JPH0922087A - Silver halide color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material having high quality even for an enlarged print. SOLUTION: This silver halide color photosensitive material is a roll type material having a photographic structural layer comprising at least each one of red-sensitive layer, green-sensitive layer, blue sensitive layer and nonphotosensitive layer formed on one surface of a transparent supporting body. The film width of the photosensitive material is 20-35mm and the area for photographing is 300-700mm<2> . At least one layer of nonphotosensitive layers of the photosensitive material contains plate-like colloidal silver.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material, and more specifically, it is suitable for enlargement printing, has excellent resistance to static fog, and has excellent desilvering property during development processing. The present invention relates to a color light-sensitive material.

[0002]

2. Description of the Related Art In recent years, silver halide color photographic light-sensitive materials contain information on photographing conditions in order to more efficiently and accurately perform development processing after photographing (image exposure) and printing on photographic paper. There is a proposal to use it effectively by recording it on a photosensitive material.

US Pat. No. 4,947,196 and WO 90/04254 disclose a roll-shaped film and a magnetic head having a magnetic layer containing magnetic particles capable of magnetic recording on the back surface of a photographic film. An imaging camera having the same is disclosed. According to the above-described improved technology, the identification information of the type and maker of the photosensitive material, information on the conditions at the time of photographing, information on the customer, information on the printing conditions, information on the conditions for additional printing, etc. are recorded on the magnetic layer on the film. By magnetically inputting / outputting the data, it is possible to improve the print quality, increase the efficiency of the printing operation, increase the efficiency of the lab work, and the like.

There is also known a method of optically recording information, that is, a method of recording information on a photographic film by using a light source and fixing the information by a developing process.
Nos. -96635 and 3-116137 disclose a method of recording image trimming information on a film with an LCD for imprinting, and Japanese Patent Laid-Open No. 3-161727 discloses optical recording of position information of a subject as a bar code on the film. The way is
Japanese Patent Laid-Open No. 3-135535 discloses a method of optically recording shooting information on a film by a dot code.
No. 5543 discloses a method of optically recording information of a photographed area on a film by numbers or characters.

These are mainly optically recorded on the non-image portion of the film, and devised so that information can be effectively recorded on a small area.

Japanese Unexamined Patent Publication Nos. 4-306649 and 4-340
No. 955, No. 4-366848, No. 4-369649
Nos. 5-45799, 5-72682 and 5
No. 165166 discloses that the film width of a roll-shaped silver halide color photographic light-sensitive material for photography has a conventional width of 35 m.
15-35 mm or 20-35 m smaller than m
and m, the shooting screen area smaller than the conventional about 860 mm ^2, there is proposed a small format to 300~700mm ^2. According to these, the picture quality is higher than that of the so-called "110 camera" and "disk camera", and the cartridge and the camera can be made smaller than the conventional one, or it is possible to add a functional part which the conventional camera does not have. .

[0007] In recent years, the downsizing and simplification of cameras have progressed, the portability has improved, and the opportunities for taking photographs have greatly increased. However, further miniaturization has been desired by users, and miniaturization while maintaining high image quality has been widely studied. Since the so-called 135 size roll film for general use is loaded in the standard format patrone,
The current situation is an obstacle to making cameras thinner. In order to reduce the size of the patrone, it is most effective and simple to reduce the thickness of the film, that is, the photosensitive material. This can be achieved by making the thickness of the support of the photosensitive material thinner than before.

On the other hand, the standard size Patrone of 135 size is currently limited to 36 pictures. There is a request to put more image information in one patrone,
This can also be achieved by making the thickness of the support of the photosensitive material thinner than before.

On the other hand, Japanese Patent Laid-Open No. 1-244446.
Nos. 3-54551, 3-84542, U.S. Pat. Nos. 4,217,441, 4,241,170, and 5,138,024 describe thin polyesters useful for color light-sensitive materials. There is disclosure of support.

Further, thin transparent supports excellent in mechanical strength are disclosed in JP-A-50-81325 and JP-A-50-10.
Nos. 9715 and 51-16358, U.S. Pat.
3,820, 5,006,613, World Patent Organization 92/02584, Japanese Patent Application Nos. 4-139473, and 4
-139474, JP-A-6-11794, 6-1
For example, there is polyethylene naphthalate shown in US Pat.

However, if the screen size of the color print, which is the final image, is the same for the reduction of the photographing screen area, the enlargement ratio is high, that is, it is necessary to form the same image with a smaller number of pixels than in the conventional case. Causes deterioration of image quality. Therefore, it is essential to improve the image quality by more than the increase of the enlargement ratio. Basically, it suffices to improve the granularity, but the balance with the sharpness is important for human visual perception of image quality.

A silver halide color light-sensitive material having a transparent magnetic recording layer for recording various information on the silver halide color light-sensitive material has a conventional, ie, a transparent magnetic recording material when a large amount of development processing is continuously performed. It was revealed that the desilvering failure is more likely to occur as compared with the silver halide color light-sensitive material having no recording layer. In particular, residual silver was detected in the layer containing colloidal silver (antihalation layer) closest to the support. It is presumed that this affects the bleaching solution in the development processing step, and it can be dealt with by improving the processing solution management method, but it is complicated.

By using a thin polyester support, the thickness of the silver halide color light-sensitive material can be reduced. However, compared with the conventional cellulose ester support, fogging due to static electricity generation under low humidity occurs. It is becoming noticeable. Particularly in the case of a polyethylene naphthalate support, the fogging of the silver halide photosensitive layer closest to the support deteriorates the image quality. It is strongly desired to solve these problems.

[0014]

Therefore, the first object of the present invention is to provide a silver halide color light-sensitive material for photographing which has a high image quality even in magnified print, and the second is to desilver by a magnetic recording layer. The present invention is to provide a silver halide color light-sensitive material having a reduced effect on the property, and the third is to provide a silver halide color light-sensitive material having excellent resistance to electrostatic fog.

[0015]

The above object of the present invention has been achieved by the following constitution.

(1) Roll-shaped silver halide color light-sensitive material having a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer on one side of a transparent support. Regarding the material, the film width of the photosensitive material is 20 to 35 mm, and the photographing screen area is 300 to 700 m.
m ² and at least 1 in the non-photosensitive layer of the light-sensitive material
A silver halide color light-sensitive material comprising a layer containing tabular colloidal silver.

(2) On one side of the transparent support, there is provided a photographic constituent layer consisting of at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer, and on the other side, In a silver halide color light-sensitive material having a transparent magnetic recording layer, at least one layer in the non-light-sensitive layer of the light-sensitive material,
A silver halide color light-sensitive material containing tabular colloidal silver.

(3) A silver halide color light-sensitive material having a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer on one side of a transparent support. The support is annealed at a temperature not higher than the glass transition temperature before coating the photographic constituent layer and has a thickness of 50 to
A silver halide color light-sensitive material, which is a 100 μm polyester film and contains tabular colloidal silver in at least one layer of the non-light-sensitive layer of the light-sensitive material.

