DE2515032A1 - METHOD OF MANUFACTURING A CARRIER FOR A PRINTING PLATE - Google Patents

Description

PATH NT / ^ N WKLl II A. GRÜNLCKER

Dir-'L.-INCi.

H. KlNKELDHY

DR.-ING.

W. STOCKMAIR

UR.-ING. ■ ACE (CALTEChIl

2515032 ^K SCHUMANN

DR. FiElR. MAT. · D1PL.-F> i! \ ^.

P. H. JAKOB

DIPU-ING.

G. BEZOLD

DR. RER. NAT. · DiPL-CHEM.

MUNICH E. K. WEIL

DR. RER. OGC. ! KG.

LINDAU

FUJI PHOTO FILM CO.y LTD. ₈ Munich 22

__ _. _ ", MAXIMIUANSTi? ASSE 43

No. 210, Nakanuma,

Minami Ashigara-Shi _p cy \ 2f \. -60 / ku

Kanagawa,

JAPAH ⁷ - ^{Aıril 1975}

Process for the production of a support for a printing plate

The invention relates to a method sur Hers' ■: RECOVERY a Träge.rs for a printing plate; it "also relates to a method for producing an aluminum plate for a planographic printing plate with an improved adhesion to the aluminum plate and the photosensitive coating.

Aluminum is used in large quantities as a carrier for planographic printing plates because it is easy to use and cheap, has a low weight, is easy to process H \ < and na.- .haltig (din-: iioioncbont ^ iIg) and dr: l. int. At the anodic on 0.-v:; / dvJLtioii an Alur,: i: iiur.pl "t - ': ö (Λ1ιι: αίη1υηΓο] .; Ιο) in a Llelctrolvtsn, v: ± o z, 3« üch-fef el acid, Ohroi.ii7i. '. r.ro,

T EJl-EX OD 29 33Ο

509842/0925

Oxalic acid, phosphoric acid and the like are provided with an aluminum oxide (Al ₂ O 4) film. Since the surface of this aluminum oxide has numerous fine pores, it absorbs a great deal of water and has high abrasion resistance. However, an aluminum plate with an anodic oxide film coating is not a satisfactory support for a planographic printing plate because the adhesion between the aluminum support and the photosensitive coating composition is insufficient and the interaction between the support and the photosensitive coating composition leads to desensitization of the photosensitive coating composition, poor development , insufficient time stability and the like. Leads. It has therefore hitherto been difficult to use, as a support for a planographic printing plate, an aluminum plate with an anodic oxide film coating, which is receptive to water and has high abrasion resistance.

There are already various methods of overcoming the disadvantages described above have been proposed in order to achieve that an aluminum plate with an anodic Oxide film coating can be used as a support for a planographic printing plate. For example, in Japanese Patent Publication No. 26 521/1971 stated that an Alurainiunplatts with an anodic oxide film coating produced by phosphoric acid electrolysis has been produced, is suitable as a support for a planographic printing plate.

That by anodic oxidation in a phosphoric acid electrolysis Oxide film coating formed on an aluminum plate makes the photosensitive coating composition excellent adheres to it and is insofar as a carrier for a planographic printing plate suitable, but on the other hand it has poor abrasion resistance and is therefore not suitable as a carrier for a planographic printing plate. Also is in the prairtischen implementation a phosphoric acid electrolrse has a very high flute;,;:

509842/0925

required because of the electrical conductivity of phosphoric acid is small and phosphoric acid is very expensive, so that the phosphoric acid electrol ^ rse is not suitable for mass production is suitable, especially since it is very dangerous to carry out the method using a high voltage.

An aluminum sheet with an oxide film coating applied by anodic oxidation by electrolysis of acidic acid and having high abrasion resistance, which is cheap and advantageous from an industrial and practical point of view, but has the disadvantage that the photosensitive coating compound (coating compound) adheres poorly to it and that the anodic oxide film coating absorbs moisture from the air, causing its fine pores to fill naturally and changing its surface properties. For this reason, the oxide film coating formed by anodic oxidation in sulfuric acid electrolysis is unsuitable for use as a support for a flat back plate. In the German Offenlegungsschrift 2 251 71O ₁ in the Belgian patent 797 180 and in the US patent application Mr. 360 488 states that the above-described insufficient adhesion between the surface of the anodic oxide film coating and the photosensitive coating composition and the instability of the surface of the anodic oxide film coating over time can be eliminated by grounding the aluminum plate with a phosphoric acid electrolysis anodic oxidation film provides. However, the speed of treatment in this method is slow and the method has poor working efficiency. In addition, high temperatures and highly concentrated solutions must be applied and expensive phosphoric acid must be used. Therefore, this method is not suitable for the production of a support for a planographic printing plate, and it is difficult to carry out its industrial application or mass production.

