JPH07261326A - Rolled silver halide photographic sensitive material with curling reduced - Google Patents

Abstract

PURPOSE:To reduce the curling in use of a functional film formed by coating a polymer film with a silver halide photographic sensitive layer, etc., by coating a heat-treated polyester substrate with the silver halide photosensitive layer. CONSTITUTION:A polymer substrate to be used for a rolled silver halide photographic sensitive material is heat-treated in humidity environment within + or -20% to the working humidity when the material is packaged, and the substrate is coated with a silver halide photosensitive layer. Meanwhile, the heat-treating temp. T, the glass transition temp. Tg and the thermal fixing temp. Ts of the substrate are limited within a range of Ts>T>=Tg-20. The polyester resin as the material forming the substrate consists essentially of the repeating unit of dicarboxylic acid and diol, and a polyester consisting essentially of aromatic dibasic acid and glycol is preferably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rolled silver halide photographic light-sensitive material having reduced curl. More specifically, the present invention can be used in a silver halide photographic light-sensitive material which is rolled and stored, such as a photographic negative film, a printing light-sensitive material and a medical light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Generally, a winding set is called a core set, and when the self-supporting film is wound, this core set has a concave permanent curvature particularly on the winding core side,
It can be explained that it is the result of the creep deformation imparted to the self-supporting film when the film is wound into a roll at ambient temperature and humidity conditions and stored. That is, a core set is generated due to a minute dimensional difference between the front and back sides of the self-supporting film in which the outer side of the self-supporting film is extended and the side of the winding core is contracted.

A core set, as used herein, can also occur when wound without a take-up core.

The curled film is in a state as shown in FIG. Here, the reciprocal of the radius of curvature r (unit is in meters) from the center of curvature O is the curvature, and this curvature is called the core set curl value or curl value of the film. Also, the reciprocal of the winding radius (in units of meters) when the film is wound is called the winding curvature or core curvature.

A phenomenon in which an undesired core set is generated during storage of a thermoplastic polymer film in a roll state is that a thermoplastic polymer film having a high tendency to core set, for example, a photosensitive film having polyethylene terephthalate as a support is used. This is particularly troublesome in the case of a transparent film or the like.

Generally, silver halide photographic light-sensitive materials are classified into a sheet form and a roll form such as an X-ray film, a plate-making film and a cut film.

A typical roll film is 35
Examples of the film include a color film or a black-and-white negative film or a roll film for printing light-sensitive material, which is accommodated in a cartridge with a width of mm or less and is used for photographing by being loaded in a general camera.

Particularly for color negative films, conventionally, mainly triacetyl cellulose (hereinafter referred to as "TAC") has been used.
A support made of a film is used.

The characteristics of the TAC film as a photographic support are that it has no optical anisotropy and high transparency, and that it has excellent properties in decurling after development processing. .

The excellent property for decurling is TAC.
It is derived from the molecular structure of the film.

That is, since the TAC film has a relatively high water absorbency as a plastic film and the molecular chain can be made to flow by the water absorbency in the developing process, the core set stored as a roll film and preserved with time is formed. The curl can be eliminated by causing rearrangement in the immobilized molecular chain.

By the way, the use of photographic light-sensitive materials has been diversified in recent years, and the speed of film transport at the time of photographing, the high magnification of photographing, and the miniaturization of photographing apparatus have been remarkably advanced. For that purpose, a support film 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 film after film formation is fragile, and it is the current situation that it is difficult to use for these purposes.

On the other hand, a polyethylene terephthalate resin (hereinafter referred to as "PET") film has excellent productivity, mechanical strength, and dimensional stability, and thus TA
It has been considered as an alternative to C film.

However, when the PET film is stored in a roll form which is widely used as a photographic light-sensitive material, the core set curl remains strongly. Therefore, for example, in a printing step for forming an image on photographic printing paper after development,
Since there are problems such as scratches, defocus, and jamming at the time of transportation, while having the above excellent properties,
It was a problem because it was difficult to use as a roll film.

In particular, as a roll film for printing, a PET film has been conventionally used, but due to the above problems, the winding diameter cannot be made too small, and the expiration date of the film is limited by winding. I am.

Therefore, various means have heretofore been devised to improve the core set of the thermoplastic polymer film.

