JPS62146694A - Aluminum alloy support for planographic printing - Google Patents

Abstract

PURPOSE:To obtain a health anodic oxidation film having the uniformity of a rough surface and the pitting resistance of a supporting base material more excellent than those of a conventional one by surface roughening treatment, especially, electrochemical surface roughening treatment, by using an aluminum alloy wherein 0.10-0.8wt% of Fe and 0.03-0.3wt% of Si are contained and the residue consists of aluminum and impurities and the amount of Si present alone is 0.012wt% or less. CONSTITUTION:By incorporating 0.10-1.8wt% of Fe and 0.03-0.30wt% of Si in an aluminum alloy, strength necessary for a support is applied to said alloy and the kind and presence state of the intermetallic compound present in the surface of an aluminum alloy plate are controlled to make the surface roughening treatment of said plate well and the kind and presence of the Al-Fe or Al-Fe-Si type intermetallic compound present in an ingot obtained under a usual casting condition after homogenizing treatment was applied to said ingot are controlled. Ti can be contained in addition to essential components of Fe and Si and an Al-Ti or Al-Ti-B (with a high Ti/B ratio) type fine pulverizing agent is used and Ti is set to 0.06wt% or less. As other impurities, B is set to 0.0010wt% or less, Cu and Zn respectively to 0.03wt% or less, V to 0.02wt% or less, Cr and Mn respectively to 0.03wt% or less and Mg to 0.05wt% or less.

Description

Detailed Description of the Invention "Object of the Invention" The present invention relates to the invention of an aluminum alloy support for lithographic printing, which has few local defects during roughening treatment and is free from stains on non-+A11 parts during printing. It is possible to create a difficult-to-use aluminum alloy support for lithographic printing.

Industrial application field An aluminum alloy support for lithographic printing that has few local defects during surface roughening treatment and is less likely to cause stains in non-image areas during printing.

BACKGROUND OF THE INVENTION Aluminum alloy supports for lithographic printing are known in the art. In other words, in general, aluminum alloys have excellent workability in terms of @ quantity, have good surface treatment properties, and are suitable for lithographic printing supports, especially JIS 1050 (
At) with a purity of 99.5 cm or higher), JISIloo (@All with a purity of 99.0 cm or higher, JIS3003 (AM -
0.05~0.2% Cu-1.0~1.5Mn
Aluminum or aluminum alloys (hereinafter simply referred to as aluminum alloys) are widely used.

These aluminum alloys are manufactured by, for example, being made with a trowel, the surface of which is roughened by a process that uses one or a combination of mechanical, chemical, or open-air methods, and then anodized. After that, a photosensitive composition (generally a photosensitive resin) is applied to the surface of the board, dried, and placed. Processed into tlPs version. This 28th plate was then image exposed and developed:
y1 A printing original plate is produced by performing plate-making processes such as water washing and gumming, and this image exposure creates a gap between the exposed and unexposed areas of the photosensitive resin layer.

This causes a difference in solubility in the developer during subsequent development,
By this development treatment, either the exposed portion or the unexposed portion is dissolved in the developer or removed, and the other portion remains on the aluminum plate serving as the support to form an image. The image area exhibits ink receptivity, and the non-image area where the photosensitive resin is dissolved and removed as described above exhibits water receptivity due to the exposed surface of the hydrophilic aluminum support.

Next, both ends of the above-mentioned printing solution are bent to form a holding part for the printing machine, and fixed to the cylindrical plate cylinder of the printing machine, and water (water or aqueous liquid) is supplied to the plate surface. The film of the dampening solution is retained in the non-image area by means of
On the other hand, printing is carried out by repeating the steps of supplying and adhering ink to the image area, transferring the ink layered on the image area to a blanket cylinder, and then transferring it to a paper surface or the like. In this printing, it is possible to obtain up to 100,000 good-quality prints by appropriately selecting the aluminum alloy used as the support, the surface finishing method, and the photosensitive composition coated on the support. However, especially aluminum alloys, such as JIS1050゜JISIL
In the case of Ae-F'e-81 alloys such as Ae-F'e-81 alloys, electrochemical surface roughening treatment is generally used for surface roughening treatment.

