JP2879251B2 - Rolled silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a roll-shaped silver halide photographic light-sensitive material. More specifically, the present invention relates to a method of using a plurality of laminated polyester resin films as a support. The present invention relates to a roll-shaped silver halide photographic material having excellent curl resolving properties.

2. Description of the Related Art Photosensitive materials are generally produced by coating at least one photosensitive 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.

Generally, photographic light-sensitive materials are typically in the form of a sheet, such as a film for X-ray, a film for plate making, and a cut film, and in the form of a roll. Typical examples of the roll film include a color film or a black-and-white negative film which is housed in a patrone with a width of 35 mm or less and is used by a general camera for photographing.

Conventionally, a support mainly composed of a TAC film has been used for a roll film. The features of the TAC film as a photographic support are that it has no optical anisotropy and high transparency, and that it also has excellent properties in decurling after development processing. The superior properties for decurling come from the molecular structure of the TAC film. In other words, the TAC film has a relatively high water absorption as a plastic film, and the molecular chains can be caused to flow by the water absorption in the development process. This can be solved by causing rearrangement in the immobilized molecular chain.

On the other hand, in the case of a photographic light-sensitive material using a film having no curl removal property, when used in a roll state,
For example, in a printing process for forming an image on photographic printing paper after development, problems such as generation of scratches, defocusing, and jamming during transport may occur.

By the way, in recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film transport during photographing, the increase in photographing magnification,
In addition, the miniaturization of the photographing apparatus has been remarkably progressed. For this purpose, a support for a photographic light-sensitive material is required to have properties such as strength, dimensional stability, and thinning.

However, since the TAC film has a rigid molecular structure, the film quality of the formed film is fragile, and there is a difficulty in using these applications.

[Problems to be Solved by the Invention] In contrast, polyethylene terephthalate resin (PE)
T) Films have been considered as an alternative to TAC films because of their excellent productivity, mechanical strength, and dimensional stability.

However, PET films are widely used as photographic light-sensitive materials, and roll curl remains strongly.Therefore, the handling properties after development are poor. Had difficulties and was a problem. As a means for solving this curling problem, Japanese Patent Application Laid-Open No. 1-244446 discloses a technique using a polyester film having a water content of 0.5% by weight or more as a support. The water content of a PET film is usually about 0.3% by weight, and in order to increase the water content, this publication attempts to increase the water content to 0.5% by weight or more by copolymerizing an aromatic dicarboxylic acid having a metal sulfonate.

According to this technology, the water content can be increased by increasing the metal sulfonate, but if it is increased too much, the mechanical strength such as the fragility and tear strength of the film deteriorates, making it unusable as a photographic support . This means that the copolymerization ratio of the aromatic dicarboxylic acid component having a metal sulfonate is 2 to 15 mol% based on the terephthalic acid component in the seventh column of the publication.
However, in Example 1, only 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, that is, 7 mol% was copolymerized with respect to 100 parts by weight of dimethyl terephthalate, and as a result, the water content was 0.7%. %. In the measurement in the same example, the water content of the TAC film was 2.6%. In order to increase the water content as much as a TAC film, it is necessary to copolymerize more aromatic dicarboxylic acid components having a metal sulfonate.
If the water content is about 0.7%, the curl is strong, and if the curl is attached, it may not be able to recover sufficiently.

Further, although there is no specific description in the publication, it is considered that the film obtained by the technique has a low tear strength and a low folding endurance, and is unsuitable for practical use.

The present invention has been made to solve the above problems,
SUMMARY OF THE INVENTION An object of the present invention is to provide a photographic light-sensitive material having excellent mechanical properties and curl removability after development processing.

[Means for Solving the Problems] An object of the present invention is to provide a roll-shaped silver halide photographic material in which at least one silver halide photographic emulsion is coated on a support made of a plurality of polyester resin films, The rolled silver halide photographic material is characterized in that the plurality of polyester resin films are obtained by laminating at least two polyester resin films having different water contents.

In the photographic light-sensitive material of the present invention, a support in which at least two polyester resin films having different moisture contents are laminated is used. At this time, at least one layer of the polyester resin film is preferably a polyethylene terephthalate resin (PET) film having a thickness of 5 μm or more and 100 μm or less.

