DE2364178A1 - RADIATION-SENSITIVE RECORDING MATERIAL FOR THE PRODUCTION OF POSITIVELY WORKING FLAT PRINT PLATES - Google Patents

Description

Radiation-sensitive recording material for manufacture positive working planographic printing plates.

The invention relates to a radiation-sensitive recording material for the production of positive-working planographic printing plates, consisting of a substrate and at least one on top applied radiation-sensitive layer made of a radiation-sensitive acrylate-diazoquinone copolymer.

It is known, for example from GB-PS 1 267 005, to use copolymers for the production of positive reliefs and photoresist materials, which are obtained by complete esterification of a copolymer from methyl methacrylate and hydroxyethyl methacrylate with a large excess of 2-diazo-1-naphthol-4-sulfonyl chloride. Included Virtually complete esterification of the hydroxyl groups was deemed necessary as it was known that diazoquinone polymers can be crosslinked with free hydroxyl groups by exposure to light. It was believed to have free, non-phenolic hydroxyl groups able to react with the ketene or carboxylic acid groups which are generated from the diazoquinone groups on exposure with the creation of cross-linking centers. Information on this can be found, for example, in US Pat 3,502 470.

The invention was based on the finding that copolymers of methyl methacrylate and hydroxyethyl methacrylate units, in which the two units are present in approximately equimolar proportions and which have been esterified with 2-diazo-1-naphthol-4-sulfonyl chloride and are used to produce positive-working printing plates, only provide panels with poor abrasion characteristics. It has been found that the ratio of methyl methacrylate to hydroxyethyl methacrylate must be increased to at least 75% in order to achieve sufficient abrasion characteristics and that to achieve the best possible abrasion characteristics, copolymers must be used whose basic structure consists of at least 80 mol-I of methyl methacrylate units. It has been shown that

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the attrition characteristics are not improved by controlling the esterification reaction to remove free hydroxyl groups remain in the photosensitive polymer. It has also been shown that if only a fraction of the hydroxyl groups, e.g. 1/10 of the hydroxyl groups are not esterified, a noticeable smearing of the printing plates can be observed.

The object of the invention is to provide a radiation-sensitive recording material for the production of positive-working planographic printing plates or lithographic printing plates to indicate the are characterized by improved abrasion characteristics and are not prone to scumming when in use, and which are further characterized by good developability.

The invention was based on the knowledge that to manufacture of printing plates and photoresist compositions in excellent Way copolymers that are built up on a mole basis are suitable for:

1. at least 75 % of recurring alkyl acrylate units;

2. 10 to 22 I acryloyloxyalkylquinonediazidic acid ester repeating units;

3. 1 to 7 I repeating acryloyloxyalkylcarboxylate units and

4. up to 4 % repeating hydroxyalkyl acrylate units.

Characteristic of those used to manufacture the planographic printing plates Polymers is that a large excess of diazoquinone reactant is not required for their preparation, and that it is furthermore not necessary that all free hydroxyl groups are completely esterified by diazoquinone radicals.

The invention thus provides a radiation-sensitive recording material for the production of positive-working Planographic printing plates or lithographic printing plates, consisting of a layer support and at least one coated thereon

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radiation-sensitive layer made of a radiation-sensitive Acrylate-diazoquinone copolymers, which is characterized in that the radiation-sensitive layer is an acrylate-diazoquinone copolymer which is built up on a MoI-I basis to:

1. 75 to 87 Ϊ from recurring alkyl acrylate units;

2. 10 to 22 % of acryloyloxyalkylquinonediazidic acid ester repeating units;

3..1 to 7 % from recurring acryloyloxyalkylcarboxylate units and

4. up to 4 % from recurring hydroxyalkylaerylateiiihei th.

Under "positive" printing plates are meant here such printing plates, which take up oleophilic printing ink in the unexposed areas.

Those suitable for making printing plates and photoresist compositions Radiation-sensitive acrylate-diazoquinone copolymers of the invention can by addition polymerization of the corresponding Monomers produced

For the production of the radiation-sensitive recording materials, copolymers are preferably used in which at least 75 mol%, preferably at least 78 mol% of the recurring Units consist of alkyl acrylate ester units, e.g. alkyl acrylate units of the following formula I:

HR ¹

f f

H C = O

OR ²

where mean:

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R ^ is a methyl radical or a hydrogen atom and R ^{2 is} an alkyl radical having 1 to 6 carbon atoms.

Surprisingly, xmrde found that such a high proportion on short-chain alkyl acrylate ester units in the copolymers leads to advantageous abrasion characteristics, so that starting of the copolymers printing plates can be produced with extremely long life, i.e. printing plates from which at least 100 prints can be made using normal printing conditions without any noticeable deterioration the quality of the last prints compared to the prints made first as a result of the destruction of the printing plate is.

For example, the repeating units of the formula I can consist of methyl methacrylate, ethyl methacrylate, n-propyl acrylate, n-butyl methacrylate, t-butyl acrylate, isoamyl methacrylate, Cyclohexyl methacrylate or n-hexyl methacrylate units.

The rest of the repeating acrylic or methacrylic Units ^ l ^ x ^ iijl ^ jrxjcxzciafiuisxxBxxicixslxrkcX ^ KXiiK »hydroxyalkyl acrylate units, xsxBxiBXtx which in turn are largely further esterified.

In order to make the polymers radiation-sensitive, 10 to 22 mol-I of the repeating units of the copolymers are further esterified with an acidic quinonediazide such as an ortho- or para-quinonediazide sulfonic acid or an ortho- or para-quinonediazide carboxylic acid.

The repeating radiation-sensitive units of the copolymers can advantageously consist of recurring units of the following formula II:

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HR ¹

ι.

II (r- C

OR ³ -OXD

where mean:

R is a methyl radical or a hydrogen atom; R is an alkylene radical having 2 to 6 carbon atoms;

0-X is an acid ester residue, e.g. a sulfonyl residue of the formula

0

II ii

- (-. 0-S -) - or a carboxyl radical of the formula - £ -0-0 -) - and

Il
0
D is a quinonediazide residue.

