JPH0477734A - Silver halide photographic sensitive layer - Google Patents

Abstract

PURPOSE:To provide the photographic sensitive material having excellent transparency, mechanical properties and property to eliminate curling after development processing by using a biaxially stretched film consisting of a mixture composed of a polyethylene terephthalate resin and a specific thermosplastic resin as a base. CONSTITUTION:The biaxially stretched film consisting of the mixture composed of the polyethylene terephthalate resin and the thermoplastic resin is used as the polyester resin film in the rolled silver halide photographic sensitive material having at least one layer of silver halide emulsion layers on a polyester resin film base. The above-mentioned thermoplastic resin is required to have compatibility with the polyethylene terephthalate resin and to have hydrophilicity. This hydrophilic thermoplastic resin has elimination groups, such as carboxyl group, sulfonic acid group and quaternary amine group or nonionic hydrophilic groups, such as hydroxyl group, acrylamide group and ether group.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photographic light-sensitive material, and more specifically, a photographic light-sensitive material that uses a polyester material as a support and has excellent curl removal properties after development. It's about materials.

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 light-sensitive materials typically come in sheet form, such as X-ray film, plate-making film, and cassette film, or in roll form. Typical roll films include color or black and white negative films that are 35 mm wide or less and are housed in cartridges and are loaded into general cameras for photographing.

Conventionally, a GoAC film support has been mainly used for roll films. The most important feature of TAC film as a photographic support is that it has no optical anisotropy and is highly transparent, as well as its excellent ability to eliminate curling after processing. be. 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 molecular chains that have been modified.

For photographic materials such as TAC film that do not have curl recovery properties, when used in roll form, for example, the printing process to form an image on photographic paper after development is difficult. This results in problems such as scratches, defocus, and jamming during transportation.

Incidentally, in recent years, the uses of photographic light-sensitive materials have been diversifying, and there has been significant progress in increasing the speed of film transportation during photography, increasing the magnification of photography, and downsizing of photographic devices. To this end, the support for the photographic photosensitive material El is required to have properties such as strength, dimensional stability, and thin film formation.

However, since T A and C have rigid molecular structures,
At present, T A and C films cannot be used for these purposes because the quality of the film after film formation is weak.

[Question 8 to be solved by the invention] On the other hand, PET film has been considered to be a substitute for TAC film because it has excellent productivity, mechanical strength, and dimensional stability.

However, when PET film is in roll form, which is widely used as a photographic material, it is difficult to handle after processing because it has curls and curls remain, and because it does not have the above-mentioned excellent properties, it cannot be used as a roll film. There was a problem that it could not be used.

As a means to solve this curling problem, Japanese Patent Laid-Open No. 1-244446 discloses a technique using a polyester film having a water content of 0.5% or more.

The moisture content of PET film is usually about 0.3%, but in the same report, a PET film with a moisture content of 0.7% was obtained by copolymerizing an aromatic dicarboxylic acid having a metal sulfonate.

Moisture content can be increased by increasing the amount of metal sulfonate used, but if the amount of metal sulfonate used is too large, it will deteriorate the mechanical strength such as brittleness and tear strength of the film, making it difficult to use as a photographic support. As a result, it becomes impractical.

However, when a PET film with a moisture content of 0.7% is strongly curled, it cannot be fully recovered and is not satisfactory. Therefore, even higher water content, i.e. TAC
There has long been a desire for a PET film with a moisture content comparable to that of PET films.

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

[Means for Solving the Problems] The above object of the present invention is to provide a roll-shaped silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a polyester resin film support. is a biaxially stretched film of a mixture of polyethylene terephthalate resin and thermoplastic resin,
The present invention has been achieved by a silver halide photographic light-sensitive material characterized in that the thermoplastic resin is a hydrophilic thermoplastic resin that is compatible with polyethylene terephthalate resin.

The present invention will be explained in more detail below.

The silver halide photographic material of the present invention uses a polyester resin as a support.

The polyester resin is a biaxially stretched film of a mixture of polyethylene terephthalate resin and thermoplastic resin.

