A METHOD OF TREATING EXPOSED AND DEVELOPED RADIATION SENSITIVE PLATES IN LITHOGRAPHIC PRINTING PLATE PRODUCTION, COMPOSITIONS FOR USE IN THE METHOD, AND THE USE OF DIAZO ELIMINATING COMPOUNDS IN IMPROVING THE INK RECEPTIVITY OF LITHOGRAPHIC PRINTING IMAGES

Abstract: The ink receptivity of lithographic printing images obtained by exposing and developing radiation sensitive coatings based on diazo compounds is improved by treating the developed coating with a compound capable of eliminat­ ing diazo groups, such as acetoacetanilide, optionally in admixture with a lithographic desensitising material such as dextrin or gum arabic.

Description: A Method of treating exposed and developed radiation sensitive plates in lithographic printing plate production, compositions for use in the method, and the use of diazo eliminating compounds in improving the ink receptivity of lithographic printing images. This invention relates to lithographic printing. As is well known, a lithographic printing plate consists of ink receptive image areas and water receptive non-image areas lying in substantially the same plane. Nowadays, virtually all lithographic plates are formed from radiation sensitive plates comprising a radiation sensitive coating on a suitable substrate. Image-wise exposure of such a radiation sensitive plate to radiation using a suitable transparency causes the coating to change its characteristics in the areas struck by the radiation. In the most common form of plate i.e. a subtractive plate, the change in characteristics allows the coating to be selectively removed from the substrate in the non-image areas by the application of a suitable developer to leave an image on the substrate. In the case of the so-called positive working plate, the radiation struck areas of the coating are removed whereas in the case of the so-called negative working plates it is the non-radiation struck areas of the coating which are removed. For health and environmental reasons, the trend in negative working plates has been away from using coatings which need an organic solvent developer to remove the non-radiation struck areas and towards those coatings where the non-radiation struck areas can be removed with a substantially aqueous developer. Coatings containing diazo compounds as the main radiation sensitive constituent are ell known for use in aqueous developable plates and, in particular, those based on the condensation products of a diazodiphenylamine and a compound containing a reactive carbonyl group such as formaldehyde. Coatings containing such condensation products are well documented in the patent literature. In this regard reference may be made to British Patent Specifications No.950,761, No.1,019,919, No.1,023,589, No.1,055,079, No.1,302,717, No.1,388,038, and, in particular No.1,312,925. However radiation sensitive plates based on such coatings have not been entirely satisfactory in that the image is frequently reluctant to accept ink. In the use of such radiation sensitive plates to produce lithographic printing plates, the coating is exposed to radiation to an extent such that sufficient diazo groups are destroyed to produce an insolubilised product in the radiation struck areas. However it has been found that, under the conditions used in practice, this photolysis process is incomplete and that the radiation struck areas contain residual diazo groups. It has also been found that, during further processing of the plate, these residual diazo groups can enter into reactions which are detrimental to the performance of the plate. More particularly, it has been found that the residual diazo groups in the radiation struck areas (which are the image areas) can react with materials such as gum arabic,- dextrin, etc. used in the final stage of the processing to desensitise and protect the non-image areas. Such desensitising materials are hydrophilic and their reaction with the diazo groups causes hydrophilic material to be incorporated or bound into the image areas making the latter reluctant to accept ink. Such a reaction can take place merely by leaving a plate that has been treated with such materials in the dark at ambient temperature. The reaction will take place much quicker at elevated temperatures of if the plate is exposed to light. It is an'object of the present invention to overcome the forgoing problem. According to one aspect of the present invention, there is provided a method of producing a litbographic printing plate from a radiation sensitive plate comprising a substrate having thereon a radiation sensitive coating containing a diazo compound, the method comprising image-wise exposing the radiation sensitive plate, developing the image-wise exposed plate to selectively remove the non-radiation struck areas of the coating from the substrate, and treating the developed plate with a finishing composition comprising a compound capable of eliminating diazo groups. It has been found that the elimination of the diazo groups takes place in preference to the aforementioned reaction between the diazo