JPH01244446A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To easily straighten a curled sensitive material after development by using a specified polyester film as the support. CONSTITUTION:A polyester film having <=3% haze and >=0.5wt.% water content is used as the support of a sensitive material. In case of <0.5wt.% water content, the straightening property is not satisfactory but an excessively high water content, e.g., >5wt.% water content deteriorates the dimensional stability. The polyester film is desirably formed with a copolymer contg. arom. dicarboxylic acid having metal sulfonate, e.g., 5-sodium sulfoisophthalate as a copolymerizable component so as to regulate the fracture strength to 8-25kg/mm<2> and the initial modulus of elasticity to 200-500kg/mm<2>. 4-20C aliphat. dicarboxylic acid, e.g., adipic acid is preferably incorporated into the copolymer as another copolymerizable component.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photographic light-sensitive material, and particularly to a photographic light-sensitive material that uses a polyester material as a support and has excellent curl removal properties after development. It is something.

BACKGROUND OF THE INVENTION Photographic materials are generally produced by coating at least one photographically sensitive layer on a plastic film support. As this plastic film, generally used are fiber-based polymers typified by triacetyl cellulose (hereinafter referred to as rTAcj) and polyester-based polymers typified by polyethylene terephthalate (hereinafter referred to as (PET)).

Conventionally, PET film has excellent productivity, mechanical strength,
It has also been considered to be a substitute for TAC due to its dimensional stability, but in roll form, which is widely used as a photographic light-sensitive material, strong curls remain, making it difficult to handle after processing. Although it has the above-mentioned excellent properties, its range of use has been limited.

In general, photographic materials are in sheet form such as X-ray film, plate-making film, and cut film, and typical roll films are 35m/m/m
It is stored in a patrone within the width or less,
It is a color or black and white film that is loaded into a general camera and used for taking pictures.

On the other hand, TAC, which is mainly used for roll films,
The most important feature of film as a photographic support is that it has no optical anisotropy and has high transparency. Even more-
One of its outstanding features is that it also has excellent properties in terms of decurling properties after development. That is, T
AC film has a relatively high water absorbency for a plastic film due to its molecular + a structure, so the curling that occurs when it is rolled as a roll film over time is caused by the molecular chains flowing due to water absorption during the development process. However, the immobilized molecular chains do not rearrange during rolling.

As a result, it has an excellent property of eliminating curls that have already formed. In the case of photographic light-sensitive materials such as 'FAC' that use films that do not have curl recovery properties, when used in roll form, for example, the printing process to form an image on photographic paper after development is difficult. in,
Problems such as scratches, defocus, and jamming during transportation may occur.

By the way, the uses of photographic photosensitive materials have diversified in recent years, such as faster film transport during photography, higher photographic magnification,
In addition, the miniaturization of imaging devices has progressed significantly. In this case, the support for the photosensitive +A material is required to have properties such as strength, dimensional stability, and thin film formation.

However, due to the rigid molecular structure of the above TAC, the quality of the film produced is fragile and cannot be used for these purposes, and even after development processing, curling is a problem in the roll film field. Although PET film has excellent mechanical properties, it has been difficult to use, and it has been desired to improve the PET film.

(Object of the Invention) Accordingly, an object of the present invention is to provide a photographic material which is made of a support having excellent transparency and mechanical properties and which can easily eliminate the curling of secals after development.

DISCLOSURE OF THE INVENTION These objects of the present invention are to provide a polyester film support.
- A photographic material having at least one photosensitive layer, characterized in that the haze of the polyester film is 3% or less and the water content is 0.5% by weight or more. .

To measure the moisture content of the polyester film of the present invention, the film is conditioned at 23°C, 130% RH for 23 hours, and then immersed in distilled water at 23°C for 15 minutes, followed by a trace moisture meter (for example, Mitsubishi Kasei (l-gacho CA-02
The drying temperature is 150°C.

The polyester film of the present invention has a water content of 0.0 as measured by this method. It is characterized in that it is 5% by weight or more, preferably 0. 6-5. It is 0% by weight.

Moisture content is 0. If the content is less than 5% by weight, curl removal after development will not be improved, and if the water content is too high, dimensional stability will deteriorate due to moisture absorption.

In the present invention, polyester is a polyester whose main components are aromatic dibasic acid and glycol. Typical dibasic acids include terephthalic acid and isophthalic acid, and glycols include ethylene glycol and propylene glycol. , butanediol, neopentyl glycol, 1°4-cyclohegizanediol, diethylene glycol, etc. Among the polyesters made of these components, from the point of view of ease of nesting, polyethylene terephthalate h(1) ET) is the most convenient.
This will be explained below using PET.

The copolymerized polyethylene terephthalate I film preferably used in the present invention is composed of a copolymerized polyethylene terephthalate film containing an aromatic dicarboxylic acid component having a metal sulfone+- as a copolymerization component.

Specific examples of the aromatic dicarboxylic acids having metal sulfone I. Su I Rium Surbeau 2,6
- Naphthalenecarboxylic acid and these Zugawa-Liu J.
, with other metals such as potassium and lithium. The copolymerization ratio of the aromatic dicarboxylic acid component having a metal sulfonate is preferably 2 to 2 to 40% relative to the telental acid component as the seed material.
15 mol %, particularly preferably 4 to 10 mol %.

Copolymerized polyethylene terephthalate 1-Fil L used in the present invention is further copolymerized with an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms to improve transparency, especially the surface of the Copolymerized polyethylene terephthalate I film. This is preferable from the viewpoint of suppressing whitening and folding durability.

Specific examples of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms include succinic acid, adipic acid, and sebacic acid, with adipic acid being particularly preferred.

The copolymerization ratio of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is preferably 3 to
25 mol%, particularly preferably 5 to 20%.

In addition, in the polyester film of the present invention, it is also possible to further copolymerize other acid components or glycol components as long as the proportion is small within a range that does not impair transparency and mechanical properties. For example, 0 to 10% by weight of polyalkylene glycol, especially polyethylene glycol, can be copolymerized. The molecular weight of the polyalkylene glycol used for this purpose is 600 to 10,
Preferably, it is 000.

Furthermore, the polyethylene terephthalate film 1 of the present invention
However, various additives may be contained therein. For example, one of the problematic properties when using a polyester film as a support for photographic +A materials is the problem of wavyness that occurs due to the high refractive index of the support. Photographic supports include triacetyl cellulose (TAC) and polyethylene terephthalate (PF).
, T) are commonly used, and one of the major differences in optical properties between TAC and PET is the refractive index. This refractive index is P
While UT is about 1.6, 1cTAc is small at 1.5.

