JP3522881B2 - Method for producing aluminum support for lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION The present invention relates to an aluminum plate for a lithographic printing plate.
The present invention relates to a method for manufacturing a metal support, particularly a brush.
Flat features that are characteristic of all processes including the graining process
Related to a method for producing an aluminum support for a plate printing plate
It is. [0002] 2. Description of the Related Art Lithographic printing is a process in which water and oil are essentially mixed.
This is a printing method that takes advantage of the fact that
The printing plate surface of the lithographic printing plate used receives water and is oily.
Area (hereinafter, this area is referred to as “non-image area”)
Say. ) And the area that repels water and accepts oil-based ink
(Hereinafter, this area is referred to as an “image section”.)
You. The aluminum support used for lithographic printing plates is
Surface is used to carry the non-image area,
Excellent in water resistance and water retention, and also provided on it
Contradiction such as excellent adhesion to the photosensitive layer
Various performances are required. When the hydrophilicity of the support is low
Ink will adhere to non-image areas during printing.
So-called soiling occurs. If the water retention of the support is low,
Unless the dampening solution is used for printing, shadows may be blocked.
I do. Therefore, the so-called water width becomes narrow. [0003] These good aluminum supports
In order to obtain, the surface of the aluminum plate is grained
It is customary to provide fine irregularities. In this grain
Is ball graining, brush graining, wire
-Mechanical roughing such as graining and blast graining
Surface treatment method, aluminum in electrolyte containing hydrochloric acid and / or nitric acid
Surface roughening method for electrolytically etching a nickel plate and rice
No. 4,476,006.
Composite combining mechanical and electrolytic surface roughening methods
Roughening methods and the like are known. These graining methods
Among them, excellent performance as a lithographic printing plate support,
Brush grini from the viewpoint of excellent mass productivity
Graining by brushing, brush graining and electricity
The graining method combined with the surface roughening method is advantageous.
You. [0004] SUMMARY OF THE INVENTION
Aluminum support grained by lining or
Combination of brush graining and electrolytic surface roughening method
Aluminum grained by multi-graining method
The support still has sufficient hydrophilicity, water retention and adhesion
Absent. That is, to improve the hydrophilicity to a desirable degree
Need to make the roughness of the rough surface shallow and smooth to some extent
However, doing so will reduce the water retention of the support,
Adhesion also worsens. Conversely, if the rough surface is deepened, water retention
In other words, the water width becomes wider, and the adhesion with the photosensitive layer is improved.
But soiling occurs. In recent years, the lithographic printing industry has
Speeding up and automation are progressing rapidly, and even more skilled workers
Printing is easy for unskilled workers
And a higher quality and more stable lithographic printing plate, namely water
There is a long-awaited need for a lithographic printing plate that is wide and stain-resistant.
Was. Accordingly, an object of the present invention is to provide a high water retention property.
Therefore, even if the dampening water is reduced, the shadow part will not be crushed.
Less stains, and better adhesion with the photosensitive layer
To provide a support for a photosensitive lithographic printing plate. [0006] Means for Solving the Problems The present inventors have achieved the above object.
As a result of intensive studies to achieve, the aluminum plate surface
In order, (a) mechanically roughened, (b) 0.5 to 30 g / m
^Two(C) 30-100A
/ Dm^TwoCurrent density of 10 to 200 coulombs / dm^Twoof
DC electrolytic surface roughening in an acidic aqueous solution with the quantity of electricity, (d)
0.5 to 10 g / m^TwoChemically etched in the range of
(e) 10 to 50 A / dm^TwoCurrent density at anode, 100 ~
500 coulomb / dm^Two In an aqueous acidic solution
In AC electrolytic surface roughening, (f) 0.1 ~ depending on the base
10g / m^TwoChemically etched in the range of (g) anode
Characterized by forming an anodized film by oxidation treatment
Method of manufacturing an aluminum support for a lithographic printing plate,
It is found that the above object is achieved and the present invention is achieved.
It has been reached. Hereinafter, aluminum for a lithographic printing plate according to the present invention will be described.
The method for producing the support will be described in detail. Used in the present invention
The aluminum plate used is a pure aluminum plate, aluminum
Alloy plate or aluminum alloy containing
Plastic with laminated or evaporated minium
Selected from among films. Included in the aluminum alloy
Foreign elements include silicon, iron, manganese, copper, and magnesium.
Chromium, zinc, bismuth, nickel, titanium, etc.
There is. The content of foreign elements in the alloy is 10% by weight or less.
You. Aluminum suitable for the present invention is pure aluminum.
