EP0689941A1 - Hydrophilized support material and recording material produced therewith - Google Patents

Abstract

A mechanically and/or electrochemically roughened, and opt. anodically oxidised, carrier is made of aluminium or its alloys. The carrier carries a hydrophilic layer made from at least one polymer with basic and acidic groups. On the layer is a further hydrophilic layer that contains at least one compound with at least one phosphono group. Also claimed a process for the prodn. of the carrier; and a recording material with a radiation sensitive layer on the carrier.

Description

The invention relates to a mechanically and / or electrochemically roughened and optionally anodically oxidized carrier material made of aluminum or its alloys with a hydrophilic layer of at least one polymer with basic and acidic groups and a radiation-sensitive recording material with a carrier and a radiation-sensitive layer from which offset printing plates are produced can.

Carrier materials for offset printing plates are provided with a light-sensitive layer (copying layer), with the help of which a printing image is generated by photomechanical means. After the printing image has been produced, the support carries the printing image areas and at the same time forms the hydrophilic image background for the lithographic printing process in the non-image areas (non-image areas).

• Die nach der Belichtung relativ löslichen Teile der lichtempfindlichen Schicht müssen während des Entwickelns leicht und rückstandsfrei vom Träger zu entfernen sein, um die hydrophilen Nichtbildstellen zu erzeugen. Eventuell auf dem Träger noch anhaftende Reste der Schicht sind als Farbschleier zu erkennen, da lichtempfindliche Schichten im allgemeinen intensiv gefärbt sind. Die Folge davon ist, daß die Druckplatte an diesen Stellen "tonen" kann.
• Die Druckplatten sind nach dem Belichten und Entwickeln häufig noch zu korrigieren, wobei unerwünschte Bildanteile abgelöst werden. Die dabei freigelegten Nichtbildbereiche sollen sich in Farbe und Helligkeit nicht von den durch den Entwickler freigelegten Nichtbildbereichen unterscheiden. Die gleichmäßige Helligkeit ist notwendig, um Meßgeräte einsetzen zu können, mit denen der Anteil der Fläche der Bildbereiche über den Helligkeitsunterschied zwischen Bild- und Nichtbildbereichen ermittelt wird.
  Die unerwünschte Helligkeitsdifferenz zwischen einer durch Korrektur und einer während des normalen Entwicklungsvorgangs entstandenen Nichtbildstelle wird als Korrekturkontrast bezeichnet.
• Der in den Nichtbildstellen freigelegte Träger muß ausreichend hydrophil sein, um beim lithographischen Druckvorgang schnell und dauerhaft Wasser anzunehmen, das die fette Druckfarbe abstößt.
• Die lichtempfindliche Schicht vor bzw. der druckende Teil der Schicht nach der Belichtung darf sich nicht vom Trägermaterial ablösen.

Aluminum, steel, copper, brass or zinc, but also plastic films or paper are suitable as the base material for such layer supports. Aluminum and its alloys have established themselves in the printing plate field. The surface of the raw material is roughened mechanically, chemically and / or electrochemically by known methods and, if necessary, anodically oxidized. However, such pretreatments are not sufficient for substrates to meet the following requirements:

• The parts of the photosensitive layer which are relatively soluble after exposure must be able to be removed easily and without residue from the support during development in order to avoid the hydrophilic non-image areas to create. Any residues of the layer still adhering to the support can be recognized as a color haze, since light-sensitive layers are generally intensely colored. The result of this is that the printing plate can "tone" at these points.
• The printing plates often have to be corrected after exposure and development, whereby undesired parts of the image are removed. The color and brightness of the exposed non-image areas should not differ from the non-image areas exposed by the developer. The uniform brightness is necessary in order to be able to use measuring devices with which the proportion of the area of the image areas is determined via the difference in brightness between image and non-image areas.
  The undesired difference in brightness between a non-image area created by correction and a non-image area created during the normal development process is referred to as correction contrast.
• The carrier exposed in the non-image areas must be sufficiently hydrophilic to quickly and permanently accept water during the lithographic printing process, which repels the bold ink.
• The light-sensitive layer before or the printing part of the layer after exposure must not detach from the carrier material.

Usually, the carrier material is additionally hydrophilized, because otherwise it would not accept enough water. The hydrophilizing agent must be sensitive to the particular light Layer should be coordinated to avoid undesirable reactions and not to impair the adhesion.

