EP1486347A1 - Aluminium alloy substrate for lithographic printing plate and method for producing the same - Google Patents
Aluminium alloy substrate for lithographic printing plate and method for producing the same Download PDFInfo
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- EP1486347A1 EP1486347A1 EP03076834A EP03076834A EP1486347A1 EP 1486347 A1 EP1486347 A1 EP 1486347A1 EP 03076834 A EP03076834 A EP 03076834A EP 03076834 A EP03076834 A EP 03076834A EP 1486347 A1 EP1486347 A1 EP 1486347A1
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- plate
- aluminium
- printing plate
- support
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- 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
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/04—Printing plates or foils; Materials therefor metallic
- B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
- B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
Definitions
- the present invention relates to a method of producing a support for planographic printing plate and more particularly relates to a method of producing an aluminium support which is superior for electrolytical graining.
- Conventional aluminium alloy substrates for a support for a lithographic printing plate are generally provided in the form of a 0.1 to 0.5 mm thick cold-rolled sheet made of an aluminium alloy such as JIS A1050, A1100, A3003, or the like.
- Such aluminium alloy cold-rolled sheets are generally produced by machining the surface of a semicontinuous-cast (DC) slab or billet, homogenization heat-treating the billet when necessary, heating the billet to a selected temperature, hot-rolling the heated billet to a hot-rolled strip, cold-rolling the hot-rolled strip with an intermediate annealing between the cold rolling passes when necessary, and final cold rolling the strip to a cold-rolled sheet.
- DC semicontinuous-cast
- the aforementioned conventional process using a DC slab or billet has drawbacks in that the process steps are complicated and take much time, the production cost is high, the casting speed is slow, the rolling and heat treatment conditions are strict, and heat treatments must be carried out many times, and the process cannot provide an aluminium alloy support with stable properties.
- Japanese Unexamined Patent Publication (Kokai) Nos. 3-79798 and 5-156414 disclosed a process of producing an aluminium alloy support for a lithographic printing plate, in which an aluminium alloy melt is continuously cast and rolled to form a strip, which is subjected to cold rolling, heat treatment, and straightening.
- An object of the present invention is to provide a method of producing a planographic printing plate support with high quality and low cost by casting molten aluminium directly and continuously into a thin aluminium plate, wherein the surface which reveals less ripple marks upon etching with an alkaline solution, is used for the manufacturing of the printing plate.
- the invention furthermore relates to a method of producing a planographic printing plate support by casting molten aluminium directly and continuously into a thin aluminium plate, wherein the side that is the top side during the casting process is used for printing.
- directly and continuously casting has to be understood as at least encompassing various methods in which aluminium or aluminium alloy or similar suitable material is molten and then transferred to suitable equipment for forming thin sheet-like material in a continuous process.
- aluminium has to be understood as including aluminium alloys.
- the invention further relates to a method for forming printing plates using a support produced with a method according to the present invention.
- the invention also relates to planographic printing plates, provided with a method according to the present invention and/or using a support according to the present invention.
- It is an object of the present invention is to provide a method of producing a planographic printing plate support with high quality and low cost by casting molten aluminium directly and continuously into a thin aluminium plate, wherein the surface which reveals less ripple marks upon etching with an alkaline solution, is used for the manufacturing of the printing plate.
- a method for continuously cast rolling a tabular plate directly from molten aluminum alloy there can be used a method employing a cooling belt such as Hazelett method or a method employing a cooling roller such as Hunter method and 3C method. Since the Hazelett method continuously casts a thick plate, a hot rolling is subsequently conducted to make the thickness reelable. On the other hand, since the Hunter method or the 3C method makes it possible to directly cast a plate having the thickness of 10 mm or lower, a hot rolling machine is not necessary.
- JP-A-60-238001, JP-A-60-240360, etc. disclose a method for preparing a coil of thin sheet. Among those a twin roller continuous casting method such as the Hunter method is preferable.
- the molten aluminum alloy is rapidly cooled by the continuous casting.
- the reference number 1 is a melt holding furnace in which an aluminum ingot is melted and retained.
- the molten aluminum is then fed to a twin-roller continuous casting machine 2, then wound on coiler 3.
- a continuous casting method using a cooling belt and a hot rolling may be applied as shown in Fig. 1(B).
- the coil wound on coiler 3 is cold rolled to a thin plate of 0.3 to 3.0 mm using cold rolling machine 4.
- an intermediate annealing may be conducted using heating machine 5 when necessary.
- heating (annealing) machine 5 there are various types such as a batch type, a continuous annealing type, an induced heating type.
- the temperature is elevated at a rate of 0.5 °C/sec or more and the preferred temperature is 300 °C or more. More preferably annealing can be applied at 480°C or more.
- the resulting thin plate is rolled again to a thickness of 0.1 to 0.5 mm using a cold rolling machine.
- correction is conducted using correcting machine 6.
- the correction may be conducted together with a finishing rolling.
- the aluminum plate thus obtained is subjected to a graining treatment.
- a graining treatment When an aluminium alloy substrate for a printing plate is electrolytically grained, it is a common practice to carry out as a pretreatment chemical etching with an acid or alkali for degreasing or removal of oxide films from the surface of the substrate.
- the electrolytic graining process is an electrolytic etching process wherein an alternating current is applied where as a counter electrode graphite or the like is used to cause electrolytic etching, thereby forming pits on the surface of the substrate to provide a grained surface.
- the above graining enhances the adhesion of a photosensitive film and improves the water retention, beneficial to printing performance, to the printing plate. Since adhesion and water retention should be provided uniformly over the whole surface of the printing plate, pits should be formed uniformly over the whole printing plate. For a printing plate provided with a photosensitive film, the grained surface should have a uniform appearance when viewed with the naked eye because the results of development after the exposure and development are evaluated by visual inspection.
- Nonuniform appearance of the grained surface means nonuniform color tone such as observation of streaks (a streak pattern) along the rolling direction or partial loss of gloss to give a cloudy appearance. This is caused by nonuniform chemical etching as a pretreatment, leaving at least one region unetched or excessive etching, and electrolytic etching as an electrolytic graining treatment and a nonuniform metallic structure.
- the nonuniform metallic structure is attributable to nonuniform aluminum crystals orientation and aluminum crystal size, coarsening and nonuniform dispersion of an intermetallic compound, and the like. Even when the nonuniformity of the metallic structure is of an extent that is not detrimental to the uniformity of electrolytic graining (including pretreatment) necessary for printing, it often makes the appearance of the grained surface remarkably nonuniform.
