JPH0764257A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To restrain curling tendency and to facilitate drawing out of the forward film end and to improve storage stability of a color image by specifying the composition of a support, its glass transition point, and the concentration of a color developing agent. CONSTITUTION:This support is made of poly(alkylene-aromatic dicarboxylate) having a glass transition point of 50-200 deg.C and heat treated in the temperature range of >=40 deg.C up to below the glass transition point and after the end of formation of the support and before or after forming an undercoat layer and before application of a silver halide photosensitive layer, and the concentration of the color developing agent is 20-70mmol/l, and this polymer is polyester made mainly from benzene or naphthalene-dicarboxylic acid and diol, preferably, polyethylene polyethylene terephthalate or polyethylene naphthalate type polyester.

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 photographic light-sensitive material, and more specifically, it improves the handling property and processing property of a film by improving the curl and curl so that the storability of the light-sensitive material is improved. The present invention relates to a method for processing a silver halide color photographic light-sensitive material having improved color image storability after color development processing.

[0002]

BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) are generally manufactured by coating at least one light-sensitive silver halide emulsion layer on a plastic film support. .. Examples of the plastic film include fibrin-based polymers represented by tri (acetyl cellulose) (hereinafter referred to as "TAC") and poly (ethylene terephthalate) (hereinafter referred to as "P").
A polyester-based polymer represented by "ET") is used. These are, for example, Research Disclosure No. 307, 1.
05 (1989, Nov.), XVII.

In general, as a photographic light-sensitive material using these supports, a photographic material such as a cut film, and a roll film typified by a 35 mm width which is housed in a cartridge and loaded into a camera and used for photographing Is. TAC is mainly used as a support for roll films, but the greatest feature of TAC is that it has no optical anisotropy and high transparency. Furthermore, it has the property of being excellent in decurling after one-point development.
That is, the characteristic of the molecular structure of the TAC film is that it has relatively high water absorption as a plastic film. It has an excellent property that the molecular chains that have flowed and fixed with the passage of time undergo rearrangement, and as a result, the curling curl once formed is eliminated.

However, in a light-sensitive material using a film having no curling curl eliminating property such as TAC, when used in a roll state, for example, "processing unevenness" or "scratch" or a film is generated during development processing. "Break" may occur in
Problems such as the occurrence of "scratches", "out-of-focus blur", and "jamming" during transportation may occur in the printing process of forming an image on photographic printing paper after development.

On the other hand, TAC is known to have a relatively high water absorption. Therefore, if the processing time of the color development processing step is long, it has an excellent property that curling due to water absorption in the development processing is eliminated as described above, but there is a problem that a lot of chemicals in the processing solution are taken in. In particular, if the color development time is long, a large amount of the color developing agent is taken in, and if the processing time of the desilvering process after the color development is short, the developing agent taken in the color developing process is not washed away and the TAC or the photosensitive material Remains in the hydrophilic colloid layer. The residual developing agent undergoes oxidation during long-term storage to generate an oxidant. This oxidant is a colored product having a spectral absorption in the visible spectrum region. For this reason, color contamination occurs due to storage over time, which greatly impairs color reproducibility and deteriorates image quality. Therefore, the desilvering process of the color developing process, especially the washing and stabilizing processes cannot be shortened and a certain processing time is required, which is one of the obstacles to speeding up the process.

Further, since TAC has high water absorption,
It is known that TAC undergoes hydrolysis to release an acid (acetic acid) during long-term storage. Therefore, when the light-sensitive material is stored for a long period of time, there are problems that the dye-forming coupler is affected by acid to cause a decrease in color density and that the formed color dye is fading to significantly reduce the fastness. However, improvement in this respect was also desired.

[0007]

SUMMARY OF THE INVENTION Therefore, the present invention eliminates the curl and makes it easier to extract the tongue end of the film even when the core is set to a small winding diameter, and allows uneven development in the color development process, It is an object of the present invention to provide a color development processing method which does not cause rear end folds and scratches and which improves the storability of a light-sensitive material over time and the storability of an obtained color image.

[0008]

The above objects of the present invention can be achieved by the processing method of a silver halide color photographic light-sensitive material described below. A silver halide color photographic light-sensitive material, in which a silver halide color photographic light-sensitive material having at least one undercoat layer and at least one silver halide light-sensitive layer on a support is color-developed with a color developing solution containing a color developing agent. In the treatment method, the support is made of a poly (alkylene aromatic dicarboxylate) polymer and has a glass transition temperature of 50 ° C.
A temperature of not less than 200 ° C. and not more than 200 ° C., and after the molding of the support, before the undercoating layer coating or after the completion of the undercoating layer coating and before the silver halide photosensitive layer coating, the substrate is heat treated at a temperature of 40 ° C. or more and less than the glass transition temperature. A method for processing a silver halide color photographic light-sensitive material, which is a color developing solution having a concentration of the color developing agent of 20 mmol / liter or more and 70 mmol / liter or less.

At least one layer of the silver halide photosensitive layer on the support contains a coupler represented by the formula [M] represented by the following chemical formula 3 or a coupler represented by the formula [m] represented by the following chemical formula 4. A method of processing a silver halide color photographic light-sensitive material as described in the above item.

[0010]

[Chemical 3]

In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a non-metal atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X ₁ represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

[0012]

[Chemical 4]

In the formula, R ₁₁ is an acyl group or a carbamoyl group, Ar is a phenyl group or one or more halogen atoms,
A phenyl group substituted with an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group or an acylamino group,
X ₁₁ represents a hydrogen atom or a coupling-off group.

The processing time for color development processing with an alkaline aqueous solution containing the color developing agent is 30 seconds or more 18
The method for processing a silver halide color photographic light-sensitive material as described in or, which is 0 second or less.

The total processing time after the color development processing is 9
The processing method for a silver halide color photographic light-sensitive material as described in any one of 1 to 3, wherein the processing time is from 0 second to 210 seconds.

The present invention will be described in detail below. First, the poly (alkylene aromatic dicarboxylate) polymer of the present invention (hereinafter referred to as the polyester of the present invention) will be described. Although there are various polyesters of the present invention, a polyester having benzenedicarboxylic acid or naphthalenedicarboxylic acid and a diol as a main component has a high performance by balancing the difficulty of curling, mechanical strength, and cost. Among them, polyethylene-terephthalate (PET) and polyethylene naphthalate-based polyester are particularly preferable. The naphthalate used in the description of the present invention means naphthalene dicarboxylate.

The polyester of the present invention is formed with an aromatic dicarboxylic acid and a diol as essential components. The aromatic dicarboxylic acid is a dicarboxylic acid having at least one benzene nucleus, and specific compounds thereof include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride,
1,4- or 1,5- or 2,6- or 2,7-
Naphthalenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, tetrachlorophthalic anhydride,

[0018]

[Chemical 5]

And the like. In addition to the essential aromatic dicarboxylic acid, dibasic acids that can be used as a copolymerization component include succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, and itacone. Acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid

[0020]

[Chemical 6]

And the like.

Next, as the diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1 -Cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol,

[0023]

[Chemical 7]

[0024]

[Chemical 8]

And the like. Further, if necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. The polyester of the present invention may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or an ester thereof) at the same time in the molecule, and examples thereof include the following.

[0026]

[Chemical 9]

Among the polyesters composed of these diols and dicarboxylic acids, more preferred are homopolymers such as poly (ethylene terephthalate), poly (ethylene naphthalate) and poly (cyclohexanedimethanol terephthalate) (PCT). And 2,6-naphthalenedicarboxylic acid (NDCA) and terephthalic acid (TP) as particularly preferable essential aromatic dicarboxylic acids.
A), isophthalic acid (IPA), orthophthalic acid (OP
A), biphenyl-4,4'-dicarboxylic acid (PPD
C), ethylene glycol (EG) as a diol,
Cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BP
A), biphenol (BP), and para-hydroxybenzoic acid (PHB) as hydroxycarboxylic acid which is a copolymerization component.
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA) is copolymerized.

Among these, more preferable are:
Copolymer of terephthalic acid, naphthalenedicarboxylic acid and ethylene glycol (mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is 0.9: 0.1 to 0.1: 0.9
Is preferable, and 0.8: 0.2 to 0.2: 0.8 is more preferable. ), Terephthalic acid and ethylene glycol,
Copolymer of bisphenol A (mixing molar ratio of ethylene glycol and bisphenol A is 0.6: 0.4 to 0:
It is preferably between 1.0 and more preferably 0.5: 0.5 to 0.1.
~ 0.9 is preferred. ), Isophthalic acid, biphenyl-4,4'-dicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; biphenyl-
The molar ratio of 4,4′-dicarboxylic acid is 0.1 to 0.5 and 0.1 to 0.5, respectively, more preferably 0.2 to 0.3 and 0.1 when terephthalic acid is 1. 2 to 0.3
Is preferred. ), Terephthalic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.
7: 0.3 is preferable, and 0.9: 0.1 is more preferable.
To 0.6: 0.4) terephthalic acid, copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1 : 0.9 to 0.7:
It is 0.3. ), Para-hydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of para-hydroxybenzoic acid, ethylene glycol is 1: 0 to
0.1: 0.9 is preferable, and 0.9: is more preferable.
Copolymers such as 0.1 to 0.2: 0.8) are preferable. These homopolymers and copolymers can be synthesized according to conventionally known polyester production methods. For example, when the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, first, the transesterification reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, it can be synthesized. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. For these polyester synthesis methods, for example,
Polymer Experiments Vol. 5 "Polycondensation and polyaddition" (Kyoritsu Shuppan, 19
80), pp. 103-136, "Synthetic Polymer V" (Asakura Shoten, 1971), pp. 187-286. The preferred average molecular weight (weight) range for these polyesters is from about 10,000 to 500,
It is 000. Furthermore, in order to improve the adhesiveness with other polyesters, these polyesters may be partially blended with another polyester, or the monomers constituting the other polyester may be copolymerized, or these polyesters may be copolymerized. A monomer having an unsaturated bond can be copolymerized therein to radically crosslink.
Polymer blends obtained by mixing two or more kinds of the obtained polymers are disclosed in JP-A-49-5482, JP-A-64-4325, JP-A-3-192718, Research Disclosure,
283, 739-41, 284, 779-82, 2
It can be easily molded according to the method described in 94, 807-14.

The glass transition temperature (Tg) in the present invention means that when 10 mg of a sample film is heated at a rate of 20 ° C./min in a helium nitrogen stream using a differential thermal analyzer (DSC), it is measured from a baseline. It is defined as the arithmetic mean temperature of the temperature at which eccentricity begins and the temperature returning to a new baseline.
However, when an endothermic peak appears, the temperature at which this endothermic peak has a maximum value is defined as Tg. The polyester of the present invention has a Tg of 50 ° C. or higher, but the conditions of use thereof are not generally handled with sufficient caution, and in particular, the temperature is often exposed up to 40 ° C. outdoors in the midsummer in many cases. From this viewpoint, the Tg of the present invention is preferably 55 ° C. or higher in consideration of safety. More preferably, Tg is 70 ° C. or higher, and particularly preferably 80 ° C. or higher. This is because the effect of improving the curling habit by this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so that the temperature is a severe condition when used by general users, that is, the temperature in summer exceeds 40 ° C. Polyesters having a glass transition temperature above the temperature are preferred. On the other hand, the upper limit of the glass transition temperature is 200 ° C. A polyester having a glass transition temperature of higher than 200 ° C. cannot provide a film having good transparency. Therefore, the Tg of the polyester used in the present invention must be 50 ° C. or higher and 200 ° C. or lower.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Polyester compound example P-0: [Terephthalic acid (TPA) / ethylene glycol (EG)) (100/100)] (PET) Tg = 80 ° C P-1: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene Glycol (EG) (100/100)] (PEN) Tg = 119 ° C. P-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. P-3: [TPA / Bisphenol A (BPA) (100/100)] Tg = 192 ° C. P-4: 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. P-6: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 12 ℃ P-7: TPA / EG / BPA (100/50/50) Tg = 105 ℃ P-8: TPA / EG / BPA (100/25/75) Tg = 135 ℃

P-9: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. P-10: IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C P-11: NDCA / NPG / EG (100/70/30) Tg = 105 ° C P-12: TPA / EG / BP (100/20/80) Tg = 115 ° C P-13: PHBA / EG / TPA (200/100/100) Tg = 125 ° C. P-14: PEN / PET (60/40) Tg = 95 ° C. P-15: PEN / PET (80/20) Tg = 104 ° C. P-16: PAr / PEN (50/50) Tg = 142 ° C. P-17: PAr / PCT (50/50) Tg = 118 ° C. P-18: PAr / PET (60/40) Tg = 101 ° C. P-19: PEN / PET / PAr (50/25 25) Tg = 108 ℃ P-20: TPA / 5- sulfonium isophthalate (SIP) / EG (95/5/100) Tg = 65 ℃

The polyester support (film base) preferably has a thickness of 50 μm or more and 100 μm or less.
If it is less than 50 μm, it cannot withstand the storage stress of the photosensitive layer generated during drying, while if it exceeds 100 μm, it is inconsistent with the purpose of reducing the thickness for compactness. However, when used as a sheet-shaped photosensitive material,
It may have a thickness of more than 100 μm. Its upper limit is 300 μm. All of the polyesters of the present invention as described above have a flexural modulus higher than that of TAC, and it was possible to realize the original thinning of the film. However, PET and PEN had strong bending elasticity among them.
With this, it is possible to reduce the film thickness, which was required to be 122 μm in TAC, to 100 μm or less.
Next, the polyester support of the present invention is characterized by being subjected to heat treatment, and in that case, it is necessary to perform the treatment at a temperature of 40 ° C. or higher and lower than the glass transition temperature for 0.1 to 1500 hours.
This effect progresses faster as the heat treatment temperature increases. However, when the heat treatment temperature exceeds the glass transition temperature, the molecules in the film move rather disorderly and conversely the free volume increases, so that the film easily flows, that is, the film is easily curled. Therefore, this heat treatment needs to be performed below the glass transition temperature. The heat treatment as used in the present invention is carried out after being formed as a support and then once lowered to a temperature of less than 40 ° C. until the undercoat layer is applied or after the undercoat layer is applied.
It is preferable to perform a separate heat treatment after the temperature has been lowered to below 0 ° C. and before the coating of the silver halide photosensitive layer.