The polyethylene terephthalate resin (PE) referred to in the present invention
T) is a polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative with ethylene glycol,
As long as the intrinsic properties of PET are not impaired, it includes those containing other polymers, additives and the like, or copolyesters obtained by copolymerizing dibasic acids other than terephthalic acid and polyhydric alcohols other than ethylene glycol.

The moisture content of the polyester resin film was measured at 23 ° C. and 30% RH for 3 hours.
Immersed in distilled water for 15 minutes, and then dried at a drying temperature of 15 using a trace moisture meter (for example, CA-02 type manufactured by Mitsubishi Kasei Corporation).
Perform at 0 ° C.

In the present invention, the polyester resin film having a high water content is preferably laminated so as to be located on the surface, and particularly preferably, the polyester resin film having a high water content is obtained by copolymerizing an aromatic dicarboxylic acid component having a metal sulfonate with a copolymer component. Is a copolymerized polyester resin film.

As the aromatic dicarboxylic acid having a metal sulfonate, specifically, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid And compounds obtained by substituting sodium with another metal such as potassium or lithium. The copolymerization ratio of the aromatic dicarboxylic acid component having a metal sulfonate is preferably 2 to 50 mol%, based on the terephthalic acid component as the main raw material.
Especially preferably, it is 4 to 30 mol%.

In the copolymerized polyester resin film used in the present invention, that an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is further copolymerized, transparency, particularly suppression of whitening of the copolymerized polyester resin film surface and It is preferable from the viewpoint of folding resistance.

Specific examples of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms include succinic acid, adipic acid, and sebacic acid, and among them, adipic acid is preferable. 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 mol%, based on the terephthalic acid component.

In the copolymerized polyester resin film used in the present invention, other acid components or glycol components can be further copolymerized as long as the transparency and mechanical properties are not impaired. For example, polyalkylene glycols, especially polyethylene glycols,
% By weight can be copolymerized. The polyalkylene glycol used for this purpose has a molecular weight of 600 to 10,000.
It is preferably in the range of 0.

Mixing another hydrophilic polymer with the copolymerized polyester is also preferably performed as long as the adhesion to the substrate is not impaired and the transparency of the support is not impaired. Specifically, poloxyalkylene glycol, polyoxyalkylene glycol / polyamide block copolymer,
The polyoxyalkylene glycol / polyester block copolymer may be mixed, and an organic or inorganic ionic compound may be further added. It is also preferable to crosslink the polyoxyalkylene glycol by introducing a reactive group.
It is also preferred to crosslink the polyester.

Further, various additives can be contained in the polyester resin film of the present invention.

One of the properties that becomes a problem when a polyester film is used as a support for a photographic light-sensitive material is a fogging problem that occurs because the support has a high refractive index.

The refractive index of PET is about 1.6, and the refractive index of gelatin used exclusively for the underlayer and the photographic emulsion layer is 1.50 to
1.55. The ratio of the refractive index of gelatin to PET is 1.5 /
1.6, which is smaller than 1, and easily reflects at the interface between the base and the emulsion layer when light enters from the film edge. Therefore, a polyester film is liable to cause a so-called light piping phenomenon (edge fogging).

In the present invention, in order to avoid such a light piping phenomenon, a dye which does not increase the film haze can be added. The dye used is not particularly limited, but is preferably a dye having a gray color tone in general properties of a photosensitive material, and has excellent heat resistance in a film forming temperature range of a polyester film and has good compatibility with polyester. Excellent ones are preferred. Specific dyes include:
From the above viewpoints, Diaresin manufactured by Mitsubishi Kasei and Kaya manufactured by Nippon Kayaku
set and the like. The dyeing density needs to be at least 0.01 or more, preferably 0.03 or more, as measured by a Macbeth color densitometer.

The polyester film may be provided with lubricity according to the application. The means for imparting lubricity is not particularly limited, but kneading of an inert inorganic compound or application of a surfactant is used as a general method. Also, a method using an internal particle system for precipitating a catalyst or the like to be added at the time of the polyester polymerization reaction can be used.

As the above-mentioned inert inorganic compound, SiO ₂ , TiO ₂ , BaSO ₄ , C
aCO ₃ , talc, kaolin and the like. As transparency is an important requirement for photographic light-sensitive material supports, select SiO ₂ , which has a refractive index relatively close to that of polyester film, or an internal particle system that can make the precipitated particle diameter relatively small It is desirable to do.