- a nonuniform appearance, i.e., the presence of cloudy color shading, in the grained surface is very inconvenient to inspection of image areas after development.
- the cloudy portions are present as they are in nonimage portions after development, and since they have a color tone similar to the image areas, it becomes difficult to visually judge whether or not the image areas can be satisfactorily developed.
- ripple mark defect a wave like pattern
- the ripple marks become visible after a sequence of surface treatments and can only clearly be observed when the final product is almost completed.
- the present inventors discovered that the marks can be made visible by simply etching the surface by alkaline.
- Aqueous solutions of sodium or potassium hydroxide are the most preferable alkali solutions and concentration is between 5 to 40 %.
- Etching operation can be done by simply dipping a sample in an alkali bath. Temperature is between 15 to 35 °C, dipping time is between 1 to 10 minutes, depending on alloy, thickness, casting conditions, etc..
- the alkali etching method the more suitable surface for planographic printing plate can be determined.
- the side to be used for graining, hydrophilizing, coating, matting, etc. in order to form a good quality lithographic printing plate was found to be the side that is the top side during the casting process.
- the present inventors discovered that usage of the side that was the bottom side during the casting as surface for subsequent graining, hydrophilizing, coating, matting, etc. runs a risk of providing a non-uniform surface, in the form of ripple marks.
- the top side during casting is much less prone to ripple mark formation, whereas the bottom side during casting quite often shows ripple marks.
- Usage of the top side drastically improves lot to lot fluctuation of casting in terms of ripple mark formation.
- the temperature in melt holding furnace 1 needs to be kept at not lower than the melting point of aluminum.
- the temperature in the melt holding furnace varies properly depending on the components of aluminum alloy. In general, it is not lower than 800 °C.
- the molten aluminum alloy is subjected to a proper treatment such as inert gas purge and fluxing.
- a preferable constitutional range of an alloy component is as follows.
- the preferable Fe content in the alloy is between 0.15 and 0.50 weight %, more preferably between 0.20 and 0.35 weight %.
- the preferable Si content is between 0.05 and 0.20 weight %, more preferably between 0.10 and 0.15 weight %.
- Si content is less than 0.05 weight %, response to electrical graining becomes weak.
- Si content is more than 0.20 weight %, toning characteristic of the printing plate becomes worse.
- the preferable Cu content is between 0.005 and 0.040 weight %, more preferably between 0.008 and 0.025 weight %.
- Cu content is less than 0.005 weight %, response to electrical graining becomes weak.
- Cu content is more than 0.040 weight %, resulting electrical graining structure becomes too coarse leading the printing plate having worse toning characteristic.
- the method for graining the support for planographic printing plate according to the present invention there is used mechanical graining, chemical graining, electrochemical graining or combination thereof.
- Examples of mechanical graining methods include ball graining, wire graining, brush graining, and liquid honing.
- electrochemical graining method there is normally used AC electrolytic etching method.
- electric current there is used a normal alternating current such as sinewaveform or a special alternating current such as squarewaveform, and the like.
- etching may be conducted with caustic soda.
- electrochemical graining it is preferably conducted with an alternating current in an aqueous solution mainly composed of hydrochloric acid or nitric acid.
- aqueous solution mainly composed of hydrochloric acid or nitric acid.
- the aluminum support is etched with an alkali.
- alkaline agents include caustic soda, caustic potash, sodium metasilicate, sodium carbonate, sodium aluminate, sodium gluconate, etc.
- concentration of the alkaline agent, the temperature of the alkaline agent and the etching time are preferably selected from 0.01 to 25%, 20 to 90 °C and 5 sec. to 5 min., respectively.
- the preferred etching rate is in the range of 0.1 to 15 g/m 2 .
- the etching rate is preferably in the range of 0.01 to 1 g/m 2 (JP-A-1-237197). Since alkaline-insoluble substances (smut) are left on the surface of the aluminum plate thus alkali-etched, the aluminum plate may be subsequently desmutted as necessary.
- the pretreatment is effected as mentioned above.
- the aluminum plate is subsequently subjected to AC electrolytic etching in an electrolyte mainly composed of hydrochloric acid or nitric acid.
- the frequency of the AC electrolytic current is in the range of 0.1 to 100 Hz, preferably 0.1 to 1.0 Hz or 10 to 60 Hz.
- the concentration of the etching solution is in the range of 3 to 150 g/l , preferably 5 to 50 g/l .
- the solubility of aluminum in the etching bath is preferably in the range of not more than 50 g/l, more preferably 2 to 20 g/l.
- the etching bath may contain additives as necessary. However, in mass production, it is difficult to control the concentration of such an etching bath.
- the electric current density in the etching bath is preferably in the range of 5 to 100 A/dm 2 , more preferably 10 to 80 A/dm 2 .
- the waveform of electric current can be properly selected depending on the required quality and components of aluminum support used but may be preferably the special alternating waveform described in U.S. Patent No. 4,087,341 (corresponding to JP-B-56-19280) and JP-B-55-19191. (The term "JP-B" as used herein means an "examined Japanese patent publication").
- the waveform of electric current and the liquid conditions are properly selected depending on required electricity as well as required quality and components of aluminum support used.
- the aluminum plate which has been subjected to electrolytic graining is then subjected to dipping in an alkaline solution as a part of desmutting treatment to dissolve smutts away.
- an alkaline agent there may be used caustic soda or the like.
- the desmutting treatment is preferably effected at a pH value of not lower than 10 and a temperature of 25 to 60°C for a dipping time as extremely short as 1 to 10 seconds.
- the aluminum plate thus etched is then dipped in a solution mainly composed of sulfuric acid.
- the sulfuric acid solution is in the concentration range of 50 to 400 g/l, and the temperature range of 20 to 70 °C. If the concentration of sulfuric acid is more than 400 g/ 1 or the temperature of sulfuric acid is more than 70 °C, the processing bath is more liable to corrosion. Further, if the aluminum plate is etched by more than 0.4 g/m 2 , the printing durability may be reduced. Thus, the etching rate is preferably controlled to not more than 0.4 g/m 2 , more preferably not more than 0.2 g/m 2 .
- the aluminum plate preferably forms an anodized film thereon in an amount of 0.1 to 10 g/m2, more preferably 0.3 to 5 g/m 2 .