(4) On one side of the transparent support, there is provided a photographic constituent layer consisting of at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer, and on the other side, In a silver halide color light-sensitive material having a transparent magnetic recording layer, the film width of the light-sensitive material is 20 to 35 mm, the photographing screen area is 300 to 700 mm ² , and the support has a glass transition temperature before coating with a photographic constituent layer. A silver halide color characterized by being a polyester film having a thickness of 50 to 100 μm which is annealed below, and containing tabular colloidal silver in at least one layer of the non-photosensitive layer of the photosensitive material. Photosensitive material.

(5) The tabular colloidal silver has an average thickness of 0.005 to 0.03 μm and an average diameter of 0.01 to 0.1.
μm, and the coating amount is 0.02 to 0.2 g / m
^The silver halide color light-sensitive material according to any one of (1) to (4), which is ² or less.

Hereinafter, the present invention will be described in detail.

In the present invention, tabular colloidal silver refers to a colloidal silver which is a metallic silver dispersion and whose silver particles have a tabular shape. Preferably, the average thickness is 0.005
The average diameter is 0.03 μm and 0.01 to 0.1 μm. The coating amount is 0.02 to 1 g / m ² , preferably 0.03 to 0.3 g / m ² , and particularly preferably 0.05 to
It is 0.2 g / m ² .

In the present invention, the method for preparing tabular colloidal silver is basically obtained by reducing a silver salt with a reducing agent or the like. For example, JP-B-1-28084 and US Pat. No. 5,246,823. Etc. can be used. It can also be obtained by reducing tabular silver halide.

In the present invention, the layer to which tabular colloidal silver is added is a non-photosensitive layer in the photographic constituent layers, preferably a non-photosensitive layer on the support side of the silver halide photosensitive layer, and particularly preferably the support. Is a non-photosensitive layer between the silver halide photosensitive layer and the support which is closest to the above, and particularly preferably an antihalation layer.

In the present invention, the film width of the silver halide color light-sensitive material for roll-shaped photographing is 20 to 35 mm, preferably 20 to 30 mm. This is JIS-
It is the film width of the general-purpose roll-shaped photographic film specified in K-7519, 7530 and a region narrower than that, but 110 size (16 mm) is excluded. Film width 25 described in Japanese Utility Model Publication No. 4-109758
mm, film width 2 described in JP-A-5-142641
1.6 mm is included. The film width of the present invention has the significance that not only the downsizing of cameras and cartridges can be achieved, but also resources can be saved and the storage space for the developed negative film can be reduced.

The photographing screen area is 300 to 700 mm ² , but if it is preferably in the range of 400 to 600 mm ² , it is possible to form a small format without deteriorating the image quality of the final photographic print, and the patrone is more than conventional. The miniaturization of the camera and the miniaturization of the camera can be achieved.
The image capturing screen area of the present invention is a so-called conventional 110 size (length × width = area; 13 mm × 17 mm = 221 m).
m ² ), disk film size (8.2 mm × 10.
6 mm = 87 mm ² ) is excluded, and half size (24 mm × 17 mm = 408 mm ² ), 126 size (28 mm × 28 mm = 784 mm ² ), panoramic size (13.7 mm × 36 mm = 493 mm ² ), actual Kaihei 4 Size described in -109758 (16.9 mm
× 25.5 mm = 431 mm ² ), JP-A-5-14426
No. 41 size (16.6 mm x 22.3 mm =
370 mm ² , 16.6 mm x 29.7 mm = 493 m
m ² , 11.8 mm × 29.7 mm = 350 mm ² ). The aspect ratio of the shooting screen is not limited, and the conventional 126 size is 1: 1, half size is 1: 1.4, and standard (135 size) is 1 :.
1.5, high definition type 1: 1.8, panorama type 1: 3, etc.

The transparent magnetic recording layer used in the present invention includes JP-A-53-109604, JP-B-57-6576, JP-A-60-45248 and US Pat. No. 4,947,196.
No., WO 90/04254, and No. 91/117
No. 50, No. 91/11816, No. 92/08165
No. 92/08227 and the like.

The optical density of the transparent magnetic layer is preferably 1.0 or less, more preferably 0.75 or less, and particularly preferably 0.02 to 0.30.

In the present invention, the magnetic layer is a layer in which ferromagnetic powder is dispersed in a binder.

The coating amount of the magnetic powder is 50 mg or less, preferably 20 mg or less, and particularly preferably 0.1 m as the amount of iron per 100 cm ^{2 of the} silver halide color light-sensitive material.
g to 5 mg.

Examples of the ferromagnetic powder include γ-F
e ₂ O ₃ powder, Co deposited γ-Fe ₂ O ₃ powder, Co deposited Fe
₃ O ₄ powder, Co-deposited FeOx (4/3 <x <3/2) powder, other Co-containing iron oxides, and other ferrites such as hexagonal ferrite are, for example, M type, W
Examples include hexagonal Ba ferrite, Sr ferrite, lead ferrite, Ca ferrite, or solid solutions or ion-substituted products of these types.

In the hexagonal ferrite magnetic powder, a part of Fe atoms, which are the constituent elements of these uniaxially anisotropic hexagonal ferrite crystals, are mixed with a divalent metal, Nb, Sb ₄ and Ta.
At least one pentavalent metal selected from the above and an element having a coercive force of 200 to 2,000 Oe substituted with 0.05 to 0.5 Sn atoms per chemical formula are used.

The divalent metal in the hexagonal ferrite is preferably an element such as Mn, Cu, or Mg that relatively well substitutes for Fe atoms in the ferrite.

In the hexagonal ferrite, divalent metal (M
The appropriate substitution amount of II) and the pentavalent metal (Mv) varies depending on the combination of MII and Mv, but is preferably about 0.5 to 1.2 per chemical formula of MII.

As for the relationship of the substitution amount of the substitution element, for example, regarding magnetoplumbite type Ba ferrite, the chemical formula of the substitution body is represented by BaFe _{12- (x + y + z)} MII _x Mv _y Sn _z O _19. . Where x, y and z are MII, Mv and Sn
It is the substitution amount of the element per one chemical formula of ferrite. MI
I, Mv and Sn are bivalent, pentavalent and tetravalent, respectively,
Since the Fe atom to be substituted is trivalent, there is a relation of y = (x−z) / 2 in consideration of valence compensation. That is, the substitution amount of Mv is uniquely determined from the substitution amount of MII and the substitution amount of Sn.

The coercive force (Hc) of the ferromagnetic powder is usually 2
It is at least 00 oersted, preferably at least 300 oersted.

The size of the magnetic powder in the major axis direction is preferably 0.3 μm or less, more preferably 0.2 μm or less.

The specific surface area of the ferromagnetic powder by the BET method is
Usually 20 m ² / g or more, preferably 25~80m ² / g.

The shape of the ferromagnetic powder is not particularly limited, and for example, any shape such as needle-like, spherical or ellipsoidal shape can be used.

