DE2902860A1 - MATERIALS NETWORKABLE BY RADIATION FOR THE PRODUCTION OF PHOTOGRAPHIC RECORDING MATERIALS - Google Patents

Description

The invention relates to a composition crosslinkable or photo-crosslinkable by irradiation for the production of photographic materials Recording materials, one made from the mass photographic recording material and a method for producing photographic images. The inventive crosslinkable mass is particularly suitable for the production of recording materials which lithographic printing plates or planographic printing plates can be produced or so-called photoresist materials, Color separation materials and the like.

For the production of lithographic printing plates or planographic printing plates and so-called photoresist materials is is known to require the use of a crosslinkable polymer that is (a) photosensitive, (b) relatively has high sensitivity and (c) is capable of providing an oleophilic, crosslinked photographic polymer. Polymers that meet these requirements are, for example, poly (vinyl cinnamates), unsaturated polyesters and cyclopropene polymers, as known, for example, from US Pat. No. 3,782,938.

In practice it has been shown that there is a need for crosslinkable polymers by irradiation, which by a further improved photographic sensitivity are characterized

So far there have been effective means of reinforcement or increase the sensitivity of crosslinkable polymers is not available, although it is known ^ enhancers for photopolymerizable To use monomers and oligomers. Such enhancers generally consist of compounds that contain free radicals but which are known not to function effectively in an oxygen-containing environment.

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It is also known, for example from the reference "Research Disclosure", Volume 133, May 1975, Publication No. 13309, editor Industrial Opportunities Ltd., Homewell, Havant, Hampshire, PO9 1EF ₅ Great Britain, gelatin by using cobalt ( III) complexes to photohardening. During hardening, the cobalt (III) is photoreductioned to cobalt (II), which in turn renders the gelatin insoluble by forming a complex. It is also known that photosensitive redox reactions of cobalt (III) complexes can be enhanced by using certain chelating agents which, in the presence of cobalt (II), are capable of providing reducing agents which reduce further cobalt (III) to produce further cobalt (II), whereby a gain is achieved. Such reactions are known, for example, from US Pat. Nos. 4,045,221 and 4,075,019. However, the combination of the teachings of these two patents does not result in enhancement of photohardening of gelatin, since the chelating agents form cobalt (II) complexes, which prevents hardening of the gelatin. Furthermore, gelatin and other hydrophilic colloids generally do not provide oleophilic polymers. As a rule, it is only possible with considerable difficulty to modify such colloids in such a way that this property is achieved, which is why hydrophilic colloids are generally not preferred compounds for the production of planographic printing plates or lithographic printing plates.

It was an object of the invention to provide a composition which can be crosslinked or photocrosslinked by irradiation and which is distinguished both by a further increased sensitivity and by advantageous oleophilic properties. Furthermore, a veraetzbare mass should be found ,, which can optionally be used in conjunction with a reinforcing agent, the insensitive to a sour substance poisoning.

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It has been found that the problem can be solved with a crosslinkable mass by irradiation, which as The main component is a polymeric binder with repeating units with one or more carbonyl groups, the to react with an amine to form carbinolamine groups and a comparatively small amount of a compound that can form an amine on irradiation, i.e. contains an irradiation-responsive or photo-responsive supplier of an amine.

Photographic recording materials can be started from such a composition which can be crosslinked or photo-crosslinked by irradiation produce in a simple manner that a layer of the mass on a suitable substrate is applied. Such a recording material can be exposed to activating radiation in a conventional manner, whereupon the exposed crosslinkable layer can be developed to produce an image.

The composition according to the invention which can be crosslinked by irradiation is suitable in particular for the production of recording materials, which in turn are used for the production of lithographic printing plates or planographic printing plates, since the polymers are advantageous Have oleophilic properties and are characterized by a particularly advantageous crosslinking sensitivity. However, the compositions according to the invention which can be crosslinked by irradiation are not only suitable for the production of recording materials of the type described. Rather, the compositions according to the invention can be used as photoresist materials, for the production of color extraction materials and the like, in all cases considerable advantages are derived from the increased crosslinking sensitivity of the compositions.

The main component of an inventive by irradiation crosslinkable mass thus consists of a polymeric binder with recurring units with one or more carbonyl

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groups with an Amiη to form carbinolamine groups are able to react, the amine required for crosslinking being supplied by the compound which upon irradiation capable of forming or delivering an amine.

Particularly advantageous compounds that are capable of delivering an amine on irradiation have proven to be thermally stable, Reducible metal complexes with amine ligands have been shown.

Reinforcement can be achieved by adding a reinforcing agent that reduces the sensitivity of the crosslinking able to increase by spontaneous generation of additional reducing agent for the complex in the presence of reduction products of the complex.

The term "main component" means in connection with the polymer that the polymer present in an amount of more than 50 wt ⁹ O, while the words "in a comparatively small amount" in connection with the compound which when irradiated an amine able to deliver means that the compound which is able to provide an amine on irradiation is present in an amount of less than 50 wt .- ° s.

The composition according to the invention, which can be crosslinked by irradiation, can be used for image production by preferably adding the composition after application to a support is exposed imagewise, which is followed by activation and development with crosslinking of the polymeric binder in the exposed Districts and removal of the non-crosslinked binder from the non-exposed areas, whereby a relief image is generated.

A wide variety of polymers with recurring units can be used to produce crosslinkable compositions according to the invention with one or more carbonyl groups associated with

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to react with an amine to produce carbinolamine groups capital. The carbinolamines obtained during the reaction can only be intermediates, from which imines are produced, for example when used as crosslinking agents primary amines can be used. Such reactions between active carbonyl compounds and amines are known, for example, from the book by R. L. Reeves, "Condensations Leading to Double Bonds", The Chemistry of the Carbonyl Group, 1966, pages 608 to 614. The formation of a carbinolamine requires that the carbonyl compound is active, i.e. is able to react chemically, in contrast to, for example, carbonyl compounds, which have steric hindrance or are prevented from reacting, for example, by adjacent substituents.

The polymers which can be used according to the invention can be recurring Have units with ketone as well as aldehyde groups. As can be seen from the quoted reference R. L. Reeves, ketones are less reactive than aldehydes. Nevertheless, carbinolamines can be made from them by use common acidic catalysts, higher reaction temperatures or longer reaction times.

The use of polymeric binders, which are ketones and thereby through, has proven to be particularly advantageous Remnants of the following formula are marked:

-CM

where M stands for a group which has a stronger electron-withdrawing effect than a methyl group, for example for a haloalkyl group with 1 to 3 carbon atoms, for example a chloromethyl or trifluoromethyl group. In an advantageous manner, M can furthermore _{stand for a radical of the formula -CH 2} M ', in which M ^f in turn stands for a nitro group or an α, ß-unsaturated alkenyl or alkynyl group, for example a propenyl or propynyl group

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group or a cyano group.

