JPH07219175A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a method for processing silver halide color photographic sensitive material with the supply of a bleaching soln. reduced, capable of suppressing the deterioration of bleaching performance due to the infiltration of a color developer in the processing stage and the increase of stains, capable of securing good photographic performance and with the discharge of pollutants to the environment decreased. CONSTITUTION:The average silver iodide content of the silver halide color photographic sensitive material is controlled to be 3 to 20-mol%, and 0.1 to 1mol/l dicarboxylic acid is incorporated into the supply bleaching soln. A polyalkylene aromatic dicarboxylate having 60 to 120mum thickness and 50 to 200 deg.C glass transition temp. and heat-treated at 40 deg.C to the glass transition temp is used for the substrate of the photosensitive material.

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. The present invention relates to a processing method capable of obtaining good photographic performance.

[0002]

BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials are image recording materials having high sensitivity and excellent image quality, and have been widely and widely used since ancient times. However, it has been pointed out that the treatment requires a large amount of treatment liquid, which makes it inconvenient to operate.In addition, in order to prevent environmental pollution due to treatment waste liquid after use, it is necessary to use the treatment liquid. A decrease in quantity is required. The processing of the silver halide color photographic light-sensitive material is usually carried out continuously using an automatic developing machine, and in order to obtain stable processing quality, each processing solution is supplemented with a replenisher. In order to reduce the amount of the processing solution used, it is most effective to reduce the replenishment amount of the replenisher. Among them, bleaching solutions for color photographic light-sensitive materials for photography, such as color negative films and color reversal films, which have a high silver iodide content, include compounds with a high chemical oxygen demand, biodegradable metal chelate compounds, and ammonium. Since a large amount of compounds such as salts that may affect the environment are contained and the processing liquid itself is expensive, there are particularly high requirements for the photofinisher to reduce the replenishment amount.

As a result of studying various replenishment methods in order to meet this demand, the replenishment amount of the bleaching solution is currently set to 1 m of the light-sensitive material.
^The method of reducing to about 120 ml per ² has been put to practical use. Examples are Bleach in Process C-41RA for Eastman Kodak Color Negative Film and Bleach in Process E-6 for Color Reversal Film. However, in such a bleaching solution having a low replenishment rate, when the amount of the color developing solution brought in in the previous step is increased due to a poor squeegee, the pH of the bleaching solution is remarkably increased to cause a bleaching failure and an increase in stain. There is a drawback that it becomes easier. For this reason, it is necessary to always consider squeegee management, which imposes a great burden on the photofinisher in terms of quality control.

To alleviate such problems, it is known to add a pH buffer to the bleaching solution. For example, JP-A-3-155548 discloses that an organic acid having a pKa of 2 to 5.5 such as formic acid, acetic acid, glycolic acid, lactic acid, oxalic acid, tartaric acid, malonic acid and succinic acid is added to a bleaching solution as 1.
A method of containing 2 mol / liter or more is disclosed. Certainly, the use of these organic acids is effective in preventing the rise in pH, but such high concentrations of organic acids have the adverse effect of suppressing the swelling of the emulsion layer of the light-sensitive material and slowing the bleaching speed. It has been known. The present inventor has found that, particularly in a small amount treatment in which the bleaching solution is remarkably concentrated by evaporation of water, extreme bleaching defects in which residual silver can be visually observed occur. Here, the small amount treatment means that the replenishment amount of the bleaching solution per day is less than 1/10 of the capacity of the bleaching solution tank.
This refers to the state where the processing amount of the photosensitive material is small. Further, in Japanese Patent Laid-Open No. 5-72694, the redox potential is 200 mV.
Less than 0.1 mol / l of the above organic acid ferric iron complex salt, pKa
It has been disclosed that a bleaching solution containing 0.1 to 0.8 mol / liter of an organic acid of 2 to 5.5 can provide good bleaching performance. However, the amount of color developing solution brought in due to poor squeegee is disclosed. It is not an effective means to increase On the other hand, Japanese Patent Laid-Open No. 5-181250 discloses a method for automatically correcting the evaporative concentration of the processing liquid. However, if the amount of color developer brought in is increasing,
If such concentration correction is carried out, the stain tends to be increased due to the decrease in the pH buffering capacity.

