JPH09204048A - Aluminum or aluminum alloy substrate with hydrophilic property imparting layer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate for an offset printing plate having a superior hydrophilic property imparting characteristic. SOLUTION: A hydrophilic property imparting layer is formed on an Al or Al alloy substrate subjected to mechanical and/or electrochemical surface roughening or further subjected to anodic oxidation if necessary by a single- process forming method using an aq. soln. The hydrophilic property imparting layer contains two kinds of components, one of the components is a polymer having basic and acidic radicals and the other is an amino acid. A recording material is obtd. by forming a radiation sensitive layer on the substrate having imparted hydrophilic property and a printing plate is produced from the recording material.

Description

Detailed Description of the Invention

The present invention has a mechanically and / or electrochemically roughened, optionally surface-roughened, having a hydrophilicity-imparting layer comprising at least one polymer having basic and acidic roots. For example, it relates to a base material made of anodized aluminum or its alloy, and a method for producing the base material.

A base material for an offset printing plate is provided with a photosensitive layer (copying layer), and a printed image is formed by a photoengraving method using the photosensitive layer. After forming the printed image, the substrate forms a hydrophilic image background for the lithographic printing process on the printed image portion and, at the same time, on the non-imaged portion (non-imaged portion).

Suitable substrates for such substrates are aluminum, steel, copper, brass or zinc, but also plastic films or paper. In the field of printing plates, the usefulness of aluminum and its alloys has been established. The surface of the raw material is mechanically, chemically and / or electrochemically roughened by known methods and, if necessary, anodized. However, such pretreatments for substrates are not sufficient to meet the following requirements.

(1) The portions of the photosensitive layer that become relatively soluble after exposure are easily and completely removed from the substrate during development to form hydrophilic non-image portions. There is a need. Since the photosensitive layer is generally strongly colored, any residue of the layer adhering to the substrate is detected as a stain. As a result, the printing plate may exhibit "scumming" at these locations.

After exposure and development, it is often necessary to modify the printing plate to remove unwanted image areas. The non-image areas thus exposed should not differ in color and brightness from the non-image areas exposed by development. Uniform brightness is required in order to be able to use a measuring device which measures the area ratio of the image part by the average of the difference in brightness between the image part and the non-image part.

The undesired lightness difference between the non-image areas formed by the correction and the non-image areas formed during the normal development process is called the corrected contrast.

(2) The substrate exposed in the non-image area has sufficient hydrophilicity that water needs to be rapidly and permanently adsorbed during the lithographic printing process. Repels printing ink of sex).

(3) The photosensitive layer before exposure and the printed portion of the layer after exposure should not be separated from the substrate.

[0009] Usually, the substrate does not adsorb water sufficiently, so that it is rendered more hydrophilic. The agent that imparts hydrophilicity must be prepared for each photosensitive layer so as to avoid undesired reactions and not impair adhesion.

The known methods of imparting hydrophilicity with the light-sensitive layer, the developer solution or the modifier have more or less drawbacks. For example, after treatment with alkali metal silicates, which give good developability and hydrophilicity, one must be prepared to degrade the photosensitive layer after a relatively long storage period. When treating the substrate with a water-soluble polymer, those
In particular, good solubility in an aqueous alkaline developer which is mainly used for developing a positive type layer significantly reduces the effect of imparting hydrophilicity. In the case of polymers containing sulfo groups, a significant adverse effect is that the free anionic acid functional groups can interact with the diazo cations of the negative-working photosensitive layer and thus are non-existent due to the diazo compound being retained after development. A significant stain is detected on the image part. When treated with a polymeric acrylic acid derivative, the obvious disadvantage is that it is a form of use which can prevent soiling, ie a solution of 0.1-10 g / l,
These materials are very viscous and it takes a lot of time to remove the excess from the surface of the substrate. Particularly sensitive to the formation of stains are those used in laser imaging (E
P-A 0364735), polymeric binders, compounds capable of free-radical polymerization and having at least one polymerizable group, and photoreducible dyes, radiation-cleavable trihalomethyl compounds and photoinitiators. Is a highly photosensitive layer containing a metallocene compound. Therefore, hydrophilic substrates are highly preferred in which no layer components are left behind in the non-image areas.