As particularly advantageous oleophilic polymers for manufacture crosslinkable compositions according to the invention have been found to be those which are aliphatic or aromatic aldehydes and repeating units have at least one of the following formulas:

(I)

where mean:

R is a hydrogen atom or a carboxyl group,

2
R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, for example one. Methyl or propyl group _f

1 is an alkylene group , for example a methylene or ethylene group or a phenylenedialkylene or alkylenepheayleE group with 1 to 5 carbon atoms in the alkylene part, for example a phenylene group or a phenylene group and

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= ϋ or 1;

(ID

- 16 -

: CH ₂ -CH-3

CHO;

(III)

CHO

and

(IV)

-fO ₉ p

where mean:

a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, for example a methyl, ethyl, Propyl or isopropyl group,

a hydrogen atom or a group of the formula:

-CHO

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provided that in at least 1R MOI of ⁰ S

Polymers R ⁶ for a group of the formula

Liiü -eit stands and

R is an alkylene group with 1 to 8 carbon atoms, e.g. a methylene, ethylene or isopropylene group

Polymers which can be used advantageously can furthermore recurring lines with aliphatic aldiiyu groups, e.g. have the following formula:

CH ₂ OU

CHO

Particularly advantageous polymers of the specified type are, for example, those which are obtained by copolymerization of Compounds on which the formulas (I) and / or (TI) are based with at least one other ethylenically unsaturated polymerizable monomer to provide the addition polymer capable of, for example, a vinyl ester, an α, 3-unsaturated Acid, a vinyl aramid, vinyl halide, vinyl nitrile, vinyl ketone, vinyl ether, olefin and / or xjiolefin permit.

Examples of such polymerizable, ethylenically unsaturated Monomers are: acrylamide; N-substituted acrylamides, for example Ν, Ν-dimethylacrylamide and N-isopropylacrylamide; Methacrylamides, methacrylonitrile; Styrene; α-methylstyrene; Vinyl chloride; Methyl vinyl ketone; Fumaric acid, maleic acid and

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/ 18-

290286D

Itaconic acid ester; 2-chloroethyl vinyl ether; Acrylic acid; acrylic and methacrylic acid esters, e.g. methyl acrylate, ethyl methacrylate, Butyl acrylate and phenyl methacrylate; Sodium methacryloyloxyethyl sulfate; Methacrylic acid; Dimethylaminoethyl methacrylate; Sodium sulfonates, e.g. 3-acryloyloxypropane-i-sulfonic acid, 2-acrylamido-2-) ethylpropane-1-sulfonic acid and 4, 4, 9-trime thy l-8-oxo-7-oxa-4-azonia-9-decene-1-sulfonic acid; N-vinyl succinimide; N-vinylphthalimide; N-vinylpyrazolidinone; 2-, 3-, or 4-vinyl pyridine; 1-vinylidazole; Butadiene; Isoprene; Vinylidene chloride and ethylene.

- 18 -

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Particularly advantageous copolymers of the type described are those with recurring units of the following formulas:

(V)

and

CHO

17 3

where R, Rj, R and η have the meaning given and χ and y stand for the molar proportions of the xiiederlcehrenden units, such _{that p} that the ratio x: y is 1:10 to 10: 1, with preferred ratios of 2: 8 up to 2: 1 and in which R stands for a repeating unit which is derived from a cationic or anionic monomer which is accessible to addition polymerization and which gives the polymer such properties that it can be processed in an aqueous medium. Examples of such monomers are listed in Table I below. On the other hand, R can also stand for the lest of a monomer of the following formula:

_R 2

CH ₇ = C

¹ 9

CO ₂ R ^y

2 9

where R has the meaning given and R is an alkyl - with 1 to S carbon atoms ,, for example a methyl or

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.StO-

Ethyl group or a radical of the following formula -NR R stands in which R and R can have the same or a different meaning and denote alkyl radicals with 1 to 5 carbon atoms, for example methyl, ethyl or propyl radicals or in which R and R together with N represent the non-metallic atoms, which are required to complete a heterocyclic ring with 4 to 6 ring atoms with the proviso that the polymer is in an aqueous acidic solution is soluble.

To produce the copolymers, several different

different comonomers with different groups R use for example with the formation of terpolymers.

Further examples of advantageous copolymers are those with repeating units of the following formulas:

(VI)

and

C = O

(G

CHO

where mean:

G is a remainder of one of the formulas:

-NHSO ₀ —U "/> or —E-

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E = -O- or -NII-;

J = -SO ₇ NH- or -NHSO, -;

ί £ » L

n ^f = 0, 1, 2, 3, 4 or 5;

R "is an alkyl group with 1 to 5 carbon atoms, for example a methyl or ethyl group or an aryl group with 6 to 10 carbon atoms, for example a phenyl or naphthyl group;

x, y, R ²

and R have the meaning already given.

Advantageous copolymers are also those with repeating Units of the following formulas:

CVII) R ²

and

C = O

CHO

2
where x, y, R and U have the meanings already given.

Further advantageous copolymers are those with repeating units of the following formulas:

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(VIII)

and

CIIO

2
where χ, y, R and G have the meaning already given,

Table I.

Examples of advantageous addition polymerization accessible Monomers which can be used for the preparation of anionic or cationic polymers, which are in aqueous Let media process

N- (2-MethacyloyloxMthyl) -N, N, N-trimethylammoniummeth * Bul £ at,

S. ·

N-Benzyl-N, N-dimethyl-N-vinylbenzylammonium chloride, Aconitic acid,

2-acrylamido-2-methylpropanesulfonic acid, S-acrylamidopropane-i-sulfonic acid, Acrylic acid,

Methacrylic acid,

4-acryloyloxkbutane-i-sulfonic acid, 3-acryloyloxypropionic acid,

S-acryloyloxibutane-i-sulfonic acid, 0

S-acryloyloxlfpropane-1-sul £ onic acid, 0

4-t ^ -Butyl-9-methyl-8-oxo-7-oxa-4-aza-9-decen-1-sulfonic acid, α-chloroacrylic acid,

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Maleic acid, chloromaleic acid, 2-methacryloyloxyethyl-1-sulfonic acid, Citraconic acid, crotonic acid, fumaric acid, mesaconic acid,

α-methylengiutaric acid, Monoethyl fumarate,

Monomethyl-a-methylene glutarate, Monomethyl fumarate, vinyl sulfonic acid, 4-styrene sulfonic acid, 4-vinylbenzylsulfonic acid, acryloyloxymethanesulfonic acid, 4-methacryloyloxybutane-1-sulfonic acid, 2-methacryloyloxyethane-1-sulfonic acid, 3-methacryloyloxypropane-1-sulfonic acid, 2-acrylamidopropane-1-sulfonic acid, 2-methacrylamido-2-methylpropane-1-sulfonic acid,

3-acrylamido-3-methylbutane-1-sulfonic acid and Maleic anhydride »

It was particularly surprising to find that the invited acidic polymers, e.g. the polymers derived from comonomers of the type listed in Table I or polymers of the Structure (I), in which R stands for a carboxyl group, can be used according to the invention, since it has always been assumed so far

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that an acidic environment is detrimental to the reduction of cobalt (III) complexes, as described in more detail below or the reduction is even prevented.

Polymers of structures (I) to (IV) can be sorted according to various Establish methods. For example, a copolymer of structure (I), wherein R is a carboxyl group

2 3

stands, R represents a hydrogen atom and R represents a Ethylene group and η = 1, according to the preparation method 1 given later.

A homopolymer of structure (II) can be produced, for example, by methods such as those described by Gibson and co-workers in the journal " J. Polym. Sci. , Poly. Chem. Ed." , 12, (1974), page 2141. Alternatively, homopolymers or copolymers with structure (II) can be produced by a catalyzed copolymerization process proceeding via free radicals in which a formylphenyl vinylbenzyl ether is copolymerized with a suitable α, ethylenically unsaturated monomer.

