U.S. patent number 3,902,976 [Application Number 05/510,909] was granted by the patent office on 1975-09-02 for corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like.
This patent grant is currently assigned to S. O. Litho Corporation. Invention is credited to John E. Walls.
United States Patent |
3,902,976 |
Walls |
September 2, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Corrosion and abrasion resistant aluminum and aluminum alloy plates
particularly useful as support members for photolithographic plates
and the like
Abstract
A process for electrolytically forming on an aluminum or
aluminum alloy sheet or plate a protective layer of film which is
corrosion- and abrasion-resistant and provided with a hydrophilic
surface. The process consists in first anodizing the aluminum or
aluminum alloy sheet or plate in an electrolyte consisting of an
aqueous solution of a mineral acid such as to form on the aluminum
or aluminum alloy surface an aluminum oxide film, and subsequently
electrolytically treating the film in an aqueous solution of sodium
silicate, such as to form a durable abrasion-resistant and
corrosion-resistant barrier layer on the sheet or plate of aluminum
or alluminum alloy which is hydrophilic and which prevents
deterioration of a light sensitive diazo resin, or the like, placed
as a photosensitive coating on the sheet or plate so as to form a
presensitized lithographic plate.
Inventors: |
Walls; John E. (Ridgely,
MD) |
Assignee: |
S. O. Litho Corporation
(Easton, MD)
|
Family
ID: |
24032681 |
Appl.
No.: |
05/510,909 |
Filed: |
October 1, 1974 |
Current U.S.
Class: |
205/127; 101/456;
205/129; 205/172; 205/201; 205/206; 101/459; 205/139;
430/278.1 |
Current CPC
Class: |
C25D
11/06 (20130101); C25F 3/04 (20130101); B41N
3/034 (20130101); C25D 11/12 (20130101) |
Current International
Class: |
C25D
11/04 (20060101); C25D 11/12 (20060101); C25F
3/00 (20060101); C25F 3/04 (20060101); B41N
3/03 (20060101); C25D 11/06 (20060101); C23b
009/00 () |
Field of
Search: |
;204/35N,38A,17,42,28,58,38E ;117/34 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Tufariello; T. M.
Attorney, Agent or Firm: Hauke, Patalidis & Dumont
Claims
Having thus described the invention by way of examples of methods
for practicing the invention, modification whereof will be apparent
to those skilled in the art, what is sought to be protected by
United States Letters Patent is as follows:
1. A method of manufacturing presensitized lithographic plates,
said method comprising the steps of graining a surface of an
aluminum oraaluminum alloy plate, anodizing the grained surface
electrolytically in an aqueous acidic solution, anodically treating
the anodized surface in an alkaline aqueous solution of sodium
silicate, and coating the treated surface with a photosensitive
material.
2. The method of claim 1 wherein said photosensitive material is a
diazo resin.
3. The method of claim 1 wherein each of the steps of anodizing and
anodically treating said plate is effected by connecting said plate
and an electrode across a source of electrical energy such that
said plate is anodic at least part of the time.
4. The method of claim 1 wherein said aqueous acidic solution is a
solution of sulfuric acid having a concentration in acid of 5% to
15%.
5. The method of claim 3 wherein said source of electrical energy
is an AC source and said electrode is a second aluminum or aluminum
alloy plate having a grained surface disposed proximate to the
grained surface of the first plate.
6. The method of claim 4 wherein said aqueous acidic solution is
maintained at a temperature of about 25.degree.C.
7. A method of manufacturing presensitized lithographic plates from
a continuous web of aluminum or aluminum alloy, said method
comprising the successive steps of cleaning said web, anodizing the
grained surface of said web electrolytically in an aqueous acid
solution, anodically treating the anodized surface in an alkaline
aqueous solution of sodium silicate, rinsing said web, drying said
web, coating the treated surface of said web with a photosensitive
material, drying said coating and cutting said web to appropriate
size.
8. The method of claim 7 wherein said photosensitive material is a
diazo resin.
9. The method of claim 7 wherein each of the steps of anodizing and
anodically treating said web is effected by connecting said web and
an electrode across a source of electrical energy such that said
web is anodic at least part of the time.
10. The method of claim 7 wherein said aqueous acidic solution is a
solution of sulfuric acid having a concentration in acid of 5% to
15%.
11. The method of claim 10 wherein said aqueous acidic solution is
maintained at a temperature of about 25.degree.C.
12. A method of manufacturing presensitized lithographic plates
from a pair of continuous webs of aluminum or aluminum alloy, said
method comprising the successive steps of cleaning of said webs,
graining a surface of each of said webs, anodizing the grained
surface of each of said webs electrolytically in an aqueous acidic
solution, anodically treating the anodized surface in an alkaline
aqueous solution of sodium silicate, rinsing each of said webs,
drying each of said webs, coating the treated surface of each of
said webs with a photosensitive material, drying the coating and
cutting each of said webs to appropriate size, wherein said webs
are disposed parallel to each other in the course of said
anodizing, and said anodically the grained surface of said webs
disposed toward each other, and said webs are electrically
connected each to a terminal of an AC source of electrical
energy.
13. The method of claim 12 wherein said aqueous acidic solution is
a solution of sulfuric acid having a concentration in acid of 5% to
15%.
14. The method of claim 13 wherein said aqueous acidic solution is
maintained at a temperature of about 25.degree.C.
Description
BACKGROUND OF THE INVENTION
I. Field of the Invention
The present invention belongs to the field of methods and processes
for forming on the surface of aluminum and aluminum alloy metallic
elements a protective layer which is corrosion and abrasion
resistant, which acts as a barrier layer preventing spontaneous
interreaction between the material of the elements and a coating
disposed thereon, and which is endowed with specific physical
characteristics or qualities different from those of the base
material. Although products obtained by way of the present
invention have a general usefulness as a result of being provided
with a corrosion, abrasion and electrical resistant surface film,
they are particularly useful as support members for
photolithographic plates and the like, and more particularly
presensitized lithographic plates.