However, pure aluminum is difficult to manufacture due to refining technology.
Since it is difficult, it may contain a slightly different element.
Thus, the aluminum plate applied to the present invention is
The composition is not specified, and it is
Material, for example, JIS A 1050, JIS A
1100, JIS A 3103, JIS A 300
5 and the like can be appropriately used. Used in the present invention
The thickness of the aluminum plate is about 0.1 mm to 0.6 mm.
mm. First, brush graining an aluminum plate
Prior to the removal of rolling oil on the surface, if desired.
Degreasing, for example, surfactants, organic solvents or alcohol
A degreasing treatment with a potassium hydroxide solution or the like is performed. However,
Depending on the degree, the degreasing treatment can be omitted. The gray
At the time of insertion, as shown in FIG.
With the brushes 2 and 4 each having two support rolls
Rolls 5, 6 and 7, 8 have the shortest distance between their outer surfaces
The brushes are arranged so that they are smaller than the outer diameters of brushes 2 and 4.
And the aluminum plate 1 is rolled by the brushes 2 and 4
Pressed between two support rolls 5, 6 and 7, 8
The aluminum plate is transported at a constant speed so that it can be
And supply the polishing slurry liquid 3 onto an aluminum plate.
Polishing the surface by rotating the roll brush
Preferably. The brush used in the present invention has a roll shape.
Nylon, polypropylene, animal hair, or
Uniform bristle length and bristle distribution of brush material such as steel wire
What was implanted with a brush hole
Or channel roll type
Is preferably used. The preferred material is
Ron, the preferred hair length after flocking is 10 to 200 mm
It is. In addition, the flocking density when implanting into a brush roll is 1
cm^Two30 to 1000 pieces are preferable, more preferably
Or 50 to 300. [0010] Thus, the aluminum plate is brush gray
After that, the surface of the aluminum plate is then chemically
It is preferable that the etching be performed beforehand. This chemical edge
The brushing process is based on brush grained aluminum
Abrasives, aluminum scraps, etc. that have cut into the surface of the aluminum plate
Has the effect of removing the
Roughening can be achieved more uniformly and effectively
it can. Details of such chemical etching methods are described in more detail in
Physically speaking, a solution that can dissolve aluminum
More specifically, it is a method of dipping in an aqueous solution of an acid or a base.
You. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphorus
Acid, nitric acid, hydrochloric acid, etc.
Sodium oxide, potassium hydroxide, sodium tertiary phosphate
System, potassium tertiary phosphate, sodium aluminate, metasilicon
Sodium acid, sodium carbonate and the like. these
Of these, the use of an aqueous solution of the latter base is particularly
This is preferable because the speed is high. Chemical etching
0.05-40% by weight aqueous solution of acid or alkali such as
At a liquid temperature of 40 ° C to 100 ° C for 5 to 300 seconds.
It is common to manage. The above chemical etching is performed using a salt
When using an aqueous base solution, aluminum
In this case, a smut is formed on the surface of the
Phosphoric acid, nitric acid, sulfuric acid, chromic acid or two or more of these
With a mixed acid containing Apply so-called desmutting
Is preferred. Subsequently, the aluminum surface is electrochemically
The surface is roughened. As this electrochemical surface roughening method,
This is performed by direct current in a hydrochloric acid or nitric acid electrolyte.
The concentration of hydrochloric acid or nitric acid is in the range of 0.01 to 3% by weight.
Preferably, it is used in an amount of 0.05 to 2.5% by weight.
It is even more preferred. Also, if necessary,
Nitrates, chlorides, monoamines, diamines, aldehydes
, Phosphoric acid, chromic acid, boric acid, aluminum oxalate
Corrosion inhibitors (or stabilizers) such as salt, uniform grain
An agent or the like can be added. Also, in the electrolyte,
Containing equivalent (1-10 g / l) aluminum ion
It may be. The temperature of the electrolyte is usually 10-60 ° C.
It is. The DC current used at this time is continuous and pulsed.
Can also be used. The current density is 30 to 100
A / dm^TwoAnd 10 to 200 coulombs / dm^TwoProcess
It is desirable. Average diameter 10-1 made up to previous process
On the 2 μm pit, an average diameter of 3 to 8 μm
Generate pits to improve water retention and printing durability
it can. Next, the average diameter formed by DC electrolytic surface roughening
When removing the rods attached to 3 to 8 μm bits,
To make the subsequent electrochemical roughening more uniform
Chemical etching to ensure effective and effective
For details of such a chemical etching method, see U.S. Pat.
