JP2001335870A - Aluminum alloy material for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aluminum alloy material for a PS (pressusitized) plate having high strength and excellent in electrolytic etching properties. SOLUTION: This aluminum alloy material for the PS plate has a composition containing 0.1 to 1.0% Fe, 0.01 to 0.3% Si, 0.1 to 0.8% Mn, 0.001 to 0.1% Ni, 0.001 to 0.1% Cu and 0.001 to 0.1% rare earth elements and containing, at request, 0.01 to 0.1% Zr, and the balance Al with inevitable impurities. The alloy material has high strength and is further excellent in etching properties. The obtained supporting body has excellent durability and a printing plate performance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum alloy material for a lithographic printing plate used in a PS plate which is used after forming a photosensitive layer in advance and developing the same, or after baking the photosensitive layer. It is.

[0002]

2. Description of the Related Art In lithographic printing, a photosensitive layer is formed in advance,
PS plates that are used as they are after the development process or after baking of the photosensitive layer are widely used, and the PS plates have a support on which a photosensitive agent is applied. The support is widely used as a material for the support, and a 1050-based aluminum alloy having excellent electrolytic etching properties is widely used. In recent years, the support has a high strength, is hardly damaged, and is cut off when attached to a printing machine cylinder. Difficult, Mn 0.9-1.5
%, A 3000 series Al-Mn alloy such as JIS A3103 has been used.

The PS plate is manufactured through a predetermined manufacturing process using the aluminum alloy material.
Prior to the application of the photosensitive agent, a surface treatment is performed. In this surface treatment, the surface of the support is usually roughened by electrolytic etching and then anodized. Before the surface roughening, cleaning such as caustic treatment for the purpose of degreasing is performed. Done. However, the general 3000
The system material tends to easily form large and uneven pits in the electrolytic etching process, which makes it difficult to use the pits after the electrolytic etching process. Therefore, at present, when an Al-Mn alloy is used, the surface is roughened by mechanical pretreatment such as brush polishing or the like, and a fine and uniform rough surface such as electrolytic etching cannot be obtained. Therefore, A
The PS plate using the l-Mn alloy has a problem that the performance as a printing plate is inferior due to, for example, low adhesiveness of a photosensitive agent and poor press life.

[0004]

The above-mentioned 3000 series alloy is superior in strength as described above, and is expected to be used more in a PS plate support, but is inferior in etching property as described above. There is a need to improve this. Specifically, in the roughened state subjected to the electrolytic etching treatment, (1) there is little unetched on the roughened surface;
(2) uniform pits due to electrolytic etching;
Is required.

[0005] From the study of the present inventor, it has been found in the course of studying the Mn content and the electrolytic etching property of the aluminum alloy material that when the Mn content is reduced to the range of 0.1 to 0.8%, It was found that the strength required for the above was almost satisfied, and the uniformity of the electrolytic etching pits, which was inferior when the Mn content was higher than that, was improved, and there was a tendency that almost no etching appeared. However, simply reducing the amount of Mn is not sufficient.
It was found that the addition of 05% improves the etching uniformity. Further, La, Ce, Pr, Nd,
0.001 to 0.1% of one or more rare earth elements of Sm
It has been found that the addition improves the uniformity of electrolytic etching and leads to a satisfactory etching property.

As a reason for the improvement of the electrolytic etching property, if the amount of Mn is large, an AlMn-based intermetallic compound is formed and the pits tend to be coarsened. Therefore, it is effective to reduce the amount of Mn. On the other hand, Ni, La, Ce, P
r, Nd, Sm, etc. are AlMn-based or AlF
e, AlMnFe, AlMnSi, AlMnFe
The properties of the intermetallic compound are changed by being taken into the Si-based intermetallic compound as a part of the composition or forming a solid solution. That is, in order for the intermetallic compound to act as a nucleus of a pit for electrolytic etching, it is necessary to be a cathode point through which a current flows, but it is considered that the effectiveness as this cathode point changes depending on the composition of the intermetallic compound. .