- the anodizing conditions vary with the electrolyte used and thus are not specifically determined. In general, it is appropriate that the electrolyte concentration is in the range of 1 to 80% by weight, the electrolyte temperature is in the range of 5 to 70 °C, the electric current density is in the range of 0.5 to 60 A/dm 2 , the voltage is in the range of 1 to 100 V, and the electrolysis time is in the range of 1 second to 5 minutes.
- the grained aluminum plate having an anodized film thus obtained is stable and excellent in hydrophilicity itself and thus can directly form a heat- or photosensitive coat thereon. If necessary, the aluminum plate may be further subjected to a surface treatment.
- a silicate layer formed by the foregoing metasilicate of alkaline metal or an undercoating layer formed by a hydrophilic polymeric compound may be formed on the aluminum plate.
- an undercoating layer Before applying the main coating layer, an undercoating layer may be applied.
- the coating amount of the undercoating layer is preferably in the range of 5 to 150 mg/m 2 .
- a heat- and/or photosensitive coating is then formed on the aluminum plate thus treated, imagewise exposed to light, and then developed, to make a printing plate, which is then mounted in a printing machine for printing.
- an aluminium plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled.
- the plate was cold rolled to a thickness of 2.2 mm, then annealed at 520°C for 8 hours, and further cold rolled to form a test material of a thickness of 0.278 mm.
- test material formed as such was subjected to alkali etching.
- the material was dipped in an aqueous solution of 25 weight % sodium hydroxide at 21°C for 7 minute, rinsed by running water, and dried.
- the top surface at the casting did not reveal any ripple formation.
- the top surface at the casting of the test material was brush grained, etched with a 25% aqueous solution of sodium hydroxide at 50°C such that etched amount was 5 g/m2, after washing the etched plate with water, the plate was immersed in an aqueous sulphuric acid of 180 g/l at 50°C for 20 seconds to desmut the plate, and the plate was washed with water.
- the support was electrochemically grained in 9 g/l of an aqueous nitric acid solution using the alternating (wave form ) electric current described in Japanese Patent No. JP-B-55-19191).
- An anode surface oxide coating of 2.5 g/m2 was formed on the support in a 20% sulfuric acid, and then dried. Furthermore a silicate layer was formed on the surface by dipping in an 2.5 wt% aqueous sodium metasilicate solution at 25°C.
- the thus obtained support was examined for non-uniform parts: the plate appeared uniform in graining quality and appearance. No non-uniformity was observed.
- an aluminium plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled.
- the plate was cold rolled to a thickness of 2.2 mm, then annealed at 520°C for 8 hours, and further cold rolled to form a test material of a thickness of 0.278 mm.
- test material formed as such was subjected to alkali etching.
- the material was dipped in an aqueous solution of 25 weight % sodium hydroxide at 21°C for 7 minute, rinsed by running water, and dried.
- the bottom surface at the casting revealed severe ripple formation.
- Example 2 the side that was the bottom side during the casting process was submitted to the same steps as in Example 1. Upon examination, the plate shows an severe wave-like pattern, which renders the substrate unsuitable for further usage as a substrate for a lithographic printing plate.
- an aluminium plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled.
- the plate was cold rolled to a thickness of 2.2 mm, then annealed at 380°C for 4 hours, and further cold rolled to form a test material of a thickness of 0.278 mm.
- a similar test was repeated 10 times.
- the top surface at the casting of the test material was brush grained, etched with a 25% aqueous solution of sodium hydroxide at 50°C such that etched amount was 5 g/m2, after washing the etched plate with water, the plate was immersed in an aqueous sulphuric acid of 180 g/l at 50°C for 20 seconds to desmut the plate, and the plate was washed with water.
- the support was electrochemically grained in 9 g/l of an aqueous nitric acid solution using the alternating ( wave form ) electric current in the manner as decribed in example 1.
- the quantity of electricity in the anode time became 180 coulomb/dm2.
- An anode surface oxide coating of 3.5 g/m2 was formed on the support in a 20% sulfuric acid, and then dried.
- Photosensitive solution Chemical g/m2 Ester compound of naphtoquinone-1,2-diazido-5-sulfonyl chloride and 0.45 pyrogallol-acetone resin Cresol fromaldehyde resin 1.10 t-Butylphenol formaldehyde resin 0.05 Tetrahydrophtalic acid anhydride 0.09 Naphtoquinone-1,2-diazido-4-sulfonyl chloride 0.03 Ethyl violet 0.05 Megafac F-176 (fluorine containing surfactant, available from Dainippon Ink and Chemicals, Inc) 0.01 Methyl Ethyl ketone 6.0 1-Methoxy-2-propanol 4.0
- the photosensitive planographic printing plate thus-prepared was subjected to exposure for 50 seconds with a metal halide lamp of 3 kw from a distance of 1 m through a transparent positive film, and then it was subjected to development with a developing solution consisting of a 2 wt% aequeous solution of sodium silicate having a SiO 2 /Na 2 O ratio of about 1.1 and furthermore containing sodium ethylenediaminetetraacetate (0.01 g/l).
- the development process is followed by water rinsing and subsequent gumming in gum arabic, whereby the planographic printing plates were prepared.
- a printing test was carried out in a usual procedure using the planographic printing plate thus-prepared. 200.000 copies with high quality were obtained from all 10 trials.
- an aluminium plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled.
- the plate was cold rolled to a thickness of 2.2 mm, then annealed at 380°C for 4 hours, and further cold rolled to form a test material of a thickness of 0.278 mm.
- a similar test was repeated 10 times.
- test material formed as such was subjected to alkali etching as described in the Example 1.
- Five out of the ten bottom surfaces at the casting revealed strong ripple formation, and 5 revealed slight ripple formation.
- an aluminium plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled.
- the plate was cold rolled to a thickness of 2.2 mm, then annealed at 520°C for 8 hours, and further cold rolled to form a test material of a thickness of 0.278 mm.
- test material formed as such was subjected to alkali etching.
- the material was dipped in an aqueous solution of 25 weight % sodium hydroxide at 21°C for 7 minute, rinsed by running water, and dried.
- the top surface at the casting did not reveal any ripple formation.
- the bottom side during casting showed a clear, wave-like pattern know as ripple mark.
- the upper surface at the casting of the test material was etched with a 25% aqueous solution of sodium hydroxide at 50°C such that etched amount was 5 g/m2, after washing the etched plate with water, the plate was immersed in an aqueous sulphuric acid of 180 g/l at 50°C for 20 seconds to desmut the plate, and the plate was washed with water.