DE-C 1134093 (= US-A
3,276,868) and US-A 4,153,4.
61 Each specification discloses that hydrophilicity can be imparted to a substrate with a phosphonic acid, particularly polyvinylphosphonic acid or a copolymer of vinylphosphonic acid and acrylic acid and vinyl acetate. It is also stated that salts of phosphonic acids are suitable. However, this is not explained in great detail.

EP-A 0069320 (= US-A
4,427,765) describes a method of imparting hydrophilicity to an aluminum substrate for lithographic printing, in which polyvinylphosphonic acid, polyvinylsulfonic acid,
Salts of polyvinylmethylphosphonic acid and other polyvinyl compounds having at least a divalent metal cation have been used.

According to EP-A 0190643, it is a homopolymer of acrylamidoisobutylenephosphonic acid or a copolymer of acrylamidoisobutylenephosphonic acid and acrylamide, or a divalent or polyvalent cation with this homopolymer or copolymer. The substrate is coated with an ionic salt. This coating has the advantage that the finished printing plate shows good hydrophilicity in the non-image areas and there is little smearing.

EP-A 0 490 231 describes:
_{(CH 2 -CH 2 -N (X} ) -) n - polyethylenimine containing structural elements of type, or - (CH ₂ -CH (N
Y ¹ Y ² )-) A method of treating a printing plate substrate with a polyvinyl imine containing structural elements of the _n -type is described (where X, Y ¹ and Y ² are optionally C-substituted. Sulfomethyl group or phosphonomethyl group). However, even with this method, optimum results have not been obtained.

DE 44231 not previously published
40.7 describes EP-A 04902 in the first step.
31 describes a method of operating with the materials described and operating with other phosphonic acid compounds in the second step. This method has the disadvantage that it has to be carried out in a two-step and expensive procedure.

It is an object of the present invention to provide a substrate for the following offset printing printing plates. It has very good hydrophilicity-imparting properties and is equally suitable for all photosensitive layers,
The photosensitive layer is not damaged by the reaction between the agent imparting hydrophilicity and the photosensitive layer during long-term storage, and the adhesiveness to the printed portion of the photosensitive layer is very good, which is technically easy to manufacture. .

The object is mechanically and / or electrochemically roughened, with a hydrophilicity-imparting layer comprising at least one polymer having basic and acidic roots, if necessary. For example, an anodized substrate of aluminum or its alloys, the hydrophilicity-imparting layer comprising a mixture of two components, one of the two components belonging to the group consisting of amino acids, the other of which is basic and acidic. It is achieved by a base material characterized by belonging to a polymer having a root part of

Other embodiments of the substrate are described in claims 2-7.

The substrate is produced by a one-step production method in which the layer containing the two components which imparts hydrophilicity is mechanically and / or electrochemically roughened with an aqueous solution and, if necessary, anodized. Applied to a base material of aluminum or its alloy. Other manufacturing process steps are described in claims 9 to 13.

The hydrophilicity-imparting layer can be applied by spraying the corresponding solution. The concentration of the hydrophilicity-imparting compound in this solution can be varied within a wide range, but the concentration is 0.1 to 20 g / l, preferably 0.3 to 5 g.
It has been found that a solution of / l, is particularly advantageous. The above amounts apply for both ingredients.

After applying the hydrophilicity-imparting layer, the substance can be washed away to remove excess hydrophilicity-imparting agent.
The hydrophilicity can be imparted at a temperature of 20 to 95 ° C, but a temperature of 30 to 65 ° C is preferable. The material to be coated is generally applied by spraying or dipping for 1 second to 5 minutes. A treatment time of less than 1 second is disadvantageous, but a treatment time of more than 5 minutes is not disadvantageous.

After the step of imparting hydrophilicity, it is advantageous to dry the coated substrate at a temperature of 100 ° to 130 ° C.

In order to confirm that the substance added for imparting hydrophilicity is actually adsorbed on the surface of the substrate, a method for measuring surface sensitivity, for example, EDX (energy dispersiveness X
Line (E nergy D ispersive X -ray) ), Auger electron spectroscopy,
SIMS (secondary ion mass spectrometry (S econdary I on M ass
S pectroscopy)), and others can be used. However, even a small amount of substance has a significant hydrophilicity-imparting effect, and thus there is a problem in measuring the weight of the applied hydrophilic coating. Moreover, the hydrophilicity-imparting agent adheres to the surface of the substrate relatively strongly. However, the amount applied is 0.5 m in each case.
It is less than g / dm ² and probably less than 0.25 mg / dm ² . The minimum amount is less than about 0.02 mg / dm ² .

