US3552315A - Offset master for imaging by diffusion transfer with nucleating agent, cadium salt and a salt of zirconium, thorium or titanium - Google Patents
Offset master for imaging by diffusion transfer with nucleating agent, cadium salt and a salt of zirconium, thorium or titanium Download PDFInfo
- Publication number
- US3552315A US3552315A US526988A US3552315DA US3552315A US 3552315 A US3552315 A US 3552315A US 526988 A US526988 A US 526988A US 3552315D A US3552315D A US 3552315DA US 3552315 A US3552315 A US 3552315A
- Authority
- US
- United States
- Prior art keywords
- salt
- master
- lithographic
- zirconium
- offset master
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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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
- G03F7/06—Silver salts
- G03F7/07—Silver salts used for diffusion transfer
Definitions
- Offset masters for offset copy work are generally of the direct image type wherein the hydrophilic lithographic surface of the master is imaged directly by the application of an oleophilic ink receptive imaging material, as by inscribing with a crayon or ink, or by transfer from a carbon sheet in response to compression or impact by stylus, typewriter key, die impression or the like.
- the nonimaged portions of the master When mounted on a lithographic press and wet with an oleophilic ink composition and an aqueous repellent, the nonimaged portions of the master accept the aqueous repellent while the ink composition is taken up by the oleophilic ink receptive imaged portions of the master for subsequent transfer either directly to copy sheets brought into surface contact with the inked master or indirectly to an offset blanket from which the image is transferred to copy sheets.
- a master of the type described has been produced wherein the hydrophilic lithographic surface is'overcoated with a water soluble, resin forming, light sensitive diazo compound in which a negative transparency is first formed of the original and then the diazo light sensitive coating is ex posed to the developed negative transparency to resinify the diazo compound in the'exposed areas while the portions of the light sensitive diazo coating in the unexposed areas are removed by washing to produce an imaged photolithographic plate.
- the photolithographic masters are somewhat similar in construction in that the master sheetis presensitized with a light sensitive material that is convertible to an ink receptive imaging material upon exposure to light.
- Such presensitized photolithographic masters are subject to a number of deficiencies including high cost, short shelf life, the need to make use of specialized equipment and materials, and the need to prepare a negative transparency by conventional photographic technique.
- lithographic or offset masters capable of being imaged by diffusion transfer technique from an exposed but underdeveloped silver halide negative have been produced in which the hydrophilic, lithographic surface is provided with a nucleating or fogging agent for reducing silver ha lide to an ink receptive, water repellent silver image whereby, when the master sheet is brought into contact with the exposed silver halide negative wet with a silver halide solvent and developer, the silver halide in the unexposed portions of the negative transfer by diffusion to the surface of the master where the silver halide or complex formed thereof is reduced to a silver, ink receptive, water repellent imaging material on the hydrophilic, water receptive lithographic surface to produce the master having an image corresponding to the original.
- the diffusion transfer reversal technique makes use of equipment and materials which are of low cost and which have heretofore found widespread use in single copy difi usion transfer reversal processes commonly employed in the field.
- the diffusion transfer process also eliminates the need for the preparation of a negative transparency and the exposure of the negative transparency to a presensitized master is also completely eliminated.
- the diffusion transfer reversal process for preparation of an imaged lithographic master from an original has been limited to use of a master sheet formed of a metal base such as aluminum, having its surface treated as by silicating, brushing, anodizing, or the like, to render the surface water receptive, hydrophilic and lithographic.
- a master sheet formed of a metal base such as aluminum, having its surface treated as by silicating, brushing, anodizing, or the like, to render the surface water receptive, hydrophilic and lithographic.
- FIG. I is a perspective view partially in section of a lithographic master prepared in accordance with the practice of this invention. 2.-
- FIG. 2 is a sectional elevational view of a modification in a lithographic master prepared in accordance w'h he practice ofthis invention
- FIG. 3 is a sectional elevational view showing the ari'angement of elements including the master shown in EIGJ and an exposed silver halide negative in position to form the image by diffusion transfer on the lithographic surface
- M is a sectional elevational view showing the ari'angement of elements including the master shown in EIGJ and an exposed silver halide negative in position to form the image by diffusion transfer on the lithographic surface
- FIG. 4 is a perspective view partially in section of the imaged master produced with the master of FIG. Ifand FIG. 5 is a perspective view partiallyin ,section of the master. of FIG. 1 having a protective plastic film.