The above-mentioned polyethylene terephthalate resin refers to a polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and ethylene glyfur, and may contain other polymers, additives, etc. as long as the original properties of PET are not impaired. Further, it is possible to include a copolyester obtained by copolymerizing a dibasic acid other than terephthalic acid and a polyhydric alcohol other than ethylene glycol.

The thermoplastic resin must be compatible with the polyethylene terephthalate resin and have hydrophilic properties.

A thermoplastic resin that is compatible with PET resin refers to a thermoplastic resin that does not form voids when stretched and molded after mixing with PET resin. At this time, it is preferable to use a compatibilizer to ensure sufficient compatibility. In the present invention, even if a thermoplastic resin is not compatible with PET resin by itself, it is possible to use a thermoplastic resin that is compatible with PET resin by using an appropriate compatibilizing agent.

A hydrophilic thermoplastic resin refers to a polymer that dissolves and/or swells in water, and includes gels made by crosslinking water-soluble polymers to make them insoluble in water.

The hydrophilic thermoplastic resin has a dissociative group such as a carboxyl group, a sulfonic acid group, or a quaternary amine group, or a nonionic hydrophilic group such as a hydroxyl group, an acrylamide group, or an ether group. In the present invention, for example, polyethylene glycol, polyvinyl alcohol, sulfone-1.
Copolymerized polyester and the like are preferably used.

Compatibilizers include carboxy-modified polyethylene, surfactants, metal soaps, silanes or titanium coupling agents, block copolymers having both a group with a large affinity for PET and a group with a large affinity for thermoplastic resins, molecules]. Examples include not-so-large polyesters and maleic anhydride copolymers.

In the present invention, methods for mixing PET resin and the above thermoplastic resin include a method of adding the above thermoplastic resin during the PET polymerization process, a method of mixing using a kneader etc. after PET polymerization, and a method of mixing the above thermoplastic resin immediately before film formation. Examples include a method of mixing, a method of melt-mixing in a film-forming extruder, or any location between the extruder and the die lip outlet.

In the present invention, dyes, ultraviolet absorbers, antioxidants, plasticizers, antistatic agents, etc. can also be added thereto.

The mixture is melt extruded and biaxially stretched according to conventional methods. That is, it is melt-extruded on a rotary cooling body at 260 to 320°C to form an amorphous sheet, and then longitudinally stretched at a temperature of 70 to 130°C, preferably 80 to 110°C, and stretched 20 to 50 times in the longitudinal direction, preferably is rolled stretched 2.2 to 40 times, and then 20 to 50 times in the transverse direction at a transverse stretching temperature of 70 to 150°C, preferably 80 to 130°C, and higher than the longitudinal stretching temperature, preferably 2.2 to 130°C. 0.1 to 1 after tenter stretching to 4.0 times and then heat setting at a temperature above the transverse stretching temperature and below 240°C, preferably at 150 to 230'C.
It is thermally relaxed by 0%, preferably 0.5 to 5%, and then cooled to room temperature and wound up. Simultaneous biaxial stretching using a tenter clip method may be used for stretching. Further, after the horizontal stretching, longitudinal stretching may be performed again.

It is also possible to impart slipperiness to the polyester resin film 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-mentioned inert inorganic compounds include SiO2, Tie, B
Examples include aSO4, CaC0, talc, kaolin, and the like. Transparency is an important requirement for a support for photographic light-sensitive materials, so we selected SiO2, 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. This is desirable.

The thickness of the film can be set as appropriate depending on the field of use of the photographic film, but is preferably 10 to 250μ, more preferably 20 to 250μ.
A thickness of 150μ is preferred.

In the present invention, an antistatic layer can be provided on the polyester film support.

The antistatic layer contains at least a reaction product of a water-soluble conductive polymer and a 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. The water-soluble conductive polymer may contain a hydroxyl 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 3000 to 1000.
00, preferably 3,500 to 50,000.

The antistatic layer may contain hydrophobic polymer particles. These hydrophobic polymer particles are composed of so-called latex, which is substantially insoluble in water. This hydrophobic polymer is obtained by polymerizing monomers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination. 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 antistatic layer according to the present invention is preferably 80 or less, particularly preferably 30 to 75.