Fatty acids can be contained in the magnetic layer of the present invention.

The above-mentioned fatty acid may be monobasic or dibasic, and in the present invention, the preferred fatty acid has 6 to 30 carbon atoms, particularly 12 to 22 carbon atoms. Preferred are myristic acid, oleic acid and stearic acid.

When a fatty acid ester is contained in the magnetic layer, the friction coefficient of the magnetic layer is lowered and the running property and durability of the magnetic recording medium of the present invention are further improved. Butyl stearate and butyl palmitate are preferred.

The above various fatty acid esters may be used alone or in combination of two or more.

The magnetic layer of the present invention may contain other fatty acid together with the above fatty acid or the above fatty acid ester.

Examples of other lubricants include silicone lubricants, fatty acid-modified silicone lubricants, fluorine lubricants, liquid paraffin, squalane, carbon black and the like. These may be used alone or in combination of two or more.

As the binder, a transparent one such as cellulose ester or gelatin is used.

A dispersion of finely divided magnetic particles in a transparent binder such as cellulose ester or gelatin using an organic solvent for cellulose ester or a solvent for the binder such as water for gelatin. Can be prepared.

As an organic solvent used in the dispersion, kneading and coating of particles, an acetone-based solvent such as acetone, methyl ethyl ketone and cyclohexanone; an alcohol-based solvent such as propanol, butanol and isobutyl alcohol; An ester system such as isopropyl acetate; an ether system such as glycol dimethyl ether; a tar system (aromatic hydrocarbon) such as xylene; a chlorinated hydrocarbon system such as methylene chloride and ethylene chloride.

Prior to coating, the support may be subjected to corona discharge treatment, plasma treatment, undercoating treatment, heat treatment, dust removal treatment, metal vapor deposition treatment, and alkali treatment. Regarding these supports, for example, West German Patent 3,338,854A
No. 59-116926, U.S. Pat. No. 4,38
No. 8,368, Yukio Mitsuishi, "Fiber and Industry", Volume 31,
pp. 50-55, 1975.

In the present invention, magnetic particles may be contained in the support.

In that case, it is preferable to concentrate on the side of the support opposite to the side on which the photographic constituent layers are coated. As a method of concentrating on one surface side of the support, after casting a dope containing a support polymer and magnetic particles, the magnetic particles are concentrated on one surface side of the support by gravity, magnetic force, etc. Kosho 30-986, WO91 / 11
As shown in 750, there is a method in which the dope containing the magnetic particles and the dope not containing the magnetic particles are simultaneously cast and concentrated on one surface side of the support, but the latter is preferable because it can be manufactured at a high speed. .

In the present invention, the cellulose acetate triacetate dope containing magnetic particles and the cellulose triacetate ester dope containing no magnetic particles may be simultaneously cast on a drum or belt and dried to form a support. It is possible to provide two casting ports on the endless belt, cast the cellulose acetate triacetate dope first, and then cast the cellulose acetate triacetate dope containing magnetic particles on the endless belt and dry it. It is also possible to form a support.

The thickness of the layer in which the magnetic particles of the present invention are present is 2
It is not more than μm, preferably not more than 1.5 μm, particularly preferably not more than 1 μm and not less than 0.1 μm. The coating amount of magnetic particles is 10 to 1000 mg / m ² , preferably 15 to 300 m.
g / m ² , particularly preferably 20 to 100 mg / m ² .

The magnetic particles are mainly composed of iron oxide, but those having a small amount of aluminum, calcium or silicon doped therein are preferably used for the purpose of the present invention. The needle ratio of the magnetic particles is preferably from 1 to 7.

In the process of casting a dope containing magnetic particles and drying it to form a magnetic layer, the magnetic particles may be regularly oriented by facing magnets, or a random magnetic field may be applied to obtain a so-called randomize. Treatment is also effective in the present invention.

In the present invention, the glass transition temperature is defined by an arithmetic mean of critical points or an endothermic peak temperature when 10 mg of a sample is heated at 20 ° C./min in a helium nitrogen stream using a differential thermal analyzer. . In the present invention, the transparent thin polyester support having excellent mechanical strength needs to have a glass transition temperature of 90 to 200 ° C., and if it is less than 90 ° C., it may be deformed in a high temperature environment where a photosensitive material is handled, It is not preferable because remarkable curling occurs. On the other hand, when the temperature is higher than 200 ° C., processing as a photographic support is extremely difficult, and requires a large amount of energy, which is not practical.

Preferred as the transparent polyester support in the color light-sensitive material of the present invention is a copolyester having an aromatic dicarboxylic acid and a glycol as a main copolymer component, which will be described below.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Among these, Particularly, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable. Examples of the glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene alcohol, and bisphenol A.

If necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group compound or an acid-containing compound may be added as a copolymerization component. Furthermore, a compound having a hydroxyl group and a carboxyl group (or ester group) at the same time may be added.

The inclusion of an aromatic dicarboxylic acid having a metal sulfonate group is effective and preferable for improving the curl characteristics of the polyester support. Examples of the aromatic dicarboxylic acid having a metal sulfonate group include 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, or Mention may be made of the indicated ester-forming derivatives and compounds in which these sodiums are replaced by other metals, for example potassium, lithium and the like.

[0061]

Embedded image

The copolyester having an aromatic dicarboxylic acid having a metal sulfonate group can be detected by hydrolyzing the copolyester, and the amount of the aromatic dicarboxylic acid having a metal sulfonate group can be detected in all carboxylic acid components. On the other hand, it is preferably 2 to 7 mol%. Amount of aromatic dicarboxylic acid having metal sulfonate group is 2 mol%
If it is less than the range, the curl of the photographic film may not be sufficiently recovered, and if it exceeds 7 mol%, a transparent support having poor heat resistance may be obtained.

Addition of polyalkylene glycol as a copolymer component is effective and preferable for improving the curl. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. What is important in the present invention is that polyethylene glycol is preferable among polyalkylene glycols. The molecular weight is usually 300 to 20,000,
It is desirable that it is ˜1,500.

In the present invention, the amount of the polyalkylene glycol added is 3 to the total weight of the copolyester.
10% by weight is preferred.

If the amount of polyalkylene glycol is less than 3% by weight, the curling habit after development processing cannot be taken and the stretchability is further lowered, so that the mechanical strength required for the film cannot be obtained. On the other hand, if it exceeds 10% by weight, a film having sufficient mechanical strength cannot be obtained due to the low mechanical properties of the polyalkylene glycol.

In the present invention, saturated aliphatic dicarboxylic acid is also effective in improving the curl. The saturated aliphatic dicarboxylic acid used for the copolyester has 4 to 20 carbon atoms.
Saturated aliphatic dicarboxylic acid or number average molecular weight of 500 to 5
000 polyethyleneoxy-ω, ω'-diacetic acid is preferred.