It is desirable to carry out this heat treatment at a temperature slightly below the glass transition temperature in order to shorten the treatment time.
The glass transition temperature is 0 ° C or higher and lower than the glass transition temperature, and more preferably 30 ° C below the glass transition temperature or higher and lower than the glass transition temperature. More preferably, it is not lower than the glass transition temperature and lower than the glass transition temperature by 15 ° C. On the other hand, when the heat treatment is performed under this temperature condition, the effect is recognized after 0.1 hour. Further, at 1500 hours or more, the effect is almost saturated. Therefore, it is preferable to perform the heat treatment for 0.1 hour or more and 1500 hours or less. In the method for heat-treating the polyester of the present invention, in order to shorten the time, it is previously heated to Tg or more for a short time (preferably, Tg is treated at 20 ° C. or higher and 100 ° C. or lower for 5 minutes to 3 hours), and then 40
It is also possible to perform heat treatment at a temperature of not less than ℃ and less than the glass transition temperature. In the heating method, the film roll may be left as it is in a heating warehouse for heat treatment, but it may be further transferred to a heating zone for heat treatment, and the latter is preferred in view of the suitability for production. Further, the roll core used in the heat treatment preferably has a structure in which an electric heater is built in or a high-temperature liquid can be poured so that the film can be hollow or heated in order to efficiently propagate the temperature to the film. The material of the roll winding core is not particularly limited, but it is preferable that the material does not have strength reduction or deformation due to heat,
Examples thereof include stainless steel and resin containing glass fiber.

Next, in order to further enhance the function of the polyester of the present invention as a photographic support, it is preferable to coexist with various additives. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the addition amount thereof is usually 0.01% by weight to 20% by weight, preferably 0.05% by weight based on the weight of the polyester film.
It is about 10% by weight to 10% by weight. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. 2,4-dihydroxybenzophenone as an ultraviolet absorber,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Benzophenone-based compounds such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
Benzotriazoles such as 3'-di-t-butyl-5'-methylphenyl) benzotriazole, salicylates such as phenyl salicylate and methyl salicylate 2,4,6
-Tris [2'-hydroxy-4 '-(2 "-ethylhexyloxy) phenyl] triazine, 2-phenyl-
Examples thereof include triazine-based UV absorbers such as 4,6-di [2′-hydroxy-4 ′-(2 ″ -ethylhexyloxy) phenyltriazine.

In addition, one of the properties that are problematic when the polyester film of the present invention is used as a support for a photographic light-sensitive material is the problem of fogging due to the high refractive index of the support. The polyester of the present invention, in particular, the aromatic polyester has a high refractive index of 1.6 to 1.7, whereas the gelatin which is the main component of the photosensitive layer coated thereon has a refractive index of 1.50 to 1.50. It is smaller than this value, which is 1.55. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging). As a method of avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film, a method of adding a dye, and the like are known. The preferred method for preventing light piping in the present invention is a method by adding a dye that does not significantly increase the film haze. The dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polyester film, and polyester Those having excellent compatibility with are preferable. As the dye, from the above viewpoint, Diaresin manufactured by Mitsubishi Kasei, manufactured by Nippon Kayaku
The purpose can be achieved by mixing a commercially available dye such as Kayaset for polyester.
Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be imparted with slipperiness depending on the application, and the slipperiness imparting means is not particularly limited.
The kneading of an inert inorganic compound or the coating of a surfactant is used as a general method. Examples of such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. Further, in addition to the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can also be adopted. Is. These slipperiness imparting means are not particularly limited, but transparency is an important requirement for a support for a photographic light-sensitive material. Therefore, in the slipperiness imparting method means, a polyester film is used as an external particle system. It is desirable to select SiO ₂ having a refractive index relatively close to, or an internal particle system capable of relatively reducing the precipitated particle size.

Further, when imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die. When any of these polymer films is used as a support, since each of these polymer films has a hydrophobic surface, a photographic layer comprising a protective colloid mainly containing gelatin on the support (for example, a photosensitive silver halide emulsion layer). , The intermediate layer, the filter layer, etc.) are very difficult to adhere firmly. As conventional techniques attempted to overcome such difficulties, (1) chemical treatment, mechanical treatment,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
After performing surface activation treatment such as glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a method of directly applying a photographic emulsion to obtain adhesive strength,
(2) There are two methods, that is, after these surface treatments are carried out once or without any surface treatment, an undercoat layer is provided and a photographic emulsion layer is coated thereon (for example, US Pat. No. 2,698,24).
No. 1, No. 2,764,520, No. 2,864,755
Issue No. 3,462,335 Issue No. 3,475,193
No. 3, 3, 431, 421, 3, 501, 301
Nos. 3,460,944, 3,674,531
No., British Patent Nos. 788,365, 804,005
No. 891, 469, Japanese Patent Publication No. 48-43122,
51-446, etc.).

All of these surface treatments are considered to be caused by forming polar groups on the surface of the support which was originally hydrophobic to some extent, and increasing the crosslink density of the surface. As a result, It is considered that the affinity of the component contained in the undercoating liquid with the polar group is increased, or the fastness of the adhesive surface is increased. In addition, various arrangements have been made for the composition of the undercoat layer. A layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and a second layer is used as a photograph. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter abbreviated as an undercoat second layer) in good contact with a layer, and a single layer of applying a single resin layer containing both a hydrophobic group and a hydrophilic group There is a law.

Among the surface treatments of (1), corona discharge treatment is the most well-known method, and any conventionally known method, for example, Japanese Patent Publication Nos. 48-5043 and 47-5.
1905, JP-A-47-20867, 49-83.
No. 767, No. 51-41770, No. 51-13157.
This can be achieved by the method disclosed in No. 6 or the like.
Discharge frequency is 50 Hz to 5000 KHz, preferably 5
KHz to several hundred KHz is suitable. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. If the frequency is too high,
A special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, 0.001 KV · A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0 in order to improve the wettability of ordinary polyester, polyolefin and other plastic films. 0.01 KV · A · min / m ^{2 to 1} KV · A · min / m ² is suitable. The gap clearance between the electrode and the derivative roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm.

In many cases, the glow discharge treatment, which is the most effective surface treatment, is performed by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-1033.
No. 6, No. 45-22004, No. 45-22005,
45-2440, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638 and 3,309. No. 299, No. 3,424,735, No. 3,462,335, No. 3,475,307, No. 3,761,299, British Patent 997,093, JP-A No. 53-129262, etc. Can be used.

The glow discharge treatment conditions are generally such that the pressure is 0.005 to 20 Torr, preferably 0.02 to 2 Torr. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow, causing the peaks to occur easily, which is dangerous and may damage the object to be treated. The electric discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. This voltage can take various values depending on the composition and pressure of the atmospheric gas, but normally, within the above pressure range, stable steady glow discharge occurs between 500 and 5000V. A particularly suitable voltage range for improving the adhesiveness is 2000 to 4000V. Further, as seen in the prior art, the discharge frequency is from DC to several tens of degrees.
00 MHz, preferably 50 Hz to 20 MHz is suitable. Regarding the discharge treatment strength, 0.01 KV · A · min / m ^{2 to 5} KV · A · min /
m ² is preferably 0.15 KV · A · min / m ^{2 to 1} KV · A · min / m ² .

Next, the undercoating method (2) will be described. All of these methods have been well studied, and for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used for the first layer of the undercoating in the multi-layer method. , Itaconic acid, maleic anhydride, and other copolymers starting from monomers selected from polyesterimine, epoxy resin, grafted gelatin, nitrocellulose, and many other polymers The properties of the two layers have been investigated mainly for gelatin.

In the single layer method, good adhesion is often achieved by swelling many supports and interfacially mixing with the hydrophilic undercoat polymer. Examples of the hydrophilic undercoating polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. As the water-soluble polymer, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, etc.,
Examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-resin. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various known gelatin hardening agents can be used in the undercoat layer of the present invention. Examples of gelatin hardening agents include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, epichlorohydrin resins, cyanuric chloride compounds (for example, Japanese Patent Publication Nos. 47-6151 and 47-33380). ,
54-25411, compounds described in JP-A-56-130740), vinyl sulfone or sulfonyl compounds (for example, JP-B-47-24259 and 50-).
35807, JP-A-49-24435, 53-4.
Nos. 1221 and 59-18944),
Carbamoyl ammonium salt compounds (for example, JP-B-56-12853, JP-A-58-32699, JP-A-4)
9-51945, 51-59625, 61-9
No. 641), amidinium salt compounds (for example, compounds described in JP-A-60-225148), carbodiimide compounds (for example, JP-A-51-251).
Nos. 126125 and 52-48311), pyridinium salt compounds (for example, Japanese Examined Patent Publication No. 58-
50699, JP-A-52-54427, JP-A-57.
-44140, 57-46538), other Belgian Patent No. 825,726, U.S. Pat. No. 3,321,313, JP-A-50-38540.
No. 52-93470, No. 56-43353, No. 58-113929, and the like.

The undercoat layer of the present invention may contain inorganic or organic fine particles as a matting agent to such an extent that the transparency and graininess of the image are not substantially impaired. As a matting agent for inorganic fine particles, silica (SiO ₂ ) and titanium dioxide (T
iO ₂ ), calcium carbonate, magnesium carbonate and the like can be used. Examples of the organic fine particle matting agent include polymethylmethacrylate, cellulose acetate propionate, polystyrene, and US Pat. No. 4,142,89.
The treatment solution-soluble substances described in No. 4 and the polymers described in US Pat. No. 4,396,706 can be used. The average particle size of these fine particle matting agents is preferably 1 to 10 μm.

In addition to this, the undercoat layer may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is a well-known coating method such as dip coating method, air-nyco coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by an extrusion coating method using a hopper described in the specification of 2,681,294. If desired, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be simultaneously coated by the method described in “Coating Engineering”, page 253 (1973, published by Asakura Shoten).

The binder of the back layer may be a hydrophobic polymer or a hydrophilic polymer used in the undercoat layer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a slip agent, a matting agent, a surfactant, a dye, an ultraviolet absorber and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, and examples of the anionic polymer electrolyte include polymers containing a carboxylic acid, a carboxylic acid salt and a sulfonic acid salt, for example, JP-A-48-22017. JP-B-46-24159, JP-A-51-30725, JP-A-51-129216,
It is a polymer as described in JP-A-55-95942. Examples of the cationic polymer include JP-A-49
There are those described in JP-A-121523, JP-A-48-91165 and JP-B-49-24582. Further, ionic surfactants are also anionic and cationic, and are disclosed, for example, in JP-A-49-85826 and JP-A-4.
9-33630, U.S. Pat. No. 2,992,108,
U.S. Pat. No. 3,206,312, JP-A-48-878
No. 26, Japanese Patent Publication No. 49-11567, Japanese Patent Publication No. 49-11
Examples thereof include compounds described in JP-A No. 568 and JP-A No. 55-70837.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₂ , SnO ₂ or Al _2.
O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO
It is fine particles of at least one crystalline metal oxide or a composite oxide thereof selected from ₃ V ₂ O ₅ .
The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. 1 as the lower limit
It is 0 ³ Ωcm. The particle size is 0.002-
The thickness is preferably 0.7 μm, particularly 0.005 to 0.3 μm.

Further, the silver halide color photographic light-sensitive material of the present invention may have a magnetic recording layer for recording various information. A known ferromagnetic material can be used. The magnetic recording layer can be provided as an upper layer (for example, a protective layer or an uppermost layer) of the support layer on the side where the photosensitive layer is coated, but it is preferably used for the back surface, and can be provided by coating or printing. Further, a space for optically recording may be provided in the photosensitive material for recording various information.

The smaller the hollow part or the spool in the center of the film used in the camera of the light-sensitive material of the present invention, the smaller the size. Can not. Therefore, in the present invention, the hollow or spool in the center of the film which is preferable in the camera is 3 mm or more, and the upper limit is 12 mm.
Is more preferable, 3 mm to 10 mm is more preferable, and 4 mm to 9 mm is particularly preferable. Also, the smaller the winding inner diameter of the spool is, the more preferable. However, if it is 5 mm or less, the photographic property is significantly deteriorated due to the pressure of the photosensitive material, and a large number of frames cannot be loaded, so that it cannot be practically used. Therefore, in the present invention, the inner diameter of the spool in the camera is preferably 5 mm or more, and the upper limit is preferably 15 mm, more preferably 6 mm to 13.5 mm, further preferably 7 mm to 13.5.
mm, particularly preferably 7 mm to 13 mm.

