CA1284912C - Light-sensitive recording material and process for the production of the material - Google Patents
Light-sensitive recording material and process for the production of the materialInfo
- Publication number
- CA1284912C CA1284912C CA000490457A CA490457A CA1284912C CA 1284912 C CA1284912 C CA 1284912C CA 000490457 A CA000490457 A CA 000490457A CA 490457 A CA490457 A CA 490457A CA 1284912 C CA1284912 C CA 1284912C
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- Prior art keywords
- light
- aromatic
- carbon atoms
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed is a light-sensitive recording material for use in the manufacture of planographic printing plates, which comprises in its light-sensitive layer, a condensation product comprising recurrent diazonium salt units and diazonium-group free units of compounds which are capable of condensation with an active carbonyl compound, and which especially include aromatic amines, phenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aromatic hetero-cyclic compounds or organic acid amides, and a binder which includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions. The recording material includes a covering layer on the light-sensitive layer which comprises a water-insoluble polymer and is produced by coating the light-sensitive layer with a stable aqueous dispersion of the water-insoluble polymer. The material yields printing plates in which ink receptivity and print run are improved.
Disclosed is a light-sensitive recording material for use in the manufacture of planographic printing plates, which comprises in its light-sensitive layer, a condensation product comprising recurrent diazonium salt units and diazonium-group free units of compounds which are capable of condensation with an active carbonyl compound, and which especially include aromatic amines, phenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aromatic hetero-cyclic compounds or organic acid amides, and a binder which includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions. The recording material includes a covering layer on the light-sensitive layer which comprises a water-insoluble polymer and is produced by coating the light-sensitive layer with a stable aqueous dispersion of the water-insoluble polymer. The material yields printing plates in which ink receptivity and print run are improved.
Description
~ ~849i2 LIGHT-SENSITIVE RECORDING MATERIAL AND PROOESS
FOR THE PRODUCTION OF THE MATERIAL
BACKGROUND OF THE INVENTION
The present invention relates to a negative-working light-sensitive recording material for use in the manufacture of planographic printing plates and to a process for the production of the recording material.
Negative-working, presensitized, planographic printing plates usually contain polycondensation pro-ducts of diazonium salts, particularly products which contain, in addition to diazonium salt units, units of non-photosensitive compounds which are capable of con-densation, for example, aromatic amines, phenols, aro-matic thioethers, aromatic hydrocarbons, heterocyclic compounds, or organic acid amides. Printing plates of this kind are described in U.S. Patent No. 3,867,147.
When the light-sensitive layers of these printing plates substantially comprise only the polycondensation product, the exposed plates are readily developed with purely aqueous solutions which appropriately include wetting agents. These plates are, however, only suitable for an average range of print runs. To obtain larger print runs, it is generally necessary to add a water-insoluble polymeric binder, for example, a poly-vinyl acetal. The printing plates thus produced, however, usually require the addition of organic solvents to the developer to achieve smooth develop-ment. If purely aqueous developer solutions are used, ~ x~9~
undissolved layer particles remain which contaminate the developer and which may deposit in the non-image areas of the plates to be developed therewith.
Binders have therefore been used which dissolve in aqueous-alkaline solutions. Printing plates of this type are described in European Published Patent Applications No. 0,048,876 and No. 0,071,881, which correspond to U.S. Patent No. 4,387,151 and Canadian Patent No. 1,172,492, respectively. These plates are readily developed with purely aqueous devel-opers, with no undissolved layer particles being formed, thus resulting in good print runs. The plates, however, frequently exhibit a retarded ink acceptance in the printing machine. It is assumed that this is caused by layer constituents reacting with hydrophylic desensitizing agents which are applied after develop-ment in order to protect the plate. Reactions of this type may occur both in the dark and in the light.
Retarded acceptance of ink may also be caused by hydrophylization of the layer surface, which is pro-duced by contact of the layer with alkaline auxiliary agents normally employed in printing.
Another disadvantage of these printing plates is that the print run is reduced when alkaline dampen-ing solutions are used. This is probably due to the relatively good solubility of the binders in alkali.
Moreover, most of the printing plates devel-oped with aqueous developers show a smoother gradationthan printing plates developed with organic solvents.
As a result, it is considerably more difficult to determine the proper development time by means of a stepwedge, and, in the printing process, a marked increase of tonal rendering occurs, compared with the screened original. Up to now, these disadvantages have, nevertheless, been tolerated in view of the eco-logical advantages of aqueous development.
J Z84~3~
It is known from U.S. Patent No. 3,136,637 to reduce the sensitivity to water and the hydrophilic character of printing plates based on the diazonium salt-formaldehyde condensation products in such a way that a covering coating comprising a water-insoluble resin can be applied to the light-sensitive layer. In this case, development must again be carried out with a developer containing organic solvents.
In German Auslegeschrift No. 15 22 501 (corresponding to British Patent No. 1,192,088), a similar printing plate is described, in which a water-insoluble, light-sensitive layer comprising a 1,4-quinone diazide, and optionally a water-insoluble resin, is applied onto a water-soluble light-sensitive layer comprising a diazonium salt condensation product.
The applied layer has a relatively low light-sensitivity, and the print run obtained from the printing forms so produced is comparatively small.
German Offenlegungsschrift No. 25 23 719 describes a light-sensitive material which comprises a water-soluble, light-sensitive layer of azides, chal-cones or diazonium salt condensates and water-soluble polymers, and an overlying layer of an organic synthe-tic resin which is permeable to and insoluble in water.
Development is carried out with water, the unexposed areas of the water-soluble, light-sensitive layer being dissolved in the process. The overlying layer of synthetic resin must then be removed by rubbing. This type of development is, to a large extent, dependent on the skill of the person carrying out processing. There is always a risk that image areas of the layer will be torn off or that the covering layer will not be pro-perly removed in the non-image areas. The material is unsuitable for automatic development in a processing line and the developer naturally contains undissolved particles of the covering layer. In addition, the ~ ~491~
plate described in this publication is not suitable for the production of large print runs.