- the offset or lithographic master embodying the features of this invention comprises a flexible base sheet 10 having a water insoluble, water receptive, ink repellent, lithographic surface 12 which is overcoated with one or more coatings 14 containing a silver halide fogging or nucleating agent, .a zirconium salt and a cadmium salt as the essential components,
- the base sheet 10 use can be made of a foil of an amphoteric metal, such as aluminum, zinc or copper, in which the surface of the metal such as aluminum is rendered hydrophilic and lithographic by treatment suchas brushing, anodizing, or preferably by silicating with a soluble silicate solution.
- a paper base sheet 10 which is resinous impregnated or treated with a resinous material for high wet strength and which is provided with a continuous water insolubilized, water receptive, ink repellent,'hydrophilic lithographic coating 12 formulated of a hydrophilic colloid of resin as a binder and a filler such as zinc oxide, satin white, clay and the like.
- Suitable binders comprise casein, starch, carboxymethylcellulose, polyacrylic acid, polyvinyl acetate, alginates, polyvinylpyrrolidone, and polyvinyl alcohol, reference being made to the following patents for illustrations of coated paper lithographic plates formulated of the above 1 materials, namely: Worthem US. Pat. No. 2,534,650 (casein Van Dusen US. Pat. No. 2,542,784 (carboxymethylcellulose); Ensink US. Pat. No. 2,806,424 (alignates); Beatty et al.
- stannous halide such as stannous chloride, stannous bromide, stannous fluoride and the like.
- stannous chloride such as stannous chloride, stannous bromide, stannous fluoride and the like.
- fogging agents such as stannous chloride, stannous bromide, stannous fluoride and the like.
- the zirconium salt comprises a water soluble salt of zirconium such as zirconyl methylate, zirconyl acetate, zirconyl propionate, zirconyl chloride, zirconyl nitrate, and other zirconyl halides and the like. While less desirable than the zirconyl salts and while not equivalent thereto in the described system, the zirconium salts can be replaced in whole or in part by the corresponding water soluble salts of thorium or titanium.
- cadmium salt use can be made of a water soluble salt of cadmium such as an organo cadmium salt represented by cadmium acetate or an inorganic salt such as cadmium chloride, cadmium bromide, cadmium nitrate, or other cadmium halide and the like.
- the cadmium salt can be replaced by an antioxidant but when use is made of an antioxidant it is preferred to make use of such antioxidant in combination with the cadmium salt.
- Representative of the antioxidants which may be employed are:
- the materials are formulated into a coating composition in the ratio of 1 part by weight stannous salt per 1.0 to 8 parts by weight of the zirconium salt and 0.01 to 0.5 parts by weight of the cadmium salt, and preferably in an amount within the range of 1 part by weight of the stannous salt to 1.7 to 3.5 parts by weight of the zirconium salt and 0.02 to 0.2 parts by weight of the cadmium salt.
- the materials can be formulated into a coating composition in which the materials are present in an amount to provide a solids content of l to percent by weight and preferably 2 to 8 percent by weight.
- the composition is applied in coating weights within the range of 0.1 to 4 grams per square meter, and preferably in an amount within the range of 0.5 to 3 grams solids per square meter.
- the three essential components can be applied in corresponding amounts in separate coatings to provide one coating containing the cadmium salt, with or without an antiox idant additive, and the other coating 22 containing the zirconium, thorium or titanium salt, and a third coating containing ,the fogging or nucleating agent, or the-materials may be formulated into two coating compositions in which the components are present in the various combinations.
- Application onto the lithographic surface can be made by conventional coating processes, such as by spray coating, roller coating, flow coating and the like, followed by air drying or drying at elevated temperature, such as up to 200 F.
