Note: Descriptions are shown in the official language in which they were submitted.
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1338~93
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PHOTOGRAPHIC LIGHT-SENSITIVE M~ RTAT.
HAVING A POLYESTER FII~ SUPPORT
FIELD OF THE INVENTION
This invention relate6 to a photographic light-
sensitive material and, more particularly, to a photo-
graphic light-sensitive material which comprises a
support of a polyester material and which has a light
transparency and excellent curl-extinguishing properties
after development proce~sing, and these properties are
i n~rpen~ nt of environment with a lapse of time .
BACRGROUND OF THE INVENTION
Photographic light-sensitive materials are
generally produced by coating at least one photographic
light-sensitive layer on a plastic film support. A8 the
plastic film, fiber type polymers represented by
triacetyl cellulose (hereinafter abbreviated as "TAC" )
and polyester type polymers represented by polyethylene
terephthalate (hereinafter abbreviatéd as "PET" ) are
generally used.
PET has conventionally been considered to
substitute for TAC due to its .~yrPl 1 ~nt productivity,
mechanical strength and dimensional stability. In the
rolled state widely employed for photographic light-
sensitive materials, however, PET has a strong tendency
-- 1 --
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~38~93
to retain the curl from being in the rolled state, and
hence its h~n~ n~ properties after development
processing are 80 poor that the scope of its application
has been limited in spite of the above-described
excellent properties.
Photographic light-sensitive materials
generally include sheet form types such as X-ray films,
platc ~-kin~ films and cut films and roll films. Typical
examples of the roll films are color or black-and-white
negative-working films of 35 mm or less in width retained
in a cartridge and adapted to be loaded in ordinary
cameras for taking photographs.
On the other hand, the greatest aspect as a
photographic support of TAC films mainly used for roll
films is that they are optically non-anisotropic and have
a high transparency. In addition, they have another
excellent aspect. That is, they possess ~YrDl 1 ~nt
properties as to curl-extinguishing after development
processing . Since TAC f ilms have comparatively high
water-absorbing properties for plastic films due to their
molecular structure, the molecular chain is fluidized
upon absorption of water during development processing
and the curling tendency imparted by being kept in a
rolled state as roll film for a long time is extinguished
as a result of rearrangement of the molecular chain which
-- 2 --
~- 13386~3
had been set ~f ter belng rolled f or a long tLme . With
photographic light-sensitLve materials using f ilms which
do not have the curling tendency-extinguishing properties
of TAC films, however, there arise problems of, for
example, flaw formation, unfocusing, and ~amming upon
conveying when used in a rolled state, for example, in
the printing step of forming an image on a photographic
printing paper af ter development .
Recently, acceleration of fil~L-conveying speed
upon photographing, enhancement of photographing
magnif ication, and reduction in size of photographing
apparatuses have become L- rk;lhle. In such situatlons,
supports for photographic light-sensitive materials are
required to have enough strength, dimensional stability,
reduction in film thickness, etc., to meet these new
advances .
However, the above-descri~ed TAC provides only
a fragile film when formed into film due to its rigid
molecular structure and cannot be used in for these
advances. Additionally, PET film~ cannot be used as a
roll film where the curling tendency is problematical, in
spite of their ~srDl 1 ~nt mechanical properties . Thus,
consi~r;~hle ~ ~ ov t in PET films is greatly desired.
-- 3 --
13386g3
U.S. Patents 4,217,441 and 4,241,170 disclose
that a PET film - 'i fied by reacting with a certain
specific - _ _ ' i8 employed as a support for a
photographic material. In thls case, however, there
arise problems that the f ilm becomes whitening by a
processing and a lapse of time, and the transparency of
the film is ~imini~h~d~ Therefore, further i.l.~r~.Y~ ts
for the trAn~rency of the film h~ve been desired.
SU~MARY OF T~}E
Therefore, an object of the present invention
is to provide a photographic light-sensitive material
which ~ a polyester film support having a hiqh
transparency and .~7rcel 7 ~nt mechanical properties, and
which has ~Yc~ nt curl-extinquishing properties after
d~ve1
-- 4 --
~,
.
~ 1338~9~
According to the invention there is provided a
photographic light-sensitive material, which comprises a polyester film
support having provided thereon at least one light-sensitive silver
halide emulsion layer, said polyester film having a haze of up to 3%, a
water content of from 0.5 wt.-% to 5.0 wt.-%, a curl-extinguishing ratio of
50% or more, and ront:linin~ as prl~nmin~nt ~nn~tih1.ontc terephthalic
acid ~ulllpu~ and a glycol component, said polyester film further
comprising an aliphatic dicarboxylic acid ~:Ulll~JUllt~ having 4 to 20
carbon atoms as a copolym~ri7~tion component in an amount of from 3
to 25 mol% based on the terephthalic acid component, wherein the haze
is measured in accordance with ASTM D1003-52 after heat treatment of
the film at a ~ ld~Ult~ of 150C for ten minutes, the water content is
measured after first moisture--nn~itionin~ the film under conditions of
23C and 30% RE~ for thr~e hours, next dipping the film in distilled water =~
at 23C for fifteen minutes and then measuring the water content using a
micro-moisture meter at a dr,ving ~ ld~Ult~ of 150C, and the curl-
extinguishing ratio is measured after first dipping the film in distilled
water at 40C for fifteen minutes, and then drying for three minutes in
air in a thermostatic chamber m~int:-in~od at 55~C while applying a load
of 50g.
D~T~TT.T~.n DT~ RTT~TI(~N OF TTIE TNVF~l~TrC?N
In the present invention, the water content of polyester film
is measured by moisture-~nn~litinnin~ the film under the l~on-iitinnc of
23C, 30% RH and 3 hours,
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1338693
dipping the film in 23C distilled water for 15 minutes,
and then using a micro-moisture meter (for example, model
CA-02, made by Mitsubishi Chemical Industries, Ltd. ) at a
drying temperature of 150C.
The polyester film in accordance with the
present invention is characterized in that the water
content measured in the above-described manner is not
less than 0 . 5 wt& and preferably is from 0 . 6 to 5 . O wt96 .
If the water content is less than 0.5 wt96,
curling tendency-extinguishing properties a~ter
development processing are not improved, whereas if the
water content is too large, .1~ n;1l stability is
deteriorated due to absorption of moisture.
The polyester film of the present invention has
a curl-extinguishing ratio of 50~ or more and preferably
80~ or more.
In the present invention, the term ~'polyester'~
means a polyester containing as pre~i~ i n~nt constituents
an aromatic dibasic acid and a glycol. Typical examples
of the dibasic acid include terephthalic acid and
isophthalic acid, and examples of the glycol include
ethylene glycol, propylene glycol, butanediol, neopentyl
glycol, l,4-cyclr~h~Y~n~ ol, diethylene glycol, etc. Of
the polyester films comprising these ~ nts, poly-
ethylene terephthalate (PET) is most convenient from the
-- 5 --
~338693
st~n~iroint of avAi l~hil ity, and hence descriptLons
hereinafter will be made by reference to PET.
Copolymerized PET films preferably used in
the present invention comprise copoly -- ~ed PET films
containing a metal ~ulfonate-containing aromatic
dicarboxylic acid ~_ ~nt as a copolymerizable
^-l t .
Specific ~ l~s of the metal sulfonate-
containing aromatic dicarboxylic acid include 5-sodium
sulfoisophthalic acLd, 2-sodium sulfoterephthalic acid,
4-sodium sulfophthallc acid, 4-sodium sulfo-2,6-
naphthalenedicarboxylic acid and c, ~ wherein
sodium of the above-described compounds is replaced by
another metal (for example, potassium or lithium). The
copolymerization proportion Qf the metal sulfonate-
containing aromatic dicarboxylic acid component is
preferably about 2 to 15 mol%, particularly preferably
about 4 to 10 mol~, based on the aromatic dibasic acid
-~nt, e.g., the terephthalic acid component.
Copolymerization of an aliphatic dicarboxylic
acid component containing 4 to 20 carbon atoms In the
copolymerized PET film is preferable in view of
transparency, particularly depression of whitening and
F~nl~i~n~ t of bending resistance of the copolymerized
PET film.
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~3869
As specific ~YAmr~ P~ of the aliphatic
dicarboxylic acid component containing 4 to 20 carbon
atoms, there are illustrated succinic acid, adipic acid,
sebacic acid, etc., with adipic acid being particularly
preferable. The copolymerization proportion of the
aliphatic tl{~ rh~ylic acid component containing 4 to 20
carbon atoms is preferably about 3 to 25 mol%, particu-
larly preferably about 5 to 20 mol%, based on the
terephthalic acid ~- ~nt.