Modified polyethyleneimine and modified polyvinylamine, and their production are described in EP-A 049.
0231 specification. In principle, these substances are prepared from the corresponding unmodified precursors by phosphonomethylation and / or sulfomethylation.

The substrate according to the invention can then be coated with various photosensitive mixtures. In principle, all mixtures which form a coating which gives a positive or negative image after imagewise exposure and subsequent development and / or fixing are suitable.
In the non-image areas, the material suitable as a printing plate retains its excellent hydrophilicity and virtually no stain is detected.

The invention also relates to a recording material having a substrate of aluminum or its alloys, which is rendered hydrophilic and coated with a radiation-sensitive layer.

The invention is illustrated by the following examples, which are not intended to limit the invention. For this purpose the following roughened and anodized printing plate is used.

Type 1 Gloss-rolled aluminum having a thickness of 0.3 mm (DIN material No. 3.0255) was treated with 2% concentration NaO at 50 to 70 ° C.
It was degreased with an H 2 washing aqueous solution. Then, the surface was electrochemically roughened by alternating current in a HNO ₃ -containing electrolyte. The R _z value of the surface roughness was 6 μm. Subsequently, anodic oxidation was performed in an electrolytic solution containing sulfuric acid. The weight of the oxide layer is about 3.0 g / m
^{Was 2} .

Type 2 Gloss-rolled aluminum having a thickness of 0.3 mm (DIN material No. 3.0515) was added with 2% concentration NaO at 50 to 70 ° C.
It was degreased with an H 2 washing aqueous solution. Then, in an electrolyte containing hydrochloric acid,
The surface was electrochemically roughened by alternating current. Surface roughness R _z
The value was 6 μm. Subsequently, anodic oxidation was performed in an electrolytic solution containing sulfuric acid. The weight of the oxide layer was about 2.0 g / m ² .

Type 3 0.2 mm thick gloss-rolled aluminum (DIN material No. 3.0255) was added to 2% NaO at 50-70 ° C.
It was degreased with an aqueous H 2 wash solution and then mechanically roughened with an abrasive (eg, quartz powder or alumina). The R _z value of the surface roughness was 4 μm. Subsequently, anodic oxidation was performed in an electrolytic solution containing phosphoric acid. The weight of the oxide layer is about 0.9 g
/ m ² .

The Type 4 substrate was treated as described for Type 2, but anodized until the oxide layer weight was 1.5 g / m ² .

The following examples illustrate the advantages of the substrate of the present invention. The hydrophilicity-imparting A ^{* to} D ^* shown in Table 1 were used in the comparative experiment, while the substrate of the present invention was hydrophilically imparted by E.

The basic roots of polymers containing basic and acidic roots are primary, secondary or tertiary amino groups, while the acidic roots are carboxyl, phosphono or sulfo groups. Is. The pH of the polymer is 4-9, especially 4.
5 to 7.5. One component of the hydrophilicity-imparting layer is selected, for example, from the group consisting of sulfo- or phosphonomethylated polyethyleneimine and polyvinylamine. This component may be a copolymer or terpolymer selected from the group consisting of substituted aminoacrylates, vinylpyrrolidone and vinylimidazole. Another component of the hydrophilicity-imparting layer is selected, for example, from the group consisting of monobasic amino acids such as glycine, aminohexanoic acid, aminobenzoic acid, diaminobenzoic acid and leucine. In the case of Examples 6 to 34, other additives are represented by letters N to S.

