JP4076705B2 - Aluminum alloy material for lithographic printing plates - Google Patents

Description

【００２８】
【表２】

【００２９】
上記表から明らかなように、本発明の供試材によれば、高い強度を有している上に、エッチングにおいて、未エッチング部が少なく、かつピットの均一性に優れており、優れた電解エッチング性を有していることが明らかになった。
一方、比較材では、電解エッチング性、強度のいずれかの点において劣っており、本発明材においてのみ、これら両方の特性を満足することが明らかとなった。
【００３０】
【発明の効果】
以上説明したように、本発明の平板印刷版用アルミニウム合金材によれば、質量％で、Ｆｅ：０．１〜１．０％、Ｓｉ：０．０１〜０．３％、Ｍｎ：０．１〜０．８％、Ｎｉ：０．００１〜０．１％、Ｃｕ：０．００１〜０．１％、希土類元素０．００１〜０．１％を含有し、所望によりＺｒ：０．０１〜０．１％を含有し、残部がＡｌおよび不可避不純物からなるので、高い強度を有し、かつ電解エッチング性に優れており、印刷板としての性能に優れているとともにその強度によって耐久性も良好である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aluminum alloy material for a lithographic printing plate used for a PS plate that is used as it is or after a photosensitive layer is burned, after a photosensitive layer is formed and developed.
[0002]
[Prior art]
In lithographic printing, a PS plate that is used in advance or after being developed and then subjected to a baking process on the photosensitive layer is widely used. The PS plate is a support on which a photosensitive agent is applied. have. As for the support, a 1050 series aluminum alloy having excellent electrolytic etching property is widely used as its constituent material. Recently, the support is high in strength, hardly scratched, and is cut off when attached to a printing press. It is difficult to use 3000-series Al—Mn alloys such as JIS A3103, which contain about 0.9 to 1.5% of Mn.
[0003]
The PS plate is manufactured through a predetermined manufacturing process using the aluminum alloy material, and is subjected to a surface treatment prior to application of the photosensitive agent. In this surface treatment, the surface of the support is usually roughened by electrolytic etching and then subjected to an anodic oxide film treatment. Before the roughening treatment, cleaning such as caustic treatment is performed for the purpose of degreasing and the like. Made. However, general 3000-based materials tend to form large and non-uniform pits in the electrolytic etching process, making it difficult to use after electrolytic etching. Therefore, at present, when an Al—Mn alloy is used, it is roughened by a mechanical pretreatment such as brush polishing, and a fine and uniform rough surface such as electrolytic etching cannot be obtained. For this reason, the PS plate using an Al—Mn alloy has a problem that the performance as a printing plate is inferior due to low adhesion of the photosensitive agent or inferior printing durability.
[0004]
[Problems to be solved by the invention]
As described above, the above-described 3000 series alloy has an advantage in strength, and an increase in use in the PS plate support is expected. However, as described above, the etching property is inferior, and this can be improved. It has been demanded. Specifically, it is required that (1) there is little unetched on the roughened surface and (2) the pits by the electrolytic etching treatment are uniform in the roughened surface state subjected to the electrolytic etching treatment.
[0005]
As a result of the study of the present inventors, it was found that the amount of Mn in the aluminum alloy material and the electrolytic etching property were examined, and if the amount of Mn was reduced to a range of 0.1 to 0.8%, it was required as a lithographic printing plate. It was found that the strength was almost satisfied, and the uniformity of electrolytic etching pits was improved, and unetched tended to hardly appear. However, it is not sufficient to reduce the amount of Mn alone, and it has been found that the etching uniformity is improved by adding 0.001 to 0.05% of Ni. Further, by adding 0.001 to 0.1% of one or more rare earth elements of La, Ce, Pr, Nd, and Sm, the uniformity of electrolytic etching is further improved, and satisfactory etching properties can be obtained. It turned out that.
[0006]
As a reason for improving the electrolytic etching property, it is effective to reduce the amount of Mn because a large amount of Mn tends to form an AlMn-based intermetallic compound and coarsen the pits. On the other hand, Ni, La, Ce, Pr, Nd, Sm, etc. are taken in or dissolved as a part of the composition in AlMn-based or AlFe-based, AlMnFe-based, AlMnSi-based, AlMnFeSi-based intermetallic compounds in the material. To change the properties of the intermetallic compound. In other words, in order for the intermetallic compound to act as the nucleus of the pits for electrolytic etching, it is necessary to be a cathode point through which an electric current flows. It is considered that the effectiveness as the cathode point varies depending on the composition of the intermetallic compound. .
[0007]
This invention is made | formed based on the said knowledge, and it aims at providing the aluminum alloy material for lithographic printing plates of an Al-Mn type | system | group which shows the characteristic outstanding in intensity | strength and electrolytic etching property.
[0008]
[Means for solving problems]
That is, the 1st invention among the aluminum alloy materials for lithographic printing plates of this invention is the mass%, Fe: 0.1-1.0%, Si: 0.01-0.3%, Mn: 0.00. 1 to 0.8%, Ni: 0.001 to 0.1%, Cu: 0.001 to 0.1%, rare earth element 0.001 to 0.1%, the balance from Al and inevitable impurities It is characterized by becoming.
[0009]
The aluminum alloy material for lithographic printing plates according to the second aspect of the present invention is characterized in that, in the first aspect of the present invention, Zr: 0.01 to 0.1% is further contained by mass%.
[0010]
The aluminum alloy material for a lithographic printing plate of the third invention is characterized in that, in the first or second invention, the rare earth element comprises one or more of La, Ce, Pr, Nd, and Sm. .
[0011]
Below, the effect | action of the composition component in this invention and the reason for limitation of the content are demonstrated. Each content is shown in mass%.
