JPH0493937A - Roll of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance mechanical properties and curl resistance after development processing by using at least 2 laminated layers of polyester films different in water content from each other. CONSTITUTION:For example, the polyester copolymer is obtained by applying the normal ester exchange reaction process to a mixture of 100 pts.wt. f dimethyl therephthalate, 90 pts.wt. of ethylene glycol, 30 pts.wt. of dimethyl 5-sodium sulfoiso-phthalate, 10 pts.wt. of dimethyl adipate, 0.1 pts.wt. of calcium acetate, and 0.03 pts.wt. of antimony trioxide, adding 0.05 pts.wt. of trimethyl phosphate to the obtained product, gradually raising temperature, reducing pressure, and finally polymerizing it at 280 deg.C and a vacuum of <= 1 mm Hg. The laminated polyester films are obtained by melt extruding one volume of this polyester copolymer and 0.68 volume of a PET resin by using 2 extruders and the coextrusion die of 3 layer multimanifold type to form 3 layer laminated films comprising the PET layer in the center and the outer 2 copolymer layers, and having the total film thickness of 700mum in a nonstrectched state.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a roll-shaped silver halide photographic light-sensitive material. The present invention relates to a roll-shaped silver halide photographic light-sensitive material having excellent curl resolving properties.

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

In general, photographic materials typically come in sheet form, such as X-ray film, plate-making film, and cut film, and those in roll form. Typical examples of roll film include color film or black and white negative film that is 35 mm wide or less and is housed in a cartridge and is loaded into a general camera for photographing.

BACKGROUND ART Conventionally, supports mainly made of TAC films have been used for roll films. The characteristics of TAC film as a photographic support are that it has no optical anisotropy, has high transparency, and also has excellent properties in terms of decurling properties after development. The excellent decurling properties result from the molecular structure of the TAC film. In other words, TAC film has relatively high water absorption for a plastic film, and its molecular chains can be made to flow by absorbing water during the development process. This can be resolved by rearranging the immobilized molecular chains.

On the other hand, with photographic materials that use films that do not have curl-reducing properties, when used in roll form, for example, the printing process that forms an image on photographic paper after development is a process that can cause scratches. Problems such as image generation, out-of-focus, and jamming during transportation may occur.

Incidentally, in recent years, the uses of photographic materials have been diversifying, and there has been significant progress in increasing the speed of transporting film during photographing, increasing the magnification of photographing, and reducing the size of photographic devices. To this end, supports for photographic materials are required to have properties such as strength, dimensional stability, and thin film formation.

However, since the TAC film has a rigid molecular structure, the quality of the film after film formation is fragile, and currently there are difficulties in using it for these purposes.

[Problem to be solved by the invention] In contrast, polyethylene terephthalate resin (PET
) film has been considered as an alternative to TAC film because it has excellent productivity, mechanical strength, and dimensional stability.

However, in roll form, which is widely used as a photographic light-sensitive material, PET film retains strong curls, making it difficult to handle after development. There were some difficulties and problems.

As a means to solve this curling problem, Japanese Patent Application Laid-Open No. 1-244446 discloses a technique in which a polyester film having a water content of 05% by weight or more is used as a support. The moisture content of PET film is usually 0.3% by weight.
In order to increase this amount, the publication attempts to increase the amount to 0.5% by weight or more by copolymerizing an aromatic dicarboxylic acid having a metal sulfonate.

According to this technology, it is possible to increase the water content by increasing the amount of metal sulfonate, but if the amount is increased too much, mechanical strength such as brittleness and tear strength of the film deteriorates, making it unusable as a photographic support. . This is because the copolymerization ratio of the aromatic dicarboxylic acid component having a metal sulfonate is 2 to 15 mol% relative to the terephthalic acid component in column 7 of the same publication.
However, in Example 1, 100 parts by weight of dimethyl terephthalate was copolymerized with only 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, that is, 7 mol%, and as a result, the water content was 0. It is estimated that it is only .7%. In the measurement in the same example, T
The moisture content of the AC film is 2.6%. TA moisture content
In order to make the film as large as C film, it is necessary to copolymerize an even larger amount of the aromatic dicarboxylic acid component having a metal sulfonate.

When the moisture content is about 0.7%, curling is strong, and if curling occurs, it may not be able to fully recover.