[0005]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide an excellent treatment which maintains stable bleaching performance even when the replenishing amount of the bleaching solution is greatly reduced and does not increase stain. To provide a method. The second object of the present invention is also for a photofinisher that processes a small amount of
It is to provide a simple processing method that does not impose a load on quality control. A third problem is to provide a treatment method that contributes to environmental protection by reducing the pollution load by reducing the replenishing amount of the bleaching solution.

As a result of earnest studies on the above problems, the present inventor has found that the problems can be achieved by the following method. That is, a silver halide color photographic light-sensitive material having an average silver iodide content of 3 to 20 mol% in all light-sensitive silver halides on a support is processed by an automatic processor while replenishing the processing solution. A method of processing with a bleaching solution while replenishing 50 to 200 ml of a bleaching solution per 1 m ^{2 of the} light-sensitive material immediately after color development, wherein the replenishing solution of the bleaching solution contains 0.1 to 10 parts of a dicarboxylic acid compound. The support of the photosensitive material contains 1 mol / liter and is composed of a poly (alkylene aromatic dicarboxylate) polymer having a thickness of 60 μm to 120 μm and a glass transition temperature of 50 to 200 ° C. Is heat-treated at a temperature of 40 ° C. or higher and lower than the glass transition temperature after molding, before coating the undercoat layer, or after coating the undercoat layer and before coating the silver halide photosensitive layer. By the processing method of androgenic halide color photographic light-sensitive material. Further, the present invention is more preferably achieved by replenishing the bleaching solution tank of the automatic processor with an amount of water calculated using the following (1) to (3) for processing. (1) Evaporation rate of water from the processing liquid tank measured in advance for each operating state of the developing machine (2) Accumulated time for each operating state of the developing machine (3) Temperature and humidity outside the developing machine

The present invention will be described in detail below. In the present invention, the dicarboxylic acid compound means a saturated dicarboxylic acid or unsaturated dicarboxylic acid having two carboxyl groups in one molecule, or an aromatic dicarboxylic acid having two carboxyl groups in one molecule, and sodium thereof. Salts such as salt, potassium salt and ammonium salt are shown. In the present invention, a saturated dicarboxylic acid or unsaturated dicarboxylic acid represented by the following general formula (K) and salts thereof are preferable. General formula (K) HOOC-L-COOH (In formula, L represents a C1-C4 unsubstituted aliphatic group.) The aliphatic group in L is saturated or unsaturated. Of these, an alkylene group and an alkenylene group are often mentioned.
Particularly preferred is an alkylene group. Specific examples of the dicarboxylic acid compound are shown below, but the invention is not limited thereto.

[0008]

[Chemical 1]

[0009]

[Chemical 2]

Of the above-exemplified compounds, (I
-2), (I-3), (I-4), (I-5), (I-
6) and (I-9), particularly (I-3) and (I-
4) and (I-6) are preferable. The dicarboxylic acid compounds may be used alone or in combination, but in the present invention, the combination use of (I-3) and (I-6) is particularly preferable. The dicarboxylic acid compound in the present invention is contained in the replenisher for the bleaching solution in the range of 0.1 to 1 mol / liter, more preferably 0.2 to 0.9 mol / liter, and further preferably 0.1. It is in the range of 4 to 0.8 mol / liter. Further, it is preferable that the bleaching solution itself is contained in a range of 1.5 to 0.3 times the concentration in the replenisher. Further, monocarboxylic acids such as acetic acid, glycolic acid, lactic acid, pyruvic acid, and propionic acid may be used in combination as long as the effects of the present invention are not impaired.

