U.S. patent number 3,853,584 [Application Number 05/331,948] was granted by the patent office on 1974-12-10 for process for the preparation of photographic materials.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Hiroyuki Kurabayashi, Nobuhiko Minagawa, Sumitaka Tatsuta, Wataru Ueno.
United States Patent |
3,853,584 |
Tatsuta , et al. |
December 10, 1974 |
PROCESS FOR THE PREPARATION OF PHOTOGRAPHIC MATERIALS
Abstract
An improvement in adhesion strength between a polystyrene resin
support and a gelatin-containing photographic emulsion layer is
attained by the pretreatment of the support in two steps in which
the first step comprises a surface-roughening treatment of the
polystyrene support and the second step comprises a subsequent
flame-treatment of the roughened polystyrene support carried out by
contacting the roughened surface of the support with a flame from a
combustible gas burner.
Inventors: |
Tatsuta; Sumitaka (Kanagawa,
JA), Ueno; Wataru (Kanagawa, JA), Minagawa;
Nobuhiko (Shizuoka, JA), Kurabayashi; Hiroyuki
(Shizuoka, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JA)
|
Family
ID: |
11886248 |
Appl.
No.: |
05/331,948 |
Filed: |
February 12, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Feb 14, 1972 [JA] |
|
|
47-15347 |
|
Current U.S.
Class: |
430/532; 430/234;
427/223; 430/536 |
Current CPC
Class: |
G03C
1/915 (20130101); C08J 7/02 (20130101); B29C
59/08 (20130101); G03C 1/795 (20130101); B29K
2025/00 (20130101) |
Current International
Class: |
B29C
59/08 (20060101); B29C 59/00 (20060101); C08J
7/00 (20060101); C08J 7/02 (20060101); G03C
1/795 (20060101); G03C 1/91 (20060101); G03c
001/78 () |
Field of
Search: |
;117/34,47A,138.8E
;96/87R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Trenor; William R.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What is claimed is:
1. A process for the preparation of a photographic material which
consists essentially of a combination in sequence of the steps of
firstly forming a plurality of minute pores having a diameter and
depth of from 0.1.mu. to 60.mu. in the surface of a polyetyrene
support by roughening, secondly subjecting the roughened surface of
the polystyrene support to flame-treatment, coating the resulting
flame-treated surface of the polystyrene support with an emulsion
or suspension containing gelatin, and drying the resulting
coating.
2. A process as claimed in claim 1 where the roughening is
performed by contacting the polystyrene with a solvent which
dissolves or swells the surface of the polystyrene to provide a
swollen surface layer and then contacting the polystyrene with a
non-solvent for the polystyrene which is miscible with the solvent,
whereby the swollen surface layer is coagulated.
3. A process as claimed in claim 1 where the polystyrene is a
homopolymer.
4. A process as claimed in claim 1 where the polystyrene is a
styrene-butadiene, styrene-acrylonitrile, styrene-propylene or
styrene-methyl methacrylate copolymer.
5. A process as claimed in claim 1 where the polystyrene contains a
white pigment.
6. A process as claimed in claim 1 where the flame treatment is
accomplished by continuously passing the polystyrene in web form in
contact with a flowing fuel gas/oxygen combustion flame.
7. A process as claimed in claim 6 where the emulsion or suspension
contains a silver halide.
8. A process as claimed in claim 6 where the emulsion or suspension
contains developing nuclei for a silver salt diffusion transfer
process.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for the preparation of a
photographic material.
2. Description of the Prior Art
Heretofore, baryta paper has been commonly used as a support base
for various photographic materials such as photographic printing
paper and diffusion transfer photographic paper. This baryta paper
is prepared by coating paper made from pulp with a kneaded mixture
consisting of fine particles of barium sulfate, a binder such as
gelatin and water. However, such a support material has often
suffered from a number of drawbacks such as poor dimensional
stability against varying moisture, shrinking which occurs after
development, delay in drying time after development and poor
resistance to water.
SUMMARY OF THE INVENTION
After elaborate studies for overcoming the above-mentioned
difficulties encountered upon the use of known baryta papers, we
reached the present invention.
The process of this invention is characterized by a two step
pretreatment, in sequence, of a polystyrene support which comprises
firstly roughening the surface of the polystyrene film support and
then flame-treating the roughened surface of the support. The
resulting support is then coated with an emulsion or suspension
containing gelatin as a binder.