If it is too low, it is not preferable from the viewpoint of film stability.

The antistatic 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 polyester film used in the present invention may be coated with a subbing layer containing a latex polymer after being subjected to a corona discharge treatment. The corona discharge treatment is particularly preferably applied at an energy value of 1rnW to IKW/min. 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 photosensitive materials having a support. 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.

As the silver halide emulsion used in the photographic light-sensitive material of the present invention, any conventional silver halide emulsion can be used.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion.

The silver halide emulsion used in the present invention is, for example, US Pat. No. 2,444,607, US Pat. No. 2,716,062, US Pat.
No. 89,380, No. 2,058,626, No. 2,
118.411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342,596, Japanese Patent Publication No. 4417-1987, West German Application Publication No. 2.149,789, Japanese Patent Publication No. 39-2
825, Special Publication No. 49-13566, etc. (TI
Compounds described in books or publications, preferably e.g. 56-drimethylene-7-hydroxyne to 5-1-
Riazolo (1,5-a,) pyrimidine, 5,6-titramethylene-7-hydroxy~s-triazolo (1,
5-a) Pyrimidine, 5-methyl-7-hydroxy-3
-triazolo(1,5-a)pyrimidine, 5-methyl-
7-Hydroxy5-)-riazolo(1,5-a)
Pyrimidine, 7-hydroxyn-8-triacylone (1
, 5-a) Pyrimidine, 5-methyl-6-promorph-
Hydroxy-Sl.liazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, F-decyl gallate, propyl gallate, sthorium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5
-Methylbenztriazole), benzimidazoles (6-nitrobenzimidazole), etc. can be used for stabilization.

Gelatin is a hydrophilic colloid that is particularly advantageously used in the photographic material of the present invention.

Seratin used in the present invention can be treated with either alkali or acid, but when ossein gelatin is used, it is preferable to remove calcium or iron. The preferred content of calcium is 1 to 9.
99 ppm, more preferably 1 to 500 ppm
The iron content is preferably 0.01 to 50 ppm, more preferably 01 to 10 ppm.

Adjustment of the amounts of calcium and iron can be achieved by passing the aqueous gelatin solution through an ion exchanger.

In the present invention, an amino compound may be contained in the silver halide photographic sensitizer and/or developer.

In order to improve the developability, a developing agent such as phenylene or hydroquinone or an inhibitor such as benzotriazole may be contained in at least one layer of the support on the side having the emulsion layer.

Alternatively, in order to increase the processing ability of the processing solution, the backing layer can contain a developing agent or an inhibitor.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

When used as a light-sensitive material for color photography, a coupler is added to the emulsion layer.

Furthermore, by coupling with a colored coupler having a color correction effect, a competing coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent,
Compounds that release photographically useful fragments such as toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and sensitizers are used.

Can the photosensitive feed be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, etc.? Are there any substances in these layers and/or emulsion layers that may flow out of the photosensitive material during the development process? Alternatively, a bleaching dye may be included.

A formalin scavenger-1 fluorescent whitening agent, a pine agent, a lubricant, an image stabilizer, a surfactant, a color fog preventer, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

The developing agents used in the development of the silver halide photosensitive + J $-4 of the present invention include catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2.3-dibromohydroquinone, 2.5 -diethylhy1~quinone, cara: ]-/l/, 4-') lorocatechol, 4-phenyl-catechol, 3-methoxy-
Examples include catechol, 4-acetyl-pyrogallol, and sodium ascorbic acid.

In addition, HO-(CH=CI-I), -NH2 type developer typically includes ortho or rose aminophenol, specifically 4-aminophenol, 2-amino-6- Phenylphenol, 2-amino-4-chloro-
Examples include 6-phenylphenol and N-methyl-p-aminophenol.

Furthermore, 82N-(CH=CH). -NH2 type developers include, for example, 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N-(4-amino-3-methylphenyl)-
Examples include morpholine and p-phenylenediamine.