On the other hand, the refractive index of ceratin, which is commonly used in photographic emulsion layers for subbing layers, is 1.50 to 1.55, and when taking the ratio of the refractive index of gelatin, it is 1.55 in PUT. 5/1
．． 6 and 1, and when light enters from the film edge, it is easily reflected at the interface between the hese and the emulsion layer. Therefore,
Polyester films cause what is called a light piping phenomenon (edge fog).

Known methods for avoiding such Lie I piping phenomenon include a method of containing inert inorganic particles in the film and a method of adding a dye. In the present invention, a preferred method for preventing Lie I/piping is a method using dye addition which does not significantly increase film haze.

There are special restrictions regarding dyes used for film dyeing.
+++Although the color tone is not very good, it is preferable to use gray dyeing due to the general properties of photosensitive materials, and the dye should be one that has excellent heat resistance in the film forming temperature range of polyester film and has excellent compatibility with polyester. preferable.

From the above point of view, as a dye, Diares manufactured by Mitsubishi Kasei is used.
The purpose can be achieved by mixing commercially available dyes for polyester, such as Kayase L manufactured by Memoto Kayaku.

Regarding the dyeing density, it is necessary that the color density is at least O801 or higher when measured in the visible light range using a color density blade manufactured by Mac\'s Co., Ltd. More preferred; If: 0.03
That's all.

The polyester film according to the present invention can be imparted with slipperiness depending on the application, and there are no particular limitations on the means for imparting slipperiness, but it is possible to incorporate an inert inorganic compound into the polyester film, or to add surface activity. It is commonly used as a method such as applying a chemical.

Such inert inorganic particles include 5iOz, TiO2,
Examples include BaSO4, CaCO2, talc, and kaolin. In addition to the above-mentioned lubricity imparting means by an external particle system in which inert particles are added to the polyester synthesis reaction system, lubricity imparting means is provided by an internal particle system in which a catalyst, etc. added during the polyester polymerization reaction is precipitated. can also be adopted.

There are no particular limitations on these means for imparting slipperiness.Since transparency is an important requirement for a support for photographic photosensitive It is desirable to select 5102, which has a refractive index relatively close to that of the film, or an internal particle system that allows the precipitated particle size to be relatively small.

Furthermore, when imparting slipperiness by kneading, it is also preferable to laminate functionally imparted layers in order to obtain greater transparency of the film. Specific examples of this means include a coextrusion method using a plurality of extruders, a field bronc, or a multi-manifold die.

In the present invention, depending on the copolymerization ratio, precipitation of low polymers may become a problem during heat treatment when forming an undercoating layer, but in this case, a normal polyester layer is laminated on at least one side of the support. It is possible to do so, and even in that case, coextrusion is used as an effective means.

The raw material polymer for the copolymerized polyethylene terephthalate film of the present invention can be synthesized according to conventionally known polyester manufacturing methods. For example, an acid component is directly esterified with a glycol component, or when a dialkyl ester is used as an acid component, a transesterification reaction is performed with a glycol component, and the excess glycol component is removed by heating under reduced pressure. Accordingly, copolymerized polyethylene terephthalate can be obtained. At this time, a transesterification reaction catalyst or a polymerization reaction catalyst may be used, or a heat-resistant stabilizer may be added, if necessary.

The copolymerized polyethylene terephthalate obtained above is generally formed into granules, dried, melt-extruded to form an unstretched sheet, and then subjected to biaxial stretching and heat treatment to form the desired film.

The biaxial stretching may be either longitudinal or horizontal sequential stretching or biaxial rotational stretching, and the stretching ratio is not particularly limited, but is usually 2.0 to 5.0 (@ is appropriate). .Also 1(
B. After the horizontal stretching, it may be re-stretched in either the dark blue direction or the horizontal direction.

As a drying method before melt extrusion according to the present invention, a vacuum drying method and a dehumidification drying method are preferable.

The temperature during stretching according to the present invention is 70 to 70°C for longitudinal stretching.
It is desirable that the 100°C 1 lateral stretching is carried out at 80 to 160°C.

The heat fixing temperature is 150-210°C1, especially 160-210°C.
Preferably it is 200°C.

The thickness of the copolymerized polyethylene terephthalate 1 film used in the present invention can be appropriately set depending on the field of use of the photographic film, but it is preferably 25 to 250 μm, more preferably 40 to 150 μm.

In the copolymer composition according to the present invention, the excellent transparency and mechanical strength originally possessed by PET are not impaired, and the film haze is 3% or less and the breaking strength is 8 to 25 kg/mm2.
, initial elastic modulus is 200-500 kg/mm2, film thickness is 50
The tear strength in μ is 30 g or more at a thickness of 120 μm. If the strength is lower than this, the excellent mechanical properties originally possessed by PET will be impaired, and the superiority over TAC will be lost.

In the present invention, transparency, breaking strength, initial elastic modulus, and tear strength are measured as follows.

[Transparency] -, -1,4- The haze of the film was measured according to ASTM-01003-52.

(Breaking strength and initial elastic modulus) According to JIS-21702-1976, width 10 mm,
A strip piece having a length of 100 mm was measured at a tensile rate of 300 kg/min for breaking strength and an initial elastic modulus of 20 mm/min.

(Measurement of tear strength) Using a light load type tear strength tester (manufactured by Toyo Seiki ■), a 13 mm incision was made in a sample size of 51 x 64 mm, and the indicated value was read when the remaining 51 mm was torn.

The polyester film J and support of the present invention are characterized by excellent curl resolving properties (hereinafter referred to as curl recovery rate) after development processing. In the present invention, it is preferable that the curl recovery rate is 50% or more, particularly 80% or more in the following method - ζ measurement.

Measurement of 1-force recovery rate] A film with a sample size of 12 cm x 35 mm was
Wound around 0mm core, 60°C x 30%RH x 72hr
After that, the sample was released from the core, immersed in distilled water at 40°C for 15 minutes, then dried in an air constant temperature bath at 55°C for 3 minutes with a load of 50g applied, and the sample was hung vertically. The sample length was measured to evaluate how much the sample length had returned to its original length of 12 cm.

The copolymerized polyethylene terephthalate l-film used in the present invention is characterized by superior adhesion to various coating layers such as emulsion layers, compared to conventional polyethylene terephthalate films.