As a result, the recurring Acryloyloxyalkylquinonediazidic acid ester units consist of:

2-methacryloyloxyäthy1-o-quinonediazidesulfonat-; Z-methacryloyloxyethyl-o-quinonediazidecarboxylate; 2-methacryloyloxyethyl-p-quinonediazidesulfonate-; Z-Acryloy.loxyäthyl-o-quinonediazide sulfonate; Z-methacryloyloxyethyl-p-quinonediazidecarboxylate; 2-acryloyloxyethyl-p-quinonediazidesulfonate-; S-acryloyloxypropyl-o-quinonediazide sulfonate-; S-methacryloyloxypropyl-o-quinonediazidecarboxylate-; 4-methacryloyloxybutyl-o-quinonediazide sulfonate-; 4-acryloyloxybutyl-p-quinonediazidecarboxylate-; S-methacryloyloxyamyl-o-quinonediazide sulfonate and ö-methacryloyloxyhexyl-o-quinonediazidecarboxylate units,

The quinonediazide radicals that are part of those used according to the invention Copolymers can have a very different

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have dene constitution, provided only that the quinonediazide group is sensitive to light.

Ortho-quinonediazides of the benzene series with one or more o-quinonediazide radicals have proven to be particularly advantageous. s en, ζ.B .:

o-benzoquinonediazide; 1,2-naphthoquinone-1-diazide; 1,2-naphthoquinone-2-diazide; 7-methoxy-1,2-naphthoquinone-2-diazide; 6-nitro-1,2-naphthoquinone-2-diazide; 5- (carboxymethyl) -1, 2-naphthoquinone idiazide; 2,3-phenanthrenequinone-2-diazide; 9,10-phenanthrenequinone-10-diazide and 3,4-chrysenequinone-3-diazide.

Surprisingly, it has been found that if 1 to 7 MoI-I der Repeating units of the acrylate copolymers are repeating hydroxyalkyl acrylate units, which are furthermore with a Carboxylic acid, an unexpected improvement in the developability of these copolymers is achieved when they are used for Manufacture of printing plates and photoresist compositions can be used. Furthermore, it has unexpectedly been found that the printing plates according to the invention have no or at most only very few Have a tendency to smear, even if up to 4 mol-I of the repeating units of the copolymers are made repeating hydroxyalkyl acrylate units exist. It has been shown that by introducing recurring acryloyloxyalkylcarboxylate units in the acrylate copolymers it is no longer necessary for a practically complete esterification of the To effect hydroxyalkyl acrylate units with a quinonediazidic acid, as previously considered necessary. this again makes it possible to use a large excess of quinonediazidic acid in the preparation of the copolymers to renounce.

The recurring acryloyloxyalkylcarboxylate units advantageously have has a structure according to the following formula III:

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HR ¹

H C = O-

OR ³ -OCR ⁴

where R and R have the meanings already given and R a hydrocarbon residue or a halohydrocarbon residue each having up to ZO carbon atoms, preferably 10 or fewer carbon atoms.

The acryloyloxyalkylcarboxylate units are advantageously made of the formula III for example from:

2-methacryloyloxyethyl acetate-; 2-methacryloyloxyethyl propionate; 2-acryloyloxyethyl butyrate; 2-methacryloyloxyethylcaproate- ; 2- Methacryloyloxyäthylmyris tat-; 2-methacryloyloxyethyl benzoate; 2-acryloyloxyethyl-a-naphthoate-; 3-acryloyloxypropyl stearate; S-acryloyloxypropyl acetate-; S-methacryloyloxypropyl caprylate; S-acryloyloxypropyl arachidate-; 4-acryloyloxybutyl acetate-; 4-methacryloyloxybutylbutyrate-; 4-acryloyloxybutyl laurate; 4-methacryloyloxybutyl benzoate-; δ-methacryloyloxyhexyl acetate-; 6-methacryloyloxyhexylbutylate-; 6-acryloyloxyhexyl stearate and 6-acryloyloxyhexyl benzoate units.

The carboxylate residues of the acryloyloxyalkylcarboxylate repeating units can consist in a corresponding manner of residues of halogenated acids, i.e. the carboxylate residues can, for example from residues of fluoroacetic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, dichloroacetic acid, trichloroacetic acid, α-chloropropionic acid, ß-chloropropionic acid, 4-iodobutyric acid or p-bromobenzoic acid exist.

As already stated, it is not necessary to have an excess

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to use on the comparatively expensive quinonediazide reaction component to virtually complete esterification of all Ensure hydroxyalkyl acrylate units.

An unexpected advantage of the invention is that it can be used to make the planographic printing plates and photoresists Light-sensitive acrylate copolymers up to 4 mol% can contain recurring hydroxyalkyl acrylate units without thereby impairing the printing ink absorption and printing ink retention properties the copolymers are adversely affected.

As a result, the copolymers used in the present invention In addition to the recurring units of the formulas I, II and III, there are also, for example, recurring units of the following formula IV exhibit: .

HR ¹

ft ^x

iv - e c - c

t!

H C = O

0-R ³ -0H

where R and R have the meanings already given.

Typically, the repeating units of the formula IV can be generated, for example, from the following compounds (consequently also the parent or precursor compounds for the recurring units of the formulas. II and III):

2-hydroxyethyl methacrylate; 2-hydroxypropyl acrylate; 3-hydroxypropyl methacrylate; 5-hydroxypentyl acrylate; 6-hydroxyhexyl acrylate and 2-hydroxyhexyl methacrylate.

The radiation-sensitive acrylate copolymers which can be used according to the invention can be according to the usual known vinyl polymer

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Establish sation methods. So can the manufacture of the polymers take place, for example, in bulk or in solution or by emulsion polymerization or so-called "bead" polymerization, preferably in the presence of a customary polymerization initiator.