Additionally, in the polyester fLlm of the
present invention, other acid - ^- ts or glycol
components may further be copolymerized in a small
proportion so as not to inhibit transparency and
mechanical properties. For example, polyalkylene glycol,
particularly polyethylene glycol, may be copolymerized in
~ proportion of 0 to 10 wt% based on the amount of the
polyester produced. The polyalkylene glycols to be used
for the above-described ob~ects preferably have a
molecular ~eight of about 600 to 10,000. The polyester
film of th~ present invention preferably comprises a
polymer having an intrinsic viscosity of about 0 . 5 to 0 . 9
measured in o-chlorophenol at 25 C .
Further, various additives may be incorporated
in the polyester fllm of the present invention.
In using a polyester film as a support for a photographic
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1338693
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light-sensitive material, one of the problems is a
problem of light piping due to a high refractive index
of the support. As photographic supports, there are
generally used triacetyl cellulose (TAC) and polyester
type polymers represented by PET. One of the great
optical differences between TAC and PET is the refractive
index. PET has a refractive index of about 1.6, whereas
TAC has a smaller refractive index of 1. 5 . On the other
hand, gelatin mainly used in the subbing layer and
photographic emulsion layer has a refractive index of
1.50 to 1.55. Thus, the ratio of the refractive index of
gelatin to that of PET is 1. 5/1. 6, which is smaller than
1. Therefore, when light streams through a film edge,
the light is liable to be reflected at the interface
between the base and emulsion layer, thus polyester type
films are liable to cause so-called light piping.
As techniques f or avoiding the light piping
r~n~ ' there are known, for example, a technique of
incorporating inert inorganic particles or the like in
the f ilm and a technique of adding a dye . A technique of
preventing light piping pref erably employed in the
present invention is the technique of adding a dye which
does not seriously raise film haze.
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1338693
Dyes to be used for dyeing film are not
particularly limited, but the tone is preferably gray in
view of the general properties of light-sensitive
materials. Dyes to be employed are preferably those
which have an ~Y~ t heat resistance in a temperature
region where polyester film is formed and have an
excellent compatibility with polyester.
From the a~ove-described point of view, dyes
commercially available as dyes for polyesters such as
Diaresin made by Nitsubishi Chemical Industries, Ltd. and
Rayaset made by Nippon ~ayaku R.R. may be used for
attaining the above-described ob~ect.
As to dyeing density, at least a color density
in the visible region of 0.01 measured by a color
densitometer made by Macbeth Co . is necessary, with O . 03
or more being more preferable.
To the polyester f ilm in accordance with the
present invention may be imparted lubricating properties
as the application demands. There are no limits as to
techniques for imparting lubricating properties, but a
technique of knP~i { n~ an inert inorganic compound into
the film or a technique of coating a surfactant is
employed in general.
~denotes trade mark
_ g _
X
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13386g3
The inert inorganic particles are illustrated
by SiO2, TiO2, BaS04, CaC03, talc, kaolin, etc. In
addition, a technique of adding the inert p2rticles to
the polyester-synthesizing reaction system to impart -=
lubricating properties by the external particle system
and a technique of precipitating catalyst or the like
having been added upon the polymerization reaction of
polyester to impart lubricating properties by the
internal particle system are also employable.
Since transparency i5 an important factor as a
support for photographic light-sensitive material6, SiO2
having a comparatively approximate refractive index to
that of polyester f ilm is pref erably ~elected a~ the
external particle system, or an internal particle system
c2pable of precipitating particles of a comparatively
small particle size is preferably selected as the
internal particle system, which, however, do not limit
the technique of imparting lubricating properties.
Further, in the case of imparting lubricating
properties by the kn~ iin~ technique, it is also prefer-
able to laminate a layer which functions to impart
transparency to the film. As the technique for lamina-
tion, there is illustrated a coextruding process using a
plurality of extruders and a feed block or multi-manifold
die .
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~ 133869~
In the present invention, precipitation of low-
polymerized product upon thermal treatment for forming a
Eubbing layer sometimes takes place with some copolymeri-
zation ratio. In such a situation, it is possible to
laminate an ordinary polyester layer on at least one side
of the support. For this lamination, too, the co-
extruding process is employed as an effective technique.
Starting polymers for the copolymerized PET
film of the present invention can be syn~h-si~ed
according to conventionally known processes for producing
polyesters. For example, copoly ~^d PET can be
obtained by directly sub~ecting the dibasic acid
^-~t and the glycol component to an esterification
reaction at a temperature of about 200C to 270C and
removing a theoretical amount of water or, by using a
lower alkyl ester as the dibasic acid ~ t, and
conducting an ester interchange reaction between the
dibasic acid c ^-~t and the glycol ~ t at a
temperature of about 100C to 250C and removing a
theoretical amount of lower alcohol to obtain a glycol
ester of the dibasic acid or a low molecular weight
polymer. Then, the product obtained is heated at a
temperature of about 200C to 300C under a pressure
gradually reduced to about l Torr to remove excess glycol
-~t. In this situation, an ester interchange
-- 11 --
' 13386~
reaction catalyst or a polymerization reaction catalyst
described in U.S. Patents 2,647,885 and 2,739,957,
British Patents 742,196 and 770,531 may be used, or a
heat resistant st~hlli~n~ agent described in the above
patents may be added thereto.
The thus-obtained copolymerized PET is
generally granulated, dried, melt-extruded to form an
unstretched film sheet, then biaxially stretched and
heat-treated to obtain the end f ilm .
The biaxial stretching may be conducted
successively in the order of longitudinal direction and
transverse direction or in the reverse order, or simulta-
neously in two directions. The stretching ratio is not
particularly limited, but is usually 2 . 0 to 5 . 0 times .
Restretching in the transverse or longitudinal direction
may be conducted af ter stretching in the transverse or
longitudinal direction.
As a drying technique in the present invention
employed before melt-extrusion, a vacuum drying technique
or a ~hllm~7iflcation-drying technique is preferable.
Stretching temperatures in the present inven-
tion are desirably from 70 to 100C upon longitudinal
stretching and from 80 to 160C upon transverse
stretching .
~ eat-setting temperatures are from 150 to
210C, particularly preferably from 60 to 200C.
-- 12 --
1'~386~3
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The thickness of the copolymerized PET film to
be used in the present invention may properly be
determined ~lep-~n~lin~ upon the end--use of photographic
film, and is desirably from 25 to 250 ,um, more desirably
from 40 to 150 ,um.
The copolymerization formulation of the present
invention does not spoil the excellent transparency and
mechanical strength which PET essentially possesses, and
provides a film haze of up to 39~, a breaking strength of
from 8 to 25 kg/mm2, an Lnitlal modulus of from 200 to
500 kg/mm2, and a tear ~trength at a thickness of 120 ,um
of not less than 30 g. If the strength is less than the
above-described range, the ~ Pl 1 Pnt mechanical strength
which PET essentially possesses is spoiled and, thus, the
superiority over TAC is lost.
In the present invention, transparency,
breaking strength, initial modulu~ and tear strength are
measured a~ follows.
Transparency
Haze of a film is measured according to ASTM
D1003-52 after a heat treatment of the film at a tempera-
ture of 150C for 10 minutes. This heat treatment is
usually sub~ected to a film support at a coating step of
a pllotographic layer.
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3869
Breakinq Strenqth and Initial Nodulus
A sample of 10 mm in width and 100 mm in length
is sub jected to mea ,ul, t according to JIS Z1702-1976
employing a pulling rate o~ 300 mm/min for measuring
breaking strength and 20 mm/min for measuring initial
modulus .
The polyeste~ film suFport of the presen~ invention
is characterized in its ~Yre~ nt curling tendency-
extinguishing properties after development processing
(hereinafter referred to as curl-extinguishing ratio).
In the present invention, the curl-extinguishing ratio
measured according to the following method is preferably
50% or more, particularly preferably 80~6 or more.
Neasurement of Curl-Extinguishing Ratio
A sample of 12 cm x 35 cm in size is wound
around a core of 10 mm in diameter and is kept under the
conditions of 60C x 30~ RH x 72 hrs. Then, it 18
unwound from the core, dipped in 40C distilled water for
15 minutes, and dried for 3 minutes in a 55C air thermo-
-- 14 --
'
133~69~
static chamber while applying a load of 50 g. The length
of the thus-treated sample is measured in a perpendicu-
larly suspended state to evaluate the degree of restora-
tion to the original length of 12 cm.
The copolymerized PET film to be used in the
present invention has a better 4dhesiveness to various
coating layers such as emulsion layers than conventional
PET f ilms .
The polyester film o~ the present inventiOn may, ii
necessary, be previously sub~ected to corona discharge
treatment, treatment with a ~ h~ l solution or f lame
treatment . Of these surf ace treatments, corona discharge
treatment is most preferably used in the present
invention, since it causes less precipitation of low-
poly 7~d product on the f ilm surf ace .