Furthermore, although there is no specific description in the publication, it is thought that the film obtained by this technique has poor tear strength and folding durability and cannot be put to practical use.

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a photographic material that has excellent mechanical properties and curl elimination properties after development processing.

[Means for Solving the Problems] An object of the present invention is to provide a roll-shaped silver halide photographic light-sensitive material in which at least one layer of silver halide emulsion is coated on a support consisting of a plurality of polyester resin films. This is achieved by a roll-shaped silver halide photographic light-sensitive material characterized in that the plurality of polyester resin films are a stack of at least two layers of polyester resin films having different moisture contents.

In the photographic light-sensitive material of the present invention, at least two
An integral support made of laminated layers of polyester resin film 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.

In the present invention, polyethylene terephthalate resin (PET
) refers to a polymer produced by polycondensation of terephthalic acid or its ester-forming derivative and ethylene glycol.
Other polymers may be used within the range that does not impair the original properties of PET.
It includes those to which additives have been added, or copolyesters copolymerized with dibasic acids other than terephthalic acid and polyhydric alcohols other than ethylene glycol.

The moisture content of the polyester resin film was measured by conditioning the film at 23°C and 30% RH for 3 hours, and then
It is immersed in distilled water at 23° C. for 15 minutes, and then dried at a temperature of 150° C. using a trace moisture meter (for example, model CA-02 manufactured by Mitsubishi Kasei ■).

In the present invention, it is preferable that a polyester resin film with a high moisture content is laminated so as to be located on the surface, and particularly preferably, this polyester resin film with a high moisture content is a copolymerized component of an aromatic dicarboxylic acid component having a metal sulfonate. This is a copolymerized polyester resin film.

Specifically, the aromatic dicarboxylic acid having a metal sulfonate includes 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, and 4-sodium sulfo-2,6-naphthalene dicarboxylic acid. and compounds in which sodium is replaced with other metals such as potassium and lithium. The copolymerization ratio of the aromatic dicarboxylic acid component having metal sulfonate is preferably 2 to 50 mol% based on the terephthalic acid component, which is the main raw material.
, particularly preferably 4 to 30 mol%.

The copolymerized polyester resin film used in the present invention is further copolymerized with an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms. Preferable from the viewpoint of bending durability.

Specific examples of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms include succinic acid, adipic acid, and sebacic acid, among which adipic acid is preferred. The copolymerization ratio of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is preferably 3 to 25 mol%, particularly preferably 5 to 20 mol%, based on the terephthalic acid component.

In addition, in the copolymerized polyester resin film used in the present invention, it is also possible to further copolymerize other acid components or glycol components as long as the transparency and mechanical properties are not impaired. For example, polyalkylene glycol, especially polyethylene glycol,
% by weight can be copolymerized. The polyalkylene glycol used for this purpose has a molecular weight of 600 to 1
Preferably, it is in the range of 0,000.

It is also preferable to mix other hydrophilic polymers with the copolyester as long as the adhesion to the substrate is not impaired and the transparency as a support is not impaired. Specifically, polyoxyalkylene glycol, polyoxyalkylene glycol/polyamide plotter copolymer, polyoxyalkylene glycol/polyester block copolymer may be mixed, and an organic or inorganic ionic compound may be further blended. It is also preferable to crosslink polyoxyalkylene glycol by introducing reactive groups. It is also preferred to crosslink the polyester.

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

One of the problematic properties when using a polyester film as a support for photographic light-sensitive materials is the problem of fringing caused by the high refractive index of the support.

The refractive index of PET is about 1.6, and the refractive index of gelatin, which is often used in subbing layers and photographic emulsion layers, is 1.
．． 50 to 1.55. The ratio of the refractive index of gelatin and PET is 1.5/1.6, which is less than 1, and when light enters from the film edge, it is easily reflected at the interface between the base and emulsion layer. Therefore, polyester films tend to cause so-called light piping phenomenon (edge fogging).

In the present invention, in order to avoid such a light piping phenomenon, a dye that does not increase film haze can be added. The dye to be used is not particularly limited, but dyes with a gray tone are preferred due to the general properties of photosensitive materials, and dyes with excellent heat resistance in the film forming temperature range of polyester films and compatibility with polyester are preferred. Excellent ones are preferred. From the above point of view, specific dyes include D 1aresin manufactured by Mitsubishi Kasei, Kayaset manufactured by Nippon Kayaku, and the like. In addition, the dyeing density has a value of at least 0.0 as measured by a Macbeth color density needle.
0.01 or more, preferably 0.03 or more.

