US3834998A - Method of producing aluminum planographic printing plates - Google Patents

Method of producing aluminum planographic printing plates Download PDF

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Publication number
US3834998A
US3834998A US00298751A US29875172A US3834998A US 3834998 A US3834998 A US 3834998A US 00298751 A US00298751 A US 00298751A US 29875172 A US29875172 A US 29875172A US 3834998 A US3834998 A US 3834998A
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US
United States
Prior art keywords
plate
aluminum
printing
anodic oxidation
etching
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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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US00298751A
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English (en)
Inventor
M Watanabe
A Ohashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3834998A publication Critical patent/US3834998A/en
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Classifications

    • 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
    • B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids

Definitions

  • ABSTRACT OF THE DISCLOSURE A process of producing aluminum containing supports, which comprises etching a grained aluminum surface with a basic or acidic etching solution within the range of 0.5 to 30 g./m. and then subjecting the etched surface to anodic oxidation.
  • aluminum includes both aluminum and aluminum alloys such as those comprising greater than 95% by Weight of aluminum and less than 5% by weight of other metals, for example, manganese, copper, zinc, titanium, iron, magnesium, chromium and the like.
  • Suitable examples of aluminum alloys which can be used in the present invention are AA 1100, AA 3003, etc. (The symbol AA is an abbreviation for American Aluminum Association.)
  • planographic printing is a method wherein reproduction is carried out by forming a water-Wettable or hydrophilic non-image area and a water-repellent and oil-miscible image area on a plate, adhering water to the non-image area and a printing ink to the image area utilizing the repellency of the water for the printing ink and then transferring the ink onto the desired copy.
  • a thin metal plate such as an aluminum or zinc plate is used as the plate support and nonimage forming material
  • a film of light-sensitive organic compound such as a bi-chromate colloid, a diazonium compound or a light-sensitive resin is used as the image forming material.
  • an aluminum or zinc plate is surface-treated and coated with a light-sensitive film and then processed so that only the image area retains a film by adhesion to the metal plate. This is usually accomplished using a photographic method (exposuredevelopment)
  • Various surface treatment methods have been proposed for the purpose of raising and strengthening the adhesive force between the image yielding film and the aluminum support as well as the adaptability of a non-image area, e.g., the hydrophilic and water-retaining properties.
  • the most commonly employed method consists in providing a fine roughness on the metal surface by a surface polishing technique such as polishing using small steel or porcelain balls with a polishing agent peculiar to the printing field, sandblasting, liquid honing or brushing.
  • a surface polishing technique such as polishing using small steel or porcelain balls with a polishing agent peculiar to the printing field, sandblasting, liquid honing or brushing.
  • immersion treatments such as using sodium silicate, fluozirconate, polycarbonate and polyphosphate have been employed.
  • a recent development in the art has been to subject an aluminum plate to anodic oxidation.
  • electrolysis through direct current in aqueous sulfuric acid is generally employed.
  • an aluminum plate which is grained and subjected to anodic oxidation through direct current electrolysis in sulfuric acid has excellent properties as a printing plate. That is to say, in comparison with a printing plate which has not been subjected to anodic oxidation, the former gives excellent results in printing with respect to abrasion resistance, printing durability, scratch resistance, hydrophilic property and water retaining property (water retaining property of a non-image area).
  • the second important problem with such prior art printing plates is that elimination of the light-sensitive layer on a non-image area (development) is diflicult. It is known that the adhesion of a film coated onto a grained surface is raised by previously subjecting it to anodic oxidation, but upon removing the film the coating ingredients remain on the grained surface to a greater extent than on a surface not subjected to anodic oxidation. In this respect, a printing plate using a support previously subjected to anodic oxidation is inferior to one using a support not subjected to anodic oxidation since a non-image area is liable to be spoiled during printing unless the developing operation is carefully carried out with a strong developer in a large amount.
  • any generally used prior art polishing method can be used including methods involving using polishing powders such as alumina, Carbonundum, diamond and pumice powder, for example, ball polishing, sandblasting, liquid honing and brush polishing.
  • the preferred degree of roughening is from about 0.2 to about 1.5 in terms of Ha value.
  • Unevenness on the surface of aluminum plates should be regulated by so-called cut off. In the present invention, the preferred cut off value is 0.75 mm., which refers to cutting off unevenness greater than 0.75 mm.
  • the etching solution used in the present invention can be chosen from any basic or acidic aqueous solution capable of dissolving aluminum. In this case, however,
  • the etching solution should be one such that there is formed on an etched surface no film derived from the aluminum or the etching solution which is diflerent from aluminum.
  • the acidic etching solution preferably has a pH value less than about 3, while the basic etching solution preferably has a pH value greater than 11.
  • the concentration of the etching agent in the solution will usually range from about 3 to about 30% by weight. Needless to say, a pH and concentration above and below the recited preferred ranges can be used, though processing may be slower.
  • Preferred etching agents are basic materials such as sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate and dipotassium phosphate, and acidic materials such as sulfuric acid, persulfuric acid and their salts.
  • acidic materials such as sulfuric acid, persulfuric acid and their salts.
  • etching agents are preferably used at a temperature and concentration so that the rate of dissolution of aluminum is about 0.3 to about 40 g./m. per 1 minute of immersion time, the temperature usually ranging from about 25 to about 90 C. of course, the rate of dissolution may be varied outside this range without encountering inoperable results.