Next, the color developing process of the present invention will be described. The color photographic light-sensitive material of the present invention is the above-mentioned R
D. No. 17643, pages 28-29, same No. 18716
651 left column to right column and same No. 307105 880 to
The development process can be carried out by the usual method described on page 881 with a color developing solution of an alkaline aqueous solution having a color developing agent concentration of 15 mmol / liter or more and 70 mmol / liter or less. The color developing solution used for the development processing of the light-sensitive material of the present invention is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component and having a concentration of 15 mmol / liter or more and 70 mmol / liter or less. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used.

In the present invention, the concentration of the color developing agent is 20 mmol / liter or more and 70 mmol / liter or less, but if the concentration is less than 20 mmol / liter, the sensitivity and gradation required for the light-sensitive material, etc. In order to obtain the above photographic performance, it is necessary to lengthen the color development time, and it is difficult to increase the processing temperature and pH. This increase in processing time runs counter to the current trend of demanding speeding up of color development processing, and is unacceptable to the laboratory industry. On the other hand, when the concentration exceeds 70 mmol / liter, it is difficult to maintain the performance of the color developing solution, and when the temperature is low, the crystallization of the color developing agent, the adhesion of the crystal product due to the liquid climbing to the upper surface of the processing tank, An increase in the amount of the developing agent oxidant and an increase in the amount of the developing agent or its oxidant adhering to the light-sensitive material and the amount of incorporation thereof are unfavorable.

In the present invention, the concentration of the color developing agent is preferably 20 mmol / liter or more and 60 mmol / liter or less. More preferably, it is in the range of 25 mmol / liter or more and 50 mmol / liter or less. A light-sensitive material using the heat-treated polyester support of the present invention in the above concentration range has a small decrease in color density over time,
Good image quality with little increase in minimum density (Dmin) immediately after color development processing, fading of color image due to aging after processing and increase in Dmin is provided.

In the present invention, the color development processing temperature is preferably 30 ° C. or higher and 55 ° C. or lower in the concentration range of the color developing agent. More preferably 35 ° C
The temperature range is from 50 ° C to 50 ° C, and a temperature range from 37 ° C to 45 ° C is particularly preferable. If the temperature is less than 30 ° C., the required photographic performance cannot be obtained unless the processing time is extended, and it is not preferable for speeding up the processing. When the treatment temperature exceeds 55 ° C., there are problems such as an increase in the heat-retaining equipment of the treatment machine and costs for maintaining the temperature, and difficulty in maintaining stable performance of the treatment liquid.

Further, in the present invention, it is preferable that the color development processing time is 30 seconds to 180 seconds in the concentration range of the color developing agent. More preferably 4
Processing time from 5 seconds to 170 seconds, 60 seconds to 1
A treatment time of 50 seconds or less is more preferable. If the processing time is less than 30 seconds, it is difficult to obtain the required photographic performance even if the color developing agent concentration, processing temperature, pH, etc. are increased.
If the processing time exceeds 180 seconds, the demand for rapid processing cannot be met.

According to the present invention, a light-sensitive material using a polyester support as described above is treated with a color developing solution having a concentration of a color developing agent of 15 mmol / liter or more and 70 mmol / liter or less to further develop the color. Occurrence of rear edge folds and scratches during non-uniform development and film processing by processing at a processing temperature of 30 ° C to 55 ° C and / or a color development time of 30 seconds to 180 seconds It is possible to provide a method for processing a light-sensitive material, which is free from the above-mentioned problems, improves the storage stability of the light-sensitive material with time, and does not cause deterioration in image quality of the obtained color image with time.

As the p-phenylenediamine type color developing agent, known compounds can be used. Representative examples of known compounds are shown below, but the invention is not limited thereto. Further, two or more known compounds can be used in combination. The concentration at that time and the concentration of the total amount used are within the above concentration range. P-1 N, N-diethyl-p-phenylenediamine P-2 2-amino-5- (N, N-diethylamino)
Toluene P-3 2-amino-5- (N-ethyl-N-laurylamino) toluene P-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline P-5 2-methyl-4 -[N-Ethyl-N- (β-hydroxyethyl) amino] aniline P-6 4-amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] aniline P-7 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-8 N, N-dimethyl-p-phenylenediamine P-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline P-10 4-amino-3-methyl-N-ethyl-N-β
-Methoxyethylaniline P-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline

In addition to the above-mentioned p-phenylenediamine type color developing agent, a compound represented by the following formula (D) can be used in the present invention. In the present invention, the compound represented by the formula (D) is color developed. It is preferably used as a main drug.

[0060]

[Chemical 10]

In the formula (D), R ₁ is a straight chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight chain or branched chain having 3 to 8 carbon atoms and a main chain having 3 to 8 carbon atoms. Represents a hydroxyalkyl group. R ₂ is a C 3-8 straight-chain or branched unsubstituted alkylene group having a main chain having 3-8 carbon atoms, or a C 3-8 straight-chain having a main chain having 3-8 carbon atoms, or It represents a branched hydroxyalkylene group. R
₃ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, or a sulfonamide group.

The formula (D) will be described in detail below.
In formula (D), R ₁ is a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or the main chain has 3 to 8 carbon atoms.
Represents a linear or branched hydroxyalkyl group having 3 to 8 carbon atoms. Here, the main chain refers to a connecting group of a nitrogen atom and a hydroxyl group to be connected, and when R ₁ has a plurality of hydroxyl groups, the main chain has the smallest carbon number. Specific examples of R ₁ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, neopentel, 3
-Hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 4-hydroxypentyl, 3-hydroxybutyl, 4-hydroxy-4-methylpentyl, 5,6-dihydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyoctyl, 8-hydroxyoctyl and the like can be mentioned.

R ₂ has 3 carbon atoms whose main chain has 3 to 8 carbon atoms
It represents a straight-chain or branched unsubstituted alkylene group having 8 to 8 carbon atoms or a straight-chain or branched hydroxyalkylene group having 3 to 8 carbon atoms in the main chain. Here, the main chain refers to a connecting chain of the nitrogen atom to which it is connected and the hydroxyl group described in the formula (D), and when R ₂ has one or more hydroxyl groups, it is The hydroxyl group bonded on the carbon atom having the smallest number of carbon atoms corresponds to the hydroxyl group described in the formula (D), and its connecting chain is the main chain. Specific examples of R ₂ include trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, 3-methylpentamethylene, 2-methylpentamethylene, 2-ethyltrimethylene, 3- (2-hydroxyethyl) trimethylene, 6-
Examples include (1,2-dihydroxyethyl) hexamethylene.

In the formula (D), R ₁ and R ₂ are R ₁
Is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and R ₂ is a straight-chain or branched unsubstituted alkylene group having 4 to 6 carbon atoms in the main chain, or R 2 ₁ is a straight-chain or branched hydroxyalkyl group having 4 to 8 carbon atoms whose main chain has 4 to 8 carbon atoms, and R ₂ has 4 to 8 carbon atoms in the main chain, and particularly 4 to 6 straight chain Alternatively, it is preferably a branched unsubstituted alkylene group. More preferably, in the formula (D), R ₁ is a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms and R ₂ is a tetramethylene group.

In formula (D), when R ₁ is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, the number of carbon atoms is more preferably 1 to 4. Of these, a methyl group, an ethyl group, and an n-propyl group are particularly preferable, and an ethyl group is most preferable.

R ₃ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, or a sulfonamide group. .
These groups may be further substituted with a substitutable group. More specifically, R ₃ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl,
n-propyl, isopropyl, sec-butyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl), alkoxy group (eg methoxy, ethoxy, isopropoxy), alkylamino group (eg ethylamino, dimethylamino, 2-hydroxyethyl) amino),
Ureido group (eg dimethylureido), sulfamoylamino group (eg N, N-dimethylsulfamoylamino), alkoxycarbonylamino group (eg ethoxycarbonylamino), sulfonamide group (eg methanesulfonamide, 2-methoxyethane) (Sulfonamide) and the like.

R ₃ is preferably an alkyl group or an alkoxy group. More preferably, R ₃ is a linear or branched alkyl group which is not substituted with a substituent, more preferably a linear alkyl group, and most preferably a methyl group or an ethyl group. Most preferably, it is a methyl group. Next, specific examples of typical developing agents represented by formula (D) in the present invention are shown, but the present invention is not limited thereto.

[0068]

[Chemical 11]

[0069]

[Chemical 12]

[0070]

[Chemical 13]

The color developing agent of the formula (D) is, for example, Journal of the American Chemical Society.
Volume 73, page 3100 (1951), British patent 807,899.
No., European Patent Publication No. 517214A1, Japanese Patent Laid-Open No. 3-2.
It can be easily synthesized according to the method described in Nos. 46543 and 4-443. Of the compounds represented by formula (D), Exemplified Compound D-12 is the most preferable compound.
Can be mentioned.

The p-phenylenediamine color developing agent may be stored as a free amine, but it is generally produced and stored as a salt of an inorganic acid or an organic acid, and becomes a free amine only when it is added to a processing solution. It is preferable to do so. Examples of the inorganic or organic acid that forms a salt of the p-phenylenediamine color developing agent include hydrochloric acid, sulfuric acid, phosphoric acid, p-
Toluenesulfonic acid, methanesulfonic acid, naphthalene-
1,5-disulfonic acid and the like can be mentioned. Of these, salts of sulfuric acid and p-toluenesulfonic acid are preferred, and salts of sulfuric acid are most preferred. For example, Exemplified Compound D-12 was obtained as a sulfate, and its melting point was 112 to 114 ° C. (recrystallized from water-ethanol).
And exemplary compound D-2 is also obtained as a sulfate,
Its melting point is 158 to 160 ° C. (recrystallized from water-ethanol).

The developing agent of the formula (D) is produced in a developing agent having a high hydrophobicity and an excellent developing activity as compared with the above-mentioned P-5 which is widely used as a developing agent for color negative at present. It is a developing agent characterized by no development inhibition. Further, in spite of its high hydrophobicity, the light-sensitive material using the above polyester-based support of the present invention does not show an increase in the minimum density with the lapse of time after the processing, and shows a good storage stability, and the image quality (color reproduction Property) is not deteriorated.

The color developing agent represented by the formula (D) can be used in combination with the compounds P-1 to P-11 exemplified as the above-mentioned representative compounds, or the compound represented by the formula (D). Can be used in combination,
In any case, the total concentration of these color developing agents in the color developing solution is in the range of 20 mmol / liter or more and 70 mmol / liter or less. It is preferably in the range of 20 to 60 mmol / l, more preferably in the range of 25 to 50 mmol / l.

The color developing solution for color developing the light-sensitive material of the present invention is an alkaline aqueous solution. The alkaline aqueous solution means that the pH value (25 ° C.) of the color developing solution is 9.0 or more. The pH value is 9.0 or more and 13.5 or less, preferably 10.0 or more and 12.5 or less, and more preferably 10.0 or more and 11.5 or less. To maintain these pH values, pH buffer agents such as carbonates, phosphates, borates, and hydroxybenzoates described below are used.

As described above, in the present invention, the glass transition temperature is 50 ° C. or higher and 200 ° C. or lower, and after forming the support, before coating the undercoat layer or after coating the undercoat layer and before coating the silver halide photosensitive layer. When a silver halide color photographic light-sensitive material was produced using a support made of a poly (alkylene aromatic dicarboxylate) polymer heat-treated at a temperature of 40 ° C. or more and less than the glass transition temperature, it was rolled into a roll. The workability of extracting the tongue end of the film is improved, the curl value after color development processing described later can be reduced, scratches and uneven development during color development processing can be reduced, and the rear edge folding of the film during color development can be reduced. can do. Further, it also improves the storage stability of the light-sensitive material over time. Further, even when the color developing treatment described later is carried out with an alkaline color developing solution having a color developing agent concentration of 20 to 70 mmol / liter, the color image after the treatment is prevented from fading over time, and the minimum density (Dmin) The effect of improving the image quality is small. The degree of improvement effect of this color image is the polymerization ratio of the support, the composition ratio of the copolymer, additives, the thickness of the support or the surface treatment method,
Although it depends on the composition of the undercoat layer and the like, it largely depends on the use of the support made of the heat-treated poly (alkylene aromatic dicarboxylate) polymer described above.

Next, other processing agents for the color developing solution used in the present invention will be described in detail. In the color developer of the present invention, a compound which directly preserves the aromatic primary amine color developing agent of the present invention is disclosed in JP-A-63-534.
No. 1, 63-106655 or JP-A-4-14.
4446, various hydroxylamines, JP-A-63-43138, hydroxamic acids, 63
Hydrazines and hydrazides described in No. 146041, phenols described in Nos. 63-44657 and 63-58443, and α described in No. 63-44656.
-Hydroxyketones and α-aminoketones, 63-
Various sugars described in No. 36244 and the like can be contained. Further, in combination with the above compound, JP-A-63-423
5, No. 63-24254, No. 63-21647,
63-146040, 63-27841 and 63-25654, and the like, 63.
-30845, 63-14640, 63-43
Diamines described in No. 139, etc., 63-21647.
Nos. 63-26655 and 63-44655, nitroxy radicals described in 63-53551, 63-43140 and 6
Alcohols described in 3-53549, 63-56
Nos. 654 and 63-23944
The tertiary amines described in No. 7 can be used. Other preservatives include various metals described in JP-A-57-44148 and 57-53749, and 59-18.
No. 0588, salicylic acids, No. 54-3582, alkanolamines, No. 56-94349, polyethylenimines, US Pat. No. 3,743.
If desired, the aromatic polyhydroxy compound described in No. 6,544 and the like may be contained. Particularly preferred preservatives are hydroxylamines represented by the general formula (I) of JP-A-3-144446, and among them, a methyl group, an ethyl group or a compound having a sulfo group or a carboxy group in these alkyl groups. preferable. The addition amount of these preservatives is 20 mmol to 200 mmol, preferably 30 mmol to 150 mmol, per liter of the color developing solution.

