JPH07306496A - Processing method of silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a processing method of a silver halide color photosensitive material featuring high safety and environmental adaptability by charging solid processing agents substantially directly into at least one of the processing tanks of an automatic developing machine. CONSTITUTION:The projecting part of a sliding cap 334 is prevented from descending by an opening/closing regulating member 35 when a housing container 33 mounted at a housing container packing means 34 is depressed in a direction C from an initial position until the container arrives at an intermediate position. The sliding cap 334 is held stopped and, therefore, when the housing container 33 is further oscillated downward, the aperture of the outlet member 332 of the housing container 33 is gradually opened. The aperture of the outlet member 332 is fully opened when the descending of the housing container 33 arrives at a prescribed position and is stopped. The solid processing agent J in the foremost row in the housing container 33 is sent into a supplying means 35. The exchange operation of the housing container 33 is executed by generation of a residual amt. detection signal when the solid processing agents J in the housing container 33 are successively consumed until no more agents are left.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color light-sensitive material, and more particularly, a halogen having excellent processing stability even in a thinned photographic film and having high safety and environmental suitability. The present invention relates to a method for processing a silver halide color light-sensitive material (hereinafter, also referred to as "color light-sensitive material" or simply "light-sensitive material").

[0002]

2. Description of the Related Art In recent years, cameras have become smaller and simpler,
The portability has improved and the opportunity for taking pictures has increased significantly. However, further miniaturization has been desired by users, and miniaturization while maintaining high image quality has been widely studied. The so-called 135 size roll film for general use is loaded in a standard format patrone,
The current situation is an obstacle to making cameras thinner. In order to reduce the size of the cartridge, it is most effective and convenient to make the film, that is, the light-sensitive material thin, and this can be achieved by making the thickness of the support of the light-sensitive material thinner than before.

On the other hand, the standard size Patrone of 135 size is currently limited to 36 pictures. For one Patrone,
There is a desire to put more image information, and 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 Nos. 1-244446 and 3-54
551, 3-84542, U.S. Pat.Nos. 4,217,441, 4,241,1
No. 70 and No. 5,138,024 disclose a thin polyester support useful for a color light-sensitive material.

Further, thin transparent supports having excellent mechanical strength are disclosed in JP-A Nos. 50-81325, 50-109715 and 51-
16358, U.S. Pat.Nos. 5,013,820, 5,006,613, World Patent Organization 92/02584, Japanese Patent Application No. 4-139473, and 4-139474.
Polyethylene naphthalate disclosed in JP-A-6-11794 and JP-A-616797.

When a color photosensitive material was prepared using the above transparent support and a practical test was conducted, it was
It was revealed that the stability of the processing level in the laboratory was poor. The cause is not clear, but it is considered to be due to the interaction between the development-inhibiting component accumulated in the processing solution and the stirring state of the processing solution. The quality of color light-sensitive materials that general users have is largely dependent on the quality of development processing when shipped from this laboratory, and this deterioration of processing stability is fatal for laboratories that develop a large amount of light-sensitive materials. Problem.

In order to improve the processing stability, the replenishment rate of the processing solution may be sequentially adjusted to strictly control the development processing level, but the replenishment solution itself needs to be controlled, which is complicated. Furthermore, in recent years, there has been a strong demand for a development processing method that also considers safety and environmental suitability for laboratory workers.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a processing method of a silver halide color light-sensitive material which has excellent processing stability even in a thinned photographic film, and is highly safe and environmentally friendly. Is to provide.

[0009]

The objects of the present invention have been achieved by the following. That is, when a silver halide color light-sensitive material having a color photographic image forming layer on one surface side on a transparent polyester support having a glass transition temperature of 90 to 200 ° C. or less is processed by the automatic developing machine, the automatic developing machine is used. A method for processing a silver halide color light-sensitive material, characterized in that a solid processing agent is introduced substantially directly into at least one processing tank of
~ 110 (mu) m or less, having a magnetic recording layer on the other side, preferably the polyester support is composed of a naphthalene dicarboxylic acid and a homopolymerized or copolymerized polyester resin mainly composed of ethylene glycol, preferably, The polyester support is heat-treated at 50 ° C. to the glass transition temperature after the production of the support and before the completion of the silver halide color light-sensitive material, and preferably the polyester support is polyethylene naphthalate. And a mixed polyester of other polyester, and preferably the polyester support has a multi-layer structure in which a plurality of polyester resins of different materials are laminated, and more preferably a treatment tank for introducing the solid treatment agent. A method of processing a silver halide color light-sensitive material which is at least a color developing tank.

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

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

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid,
Examples thereof include 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, and among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable. Examples of the glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol,
1,4-cyclohexanedimethanol, p-xylylene alcohol, bisphenol A and the like can be mentioned.

Further, as the copolymerization component, a monofunctional or trifunctional or more polyfunctional hydroxyl group compound or an acid-containing compound may be added, if necessary. 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 curling property 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 the following ( Examples thereof include ester-forming derivatives represented by Chemical formula 1) and compounds obtained by substituting these sodiums with other metals such as potassium and lithium.

[0015]

[Chemical 1]

The copolyester having an aromatic dicarboxylic acid having a metal sulfonate group can be detected by hydrolysis of 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%. The amount of the aromatic dicarboxylic acid having a 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 copolymerization component is effective and preferable for improving curl habit. 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 thereof is usually 300 to 20,000, preferably 300 to 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 polyalkylene glycol content is less than 3% by weight, the curl after the development processing cannot be removed and the stretchability is further reduced, so that the mechanical strength required for the film cannot be obtained. On the other hand, when it exceeds 10% by weight, it becomes impossible to obtain a film having sufficient mechanical strength due to the low mechanical properties of 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 is preferably a saturated aliphatic dicarboxylic acid having 4 to 20 carbon atoms or polyethyleneoxy-ω, ω'-diacetic acid having a number average molecular weight of 500 to 5000.

Examples of the saturated aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, adipic acid, sebacic acid and the like, of which adipic acid is particularly preferable. Polyethyleneoxy-ω with a number average molecular weight of 2000-4000,
ω'-diacetic acid is particularly preferred.

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

Among the homopolymerized or copolymerized polyesters in the present invention, the preferable one is ethylene glycol 50: naphthalenedicarboxylic acid (50 to 1 in mol%).
5): Terephthalic acid (0-35), ethylene glycol (0
~ 15): Neopentyl glycol (50-35): terephthalic acid (50), ethylene glycol (40): bisphenol А (10): naphthalenedicarboxylic acid (50-10): terephthalic acid (0-40), etc. . More preferably, the homopolymerized or copolymerized polyester may be added with the aromatic dicarboxylic acid having a metal sulfonate group 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 (50 to 9).
0): Polyacrylate (50-10), Polyethylene naphthalate (60): Polyethylene terephthalate (30-1)
0): Polyacrylate (10 to 30) and the like are preferable.

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 the 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 × 10 with respect to all acid components.
^-2 mol% is preferred.

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 and the like, which are appropriately added at the polymerization stage and at any stage after the polymerization.

The transparent support in the present invention preferably contains a specific copolymerized polyester 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 preferable.

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 copolyester. If the content of the antioxidant is less than 0.01% by weight, the effect of photographic performance is poor,
When it exceeds 2% by weight, the turbidity of the copolyester increases, which may not be preferable as a transparent support. The antioxidants may be used alone or in combination of two or more.

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. It is preferable to include a dye in the. The dye to be blended for such a purpose is not particularly limited in its type, but in the film forming process of the film, a dye having excellent heat resistance is preferable, and examples thereof include anthraquinone-based chemical dyes. You can 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 selected, for example, from the group consisting of the above-mentioned copolymer polyester, or an antioxidant optionally blended with this copolymer polyester, or sodium acetate, sodium hydroxide and tetraethylammonium hydroxide. After sufficiently drying the copolyester composition containing at least one of
A sheet is melt-extruded through an extruder controlled by a temperature range of 0 to 320 ° C., a filter and a die, and the molten polymer is cooled and solidified on a rotating cooling drum to obtain an unstretched film. After that, the unstretched film is biaxially stretched in the machine direction and the transverse direction, and heat-fixed to produce the film.

The stretching condition of the film cannot be uniformly specified because it varies depending on the copolymerization composition of the copolyester, but it is longitudinally stretched within the temperature range of the glass transition temperature (Tg) to Tg + 100 ° C. of the copolyester. Magnification 2.5-6.
The draw ratio is in the range of 2.5 times to 4.0 times in the temperature range of 0 times and Tg + 5 ° C. to Tg + 50 ° C. in the transverse direction. The biaxially stretched film obtained as described above is usually heat set and cooled at 150 ° C to 240 ° C. In this case, if necessary, it may be relaxed in the longitudinal direction and / or the lateral direction.

