EP1292860A2 - Utilisation de polymeres acetalytiques contenant des groupes carboxyle dans des compositions photosensibles et des plaques d'impression lithographiques - Google Patents

Utilisation de polymeres acetalytiques contenant des groupes carboxyle dans des compositions photosensibles et des plaques d'impression lithographiques

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Publication number
EP1292860A2
EP1292860A2 EP01929416A EP01929416A EP1292860A2 EP 1292860 A2 EP1292860 A2 EP 1292860A2 EP 01929416 A EP01929416 A EP 01929416A EP 01929416 A EP01929416 A EP 01929416A EP 1292860 A2 EP1292860 A2 EP 1292860A2
Authority
EP
European Patent Office
Prior art keywords
group
mol
light
formula
free
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01929416A
Other languages
German (de)
English (en)
Inventor
Robert Fuss
Harald Baumann
Udo Dwars
Hans-Joachim Timpe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Polychrome Graphics GmbH
Original Assignee
Kodak Polychrome Graphics GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kodak Polychrome Graphics GmbH filed Critical Kodak Polychrome Graphics GmbH
Publication of EP1292860A2 publication Critical patent/EP1292860A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
    • 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
    • G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
    • G03F7/0215—Natural gums; Proteins, e.g. gelatins; Macromolecular carbohydrates, e.g. cellulose; Polyvinyl alcohol and derivatives thereof, e.g. polyvinylacetals
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

Definitions

  • the present invention relates to binders and photosensitive compositions which are suitable for the production of printing plates.
  • the polymeric binders have various structural elements which can have different effects on individual properties.
  • hydrophilic structural elements such as carboxyl groups and hydroxyl groups generally promote good developability of the light-sensitive compositions in aqueous alkaline developers and partly ensure adequate adhesion to polar ones Substrates.
  • Hydrophobic structural elements hamper developability in the developers mentioned, but ensure the good acceptance of the colors in the printing process, which is absolutely necessary for printing plates.
  • Acetal polymers of aliphatic aldehydes with an unsubstituted lower alkyl group and vinyl alcohol / ethyl acetate copolymers were first described (US Pat. No. 2,179,051, EP-A-0 216 083 and DE-A-14 47 957). Such binders, however, cause problems when developing printing plates due to the low proportion of hydrophilic groups in the polymer. If you choose a low degree of acetalization for these types of polymer in order to achieve sufficient developability through a high proportion of vinyl alcohol, the print run resistance is too low.
  • DE-A-20 53 363, DE-A-20 53 364 and EP-A-0 048 876 introduced sulfonyl urethane groups into polyvinyl acetals.
  • the low acidity of these groups requires developers with a high solvent content.
  • point Microelements printing plates produced in this way have a very low adhesion, so that they are rubbed off too quickly in the printing process.
  • binders which can be prepared by acetalizing saponified copolymers of vinyl acetate and a monomer bearing carboxyl groups, such as crotonic acid or acrylic acid.
  • Aromatic aldehydes are disclosed for acetalization.
  • this type of binder leads to systems with low photosensitivity, difficult to develop and low run-time stability when used for printing forms.
  • EP-A-0 211 391 and EP-A-0 152 819 introduce the carboxyl groups by reaction of separately prepared acetals of aliphatic aldehydes with polyvinyl alcohol with intramolecular, cyclic acid anhydrides of dicarboxylic acids.
  • the synthetic effort required is great, since in addition to acetalization, the reaction with the acid anhydrides is only possible in aprotic solvents. Furthermore, the light sensitivity of the mixtures made from these binders is still too low.
  • EP-A-0 208 145 describes binders which are prepared in a three-stage synthesis starting from polyvinyl alcohol: acetalization with aliphatic aldehydes, reaction with intramolecular, cyclic acid anhydrides of dicarboxylic acids and partial esterification of the carboxyl-substituted alkyl halides. Despite the high expenditure for the synthesis of the binder, an improvement in the photosensitivity of the layers produced therefrom is desirable.
  • the complexity of the multi-stage syntheses can be avoided if, as described in WO 93/03068 and US Pat. No. 5,169,897, polyvinyl alcohol is reacted with aliphatic aldehydes and carboxyl-containing aliphatic or carboxyl-containing aromatic aldehydes.