Problems to be Solved by the Invention However, in recent years, there has been a demand for higher quality 28 plates, as well as a need for a support that is less likely to cause microscopic defects during surface roughening treatment and less stained in non-image areas during printing. On the other hand, due to the demand for improved industrial productivity, one aluminum alloy ingot is turned into a long thin coil that is several thousand meters long, and it is continuously coated with a rough surface. If the manufacturing process of the aluminum alloy support lacks appropriate control, it will be unsuitable for commercial value and printing performance as a 28th plate after continuous processing of long coils. As a result, the industrial economic loss will inevitably be large.

Here, microscopic defects in surface roughening treatment are microscopic streak-like over-etched or unetched areas (hereinafter simply referred to as micro-roughened areas) scattered on a macroscopically uniform roughened surface. In particular, when surface roughening treatment is performed electrochemically, these micro-rough surface defects are caused by the electrochemical treatment conditions as well as by the surface treatment properties of the aluminum alloy thin plate. The reality is that conventional aluminum alloy thin plates for lithographic printing cannot necessarily be said to have appropriate surface treatment properties. Staining in non-@1 image areas during printing is a phenomenon in which pitting corrosion occurs on the surface of the support that is in contact with dampening water for printing, and ink adheres there and is transferred to the printed matter (hereinafter simply referred to as "stain"). (referred to as ink stain), in order to prevent this ink stain, the support valve lI! It is important to improve the water retention and corrosion resistance of the II image area, and for this purpose, surface roughening treatment, especially electrochemical roughening treatment, improves the uniformity of the surface and the resistance of the supporting substrate. It is necessary to obtain a pitting-resistant and sound anodic oxide film.

"Structure of the Invention" Child Actor to Solve the Problems As a result of various studies based on the above-mentioned circumstances, the inventors have found that:
We obtained the knowledge that the simple substance S1 present in the support affects the uniformity of the rough surface, the pitting corrosion resistance of the base material of the support, and the integrity of the anodic oxide film.After further investigation, we determined that the electric current of the simple substance S1 was below a certain level. In this case, the present invention has been completed by polishing to improve the above properties.

That is, the non-invention is: Fe: 0.10 to 1.8 wt%, Si: 0.03
~Q, 3 wt%, with the remainder consisting of aluminum and impurities, and 5ittiH existing as a simple substance is 0012 wt.
% or less is an aluminum alloy support for lithographic printing.

Action Fe: 0.10-1.8 wt%r Si: 01
By containing 0.3 to 0.30 wt, the necessary strength is added to the support, and the gold present in the plate surface is
Control the type and state of presence of the compound to improve surface roughening properties.

In the back plate process, the simple substance S1 generated from the above-mentioned contained S1
By controlling Si to 0.012 wt% or less, the presence state of Si other than that contained in the above-mentioned intermetallic compound is controlled. Note that the simple substance S1 in the present invention is
It is a thin plate-like elemental St that precipitates mainly during the cooling process after hot rolling and intermediate annealing, and it is a thin plate-like elemental St that precipitates in the cooling process after hot rolling and intermediate annealing.
By setting the amount to 0.012 wt% or less, micro-rough surface defects during surface roughening treatment and ink stains during printing can be appropriately prevented.

If the amount of elemental Si exceeds 0.012 wt%, it will be crushed during the final cold rolling and fc thin plate-like elemental St will be locally unevenly distributed on the sheet surface, resulting in micro-rough surface defects and ink stains. Therefore, the content is set to 0.012 wt% or less to prevent this and improve the quality of the support.

EXAMPLE To explain the details of the present invention in detail, first, the composition of the components contained in the non-inventive alloy support is as follows.

That is, Fe: 0.10-1.8 wt%, 8
1; 0.03 to 0.3 wt% is contained in
This is to impart strength and improve handling during use of the support, and 1) II) to control the type and state of presence of interline compounds. The state of existence of such a compound is A1
mFe +AIBF@6 Ru or a-AU(F@・M
) Sl alone or any two of these
It is desirable that more than two types are mixed and distributed uniformly, but F
If e is less than 0.10 wt% and SI is less than 0.03 wt%, the amount of intermetallic compounds present after industrial homogenization will be insufficient and the distribution state will be non-uniform, resulting in electrochemical roughening. In the treatment, the surface becomes uneven and rough, and the strength of the support is insufficient. Fe is 1.8wt%, S amount is 0.
If the content exceeds 3 wt%, the crystallization phase of p' becomes coarse, which is not preferable. Therefore F@: 0.10
~1.8vt Chi, St: 0.03~Q, 3wt%
shall be.