509842/0925

In this method, the surface of the anodic oxide film coating is exposed to the phosphoric acid treatment solution enriching aluminum ions influenced, so that the manufacture of a carrier with uniform (constant) properties has heretofore been difficult.

The aim of the present invention is therefore to provide an improved method for producing a support for a printing plate indicate that is cheap, that causes a photosensitive Coating compound adheres excellently to it ^ and with it Help it is possible to achieve high pressure resistance. The aim of the invention is in particular to provide an industrially advantageous Specify a method for producing a carrier for a printing plate with uniform notches.

These objects are achieved according to the invention by having an aluminum plate with an anodic plate thereon Oxide film coating in an acidic or basic solution of a subjected to cathodic electrolysis.

The invention relates to a method for production a carrier for a printing plate, in particular a planographic printing plate, which is characterized in that one Aluminum plate subjected to anodic oxidation and then subjected to anodic oxide film coating Aluminum plate in an acidic or basic solution of a subjected to cathodic electrolysis.

Aluminum plates that can be used in the present invention include pure aluminum plates and aluminum alloy plates (hereinafter referred to as aluminum 'plates for the sake of simplicity). As an aluminum alloy, can various aluminum alloys are used, for example those aluminum alloys that contain metals such as silicon, Copper, Manganese, Magnesium, Chromium, Zinc, Lead, V / ismut, ITi disgust

509842/0925

and the like. Representative examples of such Aluminum alloys are given in the table below, v / obei the alloy components in Gcv; .- /? specified and the remainder is made of aluminum.

Aluminum-Si Cu Mn Mg Cr Zn alloy

2S 0.4 - - 0.6

3S - - 1.2 -

245 - 4.5 0.6 1.5

253 - 2.5 0.25 -

61S 0.6 0.25 - 1.0 0.25

753 - 1.60 - 2.50 0.30 5.60

The compositions given above contain negligible small amounts of impurities not indicated above and certain amounts of iron and iitan.

The surface of the aluminum is covered by fats and oils, ront, Dust and the like are contaminated and therefore the aluminum surface becomes generally chemical cleaning, for example solvent degreasing, alkali degreasing and the like, as described in "Kinzoku Hyomen Gijutsu Binran (Handbook of Metal Surface ^ technology) ", Pages 186-210, ITilutan Kogyo Shimbun, is given to to expose a clean aluminum surface. Then it is desired If necessary, a graining (Atifraubung) carried out. To the Achievement of the grain size or roughening can be achieved by roughening the glass beads, roughening the spheres, or roughening by means of a Sandblasting blower, the roughening by means of a brush, v: ie described in US patent application No. 284,851, an electrolytic Roughening, v / ie in Japanese Patent Publication No. 28 123/1973 and in British Patent 896 563 described, and the like. Applied v / ground. Erfinaungsgonülll hä-n any of the roughening methods described above

5 0 9 8 4 2/0925 _{0RlG! NAL} inspected

(Graining method) can be used, although the roughening (graining) is not absolutely necessary. The smooth aluminum surface itself can be used more effectively as a surface of the support for a planographic printing plate Carrier for a flat pressure plate, which has a roughened (grained) Has a surface, but retains more water than a smooth surface and can produce the desired prints (Prints) deliver. After roughening, if desired a treatment using an aluminum etching solution can be used to reduce discoloration in the non-image areas described in U.S. Patent 3,834 · 998.

Sodium hydroxide, Potassium hydroxide, sodium triphosphate and the like are used. These Treatment is not absolutely necessary and can be used especially when the light sensitive Coating compound (coating compound) has the tendency to to remain behind image-free districts.

It is zv / angular, the resulting aluminum plate then in Dip a 70/5 nitric acid to get a clean aluminum surface to expose.

An oxide coating film is formed on this aluminum plate anodic oxidation generated. This anodic oxide film coating can be formed by running a direct current through a phosphoric acid, chromic acid, oxalic acid, Sulphanidic acid, benzenesulphonic acid solution or a mixture of it and the like. Sends as electrolytes with the aluminum carrier as an anode, as for example in "Journal of the Electrochemical Society ", Volume 1C0, No. 9, Pages 4-11-4-19 (1953), is described.