Thus, first of all, alkyl acrylates, as required to produce the repeating units of the formula I, and hydroxyalkyl acrylates as required for production of the repeating units of the formula IV are required, are reacted with one another, namely with the production of copolymers, which essentially consist of recurring units of the formulas I and IV. Then the free hydroxyl groups of the repeating units of the formula IV are esterified using a suitable carboxylic acid and a quinonediazidic acid with the formation of recurring units of the formulas II and III. On the other hand, carboxylic acids can and / or quinonediazidic acids are also reacted with the alkyl acrylates and hydroxyalkyl acrylates when the copolymerization he follows. ·

The ratios of the various repeating units in the final "copolymer" can be determined by using appropriate amounts of reaction components during the copolymerization.

It has proven to be particularly advantageous to use the light-sensitive Copolymers based on copolymers of hydroxyethyl methacrylate and methyl methacrylate, since these two monomers have very similar polymerization rates exhibit. This means that copolymers of hydroxyethyl methacrylate and methyl methacrylate are particularly easy to prepare, as in the preparation of copolymers from hydroxyethyl methacrylate and methyl methacrylate polymers are easily obtained in which the ratio of repeating hydroxyethyl methacrylate units to methyl methacrylate units in relation to the concentrations of the starting monomers in the polymerization reaction.

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The use of radiation-sensitive devices has proven to be particularly advantageous Copolymers with a molecular weight of 5000 up to 20,000, although there are also some with lesser and greater Molecular weight can be used.

Unless otherwise indicated, molecular weights are used here of copolymers reported as the polystyrene equivalents average molecular weight numbers (polystyrene equivalent number average molecular weights), determined using gel permeation chromatography, as described, for example, in the book by H. Determann, "Gel-Chromatography", 2nd edition, Springer-Verlag, N.Y. , 1969 and in the journal "Journal of Polymer Science", Part A-2, Vol. 6 (1968, pp. 1567-1579.

It is known that the molecular weights and inherent viscosities of polymers are related to one another in such a way that polymers both by their molecular weight and their inherent viscosity marked.

The use of such radiation-sensitive copolymers whose inherent viscosity has proven to be particularly advantageous is 0.05 to 0.25, the inherent viscosity - if nothing else is stated - it is determined using one gram copolymer per dl 1,2-dichloroethane at 25 ° C, e.g. according to the method given in the journal "Journal of Colloid Science", Volume 1 (1946), pages 261-269 by H. CPJ \ .GC.

Coating compositions for the production of recording materials according to the invention can be prepared in a conventional manner by dispersing or dissolving the corresponding polymers in a solvent or solvent mixture that is compatible with the radiation-sensitive Copolymers does not react, at least not within the period of time during which the solvent (s) are in contact with the polymers, it being understood that the solvent or solvents used also do not have a destructive effect on the substrate should act, which is necessary for the production of the recording

materiaiien is used.

- 10a -

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Typical solvents used to make the coating Masses that can be used are, for example:

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n-propanol; Methyl ethyl ketone; 1,2-ethylene dichloride; 1-nitropropane; n-butyl acetate; Cyclohexane; Hydroxyethyl acetate; Cyclohexanone; Methyl isobutyl ketone; Toluene; "diacetone alcohol; dioxane; isobutanol;" Acetonitrile; 2-ethoxyethanol; Acetone; 4-butyrolactone; 2-methoxyethyl acetate; 2-methoxyethanol and mixtures of these solvents.

The most favorable concentration of radiation-sensitive in individual cases Copolymers in the coating solution depend on the radiation-sensitive copolymers used in the individual case, as well as the substrate and the coating method used. It has proven to be particularly expedient if the coating solutions used for coating are about 1 to 50 Weight-I, preferably about 2 to 10% by weight of the radiation-sensitive Contain copolymers. However, the copolymers can optionally also be used in higher concentrations.

The coating compositions also have customary known properties Additives are incorporated, e.g. dyes and / or pigments, if colored relief images are to be obtained with the aim of to facilitate the recognition of the images. Alizarin dyes and azo dyes, for example, have proven to be particularly suitable for this purpose proven.

Pigments such as Victoria Blue (Color Index Pigment Blue I), Palomar Blue (Color Index Pigment Blue 15) and Watchung Red B (Color Index Pigment Red 48) are used will.

A method that makes it particularly easy to recognize image areas allows, consists in the use of a print-out material with an inert dye.

For example, a green-colored inert dye, such as Alizarin Cyanine Green GHN Cone. (Color Index acid green 25) in combination with an azide copy material, e.g. diazido

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, stilbene disulphonic acid, disodium salt a green-colored copy on a blue-green background.

For the production of the recording materials according to the invention It is possible to use generally customary, known copy-out dyes. As particularly advantageous copy-out dyes however, cyanine print-out dyes such as those described in US Pat. No. 3,619,194 have been found.

In addition to dyes and pigments, other known additives which are customary, for example, can be incorporated into the coating compositions serve to improve the film-forming properties of the coating compositions and / or the coating properties, the adhesion of the coatings to the substrate, the mechanical strength, stability and the like.

The developability of the planographic printing plates may occasionally be reduced if the radiation-sensitive layer is excessively heated during exposure, e.g. This can be the case if repeated exposures take place. In order to improve the developability of plates, which on higher Temperatures are heated, it can be advantageous to add additives such as boric acid to the coating compositions and / or antioxidants, e.g. benzotriazole, hydroquinone and the like, and / or polyols, e.g. L (-) - rhamnose, glycerin or mannose and / or carboxylic acids, e.g. oxalic acid, malonic acid, sebacic acid, adipic acid, succinic acid, phthalic acid, isophthalic acid, Add citric acid and / of the butanetetracarboxylic acid.

Occasionally, aging of the plate can also lead to a certain reduction in developability. To such a tendency To avoid, heavy metal salts, for example, can be added to the coating compounds of carboxylic acid are added, for example calcium, magnesium, strontium, cobalt, manganese and zinc salts of carboxylic acids such as zinc salicylate, zinc acetate, zinc propionate, zinc acetylacetonate, zinc formate and zinc benzoate.