Examples of the saturated aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, adipic acid, sebacic acid, etc. Of these, adipic acid is particularly preferable. or,
Polyethyleneoxy-ω, ω'-diacetate having a number average molecular weight of 2000 to 4000 is particularly preferred.

When the copolymerized polyester of the present invention contains an aliphatic dicarboxylic acid as a monomer unit, the amount of the aliphatic dicarboxylic acid detected by hydrolyzing the copolymerized polyester is usually the total ester. It is preferably 3 to 25 mol% with respect to the bond.
As long as the amount of the aliphatic dicarboxylic acid is within the above range, if the copolymerized polyester contains an aliphatic dicarboxylic acid as a monomer unit, the curl of the photographic film can be easily eliminated, The transparent support can be provided with practical heat resistance.

Among the homopolymerized or copolymerized polyesters in the present invention, the preferable one is ethylene glycol 50: naphthalenedicarboxylic acid (50 to 50 mol%).
15): Terephthalic acid (0 to 35), ethylene glycol (0 to 15): neopentyl glycol (50 to 3)
5): Terephthalic acid (50), ethylene glycol (4
0): bisphenol {(10): naphthalenedicarboxylic acid (50 to 10): terephthalic acid (0 to 40) and the like. More preferably, the aromatic dicarboxylic acid having a metal sulfonate group may be added to the homopolymerized or copolymerized polyester in an amount of 2 to 7 mol% of the total aromatic dicarboxylic acid.

In the present invention, the transparent polyester support may be a mixed polyester, and in particular, one containing polyethylene naphthalate in an amount of 50% by weight or more is preferable.

Specific polyesters include polyethylene naphthalate (50 to 95): polyethylene terephthalate (50 to 5), polyethylene naphthalate (5).
0-90): polyacrylate (50-10), polyethylene naphthalate (60): polyethylene terephthalate (30-10): polyacrylate (10-30)
Are preferred.

Basically, the copolyester of the present invention is preferably obtained by an esterification reaction and / or a polycondensation reaction of a component in which an aromatic dicarboxylic acid or its ester, a glycol, a catalyst and a stabilizer are mixed.

Examples of the catalyst used in this esterification reaction and / or polycondensation reaction include acetates, fatty acid salts and carbonates of metals such as manganese, calcium, zinc and cobalt. Among these, manganese acetate,
A hydrate of calcium acetate is preferable, and a mixture of these is preferable.

During the esterification and / or polycondensation,
As long as it does not hinder the reaction or color the polymer,
It is also effective to add a hydroxide, a metal salt of an aliphatic carboxylic acid, a quaternary ammonium or the like, among which sodium hydroxide, sodium acetate and tetraethylammonium hydroxide are preferable, and sodium acetate is particularly preferable. The addition amount of these is 1 × 10 ^{-2 to} 20 with respect to all acid components.
× 10 ^-2 mol% is preferable.

The copolyester used in the present invention is phosphoric acid, phosphorous acid, and
It may contain stabilizers such as esters thereof and inorganic particles (eg silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.), or
You may contain the said inorganic particle added suitably after superposition | polymerization.

Further, the copolyester may contain a dye, an ultraviolet absorber, an antioxidant, etc., which are appropriately added at the polymerization stage or at any stage after the polymerization.

The transparent support in the present invention preferably contains a specific copolyester and an antioxidant. The antioxidant is not particularly limited, and specific examples thereof include hindered phenol-based, allylamine-based, phosphite-based, and thioester-based antioxidants. Among these, hindered phenol compounds are preferred.

The content of the antioxidant in the transparent support is usually 0.01 to 2% by weight, preferably 0.1 to 0.5% by weight, based on the copolymerized polyester. When the content of the antioxidant is less than 0.01% by weight, the effect of the photographic performance is inferior, and when it exceeds 2% by weight, the turbidity of the copolymerized polyester increases, which may not be preferable as a transparent support. In addition, the antioxidant can be used alone, or two or more thereof can be used in combination.

The transparent support in the present invention is a transparent support coated with a photographic emulsion layer for the purpose of preventing a light piping phenomenon (edge fog) which occurs when light enters from the edge of the transparent support. It is preferable to include a dye in the. The type of the dye to be blended for such purpose is not particularly limited, but a dye having excellent heat resistance is preferable in a film forming process, and examples thereof include an anthraquinone-based chemical dye. Can be. or,
As the color tone of the transparent support, gray dyeing is preferred as seen in general light-sensitive materials, and one kind or a mixture of two or more kinds of dyes can be used. As these dyes, dyes such as Sumiplast manufactured by Sumitomo Chemical Co., Ltd., Diaresin manufactured by Mitsubishi Kasei Co., Ltd., and MACROLEX manufactured by Bayer can be used alone or in an appropriate mixture.

The transparent support is, for example, selected from the group consisting of the above-mentioned copolymer polyester, or an antioxidant optionally blended with the copolymer polyester, or sodium acetate, sodium hydroxide and tetraethylammonium hydroxide. After sufficiently drying the copolymerized polyester composition containing at least one of 260
A sheet is melt-extruded through an extruder, a filter, a die and the like controlled in a temperature range of to 320 ° C., and the molten polymer is cooled and solidified on a rotating cooling drum to obtain an unstretched film. Thereafter, the unstretched film can be manufactured by biaxially stretching the film in the machine direction and the transverse direction and heat-setting.

The stretching conditions of the film cannot be uniformly specified because it varies depending on the copolymerization composition of the copolyester, but the film is stretched in the machine direction in the temperature range of the glass transition temperature (Tg) to Tg + 100 ° C. of the copolyester. Magnification 2.5 to 6.0 times, Tg + 5 ° C to Tg + 50 ° C in the lateral direction
In the temperature range of, the draw ratio is in the range of 2.5 to 4.0 times. The biaxially stretched film obtained as described above is usually heat-set at 150 to 240 ° C. and cooled. In this case, it may be relaxed in the vertical and / or horizontal direction if necessary.

The transparent support in the present invention may be a single-layer film or sheet formed by the above-mentioned method, or a film or sheet of another material by a coextrusion method or a laminating method. It may have a multi-layer structure in which a film or sheet formed by the method is laminated, but the latter is effective in preventing curling.

As the laminated multi-layer structure, for example, when a layer made of polyethylene naphthalate is A layer and a layer made of other polyester is B layer or C layer, A layer and B layer are formed.
A two-layer structure composed of layers may be used, or A layer / B layer / A layer, A
Layer / B layer / C layer, B layer / A layer / B layer or B layer / A layer / C
A three-layer structure such as a layer may be used. Further, a configuration having four or more layers is of course possible, but it is not practically preferable because the manufacturing equipment becomes complicated.

The thickness of the layer A is preferably 30% or more of the total thickness of the polyester film,
Further, the thickness is preferably 40 to 70%. In this case, the thickness of the A layer is the thickness of the layer when the A layer is only one layer, and is the sum of those thicknesses when the A layer is two or more layers. The thickness of the B layer or the C layer is 5 to 60.
μm, more preferably 10 to 50 μm. When the thickness of each layer is in the above range, transparency, mechanical strength, and dimensional stability are excellent, and since it has water absorbability, it is possible to obtain a polyester film having excellent curl recovery properties.