groups and the desensitising material. Thus, the two steps of eliminating the residual diazo groups and of desensitising the plate can be carried out simultaneously using a single composition. Accordingly, a further aspect of the present invention provides a plate finishing composition suitable for use in the above defined method which composition comprises (i) a compound capable of eliminating diazo groups, (ii) a lithographic desensitising material, and (iii) water. In a preferred embodiment the compound capable of eliminating diazo groups is a compound capable of entering into an azo coupling reaction with a diazo group. Preferably said compound contains an active methylene group and may be, for example, acetoacetanilide; 3-hydroxyacetoacetanilide; 4-chloro-2,5-dimethoxyaceto acetanilide; 4-morpholinoacetoacetanilide; N-acetoacetyl 1-phenyl-3-methyl-5-pyrazolone; benzylamine; N,N'-bisacetoacetylethylene diamine;/or N-(cyanoacetyl)morpholine. Alternative coupling compounds are 2,3-dihydroxynaphthalene; 8-aminonaphthalene2-sulphonic acid; 8-amino-1-naphthol-3, 6-disulphonic acid; m-phenylene diamine and phloroglucinol. In an alternative embodiment the compound capable of eliminating diazo groups is a compound capable of destroying the diazo groups by a reaction other than an azo coupling reaction for example by oxidation/reduction reactions or substitution reactions. Examples of such compounds are ascorbic acid, hypophosphorous acid, titanous salts, chromous salts, stannous salts, sodium hydro sulphite, sodium stannite, hydroquinone, sodium hypochlorite, cuprous chloride, alkali metal iodides, potassium xanthate or benzoquinone. The lithographic desensitising material is preferably dextrin or gum arabic. Examples of other suitable lithographic desensitising materials are alginates (such as sodium, potassium or ammonium alginate); cellulose derivatives (such as methyl cellulose, hydroxy propyl cellulose, hydroxyethyl cellulose or carboxy methyl cellulose); acrylamide homopolymer; and polymers containing structural units derived from acrylamide and from 1 to 257o by weight of structural units containing carboxyl groups. The finishing compositions are generally aqueous solutions and contain sufficient amounts of said diazo eliminating compound and said desensitising material to substantially completely destroy the residual diazo groups and to adequately desensitise the non-image areas, respectively. Generally the composition will contain from about0j5to about 50 by weight of said desensitising material and the content of said compound capable of eliminating diazo groups will be from about 0.256 by weight up to the amount required to form a saturated solution. The latter amount will depend upon the nature of the compound capable of eliminating diazo groups and on the presence of other components in the composition. Such other components may be, for example, a surfactant and/or a dispersing agent to assist in dissolution of the diazo group eliminating compound and desensitising material and/or acid oralkali to provide a pR suitable for the particular diazo group eliminating compound and desensitising material used. In this regard, the finishing composition will generally be alkaline in the case where the diazo group eliminating compound is an azo coupler having a phenolic hydroxy or reactive methylene group or acid in the case where the coupler contains an amino group e.g. m-phenylene diamine. Examples of such other components are the sodium salt of dodecylated oxydibenzene disulphonic acid, sodium polyacrylate, hydrochloric acid,potassium hydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate and sodium hydroxide. The compositions of the present invention are normally produced by stirring together the water, the diazo eliminating compound, the lithographic desensitising material and any other components as appropriate under ambient conditions. If desired, however, the mixing may be effected at slightly elevated temperature in order to assist dissolution. Thus, by way of example, the trisodium phosphate or other pH-adjusting component may be added to the water heated to about 600C followed by the addition of the sodium salt of dodecylated oxydibenzene disulphonic acid or other surfactant and then by the addition of the acetoacetanilide or other diazo eliminating compound. Thereafter the dextrin or other lithographic desensitising material is added to obtain the desired composition. By means of the present invention it is possible to increase theink receptivity of the printing images of lithographic plates formed from radiation sensitive coatings based on diazo compounds. The following Examples, in which percentages are by weight, illustrate the invention: EXAMPLE 1 Eight sheets of grained, anodised and silicated aluminium were coated with the following radiation sensitive compositions and dried to form eight radiation sensitive plates: Plate 1 : An aqueous solution of Fairmount Chemical Corporation Diazo Resin No. 4 (the reaction product of a diazodiphenylamine-formaldehyde condensate