In addition to these essential components of Fe and 81, Ti can be contained. This TI is sometimes added as an At-TS or AU-Tl-B type #refining agent to refine the crystals of the ingot, but if it causes agglomeration of Ti-B particles, the surface roughening process is Since micro-rough surface defects are likely to occur at times, an At-Ti-based refiner or an AL-Ti-B-based refiner with a high Tl/B ratio is used to contain TI, and Tt; 0. '06wt% or less is desirable.

Other impurities include B + Cu g Zn * V
+Cr, Mn+Mg, etc. may be included in some cases, but the truth is that B tends to form aggregates together with Ti, and in the coexistence with elemental St, it causes imitative Kokanda i defects during surface roughening treatment. , B: 0.0010wt
% or less. In addition, Cu and Zn are set to 0 and 3 wt% or less to prevent ink stains, respectively, but especially when the quality required for ink stains is high, it is necessary to maintain the integrity of the anodic oxide film, and for this reason Cu: 0. It is preferable that the content be 0.020 wt % or less, and since (2) tends to hinder the grain refinement of a lump, it is desirable that the content be 0.02 wt % or less, preferably 0.015 wt % or less.

Furthermore, Cr and Mn tend to form intermetallic compounds that are difficult to dissolve in electrochemical roughening treatment, so 0.03 wt.
It is desirable to restrict each to below %. Further, Mg is desirably 0.05 wt % or less, preferably 0.03 Wt % or less.

The plate making process of the aluminum metal support for -P plate printing of the present invention having the composition as described above and the plate making process as a 28 plate are explained below.

That is, after the casting slag obtained from the molten alloy having the above composition is side-faced, it is heated at a normal temperature of 460-600°C, preferably 520-600°C.
Homogenization treatment is performed by holding the sample at a temperature of 00° C. for 1 hour or more. Hot rolling and cold rolling are performed at the same time, but in hot rolling, in order to remove the intermetallic compounds present after homogenization treatment and achieve a uniform distribution, hot rolling is performed several times or more. The pass and recrystallization/precipitation are repeated, and more preferably recrystallization is carried out by leaving it for several seconds or more after each rolling pass in a reversing hot rolling mill. to complete rolling. This allows the average size of the intermetallic compound to be substantially 1 μm or less. Further, in the subsequent cold rolling, the degree of cold working is set to 50% or more in order to crush and atomize the thin plate-like single Si that precipitates during the cooling process after hot rolling. Next, intermediate purification is performed, but it is important to dissolve the finely divided elemental Sl into the matrix and to prevent the precipitation of thin plate-like elemental SL during the cooling process after heating. In annealing device N, Si: 0.0
1i400-600 when containing 3-0.15wt%
U, Sl: over 0.15wt% Q, 3wt%
If it contains up to 100°C, heat it to 500-600°C, and after reaching the specified temperature, cool it at a cooling rate of 150°C/equation or higher.
Cooling to below 0℃, preferably 500℃/s
It is desirable to perform rapid cooling by water cooling at ec or higher. This allows the amount of elemental Si to be 0.012 wt% or less. Note that any continuous annealing method can be used for the continuous annealing process, but for example, the heating method is 9P! Magnetic induction heating using gold (Transverse Flux In
The method is preferable because the amount of oxide film formed on the surface of the aluminum metal plate is small and there is little adverse effect on the surface roughening treatment. Subsequently, in order to obtain a specified strength as a supporting body, final cold rolling is performed to a working degree of 30 inches or more, preferably 50% or more, and 0.1 to 0.5
The plate thickness is m.