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Of course, the described additions are only used in comparatively low concentrations or subordinate concentrations are used, i. e. the concentration of such Additives generally make up no more than 5% by weight of the radiation-sensitive layer produced.

the radiation-sensitive layers

It has proven to be particularly advantageous if for the generation / the coating compositions in addition to the polymeric quinonediazide at least one other film-forming polymeric resin or polymer is added. This additional polymer or polymer resin is typically not radiation sensitive »although it is also Mixtures of radiation-sensitive polymers or resins are used v / can ground. The second polymer is advantageously selected from the available series of Polymers selected ^ that it is used in the preparation of the coating solution solvent used is soluble. The most favorable concentration of such a polymer in the individual case can can be very different »As a rule, it has proven to be useful to use this second polymer or resin in concentrations of about 0.2 to 5.0 parts by weight of resin per part by weight of polymer Use quinonediazide. It has proven to be particularly advantageous for the production of printing plates to use 0.2 to 1.0 parts by weight to use second polymer or resin per part by weight of polymeric quinonediazide.

Particularly advantageous film-forming polymers or resins that are not Are radiation-sensitive and are used to produce the radiation-sensitive Suitable recording materials of the invention are phenolic resins, which have become known as novolaks and resole resins and, for example, in Chapter XV of the book "Synthetic Resins in Coatings" by H.P. Preuss, Koyes Development Corporation (1965), Pearl River, New York. Suitable G-cresol-formaldehyde resins can, for example, by process as they are known from DT-PS 281454. Such resins have proven particularly advantageous.

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Phenolic resins of the type described can be broken down by condensation of phenol with formaldehyde, generally by reacting one phenolic compound with two or three reactive hydrogen atoms in an aromatic ring with an aldehyde or an aldehyde-yielding compound which is capable of entering into a phenol-aldehyde condensation reaction.

Examples of particularly suitable phenolic compounds are: cresol, xylenol, ethylphenol, buty! Phenol, isopropylmethoxyphenol, Chlorophenol, resorcinol, hydroquinone, naphthol and 2,2-bis (phydroxyphenyl) propane.

Examples of particularly suitable aldehydes are formaldehyde, acetaldehyde, Acrolein, crotonaldehyde and furfural, tin example of a compound that releases an aldehyde is 1,3,5-trioxane, Ketones and acetone are also suitable for condensation with the phenolic compounds.

The particularly suitable phenolic resins are those which are insoluble in water and trichlorethylene, but easily dissolve in common organic solvents such as methyl ethyl ketone, Acetone, methanol and ethanol solu *. Phenolic resins with a Particularly advantageous combination of properties are those that have an average molecular weight of about 350 to Have 40,000.

Other suitable film-forming resins are, for example, those made from chlorinated biphenyls, modified rosin, copolymers from maleic anhydride with styrene or vinyl methyl ether, Vinylidene chloride-acrylonitrile copolymers, terpolymers of vinylidene chloride and acrylonitrile with acrylic acid or itaconic acid, polyacrylic acids, Methyl methacrylate-methacrylic acid copolymers, cellulose esters, e.g., cellulose acetate stearate and the like.

Radiation-sensitive recording materials can be used

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Manufacture conventional known methods by applying the radiation-sensitive Polymers from solvents or solvent mixtures on a substrate, for example by spray coating, by dip coating, by whirl coating or by coating agent application rollers.

For the production of the recording materials according to the invention The usual known supports can be used, e.g. supports made of paper or with polyethylene or polypropylene coated paper, layer support made of parchment or cloth, layer support made of foils made of metals, such as Aluminum, copper, magnesium and zinc, finally substrates made of glass and glass coated with metals, e.g. Coated with chrome, chrome alloys, steel, silver, gold and platinum Glass * also supports made of conventional synthetic polymers, e.g. poly (alkyl methacrylates), e.g. poly (methy! Methacrylate) Substrates made of polyester foils, e.g. made of polyethylene terephthalate, also made of polyvinyl acetals, polyamides, e.g. of the nylon type. Furthermore, the layer supports can, for example consist of films made of cellulose esters, e.g. cellulose nitrate, cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate.

Particularly advantageous typical layer supports for radiation-sensitive Recording materials according to the invention are those "made of zinc, anodized aluminum, roughened or grained Aluminum, copper and customary metal and paper layers produced in a special way, layer carriers made of superficial hydrolyze cellulose ester films, as well as polymer layers such as polyolefins and polyesters and polyamides.

Advantageously, the. So-called adhesive layers or have adhesion-promoting layers, for example those made from polymers, copolymers and terpolymers of vinylidene chloride with acrylic monomers, e.g. acrylonitrile and methyl acrylate and un-

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Saturated dicarboxylic acids, e.g. itaconic acid, as well as further from Carboxymethyl cellulose and polyacrylamides and other polymers.

In an advantageous manner, the layer support can furthermore optionally have a so-called filter or antihalation layer made of a colored polymer, which is used for exposure

the

used radiation after being absorbed / sensitive to radiation Layer has passed, such layers avoid unwanted reflection from the substrate. One layer off a yellow dye in a polymeric binder, which can consist, for example, of one of the polymers mentioned, which is used for production An adhesive layer can be used, for example, is a particularly effective antihalation layer if for exposing the radiation-sensitive recording materials ultraviolet light is used.

The radiation-sensitive layers can be conventionally known Layer thicknesses are applied, whereby the most favorable layer thickness in individual cases can depend on various factors, E.g. the purpose of the layer, the one used in the individual case radiation-sensitive polymers and the nature of other components present in the radiation-sensitive layer ■ can be. Typically, the radiation-sensitive Schulten, for example, have a layer thickness of about 0.000127 to 0.00762 mm or more, which in the case of printing plates particularly layer thicknesses of about 0.000635 to about 0.00254 mm have proven particularly advantageous.

After the photosensitive layer has been applied, the coated Layer support dried, optionally at an elevated temperature for the purpose of removing any solvent still present.

The recording materials according to the invention can be exposed by customary known processes, for example by a trans- '

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parent negative or. Slide, using a light source, the actinic one. Emits radiation, preferably radiation rich in ultraviolet light. As light sources, for example, carbon arc lamps _s can be further used mercury vapor lamps, fluorescent light-emitting lamps, tungsten filament lamps or laser emitter.

The exposed recording materials can then be used in a conventional manner can be developed in a known manner, for example by flowing over, dipping or wiping with a solvent or Lcaingsmittelgemiscn, which a different Exercise solving power on the exposed and non-exposed areas.