A homopolymer of structure (III) can also be produced, for example, by a process as described by Gibson and Bailey in the journal " J. Polym. Sci ., Poly. Chem. Ed. ", .13, (1975), p 1951 is described. Alternatively, homopolymers and copolymers with structure (III) can also be produced by free radical polymerization of a vinylbenzaldehyde alone or with a suitable α, 3-unsaturated monomer.

The following describes the production of various according to the invention useful carbonyl group-containing polymers are described in more detail.

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Manufacturing process 1: Poly / mono-2- (4-formylphenoxy /) ethyl

T U

maleate-co-methylvinylether_ /

To a solution of 15.6 g (0.10 equivalents) of a copolymer of maleic anhydride and methyl vinyl ether in the form of a technical commercial product (Gantrez AN-119), 16.6 g (0.10 mol) of 4- (2-Hydroxliäthoxfc) benzaldehyde and 425 ml of acetonitrile, 10.1 g (0.10 moles) of triethylamine were added in four portions of 2.5 g, 2.5 g, 2.5 g and 2.6 g over the course of 5.6 7 hours. The solution was stirred for 16 hours. Then 10 ml of concentrated hydrochloric acid was added. The mixture was then poured into water, causing the polymer produced to precipitate. The polymer was isolated, washed thoroughly with water in a Waring blender type mixer, and dried at room temperature using a strong vacuum. The yield of polymer was 26.7 g, corresponding to 83.0 % of theory.

Anal. Calculated for C ₁₆ H ₁₈ O ₇ : C; 59.6; H: 5.6 Found C: 57.8; H: 6.0

The inherent viscosity of the polymer was 0.64. The glass transition temperature was 70 ^° C.

All inherent viscosities given here were determined in a solvent mixture of phenol and chlorobenzene in a weight ratio of 1: 1 at 25 ^° C. and a concentration of 0.25 g / dl solution.

Manufacturing process 2: Polymerization of m-formylphenyl

methacrylate

m-formylphenyl was prepared by adding 23.0 g of methacryloyl chloride over a period of 20 minutes to a solution, cooled to -10 ⁰ C solution of 27.0 g

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2902880

m-Hydroxlbenzaldehyd, 22.3 g of triethylamine and 133 ml of methylene chloride, the reaction temperature between -10 to +5 C was kept. The mixture was then ^{stirred for a further 25 minutes at 0} ° C. and filtered off for the purpose of removing triethylamine hydrochloride. The latter was washed with methylene chloride. After the filtrate and the washing solution were combined, they were washed three times with water, followed by drying over sodium sulfate.

A small amount of 2,6-di-t-butyl-p-cresol inhibitor was then added, whereupon the solution was concentrated in vacuo. By distilling the oily residue, 23.5 g of m-formylphenyl methacrylate, corresponding to 56.2 % of theory, were obtained. The boiling point was 56 to 73 ° C / 5 to 1Ü μ.

Anal. For C ₁₁ H ₁₀ O ₃ : C: 69.5; H: 5.3 Found C: 68.8; H: 5.5

A solution of 5.0 g of m-formylphenyl methacrylate and 20 ml of dioxane was flushed out with nitrogen. Then, 0.025 g 2,2'-azobis (2-methylpropionitrile) catalyst added, and the solution was heated in a set at 6O ⁰ C bath, with about 16 hours, nitrogen was bubbled through the solution. The solution was then poured into diethyl ether, whereupon the resulting polymer precipitated. It was separated off and dried in vacuo. The yield of polymer was 4.7 g, corresponding to 94.0 % of theory.

Anal. For C ₁₁ H ₁₀ O-: C: 69.5; H: 5.3 Found C: 67.9; H: 5.8

o- and p-formylphenyl methacrylates and their homopolymers can be produced in a corresponding manner. The physical Properties of homopolymers are summarized in Table II below.

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Table II

CHO

Anal.

CHO-
substitution {η}, dl / κ Calculated H 3 Found H fg. c P. 0 , 53 C. 5, 3 C. 5.8 98 m 0 , 31 69.5 5, 3 68.0 5.8 93 O 0 , 32 69.5 5, 67.9 5.2 108 69.5 69.0

Manufacturing process 3: Polymerization of m-formylphenyl

methacrylate and N-butyl-4-methacryloyl

oxfbenzenesulfonamide ο

A solution of 3.80 g (0.02 mole) of m-formylphenyl methacrylate, 5.94 g (0.02 mole based on 100% conversion) of n-butyl-4-methacryloyloxfbenzenesulfonamide, and 40 ml of oxoane was purged with nitrogen . 0.05 g of 2,2'-azobis (2-methylpropionitrile) was then added to the solution. The solution was ^{heated in a bath set to 60 °} C., whereupon nitrogen was bubbled through for about 16 hours. The reaction solution was then poured into diethyl ether, whereupon the precipitated polymer was separated off, washed with ether and dried in vacuo. The yield of polymer was 8.0 g, corresponding to 82.1 % of theory.

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- Yl -

Anal. Calculated for C ₂₅ H ₂₉ NO ₇ S: C: 61.6; H: 6, Ü; N: 2.9; S: 6.6 Found C: 61.2; H: 6.8; N: 2.7; S: 5.2

Data and properties of other copolymers made from the monomers described in various ratios can be found in the following Table III.

Table III

η Uli, dl / g 61 C. Calculated H 2 N SO ₂ NHC ₄ • H ₉ Found H 2 N 5 S. 50 0, 27 61 , 6 , 0 2 , 9 Anal ,8th 2 , 7 5 , 2 SO ⁺ 1, 34 59 , 6 6th , 0 3 , 9 6th , 4 3 ,1 7th ,1 m 67 ⁺ 1, 27 , 7 6th , 2 , 6 S. 61 C. 6th , 0 , 0 , 0 SO 6th 6.6 62 , 2 7th 50 6.6 58 , 4 33 8.2 , 3

Manufactured using 0.25% by weight of initiator, based on the monomers, and at a solids concentration of approximately 50 %.

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59-

Manufacturing process 4: making poly (o-formylphenyl-

vinyl benzyl ether)

100 g (0.655 equivalents) poly (vinylbenzyl chloride) from a Mixture of m- and p-vinylbenzyl chloride in a molar ratio of 60:40, 100.0 g (0.820 moles) of salicylaldehyde, 46.0 g of an 85 Sigen potassium hydroxide solution, 327 ml of denatured Ethanol and 1.21 liters of p-oxoane were heated to reflux temperature for 22.75 hours and then cooled. The reaction mixture was then poured into water to remove the formed Precipitate polymer, which is separated and in a mixer of the Waring blender type with high stirring speed Water was washed. The polymer obtained was then dissolved in tetrahydrofuran and using a 2% sodium hydroxide solution failed. The precipitated polymer was separated off and washed with water in a mixer of the type described and finally dissolved in tetrahydrofuran. The solution was filtered through a bed of diatomaceous earth and then poured in water. The precipitated polymer was then washed again with water in the mixer. After Isolation and drying overnight in a vacuum oven at a comparatively low temperature gave 113.0 g of polymer obtain. The results of further manufacturing processes are summarized in Table IV below.