For example, a relative ambient humidity of less than 100% and a temperature in the range of about 30 ° C. to the polymer Tg (glass transition temperature) is about 0.1 until the core set curl formation of the self-supporting film is reduced by at least 15%. ~ 1500 hours, heat-humidifying the film in the form of a storage roll without shrinkage or distortion (US Pat. No. 4,141,735, JP-A-51-16358), or cutting a polymer film wound into a roll into a sheet form However, there has been proposed a method (Japanese Patent Publication No. 60-16611) in which the above sheets are stacked in an atmosphere of a temperature of 10 to 40 ° C. and a dew point temperature of 25 ° C. or less, hermetically sealed and heat treated at 28 to 65 ° C. for 1 hour or more. In both cases, the heat treatment requires a long time, and there is a possibility that the surface of the film may be damaged.

When the film is wound into a roll, a reverse curl is applied stepwise or continuously from the core to the outer periphery (Japanese Patent Laid-Open No. 4-166929), or the emulsion layer side is wound outside during production. A method has been proposed in which the material is seasoned in the form of a take-up roll and is rewound so that the emulsion layer side is inwardly wound at the time of shipping (Japanese Patent Laid-Open No. 4-273239). However, this also requires new equipment and work and increases costs. Become.

Further, during the production of the polymer film, a temperature gradient Δ of more than 10 ° C. from one surface of the film to the other surface Δ
In the presence of T, the longitudinal tension of the film during stretching is 10 N / m
A method of controlling the pressure to be less than m ² (Japanese Patent Laid-Open No. 64-70748), or winding a film produced in the presence of such a temperature gradient ΔT in a roll shape, and when the ambient relative humidity is less than 100%, the temperature is from about 30 ° C to Tg. A method of heating and controlling the humidity at a temperature within a range (Japanese Patent Laid-Open No. 54254/1990), or a method of heating a photographic light-sensitive material and then cooling it (Japanese Patent Laid-Open No. Sho 54-54254).
62-31653), etc., but none of them can sufficiently reduce the core set curl.

In addition, a laminated film of two or more layers,
A method of heat treatment at Tg or lower (Japanese Patent Laid-Open No. 6-35114) has also been proposed, but heating to 50 ° C. or higher usually results in a humidity of 15% or lower without humidification. The above invention is characterized by heating above (Tg-20 ° C) under appropriately controlled humidity, but the same effect as that of the present invention cannot be obtained.

[0021]

As described above, various proposals have been made for the method of reducing the curl of the core set of the polymer film, but no sufficient curl improving effect has been obtained.

The present invention provides a method for solving the above problems and reducing the core set curl when a functional film having a photographic photosensitive layer coated on a polymer film is used to such an extent that it does not pose a practical problem. The purpose is to provide.

[0023]

[Means for Solving the Problems] As a result of detailed search and intensive study on the means for solving the problems, it was found that the above problems can be solved.

(1) In the present invention, the polyester support used in a roll-shaped silver halide photographic light-sensitive material is ± 20% of the working humidity when the photographic light-sensitive material is put in a package.
A roll-shaped silver halide photographic light-sensitive material comprising a polyester support and a silver halide light-sensitive layer coated on the polyester support after heat treatment in a humidity environment within the range.

(2) The heat treatment temperature (T) of the polyester support should be within the range represented by the following formula with respect to the glass transition temperature (Tg) and heat setting temperature (Ts) of the polyester support. A roll-shaped silver halide photographic light-sensitive material as described in (1) above.

Ts> T ≧ Tg−20 (° C.) (3) When the polyester support is a laminated support formed by laminating two or more polyester resin films, the heat treatment temperature (T) is the same as that of the polyester support. The glass transition temperature (Tg1) of the resin having the lowest glass transition temperature and the heat setting temperature (Ts) of the polyester support are within the ranges represented by the following formulas (1) or ( 2) The rolled silver halide photographic light-sensitive material described in 2). Ts> T ≧ Tg1-20 (° C.) The present invention will be described in more detail. The polyester resin as a material for forming the polyester support as referred to in the present invention is one having a repeating unit of a dicarboxylic acid and a diol as a main component, preferably a repeating unit of an aromatic dibasic acid and a glycol. Polyester as a component can be mentioned.

In the present invention, the dibasic acid is
For example, there are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc., and as glycols, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol,
Examples include diethylene glycol and p-xylene glycol. Of these, polyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents and polyethylene-2,6-naphthalate containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents are preferable. Further, a copolymer containing 85 mol% or more of these main repeating units may be used as long as the original excellent properties of polyester are not impaired, or other polymers may be blended.

The copolyesters include, among others, copolyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents, and copolyethylene-2,6 containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents. -Naphthalate is preferred.