The polyester support of the present invention
preferably has a subbing layer for ~nhAnrin~ adhesion to
a photographic layer such as a light-sensitive layer to
be coated thereon.
As the subbing layer, there are illustrated a
subbing layer using a polymer latex composed of a
styrene-butadiene type copolymer or a vinylidene chloride
copolymer and a subbing layer using a hydrophilic binder
such as gelatin
-- 15 _
I 33869~
The subbing layer using a hydrophilic binder is
pref erably used as the su~bing layer in the present
invention .
As the hydrophilic binder to be used in the
present invention, there are illustrated, for example,
water-soluble polymers, cellulose esters, latex polymers
and water-soluble polyesters. q`he water-soluble polymers
include gelatin, gelatin derivatives, casein, agar-agar,
sodium alginate, starch, polyvinyl alcohol, polyacrylic
acid copolymers and maleic anhydride copolymers, and the
cellulose esters include caLl,o~ -thyl cellulose and
ydL~xy~:thyl r~ 1 ose . The latex polymers include vinyl
rh 1 t~r~ -containing copolymers, vinylidene chloride-
containing copolymers, acrylic ester-containing
copolymers, vinyl acetate-containing copolymers and
butadiene-containing copolymers. Of these, gelatin is
most pref erable .
As compounds capable of swelling the support to
be used in the present invention, there are illustrated,
for example, resorcin, chlororesorcin, methylresorcin, o-
cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-
chlorophenol, dichlorophenol, trichlorophenol, mono-
chloroacetic acid, dichloroacetic acid, trifluoroacetic
acid, and chloral hydrate. Of these, resorcin and p-
chlorophenol are preferable.
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~38693
Various gelatin hardeners may be used in the
subbing layer of the present invention.
As the gelatin hardeners, there are illus-
trated, for example, chromium salts (e.g., chromium
alum ), a ldehydes ( e . g ., f ~ rr ~ 1 r~ r~h yde and g lut ~ r~ 1 ~i r~h yde ),
isocyanates , active halogen compounds ( e . g ., 2 , 4-
dichloro-6-hydroxy-s-tr~ n~) and epichlorohydrin resin.
The subbing layer of the present invention may
contain fine particles of 2n inorganic substance such as
SiO2 or TiO2 or fine particles ( 1 to 10 ~Lm) of polymethyl
methacrylate copolymer as matting agents.
The subbing layer of the present invention may
be coated according to a generally well known coating
process such as a dip coating process, an air knife
coating process, a curtain coating process, a wire bar
coating process, a gravure coating process, or an
extrusion coating process.
The light-sensitive material of the present
invention may have light-insensitive layers such as an
antihalation layer, an interlayer, a backing layer and a
surface protecting layer in addition to light-sensitive
layers .
The binder f or the backing layer may be a
hydrophobic polymer, or may be a hydrophilic polymer as
used f or the subbing layer .
-- 17 --
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-- 1338693
The backing layer of the light-sensitive
material in accordance with the present invention may
contain an antistatic agent, a slipping agent, a matting
agent, a surfactant, a dye, etc. The antistatic agents
to be used in the present invention are not particularly
limited and are, for example, anionic high molecular
weight electrolytes such as high molecular weight
polymers containing carboYylic acid groups, carboxylic
acid salt groups or sulf onic acid groups ( e . g ., high
polymers as described in JP-A-48-22017 (the term "JP-A"
as used herein refers to a "published l~nPy~min~d Japanese
patent application" ), JP-s-46-24159 (the term "JP-B" as
used herein refers to an "PY~minP~ Japanese patent
~rlhl ;P;~ n") ~ A--51--3072~, ~A--51-129216, 3P A JJ ~.~42) and
cationic high polymers as descrlbed Ln JP-A-49-121523,
JP-A-48-91165, JP-B-49-24582, etc. Ionic surfactants
also include anionic and cationic surfactants and are
exemplified by those which are described in JP-A-49-
85826, JP-A-49-33630, U.S. Patents 2,992,108 and
3, 206, 312, JP-A-48-87826, JP-s-49-11567, JP-B-49--11568,
JP-A-55-70837, etc.
The most preferable antistatic agents for the
backing layer of the present invention are fine particles
of at least one crystalline metal oxide selected from
among ZnO, TiO2, SnO2, A12O3, In2O3, SiO2, MgO~ BaO and
MoO3, or a composite oxide thereof.
_ 18 --
1338693
Fine particles of the conductive crystalline
oxides or their composite oxides to be used in the
present invention have a volume resistivity of up to
107 S2-cm, more preferably up to 105 ~2.cm, and have a
particle size of 0 . 01 to 0 . 7 llm, particularly preferably
0 . 0 2 to 0 . 5 )lm .
Processes for producing the fine particles of
the conductive crystalline metal oxides or their
composite oxides to be used in the present invention are
described in detail in JP-A-56-l ~3~30 (corresponding to
U.S. Patent 4,495,276) and JP-A-60-258541. They can be
easily produced f irstly by producing f ine particles of
metal oxide through baking and heat-treating the
particles in the presence of a different atom capable of
improving conductivity; secondly by allowing a different
metal capable of improving conductivity to coexist upon
production of metal oxide f ine particles through baking;
or thirdly by reducing the oxygen concentration of the
atmosphere upon production of metal oxide f ine particles
through baking to thereby introduce an oxygen
deficiency. Examples of different atoms are: Al, In,
etc., for ZnO; Nb, Ta, etc., for TiO2; and Sb, Nb,
halogen atoms, etc., for SnO2. The different atom is
added in an amount of preferably 0.01 to 30 mol%,
particularly preferably 0.1 to 10 mol%.
-- 19 --
1338~93
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Photographic layer6 of the photographic light-
sensitive material for the present invention are now
described below. The most preferable ~y~mrll~R- of the
photographic light-sensitive material in accordance with
the present invention are silver halide photographic
light-sensitive materials which are e~ ~1 i f i ed by silver
halide color negative-working films, color positive-
working f ilms, color reversal f ilms and black-and-white
negative-working f ilms .
The photographic emulsion to be used in the
present invention can be prepared by the processes
described in P. Gli~fk~ ;, Chimie et Physique Photo-
qraphique (Paul Montel, 1967), G.F. Duffin, Photographic
Rion Chemistry (The Focal Press, 1966), V.L. Zelikman
et al~, Makinq and Coating Phot~ri~r)h~c Emulsion (The
Focal Press, 1964), etc. That is, any of an acidic
process, a neutral process and an i ;AC;~1 process may
be used. As a manner of reacting a soluble silver salt
with a soluble halide salt, any of one side mixing,
simultaneous mixing, and combinations thereof may be
employed .
A process of forming silver halide grains in
the presence of excess silver ion (called reverse mixing
process ) can be employed as well . A8 one type of the
simultaneous mixing, a process called a controlled double
-- 20 --
133869~
~et process wherein the pAg in a liquid phase in which
silver halide is formed is kept constant can be employed.
This process provides a silver halide emulsion containing
silver halide gr~ins of regular crystal form having an
approximately uniform grain size.
Two or more sLlver halide emulsions having been
separately prepared may be mixed for use.
During formation or physical ripening of silver
halide grains, cadmium salts, zinc salts, lead salts,
thallium salts, iridium salts or the complex salts
thereof, rhodium salts or the complex salts thereof, iron
salts or the complex salts thereof, etc., may be allowed
to coexist.
~ 8 a binder or protective colloid f or photo-
graphic emulsions, gelatin is advantageously used.
However, other hydrophilic colloids can be used as well.
For example, proteins such as gelatin derivatives, graft
polymers between gelatin and other high molecular weight
polymers, albumin, casein, etc.; cellulose derivatives
such as llyd~ y~:~hyl cellulose, caLbol.y thyl cellulose,
cellulose sulfate, etc.; sugar derivatives such as sodium
alginate , starch derivative , etc .; and various synthetic
macromolecular substances such as homopolymers or
copolymers ( e . g ., polyvinyl alcohol , partially
acetalized polyvinyl alcohol, poly-N-vinyl pyrrolidone,
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1338693
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polyacrylic acid, polymethacrylic acid, polyacrylamider
polyvinyl imidazole, polyvinyl pyrazole, etc. ) can be
used .
As gelatin, acid-processed gelatin or enzyme-
processed gelatin as described in Bull. Soc. Sci. Phot.