The protective surface layer is obtained by a two-step anodic
electrolytic process.
II. Description of the Prior Art
Photolithographic plates currently in use today often include a
metallic support member having, for example, aluminum as its
principal component, a surface of which has been silicated by
chemical or electrochemical methods to provide a barrier layer
which prevents interreaction between the photosensitive diazonium
salts, or other photosensitive and non-photosensitive coatings,
placed upon the support member and the metal surface of the support
member. Silication of the metal surface provides a chemical
pacification which increases the shelf life of the lithographic
plate, facilitates the processing of the plate after exposure, and
improves the length of printing run and the quality of print. The
barrier layer is obtained, according to the prior art, by
subjecting the metallic surface to the action of a solution of one
or several of a plurality of compounds, examples of which include
hydrolized cellulose ester, sodium phosphate glass, alkali metal
silicates, sodium metaborate, phosphomolybdate, sodium silicate,
silicomolybdate, water-soluble alkylated methylomelamine
formaldehyde, polyalkylene-polyamime-melamine-formaldehyde resins,
urea-formaldehyde resin plus polyamide, polyacrylic acid,
polymethacrylic acid, sodium salts of carboxymethylcellulose,
carboxymethyl-hydroxyethylcellulose, zirconium hexafluoride,
etc.
An often used solution in the prior art is an aqueous solution of
sodium silicate in which the metallic plate, forming the
lithographic plate support member, is dipped, or which is applied
to a surface of the plate The solution is preferably heated before
dipping the plate therein and before applying to the surface of the
plate, and the plate surface is optionally washed with an acidic
medium in order to harden the silicated surface and neutralize any
alkali that may remain on the surface.
In addition to acting as a barrier layer between the metal of the
metallic plate and the diazo resin, the silicated surface forms a
hydrophilic surface which partially acts as an initial
water-carrying surface when the processed plate is placed in a
printing press. The hydrophilic surface thus formed is desirably
relatively insoluble in the fountain solutions used in a printing
press in order to prevent undercutting or hydration of the image
areas.
It has been postulated that the following reactions take place
during conventional silication of an aluminum surface:
1. The aluminum and the aluminum oxide at the surface of the plate
react with the solution according to the formulae:
Al + 20H .fwdarw. AlO.sub.2 + H.sub.2 ( a)
Al.sub.2 O.sub.3 + 20H .fwdarw. 2AlO.sub.2 + H.sub.2 O (b)
2. Silication, simultaneously or consecutively, takes place at the
surface, according to the following formula:
Al + AlO.sub.2 + SiO.sub.3 .fwdarw. (Al.sub.2 SiO.sub.5)2x
The aluminum silicate surface layer thus formed is substantially
insoluble, although it may be dissolved to some extent is strong
reagents, and it has been postulated that it is in the form of
large super crystals having an endless chain-like structure as
follows: ##EQU1##
However, in addition to aluminum silicate, other compounds may be
formed and included in the surface layer, which often result in
differences in the qualities of the surface layer. Some of the
compounds that may be present in the film of aluminum silicate
including Al(OH).sub.3, hydrated Al.sub.2 O.sub.3, and hydrated
sodium aluminum silicate, such as, for example Na.sub.2 O.Al.sub.2
O.sub.3.2SiO.sub.2.6H.sub.2 O, could present varied degrees of
solubility in fountain solutions used on printing presses. In
addition, if varied cations such as Ca, Mg, etc., are present, they
may also form complex double silicates with the aluminum, which may
cause further loss in quality of the formed layer.
Silication of aluminum plates by the processes of the prior art
requires control of the purity of the solution and of the process
variables as closely as feasible, such process variables being the
pH of the solution, the duration of the operation, the amount of
grain of the plate, the plate surface cleanliness, the degreasing
or desmutting processes utilized, etc. If all the process variables
are closely controlled in the prior art processes, it is possible
to obtain silicated aluminum plates of acceptable quality for use
as support members for photolithographic plates. The most important
of the desirable qualities to be achieved consist in an adequate
chemically inert surface layer which does not deteriorate with age
and is uniform and well bonded to the aluminum base material and
which protects the aluminum surface in such manner that it is
prevented from interreacting with the acidic diazo resin and will
be only slowly etched by the acidic fountain solutions, and in
providing an appropriate anchorage for the light exposed diazo
resin which permits the developing lacquer to build up on the image
area and to supply long lasting oleophilicity to the image areas,
thus insuring long runs of the plates in the printing press. Such
qualities are difficult to obtain in a repetitive manner by way of
the chemical processes of the prior art.
In U.S. Pat. No. 3,658,662 issued Apr. 25, 1972 and assigned to the
same assignee as the present application, there is disclosed an
electrolytic process for forming an improved functional surface on
aluminum and aluminum alloy plates which permits to achieve
consistent and repetitive quality of the surface and permits to
obtain a surface greatly enhancing the quality of photolithographic
plates as compared to what is achieved by prior art methods.
