JPH07261327A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material excellent in cuttability when the product is cut and formed, maintaining strength, being hardly curled and excellent in preventing curling in the width-direction after processing. CONSTITUTION:At least one silver halide photosensitive layer is provided on a polyester substrate to constitute the silver halide photographic sensitive material. In the material, the elastic modulus of the polyester film is controlled to be >=600kg/mm<2>, and the difference in elastic modulus from the silver halide photosensitive material (elastic modulus of polyester film minus elastic modulus of silver halide photographic sensitive material) is controlled to be 80-200kg/mm<2>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film used in the form of a roll, and more specifically, it has excellent cuttability when cutting and molding a product, maintains strength and is hard to curl. The present invention relates to a silver halide photographic light-sensitive material which does not cause any problems in a processor before development processing and a development processing machine and is excellent in curl of the width after processing.

[0002]

2. Description of the Related Art Photosensitive materials for photography are desired to be further miniaturized in consideration of convenience and portability, but in pursuit of miniaturization, the storage space for built-in photographic film is made compact. Is essential. Usually, a roll of film wound on a spool is built in as a photographic film, so in order to make the space compact and to secure a certain number of shots (for example, 36 shots), It is necessary to reduce the thickness of the film itself. In particular, the thickness of triacetyl cellulose (TAC) film, which is the support for photographic film, is currently 12
0 to 125 μm, thickness of the photosensitive layer (25 to 30 μm)
The thickness of the support is considered to be the most effective means for reducing the thickness of the entire photographic film, since it is considerably thicker than the thickness of the photographic film. by the way,
Since the mechanical strength of TAC film is originally weak, if it is made thinner than the current one, the strength will decrease. If the film thickness of the support is 100 μm or less, when the photosensitive material using it is developed in a cine type developing machine, Ear perforation occurred at the perforations at both ends of the film, which was not practical.

On the other hand, polyethylene terephthalate (PET) has been conventionally known as a support, and has been used for an X-ray film and a plate-making film. Due to its excellent strength, application to color negative films is also possible. However, although the polyethylene terephthalate support has excellent strength, it has a low glass transition temperature of about 70 ° C, so it can be stored for a long time by winding the film in a high temperature atmosphere at about 60 ° C, which is equivalent to the storage stability in the summer. The winding curl attached when placed is badly inferior in handleability in the processor before the development processing, and the curl is hardly removed even after the development processing. There was no practical use.

Further, since it does not have a proper anti-curl as a support, in a light-sensitive material using a thin PET film, the gelatin used in the light-sensitive layer shrinks after the development processing and the width direction is reduced. In particular, the photosensitive layer side had a concave curl, which floated in the printing process, causing problems in conveyance and causing blurring of the printing, which made it unusable for photography.

Japanese Patent Laid-Open No. 3-54551 discloses a light-sensitive material using a polyester film having an improved flexural modulus in order to improve the handleability of curl in the width direction. The curl in the width direction was not sufficiently improved, and the curling was likely to occur, which was not practical.

On the other hand, in order to improve winding curl, Japanese Patent Laid-Open No. 6-
In Japanese Patent No. 35115, a heat treatment is performed at a temperature below a glass transition temperature (hereinafter abbreviated as Tg) (hereinafter referred to as an annealing treatment,
There is known a light-sensitive material using polyethylene naphthalate, which is hard to be curled by AN).

However, since the polyethylene naphthalate film (hereinafter abbreviated as PEN) originally has too high strength, after coating a photosensitive layer on this film, it is cut into the shape of the final product and cut when molding. The blade wears badly, and the photosensitive layer contains gelatin as a component and its strength is weaker than that of PEN. Therefore, the direction of the incision at the time of cutting and the propagation direction of cracks in the incision are deviated. Since it is easy to cut into a shape, a whisker-like defect occurs at the cut edge, and the impact force at the time of cutting is easily transmitted to the photosensitive layer, causing the problem of peeling of the photosensitive layer from the polyester film and cracking of the photosensitive layer. The cuttability was remarkably inferior and it was not practical. Also, because of the use of a polyester film having a high elastic modulus, pressure fog of the light-sensitive material was significantly large in the process of cutting and the like, and there was a problem in photographic performance, so that it was not practical. In addition, the curl remarkably curls in the width direction, which causes blurring of the print, which is a practical problem.

[0008]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide excellent cuttability when cutting and molding a product,
Another object of the present invention is to provide a silver halide photographic light-sensitive material which retains strength, is hard to curl, and is excellent in curl of the width after processing.

[0009]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide light-sensitive layer on a polyester film support, and the elastic modulus of the polyester film. Is 600 kg / m
Halogen, characterized in that the difference from the elastic modulus of the silver halide photographic light-sensitive material (elastic modulus of polyester film-elastic modulus of silver halide photographic light-sensitive material) is 80 to 200 kg / mm ² at m ² or more. Achieved by silver halide photographic light-sensitive material.