  • polyvinyl alcohol is reacted with aliphatic aldehydes and carboxyl-containing aliphatic or carboxyl-containing aromatic aldehydes.
  • the light-sensitive mixtures produced from them have a reference Developability and sensitivity unfavorable ratio.
  • the carboxyl group-containing aldehydes cause high costs.
  • EP-A-0 752 430 describes acetal polymers which can be prepared by reacting polyvinyl alcohol with aliphatic aldehydes and aldehydes with a -X-N (R1) CO-Y-COOH side group.
  • the effort for the production of such polymers is high, since the special aldehydes are very expensive, the use of organic solvents cannot be dispensed with in the synthesis, and a precipitation step with a non-solvent is necessary to isolate the binders.
  • Diazonium polycondensation product and a radically polymerizable system consisting of photoinitiators and unsaturated compounds which are radically polymerizable
  • the binder consists essentially, preferably exclusively, of units A, B, C, D, where A is present in a proportion of 0.1 to 25 mol%, preferably 1 to 18 mol%, and of the formula
  • R 1 represents a hydrogen atom, an aliphatic hydrocarbon radical having 1 to 4 carbon atoms which may be unsubstituted or substituted by at least one carboxyl group, a sulfonic acid group, a hydroxyl group or at least one halogen atom, or an aromatic radical which is unsubstituted or can be substituted with at least one alkyl group, a carboxyl group, a sulfonic acid group, a hydroxyl group or at least one halogen atom, is preferably a methyl group, B in a proportion of 0.1 to 60 mol%, preferably 20 to 55 mol -%, is present and the formula
  • R 2 is a hydrogen atom, an alkyl radical having 1 to 10 carbon atoms, which may be unsubstituted or substituted with at least one carboxyl group, a sulfonic acid group, a hydroxyl group or at least one halogen atom, preferably a methyl, ethyl or
  • Is propyl group or an aryl radical which can be unsubstituted or substituted with at least one alkyl group, a carboxyl group, a sulfonic acid group, a hydroxyl group or at least one halogen atom, this unit being able to be contained several times with different radicals R 2 independently of one another, and D is present in a proportion of 1 to 20 mol%, preferably 2 to 8 mol%, and of the formula
  • COOH corresponds, where R 3 is a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms, which may be unsubstituted or substituted by a carboxyl group, preferably a hydrogen atom, a methyl group or a CH 2 COOH group.
  • Processing offset printing plates used can be significantly improved without any problems of ink acceptance.
  • such compositions are very resistant to abrasion after the normal processing steps for offset printing plate manufacture, so that the printing plates can be used for runs of more than 300,000 rollovers.
  • the first essential constituent of the photosensitive composition according to the invention is a polyvinyl alcohol which contains a carboxylic acid group bonded directly to the main chain and the OH groups of which are partially acetalized.
  • binders are simple. Copolymers of vinyl alcohol, a vinyl ester and an olefinically unsaturated carboxylic acid serve as the starting material.
  • Suitable vinyl ester components are those which are derived from C 1 -C 8 -carboxylic acids. Vinyl acetate is particularly preferred.
  • the unsaturated carboxylic acid may be unsubstituted on the ⁇ -position olefinic carbon atom or carry an alkyl radical R 3 with up to 10 carbon atoms, which is optionally substituted by a further carboxyl group. Unbranched or branched alkyl radicals are suitable, methyl groups being particularly preferred.
  • Preferred carboxylic acids are acrylic acid and methacrylic acid.
  • the acetal radicals R 2 can be introduced into the polymer molecule starting from aldehydes R 2 CHO, cyclic trimers of aldehydes (eg paraldehyde), oligomeric aldehydes (eg paraformaldehyde), or acetals of aldehydes R 2 CH (OR 4 ) 2 , where R 4 is one Represents alkyl radical.
  • the radical R 2 is preferably a branched or unbranched alkyl radical having 1 to 10 carbon atoms. The synthesis starting from acetaldehyde, propionaldehyde and butyraldehyde or their acetals from lower alcohols R 4 OH is particularly preferred.