  • Etching is ordinarly carried out by immersing a grained aluminum plate in the above mentioned etching solution or by coating the aluminum plate with the etching solution.
  • the etched plate is usually washed prior to anodic oxidation.
  • the anodic oxidation maybe carried out using any well known prior art aluminum etching system preferably in sulfuric acid, oxalic acid, phosphoric acid, chromic acid or mixed system thereof, most preferably in sulfuric acid.
  • concentration of electrolyte, current density during electrolysis and electrolysis time may be in accordance with prior art techniques, and there is no limitation on the apparatus which can be used.
  • the aluminum support processed in the present invention can be provided with a coating film of a light-sensitive material such as, for example, a mixture of a bichromate with polyvinyl alcohol, fish glue or egg albumin; a nitrogen-containing light-sensitive substance such as one containing a diazonium or tetrazonium compound; or a light-
  • a light-sensitive material such as, for example, a mixture of a bichromate with polyvinyl alcohol, fish glue or egg albumin
  • a nitrogen-containing light-sensitive substance such as one containing a diazonium or tetrazonium compound
  • Example 1 An aluminum-alloy plate (material quality: AA 3003) having a thickness of 0.3 mm. was washed with trichloroethylene to remove grease, grained by brushing with a nylon brush and an aqueous suspension of pumice powder (400 mesh) and to an Ha value of 0.40 and washed well with water. The plate was immersed in a 10% aqueous solution of sodium hydroxide at 30 C. for 30 seconds, washed with water, immersed in 20% nitric acid for 20 seconds and again washed with water. The etching rate of the grained surface reached a maximum of about 5.0 -g./m.
  • the etched plate was then subjected to anodic oxidation for 2 minutes at a current density of 1.6 A/dm. in an electrolytic bath of 15% aqueous sulfuric acid at a temperature of 27 0., followed by washing with water and drying.
  • the former plate had a plate reflection density D of 0.40- 0.43 while the latter plate had a D value of 0.700.80.
  • the former was more excellent in appearance, uniformity and whiteness as compared to the latter.
  • Both plates thus formed were suitable for use as a support for a printing plate on this point, each having a surface roughness of 0.45-0.48 micron by Ha indication.
  • Each plate was then coated with a mixture of a diazoxide resin and a phenol resin [5 parts by weight of the reaction product (prepared by reacting 62 g. of the condensation product of acetone and pyrogallol with 100 g. of Z-diazo-1-naphthol-S-sulfochloride) dissolved in parts of cyclohexane, prepared as described in British Pat. No. 1,113,759] and dried to provide a positive-positive type light-sensitive plate for plate printing.
  • a reaction product prepared by reacting 62 g. of the condensation product of acetone and pyrogallol with 100 g. of Z-diazo-1-naphthol-S-sulfochloride
  • the plate obtained in accordance with the present invention was in no way inferior to the prior art light-sensitive plate for printing with respect to the plate manufacturing operations of exposure to retouching and the printing operations, and had the advantage that discrimination of an image area was easy through the elevation in whiteness described above.
  • vIn printing it showed a durability (printing resistance) three times or more as great as an anodic oxidation-free printing plate.
  • the whiteness of a plate suitable for printing is less than 0.5 in terms of reflection density.
  • the plate When a grained aluminum plate is subjected to anodic oxidation without etching treatment, the plate usually exhibits a reflection density in the range of from about 0.7 to about 1.0 which is not preferred for printing.
  • the reflection density of the resulting surface can generally be decreased to less than 0.5.
  • Example '2 The procedure of Example 1 was repeated except that a 12% aqueous solution of trisodium phosphate at 70 C. was used in place of the 10% aqueous solution of sodium hydroxide used in Example 1 as the etching bath.
  • Example 1 The resulting aluminum support was excellent in appearance, uniformity and whiteness as in Example 1.
  • a light-sensitive printing plate similar to that of Example 1 was prepared and subjected to plate making. The working efiiciency was excellent in plate making. The printing resistance of the plate was also good.
  • Example 3 The procedure of Example 1 was repeated except that the aluminum-alloy plate was subjected to a treatment in 30% sulfuric acid at 80 C. for 60 seconds in place of the treatment with sodium hydroxide and nitric acid and then s u bjected to anodic oxidation in the same bath at the conditions described in Example 1. Similar excellent results were obtained as in Example 1.
  • Example 4 After the procedures up to the anodic oxidation treatment as described in Example 1, the aluminum-alloy plate was treated with a 0.5% aqueous solution of potassium fluozirconate at 80 C. for 60 seconds, washed with watel and dried. This plate was coated with a condensate of di phenylamine-4-di-azonium and formaldehyde (1:1 molar ratio) to prepare a negative-positive type light-sensitive printing plate. The plate making and printing adaptability thereof were excellent, i.e., the fountain solution was easily controlled and the plate was easily handled in printing.
  • Example 5 An aluminum plate (material quality: AA 1001) 0.3 mm. thick was grained by the sandblasting method using 300 mesh sand and then subjected to etching treatment as in Example 1. The plate was then subjected to anodic oxidation by direct current electrolysis for 5 minutes at a current density of 2.0 A/dm. in a aqueous solution of oxalic acid as the electrolytic bath. Using this plate as a support, a printing plate similar to that of Example 1 was prepared, providing excellent results upon printing.
  • a process of producing aluminum containing planographic printing plates which comprises mechanically graining an aluminum surface, within the range of 0.5 to 30 g./m. etching the grained aluminum surface with a basic or acidic etching solution and then subjecting the etched surface to anodic oxidation.
  • the etching solution is basic and comprises a member selected from the group consisting of sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate and dipotassium phosphate.
  • etching solution is acidic and comprises a member selected from the group consisting of sulfuric acid, persulfuric acid and their salts.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
  • ing And Chemical Polishing (AREA)
US00298751A 1971-10-21 1972-10-18 Method of producing aluminum planographic printing plates Expired - Lifetime US3834998A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP46083482A JPS5133444B2 (enrdf_load_stackoverflow) 1971-10-21 1971-10-21