Table 1 Hydrophilization A ^* None B ^* Polyvinylphosphonic acid (2 g / l, 75 ° C., pH 2) C ^* N-phosphonomethyl polyethyleneimine (1 g / l, 65 ° C., pH 4.5) D ^* first C), then B) E According to the invention, as in C ^* , additionally 1 g / l of glycine in solution

Example 1 A Type 2 substrate was rendered hydrophilic according to Table 1 and was coated with a positive-working diazo layer comprising the following mixture: 5.00% by weight, hydroxyl number according to DIN 53783/53240 of 420, weight average value according to GPC of 60
100 (polystyrene standard) cresol / xylenol / formaldehyde novolac resin, 1.20% by weight of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 1.5 mol and 2,3,4-trihydroxybenzophenone. 1 mol ester, 0.15% by weight
1,2-naphthoquinonediazide-2-diazide-4-
Sulfonyl chloride, 0.05% by weight Victoria Sky Blue (CI 44045) and a total of 1
Methyl ethyl ketone and polyethylene glycol monomethyl ether (40/60) in an amount of 00% by weight
A solvent mixture comprising.

The coated substrate was dried at 125 ° C for 1 minute. The weight of the coating was 2.4 g / m ² . A cloudy solution (20% strength aqueous solution of vinyl sulfonic acid, ethyl acrylate and styrene terpolymer) was then electrostatically sprayed onto the radiation-sensitive layer so that the average height of the protrusions was 4 μm.

These plates were evacuated in a vacuum baking frame and brought into contact with the test flats so that open step 4 was obtained with a UGRA offset test wedge corresponding to high exposure to remove film edges after development. 110 cm
Was exposed with a metal halide-doped 5 kW mercury vapor lamp.

In the developing device (VA86 manufactured by Hoechst AG),
Using potassium silicate developer (total alkali content 0.5 mol / l, K ₂ O: SiO ₂ ratio = 1: 1.2, hereinafter referred to as “developer type 1”) at 20 ° C., Development was performed at a processing speed of 1.4 m / min.

After processing 4 m ² of recording material per liter of developer (image fraction 25%), the occurrence of residual layer smearing was examined. The results are as shown in Table 2.

Example 2 A type 1 substrate was rendered hydrophilic according to Table 1 and was provided with an inverted positive tone layer comprising the following mixture. 4.80
% By weight, according to DIN 53783/53240, a hydroxyl number of 420, weight average according to GPC of 6
Cresol / xylenol / formaldehyde novolac resin, 1.05% by weight of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 3.4 mol and 2,3,4,2 ', 3', 4 '-Hexahydroxy-5,5'-dibenzoyl phenylmethane 1
Mole ester, 0.5 wt% 2- (4-styrylphenyl) -4,6-bistrichloromethyl-s-triazine, 0.10 wt% crystal violet (C.I.
I. 42555), 1.00% by weight of a silica filler having an average particle size of 3.9 μm, 0.10% by weight of a surfactant comprising dimethylsiloxane units and ethylene oxide units and a total of 100% by weight. A solvent mixture comprising an amount of tetrahydrofuran and propylene glycol monomethyl ether (55/45).

The coated substrate was dried at 125 ° C for 1 minute. The coating weight was 1.8 g / m ² . The substrate was then processed as follows. 1. Exposing for 60 seconds through the original test image in the baking frame as in Example 1. 2. Heat in a continuous heating furnace at 135 ° C for 60 seconds. 3. Cool with circulating air for 10 seconds. 4. Uniform exposure for 30 seconds with a UV-A fluorescent lamp with a radiant power of 240 watts, in the continuous device, without the original image. 5. Developing in the same apparatus as in Example 1 at a processing speed of 1.2 m / min.

The development is carried out according to DE-A 4027299 specification, with a total alkali content of 0.8 mol / l (Na ₂ O: S).
iO ₂ ratio = 1: 1) and polyglycol-1000-
A sodium silicate developer having a dicarboxylic acid content of 0.6% by weight (hereinafter, referred to as "developer type 2") was used.

After processing 4 m ² of recording material (25% image fraction) per liter of developer, the occurrence of residual layer smearing was examined. The results are as shown in Table 2.

Example 3 A Type 4 substrate was subjected to the 5 post-treatments listed in Table 1 to provide a negative working layer having the following composition. Methacrylic acid (20% by weight), methyl methacrylate (30% by weight) and glyceryl monomethacrylate (5%) having an average molecular weight M _w of 24,000 (GPC) of 2.5% by weight.
0% by weight of the copolymer, 0.5% by weight, polycondensation of 1 mol of 4,4′-bismethoxymethyldiphenyl ether with 1 mol of 3-methoxydiphenylamine-4-diazonium sulfate, which precipitates as mesitylene sulfonate. Object, 0.09% by weight Victoria Sky Blue FGA
(Basic Blue 81), 0.07% by weight of phenylphosphonic acid, 0.1% by weight, 0.1% by weight of silica filler with an average particle size of 3 μm, and a total amount of 100% by weight. , A solvent mixture comprising tetrahydrofuran, and ethylene glycol monomethyl ether (40/60).