Aromatic dicarboxylic acids containing a metal sulfonate group as a copolymerization component in the copolyester include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoisophthalic acid and 4-sodium sulfo. Examples thereof include -2,6-naphthalenedicarboxylic acid, or an ester-forming derivative represented by the following chemical formula 1, and compounds obtained by substituting these metals with other metals (potassium, lithium, etc.).

[0030]

[Chemical 1]

The copolymerized polyester preferably contains a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid as a copolymerization component within a range that does not impair the effects of the present invention.

As the polyalkylene glycol,
Polyethylene glycol, polytetramethylene glycol, etc. are used, and the molecular weight is not particularly limited,
It is 20,000, preferably 600 to 10,000, and particularly preferably 1,000 to 5,000. Polyethylene glycol is particularly preferable as the polyalkylene glycol.

Examples of the saturated aliphatic dicarboxylic acid include adipic acid, sebacic acid and the like. Particularly, ester-forming derivatives thereof are actually used, and adipic acid, dimethyl adipate, which is an ester of sebacic acid, dimethyl sebacate and the like are used. Used. Dimethyl adipate is preferred.

The polyester used in the present invention may be copolymerized with other components, or may be blended with other polymers, as long as the effects of the present invention are not impaired.

The package in the present invention means a hermetically sealed container, and any hermetically sealed container can be used as long as it can isolate the contained silver halide photographic light-sensitive material from the outside. Here, the term “isolation” refers to a state in which the outside air and the air inside the container do not substantially flow. Therefore, any container satisfying the above conditions can be used as a package regardless of the material, shape and the like. For example, a container with a lid formed of a resin having low moisture permeability such as polyethylene, polypropylene, or polyvinyl chloride can be used. Also,
Moisture-proof film (polyethylene, polypropylene,
A rolled silver halide photographic light-sensitive material packed with a polyvinyl chloride film or the like) may be packaged in a state in which air does not substantially flow.

The humidity referred to in the present invention is a relative humidity generally expressed as a ratio of the amount of water vapor actually contained in a fixed volume of air to the amount of saturated water vapor of the air, and is the working humidity. Is the relative humidity when the rolled silver halide photographic light-sensitive material is put in the package, and the processing humidity or the processing humidity is the relative humidity at the temperature for heat treatment.

However, since the working temperature when the silver halide photographic light-sensitive material is put in the package is generally about 18 to 25 ° C., the working humidity of the present invention also depends on the relative humidity in this temperature range. Say that. If the working temperature is out of this range for some reason, the humidity is calculated by converting the air temperature to 23 ° C.

The heat setting temperature of the present invention means the temperature at the time of heat setting after the polyester is stretched.

As shown in the prior art, it is generally known that polymer films are stable in physical properties and hard to curl when heat-treated at a temperature of Tg or lower. However, these methods take time until the physical properties of the polymer film are stabilized, and are lacking in practicality.

The present inventor has conducted a detailed search and earnest study on this point, and as a result, the working humidity at the time of being wound into a roll and then being put in a package is about the same as the processing humidity at the time of heat treatment of the polyester support. It was found that the polymer film having more stable curl and having stable physical properties can be obtained by the use of the above method.

Regarding the treatment temperature, if the temperature is below (Tg-20 ° C.) of the polyester support, the heat treatment takes too much time and is not practical, and the heat treatment exceeding the heat setting temperature causes physical properties such as orientation and strength of the support. Not suitable because it deteriorates.
Therefore, the heat treatment according to the present application is performed at (Tg-20 ° C) or more and below the heat setting temperature.

Since the working humidity is generally in the range of 20 to 80%, it is desirable that the humidity of the heat treatment is also in this range, and more desirably 20 to 60%.

When the polyester support is a laminated support formed by laminating two or more polyester resin films, the heat treatment temperature (T) is the glass transition temperature (Tg1) of the resin having the lowest glass transition temperature of the polyester support. And the heat setting temperature (Ts) is preferably within the range shown by the following formula.

Ts> T ≧ Tg1−20 (° C.) More preferably, Ts> T ≧ Tg2−20 (° C.) with respect to the glass transition temperature (Tg2) of the resin having the highest glass transition temperature.

The effects of the present invention will be described in the following examples.

[0046]

The present invention will be described in detail below with reference to Examples. However, the aspects of the present invention are not limited to the following examples.