Depending on the light-sensitive layer, the developer solutions or correcting agents, the known hydrophilization methods have more or less major disadvantages. After treatment with alkali silicates, which lead to good developability and hydrophilicity, the photosensitive layers must deteriorate after a long period of storage. When treating carrier materials with water-soluble polymers, their good solubility - especially in aqueous-alkaline developers, as they are mainly used to develop positive-working layers - leads to a marked weakening of the hydrophilizing effect. In the case of polymers which contain sulfonic acid groups, it has a negative effect that free anionic acid functions can interact with the diazo cations of negative-working photosensitive layers, so that after development on the non-image areas, a clear color fog can be seen due to retained diazo compounds. Polymeric acrylic acid derivatives are disadvantageous because they are very viscous in the application form in which they can prevent color fog, ie in a solution of 0.1 to 10 g / l, and an excess can only be removed from the surface of the support with great effort . Highly light-sensitive layers which are used for imaging with lasers (EP-A 0 364 735) and which are a polymer binder, a free-radically polymerizable compound with at least one polymerizable group and a photo-reducible dye, a trihalomethyl compound which can be cleaved by radiation and are particularly susceptible to the formation of color fog a metallocene compound included as photoinitiators. There are therefore particularly high demands on the hydrophilic carrier material, so that no constituents of the layer remain at the non-image areas.

From DE-C 11 34 093 (≈ US-A 3 276 868) and US-A 4 153 461 it is known to hydrophilize the support material with phosphonic acids, in particular with polyvinylphosphonic acid or copolymers of vinylphosphonic acid with acrylic acid and vinyl acetate. It is also mentioned that salts of phosphonic acids are suitable. However, this is not specified.

EP-A 0 069 320 (= US-A 4 427 765) describes a process for hydrophilizing an aluminum support material for planographic printing plates, in which salts of polyvinylphosphonic acids, polyvinylsulfonic acids, polyvinylmethylphosphinic acids and other polyvinyl compounds with at least divalent metal cations are used.

According to EP-A 0 190 643, the carrier material is coated with a homopolymer of acrylamidoisobutylenephosphonic acid or a copolymer of acrylamidoisobutylenephosphonic acid and acrylamide or with a salt of this homo- or copolymer with an at least divalent metal cation. The coating has the advantage that the finished printing plates show good hydrophilicity at the non-image areas and have a reduced color haze.

EP-A 0 490 231 describes the treatment of printing plate supports with polyethyleneimines which contain structural elements of the type - (CH₂-CH₂-N (X) -) _n - or with polyvinylamines, the structural elements of Type - (CH₂-CH (NY¹Y²) -) _n - contain, where X, Y¹ and Y² are optionally C-substituted sulfomethyl groups or phosphonomethyl groups. But even with this method, optimal results are not yet achieved.

• sehr gute Hydrophilierungseigenschaften aufweisen,
• für alle lichtempfindliche Schichten gleichermaßen geeignet sind, ohne daß die lichtempfindliche Schicht bei längerer Lagerung durch Reaktionen mit dem Hydrophilierungsmittel beeinträchtigt wird, und
• eine sehr gute Haftung zu den druckenden Teilen der Schicht besitzen.

The object of the present invention is therefore to produce substrates for offset printing plates which

• have very good hydrophilization properties,
• are equally suitable for all light-sensitive layers without the light-sensitive layer being impaired by reactions with the hydrophilizing agent in the event of prolonged storage, and
• have very good adhesion to the printing parts of the layer.

The object is achieved by a mechanically and / or electrochemically roughened and optionally anodically oxidized support material made of aluminum or its alloys with a hydrophilic layer of at least one polymer with basic and acidic groups, characterized in that the layer is followed by a further hydrophilic layer which contains at least one compound with at least one phosphono group.

The basic groups in the polymer of the first hydrophilic layer are preferably primary, secondary or tertiary amino groups, the acidic groups are preferably carboxy, phosphono or sulfo groups. The secondary and tertiary amino groups can also be part of the main polymer chain. The sulfomethylated or phosphonomethylated polyethyleneimines and polyvinylamines described in EP-A 0 490 231 are particularly preferred for this first hydrophilic layer. These polymers can also contain units from other monomers contain, for example units from substituted amino acrylates, vinyl pyrrolidones or vinyl imidazoles. Polymers with units of dialkylaminoalkyl (meth) acrylate and (meth) acrylic acid are also particularly preferred. Of these polymers, a terpolymer with units of dimethylaminomethyl methacrylate, ethyl acrylate and methacrylic acid has proven particularly useful. The polymers in the first layer are neither strongly acidic nor strongly alkaline. Their pH is approximately in the range from 4 to 9, preferably 4.5 to 7.5.