When lubricity is imparted by kneading, a method of laminating layers imparted with functions in order to obtain more transparency of the film is also preferably used. Specific examples include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

The copolymerized polyester can be synthesized according to a conventionally known polyester production method. For example, the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, the ester exchange reaction is first performed with the glycol component, and this is heated under reduced pressure to remove the excess glycol component. Thereby, a copolymerized polyester can be obtained. At this time, if necessary, a transesterification catalyst or a polymerization reaction contact may be used, and a heat stabilizer may be added.

To laminate the polyester, a coextrusion method, an in-line lamenate method, or an off-line lamination method is used.

The co-extrusion method is a method in which different resins are guided from one or more extruders to one die and superposed in the die to form a multilayered structure. There is a method using a manifold die and a method using a feed block in which a merging mechanism is provided in a layered manner at a conduit portion of a single-layer die. Usually, 2 to 9 layers can be laminated.

The in-line lamination method is a method of completing biaxial stretching orientation after laminating on an unoriented film and / or longitudinal or horizontal uniaxially oriented film before the completion of biaxial orientation in a polyester film forming step. Dry lamination, hot melt Lamination and extrusion lamination are used. Lamination using an adhesive containing a solvent is not preferable because the solvent remains.

The off-line lamination method is a method of laminating on a film after the completion of biaxial stretching molding, and the lamination method is used.

When forming a polyester film, the polymerized polyester may be subjected to a film forming step in a molten state, or may be once formed into a pellet and then subjected to a film forming step. When pelletized, it is preferable to dry it before extrusion.

For film formation, melt extrusion and biaxial stretching are preferred. That is, melt-extruded on a rotary cooling body at a melting point or higher and 350 ° C or lower to form an amorphous sheet, and then 70 to 13
Roll-stretching at 0 ° C., preferably 80-110 ° C., 2.0-5.0 times, preferably 2.2-4.0 times in the machine direction, and then 70-70 times in the transverse direction.
Tenter stretching at a temperature of 150 ° C., preferably 80 to 130 ° C. and higher than that at the time of longitudinal stretching, 2.0 to 5.0 times, preferably 2.2 to 4.0 times, and then a transverse stretching temperature or higher and 240 ° C. or lower, preferably 150 to
Heat set at 230 ° C or less, then 0.1-10%, preferably 0.1%.
Relax by 5-5% heat, then cool to room temperature and wind. For stretching, simultaneous biaxial stretching of a tenter clip system is also preferably used. After the transverse stretching, the film can be stretched longitudinally again.

In this film forming step, polyesters having different moisture contents are laminated by the coextrusion method and the inline lamination method as described above. In-line lamination can be further performed on a multilayer film by a co-extrusion method, or lamination by in-line lamination can be a multilayer.

At least one layer has a thickness of 5 μm or more and 100 μm
The following PET layer is preferable. In the laminated structure of the present invention, it is preferable that the PET layer is located on a layer not exposed to the surface, and that the layer forming the surface has a higher moisture content than the PET layer.
In order to form such a laminated structure, a co-extrusion method is preferable. The layer closer to the surface than the PET layer preferably contains a copolyester containing an aromatic dicarboxylic acid having a metal sulfonate as a copolymer component, and the water content of this layer is preferably 1.0% or more.

Accordingly, the support having a laminated structure composed of a plurality of polyester films of the present invention preferably has a three-layer laminated structure in which the central layer is a layer composed of PET. At this time, the thickness of the PET film layer is preferably 80% or less of the total thickness.

By adopting such a structure and composition, it becomes difficult to form a curl, and the curl is alleviated by water absorption during the development process, and furthermore, a support having excellent tear strength and folding resistance is obtained.

100μ thick PET with high elastic modulus and easy curling
m or less to reduce curling, by laminating a copolyester with a high water content on the PET layer to alleviate curling, and to achieve a tear strength that cannot be maintained with copolyester alone. Improved by PET. In addition, since the polyesters are laminated, the adhesiveness between the layers becomes firm.

The thickness of the polyester resin film having a laminated structure can be appropriately set depending on the application field of the photographic film.
250μ is preferred, and a thickness of 20 to 150μ is more preferred.

In the present invention, at least one antistatic layer containing a water-soluble conductive polymer can be provided on the support made of the polyester resin film.