The coated substrate is placed in a drying tunnel at 120
Dry at ℃. The dry layer weight was 1.4 g / m ² . The reproduction layer was exposed under a photographic negative for 35 seconds with a 5 kW metal halide lamp in a developing machine with friction elements,
Development was carried out with the following solution at 23 ° C. 5% by weight sodium lauryl sulfate, 2% by weight phenoxyethanol, 1
Wt% sodium metasilicate 5H ₂ O, and 92
Wt% water.

After processing 4 m ² per liter of developer, the generation of residual layer contamination was examined. Here again, it was proved that the hydrophilicity-imparting treatment of the substrate according to the invention in step E is more advantageous and easier to carry out.

Example 4 A type 3 substrate was rendered hydrophilic according to Table 1 and coated with the following solution. 3.1% by weight of 2,5-bis- (4-diethylaminophenyl) -1,3,4-oxadiazole, 3.1% by weight of styrene and maleic anhydride having a softening point of 210 ° C. Polymer, 0.02 wt% Rhod
amin ^(R) FB (C.I. 45170) and 1 in total
Ethylene glycol monomethyl ether in an amount of 00% by weight was then dried at 120 ° C. in a continuous drying heating oven. This layer was negatively charged to 450V using corona in the dark and the charged plate was imagewise exposed in a process camera,
Then an electrophotographic suspension developer comprising a 0.6% by weight magnesium sulphate dispersion and a 98% by weight solution of 1.4% by weight pentaerythritol resin ester in an isoparaffin mixture in the boiling range 185-210 ° C. Developed. After removing the excess developer liquid, the toner was fixed and delaminated in the following solution at 24 ° C. and a processing speed of 1.4 m / min. Ethanolamine 10% by weight, propylene glycol monophenyl ether 10% by weight, K ₂ HP
A solution consisting of 2% by weight of O ₄ and water in an amount of 100% by weight in total. The plate was then washed with a strong jet of water to remove the delamination agent residue. The occurrence of residual layer fouling was examined after treating 10 m ² per liter of delamination agent.

Example 5 A substrate of type 1 was rendered hydrophilic according to Table 1 and a solution having the following composition was added in each case to a layer weight of 2.
It was applied by spin coating so as to be 5 g / m ² . 10.7% by weight of the terpolymer solution described in Example 3, 5.3% by weight of triethylene glycol dimethacrylate, 0.15% by weight of olasol blue (C.I.
50315), 0.15 wt% eosin, alcohol soluble (CI 46386), 0.11 wt% 2,4-bistrichloromethyl-6- (4-styrylphenyl) -s-triazine, 0. 23% by weight of dicyclopentadienyl titanium bispentafluorophenyl, 4
2% by weight butanol and butyl acetate in a total amount of 100% by weight.

After drying, the plates were coated with polyvinyl alcohol, exposed and developed.

The recording materials of Examples 1 to 5 were evaluated with a densitometer as follows (incident light densitometer, magenta or cyan filter). + No residual layer stain, densitometer measurement value <0.01 0 Slight residual layer stain, densitometer measurement value 0.01 to 0.0
2- Residual layer dirt, densitometer measurement value> 0.02 Table 2 Evaluation of hydrophilic examples 1 2 3 4 5 A ^* − − − − − − B ^* 0 0 0 0 0 C ^* 0 0 0 0 0 0 D ^* 0 0 0 0 0 0 E + + + + + +

Examples and Comparative Examples 6-34 show the superiority of the substrate according to the invention over Comparative Examples V6-V37, which have been rendered hydrophilic according to Table 1 AD. The recording materials produced under the conditions shown in this table were tested as follows.