It is preferable that the polyester film contains naphthalenedicarboxylic acid and ethylene glycol as components. Further, among the dicarboxylic acid components of the polyester film, the naphthalenedicarboxylic acid component is
It is more preferable that the content of 70 mol% or more and the glycol component is mainly ethylene glycol.

Further, when the polyester film is heat-set at a temperature not higher than the glass transition temperature after being heat-set, or when the thickness of the polyester film is 50 to 95 μm, more remarkable effects are exhibited.

The present invention will be described in detail below. From the viewpoint of cuttability, the elastic modulus of the polyester film of the present invention is preferably 650 kg / mm ² or more, particularly preferably 700 kg / mm ² or more. The difference from the elastic modulus of the photographic light-sensitive material is preferably 100 to 1
70 kg / mm ^2, particularly preferably from 120~150kg / mm ^2.

The thickness of the polyester film used for the light-sensitive material is preferably 70 to 90 μm in view of the cuttability of the processing equipment and the transportability.

As the dicarboxylic acid component of the polyester film, the naphthalene dicarboxylic acid component is preferably 50 mol% or more in order to reduce curling, and particularly preferably 70 mol% or more for increasing the AN effect. . The glycol component is preferably 70 mol% or more of ethylene glycol, and particularly preferably 90 mol% or more from the viewpoint of wrapping and mechanical strength.

Examples of naphthalenedicarboxylic acid include
1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2,3-
Examples thereof include naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Of these, 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable. Glycol has ethylene glycol as a main component, but other components may be copolymerized or / and blended with other polyesters as long as the effects of the present invention are not impaired.

For example, as the other dicarboxylic acid component,
Aromatic dibasic acids are preferable, and there are terephthalic acid, isophthalic acid, etc., and other glycol components include propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, p-xylylene glycol, etc. However, butanediol is particularly preferable as the copolymerization component.

Further, unless the effects of the present invention are impaired,
To further improve the recoverability, an aromatic dicarboxylic acid having a metal sulfonate group may be added as a copolymerization component of the dicarboxylic acid component in the copolyester, for example, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid. Acid, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoisophthalic acid,
And their ester-forming derivatives, and these sodium with other metals (potassium, lithium, etc.)
And / or a compound having a repeating structure of an alkyleneoxy group, such as polyalkylene glycol or polyalkyleneoxydicarboxylic acid and /
Alternatively, it may contain a compound of a saturated aliphatic dicarboxylic acid and / or a derivative thereof, such as a derivative thereof.

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

The intrinsic viscosity of the preferred polyester is
It is 0.45 to 0.80, and particularly preferably 0.55 to 0.70.

The film of the present invention may be composed of a single layer of polyester, and when laminated, any number of layers such as two layers and three layers may be laminated. Generally, two layers or three layers are preferable in terms of complexity. The polyester layer of the present invention has a thickness of 2 μm or more, and the undercoat layer and the like are not included therein.

The AN treatment to be carried out after heat fixing of the film is not particularly limited, but the method described in JP-A-51-16358 can be employed, but the heat treatment temperature is preferably Tg-60 to Tg in terms of flatness. -5 (° C), particularly preferably T
It is g-40 to Tg-10 (° C.), and the treatment time is preferably 1 to 1500 hours, but when the AN treatment effect and productivity are combined, it is 10 to 1000 hours.

The polyester film of the present invention can be obtained by blending a filler in the film of the present invention to control the elastic modulus of the polyester film and the difference in elastic modulus from the photosensitive layer.

<Single-Layer Polyester Film> When it comprises a single-layer polyester layer, the dicarboxylic acid component of the polyester film of the present invention has a naphthalene dicarboxylic acid component content of 70 mol% or more because of the curl, and as a glycol component. 70 mol% or more of ethylene glycol is preferable.

For ease of handling, for example, in forming a film, a longitudinal temperature is provided by providing a temperature difference between the front and back of the film during longitudinal stretching, or a temperature difference is provided between the front and back during heat setting. It is preferable to impart anti-curl by a method such as heat fixing.

Further, it is preferable to impart an anti-curl by infiltrating an organic solvent or the like into one surface of the film of the copolyester single layer and subjecting it to heat treatment for solvent treatment.

<Structure of Laminated Polyester Film> When the film of the present invention is laminated, the thickness of each layer can be appropriately determined depending on the polyester and the copolyester to be used. A polymerized polyester layer and a polyester layer as the outer layer are preferable.