Others In the color developing solution of the present invention, various additives described in JP-A-3-144446 can be used. For example, examples of the buffering agent for maintaining the pH include carbonic acid, phosphoric acid, boric acid, hydroxybenzoic acid and the like described on page (9) of the same publication. As the chelating agent, various aminopolycarboxylic acids, phosphonic acids, and sulfonic acids on the same page are preferably ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid) and catechol-3,5-disulfonic acid are preferable. The color developer has a pH of 9.0 to 1 using these buffers.
It is preferable to maintain in the range of 3.5, and more preferably between 10 and 12.5. More preferably pH is 10 to 11.5
Is. As the development accelerator, for example, various additives described on pages (9) to (10) of the same publication can be used. Examples of the antifoggants include halide ions and organic antifoggants described on page (10) of the same publication.
In particular, the bromide ion concentration is 20 mmol to 80 mmol / l when the concentration of the developing agent in the color developing solution is as high as 20 mmol / l or higher and when the processing is performed at a high temperature of 42 ° C. or higher.
Higher, such as liter, is preferred. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

In the present invention, the processing temperature of the above-mentioned color developing solution is 30 ° C. or higher and 55 ° C. or lower. It is preferably 35 ° C. or higher and 50 ° C. or lower, and more preferably 40 ° C. or higher and 45 ° C. or lower. Processing at such a high temperature can shorten the color development processing time, and not only speeds up the processing but also in the light-sensitive material using the polyester support of the present invention, the minimum of the light-sensitive material after processing can be obtained. The increase in density is small, which is advantageous for maintaining high image quality. The processing time when the above-mentioned color developing solution of the present invention is used at the above processing temperature is preferably 30 seconds to 3 minutes and 30 seconds, more preferably 45 seconds to 3 minutes, and particularly preferably. It is in the range of 1 minute to 2 minutes and 30 seconds.

In the present invention, the color development process is usually a continuous process, but the replenishment amount of the color development in the continuous process is 60 per 1 m ² process of the light-sensitive material.
It is 0 ml or less. The supplement amount is preferably 75 to 500 ml, more preferably 75 to 30.
It is 0 ml, and a replenishing amount of 80 to 200 ml is particularly preferable. Even if such a low replenishment amount of color development processing is applied to the light-sensitive material of the present invention, there is almost no increase in the minimum concentration of the light-sensitive material after the processing although the accumulation of tired color developing solution increases. In addition, the minimum density value does not increase with time, and the processed light-sensitive material can retain high image quality.

In the present invention, the color-developed light-sensitive material is then desilvered. The entire process after the desilvering process basically consists of a bleaching process and a fixing process, but it is constituted by combining a bleach-fixing process in which these are performed simultaneously, a process combining these, and a washing or stabilizing process. It Representative examples of these are: (1) bleach-fix-stabilize (2) bleach-fix-wash-stabilize (3) bleach-bleach-fix-wash-stabilize (4) bleach-bleach-fix-fix- Wash (5) Bleach-bleach-fix-fix-stabilize (6) Bleach-bleach-fix-fix-wash-stabilize (7) Bleach-bleach-fix-stabilize (8) Bleach-bleach-fix-wash (9) Bleach Fixing-fixing-washing-stabilization (10) Bleaching fixing-fixing-stabilizing (11) Bleaching fixing-washing-stabilizing (12) Bleaching fixing-stabilizing. If necessary, washing may be carried out between bleach-fixing, bleach-bleach-fixing and bleach-fixing-fixing. Of these, (1), (6) and (8) are preferable.

In the present invention, the total processing time after desilvering is 90 seconds or more and 210 seconds or less means that from the bleaching or bleach-fixing shown as the representative example to the end of washing or stabilization processing in the final step. Processing time. A preferable total processing time after the desilvering processing is 90 seconds or more and 180 seconds or less. At the processing time of the present invention, the color reproducibility due to silver remaining due to incomplete desilvering processing,
The minimum density (Dmin) over time after color development processing due to residual developing agents incorporated in the photosensitive material including the support during color development due to rapid processing that shortens processing time.
The deterioration of the image quality that causes a remarkable increase in the image quality or changes in the hue of the color image is extremely small. Further, the color image fastness is not deteriorated. Therefore, rapid processing can be performed without degrading the image quality. Thus, even if the processing time is shortened, the deterioration of the image quality and the deterioration of the color image fastness due to the increase of Dmin after the processing is not caused. It was achieved by using materials.

As the bleaching agent used in the desilvering process, 1,3-propylenediaminetetraacetic acid iron complex salt of JP-A-4-121739, from the lower right column of the fourth page to the upper left column of the fifth page. And other bleaching agents, JP-A-4-73647
Carbamoyl bleaching agent described in JP-A-4-174
No. 432. Heterocyclic bleaching agent, N- (2-
Bleaching agents described in EP-A-520457, including carboxyphenyl) iminodiacetic acid ferric complex salts;
Ethylenediamine-N-2-carboxyphenyl-N,
Japanese Patent Application No. 3 including N ', N'-ferric triacetate acetic acid
-252775 bleaching agent, European Patent Publication No. 501
The bleaching agents described in JP-A-4-127145, the bleaching agents described in JP-A-4-127145, and (1) in JP-A-3-144446.
The ferric aminopolycarboxylic acid salt or its salt described on page 1) is preferably used. In the desilvering bath of the present invention, in addition to the bleaching agent, the rehalogenating agent, pH buffering agent and known additives described on page (12) of JP-A-3-144446, aminopolycarboxylic acids, Organic phosphonic acids and the like can be used. Further, in the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath. Examples of such bleaching accelerators include, for example, U.S. Pat. No. 3,893,858, German Patent 1,290,821, British Patent 1,138,
842, JP-A-53-95630, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide group, and JP-A-50-140129. Thiazolidine derivatives, US Pat. No. 3,706,561
Thiourea derivatives described in JP-A-58-162
35, Japanese Patent No. 2,748,
The polyethylene oxides described in Japanese Patent No. 430, and the polyamine compounds described in Japanese Patent Publication No. 45-8836 can be used. Particularly preferably, British Patent No. 1,138,842 and JP-A-2-190856.
Preferred are mercapto compounds as described in US Pat.

In the processing solution having fixing ability, a sulfite (eg sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (eg sodium acetaldehyde sodium bisulfite, particularly preferably compounds described in JP-A-3-158848) or JP-A-1.
The sulfinic acid compound etc. described in the specification of No. 231051 can be contained. Further, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like can be contained. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Cyclohexanediaminetetraacetic acid, 1,
2-Propylenediaminetetraacetic acid may be mentioned.

The processing solution having fixing ability preferably contains a compound having a pKa in the range of 6.0 to 9.0 for pH adjustment or as a buffering agent. As these compounds, imidazole compounds are preferable. The imidazole compound is preferably contained in an amount of 0.01 mol / liter or more. The more preferable addition amount of the imidazole compound is 0.1 to 10 mol / liter, particularly preferably 0.2 to 3 mol / liter. The imidazole compound represents imidazole and its derivatives, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, a halogen atom and the like. The alkyl group, alkenyl group and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom or the like. The preferred total carbon number of the substituents of the imidazole is 1 to 6, and the most preferred substituent is the methyl group. Specifically preferred compounds are imidazole, 2-methyl-imidazole and 4-methyl-imidazole, and the most preferred compound is imidazole.

Further, it is preferable that the processing solution having fixing ability is subjected to silver recovery processing. In the case of a processing solution having a bleaching ability, the overflow should be stocked and reused by using a regenerant. The solution having a fixing ability and the solution having a bleaching ability may be separated separately, or may be used as a bleach-fixing solution. When the solution having the fixing ability and the solution having the bleaching ability are separated separately, the waste solution is mainly the solution having the fixing ability, or the solution having the fixing ability is subjected to in-line silver recovery and the waste solution after the recovery is discharged. In addition to in-line recovery of silver, overflow may be collected and silver recovery processing may be performed, and the solution after processing may be recycled and reused. In the case of a bleach-fix solution, in-line silver is recovered, the waste solution after recovery is discharged, and the overflow of the bleach-fix solution is recycled and reused. The processing solution having the above fixing ability can be subjected to silver recovery by a known method. As a silver recovery method, an electrolysis method (described in French Patent No. 2,299,667) and a precipitation method (Japanese Patent Laid-Open No. Sho. 52-73037, German Patent No. 2,331,220), an ion exchange method (Japanese Patent Laid-Open No. 51-17114, German Patent No. 2,548,237), and a metal substitution method (UK Patent No. 1,353,805
No.) etc. are effective. These silver recovery methods are preferable when they are carried out in-line from the tank solution because the suitability for rapid processing is further improved. In the present invention, the processing temperature in the desilvering process comprising bleaching, bleach-fixing and fixing is 30 to 50 ° C.,
The temperature is preferably 35 to 50 ° C. pH is 3.0-9.
0, preferably 4.0 to 8.0 is preferable. The processing time of the desilvering step is preferably 20 seconds to 190 seconds, more preferably 25 seconds to 150 seconds, and particularly preferably 30 seconds to 120 seconds.

After the processing step having fixing ability, usually,
Perform a washing process. After processing with a processing solution with fixing ability,
It is also possible to use a simple treatment method in which a stabilizing treatment using a stabilizing solution is carried out without substantially washing with water. The washing water used in the washing step and the stabilizing solution used in the stabilizing step are for preventing unevenness of water droplets when the photosensitive material after processing is dried.
Various surfactants can be included. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added.
Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

The washing water and the stabilizing solution may contain various antibacterial agents and antifungal agents in order to prevent generation of water stains and molds generated in the processed light-sensitive material. Further, it is preferable to add various chelating agents to the wash water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ′, N′-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1. It is also preferable that the preservative that can be contained in the fixing solution or the bleach-fixing solution is contained in the washing water and the stabilizing solution.

It is desirable that the washing or stabilizing solution be treated by a multistage countercurrent system. The multi-stage countercurrent system may be used for a conventional transport system using a cross-over rack, but in order to improve the washing efficiency, for example, a washing bath as described in JP-A-2-240651 is separated into multiple chambers to form partition walls. It is particularly preferable to perform countercurrent washing in a multi-chamber washing method of squeezing in liquid.
The number of multiple chambers is required to be 2 or more, preferably 3 or more, and more preferably 4 or more. Further, it is preferable to increase the washing efficiency with a reverse osmosis device. The specifications of the reverse osmosis apparatus are preferably that water after permeation through the osmotic membrane is introduced into the post-bath of washing or stabilizing bath, and the concentrate is introduced into the pre-bath thereof, most preferably the permeated water is introduced into the final bath. The concentrated solution is preferably introduced into the prebath.

The stabilizing solution used in the stabilizing step is a processing solution for stabilizing the dye image, such as an organic acid or pH 3 to 10.
It is possible to use a liquid having a buffering capacity of 6, a liquid containing alkyd (for example, formalin or glutaraldehyde), and the like. The stabilizing solution may contain all compounds that can be added to the washing water, and in addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners and hardeners. Agents, alkanolamines described in US Pat. No. 4,786,583, and the like can be used.

In the stabilizing solution, compounds that stabilize the dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, dimethylolurea and N-methylol. N-methylol compounds such as pyrazole, organic acids, pH buffering agents and the like are included. The preferred addition amount of these compounds is 0.001 to 0.02 mol per liter of the stabilizing solution,
The lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, as the dye image stabilizer, m-hydroxybenzaldehyde, hexamethylenetetramine, N-
N-methylolazoles such as methylolpyrazole described in JP-A-4-270344, N, N'-bis (1,2,4-triazol-1-ylmethyl) piperazine and the like in JP-A-4-313753 and 4- 35924
Azolylmethylamines described in No. 9 are preferable. Also,
In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat. No. 4,786,58.
It is also preferable to include an alkanolamine described in No. 3 and a preservative that can be contained in the fixing solution or the bleach-fixing solution. Among these, the sulfinic acid compounds (for example, benzenesulfinic acid, toluenesulfinic acid, or salts thereof such as sodium and potassium) described in JP-A No. 1-231051 are preferable, and the stabilizer 1 is added as the addition amount thereof. 1 x 10 ^-5 to 1 x per liter
10 ⁻³ mol is preferable, and 3 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol is particularly preferable.

