U.S. patent number 3,836,437 [Application Number 05/367,068] was granted by the patent office on 1974-09-17 for surface treatment for aluminum plates.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Masataka Murata, Chiaki Osada.
United States Patent |
3,836,437 |
Osada , et al. |
September 17, 1974 |
SURFACE TREATMENT FOR ALUMINUM PLATES
Abstract
A process for anodically oxidizing aluminum plates in an aqueous
solution of trisodium phosphate at certain concentrations and
conditions is disclosed. The process provides an aluminum plate
which can be used as a printing plate support.
Inventors: |
Osada; Chiaki (Asaka,
JA), Murata; Masataka (Asaka, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JA)
|
Family
ID: |
12999506 |
Appl.
No.: |
05/367,068 |
Filed: |
June 4, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Jun 3, 1972 [JA] |
|
|
47-55471 |
|
Current U.S.
Class: |
205/50; 205/326;
430/278.1; 430/287.1; 205/153 |
Current CPC
Class: |
C25D
11/06 (20130101); B41N 3/034 (20130101) |
Current International
Class: |
C25D
11/04 (20060101); B41N 3/03 (20060101); C25D
11/06 (20060101); C07c 045/24 () |
Field of
Search: |
;204/17,58 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Tufariello; T. M.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What is claimed is:
1. A method for the surface treatment of an aluminum plate which
comprises subjecting the aluminum plate to anodic oxidation in an
aqueous solution containing 5-50 percent by weight of trisodium
phosphate (based on the total aqueous solution weight) at a liquid
temperature of 20.degree.-40.degree.C and at a current density of
5-20 volts, 0.8-3 amperes per 1 dm.sup.2 for 3-10 minutes, thereby
forming an anodically oxidized layer on said aluminum plate.
2. The method of claim 1 wherein said anodically oxidized layer is
formed in an amount of from about 10 mg to about 200 mg per square
meter of said aluminum plate.
3. A method as claimed in claim 2 wherein said anodically oxidized
layer is formed in an amount of from about 50 mg to about 100 mg
per square meter of support.
4. A printing plate comprising image and nonimage areas, the image
areas being carried on an aluminum plate which has been subjected
to anodic oxidation as in claim 1.
5. The printing plate of claim 4 wherein said image areas comprise
a photoinsulubilized polymer.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for the surface treatment of an
aluminium plate, more particularly, it is concerned with a method
for the surface treatment of an aluminum plate by an improved
anodic oxidation treatment.
2. Description of the Prior Art
Aluminum (in the present specification this term includes aluminum
alloys) has often been used as a support for printing plates
because of its excellent flexibility and dimensional stability,
light weight, price and ready availability. Utilizing these
advantages, aluminum has further been used for building materials,
improved weather resistance being obtained by forming an oxide
layer on the surface of the aluminum. The formation of such an
oxide film layer has hitherto been carried out by anodic oxidation
in an electrolytic solution of sulfuric acid, oxalic acid or
chromic acid, as is well known in the art.
While it is known that an aluminum plate can be used as a printing
plate support, various problems with maintaining the hydrophilic
property and printing resistance are encountered with such plates
produced by prior art methods.
SUMMARY OF THE INVENTION
It is the principal object of the present invention to provide a
method for the surface treatment of an aluminum plate by anodic
oxidation to provide a printing plate which is chemically inert to
an image forming layer to be coated thereon and which has an
excellent hydrophilic property as well as excellent adhesiveness to
an image forming layer.
In accordance with the invention, there is provided a method for
the surface treatment of an aluminum plate, which comprises
subjecting the aluminum plate to anodic oxidation in an aqueous
solution containing 5-50 percent by weight of trisodium phosphate
(based on the total aqueous solution by weight) at a liquid
temperature of 20.degree.-40.degree.C and at current density of
5-20 volts, 0.8-3 amperes per 1 dm.sup.2 for 3-10 minutes.