Table IV

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Table IV continued

Anal.

m η yield in %

CHO 100 O

CHO 100 O

O

O

CHO

63.0

67.2 58.3 57.6

50.2

57.4 73.2

Calculated in), dl / g CH

1.07 80.6 5.9

1.04 80.6 5.9

0.41 83.0 6.3

0.35 80.6 5.9

0.52 83.3 5.6

0.53 85.2 6.6

0.84 80.6 5.9

Found

C H

80.1 6.0

80.2 6.1 82.0 6.2 78.9 6.0

79.8 6.0

84.4 6.7

79.3 5.9

Table IV continued

50 50 76.2

CHO

CHO

CHO

Based on the starting ratio {η} Measured in chloroform.

0.52 83.0 6.3 81.5 5.8

25 75 77.5 0.53 84.3 6.5 82.7 6.3

100 0 58.3 0.68 80.6 5.9 80.2 6.0

100 0 72.4 0.50 * ⁺ 80.6 5.9 79.5 5.9

ro oo cn

Manufacturing process 5: Poly / N- (4-formylbenzyl) hexamethylene

2,4-toluene disulfonamide_7

To a solution of 9.0 g (O, O271 moles) poly (hexamethylene-2,4-toluene disulfonamide) in 87 ml of N, N-dimethylformamide 4.9 g (U, Ü2 71 moles) of tetramethylammonium hydroxide pentahydrate were added. After 2 hours, 4.2 g (0.02 71 moles) of 4-chloromethylbenzaldehyde were added added to the mixture. The mixture was then stirred for approximately 22 hours and then filtered. The filtrate was poured into water placed in a Waring blender mixer. The precipitated and washed Polymer was then separated off, washed again with water in a mixer of the type indicated, separated off and added Dried at room temperature and under a strong vacuum. The yield of polymer was 9.3 g.

Anal. Calculated for C ₂₁ H ₂₆ N ₂ S ₂ O ₅ : C: 56.0; H: 5.8; N: 6.2;

S: 14.2

Found: C: 54.1; H: 6.3; N: 6.3;

S: 14.5

The inherent viscosity of the polymer was 0.69.

The molecular weight of a polymer which can be used according to the invention is not critical. It has been found that polymers of various inherent viscosities can be used. For example, it has been shown that polymers can be used regardless of whether they have an inherent viscosity of 0.25 dl / g or 1.4 dl / g. It should be noted, however, that polymers of comparatively higher molecular weight had higher sensitivities in some cases, as resulted from a larger number of 0.3 log B-stages when the polymers after processing into a recording material exposed and developed in the manner described below.

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Any photo-responsive amine supplier or anyone through Amine suppliers which are responsive to the action of light can be used to produce a composition which can be crosslinked according to the invention. Cobalt (III) complexes have proven to be particularly advantageous amine suppliers. In an advantageous manner however, other reducible metal amine complexes can also be used, e.g. amine complexes of palladium (IV). as The use of reducible, thermally stable cobalt (III) complexes has proven to be particularly advantageous, which have amine ligands, with or without reinforcing agents. Examples of amine suppliers that can be used are Cobalt (III) complexes that respond directly to irradiation or exposure or that are completely non-responsive Cobalt (III) complexes that are combined with a photoactivator that can be addressed by exposure or irradiation.

All cobalt (III) complexes can be used in accordance with the invention with amine ligands, provided that they are used in the Processing temperatures are thermally stable. Such complexes are sometimes referred to in the literature as so-called inert complexes described. See, for example, US Pat. No. 3,862,842. Uie property of such Complexes remain stable, i.e. retain their original ligands when they are stored or in a neutral Solution can be used at room temperature until a chemically or thermally initiated reduction to cobalt (II) takes place is so well known that the term "inert" is not used herein.

Such cobalt (III) complexes consist of a molecule with a cobalt atom or cobalt ion surrounded by a group of atoms, ions, or other molecules that are whole commonly referred to as ligands. The cobalt atom or cobalt ion at the center of such a complex represents a Lewis acid, whereas the ligands are Lewis bases. Cobalt

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is known to form complexes in both the divalent and trivalent form. According to the invention, trivalent Cobalt complexes, i.e. cobalt (III) -i complexes, are used because the Ligands in such complexes are relatively retained and released when the cobalt is in its divalent Condition is reduced. This means that the reduction products of such a reaction from cobalt (II) and consist of the ligand.

Preferably used cobalt (III) complexes are those with a Coordination number of 6. The cobalt complexes can have a wide variety of amine ligands. Typical ligands Forming amines are, for example, ethylenediamine, n-propylenediamine, Diethylenetriamine, triethylenetetramine, methylamine, iminodiacetate, ethylenediaminetetraacetic acid, ammonia, Amino acids, e.g. glycine, etc. The term amino ligand used here also includes ammonia ligands.

Cobalt (III) complexes which can be used according to the invention can be neutral Be compounds that can be completely free of anions or cations. The term "anion" as used herein relates Unless otherwise stated, this refers to the non-ligand anions. The cobalt (III) complexes can, however, also have one or more cations and anions, accordingly the charge neutralization rule. Particularly advantageous cations are those which lead to easily soluble cobalt (III) complexes lead, e.g. alkali and quaternary ammonium cations.

The complexes can also have a wide variety of anions. However, it becomes a conjugated η-bond with the complex If chelate reinforcing agents are used, as will be described in more detail below, then it has been found to be advantageous proven when the mass crosslinkable by irradiation is free of anions that conjugate acids through Deprotonation of a cobalt (II) complex with the chelate enhancer form. Ls has shown that this

909831/074 *

can be achieved if less than 50 mol% of the existing Are anionic ions with a pKa value greater than 3.5.

In the few cases where a complex is only a little is soluble, increased amounts can be brought into solution by adding other anionic equivalents thereof.

Further details regarding cobalt (III) complexes can be found in the literature reference "Research Disclosure", Volume 135, July 1975, Publication No. 13505, Verlag Industrial Opportunities Ltd., Homewell, Havant, Hampshire, P09 1BF, Great Britain.

Examples of cobalt (III) complexes which can be used according to the invention are listed in Table V below.

Table V

C-1 hexa-ammine-cobalt (III) benzilate

C-2 hexa-ammine-cobalt (III) thiocyanate

C- 3 Heja-ammin-cobalt (III) trifluoroacetate

C- 4 chloropenta-ammine-cobalt (III) perchlorate

C- 5 bromopenta-ammin-cobalt (III) perchlorate

C- 6 Aquopenta-ammin-cobalt (III) perchlorate

C- 7 bis (ethylenediamine) bisazido-cobalt (III) perchlorate

C- 8 bis (ethylenediamine) diacetato-cobalt (III) trifluoroacetate

C- 9 triethylenetetramine dichloro-cobalt (III) trifluoroacetate

C-10 bis (methylamine) tetra-amine-cobalt (III) hexafluorophosphate

C-I1 Aquopenta (methylamine) cobalt (III) nitrate

C-12 chloropenta (ethylamine) cobalt (III) perfluorobutanoate

C-13 Trinitrotris-ammin-cobalt (III)

C-14 Trinitrotris (methylamine) cobalt (III)

C-15 tris (ethylenediamine) cobalt (III) perchlorate

C-16 Tris (1,3-propanediamine) cobalt (III) trifluoroacetate

C-17 N, N ¹ -ethylene bis (salicylidenimine) -bis-ammincobalt (III) perchlorate

9QÖÖ31 / 0744

C-18 p-superoxodeca-ammin-dicobalt (III) -perchlorate C-19 Penta-ammin-carbonato-cobalt (III) -perchlorate C-20 Tris (glycinato) cobalt (III)

C-21 frans / bis (ethylenediamine) chlorothio-cyanatocobalt (III) _7 perchlorate

C-22 Trans / ~ bis (ethylenediamine) diazido-cobalt (III) _ / thiocyanate

C-23 Cis / ~ ethylenediamine ammin azido cobalt (III) _7 trifluoroacetate

C-24 tris (ethylenediamine) cobalt (III) benzilate

C-25 Trans / ~ bis (ethylenediamine) dichloro-cobalt (III) _7 perchlorate

C-26 bis (ethylenediamine) dithiocyanato-cobalt (III) perfluorobenzoate

C-27 triethylenetetramine dinitro-cobalt (III) dichloroacetate

C-28 tris (ethylenediamine) cobalt (III) salicylate

C-29 Tris (tri-ethylenediamine) cobalt (III) -tri £ luoroacetate

C-30 tris (trimethylenediamine) cobalt (Hl) tetrafluoroborate

C-31 Tris (triethylenediamine) cobalt (III) trifluoromethanesulfonate and

C-32 tris (ethylenediamine) cobalt (III) hepta £ luorobutyrate.