Examples of petrocyclic type developers include 3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. -pyrazolidones,
Examples include 1-phenyl-4-amino-5-pyrazolone and 5-aminolaucil.

Further, a developer that can be effectively used in the present invention is described in The Theory of the Photographic Process, 4th edition, written by TH James.
graphic Process Fourth Ed
ition), pages 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society).
al of the American Chemical
Volume 73, page 3,100 (19
51).

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, a sulfite salt such as sodium sulfite or potassium sulfite may be used as a preservative in the developer. Furthermore, hydroxylamine, hydrazide compounds, etc. can also be used as preservatives. The amount used is 5 to 5 per developer.
500g is preferable, more preferably 20-200g.

Further, the developer may contain glycols as an organic solvent. Examples of glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-bentanediol, etc. Among these, it is preferable to use diethylene glycol. The preferred amount of glycols to be used is 5 to 500 g, more preferably 20 to 200 g per developer. These organic solvents can be used alone or in combination.

The photographic light-sensitive material of the present invention can be developed with a developer containing the above-mentioned development inhibitor to obtain a light-sensitive material with extremely excellent storage stability.

The pH value of the developer having the above composition is preferably from 9 to 3, and more preferably from IO to 12 from the viewpoint of stability and photographic properties. Regarding cations in the developer,
It is preferable that the ratio of potassium ions is higher than that of sodium because the activity of the developer can be increased.

The photographic material of the present invention can be processed under various conditions. For example, the development temperature is preferably 50°C or lower, and particularly preferably around 25°C to 40°C.

Furthermore, it is optional to employ steps such as washing with water, stopping, stabilizing, fixing, and if necessary, pre-hardening and neutralizing, and these steps can be omitted as appropriate.

Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

[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 (Preparation of polyester film support) I Vo, 68
(7) PET resin 92 parts by weight and molecular fi 20,000
8 parts by weight of polyethylene glycol were mixed and melt-extruded onto a cooling roll to create a sheet with a thickness of 700 μm. This sheet was stretched 2.6 times in the longitudinal direction at 95°C,
Then, it was stretched 27 times in the transverse direction at 110°C.

The stretching method was the usual roll tenter method.

It was then heat-set at 210°C, then thermally relaxed by 2%, cooled to room temperature, and rolled up.

The resulting film had a thickness of 100 μm and good transparency. Moreover, the moisture content was 16%.

However, the moisture content of a polyester film can be measured by conditioning the film at 23°C, 30% RH, for 3 hours, immersing it in distilled water at 23°C for 15 minutes, and then using a trace moisture meter ( For example, the drying temperature was 150° C. using Mitsubishi Kasei Model CA-02.

(Preparation of photographic light-sensitive material) After corona discharge treatment was applied to both surfaces of the prepared polyester film support, a subbing layer having the following composition was provided. The degree of corona discharge treatment was 0.02K VA·min/durability.

(Styrene-butyl acrylate-hydroquine ethyl acrylate-butadiene) latex g Distilled water 250cc Sodium α-sulfodi-2-ethylhexyl succinate
0.05gaziridine compound (C-
2) Removal of 0.02g pack' n- After applying corona discharge to one side of the support after coating the undercoat layer,
An antistatic 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) shown below were used, respectively. Further, the following curing agent (I) was added while coating.

Dry air section 90'C% Overall heat transfer coefficient 25kg/rn''・
It was dried for 30 seconds under parallel flow drying conditions of hr.degree. C., and then heat-treated at 140.degree. C. for 90 seconds.

Water-soluble conductive polymer (A) 60g/ffi
Hydrophobic polymer particles (B) 40g/ml ammonium sulfate 0.5g/ml curing agent (
H) 1.2g/ffi as a whole is IP.

2.0g/M gelatin on the coated antistatic layer
Apply it and let it dry. However, the following (H-2) was used as a hardening agent for gelatin.

Hydrophobic polymer particles (B) CH.

Hardening agent (H-2): Glyoxal water-soluble conductive polymer (A) .