Practically speaking, the process is always practiced at
atmospheric pressure, though if one wishes sub or super atmospheric
pressure can be used. Little is to be gained by such operation,
however.
DETAILED DESCRIPTION OF THE INVENTION
As the aluminum plate, pure aluminum plates and alloy plates such
as aluminum alloys with copper, zinc, magnesium and iron are used.
Such an aluminum plate is generally subjected to a pretreatment to
remove stains and oily materials, for example, by immersing in a
5-15 percent by weight aqueous solution of sodium hydroxide for
30-90 seconds, washing with water and then treating with a 10
percent by weight solution of ammonium bifluoride. Any standard art
technique for degreasing can be used in the present invention.
Other known method include trisodium phosphate treatment and
treatment with organic solvents such as trichlorostyrene, carbon
tetrachloride and the like.
The anodic oxidation treatment characteristic of the invention is
then carried out in an aqueous solution containing 5-50 percent by
weight, preferably 10-30 percent by weight, of trisodium phosphate
at a temperature of 20.degree.-40.degree.C and a current density of
5-20 volts, 0.8-3 amperes per 1 dm.sup.2, preferably 8-15 volts,
0.8-2 amperes, for 3-10 minutes, preferably 4-8 minutes. Excellent
results are provided when the anodic film is deposited in an amount
of about 10 mg to about 200 mg per square meter of support, more
practically for commercial usage, at about 50 mg to about 100 mg
per square meter of support. These ranges are not, of course,
limitative, but provide a product of excellent properties. A
relatively inert material such as lead is used as a cathode.
Needless to say, the present invention is not limited to lead as a
cathode, though this is commonly used because of its low cost and
the fact it is not corroded by the electrolytic solution. Aluminum
and other materials can also be used, though for economic reasons
lead will usually be used.
The thus obtained aluminum support is an excellent support for
plate making. In the case of using it as a support for plate
making, a thin layer of a water-soluble high molecular weight
compound can be provided on the anodic oxide film weight as
occasion demands. Excellent results are obtained when such a
water-soluble high molecular weight compound is provided in a
thickness of 0.05 microns to 0.2 microns, better yet about 0.1
micron.
Illustrative of the water-soluble high molecular weight compound
are polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone,
gelatin, hydroxyethyl cellulose, carboxymethyl cellulose, casein
and sodium alginate.
The water-soluble high molecular weight compound is generally
provided in an amount of about 10-30 per 1 m.sup.2 by coating or
immersing. The hydrophilic property of the substrate is further
increased by providing such a film of the water-soluble high
molecular weight compound. Though not especially limitative, good
results are provided when the high molecular weight compound has a
molecular weight of from about 10,000 to about 500,000, better yet
from about 50,000 to about 150,000. This includes most materials as
above as they are commercially available. Moreover, a higher
hydrophilic property is given by carrying out a graining treatment
prior to the above described anodic oxidation.
An image forming layer is then provided thereon. Various
conventional light-sensitive materials for photographic printing
plates are used as such an image forming component. However,
cinnamic acid ester type light-sensitive resins are particularly
desirable in view of this printing resistance and light
sensitivity. Typical of such light-sensitive resin are KPR (Kodak
Photo Resist, manufactured by Eastman Kodak Co. KPR has, as its
active chemical constituents the repeating group: ##SPC1##
polymeric materials as reported by Kato et al ("Gazo Gijutsu (Image
Technique)" March (1971), page 18) and polymeric materials as
disclosed in Japanese Patent Application Sho-46-22209. All of these
materials are highly sensitive and useful for the production of
printing plates.