When the film of the present invention is laminated, the layer structure, film thickness, amount of copolymerization components and the like are appropriately adjusted, and the layer structure is asymmetrical above and below the plane which divides the polyester film of the present invention into two parts. It is preferable to impart the desired anti-curl by The asymmetry referred to here is not particularly limited, for example, the order of forming the polyester layer or the copolyester layer on the top and bottom, the thickness of the layer, the main component amount of the polyester species above and below the surface to divide in half, or different,
It also includes that the copolymerization component or the amount of the copolymerization component is different, and further that the intrinsic viscosity is different.

Further, the film forming method, the solvent treatment and the like as described for the single layer film may be further used for the laminated support.

Further, in the case of laminating, in order to improve the adhesiveness between the polyester layer and the copolyester layer, the adjoining polyester layer and / or the copolyester layer are similar in composition, or the polyester layer and the copolyester layer are similar to each other. It is preferably a blend of copolyester layers.

Both the polyester and the copolyester used in the present invention are phosphoric acid, phosphorous acid and their esters and inorganic particles (silica, kaolin, calcium carbonate,
Calcium phosphate, titanium dioxide, etc.) may be contained, or the polymer may be blended with inorganic particles after polymerization. Further, a pigment, an ultraviolet absorber, an antioxidant, etc. may be added appropriately at any stage of the polymerization and after the polymerization. Examples of preferable antioxidants include hindered phenol-based ones.

To obtain the copolyester resin which constitutes the support of the present invention, melt polymerization may be carried out after the above-mentioned copolymerization component is added after transesterification, or the copolymerization component may be added before transesterification. Then, melt polymerization may be performed, or a known synthesis method such as solid phase polymerization of a polymer obtained by melt polymerization may be used. Also,
The process conditions such as the temperature during the polymerization can be appropriately adjusted as long as the effects of the present invention are not impaired. The polyester film used in the present invention may contain various additives. For example, a dye may be added to the polyester film for the purpose of preventing a light piping phenomenon (fogging) that occurs when light is incident on an edge of a film coated with a photographic emulsion layer.
The type of film dye is not particularly limited, but those having excellent heat resistance are preferable in the polyester film forming process, and examples thereof include anthraquinone chemical dyes. As for the color tone of the film, gray dyeing is preferable as seen in general light-sensitive materials, and one type or two types are preferable.
You may mix and use a dye of a kind or more.

Further, since the polyester film using naphthalenedicarboxylic acid easily absorbs light having a short wavelength and emits fluorescence, it is preferable to contain an ultraviolet absorber or a known fluorescence quencher in the polyester.

The method for producing the polyester film having a single layer according to the present invention will be described. A method for obtaining an unstretched sheet may be a conventionally known method, for example, a method in which the obtained resin is sufficiently dried, melt-extruded into a sheet through a filter and a die, cast on a rotating cooling drum, and solidified by cooling. To be

As a method for biaxially stretching the finished sheet, the following processes (A) to (D) can be adopted in the biaxial direction in the temperature range from the glass transition temperature (Tg) to Tg + 100 ° C.

(A) A method in which an unstretched sheet is first stretched in the machine direction and then stretched in the transverse direction.

(B) A method in which an unstretched sheet is first stretched in the transverse direction and then in the longitudinal direction.

(C) A method in which an unstretched sheet is stretched in the longitudinal direction in one or multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction.

(D) A method in which an unstretched sheet is stretched in the longitudinal direction in one stage or in multiple stages, then stretched in the transverse direction and again in the longitudinal direction.

The above stretching is preferably performed in an area ratio of 4 in order to obtain the elastic modulus of the polyester film necessary for the present invention.
-16 times, particularly preferably 9 to 14 times. The heat setting can be performed in the temperature range of 150 to 240 ° C. If the stretching ratio is raised too much, the effect of improving the difference in elastic modulus of the present invention, and hence the cutting property, cannot be obtained.

Further, as a method for producing the laminated film of the present invention, for example, polyester and copolyester are melt-extruded from separate extruders, and then, in a laminar flow state in a conduit of the molten polymer or in an extrusion die. Extruded by joining in multiple layers, cooled and solidified on a cooling drum to obtain an unstretched film, then biaxially stretched and heat-fixed, or melt extruded from a extruder or a polyester or copolymerized polyester simple substance, and a laminated film, and cooled. An unstretched film that has been cooled and solidified on a drum or the surface of a uniaxially oriented film that is uniaxially stretched on the unstretched film, if necessary, an anchoring agent,
There is an extrusion laminating method in which the polyester or copolymerized polyester alone and the laminated film are extrusion laminated onto the coated adhesive and then heat-fixed after completing biaxial stretching, but the process is simple. Therefore, the coextrusion method is preferable.

In this case, the stretching conditions of the film are not particularly limited, but generally, the Tg of the polyester layer or the copolyester layer having the higher glass transition temperature (Tg) is used.
It is possible to adopt the methods A to D in the same manner as the above-mentioned method for stretching the single-layer polyester layer in the biaxial direction in the temperature range of from Tg to 100 ° C. The stretching ratio is preferably in the range of 4 to 16 times in area ratio. The heat setting can be performed in the temperature range of 150 to 240 ° C.