Japan, No. 16, p. 30 (1966) may be used as well as lime-
processed gelatin, and a gelatin hydrolyzate or an
enzyme-decomposed product can also be used. As gelatin
derivatives, those obtained by reacting gelatin with
various compounds such as acid halides, acid anhydrides,
isocyanates, bromoacetic acid, alkanesultones, vinyl-
sulf l~n Am i les, r- 1 p i m i ~e compounds, polyalkylene oxides,
epoxy compounds or the like can be used. Specific
f.YArplPÇ: thereof are described in U.S. Patents 2,614,928,
3,123,945, 3,186,846, 3,312,553, British Patents 861,414,
1,033,189, and 1,005,784, JP-s-42-26845, etc.
As the aforesaid gelatin graft polymers,
products prepared by grafting to gelatin a homo- or
copolymer of a vinyl monomer ~uch as acrylic acid,
methacrylic acid, esters or amides thereof, acrylo-
nitrile, styrene or the like can be used. In particular,
graft polymers between gelatin and a polymer having some
compatibility with gelatin such as a polymer of acrylic
acid, methacrylic acid, acrylamide, methacrylamide,
hydroxyalkyl methacrylate or the like are preferable.
-- 22 --
~ 13386~3
Examples of these are described in U . S . Patents
2,763,625, 2,831,767, 2,956,884, etc.
Typical synthetLc high molecular weight
substances are those described in, for example, West
German OLS 2,312,708, U.S. Patents 3,620,751 and
3,879,205 and JP-13-43-7561.
In the photographic emulsion to be used in the
present invention, various c _ i~ for preventing fog
or stabilizing the photographic properties during
production steps, storage, or photographic processing of
the light-sensitive material may be incorporated. That
is, many ~ known as antifogging or stabilizing
agents such as azoles (e.g., benzothiazolium 6alts,
nitroindazoles, nitrnhPn7imif~A701es, chlorobenz-
imidazoles, I,r hDn7imi~1A701es, mercaptothiazoles,
mercaptobenzothiazoles, merc~ptnhPn7imirl~7oles~ mercapto-
ll-h i;~ A7Qles, Pminotriazole8, benzotriazoles, nitrobenzo-
triazoles, mercaptotetrazoles (particularly, l-phenyl-5-
mercaptotetrazole), etc. ); mercaptopyri m i.1inP~; mercapto-
tr~A7inPf:; thioketo compounds (e.g., oxazolinethione,
etc. ); ~7Aindpnp~ (e.g., ~riA7AindPnp~l tetraazaindenes
( particularly, 4-hydroxy-substituted 1, 3, 3a, 7-tetra-
in~iPneS~ etc. ); pentAAzAin~lpnp~ etc. ); benzenethio-
sulfonic acid; benzenesulfinic acid; hpn7~nDsulfonamide;
etc ., may be added. For example, those described in U. S .
-- 23 --
.
133869
Patents 3,954,474 and 3,982,947, JP-B-52-28660, etc., may
be used.
The photographic emulsion layer of the photo-
graphic light-sensitive material in accordance with the
present invention may contain a polyalkylene oxide or its
ether, ester or amide derivative, a thioether compound, a
thiomorpholine, a quaternary ammonium salt compound, a
urethane derivative, a urea derivative, an imidazole
derivative, a 3-pyr~Ql i tlnnf~ etc ., for the purpose of
r~nh~ncin~ sensitivity or contrast or for accelerating
development. ~or example, those described in U.S.
Patents 2,400,532, 2,423,549, 2,716,062, 3,617,280,
3,772,021 and 3,808,003, British patent 1,488,991, etc.,
may be used.
The photographic emulsion used in the present
invention may be spectrally sensitized ~ith methine dyes,
or the like. Suitable dyes include cyanine dyes,
merocyanine dyes, complex cyanine dyes, complex
merocyanine dyes, holopolar cyanine dyes, hemicyanine
dyes, styryl dyes, hemioxonol dyes, etc. Particularly
usef ul dyes are those belonging to cyanine dyes,
merocyanine dyes, and complex merocyanine dyes. These
dyes may contain as a basic heterocyclic nucleus any of
the nuclei usually used for cyanine dyes.
-- 24 --
.
1338~93
That is, there can be contained a pyrroline
nucleus, an oxazoline nucleus, a thiazoline nucleus, a
pyrrole nucleus, an oxazole nucleus, a thiazole nucleus,
a selenazole nucleus, an imidazole nucleus, a tetrazole
nucleus , a pyridine nucleus , etc .; nuclei wherein an
alicyclic hydrocarbon ring or rings are fused to these
nuclei; and nuclei wherein an aromatic hydrocarbon ring
or rings are fused to these nuclei, i.e., an indolenine
nucleus, a b-n7in~ 1enine nucleus, an indole nucleus,
a ban7o~rA7Qle nucleus, a naphthoxazole nucleus, a benzo-
thiazole nucleus, a naphthothiazole nucleus, a benzo-
selenazole nucleus, a b~n7imi~lA7Ole nucleus, a quinoline
nucleus, etc. These nuclei may be substituted on the
carbon atom or atoms thereo~.
Merocyanine dyes or complex merocyanine dyes
contain, as a ketomethylene structure-containing nucleus,
a 5- or 6 ` - e:d heterocyclic nucleus such as a
pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-
th i Ot~'*A 701idine- 2, 4 -dione nucleus, a thiazolidine-2, 4 -
dione nucleus, a rho~An~nr~ nucleus, a th~r~hArhituric acid
nucleus, or the like.
Useful sensitizing dyes are described in, for ==
example, German Patent 929,080, U.S. Patents 2,231,658,
2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,g59,
3,672,897, 3,694,217, 4,025,349, 4,046,572, British
Patent 1,242,588, JP-B-44-14030 and JP-B-52-24844.
-- 25 --
1 338693
These sensitizing dyes may be used alone or in
combination. Combinations of 6ensitizing dyes are often
used for attaining, in particular, supersensitization.
Typical examples thereof are described in U. S . Patents
2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641,
3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,837,862, 4,026,707,
British Patents 1,344,281 and 1,507,803, JP-B-43-4936,
JP-B-53-12375, JP-A-52-110618, and JP-A-52-109925.
Dyes which themselves do not 6how a spectrally
sensitizing action or materials which do not substantial-
ly absorb visible light, showing ~u~eL~,e.~sitivity, may be
incorporated in the ~ n together with the sensi-
tizing dyes. For example, aminostilbenes substituted by
a nitrogen-containing heterocyclic group (for example,
those described in U.S. Patents 2,933,390 and 3,635,721),
aromatic organic acid-f-~r~ hyde condensates (for
example, those described in U.S. Patent 3,743,510),
cadmium 8alt8, A7r~ i n-l~n~ compounds, etc ., may be incorpo-
rated. Combinations described in U.S. Patents 3,615,613,
3,615,641, 3,617,295, 3,635,721 are particularly useful.
The light-sensitive material of the present
inYention may contain water-soluble dyes as f ilter dyes
or f or various purposes like ant i i rr~ Ation . Such dyes
include oxonol dyes, hr~mi~xnn~l dyes, styryl dyes,
-- 26 --
~38693
merocyanine dyes, cyanine dyes, and azo dyes. of these,
oxonol dyes, hemioxonol dyes, and merocyanine dyes are
useful. Specific examples of usable dyes are described
in British Patents 584,609 and 1,177,42g, JP-A-48-85130,
JP-A-49-99620, JP-A-49-114420, JP-A-52-108115, U.S.
Patents 2,274,782, 2,533,472, 2,956,879, 3,148,187,
3,177,078, 3,247,127, 3,540,887, 3,575,704, 3,653,905,
3,718,472, 4,071,312, and 4,070,352.
In the light-sensitive material obtained
according to the present invention, photographic emulsion
layers and other hydrophilic col~ l layers may contain
fluorescent brightening agents of sti lh~n~o~, tri~in~8,
oxazoles, coumarins, etc. These agents may be of a
water-soluble type or water-insoluble type, with the
latter being used in the f orm of a dispersion . Specif ic
examples of the fluorescent brightening agents are
described in U. S . Patents 2, 632, 701, 3, 269, 840,
3, 359 ,102, British Patents 852, 075 and 1, 319, 763 .
In the practice of the present invention, the
following known dye stabilizers can be used in combina-
tion. The color image stAhi l i 7ing agents to be used in
the pre6ent invention may be used alone or in combina-
tions of two or more. The known dye st~hi 1 i ~r8 include,
for example, hydroquinone derivatives described in U.S.
Patents 2,360,290, 2,418,613, 2,675,314, 2,701,197,
-- 27 --
13386~3
2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801,
2,816,028, British Patent 1,363,921, etc., gallic acid
derivatives described in U.S. Patents 3,457,079,
3,069,262, etc., p-alkoxyphenols described in U.S.
Patents 2,735,765 and 3,698,909, JP-B-49-20977,
JP-B-52-6623, etc., p-hydroxyphenols described in U.S.