- the support was electrochemically grained in 10 g/l of an aqueous nitric acid solution using the alternating ( wave form ) electric current in the manner as decribed in example 1.
- the quantity of electricity in the anode time became 280 coulomb/dm2.
- An anode surface oxide coating of 3.5 g/m2 was formed on the support in a 20% sulfuric acid, and then dried.
- composition was coated on the support thus-prepared in a dry coated weight of 1.0 g/m2 to provide a heat-sensitive layer.
- Cyanine dye A (having the structure shown below) 0.025 g Megafac F177 manufactured by DAINIPPON INK & CHEMICALS, INC.
- Ethyl violet 0.01 g Methyl ethyl ketone 0.05 1-Methoxy-2-propanol 20.1 g 2.7 g
- the thus obtained heat sensitive plate was imaged in a Creo Trendsetter model 3244, and developed in the developer described in Example 2. Printing plates of excellent quality with good uniform appearance were obtained.
Abstract
Disclosed is a method for the production of an aluminium alloy
support for lithographic printing plates by casting molten aluminium directly
and continuously into a thin aluminium plate, wherein the surface which
reveals less ripple marks upon etching with an alkaline solution, is used for
the manufacturing of the printing plate.
Description
The present invention relates to a method of producing a support for
planographic printing plate and more particularly relates to a method of
producing an aluminium support which is superior for electrolytical graining.
Conventional aluminium alloy substrates for a support for a
lithographic printing plate are generally provided in the form of a 0.1 to 0.5
mm thick cold-rolled sheet made of an aluminium alloy such as JIS A1050,
A1100, A3003, or the like. Such aluminium alloy cold-rolled sheets are
generally produced by machining the surface of a semicontinuous-cast (DC)
slab or billet, homogenization heat-treating the billet when necessary, heating
the billet to a selected temperature, hot-rolling the heated billet to a hot-rolled
strip, cold-rolling the hot-rolled strip with an intermediate annealing between
the cold rolling passes when necessary, and final cold rolling the strip to a cold-rolled
sheet.
The aforementioned conventional process using a DC slab or billet
has drawbacks in that the process steps are complicated and take much time,
the production cost is high, the casting speed is slow, the rolling and heat
treatment conditions are strict, and heat treatments must be carried out many
times, and the process cannot provide an aluminium alloy support with stable
properties.
Japanese Unexamined Patent Publication (Kokai) Nos. 3-79798
and 5-156414 disclosed a process of producing an aluminium alloy support for
a lithographic printing plate, in which an aluminium alloy melt is continuously
cast and rolled to form a strip, which is subjected to cold rolling, heat
treatment, and straightening.
The process disclosed in Japanese Unexamined Patent Publication
(Kokai) Nos. 3-79798 and 5-156414 also has drawbacks in that, although a
continuous casting and rolling process is used, the support does not provide a
sufficiently uniform surface when electrolytically grained and fails to have a
satisfactory press life and that heat treatments are not conducted under
suitable conditions.
The process described in European Patent No. 640694B1, in which an
aluminium alloy printing plate support is manufactured with the continuous
casting method which obtains improved electrolytic graining quality by tight
specifications of alloying elements as Cu, Si and Fe is improving the situation,
although it still does not provide a sufficiently uniform surface. More
specifically a significant amount of surface defects are visible after the printing
plate manufacturing which are named ripple marks. These ripple marks can
only be noticed after the process of manufacturing the presensitised printing
plate is completed. This can give a lot of waste and a very cost inefficient
process.
An object of the present invention is to provide a method of producing
a planographic printing plate support with high quality and low cost by casting
molten aluminium directly and continuously into a thin aluminium plate,
wherein the surface which reveals less ripple marks upon etching with an
alkaline solution, is used for the manufacturing of the printing plate. The
invention furthermore relates to a method of producing a planographic
printing plate support by casting molten aluminium directly and continuously
into a thin aluminium plate, wherein the side that is the top side during the
casting process is used for printing.
In this respect directly and continuously casting has to be understood
as at least encompassing various methods in which aluminium or aluminium
alloy or similar suitable material is molten and then transferred to suitable
equipment for forming thin sheet-like material in a continuous process. In this
application aluminium has to be understood as including aluminium alloys.
The invention further relates to a method for forming printing plates
using a support produced with a method according to the present invention.
The invention also relates to planographic printing plates, provided
with a method according to the present invention and/or using a support
according to the present invention.
It is an object of the present invention is to provide a method of
producing a planographic printing plate support with high quality and low cost
by casting molten aluminium directly and continuously into a thin aluminium
plate, wherein the surface which reveals less ripple marks upon etching with
an alkaline solution, is used for the manufacturing of the printing plate.
As a method for continuously cast rolling a tabular plate directly from
molten aluminum alloy, there can be used a method employing a cooling belt
such as Hazelett method or a method employing a cooling roller such as
Hunter method and 3C method. Since the Hazelett method continuously casts
a thick plate, a hot rolling is subsequently conducted to make the thickness
reelable. On the other hand, since the Hunter method or the 3C method makes
it possible to directly cast a plate having the thickness of 10 mm or lower, a hot
rolling machine is not necessary. Moreover, JP-A-60-238001, JP-A-60-240360,
etc. disclose a method for preparing a coil of thin sheet. Among those a twin
roller continuous casting method such as the Hunter method is preferable.
In the present invention, the molten aluminum alloy is rapidly cooled
by the continuous casting. Referring to Figs. 1(A), 1(B), 1(C), 1(D) and 1(E), an
embodiment of the method of producing an aluminum alloy support according
to the present invention will be further described. As shown in Fig. 1(A), the
reference number 1 is a melt holding furnace in which an aluminum ingot is
melted and retained. The molten aluminum is then fed to a twin-roller
continuous casting machine 2, then wound on coiler 3. Alternatively, a
continuous casting method using a cooling belt and a hot rolling may be
applied as shown in Fig. 1(B).
As shown in Fig. 1(C), the coil wound on coiler 3 is cold rolled to a
thin plate of 0.3 to 3.0 mm using cold rolling machine 4. Subsequently, as
shown in Fig. 1(D), an intermediate annealing may be conducted using heating
machine 5 when necessary. As heating (annealing) machine 5, there are
various types such as a batch type, a continuous annealing type, an induced
heating type. The temperature is elevated at a rate of 0.5 °C/sec or more and
the preferred temperature is 300 °C or more. More preferably annealing can
be applied at 480°C or more. Then, the resulting thin plate is rolled again to a
thickness of 0.1 to 0.5 mm using a cold rolling machine. Next, as shown in Fig.
