JP2565370B2 - Photographic material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material excellent in decurling after development using a polyester material as a support. It is a thing.

PRIOR ART Photographic light-sensitive materials are generally prepared by coating at least one photographic light-sensitive layer on a plastic film support. As the plastic film, a fiber-based polymer represented by triacetyl cellulose (hereinafter referred to as "TAC") and a polyester-based polymer represented by polyethylene terephthalate (hereinafter referred to as (PET)) are generally used. There is.

PET film has superior productivity, mechanical strength, and
Also, it has been considered to be a substitute for TAC because it has dimensional stability, but in a roll form widely used as a photographic light-sensitive material, curling curl strongly remains, and thus the handleability after development processing is poor, Although it has the above-mentioned excellent properties, its range of use has been limited.

Generally, as photographic light-sensitive materials, sheet-like materials such as X-ray films, plate-making films and cut films, and typical roll films have a width of 35 m / m or less in a patrone. It is a color or black-and-white negative film that is stored and is used in a general camera for shooting.

On the other hand, TAC mainly used for roll film
The greatest feature of the film as a photographic support is that it has no optical anisotropy and high transparency. Another feature is that it has excellent properties in decurling after development. That is, TA
The characteristic of the molecular structure of C film is that it has a relatively high water absorption as a plastic film, so the curl curl that occurs over time in the situation of being wound as a roll film causes the molecular chains to flow due to water absorption during development processing. , The immobilized molecular chains undergo rearrangement over time.

As a result, it has an excellent property of eliminating curling curl once formed. In a photographic light-sensitive material using such a film that does not have curl curl recovery like TAC, when it is used in a roll state, for example, in a printing step for forming an image on photographic printing paper after development, etc. Problems such as occurrence of scratches, defocusing, and jamming during transportation will occur.

By the way, in recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film transportation during photographing, the increase in photographing magnification, and the miniaturization of photographing apparatus have been significantly advanced. In that case, the support for the photographic light-sensitive material is required to have properties such as strength, dimensional stability and thinning.

However, in the above-mentioned TAC, the film quality is fragile due to its rigid molecular structure, so it cannot be used for this purpose. In the above, the PET film has a problem that it cannot be used although it has excellent mechanical properties, and its modification has been desired.

(Object of the invention) Then, in order to solve this problem, US Pat.
No. 721,441 and No. 4,241,170,
It has been proposed to use a film modified by reacting PET with a specific compound for these photographic light-sensitive materials, but in this case, there is a problem that the film is whitened due to the processing process and changes with time and the transparency is impaired. Therefore, further improvement has been desired in terms of optical transparency.

Therefore, an object of the present invention is to provide a photographic light-sensitive material which is composed of a support having excellent transparency and mechanical properties and which can easily eliminate curling curls after development processing.

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a polyester film support, wherein the polyester film has a haze of 3% or less and a water content of 0.5. It is achieved by a photographic light-sensitive material characterized by having a curl recovery rate of 50% or more and a weight% or more thereof.

The water content of the polyester film of the present invention is measured by adjusting the humidity of the film at 23 ° C., 30% RH for 3 hours,
The sample is dipped in distilled water at 23 ° C for 15 minutes, and then dried at a drying temperature of 150 ° C using a trace moisture meter (for example, CA-02 type manufactured by Mitsubishi Kasei Co., Ltd.).

The polyester film of the present invention is characterized in that the water content measured by such a method is 0.5% by weight or more,
It is preferably 0.6 to 5.0% by weight.

If the water content is less than 0.5% by weight, the curling curl elimination property after development processing will not be improved, and if the water content is too high, dimensional stability will deteriorate due to moisture absorption.

In the present invention, the polyester is a polyester having an aromatic dibasic acid and glycol as main components, and typical dibasic acids are terephthalic acid and isophthalic acid, and glycol is ethylene glycol,
Examples include propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanediol, diethylene glycol and the like. Among the polyesters composed of these components, polyethylene terephthalate (PET) is the most convenient from the viewpoint of easy availability.
Will be explained.

The copolymerized polyethylene terephthalate film preferably used in the present invention is a copolymerized polyethylene terephthalate film containing an aromatic dicarboxylic acid component having a metal sulfonate as a copolymerization component.

Specific examples of the aromatic dicarboxylic acid having a metal sulfonate include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid. And compounds in which these sodiums are substituted 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 15 mol% with respect to the terephthalic acid component which is the main raw material,
Particularly preferably, it is 4 to 10 mol%.

The copolymerized polyethylene terephthalate film used in the present invention is further copolymerized with an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, and in particular transparency of the surface of the copolymerized polyethylene terephthalate film is suppressed and folding resistance is increased. From the viewpoint of.

Specific examples of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms include succinic acid, adipic acid, sebacic acid and the like, among which adipic acid is preferred.
When the aromatic dicarboxylic acid is mainly terephthalic acid, the copolymerization ratio of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is preferably 3 to 25 with respect to the terephthalic acid.
Mol%, particularly preferably 5 to 20%.

Incidentally, in the polyester film of the present invention, transparency, if a small proportion of the range that does not impair the mechanical properties,
It is also possible to copolymerize other acid component or glycol component. For example, polyalkylene glycol, especially polyethylene glycol, can be copolymerized in an amount of 0 to 10 parts by weight with respect to 100 parts by weight of polyester. The polyalkylene glycol used for this purpose preferably has a molecular weight of 600 to 10,000.

