Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/016—Diazonium salts or compounds

Definitions

• This invention relates to a novel planographic plate and in particular to a planographic plate comprising a moisture impermeable and light-harden-able coating.
• planographic printing depends upon the immiscibility of grease and water, upon the preferential retention of a greasy image-forming substance by the image areas, and a similar retention of an aqueous dampening fluid by the non-image areas.
• a greasy image is imprinted upon a suitable surface and the entire surface is then moistened with an aqueous solution, the image areas will repel the water, and the non-image areas will retain the water.
• the image portions Upon subsequent applications of greasy ink, the image portions retain the ink, whereas the moist,
• non-image areas repel it.
• the image is then transferred to paper or cloth and so on, etc., via an intermediary socalled offset or blanket cylinder, which is necessary to prevent mirror-image printing.
• a plate with a light-sensitive coating is exposed to light through a negative transparency, and the image portion of the plate becomes hard and is made insoluble to desensitizing compositions by the action of the light.
• the unexposed light-sensitive coating is then removed by a desensitizing solution leaving a water-receptive surface as a non-image area.
• non-sensitized i.e. non-light harddened
• this non-light hardened compound must have considerable solubility in desensitizing solutions.
• non-light hardened diazo compounds sufiiciently soluble to be completely removed by ordinary desensitizers are also s-ufiiciently permeable to moisture to seriously interfere with the performance of planographic plates by allowing moisture to penetrate the diazo layer, interact with interlayers between the lightsensitive diazo layer and the base plate susceptible to moisture deterioration, and even corrode the metal base plate if the particular planographic plate is metal based.
• Another object of the invention is to provide a presensitized plate useful in long press runs because of an improved bonding of the new coating to the remainder of the plate and the improved durability of the coating material when light hardened. It is also an object of this invention to provide a light-sensitive coating for planographic plates that has reduced susceptibility to undesirable chemical reactions during dark storage and thus has an increased shelf life. It is a further object of this invention to provide a novel process by which the novel moisture-resistant coating may be applied to planographic plates.
• the novel planographic plates of the present invention comprise a coating which is a product of a reaction between a diazo compound and a coupling agent which reacts with the diazo com-pound forming, surprisingly, excellent light-sensitive and moisture-resistant coatings.
• These coatings consist of an intermediate protective compound formed when a light-sensitive diazo is reacted with a coupling agent under such reaction condition that resinification and the resultant formation of a non-lightsensitive compound are avoided.
• These intermediate compounds, postulated to be addition compounds of the diazo and coupling agent are sufiiciently resistant to moisture permeation to eliminate the aforementioned problems of specking, toning, and walk-off in normal, and even severe heat and humidity.
• Diazo compounds of the type commonly used in the planographic plate industry are resinified when reacted with a coupling agent in excessively basic medium. Such a reaction is of no value as a. method of forming a protective coating for a planographic plate inasmuch as it destroys the light-sensitive potential of the diazo compound.
• a coupling agent reacted in relatively acid media form a novel moisture-resistant intermediate azo addition product which also has the light-sensitive character of the original diazo compound.
• the number of coupling agents useful for the purposes of this invention is large. They are best described by a recitation of their main characteristic, i.e. an ability to react with the chosen diazo under reaction conditions that will not cause resinification and result-ant loss of the reaction products light-sensitive characteristics. Those coupling agents reacting with the diazo in an acid medium, i.e. at a pH of about 7.5 or below, are found to be especially advantageous for the practice of the instant invention.
• the coupling agents that are suitable for use in the reaction of the present invention are hydroxy benzophenones, diphenolic acids such as 4,4-bis(4-hydroxyphenyl)pentanoic acid, resorcinol, diresorcinol, lnaphthol-3-sulfonamide, 2-naphthol-3,6-disulfonic acid disodium salt and N-alkyl-S-sulfonanthranilic acids such as the methyl and ethyl compounds.
• These materials may have as substituents groups such as aldehyde, carboxyl or sulfonic groups.
• hydroxy benzophenones suitable for the present invention are 2,4-dihydroxy-benzophenone, 2-hy-droxy-4-methoxy-benzophenone, 2,2-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2,
• plastic and paper base members are also suitable for use in constructing planographic plates of the present invention.
• the 2,2-4,4'-tetrahydroxy-benzophenone is preferr d 5
• Various metal-protective coatings may be used as interamong these compounds. layers between the light-sensitive coating and metal base
• the diazo compounds conveniently used as reactants member.
• interlaye-rs are aluminum oxide with the above-identified coupling agents are of the type (for example, as found in anodized aluminum plates), the useful on planographic printing plates generally and which reaction products of an aqueous solution of soluble silicate are capable of reacting with the coupling agent at a pH with the met-a1 base, and reaction products of aqueous sufficiently low to avoid forming a resinified reaction prodsolutions of zirconium hexahalides, like potassium zircouct with the coupling ag P t Which h nium hexachloride, with the metal base.
• the prodchamber with a number of other pre-sensitized lithouct of the foregoing reaction is the light-hardenable reacgraphic lates having conventional diazo coatings and tion product which is exceedingly well bonded to the plate otherwise characterized as follows: and thus has a longer press life than diazo coated plano- Plat A i a commercially-available plate having a digraphic plates even before storage deterioration. azo coating.
• th Plate B is a plate comprising a silicate layer interposed diazo and coupling compounds are reacted in a solvent. 40 between the aluminum base plate and a diazo layer, the The solution containing the light-sensitive intermediate manuafcture of which is described in U.S, Patent 220 product so formed is coated onthe interlayer of the 2,922,715. planog-raphic plates.
• the sol- Plate C is a plat comprising a K ZrF interlayer bevent, the moisture-resistant diazo polymer coating retween a diazo coating and an aluminum base and differs mains on the plate.
• the reaction normally has a only in the light-sensitive coating used. greater time in which to proceed.
• the most irn- The plates subjected to the test were exposed .at F. permeable and resistant coatings may be achieved. and 90% relative humidity.
• a Water solution was prepared containing 0.1% saponin and 0.25 diresorcinol. This solution was coated over the planographic plate. After a contact time between solution and plate of one to two seconds, the excess solution was wiped from the plate and the plate was dried.
• the plate was removed from the high humidity environment, exposed to light through a negative transparency, desensitized with a conventional desensitizing agent, coated with a protective lacquer, and mounted upon a press. The nin was successful, being discontinued after 8000 prints were run off. The last copies were still excellent, indicating the fine performance of the plate,
• Example 3 An aluminum offset plate inches by inches and .OOS-inch thick was coated, consecutively with a K ZrF coating and a light-sensitive diazo compound according to U.S. Patent 2,946,683.
• An isopropanol solution was prepared containing 0.1% saponin and 0.05% sodium 2.2'-dihydroxy-4,4-dimethoxy-5-sul-fobenzophenone. This solution "was coated over the planographic plate. After a contact time between solution and plate of one to two seconds, the excess solution was wiped from the plate and the plate was dried.
• An azo addition product coated the surface which was light-harden-able and impermeable to moisture as indicated by its remaining-in satisfactory condition even when subjected to 90% relative humidity and 90 F. for 45 days and its performing well in the test described in Example 2.
• Example 4 An aluminum offset plate 10 inches by 15 inches and .005-inch thick was coated, consecutively with a K ZrF coating and :a light-sensitive diazo compound according to U.S. Patent 2,946,683.
• a 50% butyl acetate and 50% water solution was prepared containing 0.1% saponin and 0.25% 2,2,4,4-tetrahydroxy-benzophenone. This solution was coated over the planographic plate. After a contact time between solution and plate of one to two seconds, the excess solution was wiped from the plate and the plate was dried.
• An azo addition product coated the surface which was light-hardenable and impermeable to moisture as indicated by its remaining in satisfactory condition even when subjected to 90% relative humidity and 90 F. for 45 days and its performing well in the test described in Example 2.
• Example 5 An aluminum offset plate 10 inches by 15 inches and .005-inch thick was coated, consecutively with a K ZrF coating and :a light-sensitive diazo compound according to U.S. Patent 2,946,683.
• a 50% acetone and 50% water solution was prepared containing 0.1% saponin and 0.40% N-ethyl-S-sulfoanthranilic acid. This solution was coated over the planographic plate. After a contact time between solution and plate of one to two seconds, the excess solution was wiped from the plate and the plate was dried.
• An azo addition product coated the surface which was light-hardenable and impermeable to moisture as indicated by its remaining in satisfactory condition even when subjected to 90% relative humidity and 90 F. for 45 days and its performing well in the test described in Example 2.
• a v 1 1 1 Example 6 An aluminum offset plate 10 inches by 15 inches and .005-inch thick was coated, consecutively with a K ZrF 6 coating and a light-sensitive diazo compound according to U.S. Patent 2,946,683.
• a Water and 10% ethanol solution was prepared containing 0.1% saponin and 0.15% 4,4-bis(4-hydroxyphenyl) pentanoic acid. This solution was coated over the planographic plate. After a contact time between solution and plate of one to two seconds, the excess solution was wiped from the plate and the plate was dried.
• An azo addition product coated the surface which was light-hardenable and impermeable to moisture as indicated by its remaining in satisfactory condition even when subjected to 90% relative humidity and 90 F. for 45 days and its performing well in the test described in Example 2.
• Example 7 An aluminum offset plate 10 inches by 15 inches and .005-inch thick was coated, consecutively with a K ZrF coating and a light-sensitive diazo compound according to U.S. Patent 2,946,683.
• a methanol solution was prepared containing 0.1% saponin and 0.30% 1-naphthol-3-sulfonamide. This solution was coated over the planographic plate. After a contact time between solution and plate of one to two seconds, the excess solution was wiped from the plate and the plate was dried.
• An azo addition product coated the surface which was light-hardenable and impermeable to moisture as indicated by its remaining in satisfactory condition even when subjected to 90% relative humidity and 90 F. for 45 days and its performing well in the test described in Example 2.
• Example 8 An aluminum offset plate 10 inches by 15 inches and .005-inch thick was coated with a K ZrF coating according to U.S. Patent 2,946,683.
• an azo addition compound coated the surface which was light-hardena'ble and impermeable to moisture as indicated by its remaining in satisfactory condition even when subjected to 90% relative humidity and 90 F. for 45 days and its performing well in the test described in Example 2.
• a moisture-resistant planographic plate which comprises a base member having coated thereon a lightsensitive, moisture-resistant compound that is the reaction product of a light-sensitive diazonium compound and a phenolic hydroxyl-containing aromatic coupling agent formed in a medium having a pH of less than about 7.5 substantially to prevent resinification.
• a moisture-resistant planographic plate which comprises a base member having coated thereon a lightsensitive moisture-resistant compound that is the reaction product of (a) a light-sensitive diazonium compound obtained by the reaction of a diazo compound and a reactive carbonyl-containing compound and (b) a phenolic coupling agent formed in a medium having a pH of less than about 7.5 substantially to prevent resinification.
• a moisture-resistant planographic plate which comprises a base member having coated thereon a light-sensitive moisture-resistant compound that is the reaction product of (a) a light-sensitive diazonium compound obtained by the reaction of a diazo-diphenylamine and formaldehyde and (b) a phenolic compound, said reaction product being formed at a pH of less than about 7.5 substantially to prevent resinification.
• a moisture-resistant planographic plate which comprises a base member having coated thereon a light-sensitive moisture-resistant compound that is the reaction product of (a) a light-sensitive diazonium compound obtained by the reaction of a diazo-diphenylamine and formaldehyde and (b) a phenolic compound selected from the group consisting of hydroxybenzophenones, diphenolic alkanoic acids, dihydroxy-benzenes, tetrahydroxy-biphenyls, naphthol sulf-onamides, naphthol sulfonic acids, naphthol sulfonic acid salts and sulfanthranilic acids, said reaction product being formed at a pH of less than about 7.5 substantially to prevent resinification.
• a moisture-resistant planographic plate which comprises a base member having coated thereon a lightsensitive moisture-resistant compound that is the reaction product of (a) a light-sensitive diazonium compound obtained by the condensation of para-diazo-diphenylamine sulfate with formaldehyde zinc chloride and (b) a coupling agent selected from the group consisting of 4,4-bis (4-hydroxyphenyl)-pentanoic acid, resorcinol, diresorcinol, l naphthol-3-sulfon-amide, 2-naphthol-3,6-disulfonic acid disodium salt, N-lower alkyl-S-sulfoanthranilic acid, 2,4-dihydroxy-benzophenone, 2-hydroXy-4-methoxybenzophenone, 2,2 dihydroxy 4,4-dimethoxy-benzophenone, 2,2',4,4'-tetrahydroXy-benzophenone, sodium 2, 2 dihydroxy 4,-4-d
• a method for the preparation of a storagestable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive, moisture-resistant compound that is the reaction of a light-sensitive diazonium compound and a phenolic hydroxyl-containing aromatic coupling agent formed in a medium having a pH of less than about 7.5 substantially to prevent resinification.
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive moisture-resistant compound that is the reaction product of (a) a light-sensitive diazonium compound obtained by the reaction of a diazo compound and a reactive carbonyl-containing compound and (b) a phenolic coupling agent formed in a medium having a pH of less than about 7.5 substantially to prevent resinification.
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive moisture-resistant compound that is the reaction product of (a) a light-sensitive diazonium compound obtained by the reaction of a diazodiphenylamine and formaldehyde and (b) a phenolic compound, said reaction product being formed at a pH of less than about 7.5 substantially to prevent resinification.
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive moisture-resistant compound that is the reaction product of (a) a light-sensitive diazonium compound obtained by the reaction of a diazO-diphenylamine and formaldehyde and (b) a phenolic compound selected from the group consisting of hydroxy-benzophenones, diphenolic alkanoic acids, dihydroXy-benzenes, tetrahydroxy-biphenyls, naphthol sulfonamides, naphthol sulfonic acids, naphthol sulfonic acid salts and sulfanthranilic acids, said reaction product being formed at a pH of less than about 7.5 substantially to prevent resinification.
• a light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive moisture-resistant compound that is the reaction product of (a) a light-sensitive diazonium compound obtained by the condensation of paradiazo-diphenylamine sulfate with formaldehyde zinc chloride and (b) a coupling agent selected from the group consisting of 4,4 bis(4 hydroxyphenyl) pentanoic acid, resorcinol, diresorcinol, 1 naphthol 3 sulfon amide, 2- naphthol 3,6 disulfonic acid disodium salt, N lower alkyl 5 sulfoanthranilic acid, 2,4 dihydroxy benzophenone, 2 hydroxy 4 methoxy benzophenone, 2,2 dihydroxy 4,4 dimethoxy benzophenone, 2,2, 4,4- tetrahydroxy benzophenone, sodium 2,2 dihydroxy- 4,4 dimethoxy 5 sulfobenzophenone, 2 hydroxy-
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate, with a light-sensitve diazonium compound, applying a phenolic hydroxyl-oontaining aromatic coupling agent to said diazonium-coated base at a pH of below about 7.5 to form a substantially unresinified light-sensitive moisture-resistant reaction product, and removing unreacted residues from said plate.
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive diazonium compound obtained by the reaction of a diazo compound and a reactive carbonyl-containing compound, applying a phenolic coupling agent to said diazonium-coated base at a pH of below about 7.5 to form a substantially unresinified lightsensitive moisture-resistant reaction product, and removing unreacted residues from said plate.
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive moisture-resistant compound that is the reaction product of a light-sensitive diazonium compound obtained by the reaction of a diazo-diphenylamine and formaldehyde, applying a phenolic coupling agent to said diazonium-coated base at a pH of below about 7.5 to form a substantially unresinified light-sensitive moisture-resistant reaction product, and removing unreacted residues from said plate.
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive diazonium compound obtained by the reaction of diazo-dipheuylamine and formaldehyde, applying a phenolic coupling agent selected from the group consisting of hydroxybenzophenones, diphenolic alkanoic acids, dihydroxy-benzenes, tetrahydroxybiphenyls, naphthol sulfonamides, naphthol sulfonic acids, naphthol sulfonic acid salts and sulfanthranilic acids to said diazonium-coated base at a pH of below about 7.5 to form a substantially unresinified light-sensitive moisture-resistant reaction product, and removing unreacted residues from said plate.
• a phenolic coupling agent selected from the group consisting of hydroxybenzophenones, diphenolic alkanoic acids, dihydroxy-benzene
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate with a light-sensitive diazonium compound obtained by the condensation of para-diazo-diphenylamine sulfate with formaldehyde zinc chloride, applying a phenolic coupling agent selected from the group consisting of 4,4- bis(4 hydroxyphenyl) pentanoic acid, resorcinol, diresorcinol, 1 naphthol 3 sulfon amide, 2 naphthol- 3,6 disulfonic acid disodium salt, N lower alkyl 5- sulfoanthranilic acid, 2,4 dihydroxy benzophenone, 2-
• a moisture-resistant planographic plate which comprises a base member having coated thereon a light-sensitive, moisture-resistant compound that is the reaction product of a light-sensitive diphenylamine diazonium compound and a phenolic hydroxyl-containing aromatic coupling agent formed in a medium having a pH of less than about 7.5 substantially to prevent resinification.
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating a base for said planographic plate With a light-sensitive, moisture-resistant compound that is the reaction product of a light-sensitive diphenylamine diazonium compound and a phenolic hydroxylcontaining aromatic coupling agent formed in a medium having a pH of less than about 7.5 substantially to prevent resinification.
• a method for the preparation of a storage-stable, light-sensitive, moisture-resistant planographic plate which comprises coating 21 base for said planographic plate with a light-sensitive diphenylamine diazonium compound, applying a phenolic hydroxyl-containing aromatic coupling agent to said diazonium-coated base at a pH of less than about 7.5 to form a substantially unresinified light-sensitive moisture-resistant reaction product, and removing unreacted residue from said plate.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Phenolic Resins Or Amino Resins (AREA)
• Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (25)

Citations (5)

• 0
  • NL NL128965D patent/NL128965C/xx active
• 1963
  • 1963-09-06 US US307025A patent/US3300309A/en not_active Expired - Lifetime
• 1964
  • 1964-08-31 SE SE10425/64A patent/SE313997B/xx unknown
  • 1964-09-02 NL NL6410224A patent/NL6410224A/xx unknown
  • 1964-09-02 DE DE1964P0034990 patent/DE1447916B2/de active Granted
  • 1964-09-07 GB GB36643/64A patent/GB1055079A/en not_active Expired
  • 1964-09-07 BE BE652748D patent/BE652748A/xx unknown

Patent Citations (5)

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