The polyester film can also be provided with slipperiness depending on the use. Although there are no particular limitations on the means for imparting slipperiness, common methods include kneading inactive inorganic compounds or coating with surfactants.

Further, a method using an internal particle system in which a catalyst, etc. added during the polyester polymerization reaction is precipitated can also be used.

The above inert inorganic compounds include 5i02, TiO2, B
Examples include aSO4, CaCOs, talc, kaolin, and the like. Transparency is an important requirement for a support for photographic light-sensitive materials, so we selected SiO□, which has a refractive index relatively close to that of polyester film, or an internal particle system that allows the precipitated particle size to be relatively small. It is desirable to do so.

When imparting slipperiness by kneading, a method of laminating functionalized layers is also preferably used in order to obtain greater transparency of the film. Specifically, a coextrusion method using multiple extruders and feed blocks, or a multi-manifold die may be mentioned.

The copolyester can be synthesized according to conventionally known polyester manufacturing methods. For example, the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, the transesterification reaction is first performed with the glycol component, and then the excess glycol component is removed by heating under reduced pressure. By doing so, a copolymerized polyester can be obtained. At this time, it is possible to use a transesterification reaction catalyst or a polymerization reaction catalyst as necessary.
A heat stabilizer can also be added.

A coextrusion method, an in-line lamination method, and an offline lamination method are used to laminate polyester.

Co-extrusion is a method in which two or more extruders lead different resins into a single die and overlap them within the die to extrude a multilayer structure. There are two types: one using a manifold die and the other using a feed block in which a layered merging mechanism is provided in the conduit part of a single layer die. Usually 2 to 9 layers can be laminated.

The in-line lamination method uses unoriented film and/or
Alternatively, it is a method of completing biaxial stretching orientation after lamination on a vertically or horizontally uniaxially oriented film, and dry lamination, hot melt lamination, or extrusion lamination is used for lamination. Lamination using adhesives containing solvents is not preferred because the solvent remains.

The offline lamination method is a method of laminating a film after completion of biaxial stretching, and the lamination method described above is used.

When polyester is formed into a film, the polyester that has completed polymerization may be subjected to the film forming process in a molten state, or may be first formed into pellets and then subjected to the film forming process. When it is pelletized, it is preferable to dry it before extrusion molding.

For film forming, melt extrusion and biaxial stretching are preferred. That is, it is formed into an amorphous sheet by melt extrusion on a rotary cooling body at a temperature above the melting point and below 350°C, and then heated at 70 to 350°C.
2.0 in longitudinal direction at 130℃, preferably 80-110℃
Roll stretching to ~5.0 times, preferably 2.2 to 4.0 times, and then transversely at 70 to 150°C, preferably 80 to
2.0 to 5.0 at 130°C and higher temperature than during longitudinal stretching
tenter stretching, preferably 22 to 4.0 times, and then transverse stretching at a temperature higher than or equal to 240°C, preferably 150 to 2.
It is heat set at 30° C. or lower, then heat relaxed by 0.1 to 10%, preferably 0.5 to 5%, and then cooled to room temperature and wound up. For stretching, simultaneous biaxial stretching using a tenter clip method is also preferably used. Further, after the transverse stretching, longitudinal stretching can be carried out again.

In this film forming process, polyesters having different moisture contents are laminated by coextrusion or in-line lamination as described above. A multilayer film formed by coextrusion may be further inline laminated, or inline lamination may be used to form a multilayer film.

The laminated structure has at least one layer with a thickness of 5 μm or more and 100 μm.
It is preferable to use the following PET layer. Further, in the laminated structure of the present invention, it is preferable that the PET layer is located in a layer that does not appear on the surface, and that the layer forming the surface has a higher water content than the PET layer. In order to form such a laminated structure, it is preferable to use a coextrusion method.

A 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 1.0%.
The above is preferable.

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

With such a structure and composition, the support becomes resistant to curling curls, the curling curls are alleviated by water absorption during development processing, and has excellent tear strength and folding durability.