The pH of the stabilizing solution is preferably 5-9, more preferably 6.0-8.5. The replenishment amount for the washing process and stabilization process is 1 of the amount carried in from the previous bath per unit area.
˜50 times, preferably 1 to 20 times, more preferably 1 to
7 times. The treatment time is preferably 2 minutes and 30 seconds or less, and more preferably 1 minute and 30 seconds or less, as a total treatment time of the washing and / or stabilizing step. Although tap water can be used as water used in these washing and stabilizing steps, water, halogen, ultraviolet germicidal lamp, etc. deionized to a Ca or Mg ion concentration of 5 mg / liter or less with an ion exchange resin or the like. It is preferred to use more pasteurized water. In addition, it is preferable to use a method in which the overflow liquid of the water washing step or the stabilization step is caused to flow into a bath having a fixing ability, which is a pre-bath, because the amount of waste liquid can be reduced.

In the process of the present invention, in order to correct the concentration due to evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, JP-A 1-2
A monitor water tank different from the bleaching tank described in Nos. 54959 and 1-254960 is installed, the evaporation amount of water in the monitor water tank is obtained, and the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of this water. However, a method of replenishing the bleaching tank with water in proportion to the amount of evaporation and JP-A-3-248155 and 3-24
No. 9644, No. 3-249645, No. 3-24964
The evaporation correction method using a liquid level sensor or an overflow sensor described in Japanese Patent No. 6 is preferable. Water for correcting the evaporation of each treatment liquid may be tap water, but deionized water preferably used in the above washing step,
It is good to use sterilized water.

From the viewpoint of preventing evaporation or preventing deterioration of the liquid, it is preferable that the area (opening area) in which the liquid comes into contact with air is as small as possible. For example, when the value obtained by dividing the opening area (cm ² ) by the volume of the processing liquid (cm ³ ) is the opening ratio, the opening ratio is preferably 0.01 (cm ⁻¹ ) or less, and 0.005 (c
m ^-1 ) or less is more preferable.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer on the support, There are no particular restrictions on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
13438, 59-113440, 61-20037, 61-20038
The couplers as described in the specification, DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is commonly used. The plural silver halide emulsion layers constituting each unit light-sensitive layer are preferably composed of two layers of high-sensitivity emulsion layer and low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. In general, it is 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 each halogen emulsion layer. Further, JP-A-57-112751, 62-200350, 62-206541, 62
A low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support as described in JP-A-206543. As a specific example, from the side farthest from the support, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) /
High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL
It can be installed in the order of / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. In addition, JP-A-56-25738 and 62
It is also possible to arrange the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification of JP-A-63936. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also,
Even in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448
No. 63-89850, a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL, is arranged adjacent to or close to the main photosensitive layer. It is preferable. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodide containing 0.5 to 30 mol% of silver iodide. It is silver chlorobromide. Particularly preferred is silver iodobromide containing 2 to 10 mol% silver iodide. When silver halide in this range is used, the effect of using the ultrafine dispersion and the processing method in the present invention is great, and higher color density and efficiency can be obtained. The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is described in, for example, Research Disclosure No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 1 thereof.
8716 (November 1979), p. 648, ibid. 307105 (November 1989)
Mon), pp.863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et.
Phisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF
Duffin, Photographic Emulsion Chemistry (Focal Pre
ss, 1966)), "Production and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Makingand Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain, or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with silver halide grains, U.S. Pat. No. 4,626,498, JP-A No. 59-214852, the inside of which is covered with silver halide particles, and colloidal silver are light-sensitively halogenated. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer: page 649, right column 4. Brightening agent: page 24, page 647, right column 868, fogging prevention 24: 25, page 649, right column 868: 870, stabilizer: light absorber, 25: Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 left column 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, a compound capable of being immobilized by reacting with a formaldehyde described in US Pat. It is preferable to add. In the light-sensitive material of the present invention, U.S. Pat. Nos. 4,740,454, 4,788,132 and JP-A-62-185 are used.
It is preferable to incorporate the mercapto compounds described in JP-A No. 39-39, JP-A 1-283551. The light-sensitive material of the present invention has
It is preferable to include a compound described in 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing. International Publication WO88
/ 04794, dyes dispersed by the method described in JP-A-1-502912 or EP 317,308A, U.S. Pat.
And the dyes described in JP-A 1-259358 are preferably contained.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and N.
o. 307105, VII-CG. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
No. 5,118,599, European Patent No. 249,473.
A, 447,969A, 482,552A
Those described in No. 10 are preferable.

In the present invention, it is preferable to use the magenta coupler represented by the above formula (M) or (m). Next, the compound represented by the formula [M] will be described in detail. Among the pyrazoloazole-based couplers represented by the formula [M], the imidazo [1,2-
b] pyrazoles, pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 4,540,654, and pyrazolo [[3,25,067] described in US Pat. 1,5-c] [1,2,4] triazole is preferred.

For details of the substituents of the azole ring represented by the substituents R ₁ , X ₁ and Z, see, for example, US Pat. No. 4,540,654, column 2, line 41 to column 8, column 27. Are listed in a row. The substituent of the azole ring represented by R ₁ and Z is preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group or the like, and X ₁ is a coupling agent with an oxidized product of a developing agent other than a hydrogen atom. A group capable of leaving during the reaction, particularly a halogen atom or an aryloxy group is preferable. Among them, JP-A-6
Pyrazoloazole couplers in which a branched alkyl group as described in 1-65245 is directly bonded to the 2, 3 or 6-position of a pyrazolotriazole ring, and a sulfonamide group in the molecule described in JP-A-61-65246. , A pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group described in JP-A-61-147254, JP-A-62-209
Nos. 457 or 63-307453, pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, and pyrazolotriazoles having a carbonamide group in the molecule described in JP-A-2-201443. Couplers are preferred. Specific examples of the pyrazoloazole coupler represented by the formula (M) are shown below, but the invention is not limited thereto.

[0105]

[Chemical 14]

[0106]

[Chemical 15]

[0107]

[Chemical 16]

[0108]

[Chemical 17]

[0109]

[Chemical 18]

[0110]

[Chemical 19]

[0111]

[Chemical 20]

[0112]

[Chemical 21]

[0113]

[Chemical formula 22]

[0114]

[Chemical formula 23]

[0115]

[Chemical formula 24]

The coupler represented by the formula [M] is represented by US Pat. Nos. 4,540,654 and 4,705,863,
JP-A-61-65245, JP-A-62-209457,
62-249155, Japanese Examined Patent Publication No. 47-27411,
It can be synthesized by the method described in US Pat. No. 3,725,067.

The compound represented by the formula [m] is described in detail below. Among the 5-pyrazolone magenta couplers represented by the formula [m], R ₁₁ is an acyl group, Ar is a phenyl group substituted with one or more halogen atoms (especially chlorine atoms), and X ₁₁ is a hydrogen atom or alkyl. Alternatively, a coupling-off group of an arylthio group or an azolyl group is preferable.

Describing in detail about these preferable groups, R ₁₁ is acetyl, pivaloyl, tetradecanoyl,
2- (2,4-di-tert-pentylphenoxy) acetyl, 2- (2,4-di-tert-pentylphenoxy) butanoyl, benzoyl, 3- (2,4-di-tert-amylphenoxyacetamido) benzoyl Acyl groups such as, which may have further substituents, which are organic substituents or halogen atoms linked by carbon, oxygen, nitrogen or sulfur atoms.

Ar is 2,4,6-trichlorophenyl,
It is a substituted phenyl group such as 2,5-dichlorophenyl and 2-chlorophenyl. X ₁₁ is preferably a group excluding a hydrogen atom and capable of splitting off during a coupling reaction with an oxidized product of a developing agent.

Preferred coupling-off groups for X ₁₁ are dodecylthio, benzylthio, 1-carboxyldodecylthio, phenylthio, 2-butoxy-5-tert-octylphenylthio, 2,5-dioctyloxyphenylthio, 2- (2- Ethoxyethoxy) -5-tert-octylphenylthio, 2-pivaloylaminophenylthio,
Alkyl or arylthio groups such as tetrazolylthio, or 1-pyrazolyl, 1-benzotriazolyl,
Or 5-chloro-1,2,4-triazole-1-
It is an azolyl group such as yl.

A preferable combination of substituents of the two-equivalent coupler having a coupling-off group is described in JP-A-57 / 57.
No. 35858 and JP-A No. 51-20826.

Specific examples of preferable couplers are listed below.

[0123]

[Chemical 25]

[0124]

[Chemical formula 26]

[0125]

[Chemical 27]

[0126]

[Chemical 28]

[0127]

[Chemical 29]

[0128]

[Chemical 30]

A method for synthesizing a typical 2-equivalent coupler having a coupling-off group is described in detail in JP-A-51-20826 and JP-A-57-35858. In addition to the specific examples of the above-mentioned couplers, WO92 / 1890
No. 1, WO92 / 18902, and WO92 / 189
No. 03, WO 93/2392 and the like can be used.

In the present invention, when the above-mentioned support of the present invention is used and a light-sensitive material containing the above-mentioned magenta coupler is processed by the processing method described later, the storability of the light-sensitive material after storage and color development processing are performed. From the viewpoint of improving the storability of color image, it is preferable to use the coupler represented by the formula [M] as compared with the coupler represented by the formula [m].

The coupler represented by formula (M) or (m) of the present invention may be used in any layer in the silver halide light-sensitive material, but it is added to the green-sensitive emulsion layer and / or its adjacent layer. Preferably. The total amount added is 1 x 1
0 ^{−3 to} 1.0 g / m ² , preferably 5 × 10 ^{−3 to} 0.8 g
/ M ² , more preferably 1 × 10 ^{-2 to} 0.5 g / m ² . The method of adding the coupler of the present invention to the light-sensitive material is in accordance with the method of other couplers described below, but the amount of the high-boiling organic solvent described below used as a dispersion solvent with respect to the magenta coupler is 0 to 3 as a weight ratio. 0.0 is preferable and 0.3
˜2.0 is more preferable, and 0.5 to 1.2 is further preferable. It should be noted that European Patent 529,72
It is preferable to use the compounds described in Nos. 7A and 529,736A in combination.

The coupler represented by the formula (M) or (m) of the present invention can be used with a known magenta coupler. As known magenta couplers, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
2,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,573,910, British patent 2,10
2,137, European Patent No. 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105, Item VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
Nos. 1,146,368 and EP 423,727A are preferred. In addition, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.
It is also preferable to use a coupler having a dye precursor group as a leaving group capable of reacting with a developing agent to form a dye as described in 4,777,120. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are
RD 17643, Item VII-F and No. 307105, VII-
Patents described in paragraph F, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
Nos. 4,248,962, 4,782,012, European Patent Nos. 520,496A, 522,371A, and 525,396A are preferable. The bleaching accelerator releasing couplers described in RD No. 11449, 24241 and JP-A-61-201247 are
It is effective in shortening the time of the processing step having a bleaching ability, and its effect is particularly large when it is added to the light-sensitive material using the tabular silver halide grains described above. Further, by using an amount less than the amount showing a remarkable bleaching promoting effect in the photosensitive layer or the non-photosensitive layer on the side farther from the support of the photosensitive material, the fluctuation of photographic properties in the running process of the photosensitive material can be suppressed. It gives a small and stable development processability. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157638 and JP-A-59-170840 are preferable. In addition, JP-A-60-107029 and 60-70
No. 252340, JP-A-1-44940, by a redox reaction with the oxidant of the developing agent described in 1-45687, a fogging agent,
A compound that releases a development accelerator, a silver halide solvent, etc. is also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after separation described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone etc.), alcohols or phenols (isostearyl alcohol, oleyl alcohol, 2,4-di
-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.),
Examples thereof include aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

In the present invention, in order to reduce the increase in the minimum density (Dmin) due to color contamination of the light-sensitive material after color development processing and further prevent the deterioration of the image quality, the above high-boiling organic solvent is added to the light-sensitive material. It is desirable to reduce the amount used. In the present invention, the amount of the high boiling point organic solvent used is
It is preferably 5.0 g or less per 1 m ^{2 of the} light-sensitive material. It is more preferably 4.0 g or less, and further preferably 3.0 g or less. The lower limit may not be contained at all, but it is preferable to include about 0.3 g as the lower limit because of the physical properties (brittleness etc.) of the film of the photosensitive material. In addition, it is preferable to use the compounds described in European Patent Nos. 529,727A and 529,736A together with the high boiling point organic solvent.

The light-sensitive material of the present invention may contain the anionic latex polymer described in European Patent (EP) 535,535A. By providing the latex polymer-containing layer on the side farther from the support with respect to two silver halide emulsion layers having different color sensitivities, the layer functions as a barrier layer for reflecting the anionic development inhibitor released from the DIR compound, Image effect (II
E) can be increased and the development inhibitor can be prevented from flowing out into the development processing solution. The latex polymer is composed of a copolymer of vinyl monomers, preferably 1% or more by weight of a monomer having an anionic pendant group (for example, sulfo, sulfino, carboxyl, oxysulfo, phosphono, oxyphosphono, or a salt thereof). The content is more preferably 1% to 20%, further preferably 3 to 10%. The latex polymer addition layer is preferably a non-photosensitive layer, and particularly preferably a protective layer (when the protective layer has two or more layers, the first protective layer closest to the support is preferable) or a yellow filter layer. .
The amount of the latex polymer added to the light-sensitive material is 0.1.
3.0 g / m ^2, preferably not 0.3 to 2.0 g / m ^2, more preferably at 0.5 to 1.5 g / m ^2.

