BACKGROUND OF THE INVENTION
1) Field of the Invention
[0001] The present invention relates to a support sheet for a photographic printing paper.
More particularly, the present invention relates to a support sheet for a photographic
printing paper having an improved applicability to a photographic emulsion-coating
machine and automatic developing machine at a high speed.
2) Description of the Related Arts
[0002] Currently, a water-resistant resin-coated support sheet is generally used as the
support sheet for a photographic printing paper, to cope with the high speed developing
treatment required for photographic papers. This support sheet is prepared by the
extrusion-lamination method in which a molten heat-resistant resin is coated on both
surfaces of a substrate sheet, and then solidified by cooling. In general, the front
surface, on which a photographic emulsion layer is to be formed, is coated with a
resinous layer containing a white pigment, and the back surface is coated with a pigment-free
resinous layer.
[0003] In the resin-coated support sheet, the surface opposite to the front surface, on
which a photographic emulsion layer is to be formed, i.e., the back surface, is roughened
to enhance a slipping property to the surface of the photographic emulsion layer when
photographic papers are piled, or to improve the typewriter printability thereof.
[0004] The roughened back surface of the support sheet is formed in a manner such that,
in a melt extrusion coating of the back surface of the substrate sheet with a resinous
layer, a surface-roughened cooling roll surface is brought into contact with and pressed
against the molten resinous layer to transfer the roughened surface pattern of the
roll to the resinous layer. Optionally, a backcoat layer is further formed on the
roughened back surface coating resinous layer. This back coat layer imparts an enhanced
writing property, printability, and electroconductivity to the photographic paper.
[0005] Generally, the photographic paper is developed by using an automatic developing machine,
and the treating speed is usually 20 to 60 m/min in a developing zone and 30 to 100
m/min in a subsequent cutting zone. During this automatic developing operation, the
back surface of the photographic paper comes into contact with many fixed guides while
the photographic paper is advancing, and causes white deposits to be formed on the
guides. These deposits often are the cause of problems in the developing operation.
If the treatment speed is as high as 50 m/min or more, the generation of these white
deposits becomes conspicuous, and if the amount of the deposits becomes very large,
it is necessary to stop and clean the machine. The removal of the deposits is not
easy, and thus the productivity at the developing treatment is lowered, and therefore,
there is a need to solve this problem.
[0006] In the production of a photographic paper sheet, not only a silver halide photographic
emulsion layer but also a protecting layer, an undercoat layer or an intermediate
layer, or a halation-preventing layer or an ultraviolet ray-absorbing layer is coated,
each as a single layer or laminated multiple layers on the support sheet for a photographic
paper.
[0007] In a color-photographic paper sheet, a blue-sensitive emulsion layer and an intermediate
layer, a green-sensitive emulsion layer and an intermediate layer, and a red-sensitive
emulsion layer and a protecting layer are coated in the form of laminated layers on
a support sheet.
[0008] Recently, to reduce costs and enhance productivity, a method has been adopted in
which many emulsion layers are simultaneously formed by one coating operation. For
example, a simultaneous lamination of many emulsion layers is now possible by coating
methods such as the slide hopper method and the curtain coating method.
[0009] Furthermore, it is important that the coating of the emulsions be carried out at
a high speed, to increase productivity, and various methods of achieving this have
been investigated.
[0010] In each of these methods, in the photographic paper sheet produced by using the above-mentioned
support sheet for a photographic paper, a photographic emulsion layer having a smooth
and high gloss surface, a low gloss surface, a silk-like surface or a fine-grained
surface is formed in accordance with the surface conditions of the front surface coating
layer of the support sheet.
[0011] Since the front surface of the support sheet for photographic paper is usually hydrophobic,
as is well-known in the art, to firmly coat the front surface with a hydrophilic photographic
emulsion layer, the front surface of the support sheet, on which the photographic
emulsion layer is to be formed, is rendered hydrophilic by applying a corona discharge
treatment, a flame treatment or a cold plasma treatment.
[0012] Where a support sheet for photographic paper having a smooth and glossy surface is
coated with a photographic emulsion, the emulsion is generally applied at a speed
of 100 to 200 m/min, but where a support sheet for photographic paper has a roughened
surface, such as a silk-like surface, a low gloss surface or a fine-gained surface,
if the emulsion-coating speed is higher than 100 m/min, sometimes disadvantages such
as mottling of the emulsion layers (hereinafter referred to as "emulsion layer mottling")
and a repelling of the emulsion occur.