It is also known to coat positive-working light-sensitive materials based on l,2-quinone diazides with water-insoluble covering layers comprising organic polymers. According to German Offenlegungsschrift No. 24 26 159 (corresponding to British Patents No. 1,478,333 and No. 1,478,334), part of the thickness of a 1,2-quinone diazide layer is replaced by a water-insoluble polymer layer, in order to enhance light-sensitivity. In this case, however, an optimum print run is not obtained, since adhesion of the covering layer is too low. According to German Offenlegungs-schrift No. 24 61 515 (corresponding to British Patent No. 1,488,350), an adhesion-promoting agent is there-fore added to the oleophilic covering layer to remedy this disadvantage. Silane, among others, is used as the adhesive agent. The developers employed comprise aqueous solutions containing considerable quantities of organic solvents. The silane compounds and/or the reaction products of these compounds, which are washed off in the development process, produce a more rapid contamination of the developer.
Moreover, it is known from European Patent No. 0,008,038 (corresponding to U.S. Patent No. 4,288,520) to produce light-sensitive layers which are developable with water, by the application of a stable aqueous dispersion of a polymer which is insol-uble in water. The dispersion contains a diazonium salt polycondensation product dissolved therein. These materials similarly do not yield optimum print runs, since the image areas exhibit a certain sensitivity to water and aqueous solutions.
J 28491~
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a light-sensitive recording material for use in the manufacture of planographic printing plates based on diazonium salt polyconden-sation products which can be developed with purely aqueous solutions.
Another object of the present invention is to provide a light-sensitive recording material for use in the manufacture of planographic printing plates based on diazonium salt polycondensation products which yields printing forms of high print run performance.
Yet another object of the present invention is to provide a light-sensitive recording material for use in the manufacture of planographic printing plates based on diazonium salt polycondensation products which is properly developed without any deposition of par-ticles in the developer.
Still yet another object of the present invention is to provide a light-sensitive recording material for use in the manufacture of planographic printing plates based on diazonium salt polyconden-sation products which produces image areas having good and permanent ink receptivity.
In accomplishing these and other objects of the present invention, there has been provided in accordance with one aspect of the present invention, a light-sensitive recording material comprising a sup-port, a light-sensitive recording layer which includes a light-sensitive compound comprising a condensation product which comprises recurrent units A-N2X and B
which are linked by divalent intermediate members derived from a carbonyl compound which is capable of condensation, and a binder, the A-N2X units being derived from compounds of the general formula 3491~
(Rl-R3-) pR2--N2X
wherein:
X is the anion of the diazonium compound, p is an integer from about 1 to 3, Rl is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group consisting of:
-(CH2)~-NR4-, -O- (CH2 ) r-NR4-, -S- (CH2) r-NR4-, -S-CH2Co-NR4-, -o-R5 -o-, --O--, -S-, and -Co-NR4-, wherein:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms, an aralkyl group ha~ing from about 7 to 12 carbon atoms or an aryl group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms and B denotes the radical of an aromatic amine, a phenol, a thiophenol, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups; the condensation product comprises from about 0.01 to 50 units B for each unit A-N2X, and the binder includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions, and a covering layer present on the light-sensitive recording layer which comprises a water-insoluble polymer.
~ Z849~L~
In a preferred embodiment, the covering layer further co~prises a diazonium salt condensation product as defined above. Additionally, it is preferable if the covering layer has a layer weight from about 0.2 to 1 g/m2, and further comprises a surface-active agent and a protective colloid. Advantageously, the water-insoluble polymer of the covering layer comprises a homopolymer or copolymer of an alkyl acrylate or an alkyl methacrylate having from about 1 to 12 carbon atoms in the alkyl group,ofavinyl ester of a carboxylic acid having from about 2 to 12 carbon atoms,ofa vinyl alkyl ether having from about 2 to 8 carbon atoms in the alkyl group, oro~a vinyl-aromatic compound having from about 8 to 12 carbon atoms.
In accordance with another aspect of the pre-sent invention, there has been provided a process for the productionof a light-sensitive recording material, which comprises the steps of coating a support with a light-sensitive recording layer which includes a light-sensitive compound comprising a condensation product which comprises recurrent units A-N2X and B, which are linked by divalent intermediate members derived from a carbonyl compound which is capable of condensation, and a binder, the units A-N2X being derived from compounds of the general formula (Rl--R3 - ) pR2--N 2X
wherein:
X is the anion of the diazonium compound, p is an integer from about 1 to 3, 0 Rl is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group ~ 2~4~
consisting of:
~(CH2)q~NR4~~
~o-(CH2)r-NR4 -S- (CH2 ) r-NR4-, -S-CH2Co-NR4-, -o-R5-O-, --O--, -S-, and -Co-NR4-, wherein:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms, an aralkyl group having from about 7 to 12 carbon atoms or an aryl group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms and B denotes the radical of an aromatic amine, a phenol, a thiophenol, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups; the condensation product comprises from about 0.01 to 50 units B for each unit A-N2X, and the binder includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions, coating the recording layer with a stable aqueous dispeesion of a water-insoluble polymer, and drying the aqueous dispersion to produce a covering layer on the recording layer.
Other objects, features and advantages of the pre-sent invention will become apparent from the detailed description of preferred embodiments which follows.
~ 28491~
DETAILED DESCRIPTION OF THE ~REFERRED EMBODIMENTS
The present invention is based on a light-sensitive recording material comprising a support and a light-sensitive recording layer which comprises, as the light-sensitive compound, a condensation product comprising recurrent units A-N2X and B which are linked by divalent intermediate members derived from a car-bonyl compound which is capable of condensation. The units A-N2X are derived from compounds of the general formula (Rl-R3-) pR2-N2X, wherein:
X is the anion of the diazonium compound, p is an integer from about 1 to 3, Rl is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group consisting of:
~(CH2)q~NR4~~
-o-(CH2)r-NR4-, -S- (CH2) r-NR4-, -S-CH2Co-NR4-, -O-R5-o-, --O--, -S-, and -Co-NR4-, whereir:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms or an aralkyl group having from about 7 to 12 carbon atoms or an aryl _g _ ~ ~491X
group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms, and B denotes the radical of an aromatic amine, a phenol, a thiophenoi, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups.
The condensation product contains, on an average, from about 0.01 to 50 units B for each unit A-~2X. The binder includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions. The recording material also includes a covering layer which comprises a water-insoluble polymer. The covering layer is present on top of the light-sensitive recording layer.
The present invention also provides a process for the production of a light-sensitive recording material, in which a light-sensitive recording layer of the above-indicated composition and a covering layer are applied to a support. The process of the invention is characterized in that the covering layer is produced by coating the recording layer with a stable a~ueous dispersion of a water-insoluble polymer which is then dried. The covering layer preferably has a layer weight in the range from about 0.2 to 1 g/m2. According to a preferred embodiment, the covering layer comprises, in addition to the water-insoluble polymer, a diazonium salt polycondensation product which is preferably water-soluble.