The invention disclosed in said patent provides an electrolytic
process for forming on the surface of a metallic plate, such as is
generally used as a support member for a coating of diazonium salts
or the like in photolithographic plates, a pacified,
corrosion-resistant, hydrophilic surface layer greatly enhancing
lithographic and printing performances as compared to the surface
layer obtained by strictly chemical processes. Although silication
obtained by prior art chemical methods provides a barrier layer
between the metallic plate and the diazonium salt compounds or the
like utilized as the photosensitive coating in photolithographic
plates, electrolytically formed surface layers are much improved as
far as lithographic hardness, and continuity and uniformity of the
layers or films are concerned. The electrolytic process of said
patent also produces surface layers which are intimately bonded to
the underlying metal, which have high hydrophilic qualities and
which result in an important improvement in the fine grain of the
plate surface. In addition, the electrolytically formed surface
layer has a much improved anchoring quality for adhesion of the
diazo resin thus reducing any tendency to image failure and
resulting in improved printing runs. The improved surface grain and
the increase in bonding quality of the electrolytically treated
surface also result in more retained diazo, more retained lacquer
and a more oleophilic image, leading to longer running and higher
quality press performances, as compared to conventional
lithographic plates.
Although the electrosilicated surface obtained by the method of
U.S. Pat. No. 3,658,662, when provided with a coating of diazonium
salts or other photosensitive material, has proved to provide
greatly improved photolithographic plates, such plates still
require to be handled with a certain amount of caution as the
surface is not entirely scratch-free.
It has now been discovered that when an aluminum or aluminum alloy
surface is first anodized in an acidic electrolyte and subsequently
electrosilicated according to the method of the aforementioned
patent, the anodized and electrosilicated surface is
scratch-resistant and at the same time all the advantageous
characteristics of the electrosilicated surface are maintained in
their entirety.
Among the advantages provided by the surface treatment obtained by
the method of the present invention relative to photolithographic
plates and printing press cylinder, rollers and other support
members, are less propensity to attack from the printing press
fountain solutions, a marked decrease in soluble film remaining on
the lithographic plate after rinsing, improved hydrophilic quality
of the plate background surface, a lithographically harder surface
and a decrease in deterioration of the plate as a result of wear.
The hard, compact surface film or layer obtained by the present
invention on the surface of aluminum or aluminum alloy elements,
because of its corrosion-resistant characteristics, its bonding and
anchoring qualities with respect to decorative or protective films
which may subsequently be applied thereto and the increase in
electrical resistivity as compared to the resistivity of the base
material, presents the added advantage of providing articles having
general usefulness in the industry.
SUMMARY OF THE INVENTION
The present invention therefore is an improvement upon the method
disclosed in U.S. Pat. No. 3,658,662 which consists in
electrolytically anodizing a sheet or plate of aluminum or aluminum
alloy in an acidic electrolyte so as to provide on the surface of
the sheet or plate a film of aluminum oxide which after being
subjected to a further anodic treatment in an electrolyte bath of
an alkaline metal salt, such as sodium silicate, provides an
effective barrier film, an anchoring surface for paint, varnish and
the like, or for a coating of photosensitive material when the
sheet or plate is used as a support member for a lithographic
plate.
These and other advantages and objects of the invention will become
apparent to those skilled in the art when the accompanying
description of some of the best modes contemplated for practicing
the invention is read in conjunction with the accompanying drawing
wherein like reference numerals refer to like or equivalent
parts.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic representation of an example of arrangement
for practicing the electrolytic process of the present
invention;
FIG. 2 is a schematic representation of a modification thereof;
FIG. 3 is a schematic representation of a further modification
thereof;
FIG. 4 is a schematic representation of a further modification
thereof;
FIG. 5 is a schematic representation of a continuous line process
for manufacturing a photolithographic plate according to the
present invention;
FIG. 6 is a view similar to FIG. 5 but showing a modification of
the method for manufacturing photolithographic plates according to
the present invention;
FIG. 7 is a schematic sectional view of an aluminum or aluminum
alloy plate having been subjected to the process of the invention;
and
FIG. 8 is a schematic sectional view of the plate of FIG. 7
provided with a coating or photosensitive material such as a diazo
resin or the like.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In order to practice the present invention, a cleaned aluminum or
aluminum alloy element such as a plate 10, as shown at FIG. 1, is
dipped in an appropriate electrolyte 12, contained in a tank 14,
the plate 10 being disposed in proximity to an electrically
conductive electrode 16. The plate 10 is connected to the positive
terminal of a DC power supply 18, and the electrode 16 is connected
to the negative terminal of the power supply, such that the plate
10 is electrolytically anodic and the conductive electrode 16 is
electrolytically cathodic. The conductive electrode 16 may be in
the form of a solid metallic plate, or in the shape of a grid or
mesh made of the same material as the metallic plate 10, or made of
a dissimilar material.
The DC power supply 18 may be a bank of storage batteries, an AC-DC
dynamo-electric or a static converter, an AC-DC rectifier or any
other convenient source of DC power. A pulsed DC current power
supply may be used, and it does not seem material whether the DC
voltage across the terminals of the power supply is constant and
steady or includes an AC ripple. An AC power supply may be also
used, which is arranged to operate on that portion of the cycle
when the metallic element 10 is substantially anodic.
EXAMPLE 1
Plates of 1100 aluminum, having an area of 25 sq. in. and .009 in.
thick were prepared by having a surface of a continuous web of the
aluminum material grained at a line speed of 12 feet per minute
using a sand slurry. The web was then cut so as to provide plates
of the indicated area.
The plates were electrolytically anodized according to the
arrangement of FIG. 1, by dipping each plate in the electrolyte at
a predetermined distance from a cathode 16 consisting of a
stainless steel grid, having an area matching that of the plate 10,
the grained surface of the plate 10 being disposed opposite the
cathode 16. The spacing between the plate and the cathode was three
inches. The electrolyte 12 used was an aqueous solution of 8%
sulfuric acid. A DC power supply 18 of 18 volts at 50 amps was
used.
After each anodizing operation, the plates 10 were rinsed with
water and dried.