The bleach used in the bleaching solution of the present invention is preferably a ferric organic acid complex salt such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, hydroxyethyliminodiacetic acid, glycol ether. Ferric complex salts such as diaminetetraacetic acid, JP-A-4-121739, page 4, lower right column-
Compounds including ferric iron complex salt of 1,3-diaminopropanetetraacetic acid described in the upper left column of page 5, European Patent Publication No. 46
Carbamoyl compounds described in JP-A-1413,
A compound having a heterocycle described in No. 174432, N-
Compounds described in European Patent Publication No. 520457, including (2-carboxyphenyl) iminodiacetic acid ferric complex salts, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid No. Compounds described in European Patent Publication No. 530828 including diiron complex salts, compounds described in European Patent Publication No. 567126 including ethylenediamine-N, N′-ferric disuccinic acid complex salts, European Patent Publication No. No. 501479, compounds described in EP-A-461670, compounds described in EP-A-430000, JP-A-3-14
The ferric iron complex salt of aminopolycarboxylic acid described on page (11) of Japanese Patent No. 4446 is preferably used. In the present invention, the bleaching agents may be used alone or in combination of two or more kinds.

Specific examples of the organic acid which constitutes the preferred bleaching agent in the present invention are shown below, but the invention is not particularly limited thereto. BL-1: N- (2-acetamido) iminodiacetic acid BL-2: Methyliminodiacetic acid BL-3: Iminodiacetic acid BL-4: Hydroxyethyliminodiacetic acid BL-5: Ethylenediaminetetraacetic acid BL-6: 1, 3-diaminopropanetetraacetic acid BL-7: 1,4-diaminobutanetetraacetic acid BL-8: diethylenethioetherdiaminetetraacetic acid BL-9: glycol etherdiaminetetraacetic acid BL-10: trans-1,2-cyclohexanediaminetetraacetic acid BL-11: ethylenediamine-N, N'-di (2-
Acetamide) diacetic acid BL-12: trans-1,2-cyclohexanediamine-N, N'-di (2-acetamido) diacetic acid BL-13: o-xylylenediaminetetraacetic acid BL-14: N- (2-carboxy) Phenyl) iminodiacetic acid BL-15: ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid BL-16: 1,3-diaminopropane-N- (2-
Carboxyphenyl) -N, N ', N'-triacetic acid BL-17: Monopropionic acid iminodiacetic acid BL-18: Monocarboxylic acid iminodipropionic acid BL-19: Ethylenediamine-N, N'-disuccinic acid BL- 20: 1,3-diaminopropane-N, N'-
Disuccinic acid BL-21: Ethylenediamine-N, N'-dimalonic acid BL-22: 1,3-Diaminopropane-N, N'-
Dimalonic acid BL-23: Diethylenetriaminepentaacetic acid BL-24: Ethylenediamine-N, N ', N'-triacetic acid-N-monopropionic acid BL-25: 1,3-Diaminopropane-N, N',
N'-triacetic acid-N-monopropionic acid

In the present invention, N is superior in desilvering property.
Compounds described in European Patent Publication No. 520457 including ferric iron complex salt of-(2-carboxyphenyl) iminodiacetic acid and ferric iron complex salt of 1,3-diaminopropanetetraacetic acid are preferable, and also biodegradable. The compounds described in European Patent Publication No. 567126 including ethylenediamine-N, N′-ferric disuccinate complex salts are preferred from the viewpoint of excellent properties. In the present invention, the organic acid ferric iron complex salt may be added and dissolved as a complexed ferric iron complex salt in advance, and the organic acid as a complex forming compound and a ferric iron salt (for example,
Ferric chloride, ferric nitrate, ferric sulfate, ferric bromide, ferric ammonium sulfate, etc.) may be allowed to coexist to form a complex in the treatment liquid. The organic acid as a complex-forming compound may be slightly in excess of the amount required for complex formation of ferric ion, and when added in excess, it is usually 1 to 15
It is preferable to make it excessive in the range of%. The ferric acid complex salt of an organic acid contained in the bleaching solution of the present invention may be used as an alkali metal salt or an ammonium salt. Examples of the alkali metal salt include lithium salt, sodium salt and potassium salt, and examples of the ammonium salt include ammonium salt and tetramethylammonium salt. From the viewpoint of rapid bleaching property, ammonium salt is preferable, but from the viewpoint of environmental protection, reduction of nitrogen atom which causes eutrophication is desired, and sodium salt and potassium salt are preferable.