The expression "emulsion or suspension containing gelatin as a
binder" used throughout the specification of this invention defines
such materials as are commonly used in this art and which are an
aqueous emulsion or aqueous suspension of gelatin containing one or
more silver halides such as silver chloride, silver bromide, silver
chlorobromide or silver iodobromide; or a light-sensitive diazo
compound, or a development nucleating substance for an
image-receiving composition used in a silver salt diffusion
transfer photographic process with or without any other substances
which may be admixed therewith as are commonly used in this
art.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be more fully explained in the following
description.
First, the support material used in this invention must be so
selected as to have equal or superior or mechanical or optical
characteristics to conventional paper since the purpose of the
present invention essentially resides in the provision of a
material to be used as a photographic printing paper. Nevertheless,
there has been found, up to the present, no synthetic resin which
possesses nearly the same degree of "toughness" or "crispiness" as
paper, with the exception of polystyrene. The present invention now
provides a process whereby a novel photographic material is
obtained by the use of polystyrene resin.
The polystyrene resin used in the process of the present invention
can be a homopolymer of styrene, or a copolymer of styrene with
other monomers, for example, styrene-butadiene copolymers,
acrylonitrile-styrene copolymers, styrene-propylene copolymers,
methylmethacrylate-styrene copolymers, .alpha.-methylstyrene
homopolymers, etc. More particularly, the use of impact-resistant
polystyrene, which is a copolymer of styrene with butadiene, is the
most desirable material for meeting the objects of the present
invention. To the above-mentioned polystyrene resin, one or more
resins of the resins such as ethylene-vinylacetate copolymers,
ethylene-acrylate copolymers, ethylene methacrylate ionomers,
ethylene-acrylic acid ionomers, butadiene-acrylonitrile copolymers,
ethylene-propylene copolymers, natural rubbers, synthetic isoprene
rubbers, butadiene rubbers, styrene-butadiene rubbers, highstyrene
content rubbers, polybutadienes, polybutene rubbers, chloropreno
rubbers, butyl rubbers, or various kinds of nitrile rubbers, may be
added and mixed therewith. The use of such resins is effective to
improve the surface flatness, molding or extruding properties,
control stiffness and increasing anti-tearing strength. These
materials are used in art-accepted amounts to improve the
properties recited.
No novelty per se is attached to the polystyrenes used in the
present invention, and they are best selected from those
polystyrenes known to the art to have excellent film forming
abilities. Such materials, and their properties, are so well
established that no further discussion will be offered thereon.
Throughout the specification, the term "polystyrene" or
"polystyrene resin" is used to include all of such homopolymers and
copolymers of styrene, unless otherwise specified.
When using polystyrene resin as the support material for
photographic printing paper, it must be preliminarily converted
into a white and opaque support. One method for effecting such
conversion comprises preliminarily admixing a white pigment into
the polystyrene resin and extruding the resultant resin compound
into a film. The white pigment used includes titanium dioxide,
barium sulfate, calcium sulfate barium carbonate, lithopone,
alumina white, calcium carbonate silica white etc. The particle
size of the white pigment is preferably less than about 1 .mu. and
the pigment may be incorporated in the range of from about 2 to
about 40 weight parts, preferably 5 to 30 weight parts, based on
100 weight parts of the resin component. Other dyestuffs or
fluorescent brightenining agents known to the art may be further
added to increase the whiteness of the resulting resin.
The polystyrene thus filled with the above pigments is then
extruded in a conventional manner, and if desired, biaxially
stretched to give a white and opaque film having excellent
properties such as textural strength, water repellency, dimensional
stability etc., which are most desirable in a support material for
photographic materials.
However, since polystyrene is inherently hydrophobic and chemically
inactive, it is most difficult to ensure firm adhesion between the
support and a hydrophilic photographic emulsion containing gelatin
which is to be applied onto the surface of the support.
The use of a polystyrene support as a transparent support material
for negative photographic films having flat surface has been
proposed. However, it has only been unsuccessfully utilized because
no practical or effective method for firmly bonding the
photographic emulsion layer to the support base has been yet
establised. In this respect, we have discovered an improved process
whereby strong adhesion between the roughened polystyrene support
and the gelatin-containing photographic emulsion layer can be
attained successfully.
The process of the present invention comprises the combination, in
sequence, of the following two steps:
1. A first step in which the surface of polystyrene support is
subjected to roughening treatment; and
2. a subsequent step in which the roughened surface of the
polystyrene support is subjected to flame-treatment.