  • the acetal radicals R 2 can be different within a binder. This means that the developability can be tailored to the corresponding system. In general, developability improves as the carbon number of R 2 becomes smaller. In contrast, the ink acceptance is better with longer-chain residues.
  • a preferred combination is acetaldehyde and butyraldehyde.
  • the acetal polymers can be prepared by known processes in the presence of catalytic amounts of acids, as disclosed, for example, in EP-A-0 216 083 and DE-C-28 38 025. Hydrochloric acid, phosphoric acid or organic sulfonic acids are preferred.
  • the reaction is preferably carried out at temperatures between 0 and 90 ° C in a solvent for the starting polymer.
  • solvents are water, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, hexamethylphosphoric triamide, N-methylpyrrolidone, formamide, N, N-dimethylformamide, dimethyl sulfoxide, mixtures of water and isopropanol. Water is particularly preferred, since in this case the reaction product fails during the reaction.
  • the end product is soluble in many organic solvents. In this case the polymer solution is used to isolate the Product in solid form introduced into a non-solvent for the polymer with stirring and filtered off.
  • Non-polar solvents or water are suitable as non-solvents for the polymer.
  • Another procedure that is also practicable is to add the non-solvent for the polymer into the synthesis solution with stirring. In both cases, thorough mixing must be carried out in order to obtain a reaction product which is easy to handle and to remove the by-products which are formed as quantitatively as possible. The precipitated reaction product is separated off, washed with water and then dried.
  • the concentration of the reactants based on the amount of solvent is preferably 3 to 25% by weight, particularly preferably 7 to 16% by weight.
  • the catalytic amount of acid added is preferably between 1 to 15% by weight, based on the product used. This amount of acid can, but need not necessarily, be neutralized after the reaction has ended by adding molar amounts of an alkaline compound in order to prevent acid-catalyzed deacetalization of the polymeric binders during storage or later use.
  • Suitable alkaline compounds are alkaline earth metal, alkali metal carbonates and hydroxides and ammonia. Sodium and potassium hydroxide are preferred.
  • the second essential component of the photosensitive composition according to the invention is a diazonium polycondensation product or a free-radically polymerizable system, consisting of photoinitiators and unsaturated compounds which are free-radically polymerizable or a
  • Hybrid system consisting of a diazonium polycondensation product and a radically polymerizable system consisting of photoinitiators and unsaturated compounds which are radically polymerizable.
  • All diazonium polycondensation products known to the person skilled in the art can be used as the diazonium polycondensation product in the light-sensitive mixtures according to the invention.
  • condensation products can, for example, in the usual way Condensation of a diazomonomer described in EP-A-0 104 863 with a condensing agent such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde or benzaldehyde can be prepared.
  • diazonium salt units contain other, non-light-sensitive units which are derived from condensable compounds, in particular aromatic amines, phenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aromatic heterocycles and organic acid amides.
  • diazonium polycondensation products are reaction products of
  • Diphenylamine-4-diazonium salts which optionally contain a methoxy group in the phenyl radical carrying the diazo group, with formaldehyde or 4,4'-bis-methoxymethyldiphenyl ether.
  • Aromatic sulfonates such as 4-tolyl sulfonate or mesitylene sulfonate, tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate or hexafluorophosphate are particularly suitable as anions of these diazo resins.
  • the diazonium polycondensation product is preferably present in the light-sensitive mixtures in a proportion of 3 to 60% by weight.
  • the correct composition of the polymer according to the invention requires optimization attempts for the respective application.
  • the developability, the photosensitivity, the acceptability for colors and the stability during storage under elevated atmospheric humidity and temperature are determined depending on the composition of the polymer.
  • the second essential component can also be a radically polymerizable system.
  • This is composed of photoinitiators which absorb in the range from 300 to 800 nm, preferably 300 to 450 nm, and free-radically polymerizable components.
  • the base bodies or derivatives of acetophenone, benzophenone, 2,4- (trichloromethyl) -1, 3,5-thazine, benzoin, benzoin ether, benzoin ketals, xanthone, thioxanthone, acridine or are preferably suitable as photoinitiators for the light-sensitive compositions according to the invention Hexarylbisimidazol.