In contrast, the compounds with at least one phosphono group used for the further hydrophilic layer are clearly acidic. They generally have a pH of less than 4, preferably 1 to 3, in aqueous solution. These compounds are also preferably polymeric, the polyvinylphosphonic acid described in US Pat. No. 4,153,461 being particularly suitable.

The sequence of the hydrophilizing layers is surprisingly of crucial importance for the quality of the product. There is no proven explanation for this, but there are hypothetical ideas. It is believed that the layer of at least one polymer with acidic and basic groups creates adsorption sites to which the connection with at least one phosphono group then attaches to a greater extent than would be the case without this activation. This is plausible insofar as various surface-sensitive methods such as energy dispersive X-ray (EDX), Auger electron spectroscopy, electron spectroscopy for chemical analysis (ESCA) and secondary ion mass spectroscopy (SIMS) can be used to demonstrate that only with this order of the layers, a particularly large amount of the active ingredients is drawn onto the surface of the carrier. The Hydrophilic layers can be continuous or discontinuous.

Finally, part of the present invention is also a method for producing the carrier materials. The two hydrophilizing layers can be applied by spraying on the corresponding solutions or by immersing them in such solutions. The concentration of the hydrophilizing compounds in these solutions can vary within wide limits. However, solutions with a concentration of 0.1 to 50 g / l, preferably 0.3 to 5 g / l, have proven to be particularly advantageous.

After the first hydrophilic layer has been applied, the material can be rinsed off to remove the unnecessary hydrophilizing agent. Drying between the two stages is not necessary, but it also does no harm. Coating can be done at temperatures from 20 to 95 ° C, but temperatures from 30 to 65 ° C are preferred. The material to be coated is generally sprayed or immersed for 1 s to 5 min. It is disadvantageous if the treatment time is shorter than 1 s, but not if it is more than 5 min.

The second hydrophilic layer is applied in generally the same way as the first. The spray or immersion solutions used have approximately the same concentration.

After the two treatment steps, the coated carrier is expediently dried at temperatures from 100 to 130 ° C.

The determination of the weight of the applied hydrophilic coating is problematic since even small amounts of the product show a clear hydrophilizing effect. The hydrophilizing agents also adhere relatively strongly to the surface of the carrier material. However, the amount applied is in any case below 0.5 mg / dm², in particular below 0.25 mg / dm². The minimum amount is about 0.02 mg / dm². The quantities given apply individually to each of the two levels.

The modified polyethyleneimine and the modified polyvinylamine and processes for their preparation are described in EP-A 0 490 231. They are generally made from polyethyleneimines and polyvinylamines by phosphonomethylation and / or sulfomethylation.

The carrier materials according to the invention can then be coated with various light-sensitive mixtures. In principle, all mixtures are suitable which produce layers which, after imagewise exposure, subsequent development and / or fixing, give a positive or negative image. At the non-image areas, the material suitable as a printing plate retains its excellent hydrophilicity and practically no longer shows any color fog.

The present invention therefore also relates to a recording material with a support made of aluminum or its alloys and a radiation-sensitive layer, which is characterized in that the support is hydrophilized as described above.

The following examples are intended to illustrate the invention without restricting it in any way. In this the following roughened and anodized plate carriers are used:

Type 1

0.3 mm thick bright rolled aluminum (DIN material no. 3.0255) was degreased with a 2% aqueous NaOH pickling solution at a temperature of 50 to 70 ° C. The electrochemical roughening of the surface was then carried out with alternating current in an electrolyte containing HNO 3. The R _z value of the surface roughness was then 6 μm. The subsequent anodic oxidation was carried out in an electrolyte containing sulfuric acid. The oxide layer weight was about 3.0 g / m².

Type 2

0.3 mm thick bright rolled aluminum (DIN material no. 3.0515) was degreased with a 2% aqueous NaOH pickling solution at a temperature of 50 to 70 ° C. The surface was electrochemically roughened using alternating current in an electrolyte containing hydrochloric acid. The R _z value of the surface roughness was then 6 μm. The subsequent anodic oxidation was carried out in an electrolyte containing sulfuric acid. The oxide layer weight was about 2.0 g / m².

Type 3

0.2 mm thick bright rolled aluminum (DIN material no. 3.0255) was degreased with a 2% aqueous NaOH pickling solution at a temperature of 50 to 70 ° C and then mechanically roughened with cutting grains (e.g. quartz powder or aluminum oxide). The R _z value of the surface roughness was then 4 μm. The subsequent anodic oxidation was carried out in an electrolyte containing phosphoric acid. The oxide layer weight was about 0.9 g / m².