Further, various additives can be contained in the polyethylene terephthalate film of the present invention. For example, one of the properties that poses a problem when a polyester film is used as a support for a photographic light-sensitive material is the problem of fogging due to the high refractive index of the support. As a photographic support, polyester polymers represented by triacetyl cellulose (TAC) and polyethylene terephthalate (PET) are generally used. One of the major differences in optical properties between TAC and PET is The first is the refractive index. This refractive index is as small as PET, which is about 1.6, while TAC is 1.5. On the other hand, the refractive index of gelatin used exclusively for the subbing layer and the photographic emulsion layer is 1.50 to 1.
55, and the ratio of the refractive index of gelatin is 1.5 / in PET.
It is smaller than 1.6 and 1, and when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging).

As a method of avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film, a method of adding a dye, and the like are known. The preferred method for preventing light piping in the present invention is a method by adding a dye that does not significantly increase the film haze.

The dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polyester film, and polyester Those having excellent compatibility with are preferable.

As the dye, from the above viewpoint, Diaresin manufactured by Mitsubishi Kasei,
The purpose can be achieved by mixing a commercially available dye for polyester such as Kayaset manufactured by Nippon Kayaku.

Regarding the dyeing density, it is necessary that the color density in the visible light region is measured with a color densitometer manufactured by Macbeth Co. and is at least 0.01 or more. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be imparted with slipperiness depending on the application, and the slipperiness imparting means is not particularly limited, but kneading with an inert inorganic compound, or surface-active The application of agents is used as a general method.

Such inert inorganic particles include SiO ₂ , TiO ₂ , and BaS.
Examples include O ₄ , CaCO ₃ , talc, kaolin and the like. Also,
Besides the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polymerization reaction of polyester is precipitated can also be adopted. .

These slipperiness imparting means are not particularly limited, but transparency is an important requirement for a support for a photographic light-sensitive material. Therefore, in the slipperiness imparting method means, a polyester film is used as an external particle system. It is desirable to select SiO ₂ having a refractive index relatively close to that, or an internal particle system capable of relatively reducing the precipitated particle size.

Furthermore, in the case of imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

In the present invention, depending on the copolymerization ratio, the precipitation of low-polymerization products may become a problem due to the heat treatment when the subbing layer is provided. At that time, an ordinary polyester layer is laminated on at least one surface of the support. It is possible and at that time,
The coextrusion method is used as an effective means.

The raw material polymer for the copolymerized polyethylene terephthalate film of the present invention can be synthesized by a conventionally known polyester production method. For example, by directly esterifying the acid component with the glycol component, or in the case of using a dialkyl ester as the acid component, transesterification reaction with the glycol component, and heating this under reduced pressure to remove the excess glycol component. , Copolymerized polyethylene terephthalate can be obtained. At this time, if necessary, a transesterification reaction catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added.

The copolymerized polyethylene terephthalate obtained above is generally formed into granules, dried, melt-extruded into an unstretched sheet, and then biaxially stretched and heat-treated to obtain a target film.

Biaxial stretching may be either longitudinal or transverse sequential stretching or biaxial simultaneous stretching, and the stretching ratio is not particularly limited, but usually 2.0 to 5.0 times is suitable. Further, after longitudinal or transverse stretching, it may be re-stretched in any of longitudinal and transverse directions.

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

As the temperature during stretching in the present invention, the longitudinal stretching is 70 to
It is desirable that the temperature is 100 ° C and the transverse stretching is 80 to 160 ° C.

The heat setting temperature is preferably 150 to 210 ° C, particularly preferably 160 to 200 ° C.

The thickness of the copolymerized polyethylene terephthalate film used in the present invention can be appropriately set depending on the field of application of the photographic film, but is preferably 25 to 250 μ, more preferably 40 to 1
A thickness of 50μ is adopted.

In the copolymer composition according to the present invention, the excellent transparency and mechanical strength originally possessed by PET are not impaired, the film haze is 3% or less, the breaking strength is 8 to 25 kg / mm ² , and the initial elastic modulus is Tear strength of 200-500kg / mm ² and film thickness of 50μ is 30g or more at 120μm thickness. If the strength is less than this
The excellent mechanical properties of T are impaired and TAC
Loses its advantage over.

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

〔transparency〕

Film haze was measured according to ASTM-D1003-52.

[Breaking strength and initial elastic modulus]

According to JIS-Z1702-1976, it is a strip with a width of 10 mm and a length of 100 mm, and the pulling speed is 300 mm / when measuring the breaking strength.
The initial elastic modulus was measured at 20 mm / min.

[Measurement of tear strength]

Using a light load type tear strength tester (manufactured by Toyo Seiki Co., Ltd.), a sample size of 51 × 64 mm was cut into a 13 mm cut, and the indicated value when the remaining 51 mm was torn was read.

The polyester film support of the present invention is characterized in that it has excellent decurling property (hereinafter referred to as curl recovery rate) after development processing. In the present invention, the curl recovery rate measured by the following method is 50% or more, and particularly preferably 80% or more.

[Measurement of curl recovery rate]

A film with a sample size of 12 cm x 35 mm is wound on a core with a diameter of 10 mm, treated at 60 ° C x 30% RH x 72 hr, and then
After releasing from the core and immersing in distilled water at 40 ° C for 15 minutes, load 50g and dry for 3 minutes in an air bath at 55 ° C, hang the sample vertically, measure the sample length, and measure the original 12cm sample. I evaluated how long I recovered. The copolymerized polyethylene terephthalate film used in the present invention is characterized in that it has excellent adhesiveness to various coating layers such as emulsion layers as compared with conventional polyethylene terephthalate films.