Patents 3,432,300, 3,573,050, 3,574,627, 3,764,337,
JP-A-52-35633, JP-A-52-147434, JP-A-52-152225, etc.,
bisphenols described in U.S. Patent 3,700,455, and the
like .
The light-sensitive material prepared by the
present invention may contain hydroquinone derivatives,
aminophenol derivatives, gallic acid derivatives,
ascorbic acid derivatives, etc., as color fog preventing
agents . Specif ic examples thereof are described in U . S .
Patents 2,360,290, 2,336,327, 2,403,721, 2,418,613,
2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300,
2,735,765, JP-A-50-92988, JP-A-50-92989, JP-A-50-
93928, JP-A-50-110337, JP-A-52-146235, JP-s--50-23813,
etc .
The present invention may be applied to a
multilayered multicolor photographic material having at
least two light-sensitive layers different in spectral
sensitivity. Multilayered color photographic materials
usually comprise a support having provided thereon at
-- 28 --
133~693
least one red-sensitive emulsion layer, at least one
green-sensitive emulsion layer and at least one blue-
sensitive emulsion layer. The order of these layers may
be optionally selected as the case demands. Usually, the
red-sensitive emulsion layer is associated with a cyan-
forming coupler, the green-sensitLve emulsion layer is
associated with a magenta-forming coupler, and the blue-
sensitive emulsion layer is associated with a yellow-
forming coupler, though dLfferent combinations are
possible in some cases.
The most preferable light-sensitive materials
of the present invention are rolled color negative f ilms
for photoqr;~rh~n~ use.
I~nown color couplers may preferably be used in
the color negative-working f ilms of the present
invention .
That is, they may contain compounds capable of
forming dyes by the reaction with an oxidation product of
an aromatic amine ( usually primary amine ) developing
agent (hereinafter abbreviated as 'couplers' ). As the
couplers, nondiffusible couplers having a hydrophobic
group called a ballast group in the molecule are
desirable. The rollrlPr~ may be of either 4-equivalent
type or 2-e~uivalent type based on silver ion. Colored
couplers having color-correcting effects or couplers
-- 29 --
13386~3
capable of releasing a development inhibitor upon
development (called DIR couplers) may also be
incorporated. Couplers may be those which form a
colorless coupling reaction product.
As yellow color-forming couplers, known open
chain ketomethylene couplers may be used. Of these,
benzoylacetAni 1 i~lP type and pivaloylace~Ani 1 i~lP type
compounds are advantageous . Specif ic example~ of usable
yellow color-forming couplers are those described in U. S .
Patents 2,875,057, 3,265,506, 3,408,194, 3,551,155,
3,582,322, 3,725,072, 3,891,445, West German Patent
1,547,868, West German Patents (OLS)-2,219,917,
2,261,361, 2,414,006, British patent l,425,020, JP-B-51-
10783, JP-A-47-26133, JP-A-48-73147, JP-A-51-102636, JP-
A--50-6341, JP-A-50-123342, JP-A--50-130442, JP-A-51-21827,
JP-A-50-87650, JP-A-52-82424, JP-A-52-115219, etc.
As magenta color-forming couplers, pyrazolone
type compounds, indazolone type compounds, cyanoacetyl
compounds, etc., may be used, with pyrazolone type
compounds being particularly advantageous. Specific
examples of usable magenta color-forming couplers are
described in U.S. Patents 2,600,788, 2,983,608,
3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429,
3,558,319, 3,582,322, 3,615,506, 3,834,908, 3,891,445,
West German Patent 1,810,464, West German patents (OLS)
-- 30 --
1338~93
-
-
2,408,665, 2,417,945, 2,418,959, 2,424,467, JP-B-40-6031,
JP-A-51-20826, JP-A-52-58922, JP-A-49-129538, JP-A-49-
74027, JP-A-50-159336, JP-A-52-42121, JP-A-49-74028,
JP-A-50-60233, JP-A-51-26541, JP-A-53-55122, etc.
As cyan color-forming couplers, phenolic
compounds , naphtholic compounds , etc ., may be used .
Specif ic examples thereof are those described in U . S .
Patents 2,369,929, 2,434,272, 2,474,293, 2,521,908,
2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563,
3,583,971, 3,591,383, 3,767,411, 4,004,929, West German
patents (OLS) 2,414,830 and 2,454,329, JP-A-48-59838,
JP-A-51-26034, JP-A--48-5055, JP-A-51-146828, JP-A-52-
69624, JP-A-52-90932, etc.
As colored couplers, those which are described
in, for example, U.S. Patents 3,476,560, 2,521,903,
3,034,892, JP-B-44--2016, JP-B-38-22335, JP-B-42-11304,
JP-B-44-32461, JP-A-51-26034, JP-A-52-42121, West German
Patent (OLS) 2,418,959, etc., may be used.
As DIR couplers, those wh$ch are described in,
for example, U.S. Patent6 3,227,554, 3,617,291,
3,701,783, 3,790,384, 3,632,345, West German patents
(OLS) 2,414,006, 2,454,301, 2,454,329, British Patent
953,454, JP-A--52-69624, JP-A-49-122335, JP-B-51--16141,
etc., may be used.
-- 31 --
1338~3
-
C ~_ ~c capable oi releasing a development
inhibitor upon development may be incorporated in the
light-sensitive material in addition to the DIR couplers,
and those described in, for example, U.S. Patents
3,297,445, 3,379,529, West German Patent (OLS) 241,794,
JP-A-52-15271, JP-A-53-9116, etc., may be used.
The above-described couplers may be used in
combinations of two or more in one and the same layer, or
the same compound may be used in two or more different
layers .
These couplers are added to a photographic
emulsion layer in an amount of 2 x 10 3 mol to 5 x 10~1
mol, preferably 1 x 10 2 mol to 5 x 10 1 mol, per mol of
silver contained in the emulsion layer.
The couplers can be introduced into silver
halide emulsion layers in a known manner described in,
for example, U.S. Patent 2,322,027. For example, they
are dissolved in an alkyl phthalate (e.g., dibutyl
phthalate or dioctyl phthalate ), a phosphoric ester
(e.g., diphenyl phosphate, triphenyl phosphate, tricresyl
phosphate , dioctylbutyl phosphate ), a citric acid ester
( e . g ., tributyl acetylcitrate ), a benzoic acid ester
(e.g., octyl benzoate), an alkylamide (e.g., diethyl-
laurylamide), a fatty acid ester (e.g., dibutoxyethyl
succinate or dioctyl azelate) or in an organic solvent
-- 32 --
13386~3
having a boiling point of about 30C to about 150C such
as a lower alkyl acetate ( e . g ., ethyl acetate or butyl
~cetate), ethyl propionate, sec-butyl alcohol, methyl
isobutyl ketone, ,3-ethoxyethyl acetate, methyl cellosolve
or the like, and the resulting solution is dispersed in a
hydrophilic colloid. The above-described high boiling
organic solvent and the low boiling organic solvent may
be mixed f or use .
A dispersing process using a polymer as
described in JP-B-51-39853 and JP-A-51-59943 may also be
employed .
With couplers having an acid group such as a
carboxylic acid or a sulfonic acid group, they are
introduced into a hydrophilic colloid as an ~lk~l in~
aqueous solution.
The light-sensitive material prepared according
to the present invention may contain in its hydrophilic
colloidal layer an ultraviolet ray absorbent. Por
example, aryl group-substituted benzotriazole compounds
(e.g., those described in U.S. Patent 3,533,794), 4-
thiazolidone 1~ ( e . g ., those described in U . S .
Patents 3,314,794 and 3,352,681), benzophenone compounds
(e.g., those described in JP-A-46-2784), cinnamic acid
esters (e.g., those described in U.S. Patents 3,705,805
and 3,707,375), butadiene .1~ (e.g., those
-- 33 --
` 133869~
described in U.S. Patent 4,045,229) or benzoxazole
compounds ( e . g ., those described in U . S . Patent
3,700,455) may be used. Further, those which are
described in U.S. Patent 3,499,~62 and JP-A-54-48535 may
be used . Ultraviolet ray-absorbing couplers ( e . g ., a-
naphtholic cyan dye-f orming couplers ) or ultraviolet ray-
absorbing polymers may also be used. These ultraviolet
ray-absorbing agents may be mordanted to a specif ic layer
or layers.
In photographic processing of the light-
sensitive material of the present invention, any of known
processes may be used. The processing temperature is
usually selected between 18C and 50C. However, temper-
atures lower than 18C or higher than 50C may be
employed .
Either of development processing forming only
silver im~ges (black-and-white photo~ri~E~h~c processing)
or color photogr~phic processing comprising dye image-
f orming development processing may be used rll~r~nA i n~ upon
the end use.