Made of PET with a large elastic modulus and curly curls, thickness 10
By thinning the layer to less than 0 μm to prevent curling curls, and by laminating copolyester with a high moisture content on the PET layer, curling curls are alleviated, and the tear strength and folding durability that cannot be maintained with copolyester alone are achieved. Improved by PET. Moreover, since polyesters are laminated together, the adhesiveness between each layer is strong.

The thickness of the polyester resin film having a laminated structure can be set as appropriate depending on the field of use of the photographic film, but it is from 10 to 10.
The thickness is preferably 250μ, more preferably 20 to 150μ.

In the present invention, an antistatic layer containing at least one 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 water-soluble conductive polymers include sulfonic acid groups, sulfuric acid ester groups, quaternary ammonium salts, tertiary ammonium salts,
Examples include polymers having at least one conductive group selected from carboxyl groups. The proportion of conductive groups is required to be 5% by weight or more per polymer molecule. Water-soluble conductive polymers contain hydroxy groups,
It may contain 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 3000 to 1000.
00, preferably 3500 to 5oooo.

The water-soluble conductive polymer layer of the present invention may contain hydrophobic polymer particles. These hydrophobic polymer particles are composed of so-called latex, which is substantially insoluble in water. This hydrophobic polymer includes styrene, styrene derivatives,
It is obtained by polymerizing monomers selected in any combination from alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile, and the like. In particular, it is preferable that at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates are contained. In particular, the content is preferably 50 moles or more.

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

The curing agent used in the present invention is preferably an aziridine compound, an epoxy compound, etc.
The following aziridine compounds, or hydroxy groups and/or
Or an epoxy compound having an ether bond is particularly preferred.

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 unfavorable from the viewpoint of film stability.

The conductive layer according to the present invention may be located closer to the support than the photosensitive layer, or may be located on the opposite side of the support from the photosensitive layer, that is, the so-called back side.

The laminated polyester resin film used as the support of the present invention may be subjected to corona discharge treatment and then coated with a subbing layer containing a latex polymer. Corona discharge treatment has an energy value of 1 mW to IKW/gomi
n is particularly preferably applied. Particularly preferably, corona discharge treatment is performed again after applying the latex undercoat layer and before applying 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. Examples include negative silver halide color or black and white photographic materials, reversal silver halide color or black and white photographic materials, and infrared photographic materials.

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

In the present invention, the silver halide emulsion is disclosed in Research Disclosure 308119 (hereinafter referred to as RD 308119).
) can be used.

The relevant entries are shown in the table below.

[Item] [Bage of RD308119] Iodine tissue 993 I
-Section A manufacturing method Section 9931-A and Section 994E Evitaquin halogen conversion Halogen substituted metal containing monodisperse 9931-A Section 1-C Section 1-C Section 1-D Section 1-F Section Solvent addition Application of Section 9951-F Sensitive material Negative 9951-H positive (including internal fog particles) 995I-H emulsion mixed and used 995I-J desalting
Section 995111-A In the present invention, it is preferable to use a silver halide emulsion that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643, No. 18716 and No. 3.
08119 (hereinafter referred to as RD17643, RD
18716 and RD 308119).

The table below shows the locations.

Item F] [Page of RD3011119]
[RD17643] [RD1B716
]Chemical sensitizer 996m-A section
23 648 Spectral sensitizer 996
TV-A-A, B, C, D, 11.11.1.
Section J 23-24 648-9 Supersensitizer
996 1V-A-E, Section J 23
~24 648~9 Antifouling agent 998
Vl 24-25
649 Stabilizer 998 Vl
24-25 649 Known photographic additives that can be used in the present invention are also described in the above Research Disclosure. The relevant entries are shown in the table below.

[Items] Color turbidity inhibitor Dye Image stabilizer Brightener Ultraviolet absorber Light absorber Light scattering agent Filter dye Binder Anti-smudge agent Hardener Lubricant Activator/coating WJ agent Matting agent Developer Contained in materials) [Page of RD30811.9] 1002 ■-r term 1001 ■-J term 998■ 1003 11-C, XmC term 1003 VM +003 [1003Vl 1003 1X +01+6 Xll! +004 X +006 Xrl 1006 X[l +005 XI +007 XV+ 1001 X・It is stated in the disclosure. The relevant entries are shown in the table below.