In order to improve the adhesion property and the wetting properties of the coating liquid, the polyester film of the present invention has been prepared with: II'
Various surface treatments such as electrical discharge treatment, chemical treatment, and fire treatment can be applied as necessary.

Among these surface treatments, the most preferably used in the present invention is corona discharge treatment, which causes less precipitation of low polymers on the film surface.

The polyester support of the present invention preferably has a subbing layer in order to increase adhesion to a photographic layer such as a photosensitive layer coated thereon.

Examples of the subbing layer include a subbing layer using a polymer latex made of a styrene-butadiene copolymer or a vinylidene chloride copolymer, and a subbing layer using a hydrophilic binder such as seratin.

The subbing layer preferably used in the present invention is a subbing layer using a hydrophilic binder.

Is water the hydrophilic binder used in the present invention? Volume 1 raw polymer, cellulose ester, latex polymer,
Examples include water-soluble polyester.

Examples of water-soluble polymers include gelatin, seratin derivatives,
These include casein, agar, sodium alginate, starch, polyhinyl alcohol, polyacrylic acid copolymer, and maleic anhydride copolymer, and cellulose esters include calhokimethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Among these, gelatin is most preferred.

As a compound that swells the support used in the present invention,
Resorcinol, chlorresorcinol, methylresorcinol, 0
Examples include -cresol, m-cresol, P-cresol, phenol, 0-chlorophenol p-/) lorphenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, l-lifluoroacetic acid, and chloral hydrate. Preferred among these are resorcinol and p-chlorophenol.

Various seratin curing agents can be used in the subbing layer of the present invention.

Chromium salt (chromium alum) is used as a ceratin hardening agent.
, aldehydes (formaldehyde, taraldehyde active halogen compound (2,4-cyclodi) - 5-,
-hydroxy-S-) riazine, etc.), epichlorohydrin resin, and the like.

The subbing layer of the present invention contains SiO. , T102, loose inorganic particles or polymethyl meccrylate copolymer particles (1 to 10 μm) can be contained as a matting agent.

The undercoating layer according to the present invention can be applied by a generally well-known coating method.
For example, Depco-1 method, air knife coating method, curtain coating method, wire barcode method, gravure coat I
・It is possible to apply by the method, extrusion coating method, etc.

In addition to the photosensitive layer, the photosensitive material of the present invention can have non-photosensitive layers such as an antihalation layer, an intermediate layer, a pack layer, and a surface protection layer.

The binder for the bank layer may be a hydrophobic polymer or a hydrophilic polymer such as that used for the subbing layer.

The hack layer of the photosensitive material of the present invention may contain antistatic agents, lubricants, matting agents, surfactants, dyes, and the like. The antistatic agent used in the hack layer of the present invention is not particularly limited, and examples of anionic polymer electrolytes include polymers containing carbonic acids, carboxylates, and sulfonates, such as those disclosed in JP-A No. 48-22017. , Special public school 4th year
6-24159, JP-A-51-30725, JP-A-51-12921.6, and JP-A-55-95942. Examples of cationic polymers include JP-A-49-121523 and JP-A-4
There are those described in No. 8-911.65 and Japanese Patent Publication No. 49-24582.

There are also anionic and cationic ionic surfactants, for example, JP-A No. 4! IJ-85826, Japanese Unexamined Patent Publication No. 4
No. 9-33630, US2,992,108, tJs3
, 206, 312, JP-A No. 48-87826, JP-A-49-1.1567, JP-A-49-1568, and JP-A-55-70837.

The most preferable antistatic agents for the hack layer of the present invention are ZnO, TiO3,5nOz, AL○3, In
2(]+ , S i 02 , MgO, BaO1Mob
They are fine particles of at least one type of crystalline metal oxide selected from item 3 [1] or a composite oxide thereof.

The conductive crystalline oxide or composite oxide particles used in the present invention have a volume resistivity of 10 7 Ω (11 or less), more preferably 10 5 Ω (m or less).

The particle size is preferably 0.0X to 0.77μ, particularly 0.02 to 0.5μ.

Regarding the method for producing fine particles of conductive crystalline metal oxide or composite oxide used in the present invention,
It is described in detail in the specifications of No. 143430 and No. 60-258541. The first method is to prepare metal oxide fine particles by firing, and then heat-treat the metal oxide particles in the presence of a different type of atom to improve conductivity.The second method is to prepare metal oxide fine particles by firing and heat-treating the metal oxide fine particles in the presence of a different type of atom to improve conductivity. A third method is to allow atoms to coexist, and a third method is to lower the oxygen concentration in the atmosphere to introduce oxygen defects when producing metal fine particles by firing. Examples containing different atoms include 8 for ZnO, In, etc., Nb, Ta, etc. for TiO2,
For 5nOz, examples include Sb, Nb, and Haloken. The amount of foreign atoms added is preferably in the range of 0.01 to 30 mo1%, but 0.01 to 30 mo1% is preferable. Particularly preferred is 1 to 10 mo 1%.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described.

The most preferable photographic materials of the present invention are silver halide photographic materials, such as silver halide color negative films, color positive films, color reversal films, and black and white negative films.

Photographic emulsion used in the present invention P, Glafkide
Written by Chimie et Physique Photo
ographique (Paul Montel Publishing, 1967), by G, F, Duffin, Ph.
otographic Emulsion Chemi
stry (The Focal Press, 19
66), V. L., Zelikman et a.
Written by l Making and Coating Yen+o
tographic Emulsion ('ihe F
ocaXPress, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, it is also possible to use a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, the so-called Chondral double-chet method.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
Katomiu J salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or iron complex salt, etc. may be coexisting.

As a binder or protective colloid for photographic emulsions, it is advantageous to use gelatin, or other hydrophilic colloids may be used.

For example, gelatin derivatives, graph 1 of gelatin and other macromolecules - polymers, proteins such as albumin, casein;
Cellulose derivatives such as xyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sugar derivatives such as alginate sorta, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylate A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of acids, polyacrylamide, polyvinyl alcohol, polyvinyl pyrazole, and the like.

Gelatin includes incision-treated gelatin, acid-treated gelatin, Bull, Soc, Sci, Phot,
Japan.

No, 16. The enzyme Seratin as described on page 30 (1966) may be used, and river water decomposition products and enzymatic decomposition products of gelatin can also be used.