Homopolymers or copolymers of alkyl acrylates or alkyl methacrylates having from about 1 to 12 carbon atoms in the alkyl group,of vinyl esters of carboxylic acids having from about 2 to 12 carbon atoms,ofvinyl alkyl ethers having from about 2 to 8 carbon atoms in the alkyl groupor of vinylaromatic compounds having from ~ ~84~1~
about 8 to 12 ca bon atoms are preferably used as the water-insoluble polymers contained in the covering layer. These polymers are preferably insoluble in aqueous alkali.
Examples of suitable polymers include polyvi-nyl acetate, polyvinyl propionate, polyvinyl versatate, polyvinyl nonanate, polystyrene, poly-4-methyl-styrene, poly-~ -chloro-styrene, polyisopropyl-styrene, poly-methyl methacrylate, polybutylacrylate, poly-2-ethyl-hexylmethacrylate, polyvinyl isobutylether and the copolymers and terpolymers of these monomers, for example, a terpolymer comprising vinyl chloride, ethy-lene and vinyl acetate.
In a covering layer comprising a diazonium salt condensation product, the latter basically can have the same structure as described above for the components of the light-sensitive layer. The anion of the salt is preferably of such a nature that the salt is water soluble. Suitable anions include, for example, sul-fates, chlorides, phospha~es and aliphatic sulfonates.
The diazonium salt condensation product, if present, is preferably included in the covering layer in a quan-titative proportion from about 10 to 50 percent by weight, relative to the non-volatile constituents of the layer.
The components of the covering layer are applied to the light-sensitive layer in the form of a stable aqueous dispersion. The dispersion comprises surface-active dispersing agents and/or protective colloids, as is typical. Production and application of the coating dispersion are known per se and are, for example, effected in the same way as described in U.S.
Patent No. 4,288,520.
The light-sensitive layer - or optionally the lower light-sensitive layer - comprises diazonium salt polycondensation products which are normally water-~ Z849~2 insoluble, as is known in the art. As already mentioned above, these condensation products are described in U.S. Patent No. 3,867,147. The layer additionally includes an àlkali-soluble polymer as a binder.
Suitable polymers are described in European Published Patent Applications No. 0,071,881 and No. 0,048,876 (corresponding to U.S. Patent No. 4,387,151 and Canadian Patent No. 1,172,492, respectively). Pre-ferred polymers include copolymers comprising carboxyl groups and polymers having sulfonyl urethane groups.
The layers generally comprise from about 5 to 90% by weight, preferably from about 10 to 70% by weight, of diazonium compound and from about 95 to 10% by weight, preferably from about 90 to 30% by weight, of poly-meric binder. The layers may additionally includeacids, for example, phosphoric acid, plasticizers, adhesion promoters, dyes, pigments, color precursors and other polymers.
The preferred support comprises aluminum which may be roughened by mechanical, chemical and/or elec-trochemical processes and which is optionally anodic-ally oxidized. Other suitable materials include, for example, steel, chromium, and other support materials which are used in the practice of planographic printing.
Processing of the present recording material is carried out in the known manner by image-wise exposing and washing off the unexposed layer areas with an aqueous-alkaline developer which usually has a pH in the range from about 8 to 14, preferably from about 10 to 13. In addition to alkali and buffer salts, the developer may include wetting agents and other customary additives. Preferably, no organic solvents are added.
In the development process, the unexposed por-tions of the light-sensitive layer and the ~ 2#4~9~X
corresponding areas of the covering layer are dissolved and/or dispersed in the developer. In these areas, the components of the covering layer are readily dispersed in the developer, while at least the major part thereof remains on the light-sensitive layer in the exposed areas. This differentiation is enhanced by adding diazonium salt condensation products to the covering layer. The water-insoluble components of the covering layer are rapidly distributed in the developer to form a stable dispersion, i.e., there are no macroscopically visible clods or particles formed and deposited, which is obviously due to the dispersing agents distributed in the covering layer.
The covering layer remains on top of the light-hardened areas of the light-sensitive layer and is firmly attached to the underlying layer. In these areas, the layer exhibits an excellent oleophilic character, i.e., the image areas of the printing form accept printing ink immediately upon the passage of the first printed sheets. The print run is also increased by the covering layer. The printing forms have a clearly steeper gradation than corresponding printing forms which are not provided with a covering layer of the type described herein.
In the following examples, preferred embodi-ments of the invention are described. Unless otherwise indicated, percentages and quantitative proportions relate to units by weight. Parts by weight (p.b.w.) and parts by volume (p.b.v.) are related as g to cm3.
Example 1 A coating solution comprising:
97.0 p.b.w. of the product obtained by reacting a polyvinyl butyral (molecular weight from 70,000 to 80,000; 71% by weight of vinyl butyral units, 2% by weight of vinyl ~ 2~491~
acetate units and 27% by weight of vinyl alcohol units) with propenyl sulfonyl isocyanate (softening point approxi-mately 161C, acid number 18.0), 48.3 p.b.w . of a diazonium salt polycondensation product obtained from 1 mole of 3-methoxydiphenylamine-4-diazonium sulfate and 1 mole of 4,4'-bis-methoxy-methyl-diphenylether in an 85% strength phosphoric acid and isolated as the mesitylene sulfonate, 4.8 p.b.w. of phosphoric acid (85% strength), 3.5 p.b.w. of Victoria Pure Blue FGA (C.I. Basic Blue 81) and 1.6 p.b.w. of phenylazodiphenylamine in 3500 p.b.w. of 2-methoxy ethanol and 1036 p.b.w. of tetrahydrofuran was applied to an electrochemically roughened and anod-ically oxidized aluminum foil which had been post-treated with polyvinyl phosphonic acid. After drying, the layer weight was 0.8 g/m2. The dry layer was coated with an aqueous emulsion based on polystyrene (Styrofan 2D ~ , manufacturer BASF; anionic emulsifier system, particle size 0.5 /um, tear strength of the film 100 kg/cm2). The dry layer had a weight of 0.5 g/m2. The presensitized printing plate was placed under a negative original and exposed for 35 seconds to the light of a 5 kW metal halide lamp.