[Items] Yellow coupler Magenta coupler Cyan coupler Colored coupler DIR coupler BAR coupler Other useful residue-releasing couplers [RD3 (page +8119) 1001 ■- Item 1001 ■- Item D 1 (101 ■- Item 1002 ■- G term 1001 ■-F term 1002 ■-F term 1001 ■-F term rRD17643] [RD18716 ■C5
- Section G ■ Section C-G ■ Section C-G ■ Section G ■ Section F The additives used in the present invention are RD 308119X I
It can be added by the dispersion method described in V.

The photosensitive material of the present invention can be provided with auxiliary layers such as the filter layer and intermediate layer described in the above-mentioned RD 308119-.

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

The photosensitive material of the present invention can have various layer structures such as normal layer, reverse layer, and unit structure as described in the above-mentioned RD 3081, Section 9-.

The present invention can be applied to various color photosensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color vapors, color positive films, and color reversal vapors.

The photosensitive material of the present invention can be developed by the conventional method described in RD 1764328-29, RD 18716647, and RD 308119 XIX.

[Example] EXAMPLES The present invention will be specifically explained below with reference to Examples.

Note that, as a matter of course, the present invention is not limited to the embodiments described below.

Example-1 100 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. Parts by weight were added, and a transesterification reaction was carried out in a conventional manner. 0.05 parts by weight of trimethyl phosphate was added to the obtained product, the temperature was gradually raised and the pressure was reduced, and finally polymerization was carried out at 280° C. and below 1 mmHg to obtain a copolymerized polyester.

This copolyester and IVo, 68 PET resin were melt-extruded into a three-layer multi-manifold type coextrusion die using two extruders, with PET in the center and copolyester in the outer layer, to a thickness of 700 μm. An unstretched sheet was molded.

This unstretched sheet was then roll-stretched 30 times in the machine direction at 100°C, then 33 times tenter-stretched in the transverse direction at 110°C, then heat-set at 220°C, and then at 150°C.
It was subjected to a 20% relaxation treatment in the middle zone of , and then cooled to room temperature and wound up.

The obtained film (A) was transparent and had a thickness of 70 μm, an inner PET layer of 30 μm, and a water content of 1.6%.

Comparative Example-1 In addition, the copolymerized polyester was molded alone to a thickness of 70
The moisture content of the μm film (B) was 26%.

Comparative Example 2 The moisture content of the 70 μm thick film (C) formed by molding the PET alone was 0.3%.

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

The results of each measurement are shown in Table 1.

Table 1 Tear strength Toyo Seiki ■ Using a light load tear tester, tear load 5
The tear propagation resistance when measured at 0.00g with a thickness of 100μ
It is converted to m, and the unit is g/100μm.

10m in the sample using a folding durability testing machine manufactured by Jyuyu Machinery Manufacturing Co., Ltd.
This is the number of times it can be folded until it is repeatedly folded and cut in m.

Example 2 (Preparation of photographic material) Lower embossed layer! After corona discharge treatment was applied to both sides of the polyester resin film (A) of the laminated structure of the present invention in Example 1 and the films (B) and (C) of Comparative Examples 1 and 2, a sublayer of the following composition was applied. Layers were provided. The degree of corona discharge treatment is 0.02K
VA·min/rrI'.

(Styrene-butyl acrylate-hydroxyethyl acrylate-butadiene) latex g Distilled water 250cc Sodium α-sulfodi-2-ethylhexyl succinate
0.05gaziridine compound (C
-1) Polyester resin film (A), (B
) and (C) were subjected to corona discharge again, and then a conductive layer having the following composition was coated to a dry film thickness of 1 μm.

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

Drying air temperature 90℃, overall heat transfer coefficient 25kg/rr?・hr
It was dried for 30 seconds under parallel flow drying conditions at .degree. C., and then heat-treated at 140.degree. C. for 90 seconds.

Water-soluble conductive polymer (A) 60g/,
Q Hydrophobic polymer particles (B) 40g/λ
Ammonium sulfate 0.5g/42 Hardening agent (H) 12g/f Overall I! ! shall be.

2.0 g/m of gelatin on the coated antistatic layer
1 and dried. However, the following (H-2) was used as a hardening agent for gelatin.

CHl hardener (H-2): Glyoxal copy" Ui9) [
The polyester resin film of the present invention provided with a construction backing layer (
The following photographic layer was provided on the side opposite to the back layer of the films (B) and (C) of A) and Comparative Examples 1 and 2.