The film of the present invention has at least one silver halide emulsion layer on at least one side thereof or on the convex side of the support under an atmosphere of 23 ° C. and 55% RH. It constitutes a photographic light-sensitive material. This silver halide emulsion layer can be coated directly on the support or can be coated through another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion,
Further, a hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, you may provide the intermediate layer which consists of hydrophilic colloids as needed. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer or a backing layer may be provided between the silver halide emulsion layer and the protective layer.
Further, a magnetic recording layer or the like may be provided on the side opposite to the silver halide emulsion layer.

The polyester film of the present invention has improved adhesiveness and improved wetting characteristics of the coating liquid.
If necessary, various surface treatments such as corona discharge treatment, chemical treatment, flame treatment and the like can be performed in advance. Of these, corona discharge treatment is most preferably used. The polyester support of the present invention preferably has an undercoat layer in order to increase the adhesive force with a photographic layer such as a photosensitive layer coated thereon. Examples of the subbing layer include a subbing layer using a polymer latex made of a styrene-butadiene copolymer or a vinylidene chloride copolymer, and a subbing layer using a hydrophilic binder such as gelatin. The undercoat layer preferably used in the present invention is a subbing layer using a hydrophilic binder. Examples of the hydrophilic binder used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers and maleic anhydride copolymers, and of these, gelatin is particularly preferable. Examples of the compound that swells the polyester film used in the present invention include resorcin and / or a derivative thereof, a cresol compound, a chloro-substituted product of phenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid and the like. Among these, resorcin and p-chlorophenol are preferable.

Various gelatin hardeners can be used in the undercoat layer of the present invention. Examples of gelatin hardening agents include chromium salts, aldehydes, isocyanates, and active halogen compounds. The undercoat layer of the present invention may contain inorganic fine particles such as silicon dioxide or titanium dioxide, or polymethylmethacrylate copolymer fine particles as a matting agent. The undercoat layer according to the present invention can be coated by a known coating method.

The silver halide used in the silver halide photographic light-sensitive material of the present invention may be of any composition. Examples are silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide and silver iodobromide. A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like can be added to the silver halide emulsion used in the present invention.

The difference between the elastic modulus of the polyester film of the present invention and the elastic modulus of the photosensitive material controls the elastic modulus of the polyester film described above, and the elastic modulus of the photosensitive layer and / or the back layer on the other side, and the sticking amount ( It can be achieved by appropriately adjusting the film thickness). In a preferred embodiment, the elastic modulus of the photosensitive layer is 450 kg / mm ² or more and the elastic modulus of the back layer is 55.
0 kg / mm ² or more.

In order to increase the elastic modulus of the photosensitive layer, the amount of hardener is increased, the content of silver halide per unit area is increased, and the amount of the high boiling point solvent in the coupler dispersion when coating the photosensitive layer is decreased. The difference in elastic modulus between the polyester film of the present invention and the elastic modulus of the light-sensitive material can be achieved by appropriately adjusting these within a range that does not impair the photographic performance of the present invention, particularly the effect of preventing pressure fog. Preferably, it is preferable to adjust the amount of solvent in the intermediate layer and protective layer that do not adversely affect photographic performance, or to adjust the amount of fine particles such as silica so as not to reduce the sensitivity of photographic performance of the present invention.

In view of cuttability, it is preferable to adjust the elastic modulus difference between the polyester film of the present invention and the photosensitive material by increasing the elastic modulus of the layer (back layer) coated on the side opposite to the photosensitive layer as much as possible. For example, the elastic modulus can be increased by increasing the amount of the antistatic agent added to the back layer, the amount of latex particles and / or the glass transition temperature. It is preferable to use fine metal particles as an antistatic agent, particularly preferable is a crystalline metal oxide, and it is more preferable to adjust the addition amount of fine particles of crystalline tin oxide.

The present invention provides the above-mentioned naphthalenedicarboxylic acid,
As long as the effect of improving the cutting property of the light-sensitive material is not impaired without lowering the mechanical strength when thinning the polyester film containing ethylene glycol as the main component,
The effects of the present invention can be achieved by appropriately adjusting the film thickness and / or elastic modulus of the above polyester film, the film thickness of the photosensitive material and / or the amount of silver halide, the amount of fine particles added to the back layer, and the like. You can do it.

To develop the silver halide photographic light-sensitive material of the present invention, for example, TH James, The Theory of the Photographic Process 4th Edition (The.
Theory of the Photographic Process ， Fourth Editio
n) Pages 291 to 334 and the Journal of the America Chemical Society.
n Chemical Society) Vol. 73, page 3100 (1951).