Color developer generally comprises an alkaline
aqueous solution containing a color developing agent. As
the color developing agent, known primary aromatic amines
such as phenyl~n~ min~ (for example, 4-amino-N,N-
di ethylani 1 ine, 3 -methyl - 4 -amino -N, N-di ethylani 1 ine, 4 -
-- 34 --
.
1338693
2mino-N-ethyl-~ yd~ u~y~Lhy1 Ani 1 i ne, 3-methyl-4-amino-
N-ethyl-N-,~-hydroxyethylAni 1 in~, 3-methyl-4-amino-N-
ethyl-N-~-methanesulfonamidoethyl~ni 1 in~ 4-amino-3-
methyl-N-ethyl-N-,~-methoxyethyl~nilin~ etc.) may be
used .
In addition, those described in L.F.A. Nason,
Photographic Processing Chemistry (Focal Press, 1966),
pp. 226 to 229, U.S. Patents 2,193,015, 2,592,364,
JP-A-48-64933, etc., may also be used.
The color developer may further contain pH
buffers such as alkali metal sulfites, carbonates,
borates and phosphates, development inhibitors or anti-
foggants such a~ I,L~ q, iodides and organic anti-
foggants and, if necessary, may contain water softeners,
preservatives such as hydroxylamine, organic solvents
such as benzyl alcohol and diethylene glycol, development
accelerator6 such as polyethylene glycol, quaternary
ammonium salt~, and amines, dye-forming couplers,
competitive couplers, fogging agents such as sodium
borohydride, auxiliary developing agents such as
l-phenyl-3-pyrazolidone, viscosity-imparting agent,
polycarboxylic acid type chelating agents described in
U.S. Patent 4,083,723, anti~llri-l~nts described in West
German Patent (ûLS) 2,622,950, and the like.
-- 35 --
133869~
-
Color developed photographic emulsion layers
are usually bleached. Bleaching may be conducted
6eparately or simultaneously with fixing. As blP~chins
agents, compounds of polyvalent metals such as iron(III),
cobalt(III), chromium(VI), copper(II), etc., peracids,
quinones, nitroso compounds, etc., are used. For
example, ferricyanides, dLchromates, organic complex
salts of iron(III) or cobalt(III) such as complex salts
of aminopolycarboxylic acids (e.g., ethylPn,~rl;AminPtetra-
acetic acid, nitrilotriacetic acid, 1, 3-diamino-2-
propanoltetraacetic acid ) or organic acids ( e . g ., citric
acid, tartaric acid, malic acid, etc. ); persulfates and
pPrr n~i~ni~te8 ; nitrosophenol ; etc ., may be used .
Couplers of the present invention show a large color-
forming 2bility even in a bleaching solution or bleach-
fixing solution containing iron(III) sodium ethylene-
diaminetetraacetate or iron(III) i illm ethylene-
diaminetetraacetate, thus being advantageous in this
point as well. Iron(III) ethylPnP~ m;netetraacetate
complex salts are useful in both an independent bleaching
solution and a monobath bleach-f ixing solution .
To the bleaching or bleach-fixing solution may
be added various additives such as bleaching accelerators
described in U.S. Patents 3,042,520, 3,241,g66, JP-B-45-
8506, JP-B-45-8836, etc., and thiol compounds described
in JP-A-53-65732.
-- 36 --
-- ~338693
The present invention is now illustrated in
greater detail by reférence to the following examples
which, however, are not to be construed as limiting the
present invention in any way. Unless otherwise speci-
fied, all percents, ratios, etc., are by weight.
EXANPLE 1 _
( 1 ) Preparation of Polyester Film
0 . 1 Part by weight of calcium acetate mono-
hydrate and 0 . 03 part by weight of antimony trioxide were
added to 100 parts by weight of dimethyl terephthalate,
70 parts by weight of ethylene glycol, 10 parts by weight
of dimethyl 5-sodium sulfoisophthalate and 10 parts by
weight of dimethyl adipate in a reactor equipped with a
fractionating column, and an ester interchange reaction
was conducted by gradually heating and removing methanol
produced. After the temperature was reached to 230C,
the reaction was continued at this temperature until
38 parts by weight of methanol was distilled out.
0 . 05 Part by weight of trimethyl phosphate was added to
the resulting product, and the mixture was transferred to
a reactor equipped with a pressure--li~ini~:hin~ device and
the temperature was gradually raised and the pressure was
l ly reduced to finally 280C and not more than 1 mm
Hg, respectively, to conduct polymerization. Thus,
copolymerized PET was obtained after the lapse of 3 hours
-- 37 --
1338693
-
-
from the start of the reduction of pressure. The
intrinsic viscosity of the copolymerized PET was 0 . 65
measured in o~chlorophenol at 25C.
The resulting copolymerized PET was dried at
130C for 5 hours, then melt-extruded at 280C to
obtain an unstretched film. The film was then
successively stretched in a longitudinal direction at
90C with a stretching ratio of 3.5 times and then in a
transverse direction at 95C with a stretching ratio of
3.7 times, and heat-set at 200C for 5 seconds to obtain
a 50 llm thick hiA~riAlly stretched film. This film had a
haze of 1.2%, a breaking strength of 12 kg/mm, and an
initial modulus of 340 kg/mm, and had good transparency
and mechanical properties.
Additionally, transparency, breaking strength
and initial modulus were measured under the following
conditions .
Transparency:
Haze of a sample f ilm was measured according to
ASTM D1003-52 after a heat treatment of the film at a
temperature of 150C for 10 minutes.
Breakinq Strenqth and Initial ~odulus:
A sample of 10 mm in width and 100 mm in length
was sub~ected to mea IUL~ L according to JIS Z1702-1976
employing a pulling rate of 300 mm/min for measuring
-- 38 --
.
1338~3
-
-
breaking strength and 20 mm/min for measuring initial
modulus .
(2) Neas,ur t of Curl-Extinguishing Ratio:
The polyester film (50 llm thick) of the present
invention prepared as described above, a commercially
available PET film (50 ,um thick) and a commercially
available TAC film (125 llm thick) were sub~ected to
measurement of water content according to the method of
the present invention.
Further, curl-extinguishing ratio was measured
in a manner described below to obtain the results shown
in Table l.
Nethod f or Evaluating Curl-Extinquishing Deqree
A sample film of 12 cm x 35 cm in size was
wound around a core of 10 mm in diameter and was
sub~ected to treatment at 60C x 30% R~ x 72 hr. Then,
the film was unwound from the core, dipped in 40C
distilled water for 15 minute~, ~nd dried for 3 minutes
in a 55C air th- -_ Latic chamber while applying a load
of 50 g. The length of the thus-treated sample was
measured in a perpendicularly suspended state to evaluate
the degree of restor2tion to the original length of
12 cm.
-- 39 --
1~386~3
.
-
TABLE
Curl-
Water Dipping Extinguishing
Sample Content Treatment Ratio
(wt%)
TAC ( 125 ,um) 2 . 6 Treated 38
Not treated 14
PET ( 5 0 llm ) O . 4 Treated 16
Not treated 16
Present 0 . 7 Treated 9 8
InventiOn(50 ~Im) Not treated 20
As is clear from Table 1, it is seen that Folyester
f ilm in accordance with the present invention having a
water content of 0.7. wt% shows an e..LL -ly large curl-
extinguishing ratio.
( 3 ) Preparation of Photographic Light-Sensitive Material
( 3-1 ) Coating of Subbing Layer:
A subbing layer of the following formulation
was coated on each of the aforesaid polyester f ilm and
commercially available PET film after corona discharge
treatment of both sides of them. The corona discharge
treatment was conducted to a degree of 0 . 02 ~VA.min/m2 .
Gelatin 3 g
Distilled Water 250 cc
Sodium-sulfo-di-2-ethylhexyl- 0 . 05 g
succinate
Fn~-l~i~hyde 0.02 g
-- 40 --
.
~33~93
,
(3-2) Coating of Backing Layer:
A backing layer of the following formulation
was coated on one side of the subbed polyester f ilms .
Preparation of a Dispersion of Tin Oxide-Antimony Oxide
Composite
230 Parts by weight of stannic chloride hydrate
and 23 parts by weight of antimony trichloride were
dissolved in 3, 000 parts by weight of ethanol to obtain a
uniform solution. A 1 N sodium hydroxide aqueous
solution was dropwise added to the solution until the pH
of the solution became 3 to obtain a coprecipitate of
colloidal stannic oxide and antimony oxide. The thus-
obtained coprecipitate was allowed to stand at 50C for
24 hours to obtain a reddish brown colloidal precipitate.
The reddish bro~n colloidal precipitate was
separated by centrifugal separation. In order to remove
excess ions, water was added to the precipitate, followed
by centrifugal separation to wash ~ith water. This
washing procedure was repeated 3 times to remove excess
ions .