The conditions for the anodic oxidation treatment vary

509842/0 9 25

Depending on the type of electrolyte used and in general, a concentration of the acid used in the electrolyte is from about 1 to about: a 80 wt .- ^ S, a solution temperature from about 5 to about 70 ⁰ C, a direct current density of about 0 .5 "to about 60 amperes (A) / dm, a voltage of about 1 to about 100 V and an electrolysis time of about 30 seconds to about 50 minutes are suitable. Prior process conditions are given in the following table.

used concentration temp. d. DC voltage Bauer electrolyte (%) solution current (V) (minutes)

(° C) density

(A / dm?)

sulfuric acid

Oxalic acid

phosphoric acid

Chromic acid

5 - 65 0.5 - 30 1-50

20-60 0.5-20 10-70
20-60 0.5-20 10-60

1 _ 70

1-20

2-60

2-30 30-60 0.5 -10 10 -

1 - 30

5-40

1 - 30 I-50

According to the process according to the invention, the resulting Aluminum plate with anodic oxide film coating in one acidic or basic solution subjected to cathodic electrolysis. A suitable pH value for the cathodic Electrolysis in an acidic solution is about 3 or less, preferably 1.5 or less, and a suitable one The pH for cathodic electrolysis in a basic solution is about 10 or more, preferably 11 or more.

As a solvent for the acidic or basic solution v / ird in general water used, but it can also use other solvents, such as. water-soluble solvents, such as Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, Methylene glycol, ethylene glycol, dimethylformamide and Like., can be used.

Suitable acids include inorganic acids such as hydrogen chloride acid, hypochlorous acid, hypobromous acid,

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"Chlorous acid, bromipe acid, iodine acid, hypoiodic acid, bromic acid, iodic acid, hydrofluoric acid, permanganic acid, nitric acid, perchloric acid, hydrocyanic acid, sulfuric acid, chromic acid, carbonic acid, sulphurous acid, silicic acid, fluorozirconic acid, boric acid, phosphoric acid, hypophosphorous acid, , an alkali metal hydrogen sulfate, metaphosphoric acid, pyrophosphoric acid, ammonium dihydrogen phosphate, an alkali metal dihydrogen phosphate, polyphosphoric acid and the like, organic acids such as acetic acid, formic acid, oxalic acid, citric acid, lactic acid, propionic acid, oleic acid, malonic acid, and mixtures thereof or more of the above-mentioned compounds.

Suitable examples of bases include hydroxides, such as sodium hydroxide, Kaliurahydroxid, lithium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, sodium aluminate, aqueous ammonia and d ^r <l ·, salts of strong bases and weak acids such as sodium triphosphate, sodium diphosphate, potassium triphosphate, potassium diphosphate, sodium carbonate and the like., Amino group-containing compounds such as triethanolamine, diethanolamine, monoethanolamine, morpholine and the like. _} and mixtures thereof.

The acidic or basic treatment solution can also be different Additives such as a metal salt, a scale inhibitor (scale inhibitor), a surface active agent and the like, contain.

The conditions for carrying out the cathodic electrolysis vary depending on the kind of the for the formation the electrolyte used in the anodic oxide film coating, the type of acid used in cathodic electrolysis or base and the like. In general, the cathodic elec-

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trolysis at a concentration of the acid or base of about 0.1 to about 70 Gev /.-%, at a temperature of about 0 to about 70 ° C, within a time of about 1 to etv / a 600 seconds and a cathode current density of

about 0.05 to about 20 A / dm, preferably at a concentration of about 0.5 to about 30 wt. 5-5, at a temperature of about 5 to about 40 ⁰ G, within a period of about 3 to about 300 seconds and with a cathode current

o Density of etv / a 0.1 to about 10 Λ / dm carried out.

The current waveforms that can be used in the cathodic electrolysis of the present invention include a direct current method, an interval method, a pulsating current method, a PH method, a direct current combination method, an alternating current plus direct current multiplication method and the like, such as them for example, in "Kinzolcu Hyomen Gijutsu (Hetal Surface Technology)", Volume 2 ^x: -, pages 34 - 42 (1973) and "Fortyeir: hth Ue et ing of KinzoZ-m Hyonen Gijutsu Kyokai (Lletal Surface Technology Association)," Pages 14 - I5 are described. A suitable range for the current frequency is about 20 to about 50 Hz, preferably 40 to 200 Hz.

An aluminum plate with an anodic oxide film coating, which has been subjected to the cathodic electrolysis described above has a good water retention property and the light-sensitive coating (coating wet) adheres to it very strong. Therefore, there is another surface dealership not required, but k-'tnn bio Rer / ünrchtenf v.llo applied v / earth.

The surface treatments include immersion in a aqueous sodium silicate solution as in the US patent 2 714 066, in a potassium fluorozirconium solution.;, as described in US Pat. No. 2,946,683, into a

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Phosphoric acid glass ((1TaIO-O _n , where η denotes an integer averaging 15) solution, as described in United States Patent 3,148,984, or the like. And the application of a primer layer (underlayer) made of a hydrophilic polymeric compound on the aluminum support.