and zinc chloride) Plate 2: An aqueous solution of Andrews Paper and Chemical,Co. Diazo Resin - P1004 (a bisulphate salt of a diazodiphenylamine-formaldehyde condensate) Plate 3: A 2-methoxyethanol/dimethyl formamide solution of the reactionproduct of a diazodiphenylamine formaldehyde condensate and -toluene sulphonic acid. Plate 4: A 2-methoxy ethanol solution of the reaction product of a diazo diphenylamine-formaldehyde condensate and 2-hydroxy-4-methoxy-benzophenone 5-sulphonic acid. Plate 5: A toluene/isopropanol solution of the reaction product of a diazodiphenylamine-formaldehyde condensate and sodium lauryl sulphate. Plate 6: A toluene/isopropanol solution of the reaction product of a diazodiphenylamine-formaldehyde condensate and tri-isopropyl naphthalene sulphonic acid. Plate 7: As plate 5 but including MACRYNAL SN510 in an amount equal to twice the weight of the diazo condensate. (MACRYNAL SN510 is an acrylic resin with hydroxyl functionality manufactured by Resinous Chemicals) Plate 8: A 2-methoxy ethanol/butyl acetate solution of the reaction product of a 3-methoxy diphenylamine 4-diazonium sulphate/4, 4 ' -bis-methoxy-methyl- diphenyl ether condensate and sodium mesitylene sulphonate. Each radiation sensitive plate was exposed beneath a negative transparency in a printing down frame and developed with an aqueous solution of iso-propanol. Separate areas of each plate were then treated respectively with a 2% aqueous solution of acetoacetanilide; 3-hydroxyacetoacetanilide; 4-chloro-2,5-dimethoxyaceto acetanilide; 4-morpholinoacetoacetanilide; N-acetoacetyl benzylamine; N,N'-bisacetoacetyl ethylene diamine; N-(cyanoacetyl) morpholine; and 2,3-dihydroxy naphthalenenas finishing solution, the solution in each case being alkaline and including a surfactant (Dowfax 2A1). Separate areas of each plate were also treated respectively with an alkaline 2 aqueous solution of 8-aminonaphthalene-2-sulphonic acid; a 2 aqueous solution of ascorbic acid and a 2 aqueous solution of hypophosphorous acid as finishing solution. One area of each plate was left untreated. The plates were dried and the whole.of the plate surfaces were treated with a desensitiser (aqueous gum arabic solution). The plates were stored in daylight for one day and then placed on an offset press. Whereas the areas on the plates which had been treated prior to being desensitised with gum arabic accepted ink within 3 or 4 revolutions of the press, the area of each plate which had been desensitised only was reluctant to take ink even after 30 revolutions. The tests were repeated but in this case the plates were stored for. one week in daylight before being placed on the press; The treated areas of each plate again took ink quickly, whereas the areas which had been desensitised only would not take ink even after several hundred revolutions. EXAMPLE 2 The procedure of Example 1 was repeated except that the following finishing composition was used in each case: Gum arabic 8.7% Acetoacetanilide 2.1 Dowfax 2A1 8.7% Water 80.5% Sodium hydroxide to pH 9.8 Dowfax 2A1 is the sodium salt of dodecylated oxydibenzene disulphonic acid and is a surfactant available from the Dow Chemical Company. When placed on the press, all the plates took ink satisfactorily, in those areas which had been treated with the finishing solution. EXANSLE 3 Example 2 was repeated except that the following finishing composition was used in each case: Dextrin 8.5; Acetoacetanilide 1.8 Dofax 2A1 4.4% Water 83.8% Trisodium phosphate to pH 10.5 Results similar to those of Example 2 were obtained. EXAMPLE 4 Example 2 was again repeated except that the following finishing composition was used in each case:- Dextrin 8.6 m-phenylene diamine 1.7% Dowfax 2A1 4 3% Water -85.4% Bydrochloric acid to pH 6 Results similar to those of Example 2 were obtained. EXAMPLE 5 Two proprietory negative working plates, namely an N6 plate manufactured by Hoechst AG and a Target plate manufactured by Frys Metals (Graphics) were image-utise exposed and developed according to the manufacturels' instructions. One half of each plate was treated with the finishing composition of Example 2 and the other half was treated with gum arabic. When placed on a press after storage as in Example 1, the half of each plate treated with the finishing composition took ink readily whereas the other half blinded and would not take ink. EXA#tPLE 6 A sheet of grained, anodised and silicated aluminium was coated with a radiation sensitive composition comprising a 2-methoxy ethanol/dimethyl formamide solution of the reaction product of a diazodiphenylamine-formaldehyde condensate and fluoroboric acid and dried. The resultant radiation sensitive plate was then treated in the same manner as the radiation sensitive plates of Example 1 and similar results were obtained. EXABIPLE 7 The procedure of Example 1 was repeated except that the following finishing composition was used in each case: Ammonium alginate 8.0 Acetoacetanilide 2 O Dowfax 2A1 4 0% Water 84.0 Trisodiumphosphate to pH 10.5 Similar results were obtained.