[0013] When the photographic paper sheet having the above-mentioned disadvantages such as
emulsion layer mottle and emulsion-repelling is subjected to photographic printing
and developing operations, the resultant photographic print has an uneven color density
and mottling occurs in a color print, and thus the photographic paper sheet is evaluated
as having a very poor quality.
[0014] Accordingly, a strong demand has arisen for a new type of support sheet for photographic
paper, which sheet has a front surface capable of being evenly coated with a photographic
emulsion at a high speed and high productivity without mottling or repelling of the
photographic emulsion.
SUMMARY OF THE INVENTION
[0015] An object of the present invention is to provide a support sheet for photographic
printing paper, which support sheet can be evenly coated with a photographic emulsion
at a high speed without a mottling or repelling of the photographic emulsion, and
is useful for producing photographic printing paper able to be developed by an automatic
developing machine at a high speed without forming white deposits.
[0016] The above-mentioned object can be attained by the support sheet of the present invention
for photographic printing paper, which comprises
a substrate sheet;
a front surface coating layer formed on the front surface of the substrate sheet (to
be coated with a photographic emulsion) and comprising a water-proof, thermoplastic
resinous material; and
a back surface coating layer formed on the back surface of the substrate sheet and
comprising a water-proof, thermoplastic resinous material,
at least one of the front and back surface coating layers having a number of fine
crater-shaped concavities adjacent to each other through ridgeline-shaped convexities.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017]
Figure 1 is an explanatory cross-sectional view of a roughened surface pattern formed
on a peripheral surface of a cooling roll by a mechanical surface-roughening method;
Fig. 2 is an explanatory cross-sectional view of a roughened surface pattern formed
by plating the roughened surface of the cooling roll shown in Fig. 1 with a metal;
and,
Fig. 3 is an explanatory cross-sectional view of a roughened surface pattern of a
resinous coating layer of a support sheet, transferred from by the roughened surface
of the cooling roll shown in Fig. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] The inventors of the present invention analyzed the white deposits produced in an
automatic developing machine to clarify the cause of this formation of white deposits,
and as a result found that, even in a support sheet having a backcoat layer, the white
deposits contain not only the backcoat composition but also a large amount of the
back surface coating layer-forming resin material (for example, polyethylene). That
is, the white deposits are formed in such a manner that, when the back surface is
in frictional contact with the fixed members of the developing machine at a high speed,
protruding portions of the backcoat layers are peeled and the resin material of the
coating layer is softened by frictional heat and protruding portions of the coating
layer are removed, and the removed portions of the backcoat layer and the coating
layer are fusion-bonded to one another. The inventors investigated this problem,
and as a result found that, when the back surface resinous coating layer has a roughened
surface pattern in which many fine crater shaped concavities are located adjacent
to each other through ridgeline shaped convexities, the production of white deposits
is reduced.
[0019] Also the inventors of the present invention carried out research into conditions
which allow a high-speed coating of a photographic emulsion on a front surface of
a support sheet without causing such disadvantages as emulsion layer mottle and repelling
of the emulsion, and as a result found that, when the front surface of the support
sheet has many smooth and round fine crater-shaped concavities adjoining one another
through ridgeline-shaped convexities, the emulsion-coating speed can be greatly increased.
[0020] It is known that a roughened surface is given to the resinous coating layer on the
front or back surface of a support sheet for photographic paper, but the conventional
roughened surface pattern has irregular mountain-valley type undulations.
[0021] In the support sheet of the present invention, at least one of the front and back
surface resinous coating layers has a number of fine crater-shaped concavities adjacent
to each other through ridgeline-shaped convexities.
[0022] The specific roughened surface of the front surface resinous coating layer of the
support sheet of the present invention effectively enables an even and smooth coating
of the photographic emulsion on the front surface resinous coating layer without mottling
and repelling of the resultant emulsion layers.
[0023] The reasons for the above-mentioned effect have not been completely elucidated, but
the following mechanism can be considered relevant thereto.