Type 4

This carrier corresponds to that of type 2, with the only difference that it has been anodized up to an oxide layer weight of 1.5 g / m 2.

The following examples show the advantages of the carrier material according to the invention. The hydrophilizations A * to D * according to Table 1 were used for the comparative experiments, while the support material according to the invention was hydrophilized according to E. Table 1 Hydrophilization A * none B * with polyvinylphosphonic acid (2 g / l at 75 C, pH 2) C * with N-phosphonomethyl-polyethyleneimine (1 g / l at 65 C, pH 4.5) D * first B), then C) E first C), then B)

example 1

A carrier of type 2 was hydrophilized in accordance with Table 1 and consisting of a positive working diazo layer
5.00% by weight cresol-xylenol-formaldehyde novolak resin with a hydroxyl number of 420 according to DIN 53783/53240 and a weight average according to GPC of 6000 (polystyrene standard),
1.20% by weight of ester from 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and 1 mol of 2,3,4-trihydrorybenzophenone,
0.15% by weight of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride,
0.05% by weight victoria pure blue (CI 44045) and
ad 100% by weight of a solvent mixture of methyl ethyl ketone and propylene glycol monomethyl ether (40/60)
Mistake. The coated support was dried at 125 ° C for 1 min. The film weight was 2.4 g / m². A matting solution (a 20% aqueous solution of a terpolymer of vinylsulfonic acid, ethyl acrylate and styrene) was then sprayed electrostatically onto the radiation-sensitive layer in such a way that the mean height of the elevations was 4 μm.

The plates were contacted in a vacuum contact copier frame by evacuation with a test assembly, exposed with a 5kW metal halide-doped mercury vapor lamp at a distance of 110 cm so that an open step 4 resulted in the UGRA offset test wedge after development, which led to high exposure Film edge removal corresponds.

Developed at 20 ° C in a developing device (VA86 from Hoechst AG) with a potassium silicate developer (total alkali content 0.5 mol / l, ratio K₂O: SiO₂ = 1: 1.2, later referred to as "developer type 1") a processing speed of 1.4 m / min.

The occurrence of residual layer fog was investigated after a developer load of 4 m² of recording material (25% image share) per liter of developer. The results are shown in Table 2.

Example 2

• 1. Belichten an einem Kopierrahmen wie in Beispiel 1 durch eine Testvorlage , 60 s,
• 2. Tempern bei 135 °C in einem Durchlaufofen, 60 s
• 3. Abkühlen mit Umluft, 10 s,
• 4. Ausbelichten ohne Vorlage mit UV-A-Leuchtstofflampen einer Strahlungsleistung von 240 Watt, 30 s in einem Durchlaufgerät,
• 5. Entwickeln in einem Gerät wie in Beispiel 1 bei einer Verarbeitungsgeschwindigkeit von 1,2 m/min.

A type 1 support was hydrophilized in accordance with Table 1 and comprised of a reversible positive layer
4.80% by weight cresol-xylenol-formaldehyde novolak resin with a hydroxyl number of 420 according to DIN 53783/53240 and a weight average according to GPC of 6000 (polystyrene standard),
1.05% by weight of ester from 3.4 mol of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1 mol of 2,3,4,2 ', 3', 4'-hexahydroxy-5,5 ' -dibenzoyldiphenylmethane,
0.05% by weight of 2- (4-styrylphenyl) -4,6-bis-trichloromethyl-s-triazine,
0.10% by weight crystal violet (CI 42555),
1.00% by weight of silica filler with an average grain size of 3.9 µm,
0.10% by weight surfactant based on dimethylsiloxane and ethylene oxide units and
ad 100 wt .-% of a solvent mixture of tetrahydrofuran and propylene glycol monomethyl ether (55/45).
Mistake. The coated support was dried at 125 ° C for 1 min. The film weight was 1.8 g / m². Thereafter, the processing was continued as follows:

• 1. Exposing on a copying frame as in Example 1 through a test template, 60 s,
• 2. Annealing at 135 ° C in a continuous furnace, 60 s
• 3. cooling with circulating air, 10 s,
• 4. exposure without original with UV-A fluorescent lamps with a radiation power of 240 watts, 30 s in a continuous flow device,
• 5. Develop in a device as in Example 1 at a processing speed of 1.2 m / min.