Seratin derivatives include gelatin, acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulponamides, maleimide compounds, polyalkylene Fs, epoxy compounds, etc. Those obtained by reacting compounds are used. Specific examples are U.S. Patent Nos. 2,614,928 and 313.
No. 29.15, No. 3186846-, No. 331255
No. 3, British Patent No. 861/114, 1.033189
It is described in Japanese Patent Publication No. 1.005784, Japanese Patent Publication No. 42-26845, etc.

The gelatin graft polymer may be a single (homo) or copolymer of vinyl monomers such as gelatin, acrylic acid, methacrylic acid, their esters, derivatives such as amides, acrylonitrile, styrene, etc. You can use the one that has been prepared. In particular,
Graft polymers with gelatin and copolymers having some degree of compatibility with polymers such as acrylic acid, methacrylic acid, acrylamide, ivy acrylamide, hyaloxyalkyl methacrylate I, etc. are preferred. Examples of these are described in US Pat. Nos. 2,763,625, 2,831,767, and 2,956,884.

Representative synthetic hydrophilic polymer substances include, for example, West German Patent Application (OLS) No. 2312708 and U.S. Patent No. 362075.
No. 1, No. 3879205, and Japanese Patent Publication No. 43-7561.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of photosensitive feed. That is, azoles such as hendithiazolium salts, nitroindazoles, nitrohenzimitazoles, chlorohenzimidazoles, promohenzimitazoles, mercaptothiazoles, mercaptohendithiazoles, mercaptohenzimidazoles, Mercaptothiadiazoles, aminotriazoles, triazoles, dichlorotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazolecaptotriazines; thiogeto compounds such as oxazolinthione; azaindene) such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted (1.3.3a,7) tetrazaindenes),
Many compounds known as antifoggants or stabilizers can be added, such as pentaazaindenes, etc.; hensensiosulfonic acid, hensensulfonic acid, hensensulfonic acid amide, etc. For example, US Patent 39
No. 54474, No. 3982947, Special Publication No. 52-28
You can do what is described in No. 660.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, poly(-)-lene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, and thiomorphs are added. It may also contain phosphorus, four-ball ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent 24.0053
No. 2, No. 2423549, No. 271.6062, No. 3617280, No. 3772021, No. 38080
03, British Patent No. 1488991, etc. can be used.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. Dyes that may be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, poropolar-cyanine dyes, hemicyanine dyes, suy-lyl dyes, and hemiogisonol dyes. Particularly useful dyes are cyanine dyes,
It is a pigment belonging to merocyanine pigments and complex norcyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

Namely, pyridine nucleus, oxabrine nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, teI-razole nucleus, pyridine nucleus, etc.; A nucleus in which an alicyclic herdsman hydrogen ring is fused to these nuclei. ; and a nucleus in which an aromatic hydrogen ring is fused to these nuclei,
That is, indolenine nucleus, henzindolenine nucleus, indole nucleus, henzoxazole nucleus, naphthothiazole nucleus, henzdiazole nucleus, naphthothiazole nucleus, henzoselenazole nucleus, henzuimidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted with two carbon atoms.

=27- The merocyanine dye or complex merocyanine dye has a getmethylene structure-containing nucleus such as birapurin-5-one nucleus, thiohydantoin nucleus, and 2-thioxazolidine-2.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thioharbiful acid nucleus, and other 5- to 6-membered heteroartic ring nuclei can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929080, US Patent No. 2231658, US Pat.
No. 03776, No. 2519001, No. 2912329
No. 3656959, No. 367289.7, No. 3
No. 6942'17, No. 4025349, No. 40465
No. 72, British Patent No. 1242588, Special Publication No. 1972i40
No. 30, No. 52-24844.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
No. 688545, No. 2977229, No. 339706
No. 0, No. 3522052, No. 3527641, No. 3
No. 617293, No. 3628964, No. 366648
No. 0, No. 3672898, No. 3679428, No. 3
No. 703377, No. 3769301, No. 381460
No. 9, No. 3837862, No. 4026707, British Patent No. 1344281, British Patent No. 1507803, Special Publication No. 4
No. 14936, No. 53-12375, JP-A-52-1
No. 10618 and No. 52-109925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
The emulsion may contain a substance that exhibits supersensitization.
1), aromatic organic acid bomaldehyde condensed rings (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. The combinations described in US Pat. Nos. 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularly useful.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

Such dyes include Oxonol Dyemoto-1 and Hemioni-1.
- Sonol winters'1, styryl dyes, merocyanine dyes, cyanine dyes and aso dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

Specific examples of dyes that can be used include U.S. Pat.
-99620, 49114/120, 52-1
No. 08115, U.S. Patent No. 2274782, U.S. Patent No. 2533
No. 472, published 2956879, July 314818,
Published 3177078, 324”) No. 121, 354
0887, 1m3575704, 1m3653905
No. 371, No. 8472, No. 4071312, No. 4
It is described in No. 070352.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers include stilhen-based, I.
It may also contain a brightening agent such as a riazine type, oxazole type, or coumarin type. These water-soluble brighteners may be used, or water-insoluble brighteners may be used in the form of a dispersion. Specific examples of fluorescent brighteners include US Patent Nos. 2,632,701, 3,269,840, and 3,359,102, and British Patent No. 85.
It is described in No. 2075, No. 1319763, etc.

When carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat. No. 2,360,290, U.S. Pat.
No. 97, No. 27047 +-3, No. 2728659, No. 2732300, No. 2735765, No. 271
No. 0801, No. 2816028, British Patent No. 13639
Hydroquinone derivatives described in US Pat. No. 21, et al., gallic acid derivatives described in US Pat. No. 3,457,079, US Pat.
No. 3698909, Special Publication No. 49-20977, No. 5
p-alkoxyphenols described in No. 2-6623, US Pat. No. 3,432,300, US Pat. No. 3,573,050,
No. 3574627, No. 3764337, JP-A-52
-35633 scrap, No. 52-147434, No. 52-]
, p-oxyphenol derivatives described in US Pat. No. 52,225, hisphenols described in US Pat. No. 3,700,455, and the like.

The photosensitive +1 composition prepared using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include U.S. Pat. No. 2403721, No. 24186
No. 13, No. 2675314, No. 2701197, No. 2704713, No. 2728659, No. 27323
No. 00, No. 2735765, JP-A-50-92988
No. 50-92989, No. 50-93928, No. 50-110337, No. 52-146235, Japanese Patent Publication No. 50-23813, etc.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The most preferred light-sensitive material of the present invention is a roll-shaped color negative film for photography.

Any known color coupler can be preferably used in the color negative film of the present invention.

