JP3177079B2 - Method for producing a lithographic printing plate support - Google Patents
Method for producing a lithographic printing plate supportInfo
- Publication number
- JP3177079B2 JP3177079B2 JP29237393A JP29237393A JP3177079B2 JP 3177079 B2 JP3177079 B2 JP 3177079B2 JP 29237393 A JP29237393 A JP 29237393A JP 29237393 A JP29237393 A JP 29237393A JP 3177079 B2 JP3177079 B2 JP 3177079B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- support
- lithographic printing
- printing plate
- plate
- 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.)
- Expired - Lifetime
Links
- 238000007639 printing Methods 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 62
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 32
- 238000009749 continuous casting Methods 0.000 claims description 22
- 238000007788 roughening Methods 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 15
- 238000005098 hot rolling Methods 0.000 claims description 14
- 238000005097 cold rolling Methods 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000006104 solid solution Substances 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 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
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000000866 electrolytic etching Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 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
- 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
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 239000010407 anodic oxide Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 102220253765 rs141230910 Human genes 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は平版印刷版用支持体の製
造方法に関する、特に電解粗面化性の良いアルミニウム
支持体の製造方法に関するものである。The present invention relates to a method for producing a lithographic printing plate support, and more particularly to a method for producing an aluminum support having good electrolytic surface roughening properties.
【０００２】[0002]
【従来の技術】印刷版用アルミニウム支持体、とくにオ
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み合わせ
（特開昭５６−２９６９９号公報）などが知られてい
る。2. Description of the Related Art An aluminum plate (including an aluminum alloy plate) is used as an aluminum support for a printing plate, particularly as a support for an offset printing plate. Generally, in order to use an aluminum plate as a support for an offset printing plate, it is necessary that the aluminum plate has 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 a uniform and dense grain. Since the surface roughening treatment has a remarkable effect on the printing performance and printing durability of the plate material when offset printing is actually performed after plate making, its quality is an important factor in plate material production. As a method of roughening the aluminum support for a printing plate, an AC electrolytic etching method is generally employed, and as the current, a special alternating waveform current such as a normal sine wave AC current or a rectangular wave is used. . The surface of the aluminum plate is roughened by alternating current using an appropriate electrode such as graphite as a counter electrode, and is usually performed in a single process, but the pit depth obtained there is generally shallow. And the printing durability was poor. For this reason, various methods have been proposed so that an aluminum plate suitable as a support for a printing plate having a grain having uniform and dense pits deeper than the diameter thereof can be obtained. Examples of the method include a surface roughening method using a special electrolytic power source waveform (Japanese Patent Application Laid-Open No. 53-67507), and a ratio of the amount of electricity between an anode and a cathode during electrolytic surface roughening using an alternating current (Japanese Patent Application Laid-Open No. Showa 54
No. 65607), power supply waveforms (Japanese Patent Laid-Open No. 55-253).
No. 81) and combinations of the amounts of current per unit area (JP-A-56-29699) are known.
【０００３】また、機械的な粗面化と組み合わせた方法
（特開昭５５−１４２６９５号公報）なども知られてい
る。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４
００〜６００ｍｍ，幅１０００〜２０００ｍｍ，長さ２
０００〜６０００ｍｍ）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。またその後組織の均一化と
平担度の良い板にする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、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。Further, a method (Japanese Patent Laid-Open No. 55-142695) combined with mechanical roughening is also known. On the other hand, as a method for manufacturing an aluminum support, an aluminum ingot is melted and held, and a slab (thickness 4) is formed.
00-600mm, width 1000-2000mm, length 2
000-6000 mm), and after passing through a face milling step of cutting the impurity structure portion of the slab surface by a face mill at a rate of 3 to 10 mm, in a soaking furnace for removing stress inside the slab and homogenizing the structure. A soaking process is performed at 480 to 540 ° C. for 6 to 12 hours, followed by hot rolling at 480 to 540 ° C. After that, annealing is performed to homogenize the rolled structure and the like to uniformize the structure and to form a plate having good flatness, and then cold-rolled to a specified thickness to correct the structure. The aluminum support thus produced was used as a support for a lithographic printing plate.