Advantageously used as a solvent for development of the exposed layers used alkaline solutions, for example aqueous alkaline solutions, which optionally contain one or more may contain short-chain alcohols and / or ketones. The most favorable alkalinity of the developing solutions in each individual case depends of the polymeric quinonediazide used in the individual case, of any other resins and polymers that may be present, as well as, where appropriate, the ratio of the various components of the light-sensitive layers from one another.

The development solutions used for development can optionally Contain dyes and / or pigments and / or hardeners.

After allowing the developing solution to take effect, the developed image can be rinsed off, e.g. with distilled water, whereupon it is dried, optionally at elevated temperatures.

The images obtained in this way can then be used in the usual are post-treated in a known manner, according to their use

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purpose, e.g. by means of desensitizing etching solutions, a plate varnish, in the case of using a printing plate and with an acidic or basic etchant or plating bath in the case of using a resist.

The following examples are intended to illustrate the invention in more detail.

Examples

A solution of a monomer to produce recurring units of the formula I, in this case methyl methacrylate, and a solution of a monomer to produce recurring units of the formula IV, in the present case 2-hydroxyethyl ^{methyl acrylate and 2,2 f} -azobis (2-methylpropionitrile) polymerization initiator in a monomer solvent were added to a reaction solvent which had been refluxed under a nitrogen atmosphere. The mixture was then refluxed under a nitrogen blanket.

The copolymer produced in this way was not sensitive to radiation, because it had no repeating units of formulas II and III.

In several attempts several different copolymers were made Units of formulas I and IV are produced. These copolymers are referred to below as starting copolymers.

The manufacturing conditions for the various starting copolymers are compiled in Table I below.

In the following table, DCÄ stands for 1,2-dichloroethane and MÄK for methyl ethyl ketone.

The starting copolymer G was made using 2-Hydroxyäthy1-

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te

acrylate produced instead of 2-hydroxyethyl methacrylate.

In the case of Table I, in which the individual monomers and Reaction solvents are not listed, all substances were put together »before they were heated.

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Table I.

Output co
polymer Output mono
mers in g
cn civ) 162.5 Initiator in g A. 275 130 8.4 B. 300 542 4.2 C. 1458 1041 20th D. 2803 50 : 57.8 E. 175 86.7 .2.25 F. 333 4.2

Monomer-solvent heating time in reaction solvent hours

H I J K

100

23.2 "

170.2 40.5 162.7 33.8 400.5 67.6 500.6 67.6

1.2

2.09

1.96

9.31

11.31 DCE-330 ml
DCÄ-16 70 ml

DCÄ-330 ml
DCÄ-16 80 ml

MÄK-3000 g
MÄK-3000 g

.MÄK-11.5 34 ml

N / A.

DCÄ-1015 ml

I) CA-333 ml
DCÄ-16 70 ml

DCÄ-100 ml
DCÄ-500 ml

MÄK-790 ml
MÄK-735 ml
MAK-1745 ml
MÄK-2 125 ml

2o 16 16

N / A.

17 16

18th

18 18 18 18

2-hydroxyethyl acrylate

The starting copolymers can be isolated in a conventional manner by adding a nonsolvent, washing and drying.

As can be seen from the following Table II, it has proven to be advantageous in most cases to esterify the Acid chloride used in the reaction mixture from common copolymers to add, which is obtained in the production of the starting copolymers, as much triethylamine as is used to neutralize the hydrochloric acid is advantageously added to the reaction mixture is required, which is obtained as a by-product in the esterification reaction.

A radiation-sensitive acid chloride and an acid chloride that is not sensitive to radiation, be in consecutive Process stages introduced.

In the present case, the radiation-sensitive acid chloride existed from 1, Z-naphthoquinone-Z-diazide-S-sulfonyl chloride, whereas the non-radiation-sensitive acid chloride from benzoyl chloride duration.

The first stage of the esterification reaction, during which only the radiation-sensitive acid chloride was present, was carried out with stirring until the reaction was complete. Then the non-radiation sensitive Acid chloride was added, stirring continued until the esterification reaction was complete. the The reaction mixture was then brought to room temperature, whereupon the resulting triethylamine hydrochloride was removed by filtration became. The radiation-sensitive copolymer would then precipitated from the filtrate by adding a non-solvent, filtered off, washed and dried.

Several copolymers were prepared in the manner described, The individual production conditions are listed in Table II below.

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Starting copolym.er, Total reactivity solvent Reaction mixture Water 15.2 1 Tab lie II Response time step Radiation I. amount used onsmis'ehJung for isolation 1538 g of the react Triethyl ratio of Time step sensitive in Total Reacti of the light temp tion mix Isopropyl alcohol amine (g) photosensitive 1, ches copoly II onmixture sensitive poly Entire reac 10 1 acidic 2. mer 7850 g the mers in liters tion mix Isopropyl alcohol chloride to non- III Entire reac 17 1 sensitive Hrs. + 5 C A: Isopropyl alcohol tion mix Isopropyl alcohol Acid chloride in g 4th Hrs. + 5 ⁰ C IV 17 1 80 g of the reac 6 1 150 301 / 17.5 16 Hrs, + 5 C B: Isopropyl alcohol tion mix Distilled 4th Hrs. + 2 ⁰ C V 17 1 819.3 of the react Water 9 I. 120 241 / 14.0 16 C: Water 87 1 tion mix . Distilled 16 Hrs. + 5 ⁰ C VI 756.7 g of the reac Water 9 1 23 8 527 / - • hours, + 5 ^° C D: tion mix Distilled 16 Hrs. O ⁰ C VII ep 1852 g the reac Water 13 1 51 129 / 33.6 4th Hrs. O ⁰ C OO E: tion mix Distilled 4th C *. J * r Or *
OtO " ⁺ 3 _n ^ VIII OO 2257 g of the Reac Water 13 1 46.6 92.8 / 5.4 16 Hrs, + 5 ⁰ C Q: measurement 4th Hrs. O ⁰ C • IX Ö 81 161 / 9.3 16 Hrs, + 5 ⁰ C cx> G; 4th , 5 hours, + 7 ⁰ C X OO 14.1 31.4 / 2.0 16 Hrs. + 7 ⁰ C H: 15, , 5 hours, + 7 ⁰ C XI 24.5 54.9 / 2.6 5 , 5 hours, + 7 ⁰ C I; 15, Hrs, + 6 ⁰ C 27.2 59.1 / 3.45 5, J; 16 Hrs. + 7 ⁰ C 55.1 1 33 / - K; 16 55.2 133 / -

The yields, inherent viscosities and molecular weights for some of the radiation-sensitive copolymers presented here are compiled in the following Table III.