The thickness of the transparent support thus obtained is not particularly limited, but is usually 120 μm or less, preferably 40 to 120 μm, more preferably 50 to
110 μm. The local variation in the thickness of the transparent support is preferably within 5 μm, more preferably 4 μm.
It is within μm, particularly preferably 3 μm or less.

When the thickness of the transparent support is within the above range, the strength and curl characteristics of the film after coating the photographic constituent layers will not be a problem and the total thickness of the film should be within the above range. You can Further, when the local variation in the thickness of the transparent support is within 5 μm, it is possible to prevent the occurrence of coating unevenness and drying unevenness when applying the photographic constituent layer.

The heat treatment methods described in JP-A-51-16358 and JP-A-6-35118 can be preferably used for the purpose of reducing the curl of the polyester photographic support. . That is, it is a method of heat treatment at a temperature of 50 ° C. to glass transition point, preferably 50 ° C. to (glass transition point −5 ° C.) for 0.1 to 1500 hours.
Since this heat treatment is carried out at a high temperature of 50 ° C. or more, if it is carried out after the application of the silver halide emulsion layer, the performance of the emulsion layer tends to deteriorate. Therefore, it is desirable to carry out the method after the production of the support and before the coating of the emulsion layer.

If necessary, a surface activation treatment such as corona discharge and / or a subbing layer is applied to the surface of the transparent support of the present invention on which the photographic constituent layer is formed, prior to the formation of the photographic constituent layer. be able to.

As this undercoat layer, for example, JP-A-59-
19941, 59-77439, 59-224
No. 841 and Japanese Patent Publication No. Sho 58-53029 can be mentioned as preferred examples. The undercoat layer provided on the surface of the transparent support opposite to the photographic component layer is also called a back layer.

The support used for the photographic film according to the present invention is preferably the above-mentioned annealed polyester film, but it is a known semi-finished material such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide. It is also possible to use a film made of synthetic or synthetic polymer.

The silver halide emulsion according to the present invention is Research Disclosure (designated as RD) 308119.
It is possible to use those described in. The places to be described are shown below.

[Item] [Page of RD308119] Iodine structure 993I-A Manufacturing method 〃 and 994E Crystal habit Normal crystal 〃 〃 Twin crystal 〃 Epitaxial〃〃 Halogen composition Uniform 993IB Not uniform 〃 〃 Halogen conversion 994I-C 〃 Substitution 〃 Metal 〃 995I-D Monodispersion 995I-F Solvent addition 〃 Latent image forming position Surface 995I-G Inner surface 〃 Application Sensitive material I-H negative 5 99 Internal fog grains are included) 〃 〃 Emulsions are mixed and used 〃 I-J Desalination 〃 II-A In the present invention, the silver halide emulsion used is physically ripened, chemically ripened and spectrally sensitized. To do. The additives used in such a process are RD17643, 1871
6 and 308119.

The description is given below.

[0094]

[Table 1]

Known photographic additives that can be used in the present invention are also described in the above RD. Below are the relevant locations.

[0096]

[Table 2]

(Containing in Photosensitive Material) Various couplers can be used in the present invention, and specific examples thereof are described in the following RD. The relevant locations are shown below.

[0098]

[Table 3]

The additive used in the present invention is RD3081.
It can be added by the dispersion method described in 19XIV.

In the present invention, the above-mentioned RD17643 is used.
28, RD18716, pages 647-8 and RD308.
The supports described in XIX of 119 can be used.

The photographic film according to the present invention has the above-mentioned RD.
An auxiliary layer such as a filter layer or an intermediate layer described in the item 308119VII-K can be provided.

The photographic film according to the present invention has the above-mentioned RD3.
Various layers and configurations such as a normal layer, a reverse layer, and a unit configuration described in section 08119VII-K can be used.

The photographic film according to the present invention is RD17 described above.
Developing can be carried out by a usual method described in XIX of pages 643, pages 28 to 29, RD18716, page 647 and RD308119.

[0104]

EXAMPLES Examples of the present invention will be shown below, but the invention is not limited thereto. In the examples, “parts” represents “parts by weight”.

Example 1 Each layer having the following composition was provided on a triacetyl cellulose transparent support (A) having a thickness of 115 μm and provided with an undercoat layer to prepare a sample 101 which was a multilayer color light-sensitive material.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is g / m ² in terms of metallic silver.
The amount expressed in units, and g for couplers and additives
/ M the amount expressed in ^two units, for Matazo sensitizing dye shown in mol per mol of silver halide in the same layer.

Sample 101 First layer: antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.002 Colored magenta coupler (CM-1) 003 high boiling solvent (OIL-1) 0.16 gelatin 1.60 second layer: intermediate layer compound (SC-1) 0.14 high boiling 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 (D-1) 0.025 High boiling point solution (OIL-3) 0.48 Gelatin 1.09 Fourth 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 cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: High Sensitive 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 DIR compound (D-3) 0. 001 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 seventh 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 DIR compound (D-1) 0.003 High boiling point solvent (OIL- 4) 0.34 gelatin 0.70 Eighth layer: intermediate layer Gelatin 0.41 Ninth layer: medium-sensitive 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-3) 0.04 Magenta coupler (M-4) 0.04 Colored magenta coupler (CM-2) 0.017 DIR compound (D-2) 0 0.025 High boiling point 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-5) 0.09 Colored magenta coupler (CM-2) 0. 011 DIR compound (D-3) 0.002 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 10th 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 Sensitizing dye (SD-10) 1.0 × 10 ⁻⁵ Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point 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 DIR compound (D-6) 0.007 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.0 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling solvent (OIL-1) 0.07 High boiling solvent (OIL-3) 0.07 Gelatin 0.65 Fifteenth layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, a coating aid Su-1, a dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, average molecular weight: 10,000
0 and an average molecular weight of two AF-s of 1,100,000
2, and the preservative DI-1 were added.

The emulsions used in the above samples are shown in Table 4 below. Incidentally, the average particle size is shown by a particle size converted into a cube. Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0109]

[Table 4]

The sample was coated with a multi-slide hopper type coater at the same time, the first layer to the eighth layer at the first time, and the ninth layer to the fifteenth layer on the second time at the same time. The silver coating amount of Sample 101 was 6.25 g / m ² , the dry film thickness was 18 μm, and the specific photographic sensitivity was ISO420.

The respective compounds used are shown below.

[0112]

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[0113]

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[0114]

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[0115]

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[0116]

[Chemical 6]

[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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Sample No. Sample No. 101 in the same manner except that the black colloidal silver of the first layer of No. 101 was changed as follows.
102-104 were produced.