Example 1 1. Preparation of Supports Support A A 100 parts by weight of terephthalic acid and 64 parts by weight of ethylene glycol were added with 0.1 part by weight of calcium acetate hydrate, and an esterification reaction was carried out by a conventional method. 28 parts by weight of ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight) (5 mol% / total acid component), polyethylene glycol (number average molecular weight 3000) 8.1 parts by weight (7% by weight / polymer), antimony trioxide 0.05 parts by weight, phosphoric acid trimethyl ester 0.13
Parts by weight were added. Then gradually raise the temperature and reduce the pressure to 280
Polymerization was performed at 0.5 ° C. and 0.5 mmHg to obtain a copolyester (herein referred to as MPET) having an intrinsic viscosity of 0.55.

The copolyester was vacuum dried at 150 ° C., melt-extruded at 285 ° C. using an extruder, and rapidly solidified while being brought into close contact with a cooling drum by an electrostatic contact method to obtain an unstretched film. Then, it was stretched 3.5 times in the vertical direction at 85 ° C., further stretched 3.5 times in the horizontal direction at 95 ° C., and then heat-set at 210 ° C. to obtain a biaxially stretched film having a thickness of 90 μm.

The glass transition temperature (Tg) of this support is 61.
It was ℃. The Tg mentioned here is a sample of 10 mg,
The glass transition temperature is set as the average value of the temperature at which the baseline starts to be biased and the temperature at which it returns to a new baseline, set in an inspection scanning calorimeter and increasing the temperature at a rate of 20 ° C / min under a nitrogen stream. And Support B After commercially available polyethylene terephthalate (generally abbreviated as PET) having an intrinsic viscosity of 0.65 is vacuum dried at 150 ° C.,
A 90 μm biaxially stretched film was obtained in the same manner as the above method. The glass transition temperature (Tg) of this support was 77 ° C.

Support C To 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 56 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added, and an esterification reaction was carried out by a conventional method. . Thereafter, the obtained product was added with 0.04 part by weight of antimony trioxide and trimethyl phosphate.
0.1 part by weight was added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was performed at 285 ° C. and 0.5 mmHg to obtain polyethylene naphthalate (generally abbreviated as PEN).

Using the obtained polyester, it was melt extruded at 300 ° C. and rapidly cooled and solidified by adhering to a cooling drum by an electrostatic adhering method to obtain an unstretched film. Then, it was stretched 3.1 times in the vertical direction at 135 ° C., further stretched 3.4 times in the horizontal direction at 130 ° C., and then heat-set at 245 ° C. to obtain a biaxially stretched film having a thickness of 90 μm. The glass transition temperature (Tg) of this support is 120.
It was ℃.

Support D Copolymerized polyester (MPET) and polyethylene terephthalate (PET) were vacuum dried at 150 ° C., respectively, and then 3
It is melt extruded at 285 ° C. using a stand extrusion unit, is joined in layers in a T-die so that PET is in the center and copolyester is on the outside, and is rapidly cooled and solidified by adhering to a cooling drum by an electrostatic adhering method. A laminated unstretched film was obtained. At this time, the extrusion amount of each material was adjusted so that the thickness of each layer was 1: 1: 1. Then, it was stretched 3.5 times in the vertical direction at 85 ° C., further stretched 3.5 times in the horizontal direction at 95 ° C., and then heat-set at 210 ° C. to obtain a biaxially stretched film having a thickness of 90 μm.

2. Heat Treatment of Support The two sides of the support obtained by the above method were subjected to an undercoating process described below, and then a back layer was applied and dried to form a two-layer back layer. Then, heat treatment was performed under the conditions shown in Tables 1 to 8.

The heat treatment was performed by winding the support on a winding core having a diameter of 300 mm, with the back surface inside, and winding it in a roll in a large constant temperature and humidity chamber in which the temperature and humidity can be controlled. Also, in order to ensure that the humidity of the air between the layers of the support wound in a roll is the same as in the constant temperature and humidity chamber, the support is installed in the constant temperature and constant temperature chamber during the heat treatment by an automatic rewinding device with the same diameter of 300 mm. I rewound the core with the back side inside.

At the end of the heat treatment, the humidity is first lowered to prevent condensation of the film, and then the rewinding device
It was wound on the original core.

However, for the heat treatment at a temperature of 100 ° C. or higher, the sheet-shaped support is put in a pressure-resistant heat treatment apparatus,
This was done by venting high temperature, high pressure steam into.

On the surface opposite to the back layer of the support obtained by the above method, each layer having the composition described below was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material.