The polyester film of the present invention may be subjected in advance to various surface treatments such as corona discharge treatment, chemical treatment and fire treatment in order to improve the adhesiveness and the wetting property of the coating liquid. Among these surface treatments,
Most preferably used in the present invention is the corona discharge treatment in which the precipitation of low polymerized substances on the film surface is small.

The polyester support of the present invention preferably has a subbing layer in order to increase the adhesive force with 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 gelatin.

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

Examples of the hydrophilic binder used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. As the water-soluble polymer, gelatin, gelatin derivatives, casein, agar,
Examples thereof include sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, and maleic anhydride copolymer, and examples of the cellulose ester include carboxymethyl 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 and butadiene-containing copolymers. Of these, gelatin is the most preferred.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, Examples include trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred.

Various gelatin hardeners can be used in the subbing layer of the present invention.

As a gelatin hardening agent, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on.

In the underlayer of the present invention, inorganic fine particles such as SiO ₂ and TiO ₂ or polymethyl methacrylate copolymer fine particles (1 to
10 μm) can be contained as a matting agent.

The undercoat layer according to the present invention can be applied by a generally well-known coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method or the like. Is.

The light-sensitive material of the present invention may have a non-light-sensitive layer such as an anti-halation layer, an intermediate layer, a back layer and a surface protective layer in addition to the light-sensitive layer.

The binder for the back layer may be a hydrophobic polymer or a hydrophilic polymer used in the underlayer.

The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a slip agent, a matting agent, a surfactant, a dye and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, and examples thereof include polymers containing anionic polymer electrolytes such as carboxylic acids and carboxylates, sulfonates, for example, JP-A-48-22017. , Japanese Examined Sho 46-241
Polymers such as those described in JP-A-59-30725, JP-A-51-129216, and JP-A-55-95942.
As the cationic polymer, for example, JP-A-49-121523,
There are those described in JP-A-48-91165 and JP-B-49-24582. Ionic surfactants also have anionic and cationic properties, and are described in, for example, JP-A-49-85826.
No. 4, JP-A-49-33630, US2,992,108, US3,206,312,
JP-A-48-87826, JP-B-49-11567, JP-B-49-11
Examples thereof include compounds described in JP-A No. 568 and JP-A No. 55-70837.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₃ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, Ba.
It is fine particles of at least one crystalline metal oxide selected from O and MoO ₃ or a composite oxide thereof.

The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The particle size is preferably 0.01 to 0.7 µ, and more preferably 0.02 to 0.5 µ.

A method for producing fine particles of a conductive crystalline metal oxide or composite oxide used in the present invention is described in JP-A-56-
It is described in detail in the specifications of 143430 and 60-258541. First, the metal oxide fine particles are produced by firing,
A method of heat treatment in the presence of a heteroatom for improving conductivity, a second method of coexisting with a heteroatom for improving conductivity when producing metal oxide fine particles by firing, and a third method: metal fine particle by firing. The method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere during the production of is easy. For example, ZnO contains Al, In, T, etc.
Examples include Nb and Ta for iO ₂ , Sb, Nb, and halogen elements for SnO ₂ . Heteroatom addition amount is 0.01-30
The range of mol% is preferable, but 0.1 to 10 mol% is particularly preferable.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The most preferable photographic light-sensitive material of the present invention is
It is a silver halide photographic light-sensitive material, and examples thereof include a silver halide color negative film, a color positive film, a color reversal film and a black and white negative film.

The photographic emulsion used in the present invention is described by P. Glafkides Chimi.
e et Physique Photographique (Paul Montel, 196
7 years), Photographic Emulsion Chemistry by GF Duffin
(The Focal Press, 1966), VLZelikman et al
By Making and Coating Photographic Emulsion (The Fo
cal Press, 1964) and the like. That is, any of an acidic method, a neutral method, ammonia, etc. may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PA in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
It is also possible to use a method of keeping g constant, that is, a so-called controlled double jet method.

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

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

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts thereof may coexist in the course of silver halide grain formation or physical ripening.

As the binder or protective colloid for the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

In addition to incised processed gelatin, acid processed gelatin and Bull.Soc.Sci.Phot.Japan.No.16, p.30 (1966)
The enzymatic gelatin as described in 1. may be used, and a hydrolyzate or an enzymatic degradate of gelatin can also be used. As the gelatin derivative, various compounds such as acid halide, acid anhydride, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds are reacted with gelatin. What is obtained is used. Specific examples thereof are U.S. Pat.
No. 2945, No. 3186846, No. 3312553, British Patent 861414
No. 1033189, No. 1005784, and Japanese Examined Patent Publication No. 42-26845.

The gelatin / graft polymer is obtained by grafting a homopolymer or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. to gelatin. Can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a copolymer of acrylic acid, methacrylic acid, acrylamide, sotaacrylamide, hydroxyalkyl methacrylate, etc. is preferable. Examples of these are described in US Pat. Nos. 2,763,625, 2831767, 2956884, and the like.

Representative synthetic hydrophilic polymer substances are, for example, West German patent application (OLS) 2312708, US Pat. Nos. 3620751, 3879205.
And Japanese Patent Publication No. 437561.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes, etc .; Ben Nchiosurufon acid, benzene sulfinic acids, can be added to many compounds known as antifoggants or stabilizers such as benzenesulfonic acids amides. For example, it can be described in U.S. Pat. Nos. 3,954,474, 39,82947 and JP-B-52-28660.

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, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, tetragonal ammonium. Salt compounds, urethane derivatives,
It may contain a urea derivative, an imidazole derivative, 3-pyrazolidones and the like. For example, US Patent Nos. 2400532 and 24235.
49, 2716062, 3617280, 3772021, 380
It is possible to use those described in 8003, British Patent 1488991 and the like.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes.