1st layer: Red-sensitive silver halide low-speed layer (1-a) Preparation of emulsion liquid for low-speed unit emulsion layer Silver iodobromide emulsion containing 6 mol% of iodine (average grain size 0.6μ, emulsion 1kg) (containing 100 g of silver halide per 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-
Sulfoblovir) - 0.1% methanol solution of thiacarbocyanine hydroxide pyridinium salt 28
Add 0 cc and then 5-methyl-7-hydroxy-2
,3,4-) 5% by weight aqueous solution of riazaindolizine 20
Cyan coupler emulsion (1) with cc and the following formulation
and 20 g of emulsion (2) were added. Furthermore, 50 cc of a 2% by weight 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 layer.

Emulsion (1) ■ 10% Seratin aqueous solution 1.000
g■ p-dodecylbenzenesulfonic acid nota'g tricresyl phosphate-1-60c cyan coupler (C-7) 70g ethyl acetate
After dissolving 100 cc of the mixture at 55°C, it was added to 2 which had been preheated at 55°C (2 Calories) and emulsified in a colloid mill.

Cyan coupler ((, -7) Emulsion (2) ■ 10% gelatin solution 1.000
g ■ p-F decyl benzene sulfone Δ father notation g Tricresyl phosphate cyan coupler 0 cc g DIR cyan coupler 91 Ethyl acetate cyan coupler is the same as above.

"DIR cyan coupler 4 g 00cc 2nd layer, red-sensitive silver halide medium-speed layer (1-b) Preparation of emulsion 11 for medium-speed unit emulsion layer The following changes were made in the above (1-a). Ta.

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

4th layer: Ceratin 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 An emulsion (size 06μ, containing 100g of silver halide and 70g of gelatin per kg of emulsion) 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 bilinnium salt 01% methanol solution 200c
c and then 5-methyl-7hydroxydi234-
1-Reassign) Add 20 cc of a 5% aqueous solution of baricin, and then add a magenta coupler emulsion (
380 g of 3) and 20 g of emulsion (4) were added.

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

Emulsion (3) ■ 10% by weight gelatin aqueous solution 1.000
g ■ Sodium p-dodecylbenzenesulfonate g Tricresyl phosphate 65cc Magenta coupler (M-7) 6g Ethyl acetate
After melting 110 cc of the mixture at 55°C, it was added to the mixture previously heated to 55°C and emulsified using a colloid mill.

Magenta coupler (M-7): 1-(2,4.

6-dolychlorophenyl)-3- [1- (2.4-
di-t-pentylphenoxyacetamide)benzamide]-5-pyrazolone emulsion (4) ■ 10% by weight aqueous gelatin solution 1.000
g ■ Sodium p-dodecylbenzenesulfonate g Tricresyl phosphate-1- 65cc macenta coupler 63 g DIR macenta coupler” 60 g ethyl acetate
Emulsification was performed in the same manner as for 110 cc emulsion (3).

“DIR magenta coupler: 1-(4- 12-
(2,4-di-t-pentylphenoxy)butanemitocophenyl)-3-(1-pyrrolidinyl)4-(1-
Phenyltetrazolyl-5-thio)5-pyrazolone 6th layer: Green-sensitive silver halide medium-speed layer (2-b) Preparation of emulsion solution for medium-speed unit emulsion layer Iodine containing 5 mol% of iodine A silver halide emulsion (average grain size 09 microns, containing 100 g of silver halide and 70 g of gelatin per kg of emulsion) was prepared in a conventional manner.

To 1 kg of this emulsion was added 50 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-2,3,1-triacaintridine 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, grains of 10g or more) is 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-
20 cc of a 5% by weight aqueous solution of 7-hydroxy2.3.4-triazaindolizine was added, followed by 200 g of emulsion (3).

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

8th layer: yellow filter layer consisting of yellow colloidal silver (dry film thickness 12 μm) 9th layer: blue-sensitive silver halide low-sensitivity layer (3-a) Preparation of emulsion solution for low-sensitivity unit emulsion layer 5 mol% A silver iodobromide emulsion containing iodine (average grain size 06 μm, containing 100 g of silver halide and 70 g of seratin per kg of emulsion) was prepared in a conventional manner.