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US (1) US3834998A (enrdf_load_stackoverflow)
JP (1) JPS5133444B2 (enrdf_load_stackoverflow)
DE (1) DE2251382B2 (enrdf_load_stackoverflow)
GB (1) GB1379850A (enrdf_load_stackoverflow)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929591A (en) * 1974-08-26 1975-12-30 Polychrome Corp Novel lithographic plate and method
US4126483A (en) * 1977-06-03 1978-11-21 Ford Motor Company Method of adherency of electrodeposits on light weight metals
US4183788A (en) * 1978-02-28 1980-01-15 Howard A. Fromson Process for graining an aluminum base lithographic plate and article thereof
EP0007233A1 (en) * 1978-07-13 1980-01-23 BICC Public Limited Company A method of treating aluminium foil or a lithographic printing plate support and products so obtained
US4256546A (en) * 1977-07-20 1981-03-17 Langbein-Pfanhauser Werke Ag Method of making a baking form for improved browning of baked goods
US4301229A (en) * 1978-03-27 1981-11-17 Fuji Photo Film Co., Ltd. Electrolytically grained aluminum support for making a lithographic plate and presensitized lithographic printing plate
US4367122A (en) * 1981-07-06 1983-01-04 Bednarz Joseph F Method for anodizing aluminum
US4396470A (en) * 1980-10-23 1983-08-02 Vickers P.L.C. Lithographic printing plates
US4397716A (en) * 1982-04-09 1983-08-09 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Variable anodic thermal control coating
US4477317A (en) * 1977-05-24 1984-10-16 Polychrome Corporation Aluminum substrates useful for lithographic printing plates
US4655136A (en) * 1983-02-14 1987-04-07 Hoechst Aktiengesellschaft Sheet material of mechanically and electrochemically roughened aluminum, as a support for offset-printing plates
US4824757A (en) * 1979-09-27 1989-04-25 Fuji Photo Film Co., Ltd. Process for preparing positive-acting photosensitive lithographic aluminum printing plate precursor using nitric acid electrokyte for graining
US4833065A (en) * 1985-10-04 1989-05-23 Fuji Photo Film Co., Ltd. Process for producing support for presensitized lithographic printing plate using alkaline electrolyte
US5269904A (en) * 1992-06-05 1993-12-14 Northrop Corporation Single tank de-oxidation and anodization process
US5288372A (en) * 1992-07-07 1994-02-22 Alumax Inc. Altering a metal body surface
US6010824A (en) * 1992-11-10 2000-01-04 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin composition containing a triazine compound and a pre-sensitized plate using the same, and photosensitive resin composition containing acridine and triazine compounds and a color filter and a pre-sensitized plate using the same
US20080003411A1 (en) * 2006-06-29 2008-01-03 Joseph Hunter Aluminum lithographic substrate and method of making
EP2381312A2 (en) 2000-08-25 2011-10-26 Fujifilm Corporation Alkaline liquid developer for lithographic printing plate and method for preparing lithographic printing plate