1st layer: Red-sensitive silver halide low-speed layer (1-a) Preparation of emulsion solution for low-sensitivity unit emulsion layer Silver iodobromide emulsion containing 6 mol% of iodine (average grain size 06μ, halogen per 1 kg of emulsion) 100g of silver.

(containing 70 g of gelatin) was prepared in a conventional manner.

Add anhydro to 1 kg of this emulsion as a red-sensitive color sensitizer.
5,5'-dichloro-9-ethyl-3,3'-di(3-
Sulfobrovir) - 01% methanol solution of thiacarbocyanine hydroxide pyridinium salt 180
cc and then 5-methyl-7-hydroxy-2,
5% by weight aqueous solution of 3,4-1 riazaindolizine 20c
330 g of cyan coupler emulsion (1) and 20 g of emulsion (2) according to the following formulation were added. Furthermore, 50 cc of a 2% aqueous solution of 2-hydroxy-4,6-cyclotriazine sodium salt was added as a gelatin hardener to prepare an emulsion solution for a low-sensitivity unit emulsion.

Emulsion (1) ■ 10% by weight gelatin aqueous solution 1.000
g ■ Sodium p-dodecylbenzenesulfonate g Tricresyl phosphate 60cc Cyan coupler (C-7) 70g Ethyl acetate
100cc of mixture at 55℃
After dissolving the mixture, the mixture was added to (2) preheated to 55°C and emulsified using a colloid mill.

Cyan coupler emulsion (2) ■ 10% by weight gelatin aqueous solution 1.000
g ■ Sodium p-dodecylbenzenesulfonate g Tricresyl phosphate cyan coupler DIR cyan coupler *1 Ethyl acetate cyan coupler is the same as above.

0cc g 4 g 00cc Second layer, red-sensitive silver halide medium-speed layer (1-b) Preparation of emulsion solution for medium-speed unit emulsion layer The following changes were made in the above (1-a).

(1-C) Preparation of emulsion liquid for high-sensitivity unit emulsion layer (1-a)
The following changes were made.

4th layer: Gelatin intermediate layer 5th layer: Green-sensitive silver halide low-sensitivity layer (2-a) Preparation of emulsion solution for low-sensitivity unit emulsion layer Silver iodobromide emulsion containing 6 mol% of iodine (average grain Size 06μ, 100g silver halide per 1kg emulsion.

(containing 70 g of gelatin) was prepared in a conventional manner.

Add 1 kg of this emulsion to 3.3' di(3) as a green-sensitive color sensitizer.
-Sulfoethyl)-9-ethyl-benzoxacarbocyanine pyridinium salt 01% methanol solution 200c
c and then 5-methyl-7-hydroxy-2,3
, 5% by weight aqueous solution of 4-1-riazaindolizine 20c
In addition, 380 g of magenta coupler emulsion (3) and 20 g of emulsion (4) according to the following formulation were added.

Furthermore, as a gelatin hardener, 2-hydroxy-4,6-
2% by weight aqueous solution of cyclotriazine sodium salt 50
cc was added to prepare an emulsion liquid for a low-sensitivity unit emulsion.

Emulsion (3) ■ 10% by weight gelatin aqueous solution i,ooo
g ■ Sodium p-dodecylbenzenesulfonate g Tricresyl phosphate 65 cc Magenta coupler (M-7) 6 g Ethyl acetate 110 cc After dissolving a mixture of ■ at 55°C, add to ■ previously heated to 55°C, It was emulsified using a colloid mill.

Magenta coupler (M-7): 1- (2,4゜6-
Dolichlorophenyl)-3-[3-(2,4-di-t-
pentylphenoxyacetamide)benzamide]-5-
Pyrazolone emulsion (4) ■ 10% by weight gelatin aqueous solution 1.000
g ■ Sodium p-dodecylbenzenesulfonate g Tricresyl phosphate 65cc Magenta coupler 63 gDIR magenta coupler” 60 g Ethyl acetate
Emulsification was performed in the same manner as for 110 cc emulsion (3).

”DIR magenta coupler: 1- (4-[2-
(2,4-di-t-pentylphenoxy)butanamido]phenyl)-3-(1-pyrrolidinyl)4-(1-phenyltetrazolyl-5-1000)-5-pyrazolone I 6th layer: green sensitive Silver halide medium-speed layer (2-b) Preparation of emulsion solution for medium-speed unit emulsion layer Silver iodobromide emulsion containing 5 mol % of iodine (average grain size 09 μ, 100 g of silver halide and 70 g of gelatin per 1 kg of emulsion) ) were prepared in a conventional manner.