1. Stain Measurements The reflection of non-image areas was measured in the visible region both on uncoated substrate samples and on non-image areas after coating, exposure and development. A two-channel simultaneous spectrometer MCS512 from Datacolor was used for this purpose. The measurement results are
E (Commission International de l'Eclairage, Public
It was used to calculate the lightness L ^{* of the} substrate surface according to ation No. 15). Details of these calculations can be found in DIN standard 6174
(1979) and 5033 (1970). In this case, illuminant D65 was used and calculated with a 2 ° observer as recommended by CIE. This lightness L ^* of the uncoated substrate is as set forth in columns 6 of Tables 5 and 6 below. Actually, the chromaticity coordinates a ^* and b ^* are also automatically obtained by this calculation, but since these correspond to the value of the lightness L ^{* in} the test on the substrate of the printing plate in question, these coordinates are Not taken into account. After these calculations, the difference dL ^* 1 between the lightness before coating and the lightness of the non-image areas after coating, exposure and development was calculated. Since the photosensitive layer actually has a dark color (compared to a light gray substrate surface), objectionable layer residues can be perceived as black stains in the non-image areas. The lightness of the non-image areas after coating, exposure and development will be less than the lightness before coating. The calculation of the difference gives a positive value dL ^* 1, the higher this value, the more pronounced the undesired stain. This value dL ^* 1 is as shown in column 7 of Tables 5 and 6.

Due to the experience of the observer and the sensitivity of the eyes, the stain is visible from a measured value of approximately 0.8. Contamination is always a cosmetic drawback of the printing plate and can, for this reason alone, lead to buyer complaints. A very high degree of smear is an indication of a large amount of layer residue in the non-image areas, which is sometimes undesirable, especially when weighing small amounts of fountain solution, which is often desirable. This may result in skimming. In this case, it is not possible to indicate the exact value of the stain.

[0054] 2. Corrected Contrast Measurement The non-image areas of the printing plate were treated with a commercially available corrector and then the lightness was measured in the corrected and uncorrected areas. Again, the difference dL ^* 2 was calculated. If this difference is significantly different from 0, i.e. the difference is in the range 0.5 to 1, then was the corrector able to further remove layer residues from the surface?
Or it attacked and damaged the surface of the non-image part itself.

[0055] 3. Hydrophilicity Measurement The printing ink was applied to the non-image area of the printing plate with a manual rubber roller and placed in diluted phosphoric acid to measure the time for diluted phosphoric acid to remove ink from the non-image area. If the substrate has good hydrophilicity, this time should not exceed 30 seconds. Diluted phosphoric acid simulates the generally acidic fountain solution used in the printing process.

The substrates of Comparative Examples V6 to V37 Types 1 and 2 were anodized and treated to impart hydrophilicity for 5 seconds in an immersion bath. The conditions are as shown in Table 3. The types of hydrophilicity imparting treatment are as described in the second column of Tables 3 to 6 below. The symbols shown there correspond to the symbols shown in Table 1. After the hydrophilicity-imparting treatment, the plate was coated with the solution described in Example 1 and exposed to light, and the above-mentioned developing apparatus VA86 was used.
And developed with type 1 and 2 developers.

Table 3 No. Hydrophilized base material Developer Brightness Stain Corrected hydrophilicity Treatment Trust type Type Type L ^* dL ^* 1 dL ^* 2 s V6 B ^* 1 1 78.33 1.33 1.39 15 V7 C ^* 1 1 78.33 1.02 1.13 15 V8 D ^* 1 1 78.28 0.33 0.17 5 V9 B ^* 1 1 78.25 2.15 2.02 15 V10 C ^* 1 1 78.37 1.24 1.34 5 V11 D ^* 1 1 78.37 0.24 0.54 5 V12 B ^* 1 2 78.33 2.24 1.83 5 V13 C ^* 1 2 78.00 1.92 2.12 5 V14 D ^* 1 2 78.39 0.43 0.41 15 V15 B ^* 2 1 79.10 3.01 1.72 15 V16 C ^* 2 1 79.03 1.75 1.43 15 V17 D ^* 2 1 79.04 0.30 0.54 5

According to Table 3, the printing plates not produced according to the invention have a sufficiently good hydrophilicity in the non-image areas, but also have significant stains or attack by corrective agents. On the other hand, it can be seen that discoloration occurs in the non-image portion, or both of them appear. Two different substrates and two different developers were used, but none of the combinations listed in the table could give good results for all properties. The hydrophilicity imparting treatment itself gives some good results, but this is a two-step treatment and is technically disadvantageous.