By employing these two steps in combination, a polystyrene support
can be readily and firmly bonded to a layer of an emulsion or
suspension containing gelatin.
It should be noted that the adhesion between the polystyrene
support and the gelatin-containing layer fails if only one of the
above two steps is applied to the support.
Flame-treatment itself has hitherto been applied to polyolefin
resins for the purpose of improving printability and adhesiveness.
In the case of polyolefin resins which have an inherently smooth
surface, a marked improvement in adhesion strength can be attained
with the use of flame-treatment alone. On the ohter hand, as will
be shown in the examples, the adhesiveness of a polystyrene resin
is not at all improved by the application of the flame-treatment
alone.
According to the process of this invention, an outstanding increase
in the adhesion strength is achieved only by carrying out
flame-treatment in combination with a preceeding roughening
treatment of the surface of the polystyrene support, and such a
result is quite surprising and unexpected from prior teachings.
In addition, it is quite an unexpected benefit that the polystyrene
support treated in accordance with the process of this invention
never loses its strong adhesion even after extended periods of
time. This is contrary to what occurs in the case of the
flame-treatment of smooth-surfaced polyolefin resins. Accordingly,
the aging stability of the adhesiveness of the polystyrene support
obtained by the process of this invention is quite unique and
satisfactory for the practical use thereof.
The details of steps (1) and (2) are described below.
The surface-roughening treatment of polystyrene support, i.e., step
(1), is carried out by contacting the polystyrene film with a
solvent capable of dissolving or swelling the polystyrene resin,
such as tetrahydrofuran, methyl acetate, ethyl acetate, acetone,
methyl ethyl ketone, methyl isobutyl ketone, methylene chloride,
ethylene chloride, cyclohexane, benzene, dimethyl formamide and
mixtures thereof, to thereby form a swollen layer on the surface of
the polystyrene, and then contacting the resultant film with a
liquid which is miscible with the above solvent but which is not
comparible with or dissolves the polystyrene resin, i.e.,
non-solvent for polystyrene, to thereby coagulate the swollen layer
while forming a roughened surface with minute protruding and
recessed portions. The contact of the film with the solvent or with
the non-solvent is practically conducted by dipping the film in the
organic solvent or by applying the organic solvent to the film with
the use of roller coaters, brushes or by spraying it, etc. The
details of the procedure are disclosed in U.S. Pat. No.
3,515,567.
The support thus treated now has formed on its surface a layer with
a number of minute pores each having a diameter and depth of from
0.1 .mu. to 50 - 60 .mu., so that incident light striking the
surface is randomly reflected to give a white and opaque surface
which can be satisfactorily utilized as a material for supporting a
gelatin-containing photographic emulsion to give a desirable
photographic printing paper, even if the support is originally
transparent.
Accordingly, it is not always necessary to preliminarily admix a
white pigment with the polystyrene support. It will thus be
understood that the polystyrene support used in this invention is
substantially white and opaque regardless of whether it is filled
with white pigment or not, and the only important factor is that
the support be a white and opaque film.
Roughening treatments other than the above-described process which
can also be used in the practice of this invention include, for
example, roughening by mechanical abrasion, foaming upon
film-forming procedure by the expansion of a suitable thermally
expanding foaming agents, roughening by selective dissolution of a
soluble foreign substance added in the support, such as ethylene
oxide, after the resin is formed into a film and the like. Any of
these known surface-roughen treatments may be employed in the
practice of the present invention without substantially impairing
the advantageous features of the invention.
The flame-treatment of this invention, i.e., step (2), is carried
out by using a burner placed transversely to the running web and by
blowing a flame generated by the combustion of a fuel gas and
oxygen onto the roughened surface of the film while optionally
cooling the opposite side of the web by contacting it with a
chilled roller.
The gaseous fuel can be a paraffinic hydrocarbon, olefinic
hydrocarbon, carbon monoxide, hydrogen or a like combustible gas.
However, the use of a paraffinic hydrocarbon is most desirable in
view of its safeness and economy.