In order to test the degree to which the plates were anodized, a
saturated solution of stannous chloride (SnCl.sub.2) was poured on
the surface of the plates on the anodized side. The better the
barrier formed by the anodization step the longer it took for the
stannous chloride to break through the barrier film and react with
the subjacent aluminum, the reaction being according to the
following formula:
2Al + 3SnCl.sub.2 .fwdarw. 3Sn + 2AlCl.sub.3
The penetration of the stannous chloride through the pores of the
aluminum oxide layer obtained by anodization is noticeable as a
plurality of dark points, and the reaction is complete when the
plate ceases to darken.
In order to determine the influence of temperature of the anodizing
bath and the influence of the duration of treatment of the plates
in the anodizing bath, a first series of runs were made while
maintaining the temperature of the electrolyte at 40.degree.C and a
second series of runs were made while maintaining the temperature
of the electrolyte at room temperature (25.degree.C). The results
achieved are tabulated in Tables 1 and 2:
TABLE 1 ______________________________________ TEMPERATURE OF
ELECTROLYTE 40.degree.C Duration of Time for SnCl.sub.2 Anodization
(sec.) to break through (min.)
______________________________________ 0 (control) immediately 3
0.25 - 0.30 (15-20 sec.) 6 2 9 6 12 11.5 15 18.0
______________________________________
TABLE 2 ______________________________________ TEMPERATURE OF
ELECTROLYTE 25.degree.C Duration of Time for SnCl.sub.2 Anodization
(sec.) to break through (min.)
______________________________________ 0 (control) immediately 3 2
5 5 10 9 15 20 20 27 ______________________________________
The test results tabulated in Tables 1 and 2 indicate clearly that
at a given concentration of the electrode the best barrier films
are provided at lower temperature of the electrolyte.
EXAMPLE 2
To further determine the influence of acid concentration in the
electrolyte, a series of tests was run for different anodization
durations with the arrangement of FIG. 1 and under the general
conditions described with respect to Example 1, maintaining the
electrolyte temperature at a constant 25.degree.C and using a 5%
solution of sulfuric acid, a 10% solution and a 15% solution. The
results achieved are tabulated in Tables 3-5:
TABLE 3 ______________________________________ 5.% solution of
H.sub.2 SO.sub.4 at 25.degree.C Duration of Anodization Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 (control) immediately 3
2.5 5 6.8 10 11.3 15 25.0 20 33.3
______________________________________
TABLE 4 ______________________________________ 10.0% solution of
H.sub.2 SO.sub.4 at 25.degree.C Duration of Anodization Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 (control immediately 3 1.8
5 4.5 10 8.2 15 18.1 20 25.0
______________________________________
TABLE 5 ______________________________________ 15.0% solution of
H.sub.2 SO.sub.4 at 25.degree.C Duration of Anodization Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 (control) immediately 3
1.5 5 4.2 10 7.8 15 17.2 20 22.0
______________________________________
EXAMPLE 3
The tests of Example 2 were repeated, at the diverse concentrations
of sulfuric acid respectively 5%, 10% and 15%, but maintaining the
electrolyte temperature at 40.degree.C. The results of the stannous
chloride attack tests are tabulated in Tables 6-8:
TABLE 6 ______________________________________ 5% solution of
H.sub.2 SO.sub.4 at 40.degree.C Duration of Anodization Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 (control) immediately 3
2.0 5 5.7 10 10.2 15 22.6 20 29.0
______________________________________
TABLE 7 ______________________________________ 10% solution of
H.sub.2 SO.sub.4 at 40.degree.C Duration of Anodization Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 (control) immediately 3
1.5 5 3.9 10 7.0 15 16.4 20 22.0
______________________________________
TABLE 8 ______________________________________ 15% solution of
H.sub.2 SO.sub.4 at 40.degree.C Duration of Anodization Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 immediately 3 1.1 5 3.7 10
6.1 15 14.8 20 20.3 ______________________________________
EXAMPLE 4
The tests of the preceding Examples were repeated, at the diverse
concentrations of electrolyte of respectively 5%, 10% and 15%
solutions of sulfuric acid, maintaining the temperature of the
anodizing electrolyte at 55.degree.C. The results achieved are
tabulated in Tables 9-11:
TABLE 9 ______________________________________ 5.0% solution of
H.sub.2 SO.sub.4 at 55.degree.C Duration of Anodizations Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 (control) immediately 3
1.8 5 5.1 10 9.3 15 20.7 20 28.2
______________________________________
TABLE 10 ______________________________________ 10.0% solution of
H.sub.2 SO.sub.4 at 55.degree.C Duration of Anodization Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 (control) immediately 3
1.1 5 3.0 10 5.9 15 13.3 20 20.1
______________________________________
TABLE 11 ______________________________________ 15.0% solution of
H.sub.2 So.sub.4 at 55.degree.C Duration of Anodization Time for
SnCl.sub.2 to react (sec.) (min.)
______________________________________ 0 (control) immediately 3
0.7 5 3.2 10 5.4 15 12.5 20 18.6
______________________________________
From the tests of Examples 1-4 it is readily apparent that the best
quality anodized plates, as far as the stannous chloride test
hereinbefore explained is concerned, are obtained for a duration of
anodization of about 20 seconds, with a relatively low
concentration of acid in the electrolyte (5%), and while operating
at room temperature, 25.degree.C.
Decreasing the concentration of acid in the electrolyte below 5%
was found not to provide sensible improvement in quality of the
surface barrier film obtained, although concentrations as small as
0.7% were found to be quite effective. Lower concentrations,
however, require slightly longer anodization durations, and if the
duration of operation is shortened by way of increasing the
voltage, and thus the current density, there results a proportional
requirement for increasing the flow of the cooling fluid, such as
water, through the cooling coils disposed in the electrolyte tank.