  • the free-radically polymerizable component of the mixture according to the invention is an acrylic or methacrylic acid derivative with one or more unsaturated groups, preferably esters of acrylic or methacrylic acid in the form of monomers, oligomers or prepolymers. It can be in solid or liquid form, with solid and viscous forms being preferred.
  • the compounds that are suitable as the monomer include trimethylolpropane triacrylate and methacrylate, pentaerythritol triacrylate and methacrylate, dipentaerythritol monohydroxy pentaacrylate and methacrylate, dipentaerythritol hexaacrylate and methacrylate, pentaerythritol tetraacrylate and - methacrylate, ditrimethylolpropane tetraacrylate and methacrylate, diethylene glycol di acrylate and methacrylate, triethylene glycol diacrylate and methacrylate or tetraethylene glycol diacrylate and methacrylate.
  • Suitable oligomers or prepolymers are urethane acrylates and methacrylates, epoxy acrylates and methacrylates, polyester acrylates and methacrylates, polyether acrylates and methacrylates or unsaturated polyester resins.
  • the photoinitiators and free-radically polymerizable constituents are to be composed in the manner known to the person skilled in the art, combinations of different photoinitiators and different free-radically polymerizable components also being advantageous.
  • the proportion by weight of the photoinitiators is preferably 0.5 to 20% by weight and that of the free-radically polymerizable constituents is 5 to 80% by weight, based on the total solids content of the photosensitive compositions.
  • a combination of the diazonium polycondensation products with a free-radically polymerizable system consisting of photoinitiators and unsaturated compounds which are free-radically polymerizable can bring advantages for certain applications.
  • Such hybrid systems preferably consist of 1 to 50% by weight of diazonium polycondensation product, 0.5 to 20% by weight of the photoinitiators and 5 to 80% by weight of the free-radically polymerizable constituents.
  • the exposure indicators which can be used in the light-sensitive compositions according to the invention are known to the person skilled in the art.
  • Prefers are exposure indicators from the series of triarylmethane dyes (such as Viktoriareinblau BO, Viktoriablau R, crystal violet) or azo dyes (such as 4-phenylazodiphenylamine, azobenzene or 4-N, N-dimethylaminoazobenzene).
  • the exposure indicators are present in the photosensitive composition in a proportion of 0.02 to 10% by weight, preferably 0.5 to 6% by weight.
  • Suitable dyes for increasing the image contrast are those which dissolve well in the solvent or solvent mixture used for coating or can be introduced as a pigment in disperse form.
  • Suitable contrast dyes include Rhodamine dyes, methyl violet, anthraquinone pigments and phthalocyanine dyes or pigments.
  • the dyes are present in the light-sensitive composition in a proportion of 1 to 15% by weight, preferably 2 to 7% by weight.
  • composition according to the invention can contain stabilizer acids.
  • stabilizing acids include Phosphoric, citric, benzoic, m-nitrobenzoic, p-anilinoazobenzenesulfonic, p-toluenesulfonic and / or tartaric acid.
  • Phosphoric acid is preferably used as the stabilizing acid.
  • the proportion of the acid added is preferably 0.2 to 3% by weight in the photosensitive composition.
  • the photosensitive composition of the invention may further contain a plasticizer.
  • Preferred plasticizers are dibutyl phthalate, triaryl phosphate and dioctyl phthalate.
  • the amounts of plasticizer used are preferably 0.25 to 2% by weight in the light-sensitive composition.
  • the photosensitive compositions according to the invention can preferably be used for the production of printing plates. Furthermore, however, they can also be used for recording materials for the production of images on suitable supports and receiving sheets, for the production of reliefs which are used as Printing form, sieves and the like can be used as light-curable varnishes for surface protection and for the formulation of UV-curable printing inks.
  • aluminum is first used as a layer support by brushing in the dry state, brushing with abrasive suspensions or by electrochemical means, e.g. in a hydrochloric acid electrolyte, roughened.
  • the roughened and optionally anodically oxidized in sulfuric or phosphoric acid plates are then subjected to a hydrophilizing aftertreatment, preferably in aqueous solutions of
  • an oxygen-blocking cover layer to the light-sensitive layer can be advantageous. This is particularly the case with radically polymerizable systems and with hybrid systems
  • the polymers suitable for the top layer include Polyvinyl alcohol, polyvinyl alcohol / polyvinyl acetate copolymers, polyvinyl pyrrolidone, polyvinyl pyrrolidone / polyvinyl acetate copolymers, polyvinyl methyl ether, polyacrylic acid and gelatin.