Regardless of the manufacturing conditions, regulation of trace impurities, control of the type and state of existence of intermetallic compounds, and especially for simple substance S1 in o, ot
zwt% or less to prevent the formation of uneven areas of minute metal fibers on the plate surface, improve the pitting corrosion resistance of the substrate, and obtain a sound anodizing treatment. It is desired that the surface be treated with a rough surface, thereby eliminating micro-rough surface defects during the surface roughening treatment and appropriately preventing ink stains during printing.

In addition, in order to pursue economic efficiency, cheap scrap is used as the core material, aluminum alloy suitable for lithographic printing Sakaide is used as the skin material, and so-called clad material is sometimes manufactured as the support. The material according to the present invention can be used as a skin material.

The aluminum alloy plate thus plate-made is subjected to processing as a 28-plate and plate-making process, and then subjected to actual marking work. That is, first, the material is subjected to an FF1 surface treatment using a mechanical graining method or a chemical graining method, and then subjected to a chemical etching treatment using an acid or alkali and a desmutting treatment by pickling. Further, if necessary, an oxide film formation treatment is performed by anodizing treatment or chemical conversion treatment, and an undercoat layer formation treatment of an alkali metal silicate, hydrophilic cellulose, etc. is performed thereon. Subsequently, an appropriate photosensitive composition (
After drying and cutting to the desired size,
You can get the version.

Desired +1 for this 28th edition! 1+ j#! Perform the exposure of
Plate-making processes such as development, washing, burning, and gumming are performed.

After the plate-made printing original plate is bent at both ends to form a gripping portion for the printing press, it is fixed to the cylindrical plate cylinder of the printing press and used for printing work.

A specific manufacturing example of the product according to the present invention will be described below.

Production Example 1 A slab of 560B thickness was prepared by a conventional method so that the composition of the final plate would be as shown in the second layer described later, and after stirring using a microporous filter, a slab with a thickness of 560B was made by DC casting. After homogenizing at 590°C and holding for 4 hours, it was hot rolled to a thickness of 6fi (C), then cold rolled to a 1.
．． The board was 5 sheets thick. Furthermore, this plate was heated in an air heating furnace for 10
After heating to 520°C at a temperature increase rate of 0C/Hr and holding for 10 minutes to perform intermediate baking treatment, it was heated with water and air-cooled (room τ).
It was cooled at three cooling rates: cold uniforming rate (average cooling rate of 1° C./sec until crystallization) and furnace cooling (which took about 5 hours to reach room temperature).

A part of the plate thus obtained was dissolved in (1+1) hydrochloric acid and hydrogen peroxide solution, and from the filtered residue, the single Sl content was determined by gravimetric method, and part of it was subjected to XRD measurement, T
It was subjected to EM observation.

Next, the intermediate annealed 7'C three types of plates were final cold rolled into plates with a thickness of 0.3 days, and subjected to XRD measurement and electrochemical roughening treatment to evaluate the quality of the finished product.

Warm chemical roughening treatment was carried out in a 10-inch NaOH water bath solution.
After preliminary etching at 0°C for 1 minute, alternating current electrolysis was performed in a nitric acid-based I11 bath, and after desmatting, the rough surface and other surfaces were visually inspected and evaluated by SEM observation, and placed in running tap water for one week. I immersed myself in it to find out a lot of food.

Table 1 below shows the evaluation results of the amount of St2, the roughening state of the final cold-rolled sheet, and the corrosion resistance.

The shape of Si after intermediate dulling is granular (size 0.1μ or less) for water-cooled materials, and thin plate-like shape (size around 10μ, several hundred angstroms thick) for air-cooled furnace-cooled materials. Most of them were. Measurements were also carried out on the final cold rolled and temporary samples, and the amount of simple St 2 was different from that after intermediate annealing, and the shape was mostly granular (size 0.1 μm or less).

- 10,000, at the final cold-rolled sheet's
(FeM)Sl was detected.

Table 1 As shown in Table 1, the heather invention examples with a small amount of element 81 have good surface roughening properties and corrosion resistance, but the element 81
In the comparative example in which the amount of C is present in an amount greater than the specified value, both surface roughening properties and corrosion resistance are at an insufficient level.