The layer containing the water-soluble conductive polymer contains at least a reaction product of the water-soluble conductive polymer and the curing agent.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from sulfonic acid groups, sulfate groups, quaternary ammonium salts, tertiary ammonium salts, and carboxyl groups. The proportion of conductive groups must be at least 5% by weight per molecule of polymer. The water-soluble conductive polymer may contain a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinyl sulfone group, and the like.

The molecular weight of the water-soluble conductive polymer is from 3000 to 100,000, preferably from 3500 to 50,000.

The water-soluble conductive polymer layer of the present invention may contain hydrophobic polymer particles. The hydrophobic polymer particles are composed of a so-called latex that is substantially insoluble in water. This hydrophobic polymer is styrene, styrene derivative, alkyl acrylate, alkyl methacrylate,
It can be obtained by polymerizing a monomer selected in any combination from olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile and the like. In particular, it is preferable that at least 30 mol% of a styrene derivative, an alkyl acrylate, or an alkyl methacrylate is contained. In particular, it is preferable to contain 50 mol or more.

In the present invention, a curing agent can be added to the antistatic layer.

As the curing agent used in the present invention, an aziridine compound, an epoxy compound, or the like is preferable, and an aziridine compound having a molecular weight of 1,000 or less, or an epoxy compound having a hydroxy group and / or an ether bond is particularly preferable.

The pH of the film surface of the conductive layer according to the present invention is preferably 8.0 or less, particularly preferably 3.0 to 7.5. If it is too low, it is not preferable because of the stability of the film.

The conductive layer according to the invention may be on the support side of the photosensitive layer, or may be on the side opposite to the photosensitive layer with respect to the support, that is, on the back side.

The polyester resin film having a laminated structure used as the support of the present invention may be provided with a subbing layer containing a latex polymer after corona discharge treatment. In the corona discharge treatment, an energy value of 1 mW to 1 KW / m ² min is particularly preferably applied. It is particularly preferable to perform the corona discharge treatment again after the application of the latex subbing layer and before the application of the conductive layer.

The present invention can be applied to all roll-shaped silver halide photographic materials having a polyester resin support having a laminated structure. For example, a silver halide color or black-and-white photographic light-sensitive material for negative, a silver halide color or black-and-white photographic light-sensitive material for reversal, and an infrared photographic light-sensitive material.

When the silver halide emulsion used in the present invention contains silver iodide, the silver halide grains preferably have silver iodide localized therein.

In the present invention, as the silver halide emulsion, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The following table shows the relevant locations.

In the present invention, it is preferable to use a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 308119.
(Hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively).

 The places to be described are shown below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned Research Disclosure. The following table shows relevant descriptions.

Various couplers can be used in the present invention, and specific examples are described in the above-mentioned Research Disclosure. The following table shows relevant descriptions.

The additives used in the present invention can be added by the dispersion method described in RD308119X IV and the like.

The light-sensitive material of the present invention can be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119VII-K.

In the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, or the like can be used.

The light-sensitive material of the present invention can have various layer constitutions such as a normal layer, a reverse layer, and a unit constitution described in the aforementioned RD308119VII-K.

The present invention can be applied to various color light-sensitive materials represented by general or movie color negative films, slide or television color reversal films, color papers, color positive films, and color reversal papers.

The light-sensitive material of the present invention is described above as RD17643 pages 28 to 29, RD18716.
Development can be carried out by a usual method described on page 647 and XIX of RD308119.

[Examples] Hereinafter, the present invention will be specifically described with reference to Examples. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example-1 To 100 parts by weight of dimethyl terephthalate, 90 parts by weight of ethylene glycol, 30 parts by weight of dimethyl 5-sodium sulfoisophthalate and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate and 0.03 part by weight of antimony trioxide were added. Then, a transesterification reaction was performed by a conventional method. 0.05 parts by weight of phosphoric acid trimethyl ester was added to the obtained product, and the temperature was gradually raised and reduced, and finally 280 ° C., 1 mmHg
Polymerization was performed as follows to obtain a copolymerized polyester.

This copolyester and IV0.68 PET resin were extruded using two extruders, and a three-layer multi-manifold type was co-extruded and melt extruded so that PET became the center and the copolyester became the outer layer in a die, 700 μm thick Was formed.