Specific examples of the latex polymer are shown below. The weight percentage of each monomer is shown in parentheses. L-1 n-butyl acrylate / 2-acrylamido-2-methylpropane sulfonic acid / 2-acetoacetoxyethyl methacrylate (88: 5: 7) L-2 n-butyl acrylate / styrene / methyl acrylamide / 2-acrylamide 2-Methylpropanesulfonic acid (59: 25: 8: 8) L-3 n-butyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid (95: 5) L-4 n-butyl acrylate / styrene / 2-acrylamido-2-methyl propane sulfonic acid (85: 10: 5) L-5 n-butyl acrylate / styrene / 2-acrylamido-2-methyl propane sulfonic acid (65: 30: 5)

The light-sensitive material of the present invention includes 1 × 10 ⁻⁵ to 4 × described in European Patent (EP) 539,729A.
It may have a reflective layer of the development inhibitor released from the DIR compound containing a polymer containing 10 ⁻³ mols / g of ion-forming functional groups. By adding the polymer-containing layer to a non-photosensitive layer between two silver halide emulsion layers having different color sensitivities, it functions as a barrier against diffusion of an anionic development inhibitor and reduces inter-image effect (IIE). Or, the sharpness can be improved by strengthening the suppression of the DIR compound to its own layer. The polymer comprises a copolymer of vinyl monomers, and comprises at least one hydrophobic vinyl monomer (eg, acrylates, methacrylates, acrylamides, methacrylamides, etc.) and at least one ion-forming functional group (eg,
A hydrophilic monomer having a primary amino, sulfo, sulfino, carboxyl, oxysulfo, phosphono, oxyphosphono, etc., or salts thereof).
The polymer may have a crosslinkable functional group with gelatin for preventing diffusion in the layer. The added layer of the polymer is preferably a non-photosensitive layer, and particularly preferably an intermediate layer between the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer or the green-sensitive silver halide emulsion layer and the blue layer. An intermediate layer between the sensitive silver halide emulsion layers is preferred. The polymer may be added to a light-sensitive emulsion layer, or may be added to a layer between two same-color-sensitive silver halide emulsion layers having different sensitivities. The amount of the polymer added to the light-sensitive material is 0.1 to 2.0 g / m ² , preferably 0.2 to 1.5 g / m ² .
m ² and more preferably 0.5 to 1.0 g / m ² .

Specific examples of the polymer are shown below. ()
The percentages inside each indicate the weight percentage of each monomer. IP-1 N-isopropylacrylamide / N- (3-aminopropyl) methacrylamide hydrochloride (90:10) IP-2 Nt-butylacrylamide / N- (3-aminopropyl) methacrylamide hydrochloride (80: 20) IP-3 Nt-butylacrylamide / allylamine sulfate (92: 8) IP-4 N-butylmethacrylate / aminoethylmethacrylate hydrochloride / hydroxyethylmethacrylate (50:30:20) IP-5N -Butyl methacrylate / sulfoethyl methacrylate sodium salt / 2-acetoacetoxyethyl methacrylate / hydroxyethyl methacrylate (60: 5: 10: 25) IP-6 Nt-butylacrylamide / acrylamide / N-2-carboxyethyl Acrylamide / N- (3-aminopropyl) methacrylamide hydrochloride (65 : 20: 5: 10)

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,363,
West German Patent Application (OLS) Nos. 2,541,274 and 2,54
It is described in No. 1,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, and the like.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and 16 μm or less. Particularly preferred. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al.
(Photogr.Sci.Eng.), Volume 19, No. 2, pp. 124-129. It can be measured by using a swellometer (swellometer) of the type, and T _1/2 is 30 in a color developer. The 90% of the maximum swollen film thickness reached when treated at ℃ for 3 minutes and 15 seconds is defined as the saturated film thickness and defined as the time required to reach 1/2 of the saturated film thickness.
The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swelling rate is 1
50 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 20 on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of μm. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%. The silver halide color photographic light-sensitive material used in the present invention is described in Japanese Examined Patent Publication No.
It can also be applied to the film unit with lens described in No. 39784.

[0145]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 (1) Support Material and the Like Each support used in this example was prepared by the following method. PEN: 100 parts by weight of commercially available poly (ethylene-2,6-naphthalate) polymer and Tinuvi as an ultraviolet absorber
n 2 parts by weight of P.326 (manufactured by Geigy) was dried by a conventional method, melted at 300 ° C., and then extruded from a T-die 14
The film was longitudinally stretched 3.3 times at 0 ° C, and then 3.3 times at 130 ° C.
Double stretching was performed, and heat setting was further performed at 250 ° C. for 6 seconds. -PET: Commercially available poly (ethylene terephthalate) polymer is biaxially stretched and heat-set according to a conventional method to have a thickness of 90 μm.
I got a film of m.・ TAC: Methylene chloride / methanol = 82/8 wt of triacetyl cellulose by an ordinary solution casting method
Ratio, TAC concentration 13%, plasticizer TPP / BDP = 2/1
(Here TPP; triphenyl phosphate, BD
15% by weight of P; biphenyl diphenyl phosphate)
The band method was used.・ PEN / PET = 4/1 (weight ratio); PE in advance
The N and PET pellets were vacuum dried at 150 ° C. for 4 hours, kneaded and extruded at 280 ° C. using a biaxial kneading extruder, and then pelletized. This polyester was formed into a film under the same conditions as the above PEN.

(2) Coating of undercoat layer Each of the above-mentioned supports is subjected to corona discharge treatment on both sides thereof, and then the undercoat liquid having the following composition is applied to provide the undercoat layer on the high temperature surface side during stretching. It was For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm width support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during processing is 9.6KHz,
The gap clearance between the electrode and the dielectric roll is 1.6.
It was mm.

Gelatin 3 g Distilled water 250 cc Sodium-α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Further, an undercoat layer having the following composition was provided on the support TAC. Gelatin 0.2g Salicylic acid 0.1g Methanol 15cc Acetone 85cc Formaldehyde 0.01g

(3) Coating of Back Layer A back layer having the following composition was coated on the surface opposite to the side on which the undercoat layer of the above support was provided after undercoating. (3-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water was redispersed in 1500 parts by weight of water, and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish average particle size of 0.1.
A fine powder of tin oxide-antimony oxide composite having a size of μm was obtained. The specific resistance of this fine particle powder was 25 Ω · cm.

A mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, roughly dispersed with a stirrer, and then
Horizontal sand mill (trade name Dyno Mill; WILLYA. BACHOFEN
It was prepared by dispersing with AG) until the residence time reached 30 minutes.

(3-2) Preparation of back layer: The following formulation [A] was applied so that the dry film thickness was 0.3 μm, and dried at 115 ° C. for 60 seconds. The following coating solution (B) for coating layer was further applied onto this so that the dry film thickness would be 1 μm.
It was dried at ℃ for 3 minutes. [Formulation A] 10 parts by weight of the conductive fine particle dispersion liquid 1 part by weight gelatin 1 part by weight water 27 parts by weight methanol 60 parts by weight resorcin 2 parts by weight polyoxyethylene nonylphenyl ether 0.01 part by weight [coating layer coating solution (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-Chlorophenol 4 parts by weight Silica particles (average particle size 0.2 μm) 0.01 parts by weight Polysiloxane 0.005 parts by weight C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (8 / 2J weight ratio) 0.01 parts by weight Dispersion (average particle size 20 nm)

(4) Heat Treatment of Support After the undercoat layer and the back layer were applied and dried and wound by the above method, heat treatment was separately performed under the conditions shown in Tables 3 to 6 below. All the heat treatments were carried out with the core having a diameter of 30 cm and the outer surface of the undercoat surface wound. On the other hand, the supports PEN, PET, P
A support which was not heat-treated at EN / PET = 4/1 (weight ratio) was also prepared.

(5) Coating of Photosensitive Layer On the support obtained by the above-mentioned method, each layer having the following composition was multilayer coated to prepare a multilayer color photosensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Hardener ExS; Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.15 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) Silver iodobromide emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.050 UV-6 0.050 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.25 Silver iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.60 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.10 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 ExC-9 0.030 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Intermediate Layer) Cpd-1 0.10 Cpd-4 0.050 HBS-1 0.20 LP-2 0.80 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExC-10 0.010 ExM-1 0.010 m-13 0.15 ExM-2 0.086 M-30 0.12 ExY-1 5.0 × 10 ^-3 HBS-1 0.14 HBS-4 0.14 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.70 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-10 0.010 m-5 0.070 M-30 0.040 ExM-2 0.030 ExY-1 8.0 × 10 ^-3 HBS-1 0.07 HBS-3 0.07 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 0.95 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExC-10 0.010 ExM-1 0.030 M-12 0.040 M-13 0.019 Cpd-3 0.067 HBS-1 0.19 HBS-2 0.080 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 ExC-11 0.06 Cpd-1 0.10 LP-4 0.75 HBS-1 0.20 Gelatin 0.80

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExC-7 0.010 ExY-1 0.020 ExY-2 0.22 ExY-3 0.30 ExY-4 0.020 ExY-5 0.22 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Medium Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion D Silver 0.37 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 ExY-4 0.010 HBS-1 0.050 Gelatin 0.78

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F Silver 0.80 ExS-7 4.0 × 10 ^-4 ExC-6 5.0 × 10 ^-3 ExY-2 0.10 ExY-3 0.10 ExY-4 0.020 HBS-1 0.070 Gelatin 0.86

Fourteenth layer (first protective layer) Silver iodobromide emulsion G Silver 0.15 UV-4 0.10 UV-5 0.10 UV-6 9.0 × 10 ^-2 L-1 1.00 HBS-1 5.0 × 10 ^-2 gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.32 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.25 gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-5, B-4 to B may be appropriately added. -6, F
-1 to F-18 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0171]

[Table 1]

In Table 1, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) Low molecular weight gelatin was used for the preparation of tabular grains according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0173]

[Chemical 31]

[0174]

[Chemical 32]

[0175]

[Chemical 33]

[0176]

[Chemical 34]

[0177]

[Chemical 35]

[0178]

[Chemical 36]

[0179]

[Chemical 37]

[0180]

[Chemical 38]

[0181]

[Chemical Formula 39]

[0182]

[Chemical 40]

[0183]

[Chemical 41]

[0184]

[Chemical 42]

[0185]

[Chemical 43]

[0186]

[Chemical 44]

[0187]

[Chemical formula 45]

[0188]

[Chemical formula 46]

The produced multilayer color light-sensitive material was processed as a sample as follows.

(6) Processing of photographic film sample The photographic film sample produced in this way was 35 mm
A film-integrated camera was manufactured by slitting the film to a width of 1.8 m, punching it, and incorporating it into a unit as shown in FIG. 1 or 2. These are designated as Samples 101 to 139. Figure 1
[FIG. 3] is a top view showing the internal structure of a film-integrated camera. In this camera 1, a unit 3 is housed inside a camera outer box 2. In this unit 3, the unexposed film 8 drawn from the cartridge 6 is wound and loaded in the supply chamber 4. Then, the film is pulled out from the supply chamber 4 and wound up in the cartridge 6 each time a photograph is taken. Reference numeral 7 is a taking lens, and 9 is a film supporting surface. 8 is a film having a length of 1.8 m.

Further, FIG. 2 shows only the unit 13 portion of another type of film-integrated camera, and this one has a spool 21 in the cartridge 16 (a description of the spool is omitted in FIG. 1). ) Outside the supply room 1
4 also has a spool 22. As the film 18, a film having a length of 1.8 m is used.

Next, as a comparative sample, one in which the temperature / time of the heat treatment of the support PEN, the spool diameter of the film-integrated camera, and the winding diameter were changed as shown in Table 6 was prepared.
These are designated as samples 140 to 143. (7) Core set The above film-integrated camera was heated at 40 ° C. for 24 hours to have a curl. This temperature condition is a condition assuming outdoor in summer. (8) Extraction of tongue end, development process, curl measurement After the above film-integrated camera with a curled curl under the above conditions was left to cool overnight in a room at 25 ° C, the tongue end was extracted with a jig. Automatic developing machine (Minilab FP-55
0B: made by Fuji Photo Film Co., Ltd.) and immediately processed to 25
Curl measurement was performed at 60 ° C. and 60% RH.

The development processing conditions are as follows. The sample used for the measurement was separately processed by running the sample which was previously subjected to imagewise exposure, and was processed using the processing solution which was used until the replenishment amount for color development was replenished by 3 times the tank volume. I did.