[0124]

[Table 5]

However, colloidal silver (A) is described in US Pat.
Prepared according to the method of Example-1, No. 21,914. Tabular colloidal silver (B) is disclosed in JP-A-5-134.
Prepared according to the method of Example-1 of No. 358. Tabular colloidal silver has an average thickness of 0.007μ and an average diameter of 0.02.
It was 5μ.

For each sample, a sensitometric measurement,
A test pattern for magenta image sharpness measurement was exposed, and a cine-type automatic developing machine for negative film (NCV-2) was used.
4, Noritsu Koki Co., Ltd.).

(Development processing) Processing content Processing time Processing temperature Replenishment amount (° C.) (cc.) Color development 3 minutes 15 seconds 38 ± 0.3 780 Bleach 6 minutes 30 seconds 38 ± 2.0 150 Water washing 3 minutes 15 seconds 20 ± 10 200 Settling 6 minutes 30 seconds 38 ± 2.0 830 Washing 3 minutes 15 seconds 20 ± 10 200 Stability 1 minute 30 seconds 38 ± 5.0 830 Drying 2 minutes 55 ± 5.0 − The replenishment amount is a value per 1 m ² of the photographic light-sensitive material.

The color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof were prepared as follows.

<Color Developer> 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water was added to make 1 liter and pH was adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150 g Glacial acetic acid 10 cc. Water was added to make 1 liter, and the pH was adjusted to 6.0 with aqueous ammonia.

<Fixer> Ammonium thiosulfate 175 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and pH was adjusted to 6.0 with acetic acid.

<Stabilizing Solution> Formalin (37% aqueous solution) 1.5 cc. Conidax (manufactured by Konica Corporation) 7.5 cc. Water was added to make 1 liter.

<Color development replenisher> Water 800 cc. Potassium carbonate 35 g Sodium hydrogencarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 6.3 g Water Potassium oxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter, and pH was adjusted to 10 with potassium hydroxide or 20% sulfuric acid. Adjusted to 18.

<Bleach Replenisher> Water 700 cc. 1/3 Ammonium iron (III) diaminopropane tetraacetate 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting the pH to 4.0 using ammonia water or glacial acetic acid, add water to 1 liter did.

<Fixing Replenisher> Water 800 cc. Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 with aqueous ammonia or glacial acetic acid, water was added to make 1 liter.

<Stable Replenisher> Same as the stabilizer.

The sharpness of each of the developed samples was measured by the following method.

<Sharpness> The sharpness is shown as a relative value when the MTF% value at a spatial frequency of 10 cycles / mm is measured by measuring the MTF of the magenta dye image and the sample 101 is set to 100. The larger the number, the better the sharpness.

On the other hand, for each sample, 24 sheets of film were prepared in accordance with the 135 size standard (JIS-K7519), stored in a cartridge, and loaded into the Konica camera "Big Mini NEO" to be used outdoors in fine weather. A photograph of the background and the person (Group A), and each sample with a film width of 26
mm, perforation on one side only, vertical 17 frames
mm, width 26 mm, image area 442 mm ² 24 shots were created and stored in a small patrone with a height of 7 mm lower, and the image frame of "Big Mini NEO", film feeding section,
It was loaded into a modified lens focal length, and the same scene was photographed (Group B).

The above-mentioned development processing was carried out for the groups A and B of each sample, and then the color printer KCP manufactured by Konica Corporation.
Konica Color QA Paper Type A5 with -5N3
And developed by Konica CPK2-23 treatment to obtain 2 L size color print groups A and B, respectively.

For each sample, after observing the prints of the group A, the prints of the group B were viewed, and the satisfaction of the image quality was evaluated according to the following four-level evaluation, and the average point of each sample was obtained.

4 ... The image quality is almost the same as the print of the group A. 3 ... Slightly inferior to the print of the group A, but within the allowable range .. 2 A general user can recognize a significant difference. Image quality deterioration is clearly observed.

<Desilvering property> On the other hand, in the development processing step, the pH of the bleaching solution is 6.5 and the bleaching processing time is 4
The desilvering property was evaluated by measuring the residual silver amount in the maximum density part of each sample in the same manner except that the time was 30 minutes.

The results are shown below.

[0145]

[Table 6]

As is clear from the results, those satisfying the constitution of claim 1 have high image quality even in enlarged print from a small screen and are excellent in desilvering property.

Example 2 (Production of Support B) 100 parts of cellulose triacetate having an acetylation degree of 61.4% and 15 parts of triphenyl phosphate were completely dissolved in 738 parts of a mixed solvent of methylene chloride-methyl alcohol to obtain a dope. It was

On the other hand, a cellulose triacetate dope containing magnetic particles was prepared as follows.

Co-adhered γ-Fe ₂ O ₃ 100 parts by weight (coercive force: 610 Oe BET surface area 35 m ² / g, major axis length 0.23 μm, acicular ratio 7) Cellulose triacetate 210 parts by weight Methylene chloride 2100 parts by weight Part Methyl ethyl ketone 1000 parts by weight The above components were mixed together with a dissolver and then dispersed with a sand grinder to obtain a dispersion liquid. The viscosity was 8.8 poise as measured by a B-type viscometer.

20 parts by weight of the above dispersion was taken and thoroughly mixed with a dope having the following composition by a dissolver.

Cellulose triacetate 13.8 parts by weight Methylene chloride 163.1 parts by weight Cyclohexanone 55 parts by weight Ethanol 3.1 parts by weight Next, each dope was filtered and kept at 27 ° C., and provided on a rotating 6 m endless stainless steel band. It was evenly cast from the two casting ports (double casting method), the solvent was evaporated until peeling became possible, and then peeled from the stainless steel band, and further dried to obtain a thickness containing magnetic particles. 115 μm cellulose triacetate base (B)
I got

The cellulose triacetate dope containing magnetic particles was dried so that the dry film thickness was 1 μm, and after casting, it was dried while carrying out orientation treatment with a facing magnet. The coating amount of magnetic particles was 50 mg / m ² .

The coercive force of the support was 670 Oe.
The optical transmission density was 0.10.

Samples 201, 202 and 203 were prepared in the same manner except that the support A of the samples 101, 103 and 104 of Example 1 was replaced with the support B having the magnetic recording layer.

After cutting each of the samples 201 to 203 into a 135 size standard, they were stored in a cartridge and photographed arbitrarily with a normal camera.

Using the development processing step of Example 1 and the photographed samples 201 to 203 in the same ratio, a new solution treatment and a running two-round treatment (running 2R (fatigue treatment solution treatment)) were performed, and then the samples were processed. The amount of residual silver in the maximum density part of 201 to 203 was measured.

(In the present invention, the running process means to continuously develop the exposed light-sensitive material and replenish the replenisher in an amount corresponding to the amount of the light-sensitive material. This model is based on the assumption of development processing conditions that are generally performed at a developing station.One round in the running processing means that the photosensitive material is equivalent to the amount in which the processing tank solution in the developing process is completely replaced by the replenisher. Therefore, the running two-round process is a process in which the processing solution after processing the photosensitive material corresponding to the replenishing solution amount twice as much as the processing tank solution amount is processed. Is shown below.