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 the layer made of polyethylene naphthalate is the A layer and the layer made of other polyester is the B layer or the C layer, a two-layer structure composed of the A layer and the B layer may be used. , A layer / B layer / A layer,
A layer / B layer / C layer, B layer / A layer / B layer or B layer / A layer /
A three-layer structure such as a C layer may be used. Further, a structure having four or more layers is of course possible, but it is not preferable in practical use because the manufacturing equipment becomes complicated.

The thickness of the layer A is preferably 30% or more, more preferably 40 to 70% of the total thickness of the polyester film. In this case, A
The layer thickness is the thickness of the layer when there is only one layer A, and the value obtained by adding the thicknesses when there are two or more layers. The thickness of layer B or C is 5 to 60 μm,
Furthermore, 10 to 50 μm is preferable. When the thickness of each layer is within the above range, the polyester film is excellent in transparency, mechanical strength, dimensional stability, and absorbs water, and thus, is also excellent in curl recovery property.

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

When the thickness of the transparent support is set within the above range, there will be no problem in the strength and curl characteristics of the film after coating the photographic constituent layers, and the total thickness of the film should be within the above range. You can Further, the local variation in the thickness of the transparent support is within 5 μm, whereby it is possible to prevent the occurrence of coating unevenness and drying unevenness when the photographic constituent layer is applied.

Further, for the purpose of reducing the curl of the photographic support made of polyester, JP-A-51-16358 and JP-A-6-35.
The heat treatment method described in No. 118 or the like can be preferably used. 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 higher, if it is carried out after the coating of the silver halide emulsion layer, it tends to cause deterioration of the performance of the emulsion layer. Therefore, it is desirable to carry out after the support is manufactured and before the emulsion layer is coated.

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

Examples of the undercoat layer include, for example, JP-A-59-199.
No. 41, No. 59-77439, No. 59-224841 and Japanese Patent Publication No. 58-5302
The undercoat layer described in No. 9 can be mentioned as a suitable example. The undercoat layer provided on the surface of the transparent support opposite to the photographic constituent layer is also referred to as a back layer.

The magnetic recording layer in the present invention refers to JP-A-53.
-109604, Japanese Examined Patent Publication No. 57-6576, Japanese Patent Laid-Open No. 60-45248, U.S. Pat. No. 4,947,196, International Publication No. 90/04254, 91/1175.
No. 0, No. 91/11816, No. 92/08165, No. 92/08227, and the like, or a transparent magnetic layer as described in JP-A-4-124642.
No. 4,124,645 and the like may be stripe-shaped magnetic layers. Further, magnetic particles may be contained in the support.

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

In the magnetic recording layer according to the present invention, the coating amount of the ferromagnetic powder is 1 m ^{2 of the} silver halide color light-sensitive material.
The amount of iron per unit is preferably 5 g or less, preferably 2
g or less, particularly preferably 0.01 to 0.5 g.

Examples of the ferromagnetic powder include γ-Fe ₂ O ₃
Powder, Co deposited γ-Fe ₂ O ₃ powder, Co deposited Fe ₃ O ₄ powder, Co deposited F
eO _x (4/3 <x <3/2) powder, other Co-containing iron oxide,
Examples of other ferrites such as hexagonal ferrites include M-type and W-type hexagonal Ba ferrites and Sr.
Examples thereof include ferrite, lead ferrite, Ca ferrite, and solid solutions or ion substitutes thereof.

As the hexagonal ferrite magnetic powder, at least some of Fe atoms, which are the constituent elements of these uniaxially anisotropic hexagonal ferrite crystals, are selected from divalent metals and Nb, Sb and Ta. One kind of pentavalent metal and 0.05 per chemical formula
Those substituted with Sn atoms in the range of up to 0.5 are used.
The divalent metal is preferably an element such as Mn, Cu, or Mg that relatively well substitutes for Fe atoms in the ferrite. The appropriate substitution amount of the divalent metal (M ^II ) and the pentavalent metal (M ^v ) depends on the combination of M ^II and M ^v , but is preferably about 0.5 to 1.2 per chemical formula of M ^II .

The coercive force (Hc) of the ferromagnetic powder is usually 200.
~ 2,000 Oersted, preferably 300-2,000 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, with myristic acid, oleic acid and stearic acid being particularly preferable. Further, 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 silver halide photographic light-sensitive material of the present invention are improved. Butyl stearate and butyl palmitate are preferred.

The magnetic layer of the present invention may contain other lubricant.

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

As the organic solvent used in the dispersion, kneading and coating of the particles, ketones such as acetone, methyl ethyl ketone and cyclohexanone; alcohols such as propanol, butanol and isobutyl alcohol in arbitrary ratios; ethyl acetate and butyl acetate , Esters such as isopropyl acetate; ethers such as glycol dimethyl ether; tars (aromatic hydrocarbons) such as xylene; chlorinated hydrocarbons 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 No. 3,338,854A, JP-A-5959
-116926, U.S. Pat. No. 4,388,368, and Yukio Mitsuishi "Fiber and Industry", Volume 31, pp. 50-55, 1975.

In the present invention, when the magnetic particles are contained in the support, it is preferable to concentrate them 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. As shown in JP-B-30-986 and International Patent No. 91/11750, there is a method of simultaneously casting a dope containing magnetic particles and a dope not containing magnetic particles to concentrate them on one surface side of the support. It is preferable that the production is faster.

The thickness of the support is preferably 50 to 110 μm,
More preferably 60 to 100 μm, particularly preferably 70 to 90 μm
Is. When it is thinner than this, in magnetically recording information at the time of manufacturing, the accuracy of writing and reading by the magnetic head with respect to the high-speed coating speed of the photosensitive material is deteriorated, which is not preferable. On the other hand, if it is thicker than this, the suitability of the exposure / developing device as a silver photosensitive material is deteriorated.

When magnetic particles are contained in the support, the thickness of the layer in which the magnetic particles are present is preferably 2 μm or less, more preferably 1.5 μm or less, particularly preferably 1 μm or less 0.1 μm.
It is more than m. The coating amount of magnetic particles is 10 to 1000 mg / m ² , preferably 15 to 300 mg / m ² , and particularly preferably 20 to 100 mg / m ^2.
Is. In this case, iron oxide having a small amount of aluminum, calcium, or silicon doped therein is preferably used as the magnetic particles. The acicular ratio of the magnetic particles is preferably 1-7.

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. It is also effective to apply a treatment.

As the polymer forming the support, polyethylene terephthalate or polyethylene naphthalate produced by the coextrusion method is preferable. In addition, cellulose triacetate ester can also be used. In the case of polyethylene terephthalate or polyethylene naphthalate, JP-A 1-244446, 1-291248, 1-298350
No. 2, No. 2-89045, No. 2-93641, No. 2-181749, No. 2-21
It is preferable to use polyethylene terephthalate or polyethylene naphthalate having a high water content as shown in Japanese Patent Application No. 4852 and Japanese Patent Application No. 2-291135, because the dispersion stability of magnetic particles is improved.

It is preferable to add a small amount of a known dye or pigment to the support to prevent halation, irradiation and light piping.

The surface roughness is set to a certain region by adding an inorganic or organic matting agent to the dope containing the magnetic particles, or by matting the surface after forming the magnetic layer. The efficiency of writing and reading can be improved.

Physical properties of the support are adjusted by adjusting the viscosity balance of the dope containing magnetic particles and the dope not containing magnetic particles, changing the solvent composition, adjusting the surface tension, and changing the plasticizer content. Can be adjusted.

After the support is formed, the process can be simplified by coating the undercoat layer or the backing layer online.

In the present invention, in addition to recording the photographing condition information on the magnetic recording layer, it is also possible to record it together with the information on the outside of the photographing screen of the color photosensitive material.

The photographic image-forming layer in the present invention is a "photosensitive layer" which contains a silver halide photographic emulsion and is exposed to light to form an image, and a photosensitive layer which is around the photosensitive layer. A layer composed of a "non-photosensitive layer" which plays a role of protecting, separating, supporting, etc. of a layer.