1 kg of this emulsion contains 23% of 5-methyl-7-hydroxyl.
20 cc of 5% by weight aqueous solution of 1-1-riazaintolidine
And 600 g of yellow coupler emulsion (5) according to the following formulation was added. Furthermore, as a ceratin hardening agent, Cl-1
2=CHS 02CH20C1-12S 02CH=C
H2 and sodium 2-hydroxy-4,6-cyclotriazine were used to prepare an emulsion solution for a low-sensitivity unit emulsion.

Emulsion (5) ■ 10 heavy gelatin aqueous solution 1.000
g ■ Sodium p-dodecylbenzene sulfonate)/Licreasyl phosphate yellow coupler Yellow DIR coupler 0 Ethyl acetate g 0cc 00 g 20cc L(, sl-1 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 heavy surface protection layer 10% by weight Seratin solution Poly(methyl methacrylate) Polymer particles 3μ F-decylbenzenesulfonic acid S102 fine particles (30μ) Sodium polystyrene sulfonate polyorganosiloxane 2-hydroxy-4,6 000cc methacrylic acid) 0mg Thorium 4 0mg 0mg g 00mg Dichlorotriazine 5mg C8FL7S ○sNa The amounts of silver coated in each of the photosensitive layers were as follows.

1st layer (1, Og/rr?), 2nd layer (0,8g/rr?)
r? ).

3rd layer (1,2g/m), 5th layer (1,2g/rn'
).

6th layer (1,0g/m), 7th layer (1,2g/rn”
).

9th layer (0.6g/m), 10th layer (0.6g/rn
').

Eleventh Layer (0.6 g/bo) The obtained color negative film was cut into a size of 35+ nm and loaded into a cartridge.

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

Processing process Temperature Time Color development 38°0 3 minutes stop
38°0 1 minute water wash
Bleach at 38°C for 1 minute Bleach at 38°C for 2 minutes Wash with water Fix at 38°C for 1 minute Wash with water at 38°C for 1 minute Stabilize bath at 38°C for 1 minute The processing solution used at 38°C for 1 minute has the following composition.

Color developer Caustic soda 2g Sodium sulfite 2g Potassium bromide
0.4 g sodium chloride
1g po sand
4g hydroxylamine sulfate 2g ethylenediaminetetraacetic acid disodium dihydrate g 4-amino-3-methyl-N-ethyl-N(β-hydroxyethyl)aniline monosulfate) 4g Add water to total volume 1 and stop solution thio Sodium sulfate 10 g Ammonium thiosulfate (70% aqueous solution) 3 (1 mQ acetic acid
30d sodium acetate
5g potash alum
Add 1.5g of water and bleach solution Ethylene diamine 4 Iron acetate dihydrate Potassium bromide Ammonium nitrate Ammonium fornic acid Water Add fixing solution Sodium thiosulfate Sodium sulfite Sodium sand Glacial Potassium acetate Add water and stabilize bath Citric fornic acid Acid soda Sodium metaphoate (tetrahydrate) Total amount 12 (m) Sodium・1,OOg 0 g 0 g g Adjust pH to 5.0 Total amount 1 50 g 5 g 2 g 5vp 0 g Total i 1ffi g g g Potash Add 15 g of alum to water for a total of 1! 3 after processing
A 5mm ril color negative film was cut to a length of 227+nrn, and the degree of curl in the length direction was measured.
” and it was at a level where there was no practical problem. However, the degree of curl is the reciprocal of the radius of a circular arc, and its unit is 1/m.

Comparative Example-1 Melt extrusion using the PET resin used in Example-1,
A transparent film support having a thickness of 100 μm was prepared by biaxial stretching. The moisture content of this film support was 0.3%.

An emulsion layer was coated on this film in the same manner as in Example 1, photographed and developed, and then the degree of curl was measured in the same manner as in Example 1 and found to be "28". Curl degree "2"
8" film had practical problems, such as being difficult to put in and take out of negative bags, easily scratched when printing on photographic paper, and difficult to transport and handle.