It was with a sodium silicate developer according to DE-A 40 27 299 with a total alkali content of 0.8 mol / l (Na₂O: SiO₂ = 1: 1) and a content of O, O'-bis-carboxymethyl-polyethylene glycol-1000 of 0 , 6 wt .-% (hereinafter referred to as "developer type 2") developed.

The occurrence of residual layer fog was investigated after a developer load of 2 m² of recording material (25% image share) per liter of developer. The results are shown in Table 2.

Example 3

A type 4 printing plate support was subjected to the four different post-treatments mentioned in Table 1 and provided with a negative working layer of the following composition:
2.5% by weight of a copolymer of methacrylic acid / methyl methacrylate / glycerol monomethacrylate (20/30/50) with an average molecular weight M _w of 24,000 (GPC),
0.5% by weight of a diazonium salt polycondensation product of 1 mol of 4-anilino-2-methoxy-benzene diazonium sulfate and 1 mol of 4,4'-bismethoxymethyl-diphenyl ether, precipitated as mesitylene sulfonate,
0.09% by weight victoria pure blue FGA (Basic Blue 81),
0.07% by weight of benzenephosphonic acid,
0.1% by weight of a silica gel filler with an average grain size of 3 µm and
ad 100 wt .-% of a solvent mixture of tetrahydrofuran and ethylene glycol monomethyl ether (40/60).

The coated supports were dried at 120 ° C. in the drying tunnel. The dry layer weight was 1.4 g / m². The reproduction layer was exposed for 35 s under a negative original with a 5 kW metal halide lamp and developed with the following solution at 23 ° C. in a developing machine with a rub-out element at 1.4 m / min:
5% by weight sodium lauryl sulfate,
2% by weight phenoxyethanol,
1 wt .-% sodium metasilicate x 5H₂O and
92% by weight of water
The occurrence of residual layer fog is investigated after a developer load of 4 m² per liter developer.

The hydrophilization E of the carrier according to the invention also proved to be more advantageous here.

Example 4

A type 3 support was hydrophilized according to Table 1 and coated with the following solution:
3.1% by weight of 2,5-bis (4-diethylamino-phenyl) -1,3,4-oxadiazole,
3.1% by weight of a copolymer of styrene and maleic anhydride with a softening point of 210 ° C.,
0.02% by weight ^(R) rhodamine FB (CI 45 170),
ad 100 wt .-% ethylene glycol monomethyl ether.
and then dried in a continuous drying oven at 120 ° C. The layer was negatively charged in the dark with a corona to 450 V, the charged plate was exposed imagewise in a repro camera and then with an electrophotographic suspension developer from a dispersion of 0.6% by weight of magnesium sulfate and a solution of 1.4% by weight. % Pentaerythritol resin ester developed in 98 wt .-% of an isoparaffin mixture with a boiling range of 185 to 210 ° C. After removing the excess developer liquid, the toner was fixed and the plate at 24 ° C in a solution
10% by weight ethanolamine,
10% by weight propylene glycol monophenyl ether,
2% by weight K₂HPO₄,
ad 100 wt .-% water
decoated at a processing speed of 1.4 m / min. The plate was then rinsed off with a powerful jet of water to remove the remainder of the stripper. The occurrence of residual layer veil was investigated after a stripper load of 10 m² per liter of stripper with an image proportion of 25%.

Example 5

A type 1 support was hydrophilized according to Table 1 and a solution of the following composition was spin-coated so that a layer weight of 2.5 g / m 2 was obtained in each case:
10.7% by weight of the terpolymer solution given in Example 3,
5.3% by weight of triethylene glycol dimethacrylate,
0.15% by weight orasol blue (CI 50 315),
0.15% by weight eosin, alcohol-soluble (CI 46 386),
0.11% by weight of 2,4-bis-trichloromethyl-6- (4-styrylphenyl) -s-triazine,
0.23% by weight of dicyclopentadienyl-titanium-bis-pentafluorophenyl,
42% by weight of butanone and
ad 100% by weight of butyl acetate.

After drying, the plate was then coated with a layer of polyvinyl alcohol, exposed and developed.