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5129329A (en) * 1974-09-06 1976-03-12 Kyoshi Nakamura Aruminiumu oyobi sonogokinnohyomenchakushokuho
JPS5182104A (ja) * 1975-01-13 1976-07-19 Riken Keikinzoku Kogyo Kk Heibaninsatsubannoseizoho
JPS51139406A (en) * 1975-05-27 1976-12-01 Oriental Photo Ind Co Ltd Method of regenerating lithographic press plate
JPS5312739A (en) * 1976-07-22 1978-02-04 Nippon Keikinzoku Sougou Kenki Desmutting method in electrolytic roughing treatment for aluminum
JPS55140592A (en) * 1979-04-20 1980-11-04 Fuji Photo Film Co Ltd Preparation of support body for lithography plate
JPS5615396A (en) * 1979-07-19 1981-02-14 Fuji Photo Film Co Ltd Manufacture of alminum support substance for lithographic plate
US4242417A (en) * 1979-08-24 1980-12-30 Polychrome Corporation Lithographic substrates
AU6138180A (en) * 1979-10-17 1981-04-30 Polychrome Corp. White lithographic substrate
DE3009103A1 (de) * 1980-03-10 1981-09-24 Hoechst Ag, 6000 Frankfurt Verfahren zur modifizierung der oberflaeche von druckplatten-traegermaterialien aus aluminium und verfahren zur herstellung von druckplatten aus diesen materialien
JPS5748733A (en) * 1980-09-08 1982-03-20 Fuji Photo Film Co Ltd Photosensitive lithographic plate
GB8515532D0 (en) * 1985-06-19 1985-07-24 Standard Telephones Cables Ltd Surface alloys treatment
JPH0351409U (enrdf_load_stackoverflow) * 1989-09-26 1991-05-20
EP0709232B1 (en) * 1994-10-25 1999-06-16 Agfa-Gevaert N.V. A method for preparing an aluminium foil for use as a support in lithographic printing plates
RU2169801C2 (ru) * 1998-06-08 2001-06-27 Акционерное общество "АвтоВАЗ" Способ получения износостойких поверхностей трения на деталях из алюминиевых сплавов
EP2481603A4 (en) 2009-09-24 2015-11-18 Fujifilm Corp LITHOGRAPHIC ORIGINAL PRESSURE PLATE
CN111334798A (zh) * 2019-10-30 2020-06-26 宁波劳伦斯汽车内饰件有限公司 一种精密蚀刻及选择性氧化着色铝饰板的加工方法
CN112007592B (zh) * 2020-09-03 2022-09-27 中科芯云微电子科技有限公司 一种消除光刻版图形保护集成电路知识产权的酸性胶体及其应用