Claims: CLAIMS: (For all states except Austria) 1. A method of producing a lithographic printing plate from a radiation sensitive plate comprising a substrate having a radiation sensitive coating containing a diazo compound by image-wise exposing the radiation sensitive plate and developing the image-wise exposed plate to selectively remove the non-radiation struck areas of the coating from the substrate, characterised in that the developed plate is treated with a finishing composition comprising a compound capable of eliminating diazo groups. 2. A method according to claim 1 wherein the compound capable of eliminating diazo groups is an azo coupling compound capable of entering into an azo coupling reaction with a diazo group. 3. A method according to claim 2 wherein the azo coupling compound is acetoacetanilide; 3-hydroxyacetoacetanilide; 4-chloro-2,5-dimethoxyacetoacetanilide; 4-morpholinoacetoacetanilide; N-(cyanoacetyl)morpholine; 1-phenyl-3-methyl-5-pyrazolone; 2,3-dihydroxynaphthalene; 8-aminonaphthalene-2-sulphonic acid; 8-amino-1- naphthol-3,6-disulphonic acid; m-phenylene diamine or phloroglucinol. 4. A method according to claim 1 wherein the compound capable of eliminating diazo groups is ascorbic acid; hypophosphorous acid, a titanous salt; a chromous salt; a stannous salt; sodium hydro sulphite; sodium stannite; hydroquinone; sodium hypochlorite; cuprous chloride; an alkali metal iodide; potassium xanthate or benzoquinone. 5. A method according to any one of the preceding claims wherein the finishing solution includes a lithographic desensitising material. 6. A plate finishing composition for treating an exposed and developed radiation sensitive plate in lithographic printing plate production and comprising a lithographic desensitising material and water characterised in that the composition additionally includes a compound capable of eliminating diazo groups. 7. A composition as claimed in Claim 6 wherein said compound is a compound capable of entering into an azo coupling reaction with a diazo group. 8. A composition as claimed in claim 7 wherein said compound is acetoacetanilide; 3-hydroxyacetoacetanilide; 4-chloro-2,5-dimethoxyacetoacetanilide; 4-morpholinoacetoacetanilide; N-acetoace#ylbenzylamine; N,N'bisacetoacetylethylene diamine; N-(cyanoacetyl) morpholine; or 1-phenyl-3-methyl-5-pyrazolone; and the composition is alkaline. 9. A composition as claimed in claim 7 wherein said compound is m-phenylene diamine and the composition is acidic. 10. A composition as claimed in claim 6 wherein said compound is 2,3-dihydroxynaphthalene; 8-aminonaphthalene-2sulphonic acid; 8-amino-1-naphthol-3, 6-disdphonic acid; phloroglucinol; ascorbic acid; hypophosphorous acid; a titanous salt; a chromous salt; a stannous salt; sodium hydro sulphite; sodium stannite; hydroquinone; sodium hypochlorite; cuprous chloride; an alkali metal iodide; potassium xanthate or benzoquinone. 11. A composition as claimed in any one of claims 6 to 10 wherein the lithographic desensitising material is dextrin; gum arabic; an alginate; a cellulose derivative; acrylamide homopolymer; or a polymer containing structural units derived from acrylamide and from 1 to 25 by weight of structural units containing carboxyl groups. 12. A composition as claimed in any one of claims 6 to 11 which additionally includes a surfactant and/or a dispersing agent. 13. The use of a composition comprising a compound capable of eliminating diazo groups for the purpose of improving the ink receptivity of a lithographic printing plate obtained by the exposure and development of a radiation sensitive coating containing a diazo compound. CbAIMS: (For Austria only) 1. A method of producing a lithographic printing plate from a radiation sensitive plate comprising a substrate having a radiation sensitive coating containing a diazo compound by image-wise exposing the radiation sensitive plate and developing the image-wise exposed plate to selectively remove the non-radiation struck areas of the coating from the substrate characterised in that the developed plate is treated with a finishing composition comprising a compound capable of eliminating diazo groups. 