Fe: 0.1 to 1.0%
Fe has an effect of forming an AlFe-based crystal precipitate to make electrolytic etching uniform, and is contained as an essential component. However, if the content is less than 0.1%, the effect of homogenization is insufficient. On the other hand, if the content exceeds 1.0%, coarse crystal precipitates are formed to make etching uneven. Set within the range of 1.0%. For the same reason, it is desirable that the lower limit is 0.2% and the upper limit is 0.4%.
[0012]
Si: 0.01 to 0.3%
Si forms an AlFeSi-based crystal precipitate and refines the recrystallized grains during hot rolling to improve the strength and make the etching uniform. Therefore, Si is contained as an essential element. However, if it is less than 0.01%, the above-described action is insufficient and coarse crystal grains are formed, so that electrolytic etching becomes non-uniform or light unetching called streak occurs. On the other hand, if it exceeds 0.3%, coarse crystal precipitates are generated and the electrolytic etching becomes non-uniform, so the Si content is set within a range of 0.01 to 0.3%. Further, for the same reason as described above, it is desirable to set the lower limit to 0.04% and the upper limit to 0.08%.
[0013]
Mn: 0.1 to 0.8%
Mn promotes the formation of pits by the formation of intermetallic compounds and increases the material strength, so 0.1% or more is contained. However, if the content exceeds 0.8%, a coarse intermetallic compound is formed and etching pits become coarse. Therefore, the Mn content is set to 0.1 to 0.8%. For the same reason as described above, it is desirable to set the lower limit to 0.2% and the upper limit to 0.5%.
[0014]
Ni: 0.001 to 0.1
Ni is incorporated into the AlFe-based crystal precipitate to form an AlFeNi-based crystal precipitate, and has the effect of uniforming the etching by strengthening the action as a cathode point when electrolytic etching is performed, so Ni is included as an essential element. However, if the amount is less than 0.001%, the effect cannot be obtained. On the other hand, if the amount exceeds 0.1%, the above action is saturated, and a coarse intermetallic compound is formed and coarse etching pits are easily formed. . Therefore, the Ni content is set to 0.001 to 0.1%. For the same reason, it is desirable that the lower limit is 0.005% and the upper limit is 0.03%.
[0015]
Rare earth elements: 0.001 to 0.1%
Rare earth elements (REM) are incorporated into the AlFe-based intermetallic compound and are dissolved to change the properties of the intermetallic compound. Due to this change, the intermetallic compound effectively acts as a nucleus at the time of electrolytic etching and improves the etching property, so that a rare earth element is contained as an essential component. However, when the rare earth element content is less than 0.001%, the effect of making the electrolytic etching uniform is insufficient. On the other hand, when a rare earth element is contained exceeding 0.1%, a coarse intermetallic compound is formed. As a result, coarse pits are formed during etching, and the etching property is lowered. Therefore, the rare earth element content is set in the range of 0.001 to 0.1%. For the same reason, it is desirable that the lower limit is 0.005% and the upper limit is 0.03%.
Examples of the rare earth element include La, Ce, Pr, Nd, and Sm. The addition of the rare earth element may be performed by adding each element singly or plurally, or in the form of misch metal. You may do. The content of the rare earth element described above is shown as the total amount of each rare earth element when a plurality of rare earth elements are contained.
[0016]
Cu: 0.001-0.1
Cu has an action of promoting the formation of pits, and the content of 0.001% or more is essential. On the other hand, if it exceeds 0.1%, coarse pits are formed and become non-uniform and the etching property is lowered, so the Cu content is set within the range of 0.001 to 0.1%. For the same reason, it is desirable to set the lower limit to 0.01% and the upper limit to 0.03%.
[0017]
Zr: 0.01 to 0.1%
Zr is a component that suppresses thermal softening and improves strength, and is contained as desired. However, if it is less than 0.01%, the effect cannot be obtained. On the other hand, if it exceeds 0.1%, the structure becomes non-uniform during casting or hot rolling, resulting in unetching and streaks (streaks on the anodized surface). Therefore, the content is set in the range of 0.01 to 0.1%. For the same reason, it is desirable that the lower limit is 0.02% and the upper limit is 0.06%.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The aluminum alloy of the present invention can be melted by a conventional method, and a component adjusted and cast within the above component range can be used.
The aluminum alloy having a predetermined component can be made into an aluminum alloy sheet through a process of hot rolling → cold rolling (1) → intermediate annealing → cold rolling (2). The rolling reduction in cold rolling (2) is preferably in the range of 70 to 90%.
In the above process, it is possible to omit the intermediate annealing, the process is shortened if the intermediate annealing is not added, and the strength before the heat treatment (photosensitive agent baking) is increased, but the decrease in strength due to the heat treatment is large, As a result, the strength as a PS plate is lowered. On the other hand, when intermediate annealing is applied, the strength is slightly reduced by recrystallization, but the strength reduction (thermal softening) due to heat treatment is reduced, resulting in high strength. Therefore, it is desirable to perform intermediate annealing in the middle of cold rolling in terms of final strength. As conditions for this intermediate annealing, conditions of 300 to 550 ° C. for 5 seconds to 1 hour can be exemplified.