+

kein Restschichtschleier, Densitometermeßwert < 0,01

0

leichter Restschichtschleier, Densitometermeßwert 0,01-0,02

-

Pestschichtschleier vorhanden, Densitometermeßwert > 0,02

Tabelle 2 Hydrophilierung Bewertung der Beispiele 1 2 3 4 5 A* - - - - - B* 0 0 0 0 0 C* 0 0 0 0 0 D* 0 0 0 0 0 E + + + + + The recording materials of Examples 1 to 5 were assessed densitometrically (incident light densitometer, magenta or cyan filter) as follows:

+

no residual layer curtain, densitometer value <0.01

0

slight residual layer veil, densitometer reading 0.01-0.02

-

Pitch layer curtain present, density reading> 0.02

Table 2 Hydrophilization Evaluation of the examples 1 2nd 3rd 4th 5 A * - - - - - B * 0 0 0 0 0 C * 0 0 0 0 0 D * 0 0 0 0 0 E + + + + +

Examples and comparative examples

Examples 6 to 34 (Table 6/7) are intended to show the superiority of the supports according to the invention over the supports of Comparative Examples V1 to V52 hydrophilized according to Tables 1, A to D. The recording materials produced according to the conditions given in the tables were examined as follows:

1. Measurement of the color haze:

Both in a sample of the uncoated support and in the non-image areas after coating, exposure and development, the reflection of the non-image areas was measured in the range of visible light. The two-channel simultaneous spectrometer MCS512 from Datacolor was used. Using the measurement results, the brightness L * of the carrier surface was calculated in accordance with CIE (Commission International de l'Eclairage, publication No. 15). Details of these calculations are described in DIN standards 6174 (1979) and 5033 (1970). In the present case, the illuminant D65 was used and a 2 ° observer was used for the calculations, contrary to the recommendation by CIE. This brightness of the uncoated substrate is given in column 6 of the following tables. In practice, these calculations automatically include the color measures a * and b *, which, however, run parallel to the values of the brightness measure L * in the relevant tests on printing plate supports and were therefore not taken into account. After these calculations, the difference in brightness before coating and in the non-image areas after coating, exposure and development was calculated. Since the photosensitive layers are colored dark in practice (compared to the light gray support surfaces), undesired layer residues became a dark haze in the non-image areas to make noticable. The brightness of the non-image areas after coating, exposure and development would be lower than that before coating. When forming the difference, a positive numerical value dL * resulted, which would be greater the more pronounced the undesired color haze is. This value is given in column 7 of table 3.

Depending on the exercise of the observer and his eye sensitivity, color veils are visible from a measured value of around 0.8. In any case, they represent a cosmetic defect in the printing plate and can therefore lead to complaints by the buyers. Should the color veil become very intense, this is an indication of a large amount of layer residues in the non-image areas, which can possibly lead to unwanted printing (toning), especially if, as is often desired, little dampening solution is dosed. An exact value of the color veil for this case cannot be given.

2. Measurement of the correction contrast:

The non-image area of a printing plate was treated with a commercially available correction agent. The brightnesses were then measured, once in the corrected and once in the uncorrected area. here too the difference dL * was formed. If it is significantly different from 0, that is to say in the range from 0.5 to 1, the correction means has either been able to remove layer residues from the surface or has even attacked and damaged the surface of the non-image area itself.

3. Determination of hydrophilicity:

The non-image area of a printing plate was coated with ink using a rubber hand roller, placed in water and the time required for the water to detach the ink from the non-image area. This time must not exceed 30 s for a well hydrophilic carrier.

Comparative Examples V1 to V52

Carriers of types 1 and 2 were anodized and treated with an aqueous solution of a polyvinylphosphonic acid in an immersion bath for 5 seconds. The conditions are given in Table 3. After the treatment with polyvinylphosphonic acid, the plates were coated with the solution given in Example 1, exposed and developed with a developer of types 1 or 2 in the above-mentioned developing device VA86. Table 3 No. carrier developer temperature concentration brightness Color veil Correction contrast Hydrophilicity Type Type ° C g / l L * dL * 1 dL * 2 s V 1 1 1 40 2.0 77.83 1.13 1.49 V 2 1 1 50 2.0 77.87 0.70 1.43 V 3 1 1 60 2.0 77.28 0.16 1.08 V 4 1 1 40 5.0 77.95 2.15 2.01 V 5 1 1 50 5.0 77.87 1.36 1.49 V 6 1 1 60 5.0 77.87 1.04 1.54 V 7 1 2nd 40 5.0 77.84 2.14 1.94 15 V 8 1 2nd 50 5.0 78.00 1.96 2.01 15 V 9 1 2nd 60 5.0 77.49 0.81 1.51 5 V10 2nd 1 40 5.0 79.10 3.46 2.81 15 V11 2nd 1 50 5.0 79.02 2.21 1.91 15 V12 2nd 1 60 5.0 78.94 2.30 2.22 5

Table 3 shows that the printing plates not produced according to the invention in the non-image areas have a sufficiently good hydrophilicity (insofar as they have been determined), but either have a clear color haze or suffer an attack by the correction agent, which leads to discoloration in the non-image areas, or both appearances. Although two different types of carrier were used and two different developers were used, none of the combinations mentioned in the table is able to show good results in all properties.