[0024] In the irregular mountain-valley type roughened surface, air is retained in the valley
portions (concavities), and when the emulsion is coated on the roughened surface at
a high coating speed, the air in the valley portions on the roughened surface is not
fully displaced by the emulsion, with the result that the emulsion layer mottle occurs,
or air on the roughened surface is inflated at the drying step, and the repelling
of the emulsion is probably caused by this inflation of air. In contrast, if an emulsion
layer is formed on the surface of the resinous coating layer having many smooth and
round fine crater shaped concavities adjoining one another, by a high-speed coating
method, the air in the craters on the roughened surface is easily and satisfactorily
displaced by the emulsion, and accordingly, it is considered that the emulsion layer
mottle or the repelling of the emulsion can be controlled.
[0025] Also, the specific roughened surface of the back surface resinous coating layer of
the support sheet of the present invention effectively prevents or restricts the production
of white deposits in the developing operation of the resultant photographic paper
sheet by an automatic developing machine.
[0026] The reason why the production of white deposits is prevented or restricted by the
specific roughened surface of the back surface resinous coating layer on the photographic
paper sheet obtained by using the support sheet of the present invention has not been
completely elucidated, but it is considered that this is probably due to the phenomenon
that only the tops of the ridgeline-shaped convexities formed between every two adjoining
fine crater-shaped concavities on the back surface of the photographic paper sheet
come into contact with the surfaces of fixed guides in the developing machine, and
since the frictional resistance therebetween is low, less heat is generated.
[0027] In the support sheet of the present invention, the crater-shaped concavities formed
on the resinous coating layer preferably have an average depth of 3 to 17 µm, more
preferably 4 to 15 µm, in terms of the ten point average surface roughness R
Z , determined in accordance with Japanese Industrial Standard (JIS) B 0601.
[0028] If the average depth of the crater-shaped concavities on the front surface is less
than 3 µm, the above-mentioned advantages of the roughened surface disappear when
the roughened front surface is coated with the photographic emulsion. Also, if the
average depth is more than 17 µm, when the emulsion is applied to the roughened surface,
the mottling and repelling of the emulsion layer often occur. If the average depth
of the crater-shaped concavities on the back surface is less than 3 µm, the back surface
of the resultant photographic paper sheet is in too close a contact with the photographic
emulsion layer surface of the next photographic paper sheet on which the above-mentioned
sheet is superimposed, and the slipping property of the back surface to the next sheet
photographic emulsion layer surface becomes unsatisfactory. Also, if the average depth
of the crater-shaped concavities or the average height of the ridgeline-shaped convexities
in the back surface coating layer is more than 17 µm, the ridgeline-shaped convexities
may scratch the photographic emulsion layer on which the back surface coating layer
is superimposed.
[0029] The crater-shaped concavities preferably have an average diameter of 5 to 30 µm,
more preferably 10 to 20 µm. If the average diameter of the crater-shaped concavities
in the front surface coating layer is less than 5 µm, the above-mentioned disadvantages
of the roughened surface disappear when the roughened front surface is coated with
the photographic emulsion.
[0030] When the average diameter of the crater-shaped concavities in the front surface coating
layer is more than 30 µm, and the resultant front surface is coated with the photographic
emulsion, the resultant photographic emulsion layer surface is mottled and irregularly
patterned.
[0031] In the roughened back surface coating layer, when the average diameter of the crater-shaped
concavities is less than 5 µm, the slipping property of the resultant roughened back
surface of the photographic paper sheet to the adjacent photographic emulsion layer
of another photographic paper sheet on which the above-mentioned sheet is superimposed
is poor, and thus the operability of the photographic paper sheets in the automatic
developing machine becomes poor. When the average diameter of the crater-shaped concavities
is more than 30 µm in the roughened back surface coating layer, the photographic emulsion
layer of the photographic paper sheet is scratched by the resultant roughened back
surface of another photographic paper sheet on which the above-mentioned sheet is
superimposed and thus the gloss of the front surface of the resultant photographic
paper sheet is reduced.
[0032] The substrate sheet usable for the support sheet of the present invention usually
consists of a paper sheet. This paper sheet is formed from a pulp material comprising
as a main component, a natural pulp, and optionally, a synthetic pulp or a synthetic
fibers. If necessary, an additive comprising at least one member selected from a sizing
agent, a strengthening agent, a fluorescent brightening agent, and an antistatic agent
may be internally added to the pulp material or coated on the paper sheet for the
support sheet.