(Processing process) Process processing time Processing temperature Replenishment amount ^* Tank capacity Color development 165 seconds 38.0 ° C 300 ml 5 liters Bleach 40 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 40 seconds 38.0 ° C-5 liters Fixed 40 seconds 38.0 ° C 420 ml 5 liters Water wash 20 seconds 38.0 ° C 980 ml 3.5 liters Stable (1) 20 seconds 38.0 ° C −3 liters Stable (2) 20 seconds 38.0 ° C 560 ml 3 liters Dry 1 minute 30 seconds 60 ° C ^* Replenishment amount Is a countercurrent system from (2) to (1) per 1 m ² of light-sensitive material, and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the washing process were each per 1 m ² of the light-sensitive material. They were 65 ml, 50 ml, 50 ml and 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 3.2 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.2 Potassium carbonate 37.5 39.0 Potassium bromide 1.7-Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 4.2 2-methyl-4- [N-ethyl-N- (γ-hydroxypropyl) amino] aniline (D-2) sulfate 6.3 (20.5 mmol) 10.1 1.0 liter of water was added. 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.45

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropaneferric Acid Ferric Acid Ammonium Monohydrate 130 195 Ammonium Bromide 70 105 Ammonium Nitrate 14 21 Hydroxyacetic Acid 25 38 Acetic Acid 40 60 Water 1.0 liter 1.0 liter pH [prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (P
H7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution 280 ml 840 ml (700 g / l) Imidazole Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH [ammonia Prepared with water and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-Triazole 1.3 1,4-Bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Hydroxyethylcellulose 0.1 (Daicel Chemistry HEC SP-2000) Water was added to 1.0 liter pH 8.5

Further, in order to examine the change in the minimum density (Dmin) with time after color development processing, for the samples subjected to the development processing of the unexposed sample, the B density was measured and then these samples were subjected to 80 ° C. and relative humidity. After being stored under the condition of 70% for 2 months, the B concentration was measured again to determine the increase of the B concentration (ΔDmin) due to the storage. These results are summarized in Table 2
It shows in Table 5.

[0202]

[Table 2]

[0203]

[Table 3]

[0204]

[Table 4]

[0205]

[Table 5]

In Tables 2 to 5, "after-treatment ANSI curl value" means ANSI / ASC, pH 1.29-19.
The degree of curl measured according to Test Method A of No. 85 is expressed as 1 / R (R is the curl radius [unit.m]). From the results shown in Tables 2 to 5, in the film-integrated camera using the film made of the polyester support that has been preheated according to the present invention, the curl value is small even when the spool diameter is small, and the tongue tip extraction work is performed. It was also easy to carry out, and there were no problems such as uneven development of the film, scratches on the film, and breakage of the trailing edge. On the other hand, the TAC and the polyester film not subjected to the heat treatment could not satisfy all of the tongue end extraction work, the development unevenness, the scratches, and the rear end fold at the same time. Although not shown in Tables 2 to 5 here, even if the type of support is PET or PEN,
When the thickness of the support was less than 50 μm, the support could not have flexural elasticity to withstand the shrinkage stress of the photosensitive layer, resulting in gutter-like curl and scratches in the development processing step. The same was true for other polyesters. Also,
When the support has a thickness of 100 μm or more, it is difficult to wind it up on a spool and store it in a cartridge or a supply chamber. Therefore, it becomes impossible to downsize the camera and the cartridge.

As a polymer having a glass transition temperature Tg of more than 200 ° C., poly (oxyisophthalooxy-2,6-dimethyl-1,4-phenyleneisopropylidene-3,5-dimethyl-1,4) having a Tg of 225 ° C. is used. -Phenylene) could not be applied to a light-sensitive material because a transparent support was not obtained.

On the other hand, it is clear that the change in Dmin during the time-lapse storage of the film after the color development treatment shows that the increase of Dmin is small for the polyester support but the increase of Dmin is large for the TAC support. Further, it can be seen that even with the polyester support, the heat-treated support has a smaller increase in Dmin during storage after treatment and is more preferable. Note that D shown in Tables 2 to 5 above
The difference in min value seems to be small at first glance, but it is accompanied by a change in hue, and the exposure time during printing on color photographic paper must be lengthened. It is shown.

Example 2 Samples 101, 107 and 11 produced and processed in Example 1
Re-prepare the same sample as 3, 122, 128 and 134,
The samples were exposed to a wedge of white light (color temperature of the light source: 4800 ° K) by using substantially the central portion of these samples, and the replenishing amount of the color developing solution in the color developing process of Example 1 was set to 300.
Ml / m ^2, the treatment time was changed as shown in Table 6 in the same process steps were performed the process by changing the composition of the color developing solution as also shown in Table 6.

[0210]

[Table 6]

The treated sample was measured for each of B, G and R concentrations, stored for 2 months under the conditions of 60 ° C. and 70% relative humidity, and then again measured for the minimum concentration (Dmin The difference (ΔDmin) between the value immediately after processing and the value after storage for 2 months at 80 ° C. and 70% relative humidity was determined. The results are shown in Table 7.

[0212]

[Table 7]

From Table 7, when the sample using the polyester support was treated with the color developing solution having the concentration of the color developing agent in the range of 20.5 to 69.8 mmol / liter, the Dmin of the sample after the treatment was changed with time. However, it can be seen that the sample of the polyester support subjected to the heat treatment of the present invention has a small increase in Dmin as compared with the sample not subjected to the heat treatment. Even when the color developing agent concentration is 16.1 mmol / liter, the increase in Dmin is small and preferable, but the characteristic curve obtained from the B, G, and R concentration measurements shows that the concentration is 20.5 mmol / liter.
When compared with that of liter, when the color development time is 165 seconds, the feeling is low and the color density is low, which is unsatisfactory from the viewpoint of rapid processing. It was also found that the Dmin value immediately after color development was higher than the Dmin value of 20.5 mmol / liter when the concentration of the color developing agent was high, particularly 80.1 mmol / liter. Since the Dmin value further increases with time, the concentration is 80.1 mmol /
It can be seen that when the value becomes liter, the image quality is greatly deteriorated due to the increase of the Dmin value, which is not preferable. Further, it was observed that the hue of the Dmin portion of the sample having a high Dmin, particularly the light-sensitive material using the TAC support, was slightly different from that of the sample having a low Dmin of the present invention. Separately, using a long film, the tongue extraction workability, curl elimination, scratches during processing, development unevenness and rear edge fold were examined, but a film using the heat-treated polyester support of the present invention was used. It was confirmed that it was as easy as Example 1 and there was no problem.

Example 3 Samples 101, 107, 113 and 12 prepared in Example 1
2, 128 and 134 7th to 9th layers, couplers (m-13, M-30) and (m-5) used in the green emulsion layer.
As shown in Table 8, M-30) and (M-12, M-13) are equimolar to the other couplers represented by the formula [M] and the formula [m] (m-13 is 1 constituting unit). Samples 301 to 318 were prepared by replacing (converted as mol).

[0215]

[Table 8]

These prepared samples are samples 101, 10
One set, including 7, 113, 122, 128 and 134, was stored at 40 ° C. and 70% relative humidity for 2 months, and the other set was stored at 5 ° C. and 35% relative humidity for the same period. . After storage, these two sets of samples were subjected to white light wedge exposure, and the color development processing described in Example 1 was performed.
Density measurement was performed for each of G and R densities to obtain their characteristic curves. From the point of the exposure amount giving the minimum concentration +0.2 of the sample stored at 5 ° C. and 35% relative humidity to the high exposure side, logE = 1 Read the density (D ₀ ) at the exposure dose point of 0.5,
The density (D ₁ ) at the same exposure point of the sample stored at 40 ° C. and 70% relative humidity of the same sample was determined, and (D ₁ / D ₀ ) × 100 was calculated as the storability of the light-sensitive material over time. On the other hand, the prepared sample was subjected to white light wedge exposure and subjected to the color development processing described in Example 1 to measure the B, G and R densities of the sample at 80 ° C. and a relative humidity of 70%. The sample was stored for 1 month under the conditions and the concentration was measured again. Immediately after the treatment of the minimum concentration value measured at the G concentration and at 80 ° C, relative humidity 70
% Difference of the minimum density value when stored in% (ΔDmin) and the density of the exposure amount that gives the density of the minimum density +1.5 immediately after the processing after reading, and calculate the residual ratio of the color image. Color image fastness. The results are shown in Table 9.

[0217]

[Table 9]

From the results shown in Table 9, the magenta couplers of the seventh to ninth layers of the green-sensitive emulsion layer of the heat-treated polyester support of the present invention are represented by the formula [M] or the formula [m] of the present invention. Like Samples 122, 128, and 134, Samples 310 to 318 in which the coupler of Example No. 3 was replaced were excellent in storability of the light-sensitive material over time, had a small decrease in color density, were excellent in color image fastness, and increased Dmin. It can be seen from the comparison with the comparative sample that the color image is small and has good color image storability. Further, comparing the couplers represented by the formula [M] and the formula [m], the formula [M] is superior to the coupler represented by the formula [m] in both the storage stability of the light-sensitive material and the color image storage stability. For example, the samples 310 and 311 and the sample 31 are
2. It is clear from the comparison between Samples 313 and 314 and Sample 315. Further, it is clear that even if the same polyester support is used, the heat-treated polyester support of the present invention is excellent in storage stability of the above-mentioned light-sensitive material and color image.

Example 4 Using the same 6 kinds of samples as in Example 2, the amounts of the color developing agent D-2 sulfate and potassium bromide in the composition of the color developing solution shown in Table 6 of Example 2 were used. The color development processing time and temperature were changed as shown in Table 10 and the replenishment rate was 300 ml / m ² in the same manner as in Example 2 from the characteristic curve to show the change in Dmin with time after color development processing. Examined. The results are shown in Table 11.

[0220]

[Table 10]

[0221]

[Table 11]

From the results shown in Table 11, the concentration of the color-developing agent was adjusted to 20.5% while changing the amount of potassium bromide added in order to suppress the development of the sample using the polyester support.
The samples having different color development processing temperatures and times in the range of 69.8 mmol / l showed that the increase in Dmin with time was T.
It can be seen that it is clearly smaller than the AC support,
It can also be seen that even with the same polyester support, the heat-treated polyester support has a smaller increase in Dmin than the non-heat-treated polyester support. Even if the concentration of the color developing agent is within the range of the present invention in the photosensitive material using the heat-treated polyester support, the color developing processing temperature and processing time are 30 to 55 ° C. and 30 to 180 seconds, respectively. It can also be seen that the processing temperature is preferably 35 to 50 ° C. Moreover, regarding the processing temperature, it was observed that the coloring of the color developing solution increased as the temperature became higher. As the processing time, it is preferable that the processing time is short in terms of rapid processing, but it is necessary to raise the processing temperature when trying to carry out processing for a short time.
As mentioned above, when the temperature is high, the liquid is heavily contaminated, and the result is that it can be seen from the density measurement that the Dmin is higher than that of other photographic materials immediately after the color development processing also using the TAC support. It was found that it was not preferable. Also, using another long film, the same tongue extraction work as in Example 1, curl measurement, scratches during processing, development unevenness and trailing edge breakage were examined. It was found that a film made of the above polyester support gave good results as in Example 1.

Example 5 Using the same six kinds of samples as in Example 2, white light was subjected to wedge exposure to the composition, processing temperature and replenishing amount of the color developing solution as shown in Table 12, and the processing time was 150. After the color development in seconds, the color development processing was carried out in the same manner as in Example 1. Next, the color developing agent D-2 sulfate of Table 12 is replaced with the sulfate of the color developing agent D-15 represented by the formula (D) in an equimolar amount, and the processing time is shortened to 140 seconds, and the others are changed. Color development processing was carried out without any notice. These color developing solutions are referred to as 5B-1 to 5B-5 (5B-1 is 5
A-1, ..., 5B-5 correspond to 5A-5, respectively.
same as below. ). Subsequently, the color developing agent D-2 sulfate was added to D
-18 was replaced with an equimolar amount, the processing time was changed to 150 seconds, 1/2 of the color developing agent D-2 sulfate was replaced with an equimolar amount of P-5, and the processing time was changed to 175 seconds to perform color development in the same manner. Processed. These color developing solutions are 5C-1 to 5C.
-5 and 5D-1 to 5D-5. The color developing solution was used after the sample which had been imagewise exposed separately was continuously processed until the amount of the replenishing solution became three times the tank volume.

[0224]

[Table 12]

The treated samples were each subjected to B, G, and R concentration measurement in the same manner as in Example 1, then stored at 80 ° C. and 70% relative humidity for 2 months, and then again subjected to concentration measurement. Difference between Dmin immediately after processing and after storage (ΔDmin)
I asked. The results are shown in Tables 13 to 16. The color developing solution using the color developing agent, the processing time, the processing temperature, the characteristic curve of the processed sample of each sample processed with the replenishment amount, and the characteristic curve measured by the G concentration were almost the same.

[0226]

[Table 13]

[0227]

[Table 14]

[0228]

[Table 15]

[0229]

[Table 16]

From the results shown in Tables 13 to 16, the photosensitive materials using the polyester support show a greater increase in Dmin with time than the photosensitive materials using the TAC support, even when the treatments with different color developing agents are carried out. You can see that it is small. It can also be seen that even with the same polyester support, the heat-treated polyester support of the present invention has a smaller increase in Dmin than the non-heat-treated polyester support.
Further, a color developing agent is prepared from D-2 sulfate to formula (D)
Using a highly hydrophobic color developing agent of D-15 sulfate, D-18 sulfate or D-2 sulfate and P-5 sulfate in a 1: 1 (molar ratio) mixture, a color developing solution represented by sensitivity,
It can be seen that the heat-treated polyester support of the present invention has a small increase in Dmin with time even in the sample processed by adjusting the development processing time so that the gradation is almost the same in G concentration. On the other hand, in the TAC support, the formula (D)
It can also be seen that the use of the color developing agent represented by the formula (1) increases the increase of Dmin. Further, the light-sensitive material using the heat-treated polyester support of the present invention has a time-dependent D even when subjected to a high replenishment color development process with almost no discharge at high temperature.
It can also be seen that the increase in min is small. It is also apparent from Table 11 and Tables 12 to 14 that the use of the color developing agent represented by the formula (D) can shorten the color development time and perform rapid processing. On the other hand, separately using a long film, the workability of extracting the tongue end of the film during color development processing, curl elimination, scratches during processing, development unevenness and rear edge fold were investigated.
The film using the heat-treated polyester support of the present invention was able to obtain the same good result as in Example 1 even when color development processing was performed by changing the developing agent. Further, the change in the color density due to the storage of the light-sensitive material with time was examined in the same manner as in Example 3, and samples 101 and 1 shown in Table 9 of Example 3 were examined.
Results similar to 07, 113, 122, 128 and 134 could be obtained.