Next, the unstretched sheet is roll-stretched 3.0 times in the longitudinal direction at 100 ° C., then tenter-stretched in the transverse direction at 110 ° C., then heat-set at 220 ° C., and then subjected to a 2.0% relaxation treatment in an intermediate zone at 150 ° C. Then, it was cooled to room temperature and wound up.

The obtained film (A) is transparent and has a thickness of 70 μm.
The PET layer was 30 μm and the water content was 1.6%.

Comparative Example-1 A thickness of 70 obtained by molding the copolymerized polyester alone.
The moisture content of the μm film (B) was 2.6%.

Comparative Example 2 A 70 μm-thick film (C) formed by molding the PET alone had a water content of 0.3%.

Next, the tear strength and the fold resistance of the films (A), (B) and (C) were measured.

 Table 1 shows the measurement results.

Tear strength Toyo Seiki Co., Ltd. Using a light load tear tester, the tear propagation resistance when measured at a tear load of 500 g with a thickness of 100μ.
Converted to m and expressed in the unit g / 100 μm.

Folding strength Using a folding strength tester of Kamishima Machinery Co., Ltd., sample width
It represents the number of bends before repeated bending and cutting at 10 mm.

Example 2 (Preparation of photographic light-sensitive material) Coating of undercoat layer On both sides of polyester resin film (A) having a laminated structure of the present invention in Example 1 and films (B) and (C) of Comparative Examples 1 and 2 After the corona discharge treatment, an undercoat layer having the following composition was provided. The degree of corona discharge treatment is 0.02KVA
Min / m ² .

(Styrene-butyl acrylate-hydroxyethyl acrylate-butadiene) latex 3 g distilled water 250 cc sodium α-sulfodi-2-ethylhexyl succinate 0.05 g aziridine compound (C-1) 0.02 g Coating of back layer (antistatic layer) Polyester resin film (A) after layer coating,
After performing corona discharge again on one surface of (B) and (C), a conductive layer having the following composition was applied so as to have a dry film thickness of 1 μm.

However, the water-soluble conductive polymer (A), the hydrophobic polymer particles (B) and the curing agent (H) used were those exemplified above. The curing agent (H) was added while applying.

Drying air temperature 90 ° C., in a parallel flow drying condition of overall heat transfer coefficient ^{25kg / m 2 · hr · ℃} , dried for 30 seconds, further followed, 140 ° C., 9
Heat treatment was performed for 0 seconds.

Water-soluble conductive polymer (A) 60 g / l Hydrophobic polymer particles (B) 40 g / l Ammonium sulfate 0.5 g / l Curing agent (H) 12 g / l

Gelatin was applied on the applied antistatic layer to a concentration of 2.0 g / m ² and dried. However, the following (H-2) was used as a hardener for gelatin.

Coating of photographic layer The polyester resin film (A) of the present invention provided with a back layer and the films (B) and (C) of Comparative Examples 1 and 2
The following photographic layer was provided on the side opposite to the back layer.

First layer: Red-sensitive silver halide low-sensitivity layer (1-a) Preparation of emulsion for low-sensitivity unit emulsion layer Silver iodobromide emulsion containing 6 mol% iodine (average grain size 0.6 μm, per kg of emulsion) 100g silver halide, 70g gelatin
Was prepared in the usual manner. Anhydro-5,5'-dichloro-9 was added as a red-sensitive color sensitizer to 1 kg of this emulsion.
-Ethyl-33'-di (3-sulfopropyl) -thiacarbocyanine hydroxide
180 cc of a 1% methanol solution is added, and then 5-methyl-7
20 cc of a 5% by weight aqueous solution of -hydroxy-2,3,4-triazaindolizine, 330 g of a cyan coupler emulsion (1) and 20 g of an emulsion (2) according to the following formulation 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 prepare an emulsion for a low-sensitivity unit emulsion.

Emulsion (1) 10% by weight aqueous gelatin solution 1.000 g p-Dodecylbenzenesulfonate sodium 5 g tricresyl phosphate 60 cc cyan coupler (C-7) 70 g Ethyl acetate 100 cc In addition to heating to ° C, the mixture was emulsified in a colloid mill.

Cyan coupler Emulsion (2) Second layer: red-sensitive silver halide medium-sensitive layer (1-b) Preparation of emulsion for medium-speed unit emulsion layer The following changes were made in (1-a) above.