Examples of suitable hydrophilic polymeric compounds for Production of the primer layer (underlayer) are polyvinylbenzenesulfonic acid, polyacrylic acid, carboxymethyl cellulose, Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone ,, a polyethylene / maleic anhydride copolymer and the like. The primer layer made of the hydrophilic polymeric compound can be in the form of an aqueous solution, preferably in the form of a solution of an organic solvent, which is from 0 to 50 vol. Contains water. Examples of suitable organic solvents are alcohols, amides, ketones, glycol monoethers and the like. Particularly preferred organic solvents are methyl alcohol, ethyl alcohol, propyl alcohol, acetone, Methyl ethyl clay, ethylene glycol monomethyl ether, ethylene glycol monoeth hy lather, itthyl englykolraonopropy lather, xthyleneglykolmonomethylätheracetat, Ethylene glycol morioethyl ether acetate, Dimethylformamide, dimethyl sulfoxide and the like.

A suitable amount for the application of the primer coat

is about 400 mg / m or less, preferably about 5

up to about 150 mg / m. The surface treatments described above can if desired also in combination with each other applied v / earth.

A light-sensitive coating area in the form of a layer is applied to the support obtained in this way in order to produce a planographic printing plate. Examples of suitable light-sensitive Beschiolitungsmassen are Idazoharse, DiazQo :: id, p-DiazoiTiindinzoh-rse and the like. _S and a typical Beispiel'für a photosensitive Beschichtungsraasse (Überzugrsiaasrso) it

509842/0 925

a p-diazodiphenylamine-formaldehyde condensate. These photosensitive Coating masks are, for example, in the U.S. Patents 2,649,373, 3,046,121, 3,046,122, and 3,046,123.

In addition, those compounds can be used which are dimerized by irradiation with active light. In addition include e.g. polyvinyl cinnamate, polyvinyloxyethyl cinnamate, Homopolymers or copolymers of acryloxyethyl cinnamate. Homopolymers or copolymers of Llethacryloxyäthylcinnamat (as described in US Pat. No. 3,799), polyparavinylbenzalacetophenone, or derivatives thereof, acrylic acid, allyl prepolymers and dex ^ ivate thereof, Polyester derivatives composed of paraphenylenediacrylic acid and a polyhydroxy alcohol, e.g., such compounds as in U.S. Patent 3,030,208 and Japanese Patent Publication ITr. 2 042/1973 ".

In addition, those compounds can be used which are polymerized by irradiation with active light. These compounds are compounds with two or more terminal jithylene groups, as described, for example, in US Pat , Triethylene glycol diacrylate and dimethacrylate, dipropylene glycol diacrylate and dimethacrylate, and the like. Azide resins can also be used, such as those described, for example, in US Patents 3,002,003, 3,092,494, 3,469,982 and 3,418,295, in British Patent 892,811 and "Kinzoku Kagaku (Metal Chemistry)", Volume 9, Pages 1-17 (Jan. 1972). Representative examples of such azide resins are 4,4-diazidostilbene, 4,4-diazidophenylme: han, 4,4-diazidobenzalacetone, 2,6-di- (4 ¹ -azidobenzal) cyclohexane, 4,4'-diazidoutilbene-a-carbonii .'Iiire and the like.

509842/0925 originally inspected

Other photosensitive coating compositions that according to the invention used are such connections on, which can be changed by irradiation with active rays, for example a silver halide emulsion, a dichromic acid colloid and like

The photosensitive resin used in the present invention can also a resin as a binder, a sensitizer, a thermal polymerization inhibitor, a colorant, a calibrator and the like. Included. Resins such as those in Japanese, for example, can also be used as binders Patent publications ITr. 8 495/1972 and 5093/1970 are. In addition, addition polymers such as a Vinyl ester polymer or copolymer, polyvinyl alcohol, Polyvinyl acetate, polyvinyl butyral a polyvinyl acetate., Such as Polyvinyl butyral and polyvinyl formal and the like, as well as polymers of the alkyd type such as saturated or unsaturated Polyglycerin phthalate, polyglycerin maleate and the like are used will.

Representative examples of suitable sensitizers are anthracene, phenanthrene, chrysene, ο-nitroanisole, ß-nitrostyrene, p-Nitrodiphenyl, 5-Nltro-2-aminotoluene, 4-Hitroaniline, 2-Keto-3-methyl-1,3-diazobenzanthrone, 1,2-benzanthraquinone, 9,10-anthraquinone, leukotriphenylmethane and the like. As thermal Polymerization inhibitors can use compounds such as hydroquinone, p-methoxyphenol and the like. Also can a dye and a pigment are used as a coloring agent for developing an image, and such compounds are preferred, which have no absorption in the effective length range of the photosensitive resin. As a plasticizer, it is possible to use compounds which are found in the light-sensitive Coating compounds are mutually soluble, e.g. Dibutyl phthalate, dioctyl phthalate and the like.