That is, it may contain a compound (hereinafter abbreviated as a coupler) that reacts with an oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye.

The coupler is preferably a non-diffusible coupler having a hydrophobic group called a Halas I group in its molecule. The coupler may be either 4- or 2-common to silver ions. There are also colored couplers that have a color correction effect, or couplers that release a development inhibitor during development (so-called DI
R coupler). The coupler may be such that the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, specific examples of hensoylacetanilide type and pivaloylacetanilide yellow coloring couplers are U.S. Patent No. 2875057, U.S. Pat.
No. 1155, No. 3582322, No. 3725072, No. 3891445, West German Patent No. 1547868, West German Application No. 2219917, No. 2261361-,
No. 2414006, British Patent No. 1425020, Japanese Patent Publication No. 10783/1983, Japanese Patent Publication No. 26133/1982, No. 48-73147, No. 51-102636, No. 50
-6341, 50-123342, 50-13
No. 0442, No. 51-21827, No. 50-8765
No. 0, April 52-8242, and No. 52-115219.

As the magenta coloring coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

A specific example of a magenta color-forming coupler that can be used is disclosed in U.S. Pat.
No. 600788, No. 2983608, No. 306265
No. 3, 31"! -1' 2 6 9, 3311
No. 476, No. 3419391, No. 3519429,
No. 3558319, No. 3582322, No. 3615
No. 506, No. 3834908, No. 3891445,
West German Patent No. 1810464, West German Patent Application (OLS) 2
No. 408665, No. 2417945, No. 241895
No. 9, No. 2424467, Special Publication No. 40-6031,
JP 51-20826, JP 52-58922, JP 49-129538, JP 49-74
0 2 7, 50-159336, 52-4
No. 2121, No. 49-74028, No. 50-6023
No. 3, No. 5m-26541, No. 53-55122, etc.

As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used. Specific examples thereof include U.S. Pat.
No. 26, No. 3034892, No. 3311476, No. 3458315, No. 3476563, No. 35839
No. 71, No. 3591383, No. 37674 1 1, No. 4004929, West German Patent Application (OLS) 241
No. 4830, No. 2454329, JP-A-48-598
No. 38, No. 51-26034, No. 48-5055,
No. 51-146828, No. 52-69624, No. 5
It is described in No. 1-9 09 3 2.

As a colored coupler, for example, U.S. Patent No. 34765
No. 60, No. 2521908, No. 3034892, Special Publication No. 41-2016, No. 38-22335, No. 42
-11304, No. 44-32461, JP-A-1983-
Those described in Specification No. 26034, Specification No. 52-42121, and West German Patent Application (OLS) No. 24 18959 can be used.

As a DIR coupler, for example, US Pat. No. 32,275
No. 54, No. 3617291, No. 3701783, No. 3790384, No. 3632345, West German Patent Application (oLs) No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, JP-A-5
2-6 9 6 24, 49-122335,
Those described in Japanese Patent Publication No. 51-16141 can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development, such as U.S. Pat. No. 3,297,445, U.S. Pat. -1
Those described in No. 5271 and JP-A-53-91.16 can be used.

Two or more of the above couplers may be included in the same layer. The same compound may be contained in two or more different layers.

These couplers are generally added in an amount of 2.times.10" moles to 5.times.10" moles, preferably 1.times.10@-2 moles to 5.times.10@-' moles per mole of silver in the emulsion layer.

In order to introduce the above-mentioned couplers into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 can be used. For example, phthalic acid argyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenylph A sulfate, 1-
liphenyl phosphate-1, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl lauryl amide), Fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelet-1-), etc., or aqueous solvents with a boiling point of about 30"C to 150°C, such as lower argylacetate-1-, fropion, such as ethyl acetate, butyl acetate, etc. After dissolving in ethyl acid, dibutyl alcohol, methyl isobutyl ketone, β-ethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid.The above high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-59943
It is also possible to use the polymer dispersion method described in .

When the coupler has an acid group such as carbonic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, henzotriazur compounds substituted with an aryl group (such as those described in US Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in US Pat. No. 3,314,794 and US Pat.
681), hensifhenone compounds (e.g., those described in JP-A-46-2784), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705,805,
No. 3,707,375), butadiene compounds (e.g., those described in U.S. Pat. No. 4,045,229) or hendioxizole compounds, e.g., U.S. Pat.
00455) can be used. Furthermore, U.S. Patent No. 3,499,762, Japanese Patent Application Publication No. 5.4-485
Those described in No. 35 can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may also be used. These UV absorbers may be mordanted into certain layers.

Any known method can be used for the photographic processing of the light-sensitive material of the present invention. A known treatment liquid can be used. The processing temperature is usually chosen between 18°C and 50°C, but temperatures lower than 18°C or 50°C
The temperature may exceed .

Development processing to form a silver image depending on the purpose (black photographic processing)
Alternatively, any color photographic process consisting of a development process to form a dye image can be applied.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g. 4-amino-N, N-diethylaniline, 3-methyl-4
-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-
amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition to this, Photogr by F. A. Mason
aphicProcessing Chemistry
22 of y (Focal Press, 1966)
pp. 6-229, U.S. Patent No. 2193015, U.S. Patent No. 2592
Those described in No. 364 and JP-A No. 48-64933 may be used.

Color developers also contain buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. be able to. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as hensyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and pigment-forming couplers, competitive couplers, fogging agents such as sodium borohydrite, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat. No. 4,083,723, West Germany Publication (OLS) 262
It may also contain antioxidants such as those described in No. 2950.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include 钖 (■) and cobalt (■
), chromium (■), copper (H), and other polyvalent metal compounds;
Peracids, quinones, nitroso compounds, etc. are used.

For example, ferricyanide, dichromate, iron (TI
I) or organic complex salts of cobalt (1), such as ethylenediaminetetraacetic acid, ditrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid, etc., or organic acids such as citric acid, tartaric acid, malic acid, etc. complex salts; persulfates, permanganates; nitrosophenols, etc. can be used.

Among these, the coupler of the present invention also exhibits great coloring properties in the bleached W fixing solutions of ethylenecyaminetetraacetic acid iron (TII) sodium and ethylenediaminetetraacetic acid iron (III) ammonium salt bleaching solutions, and is advantageous in this respect as well. Ethylenecyaminetetraacetic acid iron (III) complexes are useful both in stand-alone bleach solutions and in bath bleach-fix solutions.

Bleaching or bleach-fixing solutions include bleaching accelerators described in U.S. Pat. No. 3,042,520, U.S. Pat.
In addition to the thiol compound described in No. 3-65732, various additives can also be added.

(Example) The present invention will be further explained below with reference to Examples.

Example-1 1) Creation of polyethylene terephthalate film 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol
Part by weight, 1 dimethyl 5-sodium sulfoisophthalate
0 parts by weight and 10 parts by weight of dimethyl adihinate, and 0.0 parts by weight of calcium acetate. 1 part by weight and 0.0 parts by weight of antimony dioxide.
03 parts by weight was added, and transesterification was carried out by a conventional method. The obtained product contains phosphoric acid trimethyl ester o,
05 was added, the temperature was gradually raised and the pressure was reduced, and finally polymerization was carried out at 280'C1l mm Hg or less to obtain copolymerized polyethylene terephthalate.

After drying the copolymerized polyethylene terephthalate in a conventional manner, it was melt-extruded at 280°C to prepare an unstretched sheet. Next, it was sequentially stretched 3.5 times in the longitudinal direction at 90°C and 3.7 times in the transverse direction at 95°C, and then heat-set at =44-200°C for 5 seconds to form a biaxial film with a thickness of 100μ. A stretched film was obtained. Film characteristics include haze of 1.2%,
Breaking strength is 12 kg/mm, initial elastic modulus is 340
kg/n++n, and the transparency and mechanical properties were good.

Note that transparency, breaking strength, and initial elastic modulus were measured under the following conditions.

Transparency: Film haze was measured according to ASTN-D1003-52.

Breaking strength and initial elastic modulus: Width 101n according to JIS-21702'-1976
1n, length of 100 mm, the tensile speed was 300 mm/min when measuring the breaking strength, and the initial elastic modulus was 20 m.
Measured in m/min.

2) Measurement of curl recovery rate The PET film (thickness: 50 μm) according to the present invention prepared as described above, a commercially available PET film (same thickness), and a commercially available TAC film (thickness: 125 μm) were measured by the method of the present invention. The moisture content was measured.

Furthermore, the curl recovery power was measured by the following method, and the results shown in Table 1 were obtained.

[How to evaluate curl] A sample size of 12 cm x 35 mm film was
Wound around 0mm core, 60°C x 30%RHX 72h
After that, it was released from the winding core, immersed in distilled water at 40°C for 15 minutes, and then heated to 55°C under a load of 50g.
The sample was dried for 3 minutes in an air constant temperature bath, hung vertically, and the sample length was measured to evaluate whether it had recovered to its original 12 cm sample length.

As is clear from Table 1, the PET film according to the present invention having a moisture content of 0.7% by weight has an extremely excellent curl recovery rate.

3) Preparation of photographic material 3-1) Coating of subbing layer
After each ET film was subjected to corona discharge treatment on both sides, a subbing layer having the following composition was provided. The degree of corona discharge treatment was 0.02 KVA·min/nτ.

gelatin 3g distilled water
250cc Sodium α-sulfodi 2-ethylhexylsaccine-1-0.05g Hol 1, aldehyde 0.02g3-2
) Coating of hack layer A hack layer having the following composition was coated on one side of the PET film after undercoating.

[Preparation of soot oxide-antimony oxide composite dispersion] 230 parts by weight of stannic chloride hydrate and ammonium trichloride, i7
- 23 parts by weight of Dimon was dissolved in 300 parts of ethanol to obtain a homogeneous solution. An aqueous solution of thorium hydroxide IN was added dropwise to this solution until the pI of the solution reached 3 to 3 to obtain a coprecipitate of colloidal sulfur oxide and antimony oxide. The obtained coprecipitate was left at 50°C for 24 hours to obtain a reddish brown colloidal precipitate.

A reddish-brown colloidal precipitate was separated by centrifugation. In order to remove excess ions, water was added to the precipitate and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions.

200 parts by weight of Colloid I precipitate from which excess ions have been removed are redispersed in 1500 parts by weight of water and sprayed into a firing source heated to 600'C to form a bluish tin oxide with an average particle size of 0.2μ. A fine powder of antimony oxide composite was obtained. The specific resistance of this fine particle powder was 25 Ω·cm.

A mixed solution of 40 parts by weight of the above fine particle powder and 60 parts by weight of water is
After adjusting the temperature to 7.0 and coarsely dispersing it with a stirrer, use a horizontal Zantmill (trade name: Quinomil, WILL YA, BA).
(manufactured by CHOFEN AG) until the residence time reached 30 minutes.

(Coating of hack layer) The following formulation [A] was coated so that the dry film thickness was 0.3 μm and dried at 130° C. for 30 seconds. Further, the following coating layer coating solution (B) was coated onto this to give a dry film thickness of 0.1 μm, and dried at 130”C for 2 minutes.

[Formulation A] Polyoxyethylene nonylphenyl ether 0.01 part by weight [Coating liquid for coating layer (B)] 3-3) Coating of photographic layer The PET film of the present invention provided with the hack layer as described above and the commercially available A photographic layer as described below was provided on the opposite side of the PET film.

1st layer: Red-sensitive silver halide low-speed layer (1-a) Preparation of emulsion liquid for low-sensitivity unit emulsion layer Silver iodobromide emulsion containing 6 mol% of iodine (average grain size of 0.6μ, emulsion ], k
(Contains 100g of silver halide and 70g of gelatin per gram)
was prepared in a conventional manner. 1 kg of this emulsion was added with 0.00% of anhydro-5,5'-cyclo9-ethyl-3,3'-di(3-sulfobrovir)thiacalphocyanine hydroxide pyricinium salt as a red-sensitive color sensitizer.
Add 180 cc of a 1% methanol solution, then add 5-methyl-7-hydroxy 2. 3. 4-1-5% water by weight of riazaindolizine? 20 cc of @liquid, 330 g of cyan coupler emulsion (1) and 20 g of cyan coupler emulsion (2) according to the following formulation were added. Furthermore, 50 cc of a 2% by weight aqueous solution of 2-hydroxy-436-cyclotriazine sodium salt was added as a gelatin hardener to prepare an emulsion solution for a low-sensitivity unit emulsion.

Emulsion (1) ■ 10% by weight gelatin aqueous solution 1.000g ■ p
-Dotesylhenzensulfonic acid sodium 5gI・Liclesyl phosphate 60(・C cyan coupler(
C-7) 70g ethyl acetate
After dissolving the mixture of 100 (:c) at 55°C, it was added to ■, which had been previously heated to 55°C, and emulsified using a colloid mill.

Cyan coupler emulsion (2) ■ 10% by weight gelatin water? Yongnya 1.000g■
Sodium p-dodecylhenzensulfonate 5g1・Licresyl phosphate 60cc Cyan coupler 9
6gDIR cyan coupler**
64 g ethyl acetate
100cc*Cyan coupler is the same as above.

2nd layer: Red-sensitive silver halide medium-speed layer (1-b) Preparation of emulsion solution for medium-speed unit emulsion layer The following changes were made to the above (1-a).

-52= Third layer: red-sensitive silver halide high-sensitivity layer (1-c) The following changes were made in the preparation of the emulsion solution for the high-sensitivity unit emulsion layer (1-a).

4th layer: Gelatin intermediate layer 5th layer: Green-sensitive silver halide low-speed layer (2-a) Preparation of emulsion solution for low-sensitivity unit emulsion layer Silver iodobromide emulsion containing 6 mol% of iodine (average grain Size: 0.6μ, emulsion: 1kg
(containing 100 g of silver halide and 70 g of gelatin) was prepared in a conventional manner. 1 kg of this emulsion was added with 0.00% of 3,3'-di(3-sulfoethyl)-9-ethyl-benzoxacarbocyanine viridinium salt as a green-sensitive color sensitizer.
Add 200 cc of 1% methanol solution, and then add 5-methyl-7-hydroxy-2,3,4-1-lyaripan I.
20 cc of a 5% by weight aqueous lysine solution was added, and 380 g of magenta coupler emulsion (3) and 20 g of magenta coupler emulsion (4) according to the following formulation were added.

Furthermore, 2-hydroxy-4,6-
2% by weight aqueous solution of cyclotriazine sodium salt 50
An emulsion solution for a low-sensitivity unit emulsion was obtained by changing cc.

Emulsion (3) ■ 10-layer gelatin aqueous solution 1.000g ■ p
-F Sodium decylhenzenesulfonate 5g tricresyl bosphate 65 (C magenta coupler (M
-7) After dissolving a mixture of 6 g ethyl acetate (110 cc) at 55°C, heat the mixture to 55°C in advance.
In addition, it was emulsified using a colloid mill.

Magenta coupler (M-7): 1- (2,4,6-
trichlorophenyl)-3-(3-(2,4-sheet t-
pentylphenoni-1-cyacetamine F]
-5-pyrazolone emulsion (4) ■ 10-layer gelatin aqueous solution 1.000g ■ p
- Sodium dodecylhenzenesulfonate 5g Tricresyl Phosphe-1-55cr: Magenta Coupler 9638 DIR-Nzenta Coupler'', 60g Ethyl acetate 110cc Emulsified in the same manner as in Emulsion (3).

**DIR magenta coupler: 1- (4-(2-(
2,i-di-t-pentylphenoxy)fucunamide]
Phenyl)-1-(1-pyrrolidinyl)4-(1-phenyltetrazuryl-5-1000)-5-pyrazolone=55=6th layer: green-sensitive silver halide medium-speed layer (2-b ) Preparation of emulsion solution for medium-sensitivity unit emulsion layer Silver iodobromide emulsion containing 5 mol% of iodine (average grain size 0.9μ, emulsion 1k)
(Contains 100g of silver halide and 70g of seratin per gram)
was prepared in a conventional manner. To 1 kg of this emulsion, (2-a
) 150 cc of methanol solution of green-sensitive color sensitizer
and then 5-methyl-7-hydroxy-2,3゜4
20 (C) of a 5% by weight aqueous solution of -1-riazaintolidine was added. Furthermore, 285 g of the above emulsion (3) and the same (4) were added.
15g of was added.

Furthermore, as a gelatin hardening agent, a 2% by weight aqueous solution of 2-hydroxy-4゜6-cyclotriazine sodium salt 50
cc was added to prepare an emulsion solution for a medium-sensitivity unit emulsion layer.

7th layer: Green-sensitive silver halide high-sensitivity layer (2-c) Preparation of emulsion liquid for high-sensitivity unit emulsion layer Silver iodobromide emulsion containing 6 mol% of iodine (average grain size of 1.1 μ, 1 Grains of 0.0 μm or larger (50% by weight of the total, containing 100 g of silver halide and 70 g of gelatin per kg of emulsion) were prepared by a conventional method. 80 cc of a methanol solution of the green-sensitive color sensitizer shown in (2-a) was added to 1 kg of this emulsion, and then a 5% by weight aqueous solution of 5-methyl-7-hydroxy-2,3,4-)riazaintolidine was added. Add 20cc and further emulsion (3
) was added.

Furthermore, as a gelatin hardener, 2-hydroxy-4,6-
50 cc of cyclotriacin sodium aqueous solution was added to prepare an emulsion solution for a high-sensitivity unit emulsion.

8th layer: Yellow filter layer consisting of yellow colloidal silver (
(Dry IIK thickness 1.2 μm) 9th layer: Blue-sensitive layer Silver halide low-sensitivity layer (3-a) Preparation of emulsion solution for low-sensitivity unit emulsion layer - (1) Iodobromide containing 5 mol% of iodine A silver emulsion (average grain size 0.6 microns, containing 100 g of silver halide and 70 g of gelatin per kg of emulsion) was prepared in a conventional manner. 5-
20 cc of a 5% by weight aqueous solution of methyl-7-hydroxy-2.3.4-triazaindolizine and 600 g of yellow coupler emulsion (5) according to the following formulation were added. Further, 50 cc of 2-hydroxy-4,6-cyclotriacin sodium solution was added as a ceratin hardener to prepare an emulsion solution for a low-sensitivity unit emulsion.

Emulsion (5) ■ 10% by weight aqueous gelatin solution 1. OOOg■ P
- Sodium dodecylhensensulfonate 5g tricresyl bosphate 80 (・C yellow coupler”
100g yellow DIR coupler 0 ethyl acetate 120ccC$ \tC,I-(.

10th layer: blue-sensitive silver halide medium-speed layer (:3-
a) was changed as follows.

average grain size of kej 0.9μ, amount of emulsion added 400g 11th layer; blue-sensitive silver halide high-sensitivity layer (3-a)
) was changed as follows.

12th layer: Surface protective layer 10% by weight gelatin solution 1000cc Sodium todecylhenzensulfonate 0mg Si○2 fine particles (3.0μ) 50mg Sodium polystyrene sulfonate 1g 2-Hydroxy-4,6-dichlorotriazine 0mg The amount of silver coated in each of the photosensitive layers was as follows.