3. Preparation of photosensitive material Both sides of the support were subjected to a corona discharge treatment of 8 W / (m ² · min), and one side of the film was coated with the undercoating coating solution B-3 shown below so as to have a dry film thickness of 0.8 μm. To form an undercoat layer B-3,
An undercoat layer B-4 was formed by coating the following undercoat coating solution B-4 on the other surface of the support so that the dry film thickness was 0.8 μm.

<Undercoating Coating Liquid B-3> A copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content: 30%). %) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml <Undercoating solution B-4> 40% by weight butyl acrylate, 20% by weight styrene and glycidyl Acrylate 40 wt% copolymer latex liquid (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml Further undercoat layer B- 8 and W / (m
² min) of corona discharge is applied, and the following coating solution B-5 is applied on the undercoat layer B-3 to a dry film thickness of 0.1 μm to form an undercoat layer B-5. On the undercoat layer B-4, the following coating liquid B-6 was applied so as to have a dry film thickness of 0.8 μm to form an undercoat layer B-6 having an antistatic function.

<Coating Liquid B-5> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle diameter: 3 μm) 0.1 g Finish with water 1000 ml <Coating liquid B-6> Water-soluble conductive polymer (UL-4) 60 g Latex liquid containing compound (UL-5) as a component (solid content 20%) 80 g Ammonium sulfate 0.5 g Curing agent (UL-6) 12 g Polyethylene Glycol (weight average molecular weight 600) 6 g Finished with water 1000 ml The structures of the compounds (UL-1 to 6) used are summarized below.

Then, 25 W / (m ² · mi) was formed on the undercoat layer B-5.
n) Corona discharge was applied, and 8 W / on the undercoat layer B-6.
A corona discharge of (m ² · min) was applied. Further, the following emulsion layers and the like were sequentially formed on the undercoat layer B-5, and the following back layer was sequentially formed on the undercoat layer B-6 to prepare a multilayer color photographic light-sensitive material.

In the following <Back layer> and <Emulsion layer>, the quantity is shown per m ² .

<Back Layer> First Layer; Gelatin 4.5 g Sodium-di-(-2-ethylhexyl) -sulfosuccinate 1.0 g Sodium tripolyphosphate 76 mg Citric acid 16 mg Carboxyalkyl dextran sulfate 49 mg Vinyl sulfone type hardener 23 mg Second layer (outermost layer); gelatin 1.5 g Polymer beads (average particle size: 3 μm, polymethylmethacrylate) 24 mg Sodium-di-(-2-ethylhexyl) -sulfosuccinate 15 mg Carboxyalkyl dextran sulfate 12 mg Vinyl sulfone type Hardener 30mg Fluorosurfactant (SB-2 and SB-3 molar ratio 1: 1) 45mg Compound SB-1 230mg <Emulsion layer> 1st layer; Antihalation layer (HC) Black colloidal silver 0.15g UV absorption Agent (UV-1) 0.20g Compound (CC-1) 0.02g High boiling point solvent (Oil-1) 0.20g High Point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Average grain size 0.3 μm, average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ (mol / Silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C- 1) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitive dye (S-1) 1.7 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-2) 1.6 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer: Intermediate layer (IL-2) 0.8 g of gelatin Sixth layer: Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.6 g iodine Silver bromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / mole of silver) magenta coupler (M-1) 0.17 g magenta coupler (M-2) 0.43 g colored magenta coupler (CM-1) 0.10 g D R compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content) Amount 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ⁻⁴ (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D- 3) 0.004g High boiling point solvent (Oil-2) 0.35g Gelatin 1.0g 8th layer; Yellow filter layer (YC) Yellow colloidal silver 0.1g Additive (HS-1) 0.07g Additive (HS-2) 0.07g Additive (SC-1) 0.12g High boiling point solvent (Oil-2) 0.15g Gelatin 1.0g 9th layer; low sensitivity blue sensitivity Agent layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.25 g increase Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D -2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm, average iodine content 8.5 mol%) ) 0.5 g Sensitizing dye (S-10) 3 x 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 x 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 2.0 g 11th layer; 1st protective layer (PRO-1) ) Silver iodobromide emulsion (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2 ) 0.1g High boiling point solvent (Oil-1) 0.07g High boiling point solvent (Oil-3) 0.07g Gelatin 0.8g 12th layer; 2nd protective layer (PRO-2) Compound (Compound A) 0.04g Compound (Compound B) ) 0.004g Polymethylmethacrylate (average particle size: 3 μm) 0.02g Methylmethacrylate: ethylmethacrylate: methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size: 3 μm) 0.13g Gelatin 0.7 g The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

—Preparation of silver iodobromide emulsion— Monodisperse silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content 2
mol%) was used as a seed crystal to prepare a silver iodobromide emulsion by the double jet method.