The molecular weights and inherent viscosities have been reported in the as described, unless otherwise stated. As can be seen from the data in the table, the Molecular weights and inherent viscosities of all of the radiation-sensitive copolymers listed within the range as preferred specified areas.

Tabel III yield
in g Radiation Sensitivity
Lich copolymer Inherent
Viscosity Molecular
weight 543 I. 0.13 + 5370 II 0.14 + 1925 III 0.16 523 IV 0.11 9100 255 V 0.20 26700 508 VI 0.20 + 575.3 χ " 0.16 7100 669.1 XI 0.10 8300

+ not determined

The ratios of the recurring units to one another are in mol! listed in Table IV below. The recurring Units are used as recurring units (I), (II), (III) and (IV), in accordance with the general formulas given earlier. In the following table IV, the copolymer XII is also listed. This copolymer was made like the other copolymers. It makes a difference differs from the other copolymers only in the concentration ratios of the repeating units.

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Table IV

Radiation
sensitive
ches copoly
mer Recurring
CD (Π) 45 Units -
(III) Mol%
CIV) Developable-
speed Well
Well Pressure behavior Abrasives
societies XII 50 28 5 bad Well
Well
Well smeared - + + I. 68.8 22.5 3.1 0.1 π Well dd bad II 75 10.6 2.5 - moderate bad low ver
lubricate moderate III 77.8 12.1
16.3 - 11.6 It bad smeared Well 28607 IV
V. 77.8
81.8 15th
15.0+
10 6.1
1.9 4, C no smear
ren
no smear
ren Il
dd 8/0788 VI
VII
VIII 83.3
83.3
85 12.1 1.7
1.7+
1 4th no smear
ren
no smear
ren
no smear
ren dd
Cf
Il
Il IX 86.3 11 1.3 0.3 no smear
ren 11 X '89 9 - - no smear
ren It XI 91 - - no smear
ren dd

+ Made using 2-hydroxyethyl acrylate not examined

OO

The radiation-sensitive copolymers listed in Table IV were made into planographic printing plates in the manner described below:.

Starting from the copolymers listed in Table IV, radiation-sensitive coating compositions were prepared by mixing the The components listed in Table V below are produced, the individual coating compositions only differing in each individual case used radiation-sensitive copolymer differentiated.

Table V

Radiation sensitive copolymer 6.0 g

Cresol-formaldehyde resin. (Alnovol 429 K) 3.0 g

Alizarin-Cyanine Green (GUN Conc.). 0.3 g

2-methoxyethanol -34.0 ml

2-methoxyethyl acetate 34.0 ml

ethyl ethyl ketone 2 7.0 ml

1,2-dichloroethane 42.0 ml

Diacetone alcohol '4.0 ml

The radiation-sensitive copolymers and those produced from them Printing plates were found to be insensitive to yellow light and light of longer wavelengths. Infqlge-of that could the copolymers and sheets, unless otherwise specified, are processed in yellow light.

The manufacture of the recording materials was carried out characterized in that the individual coating compositions according to the spin coating method on roughened, anodized with phosphoric acid aluminum substrate were coated with a PoIyacrylamidhaftschicht, after its preparation, the individual plates were incubated at 6O ⁰ C for 20 hours to thereby simulate the effects, which occur in practice when storing the printing plates.

The printing plates then became imagewise transparent Slide exposed for 4 minutes using a carbon arc lamp with 215 28 Ix. The panels were then wiped off developed with an aqueous alkaline solution of the composition given in Table VI below.

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T able VI

Triethanolamine 10 ml

Isopropyl alcohol 30 ml

Sodium hydroxide 0.5 g

Water 60 ml

In the case of plates showing poor developability according to Table IV it has proven very difficult to remove all of the radiation-sensitive polymer from the exposed Areas to be removed without removing the radiation-sensitive layer in the image areas, i.e. non-exposed areas. Districts, not to damage. In the case of plates with poor developability, it has been found difficult to completely remove all of the exposed polymer to remove. In the case of plates with good developability, the polymer could be removed from the exposed areas during development. removal process well and easily.

The developed panels were then subjected to a Sehne11 abrasion test, by placing documents under either the printing plate or the offset printing blanket of the printing plate to avoid an abnormal to produce high plate blanket printing. The abrasion was increased on this s'veise by a factor of at least 2.5, i.e. one Plate from which TOO 000 prints can normally be made under normal printing conditions is not suitable for production of more than 40,000 copies under the conditions of the 'rapid abrasion test.

The abrasion characteristics were defined as follows.

Poor abrasion properties 40,000 prints

Moderate abrasion properties 40,000 - 60,000 prints

Good abrasion properties. 60,000 prints

The abrasion properties listed in Table IV correspond these criteria.

The printing behavior listed in Table IV resulted from the

4.098.28 / 07

Background areas smeared during printing. The smear is once ^ for the degree of deposition of printing ink in the background areas, i.e. the exposed areas of the panels. While plates with a low degree of blending are suitable for the production of printed images, in most cases the aim is to obtain printing plates, that don't smear.

From the data summarized in Table IV it can be seen that printing plates made using radiation sensitive copolymers with less than 75 MoI-I recurring linear units Formula I have poor abrasion or wear properties exhibit. To have particularly advantageous abrasion properties obtain is the presence of about 78 MoI-I repeating units of the formula I required. Since increased concentrations of recurring units of the formula I these To improve printing plate properties, there is no real max Ratio of x repeating units of the formula I, what the As far as abrasion properties are concerned. However, very high concentrations of recurring units of the formula I prevent their presence sufficient concentrations of the other repeating units that are available to achieve good developability meant to be. It has been shown that in practice the recurring units of the formula I do not exceed 87 mol-I of should make up recurring units.