The concentration of ferric organic acid complex salt in the bleaching solution is
The range of 0.05 to 1 mol / liter is preferable, and particularly 0.1.
˜0.7 mol / l, more preferably 0.15 to 0.5 mol / l. In the replenisher, the amount is preferably 1.1 to 2 times, more preferably 1.2 to 1.6 times. Bleach p
In the running state, H is preferably 3.5 to 5.5, and particularly preferably 4 to 5. In addition, in the replenishing solution, in order to maintain the pH against the mixture of alkali due to the carry-in of the color developing solution, the replenisher solution should be kept at 0.5 than the running state.
A pH as low as ~ 1 is selected. To adjust to such a pH, in addition to the dicarboxylic acid compound of the present invention, if necessary, a monocarboxylic acid such as acetic acid, an inorganic acid such as nitric acid, sulfuric acid, hydrochloric acid, ammonia, sodium hydroxide, potassium hydroxide, etc. It is preferable to use the alkali.

In the present invention, the treatment with the bleaching solution is
Immediately after color development without interposing other processing solutions
Be done. This is a simple process that does not require steps such as stop solution and intermediate washing.
This is a method that is widely used in recent years.
is there. The replenishing amount of the bleaching solution in the present invention is such a value.
In the process of processing, photosensitive material 1m ²Per 50 to 200
Set to milliliters. From the viewpoint of environmental protection, replenishment amount is acceptable
It is preferable that the number is as small as possible, especially 50 to 120 mm
L, and more preferably 50 to 100 ml. Fifty
At replenishments less than milliliters, the appropriate pH and bleach concentration
Maintaining degrees is difficult.

In the present invention, in addition to a bleaching agent, a rehalogenating agent described on page 12 of JP-A-3-144446 and a nitrate as a metal corrosion inhibitor are used in the bleaching solution. As the rehalogenating agent, sodium bromide, potassium bromide, ammonium bromide, potassium chloride or the like is preferably used, and the content thereof is 0.1
-1 mol / liter is preferable, and 0.2-0.8 mol is more preferable. Further, in the present invention, various bleaching accelerators can be added to the bleaching solution. Regarding such a bleaching accelerator, for example, U.S. Pat. No. 3,893,858, German Patent No. 1,290,821, British Patent No. 1,138,842, JP-A No. 53-95
No. 630, Research Disclosure No. 171
No. 29 (July, 1978), a compound having a mercapto group or a disulfide group, JP-A-50-140.
No. 129, a thiazolidine derivative described in US Pat. No. 3,706,561.
The iodide described in JP-A-58-16235, the polyethylene oxides described in German Patent 2,748,430, and the polyamine compound described in JP-B-45-8836 can be used. . further,
The compounds described in US Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. The mercapto compounds described in JP-A-2-190856 are preferred.

In the present invention, the treatment time with the bleaching solution is 1
It is set within the range of 5 seconds to 6 minutes and 30 seconds. For quick bleaching, increase the concentration of ingredients in the bleaching solution for 15 seconds to 1
The time is preferably 30 minutes. Further, from the viewpoint of environmental protection and economical efficiency, when it is important to reduce the concentration of components in the bleaching solution, it is preferably 2 minutes to 6 minutes. Further, it is preferable to aerate the bleaching solution during the treatment.
By aeration, the ferrous complex salt generated by bringing in a color developing solution or silver bleaching can be oxidized into a ferric complex salt, and the bleaching performance can be appropriately maintained. Means known in the art can be used for the aeration, and specifically, blowing of air by a blower or absorption of air using an ejector can be performed. For more information on aeration, see Z-12 published by Eastman Kodak Company.
1. Yousing Process C-41 3rd Edition (1982)
Year), and the items described on pages BL-1 to BL-2 can be used. In the process using the bleaching solution of the present invention, it is particularly preferable that the stirring is intensified. The contents described in the two lines can be used.