The present invention has been made based on the above findings, and has as its object to provide an Al-Mn-based aluminum alloy material for a flat plate printing plate exhibiting excellent properties in strength and electrolytic etching properties.

[0008]

That is, the first invention of the aluminum alloy material for a lithographic printing plate according to the present invention is characterized in that Fe: 0.1 to 1.0% and Si: 0.01 to 100% by mass. 0.
3%, Mn: 0.1-0.8%, Ni: 0.001-
0.1%, Cu: 0.001 to 0.1%, rare earth element 0.001 to 0.1%, with the balance being Al and unavoidable impurities.

[0009] The aluminum alloy material for a lithographic printing plate according to the second invention is the aluminum alloy material according to the first invention, further comprising:
r: characterized by containing 0.01 to 0.1%.

A third aspect of the present invention is the aluminum alloy material for a lithographic printing plate according to the first or second aspect, wherein the rare earth element is at least one of La, Ce, Pr, Nd, and Sm. Features.

In the following, the action of the composition component in the present invention and the reason for limiting the content thereof will be described. In addition, each content is shown by 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 it is less than 0.1%, the effect of homogenization is insufficient, while if it exceeds 1.0%, coarse crystal precipitates are formed and etching becomes non-uniform. 1.
Determine within the range of 0%. For the same reason, it is desirable to set the lower limit to 0.2% and the upper limit to 0.4%.

Si: 0.01-0.3% Si forms an AlFeSi-based crystal precipitate, has a function of making recrystallized grains finer at the time of hot rolling, improving strength, and making etching uniform. Therefore, it is contained as an essential element. However, if it is less than 0.01%, the above effect is insufficient and coarse crystal grains are generated, so that the electrolytic etching becomes non-uniform, or light etching called streak occurs. On the other hand, if it exceeds 0.3%, coarse crystal precipitates are formed and the electrolytic etching becomes non-uniform.
The i content is set in the range of 0.01 to 0.3%. Further, the lower limit is set to 0.04% and the upper limit is set to 0.
It is preferably set to 08%.

Mn: 0.1-0.8% Mn promotes the formation of pits due to the formation of intermetallic compounds, and also increases the material strength by 0.1% or more. However, when the content exceeds 0.8%, a coarse intermetallic compound is formed, and the etching pit becomes coarse. Therefore, the Mn content is set to 0.1 to 0.8%. For the same reason as above, it is desirable to set the lower limit to 0.2% and the upper limit to 0.5%.

Ni: 0.001 to 0.1 Ni is incorporated into AlFe-based crystal precipitates and AlFeNi
A crystal precipitate of the system is formed, and has a function of strengthening the function as a cathode point at the time of electrolytic etching to make the etching uniform, so that it is contained as an essential element. However, 0.
If the content is less than 001%, the effect cannot be obtained.
If the temperature exceeds the above range, the above-mentioned action is saturated, and coarse intermetallic compounds are formed, so that coarse etching pits are easily formed. Therefore, the content of Ni is reduced to 0.001 to 0.1%.
Set forth in For the same reason, it is desirable to set the lower limit to 0.005% and the upper limit to 0.03%.

Rare earth element: 0.001 to 0.1% The rare earth element (REM) is taken into the AlFe-based intermetallic compound and forms a solid solution to change the properties of the intermetallic compound.
Due to this change, the intermetallic compound effectively acts as a nucleus during electrolytic etching and improves the etching property, so that a rare earth element is contained as an essential component. However,
When the content of the rare earth element is less than 0.001%, the effect of making the electrolytic etching uniform is insufficient. On the other hand, 0.1%
When a rare earth element is contained in excess of the above, a coarse intermetallic compound is formed, and as a result, coarse pits are formed at the time of etching, and the etching property is deteriorated. Therefore, the content of the rare earth element is set in the range of 0.001 to 0.1%.
For the same reason, the lower limit is 0.005% and the upper limit is 0.0
It is desirable to set it to 3%. As the rare earth element, L
a, Ce, Pr, Nd, and Sm. The rare earth element may be added singly or plurally, or may be added in the form of misch metal. Good. The content of the rare earth element described above is indicated as the total amount of each rare earth element when a plurality of rare earth elements are contained.