[0158]

[Table 7]

As is clear from the results, even if the support B having the magnetic recording layer is replaced, the one satisfying the constitution of claim 2 can be removed not only by the new solution treatment but also by the two rounds of the running treatment (fatigue treatment solution treatment). It can be seen that the silveriness is excellent. In addition, it was found that the sample 201 after two rounds of running treatment (fatigue treatment liquid treatment) had a yellowish brown stain that was thought to be caused by the residual silver, which affected the color reproducibility.

Example 3 <Production of Support> Polyester A to
Polyester F was prepared.

(Polyester A) 100 parts of dimethyl 2,6-naphthalenedicarboxylic acid, ethylene glycol 60
Calcium acetate hydrate 0.
1 part was added, and transesterification was carried out according to a conventional method. 0.05 parts of antimony trioxide,
0.03 part of phosphoric acid trimethyl ester was added. Then, gradually raise the temperature and reduce the pressure to 290 ° C and 0.5 mmHg.
Polyethylene-2 having an intrinsic viscosity of 0.60,
6-naphthalate was obtained.

(Polyester B) 100 parts of dimethyl 2,6-naphthalenedicarboxylic acid, ethylene glycol 60
Calcium acetate hydrate 0.
1 part was added, and transesterification was carried out according to a conventional method. 5-sodium sulfo-di (β
-Hydroxyethyl) isophthalic acid in ethylene glycol solution (35 wt% concentration) 5 parts, antimony trioxide 0.
05 parts, 0.03 part of phosphoric acid trimethyl ester, 0.2 part of Irganox 1010 (manufactured by Ciba Geigy) and 0.04 part of sodium acetate were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was performed at 290 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.55.

(Polyester C) 0.05 part of magnesium acetate hydrate as an ester exchange catalyst was added to 100 parts of dimethyl terephthalate and 65 parts of ethylene glycol,
The transesterification reaction was performed according to a conventional method. To the obtained product, 0.05 part of antimony trioxide and 0.03 part of phosphoric acid trimethyl ester were added. Next, the temperature was gradually raised and the pressure was reduced, and polymerization was performed at 280 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.65.

(Polyester D) To 100 parts of dimethyl terephthalate and 65 parts of ethylene glycol were added 0.05 part of magnesium acetate hydrate as an ester exchange catalyst,
The transesterification reaction was performed according to a conventional method. The obtained product was added to a solution of 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid in ethylene glycol (35 wt
% Concentration) 5 parts, antimony trioxide 0.05 part, phosphoric acid trimethyl ester 0.03 part, Irganox 1010
0.2 parts (manufactured by Ciba Geigy) and 0.04 parts of sodium acetate were added. Then, the temperature was gradually raised and the pressure was reduced to carry out polymerization at 280 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.62.

(Polyester E) Dimethyl 2,6-naphthalenedicarboxylate 100 parts, ethylene glycol 60
0.05 part of magnesium acetate hydrate was added as a transesterification catalyst to the parts, and transesterification was carried out according to a conventional method. The obtained product was added with 18 parts of an ethylene glycol solution of 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (35 wt% concentration), 6 parts of polyethylene glycol (number average molecular weight: 3000), antimony trioxide (0.1 part). 05 parts, phosphoric acid trimethyl ester 0.03
Department, Irganox 1010 (manufactured by Ciba Geigy)
0.2 part and 0.04 part of sodium acetate were added. Then, gradually raise the temperature and reduce the pressure to 290 ° C and 0.5 mmH.
Polymerization was performed at g to obtain a polyester having an intrinsic viscosity of 0.55.

(Polyester F) Polyester A and polyester C were blended in a tumbler type mixer in a ratio of 80/20 (weight ratio).

Using each of the polyesters obtained as described above, a film was prepared as follows.

(Film 1) Polyester A is added to 150 ° C.
After vacuum-drying for 8 hours at 300 ° C., it was melt-extruded in a layer form from a T-die at 300 ° C. and was closely adhered to a cooling drum at 50 ° C. while being electrostatically applied to be cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched at 50% of the total transverse stretching ratio in the first stretching zone at 145 ° C. using a tenter type transverse stretching machine, and further in the second stretching zone at 155 ° C. in total transverse stretching ratio of 3 It was stretched so as to have a stretch ratio of 3 times. Then 10
Heat treatment at 0 ℃ for 2 seconds, then the first heat setting zone 200 ℃
Was heat-set for 5 seconds, and second heat-setting zone was set at 240 ° C. for 15 seconds. Next, while doing 5% relaxation treatment in the lateral direction, 3
The mixture was gradually cooled to room temperature over 0 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

(Film 2) Polyester F was added at 150 ° C.
After vacuum-drying for 8 hours at 300 ° C., it was melt-extruded in layers from a T-die at 300 ° C., and was electrostatically applied to a cooling drum at 40 ° C. for close contact to cool and solidify to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 130 ° C. using a roll type longitudinal stretching machine.

The resulting uniaxially stretched film was stretched in a first stretching zone at 140 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 150 ° C. in a total transverse stretching ratio of 3 It was stretched so as to have a stretch ratio of 3 times. Then 10
Heat treatment at 0 ℃ for 2 seconds, then the first heat setting zone 200 ℃
Was heat-set for 5 seconds, and second heat-setting zone was set at 240 ° C. for 15 seconds. Next, while doing 5% relaxation treatment in the lateral direction, 3
The mixture was gradually cooled to room temperature over 0 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

(Film 3) Polyester A and polyester B were respectively vacuum-dried at 150 ° C. for 8 hours, then melt-extruded at 300 ° C. by using two extruders, joined in layers in a T-die, and dried at 40 ° C. While being electrostatically applied onto the cooling drum, they were brought into close contact with each other to be cooled and solidified to obtain a laminated unstretched sheet having a two-layer structure. At this time, the extrusion rate of each extruder was adjusted so that the thickness ratio of each layer was 1: 1. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 155 ° C. in a total transverse stretching ratio of 3 It was stretched so as to have a stretch ratio of 3 times. Then 11
Heat treatment at 0 ℃ for 2 seconds, then the first heat setting zone 200 ℃
Was heat-set for 5 seconds, and second heat-setting zone was set at 240 ° C. for 15 seconds. Next, while doing 5% relaxation treatment in the lateral direction, 3
The mixture was gradually cooled to room temperature over 0 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

(Film 4) Polyester C and polyester D were respectively vacuum dried at 150 ° C. for 8 hours, and then melt-extruded at 285 ° C. by using two extruders, joined in layers in a T-die, and heated at 30 ° C. While being electrostatically applied onto the cooling drum, they were brought into close contact with each other to be cooled and solidified to obtain a laminated unstretched sheet having a two-layer structure. At this time, the extrusion rate of each extruder was adjusted so that the thickness ratio of each layer was 1: 1. This unstretched sheet was stretched 3.3 times in the machine direction at 95 ° C. using a roll-type machine.