Next, the support of the present invention and the effect of reducing the replenishing amount of the bleaching solution will be described. Between the color developing solution and the bleaching solution, in order to reduce the carry-in amount of the color developing solution,
A jig for draining liquid such as a pair of wiper blades made of silicone rubber or various plastics and a nip roller made of hard vinyl chloride is attached. These are generally called squeegee.By passing the photosensitive material through a narrow gap between blades and rollers, the processing liquid adhering to the photosensitive material is wiped off, and the processing liquid of the previous process is transferred to the processing liquid of the next process. The amount of contamination is reduced. However,
The drainage effect depends on the state of the squeegee gap, and a slight looseness of the gap causes a large change in the carry-in amount.
In addition, if the contact between the squeegee and the photosensitive material is excessively strengthened in order to reduce the carry-in amount, the photosensitive material is damaged, and the adjustment is a very laborious task. The present inventor has found that such a squeegee effect is significantly changed depending on the support of the light-sensitive material.
As a result of earnest research, they have found that the support of the present invention, which will be described in detail below, significantly improves and stabilizes the squeegee effect, and makes adjustment very easy. The present inventor has achieved the objective of the present invention to reduce the replenishment amount of the bleaching solution by combining the squeeze effect of the support with the dicarboxylic acid of the bleaching solution. In the present invention, the material used for squishy is disclosed in
130432, page 16, upper left column, line 6 to lower right column, second
Line 0 is preferable, and a nip roller made of hard vinyl chloride or urethane foam, or a wiper blade type squeegee made of silicone rubber is particularly preferable.

Next, 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 winding, mechanical strength, and cost. Among them, polyethylene terephthalate (PET) and polyethylene naphthalate-based polyester are preferable. In addition,
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,

[0021]

[Chemical 3]

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,

[0023]

[Chemical 4]

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,

[0026]

[Chemical 5]

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.

[0028]

[Chemical 6]

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, 0.1 to 0.5, and more preferably 0.2 to 0.3, 0. 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 methods for producing polyesters. 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. Regarding these polyester synthesis methods, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pp. 103-136.
Page, "Synthetic Polymer V" (Asakura Shoten, 1971), 18th
It can be performed with reference to the descriptions on pages 7 to 286. The preferred average molecular weight (weight) range for these polyesters is about 10,000 to 500,000. 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. A polymer blend obtained by mixing two or more kinds of the obtained polymers is disclosed in JP-A-49-
5482, 64-4325 and JP-A-3-19271.
8, Research Disclosure, 283, 739-
41, 284, 779-82, 294, 807-1.
It can be easily molded according to the method described in 4.

The glass transition temperature (Tg) in the present invention means that when a sample film of 10 mg is heated in a helium nitrogen stream at a temperature of 20 ° C./minute 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 use conditions thereof are not generally handled with sufficient caution, and in particular, the temperature is often exposed 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.

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 = 105C P-12: TPA / EG / BP (100/20/80) Tg = 115C 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 ° C. P-20: TPA / 5-sulfoisophthalic acid (SIP) / EG (95/5/100) Tg = 65 ° C.

In the present invention, the thickness of the polyester support (film base) is 60 μm to 120 μm, preferably 60 μm to 100 μm, more preferably 70 μm to 90 μm. If it is less than 60 μm, the storage stress of the photosensitive layer generated during drying cannot be withstood, while if it exceeds 120 μm, the above-mentioned squeeze effect is reduced and the object of the present invention cannot be achieved. Among the above polyesters, PET and PEN are particularly preferable supports in the present invention. Next, the polyester support of the present invention is characterized by being subjected to a 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. The heat treatment referred to 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 and the temperature is less than 40 ° C. It is preferable to perform a separate heat treatment after the temperature is lowered to the temperature and before the coating of the silver halide photosensitive layer.

This heat treatment is preferably carried out at a temperature slightly below the glass transition temperature in order to obtain the effects of the present invention, and is 40 ° C. or more and less than the glass transition temperature, more preferably
It is at least 30 ° C. below the glass transition temperature and less than the glass transition temperature. More preferably, the glass transition temperature is 15
The temperature is lower than ℃ and lower than the glass transition temperature. 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. Further, 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 of 20 or less).
It is also possible to perform heat treatment at 40 ° C. or higher and lower than the glass transition temperature after heat treatment at a temperature of 40 ° C. or higher and 100 ° C. or lower for 5 minutes to 3 hours. In the heating method, the film roll may be left as it is in the heating warehouse for heat treatment,
Further, it may be conveyed to the heating zone for heat treatment. The latter is preferable in consideration of manufacturing suitability. 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 undergo strength reduction or deformation due to heat, and examples thereof include stainless steel and glass fiber-containing resin.

Next, in order to further enhance the function of the polyester of the present invention as a photographic support, it is preferable to make various additives coexist. 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.