[0033] In the support sheet of the present invention, the back or front surface coating
layer is formed from a thermoplastic, water-proof resinous material. There is no restriction
on the type of the resinous material, but preferably the thermoplastic resinous material
comprises a polyolefin resin, more preferably a polyethylene resin.
[0034] The thermoplastic resin coating layer can be easily surface-roughened by contact
with a roughened peripheral surface of a cooling roller when the thermoplastic resin
is extrusion coated onto a surface of a substrate sheet and while the coated thermoplastic
resin layer on the substrate sheet surface remains soft. The roughened surface of
the present invention having a number of crater-shaped concavities surrounded by a
number of ridgeline-shaped convexities is preferably formed by the following methods,
but the roughened surface-forming methods are not limited to those methods.
[0035] For example, a low gloss roughened surface can be formed on the thermoplastic resin
coating layer by the following method.
[0036] Referring to Fig. 1, a smooth peripheral surface of a steel roller plated or not
plated with copper, is mechanically roughened by applying a sand-blasting treatment
or a liquid honing treatment thereto to provide a number of fine convexities 1 and
concavities 2 on the peripheral surface.
[0037] The surface roughness of the resultant roughened surface of the steel roller is preferably
controlled to, for example, 3 to 17 µm, more preferably 4 to 15 µm, determined by
the ten point average surface roughness (R
Z) method, JIS B 0601.
[0038] After the peripheral surface of the steel roller is roughened to a predetermined
surface roughness, the resultant roughened surface is plated with a metal to form
a plating layer 3 as shown in Fig. 2, to cover the convexities 1 and the concavities
2 on the roller surface, and a number of hemisphere-shaped convexities 4 adjoining
each other through narrow concavities 5 are formed in the plating layer.
[0039] The metal to be plated is not limited to a specific group of metals, but in view
of the plating operability, hardness, and wear-resistance, the plating metal is preferably
a chromium material, more preferably a hard chromium material. Usually, the plating
layer has a thickness of 10 to 60 µm, more preferably 10 to 50 µm.
[0040] The resultant surface-roughened roller is used as a cooling roller for the coating
layer applied on the substrate sheet and comprising the thermoplastic resin.
[0041] When a thermoplastic resin is melt-extrusion coated on a surface of a substrate sheet,
the roughened peripheral surface of the cooling roller is pressed against the thermoplastic
resin coating layer to transfer the roughened surface pattern of the cooling roller
surface to the surface of the thermoplastic resin coating layer, to form a number
of crater-shaped concavities 6 adjoining each other at ridgeline (or narrow spin)-shaped
convexities 7 as shown in Fig. 3. Note, of course the concavities and convexities
on the cooling roller surface are inverse to the convexities and concavities on the
coating layer surface.
[0042] If the thickness of the plating metal layer on the cooling roller surface is less
than 10 µm, it is difficult to form hemispherical convexities having smooth and round
surfaces around the convexities formed on the cooling roller surface by the mechanical
surface roughening methods. Also, the resultant support sheet has an unsatisfactorily
roughened coating layer surface, and is not suitable for a photographic emulsion-coating
procedure at a high speed or for a developing procedure at a high speed.
[0043] If the thickness of the plating metal layer is more than 60 µm, the resultant plated
roller surface exhibits an unsatisfactory surface roughness, i.e., the resultant convexities
on the cooling roller surface have a low height, and thus the resultant crater-shaped
concavities on the coating layer have an excessively small depth.
[0044] This excessively small depth of the crater-shaped concavities on the coating layer
results in a poor gloss and feel of the photographic emulsion layer or in a poor processability
of the resultant photographic paper sheet in the automatic developing machine.
[0045] In the plating procedure for the mechanically surface-roughened cooling roller, there
is no specific restriction on the plating conditions, but the temperature of the plating
bath and the plating electric current density and other plating conditions should
be controlled to obtain a predetermined thickness of the plating metal layer.