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929591A (en) * 1974-08-26 1975-12-30 Polychrome Corp Novel lithographic plate and method
US4477317A (en) * 1977-05-24 1984-10-16 Polychrome Corporation Aluminum substrates useful for lithographic printing plates
US4126483A (en) * 1977-06-03 1978-11-21 Ford Motor Company Method of adherency of electrodeposits on light weight metals
US4256546A (en) * 1977-07-20 1981-03-17 Langbein-Pfanhauser Werke Ag Method of making a baking form for improved browning of baked goods
US4183788A (en) * 1978-02-28 1980-01-15 Howard A. Fromson Process for graining an aluminum base lithographic plate and article thereof
US4301229A (en) * 1978-03-27 1981-11-17 Fuji Photo Film Co., Ltd. Electrolytically grained aluminum support for making a lithographic plate and presensitized lithographic printing plate
EP0007233A1 (en) * 1978-07-13 1980-01-23 BICC Public Limited Company A method of treating aluminium foil or a lithographic printing plate support and products so obtained
US4824757A (en) * 1979-09-27 1989-04-25 Fuji Photo Film Co., Ltd. Process for preparing positive-acting photosensitive lithographic aluminum printing plate precursor using nitric acid electrokyte for graining
US4396470A (en) * 1980-10-23 1983-08-02 Vickers P.L.C. Lithographic printing plates
US4367122A (en) * 1981-07-06 1983-01-04 Bednarz Joseph F Method for anodizing aluminum
US4397716A (en) * 1982-04-09 1983-08-09 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Variable anodic thermal control coating
US4655136A (en) * 1983-02-14 1987-04-07 Hoechst Aktiengesellschaft Sheet material of mechanically and electrochemically roughened aluminum, as a support for offset-printing plates
US4833065A (en) * 1985-10-04 1989-05-23 Fuji Photo Film Co., Ltd. Process for producing support for presensitized lithographic printing plate using alkaline electrolyte
US5269904A (en) * 1992-06-05 1993-12-14 Northrop Corporation Single tank de-oxidation and anodization process
US5288372A (en) * 1992-07-07 1994-02-22 Alumax Inc. Altering a metal body surface
US6010824A (en) * 1992-11-10 2000-01-04 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin composition containing a triazine compound and a pre-sensitized plate using the same, and photosensitive resin composition containing acridine and triazine compounds and a color filter and a pre-sensitized plate using the same
EP2381312A2 (en) 2000-08-25 2011-10-26 Fujifilm Corporation Alkaline liquid developer for lithographic printing plate and method for preparing lithographic printing plate
US20080003411A1 (en) * 2006-06-29 2008-01-03 Joseph Hunter Aluminum lithographic substrate and method of making

Also Published As

Publication number Publication date
JPS4849501A (enrdf_load_stackoverflow) 1973-07-12
JPS5133444B2 (enrdf_load_stackoverflow) 1976-09-20
DE2251382A1 (de) 1973-04-26
GB1379850A (en) 1975-01-08
DE2251382B2 (de) 1979-06-07

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