1(E), correction is conducted using correcting machine 6. The correction may
be conducted together with a finishing rolling.
The aluminum plate thus obtained is subjected to a graining
treatment. When an aluminium alloy substrate for a printing plate is
electrolytically grained, it is a common practice to carry out as a pretreatment
chemical etching with an acid or alkali for degreasing or removal of oxide films
from the surface of the substrate. The electrolytic graining process, as such, is
an electrolytic etching process wherein an alternating current is applied where
as a counter electrode graphite or the like is used to cause electrolytic etching,
thereby forming pits on the surface of the substrate to provide a grained
surface.
The above graining enhances the adhesion of a photosensitive film
and improves the water retention, beneficial to printing performance, to the
printing plate. Since adhesion and water retention should be provided
uniformly over the whole surface of the printing plate, pits should be formed
uniformly over the whole printing plate. For a printing plate provided with a
photosensitive film, the grained surface should have a uniform appearance
when viewed with the naked eye because the results of development after the
exposure and development are evaluated by visual inspection.
Under nonuniform electrolytic graining is to be understood, that
proper surface roughness cannot be attained due to excessive etching
(dissolution type) or the presence of a region remaining unetched in the
electrolytic etching. In this case, a problem occurs associated with the
suitability of the plate for use in printing. Specifically, the adhesion of a
photosensitive film to the printing plate becomes poor, and, further, the water
retention or corrosion resistance in nonimage areas deteriorates, which in turn
leads to tinting or scumming in nonimage areas during printing.
Nonuniform appearance of the grained surface means nonuniform
color tone such as observation of streaks (a streak pattern) along the rolling
direction or partial loss of gloss to give a cloudy appearance. This is caused by
nonuniform chemical etching as a pretreatment, leaving at least one region
unetched or excessive etching, and electrolytic etching as an electrolytic
graining treatment and a nonuniform metallic structure.
The nonuniform metallic structure is attributable to nonuniform
aluminum crystals orientation and aluminum crystal size, coarsening and
nonuniform dispersion of an intermetallic compound, and the like. Even when
the nonuniformity of the metallic structure is of an extent that is not
detrimental to the uniformity of electrolytic graining (including pretreatment)
necessary for printing, it often makes the appearance of the grained surface
remarkably nonuniform.
A nonuniform appearance, i.e., the presence of cloudy color shading, in
the grained surface is very inconvenient to inspection of image areas after
development. Specifically, the cloudy portions are present as they are in
nonimage portions after development, and since they have a color tone similar
to the image areas, it becomes difficult to visually judge whether or not the
image areas can be satisfactorily developed.
One of the defects which negatively influences the quality of the final
printing plate is the ripple mark defect; a wave like pattern In the prior art
methods the ripple marks become visible after a sequence of surface
treatments and can only clearly be observed when the final product is almost
completed. However the present inventors discovered that the marks can be
made visible by simply etching the surface by alkaline. Aqueous solutions of
sodium or potassium hydroxide are the most preferable alkali solutions and
concentration is between 5 to 40 %. Etching operation can be done by simply
dipping a sample in an alkali bath. Temperature is between 15 to 35 °C,
dipping time is between 1 to 10 minutes, depending on alloy, thickness, casting
conditions, etc.. By the alkali etching method, the more suitable surface for
planographic printing plate can be determined.
According to the method of this invention, the side to be used for
graining, hydrophilizing, coating, matting, etc. in order to form a good quality
lithographic printing plate, was found to be the side that is the top side during
the casting process. The present inventors discovered that usage of the side
that was the bottom side during the casting as surface for subsequent
graining, hydrophilizing, coating, matting, etc. runs a risk of providing a non-uniform
surface, in the form of ripple marks. Especially when casting
operation extended over multiple coils over multiple lots, the top side during
casting is much less prone to ripple mark formation, whereas the bottom side
during casting quite often shows ripple marks. Usage of the top side
drastically improves lot to lot fluctuation of casting in terms of ripple mark
formation.
Further, referring to the preparation conditions, the temperature in
melt holding furnace 1 needs to be kept at not lower than the melting point of
aluminum. The temperature in the melt holding furnace varies properly
depending on the components of aluminum alloy. In general, it is not lower
than 800 °C.
In order to inhibit the production of oxides of molten aluminum alloy
and remove alkaline metals which impair the quality of the aluminum plate,
the molten aluminum alloy is subjected to a proper treatment such as inert gas
purge and fluxing.
In the present invention, a preferable constitutional range of an alloy
component is as follows. In order to obtain an excellent property for a support
for a planographic printing plate, the preferable Fe content in the alloy is
between 0.15 and 0.50 weight %, more preferably between 0.20 and 0.35
weight %. When Fe content is less than 0.15 weight %, mechanical strength of
the sheet becomes insufficient. When Fe content is more than 0.50 weight %,
electrical graining structure becomes uneven. The preferable Si content is
between 0.05 and 0.20 weight %, more preferably between 0.10 and 0.15
weight %. When Si content is less than 0.05 weight %, response to electrical
graining becomes weak. When Si content is more than 0.20 weight %, toning
characteristic of the printing plate becomes worse. The preferable Cu content
is between 0.005 and 0.040 weight %, more preferably between 0.008 and 0.025
weight %. When Cu content is less than 0.005 weight %, response to electrical
graining becomes weak. When Cu content is more than 0.040 weight %,
resulting electrical graining structure becomes too coarse leading the printing
plate having worse toning characteristic. These values have been found to be
valid for at least the alloys used in the experiments as discussed hereafter.
As the method for graining the support for planographic printing plate
according to the present invention, there is used mechanical graining,
chemical graining, electrochemical graining or combination thereof.
Examples of mechanical graining methods include ball graining, wire
graining, brush graining, and liquid honing. As electrochemical graining
method, there is normally used AC electrolytic etching method. As electric
current, there is used a normal alternating current such as sinewaveform or a
special alternating current such as squarewaveform, and the like. As a
pretreatment for the electrochemical graining, etching may be conducted with
caustic soda.