The mixing ratio of the fuel gas to oxygen is determined so that
oxygen is present in a greater than equivalent amount to the fuel
gas. In general, the larger the proportion of oxygen, the better
will be the flame stability and the higher will be the
effectiveness of the flame-treatment. However, too much oxygen will
cause "flash back" or "back fire" and will lead to the
extinguishment of the flame. It is therefore important to
appropriately adjust the amount of oxygen so as not to invite such
an undesirable phenomenon whatever gaseous fuel is used. The limit
of oxygen ratio will be easily determined by the results of simple
experiments, i.e., if flash back occurs, decrease oxygen until
steady burning is achieved.
It is supposed that the surface treatment of the polystyrene film
during the flame-treatment reaches as high as
300.degree.-2,000.degree.C at instantaneous moments, and the degree
of the surface temperature is dependent not only on the flow rates
of the fuel gas and oxygen or air but also on the running speed of
the web. The exact conditions chosen will, of course, depend to a
certain extent upon the exact apparatus used, but optimum
conditions can always be determined empirically, if necessary.
Generally speaking, one can select one or more variables to be held
constant and then alter one other variable, e.g., hold fuel gas and
oxygen flow rate constant while varying web speed, to determine
optimum conditions which yield the most suitable product for the
specific end use proposed.
In the case when the support treated is a stretched polystyrene
film, care must be taken so as not to heat the film to a
temperature over the glass transition point to prevent the film
from softening and shrinking.
As long as the flame-treatment of the roughened polystyrene support
is carried out under carefully controlled conditions in the manner
as described above it is not only possible to impart excellent
adhesion over relatively wide conditions as opposed to the rather
narrow conditions employed in case of the flame-treatment of
polyolefins which is conducted under strictly restricted conditions
such as controlled oxygen content, flame temperature and
temperature difference between the film surface and back of the
film during the treatment.
The invention will be more fully illustrated in detail by referring
to the following examples. The method for testing the adhesion
strength between the polystyrene support and the layer of the
emulsion or suspension coated thereon employed in the following
examples was as follows:
1. Test of Adhesion Strength in the Dry State
Onto a sample piece prepared by coating a polystyrene support with
an emulsion containing gelatin as a binder to form coated film
there was bonded a cellulose triacetate film 0.14 mm thick with an
epoxy resin adhesive. The bonded film was allowed to stand for 24
hours at a temperature of 23.degree.C under a relative humidity of
65 percent and then cut into a strip 1 cm wide and 15 cm long.
Thereafter, the cellulose triacetate film was stripped off by
peeling it at a drawing speed of 7.38 cm/min. The stripping
strength was measured with the use of a resistance strain meter. In
the examples, the expression "good adhesion" means that the test
sample had an adhesion strength of at least 8 g/mm, which
corresponds to a sufficient stripping strength for the practical
use of the film as a photographic material.
2. Test of Adhesion Strength in the Wet State
A polystyrene/emulsion sample as was used in the test (1) was
wetted after it had been developed, fixed or water-rinsed, and a
cellulose triacetate film was bonded thereto with a cyanoacrylate
adhesive in the same manner as in test (1). The bonded film was
then directly subjected to measurement of the stripping resistance.
In the wet test, the expression "good adhesion" means, similarly to
test (1), a stripping strength of more than 2 g/mm. In the
following examples, "part" or "parts" means "part or parts by
weight."
EXAMPLE 1
An impact resistant biaxially stretched polystyrene film 0.2 mm was
dipped in acetone for 3 seconds than immersed in methanol for
another 30 seconds to give a white, opaque support having on its
surface a minute porous layer. The support was then conveyed at a
running speed of 80 m/min. while blowing flame onto the roughened
surface from a burner placed at a distance (burner tip to the film)
of 8 mm and having a 10 cm nozzle (flame width) with a slit gap of
0.2 mm. The burner was fed with a gaseous mixture of propane and
oxygen at a rate of 80 lit./hr. and 500 lit./hr., respectively.
The thus flame-treated film was then coated with a black-and-white
silver halide photographic emulsion having the following
composition (material per square meter of the film):
Silver Chlorobromide 3.5 g Gelatin (binder) 13.0 g Formaldehyde 0.1
g Saponi (wetting agent) 0.03 g Water to make the entire emulsion
130 cc.
The results of a stripping test of the film coated with the above
emulsion to examine the adhesion strength between the film support
and the coated emulsion layer showed that the film had good
adhesion, i.e., a stripping strength of 19 g/mm in the dry state
and 6 g/mm in the wet state.