Although decreasing the temperature of the electrolyte below
25.degree.C permits to improve the quality of the barrier film
formed by anodization of the plate surface, such increase in
quality does not warrant the expenditure in refrigeration equipment
and in energy used to control the temperature of the
electrolyte.
The stannous chloride test, hereinbefore referred to, provides a
good indication of the amount of porosity of the anodized surface
and of the thickness of the anodized oxide layer. The time taken
for the stannous chloride solution to reach the aluminum surface is
directly proportional to the thickness of the layer, and for layers
of equal thickness, the time is inversely proportional to the
porosity of the oxide layer. Such test does not provide any
information about the hardness of the oxide layer or, in other
words, its resistance to abrasion.
Two additional tests were developed which although incapable of
providing an absolute quantitative determination of the resistance
to abrasion of the oxide layer were capable of providing a good
comparison between the quality of a plate and the quality of
another plate.
The first test consists in stroking a soft, non-metallic ordinary
eraser across the surface of the plates, the eraser being applied
to the surface of the plates with an even pressure. The resistance
to abrasion of the plate surface is determined by counting the
number of strokes required to break through the surface layer. The
strokes are applied repetitively to the same area of the plates and
the moment at which the anodized layer is broken through is
recognized by the surface of the eraser turning black.
The other comparative test consists of pouring a saturated solution
of stannous chloride over the surface of the plates and, with an
even pressure in stroking an ordinary bristle brush across the
surface of the plates. The bristles of the brush abrade the
anodized oxide film on the surface of the plates, and the reaction
of the stannous chloride with the aluminum indicates to what extent
the surface is damaged.
Both tests may be effected by means of an appropriate fixture for
the purpose of removing human error in applying the eraser or the
brush with an even pressure over the surface of the plates. The
plates are placed on the table of a machine tool such as a milling
machine, and the eraser or the brush is mounted on the machine tool
holder. The table is reciprocated by way of the table slides, the
eraser end or the brush bristles being engaged with the surface of
the plates being tested. A spring loaded holder is preferably used
for mounting the eraser and applying the eraser with a constant
pressure to the plate surfaces.
Using both the eraser test and the brush test, a direct correlation
was established between the resistance of the anodized plates to
penetration by the stannous chloride solution of Examples 1-4, and
the relative time that it took to break through the anodized
surface layer by means of the eraser test and the brush test.
The stannous chloride test, the eraser test and the brush test are
indicative of the mechanical quality of the plate anodized surface,
namely the degree of porosity of the anodized barrier film, its
hardness, and its resistance to abrasion. They are not indicative
of a further desirable quality for lithographic plates, namely the
hydrophilic quality of the plate surface.
The hydrophilicity of the plate surface is tested by means of a dry
ink test and by means of a wet ink test. The dry ink test consists
in rubbing the surface of the plate with a rag impregnated with
printer's ink which has been allowed to dry. The wet ink test
consists in rubbing the surface of the plate with wet printer's
ink. To be acceptable for use as a lithographic plate, the surface
should not smudge when subjected to the wet ink test, and it should
not ink readily when subjected to the more stringent dry ink
test.
It will be appreciated that anodized aluminum or aluminum alloy
plates have commonly been used for lithgraphic plate support
members, after coating the anodized surface with an appropriate
light-sensitive material such as water soluble diazo resins or the
like. However, the lithographic quality of such plates leaves much
to be desired, as the hydrophilicity of the surface in somewhat on
the weak side. Plates anodized according to the procedure described
at Examples 1-4 were subjected to the wet and dry ink tests and
failed to pass the test satisfactorily, especially the dry ink
test.
EXAMPLE 5
Plates of 1100 aluminum were prepared by being cut from a web of
aluminum material grained at a line speed of 12 feet per minute
using a sand slurry. After rinsing, the plates were
electrolytically anodized according to the arrangement of FIG. 1,
by dipping each plate in the electrolyte at a distance of 3 inches
from the cathode 16 consisting of a stainless steel plate having
the same area as that of the plate 10. The grained surface of the
plate 10 was disposed opposite the cathode 16. For the purpose of
determining the effect of using an acidic electrolyte containing an
acid other than sulfuric acid, diverse electrolytes at
concentrations of 5%, 10% and 15% of an organic or inorganic acid
were used, repeating the runs of Examples 1-4, and subjecting the
anodized plates to the diverse tests hereinbefore mentioned. The
results achieved were as follows:
The anodized oxide layer obtained with nitric acid electrolytes was
thin, non-resistant to any of the mechanical tests and accepted ink
readily in the course of the wet ink test as well as the dry ink
test.
The anodized layer obtained by anodizing with a hydrochloric acid
electrolyte was also relatively thin and not very resistant to the
abrasion tests. The sample plates did not pass the dry ink test,
but were found to be acceptable when subjected to the wet ink
test.
Plates anodized with acetic acid electrolytes were provided with a
surface anodized film which was fairly resistant to abrasion. The
film was not at all dark in appearance, contrary to the surface
film obtained by anodization with other electrolytes. The anodized
surface was not receptive to ink when subjected to the dry ink
test.
The anodized suface layers obtained by using electrolytes of
chromic acid and of boric acid were comparable in lack of
resistance to the abrasion test, and therefore were considered
unacceptable for the purpose intended as a support member for a
lithographic plate.
The anodized surface layers obtained by electrolytes of phosphoric
acid were in all points comparable with those obtained with the
sulfuric acid electrolytes of Examples 1-4, from the point of view
of lithographic quality, and they even appeared to be slightly
superior when subjected to the stannous chloride penetration test
and the diverse abrasion tests. The quality of the surface layers
obtained with phosphoric acid electrolytes is apparently not as
affected by the temperature of the electrolytes as is the case when
using sulfuric acid dlectrolytes. Phosphoric acid electrolytes
would therefore be quite acceptable for anodizing aluminum and
aluminum alloy plates for support members for lithographic plates,
if the price of phosphoric acid was not two times the price of
sulfuric acid.