【０００４】これに対し、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，熱処理を行ない、さらに矯
正を行なったアルミニウム支持体を、粗面化することを
特徴とする平版印刷版用支持体の製造方法を提案してい
る。（特開平３−７９７９８号公報）[0004] On the other hand, the present applicant has previously prepared a lithographic printing plate of excellent quality and good yield by reducing the variation in the material of the aluminum support and improving the yield of electrolytic surface roughening treatment. As a method for producing the aluminum support, casting and hot rolling are continuously performed from a molten aluminum to form a hot-rolled coil of a thin plate, then cold rolling and heat treatment are performed, and the aluminum support that has been straightened is roughened. A method for producing a lithographic printing plate support characterized in that the support is formed. (JP-A-3-79798)
【０００５】[0005]
【発明が解決しようとする課題】ところが、先に提案し
た本出願人の製造方式についても、最終的な冷間圧延又
は熱処理後のアルミニウム板表面のアルミニウム結晶粒
の大きさが粗面化後の面質に大きく影響していることが
わかった。さらに微量合金成分の内、特にＦｅが一定以
上マトリックスに固溶していることが、均一な粗面化を
実施する上で非常に重要であることがわかった。However, in the manufacturing method proposed by the applicant of the present invention, the size of the aluminum crystal grains on the surface of the aluminum plate after the final cold rolling or heat treatment is reduced. It turned out that it greatly affected the surface quality. Further, it has been found that it is very important that, among the trace alloy components, Fe is dissolved in the matrix in a certain amount or more, in order to achieve uniform surface roughening.
【０００６】本発明の目的は、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
せると共に、粗面化後の面質の優れた、得率のよい平版
印刷版を作れる平版印刷版用支持体の製造方法を提供す
ることにある。SUMMARY OF THE INVENTION It is an object of the present invention to reduce variations in the material of an aluminum support, improve the yield of electrolytic surface roughening treatment, and improve the quality of lithographic printing with excellent surface quality after roughening. An object of the present invention is to provide a method for producing a lithographic printing plate support capable of forming a plate.
【０００７】[0007]
【課題を解決するため手段及び作用】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
て来た結果、本発明を見出したものである。即ち、本発
明の上記目的は、アルミニウム溶湯から双ベルト方式で
直接板状に連続鋳造したのち、熱間圧延，冷間圧延，熱
処理を各々１回以上行い、さらに矯正を行なったアルミ
ニウム支持体を粗面化する平版印刷版用支持体の製造方
法において、Ｆｅの含有量が０．４％〜０．２％，Ｓｉ
の含有量が０．２０％〜０．０５％、Ｃｕの含有量が
０．００２％〜０．０２％、Ａｌ純度が９９．５％以
上、連続鋳造熱間圧延後のアルミニウム板の結晶粒径が
鋳造進行方向に垂直な断面において５μｍから５００μ
ｍであって、かつ最終的な冷間圧延または焼鈍後のアル
ミ板の結晶粒径が、鋳造および圧延進行方向に垂直な断
面において５μｍから１００μｍであることを特徴とす
る平版印刷版用支持体の製造方法。さらに好ましくはＦ
ｅの固溶量が１０ｐｐｍ以上である、上記記載の平版印
刷版用支持体の製造方法。によって達成される。The present inventors have made intensive studies on the relationship between the aluminum support and the electrolytic surface-roughening treatment and have found the present invention. That is, the above object of the present invention is to provide an aluminum support which has been subjected to direct casting continuously from a molten aluminum into a plate shape by a twin belt method, and then subjected to hot rolling, cold rolling and heat treatment at least once and further straightened. In the method for producing a lithographic printing plate support having a roughened surface, the Fe content is 0.4% to 0.2%,
Content of 0.20% to 0.05%, Cu content of 0.002% to 0.02%, Al purity of 99.5% or more, crystal grain of aluminum plate after continuous casting hot rolling 5 μm to 500 μm in cross section whose diameter is perpendicular to the direction of casting