The uniaxially stretched film thus obtained was stretched by a tenter type transverse stretching machine at 100 ° C. in the first stretching zone at 50% of the total transverse stretching ratio, and further at 115 ° C. in the second stretching zone at 3 ° in the total transverse stretching ratio. It was stretched so as to have a stretch ratio of 3 times. Then 70
Heat treatment was carried out for 2 seconds at 150 ° C., further heat setting was carried out for 5 seconds at 150 ° C. in the first heat setting zone and heat setting was carried out for 15 seconds at 230 ° C. in the second heat setting zone. Next, while performing 5% relaxation treatment in the lateral direction, 30
The mixture was gradually cooled to room temperature over a period of 2 seconds to obtain a biaxially stretched film having a thickness of 90 μm.

(Film 5) Polyester A and polyester E were respectively vacuum dried at 150 ° C. for 8 hours, melt-extruded at 300 ° C. by using three extruders, and layer-bonded in a T-die at 50 ° C. While being electrostatically applied on the cooling drum, they were brought into close contact with each other to be cooled and solidified to obtain a laminated unstretched sheet having a three-layer structure. At this time, the thickness ratio of each layer is E: A: E = 1: 3:
The extrusion rate of each extruder was adjusted so as to be 3. This unstretched sheet was stretched 3.5 times in the machine direction at 135 ° C. using a roll-type machine.

The obtained uniaxially stretched film was stretched at 50% of the total transverse stretching ratio in the first stretching zone at 145 ° C. using a tenter type transverse stretching machine, and further in the second stretching zone at 155 ° C. in total transverse stretching ratio of 3 It was stretched so as to have a stretch ratio of 6 times. Then 10
Heat treatment at 0 ℃ for 2 seconds, then the first heat setting zone 200 ℃
Was heat-set for 5 seconds, and second heat-setting zone was set at 240 ° C. for 15 seconds. Next, while doing 5% relaxation treatment in the lateral direction, 3
The mixture was gradually cooled to room temperature over 0 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

(Film 6) A biaxially stretched film having a thickness of 80 μm was produced in the same manner as in Film 1 except that polyester C was used instead of polyester A.

Table 8 shows the characteristic values of each biaxially stretched film thus obtained.

[0180]

[Table 8]

The intrinsic viscosity, the glass transition temperature (Tg) and the melting point of each of the obtained biaxially stretched polyester-only films were as follows.

Viscosity Tg Melting point Polyester A 0.58 120 ° C. 270 ° C. Polyester B 0.52 123 ° C. 265 ° C. Polyester C 0.63 76 ° C. 260 ° C. Polyester D 0.60 85 ° C. 255 ° C. Polyester E 0.52 100 ° C. 260 C. polyester F 0.60 105.degree. C. 267.degree. C. Also, since the film 3 showed a convex curl on the polyester A side, the film 4 on the polyester C side, and the film 5 showed a convex curl on the side of the thin layer made of polyester E, The following processing was performed so that the convex surface side became the photographic photosensitive layer side.

<Heat Treatment> 110 for each film
Annealing treatment was performed at 7 ° C. for 7 hours.

<Coating of Undercoat Layer> An undercoat layer was provided on both sides of each transparent support as follows.

That is, 100 parts by weight of a resin liquid for undercoat layer obtained by emulsion polymerization of the following composition, 0.2 part by weight of the following surfactant, hexamethylene-1,6-bis (ethyleneurea) 0. A coating liquid for an undercoat layer consisting of 3 parts by weight and 900 parts by weight of water was applied and dried so that a wet film thickness was 20 μm.

<Composition> 2-Hydroxyethyl methacrylate 75 parts Butyl acrylate 90 parts t-Butyl acrylate 75 parts Styrene 60 parts Sodium dodecylbenzene sulfonate 6 parts Ammonium persulfate 1 part Water 700 parts Surfactant

[0187]

Embedded image

(Preparation of Color Photosensitive Material) Sample No. 1 of Example 1 was placed on the transparent support (films 1 to 6). Photographic layers 101 and 103 were provided to prepare samples 301 to 308, which are multilayer color light-sensitive materials.

[0189]

[Table 9]

For each sample, 25 ° C., 20% relative humidity
The back side of the sample (the side opposite to the photographic constituent layer) was rubbed with a rubber roller 20 times each in a dark room of No. 1 to forcibly generate static electricity. After that, development processing was performed, and the state of generation of static marks was visually evaluated. The desilvering property was also evaluated by the method of Example 1. The results are shown below.

[0191]

[Table 10]

* Evaluation Rank A ... No occurrence at all B ... Slight occurrence but no problem C ... Slight occurrence D ... Significant occurrence As is apparent from Table 10. In addition, it can be seen that the constitution of the present invention has high static (electrostatic) fog resistance and excellent desilvering property.

[0193]

According to the present invention, firstly, a silver halide color light-sensitive material for photographing having high image quality even in enlarged print is provided, and secondly, the influence of the magnetic recording layer on the desilvering property is reduced. It was possible to provide the silver halide color light-sensitive material thus prepared, and thirdly, the silver halide color light-sensitive material excellent in resistance to electrostatic fog.

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Claims (5)

[Claims] 1. A roll-shaped silver halide color light-sensitive material having on one side on a transparent support a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer. In the above, the film width of the photosensitive material is 20 to 35 mm, and the photographing screen area is 300 to 700 mm ^2.
And a tabular colloidal silver is contained in at least one layer of the non-photosensitive layer of the light-sensitive material. 2. A transparent support having on one side thereof a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer, and transparent on the other side. A silver halide color light-sensitive material having a magnetic recording layer, characterized in that tabular colloidal silver is contained in at least one of the non-light-sensitive layers of the light-sensitive material. 3. A silver halide color light-sensitive material having a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer on one side of a transparent support, The support is annealed at a temperature not higher than the glass transition temperature of 50 to 10 before coating the photographic constituent layers.
A silver halide color light-sensitive material which is a 0 μm polyester film and contains tabular colloidal silver in at least one layer of the non-light-sensitive layer of the light-sensitive material. 4. A transparent support having on one side thereof a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer, and transparent on the other side. In a silver halide color light-sensitive material having a magnetic recording layer, the light-sensitive material has a film width of 20 to 35 mm and a photographing screen area of 300 to 700 mm ² , and the support has a glass transition temperature of not more than a glass transition temperature before coating with a photographic constituent layer. A silver halide color sensitized film which is a polyester film having a thickness of 50 to 100 μm and which is annealed in 1. and contains tabular colloidal silver in at least one layer of the non-photosensitive layer of the photographic material. material. 5. The tabular colloidal silver has an average thickness of 0.
005 to 0.03 μm, average diameter 0.01 to 0.1 μm
And the coating amount thereof is 0.02 to 0.2 g / m ² or less, and the silver halide color light-sensitive material according to any one of claims 1 to 4.