[0046] To form a silk-like roughened surface on the front surface coating layer, an iron
core roller is optionally plated with copper and is subjected to a embossing treatment
using an embossing roller having, for example, a hexagonal pattern, the embossed surface
is subject to a mechanical roughened treatment to form very fine convexities and concavities
on the embossed surface, and the roughened surface is then plated. Where a satin gloss
is demanded for the front surface of the photographic paper sheet, the roughness of
the cooling roller surface is preferably 4 to 18 µm in terms of R
Z. The plating is preferably carried out with chromium, more preferably hard chromium.
Also, preferably the thickness of the plating layer is 10 to 60 µm. When this surface-roughened
cooling roller is used, the resultant front surface coating layer of the support sheet
has a silk-like roughened surface.
[0047] In the support sheet of the present invention, the front surface coating layer is
optionally coated with a sub-coat layer comprising a hydrophilic polymeric binder,
to enhance an adhesive force of the support sheet to the photographic emulsion layer.
Also, the back surface coating layer is optionally coated with a back-coat layer comprising
a hydrophilic polymeric binder and a pigment, to enhance the writing property, typewriting
property and antistatic property of the back surface of the resultant photographic
paper sheet.
EXAMPLES
[0048] The present invention will now be further explained with reference to the following
specific examples, which are only representative and do not limit the scope of present
invention in any way.
Example 1 and Comparative Example 1
[0049] In Example 1, a substrate sheet consisting of a paper sheet having a weight of 170
g/m² was activated by a corona discharge treatment and then coated on the front surface
thereof, on which a photographic emulsion layer was to be formed, with a resin composition
consisting of 64 parts by weight of a low density polyethylene resin having a density
of 0.92, 25 parts by weight of high-density polyethylene having a density of 0.96,
10 parts by weight of anatase type titanium dioxide powder, and 1 part by weight of
an additive comprising a pigment and an antioxidant, by a melt-extrusion laminating
method, to form a front surface coating layer having a thickness of 30 µm. Also, the
back surface of the substrate sheet was activated by a corona discharge treatment
and then coated, by the same method as mentioned above, with a resin composition consisting
of 50 parts by weight of low-density polyethylene having a density of 0.92 and 50
parts by weight of high-density polyethylene having a density of 0.96, to form a back
surface coating layer having a thickness of 30 µm.
[0050] When the melt-extrusion coating was carried out on the back surface of the substrate
sheet, a cooling roller having a roughened surface on which many hemispherical convexities
having an average diameter of 13 µm were formed was used and thus, on the roughened
surface of the back surface coating layer formed by using this cooling roll, many
fine crater-shaped concavities adjoining one another through ridgeline-shaped convexities
were formed. The average diameter of the craters was 13 µm, and the 10-point average
roughness of the roughened surface of the back surface coating layer was 6.0 µm.
[0051] The front surface coating layer on the substrate sheet was activated by a corona
discharge treatment and then coated with a gelatin solution containing a curing agent,
instead of a photographic emulsion, and dried to form a gelatine layer having a thickness
of 80 µm after drying.
[0052] The resultant gelatin layer-coated substrate sheet was slittered and rolled at a
width of 10 cm, and continuously fed from the roll into a cutter of a color printer
at the forwarding speed as shown in Table 1. After 200 meters of the sheet had passed
through the cutter, it was determined whether or not white deposits were produced
on the peripheral surfaces of fixed guides in the cutter.
[0053] The results of this determination are shown in Table 1.
[0054] In Comparative Example 1, the same procedures as in Example were carried out except
that the peripheral surface of the cooling roller had a number of groove-shaped concavities
spaced from each other, and exhibited a ten point average surface roughness (R
Z) of 8.4 µm, and the resultant back surface coating layer had an irregular mountain-valley
type roughened surface.
[0055] The results of the determination are shown in Table 1.
Table 1
Item |
|
Formation of white deposits |
|
|
Forwarding speed (m/min) |
Example No. |
Roughened surface pattern of back surface coating layer |
20 |
40 |
60 |
80 |
Example 1 |
Crater-ridgeline type |
None |
None |
None |
None |
Comparative Example 1 |
Irregular mountain-valley type |
(*)₁ Slight |
(*)₁ Slight |
(*)₂ Remarkable |
(*)₂ Remarkable |
(*)₁ ... A certain amount of white deposits was formed, but no cleaning operation
for the guide members was necessary. |
(*)₂ ... A large amount of white deposits was found, and cleaning of the guide members
was necessary. |
[0056] Table 1 clearly shows that the specific roughened surface of the back surface coating
layer of the present invention effectively prevents or restricts the production of
the white deposits in the automatic developing machine, even at a very high speed
of 80 m/min.