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

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

Further, as a gelatin hardener, 2-hydroxy-4,6-
50cc of 2% by weight aqueous solution of dichlorotriazine sodium salt
Was added to obtain an emulsion for a low-sensitivity unit emulsion.

Emulsion (3) 10% by weight aqueous gelatin solution 1.000 g p-Dodecylbenzenesulfonate sodium 5 g tricresyl phosphate 65 cc Magenta coupler (M-7) 6 g Ethyl acetate 110 cc A mixture of 55 deg. In addition to heating to ° C, the mixture was emulsified in a colloid mill.

Magenta coupler (M-7): 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-t-pentylphenoxyacetamide) benzamide] -5-pyrazolone emulsion (4) Sixth layer: green-sensitive silver halide medium-sensitive layer (2-b) Preparation of emulsion for medium-speed unit emulsion layer Silver iodobromide emulsion containing 5 mol% iodine (average grain size 0.9 μm, per kg of emulsion) 100g silver halide, 70g gelatin
Was prepared in the usual manner. To 1 kg of this emulsion,
A methanol solution of the green-sensitive color sensitizer represented by (2-a) 15
0 cc 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 above-mentioned 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 prepare an emulsion for a medium sensitivity unit emulsion layer.

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

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

Eighth layer: yellow filter layer composed of yellow colloidal silver (dry thickness 1.2 μm) Ninth layer: blue-sensitive layer Silver halide low-sensitivity layer (3-a) Preparation of emulsion for low-sensitivity unit emulsion layer- ( 1) Silver iodobromide emulsion containing 5 mol% iodine (average grain size 0.6μ, silver halide 100g / kg emulsion, gelatin 70g)
Was prepared in the usual manner. 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. Furthermore as a gelatin hardening _{agent, CH 2 = CHSO 2 CH 2} OCH 2 SO 2 CH = CH 2 and 2-hydroxy-4,6-low sensitivity units emulsions by adding 2 wt% aqueous solution 50cc of dichlorotriazine sodium salt An emulsion was prepared.

Emulsion (5) Tenth layer: blue-sensitive middle layer of light-sensitive silver halide The above (3-a) was changed as follows.

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

12th layer: Surface protective layer 10% by weight gelatin solution 1000cc Poly (methyl methacrylate-methacrylic acid) Polymer particles 3μ 50mg Sodium dodecylbenzenesulfonate 40mg SiO ₂ fine particles (3.0μ) 50mg Sodium polystyrene sulfonate 1g Polyorganosiloxane 100mg 2 -Hydroxy-4,6-dichlorotriazine 50 mg C ₈ F ₁₇ SO ₃ Na 5 mg The amount of silver applied to each photosensitive layer was as follows.

First layer (1.0 g / m ² ), second layer (0.8 g / m ² ), third layer (1.2 g / m ² ), fifth layer (1.2 g / m ² ), sixth layer (1.0 g / m ² ) / m ² ), 7th layer (1.2 g / m ² ), 9th layer (0.6 g / m ² ), 10th layer (0.6 g / m ² ), 11th layer (0.6 g / m ² ) The three color negative films (1), (2) and (3) obtained in the above were cut into 35 mm sizes, respectively, and these were loaded into a patrone.

After standing at 40 ° C. for 10 days, images were taken with a normal camera, and the following development processing was performed.

Processing time Temperature Color development 38 ° C 3 minutes Stop 38 ° C 1 minute Rinse 38 ° C 1 minute Bleach 38 ° C 2 minutes Rinse 38 ° C 1 minute Fix 38 ° C 2 minutes Rinse 38 ° C 1 minute Stabilize bath 38 ° C The processing solution used for one minute has the following composition.