To 1 kg of this emulsion was added 150 cc of a methanol solution of the green-sensitive color sensitizer shown in (2-a), and then 5-methyl-
20 cc of a 5% by weight aqueous solution of 7-hydroxy-2,3,4-triazaindolizine was added. Furthermore, the above emulsion (
285 g of 3) and 15 g of emulsion (4) were added.

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

7th layer: Green-sensitive silver halide high-sensitivity layer (2-c) Preparation of emulsion liquid for high-sensitivity unit emulsion layer Silver iodobromide emulsion containing 6 mol% of iodine (average grain size 11μ, 1.0g or more) The grains are 50% by weight of the total, 1 silver halide per 1 kg of emulsion.
00g, containing 70g gelatin) was prepared in the usual manner. 80 cc of a methanol solution of the green-sensitive color sensitizer shown in (2-a) was added to 1 kg of this emulsion, and then 5-methyl-
5 of 7-hydroxy-2,34-)riazaintolidine
Add 20 cc of wt% aqueous solution, and then add 20 cc of emulsion (3).
Added 00g.

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

8th layer: Yellow filter layer consisting of yellow colloidal silver (dry film thickness 12 μm) 9th layer: Blue-sensitive layer Silver halide low-sensitivity layer (3-a) Preparation of emulsion solution for low-sensitivity unit emulsion layer 5 mol% Silver iodobromide emulsion containing iodine (average grain size 06μ, silver halide 100g per 1kg emulsion).

(containing 70 g of gelatin) was prepared in a conventional manner.

5-methyl-7-hydroxy-23,
4-) 20 cc of a 5% by weight aqueous solution of riazaindolizine and yellow coupler emulsion (5) according to the following formulation were added to 6
Added 00g. Furthermore, as a gelatin hardener, CH2=
CHS O2CH20CH2S O2CH=CH2 and 2
50 cc of a 2% by weight aqueous solution of -hydroxy-4,6-cyclotriazine sodium salt was added to prepare an emulsion solution for a low-sensitivity unit emulsion.

Emulsion (5) ■ 10% by weight gelatin aqueous solution 1.000
g ■ Sodium p-dodecylbenzenesulfonate g Tricresyl phosphate yellow coupler Yellow DIR coupler 0 Ethyl acetate 0 cc 00 g 20 cc 10th layer: Blue-sensitive silver halide medium-sensitivity layer above (3-a
) was changed as follows.

11th layer: Blue-sensitive silver halide high-sensitivity layer (3-a
) was changed as follows.

12th layer two surface protective layers 10% by weight gelatin solution Poly(methyl methacrylate) Polymer particles 3μ Sodium dodecylbenzenesulfonate SiO□ fine particles (30μ) Sodium polystyrene sulfonate polyorganosiloxane 2-hydroxy-4,6-dichloro 000cc rate - methacrylic acid) 0mg Rium 40mg 0mg 1g 00mg triazine 　0mg 5mg C@F 17S OsNa The amounts of silver coated in each of the photosensitive layers were as follows.

1st layer (1, 0g/proof), 2nd layer (0, 8g/bo) 3rd layer
layer (1,2 g/bo), 5th layer (1,2 g/bo), 6th layer (
1,0g/r+), 7th layer (1,2g/r+?), 9th layer (
0.6g/rr? ), 10th layer (0.6 g/proof).

11th layer (0.6g/resistance) Three types of color negative films obtained in this way (1
), (2) and (3) were each cut to a size of 35 mm, and these were loaded into a cartridge.

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

Processing process Temperature Time Color development 38℃ Stop for 3 minutes
3880 1 minute water wash
Bleach at 38℃ for 1 minute
38°C 2 minutes water washing 38°C
Fixed for 1 minute 38°0
Washing with water for 2 minutes Stabilizing bath at 38°C for 1 minute The treatment solution used has the following composition.