[0051]

The present invention will be described in more detail with reference to the following examples.

Example 1 and Comparative Example 1 (Production of Polyester) To 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 56 parts by weight of ethylene glycol, 0.1 part by weight of hydrate of calcium acetate as an ester exchange catalyst was added, The transesterification reaction was carried out by a conventional method. Then, 0.04 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate were added to the obtained product. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 285 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.5 (hereinafter sometimes abbreviated as PEN). The glass transition temperature was 120 ° C.

(Preparation of Support) The obtained polyester was vacuum dried at 150 ° C., melt-extruded from a T die at 300 ° C. using an extruder, and rapidly cooled and solidified in a cooling drum to give an unstretched film. Obtained. At this time, the film thickness of the unstretched film was changed by changing the speed. Then, after preheating to 125 ° C, longitudinal stretching (3.1 times) was performed, and then lateral stretching at a temperature of 130 ° C (3.4 times).
Then, heat-fix at 240 ℃, and the film thickness 4 shown in Table 2
A biaxially stretched film of 0 to 110 μm was obtained. The glass transition temperature of the obtained polyester film was 120 ° C., which was the same as the glass transition temperature of polyester.

(Hereinafter, it may be referred to as a support) <Tin oxide dispersion> After adjusting a pH of a mixed solution of 400 g of powder of antimony-doped tin oxide SN-100P manufactured by Ishihara Sangyo Co., Ltd. and 600 g of water to pH 7.0. A dispersion liquid A was prepared by dispersing with a stirrer and a sand mill.

<Preparation of Photosensitive Material> The support thus prepared was subjected to an undercoating process as described below to form a back layer and an emulsion layer.

Both sides of the support were subjected to a corona discharge treatment of 8 W / (m ² · min), and one side of the support was coated with the undercoat coating solution A.
-1 is applied to a dry film thickness of 0.8 μm to form an undercoat layer A-
1 is formed on the undercoat layer A-1 and 8 W / (m ² · mi
n) is subjected to corona discharge, and the following subbing coating solution A-2 is applied onto the subbing layer A-1 to give a dry film thickness of 0.1 μm.
Formed 2.

On the other surface of the support, the following coating liquid B-1 was applied.
Is applied so that the dry film thickness is 0.6 μm, and the conductive layer B-
1 was formed.

<Subbing Coating Solution A-1> Copolymer latex solution 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 (Tg 30 ° C. ) (Solid content 30%) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml <Undercoating liquid A-2> Gelatin 10g Compound (UL-1) ) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size 3 μm) 0.1 g Finish with water 1000 ml In the following formulation, LX-1 represents a latex.

<Coating Liquid B-1> Aqueous dispersion of LX-1 (solid content 30% by weight) 270 g Compound (UL-1) 0.6 g Dispersion A 560 g Finish with water 1000 ml <LX-1> 5-Sulfoisophthalate Acid 5 mol% Isophthalic acid 15 mol% Terephthalic acid 30 mol% Ethylene glycol 25 mol% Diethylene glycol 25 mol% (Average particle size 60 nm)

[0060]

[Chemical 1]

Further, 8 W / on the conductive layer B-1.
Corona discharge of (m ² · min) was applied and the following coating liquid MC-1
Was applied to give a dry film thickness of 1 μm.

<MC-1> Nitrocellulose 35 parts by weight Polyurethane resin 35 parts by weight Lauric acid 1 part by weight Oleic acid 1 part by weight Butyl stearate 1 part by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight Co Deposition γ -Fe ₂ O ₃ (long axis 0.2 μm, short axis 0.02 μm, Hc = 650 Oersted) 5 parts by weight Furthermore, on the coating layer of MC-1, the following coating solution OC-1
Was applied at 10 ml / m ² .

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml However, when the polyester film has anti-curl, a back layer was applied on the concave surface side at 23 ° C. and 55% RH atmosphere.

(Annealing Treatment) Each of the polyester films provided with the back layer as described above was wound on a paper core having a diameter of 16 cm and an inner diameter of 14 cm while the back layer was wound inside.
In the wound state, hot air was blown at 80 ° C. for 24 hours, and an annealing treatment was performed by blowing from the outside of the wind at a wind speed of about 0.5 m / min.

Further, on the undercoat layer A-2, 25 W / (m ² ·
min) corona discharge is performed to sequentially form the following photographic constituent layers to prepare a multilayer color photographic light-sensitive material, and the evaluation results are shown in Table 2. (Sample Nos. 1 to 6) For silver halide and colloidal silver, the coating amount in the photographic constituent layers shown below is the amount expressed in units of g / m ² in terms of metallic silver, and the coupler. The amounts of the additives are shown in units of g / m ² , and the sensitizing dyes are shown in the number of moles per mole of silver halide in the same layer.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD- 2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (Di-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C-1) ) 0.33 Colored Nkapura (CC-1) 0.013 DIR compound (Di-1) 0.02 High boiling solvent (OIL-1) 0.16 Gelatin 0.79 Fifth Layer: High Sensitivity Red-Sensitive Layer.

Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.2 × 10 ⁻⁵ Cyan Coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 7th layer: low-sensitivity green-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium sensitivity green-sensitive layer silver iodobromide emulsion B 0.30 silver iodobromide emulsion C 0.34 sensitizing dye (SD-6) 1.2 × 10 -4 sensitizing dye (SD-7) 1.2 × 10 -4 sensitizing dye SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (Di-2) 0.025 DIR compound (Di-3) 0.002 High boiling solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: High sensitivity green sensitive layer.

Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 ⁻⁵ Sensitizing dye (SD-7) 7.1 × 10 ⁻⁵ Sensitizing dye (SD-8) 7.1 × 10 ⁻⁵ Magenta Coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL) -2) 0.19 gelatin 1.10 12th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 increase Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (Di-4) 0.04 DIR compound (Di-5) 0.02 High boiling solvent (OIL- 2) 0.42 Gelatin 1.40 13th layer: High-sensitivity blue-sensitive layer.

Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1 and dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

The emulsions used for the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0071]

[Table 1]

The samples were simultaneously coated with a multi-slide hopper type coater at the first time from the first layer to the eighth layer, and at the second time onto the ninth layer to the fifteenth layer.
Sample 101 had a silver coating amount of 6.25 g / m ² , a dry film thickness of 18 μm, and a specific photographic speed of ISO 420.

[0073]

[Chemical 2]

[0074]

[Chemical 3]

[0075]

[Chemical 4]

[0076]

[Chemical 5]

[0077]

[Chemical 6]

[0078]

[Chemical 7]

[0079]

[Chemical 8]

[0080]

[Chemical 9]

[0081]

[Chemical 10]

[0082]

[Chemical 11]

The methods for measuring and evaluating the physical properties of the obtained support and photosensitive material are shown below.

<< Elasticity Modulus >> During film formation, the machine direction of coating the photosensitive layer is vertical, and the sample is 200 mm in length and 10 m in width.
m, cut into a temperature of 23 ℃, relative humidity of 20% RH in an atmosphere of 24
The measurement was performed after time humidity control. The measurement condition is a distance between chucks of 10
It was performed at 0 mm and a pulling speed of 100 mm / min.

<< Glass Transition Temperature >> From the Film Obtained
A 10 mm sample was taken, set on an inspection scanning calorimeter, and heated up at a rate of 20 ° C / min under a nitrogen stream, and the temperature at which the baseline began to become eccentric and the temperature at which it returned to the new baseline The average value was taken as the glass transition temperature.

Two or more glass transition temperatures are observed in the case of lamination, blending of polyester and copolyester, or lamination, and in this case, the value on the low temperature side was taken as the glass transition temperature.

The glass transition temperature of the polyester film is, after the preparation of the light-sensitive material, the silver halide emulsion layer and / or the gelatin back layer, the subbing layer, the magnetic recording layer, etc. on both sides coated on the support of the light-sensitive material. The same value was obtained by cutting out the support peeled off using pancreatin, or an aqueous solution of sodium hypochlorite, and the substantially same value was obtained. Good.

<Cutability> A wide sample obtained by coating a polyester film support with a photosensitive layer was fed at a conveying speed of 100 m /
In a minute, a slit was cut into a width of 35 mm, and perforations were simultaneously punched, and then cut into a photosensitive material having a length of 120 cm.

Twenty prepared samples were used, wound on a core having a diameter of 8 mm, released one day later, and subjected to a usual minilab development process used in the market, and then the following peeling and pressure fog were evaluated.

<< Peeling >> The peeling of the silver halide emulsion layer in the slit portion and perforation portion of the sample after the development treatment was observed and the following two-stage visual evaluation was carried out. Practically ○
Grade is required.

◯: No peeling occurred in both the slit portion and the perforation portion.

X: Peeling is observed in either the slit portion or the perforation portion.

<< Pressure Fogging >> The frequency of occurrence of a blackened portion, which is a fog caused by the pressure at the time of cutting the perforation portion after the development processing, was obtained and evaluated in the following two stages. A grade of ○ is necessary for practical use.

◯: Occurrence rate is less than 3% x: Occurrence rate is 3% or more, or fogging exceeding a length of 2 mm is observed.

<< Transportability >> Twenty photosensitive materials were prepared in the same manner as above. Wrap around a core with a diameter of 8 mm, heat-treat at 55 ° C, 20RH% for 4 hours, then release from the core and use a film splicer processor (PS-35-2: Noritsu Koki Co., Ltd.) used in the market. After joining with a film, the film automatic development processor (NC
V60: manufactured by Noritsu Koki Co., Ltd.) and subjected to normal development processing.