The light-sensitive coating material (coating material) is

509842/0 9 2 5

generally dissolved in water, an organic solvent or a mixture thereof, applied in form of a layer to the substrate produced by the process according to the invention and dried in order to evaporate the solvent. A suitable coating amount for the photosensitive coating material is approximately: a 0.1 to ¹ et ..τι 3.5 »bis'2,5 preferably 0.5 g / m support. the photosensitive printing plate prepared according to the methods described above is placed under a transparent support having an image and using Light source rj. Exposed imagewise with active light, such as a carbon arc lamp, a xenon bulb, a mercury lamp or another lamp emitting ultraviolet light. \ Lenii a light-sensitive coating material for a planographic printing plate or an intaglio printing plate is applied in the form of a layer an image created by selective removal of the non-image areas and exposed Areas of the photosensitive coating film on the support with a developer, then a varnish and a coloring solution (tincture) are applied to the non-image areas in the form of a layer, for example by gently rubbing the surface with an absorbent cotton cloth after the image is formed, and then the image areas are removed by means of a brush, an image consisting of the varnish and the color solution (tincture) being obtained. The developing process used and the composition of the developer are the same as those used in the conventional planographic printing plate or intaglio printing method.

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto. The ones specified therein Parts, percentages, ratios and the like are based on weight, unless otherwise specified.

509 8 42/0925

ORIGINAL INSPECTED

example 1

An aluminum plate (2S) which had been roughened with a brush in the manner described in the example of U.S. Patent Application No. 284,851 was immersed in a 10% aqueous sodium hydroxide solution of 55 ° G for 20 seconds and then washed . The surface of the aluminum plate is gray. Then, the aluminum plate was immersed in 70% nitric acid at room temperature (ie, about 20 to about 30 ° G) for 60 seconds and washed to expose a white aluminum surface. With the pretreated aluminum lath as the anode and a lead cathode, anodic electrolysis was carried out in a 20% strength aqueous sulfuric acid solution box at a temperature of 50 ° C. and a direct current density

of 2A / dm for 3 minutes. At this time the amount of the oxide film formed on the roughened surface was 3 »C" g / m. The aluminum platonite thus pretreated An anodic oxide coating was used in the following Table I specified conditions using a lead cathode, a stainless steel cathode, a Duralunin cathode, a platinum cathode and the like. A cathodic Subjected to electrolysis. The aluminum plate thus obtained was immersed in an aqueous sodium silicate solution of the following indicated composition of 65 ° C for 20 seconds and then washed.

ITatr iunsilicate Behar-dlun p-s solution

ITatriuiasilicate. (40 '; 5% aqueous solution) 250 g water 4000 g

The following was applied to the aluminum plate Solution in the form of a layer by means of a spinner

turig at room temperature in an amount of 100 ml per square meter with the formation of a primer layer (underlayer).

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Polyvinylpyrrolidone (trade name

E-90, a product de :? Pima General

Aniline and PiIn Co.) 0.5 G

Methyl alcohol 1000 ml

Then, the indicated below photosensitive coating using a Schletidervorrichtung in the form of a layer was applied to the aluminum plate and dried at 100 minutes ⁰ G long.

1, > \ ~ Di-ß-hydr oxyäthoxycyc lohexan-

p-phenyldendiacrylic acid condensate

(average molecular weight

8000) 10.0 g

5-nitroacenaphthene 1.0 g

Dibutyl phthalate 4.0 g

Phthalocyanine blue. 2.0g

Monochlorobenzene 300 g

The amount of photosensitive coating applied-

2
mass was 1.7 g / m · The Aluniniumplatte was Ver ^v .endung a 30 amp Kohlelichtbogcnlampe at a distance of cm JO seconds through a negative film bilchiäiiig exposed, then the plate was gently rubbing with a with a developer having the following The adhesion of the image areas to the support during development is given in Table II below.