Further, one of the properties which are problematic when the polyester film of the present invention is used as a support for a photographic light-sensitive material is a problem of fogging due to the high refractive index of the support. The polyester of the present invention, particularly the aromatic polyester has a high refractive index of 1.6 to 1.7, while 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 dyeing the film is not particularly limited, but the color tone is preferably gray dyeing due to the general properties of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polyester film. Further, those having excellent compatibility with polyester 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 according to the intended use, and the slipperiness imparting means is not particularly limited.
A general method is kneading an inactive inorganic compound or coating a surfactant. 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 described above, 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. 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, a method of forming an undercoat layer and coating a photographic emulsion layer on the undercoat layer after the surface treatment is performed once or without the surface treatment (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 thought to be caused by the formation of polar groups on the surface of the support which was originally hydrophobic, and the increase of the crosslink density of the surface. It is considered that the affinity of the component contained in the undercoat liquid with the polar group is increased, or the fastness of the adhesive surface is increased. Also, various arrangements have been made for the composition of the undercoat layer, and a layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and the second layer is photographed as the second layer. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter, abbreviated as the second undercoat layer) in good contact with the layer, and a single layer of applying only one 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 carried out 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, which will easily cause a spike, 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 of the atmospheric gas and the pressure, 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, regarding the undercoating method (2), all of these methods have been well studied, and for the first undercoating layer in the multilayer method, for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used. , 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. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like.
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-based compounds (for example, compounds described in JP-A-60-225148), carbodiimide-based compounds (for example, JP-A-51-
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 patents 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 liquid-soluble ones described in US Pat. No. 4, the polymers described in US Pat. No. 4,396,706 and the like can be used. The average particle size of these fine particle matting agents is preferably 1 to 10 μm.

In addition to the above, 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 3, Issue 3,508,947, Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be coated simultaneously 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.

Most preferred as an antistatic agent for the back layer of the present invention
Preferred are ZnO and TiO₂, SnO₂, Al₂
O₃, In₂O₃, SiO₂, MgO, BaO, MoO
₃V ₂O_FiveAt least one crystalline gold selected from
It is a fine particle of a group oxide or a complex oxide of these.
Conductive crystalline oxide used in the present invention or composite thereof
Oxide particles have a volume resistivity of 10⁷Ωcm or less
More preferably 10^FiveΩcm or less. 1 as the lower limit
0³Ωcm. The particle size is 0.002-
0.7 μm, especially 0.005-0.3 μm
desirable.

Further, the silver halide color photographic light-sensitive material using the above-mentioned support 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 emulsion layer coated on the support of the present invention is not particularly limited, and a binder typified by gelatin may be used as a binder, which is conventionally known. In addition to emulsions, sensitizing dyes, couplers and dyes, various additives such as development accelerators and development inhibitors can be used. Further, as the surface active agent, antistatic agent, hardener, plasticizer and the like, conventionally known materials can be used. When the present invention is applied to a color photographic light-sensitive material, the silver halide emulsion used, its manufacturing method and various additives are described in, for example, European Patent No. 52843.
Those described on page 49, line 55 to page 55, line 16 of No. 5A can be preferably used.

In the present invention, it is particularly preferable to add an appropriate amount of water to the bleaching solution in order to correct the evaporation of water. In order to achieve the object of the present invention, it is particularly preferable to use an appropriate amount of water in a system in which an amount calculated using the data described in (1) to (3) below is automatically added. (1) Evaporation rate of water from the bleaching solution tank measured in advance for each operating state of the developing machine (2) Accumulated time for each operating state of the developing machine (3) Temperature and relative humidity outside the developing machine The water to be replenished is preferably obtained from a replenishing tank for washing water. In the present invention, the above evaporation correction is
It is particularly preferable to perform it when the residence time in the bleaching solution tank exceeds 10 days in order to exert its effect. Here, the residence time is the number of days required until the amount of the replenisher solution equal to the capacity of the bleaching solution tank is replenished. In the case of continuous treatment, the residence time is 10 days. In the present invention, the residence time of more than 10 days means that the bleaching bath having a capacity of 10 liters is replenished with an average of less than 1 liter per day. Therefore, the smaller the replenishment amount is, the longer the residence time is, and the evaporative concentration proceeds. Exert.