Cu: 0.001 to 0.1 Cu has an effect of promoting the formation of pits.
The content must be 1% or more. On the other hand, if the content exceeds 0.1%, coarse pits are formed, and the pits become non-uniform and the etching property deteriorates.
It is within the range of 1%. The lower limit is set to 0.0 for the same reason.
It is desirable to set the upper limit to 1% and the upper limit to 0.03%.

Zr: 0.01-0.1% Zr is a component which suppresses thermal softening and improves strength.
Include if desired. However, if the content is less than 0.01%, the effect cannot be obtained. On the other hand, if the content is more than 0.1%, the structure becomes uneven during casting or hot rolling, and unetching or streaks (streaks on the anodized surface) occur. Therefore, its content is set in the range of 0.01 to 0.1%. For the same reason, it is desirable to set the lower limit to 0.02% and the upper limit to 0.06%.

[0018]

BEST MODE FOR CARRYING OUT 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-mentioned component range can be used. Aluminum alloy having a predetermined component is hot-rolled → cold-rolled (1)
→ Intermediate annealing → Cold rolling (2) can be made into an aluminum alloy thin plate. It is desirable that the rolling reduction in the cold rolling (2) be in the range of 70 to 90%.
In the above process, it is also possible to omit the intermediate annealing,
If the intermediate annealing is not added, the process is shortened, and the strength before the heat treatment (photosensitive agent baking) is increased, but the strength is largely reduced by the heat treatment, and as a result, the strength as a PS plate is reduced. On the other hand, when the intermediate annealing is added, although the strength is slightly reduced by recrystallization, the strength reduction (thermal softening) due to the heat treatment is reduced, and as a result, the strength is increased. Therefore, it is desirable to perform intermediate annealing in the middle of cold rolling in terms of final strength. Examples of the condition of the intermediate annealing include a condition of 300 to 550 ° C. for 5 seconds to 1 hour. Further, when the rolling reduction in the cold rolling (2) is smaller than 70%, the strength before the heat treatment becomes too small. On the other hand, when the rolling reduction exceeds 90%, the strength decreases after the heat treatment. desirable.

In the production method without intermediate annealing (hot rolling → cold rolling (3)), as described above, the heat softening property is slightly inferior, but there is an advantage that the intermediate annealing is not required and the process can be shortened. . The rolling reduction in cold rolling (3) is 90-9.
It is desirable to set it to 5%. When the rolling reduction is smaller than 90%, the strength before the heat treatment becomes too small.
%, The work hardening makes rolling difficult, so the above range is desirable. The aluminum alloy thin plate obtained through the above steps is used as a PS plate support.

As described above, the support is subjected to a surface treatment prior to the application of the photosensitive agent. In the surface treatment, cleaning is usually performed for the purpose of removing oil, dirt, and the like adhering to the surface as described above. This cleaning is usually performed by a caustic treatment using caustic soda. However, the present invention may include an acid treatment and other treatments, or may include a treatment that does not include a caustic treatment. In other words, the treatment may be any process for cleaning. . The present invention is not particularly limited with respect to the solution used for washing, the washing procedure, conditions, and the like, and the washing can be performed by a conventional method.

The aluminum alloy sheet whose surface has been cleaned is thereafter subjected to a surface roughening treatment in order to roughen the surface. This surface roughening treatment is performed by electrolytic etching. The purpose of this roughening is to firmly fix a photosensitive agent to be described later on the surface of the support. Therefore, it is desirable that the surface of the thin plate is uniformly etched. In the present invention, the conditions of the electrolytic etching are not particularly limited, and the electrolytic etching can be performed by a conventional method. However, in the present invention, the etching property is improved by appropriately selecting the components, and therefore, the etching can be performed in a shorter time. The material of the present invention is excellent in electrolytic etching properties, and has an advantage that etching can be performed efficiently and etching can be performed uniformly.