4-butyrolactone 1000 ml

Glycerin 100 nl

Methyl abietate 10 ml

hydrogenated tree resin (trade name Staybelite Resin, a product of Hercules Powder Oo.) 1 ml

wetting agent (Haniels name Zon; / 1 A,

an I product from Du Pont Co.) 10.2 ml

distilled water 100

Jr5 capable phosphoric acid 25 AD

509842/0925 ° * iGi _Nf , "

Table I. conditions Treat Cathode raw density (A / dm ² ) 4th the cathode
electrical elec
trolysis * lung s-
duration
(Sec.) 0 1 2 Well example
20 ⁰ C,
2 ^c / o sodium
triphosphate 30th detached
away Well Well dd 30 ⁰ C,
5 % sodium
carbonate 30th ti It ti dd 65 ° C,
1 ^c / o oxalic acid 180 dd It Il Il , 30 ° c,
1 '/} sodium
polyphosphate 30th Il Il Il dd Comparison
example 3 <5 ° n
4 ° / o phosphorus
acid 300 ti ti Il 4 % phosphorus
acid 600 Il

* An aqueous solution of the electrolyte was used.

In the case of the tracer that is not cationic according to the invention Had been subjected to electrolysis, a peeling occurred in the development of the image areas even if this was not an absorbent cotton cloth impregnated with the developer was gently rubbed while the image area of the substrate which had been subjected to cathodic electrolysis did not become detached from the surface of the carrier even when rubbed firmly during development, and consequently the adhesion was good.

"If in the treatment according to the invention a 4% phosphoric acid of 25 C has ended within JOO seconds.

509842/0925

a carrier with excellent adhesion properties (cathode stroy density 1 to 4 A / dm), while when using the in the above-mentioned patents, ie in the German Offenlegungsschrift 2 251 710, in the Belgian patent 797 180 and in the U3 patent :. mneldu] ?. _t ; No. 360,488, described method "and using the same treatment solution, a carrier having excellent adhesive properties was not obtained even if the treatment was carried out for 600 seconds, much less if the treatment was carried out for 300 seconds.

Each of the listed in Table I below, under Airvc-etching the treatment according to the invention in a cathodic surgery.

O
Dense printing plates of 2 A / dm "with a carrier were attached to a printing device (Heider G ¹ I ¹ O) and printing was carried out with it, the 50 OCO. print still having practically the same color density as the obtained at the start of printing.

Example 2

An aluminum plate (3 ^) which had been roughened in the same way as in Example 1 was immersed in a 20% aqueous sodium triphosphate solution of 70 ° G for 60 seconds and washed. When this aluminum plate was immersed for 1 minute in a 70% aqueous nitric acid solution at a temperature in the center and washed, a white aluminum surface was exposed. With the aluminum plate pretreated in this way in the anode and a lead cathode, anodic electrolysis was carried out for 3 minutes in a fig aqueous sulphuric acid solution at a temperature of 30 ° C. and a global current density of 2 A / dm. The hon; _; e of the gobilieten on the roughened surface G ^ idfilur: Viit-L "3.2 g / n. The AluniniTiriplatto / lit dan rno ^" obtained in this way. ^{R 'is} CH: n O; idfili'.iiborsug was among those in the n .- ^ CHF lgonden ^r i'u:;. JII. II angogswith the conditions of the iridation law on cathodirob cn

509842/092

Subjected to electrolysis.

(Dabeile II

cathodic treatment ^ - cathode current density electrolysis time (sec.)
bed! nine '"en *

example 20 ° C, 65 ⁰ C 50 ° c, Comp.- 50 ° c, 30th 2 ^c , 'j sodium 1 ^c / o oxalic acid ¹ V ^c , o phosphorus example 4? 5 phosphorus triphosphate 40 ° C, acid acid 65 ⁰ C 1 % sodium 120 10 70 sulfur polyphosphate acid 4-0 ⁰ C, 1 % sodium car 180 bonat 20th 30th 30th 120

peeled off well well **

* An aqueous solution of the electrolyte was used ** Film adhesion

On the aluminum plate, that of the treatment according to the invention was subjected, the following photosensitive coating was wet by means of a spinner applied in the form of a layer and dried at 1CC C for 2 minutes. The lerigo of the angry light-

ο sensitive Besc'aichtun ^ sinasse was 1.5 g / n ^£ ".

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ORIGINAL IHEP

Menf-re (ρ;) polyvinylpyrrolidone (Κ-90) 4.5

Hydroxypropyln -thr / lcellulose

(Trade name Metlose 60 SH

4C00, a product of the company

Shinetsu Kagaku Kogyo Go.) 0.25

Sodium salt of 4,4'-diazidostilbene-2,2'-disulfonic acid 0.25

Crystal Violet (CI. 42 555) 0.05

Cyclohexane 5 * 0

Ν, ΪΤ-dimethylformamide 20.0

The aluminum plate π it the applied photosensitive Coating compound vmrde for 15 seconds by a Po-itiv - film with the radiation from a '50 ampere carbon arc lamp exposed at a distance of 7-0 -cm. The on this The image-wise exposed plate obtained in this way is developed by pouring water at room temperature all at once on the photosensitive plate Coating layer poured and the surface with a absorbent cotton cloth impregnated with water strongly rubbed. The film adhesion of the coating filias in this development is given in Table II above. The carrier that had been subjected to the treatment according to the invention was the adhesion to the image areas excellent and to the non-image areas No light-sensitive coating remained on the surfaces; orv: .rjse return. However, dissolved in the carrier that had not been subjected to the cathodic electrolysis according to the invention was to wipe the picture surfaces gently with an absorbent cotton cloth impregnated with water.