In the present invention, the calculation of the amount of water using the data described in (1) to (3) above is basically performed by the following equation-1. Q = V _d × T _d + V _s × T _s + V _o × T _o (Formula-1) In Formula-1, Q: Amount of water replenished in the processing tank (milliliter / day) _Vd : Average in the drive state of the developing machine Evaporation rate (milliliter / hour) T _d : Accumulated time of drive state of the developing machine per hour (hour) Vs: Average evaporation rate of developing machine in standby state (ml / hour) T _s : Development per day Accumulated time in the stand-by state of the machine (hours) V _o : Average evaporation rate in the stopped state of the developing machine (mL /
Time) T _o: cumulative time of the stop state of the developing machine per day (hours)

A supplementary explanation will be given regarding the state of the developing machine. The drive state of the developing machine refers to a state in which the transport mechanism of the developing machine is operating and the photosensitive material is being processed. The standby state means a state in which the temperature adjusting mechanism for the processing liquid is working but the transport mechanism is stopped and the photosensitive material is not processed. Finally, the hibernation state refers to a state in which the power supply is cut off and both the transport mechanism and the temperature adjustment mechanism are stopped. That is, in the present invention, the operating state of the developing machine is grasped as the above three states of drive, standby, and stop, the average evaporation rate in each state is measured in advance, and the average evaporation rate and the integration time in that state are measured. Calculated as the sum of products of
However, the average evaporation rate in each state changes depending on the temperature and relative humidity outside the developing machine. Therefore, the change due to the installation environment condition is corrected by the following Expression-2 to Expression-4. However, Formula-2 is an empirical formula. _{p s = Exp {(t +} 26.013) /16.339} ( Equation _{-2) p = p s Φ /} 100 ( equation -3) where t: temperature of the developing machine external environment (° C.) [Phi: developing machine External relative humidity (%) p: vapor pressure (mmHg) p _s: saturated vapor pressure (mmHg)

Using the vapor pressure obtained by the above equation-3, the evaporation rate in each state of the developing machine is corrected by the following equation-4. V = b-ap (Formula-4) In Formula-4 V: Average evaporation rate in each state of the developing machine (milliliter /
Time) p: vapor pressure (mmHg) a, b: coefficient V obtained by Equation-4 is an evaporation rate corrected by environmental conditions. It is expressed as 5. _{Q = (b d -a d p} ) × T d + (b s -a s p) × T s + (b o -a o p) × T o ( Equation -5)

Further, the amount of rack washing water added to the bleaching solution tank of the developing machine is deducted as α, and finally the amount of water Q calculated by the following formula-6 is replenished to the bleaching solution tank per day. . _{Q = (b d -a d p} ) × T d + (b s -a s p) × T s + (b o -a o p) × T o -α in (Equation -6) above, the coefficient b _d , B _s , b _o , a _d , a _s , a
_o is an experimental value calculated from previously measured experimental data on the relationship between vapor pressure and evaporation rate. In the present invention, the above-mentioned water amount Q may be replenished once a day or may be replenished in a plurality of times, but for the convenience of operation, it is replenished once a day at the start of operation of the developing machine. Is preferable, and the effect on the evaporation correction is sufficiently exhibited.

The water to be replenished may be supplied from anywhere, but it is preferable to supply it from the replenishing tank for the washing water of the developing machine in terms of simplicity of the apparatus. General tap water is sufficient as the replenishing water, but deionized water treated with an ion exchange resin or a reverse osmosis membrane may also be used, and chlorinated sodium isocyanurate or isothiazolone fungicide or sterilizer. It may contain an agent or may be UV-sterilized. Regarding the water used for replenishing the bleaching solution, see JP-A-5-1885.
No. 49, column 22, line 42 to column 23, 49
It is possible to cite the description of flush water up to the line.