The exposed layer was treated with a developer solution of the following composition:
5 p.b.w. of sodium lauryl sulfate 1.5 p.b.w. of sodium metasilicate x 5 H2O, 1 p.b.w. of trisodium phosphate x 12 H2O, 92.5 p.b.w. of water ~ X~49~2 using a plush pad, the unexposed layer areas being removed in the process which was followed by rinsing with water and drying.
In an offset printing machine, two plates, i.e., the plate prepared as described above and a corresponding plate without a covering layer, were clamped side by side to a cylinder. One half of each plate was treated with a strongly alkaline roller washing fluid (Feuchtofix ~ , while the other half was left untreated. The four areas of the plate cylinder accepted ink at different rates. The following table indicates, in each case, the number of printed sheets produced until ink was completely accepted.
Plate With Plate Without _ Coverina Layer Coverinq Layer ._ _ _ _ alkaline-treated 30 100 untreated 15 20 The table shows that the plate produced according to the present invention was by far less sen-sitive to alkali than a corresponding plate without a covering layer.
Gradation in the inked state, i.e., the number of intermediate steps which were not completely blackened, was 2 in the plate of the invention and 4 in the comparative plate (KALLE stepwedge BK 01). The print run increased by 20%, in comparison with the uncovered comparative plate.
Example 2 Example 1 was repeated with the following differences:
a) the binder of the organic coating solution was replaced by the same quantity of a copolymer comprising styrene and maleic anhydride (1:1);
4~
b) the solution used for the development included 5 p.b.w. of the triethanol ammonium salt of lauryl sulfate, 1 p.b.w. of sodium metasilicate x 5 H2O and 1.5 p.b.w. of trisodium phosphate x 12 H2O in 92.5 p.b.w. of water;
c) the covering layer was produced by coating with a solution of 3 p.b.w. of an aqueous emulsion of polyvinyl isobutyl-ether (particle size 0.5 to 3 /um), 1 p.b.w. of a diazonium salt polycondensation product prepared from 1 mole of 3-methoxydiphenyl-amine-4-diazonium sulfate and 1 mole of 4,4'-bis-methoxymethyl-diphenylether in an 85% strength phosphoric acid and isolated as the methane sulfonate, and l.p.b.w. of a non-ionic wetting agent based on an ethoxylated alkyl phenol (Triton x 100 ~ .
The weight of the dry covering layer was 0.65 g/m2. Processing was carried out in a manner analogous to Example 1. The sensitivity to alkali was even lower than in the case of using a covering layer without diazo compound. Particularly noticeable was a facili-tated determination of exposure time (hard gradation) and an improved visual contrast upon exposure.
Example 3 Example 1 was repeated, except that an emulsion of a terpolymer comprising vinyl chloride, ethylene and vinyl acetate was used as the polymeric binder of the covering layer. The results were similar to those of Examples 1 and 2.
FOR THE PRODUCTION OF THE MATERIAL
BACKGROUND OF THE INVENTION
The present invention relates to a negative-working light-sensitive recording material for use in the manufacture of planographic printing plates and to a process for the production of the recording material.
Negative-working, presensitized, planographic printing plates usually contain polycondensation pro-ducts of diazonium salts, particularly products which contain, in addition to diazonium salt units, units of non-photosensitive compounds which are capable of con-densation, for example, aromatic amines, phenols, aro-matic thioethers, aromatic hydrocarbons, heterocyclic compounds, or organic acid amides. Printing plates of this kind are described in U.S. Patent No. 3,867,147.
When the light-sensitive layers of these printing plates substantially comprise only the polycondensation product, the exposed plates are readily developed with purely aqueous solutions which appropriately include wetting agents. These plates are, however, only suitable for an average range of print runs. To obtain larger print runs, it is generally necessary to add a water-insoluble polymeric binder, for example, a poly-vinyl acetal. The printing plates thus produced, however, usually require the addition of organic solvents to the developer to achieve smooth develop-ment. If purely aqueous developer solutions are used, ~ x~9~
undissolved layer particles remain which contaminate the developer and which may deposit in the non-image areas of the plates to be developed therewith.
Binders have therefore been used which dissolve in aqueous-alkaline solutions. Printing plates of this type are described in European Published Patent Applications No. 0,048,876 and No. 0,071,881, which correspond to U.S. Patent No. 4,387,151 and Canadian Patent No. 1,172,492, respectively. These plates are readily developed with purely aqueous devel-opers, with no undissolved layer particles being formed, thus resulting in good print runs. The plates, however, frequently exhibit a retarded ink acceptance in the printing machine. It is assumed that this is caused by layer constituents reacting with hydrophylic desensitizing agents which are applied after develop-ment in order to protect the plate. Reactions of this type may occur both in the dark and in the light.
Retarded acceptance of ink may also be caused by hydrophylization of the layer surface, which is pro-duced by contact of the layer with alkaline auxiliary agents normally employed in printing.
Another disadvantage of these printing plates is that the print run is reduced when alkaline dampen-ing solutions are used. This is probably due to the relatively good solubility of the binders in alkali.
Moreover, most of the printing plates devel-oped with aqueous developers show a smoother gradationthan printing plates developed with organic solvents.
As a result, it is considerably more difficult to determine the proper development time by means of a stepwedge, and, in the printing process, a marked increase of tonal rendering occurs, compared with the screened original. Up to now, these disadvantages have, nevertheless, been tolerated in view of the eco-logical advantages of aqueous development.
J Z84~3~
It is known from U.S. Patent No. 3,136,637 to reduce the sensitivity to water and the hydrophilic character of printing plates based on the diazonium salt-formaldehyde condensation products in such a way that a covering coating comprising a water-insoluble resin can be applied to the light-sensitive layer. In this case, development must again be carried out with a developer containing organic solvents.
In German Auslegeschrift No. 15 22 501 (corresponding to British Patent No. 1,192,088), a similar printing plate is described, in which a water-insoluble, light-sensitive layer comprising a 1,4-quinone diazide, and optionally a water-insoluble resin, is applied onto a water-soluble light-sensitive layer comprising a diazonium salt condensation product.
The applied layer has a relatively low light-sensitivity, and the print run obtained from the printing forms so produced is comparatively small.
German Offenlegungsschrift No. 25 23 719 describes a light-sensitive material which comprises a water-soluble, light-sensitive layer of azides, chal-cones or diazonium salt condensates and water-soluble polymers, and an overlying layer of an organic synthe-tic resin which is permeable to and insoluble in water.