The reduction of the cobalt (III) complexes can be initiated directly or activate by exposure to activating radiation of a wavelength less than about 300 nm. On the other hand, however, a reduction can be achieved by irradiating a photoactivator with radiation of one wavelength greater than about 300 nm. Suitable photoactivators include both photo-reducing agents and spectral sensitizers, which photoreductants are effective even when exposed, before they are brought into contact with the cobalt (III) complex, the contact only during development needs to be done. In contrast, spectral sensitizers must be irradiated or exposed if they are in contact or reactive relationship with the complex.

909831/0744

A wide variety of photoreduction agents can be used, for example metal carbonyl compounds, for example benzene chromium tricarbonyl; β-ketosulfides, e.g., 2- (4-tolylthio) chromanone; Diketones, e.g., Furil; Carboxylic acid azides such as 4-bromo-1-hydroxy-2-naphthoic acid azide; organic benzilates such as N-methylacridinium benzilate; ipyridinium salts, e.g., N, N'-bis (2,4-dinitrophenyl) -4,4'-dipyridinium hexafluorophosphate; Diazonaphthones, e.g., 4-diazo-2-methyl-1-naphton; Phenazine; Phenazine N-oxides; Quinones; Disulfides; Diazoanthrones; Diazonium salts; Diazophenanthrones and aromatic azides; Carbazides; Azosulfonate photoreductants and the like. Such photoreductors and others are, for example described in more detail in the reference "Research Disclosure", Volume 126, October 1974, Publication No. 12617, Part II. Other photoreduction agents which can be used in accordance with the invention include, for example, 2-isopropoxy-3-chloro-1,4-naphthoquinone; 2-dibenzylamino-3-methyl-1,4-naphthoquinone and 2-isopropoxy-1,4-antraquinone.

A variety of spectral sensitizers can be used in a similar manner. Preferably xverden those sensitizers are used which have an oxidation potential in the ground state which is unfavorable for the Reduction of the cobalt (III) complex is. Such a oxidation potential in the ground state is advantageous because this results in a spontaneous reduction of the cobalt (III) complex in Absence of actinic radiation is avoided. In general, it has proven to be beneficial if that Oxidation potential of the pectral sensitizer in the ground state is in such a relationship with the reduction potential with cobalt (III) complex, which is a Electron transfer from the spectral sensitizer to the cobalt (III) complex an energy gain occurs. The disadvantageous one Energy gradient then ensures a reduction of the cobalt (III) complex in the absence of externally supplied Energy. Examples of suitable spectral sensitization

909831 / 07U

mediums are acridines, anthrones, azo dyes, azomethines, cyanines, merocyanines, styryl compounds and basic ones Styryl dyes, polycyclic hydrocarbon dyes, ketone dyes,! Nitro dyes, oxonols, sulfur, triphenyl methane and xanthene dyes and the like. According to the invention Spectral sensitizers which can be used are further described in more detail, for example, in US Pat Research Disclosure, Volume 130, February 1975, Publication No. 13023, Part III.

If either a photoreductor or a spectral sensitizer is used, development will stop the exposed material preferably includes a heating step to reduce the rate of reduction of the complex to increase and, as a result, the cross-linking of the polymer.

To increase the sensitivity of the reaction, an enhancing agent can be used, for example in admixture with the Cobalt (III) complex.

A particularly advantageous class of reinforcing agents consists of compounds with a conjugated n-bond system, capable of forming at least one bidentate chelate with cobalt (III). Conjugated η-bond systems can be known to be easily generated by combinations of atoms such as carbon, nitrogen, oxygen and / or sulfur atoms. Typically, such systems include groups that provide or have double bonds, for example vinyl, azo, azinyl, imino, formimidoyl, carbonyl and / or thiocarbonyl groups in such an arrangement, that the double bonds are conjugated or are in a conjugate relationship to one another.

A large number of compounds are known which have a conjugated n-bond system and which are at least prior to

909831 / Ö7 44

Formation of bidentate chelates are suitable. Examples of particularly advantageous chelating agents of this type are Nitroso-aroles, dithiooxamides, formazan, aromatic azo compounds, Hydrazones and so-called Schiff bases. For further details on such chelating agents, see the already cited reference "Research Disclosure", Publication No. 13505, Part III.

The reinforcing agents act as reducing agent precursor compounds for the further reduction of cobalt (III) complexes. The redox reaction that takes place and causes the reinforcement can be summarized as follows:

(i) Q (photoactivator) + Co ¹¹¹ A, (original

Ligands)

Exposure _dd

- - ^ Co and A ^

Heat

(Reinforcement)

(ii) Co ¹¹ + CC (chelating agent) J Co ¹¹ CC

(iii) (Co ¹¹ CC) + Co ¹¹¹ A ₆ C o ^U ₊ A ₆ + (Co ¹¹¹ CC)

It is of course the amine ligands (A ₆ ) that bring about the photo-crosslinking with the carbonyl groups of the polymeric binder.

Other reinforcing agents used according to the invention are those that react with released amines to form further reducing agents. the However, the reaction should not be able to proceed so easily for the amines that practically no amine remains to remove the

909831/0744

To effect crosslinking of the polymeric binder. For example uses a quinone which is in at least one quinoid ring position adjacent to a carbonyl group is not substituted (e.g. in a 2- or 3-ring position in the case of 1,4-benzoquinones and 1,4-naphthoquinones), see above For example, an amine such as ammonia can react with the quinone in the unsubstituted ring position to produce the corresponding amino-1,4-hydroquinone. The hydroquinone then provides a reducing agent for the Cobalt (III) complex, in which case more reduction products of the complex are generated. The quinone can do it originally act as a photo-reducing agent or a special photo-reducing agent can be added, to reduce the amine containing cobalt (III) complex and liberate the amine.

A chelating agent can also be used in place of a reinforcing agent use, which has a higher affinity for Co (II) than the ligands. This will cause the amine ligands to be released guaranteed after reduction, especially when the ligands are diamines. An example one such non-enhancing chelating agent is 2,2'-bipyridine.

As already stated, the composition according to the invention which can be crosslinked by irradiation contains the polymer as the main part Binder, whereas the cobalt (III) complex in a comparatively small amount is present. Any other components present, e.g. photoactivator and / or Reinforcing agents can be present in amounts of 0.1 to 20 moles per mole of cobalt (III) complex.