If electrochemical graining is conducted, it is preferably conducted
with an alternating current in an aqueous solution mainly composed of
hydrochloric acid or nitric acid. The electrochemical graining will be further
described hereinafter.
First, the aluminum support is etched with an alkali. Preferred
examples of alkaline agents include caustic soda, caustic potash, sodium
metasilicate, sodium carbonate, sodium aluminate, sodium gluconate, etc. The
concentration of the alkaline agent, the temperature of the alkaline agent and
the etching time are preferably selected from 0.01 to 25%, 20 to 90 °C and 5
sec. to 5 min., respectively. The preferred etching rate is in the range of 0.1 to
15 g/m2.
In particular, if the support contains a large amount of impurities, the
etching rate is preferably in the range of 0.01 to 1 g/m2 (JP-A-1-237197). Since
alkaline-insoluble substances (smut) are left on the surface of the aluminum
plate thus alkali-etched, the aluminum plate may be subsequently desmutted
as necessary.
The pretreatment is effected as mentioned above. In the present
invention, the aluminum plate is subsequently subjected to AC electrolytic
etching in an electrolyte mainly composed of hydrochloric acid or nitric acid.
The frequency of the AC electrolytic current is in the range of 0.1 to 100 Hz,
preferably 0.1 to 1.0 Hz or 10 to 60 Hz.
The concentration of the etching solution is in the range of 3 to 150 g/l
, preferably 5 to 50 g/l . The solubility of aluminum in the etching bath is
preferably in the range of not more than 50 g/l, more preferably 2 to 20 g/l.
The etching bath may contain additives as necessary. However, in mass
production, it is difficult to control the concentration of such an etching bath.
The electric current density in the etching bath is preferably in the
range of 5 to 100 A/dm2, more preferably 10 to 80 A/dm2. The waveform of
electric current can be properly selected depending on the required quality and
components of aluminum support used but may be preferably the special
alternating waveform described in U.S. Patent No. 4,087,341 (corresponding to
JP-B-56-19280) and JP-B-55-19191. (The term "JP-B" as used herein means an
"examined Japanese patent publication"). The waveform of electric current and
the liquid conditions are properly selected depending on required electricity as
well as required quality and components of aluminum support used.
The aluminum plate which has been subjected to electrolytic graining
is then subjected to dipping in an alkaline solution as a part of desmutting
treatment to dissolve smutts away. As such an alkaline agent, there may be
used caustic soda or the like. The desmutting treatment is preferably effected
at a pH value of not lower than 10 and a temperature of 25 to 60°C for a
dipping time as extremely short as 1 to 10 seconds.
The aluminum plate thus etched is then dipped in a solution mainly
composed of sulfuric acid. It is preferred that the sulfuric acid solution is in
the concentration range of 50 to 400 g/l, and the temperature range of 20 to
70 °C. If the concentration of sulfuric acid is more than 400 g/ 1 or the
temperature of sulfuric acid is more than 70 °C, the processing bath is more
liable to corrosion. Further, if the aluminum plate is etched by more than 0.4
g/m2, the printing durability may be reduced. Thus, the etching rate is
preferably controlled to not more than 0.4 g/m2, more preferably not more than
0.2 g/m2.
The aluminum plate preferably forms an anodized film thereon in an
amount of 0.1 to 10 g/m2, more preferably 0.3 to 5 g/m2. The anodizing
conditions vary with the electrolyte used and thus are not specifically
determined. In general, it is appropriate that the electrolyte concentration is in
the range of 1 to 80% by weight, the electrolyte temperature is in the range of
5 to 70 °C, the electric current density is in the range of 0.5 to 60 A/dm2, the
voltage is in the range of 1 to 100 V, and the electrolysis time is in the range of
1 second to 5 minutes.
The grained aluminum plate having an anodized film thus obtained is
stable and excellent in hydrophilicity itself and thus can directly form a heat-
or photosensitive coat thereon. If necessary, the aluminum plate may be
further subjected to a surface treatment.
For example, a silicate layer formed by the foregoing metasilicate of
alkaline metal or an undercoating layer formed by a hydrophilic polymeric
compound may be formed on the aluminum plate.
Before applying the main coating layer, an undercoating layer may be
applied. The coating amount of the undercoating layer is preferably in the
range of 5 to 150 mg/m2.
A heat- and/or photosensitive coating is then formed on the aluminum
plate thus treated, imagewise exposed to light, and then developed, to make a
printing plate, which is then mounted in a printing machine for printing.
The present invention will be further described in the following nonlimiting
examples. Unless otherwise indicated, all parts, percents, ratios and
the like are by weight.
By the continuous casting apparatus shown in Fig 1A, an aluminium
plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled. The
plate was cold rolled to a thickness of 2.2 mm, then annealed at 520°C for 8
hours, and further cold rolled to form a test material of a thickness of 0.278
mm.
The test material formed as such was subjected to alkali etching. The
material was dipped in an aqueous solution of 25 weight % sodium hydroxide
at 21°C for 7 minute, rinsed by running water, and dried. The top surface at
the casting did not reveal any ripple formation.
The top surface at the casting of the test material was brush grained,
etched with a 25% aqueous solution of sodium hydroxide at 50°C such that
etched amount was 5 g/m2, after washing the etched plate with water, the
plate was immersed in an aqueous sulphuric acid of 180 g/l at 50°C for 20
seconds to desmut the plate, and the plate was washed with water.
Furthermore the support was electrochemically grained in 9 g/l of an
aqueous nitric acid solution using the alternating (wave form ) electric current
described in Japanese Patent No. JP-B-55-19191). As the electrolytic
conditions, the anode and cathode voltages were selected to be Va=14V and
Vo=12V respectively so that the quantity of electricity in the anode time
became 250 coulomb/dm2.
An anode surface oxide coating of 2.5 g/m2 was formed on the support
in a 20% sulfuric acid, and then dried. Furthermore a silicate layer was
formed on the surface by dipping in an 2.5 wt% aqueous sodium metasilicate
solution at 25°C.
The thus obtained support was examined for non-uniform parts: the
plate appeared uniform in graining quality and appearance. No non-uniformity
was observed.
The following composition was coated on the support thus-prepared in
a dry coated weight of 1.3 g/m2 to provide a photosensitive layer.
The photosensitive planographic printing plate thus-prepared was subjected to
exposure for 50 seconds with a metal halide lamp of 3 kW from a distance of 1
m through a transparent negative film, and then it was subjected to
development with a developing solution of the following composition, followed
by gumming in gum arabic, whereby the planographic printing plates were
prepared.