When using the treatment according to the invention using a 4% phosphoric acid at 25 ° C., a carrier with excellent adhesive properties was obtained within 15 seconds (cathode current density 1 to 5 A / dm ""), while the users of the patent specifications cited above, ie i) .i of the German disclosure document 2 25 '710, the b'ilg: ir; dioii patent specification 797 180 and in the US patent application Wr. > oC 438.

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BATH ORIGINAL

described method and when applying the same. Treatment solution could not obtain a carrier having excellent adhesive properties even within 120 seconds, and much less within 30 seconds. At this concentration, a carrier having excellent adhesive properties could only be obtained when the temperature was raised by 15 ° C. to 65 ° C. and the treatment was carried out for 30 seconds. On the support with the image, wherein the treatment of the invention using a cathode current density of 1 A / dm ¹ 'Lacquer S "(" was as indicated in Table II above, subjected to a commercial paint was "trade name for a product of Hanns Eggen Co.) for a flat cover plate and an intaglio printing plate applied in the form of a layer by rubbing the surface with an absorbent cotton cloth impregnated with it. Then a tincture (trade name RG 42-100, a product from Caley Co.) applied in the form of a layer by rubbing the surface with a sponge impregnated with the tincture was immersed at room temperature containing aqueous solution, the photosensitive coating film, which was the main component component contained polyvinylpyrrolidone, and the varnish layer and the tincture layer applied on the photosensitive coating film were removed by rubbing with a brush, thereby creating image areas and exposing the hydrophilic aluminum surface. The printing plate obtained in this way with the image thereon was attached to a printing device (Heider G-TO) and used for printing, the 4-0,000th print (impression) having the same color density as that made at the beginning of printing.

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Example 5

Using an aluminum plate, which had been roughened in the same way as in Example 1, as an anode, an aqueous solution containing 0.25 mol per liter of oxalic acid and 0.25 mol per liter of potassium oxalate was added anodic electrolysis was carried out at a temperature of ^ A- ⁰ C and a direct current density of 2 A / dm 4 LIinuton. A lead cathode was used / ended. The amount of anodic acid film produced was 3.2 g / in. The aluminum plate obtained in this way was subjected to the following treatment under the conditions given in Table TII below _: j underv; orf en.

ORIGINAL INSPECTED 509842/0925

Table III

Cathodic treatment- Kat h ο der; βt ro nd.i cht ο (■■ / φι ") Electrolysis time (sec.) 0 1 2 ^l '- conditions *

Good Good

example 2O ⁰ G, 45 solved Well 2 -ο Hatriunitri- get rid of ** phosphate 60 ° G, 80 Il ti 5 % sulfur acid 65 ⁰ G 100 It Il 1 yi oxalic acid 4O ⁰ G, 30th It Il 1 % sodium carbonate 40 ⁰ G, 30th Il Il 1 ';'■> Natri UEi- polyphosphate 50 ° G. " 30th II M.

1 ';') phosi) boric acid

Yergl, -beisniel

50 ° C, 120 »

4 % phosphoric acid

70 ⁰ G, 30 good 4 ^c / o phosphoric acid

50 ⁰ G '30 "20 Ji phosphoric acid

* 32s • Was a v / aqueous solution of the electrolyte used ** Film liability

509842/0925

Then the treatment with sodium silicate, the application the primer layer, the application of the photosensitive Solution, exposure and development carried out as in Example 1. The adhesion of the photosensitive The development layer is given in Table III above, i.e. when the support is not according to the invention Was subjected to treatment, the image surfaces came off just by gently rubbing them with your Developer impregnated absorbent whole tree cloth from the aluminum surface, while the carrier, which has been subjected to the treatment according to the invention, the film adhesion (five strength) firm and good v / ar.

In carrying out the erfindungsgemänen treatment using a '+ ^ weight phosphoric acid at 5O ° C, a carrier is, for example, within 30 seconds of having excellent adhesion properties, while use of in the above-mentioned patent specifications, that is, in German Offenlegungsschrift 2,251,710, in the Belgian patent 797 180 and in the US patent ame Idling ITr. 360 480, and using the same treatment solution, no carrier with excellent adhesive properties was obtained even within 120 seconds. At this concentration, a carrier having excellent adhesive properties was obtained only when the temperature was increased by 15 ° C. to 65 ° C. and the treatment was carried out for 30 seconds. Even when using a phosphoric acid solution of 30 ⁰ G to produce a carrier with good adhesion properties, which were equivalent to those obtained according to the invention, a 3 ^U second treatment with a phosphoric acid solution with a concentration of 20 ^c , '-> was necessary .