Particularly advantageous crosslinkable compositions are those in which the polymeric binder makes up 50 to 95 mols of the composition, the cobalt (III) complex is present in quantities of 3 to 49 mol-I, the photoactivator in amounts of 2 to 25 MoI-I and that

909831/0744

Reinforcing agents in amounts of 2 to 25 mol-o.

A recording material can be produced by producing a layer from the mass which can be crosslinked by irradiation, preferably on a carrier. A layer of the crosslinkable composition can be applied to a support by customary coating methods, for example by applying a solution of the crosslinkable composition to a layer support. The optimum solvent in the individual case depends on the composition of the crosslinkable material, in particular on the polymeric binders used in the individual case. Typical advantageous solvents that can be used alone or in combination with one another are short-chain alkanols, e.g. methanol, ethanol, isopropanol, t-butanol, methoxyethanol and the like, also ketones, e.g. methyl ethyl ketone, acetone, cyclopentanone and the like, also chlorinated hydrocarbons, such as chloroform, ethylene chloride and carbon tetrachloride and also ether _s for example dioxane.

The recording layer is advantageously applied to a support in such a way that the concentration of the polymeric bin
area is =

polymeric binder at about 2 to about 100 mg / dm carrier

Customary known photographic supports can be used to produce the recording materials according to the invention. Typically, the supports consist of transparent supports such as film supports and glass supports as well as opaque or opaque supports _, for example made of metal or photographic paper = the support can be rigid or flexible . The substrate of a recording material according to the invention can thus advantageously consist of a paper substrate, e.g. one with a matting layer or a matting layer.

© 8 ^ 1/0144

29Q2860

Finish or also from a metal plate or a transparent one Film support, for example made of poly (ethylene terephthalate). Typical substrates used for manufacture inventive recording materials can be used, are described, for example, in the reference "Product Licensing Index", Volume 92, December 19 71, Publication No. 9232, page 108.

Is a back-colored water differentiation desired, like in the case of the manufacture of planographic printing plates or lithographic printing plates, this is the case for the support selected material is preferably hydrophilic. This is because the photo-hardened layer is oleophilic. examples for Such hydrophilic layers are those made of paper or metal plates.

The support may optionally have one or more adhesive or sub-layers for the purpose of changing its surface properties, for example in order to improve the adhesion of the radiation-sensitive layer to the support. The coating of the substrate can be carried out according to customary known methods _9, for example, by applying the coating material by means of a fluidized coating device, by coating with an application brush, by coating with a so-called coating knife or by coating with a conventional pouring device.

After the coating compound has been applied, the solvent is removed. Typical coating processes that can be used are described in more detail in the journal "Product Licensing Index", Volume 92, December 197I ₂ Publication No. 9232 _S page 109. The customary known coating auxiliaries can be added to the coating material.

* 3

29028J60

The recording materials can be exposed or exposed by the customary known methods. The exposure level can advantageously, for example, at

2 R 2

500 erg / cm to about 10 erg / cm are at one wavelength from about 300 to about 600 mn, depending on whether and in which case To the extent that a reinforcing agent and / or photoactivator was used.

The exposure of the recording materials can be made using common known devices and exposure sources.

A recording material is preferably developed in a two-step process with a first step in which the material is heated in order to activate the photo-crosslinking in the exposed areas and a second washing step in which the non-crosslinked polymer parts are removed will. The heating parameters are not critical. For example, the Brhitzungstemperatur may be about 80 to about 160 ⁰ C, for example at a heating time of about 2 to about 100 seconds. In general, the higher the temperature, the shorter the heating time.

It is believed that the crosslinking reaction that takes place during the development process, can be represented by at least one of the following reactions, if the active carbonyl group consists of an aldehyde group:

O ₁ R ¹² OH

) T'CH-NH Δ ν T'-CH = NR ¹ _R 12 -H ₂ O

(I _x I 12

(A) T'CH + HNH) T'CH-NH Δ ν T'-CH = NR ^1Z

_R 1

OH 0 OH

I I! , II

(B) T ¹ CH-NH + T ¹ CH f T ¹ CH-N-CH-T

'12

R ^IZ

9Q9831 / Q7U

(C) OH R ¹ BlI T ¹ CH-N-CH-T '

OH

) T ¹ -C = NC-T '

Δ / -Η ₂ Ο Η

T'-Δ

OH .CH-T ¹

"OH. '-CII _x I / -f 1 "- CH-N _x

Vh-t '

I OH

where mean:

a hydrogen atom or an organic group which may optionally have one or more primary or secondary amine groups and

T ¹ the remainder of the polymer.

As can be seen from reaction equation (C), this reaction can only take place if R is a hydrogen atom, so that the condensation reaction can take place or the tertiary substitution of the amine.

Corresponding reactions take place when the polymer consists of a ketone.

The unexposed or unexposed polymer can be remove in various ways. For example, after heating the exposed material in a moving solvent be immersed. The solvent is chosen so that the unexposed polymer areas can be washed off, but not the crosslinked polymer. Examples of suitable solvents are those above mentioned solvents, which are used for the preparation of the coating compositions can be used and in some cases alkali

909831 / 07U

-ks-

aqueous solvents. The immersion time of the exposed Material in the solvent is not critical. For example, the immersion time can range from about 5 to about 10 hours lie.

In certain cases, additional processing steps may be required. For example, dyes, couplers, Curing agents and metallization catalysts in the Recording material are introduced by immersion in a suitable bath, before or after carrying out the Development using conventional methods known in the art.

The following examples are intended to further illustrate the invention.

example 1

In 1.8 g of a 10% solution of a polymer with repeating Units of the following formula:

CHO

20 mg of 2-isopropoxy-1,4-naphthoquinone as photoactivator and 5 mg of 2,2 "-bipyridine, ie a chelating agent for cobalt II, were dissolved in tetrahydrofuran. A solution of 20 mg / ~ (NH ₂ ^ ~ CH ₂ _7 ₃ NH) Co J (CF ₃ CO ₂ ) ₃ I tris (triethylenediamine) cobalt (III) trifluoroacetate-7, in 200 mg of 2-methoxyethanol Adhesive coated poly (ethylene terephthalate) base was applied with a 100 micron coating knife and the dried layer was applied

909831/0744

• iffc.

was irradiated with light of a wavelength of 350 nm with 3200 erg / cm beliciitet, after which the material for 10 seconds with the coating side up, on a hot block at 90 ⁰ C heated. The exposure was carried out in a conventional spectral sensitometer. The water-filtered radiation emitted by an air-cooled, 1000 watt xenon high-pressure lamp was guided through quartz optics and focused on the entry slits of a high-intensity monochromator, made by Bausch and Lomb. The light emitted by the monochromator was filtered'-

. and then passed through an electronic shutter and finally onto the photographic one Material allowed to hit. The exposures were time modulated around the range of exposures desired to create. To calculate the illuminance of the sensitometer it was first necessary to measure the energy that were present in each of the wavelength ranges at which exposure occurred. The illuminance per unit time was measured at a predetermined exposure distance by means of an Iiewlett-Packard flow meter, Model 833ΟΛ and a Hewlett-Packard flow detector, Model 8334A intended. The exposure at 350 nm in Example 1 was at a wavelength near λ des

ITl el X

2-Isopropoxy-1,4-naphthoquinones (.X _n , "^ = 327 nm) so long that an exposure of 3200 ergs / cm was achieved.