Development is carried out with water, the unexposed areas of the water-soluble, light-sensitive layer being dissolved in the process. The overlying layer of synthetic resin must then be removed by rubbing. This type of development is, to a large extent, dependent on the skill of the person carrying out processing. There is always a risk that image areas of the layer will be torn off or that the covering layer will not be pro-perly removed in the non-image areas. The material is unsuitable for automatic development in a processing line and the developer naturally contains undissolved particles of the covering layer. In addition, the ~ ~491~
plate described in this publication is not suitable for the production of large print runs.
It is also known to coat positive-working light-sensitive materials based on l,2-quinone diazides with water-insoluble covering layers comprising organic polymers. According to German Offenlegungsschrift No. 24 26 159 (corresponding to British Patents No. 1,478,333 and No. 1,478,334), part of the thickness of a 1,2-quinone diazide layer is replaced by a water-insoluble polymer layer, in order to enhance light-sensitivity. In this case, however, an optimum print run is not obtained, since adhesion of the covering layer is too low. According to German Offenlegungs-schrift No. 24 61 515 (corresponding to British Patent No. 1,488,350), an adhesion-promoting agent is there-fore added to the oleophilic covering layer to remedy this disadvantage. Silane, among others, is used as the adhesive agent. The developers employed comprise aqueous solutions containing considerable quantities of organic solvents. The silane compounds and/or the reaction products of these compounds, which are washed off in the development process, produce a more rapid contamination of the developer.
Moreover, it is known from European Patent No. 0,008,038 (corresponding to U.S. Patent No. 4,288,520) to produce light-sensitive layers which are developable with water, by the application of a stable aqueous dispersion of a polymer which is insol-uble in water. The dispersion contains a diazonium salt polycondensation product dissolved therein. These materials similarly do not yield optimum print runs, since the image areas exhibit a certain sensitivity to water and aqueous solutions.
J 28491~
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a light-sensitive recording material for use in the manufacture of planographic printing plates based on diazonium salt polyconden-sation products which can be developed with purely aqueous solutions.
Another object of the present invention is to provide a light-sensitive recording material for use in the manufacture of planographic printing plates based on diazonium salt polycondensation products which yields printing forms of high print run performance.
Yet another object of the present invention is to provide a light-sensitive recording material for use in the manufacture of planographic printing plates based on diazonium salt polycondensation products which is properly developed without any deposition of par-ticles in the developer.
Still yet another object of the present invention is to provide a light-sensitive recording material for use in the manufacture of planographic printing plates based on diazonium salt polyconden-sation products which produces image areas having good and permanent ink receptivity.
In accomplishing these and other objects of the present invention, there has been provided in accordance with one aspect of the present invention, a light-sensitive recording material comprising a sup-port, a light-sensitive recording layer which includes a light-sensitive compound comprising a condensation product which comprises recurrent units A-N2X and B
which are linked by divalent intermediate members derived from a carbonyl compound which is capable of condensation, and a binder, the A-N2X units being derived from compounds of the general formula 3491~
(Rl-R3-) pR2--N2X
wherein:
X is the anion of the diazonium compound, p is an integer from about 1 to 3, Rl is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group consisting of:
-(CH2)~-NR4-, -O- (CH2 ) r-NR4-, -S- (CH2) r-NR4-, -S-CH2Co-NR4-, -o-R5 -o-, --O--, -S-, and -Co-NR4-, wherein:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms, an aralkyl group ha~ing from about 7 to 12 carbon atoms or an aryl group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms and B denotes the radical of an aromatic amine, a phenol, a thiophenol, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups; the condensation product comprises from about 0.01 to 50 units B for each unit A-N2X, and the binder includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions, and a covering layer present on the light-sensitive recording layer which comprises a water-insoluble polymer.
~ Z849~L~
In a preferred embodiment, the covering layer further co~prises a diazonium salt condensation product as defined above. Additionally, it is preferable if the covering layer has a layer weight from about 0.2 to 1 g/m2, and further comprises a surface-active agent and a protective colloid. Advantageously, the water-insoluble polymer of the covering layer comprises a homopolymer or copolymer of an alkyl acrylate or an alkyl methacrylate having from about 1 to 12 carbon atoms in the alkyl group,ofavinyl ester of a carboxylic acid having from about 2 to 12 carbon atoms,ofa vinyl alkyl ether having from about 2 to 8 carbon atoms in the alkyl group, oro~a vinyl-aromatic compound having from about 8 to 12 carbon atoms.
In accordance with another aspect of the pre-sent invention, there has been provided a process for the productionof a light-sensitive recording material, which comprises the steps of coating a support with a light-sensitive recording layer which includes a light-sensitive compound comprising a condensation product which comprises recurrent units A-N2X and B, which are linked by divalent intermediate members derived from a carbonyl compound which is capable of condensation, and a binder, the units A-N2X being derived from compounds of the general formula (Rl--R3 - ) pR2--N 2X
wherein:
X is the anion of the diazonium compound, p is an integer from about 1 to 3, 0 Rl is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group ~ 2~4~
consisting of:
~(CH2)q~NR4~~
~o-(CH2)r-NR4 -S- (CH2 ) r-NR4-, -S-CH2Co-NR4-, -o-R5-O-, --O--, -S-, and -Co-NR4-, wherein:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms, an aralkyl group having from about 7 to 12 carbon atoms or an aryl group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms and B denotes the radical of an aromatic amine, a phenol, a thiophenol, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups; the condensation product comprises from about 0.01 to 50 units B for each unit A-N2X, and the binder includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions, coating the recording layer with a stable aqueous dispeesion of a water-insoluble polymer, and drying the aqueous dispersion to produce a covering layer on the recording layer.
Other objects, features and advantages of the pre-sent invention will become apparent from the detailed description of preferred embodiments which follows.
~ 28491~
DETAILED DESCRIPTION OF THE ~REFERRED EMBODIMENTS
The present invention is based on a light-sensitive recording material comprising a support and a light-sensitive recording layer which comprises, as the light-sensitive compound, a condensation product comprising recurrent units A-N2X and B which are linked by divalent intermediate members derived from a car-bonyl compound which is capable of condensation. The units A-N2X are derived from compounds of the general formula (Rl-R3-) pR2-N2X, wherein:
X is the anion of the diazonium compound, p is an integer from about 1 to 3, Rl is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group consisting of:
~(CH2)q~NR4~~
-o-(CH2)r-NR4-, -S- (CH2) r-NR4-, -S-CH2Co-NR4-, -O-R5-o-, --O--, -S-, and -Co-NR4-, whereir:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms or an aralkyl group having from about 7 to 12 carbon atoms or an aryl _g _ ~ ~491X
group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms, and B denotes the radical of an aromatic amine, a phenol, a thiophenoi, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups.