2. A method according to claim 1 wherein the compound capable of eliminating diazo groups is an azo coupling compound capable of entering into an azo coupling reaction with a diazo group. 3. A method according to claim 2 wherein the azo coupling compound is acetoacetanilide; 3-hydroxyacetoacetanilide; 4-chloro-2,5-dimethoxyacetoacetanilide; 4-morpholinoacetoacetanilide; N-acetoacetyl benzylamine; N,N'-bisacetoacetylethylene diamine; N-(cyanoacetyl) morpholine; 1-phenyl-3-methyl-5-pyrazolone; 2,3-dihydroxynaphthalene; 8-aminonaphthalene-2-sulphonic acid; 8-amino-1-naphthol-3,6-disulphonic acid; m-phenylene diamine or phloroglucinol. 4. A method according to claim 1 wherein the compound capable of eliminating diazo groups is ascorbic acid; hypophosphorous acid; a titanous salt; a chromous salt; a stannous salt; sodium hydro sulphite; sodium stannite; hydroquinone; sodium hypochlorite; cuprous chloride; an. alkali metal iodide; potassium xanthate or benzoquinone. 5. A method according to any one of the preceding claims wherein the finishing solution includes a lithographic desensitising material. 6. A method of forming a composition for treating an exposed and developed radiation sensitive plate in lithographic printing plate production ¯chara;cterTsed Yin that it comprises admixing together a compound capable of eliminating diazo groups, a lithographic desensitising material, and water to obtain the desired composition. 7. A method in accordance with claim 6 of forming such a composition which additionally includes a pH-adjusting component and a surfactant which method comprises the sequential steps of heating the water; adding the pR-adjusting component to the water; adding the surfactant to the water; adding the diazo eliminating compound to the water; and adding the lithographic desensitising material to the water to obtain the desired composition. 8. A method according to claim 7 wherein the surfactant is the sodium salt of dodecylated oxydibenzene disulphonic acid. 9. A method according to claim 6, 7 or 8 wherein said compound is a compound capable of entering into an azo coupling reaction with a diazo group. 10. A method according to claim 9 wherein said compound is acetoacetanilide; 3-hydroxyacetoacetanilide; 4-chloro-2,5-dimethoxyacetoacetanilide; 4-morpholinoacetoacetanilide; N-acetoacetylbenzylamine; N,N'- bisacetoacetylethylene diamine; N-(cyanoacetyl) morpholine; 1-phenyl-3-methyl-5-pyrazolone; m-phenylene diamine; 2,3-dihydroxynaphthalene; 8-aminonaphthalene-2sulphonic acid; 8-amino-1-naphthol-3, 6-disulphonic acid; or phloroglucinol. 11. A method according to claim 6, 7 or 8 wherein said compound is ascorbic acid; hypophosphorous acid; a titanous salt; a chromous salt; a stannous salt; sodium hydro sulphite; sodium stannite; hydroquinone; sodium hypochlorite; cuprous chloride; an alkali metal iodide; potassium xanthate or benzoquinone. 12. A method according to any one of claims 6 to 11 wherein the lithographic desensitising material is dextrin; gum arabic; an alginate; a cellulose derivative; acrylamide homopolymer; or a polymer containing structural units derived from acrylamide and from 1 to 25% by weight of structural units containing carboxyl groups. 13. The use of a composition comprising a compound capable of eliminating diazo groups for the purpose of improving the ink receptivity of a lithographic printing plate obtained by the exposure and development of a radiation sensitive coating containing a diazo compound.

Inventors: DAWSON, ELIZABETH ANNE, GATES, ALLEN PETER
Applicants: VICKERS LIMITED
Application year: 1980
Main classification: G03F7
IPC codes: B41N3, G03F7