These materials are high molecular weight compounds having the
following recurring structural unit (generally, these materials are
available at a molecular weight of from about 10,000 to about
500,000, and are most preferably used at a molecular weight from
about 50,000 to 100,000): ##SPC2##
One of these light-sensitive high molecular weight compounds is
dissolved in a suitable solvent, for example, cellosolve acetate,
in which a pigment and/or a sensitizer is dispersed, and then
coated onto the aluminum plate subjected to the above mentioned
anodic treatment, thus obtaining the desired plate for printing
plate manufacture. The thus resulting material is then brought into
intimate contact with a transparent negative and exposed to a high
voltage mercury lamp to yield insoluble exposed areas. The
non-exposed areas, i.e., background, can be removed with a suitable
organic solvent such as dimethylformamide or cellosolve acetate
which does not affect the exposed areas. When a pigment is
contained in the image area of the resulting printing plate, the
quality of the image can readily be distinguished.
As the sensitizer, 5-nitroacenaphthene, Michler's ketone and
2,4,7-trinitrofluorenone are preferably used. A suitable pigment is
copper phthalocyanine. When the plate is fitted to an offset press
and printing is carried out on a sheet of paper with a printing
ink, a print of good image quality can be obtained with a printing
resistance of one hundred thousand or more.
The amount of sensitizer can vary greatly, and can easily be
selected by one skilled in the art depending upon the high
molecular weight compound used and the sensitizer selected.
Generally speaking, however, from about 1 percent to about 15
percent of a sensitizer, more preferably 3 weight percent to 10
weight percent, is used in most commonly encountered systems, and
such usually provides excellent results. This range is not,
however, limitative.
As is apparent from the foregoing description, the printing plate
using the aluminum plate processed according to the invention is
excellent with respect to adhesiveness to an image forming film,
water maintenance on non-image areas prevention of adherence of ink
to incorrect portions of the printing plate and maintenance of
water on correct portions of the printing plate and wear
resistance, that is, printing resistance, which are favourably
compared with those of the prior art.
The following examples are to illustrate the invention in more
detail without limiting the same. Unless otherwise indicated, in
all examples parts are part by weight.
EXAMPLE 1
An aluminum plate, the surface of which was grained by brushing,
was immersed in a 10 percent by weight aqueous solution of caustic
soda at room temperature for 30 seconds, washed with water and
immersed in a 10 percent by weight aqueous solution of ammonium
bifluoride for 90 seconds at room temperature to remove stains and
oily matters on the surface. The aluminum plate was then washed
well with distilled water, dried and then subjected to anodic
oxidation by immersing it as an anode in a 20 percent by weight
aqueous solution of trisodium phosphate at a liquid temperature of
30.degree.C for 5 minutes with a lead plate cathode. The voltage
was 10 volts and the current density was 1 ampere per 1
dm.sup.2.
The plate was then taken out of the electrolytic bath and washed
well with water. The thus treated aluminum plate was coated with a
solution forming a light-sensitive layer having the following
composition, followed by drying.
______________________________________
poly-.beta.-cinnamoyloxyvinyl ether 1 part (limit viscosity
[.eta.]=0.216 dl/g determined in methyl ethyl ketone)
5-nitroacenaphthene 0.08 part dibutyl phthalate 0.1 part ethyl
cellosolve acetate 19 parts
______________________________________
The thickness of the light-sensitive layer coated was about 1.5
microns.
The resulting printing plate was brought into intimate contact with
a transparent negative, exposed for about 80 seconds with a 50 watt
mercury lamp at 10 cm using a Plano PS Printer A 3 (made by Fuji
Photo Film Co.) and developed, by rubbing the surface with an
absorbent cotton pad impregnated with cellosolve acetate at room
temperature for about half a minute. The high molecular weight
compound at non-exposed areas was dissolved and the hydrophilic
surface appeared.
When the resulting plate was fitted to an offset press and printing
was carried out with wetting water, about sixty thousand prints of
good image quality were obtained.
EXAMPLE 2
An aluminum plate as in Example 1 was subjected to anodic oxidation
as in Example 1 and coated with a 0.3 percent by weight aqueous
solution of polyacrylamide (molecular weight=12,000) in a coating
amount of about 30 mg/m.sup.2 and dried. Then, the plate was coated
with a light-sensitive solution having the following composition
and dried.