As can also be seen from Table IV, the printing properties of the printing plates are adversely affected if recurring units of the formula IV and no recurring units of the formula III are present in the polymers. Furthermore, smearing is observed, even in the presence of repeating units of the formulas III and IV, if repeating units of the formula II are present in concentrations of more than 2.5 mol % . With concentrations of less than 2 2 MoI-I of recurring units of the formula II and small amounts of recurring units of the formula III, eg * B / 1 MoI-I, up to 4 MoI-I

409828/0788

repeating units of the formula IV may be present without this has an adverse effect on the printing plates.

As can be seen from Table IV, in order to achieve a good Developability certain ratios of recurring units the formula II and the formula III required.

If polymers without repeating units of the formula II are used, they become non-radiation-sensitive and non-developable Panels preserved. It is surprising, however, that when using polymers with very high concentrations of recurring Units of the formula II of, for example, over 22.5 mol-I the The developability of the plates becomes worse. In the case of polymers with 22.5 mol-I of recurring units of the formula II and if repeating units of the formula III are present, moderate developability is observed. With only 10 The plates show MoI-I repeating units of the formula II and only one MoI-I of repeating units of the formula III a good development platform. i, on the other hand, becomes the concentration of recurring units of the formula II are left at about -10 mol-I and there are no recurring units of the formula III before, the plate developability is poor.

The results in Table IV can thus be seen that advantageous Long-life planographic printing plates can be obtained using radiation-sensitive copolymers, which consist of 75 to 87 mol-I of recurring alkyl acrylate. units (I), to 10 to 22 mol-I of repeating acryloyloxyalkylquinonediazidic acid ester units (II), to 1 to 7 MoI-I from recurring acryloyloxyalkylcarboxylate units (III) and up to 4 MoI-I from repeating hydroxyalkyl acrylate units (IV).

Particularly advantageous copolymers have proven to be those which have at least 78 mol-I of repeating units of the formula I.

409828/0788

consist and at most about 17 mol ⁰ S from recurring units of the formula II.

to the adverse effect of repeating hydroxyl groups To illustrate units in radiation-sensitive copolymers without repeating units of the formula III, and in addition to the tolorability of hydroxyl groups To illustrate repeating units, when repeating units of Formula III are present, two different ones have been made produced radiation-sensitive copolymers and processed in the manner described to form planographic printing plates.

The repeating units (I), (II), (III) and (IV) were identical to those of the copolymers of Table IV and the plates did not differ significantly from those of Table IV, the were made in the same way. The composition of the radiation-sensitive The following table shows copolymers and the behavior of the printing plates produced in the printing press VII.

Tabel 15th
11.8 1.6 VII Behavior on
Printing press the Plates-
No. Radiation sensitive
(D (ID (HI) Copolymer
'(IVj minor verse
excellent
Smear : hmiere
- no A.
B. 83.4
83.4 1.6
3.2

As is apparent from the data of Table VII, occurs in the case of using a copolymer with 1.6 MOI ⁰ J recurring units of the formula IV a low smearing, whereas an excellent performance on the printing press obtained when the amount of repeating units of the formula IV is doubled and if repeating units of the formula III are present. This comparison clearly illustrates the knowledge on which the invention is based that radiation-sensitive copolymers with recurring units of the formula 111 enable the production of printing plates with superior printing behavior and that

409828/0788

with considerable concentrations of recurring lines of formula IV can be tolerated without adverse effects on the performance of the printing plates.

In a further series of tests, further printing plates were produced using the polymers listed in Table IV, This time, however, for the production of the printing plates, the brushing dimensions listed in Table VIII below Composition were used:

Table VIII

Radiation sensitive copolymer * 6.0 g

Cresol formaldehyde resin (Alnovol 429K) 3.0 g

Alizarin Cyanine Green 0.1 g

2-iiethoxyethanol 34.0 ml

2-methoxyethyl acetate 34.0 ml

Ethylathy! Ketone 27.0 ml

1,2-dichloroethane 42.0 ml

Diacetone alcohol 4.0 ml

Zinc salicylate 0.2 g

Boric acid 0.3 g

Benzotriazole. 0.2 g

L (-) - rhamnose 0.2 g 1,3, 3-trimethy "1-1 '- (N-methylanilino) - 4', 6 '-

di-p-tolyl-indo-2 ¹ -pyridocarbocyanine perchlorate 0.1 g

After the plates were exposed, print-out images were visible on them visible on a green background due to the presence of the cyanine print-out dye. Kurds If the plates were successively re-exposed, without the intervention of cooling periods, the plates remained easily developable, whereas on the other hand corresponding plates made without using the combination of boric acid, benzotriazole and L (-) - rhamnose, somewhat were more difficult to develop when exposed under the same conditions.

In a further series of tests, additional radiation-sensitive Copolymers of that given in Table IV. Type produced, namely with 83.4 MoI-I repeating methyl methacrylate units, 15 MoI-I recurring Hethacryloyloxyäthylnaphthoquinonediazid-

409828/0788

sulfonic acid ester units and 1.6% of recurring 2-hydroxyethyl methacrylate units, this time with p-liromobenzoyl chloride, acetyl chloride or myristyl chloride and not with benzoyl chloride
were esterified. In all cases, planographic printing plates excellent in properties were obtained. All plates drew
excelled in "excellent developability and excellent pressure abrasion characteristics, and did not smear.

With the same success as for the production of planographic printing plates or lithographic printing plates can be those used in the present invention Copolymers can also be used for other purposes, for example for the production of photoresist compositions and so-called photoresists using well known techniques.