Specific examples of the non-photosensitive layer include an undercoat layer, an antihalation layer, an intermediate layer, a color turbidity prevention layer, a filter layer and a protective layer, which are arranged in this order from the support side. May be Further, it may contain a non-photosensitive silver halide emulsion or a silver halide emulsion which is photosensitive but does not contribute to image formation.

The color light-sensitive material of the present invention can be a full-color photographic light-sensitive material. A full-color photographic light-sensitive material generally has a red-sensitive layer containing a cyan coupler, a green-sensitive layer containing a magenta coupler, and a blue-sensitive layer containing a yellow coupler. Each of these photosensitive layers may be a single layer or may be composed of a plurality of layers.

The stacking order of the photosensitive layers is not particularly limited,
Various stacking orders can be adopted depending on the purpose. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer can be laminated in this order from the support side, and conversely, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer can be laminated in that order from the support side. can do.

Further, the photosensitive layers having different color sensitivities may be sandwiched between two photosensitive layers having the same color sensitivities. Further, for the purpose of improving color reproducibility, in addition to the three layers of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer, a fourth or more photosensitive layer having a color sensitivity can be provided. Fourth
And a layer structure using a photosensitive layer having a color sensitivity higher than that of JP-A-61-34541, JP-A-61-201245, and JP-A-61-19
8236 and 62-160448, which can be referred to.

In this case, the fourth or more photosensitive layers having color sensitivity may be arranged at any laminating position. The fourth or more color-sensitive photosensitive layer may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the above-mentioned photosensitive layers and as the uppermost layer and the lowermost layer. These non-photosensitive layers include those disclosed in JP-A-61-43748, JP-A-59-113438 and JP-A-59-113440.
Nos. 61-20037, 61-20038, etc., may contain a coupler, a DIR compound, etc., and may contain a color mixing inhibitor as commonly used. Further, these non-photosensitive layers may be auxiliary layers such as filter layers and intermediate layers described in Research Disclosure (RD) No. 308119, page 1002, item VII-K.

Examples of the layer structure that can be adopted in the light-sensitive material of the present invention include the forward layer, the reverse layer and the unit structure described in RD No. 308119, page 1002, item VII-K.

When there are two light-sensitive layers having the same color sensitivity, these light-sensitive layers may be the same and a high-sensitivity emulsion layer and a low-sensitivity layer as described in West German Patent 923,045. It may have a two-layer structure of emulsion layers. In this case, it is usually preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between the emulsion layers. Also, JP-A-57-112751 and 62-20
No. 0350, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be arranged on the side farther from the support, and a high-sensitivity emulsion layer may be arranged on the side closer to the support. .

As a specific example, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or BH
/ BL / GL / GH / RH / RL, or BH / BL
Installation in the order of / GH / GL / RL / RH can be mentioned.

Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH
It is also possible to arrange in the order of / GL / RL. In addition,
As described in Nos. 56-25738 and 62-63936, from the side farthest from the support, the blue-sensitive layer / GL / RL / GH / R
It is also possible to arrange them in the order of H.

Further, as described in JP-B-49-15495, three photosensitive layers having different sensitivities and having the same color sensitivity can be used. These three layers are arranged with a high-sensitivity silver halide emulsion layer as an upper layer, a middle-sensitivity silver halide emulsion layer as an intermediate layer, and a low-sensitivity silver halide emulsion layer as a lower layer. In addition,
As described in JP-A-59-202464, a medium-speed silver halide emulsion layer, a high-speed silver halide emulsion layer and a low-speed silver halide emulsion layer may be arranged in this order from the side remote from the support.

When three layers having different sensitivities are formed, the order of laminating these three layers is arbitrary. For example, the order of laminating is a high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide emulsion layer. , Middle silver halide emulsion layer order,
Alternatively, a low-sensitivity silver halide emulsion layer, a medium-sensitivity silver halide emulsion layer, a high-sensitivity silver halide emulsion layer and the like can be mentioned.
Further, the number of photosensitive layers having the same color sensitivity may be four or more. Also in this case, the arrangement is arbitrary as described above.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The silver halide emulsion used in the present invention is, for example, RD No. 17643, pages 22 to 23 (December 1978) I. Emulsion production
(Emulsion preparation and types), and No.1871
6, 648, "The Physics and Chemistry of Photography" by Graphkides, published by Paul Montel (P.Glafkides, Chemic et Phisique Phot
Ographique, Paul Motel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photog
raphic Emulsion Chemistry Focal Press, 1966), "Manufacturing and Coating of Photographic Emulsions" by Zelikman et al., V.L. Zelikman et al, Making and Coating Ph
Otographic Emulsion, Focal Press, 1964) and the like.

Emulsions are disclosed in US Pat. Nos. 3,574,628 and 3,665,3.
Monodisperse emulsions described in, for example, 94 and British Patent 1,413,748 are also preferable.

The emulsion used in the light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a process include RD No. 17643 and RD No. 18716 mentioned above.
And various compounds described in No. 308119 can be used. The types and locations of the compounds described in these three RDs are listed below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, Item J 23-24 648-9 Supersensitizer 996 IV-AE, Item J 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C, XIII-C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter Dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matte Agent 1007 XVI Developer (included in light-sensitive material) Item 1011 XXB Described in U.S. Pat. Nos. 4,411,987 and 4,435,503 in order to prevent deterioration of photographic performance due to formaldehyde gas in the light-sensitive material of the present invention. Reacts with the formaldehyde, it is preferable to add a compound capable of immobilizing the photosensitive material.

The silver halide emulsion used in the present invention preferably contains silver iodobromide having an average silver iodide content of 4 to 20 mol%, and iodide having an average silver iodide content of 5 to 15 mol%. It is particularly preferable to contain silver halide. You may contain silver chloride in the range which does not impair the effect of invention.

As the silver halide emulsion, those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

The grain size of the silver halide grains may be fine grains of about 0.2 μm or less, large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

Various color couplers can be used in the color light-sensitive material of the present invention. As the yellow coupler, for example, U.S. Patents 3,933,051 and 4,022,620,
No. 4,326,024, No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 4,314,023,
Those described in JP-A-4,511,649 and European Patent 249,473A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat.
4,310,619, 4,351,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, RD No. 24220, No. 2
4230 (June 1984), JP-A-60-33552, JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Patent Nos. 4,500,630 and 4,540,654.
Nos. 4,556,630 and WO88 / 04795 are particularly preferable.

Examples of cyan couplers include known phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,228,233, 4,296,200, 2,369,929, and US Pat.
2,810,171, 2,772,162, 2,895,826, 3,77
2,002, 3,758,308, 4,334,011, 4,327,173
, West German Patent Publication 3,329,729, European Patent 121,365A,
No. 249,453A, US Pat. No. 3,446,622, and 4,333,999.
No., No. 4,775,616, No. 4,451,559, No. 4,427,767,
Those described in, for example, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are disclosed in US Pat. No. 4,163,670, Japanese Patent Publication No. 57-39.
Those described in 413, US Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368 are preferable. US patent
A coupler that corrects unnecessary absorption of a coloring dye by the fluorescent dye released at the time of coupling described in 4,744,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 which has a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,570.
Those described in Japanese Patent No. 3, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820, 4,080,211 and 4,367,28.
No. 2, 4,409,320, 4,576,910, British patent 2,102,1
No. 73 etc.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in JP-A-57-15
1944, 57-154234, 60-184248, 63-37346
Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise upon development, there are described in British Patent 2,097,140.
No. 2,131,188, JP-A-59-157638, and 59-170840.
Those described in No. 10 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427, US Pat. Nos. 4,283,472, and 4,338,393.
No. 4,310,618, multi-equivalent couplers, JP-A-60-
185950, DIR redox compound releasing coupler described in JP-A-62-24252, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox releasing redox compound, and post-breakdown multicolor described in European Patent 173,302A. RD No.1144, a coupler that releases dye
9, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in US Pat. No. 4,553,477, couplers releasing leuco dyes described in JP-A-63-75747. Etc.

Various couplers can be further used in the present invention, specific examples of which are described below in RD No. 17643 and No. 308.
119. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C-G item Magenta coupler 1001 VII-D item VII C-G item Colored coupler 1002 VII-G item VII G item DIR Coupler 1001 VII-F Item VII F Item BAR Coupler 1002 VII-F Other useful residue 1001 VII-F Item Release coupler Alkali-soluble coupler 1001 VII-E Additive used in the present invention is RD No. 308119, It can be added by the dispersion method described in XIV. The solid processing agent in the present invention means a powder processing agent, tablets, pills,
It is a solid processing agent such as granules, which is optionally subjected to moisture-proof treatment. The solid processing agent of the present invention does not include those which are regulated with transportation risk.