First layer (1.0 g/bo), second layer (0.8 g/bo).

3rd layer (1.2 g/n?), 5th layer (1.2 g/n?)
em).

6th layer (1.0g/po), 7th layer (1.2g/rrr
).

9th layer (0.6g/n), 10th layer (0.6g/n)
.

Eleventh Layer (0.6 g/po) The color negative film thus obtained was cut into a size of 35 m/m and loaded into a cartridge.

After being left at 40°C for 10 days, it was photographed using an ordinary camera and developed as follows.

-60= Processing process Temperature Time Development color development
38°c 3 minutes stop 38°
c 1 Water washing
1 Bleaching 2
〃Water wash 1〃Set
Arrival 2 Wash with water
1 Stable bath 1
〃 The treatment liquid used had the following composition.

Color developer Caustic soda 2g Sodium sulfite 2g Potassium bromide
0.4g sodium chloride
1g ho sand
4g hydroxylamine sulfate
2g Ethylenediaminetetraacetic acid 2-sodium dihydrate 2g 4-amino-3-methyl-N-ethyl-N-(β-human V:] quinethyl aniline monosulfate) 4g Add water Total amount 1r Stop solution Sodium thiosulfate 10g Ammonium 1000 sulfate (70% water) 30rrl acetic acid 30m℃Sodium acetate
5g Cali starch
Add 15g of water to 11%
Total amount: 1 bleach 1 night Ethylenediamine Tetraacetate Iron (IIt) Sodium dihydrate 100g Potassium bromide 50g Ammonia saccharide 508 Formic acid
58 Ammonia water p
Adjust H to 5.0 Add water Total amount IC fixing solution Sodium thiosulfate 150g Sodium sulfite 15g Borax
12g glacial acetic acid
15m! potash alum
Add 20g water to total amount
II! .

Stable bath Pholic acid 5g Sodium citrate 5g Sodium metaphoate (tetrahydrate) 3g Potassium alum
15g water:! :In addition
Regarding the curl condition after the total amount 1r development process, in the case of a photosensitive material using a commercially available PET film as a support, curling was not resolved, but in the case of a photosensitive material using a PIET film according to the present invention as a support. There was almost no curl.

(Effects of the Invention) The photosensitive material of the present invention uses a polyester film having excellent mechanical strength as a support, and can eliminate curling after development while maintaining its properties.

The light-sensitive material of the present invention has excellent mechanical properties and can easily eliminate curls after development processing, so even in the case of roll film, the thickness of the support can be significantly reduced, and the shape of can be compacted, and long films can be loaded in the same cartridge. The polyester film of the present invention can be produced at a low casting temperature, does not tear during stretching, has a high water content, and still has the original merits of Polyester Film J.

Furthermore, although the water content is high, there is very little oligomer precipitation, and there is no adverse effect on photographic performance.

Furthermore, since the humidity inside the packaging case for photosensitive materials can be lowered, photographic performance is less likely to change over time.

Preferred embodiments of the invention are as follows.

1) The photosensitive material according to claims 1 to 3, wherein the polyester film is polyethylene terephthalate (PET).

2) The moisture content of polyester is 0. 6-5.0% by weight
The photosensitive material according to any one of claims 1 to 3.

3) The aromatic dicarboxylic acid having a metal sulfonate is 5-sodium sulfoisophthalic acid, 2-strium sulfoterephthalic acid, 4-sodium sulfoclic acid,
Claims 2 and 3 and ``Two layer 1) selected from 4-sodium sulfo-2,6-naphthalene dicarphonic acid and compounds in which sodium is substituted with potassium or halitium.
2) Photosensitive material.

4) The photosensitive material according to claims 2 and 3, and 3) above, wherein the copolymerized amount of the aromatic dicarboxylic acid component having metal sulfone-1- is 2 to 15 mol% relative to the terephthalic acid component.

5) Claim 3 and above 1) - wherein the aliphatic dicarboxylic acid component is selected from succinic acid, adipic acid and sebacic acid.
4) Photosensitive material.

6) An aliphatic dicarboxylic acid having 4 to 20 carbon atoms such as succinic acid, adipic acid or sebacic acid is used as a copolymerization component in an amount of 3 to 25 mol % based on the terephthalic acid component.
and the photosensitive materials 1) to 6) above.

7) The photosensitive material of 6) above, which further contains polyalkylene glycol as a copolymer component.

8) Above 1) containing dye in polyester film
-7) Photosensitive material.

9) The photosensitive material of 1) to 8) above, characterized in that the polyester film has been subjected to a corona discharge treatment.

10) The photosensitive material of 1) to 9) above, which has a gelatin subbing layer on the surface of the polyester film.

11) The photosensitive materials of 1) to 10) above, wherein the photosensitive layer is a photosensitive silver halide emulsion layer.

12) The photosensitive material according to 1.11), wherein the photosensitive material is in the form of a roll film.

13) It has at least one red-sensitive layer, at least one green-sensitive layer, and at least one blue-sensitive layer.
1.11) Color non-woven film.

14) The photosensitive material of claims 1 to 4 and items 1) to 13) above, wherein the polyester film has a curl recovery rate of 50% or more.

15) The photosensitive material of 14) above, which has a polyester film curl recovery rate of 80% or more.

16) Thickness of polyester film is 30 to 120 μm
The photosensitive material according to claims 1 to 4) and 1) to 15) above.

17) Thickness of polyester film is 40 to 100 μm
The photosensitive material of 16) above.

Representative patent attorney (8107) Kiyotaka Sasaki (3 idiots)

Claims (1)

[Scope of Claims] 1) A photographic material comprising at least one photosensitive layer on a polyester film support, wherein the polyester film has a haze of 3% or less and a water content of 0.
A photographic material characterized in that the content is 5% by weight or more. 2) The polyester film is a copolymerized polyester film containing an aromatic dicarboxylic acid having a metal sulfonate as a copolymerization component, and its breaking strength is 8 to 25 kg/m.
m^2, initial elastic modulus is 200 to 50025 kg/mm^
2. The photographic material according to claim 1. 3) The photographic light-sensitive material according to claim 2, wherein the support is a copolymerized polyester film obtained by copolymerizing an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms as a copolymerization component other than the aromatic dicarboxylic acid component having a metal sulfonate. . 4) The photographic material according to claim 3, wherein the copolymerization ratio of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is 3 to 25 mol % based on the terephthalic acid component.