The condensation product contains, on an average, from about 0.01 to 50 units B for each unit A-~2X. The binder includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions. The recording material also includes a covering layer which comprises a water-insoluble polymer. The covering layer is present on top of the light-sensitive recording layer.
The present invention also provides a process for the production of a light-sensitive recording material, in which a light-sensitive recording layer of the above-indicated composition and a covering layer are applied to a support. The process of the invention is characterized in that the covering layer is produced by coating the recording layer with a stable a~ueous dispersion of a water-insoluble polymer which is then dried. The covering layer preferably has a layer weight in the range from about 0.2 to 1 g/m2. According to a preferred embodiment, the covering layer comprises, in addition to the water-insoluble polymer, a diazonium salt polycondensation product which is preferably water-soluble.
Homopolymers or copolymers of alkyl acrylates or alkyl methacrylates having from about 1 to 12 carbon atoms in the alkyl group,of vinyl esters of carboxylic acids having from about 2 to 12 carbon atoms,ofvinyl alkyl ethers having from about 2 to 8 carbon atoms in the alkyl groupor of vinylaromatic compounds having from ~ ~84~1~
about 8 to 12 ca bon atoms are preferably used as the water-insoluble polymers contained in the covering layer. These polymers are preferably insoluble in aqueous alkali.
Examples of suitable polymers include polyvi-nyl acetate, polyvinyl propionate, polyvinyl versatate, polyvinyl nonanate, polystyrene, poly-4-methyl-styrene, poly-~ -chloro-styrene, polyisopropyl-styrene, poly-methyl methacrylate, polybutylacrylate, poly-2-ethyl-hexylmethacrylate, polyvinyl isobutylether and the copolymers and terpolymers of these monomers, for example, a terpolymer comprising vinyl chloride, ethy-lene and vinyl acetate.
In a covering layer comprising a diazonium salt condensation product, the latter basically can have the same structure as described above for the components of the light-sensitive layer. The anion of the salt is preferably of such a nature that the salt is water soluble. Suitable anions include, for example, sul-fates, chlorides, phospha~es and aliphatic sulfonates.
The diazonium salt condensation product, if present, is preferably included in the covering layer in a quan-titative proportion from about 10 to 50 percent by weight, relative to the non-volatile constituents of the layer.
The components of the covering layer are applied to the light-sensitive layer in the form of a stable aqueous dispersion. The dispersion comprises surface-active dispersing agents and/or protective colloids, as is typical. Production and application of the coating dispersion are known per se and are, for example, effected in the same way as described in U.S.
Patent No. 4,288,520.
The light-sensitive layer - or optionally the lower light-sensitive layer - comprises diazonium salt polycondensation products which are normally water-~ Z849~2 insoluble, as is known in the art. As already mentioned above, these condensation products are described in U.S. Patent No. 3,867,147. The layer additionally includes an àlkali-soluble polymer as a binder.
Suitable polymers are described in European Published Patent Applications No. 0,071,881 and No. 0,048,876 (corresponding to U.S. Patent No. 4,387,151 and Canadian Patent No. 1,172,492, respectively). Pre-ferred polymers include copolymers comprising carboxyl groups and polymers having sulfonyl urethane groups.
The layers generally comprise from about 5 to 90% by weight, preferably from about 10 to 70% by weight, of diazonium compound and from about 95 to 10% by weight, preferably from about 90 to 30% by weight, of poly-meric binder. The layers may additionally includeacids, for example, phosphoric acid, plasticizers, adhesion promoters, dyes, pigments, color precursors and other polymers.
The preferred support comprises aluminum which may be roughened by mechanical, chemical and/or elec-trochemical processes and which is optionally anodic-ally oxidized. Other suitable materials include, for example, steel, chromium, and other support materials which are used in the practice of planographic printing.
Processing of the present recording material is carried out in the known manner by image-wise exposing and washing off the unexposed layer areas with an aqueous-alkaline developer which usually has a pH in the range from about 8 to 14, preferably from about 10 to 13. In addition to alkali and buffer salts, the developer may include wetting agents and other customary additives. Preferably, no organic solvents are added.
In the development process, the unexposed por-tions of the light-sensitive layer and the ~ 2#4~9~X
corresponding areas of the covering layer are dissolved and/or dispersed in the developer. In these areas, the components of the covering layer are readily dispersed in the developer, while at least the major part thereof remains on the light-sensitive layer in the exposed areas. This differentiation is enhanced by adding diazonium salt condensation products to the covering layer. The water-insoluble components of the covering layer are rapidly distributed in the developer to form a stable dispersion, i.e., there are no macroscopically visible clods or particles formed and deposited, which is obviously due to the dispersing agents distributed in the covering layer.
The covering layer remains on top of the light-hardened areas of the light-sensitive layer and is firmly attached to the underlying layer. In these areas, the layer exhibits an excellent oleophilic character, i.e., the image areas of the printing form accept printing ink immediately upon the passage of the first printed sheets. The print run is also increased by the covering layer. The printing forms have a clearly steeper gradation than corresponding printing forms which are not provided with a covering layer of the type described herein.
In the following examples, preferred embodi-ments of the invention are described. Unless otherwise indicated, percentages and quantitative proportions relate to units by weight. Parts by weight (p.b.w.) and parts by volume (p.b.v.) are related as g to cm3.