No. 3,834,998. More
Physically speaking, a solution that can dissolve aluminum
More specifically, it is a method of dipping in an aqueous solution of an acid or a base.
You. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphorus
Acid, nitric acid, hydrochloric acid, etc.
Sodium oxide, potassium hydroxide, sodium tertiary phosphate
System, potassium tertiary phosphate, sodium aluminate, metasilicon
Sodium acid, sodium carbonate and the like. these
Of these, the use of an aqueous solution of the latter base is particularly
This is preferable because the speed is high. Chemical etching
0.05-40% by weight aqueous solution of acid or alkali such as
At a liquid temperature of 40 ° C to 100 ° C for 5 to 300 seconds.
It is common to manage. Base chemical etching
When using an aqueous solution of
In this case, phosphorous is formed because smut is formed on the surface of the
Acid, nitric acid, sulfuric acid, chromic acid or two or more of these
Treatment with a mixed acid containing acid, so-called desmut treatment
Is preferred. Subsequently, the aluminum surface is electrochemically
The surface is roughened. Hydrochloric acid is used as an electrochemical surface roughening method.
Alternatively, it is a method of carrying out an alternating current in a nitric acid electrolyte. Ma
It is disclosed in Japanese Patent Application Laid-Open No. 54-63902.
It is also possible to use a method combining DC and AC
I can do it. The concentration of hydrochloric acid or nitric acid is 0.01 to 3% by weight
It is preferable to use in the range of 0.05 to 2.5 times
It is more preferable if the amount is%. Also required for this electrolyte
Nitrate, chloride, monoamines, diamines,
Aldehydes, phosphoric acid, chromic acid, boric acid, oxalic acid
Corrosion inhibitors (or stabilizers) such as luminium salts, grain
Can be added. Also in the electrolyte
Is a method for adding an appropriate amount (1 to 10 g / l) of aluminum ions.
May be included. The temperature of the electrolyte is usually 10-60 ° C.
It is processed. The alternating current used at this time is
If the gender is alternated, square, trapezoidal,
Any sine wave can be used,
Single-phase and three-phase alternating currents can be used. Also
Current density is 5-100 A / dm^TwoIn, 10-300 seconds
It is desirable to perform interim processing. In this step, a 1 to 2 μm
In addition to water retention and printing durability,
Has the effect of improving prevention. The aluminum plate thus roughened
If necessary, 10 to 50% hot sulfuric acid (40 to 60%
° C) or diluted alkali (such as sodium hydroxide)
Preferably, the smut attached to the surface is removed. Al
If the potash is removed, the acid (nitric acid) is subsequently used for cleaning.
Or sulfuric acid) to neutralize. [0015] Next, to improve the water retention and abrasion resistance of the surface.
An anodic oxidation treatment is performed. Anodic acid on aluminum plate
A porous oxide film is used as the electrolyte used for
Anything that can be used
And generally sulfuric acid, phosphoric acid, oxalic acid, chromic acid or
For these, their mixed acids are used. The concentration of those electrolytes
It is appropriately determined according to the type of the electrolyte. Anodizing treatment
Conditions vary widely depending on the electrolyte used, so
Although not obtained, the concentration of the electrolyte is generally 1 to 80% by weight.
Liquid, liquid temperature is 5 to 70 ° C, current density is 1 to 60A / dm^Two,
Voltage 1-100V, electrolysis time 10 seconds-5 minutes
Is appropriate. The sulfuric acid method is usually treated with direct current
However, it is also possible to use an alternating current. The concentration of sulfuric acid is 5
Used at 30%, 5-25 in a temperature range of 20-60 ° C
Electrolyzed for 0 seconds. This electrolyte contains aluminum
It is preferable that ions are contained. Further at this time
Current density is 1 to 20 A / dm^TwoIs preferred. Phosphoric acid method
In the case, a concentration of 5 to 50% and a temperature of 30 to 60 ° C.
0 to 300 seconds, 1 to 15 A / dm^TwoProcess at current density of
Is done. 1.0 g / m of anodic oxide film^TwoAbove is preferred
But more preferably 2.0 to 6.0 g / m^TwoRange of
It is an enclosure. 1.0 g / m anodic oxide film^TwoLess
Insufficient printing durability or scratches on non-image areas of lithographic printing plates
And ink adheres to scratches during printing.
So-called “scratch dirt” easily occurs. After being subjected to anodizing treatment, aluminum
The surface is subjected to a hydrophilic treatment if necessary. Used in the present invention
The hydrophilic treatment to be performed is described in US Pat.