200 parts by weight of the colloidal
precipitate freed of excess ions was again dispersed in
1,500 parts by weight o~ water, and sprayed into a 600C
heated baking furnace to obtain a fine powder of a bluish
tin oxide-antimony oxide composite having an average
-- 41 --
1338693
particle size of 0 . 2 ,um. This fine powder had a specific
resistance of 25 Q.cm.
A mixture of 40 parts by weight of the above-
described fine powder and 60 parts by weight of water was
ad~usted to 7 . 0 in pH and, after being roughly dispersed
by a stirrer, the mixture was dispersed by a horizontal
sand mill (trade name: Dyno mill made by WILLY A.
BAC~OFEN AG) until a residential time became 30 minutes.
Coatinq of Backinq Layer
Formulation (A) shown below was coated in a dry
thickness of 0.3 ~m, and dried at 130C for 30 seconds.
Coating Solution (B) shown below was coated in a dry
thickness of 0.1 llm and dried at 130C for 2 minutes.
Formulation (A): parts by weiqht ~=
Dispersion of Conductive Fine 10
Particles
Gelatin
Water 27
Methanol 6 0
Resorcin 2
Polyoxyethylene Nonylphenyl Ether 0 . 01
- 42 --
1338693
Coatinq Solution (B~ for Forminq Coatinq Layer
parts by weiqht
Cellulose Triacetate
Acetone 7 0
Methanol 15
Dichloromethylene 10
p-Chlorophenol 4
( 3-3 ) Coating of Photographic Layers:
Photographic layers as described below were
provided on the side opposite to the backing layer-
coated side of the PET film of the present invention and
the commercially available PET film.
First Layer: Red-Sensitive Silver EIalide Low Sensitive
Layer
(1-a) Preparation of an Emulsion Solution for Forming
Low Sensitive Emulsion Layer
A silver bromoiodide emulsion containing 6 mol%
iodide taverage grain size: 0.6 llm; containing 100 g of
silver halide and 70 g of gelatin per kg of emulsion) was
prepared in an ordinary manner. To 1 kg of this emulsion
was added 130 cc of a 0.1 wt96 methanol solution of
anhydro-5, 5 ' -dichloro-9-ethyl-3, 3 ' -di ( 3-sulfopropyl ) -
thiacarbocyanine hydroxide pyridinium salt as a red-
sensitive sensitizer. Then, 20 cc of a 5 wt96 aqueous
s o lution of 5 -methyl- 7 -hydroxy- 2, 3, 4 -tr i ~ 7 S- i n~ l izine,
-- 43 --
133869~
330 g of Cyan Coupler Emulsion (1) of the following
formulation, and 20 g of Emulsion (2) were added thereto.
Further, 50 cc of a 2 wt% aqueous solution of
2-hydroxy-4, 6-dichlorotriazine sodium salt was added
thereto as a gelatin hardener to prepare an emulsion for
forming a low sensitive emulsion.
Emulsion ( 1 )
(i) 10 wt% Gelatin Aqueous Solution - 1,000 g
(ii) Sodium p-Dodecylbenzenesulfonate 5 g
Tricresyl Phosphate 60 cc
Cyan Coupler (C-7) 70 g
Ethyl Acetate 100 cc
A mixture of ( ii ) was made into a solution at
55C, and the resulting solution was added to (i)
previously heated to 55C, followed ~y emulsification in
a colloid mill.
Cyan Coupler ( C-7 ): _
0~ CO~U - (Cll ~ c . h ! ( t)
-- 44 --
1338~93
~~ Emulsion (2)
(i) 10 vt9s Gelatin Aqueous Solution 1,000 g
(ii) Sodium p-Dodecylbenzenesulfonate 5 g
Tricresyl Phosphate 60 cc
Cyan Coupler ( C-7 ) 6 g
DIR Cyan Coupler* 64 g
Ethyl Acetate lO0 cc
DIR Cyan Coupler:
~C ONH~
; O C l .H 2q
~N--N
~.
Second Layer: ~ed-SensitLve Silver Halide Middle
Sensitive Layer
(l-b) Preparation of an Emulsion Solution for Forming
Niddle-Sensitive Emulsion Layer
The following changes were conducted in the
above-described ( l-a ) .
Average grain size of emulsion: 0.9 llm
Amount of added red-sensitive sensitizing agent: 140 cc
-- 45 --
133869~
,
Amount of added emulsion: Emulsion (1), 240 g
r l Ri ~n ( 2 ), 10 g
Third Layer: Red-Sensitive Silver Halide Hiqh Sensitive
Layer
(l-c) Preparation of an Emulsion Solution for Forming
High Sensitive Emulsion Layer
The f ollowing changes were conducted in the
above ( l-a ) .
Average grain size of emulsion: 1.1 ,~Lm (grains of 1. 0 llm
or more in 6ize accounting for 50 wt% of the
total grains )
Amount of added red-sensitive sensitizing agent: 100 cc
Amount of added: lRi~n: Emulsion (l), 150 g
Fourth Layer: Gelatin Interlayer .
Fifth Layer: Green-Sensitive Silver ~alide Low Sensitive
Layer
(2-a) Preparation of an Emulsion Solution for Formlng
Low Sensitive Emulsion
A silver bromoiodide emulsion containing 6 mol~
iodide (average grain size: 0 . 6 llm; contaLning 100 g of
silver halide and 70 g of gelatin per kg of emulsion) was
prepared in a conventional manner. To l kg of this
emulsion was added 200 cc of a 0.1 wt% methanol solution
of 3, 3 ' -di ( 3-sulfoethyl ) -9-ethylbenzoxacarbocyanine
pyridinium salt as a green-sensitive sensitizing agent.
-- 46 --
.
1338693
-
Then, 20 cc of a 5 wt~ aqueous solution of 5-methyl-7-
hydroxy- 2, 3, 4 -~ r i A 7A i nd~)liz ine was added thereto, and
380 g of Magenta Coupler Emulsion (3) and 20 g of Nagenta
Coupler Emulsion (4) of the following formulations were
added thereto.
Further, 50 cc of a 2 wt% aqueous solution of
2-hydroxy-4,6-dichlorotriA 7~ n~ sodium salt was added
thereto as a gelatin hardener to prepare an emulsion
solution for forming a low sensitive emulsion.
Emulsion ( 3 )
(i) 10 wt~ Gelatin Aqueous Solution 1,000 g
(ii) Sodium p-Dodecylbenzenesulfonate 5 g
Tricresyl Phosphate 65 cc
Magenta Coupler (M-7 ) 6 g
Ethyl Acetate 110 cc
A mixture of ( ii ) was made into a solution at
55C, and the resulting solution was added to (i)
previously heated to 55C, followed by emulsification in
a colloid mill.
Maqenta Coupler (~-7 ):
1- ( 2, 4, 6 -trichlorophenyl ) - 3- ~ 3 - ( 2, 4 -di-t-pentyl-
phenoxyacetamido ) benzamido ] -5 -pyra zolone
-- 47 --
13386~3
Emulsion ( 4 )
(i) 10 wt% Gelatin Aqueous Solution 1,000 g
(ii) Sodium p-Dodecylbenzenesulfonate 5 g
Tricresyl Phosphate 65 cc
~agenta Coupler* 63 g
DIR Magenta Coupler** 60 g
Ethyl Acetate 110 cc
Emulsification was conducted in the same manner
a~ with Emulsion ( 3 ) .
** DIR Magenta Coupler:
1-{4-[2-(2,4-di-t-pentylphenoxy)but~n~m~ ]phenyl}-
3- ( 1-pyrrolidinyl ) -4- ( 1-phenyltetrazolyl-5-thio ) -5-
pyrazolone
* ~aqenta Coupler~
tC,H"~OCHtCO~;r~ N~` /~C
C ~ ~C .
C o
-- 48 --
, 1338~93
Sixth Layer: Green-Sensitive Silver Halide Middle
Sensitive Layer .
(2-b) Preparation of an Emulsion Solution for Forming -~
Middle-Sensitive Emulsion Layer
A silver bromoiodide emulsion containing 5 mol%
of iodide (average grain size: 0.9 ~lm; containing 100 g
of silver halide and 70 g of gelatin per kg of emulsion)
was prepared in a conventional manner.- To 1 kg of this
emulslon was added 150 cc of a methanol solution of the
green-sensitive sensitizer shown in (2-a). Then, 20 cc
of a 5 wt9~ aqueous solution of 5-methyl-7-hydroxy-2, 3, 4-
~riA7~inri~1izine was added thereto. Furthe~, 285 g of
the above-described Emulsion (3) and 15 g of the above-
described Emulsion ( 4 ) were added thereto .
