weight, 0 ≦ Cu <0.05% by weight
The aluminum alloy support for a lithographic printing plate according to claim 1, comprising:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6184900A JPH0849034A (en) | 1994-08-05 | 1994-08-05 | Aluminum alloy supporting body for planographic printing plate |
| US08/504,676 US5779824A (en) | 1994-08-05 | 1995-07-20 | Aluminum alloy support for planographic printing plate and method for producing the same |
| EP95111464A EP0695647B1 (en) | 1994-08-05 | 1995-07-20 | Aluminum alloy support for planographic printing plate and method for producing the same |
| DE69507398T DE69507398T2 (en) | 1994-08-05 | 1995-07-20 | Aluminum alloy carrier for a high pressure plate and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6184900A JPH0849034A (en) | 1994-08-05 | 1994-08-05 | Aluminum alloy supporting body for planographic printing plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0849034A true JPH0849034A (en) | 1996-02-20 |
Family
ID=16161298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6184900A Pending JPH0849034A (en) | 1994-08-05 | 1994-08-05 | Aluminum alloy supporting body for planographic printing plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0849034A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1625944A1 (en) | 2004-08-13 | 2006-02-15 | Fuji Photo Film Co., Ltd. | Method of manufacturing lithographic printing plate support |
| EP1712368A1 (en) | 2005-04-13 | 2006-10-18 | Fuji Photo Film Co., Ltd. | Method of manufacturing a support for a lithographic printing plate |
| WO2010038812A1 (en) | 2008-09-30 | 2010-04-08 | 富士フイルム株式会社 | Electrolytic treatment method and electrolytic treatment device |
| JP2010256636A (en) * | 2009-04-24 | 2010-11-11 | Kanagawa Acad Of Sci & Technol | Aluminum base material for manufacturing stamper and method for manufacturing stamper |
| WO2010150810A1 (en) | 2009-06-26 | 2010-12-29 | 富士フイルム株式会社 | Light reflecting substrate and process for manufacture thereof |
| WO2011078010A1 (en) | 2009-12-25 | 2011-06-30 | 富士フイルム株式会社 | Insulated substrate, process for production of insulated substrate, process for formation of wiring line, wiring substrate, and light-emitting element |
| CN104894495A (en) * | 2015-06-03 | 2015-09-09 | 天津市航宇金属加工有限公司 | Device capable of removing machining hole stress of aluminum alloy product |
-
1994
- 1994-08-05 JP JP6184900A patent/JPH0849034A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1625944A1 (en) | 2004-08-13 | 2006-02-15 | Fuji Photo Film Co., Ltd. | Method of manufacturing lithographic printing plate support |
| EP1712368A1 (en) | 2005-04-13 | 2006-10-18 | Fuji Photo Film Co., Ltd. | Method of manufacturing a support for a lithographic printing plate |
| WO2010038812A1 (en) | 2008-09-30 | 2010-04-08 | 富士フイルム株式会社 | Electrolytic treatment method and electrolytic treatment device |
| JP2010256636A (en) * | 2009-04-24 | 2010-11-11 | Kanagawa Acad Of Sci & Technol | Aluminum base material for manufacturing stamper and method for manufacturing stamper |
| WO2010150810A1 (en) | 2009-06-26 | 2010-12-29 | 富士フイルム株式会社 | Light reflecting substrate and process for manufacture thereof |
| WO2011078010A1 (en) | 2009-12-25 | 2011-06-30 | 富士フイルム株式会社 | Insulated substrate, process for production of insulated substrate, process for formation of wiring line, wiring substrate, and light-emitting element |
| CN104894495A (en) * | 2015-06-03 | 2015-09-09 | 天津市航宇金属加工有限公司 | Device capable of removing machining hole stress of aluminum alloy product |
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