The arrangement of FIG. 1 for batch anodizing of aluminum or
aluminum alloy plates or sheets may be modified to anodize a pair
of plates 10 by placing a second plate 10 a predetermined distance
from the cathode 16 in the tank 14, such as three inches away from
the cathode, on the other side of the cathode and connecting both
plates 10 to the negative terminal of the power supply 18. If it is
desired to anodize both surfaces of a plate 10, the arrangement of
FIG. 2 is used, a pair of cathodes 16 and 16' being disposed on
both sides of the plate 10 and connected to the negative terminal
of the power supply 18.
Instead of using a DC power supply, an AC power supply may be used,
as shown at 18 at FIG. 3, each terminal of the power supply being
connected to one of the two aluminum or aluminum alloy plates 10
and 10'. When it is desired to anodize both sides of the plate, the
arrangement of FIG. 4 may be used, utilizing an AC power supply
18', and the diverse plates being connected electrically as shown,
with the results that plates 10a', 10b, 10b' and 10c are anodized
on both surfaces, and the plates 10a and 10c' are anodized on the
surface disposed respectively towards plates 10a' and 10c.
The present invention contemplates manufacturing presensitized
lithographic plates by a method which includes as one of its steps
an anodization step prior to subjecting the aluminum or aluminum
alloy plate member to electrosilication according to the method
disclosed in said U.S. Pat. No. 3,658,662, thus obtaining a support
member which, once coated with a photosensitive material, provides
a presensitized lithographic plate of high quality, not subject to
the formation of "black spots," and provided with an effective
barrier layer between the subjacent metal of the support member and
the photosensitive coating preventing spontaneous reaction between
the two until the photolithographic plate is removed from its
wrapper, exposed and developed.
The conditions of operation for the electrosilication step in the
method may be any one of those disclosed in the aforesaid U.S.
Patent and consist generally in anodically treating the anodized
plates by means of DC, AC or pulse current in an alkaline
electrolyte made of an aqueous solution of sodium silicate
containing from about 0.5% to about 37% by weight of sodium
silicate, the electrolyte being maintained at a temperature between
20.degree.C and the boiling temperature of the electrolyte, the
plate to be treated and the other electrode in the electrolytic
bath being in close proximity to each other, the voltage being
anywhere between 6 and 220, or more, volts, and the duration of the
electrosilication step being only a few seconds.
EXAMPLE 6
A plurality of plates of 1100 aluminum were grained in a sand
slurry and anodized in an electrolyte made of a 5% aqueous solution
of sulfuric acid, using 18 volts DC, passing the current for 15
seconds and maintaining the temperature of the electrolyte at
25.degree.C.
The plates were then rinsed and placed in a tank containing an
aqeous solution of 17% sodium silicate by weight. The plates were
connected to the positive terminal of a 36 volt DC power supply,
and the temperature of the electrolyte was maintained at
70.degree.C. The period of time during which the current was turned
on was varied from plate to plate, the minimum duration being 2
seconds and the maximum duration being 60 seconds.
The plates were then submitted to the diverse tests described
hereinbefore, and no significant difference in quality was found
between plates having been subjected to electrosilication for a
short period of time and those having been subjected to
electrosilication for a long period of time. For that reason, a
duration of electrosilication of 15 seconds was arbitrarily
selected as a practical duration of the electrosilication step in a
continuous web process wherein the duration of the anodization step
is also arbitrarily selected to be 15 seconds, such that identical
tanks may be used in the process for the anodization step and for
the electrosilication step.
When subjected to the stannous chloride penetration test, the
diverse plates having been subjected to an anodization step
followed by an electrosilication step showed no attack by the test
solution a duration of more than an hour. Plates having been
subjected to anodization alone were used as control plates in the
eraser comparision test with plates having been subjected to the
electrosilication step following the anodization step. The number
of eraser strokes necessary to break through the layer of film
formed on the plates having been subjected to both the anodizing
the electrosilication steps were between 2.7 and 3.1 times greater
than the number of strokes required to break through the surface
layer film of the plates having been only anodized.
The comparative brush test yielded the same results. Repetitively,
the plates provided with an anodized surface were affected by the
brush test, while the plates anodized and electrosilicated remained
unaffected.
Plates which had been anodized only and plates which had received
the anodizing and electrosilication treatments were subjected to
the dry ink test, side by side. The plates which had only been
anodized readily accepted the ink and toned. The plates which had
been electrosilicated in addition to having been anodized did not
accept ink, when subjected to the dry ink test as well as the wet
ink test.
EXAMPLE 7
Plates which had been anodized and electrosilicated according to
the process disclosed relative to Example 6 were coated, on their
face provided with a barrier film, with a conventional diazo resin
according to conventional methods in the lithographic plate
manufacturing industry. A 6% solution of type "L" diazo
manufactured by Fairmount Chemical Company was used for coating the
plates. Control plates subjected only to anodizing were coated in
the same manner. After drying of the coating, both types of plates
were exposed to a mercury vapor light source for 30 seconds and
developed with a subtractive developer, such as the subtractive
developer in copending application Ser. No. 500,475. After
development, the image area of both types of plates was subjected
to the eraser test. The plates having received only the anodizing
treatment were abraded at the image area in half as many strokes as
were required to abrade the image area of the plates which had
received both the anodizing and the electrosilication
treatments.
One-half of each type of plate was reexposed to the mercury light
source for 30 seconds and redeveloped. The plates were dry inked.