Example-2 100 parts by weight of dimethyl terephthalate, 80 parts by weight of ethylene glycol, 23 parts by weight of dimethyl 5-striasulfoisophthalate, and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate and 0 part by weight of antimony trioxide.
03 heavy poison moiety was added, and a transesterification reaction was carried out by a conventional method. 0.0% of phosphoric acid trimethyl ester was added to the obtained product.
05 parts were added, the temperature was gradually raised and the pressure was reduced, and finally polymerization was carried out at 280'Cb or less to obtain a copolyester.

30 parts by weight of the obtained copolyester and TVo, 68 P
ET resin A film was prepared by melt-extruding the resin and biaxially stretching the resin.

However, extrusion was adjusted so that the film thickness was 70 μm. The moisture content of the film was 22%.

Next, an emulsion layer was applied in the same manner as in Example 1, and photographed and developed. When the degree of curl was measured in the same manner as in Example 1, it was found to be "3", which is at a level that causes no practical problems.

Example-3 Dimethyl terephthalate (DMT) 36.89 parts by weight, dimethyl isophthalate (DMI) 30.44f
fi parts, 9.85 parts by weight of 5-sulfoisophthalic acid dimethyl sodium salt (S I PM), 5189 parts by weight of ethylene glycol, 0069 parts by weight of calcium acetate hydrate, and 0023 parts by weight of mankan acetate tetrahydrate in a nitrogen stream. After carrying out the transesterification reaction while distilling methanol off at 170 to 220°C, trimethyl phosphate 005
parts by weight, 0.04 parts by weight of antimony trioxide as a polycondensation catalyst and 1,4-cyclohexanedicarboxylic acid (CHDA).
) 16.36 parts by weight and 5.10 parts of polyethylene glycol (number average molecule Jil, 000) were added to 220
Esterification was carried out by distilling off approximately the theoretical amount of water at a reaction temperature of ~235°C. Thereafter, the pressure in the reaction system was further reduced and the temperature was increased to 280° C. and 0.2 mmHg, and polycondensation was carried out for 3 hours to obtain a copolymerized polyester.

35 parts by weight of the obtained copolymerized polyester, 60 parts by weight of PET resin of IV072, and 5 parts by weight of carboxyl-modified polyethylene were mixed, and the mixture was prepared in the same manner as in Example-1 to a thickness of 100 parts by weight.
A μm film was obtained. The moisture content was 26%.

Next, an emulsion layer was coated in the same manner as in Example 1, photographed and developed, and then the degree of curl was measured and found to be "2", which was at a level that caused no practical problems.

Comparative Example-2 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate and 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate and 0 part by weight of antimony trioxide.
．． 03 parts by weight was added, and transesterification was carried out by a conventional method. The resulting product contains 0 phosphoric acid trimethyl ester
．． 05 parts by weight was added, the temperature was gradually raised and the pressure was reduced, and finally polymerization was carried out at 2 80' C1 lmmHg or less to obtain copolymerized polyethylene terephthalate.

After drying the copolymerized polyethylene terephthalate in a conventional manner, it was melt-extruded at 280°C to prepare an unstretched sheet.

Next, it was sequentially stretched 3.5 times in the longitudinal direction at 90°C and 37 times in the transverse direction at 95°C, and then heat-set at 200'C for 5 seconds to obtain a biaxially stretched film with a thickness of 100μ. .

The moisture content of this film was 0.7%.

Next, the emulsion layer was coated, photographed, and developed in the same manner as in Example 1, and then the degree of curling was measured, and it was found to be "38", indicating that the curling was strong and the handleability was poor.

[Effects of the Invention] As explained in detail above, the present invention has been able to provide a photographic material that is excellent in transparency, mechanical properties, and curl elimination properties after development.

Claims (1)

[Claims] In a roll-shaped silver halide photographic material having at least one silver halide emulsion layer on a polyester resin film support, the polyester resin film is a biaxially stretched film of a mixture of polyethylene terephthalate resin and thermoplastic resin. A silver halide photographic light-sensitive material characterized in that the thermoplastic resin is a hydrophilic thermoplastic resin that is compatible with polyethylene terephthalate resin.