Example 1 A coating solution comprising:
97.0 p.b.w. of the product obtained by reacting a polyvinyl butyral (molecular weight from 70,000 to 80,000; 71% by weight of vinyl butyral units, 2% by weight of vinyl ~ 2~491~
acetate units and 27% by weight of vinyl alcohol units) with propenyl sulfonyl isocyanate (softening point approxi-mately 161C, acid number 18.0), 48.3 p.b.w . of a diazonium salt polycondensation product obtained from 1 mole of 3-methoxydiphenylamine-4-diazonium sulfate and 1 mole of 4,4'-bis-methoxy-methyl-diphenylether in an 85% strength phosphoric acid and isolated as the mesitylene sulfonate, 4.8 p.b.w. of phosphoric acid (85% strength), 3.5 p.b.w. of Victoria Pure Blue FGA (C.I. Basic Blue 81) and 1.6 p.b.w. of phenylazodiphenylamine in 3500 p.b.w. of 2-methoxy ethanol and 1036 p.b.w. of tetrahydrofuran was applied to an electrochemically roughened and anod-ically oxidized aluminum foil which had been post-treated with polyvinyl phosphonic acid. After drying, the layer weight was 0.8 g/m2. The dry layer was coated with an aqueous emulsion based on polystyrene (Styrofan 2D ~ , manufacturer BASF; anionic emulsifier system, particle size 0.5 /um, tear strength of the film 100 kg/cm2). The dry layer had a weight of 0.5 g/m2. The presensitized printing plate was placed under a negative original and exposed for 35 seconds to the light of a 5 kW metal halide lamp.
The exposed layer was treated with a developer solution of the following composition:
5 p.b.w. of sodium lauryl sulfate 1.5 p.b.w. of sodium metasilicate x 5 H2O, 1 p.b.w. of trisodium phosphate x 12 H2O, 92.5 p.b.w. of water ~ X~49~2 using a plush pad, the unexposed layer areas being removed in the process which was followed by rinsing with water and drying.
In an offset printing machine, two plates, i.e., the plate prepared as described above and a corresponding plate without a covering layer, were clamped side by side to a cylinder. One half of each plate was treated with a strongly alkaline roller washing fluid (Feuchtofix ~ , while the other half was left untreated. The four areas of the plate cylinder accepted ink at different rates. The following table indicates, in each case, the number of printed sheets produced until ink was completely accepted.
Plate With Plate Without _ Coverina Layer Coverinq Layer ._ _ _ _ alkaline-treated 30 100 untreated 15 20 The table shows that the plate produced according to the present invention was by far less sen-sitive to alkali than a corresponding plate without a covering layer.
Gradation in the inked state, i.e., the number of intermediate steps which were not completely blackened, was 2 in the plate of the invention and 4 in the comparative plate (KALLE stepwedge BK 01). The print run increased by 20%, in comparison with the uncovered comparative plate.
Example 2 Example 1 was repeated with the following differences:
a) the binder of the organic coating solution was replaced by the same quantity of a copolymer comprising styrene and maleic anhydride (1:1);
4~
b) the solution used for the development included 5 p.b.w. of the triethanol ammonium salt of lauryl sulfate, 1 p.b.w. of sodium metasilicate x 5 H2O and 1.5 p.b.w. of trisodium phosphate x 12 H2O in 92.5 p.b.w. of water;
c) the covering layer was produced by coating with a solution of 3 p.b.w. of an aqueous emulsion of polyvinyl isobutyl-ether (particle size 0.5 to 3 /um), 1 p.b.w. of a diazonium salt polycondensation product prepared from 1 mole of 3-methoxydiphenyl-amine-4-diazonium sulfate and 1 mole of 4,4'-bis-methoxymethyl-diphenylether in an 85% strength phosphoric acid and isolated as the methane sulfonate, and l.p.b.w. of a non-ionic wetting agent based on an ethoxylated alkyl phenol (Triton x 100 ~ .
The weight of the dry covering layer was 0.65 g/m2. Processing was carried out in a manner analogous to Example 1. The sensitivity to alkali was even lower than in the case of using a covering layer without diazo compound. Particularly noticeable was a facili-tated determination of exposure time (hard gradation) and an improved visual contrast upon exposure.
Example 3 Example 1 was repeated, except that an emulsion of a terpolymer comprising vinyl chloride, ethylene and vinyl acetate was used as the polymeric binder of the covering layer. The results were similar to those of Examples 1 and 2.
Claims (7)
1. A light-sensitive recording material, comprising:
a support;
a light-sensitive recording layer which includes a light-sensitive compound comprising a con-densation product which comprises recurrent units A-N2X
and B which are linked by divalent intermediate members derived from a carbonyl compound which is capable of condensation, and a binder, said A-N2X units being derived from compounds of the general formula (R1-R3-)pR2-N2X
wherein:
X is the anion of the diazonium compound, p is an integer from about 1 to 3, R1 is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group consisting of:
-(CH2)q-NR4--O-(CH2)r-NR4-, -S-(CH2)r-NR4, -S-CH2CO-NR4-, -O-R5-O-, -O-, -S-, and -CO-NR4-, wherein:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms, an aralkyl group having from about 7 to 12 carbon atoms or an aryl group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms, and B denotes the radical of an aromatic amine, a phenol, a thiophenol, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups, said condensation product comprising from about 0.01 to 50 units B for each unit A-N2X, said binder comprising a water-insoluble polymer which is soluble in aqueous-alkaline solutions; and a covering layer on said light-sensitive recording layer which comprises a water-insoluble polymer.
a support;
a light-sensitive recording layer which includes a light-sensitive compound comprising a con-densation product which comprises recurrent units A-N2X
and B which are linked by divalent intermediate members derived from a carbonyl compound which is capable of condensation, and a binder, said A-N2X units being derived from compounds of the general formula (R1-R3-)pR2-N2X
wherein:
X is the anion of the diazonium compound, p is an integer from about 1 to 3, R1 is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group consisting of:
-(CH2)q-NR4--O-(CH2)r-NR4-, -S-(CH2)r-NR4, -S-CH2CO-NR4-, -O-R5-O-, -O-, -S-, and -CO-NR4-, wherein:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms, an aralkyl group having from about 7 to 12 carbon atoms or an aryl group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms, and B denotes the radical of an aromatic amine, a phenol, a thiophenol, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups, said condensation product comprising from about 0.01 to 50 units B for each unit A-N2X, said binder comprising a water-insoluble polymer which is soluble in aqueous-alkaline solutions; and a covering layer on said light-sensitive recording layer which comprises a water-insoluble polymer.
2. A recording material as claimed in Claim 1, wherein said covering layer further comprises a diazonium salt condensation product.
3. A recording material as claimed in Claim 1, wherein said covering layer has a layer weight from about 0.2 to 1 g/m2.
4. A recording material as claimed in Claim 1, wherein said water-insoluble polymer of said covering layer comprises a homopolymer or copolymer of an alkyl acrylate or an alkyl methacrylate having from about 1 to 12 carbon atoms in the alkyl group, of a vinyl ester of a carboxylic acid having from about 2 to 12 carbon atoms, of a vinyl alkyl ether having from about 2 to 8 carbon atoms in the alkyl group, or of a vinyl-aromatic compound having from about 8 to 12 carbon atoms.