The plates which had only been anodized became slightly toned where
subjected to single exposure, but the area subjected to double
exposure readily scummed. The plates which had been anodized and
electrosilicated remained clean in the background areas of the
double exposed portion as well as on the single exposed
portion.
Electrosilication of aluminum and aluminum alloy plates following
anodization may be effected by batches, under the condition of
operation disclosed in the aforesaid U.S. Patent and according to
any one of the arrangements of FIGS. 1-4, substituting for the acid
electrolyte 12 a sodium silicate alkaline electrolyte, connecting
the plate 10 as an anode to the positive terminal of a DC power
supply 18, using a stainless steel or other conductive cathode 16
connected to the negative terminal of the power supply (FIG. 1). If
both faces of plate 10 have been anodized previously, both faces
may be electrosilicated by using a pair of cathode electrodes 16
and 16', connected as shown at FIG. 2. Using an AC power supply 18,
the arrangement of FIG. 3 or FIG. 4 may be used.
Referring now to FIG. 5, there is schematically illustrated a
continuous process for making photolithographic plates according to
the present invention. A web 20 of aluminum or aluminum alloy foil
is unwound from a coil 22 mounted on an appropriate support 24. The
web 20 is continuously fed in the direction of the arrows,
appropriate feed means, such as shown at 26, being disposed at
appropriate locations along the manufacturing line. By means of
appropriate rollers, the continuously traveling web 20 is deflected
into successive tanks in which appropriate steps of the process are
accomplished. The web 20 is first cleaned in the cleaning tank 28,
containing an appropriate cleaning or degreasing fluid such as
trichloroethylene, perchlorethylene, or the like, and from the
cleaning tank the web is passed into a cleaning tank 30 in which a
surface of the web 20 is grained under the action of a sand slurry
32 contained in the tank and frictionally applied to a surface of
the web by means of a rotating brush 34. The web 20 is then rinsed,
as shown at 36, and after rinsing the web is caused to pass through
an anodizing tank 38 wherein it is linearly displaced in proximity
to an electrode 16, the grained surface of the web being directed
toward the electrode 16. In the process of FIG. 5, the electrode 16
is connected to the negative terminal of a DC power supply 18,
while the positive terminal of the power supply 18 is connected to
the web 20 by way of appropriate electrical contact making rollers
40. The anodizing tank contains an electrolyte 12 made of an
aqueous solution of an appropriate acid such as sulfuric acid or
the like, at the concentrations disclosed at Examples 1-4
hereinbefore, and the other parameters of operation, such as
voltage of the power supply 18 and temperature of the electrolyte,
may be one of the parameters hereinbefore disclosed. For example,
and preferably, the power supply 18 has a voltage of 36 volts, the
electrolyte 12 consists of a 5% aqueous solution of sulfuric acid
and is maintained, by 36 of appropriate cooling means, not shown,
at a temperature of 25.degree.C. The grained surface of the web 20
is translated at a distance of 3 inches from the electrode 16, and
the relative length of the electrode 16 and the speed of
translation of the web 20 are chosen to provide anodization of the
grained surface of the web for about 15 seconds. At the selected
continuous speed of translation of the web 20 of 12 feet per minute
(3.65 meters/min.), which is a convenient speed of translation of
the web, the electrode 16 has a length of 36 inches (91.5 cm.). The
web 20 is conveniently obtained in 291/2 inches (75 cm.), and the
width of the electrode 16 is at least the width of the web 20.
Preferably, the electrode 16 is a stainless steel plate or
grid.
The web 20, having been now provided with a grained and an anodized
surface, is subsequently passed through a rinsing tank 42 for
removing traces of the acid electrolyte and is subsequently passed
through an electrosilication tank 44. In the electrosilication tank
44, the web 20 is translated with its grained and anodized face
disposed, for example, 3 inches (75 mm.) away from an electrode 46,
made of stainless steel, for example, conconnected to the negative
terminal of the power supply 18. As previously mentioned, the web
is maintained connected to the positive terminal of the power
supply by means of electrical contact establishing rollers 40. The
electrolyte 48 in the electrosilication tank 44 consists of an
appropriate aqueous solution of sodium silicate, as disclosed in
the hereinbefore referred to U.S. Patent, for example an aqueous
solution of 17% by weight of sodium silicate, such as the Star
Brand sodium silicate marketed by Philadelphia Quartz Company, and
the temperature of the electrolyte 48 is maintained at, for
example, 70.degree.C by means of appropriate thermostatically
controlled heating coils, not shown. The grained and anodized
surface of the web 20 is subjected to electrosilication for about
15 seconds, although other durations may be used, which
necessitates providing the electrode 46 with a length of 36 inches
(91.5 cm.).
After emerging from the electrosilication tank 44, the continuous
web 20 is passed through a rinsing tank 50, and then dried by being
passed through a tunnel oven 52 or the like. The grained, anodized
and electrosilicated surface of the web 20, after drying of the
web, is coated with an appropriate photosensitive material such as
a conventional aqueous solution of diazonum resin. The coating
operation is effected by any conventional means such as roller
coating 54 or spraying followed by calendering. After coating of
its grained, anodized and electrosilicated surface, the web is
passed through a drying oven 56 for drying the coating of
photosensitive material, and the coated web is fed to a cutting
station 58 where it is cut to appropriate lengths, thus providing
presensitized photolithographic plates 60 which, after further
cutting to appropriate sizes if so required, are appropriately
packaged and shipped to the user. The coating and subsequent steps
are effected under yellow light which is nonactinic to diazo type
photosensitive materials.
Although the continuous line process of manufacturing
photolithographic plates schematically illustrated in FIG. 5 has
been described as including a DC power supply 18 for the
anodization and electrosilication steps, it will be appreciated
that an AC power supply may be substituted for the DC power supply
18, or a pulse DC power supply may be used, for effecting both the
anodizing step and the electrosilication step, or for effecting any
one of these steps.