  • the layer thicknesses of the oxygen barrier include Polyvinyl alcohol, polyvinyl alcohol / polyvinyl acetate copolymers, polyvinyl pyrrolidone, polyvinyl pyrrolidone / polyvinyl acetate copolymers, polyvinyl methyl ether, polyacrylic acid and gelatin.
  • the cover layer is preferably 0.1 to 4 g / m 2 and particularly preferably 0.3 to 2 g / m 2 .
  • the printing plates thus produced are exposed and developed in the manner known to those skilled in the art.
  • the developed plates are usually treated with a preservative ("gum").
  • the preservatives consist of aqueous solutions of hydrophilic polymers, wetting agents and other additives.
  • the developed plate is first treated with a solution which protects the non-image parts in such a way that the heat treatment does not cause the areas to accept color.
  • a solution suitable for this is described, for example, in US Pat. No. 4,355,096.
  • Butyraldehyde (163.61 g (98.7%); 2.24 mol) and acetaldehyde (99.14 g (99.5%); 2.24 mol) are added to the polyvinyl alcohol solution.
  • an oxidation stabilizer such as 2,6-di-tert-butyl-4-methylphenol (Ralox BHT ® Raschig) may be added.
  • the reaction mixture is cooled to 10 ° C. and hydrochloric acid (1190 ml, 20%) is metered in at this temperature over a period of 180 minutes.
  • the mixture is heated to an internal temperature of 40 ° C. within 120 minutes and left there for 2 hours.
  • the solid reaction product is filtered off and washed sufficiently with deionized water. Then it is adjusted to pH 12 with sodium hydroxide solution (10%). About 200 ml of lye are required for this.
  • the mixture is then heated to an internal temperature of 55 ° C. and a sample is taken after 30 minutes. If the product reacts alkaline, the after-treatment is stopped. It is then dried in an oven or a fluidized bed dryer. Weight: 659 g (dry matter 97.3%), corresponds to> 97.5% of
  • reaction mixture is cooled to 10 ° C. and hydrochloric acid (1189 ml, 20%) is metered in at this temperature over a period of 180 minutes.
  • the mixture is heated to an internal temperature of 40 ° C. within 120 minutes and left there for 2 hours.
  • the solid reaction product is filtered off and washed sufficiently with deionized water. Then it is adjusted to pH> 12 with sodium hydroxide solution (10%). About 200 ml of lye are required for this.
  • the mixture is then heated to an internal temperature of 55 ° C. and a sample is taken after 30 minutes. If the product reacts alkaline, the after-treatment is stopped. It is then dried in an oven or a fluidized bed dryer.
  • Weight 626 g (dry matter 98.9%), corresponds to 87% of theory.
  • the viscosity in ethanol (10%, Höppler DIN 53015) is 128 mPas.
  • the glass point according to DSC analysis is 81 ° C (DIN 53765).
  • hydrochloric acid (806 ml, 20%) is metered in at this temperature over a period of 180 minutes.
  • the mixture is heated to an internal temperature of 40 ° C. within 120 minutes and left there for 2 hours.
  • the solid reaction product is filtered off and washed sufficiently with deionized water. Then it is adjusted to pH 7 to 8 with sodium hydroxide solution (10%). About 150 ml of lye are required for this.
  • the mixture is then heated to an internal temperature of 55 ° C. and a sample is taken after 30 minutes. If the product reacts alkaline, the after-treatment is stopped.
  • the solid product is separated off, washed and then dried in an oven or fluidized bed dryer. Weight: 639 g; corresponds to 93% of theory.
  • the viscosity in ethanol (5%, Höppler DIN 53015) is 26.4 mPas.
  • the glass point according to DSC analysis is 91 ° C (DIN 53765).
  • Vinyl acetate and 2 mol% acrylic acid which as a 4% solution at 20 ° C has a viscosity of 11.0 mPas, is dissolved in 36.8 l deionized water at 95 ° C for 30 minutes and then at room temperature using a 5th Filtered ⁇ filter.