The following three grades were used for evaluation. Practically, there is no problem as long as the grade is Δ, but the grade ◯ is preferable.

◯: No edge breakage Δ: Partial edge breakage occurred at the joint between the films ×: Edge breakage occurred on the entire surface of the film << Removal of curl and curl >> Photosensitive material having a width of 35 mm and a length of 120 cm as described above 5 pieces were used. Wrap around a core with a diameter of 10 mm, 55 ℃, 20
Heat treatment was performed at RH% for 4 hours. Then, it was released from the core and processed in a minilab type automatic processor for about 7 minutes used on the market. After the development, the film was hung at 23 ° C. in an atmosphere of 55% by grabbing one end on the outer side of the roll and conditioned for one day. The length of the portion 12 cm from the tip corresponding to the core when naturally hanging was measured, the ratio to the original length was obtained, and the average of 5 was evaluated in the following 3 grades. In terms of photographic film performance, a grade of Δ or higher is preferable.

◯: 70% or more Δ: 50 to 70% ×: less than 50% << Width curl >> The sample after the above development treatment was cut out in a lengthwise direction of 2 mm and evaluated. After the humidity was controlled for 1 day in an atmosphere of 23 ° C and 55%, the width of the curl was measured.

The photographic film is required to have an appropriate curl so that the emulsion surface will not be damaged when it is used as a light-sensitive material. The curl here is the radius of curvature measured as plus when the emulsion layer side is concave (unit:
It is the reciprocal of m).

Although there is no problem with Δ in terms of the performance of the photographic film, a grade of ◯ is preferable.

[0102] ○: 10~25m ^-1 △: 5~10m ^-1 or, 25~35m ^-1 ×: a polyester film having a thickness of 100μm Comparative Example 2 Example 1 exceeding 5 m ^-1 or less than 35m ^-1 Use the following subbing coating solution B-2 instead of B-1 to dry film thickness
The undercoat layer B-2 was formed by coating so as to have a thickness of 0.8 μm.

<Undercoating Coating Liquid B-2> Copolymer latex liquid of butyl acrylate 40% by weight, styrene 20% by weight and glycidyl acrylate 40% by weight (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexa Methylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml Further, after subjecting the undercoat layer B-2 to corona discharge of 8 W / (m ² · min), the undercoat layer B-2 On the top, the following coating liquid B-
3 was applied to give a dry film thickness of 0.8 μm to form an undercoat layer B-3 having an antistatic function.

<Coating Liquid B-3> 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) 12g Polyethylene glycol (number average molecular weight 600) 6g Finish with water 1000ml

[0104]

[Chemical 12]

Then, on the undercoat layer B-3, 8 W / (m ² · m
in) corona discharge. On the surface of the undercoat layer B-3,
The following back layers were sequentially formed. Then, after annealing as in Example 1, each layer of the same composition as in Example 1 was sequentially applied from the first layer to the surface of the obtained support opposite to the back phase, in the same manner as in Example 1. Then, a multilayer color photographic light-sensitive material was prepared.

In addition, the display of the quantity in the <back layer> below shows the quantity 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 (F-1 and F-2 molar ratio 1: 1) 45mg

[0108]

[Chemical 13]

Table 2 shows the measurement results evaluated in the same manner as in Example 1.
Shown in. (Sample No. 7) Comparative Example 3 The procedure of Example 1 was repeated except that the polyester film having a thickness of 50 μm of Example 1 was used and the amount of gelatin on the emulsion layer side was increased by 1.5 times. After coating, an annealing process was performed to produce a photosensitive material. The evaluation results are shown in Table 2. (Sample No. 8) Example 2 (Production of polyester) 70 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, 24 parts by weight of dimethyl terephthalate (molar ratio: naphthalenedicarboxylic acid / terephthalic acid = 70% / 30)
%), 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added to 56 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. Then, 0.04 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate were added to the obtained product. Then gradually raise the temperature,
The pressure was reduced and polymerization was carried out at 285 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.5 (hereinafter sometimes abbreviated as MPEN). The glass transition temperature was 107 ° C.

(Preparation of Support) The obtained copolyester was dried in vacuum at 150 ° C., and then was extruded at 295 ° C.
Was melt-extruded from a T-die and rapidly cooled and solidified in a cooling drum shape to obtain an unstretched film. Then, after preheating to 110 ° C, longitudinal stretching (3.1 times) was performed, and then transverse stretching (3.4 times) at a temperature of 115 ° C.
And heat setting at 230 ℃, and the film thickness shown in Table 9
A 0 μm biaxially stretched film was obtained.