Claims (22)

Claims M ./ Radiation-sensitive recording material for the production of positive-working planographic printing plates, consisting of a layer support and at least one radiation-sensitive layer applied thereon made of a radiation-sensitive acrylate-diazoquinone copolymer, characterized in that the radiation-sensitive layer contains an acrylate-diazoquinone copolymer which is based on mol- ⁰ S base to: I. 75 to 8 7 % from recurring alkyl acrylate units, II. 10 to 22 I from recurring acryloyloxyalkylquinonediazidic acid ester units, III. 1 to 7 % from acryloyloxyalkylcarboxylate repeating units and IV. Up to 4 l of repeating hydroxyalkyl acrylate units. 2. Radiation-sensitive recording material according to claim 1, characterized in that there is a layer of a radiation sensitive Contains acrylate-diazoquinone copolymer, which consists of 78 to '87 HoI-I from alkyl acrylate units. 3. Radiation-sensitive recording material according to claim 1, characterized in that it is a radiation-sensitive layer from an acrylate-diazoquinone copolymer, which consists of 10 to 17 mol% of Acryl.oyloxyalkylquinone-diazide acid ester units. 4. Radiation-sensitive recording material according to claim 1, characterized characterized in that it contains a radiation-sensitive layer made of an acrylate-diazoquinone copolymer which has an inherent "Has viscosity from 0.05 to 0.25. 409828/078 8 5. Radiation-sensitive recording material according to claim 1, characterized in that it is a radiation-sensitive layer with an acrylate-diazoquinone copolymer with a molecular weight of 5000 to 20,000. 6. Radiation-sensitive recording material according to claim 1, characterized in that it is in the radiation-sensitive Layer contains a dye. 7. Radiation-sensitive recording material according to claim 1, characterized in that it contains a copy-out dye in the radiation-sensitive layer. 8. Radiation-sensitive recording material according to claim 7, characterized characterized in that it contains a cyanine copy-out dye in the radiation-sensitive layer. 9. Radiation-sensitive recording material according to claim 1, characterized characterizedj that it is in the radiation-sensitive layer contains a comparatively small amount of an acid. 10. Radiation-sensitive recording material according to claim 9, characterized characterized in that it is in the radiation-sensitive layer contains a comparatively small amount of a carboxylic acid. 11. Radiation-sensitive recording material according to claim 10, characterized in that it contains a comparatively small amount of boric acid in the radiation-sensitive layer. 12. Radiation-sensitive recording material according to claim 1, characterized characterized in that there is 0.2 to 1.0 part by weight per part by weight of radiation-sensitive copolymer in the radiation-sensitive layer a film-forming second polymer. 13. Radiation-sensitive recording material according to claim 1, da- 4 0 9 8 2 8/0788 characterized in that the radiation-sensitive layer contains an acrylate-diazoehinone copolymer, which is built up on mol% Basis for: I. 75 to 87 % from recurring alkyl acrylate units of the following formula: HR ¹ I I J Γ H C = O 0 II. 10 to 22 % of recurring acryloyloxyalkylquinone diazidic acid ester units of the following formula: HR ¹ Il (II) - £ - C - C ι i H C = O III «1 to 7 I from recurring acryloyloxyalkylcarboxylate units of the following formula: HR ¹ It (in) —e c - c -} - i ι H C = O I ^ΰ « Χ Η λ 0-R ^ -O'CR ⁴ 409828/0788 IV. Up to 4 % from repeating hydroxyalkyl acrylate units of the following formula: HR ¹ C-. c H C = O 0-R ⁵ -0H where mean: R is a methyl radical or a hydrogen atom; R is an alkyl radical having 1 to 6 carbon atoms; R is an alkylene radical having 2 to 6 carbon atoms; R is a hydrocarbon residue or ilalohydrocarbon residue up to 20 carbon atoms; 0-X is an acid ester residue and. D is a quinonediazide residue. 14. Radiation-sensitive recording material according to claim 13, characterized in that the radiation-sensitive layer contains an acrylate-diazoquinone copolymer, its repeating Units of the formula I consist of methyl methacrylate units. 15. Radiation-sensitive recording material according to claim 13, characterized in that the radiation-sensitive layer contains an acrylate-diazoquinone copolymer whose recurring units of the formula II consist of 2-hydroxyethyl methacrylate units which are esterified with a naphthoquinodiazide acid halide. - _; ; ;; ■ ·. ;. ^; - ^iVi : · 409828/0788 16 / Radiation-sensitive recording material according to Claim 13, characterized in that the radiation-sensitive layer contains an acrylate-diazoquinone copolymer, its repeating Units of the formula III consist of methacryloyloxyethylbenzoate units. 17. Radiation-sensitive recording material according to claim 13, characterized in that the radiation-sensitive layer contains an acrylate-diazoquinone copolymer, its recurring Units of the formula IV from 2-hydroxyethyl methacrylate units exist. 18. Radiation-sensitive recording material according to claim 1, characterized in that the radiation-sensitive layer is a Contains acrylate-diazoquinone copolymer, which is based on MoI-I Basis for: I. 78 to 87 i of repeating methyl methacrylate units; II. 10 to 17 % repeating acryloyloxyethylnaphthoquinone diazidic acid ester units; III. 1 to 7 % from recurring Acryloyloxyäthylcarboxylateinheit and IV. Up to 4 % of recurring 2-hydroxyethyl acrylate units. 19. Radiation-sensitive recording material according to claim 18, characterized in that the repeating acryloyloxyethylcarboxylate units consist of recurring acryloyloxyethylbenzoate units. 20. Radiation-sensitive recording material according to claim 18, characterized in that the radiation-sensitive layer is a comparatively small amount of boric acid, benzotriazole and L (-) - rhamnose contains. 409828/0788 21. Radiation-sensitive recording material according to claim 12, characterized in that the radiation-sensitive layer contains a phenol-formaldehyde resin as the film-forming resin. 22. Radiation-sensitive mass for the production of photoresists, characterized in that it is used as a radiation-sensitive copolymer contains a copolymer which is built up on a MoI-I basis to: I. 75 to 87 % of repeating alkyl acrylate units; II. 10 to 22 % of recurring acryloyloxyalkylquinone-uiazidic acid ester units; III. 1 to 7 % from acryloyloxyalkylcarboxylate repeating units and IV. Up to 4 l of recurring Ilydroxyalkylacrylateinheit. 409828/0788