The material was then converted into a mixture of two parts by volume of tetrahydrofuran and one part by volume of p-dioxane submerged. The mixture was kept in motion. The non-exposed areas were removed, with a negative image was left behind.

Example 2

This example demonstrates the use of a sensitivity enhancing reinforcing agent.

909831/0744

- it -

kl-

A coating compound was used as described in Example 1, with the exception, however, that the 2,2′-βipyridine was replaced by 5 mg of 1- (2-pyridylazo) -2-naphthol as a reinforcing agent. The dried layer was exposed to light with a wavelength of 350 nm at 1000 erg / cm ^{4 'and developed as described in Example 1.} Again, the unexposed areas were removed, leaving a negative image.

Example 3

Another recording material was used as in Example 1 with the exception that this time a polymer having recurring units of the following Formula was used:

The dried material was then exposed for 0.5 seconds through a step wedge at neutral density levels of 1.0 in an IBM Microscope IID exposure machine. Then, the exposed material with the exposed layer to the top five seconds was heated on a heated at 140 ⁰ C block long, was placed whereupon the material in a strong turbulent Dioxanbad. In this way a clean negative relief image was obtained.

Example 4

This example illustrates the use of one according to the invention Materials in an offset printing press. The following were dissolved in 20 g of acetone:

909831/0744

1bO mg / (Nh ₇ (CJL) -NH ₇ ), CoJ (BF,) -! TrisCtrimethylene

^{Δ ύ £} * - ⁴ ^ diamine) cobalt (III)

tetrafluoroborate

2OJ iag / "(NM ₇ (CII ₇ ) -NIL), CoZ (CF-Xu ₇ ). ,, Tris (trimethylene

¹ ^ ύζύ-.ύ ^ ύ diamine) cobalt (III)

trifluoroacetate

mg / OnIL (Ui ₇ ), NIL), Co7 CCF ^ SO,) ,, Tris (trimethylene

^L - ·> ζ λ - ό ύ ά diamine) cobalt (III)

trifluoromethanesulfonate

800 mg of 2-isopropoxy-1,4-napthoquinone (Photoactivator)

60.7 g of tetrahydrofuran and 20 g of a 20% strength solution of that described in Example 3 were then added to the solution obtained Polymers given in cyclopentanone.

The coating compound was then applied by the fluidized coating method at 90 revolutions per minute to a roughened, anodized aluminum substrate. The coated layer was long then one hour and then for 2 minutes average in a vacuum frame with a 1000 watt mercury vapor lamp pressure, which had been set in the distance of 1.22 illuminated dried at 5O ⁰ C, in a vacuum oven. The plate was then placed in an oven at a temperature of 135 ° C. for 90 seconds. The plate was then developed by wiping it with a 1: 1 mixture of ethyl propionate and a two-phase resist desensitizer. The resist desensitizer had an organic phase containing a film forming polymer and an aqueous phase containing a phosphate salt, thickeners, fungicides and surface active compounds.

100 high quality copies of the plate were made on a conventional offset printing press.

There was no difference in the quality of the copies from the first to the last copy.

ÖOÖÖ31 / 0744

■ Μ-

Examples 5 to 17

This has been done using the crosslinking of individual polymers of the test procedure described below.

20 mg of 2-isopropoxy-1,4-naphthoquinone as a photoactivator, 12 mg of tris (trimethylenediamine) cobalt (III) trifluoroacetate and 5 mg of 2,2'-bipyridine were added to 2 g of a 10 % solution of the polymer in acetone. The resulting solution was then coated onto an adhesive coated poly (ethylene terephthalate) base with a 100 micron coating knife. The resulting material was then exposed for 0.5 seconds through a silver step wedge at 0.3 log L density levels in an IBM microcopier IID exposure machine. The material was then heated with the exposed side up for 5 seconds on a heated block. The block temperatures used / documents at 140 to 160 ⁰ C. They proved to be not critical. The recording material was then wiped off with acetone, the non-crosslinked areas being removed. The number of crosslinking stages was determined by visual inspection or by using a dye in an acetone wash. The data obtained are summarized in Table VI below. Unless otherwise stated, all of the polymers in these examples were found to be oleophilic.

It should be noted that in the case of Examples 9, 10 and 13 no 2,2'-bipyridine was used. The specified ratios are the molar ratios of the monomers used.

- 49 -

900 * 31/0744

example

5 6

10

13th

15 16 17

Number of 0.3 log II levels

3 3

2-1 / 2

-SO-

Table VI polymer

Poly (m-formylphenyl methacrylate)

Poly (N-butyl-4-methacryloyloxybenzene-sulfonamide-co-m-formylphenyl methacrylate) CSO: 50)

Poly (N-butyl-4-methacryloyloxybenzo1-sulfonamide-co-m-formylphenyl methacrylate) (50:50)

Poly (N-butyl-4-methacryloyloxybenzene sulfonamide-co-m-formylphenyl methacrylate X67: 33)

Poly (O-formylphenylvinylbenzyl ether-co-methyl methacrylate)

(50:50)

Poly / o-formylphenylvinylbenzyl

ether-co-methyl vinyl ketone /
(50:50)

Poly (N -butyl-N-methacyloylsulfanilamide-co-o-formylphenylvinylbenzyl ether) (50:50)

Poly (o-formylphenylvinylbenzyl ether-co-4-vinyl methanesulfonanilide) (50:50)

Poly (N-butyl-4-methacryloyloxybenzenesulfonamide-co-o-formylphenylvinylbenzyl ether) (50:50)

Poly (N-butyl-4-methacryloyloxybenzenesulfonamide-co-o-formylphenylvinylbenzyl ether) (50:50)

Poly (N-butyl-4-methacryloyloxybenzenesulfonamide-co-o-formylphenylvinylbenzyl ether) (67:33)

Poly / N- (4-formylbenzyl) hexamethylene-2,4-tolylenedisulfonamide 7

Poly / mono-2- (4-formylphenoxy) ethyl maleate-co-methyl vinyl ether 7 ⁺⁺ +

0.27

1.34

0.59

0.68

909831/0744

-SfJ-

18 4 Polymer from manufacturer

procedure 5

19 6 poly / m-formylphenyl methacryl-0.48

lat: ~ N- (4-vinylphenyl) -p_- toluenesulfonamide 7 50:50

20 2 poly / m-formylphenyl methacrylate 0.45

lat: "N- (p_-toluene sulfonyl) methacrylamide / 50:50

21 2 poly / m-formylphenyl methacrylic 0.10

lat: ~ N-phenyl-4-methacryloyloxybenzenesulfonamide / 50:50

This polymer was soluble in aqueous alkaline solutions and, on the other hand, was oleophilic.

The examples result in an increased sensitivity of at least one level (example 9), produced by one Exposure for only half a second. The sensitivity is at least equal to the sensitivity achieved by most common planographic printing plates, though these are tested under appropriate conditions.

Example 22

Example 17 was repeated with the exception, however, that the wiping off with a solution of 1.0 g of sodium carbonate and 0.8 g of sodium bicarbonate and 1.01 ml of a 10% solution of a nonylphenoxypolyglycerin (surface-active Medium) in 100 ml of water. After this treatment, 4 crosslinked 0.3 log E levels remained.