On the other hand, another photographic material prepared by
coating the surface-roughened impact-resistant polystyrene support
with the above photographic emulsion without flame treatment had a
stripping strength of 0.5 g/mm in the dry state and 0 g/mm in the
wet state. A similar experiment under the same condition but
without the surface roughening treatment showed a complete absence
of adhesive strength in both the dry state and the wet state.
EXAMPLE 2
An impact resistant polystyrene film containing 13 percent titanium
dioxide having a thickness of 0.25 mm was treated with methyl ethyl
ketone on one side and dried to give a support film having a
lustrous surface with an extremely minute porous structure. The
solvent-treated side of the support was subjected to
flame-treatment with the use of the burner described in Example 1
at a support conveying speed of 80 m/min. while feeding propane and
oxygen to the burner at a rate of 100 lit./hr. and 1,600 lit./hr.,
respectively. The distance of the support to the burner tip was 5
cm.
The thus treated surface of the film was coated with an aqueous
gelatin solution of the follwing composition as an undercoat
liquid:
Gelatin 10 g Formalin (a 20 % aqueous solution) 4 cc Water 190
cc
Onto the resultant undercoat layer, there was coated a color-type
photographic silver halide emulsion of the following
composition:
Silver chlorobromide 3.0 g Gelatin 3.5 g Emulsified dispersion
containing an aqueous solution containing 1 g of
benzoylaceto-2-chloro-5-dodecyloxycarbonyl anilide (yellow
coupler)., 1 g of gelatin and 0.5 g of dibutylphthalate 14.0 g
Triethylene phosphamide (3 % solution in acetone) 3.0 ml. Polyvinyl
pyrolidone 0.7 g
A stripping test on the resultant film coated with the above color
photographic emulsion indicated an adhesion strength as required in
a color photographic material.
On the other hand, a similar photographic material prepared by
coating with the same liquids used above onto a roughened,
filler-containing and impact resistant polystyrene film without a
flame treatment completely failed to bonding in the dry or wet
state.
EXAMPLE 3
A polystyrene support 0.1 mm thick was dipped in methyl isobutyl
ketone for 2 seconds, dried in air for 30 seconds and then soaked
for 30 seconds in ethanol to give a white and opaque polystyrene
film having a microporous layer on the support surface. The thus
roughened polystyrene support was flame-treated under the same
conditions as employed in Example 2 and thereafter coated with the
following liquid (per square meter of film) so as to form an image
receiving layer to be used in a silver salt diffusion transfer
process.
______________________________________ Gelatin (binder) 3 g
Colloidal silver sulfide (developing nuclei) 0.001 g Phenyl
mercaptotetrazol (toning agent) 0.001 g Saponin (wetting agent)
0.02 g ______________________________________
A stripping test on the thus prepared image-receiving material
proved that it had a sufficiently high adhesion strength for use as
an image-receiving material in a silver salt diffusion transfer
photographic process, whereas, an otherwise identical support to
which flame-treatment had not been applied or on which the
surface-roughening treatment had not been effected showed a
complete lack of adhesiveness between the coated layer and the
support.
EXAMPLE 4
A roughened, white and opaque impact resistant polystyrene support
obtained in the same manner as Example 2 was flame-treated under
the following conditions:
Propane flow rate: 200 lit./hr. Oxygen flow rate: 2500 lit./hr.
Distance between burner tip and film: 3 cm
During the flame treatment the temperature of a chilling roll
contacting the film at the opposite side of the suppport with
respect to the burner was kept at 35.degree.C.
The thus treated film was coated with a black-and-white silver
halide emulsion as in Example 1, dried and then subjected to a
strippint test. The film exhibited good adhesion between the coated
emulsion layer and the support.
The resultant black-and-white photographic film formed a beautiful
positive picture image after being printed with a negative
picture.
EXAMPLE 5
On a polystyrene film 0.2 mm thick filled with 10 percent by weight
titanium dioxide there were blown fine particles of silica sand of
a specific gravity of 2.2 and a particle size of 80 mesh at the
distance of 60 cm. to give a roughened polystyrene support having a
number of minute cavities of a depth of 1-3 .mu.. The thus
roughened film was flame-treated under the same conditions as
employed in Example 4 and then coated with a black-and-white silver
halide emulsion as used in Example 1 to give coated film with
extremely good adhesion. A picture printed on the resultant
photographic material through a negative picture gave a positive
picture image with a beautiful mat face and magnificient
feeling.
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.
* * * * *