Further, the support is usually provided with an anodic oxide film after the surface roughening treatment for corrosion prevention and abrasion resistance.
This coating treatment can be performed by a conventional method, and the present invention is not particularly limited in terms of production conditions and coating properties. After forming the anodic oxide film, a desired photosensitive agent 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. In addition, a device, a coating method, and a coating amount used for coating the photosensitive agent are appropriately selected.

After the application of the photosensitive agent, it is supplied as a PS plate,
Thereafter, plate making processes such as exposure and development are performed. Furthermore, in order to firmly fix the photosensitive agent, a heat treatment for heating the PS plate to burn the photosensitive agent can be performed. This heat treatment can also be performed by an ordinary method, but the condition is 2
Heating conditions at 40 to 300 ° C. for 3 to 10 minutes can be exemplified. The material of the present invention has high strength after the heat treatment.

[0024]

An embodiment of the present invention will be described below. (Production of Material) An aluminum alloy was melt-cast with the composition shown in Table 1, and the surface of the obtained slab was beveled to obtain 540 to 5
The homogenization treatment was performed at 80 ° C. for 4 hours. Then 520
After heating to ℃, it was hot rolled and rolled to a thickness of 4.5 mm. 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 was performed to a thickness of 3.0 mm by cold rolling, intermediate annealing was performed at 450 ° C. for 10 seconds, and further cold rolling was performed to a thickness of 0.3 mm. (Step B) Examples 1, 3 and Comparative Examples 1, 3, 4, 7 Rolled to a thickness of 2.5 mm by cold rolling, subjected to intermediate annealing at 450 ° C. for 10 seconds, and further cooled to a thickness of 0.3 mm. Rolled. (Step C) Examples 5 and 7 and Comparative Examples 2 and 5 Cold rolling was performed by cold rolling to a thickness of 0.3 mm (no intermediate annealing).

With respect to the above test materials, 2% hydrochloric acid, 25 ° C., 5
Electrolytic etching treatment was performed at 0 Hz, 60 A / dm ² , and 40 seconds. (Unetched: Evaluation method A) The surface of the sample material after etching was observed with a SEM of 500 times, and the area ratio of the unetched portion exceeded 30% × 20-30% △ Less than 20% ○ evaluated.

(Pit uniformity: Evaluation method B) In order to further evaluate the pit uniformity, the surface subjected to the electrolytic etching treatment described above was observed, and large pits having a circle equivalent diameter exceeding 15 μm had an area with respect to all pits. The ratio was 10% or more, and x was less than 10%. The evaluation results are shown in Table 2. (Material Strength) The specimen 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]

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 portions and excellent pit uniformity. It was revealed that the film had excellent electrolytic etching properties. On the other hand, the comparative material was inferior in either of the electrolytic etching properties and the strength, and it was revealed that only the material of the present invention satisfies both of these characteristics.

[0030]

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:
0.1-0.8%, Ni: 0.001-0.1%, C
u: 0.001 to 0.1%, rare earth element 0.001 to
0.1%, if desired, Zr: 0.01-0.1
%, And the balance consists of Al and unavoidable impurities, so that it has high strength, is excellent in electrolytic etching properties, is excellent in performance as a printing plate, and has good durability due to its strength.

Claims (3)

[Claims] 1. Fe: 0.1 to 1.0% by mass%, S:
i: 0.01 to 0.3%, Mn: 0.1 to 0.8%, N
i: 0.001-0.1%, Cu: 0.001-0.1
%, A rare earth element of 0.001 to 0.1%, with the balance being Al and unavoidable impurities. 2. Zr: 0.01% by mass%
2. The aluminum alloy material for a lithographic printing plate according to claim 1, containing 0.1%. 3. The rare earth element is La, Ce, Pr, N
3. The aluminum alloy material for a lithographic printing plate according to claim 1, wherein the aluminum alloy material comprises at least one of d and Sm.