  • Butyraldehyde 1210.9 g (98.6%); 16.56 mol
  • acetaldehyde 314.7 g (99.5%); 7.1 mol
  • an oxidation stabilizer such as 2,6-di-tert-butyl-4-methylphenol (Ralox BHT ® Raschig) may be added.
  • reaction mixture is cooled to 8 ° C. and hydrochloric acid (6278 ml, 20% strength) cooled to 5 ° C. is metered in at this temperature over a period of 180 minutes.
  • the mixture is heated to an internal temperature of 40 ° C. within 120 minutes and left there for 2 hours.
  • the solid reaction product is filtered off and washed sufficiently with deionized water. Then it is adjusted to pH 6.5 to 7 with sodium hydroxide solution (10%). About 500 ml of lye are required for this.
  • the mixture is then heated to an internal temperature of 30 ° C and left for 300 minutes.
  • the filtered product is washed with deionized water and then dried in an oven or fluidized bed dryer.
  • Production example 8 (comparative example based on DE-A-20 533 63)
  • polyvinyl butyral (® Mowital B60T Fa. Clariant GmbH with an acetal content of 70 wt .-%, a vinyl alcohol content of 26 wt .-% and an acetate content of 3 wt .-%) are dissolved in 752 g of dried 1, 4-dioxane solved at 40 ° C. Then 27.2 g of p-toluenesulphonyl isocyanate are added dropwise over the course of 20 minutes at the same temperature. The mixture is stirred for a further 4 hours at 40 ° C. and the polymer is precipitated in an excess of water. After thorough washing with water, the product is suctioned off and dried in a forced-air drying cabinet at 40 ° C. for 24 hours.
  • polyvinyl butyral ® Mowital B60T Fa. Clariant GmbH with an acetal content of 70 wt .-%, a vinyl alcohol content of 26 wt .-% and an acetate content of 3
  • Examples 1 to 6 coating solutions containing the binders of Preparation Examples 1 to 6 are prepared from the following components: 2.19 g of binder according to Preparation Examples 1 to 6 2 g of polycondensation product from 1 mol of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mol of 4.4 '-Bis-methoxymethyldiphenyl ether precipitated as mesitylene sulfonate 5.55 g of a 13.8% by weight dispersion in propylene glycol monomethyl ether, the solids of which consist of 1 part of the binder
  • the weight of the copying layer is approximately 1 g / m 2 .
  • the copying layer is placed under a silver film halftone step wedge with a density range of 0.15 to 1.95, the density increments being 0.15, as a negative template with a metal halide lamp (MH burner, from W. Sack)
  • the exposed layer is composed of a developer solution
  • Nekal ® BX paste sodium salt of one
  • the developer solution is then rubbed on the surface again with a tampon for 30 seconds and then the entire plate is rinsed off with water. After this treatment, the exposed parts remain on the plate.
  • the plate is blackened with a printing ink when wet.
  • the products PC 904 ® (from Polychrome) and RC 43 ® (from Hoechst) are used.
  • Production example 1 4 full stages 8 partially covered stages
  • Production example 2 4 full stages 6 partially covered stages
  • Production example 3 4 full stages 8 partially covered stages
  • a copying layer is applied to the aluminum foil, exposed, developed and, after rinsing, the developed plate is scraped off with water and rubbed with an aqueous solution of 0.5% phosphoric acid and 6% gum arabic, as indicated above.
  • the plate thus produced is clamped in a sheetfed offset printing press and delivers 180,000 copies of good quality under normal printing conditions. The plate could continue to be printed.
  • a coating solution is prepared from the following components: 5.2 g of polymer according to Preparation Example 1
  • the constituents mentioned are composed of 100 ml of a mixture with stirring
  • the plate is exposed, developed, blackened and printed in the manner described in Example 1.
  • the color acceptance of the plate is good and exposed microlines are reproduced very well.
  • the fourth stage of the gray wedge is complete and the stages up to 10 are partially covered.
  • the plate thus produced is clamped in a sheetfed offset printing press and delivers 100,000 copies of good quality under normal printing conditions.
  • the plate could continue to be printed.