The recording materials according to Table 4 were produced with a type 2 support and treated with a phosphonomethylated polyimine according to EP-A 0 490 231. This polymer had a molecular weight M _w of about 80,000. Table 4 No. temperature concentration brightness Color veil Correction contrast Hydrophilicity ° C g / l L * dL * 1 dL * 2 s V13 22 2.0 78.93 2.08 1.75 5 V14 30th 2.0 78.94 0.96 1.28 15 V15 40 2.0 78.95 0.86 1.13 5 V16 50 2.0 79.02 0.53 0.80 5 V17 60 2.0 79.00 0.41 0.76 5 V18 22 1.0 78.97 2.31 1.88 5 V19 30th 1.0 79.01 0.67 0.96 5 V20 40 1.0 78.44 0.57 1.08 5 V21 50 1.0 79.00 0.51 0.62 15 V22 60 1.0 78.96 0.25 0.57 15 V23 22 0.5 79.05 2.06 0.98 5 V24 30th 0.5 79.02 1.20 0.95 5 V25 40 0.5 79.00 1.09 0.36 5 V26 50 0.5 78.96 0.12 0.46 5 V27 60 0.5 78.93 0.12 1.40 5 V28 22 0.2 78.98 2.67 1.89 5 V29 30th 0.2 79.05 2.53 1.74 5 V30 40 0.2 78.97 2.88 1.83 15 V31 50 0.2 79.01 2.53 1.66 5 V32 60 0.2 78.92 2.58 1.35 5

With these printing plates, which all show good hydrophilicity in the non-image areas, the measured values for the color haze and / or the correction contrast are unsatisfactory. V26 has good values, but does not fit into the course of the other samples and must therefore be rated as an outlier. This type of carrier treatment cannot be carried out in a statistically controlled manner and is not suitable for a safe production process.

The same applies to the comparative examples in Table 5. Here supports of type 2 were first treated in succession with a solution of polyvinylphosphonic acid in water and - after a rinsing step - with a solution of the above-mentioned phosphonomethylated polyimine. The diving time in both baths was 5 s. Concentration 1 given in the table is the concentration of polyvinylphosphonic acid, concentration 2 is that of phosphonomethylated polyimine.

Here too, the values of the color haze and the correction contrast are generally too high. There are some good results here too (V34, V36 and V38) and in some pairs there is a tendency to improve at higher temperatures, but this is not always reliable. Therefore, this type of carrier treatment is not suitable for the safe management of a production process. Table 5 No. temperature Concentration 1 Concentration 2 brightness Color veil Correction contrast Hydrophilicity ° C g / l g / l L * dL * 1 dL * 2 s V33 40 2.2 2.0 78.94 0.62 0.98 15 V34 60 2.2 2.0 78.98 -0.08 1.46 5 V35 40 2.2 1.0 79.20 0.83 1.00 5 V36 60 2.2 1.0 79.07 -0.03 1.45 5 V37 40 2.2 0.5 79.10 1.28 1.44 5 V38 60 2.2 0.5 79.09 0.01 0.52 5 V39 40 2.2 0.2 79.19 2.15 2.15 5 V40 60 2.2 0.2 78.97 0.66 1.17 5 V41 40 2.2 0.1 79.17 2.19 2.19 5 V42 60 2.2 0.1 78.63 1.56 1.84 5 V43 40 1.0 10.0 78.83 0.25 1.14 15 V44 60 1.0 10.0 78.93 0.23 0.93 15 V45 40 0.5 5.0 78.98 3.07 2.59 5 V46 60 0.5 5.0 78.97 2.41 2.67 5 V47 40 0.2 0.5 79.08 2.00 1.28 5 V48 60 0.2 0.5 79.02 1.36 0.53 5 V49 40 0.1 0.2 78.99 1.94 1.19 5 V50 60 0.1 0.2 79.07 2.65 1.53 15 V51 40 0.1 0.1 79.16 3.17 2.91 5 V52 60 0.1 0.1 79.11 3.03 2.47 5