In the same manner as in Example 1, a subbing back layer was applied, annealed, and thereafter a photosensitive material was prepared in the same manner, and the evaluation results are shown in Table 2. (Sample No.
9) Comparative Example 4 (Production of polyester) 48 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 40 parts by weight of dimethyl terephthalate (molar ratio: naphthalenedicarboxylic acid / terephthalic acid = 40% / 60)
%), 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added to 56 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. Then, 0.04 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate were added to the obtained product. Then gradually raise the temperature,
The pressure was reduced and polymerization was carried out at 285 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.5 (hereinafter sometimes abbreviated as MPEN). The glass transition temperature was 100 ° C.

(Preparation of Support) The copolymerized polyester obtained was used in the same manner as in Example 2 to give a film thickness of 90 μm shown in Table 2.
A biaxially stretched film of m was obtained. Similar to Example 1, after applying an undercoating back layer and performing an annealing treatment, a light-sensitive material was prepared in the same manner, and the evaluation results are shown in Table 2. (Sample No. 10) Comparative Example 5 (Production of polyester) 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added to 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, and the ester exchange reaction was carried out by a conventional method. I went. Then, 0.04 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate were added to the obtained product. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 285 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.5 (hereinafter sometimes abbreviated as PET). The glass transition temperature was 80 ° C.

(Preparation of Support) The copolymerized polyester thus obtained was vacuum dried at 150 ° C. and then at 295 ° C. using an extruder.
Was melt-extruded from a T-die and rapidly cooled and solidified in a cooling drum shape to obtain an unstretched film. Next, after preheating to 90 ° C, longitudinal stretching (3.1 times) and then transverse stretching at a temperature of 100 ° C (3.4 times)
And then heat set at 220 ° C to obtain a film thickness of 80 μm as shown in Table 2.
A biaxially stretched film of was obtained.

Similar to Example 1, a subbing back layer was applied and annealed, and then a photosensitive material was prepared in the same manner, and the evaluation results are shown in Table 2. (Sample No. 11) Example 3 (Preparation of Support) The polyester (P
EN) and the polyester (PET) obtained in Comparative Example 5 were mixed at a mixing weight ratio of PEN / PET = 50/50, and then a biaxially stretched film having a thickness of 90 μm shown in Table 2 was prepared in the same manner as in Example 2. Got The glass transition temperature of the obtained polyester film was 98 ° C. Similar to Example 1, after applying an undercoating back layer and performing an annealing treatment, a light-sensitive material was prepared in the same manner, and the evaluation results are shown in Table 2.
(Sample No. 12) Example 4 (Preparation of support) The polyester (P
EN) and the polyester (PET) obtained in Comparative Example 5 were vacuum-dried at 150 ° C., respectively, and then two extruders were used.
Melt extruded at 00 ° C, joined in layers in a T-die so that the lamination ratio of each layer of PEN layer and PET layer was PEN / PET = 2/1, and rapidly cooled and solidified in a cooling drum to laminate unstretched I got a film. Then stretched vertically at 125 ℃ (3.2 times)
Later, after transverse stretching (3.2 times) at a temperature of 130 ℃, 230 ℃
Heat fixing was carried out to obtain a biaxially stretched film having a film thickness of 90 μm. The glass transition temperature of the obtained polyester film is
It was 95 ° C. Similar to Example 1, after applying an undercoating back layer and performing an annealing treatment, a light-sensitive material was prepared in the same manner, and the evaluation results are shown in Table 2. (Sample No.1
3)

[0115]

[Table 2]

The difference in the elastic modulus of the polyester film in the present invention and the elastic modulus of the polyester film and the photosensitive material in the present invention is excellent in cutting property when molding the product,
It is a silver halide photographic light-sensitive material that retains strength, is hard to curl, and has excellent curl on the width of the post-processing. Further, those in the present invention were excellent without any particular problems in photographic performance.

[0117]

Industrial Applicability According to the present invention, a silver halide photographic light-sensitive material which has excellent cuttability when cutting and molding a product, retains strength, is hard to be wound, and has excellent curl after processing. Material could be provided.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material comprising a polyester film support and at least one silver halide light-sensitive layer, wherein the polyester film has an elastic modulus of 600 kg / mm ² or more. A silver halide photographic light-sensitive material characterized by having a difference from the elastic modulus of a silver photographic light-sensitive material (elasticity of polyester film-elasticity of silver halide photographic light-sensitive material) of 80 to 200 kg / mm ² . 2. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester film contains naphthalenedicarboxylic acid and ethylene glycol as components. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the naphthalene dicarboxylic acid component of the dicarboxylic acid component of the polyester film is 70 mol% or more and the glycol component is mainly ethylene glycol. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the polyester film is heat-set and then heat-treated at a glass transition temperature or lower. 5. The thickness of the polyester film is 50 to 50.
95 μm, claim 1, 2, 3 or 4
The described silver halide photographic light-sensitive material.