No. 66, No. 3,181,461, No. 3,280,
734 and 3,902,734.
Alkali metal silicates as shown (eg silica
(Aqueous sodium acid solution) method. In this method,
The support is immersed in an aqueous solution of sodium silicate.
Or electrolytic treatment. In addition, Japanese Patent Publication No. 36-22063
Potassium fluoride zirconate and rice disclosed in the patent application
National Patent No. 3,276,868, No. 4,153,461
No. and No. 4,689,272.
Treatment with polyvinyl phosphonic acid
Used. After graining and anodic oxidation, sealing
A treated one is also preferred. Such sealing treatment is performed with hot water
Immersion in a hot aqueous solution containing inorganic and organic salts and
It is performed by a steam bath or the like. The aluminum support for a lithographic printing plate is shown in the above table.
After the surface treatment is performed, the undercoat is applied and the photosensitive layer is applied.
You. Organic undercoat layers and photosensitive layers are described in JP-A-6-135.
No. 175 can be used.
Wear. [0018] 【Example】 (Example-1) JIS A 105 having a thickness of 0.24 mm
0 aluminum plate, nylon brush and average particle size of about 21
Brush nin with a suspension of water
And then washed well with water, and then
Immerse in sodium at 60 ° C for 35 seconds to etch,
After washing with running water, neutralization washing with 30% sulfuric acid and washing with water were performed.
These were subjected to DC electrolytic surface roughening treatment under the conditions shown in Table 1.
Was. After washing with water, subsequently, 26% by weight sodium hydroxide
For 15 seconds at 60 ° C for etching.
After washing with water, neutralization washing with 30% sulfuric acid and washing with water were performed. these
Using a trapezoidal alternating current waveform (Fig. 2), 1% sulfuric acid
160 coulomb / dm in aqueous solution^TwoOf electricity at the anode
A surface roughening treatment was performed. Subsequently, 5% by weight of sodium hydroxide
After immersion in 35% C for 40 seconds in 30% sulfuric acid solution
It was immersed in the solution and desmutted at 60 ° C. for 40 seconds.
Then, in a 20% sulfuric acid aqueous solution, the current density is 2 A / dm.^Twosmell
1.6g / dm^TwoWith a direct current so that the oxide film weight of
Anodizing was performed to produce a substrate. The following sets are provided on the surface of the substrate thus treated.
An undercoat solution was applied and dried at 80 ° C. for 30 seconds. Dry
The coating amount after drying is 30 mg / m^TwoMet.   (Undercoat liquid treatment method)       Aminoethylphosphonic acid 0.10 g       0.15 g of phenylphosphonic acid       β-alanine 0.10g       40 g of methanol       60g pure water Thus, a substrate was produced. Next, the following photosensitive liquid is applied on this substrate,
Dry at 10 ° C for 1 minute to obtain a positive photosensitive lithographic printing plate
Was. The coating amount after drying is 1.7 g / m^TwoMet.   (Photosensitive liquid)   1,2-diazonaphthoquinone-5-sulfonyl chloride and     Esterified product with pyrogallol-acetone resin (US     No. 3,635,709 in Example 1.     0.45g   Cresol-formaldehyde nopolak resin (meta,     La ratio: 6 to 4, weight average molecular weight 3,000, number average molecule     1.1 g in an amount of 1,100, containing 0.7% of unreacted cresol)   m-cresol-formaldehyde nopolak resin (weight     Average molecular weight 1,700, number average molecular weight 600, unreacted     0.3 g containing cresol 1%)   Poly (N- (p-aminosulfonylphenyl) acrylia     Mido-Cornormal butyl acrylate-Kojiethyl     Glycol monomethyl ether methacrylate)     Each model is described in Japanese Unexamined Patent Publication No. Hei 3-311241.     The molar ratio of the nomers is 40:40:20 in order, and the weight average molecule.     Weight 40,000, number average molecular weight 20,000) 0.2 g     p-Normal octylphenol-formaldehyde resin       (As described in U.S. Pat. No. 4,123,279)       0.02g     Naphthoquinone-1,2-diazide-4-sulfonic acid chloride       Id 0.01g     0.1 g of tetrahydrophthalic anhydride     Benzoic acid 0.02 g     4- (p-N, N-bis (ethoxycarbonylmethyl) a       Minophenyl) -2,6-bis (trichloromethyl)-       S-triazine 0.01 g     4- (p-N- (p-hydroxybenzoyl) aminophen       Nil) -2,6-bis (trichloromethyl) -S-tri       Azine 0.02g     2-trichloromethyl-5- (4-hydroxystyryl)       -1,3,4-oxadiazole 0.01 g     Victoria Pure-BOH with 1-naphtha       Dye converted to lensulfonic acid 0.02 g     Modiva-F-200 (fluorinated surfactant manufactured by NOF Corporation)       Agent, 30% by weight of methyl ethyl ketone and methyl isobutyrate       Luketone mixed solvent solution) 0.06 g     Megafac F177 (Fluorine manufactured by Dainippon Ink and Chemicals, Inc.)       Surfactant, dissolved in 20% by weight of methyl isobutyl ketone       Liquid) 0.02g     15 g of methyl ethyl ketone     1-methoxy-2propanol 10g On the photosensitive layer thus coated,
According to the method described in Example 1 of JP-A-61-28986.