The powder used in the present invention refers to an aggregate of fine crystal grains. The granules referred to in the present invention are those obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm. The tablet in the present invention refers to a powder or granules compression-molded into a certain shape.

Of the above solid processing agents, tablets are preferably used because they have high replenishment accuracy and easy handling.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is mixed with a water-soluble binder. It is possible to employ any means such as forming a coating layer by spraying (Japanese Patent Laid-Open No. 4-29136, 4-85535,
4-85536, 4-85533, 4-85534, 4-172341).

A preferable tablet manufacturing method is a method in which a powdery solid processing agent is granulated and then a tableting step is performed to form the tablet. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by mixing the solid processing agent components.

The granulation method for tablet formation includes rolling granulation,
Known methods such as extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used.

Next, when compressing the obtained granulated product under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketching machine should be used. You can The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity and handleability, or from the problem of dust when used on the user side, it is a cylindrical type, so-called tablet. Is preferred.

More preferably, during granulation, the above-mentioned effects become more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a bleaching agent, a preservative and the like.

A method for producing a tablet processing agent is described in, for example, JP-A-51.
-61837, 54-155038, 52-88025, British Patents 1,2
It can be produced by a general method described in 13,808 and the like, and the granule treating agent is, for example, JP-A Nos. 2-109042 and 2-109043.
No. 3-39735 and 3-39739, etc. Further, the powder processing agent can be produced by a general method as described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861.

The solid processing agents used in the present invention are used in photographic processing agents such as color developing agents, black-and-white developing agents for reversal, bleaching agents, fixing agents, bleach-fixing agents and stabilizers. The color developer has a great effect of stabilizing photographic performance.

Further, the reason why the regulation of liquid dangerous substances can be excluded is
It is a black and white developer, a color developing agent, a bleaching agent, a bleach-fixing agent and a stabilizer.

The solid processing agent used in the present invention is also within the scope of the present invention in which only a part of the components of a certain processing agent is solidified, but preferably all the components of the processing agent are solidified. That is.

In the case of solidifying a color developing agent, all of the alkaline agent, the color developing agent and the reducing agent should be solid processing agents, and in the case of tablets, at least 3 agents or less, most preferably 1 agent should be used. Is a preferred embodiment of.

In the present invention, as the means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, JP-B-63-137783, JP-B-63-97522, JP-B-1-857 are used.
Although there is a known method such as No. 32, any method may be used as long as it has at least the function of supplying tablets to the processing tank. When the solid processing agent is granules or powder,
No. 62-81964, No. 63-84151, the gravity drop method described in Japanese Patent Laid-Open No. 1-292375, No. 63-105159, No. 63-195345
There is a screw or screw type as described in No.
It is not limited to these.

The solid processing agent may be charged in a processing tank, but preferably, it is communicated with a processing section for processing a light-sensitive material and a processing solution flows between the processing section and the processing section. It is preferable that there is a certain amount of circulating treatment liquid between the treatment unit and the dissolved components move to the treatment unit.
The term "practically directly" in the present invention includes such a form. The solid processing agent is preferably added to the temperature-controlled processing liquid.

Generally, in an automatic processor, the temperature of a processing solution is controlled by an electric heater for temperature control. A heat exchange section is provided in an auxiliary tank connected to a processing tank as a processing section, a heater is installed, and the replenishment is performed. A pump is arranged in the tank so as to feed the liquid from the processing tank in a constant circulation amount and make the temperature constant. Usually, a filter is arranged for the purpose of removing the crystalline foreign matter that is mixed into the treatment liquid or is generated by crystallization, and plays a role of removing the foreign matter.

The most preferable method is to add the solid processing agent to a place where the temperature is adjusted, such as a place communicating with the processing section such as this auxiliary tank. This is because the insoluble component in the supplied processing agent is blocked from the processing section by the filter section, and the solid content can be prevented from flowing into the processing section and adhering to the photosensitive material.

Further, when the processing agent input section is provided in the processing tank together with the processing section, it is preferable to devise a shield or the like so that the insoluble component does not come into direct contact with the film or the like.

According to the present invention, the solid processing agent is put into the processing tank, so that a tank for storing the replenishing liquid is not required, and the automatic developing machine becomes compact. Further, when the circulating means is provided, the solubility of the solid processing agent becomes very good.

FIG. 1 shows an example of a cross-sectional view of a processing agent charging section and a processing agent supply means of a color developing tank which is a processing tank of an automatic developing machine used in the present invention. The bleach-fixing tank, the stabilizing tank, and the like have the same structure as the color developing tank.
As described below. It should be noted that, in the drawing, a transporting means for transporting the photosensitive material and the like are omitted in order to make the configuration easy to understand.
Further, in this example, the case where a tablet is used as the solid processing agent will be described.

The processing bath 1 for processing the light-sensitive material comprises a solid processing agent charging section 20 for supplying a solid processing agent (tablet) J integrally provided on the outside of a partition wall forming the processing tank 1, and a constant temperature bath 2.
Have. The processing bath 1 and the constant temperature bath 2 are partitioned by a partition wall 21A having a communication window 21 formed therein so that the processing liquid can flow. Further, since the solid processing agent injection section 20 provided above the constant temperature tank 2 is provided with the enclosure 25 for receiving the solid processing agent J, the solid processing agent J does not move to the processing tank 1 in a solid state. It should be noted that the enclosure 25 has a net-like or filter-like shape that allows the treatment liquid to pass through, but does not allow the solid treatment agent J to pass until it is completely dissolved.

The tubular filter 22 is provided below the constant temperature bath 2 so as to be replaceable, and has a function of removing insoluble matter in the treatment liquid, such as paper waste. The inside of the filter 22 communicates with the suction side of a circulation pump 24 (circulation means) via a circulation pipe 23 that penetrates the lower wall of the thermostatic chamber 2.

The circulation system is composed of the circulation pipe 23 forming the liquid circulation passage, the circulation pump 24, the processing tank 1 and the like. The other end of the circulation pipe 23, which communicates with the discharge side of the circulation pump 24, penetrates the lower wall of the processing tank 1 and communicates with the processing tank 1. With such a configuration, the circulation pump
When 24 operates, the treatment liquid is sucked from the constant temperature bath 2 and discharged to the treatment bath 1, the treatment liquid mixes with the treatment liquid in the treatment bath 1, and the circulation into the constant temperature bath 2 is repeated. The circulation direction of the processing liquid is not limited to the direction shown in FIG. 1 and may be the opposite direction.

The waste liquid pipe 11 is for overflowing the processing liquid in the processing tank 1. The waste liquid pipe 11 keeps the liquid surface level constant, and the components brought into the photosensitive material from other processing tanks and the photosensitive material. It helps prevent the build-up of leaching ingredients from the material and prevent them from increasing.

The rod-shaped heater 26 is arranged so as to penetrate the upper wall of the constant temperature bath 2 and be immersed in the treatment liquid in the constant temperature bath 2. The heater 26 heats the treatment liquid in the constant temperature bath 2 and the treatment bath 1. In other words, the treatment liquid in the treatment bath 1 is kept in a temperature range suitable for the treatment (for example, 20 to 55 ° C.). Temperature adjusting means.

The processing amount information detecting means 31 may be provided at the entrance of the automatic developing machine and used for detecting the processing amount of the photosensitive material to be processed. This processing amount information detecting means 31
Has a plurality of detection members arranged in the left-right direction, and functions as an element for detecting the width of the photosensitive material and for counting the detected time. Since the conveying speed of the photosensitive material is mechanically preset, the processing area of the photosensitive material can be calculated from the width information and the time information. The processing amount information detecting means 31 may be any one capable of detecting the width and the conveyance time of the photosensitive material such as an infrared sensor, a micro switch, an ultrasonic sensor. Further, it may be one that can indirectly detect the processed area of the photosensitive material, for example, one that detects the number of processed photosensitive materials having a predetermined area. Further, the timing of detection may be before processing, after processing, or while being immersed in the processing liquid (in such a case, a position where the processing amount information detecting means 31 is provided can be detected after processing). Alternatively, the position can be detected during the processing as appropriate). Further, it is not necessary to provide the processing amount information detecting means 31 for each processing tank, and it is preferable to provide one processing amount information detecting means 31 for one automatic developing machine. Reference numeral 32 is a processing amount supply control means for receiving the signal from the processing amount information detecting means 31 and controlling the processing amount supply of the processing agent.