Examples 2 to 4 and Comparative Examples 2 to 4
[0057] In each of Examples 1 to 4 and Comparative Examples 2 to 4, a paper sheet having
a weight of 170 g/m² was used as a substrate sheet. A front surface on which a photographic
emulsion was to be coated, and a back surface opposite to the front surface, of the
substrate sheet were activated by a corona discharge treatment.
[0058] The activated back surface of the substrate sheet was melt-extrusion coated with
a mixture of high-density polyethylene (density = 0.94 g/cm³, melt index MI = 8.0)
and low-density polyethylene (density = 0.92 g/cm³, MI = 4.6) in a mixing weight ratio
of 1:1 at a resin temperature of 330°C to form a back surface coating layer having
a thickness of 30 µm.
[0059] The activated front surface of the substrate sheet was melt-extrusion coated with
a mixture of high-density polyethylene (density = 0.94 g/cm³, MI = 8.0) and low-density
polyethylene (density = 0.918 g/cm³, MI = 7.0), each containing 10% of titanium dioxide
(available under the trademark of A-220 from Ishihara Sangyo) in a mixing weight ratio
of 1:3 at a resin temperature of 320°C to form a front surface coating layer having
a thickness of 30 µm.
[0060] In the surface-coating procedures, a cooling roller having a roughened surface was
used to surface roughen the front surface coating layer in the pattern as indicated
in Table 2.
[0061] In Examples 2 to 4, the resultant roughened surface patterns were of the crater-ridgeline
type. The front surface coating layer had a low gloss face having an R
Z of 5.2 µm, in Example 2 a fine grained face having an R
Z of 7.5 µm in Example 3, and a silk-like roughened face having an R
Z of 13.4 µm in Example 4.
[0062] In Comparative Examples 2 to 4, the resultant roughened surface patterns were of
the mountain-valley type. The front surface coating layer had a low gloss face having
an R
Z of 6.5 µm in Comparative Example 2, a fine grained face having an R
Z of 7.1 µm in Comparative Example 3, and a silk-like roughened face having an R
Z of 16.3 µm in Comparative Example 4.
[0063] Each of the resultant front surface coating layers was activated by a corona discharge
treatment and a photographic emulsion was applied to the activated surface of the
front surface coating layer, at the coating speeds as indicated in Table 2.
[0064] In the photographic emulsion-coating procedure, it was observed whether or not mottling
and repelling of the emulsion were generated on the front surface coating layer.
[0065] The results of the observation are shown in Table 2.
Table 2
Item |
Back surface coating layer |
Photographic emulsion layer |
|
|
|
|
|
Coating speed (m/min) |
Rz |
Glossness |
Example No. |
Type |
Roughened surface pattern |
100 |
120 |
140 |
180 |
1 µm |
(%) |
Example 2 |
Low gloss |
Crater-ridgeline |
(*) Good |
Good |
Good |
Good |
5.2 |
75.0 |
Comparative Example 2 |
" |
Mountain-valley |
Not good |
Bad |
Bad |
Bad |
6.5 |
72.5 |
Example 3 |
Fine grained |
Crater-ridgeline |
Good |
Good |
Good |
Good |
7.5 |
63.2 |
Comparative Example 3 |
" |
Mountain-valley |
Not good |
Bad |
Bad |
Bad |
7.1 |
65.7 |
Example 4 |
Silk-like roughened |
Crater-ridgeline |
Good |
Good |
Good |
Good |
13.4 |
38.5 |
Comparative Example 4 |
" |
Mountain-valley |
Not good |
Bad |
Bad |
Bad |
16.3 |
33.5 |
Note: |
|
|
|
|
|
|
|
|
Good .... No mottling and repelling of emulsion found. |
Not good ... Mottling and repelling of emulsion were found at the initial portion
of the coated emulsion layer. |
Bad ..... Mottling and repelling of emulsion were found over the entire coated emulsion
layer. |
[0066] Table 2 clearly shows that the specific roughened surfaces of the front surface coating
layers are effective for enabling an even, smooth coating of the photographic emulsion
thereon.