m, and the crystal grain size of the aluminum plate after final cold rolling or annealing is 5 μm to 100 μm in a cross section perpendicular to the direction of casting and rolling. Manufacturing method. More preferably, F
The method for producing a lithographic printing plate support as described above, wherein the solid solution amount of e is 10 ppm or more. Achieved by
【０００８】本発明のアルミニウム溶湯から双ベルト方
式を用い連続的に鋳造したコイルを形成させる方法とし
ては、金属ベルトを用いるハズレー法、キャタピラ状の
ブロックを用いるアルスイスキャスターＩＩなどの連鋳
技術が実用化されている。双ベルトを用いる連続鋳造法
は、ハンター法等の、双ロールを用いる連続鋳造に比べ
て生産能力が非常に大きいことが知られている。本発明
はアルミニウム溶湯から双ベルト方式で連続鋳造する
際、結晶粒径を一定範囲におさめることで、結晶粒界に
集まりやすい合金成分の分布を一定範囲におさめること
ができる。さらに連続鋳造後の冷間圧延や焼鈍工程にお
いて粒界を変形させ、合金成分を拡散させることで、最
終的なアルミ板中の合金成分の分布を均一にすることが
できるが、結晶粒界の影響を皆無にすることはできない
ため、最終的なアルミ板の結晶粒径を一定範囲におさめ
る。これらの方法により粗面化時にムラのない上質な表
面を持つ品質上すぐれた平版印刷版用支持体を低コスト
でかつ得率よく製造することができる。特に双ベルト方
式の連続鋳造を行なうことで、双ロール方式のような他
の連続鋳造に比べて大きな生産能力を達成することがで
きる。図１の工程概念図を用いて本発明に用いるアルミ
ニウム支持体の製造方法の実施態様について更に具体的
に説明する。１は溶解保持炉でここでインゴットは溶解
保持される。ここから双ベルト方式連続鋳造機２に送ら
れる。つまりアルミニウム溶湯から直接薄板材を形成
し、引きつづき熱間圧延機３で厚みを減少させ、コイラ
ー４によって巻取っても良いし、さらに引続いて，冷間
圧延機５，熱処理６，矯正装置７にかけてもよい。As a method of forming a coil continuously cast from the molten aluminum of the present invention by using the twin belt method, a continuous casting technique such as a Hazelley method using a metal belt and an Al Swiss Caster II using a caterpillar block are used. Has been put to practical use. It is known that the continuous casting method using twin belts has a much larger production capacity than continuous casting using twin rolls, such as the Hunter method. According to the present invention, when continuous casting is performed from a molten aluminum by a twin belt method, the distribution of alloy components that tend to gather at the crystal grain boundaries can be kept within a certain range by keeping the crystal grain size within a certain range. Furthermore, by deforming the grain boundaries in the cold rolling or annealing process after continuous casting and diffusing the alloy components, the distribution of the alloy components in the final aluminum plate can be made uniform. Since the influence cannot be completely eliminated, the crystal grain size of the final aluminum plate is kept within a certain range. By these methods, a high quality lithographic printing plate support having a high quality surface with no unevenness at the time of roughening can be produced at low cost and with high yield. In particular, by performing twin-belt continuous casting, a large production capacity can be achieved as compared with other continuous casting such as a twin-roll type. An embodiment of the method for producing an aluminum support used in the present invention will be described more specifically with reference to the process conceptual diagram of FIG. Reference numeral 1 denotes a melting and holding furnace in which the ingot is melted and held. From here, it is sent to the twin belt type continuous casting machine 2. That is, a thin sheet material is formed directly from the molten aluminum, and subsequently, the thickness may be reduced by the hot rolling mill 3 and wound up by the coiler 4, and subsequently, the cold rolling mill 5, the heat treatment 6, and the straightening device It may be over seven.