Examples 6 to 34

Carriers of type 2 in Table 6 and of type 4 in Table 7 were first immersed in an aqueous solution of the phosphonomethylated polyimine and then - after a rinsing step - in an aqueous solution of polyvinylphosphonic acid for 5 s. Diving times of up to a few minutes have the same effect. However, a minimum immersion time of 1 s per bath must be observed. Table 6 No. temperature Concentration 1 Concentration 2 brightness Color veil Correction contrast Hydrophilicity ° C g / l g / l L * dL * 1 dL * 2 s 6 40 3.94 4.00 77.85 -0.35 0.05 15 7 50 3.94 4.00 77.51 -0.74 0.00 5 8th 60 3.94 4.00 77.53 -0.61 0.07 5 9 40 2.63 2.00 77.54 -0.13 0.33 5 10th 50 2.63 2.00 77.62 -0.44 0.23 5 11 60 2.63 2.00 77.56 -0.66 0.00 5 12th 40 1.32 1.00 77.65 -0.02 0.47 5 13 50 1.32 1.00 77.72 0.09 0.41 5 14 60 1.32 1.00 77.62 -0.48 0.11 5 15 40 0.53 0.25 77.87 0.26 0.56 5 16 50 0.53 0.25 77.88 -0.04 0.27 5 17th 60 0.53 0.25 77.85 -0.12 0.21 5 18th 40 0.20 4.00 77.62 0.10 0.69 15 19th 50 0.20 4.00 77.83 0.33 0.82 15 20th 60 0.20 4.00 77.85 -0.09 0.60 15 No. temperature Concentration 1 Concentration 2 brightness Color veil Correction contrast Hydrophilicity ° C g / l g / l L * dL * 1 dL * 2 s 21 40 0.50 4.00 79.05 0.99 0.71 5 22 50 0.50 4.00 79.10 0.60 0.31 5 23 60 0.50 4.00 79.04 0.40 0.30 5 24th 40 0.50 2.00 79.11 0.55 0.34 5 25th 50 0.50 2.00 79.09 0.38 0.14 5 26 60 0.50 2.00 79.15 0.31 0.08 5 27 40 1.00 2.20 79.28 0.22 0.55 5 28 50 1.00 2.20 79.31 0.29 0.53 5 29 60 1.00 2.20 79.29 0.25 0.50 5 30th 40 0.50 2.20 79.40 0.45 0.44 5 31 50 0.50 2.20 79.41 0.33 0.34 5 32 60 0.50 2.20 79.39 0.18 0.40 5 33 50 0.20 2.20 79.32 0.72 0.74 5 34 60 0.20 2.20 79.36 0.81 0.72 5

It can be seen that good values for color fog and correction contrasts are achieved in all cases. Negative numerical values mean that not only the photosensitive layer was removed during the development process, but the surface of the support was additionally cleaned, which is to be regarded as positive. The hydrophilicity is as good as in the other cases.

Claims (10)

Mechanically and / or electrochemically roughened and optionally anodically oxidized support material made of aluminum or its alloys, onto which a hydrophilic layer of at least one polymer with basic and acidic groups is applied, characterized in that another hydrophilic layer follows at least one layer Contains compound with at least one phosphono group. Support material according to claim 1, characterized in that the basic groups in the polymer containing basic and acidic groups are primary, secondary or tertiary amino groups and the acidic groups are carboxy, phosphono or sulfo groups. Support material according to claim 1 or 2, characterized in that the polymer with basic and acidic groups has a pH in the range from 4 to 9, preferably 4.5 to 7.5. Support material according to one of the several of claims 1 to 3, characterized in that the compound containing at least one phosphono group in the further hydrophilic layer is a polymer, preferably polyvinylphosphonic acid. A process for the production of the carrier material according to one or more of claims 1 to 4, characterized in that on the roughened and optionally anodically oxidized carrier material made of aluminum or its alloys, only a hydrophilic layer of at least one polymer with basic and acidic groups and then another hydrophilic layer, which contains a compound with at least one phosphono group, is applied. A method according to claim 5, characterized in that the hydrophilic layers are applied in each case by spraying an aqueous solution or immersion in an aqueous solution. A method according to claim 5 or 6, characterized in that the aqueous solutions of the hydrophilizing compounds each have a concentration of 0.1 to 50 g / l, preferably 0.3 to 5 g / l. Method according to one or more of claims 5 to 7, characterized in that the hydrophilic layers are applied at temperatures from 20 to 95 ° C, preferably from 30 to 65 ° C. Method according to one or more of claims 5 to 8, characterized in that the carrier material is dried at temperatures of 100 to 130 ° C after the application of the two hydrophilization layers. Recording material with a support made of aluminum or its alloys and a radiation-sensitive layer, characterized in that the support according to claims 1 to 6 is hydrophilized.