That is, 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, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus of fused aromatic hydrogen ring, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benz Imidazole nucleus, quinolinic acid, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, or thiobarbituric acid nucleus can be applied.

Useful sensitizing dyes are, for example, German Patent No. 929080, U.S. Patent Nos. 2,231,658, 2493748, 2503776, and 2519001.
No. 2912329, 3656959, 3672897, 36942
No. 17, No. 4025349, No. 4046572, British Patent 1242588
Nos. 4414030 and 52-24844.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. A typical example is a US patent
No. 2688545, No. 2977229, No. 3397060, No. 3522052,
3527641, 3617293, 3628964, 3666480
No. 3672898, No. 3679428, No. 3703377, No. 37693
No. 01, No. 3814609, No. 3837862, No. 4026707, British Patent No. 1344281, No. 1507803, Japanese Patent Publication No. 43-4936, No. 53
-12375, JP-A Nos. 52-110618 and 52-109925.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic ring groups (for example, those described in US Pat. Nos. 293390 and 3635721), aromatic organic acid formaldehyde condensed rings (for example, those described in US Pat. No. 3743510). , A cadmium salt, and an azaindene compound may be included. US Patent
The combinations described in 3615613, 3615641, 3617295, and 3635721 are particularly useful.

The light-sensitive material prepared by 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 prevention of irradiation.
Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include U.S. Pat.
1177429, JP-A-48-85130, 49-99620, 4
9-114420, 52-108115, U.S. Pat.
No. 2533472, No. 2956879, No. 3148187, No. 3177078,
3247127, 3540887, 3575704, 3653905
No. 3714872, No. 4071312, and No. 4070352.

In the light-sensitive material produced by using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightening agent. These water-soluble whitening agents may be used, or a water-insoluble whitening agent may be used in the form of a dispersion. Specific examples of optical brighteners are U.S. Pat. Nos. 2632701 and 32698.
40, 3359102, British Patents 852075, 1319763 and the like.

In carrying out the present invention, the following known color fading inhibitors can be used in combination, and the color image stabilizers used in the present invention can be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat.
No. 13, 2675314, 2701197, 2704713, 272
8659, 2732300, 2735765, 2710801, 2
No. 816028, British Patent No. 1363921, hydroquinone derivatives described in, U.S. Patent Nos. 3457079, 3069262,
Gallic acid derivative described in US Patent No. 2735765,
P-alkoxyphenols described in JP-B-3698909, JP-B-49-20977 and JP-B-52-6623, U.S. Pat.
No. 3573050, No. 3574627, No. 3764337, JP-A-5
2-35633, 52-147434, and 52-152225, p-oxyphenol derivatives, and bisphenols described in U.S. Pat. No. 3,700,455.

The light-sensitive material produced by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color antifoggant, and specific examples thereof are U.S. Pat.
No. 27, No. 2403721, No. 2418613, No. 2675314, No. 270
1197, 2704713, 2728659, 2732300, 2
735765, JP-A-50-92988, 50-92989, 50-
93928, 50-110337, 52-146235, Japanese Patent Sho 50
-23813 etc.

The present 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 required. It is usual to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases.

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

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) which reacts with an oxidation product of an aromatic amine (usually primary amine) developing agent to form a dye. The coupler is preferably a non-diffusing coupler having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be contained. The coupler may be such that the product of the coupling reaction is colorless.

As the yellow color coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color couplers that can be used include U.S. Pat.Nos. 2875057, 3265506, 3408194, and 3
No. 551155, No. 3582322, No. 3725072, No. 3891445,
West German Patent 1547868, West German Application Publication No. 2219917, 226136
1, No. 2414006, British Patent No. 1425020, Japanese Patent Publication No. 51-107
83, JP-A-47-26133, 48-73147, 51-1026
No. 36, No. 50-6341, No. 50-123342, No. 50-130442
No. 51-21827, No. 50-87650, No. 52-82424,
No. 52-115219 and the like.

As a magenta color coupler, a pyrazolone compound,
Indazolone compounds and cyanoacetyl compounds can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta color couplers that can be used include U.S. Pat.Nos. 2600788, 2983608, 3062653, and 3127269.
No. 3311476, No. 3413991, No. 3519429, No. 35583
No. 19, No. 3582322, No. 3615506, No. 3834908, No. 389
1445, West German patent 1810464, West German patent application (OLS) 2408
No. 665, No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 40-6031, JP-A No. 51-20826, No. 52-58922,
49-129538, 49-74027, 50-159336, 52
-42121, 49-74028, 50-60233, 51-265
41 and 53-55122.

As the cyan color coupler, a phenol compound, a naphthol compound or the like can be used. Specific examples thereof are U.S. Patent Nos. 2369929, 2434272, 2474293,
No. 2521908, No. 2895826, No. 3034892, No. 3311476
No. 3, 3458315, 3476563, 3583971 and 35913.
No. 83, No. 3767411, No. 4004929, West German patent application (OL
S) 2414830, 2454329, JP-A-48-59838, 51
-26034, 48-5055, 51-146828, 52-696
No. 24 and No. 52-90932.

Examples of colored couplers include U.S. Pat.
No. 2521908, No. 3034892, Japanese Patent Publication No.44-2016, No.
38-22335, 42-11304, 44-32461, JP-A-5
Those described in the specifications of 1-26034, 52-42121 and West German patent application (OLS) 2418959 can be used.

Examples of the DIR coupler include U.S. Pat.
No. 3617291, No. 3701783, No. 3790384, No. 3632345
, West German patent application (OLS) 2414006, 2454301, 2
No. 454329, British Patent No. 953454, Japanese Patent Laid-Open No. 52-69624, No. 4
Those described in 9-122335 and JP-B-51-16141 can be used.