【０００９】それらの製造条件について更に詳しく説明
すると、溶解保持炉１ではアルミニウムの融点以上の温
度に保持させる必要があり、その温度はアルミニウム合
金成分によって適時変化する。一般に８００℃以上であ
る。また、アルミニウム溶湯の酸化物発生の抑制、品質
上有害となるアルカリ金属の除去策として、適宜不活性
ガスパージ、フラックス処理等が行なわれる。引き続き
双ベルト方式連続鋳造機２によって鋳造される。鋳造方
式にはいろいろあるが、現在工業的に稼働しているのは
バズレー法，アルスイスキャスターＩＩなどが殆どであ
る。鋳造温度は鋳型の冷却条件で異なるが、７００℃付
近が最適である。連続鋳造後の結晶粒径、冷却条件、鋳
造速度と、鋳造中の板厚変化量が制御され、この様に連
続鋳造によって得られた板材に、引きつづき熱間圧延機
３、冷間圧延機５によって、規定の厚みに圧延する。そ
の際、結晶粒を所定の大きさにそろえるため、中間焼鈍
等の熱処理機６にかけ、更に冷間圧延機５をさし挟んで
行なってもよい。つぎに矯正装置７によって矯正を行な
い、所定の平面性を与え、アルミニウム支持体を作り、
これを粗面化する。また、矯正は最後の冷間圧延に含め
て行うこともある。この際アルミニウム結晶粒の大きさ
は鋳造・圧延の進行方向に対し垂直な断面において、連
続鋳造熱間圧延後は５〜５００μｍ，最終状態において
５〜１００μｍになるようにする。The production conditions will be described in more detail. In the melting and holding furnace 1, it is necessary to maintain the temperature at a temperature equal to or higher than the melting point of aluminum, and the temperature varies depending on the aluminum alloy component. Generally, it is 800 ° C. or higher. In addition, as a measure for suppressing the generation of oxides in the molten aluminum and removing alkali metals that are harmful to quality, an inert gas purge, a flux treatment, or the like is appropriately performed. Subsequently, it is cast by a twin belt type continuous casting machine 2. Although there are various casting methods, most of them currently operating industrially include the Buzzley method and the Al Swiss Caster II. The casting temperature varies depending on the cooling conditions of the mold, but is optimally around 700 ° C. The crystal grain size after continuous casting, cooling conditions, casting speed, and the thickness change during casting are controlled, and the sheet material obtained by continuous casting is successively added to the hot rolling mill 3, the cold rolling mill According to 5, it is rolled to a specified thickness. At that time, in order to make the crystal grains have a predetermined size, the crystal grains may be subjected to a heat treatment machine 6 such as intermediate annealing or the like, and may be further sandwiched by a cold rolling mill 5. Next, straightening is performed by the straightening device 7 to give a predetermined flatness, and an aluminum support is made.
This is roughened. The straightening may be performed in the last cold rolling. At this time, the size of the aluminum crystal grains is set to be 5 to 500 μm after continuous casting hot rolling and 5 to 100 μm in the final state in a cross section perpendicular to the direction of the casting and rolling.
【００１０】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られる。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。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。以下詳細な説明する。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５
ｓｅｃ〜５ｍｉｎ間の範囲から選択されるのが適当でて
あり、好ましいエッチング量としては０．１〜５ｇ／ｍ
2 である。特に不純物の大い支持体の場合、０．０１〜
１ｇ／ｍ2 が適当である（特開平１−２３７１９７号公
報参照）。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。In the present invention, various methods such as mechanical surface roughening, chemical surface roughening, electrochemical surface roughening, and a combination thereof are used for the surface roughening method of the lithographic printing plate support. Mechanical graining methods include, for example, ball grain, wire grain, brush grain, and liquid honing. As electrochemical graining method also AC electrolytic etching method has been generally adopted, as the current, usual sine wave alternating current or rectangular wave of throat special alternating current is used. In addition, as a pretreatment for the electrochemical graining, an etching treatment with caustic soda may be performed. When electrochemical surface roughening is performed, the surface is preferably roughened by an alternating current with an aqueous solution mainly composed of hydrochloric acid or nitric acid. The details will be described 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.
Concentration 0.01-20%, temperature 20-90 ° C, time 5
It is appropriate to select from a range between sec to 5 min, and a preferable etching amount is 0.1 to 5 g / m 2.
2 Particularly in the case of a support having a large impurity, 0.01 to
1 g / m 2 is appropriate (see JP-A- 1-237197 ). Subsequently, since a substance (smut) insoluble in alkali remains on the surface of the alkali-etched aluminum plate, desmutting may be performed as necessary.
【００１１】前処理は上記の通りであるが、引き続き、
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／
ｌ，より好ましくは５〜５０ｇ／ｌ，浴内のアルミニウ
ムの溶解量としては５０ｇ／ｌ以下が適当であり、より
好ましくは２〜２０ｇ／ｌ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５５−１９１９
１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、電気量と共に求める品
質，使用されるアルミニウム支持体の成分などによって
適時選択される。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／ｌ，温度２５
〜６５℃が好ましい。硫酸の濃度を４００ｇ／ｌ以上，
又は温度を６５℃以上にすると処理層などの腐食が大き
くなり、しかも、マンガンが０．３％以上あるアルミニ
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 以上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。陽極酸
化被膜は、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てないが、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。The pre-processing is as described above.