The solid processing agent replenishing device 30 is set above the processing tank of the photosensitive material processing device for processing the exposed photosensitive material, and contains a container 33, a container loading means 34, a supplying means 35,
It is composed of drive means 36 and is sealed by the inside of the upper cover 301. The upper cover 301 includes a main body 101 for accommodating the processing bath 1 and the constant temperature bath 2 and a support shaft 3 at the back of the main body.
The upper cover 301 is swingably connected by 02.
Can be inspected for the solid processing agent replenishing device 30 and the filter 22 can be replaced by lifting the operator in the direction of the one-dot chain line A in the figure to open the front and upper surfaces of the operator.

Further, a skylight 303 is swingably coupled to a part of the upper surface of the upper cover 301, and the skylight 303 is opened in the direction of the alternate long and short dash line B in the drawing to mount and replace the storage container 33. I do.

Inside the main body 101 of the photosensitive material processing apparatus, a replenishing water supply means 40 is installed near the constant temperature bath 2. The supplementary water supply means 40 comprises a supplementary water tank 41, a bellows pump 42, a water suction pipe 43, and a water supply pipe 44. The replenishment water W contained in the replenishment water tank 41 is sucked through the suction pipe 43 by the suction action of the bellows pump 42, and is continuously supplied through the water supply pipe 44 to above the treatment liquid level in the constant temperature bath 2. .

The drive motor of the bellows pump 42 is driven and rotated by timing control by the replenishment water supply control means 45 to intermittently replenish.

FIG. 2 shows a storage container 33 and a storage container loading means 34.
FIG. 7 is a side sectional view for explaining the operation of the supply means 35 and the drive means 36.

The fixed frame 341 of the storage container loading means 34, the housing member 351 of the supply means 35, and the drive means 36 are the main body 1
It is fixed at the top of 01.

The supply means 35 is rotatably arranged on the inner peripheral surface of the housing member 351 and the housing member 351, and receives a fixed amount of the solid processing agent J in the storage container 33 from the inlet portion 351A and the outlet portion 351B. It is composed of a rotatable processing agent receiving member (rotor) 351 having a pocket portion 352A to be moved to and a shutter member 353 capable of opening and closing the outlet portion 352B.

An opening / closing restriction member for restricting the opening / closing of the slide lid is provided above the entrance of the housing member 351 of the supply means 35.
355 is fixed. That is, when the storage container 33 mounted on the storage container loading means 34 is pushed down from the initial position (dotted line in the drawing) in the direction C in the drawing and reaches the intermediate position (dotted line in the drawing), the protrusion of the slide lid 334 causes the opening / closing restriction. The member 35 prevents the descent. When the storage container 33 is further swung downward, the slide lid 334 remains stopped, so that the opening of the outlet member 332 of the storage container 33 is gradually opened. When the lowering of the storage container 33 reaches a predetermined position and is stopped, the opening of the outlet member 332 is fully opened, and the solid processing agent J in the front row in the storage container 33 is fed into the supply means 35. The solid line in the drawing shows this fully opened state.

Next, when the solid processing agent J in the storage container 33 is sequentially consumed and becomes empty, the storage container 33 is replaced by the generation of the remaining amount detection signal. That is, when the storage container 33 is retracted rearward, the storage container 33 and the container holding member 343 rotate clockwise and the left end portion thereof rises. In the first half of this climbing process,
Since the opening / closing restriction member 355 retains the slide lid 334 and raises only the main body portion including the outlet member 332 of the storage container 33 and the container main body 331, the opening portion of the outlet member 332 is closed by the slide lid 334. Become. Further, in the latter half of the process of raising the storage container 33, the opening state is kept closed and is returned to the initial state which is the top dead center.

The container body 341 of the storage container 33, the outlet member 3
The cap member 333 and the cap member 333 are made by synthetic resin molding, integrally molding, or separately molding and then bonding. In the state where the slide lid 334 is attached to the discharge opening of the storage container and closed, the inside is shut off from the outside air and is kept in a moisture-proof state. That is, when the container housing 33 containing the solid processing agent J is removed from the solid processing agent replenishing device 30, the slide lid 334 is automatically closed as described above. It is cut off from the outside air.

[0135]

EXAMPLES Examples of the present invention will be shown below, but the invention is not limited thereto. In addition, "part" in an Example represents a "weight part."

Example 1 <Manufacture of Support> Polyesters A to
Polyester F was prepared.

(Polyester A) 0.1 part of calcium acetate hydrate as an ester exchange catalyst was added to 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 60 parts of ethylene glycol, and transesterification reaction was carried out according to a conventional method. Antimony trioxide (0.05 parts) and phosphoric acid trimethyl ester (0.03 parts) were added to the obtained product. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was performed at 290 ° C. and 0.5 mmHg to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60. (Polyester B) 0.1 part of calcium acetate hydrate as an ester exchange catalyst was added to 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 60 parts of ethylene glycol, and transesterification reaction was carried out according to a conventional method. The resulting product has 5-
5 parts of ethylene glycol solution of sodium sulfo-di (β-hydroxyethyl) isophthalic acid (35 wt% concentration), antimony trioxide 0.05 part, phosphoric acid trimethyl ester 0.03 part,
Irganox 1010 (manufactured by Ciba Geigy) and 0.2 part of sodium acetate and 0.04 part of sodium acetate were added. Next, gradually raise the temperature and reduce the pressure, and polymerize at 290 ° C and 0.5 mmHg to obtain an intrinsic viscosity.
A polyester of 0.55 was obtained.

(Polyester C) Dimethyl terephthalate
To 100 parts of ethylene glycol and 65 parts of ethylene glycol, 0.05 part of magnesium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out according to a conventional method. Antimony trioxide (0.05 parts) and phosphoric acid trimethyl ester (0.03 parts) were added to the obtained product. Next, gradually raise the temperature and reduce the pressure to 280 ° C.
Polymerization was performed at 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.65.

(Polyester D) Dimethyl terephthalate
To 100 parts of ethylene glycol and 65 parts of ethylene glycol, 0.05 part of magnesium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out according to a conventional method. The resulting product has 5-
5 parts of an ethylene glycol solution of sodium sulfo-di (β-hydroxyethyl) isophthalic acid (35 wt% concentration), 0.05 parts of antimony trioxide, trimethyl phosphate of 0.
03 parts, Irganox 1010 (manufactured by Ciba Geigy) 0.
2 parts and 0.04 part sodium acetate were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.62.

(Polyester E) 0.05 part of magnesium acetate hydrate as an ester exchange catalyst was added to 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 60 parts of ethylene glycol, and transesterification reaction was carried out 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) 18 parts, polyethylene glycol (number average molecular weight:
3000) 6 parts, antimony trioxide 0.05 part, phosphoric acid trimethyl ester 0.03 part, Irganox 1010 (manufactured by Ciba Geigy) 0.2 part and sodium acetate 0.04 part 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 F) Polyester A and polyester C were blended in a tumbler type mixer at 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 was vacuum dried at 150 ° C. for 8 hours, melt-extruded in layers from a T-die at 300 ° C., and then adhered to a cooling drum at 50 ° C. while electrostatically applied to cool and solidify. An unstretched sheet was obtained. This unstretched sheet was stretched in the longitudinal direction at 135 ° C using a roll-type longitudinal stretching machine.
It was stretched twice.

The uniaxially stretched film thus obtained 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, it was heat-treated at 100 ° C. for 2 seconds, further heat-set at first heat-setting zone 200 ° C. for 5 seconds, and second heat-setting zone 240 ° C. for 15 seconds. Next, while being relaxed in the transverse direction by 5%, the mixture was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

(Film 2) Polyester F was vacuum dried at 150 ° C. for 8 hours, melt-extruded in layers from a T-die at 300 ° C., and adhered to a cooling drum at 40 ° C. while electrostatically applied to cool and solidify. An unstretched sheet was obtained. This unstretched sheet was stretched in the longitudinal direction at 130 ° C using a roll-type longitudinal stretching machine.
It was stretched twice.

The uniaxially stretched film thus obtained 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 3.3. It was stretched so as to be doubled. Then, it was heat-treated at 100 ° C. for 2 seconds, further heat-set at first heat-setting zone 200 ° C. for 5 seconds, and second heat-setting zone at 240 ° C. for 15 seconds. Next, while being relaxed in the transverse direction by 5%, the mixture was gradually cooled to room temperature over 30 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, melt-extruded at 300 ° C. by using two extruders, joined in layers in a T-die, and then 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 machine direction at 135 ° C. using a roll-type machine.

The uniaxially stretched film thus obtained 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 then at a second stretching zone at 155 ° C. in a total transverse stretching ratio of 3.3. It was stretched so as to be doubled. Then, it was heat-treated at 110 ° C. for 2 seconds, further heat-set at first heat-setting zone 200 ° C. for 5 seconds, and second heat-setting zone 240 ° C. for 15 seconds. Next, while being relaxed in the transverse direction by 5%, the mixture was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 80 μm. (Film 4) Polyester C and polyester D respectively
After vacuum drying at 150 ℃ for 8 hours, use 2 extruders to
It was melt extruded at 85 ° C., joined in layers in a T-die, and adhered to a cooling drum at 30 ° C. while being electrostatically applied to cool and solidify 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 using a roll-type longitudinal stretching machine.
It was stretched 3.3 times in the machine direction at 0 ° C.

The obtained uniaxially stretched film was stretched in a first stretching zone at 100 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and then at a second stretching zone at 115 ° C. in a total transverse stretching ratio of 3.3. It was stretched so as to be doubled. Then, it was heat-treated at 70 ° C. for 2 seconds, further heat-set at the first heat-setting zone 150 ° C. for 5 seconds, and second-heat setting zone at 230 ° C. for 15 seconds. Next, while being relaxed in the transverse direction by 5%, it was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 90 μm. (Film 5) Polyester A and polyester E respectively
After vacuum drying at 150 ° C for 8 hours, use 3 extruders for 3
Melt extruded at 00 ° C, joined in layers in a T-die, adhered to a cooling drum at 50 ° C while being electrostatically applied to cool and solidify, and a laminated unstretched sheet with a three-layer structure of polyester E: A: E Got At this time, the thickness ratio of each layer is E: A: E = 1: 3: 3.
The extrusion rate of each extruder was adjusted so that This unstretched sheet was stretched in the longitudinal direction at 135 ° C using a roll-type longitudinal stretching machine at 3.5
It was stretched twice.

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 3.6. It was stretched so as to be doubled. Then, it was heat-treated at 100 ° C. for 2 seconds, further heat-set at first heat-setting zone 200 ° C. for 5 seconds, and second heat-setting zone at 240 ° C. for 15 seconds. Next, while being relaxed in the transverse direction by 5%, the mixture was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 80 μm. (Film 6) The thickness is the same as in Film 1 except that polyester C is used instead of polyester A.
An 80 μm biaxially stretched film was prepared.

Table 5 shows the characteristic values of each biaxially stretched film thus obtained.

[0152]

[Table 1]

When the intrinsic viscosity, glass transition temperature (Tg) and melting point of each polyester were measured, they were as follows.

[0154] However, since the film 3 showed a curl on the polyester A side, the film 4 on the polyester C side, and the film 5 on the thin layer side of the polyester E, the convex side was the photographic photosensitive layer side. After that, the subsequent processing was performed.

<Coating of Undercoat Layer> An undercoat layer was provided on both surfaces 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 (ethylene urea) 0.3 parts by weight,
An undercoat layer coating liquid consisting of 900 parts by weight of water was applied and dried to a wet film thickness of 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

[0158]

[Chemical 2]

Furthermore, 8 W / (m ² · min) on the undercoat layer
Corona discharge was applied, and the magnetic recording layer coating liquid containing the following components was applied so as to have a dry film thickness of 2 μm.

However, the coating solution was prepared by mixing the following components together with a dissolver and then dispersing with a sand mill to obtain a dispersion.

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 (Major axis 0.2 μm, Minor axis 0.02 μm, Hc = 650 Oersted) 5 parts by weight Furthermore, the following wax layer is provided on the magnetic recording layer in an amount of 10 cc /
It was applied so as to be m ² .

Carnauba wax 1 g Toluene 700 cc Methyl ethyl ketone 300 cc Further, 25 W / on the undercoat layer on the side opposite to the magnetic recording layer.
A corona discharge of (m ² · min) was applied to successively form the following photographic constituent layers to prepare a multilayer color light-sensitive material.

Original (Preparation of Color Photosensitive Material) The transparent support (film 1)
.About.6), each layer having the composition as shown below was provided thereon to prepare samples 101 to 106 which are multilayer color light-sensitive materials.

(Composition of photographic image forming layer) The coating amount of silver halide and colloidal silver is g in terms of metallic silver.
/ M ² units, for couplers, additives and magenta, the amounts added in g / m ² units, and for sensitizing dyes, the moles per mole of silver halide in the same layer. It is shown by the number.

First layer: Antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.20 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm , Silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-2) 0.020 High boiling solvent ( Oil-1) 0.53 Gelatin 1.30 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 m %) 0.62 Silver iodobromide emulsion (average grain size 0.38 .mu.m, a silver iodide content of 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 -4 Sensitizing dye (SD-2) 1.2 × 10 - ⁴ Sensitizing dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) ) 0.030 DIR compound (D-2) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer: high sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) ) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored Cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 6th layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Zera Chin 0.80 7th layer: Low sensitivity green sensitive layer Silver iodobromide emulsion (Em-103) 0.80 Magenta coupler (M-1) 0.41 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.33 Gelatin 1.95 Eighth layer: Medium sensitivity green sensitive layer Silver iodobromide emulsion (Em-102) 0.87 Magenta coupler (MA) 0.12 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-) 3) 0.002 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 9th layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion (Em-101) 1.27 Magenta coupler (MA) 0.10 Colored magenta coupler (CM-1) 0.012 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 10th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-1) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent Medium (Oil-2) 0.19 Gelatin 1.10 11th layer: Intermediate layer Formalin scavenger (HS-2) 0.20 Gelatin 0.60 12th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, containing silver iodide) Rate 8.0 mol%) 0.22 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.03 sensitizing dye (SD-4) 4.2 × 10 ^-4 sensitizing dye (SD-5) 6.8 × 10 ^-5 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 13th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.30 Sensitizing dye (SD-4) 1.6 × 10 ^-4 Sensitizing dye (SD-6) 7.2 × 10 ^-5 Yellow coupler (Y-) 0.10 DIR compound (D- 1) 0.010 High boiling solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8. 0 mol%) 0.85 Sensitizing dye (SD-4) 7.3 × 10 ^-5 Sensitizing dye (SD-6) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 Fifteenth layer: First protective layer Silver iodobromide (average particle size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.26 UV absorber (UV-2) 0.13 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Formalin scavenger (HS-3) 0.10 Gelatin 1.31 16th layer: 2nd protective layer Alkali-soluble matting agent (PM-1, Average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 The above-mentioned light-sensitive material further comprises compounds SU-1 and SU-.
2, SU-3, SU-4, viscosity modifier, hardener H-1,
H-2, stabilizer ST-1, antifoggant AF-1, AF
-2 (weight-average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2, AI-3 and compound D
I-1 (9.4 mg / m ² ) is contained.

The structures of the compounds added to the respective layers of the above light-sensitive material are shown below.

SU-1: Dioctyl sulfosuccinate / sodium SU-2: Sodium tri-i-purpyrunaphthalene sulfonate SU-3: N-perfluorooctylsulfonyl-N-purpyruglycine / sodium SU-4: Trimethyl・ 3-Octylsulfonamidopropylammonium bromide H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium H-2: di (vinylsulfonylmethyl) ether ST-1: 4-hydroxy-6-methyl -1,3,3a, 7-Tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole AF-2: Poly-N-vinylpyrrolidone Oil-1: Dioctylphthalate Oil-2: Tricresylphosphate Oil- 3: Dibutyl phthalate HS-2: 4-Ureidohydantoin HS-3: Hydantoin

[0168]

[Chemical 3]

[0169]

[Chemical 4]

[0170]

[Chemical 5]

[0171]

[Chemical 6]

[0172]

[Chemical 7]

[0173]

[Chemical 8]

[0174]

[Chemical 9]

[0175]

[Chemical 10]

Samples 101 to 106 were each made into a standard 135
After cutting to size 24 shots standard, after exposing the test pattern (pattern that statistically processed the exposure level and color balance of the scene shot by general users and averaged),
The development processes A and B described later are performed for each of 6 series (A _{1 to} A ₆ , B ₁
~ B ₆ ) Prepared and subjected to the same running treatment as the method generally used in a developing laboratory.

Experiment No. Development Treatment Sample No. Film No. Polyester Type 1 A ₁ 101 1 (A) 2 A ₂ 102 2 (F) 3 A ₃ 103 3 (Layer of A and B) 4 A ₄ 104 4 ( C and D) 5 A ₅ 105 5 (A and E) 6 A ₆ 106 6 (C) 7 B ₁ 101 1 (A) 8 B ₂ 102 2 (F) 9 B ₃ 103 3 (A and B layer) 10 B ₄ 104 4 (C and D layer) 11 B ₅ 105 5 (A and E layer) 12 B ₆ 106 6 (C) (Development processing A) Processing content Processing time Processing temperature (° C) Replenishment amount (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 Stationary 6 minutes 30 seconds 38 ± 2.0 830 Water washing 3 minutes 15 Second 20 ± 10 200 Stability 1 minute 30 seconds 38 ± 5.0 830 Dry 2 minutes 55 ± 5.0-Replenishment amount is the value per 1 m ² of 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 the 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 with ammonia water.
Adjusted to 6.0.

<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 6.0 was adjusted using acetic acid.

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

<Color development replenisher> Water 800cc Potassium carbonate 35g Sodium hydrogen carbonate 3g Potassium sulfite 5g Sodium bromide 0.4g Hydroxylamine sulfate 3.1g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxy Ethyl) aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter, and the pH was adjusted to 10.18 with potassium hydroxide or 20% sulfuric acid.

<Bleach replenisher> Water 700 cc 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Ammonia water or glacial acetic acid is used to adjust to pH 4.0 After adjustment, water was added to make 1 liter.

<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 using aqueous ammonia or glacial acetic acid, water was added to make 1 liter.

<Stable Replenisher> Same as the stabilizer.

The sensitivity values of the red photosensitive layer at 1/2 rotation and 1 rotation with respect to the start of running were calculated as relative values with 100 at the start.

Next, the development processing B with the following solid processing agent was prepared in the same manner.

A color negative film processing tablet used in the present invention was prepared according to the following procedure.

(Color Development Replenishing Tablet for Color Negative) Operation (1) Potassium carbonate 3750.0 g, sodium sulfite 580.0 g, diethylenetriaminepentaacetic acid 5 sodium 240.0 g, sodium p-toluenesulfonate 500.0 g and bis (2-sulfoethyl) hydroxyl 500.0 g of amine disodium is ground in a commercial Van Dam mill to an average particle size of 10 μm. After granulating 500.0 g of PEG # 600 (manufactured by Tokyo Kasei) and 800.0 g of mannitol into this fine powder by adding 160 cc of water for about 7 minutes at room temperature in a commercially available stirring granulator,
The granulated product is dried at 70 ° C. for 120 minutes using a fluidized bed dryer to almost completely remove the water content of the granulated product.

Operation (2) 360.0 g of hydroxylamine sulfate and 40.0 g of potassium bromide
And disodium pyrocatechol-3,5-disulfonate 20.
After crushing 0 g in the same manner as in the operation (1), 20.0 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) is added, mixed and granulated. The amount of water added is 3.5 cc, and after granulation, the granulated product is dried for 60 minutes to remove water almost completely.

Operation (3) 650.0 g of the developing agent CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] 650.0 g was pulverized in the same manner as in the operation (1) and then at room temperature. At about 7 minutes, the granulated product is dried almost completely to remove water.

Operation (4) The granules prepared in the above operations (1) to (3) were mixed at room temperature for 10 minutes using a commercially available cross rotary type mixer, and 40.0 g of sodium N-myristoylalanine was added. ,
Mix for 3 minutes. The mixed granules thus obtained are
Continuous tableting was carried out using a rotary tableting machine (Kikusui Seisakusho: Clean Press Collect H18) to obtain 600 color developing film supplementing tablets having a diameter of 30 mm and a weight of 12.0 g for color negative film.

(Bleach Replenishing Tablet for Color Negative) Operation (5) 40 g of 1,3-propanediamine, ferric ammonium acetate 1
1900 g of hydrosalt, 95.0 g of 1,3-propanediaminetetraacetic acid, 860.0 g of potassium bromide, 984.0 g of succinic acid and 401.0 g of disodium succinate hexahydrate were crushed in the same manner as in operation (1), and demolition MS (Kao) 30.0 g and Mannite 15.0 g are added and mixed, and the amount of water added is adjusted to 90 cc to granulate. After the granulation, the granulated product is dried at 60 ° C. for 120 minutes to almost completely remove the water content of the granulated product.

Operation (6) β-Cyclodextrin 5 was added to the granules prepared in operation (5).
Add 0.0 g and mix for 10 minutes as in step (3), then N-
Add 95.0 g of sodium lauroyl sarcosine and mix for 3 minutes. Next, the mixture was continuously tableted in the same manner as in the operation (4) to prepare 400 bleach replenishing tablets for color negative having a diameter of 30 mm and a weight of 11.0 g.

(Fixing Replenishing Tablet for Color Negative) Operation (7) Ammonium thiosulfate 2500.0 g, sodium sulfite 180.
0 g, potassium carbonate 20.0 g and ethylenediaminetetraacetic acid disodium 20.0 g are pulverized in the same manner as in the operation (1), and pine flow (Matsuya Chemical Co., Ltd.) 65 g is added and mixed and granulated. The amount of water added is 50 cc, and after granulation, the granules are dried for 120 minutes to almost completely remove water.

Operation (8) The granules prepared in operation (7) and 14.0 g of N-lauroyl sarcosine sodium are mixed for 3 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho at a filling amount of 10.0 g per tablet to prepare 250 replenishing fixing tablets for color negative.

(Stable Replenishing Tablet for Color Negative) Operation (9) m-Hydroxybenzaldehyde 1500.0 g, Megafac
F116 (Dainippon Ink and Chemicals) 50.0 g, ethylenediaminetetraacetic acid disodium 200.0 g and lithium hydroxide monohydrate 1
60.0 g is crushed in the same manner as in the operation (1), 100.0 g of pine flow (manufactured by Matsutani Chemical Co., Ltd.) is added, mixed and granulated. The amount of water added was 80 cc, and after granulation, the granulated product was dried at 50 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (10) The granules prepared in operation (9) were continuously tableted in the same room as in operation (1) in a room where the humidity was adjusted to 25 ° C. and 40% RH or less.
200 stable replenishment tablets for color negative having a size of 9.0 mm and a weight of 9.0 g were prepared.

(Development Processing B) Next, a method of processing a photosensitive material using the automatic processor according to the present invention will be described below.

Konica Color Negative Film Processor CL
-The tablet processing function, liquid level detection function, hot water supply function, etc. were installed on the KP-50QA by modification, and the following treatment experiments were conducted. The standard processing conditions are shown below.

Treatment process Temperature Time Color development 38 ± 0.3 ℃ 3 minutes 15 seconds Bleach 38 ± 1.0 ℃ 45 seconds Fixing -1 38 ± 1.0 ℃ 45 seconds Fixing-2 38 ± 1.0 ℃ 45 seconds Stability -1 38 ± 3.0 ℃ 20 seconds Stable-2 38 ± 3.0 ℃ 20 seconds Stable-3 38 ± 3.0 ℃ 20 seconds Dry 60 ℃ 60 seconds Stabilizer is replenished in the 3rd tank (Stable-3), and the second
The second tank (fixing-2) is replenished with the fixing agent in the first tank (fixing-1), and the overflow liquid flows into the first tank (fixing-1). .

Each processing solution was prepared according to the following formulation, and the temperature was adjusted.

<< Color development tank liquid >> (per liter) Potassium carbonate 30.0 g Potassium bicarbonate 4.2 g Sodium sulfite 4.5 g Diethylenetriaminepentaacetic acid 5 sodium 2.6 g Polyethylene glycol # 6000 (manufactured by Tokyo Kasei) 5.0 g p-toluenesulfonic acid Sodium 3.0g Mannitol 3.0g Hydroxylamine sulfate 4.0g Potassium bromide 1.7g Potassium iodide 4mg Pyrocatechol-3,5-disodium disodium salt 0.2g Pine flow (Matsuya Chemical Co., Ltd.) 0.32g CD-4 [4-amino -3-Methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] 5.0 g N-myristoylalanine sodium 0.3 g Sulfuric acid or potassium hydroxide is used to adjust the pH to 10.0 ± 0.05.

Bleaching liquid (per liter) 1,3-Propanediaminetetraacetic acid Ferric ammonium monohydrate 140.0 g 1,3-Propanediaminetetraacetic acid 6.7 g Potassium bromide 60.0 g Succinic acid 70.0 g Succinic acid Disodium hexahydrate 28.1 g Mannitol 14.0 g Demol MS (manufactured by Kao) 2.1 g β-Cyclodextrin 3.5 g N-lauroyl sarcosine sodium 7.2 g Potassium carbonate and pH = 4.35 ± 0.5.

<Fixer> (per liter) Ammonium thiosulfate 225.0 g Sodium thiosulfate 25.0 g Sodium sulfite 18.0 g Ethylenediaminetetraacetic acid disodium 3.5 g Pine flow (Matsuya Chemical Co., Ltd.) 10.0 g N-lauroyl sarcosine sodium 1.5 g Potassium carbonate PH = 7.0 ± 0.5.

<< Stabilizer >> (per liter) m-Hydroxybenzaldehyde 1.5 g Megafac F116 (Dainippon Ink and Chemicals) 0.05 g Lithium hydroxide monohydrate 0.16 g Ethylenediaminetetraacetic acid disodium 0.2 g Pine flow (Matsutani Chemical (Manufactured) 0.1 g potassium hydroxide and pH = 8.5 ± 0.5.

While controlling the temperature of each processing tank, 20 tablets for each supplement were set in the supplement tablet feeder. These 135 tablets of replenishing tablets are replenished in the processing tank according to the number of processed films when a 135 size 24 film is processed. Color development replenishment tablet is 1 for every 7.5 films processed
One bleach replenishment tablet is placed in every 5 films, and one fixing replenishment tablet is placed in each film. At the same time, each time 2 replenishment hot water is processed from the hot water supply device, it is transferred to the color developing tank. 40.0cc, bleaching tank 10.0cc, fixing tank 6
It was set to supply 0.0cc and 70cc to the stabilizing tank.

The results are shown in Table 2.

[0210]

[Table 2]

In the processing method of the present invention, it is clear that the sensitivity fluctuation during running is small, that is, the processing stability is excellent.

Example 2 Samples 201 to 103 and 105 in Example 1 prepared in the same manner except that the support is heat-treated at 70 ° C. for 2 hours before coating the photographic image forming layer. 203 and 205
When treated in the same manner as in Example 1, curling hardly occurred and the treatment stability was further excellent.

[0213]

According to the present invention, it is possible to provide a method of processing a silver halide color light-sensitive material which has excellent processing stability even when a thin support is used and which is highly safe and environmentally friendly.

[Brief description of drawings]

FIG. 1 is a sectional view of an automatic processor according to the present invention.

FIG. 2 is a sectional view of a container filling means and a supply means.

[Explanation of symbols]

 1 Processing Layer 2 Constant Temperature Layer 20 Solid Processing Agent Injecting Unit 30 Solid Processing Agent Filling Device 31 Processing Quantity Information Detecting Device 32 Solid Processing Agent Supply Controlling Device 33 Storage Container (Cartridge) 34 Storage Container Filling Device 35 Supplying Device 40 Replenishing Water Supplying Device 41 Replenishment water tank 42 Bellows pump 43 Water supply pipe 44 Water supply pipe 45 Replenishment water supply control means J Tablet type solid processing agent W Replenishment water

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 27, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0165

[Correction method] Change

[Correction content]

First layer: Antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.20 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm , Silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-2) 0.020 High boiling solvent ( Oil-1) 0.53 Gelatin 1.30 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 m %) 0.62 Silver iodobromide emulsion (average grain size 0.38 .mu.m, a silver iodide content of 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 -4 Sensitizing dye (SD-2) 1.2 × 10 - ⁴ Sensitizing dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) ) 0.030 DIR compound (D-2) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer: high sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) ) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored Cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 6th layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Zera Chin 0.80 7th layer: low sensitivity green sensitive layer Silver iodobromide emulsion ( average grain size 0.27 μm, silver iodide content 2.0 mol% ) 0.80 Sensitizing dye (SD-7) 7.4 × 10 ⁻⁵ Sensitizing dye ( SD-8) 6.6 × 10 ^-4 Magenta coupler (M- B ) 0.41 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.33 Gelatin 1.95 Eighth layer: Medium sensitivity green-sensitive layer Silver iodobromide Emulsion ( average grain size 0.52 μm, silver iodide content 8.0 mol% ) 0.87 Sensitizing dye (SD-9) 2.4 × 10 ^-4 Sensitizing dye (SD-10) 2.4 × 10 ^-4 Magenta coupler ( ^MA ) ) 0.12 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 9th layer: High sensitivity green sensitive layer Iodobromide Silver emulsion ( average grain size 1.00 μm, silver iodide content 8.0 mol% ) 1.27 Sensitizing dye (SD-9) 7.1 × 10 ^-5 Sensitizing dye (SD-10) 7.1 × 10 ^-5 Sensitizing dye (SD-11) 7.1 × 10 ^-5 Magenta coupler (MA) 0.10 Colored magenta coupler (CM-1) 0.012 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 10th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-1) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer: Intermediate layer Formalin scavenger (HS-2) 0.20 Gelatin 0.60 Layer 12: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.22 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.03 Sensitizing dye (SD-4) 4.2 × 10 ^-4 Sensitizing dye (SD-5) 6.8 × 10 ^-5 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 13th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.30 Sensitizing dye (SD-4) 1.6 × 10 ^-4 Sensitizing dye (SD-6) 7.2 × 10 ^-5 Yellow coupler (Y- 1 ) 0.10 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, containing silver iodide) Ratio 8.0 mol%) 0.85 Sensitizing dye (SD-4) 7.3 × 10 ^-5 Sensitizing dye (SD-6) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 15th layer: 1st protective layer Silver iodobromide (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.26 UV absorber (UV-2) 0.13 High boiling point Solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Formalin scavenger (HS-3) 0.10 Gelatin 1.31 16th layer: 2nd protective layer Alkali-soluble matting agent (PM-1, 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, the above-mentioned photosensitive The materials are compounds SU-1, SU-
2, SU-3, SU-4, viscosity modifier, hardener H-1,
H-2, stabilizer ST-1, antifoggant AF-1, AF
-2 (weight-average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2, AI-3 and compound D
I-1 (9.4 mg / m ² ) is contained.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0167

[Correction method] Change

[Correction content]

SU-1: Dioctyl sulfosuccinate / sodium SU-2: Sodium tri-i-purpyrunaphthalene sulfonate SU-3: N-perfluorooctylsulfonyl-N-purpyruglycine / sodium SU-4: Trimethyl・ 3- Perfluorooctylsulfonamidopropylammonium bromide H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium H-2: di (vinylsulfonylmethyl) ether ST-1: 4-hydroxy-6 -Methyl-1,3,3a, 7-tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole AF-2: Poly-N-vinylpyrrolidone Oil-1: dioctylphthalate Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate HS-2: 4-ureidohydantoin HS-3: hydantoin

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0173

[Correction method] Change

[Correction content]

[0173]

[Chemical 8]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0174

[Correction method] Change

[Correction content]

[0174]

[Chemical 9]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 1/76 502 5/26 520 7/407 // G03D 3/06 Z

Claims (7)

[Claims] 1. A silver halide color light-sensitive material having a color photographic image forming layer on one surface side on a transparent polyester support having a glass transition temperature of 90 to 200 ° C. is processed by an automatic processor. A method of processing a silver halide color light-sensitive material, which comprises charging a solid processing agent substantially directly into at least one processing tank of a developing machine. 2. The polyester support has a thickness of 50 to 110.
and a magnetic recording layer on the other surface side.
A method for processing a silver halide color light-sensitive material as described above. 3. The method of processing a silver halide color light-sensitive material according to claim 1, wherein the polyester support comprises a homopolymerized or copolymerized polyester resin containing naphthalenedicarboxylic acid and ethylene glycol as main components. 4. The polyester support has a temperature of 50.degree. C. between the production of the support and the completion of the silver halide color light-sensitive material.
3. A heat-treated product at a glass transition temperature.
Or the processing method of the silver halide color light-sensitive material described in 3 above. 5. The method for processing a silver halide color photographic material according to claim 1, wherein the polyester support is a mixed polyester of polyethylene naphthalate and another polyester. 6. The method for processing a silver halide color light-sensitive material according to claim 1, wherein the polyester support has a multilayer structure in which a plurality of polyester resins made of different materials are laminated. 7. The method of processing a silver halide color light-sensitive material according to claim 1, wherein the processing tank into which the solid processing agent is charged is at least a color developing tank.