As previously explained herein, an AC power supply may be used for
accomplishing the anodizing step and, as disclosed in the
aforementioned patent, alternating current may be used for
electrosilication of aluminum and aluminum alloys. When an AC power
supply is used, it has been found advantageous to use higher
voltages than normally used in direct current anodization and
electrosilication process. It is convenient to utilize alternating
current at 115 volts (RMS) as supplied directly from the mains.
When utilizing an AC power supply, it is further advantageous to
utilize the arrangement schematically illustrated at FIG. 6,
comprising two continuous lines of aluminum or aluminum alloy webs
as shown at 20 and 20', respectively, adapted to be translated
parallel to each other, in the same direction as shown, or in
opposite directions to each other. As shown at FIG. 6, the first
web 20 is obtained from a coil 22, and the second web 20' is
obtained from a second coil 22'. Each web, while being translated,
is successively passed through a cleaning tank 28, 28', a graining
station 30, 30' to provide a surface of each web with a grained
surface, and subsequently to graining each web is passed through a
rinsing station as shown at 36 and 36', respectively. It is to be
noted that the surface of the web 20 which is grained and the
surface of the web 20' which is grained are caused to pass through
the anodizing bath in the anodizing tank 38 facing one another. The
two webs 20 and 20' are displaced through the anodizing tank 38,
parallel to each other, in close relative proximity, 3 inches for
example, through an appropriate electrolyte 12, made for example of
an aqueous solution of sulfuric acid, having the concentration
hereinbefore indicated, preferably maintained at a temperature of
25.degree.C by means of appropriate cooling coils, not shown. One
of the webs is connected to a terminal of an AC power supply 18',
and the other web is connected to the other terminal of the power
supply by means of appropriate contact making rollers 40 and 40',
respectively.
After anodization in the anodizing tank 38, the webs 20 and 20' are
rinsed by being passed through a rinsing tank 42, and are passed
through an electrosilication tank 48, being maintained parallel to
each other with the grained and anodized faces opposite to each
other and separated by a distance of, for example, 3 inches. After
electrosilication in the electrosilication tank 44 for a period of
time substantially equal to the period of time during which they
are subjected to anodization, for example, 15 seconds, the two webs
20 and 20' are passed through a rinsing tank, as shown at 50, and
they are dried in an oven, as shown at 52. Each of the webs are
then caused to pass separately through a coating station, as shown
respectively at 54 and 54', where the grained, anodized and
silicated surface of each web is coated with a coating of
photosensitive material, such as a diazo resin, as previously
explained. The coating of photosensitive material is subsequently
dried in the drying oven, as shown at 56 and 56', respectively. The
coated webs are then cut at a cutting station, 58 and 58',
respectively, to appropriate lengths for providing presensitized
photolithographic plates 60 and 60'.
FIG. 7 schematically illustrates, is a grossly exaggerated manner,
a section through an aluminum or aluminum alloy plate 10 provided
with an anodized oxide film 62 on a surface thereof. The anodized
film 62 is, as previously mentioned, hard and corrosion resistant,
although not endowed with highly hydrophilic qualities. In
addition, the anodized layer 62 is substantially porous and, if its
surface was provided with a coating of, for example, photosensitive
material such as a diazo resin, the oxide layer 62 would be easily
penetrated in view of its porosity by the coating material, which
may result in a spontaneous reaction occurring between the metal of
the support base 10 and the material of the coating. This presents
many disadvantages if a simply anodized aluminum plate is utilized
as a support member for photosensitive coatings such as diazo
resins for the purpose of providing a presensitized lithographic
plate. Such a lithographic plate has a very short shelf life, as
the reaction betweeen the diazo resin having transpired through the
oxide film 62 to the subjacent aluminum of the support base 10
tends to spontaneously react and spontaneously form black spots,
that is spots resulting from areas of the diazo resin having
spontaneously chemically reacted with the subjacent aluminum, the
resultant material being highly oleophilic and incapable of being
dissolved in the course of developing the lithographic plate
following exposure.
However, when the anodized face of the aluminum or aluminum alloy
plate 10 is subjected to electrosilication, according to the
present invention, the electrosilication step actually seals the
pores of the oxide layer 62, in addition to electrolytically
transforming the surface 64 of the oxide layer 62 from a mildly
hydrophilic to a highly hydrophilic surface. The result achieved is
that an effective chemical barrier is created between the subjacent
metallic support base 10 and a coating, such as a coating of diazo
resin 66 (FIG. 8) which is subsequently applied to the surface 64
of the oxide layer 62. The resulting presensitized lithographic
plate has a long shelf life because, as a result of the
electrosilication step, the oxide layer 62 provided by the
anodization step has been effectively sealed, thus creating an
effective barrier preventing spontaneous reaction between the diazo
resin and the metal of the subjacent support base 10. In addition,
the resulting lithographic plate, after exposure and processing, is
provided with hydrophilic non-image areas as the surface 64 of the
oxide layer 62 has been, in the course of the electrosilication
step, further modified from a slightly hydrophilic surface to a
highly hydrophilic surface, without any loss in the quality of the
oxide layer to provide a corrosion and abrasion resistant film. The
advantage procured by electrosilication of an aluminum or aluminum
alloy surface relating to providing a good anchoring surface for
paint, lacquer, and photosensitive materials, such as diazo resins,
remains entirely unaffected by the prior anodization step with the
result that presensitized lithographic plates manufactured accordng
to the method of the present invention have a shelf life several
times that of conventional presensitized lithographic plates,
without formation of any black spots or other deterioration of the
plates during storage, or after the plates have been exposed and
developed.
* * * * *