Further, if the rolling reduction in the cold rolling (2) is less than 70%, the strength before the heat treatment becomes too small, while if it exceeds 90%, the strength decrease after the heat treatment becomes large. desirable.
[0019]
In addition, in the manufacturing method (hot rolling-> cold rolling (3)) which does not perform an intermediate annealing, as above-mentioned, although heat softening property is a little inferior, since an intermediate annealing becomes unnecessary, there exists an advantage which can shorten a process. The rolling reduction in the cold rolling (3) is desirably 90 to 95%.
If this rolling reduction is less than 90%, the strength before heat treatment becomes too small, while if it exceeds 95%, rolling becomes difficult due to work hardening, so the above range is desirable.
The aluminum alloy thin plate obtained through the above steps is used as a PS plate support.
[0020]
As described above, the support is subjected to surface treatment prior to application of the photosensitive agent. In the surface treatment, cleaning is usually performed for the purpose of removing oil, dirt, etc. adhering to the surface as described above. This washing is usually performed by caustic treatment using caustic soda. However, the present invention may include an acid treatment and other treatments, or may comprise a treatment that does not include a caustic treatment. .
The solution used for washing, the washing procedure, conditions, etc. are not particularly limited as the present invention, and can be carried out by a conventional method.
[0021]
The aluminum alloy thin plate whose surface has been cleaned is then subjected to a roughening treatment in order to roughen the surface. This roughening treatment is performed by electrolytic etching. The roughening is intended to firmly fix the photosensitive agent described later on the surface of the support, and therefore it is desirable that the surface of the thin plate be etched uniformly. In the present invention, the conditions for this electrolytic etching are not particularly limited, and can be performed by a conventional method. However, in the present invention, the etching property is good by appropriately selecting the components, and therefore, the processing can be performed in a shorter time during the etching.
The material of the present invention is excellent in electrolytic etching property, and has an advantage that etching can be performed efficiently and etching can be performed uniformly.
[0022]
Further, in the above support, an anodized film is usually formed after the roughening treatment for corrosion prevention and wear resistance. This film treatment can be performed by a conventional method, and the present invention is not particularly limited with respect to production conditions and film properties. After forming the anodized film, a desired photosensitizer is applied to the surface. The type of the photosensitive agent is not limited in the present invention, and a known photosensitive agent can be used. Further, an apparatus, a coating method, and a coating amount used for coating the photosensitive agent are appropriately selected.
[0023]
After application of the photosensitive agent, it is supplied as a PS plate, and thereafter, plate making processing such as exposure and development is performed. Furthermore, in order to firmly fix the photosensitive agent, a heat treatment can be performed in which the PS plate is heated and the photosensitive agent is baked. Although this heat treatment can also be performed by a conventional method, examples of conditions include heating conditions of 240 to 300 ° C. and 3 to 10 minutes.
The material of the present invention has high strength after the heat treatment.
[0024]
【Example】
An embodiment of the present invention will be described below.
(Production of materials)
An aluminum alloy was melt cast with the composition shown in Table 1, the surface of the obtained slab was chamfered, and a homogenization treatment was performed at 540 to 580 ° C. for 4 hours. Subsequently, after heating to 520 degreeC, it hot-rolled and rolled to 4.5 mm thickness. A cold rolled material was obtained from this rolled material through any of the following steps.
(Step A) Examples 2, 4, 6 and Comparative Example 6
Cold rolling to 3.0 mm thickness, intermediate annealing for 10 seconds at 450 ° C., and further cold rolling to 0.3 mm thickness.
(Step B) Examples 1 and 3 and Comparative Examples 1, 3, 4, and 7
Cold rolling to 2.5 mm thickness, intermediate annealing at 450 ° C. for 10 seconds, and further cold rolling to 0.3 mm thickness.
(Step C) Examples 5 and 7 and Comparative Examples 2 and 5
Cold-rolled to a thickness of 0.3 mm by cold rolling (no intermediate annealing).
[0025]
The test material was subjected to an electrolytic etching treatment of 2% hydrochloric acid, 25 ° C., 50 Hz, 60 A / dm ² for 40 seconds.
(Unetched: Evaluation method A)
The surface of the test material after etching was observed by SEM 500 times, and the area ratio of the unetched part exceeded 30%.
20-30%
Less than 20% ○
As for the unetched situation.
[0026]
(Pit uniformity: Evaluation method B)
Further, in order to evaluate the uniformity of pits, the surface subjected to the above-described electrolytic etching treatment was observed, and large pits having an equivalent circle diameter exceeding 15 μm had an area ratio of 10% or more with respect to all pits.
Less than 10% ○
As for the uniformity of pits.
These evaluation results are shown in Table 2.
(Material strength)
The sample material was heat-treated at 260 ° C. for 10 minutes and then subjected to a tensile strength test at room temperature. The test results are shown in Table 2.
[0027]
[Table 1]