AC electrolytic etching is performed in an electrolytic solution mainly containing hydrochloric acid or nitric acid. The frequency of the AC electrolytic current is 0.1
To 100 Hz, more preferably 0.1 to 1.0 or 10
６０60 Hz. The liquid concentration is 3 to 150 g /
1, more preferably 5 to 50 g / l, and the amount of aluminum dissolved in the bath is suitably 50 g / l or less, more preferably 2 to 20 g / l. Additives may be added if necessary, but in the case of mass production, it becomes difficult to control the liquid concentration. The current density is 5 to 100 A /
Although dm 2 is appropriate, 10 to 80 A / dm 2 is more preferable. The power supply waveform is appropriately selected depending on the quality required and the components of the aluminum support used. Japanese Patent Publication No. 56-19280 and Japanese Patent Publication No. 55-1919
It is more preferable to use the special alternating waveform described in each of the publications. Such waveform and liquid conditions are appropriately selected depending on the quality required together with the quantity of electricity, the components of the aluminum support used, and the like. The electrolytically roughened aluminum is then immersed in an alkaline solution as part of the smut treatment to dissolve the smut. As the alkaline agent, there are various types such as caustic soda, and it is preferable to perform the treatment in a very short time of 10 or more at a pH of 10 or more and at a temperature of 25 to 60 ° C.
Next, it is immersed in a liquid mainly composed of sulfuric acid. As the sulfuric acid solution conditions,
Concentration 50-400 g / l, temperature 25
~ 65 ° C is preferred. The concentration of sulfuric acid is more than 400g / l,
Alternatively, when the temperature is set to 65 ° C. or higher, corrosion of the treatment layer and the like becomes large, and in the case of an aluminum alloy containing manganese of 0.3% or more, the grain which is electrochemically roughened is broken. Also, the dissolution amount of the aluminum base was 0.2 g /
If the film is etched by m 2 or more, the printing durability is reduced. Therefore, it is preferable that the amount be 0.2 g / m 2 or less. The anodic oxide coating has a thickness of 0.1 to 10 g / m 2 , more preferably 0.1 to 10 g / m 2 .
It is preferable to form 3 to 5 g / m 2 on the surface. The anodizing treatment conditions vary depending on the electrolytic solution used, and thus are not generally determined. However, in general, the concentration of the electrolytic solution is 1 to 80% by weight, the liquid temperature is 5 to 70 ° C, and the current density is 0.5 ~
60A / cm 2 , voltage 1-100V, electrolysis time 1 second-5
A range of minutes is appropriate.
【００１２】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、先に記載した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設け、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 grained aluminum plate having an anodized film obtained in this manner is stable and excellent in hydrophilicity. Therefore, a photosensitive film can be immediately provided on the aluminum plate. Can further apply a surface treatment. For example, a silicate layer of the alkali metal silicate described above or an undercoat layer of a hydrophilic polymer compound can be provided. The coating amount of the undercoat layer is 5-150 mg
/ M 2 is preferred. Next, a photosensitive coating film is provided on the aluminum support treated in this way, and after image exposure, development and plate making, it is set in a printing machine and printing is started.