A printing test was carried out in a usual procedure using the planographic
printing plate thus-prepared: 200.000 copies could be printed with a good
quality.
Photosensitive solution: | |
Chemical | g/m2 |
Polyurethane consisting of 4,4'-diphenylmethane diisocyanate / 1,6-hexamethylene diisocyanate / 2,2-bis(hydroxymethyl)-1-propionic acid / tetraethyleneglycol ( 80 / 20 / 20 / 80 mol %, MW = 150000) | 1.01 |
Dodecylbenzene sulfonic acid salt of the condensate of p-diazodiphenylamine and paraformaldehyde | 0.15 |
Phenylphosphonic acid | 0.06 |
Victoria Pure blue | 0.05 |
Surfactant | 0.03 |
1-Methoxy-2-propanol | 6 |
Methyl ethyl ketone | 8 |
| 5 |
Developing solution: | |
Chemical | g/l |
Sodium sulfite | 5.0 |
Benzyl alcohol | 30 |
Sodium carbonate | 5.0 |
Sodium isopropylnaphthalenesulfonate | 12.0 |
Purified water | to make 1 ltr |
By the continuous casting apparatus shown in Fig 1A, an aluminium
plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled. The
plate was cold rolled to a thickness of 2.2 mm, then annealed at 520°C for 8
hours, and further cold rolled to form a test material of a thickness of 0.278
mm.
The test material formed as such was subjected to alkali etching.
The material was dipped in an aqueous solution of 25 weight % sodium
hydroxide at 21°C for 7 minute, rinsed by running water, and dried. The
bottom surface at the casting revealed severe ripple formation.
This time, the side that was the bottom side during the casting
process was submitted to the same steps as in Example 1. Upon examination,
the plate shows an severe wave-like pattern, which renders the substrate
unsuitable for further usage as a substrate for a lithographic printing plate.
By the continuous casting apparatus shown in Fig 1A, an aluminium
plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled. The
plate was cold rolled to a thickness of 2.2 mm, then annealed at 380°C for 4
hours, and further cold rolled to form a test material of a thickness of 0.278
mm. A similar test was repeated 10 times.
Each test material formed as such was subjected to alkali etching as
described in the Example 1. None of the top surfaces at the casting did not
reveal any ripple formation.
The top surface at the casting of the test material was brush grained,
etched with a 25% aqueous solution of sodium hydroxide at 50°C such that
etched amount was 5 g/m2, after washing the etched plate with water, the
plate was immersed in an aqueous sulphuric acid of 180 g/l at 50°C for 20
seconds to desmut the plate, and the plate was washed with water.
Furthermore the support was electrochemically grained in 9 g/l of an
aqueous nitric acid solution using the alternating ( wave form ) electric current
in the manner as decribed in example 1. The quantity of electricity in the
anode time became 180 coulomb/dm2.
An anode surface oxide coating of 3.5 g/m2 was formed on the support
in a 20% sulfuric acid, and then dried.
Each sample of thus obtained support was examined for non-uniform
parts: all plates appeared uniform in graining quality and appearance. No non-uniformity
was observed.
The following composition was coated on the support thus-prepared in
a dry coated weight of 1.7 g/m2 to provide a photosensitive layer.
Photosensitive solution: | |
Chemical | g/m2 |
Ester compound of naphtoquinone-1,2-diazido-5-sulfonyl chloride and | 0.45 |
pyrogallol-acetone resin Cresol fromaldehyde resin | 1.10 |
t-Butylphenol formaldehyde resin | 0.05 |
Tetrahydrophtalic acid anhydride | 0.09 |
Naphtoquinone-1,2-diazido-4-sulfonyl chloride | 0.03 |
Ethyl violet | 0.05 |
Megafac F-176 (fluorine containing surfactant, available from Dainippon Ink and Chemicals, Inc) | 0.01 |
Methyl Ethyl ketone | 6.0 |
1-Methoxy-2-propanol | 4.0 |
The photosensitive planographic printing plate thus-prepared was
subjected to exposure for 50 seconds with a metal halide lamp of 3 kw from a
distance of 1 m through a transparent positive film, and then it was subjected
to development with a developing solution consisting of a 2 wt% aequeous
solution of sodium silicate having a SiO2/Na2O ratio of about 1.1 and
furthermore containing sodium ethylenediaminetetraacetate (0.01 g/l). The
development process is followed by water rinsing and subsequent gumming in
gum arabic, whereby the planographic printing plates were prepared.
A printing test was carried out in a usual procedure using the
planographic printing plate thus-prepared. 200.000 copies with high quality
were obtained from all 10 trials.
By the continuous casting apparatus shown in Fig 1A, an aluminium
plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled. The
plate was cold rolled to a thickness of 2.2 mm, then annealed at 380°C for 4
hours, and further cold rolled to form a test material of a thickness of 0.278
mm. A similar test was repeated 10 times.
Each test material formed as such was subjected to alkali etching as
described in the Example 1. Five out of the ten bottom surfaces at the casting
revealed strong ripple formation, and 5 revealed slight ripple formation.
The bottom surface at the casting of each trial was treated as
described in Example 2, and examined for non-uniform parts: Five out of ten
plates showed a wave-like pattern, which renders the substrate unsuitable for
further usage as a substrate for a lithographic printing plate. Five plates
showed slight wave-like pattern, which is acceptable but not desirable.
By the continuous casting apparatus shown in Fig 1A, an aluminium
plate (alloy AA1050) having a thickness of 5.0 mm was formed and coiled. The
plate was cold rolled to a thickness of 2.2 mm, then annealed at 520°C for 8
hours, and further cold rolled to form a test material of a thickness of 0.278
mm.
The test material formed as such was subjected to alkali etching. The
material was dipped in an aqueous solution of 25 weight % sodium hydroxide
at 21°C for 7 minute, rinsed by running water, and dried. The top surface at
the casting did not reveal any ripple formation. The bottom side during casting
showed a clear, wave-like pattern know as ripple mark.
The upper surface at the casting of the test material was etched with
a 25% aqueous solution of sodium hydroxide at 50°C such that etched amount
was 5 g/m2, after washing the etched plate with water, the plate was
immersed in an aqueous sulphuric acid of 180 g/l at 50°C for 20 seconds to
desmut the plate, and the plate was washed with water.