Example 6 The same six kinds of samples as in Example 2 were used, and a wedge exposure of white light was applied to the sample, so that the processing time from the bleaching to the stabilizing process after color development of the color developing process used in Example 1 was changed. The treatment was carried out with the changes shown in Table 17. 6A for these processes
-1 to 6A-6.

[0232]

[Table 17]

Next, color development was carried out by the color developing solution of Example 1,
The treatment was carried out at the treatment temperature and the amount of replenishment, and the subsequent treatment including bleaching was conducted in the same manner as described above with the treatment steps and treatment liquid compositions shown below. These processes are 6B-1 and 6B-2.

(Treatment process) Process Treatment time Treatment temperature Replenishment amount Tank capacity 6B-1 6B-2 Bleach 45 seconds 40 seconds 38.0 ° C 140 ml 5 liter Fixing (1) 40 seconds 20 seconds 38.0 ° C-5 liter Fixing ( 2) 40 seconds 20 seconds 38.0 ° C 780 ml 5 liters Stable (1) 15 seconds 10 seconds 38.0 ° C-3 liters Stable (2) 15 seconds 10 seconds 38.0 ° C-3 liters Stable (3) 20 seconds 20 seconds 38.0 ° C 1100 ml 3 liters Total processing time 175 seconds 120 seconds * Replenishment amount per 1 m ² * Fixing is countercurrent method from (2) to (1) * Stable is countercurrent method from (3) to (1) The amount of photographic material brought into the bleaching process and the amount of fixing solution brought into the stabilizing process are 6 per 1 m ² of light-sensitive material.
It was 5 ml and 50 ml.

The composition of the processing liquid is shown below. (Bleaching solution) Tank solution (g) Replenisher solution (g) 1,3-Diaminopropane tetraacetic acid secondary 144.0 206.0 Ammonium iron monohydrate 1,3-Diaminopropane tetraacetic acid 2.8 4.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Ammonia Water (27%) 10.0 1.8 Acetic acid (98%) 51.1 73.0 Potassium carbonate 10.0-Add water 1.0 liter 1.0 liter pH (adjust with ammonia water and acetic acid) 4.3 3.4

(Fixer) Common to tank and replenisher (unit: g) Ethylenediaminetetraacetic acid disodium salt 1.7 Sodium sulfite 14.0 Sodium bisulfite 10.0 Ammonium thiosulfate aqueous solution (700 g / liter) 210.0 mL Ammonium thiocyanate 163.0 Thiourea 1.8 Water In addition 1.0 liter pH 6.5

(Stabilizer) Common to tank liquid and replenisher (unit: g) Surfactant 0.2 [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] Polymaleic acid (average molecular weight 2000) 0.1 1, 2-Benzisothiazolin-3-one 0.05 Hexamethylenetetramine 5.5 Water was added to 1.0 liter pH 8.5

Subsequently, as in the above, color development was carried out with the color developing solution of Example 1, the processing temperature and the replenishing amount, and the subsequent processing including bleaching was carried out with the processing steps and processing solution compositions shown below. The treatment was carried out in the same way. 6C for these processes
-1, 6C-2.

(Treatment process) Process Treatment time Treatment temperature Replenishment amount Tank capacity 6C-1 6C-2 Bleach 40 seconds 30 seconds 38 ° C 700 ml 5 liters Bleach solution overflow flows into bleach-fix solution tank 90 seconds bleach-fix 80 s 38 ℃ 1700 ml 5 liter Water wash (1) 15 s 10 s 38 ℃ 3.5 liter from (2) to (1) Countercurrent piping water rinsing (2) 15 s 10 s 38 ℃ 1300 ml 3.5 liter Stable 20 s 20 seconds 38 ℃ 1100 ml 3 liters Total processing time 180 seconds 150 seconds * Replenishment amount per 1 m ²

The composition of the processing liquid is shown below. (Bleaching solution) Tank solution Replenisher (g / l) (g / liter) Bleach accelerator 0.007 mole 0.007 mole _{(CH 3) 2 N-CH} 2 -CH 2 -SS-CH 2 -CH 2 -N (CH 3 ) adjusted with ₂ · 2HCl ethylenediaminetetraacetic acid ferric ammonium 130.0 130.0 dihydrate ammonium bromide 140.0 140.0 aqueous ammonia (27%) 15.0 ml 15.0 ml ammonium nitrate 30.0 35.0 pH (nitric acid and aqueous ammonia) 5.8 5.5

(Bleach-fixing solution) Tank solution Replenishing solution (g / liter) (g / liter) Ethylenediaminetetraacetate ammonium ferric acid 60.0-Dihydrate Ammonium thiosulfate aqueous solution 240.0 ml 320.0 ml (700 g / liter) Sodium sulfite 15.0 20.0 Ethylenediaminetetraacetic acid disodium salt 1.0 1.0 Ammonia water (27%) 6.0 ml-pH (using nitric acid and ammonia water) 6.8 7.3

(Washing solution) Common to tank solution and replenisher solution 20 mg of sodium isocyanurate dichloride in deionized water
/ L and 0.15 g / L of sodium sulfate were added.
The pH was in the range 6.5-7.5.

(Stabilizing Solution) Common to Tank Solution and Replenishing Solution Same as in Example 1.

Further, color developer 5 used in Example 5 was used.
After C-4 was carried out at the same processing temperature and the replenishing amount, the treatments after bleaching were carried out using the treatments of 6A-4, 6B-2 and 6C-2.

A total of 13 types of processed samples, 10 types of treatments after bleaching and 3 types of treatments with different color developers, were measured for B, G and R densities respectively, and their characteristic curves were measured. After obtaining, 8 as in the previous embodiment
After storing for 2 months under conditions of 0 ° C. and 70% relative humidity, the density was measured again, and the difference (ΔDmin) between the Dmin value immediately after color development and the Dmin value after storage was obtained. The results are shown in Table 1.
8 and Table 19.

[0246]

[Table 18]

[0247]

[Table 19]

From the results shown in Tables 18 and 19, for the light-sensitive material using the polyester support, the processing from bleaching to stabilization after color development processing was changed to shorten the processing time, and incorporated into the light-sensitive material during color development. It is apparent that the increase in Dmin with time is smaller than that in the light-sensitive material using the TAC support even in the treatment in which the washing-out time of the removed chemical is shortened. Further, it is clear that the photosensitive material using the heat-treated polyester support of the present invention is smaller than that of the photosensitive material using the unheated polyester support. It can also be seen that the light-sensitive material using the heat-treated polyester support of the present invention shows a small increase in Dmin even when the color developing agent is changed, and exhibits excellent image storability. When the total processing time from bleaching to stabilization is set to 90 seconds, even in a light-sensitive material using the heat-treated polyester support of the present invention, Dmi
There is a slight increase in n. Therefore, the total processing time is 2
It is in the range of 10 seconds to 90 seconds. It was also found that the 80-minute processing (6A-6) in which the processing time was further shortened further increased Dmin, but apart from that, the Dmin value immediately after color development processing was higher than other processing. Further examination of this revealed that a large amount of silver remained in the processed photosensitive material, and it was found that desilvering failure occurred. Therefore, regarding desilvering property, it is also preferable to avoid the processing time shown in 6A-6 and to take the processing time of 6A-5 of at least 90 seconds. In addition, from this example, it is possible to accelerate the bleaching-stabilization process after the color development process, and it is possible to accelerate the color development process as a whole together with the color development process of Example 5. Recognize. Furthermore, it was easy to examine the workability of extracting the tongue end of the film using another long film, and the color resolving property was good even in the color development process in which the process of the bleaching-stabilization process was changed. No scratches, uneven development, or rear edge breakage were observed. On the other hand, the color image storability of the sample after color development processing was carried out according to Example 3, but the sample having a processing time of 180 seconds to 90 seconds after color development processing was Sample 101 obtained in Example 3. The results were similar to 107, 113, 122, 128 and 134. However, the sample having a treatment time of 80 seconds had a low value (numerical value 1 to 3) as a whole, and a deterioration tendency was observed. The aging stability of the light-sensitive material was also examined by the same method as in Example 3, but the results have the same tendency as in Samples 101, 107, 113, 122, 128 and 134 obtained in Example 3, and thus the results of the present invention are shown. Samples 122, 128 and 134 of the composition were better than the comparative sample.

Example 7 P-2 as a preferred specific compound example of polyester
~ P-6, P-9, P-11, P-16, P-19 were used, and an ultraviolet absorber was added and melted according to the method described in (1) PEN support of Example 1. Then, extrusion molding, longitudinal stretching and transverse stretching were carried out to obtain a support having a thickness of 85 μm. These supports were similarly coated with the undercoat layer and the back layer described in Example 1 and were heat-treated at a temperature 10 ° C. lower than Tg for 48 hours, respectively, and then the photosensitive layer of Example 1 was formed. Coating was performed to prepare samples 701 to 709.

These prepared Samples 701 to 709 were put in a supply chamber having an inner diameter of 13.02 mm in accordance with the processing of the film sample of (6) described in Example 1,
After the core setting treatment of (7) was applied to give a curl, the sample was taken out from these film-integrated cameras and allowed to cool overnight in a room at 25 ° C. Table 20
As shown in FIG.
Using 4-G of Example 4 and 5B-2 of Example 5, bleaching-stabilizing treatment was carried out in Example 1, 6B-1 and 6C.
-1 was used in combination, and the increase in ΔDmin with time after these treatments was examined by the method described in Example 1 above. The results are also shown in Table 20.

[0251]

[Table 20]

From Table 20, it can be seen that the light-sensitive material using the polyester support of the present invention which has been heat-treated at a temperature of 40 ° C. or higher and lower than the glass transition temperature has a Dmin value with time after color development processing.
The fact that the degree of increase is small means that the above-mentioned Examples 1, 2, 4,
It can be seen from the comparison between the data of the samples of the present invention of Nos. 5 and 6 and the data of the comparative samples, and it is understood that a photosensitive material having improved image quality deterioration over time after processing is provided. In addition, it was easy to examine the workability of pulling out the tongue end of the film using another long film, and it was easy to remove curl after color development processing, and scratches during color development processing, uneven development and No edge breakage was observed, and similar results to those of the film using the heat-treated polyester support of Example 1 were obtained.

[0253]

EFFECTS OF THE INVENTION According to the present invention, a film wound in a roll shape eliminates curling, is easy to handle, has a small curl during development processing, and has scratches, uneven development, and
It is possible to provide a method for processing a silver halide color photographic light-sensitive material which is less likely to be broken at the trailing edge of the film and has excellent storability and color image storability of the light-sensitive material.

[Brief description of drawings]

FIG. 1 is a top view showing the internal structure of one type of film-integrated camera of the present invention.

FIG. 2 shows a partial cross-sectional top view of the unit of another type of film-integrated camera of the present invention.

[Explanation of symbols]

 1 ... ・ Camera integrated with film 2 ... Camera outer box 3, 13 ... Units 4 and 14 ... Supply room 5 and 15 ... Hoisting room 6 and 16 ... Patrone 7 ... Lens 8 ... Film 9 ... Film support surface 17 ... Lens unit 18 ... Film 20 ... Exposed frame 21, 22 ... Spool

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication G03C 7/38

Claims (4)

[Claims] 1. A silver halide in which a silver halide color photographic light-sensitive material having at least one undercoat layer and one silver halide light-sensitive layer on a support is color-developed with a color developer containing a color developing agent. In the method for processing a color photographic light-sensitive material, the support is composed of a poly (alkylene aromatic dicarboxylate) polymer, the glass transition temperature thereof is 50 ° C. or higher and 200 ° C. or lower, and the undercoat is formed after completion of the molding of the support. A support which is heat-treated at a temperature of 40 ° C. or higher and lower than the glass transition temperature before coating a silver halide photosensitive layer after coating a layer or after coating an undercoat layer, and the concentration of the color developing agent is 20 mmol / liter. A method of processing a silver halide color photographic light-sensitive material, which is not less than 70 mmol / liter. 2. The silver halide photosensitive layer has the following formula [M]:
2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, further comprising a coupler represented by the formula or a coupler represented by the formula [m]. [Chemical 1] In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a non-metal atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X ₁ represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. [Chemical 2] In the formula, R ₁₁ is an acyl group or a carbamoyl group, Ar is a phenyl group or one or more halogen atoms, an alkyl group,
A phenyl group substituted with a cyano group, an alkoxy group, an alkoxycarbonyl group or an acylamino group, and X ₁₁ represents a hydrogen atom or a coupling-off group. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing time for the color development processing is 30 seconds or more and 180 seconds or less. 4. The total processing time after the color development processing is 90.
4. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing time is from 2 seconds to 210 seconds.