Color developer Caustic soda 2g Sodium sulfite 2g Potassium bromide
0.4 g sodium chloride
1g ho sand
4g hydroxylamine sulfate 2g ethylenediaminetetraacetic acid disodium dihydrate g 4-amino-3-methyl-N-ethyl-N(β-hydroxyethyl)aniline monosulfate)
Add 4g water
Total volume 1 Stop solution Sodium thiosulfate 10 g Ammonium thiosulfate (70% aqueous solution) 30 nQ acetic acid
30d sodium acetate
Add 5g of potassium alum water, bleach solution, ethylene diamine, tetraacetic acid, iron dihydrate, potassium bromide, ammonium nitrate, ammonia fornic acid, water, fixer solution, sodium thiosulfate, sulfite, soda sand, glacial acetate, potassium alum water, stabilize bath, formic acid. Sodium citrate 5g Total amount 12 (m) Sodium・00g 0 g 0 g g Adjust pH to 5.0 Total amount 1! 50 g 5 g 2 g 51 g 0 g Total amount 1! g g Sodium metaphoate (tetrahydrate) 3g potash alum 15g Add water
Total amount: 1 film after processing (1
), (2) and (3) were cut to a length of 227 mm and the degree of curl was measured for each. The results are shown in Table 2.

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

Films (1) and (2) in Table 2 had no practical problems, but film (3) was strongly curled and difficult to handle.

Example 3 The PET used in Example 1 was individually molded to a thickness of 30 μm. At this time, between the longitudinal stretching process and the transverse stretching process, the copolymerized polyester copolymerized in Example-1 was melt-extruded and laminated using an extruder. Lamination was performed on both sides by inverting the film, and the extrusion amount was adjusted so that the total thickness of the completed film was 70 μm.

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

Example-4 The PET used in Example-1 alone was formed into a film with a thickness of 60 μm. The copolyester prepared in Example 1 was melt-extruded and laminated onto this film. Both sides were laminated to a total thickness of 120 μm.

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

[Effects of the Invention] According to the present invention, there is provided a roll-shaped silver halide photographic light-sensitive material in which a silver halide photographic emulsion is coated on a polyester resin film, and the polyester resin film is a lamination of polyester resin films having different water contents. By thinning PET, which has a high elastic modulus, and laminating a copolyester with a higher water content, it has excellent curl recovery ability, that is, curl removal after development processing, and has a tear strength and folding durability that are suitable for practical use. It has the remarkable effect of having excellent mechanical properties such as strong adhesion of each layer.

Claims (7)

[Claims] (1) A roll-shaped silver halide photographic light-sensitive material in which at least one layer of silver halide photographic emulsion is coated on a support consisting of a plurality of polyester resin films, wherein the plurality of polyester resin films have at least one layer of different water contents. A roll-shaped silver halide photographic material comprising two layers of polyester resin films laminated together. (2) The roll-shaped silver halide photographic light-sensitive material according to claim 1, wherein one layer of the plurality of polyester resin films is a polyethylene terephthalate resin film having a thickness of 5 μm or more and 100 μm or less. (3) The plurality of polyester resin films have a laminated structure of three or more layers, the layer made of the polyethylene terephthalate resin film is located in a layer that does not appear on the surface, and the moisture content of the polyester resin film of the layer forming the surface is 3. The roll-shaped silver halide photographic light-sensitive material according to claim 2, wherein the water content is higher than that of the polyethylene terephthalate resin constituting the layer that does not appear on the surface. (4) In the support composed of the plurality of polyester resin films, the polyester resin film in the layer closer to the surface than the layer composed of the polyethylene terephthalate resin film contains an aromatic dicarboxylic acid having a metal sulfonate as a copolymerization component. The roll-shaped silver halide photographic light-sensitive material according to claim 2 or 3, which is made of polyester. (5) A rolled silver halide photograph according to claim 1, wherein the support made of the plurality of polyester resin films has a laminate structure made of at least two layers formed by a coextrusion method. photosensitive material. (6) After laminating one or more layers of polyester resin film with a higher moisture content on a polyethylene terephthalate resin film in which a support consisting of a plurality of polyester resin films is uniaxially stretched or oriented in the vertical or horizontal direction, 2. The roll-shaped silver halide photographic material according to claim 1, which has a laminated structure stretched and oriented in a uniaxial direction. (7) Claims 2, 3 and 4, characterized in that the thickness of the polyethylene terephthalate resin film is 80% or less of the total thickness of the polyester resin film;
The roll-shaped silver halide photographic material according to item 5 or 6.