5. A recording material as claimed in Claim 1, wherein said covering layer further comprises a surface-active agent.
6. A recording material as claimed in Claim 1, wherein said covering layer further comprises a pro-tective colloid.
7. A process for the production of a light-sensitive recording material, which comprises the steps of:
coating a support with a light-sensitive recording layer which includes a light-sensitive com-pound comprising a condensation product which comprises recurrent units A-N2X and B, which are linked by divalent intermediate members derived from a car-bonyl compound which is capable of condensation, and a binder, the units A-N2X being derived from compounds of the general formula (R1-R3-)pR2-N2X
wherein:
X is the anion of the diazonium compound, p is an integer from 1 to 3, R1 is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group consisting of:
-(CH2)q-NR4-, -O-(CH2)r-NR4, -S-(CH2)r-NR4-, -S-CH2CO-NR4-, -O-R5-O-, -O-, -S-, and -CO-NR4-, wherein:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms, an aralkyl group having from about 7 to 12 carbon atoms or an aryl group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms, and B denotes the radical of an aromatic amine, a phenol, a thiophenol, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups, said condensation product comprising from about 0.01 to 50 units B for each unit A-N2X, said binder includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions;
coating said recording layer with a stable aqueous dispersion of a water-insoluble polymer; and drying said dispersion to produce a covering layer on said recording layer.
coating a support with a light-sensitive recording layer which includes a light-sensitive com-pound comprising a condensation product which comprises recurrent units A-N2X and B, which are linked by divalent intermediate members derived from a car-bonyl compound which is capable of condensation, and a binder, the units A-N2X being derived from compounds of the general formula (R1-R3-)pR2-N2X
wherein:
X is the anion of the diazonium compound, p is an integer from 1 to 3, R1 is a carbocyclic or heterocyclic aromatic radical which is capable of condensation in at least one position, R2 is an arylene group of the benzene or naphthalene series, R3 is a single bond or one selected from the group consisting of:
-(CH2)q-NR4-, -O-(CH2)r-NR4, -S-(CH2)r-NR4-, -S-CH2CO-NR4-, -O-R5-O-, -O-, -S-, and -CO-NR4-, wherein:
q is an integer from about 0 to 5, r is an integer from about 2 to 5, R4 is a hydrogen atom, an alkyl group having from about 1 to 5 carbon atoms, an aralkyl group having from about 7 to 12 carbon atoms or an aryl group having from about 6 to 12 carbon atoms, and R5 is an arylene group having from about 6 to 12 car-bon atoms, and B denotes the radical of an aromatic amine, a phenol, a thiophenol, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound or an organic acid amide, which is free from diazonium groups, said condensation product comprising from about 0.01 to 50 units B for each unit A-N2X, said binder includes a water-insoluble polymer which is soluble in aqueous-alkaline solutions;
coating said recording layer with a stable aqueous dispersion of a water-insoluble polymer; and drying said dispersion to produce a covering layer on said recording layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843433911 DE3433911A1 (en) | 1984-09-15 | 1984-09-15 | LIGHT-SENSITIVE RECORDING MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
| DEP3433911.6 | 1984-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1284912C true CA1284912C (en) | 1991-06-18 |
Family
ID=6245476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000490457A Expired - Fee Related CA1284912C (en) | 1984-09-15 | 1985-09-11 | Light-sensitive recording material and process for the production of the material |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0175244B1 (en) |
| JP (1) | JPS6177845A (en) |
| BR (1) | BR8504423A (en) |
| CA (1) | CA1284912C (en) |
| DE (2) | DE3433911A1 (en) |
| ES (1) | ES8701996A1 (en) |
| ZA (1) | ZA857031B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5326674A (en) * | 1991-04-30 | 1994-07-05 | Fuji Photo Film Co., Ltd. | Method for processing photosensitive copying materials |
| DE4308122A1 (en) * | 1993-03-15 | 1994-09-22 | Basf Lacke & Farben | Photostructurable multilayer element, process for its production and printing and embossing mold made therefrom |
| EP0883835B9 (en) * | 1996-11-20 | 2004-01-28 | Latran Technologies LLC | Protective overcoat useful for enhancing the resistance of a printing plate precursor to ambient humidity |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE620097A (en) * | 1958-11-26 | |||
| NL270834A (en) * | 1960-10-31 | |||
| NL7007827A (en) * | 1970-05-29 | 1971-12-01 | ||
| JPS50152803A (en) * | 1974-05-29 | 1975-12-09 | ||
| DE2834059A1 (en) * | 1978-08-03 | 1980-02-14 | Hoechst Ag | LIGHT SENSITIVE COPY MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
| DE3516387A1 (en) * | 1984-05-07 | 1985-11-07 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | Light-sensitive compositions and recording materials |
| US4600679A (en) * | 1984-05-25 | 1986-07-15 | W. R. Grace & Co. | Water-developable, negative-working, diazo lithographic printing plate with oleophilic ester overlayer |
-
1984
- 1984-09-15 DE DE19843433911 patent/DE3433911A1/en not_active Withdrawn
-
1985
- 1985-09-07 EP EP85111329A patent/EP0175244B1/en not_active Expired - Lifetime
- 1985-09-07 DE DE8585111329T patent/DE3577146D1/en not_active Expired - Fee Related
- 1985-09-11 CA CA000490457A patent/CA1284912C/en not_active Expired - Fee Related
- 1985-09-12 JP JP60200737A patent/JPS6177845A/en active Pending
- 1985-09-13 ZA ZA857031A patent/ZA857031B/en unknown
- 1985-09-13 ES ES546982A patent/ES8701996A1/en not_active Expired
- 1985-09-13 BR BR8504423A patent/BR8504423A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES8701996A1 (en) | 1986-12-01 |
| EP0175244B1 (en) | 1990-04-11 |
| BR8504423A (en) | 1986-07-15 |
| EP0175244A2 (en) | 1986-03-26 |
| EP0175244A3 (en) | 1987-01-14 |
| ZA857031B (en) | 1986-04-30 |
| ES546982A0 (en) | 1986-12-01 |
| DE3433911A1 (en) | 1986-03-27 |
| JPS6177845A (en) | 1986-04-21 |
| DE3577146D1 (en) | 1990-05-17 |
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