- compositions which may be applied as coatings onto the lithographic surface in the preparation of diffusion transfer offset masters embodying the features of this invention:
- Example 1 Parts by Zirconium acetate solution (13% as weight ZIOz) 20 Distilled water 8O Stannous chloride 1 Cadmium acetate 0. 2
- Example 2 Parts by Zirconium acetate solution (13% as weight ZrO 20 Distilled water Stannous chloride 2 Cadmium acetate 02 Hydroquinone monomethyl ether 20
- Example 3 Parts by weight Zirconium chloride (13% solution) 2O Distilled water 80 Stannous acetate 2 Cadmium acetate O. 2 Ascorbic acid O. 2
- Example 4 Parts by Zirconium acetate solution (13% as weight ZIOz) 20 Water 80 Stannous chloride 2 Hydroquinone monomethyl ether 0. 2
- Example 5 Parts by Thorium chloride or titanium chloride weight (10% solution) 20 Distilled water 80 Stannous chloride 2 Cadmium acetate 0. 2 Antioxidant 0. 2
- Example 6 Part A Parts by Zirconium acetate solution (13% as weight ZrO 20 Distilled water 80
- Stannous chloride 2 Parts by Part B weight Cadmium acetate 0. 1 Pyrogallic acid 0. 2 Distilled water 80
- the applied coating 14 is either air dried or drying can be accelerated by heating to an elevated temperature of about 200 F. to produce the finished master.
- a coated paper direct image plate formed of high wet strength paper base sheet 10 having a lithographic coating 12 provided thereon as described in the Worthem US. Pat. No. 2,534,650, or the Van Dusen US. Pat. No. 2,542,784, or the Ensink US. Pat. No. 2,806,424, or the Beatty et al. US. Pat. No. 2,760,431.
- the lithographic surface of the coated paper base sheet is over coated with a composition of one of the examples 1 to 5 applied to provide an overall coating having a coating weight of 0.5 to 3.0 grams per square meter.
- the applied coating is dried at elevated temperature within the range of 200 F.
- part A is applied first onto the lithographic surface and then dried, after which part B is applied and dried to provide the plural coatings and 22.
- the shelf life of the masters prepared in accordance with the practice of this invention can be greatly extended and improved when the coating or coatings, applied in accordance with the practice of this invention, is covered with a removable film 16 of plastic material, such as a film of polystyrene, Teflon, polyvinylidene chloride, polyvinyl chloride, chlorinated rubber and the like.
- More than one coating of the composition embodying the features of this invention can be applied onto the lithographic surface. Such plural coatings will enhance the protective features of one coating for another to resist oxidation and deterioration. ln such event, the need for a protective film 16 is greatly minimized.
- a negative in the form of a base sheet 32 having a light sensitive, silver halide gelatin coating 34.
- suitable negatives are Gevaert GS negative (Gevaert Photo Production of Antwerp, Belgium); Oricopy (Oriental Photocopy Company, Tokyo, Japan), or Anken Photo Rapid negative, of the Anken Chemical Company of the United States.
- the negative 30 is exposed to the original in a conventional photographic exposure apparatus.
- the exposed negative is then brought into pressure contact with the coated surface of the master sheet after one or both of the surfaces have been wet with a monobath developer, as represented by the following example:
- Example 7 Parts Water 815 Phenidone 2. 5 Anhydrous sodium sulfite 114 4 Hydroquinoue 24 Sodium hydroxide 24 Sodium thiosulfate 9. 8 Potassium bromide 1. 6 Carboxymethylcellulose 8. 0
- the sheets can be processed through an A, B. Dick 110 Photocopier filled with the monobath solution.
- the monobath operates to form a soluble complex of the silver halide in the unexposed portions of the negative for transfer of the complex of silver halide by diffusion to the coated surface of the master where the silver halide is nucleated to deposit dense masses of silver 36 concentrated at the surface of the master to form an ink receptive, highly hydrophobic image 38 on the lithographic hydrophilic surface.
- the formed silver image remains strongly bonded to the lithographic surface.
- the imaged plate is wet with a-conventional fixer or conditioner, such as the CT offset fixer of Eastman Kodak or 0 84-4966 A. B. Dick Photoplax Conditioner, which operates to make the nonimaged areas hydrophilic and fix the image onto the master.
