CA1338693C - Photographic light-sensitive material having a polyester film support - Google Patents

Abstract

A photographic light-sensitive material is disclosed, which comprises a polyester film support having provided thereon at least one light-sensitive silver halide emulsion layer, the polyester film having a haze of up to 3% and a water content of not less than 0.5 wt%.

Description

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1338~93 -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 .
~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 ~- 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.

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 ~, .

~ 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, -4a -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 ~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 .

-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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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 .

~ 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 ' 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.

1'~386~3 --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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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-' 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 .

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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 --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%.

1338~93 -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 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, .

--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.

~ 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 .

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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.

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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.

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, ~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, 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 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 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) 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.

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 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 ` 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 -.

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.

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.

-- ~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 --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 .
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.

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 .
~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 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 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, 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) 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 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.

.

-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 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 , 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 .
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.

~ 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

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 ( 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 - - =

. 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 ~ 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 ~ .
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 .

,

Claims (13)

1. 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 containing as predominant constituents tereph-thalic acid component and a glycol component, said polyester film further comprising an aliphatic dicarboxylic acid com-ponent having 4 to 20 carbon atoms as a copolymerization 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 temperature of 150°C for ten minutes, the water content is measured after first moisture-conditioning the film under conditions of 23°C and 30% RH for three hours, next dipping the film in distilled water at 23°C for fifteen minutes and then measuring the water content using a micro-moisture meter at a drying temperature of 150°C, and the curl-extinguishing ratio is measured after first dipping the film in distilled water at 40°C for fifteen minutes, and then drying for three minutes in air in a thermostatic cham-ber maintained at 55°C while applying a load of 50g.

2. The photographic light-sensitive material as claimed in claim 1, wherein said polyester film is a polyester film containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component and having a brea-king strength of from 8 to 25 kg/mm2 and an initial modulus of from 200 to 500 kg/mm2.

3. The photographic light-sensitive material as claimed in claims 1 or 2, wherein said polyester film is a copolymeriz-ed polyethylene terephthalate film.

4. The photographic light-sensitive material as claimed in claim 2, wherein said aromatic dicarboxylic acid having a metal sulfonate group is selected from the group consisting of 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 2-sodium sulfotereph-thalic acid, 2-potassium sulfoterephthalic acid, 2-lithium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-po-tassium sulfophthalic acid, 4-lithium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, 4-potassium sulfo-2,6-naphthalenedicarboxylic acid, and 4-lithium sulfo-2,6-naphthalenedicarboxylic acid.

5. The photographic light-sensitive material as claimed in claim 2, wherein said polyester film mainly comprises terephthalic acid as a dicarboxylic acid component, and the copolymerization amount of said aromatic dicarboxylic acid component having a metal sulfonate group is 2 to 15 mol% based on the terephthalic acid component.

6. The photographic light-sensitive material as claimed in claim 1, wherein said aliphatic dicarboxylic acid component is selected from the group consisting of succinic acid, adipic acid and sebacic acid.

7. The photographic light-sensitive material as claimed in claim 1, wherein a polyalkylene glycol is used as an addi-tional copolymerizable component.

8, The photographic light-sensitive material as claimed in claim 3, wherein said polyester film contains a dye.

9. The photographic light-sensitive material as claimed in claim 3, wherein said polyester film has a subbing layer on its surface.

10. The photographic light-sensitive material as claimed in claim 1, wherein said light-sensitive material is a roll film.

11. The photographic light-sensitive material as claimed in claim 1, wherein said polyester film has a curl-extinguish-ing ratio of 80% or more.

12. The photographic light-sensitive material as claimed in claims 1 or 2, wherein said polyester film has a thickness of from 25 to 250 µm.

13. The photographic light-sensitive material as claimed in claim 12, wherein said polyester film has a thickness of from 40 to 150 µm.