In addition to the DIR coupler, a compound which releases a development inhibitor upon development may be contained in the light-sensitive material. For example, US Patent Nos. 3297445 and 3379529, West German Patent Application (OL
S) 241794, JP-A-52-15271 and JP-A-53-9116 can be used.

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

These couplers are generally used in an amount of 2 × 10 ^-3 mol to 5 × 10 ^-1 mol, preferably ¹ × 10 ^-1 mol, per mol of silver in the emulsion layer.
^-2 mol to 5 × 10 ^-1 mol is added.

To introduce the above coupler into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2322027 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citrate ester (eg tributyl acetyl citrate), benzoate ester (eg octyl benzoate), alkyl amide (eg Diethyl lauryl amide), fatty acid esters (such as dibutoxyethyl succinate, dioctyl azelate), etc., or organic solvents having a boiling point of about 30 ° C. to 150 ° C., such as ethyl acetate, lower alkyl acetates such as butyl acetate, ethyl flopionate, After being dissolved in 2-sphere butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., they are dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Also, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can be used.

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

The light-sensitive material produced by using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group (for example, those described in US Pat. No. 3,533,794), a 4-thiazolidone compound (for example, those described in US Pat. −2784
No.), cinnamic acid ester compounds (for example, those described in US Pat. Nos. 3,705,805 and 3707375), butadiene compounds (for example, those described in US Pat. No. 4045229), or benzoxazole compounds such as US Pat. No. 3700455. Those described in 1.) can be used. Further, those described in U.S. Pat. No. 3,499,762 and JP-A-54-48535 can be used. Ultraviolet absorbing couplers (for example, α-naphthol type cyan dye forming couplers) and ultraviolet absorbing polymers may be used. These UV absorbers may be mordanted in a specific layer.

For the photographic processing of the light-sensitive material of the present invention, any known method can be used. A known treatment liquid can be used. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, either development processing for forming a silver image (black photographic processing) or color photographic processing including development processing for forming a dye image can be applied.

The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 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
-Methanesulfamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline).

LFA Mason Photographic Processing Chemi
Those described in stry (Focal Press, 1966), pages 226 to 229, U.S. Pat. Nos. 2,193,015 and 2,952,364, and JP-A-48-64933 may be used.

The color developer may further contain a pH buffering agent such as alkali metal sulfite, carbonate, borate and phosphate, a development inhibitor or an antifoggant such as bromide, iodide and an organic antifoggant. it can. If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol and diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as an amine, a dye-forming coupler, a competitive coupler, sodium. Fogging agent such as borohydride, auxiliary developing agent such as 1-phenyl-3-pyrazolidone, viscosity imparting agent, polycarboxylic acid type chelating agent described in U.S. Pat. No. 4,083,723, oxidation described in West German publication (OLS) 2622950. Inhibitors may be included.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids, quinones and nitroso compounds are used. For example, a ferricyanide compound, a dichromate, an organic complex salt of iron (III) or cobalt (III), for example, an aminopolycaponate such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates; nitrosophenol and the like can be used. Of these, the couplers of the present invention also show a large color forming property in a bleaching solution and a bleach-fixing solution containing ethylenediaminetetraacetic acid iron (III) sodium and ethylenediaminetetraacetic acid iron (III) ammonium and having a weak oxidizing power. It is advantageous. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

For bleaching or bleach-fixing solutions, U.S. Pat.
Various additives such as a bleaching accelerator described in JP-B No. 241966, JP-B No. 45-8506, and JP-B No. 45-8836, a thiol compound described in JP-A No. 53-65732, and the like can also be added.

(Examples) The present invention will be further described with reference to examples.

Example-1 1) Preparation of polyethylene terephthalate film 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 adibate were added to 0.1 part of calcium acetate monohydrate. Parts by weight and antimony trioxide
0.03 parts by weight was added, and transesterification reaction was carried out by a conventional method. Phosphoric acid trimethyl ester 0.05 was obtained.
Add parts by weight, gradually raise the temperature and reduce the pressure, and finally add 280
Polymerization was carried out at a temperature of 1 mmHg or less to obtain a copolymerized polyethylene terephthalate.

The obtained copolymerized polyethylene terephthalate had an intrinsic viscosity of 0.657 measured in o-chlorophenol at 25 ° C.

Copolyethylene terephthalate was dried by a conventional method and then melt extruded at 280 ° C. to prepare an unstretched sheet.
Next, at 90 ℃, 3.5 times in the machine direction and 3.7 times in the transverse direction at 95 ℃, and then draw the film successively, and heat-set at 200 ℃ for 5 seconds to obtain a 100μ thick film.
An axially stretched film was obtained. The film has a haze of 1.2.
%, The breaking strength was 12 kg / mm, the initial elastic modulus was 340 kg / mm, and the transparency and mechanical properties were good.

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

Clarity: The haze of the film was measured according to ASTM-D1003-52.

Breaking strength and initial elastic modulus: According to JIS-Z1702-1976, it is a strip with a width of 10 mm and a length of 100 mm, and the pulling speed is 300 mm / when measuring the breaking strength.
The initial elastic modulus was measured at 20 mm / 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 T film
The water content of the AC film (thickness 125 μm) was measured by the method of the present invention.

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

[Curl Evaluation Method] A film having a sample size of 12 cm x 35 mm is wound on a core having a diameter of 10 mm, treated at 60 ° C x 30% RH x 72 hr, and then,
After releasing from the core and immersing in distilled water at 40 ° C for 15 minutes, load 50g and dry for 3 minutes in an air bath at 55 ° C, hang the sample vertically, measure the sample length, and measure the original 12cm sample. I evaluated how long I recovered.

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

3) Preparation of photographic light-sensitive material 3-1) Coating of subbing layer Each of the PET film according to the present invention and a commercially available PET film was subjected to corona discharge treatment on both sides thereof, and then a subbing layer having the following composition was provided. . The degree of corona discharge treatment is 0.02KV
It was A · min / m ² .

Gelatin 3 g Distilled water 250 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g 3-2) Coating of back layer A back layer having the following composition was coated on one side of the PET film after undercoating.

[Preparation of tin oxide-antimony oxide composite dispersion]

230 parts by weight of stannic chloride hydrate and 23 antimony trichloride
A part by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The coprecipitate obtained is heated to 50 ° C.
After standing for 24 hours, a reddish brown colloidal precipitate was obtained.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions.

200 parts by weight of colloidal precipitate from which excess ions have been removed
It was redispersed in 500 parts by weight and sprayed onto a calcined filter heated to 600 ° C. to obtain a tin-tin-antimony oxide composite fine particle powder having a bluish average particle size of 0.2 μm. The specific resistance of this fine particle powder was 25 Ω · cm.

A pH of 7.
After adjusting to 0 and coarsely dispersing with a stirrer, residence time in a horizontal sand mill (trade name Dynomill; manufactured by WILLYA.BACHOFEN AG)
It was prepared by dispersing for 30 minutes.

(Coating of Back Layer) The following formulation [A] was applied to a dry film thickness of 0.3 μm and dried at 130 ° C. for 30 seconds. The coating solution (B) for coating layer described below was further applied thereon to a dry film thickness of 0.1 μm, and dried at 130 ° C. for 2 minutes.

3-3) Coating of photographic layer The following photographic layer was provided on the opposite side of the PET film of the present invention and the commercially available PET film having the back layer as described above.

First layer: Red-sensitive silver halide low-sensitivity layer (1-a) Preparation of emulsion liquid for low-sensitivity unit emulsion layer Silver iodobromide emulsion containing 6 mol% iodine (average grain size 0.6 µ, emulsion 1 kg Per 100g silver halide, 70 gelatin
g) was prepared in the usual way. Anhydro-5,5'-dichloro-9 was added to 1 kg of this emulsion as a red-sensitive color sensitizer.
-Ethyl-3,3'-di (3-sulfopropyl) thiacarbocyanine hydroxide of pyridinium nalto.
180cc of 1% methanol solution was added, and then 5-methyl-7
20 cc of a 5% by weight aqueous solution of -hydroxy-2,3,4-triazaindolizine, 330 g of the cyan coupler emulsion (1) and 20 g of (2) according to the following formulation were added. Further, as a gelatin hardening agent, 50 cc of a 2% by weight aqueous solution of 2-hydroxy-4,6-dichlorotriazine sodium salt was added to prepare an emulsion liquid for a low sensitivity emulsion.

Emulsion (1) 10% by weight aqueous gelatin solution 1.000 g p-dodecylbenzene sulfonic acid soda 5 g tricresyl phosphate 60 cc cyan coupler (C-7) 70 g Ethyl acetate 100 cc After dissolving the mixture at 55 ℃, preheat to 55 ℃. In addition to being heated, it was emulsified with a colloid mill.

Emulsion (2) 10% by weight aqueous gelatin solution 1.000 g p-dodecylbenzene sulfonate sodium 5 g tricresyl phosphate 60 cc Cyan coupler ^* 6 g DIR Cyan coupler ^** 64 g Ethyl acetate 100 cc * Cyan coupler is the same as above.

Second layer: red-sensitive silver halide medium-sensitivity layer (1-b) Preparation of emulsion solution for medium-sensitivity emulsion layer The following changes were made in the above (1-a).

Third layer: red-sensitive silver halide high-sensitivity layer (1-c) Preparation of emulsion liquid for high-sensitivity emulsion layer The following changes were made in (1-a).

Fourth layer: gelatin intermediate layer Fifth layer: green light-sensitive silver halide low-sensitivity layer (2-a) Preparation of emulsion solution for low-sensitivity emulsion layer Silver iodobromide emulsion containing 6 mol% iodine (average grain size 0.6μ, 100g silver halide per 1kg emulsion, 70 gelatin
g) was prepared in the usual way. 1 kg of this emulsion contained 3,3'-di (3-sulfoethyl) -9 as a green-sensitive color sensitizer.
200 ml of a 0.1% solution of ethyl-benzooxacarbocyanine pyridinium salt in methanol was added, followed by addition of 5-methyl-7-hydroxy-2,3,4-triazaindolizine 5
A 20% by weight aqueous solution was added, and further 380 g of the magenta coupler emulsion (3) and 20 g of the same (4) according to the following formulation were added.

Further, as a gelatin hardener, 2-hydroxy-4,6-
50cc of 2 wt% aqueous solution of dichlorotriazine sodium salt
Was added to prepare an emulsion liquid for low-speed emulsion.

Emulsion (3) 10% by weight aqueous gelatin solution 1.000 g p-dodecylbenzene sulfonic acid soda 5 g tricresyl phosphate 65 cc Magenta coupler (M-7) 6 g Ethyl acetate 110 cc After dissolving the mixture at 55 ℃, pre-heat to 55 ℃. In addition to being heated, it was emulsified with a colloid mill. Magenta coupler (M-7): 1- (2,4,6-trichlorophenyl) -3-
[3- (2,4-di-t-pentylphenoxyacetamide) benzamide] -5-pyrazolone emulsion (4) 10% by weight gelatin aqueous solution 1.000 g p-dodecylbenzene sulfonic acid soda 5 g tricresyl phosphate 65 cc Magenta coupler ^* 63g DIR Magenta coupler ^** 60g Ethyl acetate 110cc Emulsified by the same operation as the emulsion (3).

** DIR Magenta coupler: 1- (4- [2- (2,4-di-
t-pentylphenoxy) butanamide] phenyl)-
3- (1-pyrrolidinyl) 4- (1-phenyltetrazolyl-5-thio) -5-pyrazolone Sixth layer: Green-sensitive silver halide medium-sensitive layer (2-b) Preparation of emulsion solution for medium-sensitive emulsion layer Silver iodobromide emulsion containing 5 mol% iodine (average grain size 0.9 μm, per 1 kg emulsion) Halogen silver 100g, gelatin 70
g) was prepared in the usual way. To 1 kg of this emulsion,
A solution of the green-sensitive color sensitizer shown in (2-a) in methanol 15
0cc was added, and then 5-methyl-7-hydroxy-2,3,4-
20 cc of a 5% by weight aqueous solution of triazaindolizine was added.
Further, 285 g of the emulsion (3) and 15 g of the emulsion (4) were added.

Further, 50 cc of a 2% by weight aqueous solution of 2-hydroxy-4,6-dichlorotriazine sodium salt was added as a gelatin hardener to give an emulsion liquid for a medium-speed emulsion layer.

Seventh layer: Green-sensitive silver halide high-sensitivity layer (2-c) Preparation of emulsion solution for high-sensitivity emulsion layer Silver iodobromide emulsion containing 6 mol% iodine (average grain size 1.1 µ, 1.0 µ or more) 50% by weight of total particles, emulsion 1k
100 g of silver halide and 70 g of gelatin were contained per g) were prepared by a usual method. To 1 kg of this emulsion was added 80 cc of a methanol solution of the green-sensitizing color sensitizer shown in (2-a), and then a 5% by weight aqueous solution of 5-methyl-7-hydroxy-2,3,4-triazaindolizine. Add 20 cc and add 20 more emulsion (3)
Added 0g.

Further, as a gelatin hardener, 2-hydroxy-4,6-
50cc of 2 wt% aqueous solution of dichlorotriazine sodium salt
Was added to prepare an emulsion for high-sensitivity emulsion.

Eighth layer: Yellow filter layer made of yellow colloidal silver (dry film thickness 1.2 μm) Ninth layer: Blue photosensitive layer Silver halide low-sensitivity layer (3-a) Preparation of emulsion liquid for low-sensitivity emulsion layer- (1 ) Silver iodobromide emulsion containing 5 mol% iodine (average grain size of 0.6μ, 100 g of silver halide per kg of emulsion, 70 g of gelatin)
g) was prepared in the usual way. 5 to 1 kg of this emulsion
20 cc of a 5% by weight aqueous solution of methyl-7-hydroxy-2,3,4-triazaindolizine and 600 g of a yellow coupler emulsion (5) having the following formulation were added. Further, as a gelatin hardening agent, 50 cc of a 2% by weight aqueous solution of 2-hydroxy-4,6-dichlorotriazine sodium salt was added to prepare an emulsion liquid for a low sensitivity emulsion.

Emulsion (5) 10% by weight aqueous gelatin solution 1.000 g p-dodecylbenzene sulfonic acid soda 5 g tricresyl phosphate 80 cc yellow coupler ^* 100 g yellow DIR coupler ^** 10 g ethyl acetate 120 cc 10th layer: Blue-sensitive silver halide intermediate sensitivity layer The above (3-a) was changed as follows.

Eleventh layer: Blue-sensitive silver halide high-sensitivity layer (3-a) above was changed as follows.

12th layer: Surface protection layer 10% by weight gelatin solution 1000cc Sodium dodecylbenzene sulfonate 40mg SiO ₂ fine particles (3.0μ) 50mg Sodium folistyrenesulfonate 1g 2-Hydroxy-4,6-dichlorotriazine 50mg The above photosensitive layers The amount of coated silver was as follows.

1st layer (1.0g / m ² ), 2nd layer (0.8g / m ² ), 3rd layer (1.
2g / m ² ), 5th layer (1.2g / m ² ), 6th layer (1.0g / m ² ), 7th layer (1.2g / m ² ), 9th layer (0.6g / m ² ), 10th layer (0.6g / m
² ), 11th layer (0.6 g / m ² ) The color negative film thus obtained was cut into a size of 35 m / m and loaded into a patrone.

After leaving it at 40 ° C. for 10 days, it was photographed with an ordinary camera and the following development processing was performed.

Treatment process Temperature Time Color development 38 ℃ 3 minutes Stop 38 ℃ 1 minute Water wash 〃 1 〃 Bleach 〃 2 〃 Water wash 〃 1 〃 Fixed 〃 2 〃 Water 〃 1 〃 Constant 〃 The treated liquid has the following composition.