  • a coating solution is made up of the following components:
  • the constituents mentioned are composed of 100 ml of a mixture with stirring
  • An oxygen barrier layer of 1.8 g / m 2 dry layer weight is then applied in an analogous manner by coating with a solution of the following composition:
  • the plate is exposed in the manner described in Example 1, but with an amount of light of 20 mJ / m 2 . Immediately after exposure, the plate is
  • the plate thus produced is clamped in a sheetfed offset printing press and delivers 100,000 copies of good quality under normal printing conditions.
  • the plate could continue to be printed.
  • Comparative Example 1 A coating solution is prepared from the following components:
  • the constituents mentioned are composed of 200 ml of a mixture with stirring
  • the plates produced in this way prove to be very difficult to develop. Strong mechanical support is the only way to free unexposed areas from adhering layer residues. The unexposed parts of the layer are partly Insoluble in the developer and tend to deposit on the plate and in the machines used for development. The resolution is poor because the gaps between fine details are not developed properly.
  • a coating solution is made up of the following components:
  • the constituents mentioned are composed of 200 ml of a mixture with stirring
  • the ink acceptance of the plate is worse than that of the printing plates produced according to the invention.
  • the first 2 levels of the gray wedge are complete and the levels up to 8 are partially covered.
  • the plate produced in this way is clamped in a sheetfed offset printing machine and, under normal printing conditions, shows strong losses of microelements after 100,000 copies and signs of wear begin to become visible in the full areas.
  • a coating solution is made up of the following components:
  • the constituents mentioned are composed of 200 ml of a mixture with stirring
  • the plate is exposed, developed, blackened and printed in the manner described in Example 1.
  • the ink acceptance of the plate is worse than that of the printing plates produced according to the invention.
  • the first 2 levels of the gray wedge are complete and the levels up to 8 are partially covered.
  • the plate thus produced is in a
  • Sheet-fed offset machine clamped shows under normal printing conditions after 100,000 copies severe losses of micro-elements and beginning signs of wear in the full areas.
  • a coating solution is made up of the following components:
  • the constituents mentioned are composed of 200 ml of a mixture with stirring
  • the plate is exposed, developed, blackened and printed in the manner described in Example 1.
  • the reproduction of fine halftone dots is sufficient.
  • the first stage of the gray wedge is complete and the stages up to 7 are partially covered.
  • the polymers produced according to the invention have a higher sensitivity.
  • the constituents mentioned are composed of a mixture with stirring
  • the plate is exposed, developed and blackened in the manner described in Example 1.
  • the plate turns out to be very slow to develop.
  • the first 2 levels of the gray wedge are complete and the levels up to 5 are partially covered.
  • the plate thus produced is clamped in a sheetfed offset machine and shows, under normal printing conditions, severe losses of microelements after 100,000 copies and signs of wear begin to become visible in the full areas.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne une composition photosensible contenant: (i) au moins un produit de polycondensation de diazonium ou au moins un système pouvant subir une polymérisation radicalaire, constitué de photo-initiateurs et de composés non saturés pouvant subir une polymérisation radicalaire, ou bien au moins un système hybride constitué d"un produit de polycondensation de diazonium et d"un système pouvant subir une polymérisation radicalaire constituée de photo-initiateurs et de composés insaturés pouvant subir une polymérisation radicalaire; (ii) au moins un liant et, éventuellement, au moins un indicateur d"exposition, au moins un colorant servant à augmenter le contraste de l"image, ainsi qu"au moins un acide servant à stabiliser la composition photosensible. La composition photosensible présentée se caractérise en ce que le liant est constitué essentiellement d"unités (A, B, C, D), A correspondant à la formule (I), B correspondant à la formule (II), C correspondant à la formule (III), et D correspondant à la formule (IV). L"invention concerne également l"utilisation de cette composition photosensible pour recouvrir des plaques d"impression, ainsi que des plaques d"impression qui sont recouvertes de cette composition photosensible.