Color developing solution Caustic soda 2 g Sodium sulfite 2 g Potassium bromide 0.4 g Sodium chloride 1 g Eagle sand 4 g Hydroxylamine sulfate 2 g Ethylenediaminetetraacetic acid disodium dihydrate 2 g 4-Amino-3-methyl-N-ethyl -N- (β-Hydroxyethyl) aniline monosulfate) 4 g Add water to make a total of 1 Stop solution Sodium thiosulfate 10 g Ammonium thiosulfate (70% aqueous solution) 30 mL Acetic acid 30 mL Sodium acetate 5 g Potassium alum 15 g In addition, the total amount of 1 bleach solution Sodium ethylenediaminetetraacetate (III) sodium dihydrate 100 g Potassium bromide 50 g Ammonium nitrate 50 g Folic acid 5 g Adjust the pH to 5.0 Add water to the total amount 1 Fixer Sodium thiosulfate 150 g Sodium sulfite 15 g Hoe sand 12 g Glacial acetic acid 15 ml Potassium alum 20 g Add water 1 stabilization bath Folic acid 5 g Sodium citrate 5 g Sodium metafolate D (tetrahydrate) 3 g Potassium alum 15 g Add water to make a total of 1 Add the developed film (1), (2) and (3) to 22
The pieces were cut into 7 mm lengths, and the curl degree was measured for each piece. The results are shown in Table 2.

 The curl degree is represented by the reciprocal of the radius as 1 / m.

The films (1) and (2) had no problem in practice, but the film (3) was strongly curled and poor in handling.

Example-3 The PET used in Example-1 alone was subjected to a molding step to a thickness of 30 µm. At this time, between the longitudinal stretching step and the transverse stretching step, the copolymerized polyester copolymerized in Example 1 was melt-extruded with an extruder and laminated. Lamination is performed on both sides by inverting the film, and the resulting film has a total thickness of 70
The extrusion amount was adjusted to be μm.

The obtained film had good curl-removing properties as in Example-1.

Example-4 The PET used in Example-1 was used alone to form a film with a thickness of 60 µm. The copolymerized polyester prepared in Example 1 was melt-extruded and laminated on this film. Laminated on both sides,
The total thickness was 120 μm.

The obtained film had good curl-removing properties as in Example-1.

[Effects of the Invention] According to the present invention, a rolled silver halide photographic light-sensitive material in which a silver halide photographic emulsion is coated on a polyester resin film, wherein the polyester resin film is obtained by laminating polyester resin films having different water contents. By thinning PET with a high elastic modulus and laminating a copolyester with a higher moisture content, it has excellent curl recovery ability, that is, excellent curl removal after development, and tear strength and fold resistance are practical strength. And a remarkable effect of having excellent mechanical performance such as firm adhesion of each layer.

Claims (7)

(57) [Claims] 1. A roll-shaped silver halide photographic light-sensitive material comprising at least one silver halide photographic emulsion coated on a support comprising a plurality of polyester resin films, wherein the plurality of polyester resin films have a water content. A roll-shaped silver halide photographic material comprising a laminate of at least two different polyester resin films. 2. A roll-shaped silver halide photographic light-sensitive material according to claim 1, wherein one of said plurality of polyester resin films is a polyethylene terephthalate resin film having a thickness of 5 μm or more and 100 μm or less. material. 3. The polyester resin film of the layer forming the surface, wherein the plurality of polyester resin films have a laminated structure of three or more layers, and the layer composed of the polyethylene terephthalate resin film is located on a layer not exposed on the surface. 3. The roll-shaped silver halide photographic light-sensitive material according to claim 2, wherein the water content of the polyethylene terephthalate resin constituting the layer not exposed on the surface is higher than the water content. 4. A support comprising a plurality of polyester resin films, wherein a polyester resin film in a layer closer to the surface than a layer made of a polyethylene terephthalate resin film comprises an aromatic dicarboxylic acid having a metal sulfonate as a copolymer component. 4. A roll-shaped silver halide photographic light-sensitive material according to claim 2, which is a copolyester. 5. The method according to claim 1, wherein said support comprising said plurality of polyester resin films is formed by a co-extrusion method.
2. The roll-shaped silver halide photographic light-sensitive material according to claim 1, which has a laminated structure composed of layers. 6. A polyethylene terephthalate resin film in which a support composed of a plurality of polyester resin films is stretched and oriented in a longitudinal or horizontal uniaxial direction, and after laminating one or more polyester resin films having a higher water content,
2. The roll-shaped silver halide photographic material according to claim 1, wherein the roll-shaped silver halide photographic material has a laminated structure stretched and oriented in a uniaxial direction in a horizontal or vertical direction. 7. The method according to claim 2, wherein the thickness of the polyethylene terephthalate resin film is 80% or less of the total thickness of the polyester resin film.
Item 7. A roll-shaped silver halide photographic light-sensitive material according to item 6 or 7.