Production Example 2 The composition of the final plate is the composition of Alloy B and C shown in Table 2 below. After making a bath using the usual method and filtering it using a microporous filter, Alloy B was prepared. is 5 at DC@zo
A slab with a thickness of 60 m and 406 m + thickness for alloy C was obtained, and after homogenization treatment at 560°C for 4 hours for alloy B and 4 hours at 590°C for alloy C, it was rolled using a reverse rolling mill. Both alloys were hot rolled to a thickness of 6 mm, and then cold rolled into plates of 1.0 mm. After that, both alloys are magnetic induction 7JO heat equipment +? Intermediate annealing was carried out continuously using t, but for alloy B, the temperature was increased from 380 to 550°C x 5 at a temperature increase rate of 150°C/see.
sec and water cooling at a rate of over 500°C/sPe, for alloy C at a heating rate of 150°C/sPe.
Holding at 00°C for 5 seconds and cooling with water at a rate of at least 500°C were carried out. Both continue to be 0 and 3.
Final cold rolling to a thickness of m to produce the desired planographic printing aluminum alloy plate.

Regarding the obtained alloy, XRD measurement similar to that of Forging Example 1,
The amount of simple St was measured.

Subsequently, the alloy plate was used as a printing support by filling the plate with 11 embeddings, and its surface roughening properties and printability were evaluated. That is, these aluminum alloys were grained with a rotating nylon brush in a suspension of pumice stone and water, etched with a 20 wt% caustic soda aqueous solution, then washed with water, and etched in a 25 wt% ilnic acid water bath. r evening trip and second time 1
After washing the skin with water, it was electrolyzed in an electrolytic bath containing nitric CRO, 5 to 2.5 wt%, at a DC density of 20 A/c/* or more, and then dissolved in a 50°C water bath containing 15 wt% sulfuric acid. After cleaning the surface by immersing it in water for 3 minutes,
Anodization treatment was carried out at 30° C. in a solution containing sulfuric acid as a main component.

Regarding the 81 metabolization properties of the support obtained in the above manner, the bottom surface was inspected for 1↓ and SEMi4% to observe micro-rough surface defects, and the plate-making process was performed as a printing plate. We conducted an evaluation as follows.

That is, the following photosensitive layer was applied to the above support with a dry weight of 25
2/A.

Compound of naphthoquinone-1,2-diazido-5-sulfonyl chloride and inverted pyrogallol acetone (described in Example A of US Pat. No. 365,709) 0.759 Cresol novolak tree 11 effects
2.00r Oil Blue #603 (Orient Chemical Co., Ltd.) 0.04f ethylene dichloride
1692-methoxyethyl acetate 1
22 The obtained photosensitive lithographic printing plate was placed on its side and exposed to a PS light (Toshiba metal halide lamp MU2000-2-OL type, with a 3-tone light source) from a distance of 1 m.
After 0 seconds of exposure, 5 wt% sodium silicate
It was immersed in water % #L for about 1 minute to develop and dried before drying to obtain a printing original plate.

Attach these printing plates to the offset printing machine KOR,
A printing test of 100,000 copies was conducted.

The results of the above measurements or multiple tests are shown in Table 3 below.

According to XRD measurement, alloy B has A1f3
For Fe, Alloy C, 'VmFe, A1. BFe
was detected.

As is clear from Table 3, that is, the material of the present invention has a single substance of 81
It has been shown that by using the side legs of the box, a printing machine that is free from micro-rough surface defects and has excellent ink stains during printing can be obtained. In addition, the strength of the support at 1 year old according to the present invention shown in No. 3 was 13 Kr/wn" or more when side-molded with 0.2% + mt force using a conventional method, and the strength of the support was 13 Kr/wn" or more, 1) It also has good handling properties.

"Effect of 0.1" When using an aluminum alloy support for semi-JW printing of F1 as explained above, compared to conventional materials, it can appropriately prevent micro-rough surface defects during surface roughening and improve printing. Since it has excellent permeability, it is possible to provide products with stable quality and high durability, and this invention is industrially very effective.

Claims (1)

[Claims] Contains Fe: 0.10 to 1.8 wt% Si: 0.03 to 0.3 wt%, the remainder consists of aluminum and impurities, and the amount of Si present as a simple substance is 0.012 wt% An aluminum alloy support for lithographic printing characterized by the following: