US3474719A - Offset printing plates - Google Patents

Offset printing plates Download PDF

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US3474719A
US3474719A US562513A US3474719DA US3474719A US 3474719 A US3474719 A US 3474719A US 562513 A US562513 A US 562513A US 3474719D A US3474719D A US 3474719DA US 3474719 A US3474719 A US 3474719A
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diazo
plate
layer
resin
light
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Steven Levinos
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Eastman Kodak Co
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GAF Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/016—Diazonium salts or compounds
    • G03F7/0163—Non ionic diazonium compounds, e.g. diazosulphonates; Precursors thereof, e.g. triazenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B41N3/036—Chemical or electrical pretreatment characterised by the presence of a polymeric hydrophilic coating
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/14—Multiple imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers

Definitions

  • Light-sensitive material having on a metal base an anchoring layer of a thermoplastic alkali-soluble filmforming acrylic esteracrylic acid copolymer resin containing 1-20 mol percent acrylic acid and 8099 mol percent acrylic ester units, and an overlying light-sensitive layer containing a water-insoluble alkali resistant resin and a light-sensitive water-insoluble diazo oxide; and a process for making offset printing plates therewith by image-wise exposure to light and development with a liquid polyhydroxy compound or mixture of the latter with an alkaline compound whereby the light struck areas of the diazo oxide layer and the overlying anchoring layer are removed.
  • the present invention relates to pre-sensitized positive or negative working, offset printing plates derived from a metallic plate having a hydrophobic resinous layer sensitized with a diazonium compound, said resinous layer being capable of being rendered hydrophilic, after exposure of the plate, at the light-struck portions of the same and wherein said printing plate is provided with an adhesive intermediate, i.e., anchoring layer which serves to provide improved adhesion between the sensitized resinous layer and the metallic support and to the preparation and processing of such plates.
  • an adhesive intermediate i.e., anchoring layer which serves to provide improved adhesion between the sensitized resinous layer and the metallic support and to the preparation and processing of such plates.
  • the diazotype process is ideal. This process, as is understood, involves the sensitization of a base with a light-sensitive diazonium compound, the exposure of the sensitive element under a pattern, and the treatment of the element with a base in the presence of a coupling component to produce an azodye in those portions where the sensitized element has not been struck by light. To a large degree, the success of this system can be attributed to the variety of originals capable of duplication without special preparations.
  • the offset printing method is especially interesting since the copies prepared using the offset press possess several advantages over competitive processes.
  • the image produced by the offset press is composed of a permanent carbon or other pigment in a suitable carrier material while the image in a diazotype or spirit reproduction is composed of dye which in time may fade.
  • the non-image areas contain photo-decomposition products which are prone to cause a yellow discoloration, especially if the print be exposed to strong light.
  • stability against premature color formation in diazotype papers is brought about through the use of a heavy load of acid in the sensitive layer and some loss of strength of the paper may occur on aging.
  • the quality of the printing produced by the offset press is outstanding.
  • the use of the offset press has heretofore involved either the manual recopying of an original onto a so-called direct image master plate or the use of expensive, light-sensitive master plates either negative-working or positive-working.
  • the preparation of master plates using a negative-working photosensitive ofiset plate involves several time-consuming operations and expensive photographic equipment which have rendered the use of these plates in conjunction with the offset press impractical and decidedly overly expensive for the duplicating field.
  • much effort has been directed toward the development of a direct-positive, photo-offset plate which would allow the translucent original of the diazotype process to also serve as the original in applications requiring more copies than the diazotype process can economically produce.
  • the base plate is preferably aluminum over which is electroplated a thin layer of copper (Lithengrave plate developed by the Lithographic Technical Foundation), or it may carry an additional surface of metal by electrodeposition of chromium on the copper layer.
  • Such plates after pre-treatment are coated with a resin layer designed to tenaciously anchor the resin matrix containing the alkali-resistant resin and diazo oxide to the surface of the metal and to relax adhesion of the unexposed areas during processing so that they may be removed during the washing step.
  • An aluminum plate coated with copper will eventually lead to a positive plate.
  • a plate which carries an additional chromium layer will eventually produce a negative plate.
  • the film-forming alkaline soluble resin materials contemplated for use in accordance with the present invention are preferably derived from the polymerization of one or more monomers of the alpha, beta-monoethylenically unsaturated carboxylic acid series including their esters and salts.
  • Suitable monomers include for example, acrylic acid, methacrylic acid, methylacrylate, ethylacrylate, butylacrylate, etc., methylmethacrylate, ethylmethacrylate, butylmethacrylate and the like.
  • Resins of this type are readily available commercially such as the product Carboset from the B. F. Goodrich Chemical Co., e.g., Carboset 525, Although beneficial results may be obtained with the use of alkaline soluble resins of the general type encompassed by the aforestated definition, it has nevertheless been determined that optimum realization of the improvements made possible by the present invention are obtained with those polymeric materials containing within their skeletal structure, on a mole basis, from about to about 99% of units of the following structural formula:
  • R represents hydrocarbon, e.g., alkyl, aralkyl, aryl and alkaryl and preferably lower alkyl of 1 to 4 carbon atoms, e.g., methyl, ethyl, butyl, etc. and wherein R represents lower alkyl; and from about 1% to about 20% of units of the following structural formula:
  • R has the above defined significance.
  • the presence of the carboxyl pendent groups may result from the fact that a corresponding proportion of acrylic acid type monomers was present in the initial polymerizable monomer mixture or alternatively, such carboxy groups may be introduced into the polymer skeletal chain by subjecting an acrylate polymer, i.e., one containing no free acid group, to a suitable hydrolysis after treatment.
  • an acrylate polymer i.e., one containing no free acid group
  • the manner in which the polymer is prepared is not a particularly critical factor in the practice of the present invention so long as the relative proportions of the carboxy solubilizing substituents in the polymer chain are maintained within the above defined limitations.
  • the acrylate monomers may be employed in admixtures of 2, 3. or more.
  • methyl acrylate; ethyl acrylate; butyl acrylate monomer systems have been found to provide polymers eminently suited to the purposes of the present invention.
  • the resin is applied in the form of an 0.5 to 1% solution in isopropyl alcohol, although other solvents such as methanol, ethanol, acetone, diacetone alcohol, methyl cellosolve, dioxane, cyclohexanol, ethyl acetate and the like may be used.
  • a small quantity of oleic acid and a surface-active agent such as Alkaterge A (Commercial Solvents Corporation) is advantageous in promoting uniform wetting when the resin is applied to the metal surface.
  • the molecular weight of the resinous material is likewise not of critical miport so long as it be capable of depositing continuous films from solvent media.
  • the molecular weight may range from 5,000 to 10,000 up to several million.
  • resin materials having a molecular weight of from about 500,000 to 1,000,- 000 are preferred.
  • the resin is applied in the form of an 0.5 to 1% solution in isopropyl alcohol, although other solvents such as methanol, ethanol, acetone, diacetone, alcohol, methyl cellosolve, dioxane, cyclohexanol, ethyl acetate, and the like may be used.
  • solvents such as methanol, ethanol, acetone, diacetone, alcohol, methyl cellosolve, dioxane, cyclohexanol, ethyl acetate, and the like
  • Alkaterge A Common Solvents Corporation
  • Alkaterge A is a substituted oxazoline of the following general formula:
  • R is a long chain alkyl group such as pentadecyl or heptadecyl, While R and R are lower alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl and the like. In its preferred form, R is heptadecyl and R and R are methyl or ethyl.
  • the adhesive interlayer comprising the alkaline soluble, thermoplastic, film-forming acrylic resin following application, e.g., flow coating to the metal plate is thereafter directly overcoated with the sensitized layer comprising the light-sensitive diazo oxide and alkali-resistant resin.
  • the diazo oxide compounds found to be eminently suitable for use herein can be characterized as being waterinsoluble but which display solubility to the extent of at least 1% in a solvent which is a liquid and is an aliphatic ester, an aliphatic ketone or an aliphatic alcohol, i.e., alcohols in which the OH group is aliphatically linked.
  • solvents examples include ethylacetate, butylacetate, amylacetate and the like, acetone, diethylketone, methylpropylketone, methylisobutylketone, dipropylketone, methylethylketone, methylbutylketone and the like, ethyl alcohol, 'isopropyl alcohol, butyl alcohol, diacetone alcohol, benzyl alcohol, and the like.
  • Many diazo oxides of extremely high molecular weight and complex structure are of such a mixed, polar-non-polar character that they are only soluble in such powerful solvents as dimethylformamide, dimethylacetarnide, dioxane or methyl cellosolve. Since the solubilizing effects of the latter mentioned solvents would, in all likelihood, deleteriously affect the adhesive interlayer, it is preferred that such diazo oxides be employed which possess the solubility characteristics mentioned hereinbefore.
  • Diazo oxides within the broad class which have been found to be particularly suitable are those derived by amidation or esterification of 2 diazo 1 naphthol 5- sulfonyl chlorides or Z-naphthol-l-diazo-S-sulfonyl chlorides with comparatively simple amines or alcohols or with more complex compounds which possess a saturated, unconjugated, non-polar molecule such as rosin amines, rosin alcohols and their derivatives.
  • the above diazo oxides may be formulistically represented as follows:
  • R is alkoxy, i.e., methoxy, ethoxy, propoxy, aryloxy such as phenoxy, naphthoxy and the like, amino such as primary amino, alkyl amino, i.e., methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, butylamino, dibutylamino, arylamino such as phenylamino, naphthylamino and the like, aralkylamino such as benzylamino, dehydroabietylamino, didehydroabietylamino, and the like, carbalkoxyalkylamino such as carbmethoxymethylamino, carbethoxymethylamino, carbethoxyethylamino and the like.
  • diazo oxides embraced by these formulae are:
  • the light-sensitive diazo oxide as noted is laid down with an alkali-resistant adhesive resin preferably lipophilic in order to ensure adequate adhesion to the acrylic resin interlayer.
  • an alkali-resistant adhesive resin preferably lipophilic in order to ensure adequate adhesion to the acrylic resin interlayer.
  • resin there may be employed any water-insoluble, alkali-resistant resinous material which is soluble in any of the aforementioned limited classes of solvents for the diazo oxide, at least to an extent of 1% by weight.
  • the resin must be resistant to or impervious to the action of the solutions utilized in the processing of the raw plate to the finished offset printing plate. The resin should thus withstand a contact time of one-half minute or longer with such reagents and resist removal from the anchorage layer during such period of contact in the absence of the photodecomposition products. It is advantageous but not essential that the resin be of low or moderate molecular weight since such resins have improved adhesive character and are more readily removed in the presence of the photodecomposition products.
  • the photodecomposition products of the diazo oxide are soluble or sWellable in liquid aliphatic polyhydroxy compounds, thus permitting the selective removal of the photodecomposition products and the adhesive resin commingled therewith.
  • the polyhydroxy compound utilized for removal of the decomposition products and the adhesive resin is any liquid aliphatic polyhydroxy compound such as the various alkyl glycols, i.e., ethylene glycol, propylene glycol, diethylene glycol, 1-3-butylene gyco, 2-3 butyene glycol, dipropylene glycol, hexylene glycol, trihydric alcohols such as glycerin and the like.
  • Such polyhydroxy compounds may be used alone or in admixture with suitable mixtures including for example, ethylene glycol with glycerin, hexylene glycol with glycerin, 2,3-butylene glycol with glycerin, propylene glycol with ethylene glycol and the like. It has been found that the solubility or swellability of the diazo oxide photodecornposition products in liquid aliphatic polyhydroxy compounds is a general phenomenon and, hence, any such solvent is suitable for use.
  • the alkaline-soluble acrylic resin utilized as the adhesive interlayer is soluble in alkaline media.
  • a suitable alkaline reagent in the solution containing the above-described polyhydroxy compound, there is accomplished a simultaneous removal of both the exposed areas of the diazo oxide layer and those portions of the acrylic resin adhesive layer lying directly therebeneath.
  • this represents a particularly desirable feature since it makes possible the elimination of the added steps which would otherwise be necessary.
  • the metal surface is laid bare by a single solvent treatment being thus available directly for treatment with the metal etching medium.
  • the plate structure would comprise, for example, a copper-coated aluminum base, the copper surface being directly coated with the alkaline-soluble acrylic resin adhesive interlayer the latter in turn being directly overcoated with the light-sensitive diazo oxide layer.
  • the light struck areas of the diazo oxide layer as well as the corresponding portion of the subjacent surface layer are removed by the employment of a single solvent solution comprising for example, diethanolamine and ethylene glycol.
  • the copper portion of the bimetallic plate laid bare by the foregoing solvent treatment can then be readily etched out by the use of a suitable etching solution, e.g., ferric chloride, in order to expose the aluminum surfaced disposed therebeneath.
  • a suitable etching solution e.g., ferric chloride
  • the remaining portions of the diazo oxide layer, i.e., those unaffected by the exposure radiation are then removed by treatment with an organic solvent for the resin, e.g.,
  • the present invention can likewise be applied to distinct advantage in the preparation of printing plates of the type described in US. Patent 2,772,972 (C. E. Herrick, Jr., et a1.) i.e., in which the raised portions of the diazo oxide layer which remain following the post-exposure wash-out operation comprise the grease receptive printing areas.
  • those portions of the sub-stratum layer laid bare by wash-out of the diazo oxide layer must be rendered hydrophilic by a solvent treatment distinct from the wash-out operation unless hydrophilic character be imparted to such sub-stratum layer simultaneously with the wash-out operation by replacing a part of the polyhydroxy compound with a substantially equivalent amount of alkylola-mine.
  • the present invention obviates the necessity of resorting to a separate treatment as regards imparting hydrophilic character to the sub-stratum layer since the resin materials described herein for such purposes inherently possess the required degree of hydrophilicity. It will be understood, of course, that the pro duction of such a printing plate would require omitting any alkaline reagent from the solution employed in the Wash-out of the diazo oxide layer in order to exclude any possibility of removing the alkaline-soluble acrylic resin comprising the adhesive interlayer.
  • a negative-working plate could be readily effected by employing as the metal support a copper-coated aluminum sheet further provided on the copper surface with a layer of chromium.
  • a chromium etch in the processing of the exposed plate, the printing areas of the plate will correspond to the exposed areas of the diazo oxide layer, the copper being exposed in such portions as a result of the chromium etch.
  • EXAMPLE I A copper surfaced aluminum plate in rinsed with warm water to remove the protective gum layer. It is then flushed with nitric acid (2 ounces per gallon of water) for about 30 seconds. It is rinsed thoroughly again with water, followed by an acetone rinse. After drying, the plate is coated with the following compositron:
  • This solution is filtered and then applied to the copper surface by flow coating, using 5 cc. per square foot of area to be coated.
  • the coating is allowed to dry for a period of 15 to 20 minutes and then overcoated in subdued light with a mixture of the following composition:
  • a ferric chloride etch solution of the type described on page 214 of Offset Platemaking (Lithographic Technical Foundation, 1955) is now spread evenly over the entire plate. entire plate.
  • This solution has the following composition:
  • An ungummed trimetallic chromium-copper-aluminum plate is coated on its chromium surface with the Carboset and diazo oxide compositions described in Example I. Following exposure through a photographic positive, followed by washout, drying and removal of the undercoating as described in Example I, the plate was dried for 5 minutes with a warm air blast.
  • a chromium etch solution of the type described on page 182 of Offset Platemaking (Lithographic Technical Foundation, 1955 is then used to etch away the chromium in the exposed image areas. This solution has the following composition:
  • Example III Aluminum chloride solution, 32 B. cc 750 Zinc chloride g 630 Phosphoric acid, 85% cc 40 EXAMPLE IV The procedure is the same as in Example III excepting that the diazo oxide layer is prepared utilizing the composition of Example II.
  • EXAMPLE V An ungummed aluminum plate is coated as described in Example I. Following exposure, the diazo oxide layer was swabbed with a pad moistened with the following solution:
  • the sensitizing layer is thus rapidly removed in the regions of the plate which were unprotected during the exposure by opaque portions of the orginal. The completeness of this removal can be conveniently followed by the presence of color on the exposed surface since the exposed sensitizing layer is brownish in hue. Since no alkaline material is present in the washout solution, the resinous adhesive layer remains intact and the plate is directly available for inking, the raised portions of the diazo oxide layer serving as the grease-receptive printing areas. Since the adhesive interlayer possesses the requisite hydrophilicity to repel greasy inks, further solution treatments are totally unnecessary.
  • EXAMPLES VI THRU X Examples 1 through V are repeated utilizing as the resin component in the anchoring layer composition a polymer containing on a mole basis 90.4% of a mixture of methyl acrylate, ethyl acrylate and butyl acrylate polymer units and 19.6% acrylic acid polymer units.
  • offset printing plates produced according to the foregoing examples exhibit excellent structural stability throughout the entire processing as evidenced by the fact that the various layer strata display no tendency to peel or otherwise separate from the element. Moreover, such plates provided offset prints characterized by excellent reproduction quality.
  • results similar to those described in the foregoing examples are obtained for example, when the ethanolamine component of the washout solution is replaced by an aqueous solution of ammonia, trisodium phosphate, etc.
  • the nature of the alkaline material employed for simultaneous removal of the diazo oxide and adhesive layers is not particularly critical, the primary requirement being that it be present in amounts sufficient to yield a pH on the order of 7.5 to 8.0 or higher.
  • a light-sensitive material comprising a unitary metallic base carrying on one side thereof a thermoplastic, alkaline-soluble, film-forming acrylic resin as an anchoring layer, said resin containing on a mole basis from about to 99% of acrylate units of the structural formula:
  • R is an alkyl, arakyl, aryl or alkaryl group and R is a lower alkyl group and from about 1 to about 20% of acrylic acid units, said anchoring layer being overcoated with a light-sensitive layer comprising 150% by weight of a water-insoluble alkali-resistant resin and a light-sensitive water-insoluble diazo oxide.
  • a light-sensitive material according to claim 1 wherein said unitary metallic base comprises aluminum having an outer metallic surface layer selected from the group consisting of copper and chromium said outer metallic sucface serving as the support for said anchoring and light-sensitive diazo oxide layers.
  • alkaline-soluble, film-forming acrylic resin comprises an interpolymer of methyl acrylate, ethyl acrylate, butyl acrylate and acrylic acid.
  • a light-sensitive material according to claim 4 wherein said water insoluble alkali-resistant resin comprises polyvinyl acetate.
  • a light-sensitive material according to claim 1 Disclaimer 3,474,719.Steven Levinos, Vestal, N.Y. OFFSET PRINTING PLATES. Patent dated Oct. 28, 1969. Disclaimer filed Sept. 30, 1982, by the assignee, Eastman Kodak Co.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US562513A 1966-04-15 1966-07-05 Offset printing plates Expired - Lifetime US3474719A (en)

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US54275766A 1966-04-15 1966-04-15
US56251366A 1966-07-05 1966-07-05

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FR (1) FR1519211A (de)
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NL (1) NL6705269A (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629036A (en) * 1969-02-14 1971-12-21 Shipley Co The method coating of photoresist on circuit boards
US3637384A (en) * 1969-02-17 1972-01-25 Gaf Corp Positive-working diazo-oxide terpolymer photoresists
US3772016A (en) * 1973-01-30 1973-11-13 Ibm Method of producing multicolor planographic printing surface
US4093464A (en) * 1972-07-27 1978-06-06 Hoechst Aktiengesellschaft Light sensitive o-quinone diazide containing transfer composition
US4405394A (en) * 1980-05-27 1983-09-20 E. I. Du Pont De Nemours And Company Laminating process
US5126229A (en) * 1988-04-22 1992-06-30 Fuji Photo Film Co., Ltd. Process for preparing positive or negative lithographic printing plates using a developer having at least one alkali-soluble mercapto compound and/or thioether compound
US20130295747A1 (en) * 2011-03-08 2013-11-07 Lg Hausys, Ltd. Adhesive composition for a wafer processing film
CN110032041A (zh) * 2019-05-07 2019-07-19 深圳市华星光电半导体显示技术有限公司 光阻组合物、显示面板及其制备方法

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
CA1051707A (en) * 1973-10-25 1979-04-03 Michael Gulla Photoresist film with non-photosensitive resist layer

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US2464826A (en) * 1943-12-30 1949-03-22 Rohm & Haas Acrylic resin laminations
US2760863A (en) * 1951-08-20 1956-08-28 Du Pont Photographic preparation of relief images
US2772972A (en) * 1954-08-20 1956-12-04 Gen Aniline & Film Corp Positive diazotype printing plates
US2884126A (en) * 1955-11-18 1959-04-28 Minnesota Mining & Mfg Pressure-sensitive adhesive sheet material
US3210187A (en) * 1960-04-28 1965-10-05 Du Pont Photopolymerizable elements and processes
US3264104A (en) * 1961-07-28 1966-08-02 Azoplate Corp Reversal-development process for reproduction coatings containing diazo compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2464826A (en) * 1943-12-30 1949-03-22 Rohm & Haas Acrylic resin laminations
US2760863A (en) * 1951-08-20 1956-08-28 Du Pont Photographic preparation of relief images
US2772972A (en) * 1954-08-20 1956-12-04 Gen Aniline & Film Corp Positive diazotype printing plates
US2884126A (en) * 1955-11-18 1959-04-28 Minnesota Mining & Mfg Pressure-sensitive adhesive sheet material
US3210187A (en) * 1960-04-28 1965-10-05 Du Pont Photopolymerizable elements and processes
US3264104A (en) * 1961-07-28 1966-08-02 Azoplate Corp Reversal-development process for reproduction coatings containing diazo compounds

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629036A (en) * 1969-02-14 1971-12-21 Shipley Co The method coating of photoresist on circuit boards
US3637384A (en) * 1969-02-17 1972-01-25 Gaf Corp Positive-working diazo-oxide terpolymer photoresists
US4093464A (en) * 1972-07-27 1978-06-06 Hoechst Aktiengesellschaft Light sensitive o-quinone diazide containing transfer composition
US3772016A (en) * 1973-01-30 1973-11-13 Ibm Method of producing multicolor planographic printing surface
US4405394A (en) * 1980-05-27 1983-09-20 E. I. Du Pont De Nemours And Company Laminating process
US5126229A (en) * 1988-04-22 1992-06-30 Fuji Photo Film Co., Ltd. Process for preparing positive or negative lithographic printing plates using a developer having at least one alkali-soluble mercapto compound and/or thioether compound
US20130295747A1 (en) * 2011-03-08 2013-11-07 Lg Hausys, Ltd. Adhesive composition for a wafer processing film
US9153471B2 (en) * 2011-03-08 2015-10-06 Lg Hausys, Ltd. Adhesive composition for a wafer processing film
CN110032041A (zh) * 2019-05-07 2019-07-19 深圳市华星光电半导体显示技术有限公司 光阻组合物、显示面板及其制备方法

Also Published As

Publication number Publication date
NL6705269A (de) 1967-10-16
DE1671617A1 (de) 1971-01-14
GB1177527A (en) 1970-01-14
FR1519211A (fr) 1968-03-29

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