EP01929416A 2000-03-09 2001-03-07 Utilisation de polymeres acetalytiques contenant des groupes carboxyle dans des compositions photosensibles et des plaques d'impression lithographiques Withdrawn EP1292860A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10011096A DE10011096A1 (de) 2000-03-09 2000-03-09 Verwendung von carboxylgruppenhaltigen Acetalpolymeren in lichtempfindlichen Zusammensetzungen und lithographischen Druckplatten
DE10011096 2000-03-09
PCT/EP2001/002543 WO2001067179A2 (fr) 2000-03-09 2001-03-07 Utilisation de polymeres acetalytiques contenant des groupes carboxyle dans des compositions photosensibles et des plaques d"impression lithographiques

Publications (1)

Publication Number Publication Date
EP1292860A2 true EP1292860A2 (fr) 2003-03-19

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EP01929416A Withdrawn EP1292860A2 (fr) 2000-03-09 2001-03-07 Utilisation de polymeres acetalytiques contenant des groupes carboxyle dans des compositions photosensibles et des plaques d'impression lithographiques

Country Status (5)

Country Link
US (1) US6808858B2 (fr)
EP (1) EP1292860A2 (fr)
BR (1) BR0109106A (fr)
DE (1) DE10011096A1 (fr)
WO (1) WO2001067179A2 (fr)

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JP4248137B2 (ja) * 2000-11-22 2009-04-02 富士フイルム株式会社 ネガ型感光性平版印刷版
DE10319198A1 (de) * 2002-07-04 2004-01-15 Kuraray Specialities Europe Gmbh Vernetzte Polyvinylacetale
DE10233631B4 (de) * 2002-07-24 2004-09-30 Kodak Polychrome Graphics Gmbh Lithographie-Druckplattenvorläufer mit zwei strahlungsempfindlichen Schichten
DE10257131B4 (de) * 2002-12-05 2005-07-28 Kuraray Specialities Europe Gmbh Beschichtetes Material zur Tintenstrahlbedruckung, Verfahren zu seiner Herstellung
US7511096B2 (en) * 2003-01-09 2009-03-31 Kuraray Europe Gmbh Crosslinked polyvinyl acetals
WO2004063232A1 (fr) * 2003-01-09 2004-07-29 Kuraray Specialities Europe Gmbh Polyvinylacetals reticules
CA2610282C (fr) 2005-06-03 2011-03-15 American Dye Source Inc. Copolymeres d'acetals absorbant l'infrarouge proche thermiquement reactifs, procedes de preparation et procedes d'utilisation
US7723013B2 (en) * 2007-01-11 2010-05-25 Southern Lithoplate, Inc. Negative-acting photolithographic printing plate with improved pre-burn performance
EP2366545B1 (fr) 2010-03-19 2012-12-05 Agfa Graphics N.V. Précurseur de plaque d'impression lithographique
BR112015014898B1 (pt) 2012-12-19 2021-12-07 Ibf Industria Brasileira De Filmes S/A. Chapas para impressão sensível à radiação no espectro eletromagnético e gráfica e processo de revelação de imagem
CN104870193B (zh) 2013-01-01 2017-12-22 爱克发印艺公司 (乙烯、乙烯醇缩醛)共聚物和它们在平版印刷版前体中的用途
EP2933278B1 (fr) 2014-04-17 2018-08-22 Agfa Nv Copolymères (éthylène, acétal de vinyle) et leur utilisation dans des précurseurs de plaque d'impression lithographique
ES2617557T3 (es) 2014-05-15 2017-06-19 Agfa Graphics Nv Copolímeros (de etileno, vinilacetal) y su uso en precursores de plancha de impresión litográfica
ES2660063T3 (es) 2014-06-13 2018-03-20 Agfa Nv Copolímeros (de etileno, vinilacetal) y su uso en precursores de plancha de impresión litográfica
EP2963496B1 (fr) 2014-06-30 2017-04-05 Agfa Graphics NV Précurseur de plaque d'impression lithographique comprenant des copolymères (éthylène, acétal de vinyle)
JP2020064082A (ja) 2017-02-17 2020-04-23 富士フイルム株式会社 ポジ型平版印刷版原版、及び、平版印刷版の作製方法

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Also Published As

Publication number Publication date
WO2001067179A2 (fr) 2001-09-13
WO2001067179A3 (fr) 2002-01-17
BR0109106A (pt) 2002-12-03
DE10011096A1 (de) 2001-10-11
US6808858B2 (en) 2004-10-26
US20030180654A1 (en) 2003-09-25

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