(Methyl methacrylate / ethyl acrylate
/ Sodium acrylate = 68/20/12) copolymer water
A mat layer was provided by electrostatic spraying of the solution. The photosensitive lithographic printing plate thus produced
In a vacuum furnace, through a transparent positive film.
m from a 3m metal halide lamp from a distance of 5m
After exposure for 0 second, SiO 2 was used as a developing solution._Two/ N
a_Two5.26 of sodium silicate having a molar ratio of O of 1.74
% Aqueous solution (pH = 12.7)
Fuji with FR-3 (1: 7) manufactured by Shin Film Co., Ltd.
Passed through an automatic development stublon 900D manufactured by Photographic Film Co., Ltd.
And processed. After leaving this planographic printing plate for one day, print evaluation
did. The printing press dries Harris Aurelia A-125
Shimizu is EU-3 (1:10) manufactured by Fuji Photo Film Co., Ltd.
0), and the ink was Mark Fiveni manufactured by Toyo Ink Co., Ltd.
Black ink was used. The dampening solution is squeezed on the printing press to remove the non-image area.
Visually observe the stains on the keys, A ... excellent, B ...
Good, C: somewhat poor, D: poor. Shi
About Tsumari of the shadow part, when dampening water is squeezed, 2%
Judgment was made based on whether halftone dots were open. In addition, about Tsumari
The degree is indicated by the following display. A: It is completely open. B: almost open
To C: Somewhat crumbled D: Crumbling Both stains and shadows in the shadow area resulted in a favorable printed matter.
This is the level above B. As a result, the present invention
The lithographic printing plate using the support made by the manufacturing method is
The dirt is hardly generated, and even if the dampening solution is reduced,
The clogging of the dough did not occur. Print 100,000 sheets
However, good printed matter was obtained. The results are summarized in Table 1.
You. [0024] [Table 1] (Comparative Example-1) Same as Example-1 except that the DC electrolytic surface roughening treatment is not performed
Processed. Table 1 shows the processing steps and results. Shown in Table 1
As described in Examples 1 to 3 of the present invention,
Lithographic printing plate is a comparative exampleA-BHarder to soil compared to
Good performance without shadow blockage
did. [0026] The present inventionProcessing related toaluminum
The printing plate made from the PS plate using the support is printed on a printing press.
Unskilled because dirt and shadow blockage are unlikely to occur
Easy to print for people and higher quality and stable than conventional one
Printed matter is selected.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side view of an embodiment of a brush grain which is a part of the process of the present invention. FIG. 2 is an embodiment of a trapezoidal wave current at the time of AC electrolytic surface roughening used in the present invention. Waveform diagram of example [Description of symbols] 1 ... Aluminum plate 2 ... First brush roll 3 ... Abrasive slurry liquid supply device 4 ... Second brush roll 5, 6, 7, 8 ... Support roll

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-171260 (JP, A) JP-A-3-104694 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41N 3/03-3/04

Claims (1)

(57) [Claims] 1. The surface of an aluminum plate is sequentially (a) mechanically roughened, and (b) chemically etched in a range of 0.5 to 30 g / m ^2. (C) current density of 30-100 A / dm ² , 50-100
DC electrolytic surface roughening in an acidic aqueous solution with an amount of electricity of coulomb / dm ² , (d) chemically etching in a range of 0.5 to 10 g / m ² , (e) an anode of 10 to 50 A / dm ² Current density, 100-
AC electrolytic surface roughening in an acidic aqueous solution at an anode charge of 500 coulombs / dm ² , (f) chemically etching with a base in the range of 0.1 to 10 g / m ² , and (g) anodizing treatment A method for producing an aluminum support for a lithographic printing plate, characterized by forming an anodic oxide film by heating.