【００１３】[0013]
【実施例】（実施例１−４，比較例１〜９） 第１図（Ａ）に示したような連続鋳造装置２及び熱間圧
延機３にて７ｍｍの板厚のアルミニウム板材を形成さ
せ、更に１ｍｍの板厚まで冷間圧延し、４００℃での焼
鈍工程後更に０．３ｍｍ迄冷間圧延（矯正を含む）して
ＪＩＳ１０５０材を形成した。この際、表１に示す組成
のアルミニウム材及び鋳造条件、圧延、焼鈍条件を適宜
変更し、連続鋳造熱間圧延後及び最終状態における粒子
径の組合せにつてい、本発明の実施例１〜４及び比較例
１〜９として作成した。この板材の鋳造、圧延方向に垂
直な断面（図２参照）を、バフにて鏡面に加工し、フッ
酸１０％液中でエッチングを施し、偏光顕微鏡を用いて
表面の結晶粒径の観察測定を行なった。また、最終状態
におけるアルミニウム板材から、金属間化合物として存
在するＦｅを抽出することで、固溶しているＦｅ量の測
定を行った。EXAMPLES (Example 1-4, Comparative Example 1 to 9) to form an aluminum plate of thickness of 7mm in Figure 1 continuous casting apparatus as shown in (A) 2 and the hot rolling mill 3 The sheet was further cold-rolled to a thickness of 1 mm, and after the annealing step at 400 ° C., was further cold-rolled (including straightening) to 0.3 mm to form a JIS 1050 material. At this time, the aluminum material having the composition shown in Table 1 and the casting conditions, rolling and annealing conditions were appropriately changed, and the combinations of the particle diameters after the continuous casting hot rolling and in the final state were determined according to Examples 1 to 4 of the present invention. And Comparative Examples 1 to 9 . A section perpendicular to the casting and rolling directions of this sheet material (see FIG. 2) is processed into a mirror surface with a buff, etched in a 10% hydrofluoric acid solution, and observed and measured for the crystal grain size on the surface using a polarizing microscope. Was performed. Further, the amount of Fe in solid solution was measured by extracting Fe present as an intermetallic compound from the aluminum plate material in the final state.
【００１４】[0014]
【表１】 [Table 1]
【００１５】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、次に５％苛性ソーダ水溶
液で温度６０℃でエッチング量が５ｇ／ｍ2 になる様に
エッチングし、水洗後、１５０ｇ／１，５０℃の硫酸液
中に２０ｓｅｃ浸漬してデスマットし、水洗した。更に
支持体を１６ｇ／ｌの硝酸水溶液中で、特公昭５５−１
９１９１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Ｖ
A ＝１４Ｖ，カソード電圧ＶC ＝１２Ｖとして、陽極時
電気量が、３５０クーロン／ｄｍ2 となる様にした。以
上の如くして作成したとき基板に、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および、基板の表面を走査形電子顕
微鏡（ＳＥＭ）で拡大観察し、砂目形状の均一さを評価
した。感光性平版印刷版に、ネガフィルム又はポジフィ
ルムを通して露光を行なった後、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
又は画像部となるため、基板表面の砂目形状や面質自体
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。表１に示す試料の感光層塗布前の評価結果は表２
の通りとなった。The aluminum plate thus obtained was used as a support for a lithographic printing plate, and then etched with a 5% aqueous sodium hydroxide solution at a temperature of 60 ° C. so that the amount of etching became 5 g / m 2. / 1, immersed in a sulfuric acid solution at 50 ° C. for 20 seconds, desmutted, and washed with water. Further, the support was placed in a 16 g / l aqueous nitric acid solution,
The surface was electrochemically roughened using an alternating waveform current described in JP-A-9191. Electrolysis conditions include anode voltage V
A = 14 V and cathode voltage V C = 12 V, so that the quantity of electricity at the anode was 350 coulombs / dm 2 . When prepared as described above, a photosensitive lithographic printing plate is obtained by applying a photosensitive liquid to the substrate. Here, the surface quality of the substrate before the application of the photosensitive liquid and the surface of the substrate are measured by a scanning electron microscope. (SEM) was observed under magnification to evaluate the uniformity of the grain shape. The photosensitive lithographic printing plate is exposed through a negative film or a positive film, and then developed. (If the photosensitive layer is removed, the surface of the substrate itself becomes the non-image portion or image portion of the lithographic printing plate.) This is because the grain shape and surface quality of the substrate surface have a great effect on printability and visibility of the printing plate. Table 2 shows the evaluation results of the samples shown in Table 1 before coating the photosensitive layer.
It was as follows.
【００１６】[0016]
【表２】 [Table 2]
【００１７】上記の表のとおり、本発明によらない試料
Ｎｏ．５〜１１ではスジ状のムラ発生し、品質上不良で
あった。同じく、Ｆｅの固溶量の少ないＮｏ．１２，１
３は砂目形状が不均一であった。また、このスジ状のム
ラは、結晶粒径が不均一なため、粒界に折出し易い合金
成分が圧延、焼鈍の工程で充分均質化しきれないために
発生したものである。また、砂目形状が不均一になるの
は、マトリックスに固溶しているＦｅ量が少ないためで
ある。これに対して本発明の試料Ｎｏ．１〜４はスジ状
のムラの発生もなく、砂目形状も均一な優れた面質のも
のであった。As shown in the above table, Sample No. not according to the present invention. In Nos. 5 to 11, streak-like unevenness occurred and the quality was poor. Similarly, No. 3 having a small amount of solid solution of Fe. 12,1
In No. 3, the grain shape was uneven. Further, the streak-like unevenness is generated because the crystal grain size is non-uniform, so that the alloy component that easily breaks out at the grain boundary cannot be sufficiently homogenized in the rolling and annealing steps. Further, the grain shape becomes non-uniform because the amount of Fe dissolved in the matrix is small. On the other hand, in the sample No. of the present invention. Nos. 1 to 4 had no streak-like unevenness, and had excellent surface quality with a uniform grain shape.
【００１８】[0018]
【発明の効果】上記のように、本発明の平版印刷版用支
持体の製造方法によって製造された平版印刷版は、従来
のものに比べ、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と共に粗面
化後の面質を著しく向上させ版面のムラがなく砂目も優
れたものとなる。更にアルミニウム支持体の製造工程が
合理化されたことによる原材料コストの低減の効果も大
きく、特に平版印刷版用支持体の品質向上及びコスト低
減に大きく貢献する。また、双ベルト方式の連続鋳造方
法を用いることにより、双ロール方式等、他の連続鋳造
方法に比べて大きな生産能力を確保することができる。As described above, the lithographic printing plate manufactured by the method for manufacturing a lithographic printing plate support of the present invention has less variation in the material of the aluminum support than the conventional lithographic printing plate. The yield of the surface treatment is improved, and the surface quality after the surface roughening is remarkably improved, so that the plate surface is not uneven and the grain is excellent. Furthermore the manufacturing process of the aluminum support effect is large reduction in raw material costs due to streamlined, especially contributes greatly to the quality improvement and cost reduction of the lithographic printing plate support. In addition, by using the twin-belt continuous casting method, a large production capacity can be secured as compared with other continuous casting methods such as a twin-roll method.
【図１】本発明の平版印刷版用支持体の製造方法の一実
施例の概念図（Ａ）〜（Ｄ）Figure 1 is a conceptual diagram of an actual <br/>施例the method of manufacturing a lithographic printing plate support of the present invention (A) ~ (D)
【図２】連続鋳造熱間圧延後の断面から結晶粒径を観察
する概念図FIG. 2 is a conceptual diagram of observing a crystal grain size from a cross section after continuous casting hot rolling.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−47349（ＪＰ，Ａ) 特開 平７−39906（ＪＰ，Ａ) 特開 平６−218495（ＪＰ，Ａ) 特許2982093（ＪＰ，Ｂ２) 特公 平４−19293（ＪＰ，Ｂ２) 特公 平５−28198（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) B21B 1/46 B21B 3/00 B41N 1/08 B41N 3/00 C22F 1/04 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-47349 (JP, A) JP-A-7-39906 (JP, A) JP-A-6-218495 (JP, A) Patent 282993 (JP, A) B2) Japanese Patent Publication No. 4-19293 (JP, B2) Japanese Patent Publication No. 5-28198 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name) B21B 1/46 B21B 3/00 B41N 1 / 08 B41N 3/00 C22F 1/04
Claims (2)
接板状に連続鋳造したのち、熱間圧延，冷間圧延，熱処
理を各々１回以上行い、さらに矯正を行なったアルミニ
ウム支持体を粗面化する平版印刷版用支持体の製造方法
において、Ｆｅの含有量が０．４％〜０．２％，Ｓｉの
含有量が０．２０％〜０．０５％、Ｃｕの含有量が０．
００２％〜０．０２％、Ａｌ純度が９９．５％以上、連
続鋳造、熱間圧延後のアルミニウム板の結晶粒径が鋳造
進行方向に垂直な断面において５μｍから５００μｍで
あって、かつ最終的な冷間圧延または焼鈍後のアルミ板
の結晶粒径が、鋳造および圧延進行方向に垂直な断面に
おいて５μｍから１００μｍであることを特徴とする平
版印刷版用支持体の製造方法。1. A continuous casting of molten aluminum from a molten aluminum directly into a plate by a twin belt method, followed by hot rolling, cold rolling and heat treatment at least once each, and further roughening the corrected aluminum support. In the method for producing a lithographic printing plate support, the content of Fe is 0.4% to 0.2%, the content of Si is 0.20% to 0.05%, and the content of Cu is 0.1%.
002% to 0.02%, the Al purity is 99.5% or more, and the crystal grain size of the aluminum plate after continuous casting and hot rolling is 5 μm to 500 μm in a cross section perpendicular to the casting progress direction, and the final A method for producing a lithographic printing plate support, characterized in that the crystal grain size of the aluminum plate after the cold rolling or annealing is 5 μm to 100 μm in a cross section perpendicular to the direction of casting and rolling.
接板状に連続鋳造したのち、熱間圧延，冷間圧延，熱処
理を各々１回以上行い、さらに矯正を行なったアルミニ
ウム支持体を粗面化する平版印刷版用支持体の製造方法
において、Ｆｅの含有量が０．４％〜０．２％，Ｓｉの
含有量が０．２０％〜０．０５％、Ｃｕの含有量が０．
００２％〜０．０２％、Ａｌ純度が９９．５％以上、Ｆ
ｅの固溶量が１０ｐｐｍ以上、連続鋳造、熱間圧延後の
アルミニウム板の結晶粒径が鋳造進行方向に垂直な断面
において５μｍから５００μｍであって、かつ最終的な
冷間圧延または焼鈍後のアルミ板の結晶粒径が、鋳造お
よび圧延進行方向に垂直な断面において５μｍから１０
０μｍであることを特徴とする平版印刷版用支持体の製
造方法。2. A continuous casting of molten aluminum from a molten aluminum directly into a plate shape by a twin belt method, followed by hot rolling, cold rolling and heat treatment at least once each, and further roughening the corrected aluminum support. In the method for producing a lithographic printing plate support, the content of Fe is 0.4% to 0.2%, the content of Si is 0.20% to 0.05%, and the content of Cu is 0.1%.
002% to 0.02%, Al purity is 99.5% or more, F
e has a solid solution amount of 10 ppm or more, the crystal grain size of the aluminum plate after continuous casting and hot rolling is 5 μm to 500 μm in a cross section perpendicular to the casting progress direction, and after final cold rolling or annealing. The crystal grain size of the aluminum plate is 5 μm to 10 μm in a section perpendicular to the direction of casting and rolling.
A method for producing a lithographic printing plate support, wherein the thickness is 0 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29237393A JP3177079B2 (en) | 1993-10-29 | 1993-10-29 | Method for producing a lithographic printing plate support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29237393A JP3177079B2 (en) | 1993-10-29 | 1993-10-29 | Method for producing a lithographic printing plate support |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07124609A JPH07124609A (en) | 1995-05-16 |
| JP3177079B2 true JP3177079B2 (en) | 2001-06-18 |
Family
ID=17780965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29237393A Expired - Lifetime JP3177079B2 (en) | 1993-10-29 | 1993-10-29 | Method for producing a lithographic printing plate support |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3177079B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3693485B2 (en) | 1998-03-09 | 2005-09-07 | 日本軽金属株式会社 | Manufacturing method of aluminum alloy base plate for lithographic printing plate |
| JP4410714B2 (en) | 2004-08-13 | 2010-02-03 | 富士フイルム株式会社 | Method for producing support for lithographic printing plate |
| EP1712368B1 (en) | 2005-04-13 | 2008-05-14 | FUJIFILM Corporation | Method of manufacturing a support for a lithographic printing plate |
| JP5405475B2 (en) | 2008-09-30 | 2014-02-05 | 富士フイルム株式会社 | Electrolytic roughening treatment method and electrolytic roughening treatment apparatus |
| EP2448024A1 (en) | 2009-06-26 | 2012-05-02 | FUJIFILM Corporation | Light reflecting substrate and process for manufacture thereof |
| US20120256224A1 (en) | 2009-12-25 | 2012-10-11 | Fujifilm Corporation | Insulated substrate, process for production of insulated substrate, process for formation of wiring line, wiring substrate, and light-emitting element |
| CN104264011B (en) * | 2014-09-30 | 2017-06-20 | 石家庄新日锌业有限公司 | A kind of aluminium wire |
-
1993
- 1993-10-29 JP JP29237393A patent/JP3177079B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07124609A (en) | 1995-05-16 |
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