- the imaged master can be mounted on the plate cylinder of a conventional lithographic press and sequentially wet with aqueous repellent and oleophilic ink whereby the repellent wets out the nonimaged portions of the plate while the ink wets out the imaged portions of the plate thereby to enable production of thousands of copies of good quality.
- An offset master for imaging to provide an oleophilic ink receptive image by diffusion transfer from an exposed silver halide negative comprising a base sheet having a water insoluble, water receptive, hydrophilic, lithographic surface, said master having on the lithographic surface the combination of a nucleating agent for silver halide a water soluble salt of cadmium as a component separate and apart from the nucleating agent and present in an amount within the range of 0.01 to 0.5 parts by weight of the cadmium salt to 1 part by weight of the nucleating agent, and a water soluble salt of a metal selected from the group consisting of zirconium, thorium and titanium as a component separate and apart from the nucleating agent and present in an amount within the range of l to 8 parts by weight of the metal salt to 1 part by weight of the nucleating agent.
- nucleating agent comprises a stannous halide.
- An offset master as claimed in claim 2 in which the salts are present in the ratio of 1 part by weight of the stannous salt to 1.7 to 3.5 parts by weight of zirconium salt and 0.02 to 0.2 parts by weight of cadmium salt.
- An offset master as claimed in claim 2 in which the salts are present on the lithographic surface in a coating weight within the range of 0.1 to 4 grams per square meter.
- An offset master as claimed in claim 2 in which the salts are present on the lithographic surface in a coating weight of 0.5 to 3 grams per square meter.
- An offset master as claimed in claim 1 which includes a film of plastic material as a cover over the coated lithographic surface.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Printing Plates And Materials Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US52702866A | 1966-02-14 | 1966-02-14 | |
US52698866A | 1966-02-14 | 1966-02-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3552315A true US3552315A (en) | 1971-01-05 |
Family
ID=27062280
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US526988A Expired - Lifetime US3552315A (en) | 1966-02-14 | 1966-02-14 | Offset master for imaging by diffusion transfer with nucleating agent, cadium salt and a salt of zirconium, thorium or titanium |
US527028A Expired - Lifetime US3552316A (en) | 1966-02-14 | 1966-02-14 | Dtr offset master and composition for preparation of same |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US527028A Expired - Lifetime US3552316A (en) | 1966-02-14 | 1966-02-14 | Dtr offset master and composition for preparation of same |
Country Status (6)
Country | Link |
---|---|
US (2) | US3552315A (xx) |
BE (1) | BE694055A (xx) |
DE (1) | DE1522477A1 (xx) |
FR (1) | FR1515292A (xx) |
GB (1) | GB1169774A (xx) |
NL (1) | NL6701955A (xx) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3860426A (en) * | 1972-12-22 | 1975-01-14 | Eastman Kodak Co | Subbed lithographic printing plate |
US3929481A (en) * | 1972-02-25 | 1975-12-30 | Fuji Photo Film Co Ltd | Etch bleaching processes for making lithographic printing plates using silver halide and/or diffusion transfer layers and a hydrophilic layer |
US6014929A (en) * | 1998-03-09 | 2000-01-18 | Teng; Gary Ganghui | Lithographic printing plates having a thin releasable interlayer overlying a rough substrate |
US20040115449A1 (en) * | 2002-12-13 | 2004-06-17 | Eastman Kodak Company | Display panel |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3971660A (en) * | 1974-04-04 | 1976-07-27 | Eastman Kodak Company | Lithographic printing plate comprising hydrophilic layer of polyvinylacetate crosslinked with tetraethylorthosilicate |