Recording materials of Table 4 were prepared using a type 2 substrate. These recording materials are subjected to a hydrophilicity-imparting treatment which is not in accordance with the present invention, that is, they are immersed in an aqueous solution containing phosphonomethylated polyimine as one component and other additives,
Was performed. Polyimine concentration is 1 g / l in all cases
Met. The type of the second component and the treatment temperature are as shown below.

Examples of additives not according to the invention F 60 ° C. phthalic acid G 65 ° C. maleic acid H 65 ° C. malic acid I 55 ° C. dioxaoctanoic acid J 55 ° C. malic acid K 60 ° C. nicotinic acid L Fumaric acid at 60 ℃ M Lactic acid at 55 ℃

Table 4 No. Hydrophilic Concentration Lightness Dirt Stain Corrected Hydrophilic Treatment Trust Type g / l L ^* dL ^* 1 dL ^* 2 s V18 F 2.0 77.83 1.08 1.64 5 V19 G 2.0 77.94 1.66 1.24 15 V20 H 2.0 77.95 0.96 1.32 5 V21 I 2.0 77.52 0.93 1.21 5 V22 J 2.0 79.60 0.81 0.44 5 V23 K 2.0 78.07 2.13 1.76 5 V24 L 2.0 79.41 0.88 1.69 5 V25 M 2.0 79.54 0.97 1.78 5 V26 F 5.0 79.60 0.55 0.95 15 V27 G 1.0 78.06 0.77 0.57 15 V28 H 78.95 1.56 1.01 5 V29 I 5.0 79.02 2.20 0.85 5 V30 J 5.0 79.10 2.09 0.63 5 V31 K 5.0 78.07 0.12 1.11 15 V32 L 5.0 77.83 0.12 1.41 5 V33 M 5.0 78.88 2.01 1.55 5 V34 M 1.0 78.27 2.53 1.34 5 V35 35 2.08 1.73 15 V36 M 10.0 79.01 2.42 1.75 5 V37 M 20.0 78.92 2.22 1.21 5

In the case of these printing plates, all have good hydrophilicity in the non-image areas, but the values measured for smear and / or modified contrast are not preferred.

Examples 6-34 Table 5 shows the results obtained with the type 2 substrate and Table 6 shows the results obtained with the type 4 substrate. These substrates were subjected to the hydrophilicity-imparting treatment according to the present invention, that is, they were immersed in an aqueous solution containing phosphonomethylated polyimine as one component and amino acid as another additive. The concentration of polyimine is displayed as "concentration 1" and the second component is displayed as "concentration 2". The type of the second component and the treatment temperature are as shown below. Immersion time is 5 seconds in most cases. Immersion times of 15 seconds to several minutes have the same effect.
However, the immersion time should not be less than 1 second.

Examples of other additives according to the invention N 2-aminoadipic acid O aminopropionic acid P phenylglycine Q aminohexanoic acid R diaminobenzoic acid S methylglutamic acid

Table 5 Type 2 substrate experiments No. Hydrophilic Temperature Density 1 Density 2 Brightness Dirt Correction Con Hydrophilic Treatment Trust Type ℃ g / lg / l L ^* dL ^* 1 dL ^* 2 s 6 E 40 5.0 0.5 78.9 -0.20 0.00 15 7 E 50 5.0 0.5 78.5 -0.24 0.05 5 8 E 60 5.0 0.5 78.3 -0.51 0.06 15 9 E 40 2.0 0.5 78.4 -0.14 0.20 5 10 E 50 2.0 0.5 78.3 -0.46 0.24 5 11 E 60 2.0 0.5 77.9 0.55 0.01 5 12 E 40 1.0 1.0 77.7 0.22 0.06 5 13 E 50 1.0 1.0 78.1 0.23 0.15 5 14 E 60 1.0 1.0 77.6 -0.41 0.41 5 15 E 40 0.5 1.0 77.8 -0.16 0.55 5 16 E 50 0.5 1.0 78.9 -0.14 0.27 5 17 E 60 0.5 1.0 77.9 0.12 0.22 5 18 E 40 0.2 1.0 77.6 0.11 0.59 15 19 E 50 0.2 1.0 78.1 0.03 0.55 15 20 E 60 0.2 1.0 77.8 -0.07 0.61 15