A printing plate made using the invention according to the invention.

509842/0925

The carrier produced according to the method was attached to a printing device (Heider GTO) and thus v / urde printed, whereby the 50,000th print (imprint) had a good color density similar to that which the had received prints at the start of printing.

Example 4-

In the same manner as in Example 1, an aluminum plate was roughened and. provided with an anodic oxide coating film. The aluminum plate obtained in this way was subjected to cathodic electrolysis under the conditions given in Table IY below, the aluminum concentration in the phosphoric acid solution being increased. The aluminum ion concentrations were 0%, 0.3 / ', 0.6 ^c ; o and 1.0 ⁰ A.

Table IV

Treatment conditions _ Aluniniumionenkonzontra-

Electric time advice (Gew.-fQ

(Sec.) Denstrom- _{n n 7 n A Λ} density ^{ü υ} '^ ^u ' ^b '»

lyt

Beisi) iel

5? O phosphoric acid

JO

Well

well well well

Compare-example

70 ⁰ G, 20 3% phosphoric acid

Well

peeled peeled peeled peeled off

Pilm adhesion

The aluminum support thus obtained was using a centrifugal device a clear polvvinvl - cinnamate resin (Handelsbeseiclinunfj; Kodak Photo Hesist, a

509842/0925

Product of Kodak Eastnan Go.) Applied in the form of a layer and dried for 2 minutes at 10O ⁰ C.

The amount of the photosensitive resin applied was 1j5 CiAi · The photosensitive printing plate obtained in this way was through an original transparent image for 3 minutes with the radiation from a 30 Aupere carbon arc lamp exposed at a distance of 70 cm. Then the printing plate in iithyleneglykolnonomethylätheracetat at room temperature dipped and by gently rubbing the image areas with an organic solvent mentioned above impregnated absorbent cotton cloth. The adhesion of the image areas to the support during development is indicated in Table IV above, ", 'emi the carrier according to the ancestor according to the invention had been treated, was the Adhesion of the image areas good, even if the aluminum ion concentration increases -.rarde, while with the carrier, which only had been subjected to an immersion treatment, the adhesion of the image areas increased as the aluminum ion concentration increased decreased and these eventually detached from the carrier.

One using the method according to the invention The printing plate made of the carrier produced was attached to a printing device (Heider GTO) and therewith was attached printed, whereby the 30,000th print (impression) was still as good as the prints received at the beginning of the printing.

Although the invention has been preferred with reference to FIG Embodiments explained in more detail, but it is for it goes without saying to the person skilled in the art that it is by no means restricted thereto, but that it is modified in many ways and can be modified without departing from the faucets of the present invention.

Pat ent ansnr " clv- ·:

509842/0925 originally inspected

Claims (3)

Claims ⁵ 1. / A method for producing a support for a printing plate, characterized in that nan subjects an aluminum plate to anodic oxidation and then subjects the aluminum plate, which has an anodic oxide film coating, to cathodic electrolysis in an acidic or basic solution. 2. The method according to claim 1, characterized in that the aluminum plate is a pure aluminum plate or a Aluraini unalloy plate used. 3. The method according to claim 1 and / or 2, characterized in that the anodic oxide film coating by anodic Oxidation at an acid concentration of about 1 to about 80 Ge "/.-/?, a solution temperature of about 5 to about 70 G, a direct current dielite from about 0.5 to about 60 A / dm, a voltage of about 1 to about 100 V and an electrolysis time of about 30 seconds to about 5 ° minutes. 4 ·. Method according to at least one of claims 1 to 3 _? characterized in that the cathodic electrolysis is carried out at an acid or base concentration of about 0.1 to about 70% by weight, a treatment temperature of about 0 to about 70 °, an electrolysis time of about 1 to about 600 seconds and at an Eathodonstra density of about 0.05 to about 20 A / dm ² . 5 »method according to claim 4, characterized in that nan the cathodic electrolysis in an acid odor Basonkonzentration of 0.5 to 30 parts by weight vj, a Bohandlungctcrriperatur from 5 to 40 ⁰ C, einor Eleiktrolyscdriuer from 3 to 3OO Seirunden and a cathode current density of 0.1 to 10 A / cba ^2. " 509842 / Ö925 ORIGINAL INSPECTED