DE69023180T2 (de) * | 1989-07-25 | 1996-06-13 | Agfa Gevaert Nv | Nach dem DTR-Verfahren hergestellte lithographische Aluminium-Offset-Druckform. |
US5345870A (en) * | 1993-02-10 | 1994-09-13 | Miles Inc. | "Direct-to-press" positive lithographic printing plate and method for making same |
DE29701585U1 (de) * | 1997-01-31 | 1997-03-13 | Roland Man Druckmasch | Druckplatte |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2352014A (en) * | 1941-07-21 | 1944-06-20 | Rott Andre | Photomechanical printing process and printing material for carrying out the same |
US2814988A (en) * | 1954-05-19 | 1957-12-03 | Armour Res Found | Printing plates and the production thereof |
BE565696A (xx) * | 1955-03-31 | 1958-03-31 | ||
GB830623A (en) * | 1956-04-18 | 1960-03-16 | Agfa Ag | A planographic printing process using greasy or fatty ink |
GB856770A (en) * | 1957-09-07 | 1960-12-21 | Kalle & Co Ag | Improvements in or relating to photographic reproduction |
US3169065A (en) * | 1960-10-11 | 1965-02-09 | Harris Intertype Corp | Method of making resist and deep etch lithographic printing plates with ferric ammonium compound sensitized plates |
US3220837A (en) * | 1955-07-22 | 1965-11-30 | Polaroid Corp | Diffusion transfer to stratum of a silver image inked and used in printing |
US3309990A (en) * | 1961-01-25 | 1967-03-21 | Azoplate Corp | Process for the preparation of printing plates |
US3311473A (en) * | 1962-06-28 | 1967-03-28 | Eastman Kodak Co | Silver halide diffusion process and products therefor |
-
1966
- 1966-02-14 US US526988A patent/US3552315A/en not_active Expired - Lifetime
- 1966-02-14 US US527028A patent/US3552316A/en not_active Expired - Lifetime
-
1967
- 1967-02-09 NL NL6701955A patent/NL6701955A/xx unknown
- 1967-02-13 FR FR94615A patent/FR1515292A/fr not_active Expired
- 1967-02-14 BE BE694055D patent/BE694055A/xx unknown
- 1967-02-14 GB GB7138/67A patent/GB1169774A/en not_active Expired
- 1967-02-14 DE DE19671522477 patent/DE1522477A1/de active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2352014A (en) * | 1941-07-21 | 1944-06-20 | Rott Andre | Photomechanical printing process and printing material for carrying out the same |
US2814988A (en) * | 1954-05-19 | 1957-12-03 | Armour Res Found | Printing plates and the production thereof |
BE565696A (xx) * | 1955-03-31 | 1958-03-31 | ||
US3220837A (en) * | 1955-07-22 | 1965-11-30 | Polaroid Corp | Diffusion transfer to stratum of a silver image inked and used in printing |
GB830623A (en) * | 1956-04-18 | 1960-03-16 | Agfa Ag | A planographic printing process using greasy or fatty ink |
GB856770A (en) * | 1957-09-07 | 1960-12-21 | Kalle & Co Ag | Improvements in or relating to photographic reproduction |
US3169065A (en) * | 1960-10-11 | 1965-02-09 | Harris Intertype Corp | Method of making resist and deep etch lithographic printing plates with ferric ammonium compound sensitized plates |
US3309990A (en) * | 1961-01-25 | 1967-03-21 | Azoplate Corp | Process for the preparation of printing plates |
US3311473A (en) * | 1962-06-28 | 1967-03-28 | Eastman Kodak Co | Silver halide diffusion process and products therefor |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3929481A (en) * | 1972-02-25 | 1975-12-30 | Fuji Photo Film Co Ltd | Etch bleaching processes for making lithographic printing plates using silver halide and/or diffusion transfer layers and a hydrophilic layer |
US3860426A (en) * | 1972-12-22 | 1975-01-14 | Eastman Kodak Co | Subbed lithographic printing plate |
US6014929A (en) * | 1998-03-09 | 2000-01-18 | Teng; Gary Ganghui | Lithographic printing plates having a thin releasable interlayer overlying a rough substrate |
US20040115449A1 (en) * | 2002-12-13 | 2004-06-17 | Eastman Kodak Company | Display panel |
Also Published As
Publication number | Publication date |
---|---|
DE1522477A1 (de) | 1969-08-28 |
US3552316A (en) | 1971-01-05 |
FR1515292A (fr) | 1968-03-01 |
NL6701955A (xx) | 1967-08-15 |
BE694055A (xx) | 1967-07-17 |
GB1169774A (en) | 1969-11-05 |
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