Color developer Caustic soda 2g Sodium sulfite 2g Potassium bromide 0.4g Sodium chloride 1g Hoh sand 4g Hydroxyamine sulphate 2g Ethylenediaminetetraacetic acid disodium dihydrate 2g 4-Amino-3-methyl-N-ethyl-N- (β- Hydroxyethyl 1 aniline monosulfate 4g Water added to a total volume of 1 Stop solution Sodium thiosulfate 10g Ammonium thiosulfate (70% aqueous solution) 30ml Acetic acid 30ml Sodium acetate 5g Potassium alum 15g Water added to a total volume of 1 Ethylenediamine tetrairon acetate ( III) Sodium dihydrate 100 g Potassium bromide 50 g Ammonium nitrate 50 g Horic acid 5 g Ammonia water Adjust the pH to 5.0 and add water 1 Total fixer 1 Sodium thiosulfate 150 g Sodium sulfite 15 g Hosoda 12 g Glacial acetic acid 15 ml Potassium alum 20 g Water 1 total stabilizing bath formic acid 5 g sodium citrate 5 g sodium metaphoric acid (tetrahydrate) 3 g Potassium alum 15g Water was added and the total amount was 1. The curl situation after development was not resolved in the case of a photosensitive material having a commercially available PET film as a support, but the PET film according to the present invention In the case of a light-sensitive material using as a support, almost no curling occurred.

Comparative Example 1 1) Instead of 10 parts by weight of dimethyl adipate, a molecular weight of 40
A biaxially stretched copolymerized polyethylene terephthalate film having a thickness of 100 μm (having an intrinsic viscosity of 0.6) was prepared in the same manner as in Example 1 except that 10 parts by weight of polyethylene glycol of 00 was used.
7) got. The film has a haze of 4.5% and a breaking strength.
8 kg / mm ² and an initial elastic modulus of 320 kg / mm ² , the transparency was poor and it was not preferable as a support for a photographic light-sensitive material.

2) A photographic light-sensitive material was produced in the same manner as in Example 1 by using the biaxially stretched copolymer polyethylene reterephthalate film. The exposed film of the film after development was opaque and the image was blurred, and was not suitable as a photographic light-sensitive material.

(Effects of the Invention) The light-sensitive material of the present invention uses a polyester film having excellent mechanical strength as a support, while maintaining its characteristics,
The curling curl after the development process could be eliminated.

The light-sensitive material of the present invention has excellent mechanical performance and can easily eliminate curling curls after development, so that the thickness of the support can be significantly reduced even in the case of a roll film, and the shape of the cartridge can be made compact. It is possible to load a long film in the same cartridge. The polyester film of the present invention can be produced at a low casting temperature, does not break during stretching, has a high water content, and has the original merit of the polyester film.

Further, although the water content is high, the precipitation of oligomers is extremely small, and the photographic performance is not adversely affected.

Further, since the humidity inside the case for packaging the light-sensitive material can be lowered, the photographic performance does not change with time.

 A preferred embodiment of the present invention is as follows.

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

2) The light-sensitive material according to claims 1 to 3, wherein the water content of the polyester is 0.6 to 5.0% by weight.

3) Aromatic dicarboxylic acids having metal sulfonates include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid and their sodium as potassium. Or a compound selected from a compound substituted with halithium and the above 1),
2) Photosensitive material.

4) The copolymerization amount of the aromatic dicarboxylic acid component having a metal sulfonate is 2 to 15 mol% with respect to the terephthalic acid component.
The light-sensitive material according to claim 2 or 3, and 3) above.

5) The aliphatic dicarboxylic acid component is selected from succinic acid, adipic acid and sebacic acid, and the above 1) to 1).
4) Photosensitive material.

6) An aliphatic dicarboxylic acid having 4 to 20 carbon atoms such as succinic acid, adipic acid or sebacic acid as a copolymerization component is 3 to 25 mol% with respect to the terephthalic acid component, and the above 1) to 6). Photosensitive material.

7) The light-sensitive material according to 6) above, which further contains polyalkylene glycol as a copolymerization component.

8) The above 1) in which a polyester film contains a dye.
Light-sensitive material of 7).

9) The photosensitive material as described in 1) to 8) above, wherein the polyester film is subjected to corona discharge treatment.

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

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

12) The above 11) in which the photosensitive material is in the form of a roll film.
Photosensitive material.

13) The above which has at least one red photosensitive layer, at least one green photosensitive layer and at least one blue photosensitive layer
11) Color negative film.

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

15) The photosensitive material according to 14) above, wherein the curl recovery rate of the polyester film is 80% or more.

16) The photosensitive material according to any one of claims 1 to 4) and 1) to 15) above, wherein the polyester film has a thickness of 30 to 120 µm.

17) The photosensitive material according to 16) above, wherein the polyester film has a thickness of 40 to 100 μm.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoaki Ueda 4845 Mishima City, Shizuoka Prefecture (No town, chome display) Inside the Mishima Plant of Toray Industries, Inc. (72) Kenji Kita 4845 Mishima City, Shizuoka Prefecture (town, (Not displayed) Toray Industries, Inc. Mishima Plant (56) Reference JP-A-1-236247 (JP, A) JP-A-63-35328 (JP, A) JP-A-56-102849 (JP, A)

Claims (4)

(57) [Claims] 1. A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a polyester film support, wherein the haze of the polyester film is 3.
%, A water content of 0.5% by weight or more, and a curl recovery rate of 50% or more. 2. A polyester film is a copolyester film containing an aromatic dicarboxylic acid having a metal sulfonate as a copolymerization component, and has a breaking strength of 8 to 25 kg.
/ mm ^2, photographic material as claimed in claim 1 initial modulus of 200~500kg / mm ^2. 3. A copolymerized polyester film obtained by copolymerizing an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms as a copolymer component other than an aromatic dicarboxylic acid component having a metal sulfonate as a support. Photographic light-sensitive material. 4. The main acid component of the polyester constituting the copolymerized polyester film is terephthalic acid,
The photographic light-sensitive material according to claim 3, wherein the copolymerization ratio of the aliphatic dicarboxylic acid having 4 to 20 carbon atoms to the terephthalic acid is 3 to 25 mol%.