Furthermore the support was electrochemically grained in 10 g/l of an
aqueous nitric acid solution using the alternating ( wave form ) electric current
in the manner as decribed in example 1. The quantity of electricity in the
anode time became 280 coulomb/dm2.
An anode surface oxide coating of 3.5 g/m2 was formed on the support
in a 20% sulfuric acid, and then dried.
Each sample of thus obtained support was examined for non-uniform
parts: all plates appeared uniform in graining quality and appearance. No non-uniformity
was observed.
The following composition was coated on the support thus-prepared in
a dry coated weight of 1.0 g/m2 to provide a heat-sensitive layer.
Chemical | g/m2 |
m,p-Cresol novolac (m/p ratio = 6/4; weight average molecular weight: | 0.95 g |
7,500; containing 0.8 wt.% of unreacted cresol) | |
Cyanine dye A (having the structure shown below) | 0.025 g |
Megafac F177 manufactured by DAINIPPON INK & CHEMICALS, INC. Ethyl violet | 0.01 g |
Methyl ethyl ketone | 0.05 |
1-Methoxy-2-propanol | 20.1 g |
2.7 g |
The thus obtained heat sensitive plate was imaged in a Creo
Trendsetter model 3244, and developed in the developer described in Example
2. Printing plates of excellent quality with good uniform appearance were
obtained.
Claims (13)
- A method of producing a planographic printing plate support by casting molten aluminium directly and continuously into a thin aluminium plate, wherein the surface which reveals less ripple marks upon etching with an alkaline solution, is used for the manufacturing of the printing plate.
- A method of producing a planographic printing plate support by casting molten aluminium directly and continuously into a thin aluminium plate, wherein the top surface during the casting is used for the manufacturing of the printing plate.
- A method according to claim 1 or 2, wherein said casting is done by a twin roller continuous casting method.
- A method as claimed in one of the claims 1 to 3, in which, after the aluminium is continuously cast directly from molten aluminium into a thin aluminium plate, the aluminium thin plate is subjected to cold rolling, optional heat treatment and flattening to obtain an aluminium support.
- A method according to claim 1 or 2, in which the thin aluminum plate has a thickness from 1 to 10 mm.
- A method according to any one of claims 1 - 5, wherein the aluminium support, at least in the side to be used for printing, is subjected to surface roughening.
- A method according to claim 6, in which graining is used for surface roughening.
- A method according to any one of claims 1-7, wherein an aluminium alloy is used containing between 0.15 and 0.50 weight% FE and/or 0.05 and 0.20 weight% SI and/or 0.005 and 0.040 weight% CU.
- A method according to claim 8, wherein an aluminium alloy is used containing between 0.20 and 0.35 weight% FE and/or 0.10 and 0.15 weight% SI and/or 0.008 and 0.025 weight% CU.
- A method according to any one of claims 1 - 9, wherein on the surface to be used for printing at least a heat and/or photosensitive layer is provided.
- A support provided with a method according to any one of claims 1-9.
- A printing plate, comprising a support according to claim 11 and at least a heat- and/or photosensitive layer.
- A method of using the printing plate of claim 12 in a planographic printing process.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03076834A EP1486347A1 (en) | 2003-06-12 | 2003-06-12 | Aluminium alloy substrate for lithographic printing plate and method for producing the same |
EP04076742A EP1486348B1 (en) | 2003-06-12 | 2004-06-11 | Method of producing a planographic printing plate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03076834A EP1486347A1 (en) | 2003-06-12 | 2003-06-12 | Aluminium alloy substrate for lithographic printing plate and method for producing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1486347A1 true EP1486347A1 (en) | 2004-12-15 |
Family
ID=33185912
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03076834A Withdrawn EP1486347A1 (en) | 2003-06-12 | 2003-06-12 | Aluminium alloy substrate for lithographic printing plate and method for producing the same |
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EP (1) | EP1486347A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102173192A (en) * | 2009-12-27 | 2011-09-07 | 青岛凤凰印染有限公司 | Iron wax-printing cylinder |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4523627A (en) * | 1981-07-09 | 1985-06-18 | Societe De Vente De L'aluminium Pechiney | Process for high-speed vertical continuous casting of aluminium and alloys thereof |
EP0603476A2 (en) * | 1992-11-20 | 1994-06-29 | Fuji Photo Film Co., Ltd. | Support for a planographic printing plate and method for producing same |
EP0640694A1 (en) * | 1993-08-31 | 1995-03-01 | Nippon Light Metal Co., Ltd. | Aluminium alloy substrate for lithographic printing plate and process of producing same |
EP0653497A1 (en) * | 1993-11-15 | 1995-05-17 | Fuji Photo Film Co., Ltd. | Method of producing support for planographic printing plate |
WO1998032559A1 (en) * | 1997-01-24 | 1998-07-30 | Alusuisse Technology & Management Ag | Method for vertical continuous casting of metals |
US6156135A (en) * | 1997-03-14 | 2000-12-05 | Fuji Photo Film Co., Ltd. | Aluminum substrate for lithographic printing plate and process for producing the same |
-
2003
- 2003-06-12 EP EP03076834A patent/EP1486347A1/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4523627A (en) * | 1981-07-09 | 1985-06-18 | Societe De Vente De L'aluminium Pechiney | Process for high-speed vertical continuous casting of aluminium and alloys thereof |
EP0603476A2 (en) * | 1992-11-20 | 1994-06-29 | Fuji Photo Film Co., Ltd. | Support for a planographic printing plate and method for producing same |
EP0640694A1 (en) * | 1993-08-31 | 1995-03-01 | Nippon Light Metal Co., Ltd. | Aluminium alloy substrate for lithographic printing plate and process of producing same |
EP0653497A1 (en) * | 1993-11-15 | 1995-05-17 | Fuji Photo Film Co., Ltd. | Method of producing support for planographic printing plate |
WO1998032559A1 (en) * | 1997-01-24 | 1998-07-30 | Alusuisse Technology & Management Ag | Method for vertical continuous casting of metals |
US6156135A (en) * | 1997-03-14 | 2000-12-05 | Fuji Photo Film Co., Ltd. | Aluminum substrate for lithographic printing plate and process for producing the same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102173192A (en) * | 2009-12-27 | 2011-09-07 | 青岛凤凰印染有限公司 | Iron wax-printing cylinder |
CN102173192B (en) * | 2009-12-27 | 2013-09-25 | 青岛凤凰印染有限公司 | Iron wax-printing cylinder |
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