Table 6 Experiments with Type 4 Substrates No. Hydrophilic Temperature Density 1 Density 2 Brightness Dirt Stain Corrected Hydrophilic treatment Trust type ℃ g / lg / l L ^* dL ^* 1 dL ^* 2 s 21 E 40 2.0 4.0 78.5 0.09 0.45 5 22 E 50 2.0 4.0 78.5 0.65 0.32 5 23 E 60 2.0 4.0 78.4 0.45 0.30 5 24 E 40 1.0 2.0 78.0 0.50 0.32 5 25 E 50 1.0 2.0 78.7 0.24 0.16 5 26 E 60 1.0 2.0 77.7 0.37 0.07 5 27 E 40 1.0 1.0 78.3 0.21 0.50 5 28 E 50 1.0 1.0 78.3 0.19 0.49 5 29 E 60 1.0 1.0 78.4 0.34 0.50 15 30 E 40 0.5 1.0 78.4 0.27 0.43 5 31 E 50 0.5 1.0 78.4 0.23 0.43 5 32 E 60 0.5 1.0 78.0 0.43 0.40 5 33 E 50 0.5 1.0 78.3 0.50 0.34 5 34 E 60 0.5 1.0 78.9 0.45 0.32 5

Good values have been achieved in all cases for dirt and modified contrast. A negative number means that not only the photosensitive layer was removed in the development step, but also the substrate surface was washed, which should be considered as an advantage. The hydrophilicity is as good as in other cases.

Claims (14)

[Claims] 1. A hydrophilicity-imparting layer comprising at least one polymer having basic and acidic roots,
A mechanically and / or electrochemically roughened and optionally anodized substrate of aluminum or its alloys, the hydrophilicity-providing layer comprising a mixture of two components, A base material characterized in that one of the two components belongs to the group consisting of amino acids and the other belongs to a polymer having basic and acidic roots. 2. A polymer having a basic and acidic root moiety, wherein the basic root moiety is a primary, secondary or tertiary amino group, and the acidic root moiety is a carboxyl, phosphono or sulfo group. The substrate according to claim 1, which is present. 3. The substrate according to claim 1, wherein the pH of the polymer having basic and acidic roots is 4-9. 4. The substrate according to claim 3, wherein the pH of the polymer having basic and acidic roots is 4.5 to 7.5. 5. The substrate according to claim 1, wherein one component is selected from the group consisting of sulfomethylated or phosphonomethylated polyethyleneimine and polyvinylamine. 6. A substrate according to claim 1, wherein one component is a copolymer or terpolymer selected from the group consisting of substituted amino acrylates, vinylpyrrolidone and vinylimidazole. 7. The substrate according to claim 1, wherein the other component is selected from the group consisting of monobasic amino acids such as glycine, aminohexanoic acid, aminobenzoic acid, diaminobenzoic acid and leucine. 8. A one-step production method, wherein a hydrophilicity-imparting layer containing two components is mechanically and / or electrochemically surface-roughened with an aqueous solution and, if necessary, anodized, aluminum or an alloy thereof. The method for producing a base material according to claim 1, wherein the base material is applied to the base material. 9. The method according to claim 8, wherein the hydrophilicity-imparting layer is applied by spraying or dipping in an aqueous solution. 10. The hydrophilicity-imparting layer is formed at a temperature of 20 to 95 ° C., particularly 30 to 65 ° C., in the hydrophilicity imparting layer.
Or the method of 9. 11. The hydrophilicity-imparting layer has an aqueous solution concentration of 0.1 to 10.
The method according to claim 8 or 9, which is 50 g / l, in particular 0.3 to 5 g / l. 12. After coating the hydrophilicity-imparting layer, the excess hydrophilicity-imparting layer is washed off, and then the coated substrate is heated to a temperature of 100.
Drying at ˜130 ° C. 11.
The method described in the section. 13. The method according to claim 9, wherein the spraying time on the substrate or the dipping time of the substrate is 1 second to 5 minutes. 14. A recording material having a base material of aluminum or its alloy, which has been rendered hydrophilic by the method according to any one of claims 8 to 13 and is coated with a radiation-sensitive layer.