Example 23

To illustrate the effectiveness of a reinforcing agent, 23 mg of tris (ethylenediamine) cobalt (III) heptafluorobutyrate were added to 1 g of 2-methoxyethanol and 20 mg of tris (ethylenediamine) cobalt (III) trifluoromethanesulfonate dissolved. 0.4 g of this Solution were added to 3.6 g of a 10 "own solution of poly (N-butyl-4-methacryloyloxybenzenesulfonamide-co-m-formylphenyl-

909831/0744

methacrylate) (50:50) in acetone. With a red safety light, & mg of 4- (2-pyridylazo) resorcinol were added as a reinforcing agent and 40 mg of 2- (dibenzylamino) -3-iuethyl-1,4-naphthoquinone as a photoactivator. After this compound had been dissolved, the solution was applied to a roughened, anodized aluminum film support at a thickness of 25 microns by means of a coating device. Üie layer was irradiated with light of a wavelength of 500 mn was heated on a heated at 150 ⁰ C and block abgeschwabbert with acetone with 600 erg / cm ^ exposed with the exposed side up 10 seconds. This left a negative polyra-image of increased sensitivity.

Example 24

To 0.8 g of a 25% strength by weight aqueous solution of a polymer with recurring units of the formula:

were admitted:

0.2 g 2-methoxyethanol, 20 mg 2- (ß-liydroxyäthyl) -i, 4-napnthochinon, 8 mg tris (trimethylenedianine) cobalt (III) trifluoroacetate and 1 g of distilled water. The coating compound obtained was then as described in Example 5 on a Carrier applied, exposed and heated. After wiping with water to remove non-crosslinked ™ Polymer left a visible 5-step image.

909831/0744

Claims (21)

Claims 1. Composition crosslinkable by irradiation for the production of photographic recording materials, characterized in that that it is a polymeric binder with repeating units with one or more units as the main component Carbonyl groups which are able to react with an amine to form carbinolamine groups, as well as a comparative one contains a small amount of a compound capable of forming an amine upon irradiation. 2. Crosslinkable composition according to claim 1, characterized in that it is a binder with aldehyde groups as carbonyl groups contains. 3. Crosslinkable composition according to claim 1, characterized in that it is a binder with recurring units of the contains the following structural formula: CHO where mean: R is a hydrogen atom or a carboxyl group, 2
R represents a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, R is an alkylene, phenylene dialkylene or alkylene phenylene group with 1 to 5 carbon atoms in the alkylene part, or a phenylene group and η = 0 or 1. 4. Crosslinkable composition according to claim 1, characterized in that it is a binder with recurring units
contains the following formula: (10383 1 / <mt _0RielN AL INSPECTED 2802860 CHO worm R represents a hydrogen atom or an alkyl group with 1 to 3 carbon atoms. 5. Crosslinkable composition according to claim 1, characterized in that it is a binder with recurring units of the contains the following formula: -f CH ₂ -C CHO 6. Crosslinkable composition according to claim 1, characterized in that it contains a condensation polymer as a binder. OBlGlMAL INSPECTED -. ♦ ■ - 7. Crosslinkable composition according to claim 1, characterized in that it is a polymer with recurring binder Contains units of the following formula: -6O ₇ S where mean: R ^{5 is} a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, R ^{6 is} a hydrogen atom or a group of the following formula: : ho with the proviso that in at least 10 moles of the polymer R is a group of the formula is and
R is an alkylene group with 1 to 8 carbon atoms. 8. Crosslinkable composition according to any one of claims 1 to 7, characterized in that it is used as a compound which upon irradiation able to form an amine, contains a thermally stable, reducible cobalt (III) complex with amine ligands. 909831/0744 9. Crosslinkable composition according to claim 8, characterized in that it additionally contains a photoactivator, which at Irradiation with activating radiation with a wavelength longer than about 300 nm is able to reduce the complex. 10. Crosslinkable composition according to claim 8, characterized in that it further comprises a precursor compound for a reducing agent contains which, in the presence of reduction products of the cobalt (III) complex, form the cobalt (III) n complex able to reduce with reinforcement of the crosslinking of the binder. 11. Crosslinkable composition according to claim 1, characterized in that it is a polymeric binder with at least two different has recurring units of the following formulas: —FCII CH ^ - and ₂ ^ CO ₇ HC = O OCh ' 2, 3 CH ₂ CH ₂ -O CHO
where represent: χ and y numerical values that reflect the molar proportions of the recurring units, such that the ratio of x: y is about 2: 8 to about 2; Amine is able to deliver a thermally stable _s reducible / 0744 Contains cobalt (III) complex with amine ligands. 12. Crosslinkable composition according to claim 11, "characterized in that it consists of a complex as a cobalt (III) complex Contains tris (trimethylenediamine) cobalt (III) trifluoroacetate. 13. Crosslinkable composition according to claim 1, characterized in that that it contains a polymer with at least two repeating units of the following formulas as the polymeric binder: CHO and SO ₂ NHC ₄ H ₉ whereby χ and y denote the molar proportions of the repeating units in such a way that the ratio of x: y is from about 2: 8 to about 2: 1 and, furthermore, that the compound, as a compound, is formed upon irradiation able to deliver an amine, a thermally stable, reducible cobalt (III) complex with Contains amine ligands. 14. Crosslinkable composition according to claim 13, characterized in that that it contains tris (trimethylenediamine) cobalt (III) trifluoroacetate as a complex. 9Ö9Ö31 / 07U 15. Crosslinkable composition according to claim 1, characterized in that it is a polymeric binder with at least two repeating units "of the following formulas: —FCH.-CH} - and where mean: .10 or a radical of one of the formulas -SO-NH-R -NHSO ₂ -R ¹⁰ , where R stands for an alkyl group with 1 to 5 carbon atoms and χ and Numerical values that characterize the molar proportions of the recurring units in such a way that the The ratio of x: y is from about 2: 8 to about 2r1 and it is also valid that the crosslinkable composition as Compound that is capable of providing an amine on irradiation is a thermally stable, reducible one Contains cobalt (III) complex with amine ligands. 16. Crosslinkable mass according to claim 15, characterized in that that they are tris (trimethylenediamine) cobaltCHI) trifluoroacetate as a complex contains. 909Ö31 / 0744 - 'if - 17. Photosensitive recording material with a layer support and at least one layer which can be crosslinked by irradiation and is composed of a crosslinkable composition according to claims 1 to 16. 18. Recording material according to claim 17, characterized in that that the crosslinkable by irradiation layer contains a photoactivator that the compound that in Irradiation can deliver an amine upon exposure to activating radiation with a wavelength longer than able to reduce about 300 nm. 19. Recording material according to claim 17, characterized in that that it is in the layer crosslinkable by irradiation as a compound which, upon irradiation, becomes an amine able to form a cobalt (III) complex with amine ligands and also contains a precursor compound for a reducing agent which, in the presence of reduction products of the cobalt (III) complex, amplifies the complex able to reduce the crosslinking of the binder. 20. Recording material according to claim 17, characterized by: a) a hydrophilic substrate on which are applied: b) a crosslinkable mass with: i) a thermally stable, reducible cobalt (III) complex with amine ligands, ii) an oleophilic polymer with repeating units with one or more carbonyl groups which are able to react with an amine to crosslink the polymer and §09811 / 0744 • 3- 290286Q iii) a precursor compound for a reducing agent that increases the rate of the crosslinking reaction can increase, namely by the formation of additional reducing agent for the complex in the presence of reduction products of the complex. 21. Process for the preparation of photographic images characterized in that a recording material according to Claims 17 to 20 is imagewise activating radiation and the exposed crosslinkable layer developed to form an image. 909831/0744