In addition, 50 cc of a 2 wt~ aqueous solution
of 2-hydroxy-4,6-dichloro~r1A~1nf- sodLum salt was added
thereto as a gelatin hardener to prepare an emulsion
solution for forming a middle sensitive emulsion.
Seventh Layer: Green-Sensitive Silver Halide Hi~h
Sensitive Layer
(2-c) Preparation of an Emulsion Solution for Forming
High SensitLve Emulsion Layer
A silver bromoiodide emulsion containing 6 mol%
iodide (average grain size: 1.1 ,um; 50 wt% of the grains
based on the whole grains having a grain size of 1. 0 um
-- 49 --
1338693
.
or more; containing 100 g of silver halide and 70 g of
gelatin per kg of emulsion) was prepared in a conven-
tional manner. To 1 kg of this emulsion was added 80 cc
of a methanol solution of the green-sensitive sensitizing
agent shown in (2-a). Then, 20 cc of a 5 wt~ aqueous
solution of 5-methyl-7-hydroxy-2, 3, 4-1 ri A ~A ~ n~inlizine was
added thereto and, further, 200 g of Emulsion (3) was
added thereto.
5 0 cc of a 2 wt~ aqueous solution of 2-hydroxy-
4,6-dichlorotriA~;ne sodium salt was further added
thereto as a gelatin hardener to prepare an emulsion
solution for forming a high sensitive emulsion.
Eiqhth Layer: Yellow Filter Layer (dry thickness: _
1. 2 um) Comprisinq Yellow Colloidal Silver
Ninth Layer: ~lue-Sensitive SiLver Halide Low Sensitive
Layer
(3-a) Preparation of an Emulsion Solution for Forming
Low Sensitive Emulsion Layer
A silver bromoiodide emulsion containing 5 mol~
iodide (average grain size: 0.6 ,um; containing 100 g of
silver halide and 70 g of gelatin per kg of the emulsion)
was prepared in a conventional manner. To 1 kg of this
emulsion were added 20 cc of a 5 wt~ aqueous solu~ion of
5-methyl-7-hydroxy-2,3,4-~riA~n~ lizine and 600 g of
Yellow Coupler Emulsion (5) of the following formulation.
-- 50 --
~ 338693
.
Further, 50 cc of a 2 wt% aqueous solution of 2-hydroxy-
4,6-dichlorotr;~7in~ sodium salt was added thereto as a
gelatin hardener to prepare an emulsion solution for
forming a low sensitive emulsion.
Emulsion ( 5 )
(i) 10 wt% Gelatin Aqueous Solution 1,000 g
(ii) Sodium p-Dodecylbenzenesulfonate 5 g
Tricresyl Phosphate - 80 cc
Yellow Coupler* lO0 g
Yellow DIR Coupler** lO g
Ethyl Acetate 120 cc
* Yellow Coupler: _
~NH C O C1~H"
H,CO~COCH;CONH~
C O
** Yellow DIR Coupler
T ~ C .e
C ~: --C--C O--C H C O N H ~)
CH3 \~THCO(CH~
l t C,Ht,~O
N=N
t CsX
-- 51 --
1338693
Tenth Layer: Blue-Sensitive Silver Halide Middle
Sensitive Layer
The following changes were conducted in the
above ( 3-a ) .
Average grain size of emulsion: 0 . 9 llm
Amount of added emulsion: 400 g
Eleventh Layer: Blue-Sensitive Silver Halide High
Sensitive Layer - =-
The following changes were conducted in the
above ( 3-a ) .
Average grain size of emulsion: 1.1 llm (prdvided that
grains larger than 1. 0 ~m account for 50 wt% of
the total grains )
Amount of added emulsion: 200 g
Twelfth Layer: Surface Protectinq Layer
10 wt~ Gelatin Solution 1,000 cc
Sodium Dodecylbenzenesulf onate 4 0 mg
SiO2 Fine Particles (3.0 ,um) 50 mg
Sodium Polystyrenesulfonate 1 g
2-Hydroxy-4, 6-dichlorotriazine 5 0 mg
Additionally, amounts of coated silver for the
respective light-sensitive layer~ described above were as
follows: first layer (1.0 g/m2); second layer (0.8 g/m2);
third layer (1.2 g/m2); fifth layer (1.2 g/m2); sixth
layer ( 1. 0 g/m2 ); seventh layer ( 1. 2 g/m2 ); ninth layer
-- 52 --
1338693
( 0 . 6 g/m2 ); tenth layer ( 0 . 6 g/m2 ); and eleventh layer
(0.6 g/m ).
The thus-obtained color negative f ilm was cut
into a 35 mm size, and was loaded in a cartridge. After
leaving it for 10 days at 40C, photographing was
conducted using an ordinary camera, followed by
development processing the film as follows.
Processing Ste TemPerature Time
P ( C) (min)
Color Development 38 3
Stopping "
Washing with Water "
Bleaching " 2
Nashing with Water "
Fixing '~ 2
Washing with Water ~ 1
St~hili7in~ Bath "
1338~3
-
Processing solutions used have the following
f ormulations .
Color Developer:
Sodium Hydroxide 2 g
Sodium Sulf ite 2 g
Potassium Bromide O, 4 g
Sodium Chloride 1 g
Borax - 4 g
Hydroxylamine Sulfate 2 g
Disodium Ethyl~n~ mi n~tetraacetate 2 g
Dihydrate
4-Amino-3-methyl-N-ethyl-N- ( !3- 4 g
hydroxyethyl ) aniline Nonosulf ate
Water to make 1
Stopping Bath:
Sodium Thiosulfate 10 g
Ammonium Thiosulfate (70 wt~ aq. soln. ) 30 ml
Acetic Acid 30 ml
Sodium Acetate 5 g
Potash Alum 15 g
Water to make 1
-- 54 --
- - =
1338693
. I
.
Bleachinq Solution: .
Iron(III) Sodium Ethyl.onf~ m~n~tetra- 100 g
acetate Dihydrate
Potassium Bromide 50 g
Ammonium Nitrate 50 g
Borax 5 g
Aqueous Ammonia to ad~ust pH to 5 . 0
Water to make 1
Fixinq Solution:
Sodium Thiosulfate 150 g
Sodium Sulfite 15 g
Borax 12 g
Glacial Acetic Acid 15 ml
Potash Alum 20 g
Water to make 1
Stabilizinq Bath:
Borax 5 g
Sodium Citrate 5 g
Sodium Metaborate ~ tetrahydrate ) 3 g
Potash Alum 15 g
Water to make 1 ~
The curling state after development processing
was as follows. Light-sensitive materials containing a
commercially available PET film as a support failed to
extinguish curling properties, whereas light-sensitive
-- 55 --
~ 338693
material6 contalning polyester fiLm of the present
~nvention scarcely curled.
The light-sensitive material of the present
invention contains as a support a polyester film with an
P~rcPl 1Pnt mechanical strength, and enables removal of
curling properties while maintaining the mechanical
properties .
COMPARATIVE EXAMPLE
A 50 ,um thick hl~ l ly stretched
.... _ . _
polyester film having an intrinsic viscosity of
0 . 6 7 was prepared in the same manner as described in
Example 1 except that 10 parts by weight of polyethylene
glycol having a molecular weight of 4, 000 was used in
place of the same amount of dimethyl adipate. The
resulting film had a haze of 4.596, a breaking strength of
8 kg/mm2, an initial modulus of 320 kg/mm2, and very poor
transparency. When this film was not subjected to a heat
treatment for the measurement of haze, it had a high
transparency and had a haze of 2 . 0% .
A light-sensitive material was prepared in the
same manner as described in Example 1 using the hi i~ri il l Iy
stretched poLyester - film obtained above. After
development treatment, the exposed part of the f ilm
became opaque and developed images were not sharp. It is
clear from the above that the poLyester -film
-- 56 -
1338693
~ .
prepared in Comparative Example 1 above is not useful as
a support for a light-sensitive material.
Since the light-sensitive materials of the
present invention have ~c~ nt mechanical properties
and enable easy extinguishing of curling, they permit a
marked reduction in the thickness of the support even
when used as roll films and therefore render the size of
the cartridge compact or, in using the- same cartridge,
enable loading of longer f ilm . The polyester f ilm of the
present invention can be produced at a low casting
temperature and is not broken upon stretching and, in
spite of its high water content, it maintains the
essential merits of polyester film.
In addition, it suffers ~LL~ ly less
precipitation of oligomers in spite of the high water
content, thus suffering no detrimental influences on
photographic properties.
Further, it enables reduction of the humidity
of the wrapping case of light-sensitive materials, and
hence photographic properties change less with time
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 modif ications can be made
therein without departing f rom the spirit and scope
thereof .
-- 57 --
,