A solution <G-1> having the following composition was treated at a temperature of 70 ° C. and pA.
While maintaining g7.8 and pH 7.0, a seed emulsion corresponding to 0.34 mol was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, a solution <H-1> having the following composition and a solution <S- having the following composition:
1> and 1> were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes while maintaining the flow rate ratio of 1: 1.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, <H-2> and <S> while maintaining pAg10.1 and pH6.0.
-2> and was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse them, and the pH is adjusted to 40 ° C.
And pAg were prepared at 5.8 and 8.06, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ocein gelatin 100.0 g 10% by weight solution of the following compound-I in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml * Compound-I: polypropyleneoxy Polyethyleneoxy-di-succinate-Natrium <H-1> Oscein gelatin 82.4g Potassium bromide 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% ammonia solution equivalent Finish with water 1030.5ml <H-2> Ocein gelatin 302.1g Potassium bromide 770.0g Potassium iodide 33.2g Finish with water 3776.8ml <S-2> Silver nitrate 1133.0g 28% ammonia solution equivalent Finish with water 3776.8ml Other than 10th layer For the silver iodobromide emulsion used in the emulsion layer, the average grain size of seed crystal, temperature, pAg, p
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing H, flow rate, addition time, and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

The above-mentioned light-sensitive material further comprises compounds Su-1, Su-2, a viscosity adjusting agent, a film hardener H-1, and H-.
2, stabilizer ST-1, antifoggant AF-1, AF-2
(Weight average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1
(9.4 mg / m ² ) is contained.

The structure of each compound used for forming the silver halide photographic light-sensitive material is shown below.

[0074]

[Chemical 2]

[0075]

[Chemical 3]

[0076]

[Chemical 4]

[0077]

[Chemical 5]

[0078]

[Chemical 6]

[0079]

[Chemical 7]

[0080]

[Chemical 8]

[0081]

[Chemical 9]

[0082]

[Chemical 10]

[0083]

[Chemical 11]

4. Evaluation Method The light-sensitive materials prepared as described above were evaluated by the evaluation methods described below, and the results are shown in Tables 1-8.

<Core set curl value> Width 35 mm, length 150 m
After conditioning the photosensitive material film of m under the following environmental conditions A to B for 24 hours, wind it on a spool of photographic negative film with a diameter of 10.8 mm in the same environment, put it on a resin tube for photographic negative film and cover it. After sealing, they were put together in a humidity-uncontrolled room at 23 ° C for 150 days, the lid was opened, and the core set curl value was measured. However, the humidity at the time of measuring the core set curl value was 60%.

Environment A: 23 ° C 20% RH Environment B: 23 ° C 60% RH

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

[Table 4]

[0091]

[Table 5]

[0092]

[Table 6]

[0093]

[Table 7]

[0094]

[Table 8]

As can be seen from these results, if the heat treatment temperature (T) of the support is T ≧ Tg−20 ° C. and the processing humidity is within ± 20% of the working humidity, the winding can be performed even if the processing time is short. A light-sensitive material film that is hard to stick can be obtained.

[0096]

Industrial Applicability According to the present invention, a silver halide photographic light-sensitive material in which a functional film having a polymer film coated with a silver halide photographic light-sensitive layer or the like is less likely to be curled when used is obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing a state of a curled film.

[Explanation of symbols] r radius of curvature o center of curvature

Claims (3)

[Claims] 1. A polyester support used in a rolled silver halide photographic light-sensitive material is heat-treated in a humidity environment within ± 20% of the working humidity when the photographic light-sensitive material is put in a package, A roll-shaped silver halide photographic light-sensitive material characterized in that a silver halide light-sensitive layer is coated on the polyester support. 2. The heat treatment temperature (T) of the polyester support is the glass transition temperature (T) of the polyester support.
The rolled silver halide photographic light-sensitive material according to claim 1, characterized in that the content is within the range represented by the following formula with respect to g) and the heat setting temperature (Ts). Ts ＞ T ≧ Tg-20 (℃) 3. When the polyester support is a laminated support formed by laminating two or more polyester resin films, the heat treatment temperature (T) is the glass transition temperature of the resin having the lowest glass transition temperature of the polyester support. The roll-shaped silver halide photographic light-sensitive material according to claim 1 or 2, wherein (Tg1) and the heat setting temperature (Ts) of the polyester support are within the ranges represented by the following formulas. . Ts> T ≧ Tg1-20 (℃)