[0028]
[Table 2]

[0029]
As is clear from the above table, according to the test material of the present invention, in addition to having high strength, in etching, there are few unetched parts, excellent pit uniformity, and excellent electrolysis. It became clear that it has etching property.
On the other hand, the comparative material is inferior in either the electrolytic etching property and the strength, and it has been clarified that only the material of the present invention satisfies both of these characteristics.
[0030]
【The invention's effect】
As described above, according to the aluminum alloy material for a lithographic printing plate of the present invention, Fe: 0.1-1.0%, Si: 0.01-0.3%, Mn: 0.00% by mass. 1 to 0.8%, Ni: 0.001 to 0.1%, Cu: 0.001 to 0.1%, rare earth element 0.001 to 0.1%, optionally Zr: 0.01 It contains ~ 0.1%, and the balance is made of Al and inevitable impurities, so it has high strength and excellent electrolytic etching properties, and has excellent performance as a printing plate and durability due to its strength. It is good.

Claims (3)

In mass%, Fe: 0.1-1.0%, Si: 0.01-0.3%, Mn: 0.1-0.8%, Ni: 0.001-0.1%, Cu: An aluminum alloy material for a lithographic printing plate comprising 0.001 to 0.1%, rare earth element 0.001 to 0.1%, and the balance being made of Al and inevitable impurities The aluminum alloy material for lithographic printing plates according to claim 1, further comprising, in mass%, Zr: 0.01 to 0.1%. The aluminum alloy material for a lithographic printing plate according to claim 1 or 2, wherein the rare earth element comprises one or more of La, Ce, Pr, Nd, and Sm.