______________________________________ p-phenylene diethoxy
acrylate- 1 part 1,4-di-.beta.-hydroxyethoxycyclo- hexane
polycondensate (1:1 molar) (2-benzoylmethylene)-1-methyl- 0.08 part
.beta.-naphthothiazoline hydroquinone 0.02 part monochlorobenzol 19
parts pigment (Heliogen Blue K) 0.2 part
______________________________________
When the resulting plate was exposed for about 100 seconds using
the light source of Example 1, developed with .gamma.-butyrolactone
as in Example 1 washed with water, fitted to an offset press and
printing was carried out, about 150,000 prints of good image
quality were obtained.
EXAMPLE 3
An aluminum plate which had not been sand set was treated by
immersion in a 10 percent by weight aqueous solution of caustic
soda for 30 seconds and then in a 10 percent by weight aqueous
solution of ammonium bifluoride for 90 seconds and washed well with
distilled water. All processings were at room temperature.
Then the treated plate was then subjected to anodic oxidation by
immersing it as an anode in a 20 percent by weight aqueous solution
of trisodium phosphate at a liquid temperature of 30.degree.C for
about 6 minutes with a lead plate cathode. The voltage was 12 volts
and the current density was 1.2 amperes per 1 dm.sup.2.
The plate was then taken out of the electrolytic bath and washed
well with water. The resulting aluminum plate was coated with the
light-sensitive solution used in Example 1 to a thickness of about
1.5 microns, followed by drying.
When the resulting plate was exposed and developed, followed by
printing, all as in Example 1, about thirty thousands good image
quality prints were obtained, but the printing resistance was
inferior to that of Example 1. This was possibly due to the fact
that the water maintenance was lowered due to lack of sand
setting.
EXAMPLE 4
An aluminum plate which had previously been grained by brushing was
immersed at room temperature in a 10 percent by weight aqueous
solution of caustic soda for 30 seconds and then in a 10% by weight
aqueous solution of ammonium bifluoride for 90 seconds to remove
oily substances thereon and washed with distilled water for 10
minutes. All these processings were at room temperature.
The thus treated aluminum plate was then subjected to anodic
oxidation by immersing it as an anode in a 25 percent by weight
aqueous solution of trisodium phosphate at a liquid temperature of
30.degree.C and applying a voltage of 12 volts at a current density
of 1.5 ampere/dm for 4 minutes, using an apparatus as described in
Example 1.
The plate was then taken out of the electrolytic bath, washed well
with water and dried.
The plate was then coated with a 0.2 percent by weight aqueous
solution of polyvinyl alcohol (hydrolysed to 90 percent, molecular
weight = about 10,000) followed by drying, the dry thickness of the
polyvinyl alcohol layer was 0.05 .mu.) and then coated with a
light-sensitive solution having the following composition to give a
coating thickness of about 2 microns and a proportion of about 2.3
g/m.sup.2.
______________________________________
poly-.gamma.-cinnamoyloxy-.beta.-oxypropyl 1 part methacrylate
(molecular weight about 150,000-170,000)
N-acetyl-4-nitronaphthylamine 0.08 part dioctyl phthalate 0.1 part
pigment (Microlith Blue 4GK) 0.15 part methyl cellosolve acetate 6
parts methyl ethyl ketone 10 parts
______________________________________
The thus resulting printing plate, being dark blue, was brought
into contact with a transparent negative, exposed for 100 seconds
at a distance of 25 cm from a lamp (Toshiba SHL-100 UV) and then
the organic substance at non-exposed areas dissolved off by rubbing
with a cotton pad impregnated with dimethylformamide, followed by
washing with water. There was thus obtained a sharp plate
containing the pigment in exposed areas. When printing was carried
out by means of an ordinary offset press, about twelve thousand
sharp image prints were obtained.
While the invention has been described in detail and with reference
to specific embodiments thereof, it will be apparent to one skilled
in the art that various changes and modifications can be made
therein without departing from the spirit and scope thereof.
* * * * *