As the temperature and relative humidity sensors used in the present invention, those described in JP-A-5-181250, column 8, lines 3 to 20 can be used. Regarding a series of operations such as detection of environmental conditions by sensors, calculation, and water replenishment, the method described in column 18, line 42 to column 22, line 3 (Example 4) of the same publication, and FIG. You can quote the method. Regarding the correction using the temperature and the relative humidity outside the developing machine, a method of calculating the value of the correction coefficient fi as a value which continuously changes depending on the environmental conditions, as described in column 20, line 24 to line 36 of the same publication. Alternatively, a method of selecting from a preset table is preferable for more accurate correction.

Next, other processing steps used in the present invention will be sequentially described. The preferred treatment steps in the present invention are listed below, but the present invention is not limited thereto. Color development-bleach-fix-wash-stable-dry Color development-bleach-bleach-fix-fix-wash-stable-dry Color develop-bleach-bleach-fix-wash-stable-dry Color-bleach-wash-fix-wash -Stable-Drying In the above treatment step, washing with water in the step before stabilization can be omitted. It is also possible to omit the final stabilizing solution. The present invention can be applied to any color light-sensitive material, but a color negative film or a color reversal film is particularly preferable. When processing a color reversal light-sensitive material, black-and-white development, reversal exposure or treatment with a reversal bath and, if necessary, a water washing step are performed prior to the above steps.

Regarding the processing liquid used for the processing of the color negative film or the color reversal film, see Japanese Patent Application Laid-Open No.
The description from column 81, line 8 to column 93, line 17 of Japanese Patent No. 34887 can be cited. Particularly, as a color developing solution, JP-A-3-158849 and 3-174152.
A liquid containing a hydroxylamine having a substituent as described in JP-A No. 2004-108242 is preferable, and a liquid containing a hydroxylamine having a sulfoalkyl group as a substituent is particularly preferable. Further, those containing diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and 4,5-dihydrosibenzene-1,3-disulfonic acid as the chelating agent are preferable. The replenisher for the color developing solution has a bromide ion concentration of 0.0 to reduce the replenishment amount.
It is preferably reduced to 04 mol / liter or less, and particularly preferably a bromide ion concentration of 0.002 mol / liter or less. Preferred examples of these color developing solutions include:
Fuji Photo Film Co., Ltd. process CN-16X,
Examples thereof include a color developing solution and a color developing replenishing solution of CN-16Q and CN-16FA, and a color developing solution and a color developing replenishing solution of Process CR-56P.

As the fixing liquid, sulfinic acid derivatives and sulfite ion-releasing compounds as preservatives, imidazoles and thiosulfonic acids as buffers or fixing accelerators,
Those containing a mesoion or thioether described in JP-A-4-365037, a mesoionic thiolate compound described in JP-A-5-80450, and a water-soluble mercapto compound described in JP-A-5-72696 are preferable.
Preferred examples of such a fixing solution include Process CN-16X and CN-16X manufactured by Fuji Photo Film Co., Ltd.
Q, CN-16FA, CR-56P fixer and fixer replenisher are preferred. Conventionally, washing with water is carried out with an amount of water of 3 to 30 liters per 1 m ^{2 of} the light-sensitive material, and washing water has been used in the range of 24 ° C to 40 ° C. The present invention can be applied without any particular change even in the case of such conventional washing with water or in the case of saving water described below. The amount of water in the water-saving treatment is from 100 ml per 1 m ² of the light-sensitive material to 1.
It is preferably 5 liters, particularly preferably 250 ml to 1 liter, more preferably 300 ml to 900 ml.

The temperature in the water-saving treatment is preferably set to 30 ° C. to 45 ° C., and particularly preferably 33 ° C. to 42 ° C. in order to enhance the washing efficiency. For the purpose of enhancing the washing efficiency, jet stirring in which a jet of washing water collides with the emulsion surface of the light-sensitive material and squeeze in liquid using a wiper blade are also preferably used. In addition, deionized water is preferably used as the washing water in the water-saving treatment in order to prevent bacterial growth, and it is also preferable to perform the water-saving treatment while performing the reverse osmosis membrane treatment described in JP-A-3-200145. Other antibacterial agents, antifungal agents, chelating agents, surfactants and the like can be used according to the purpose. It is also possible to carry out the above water-saving treatment with a stabilizing solution instead of washing water. In order to prevent the sulfurization phenomenon due to the thiosulfate in the bath having fixing ability, the stabilizing solution in this case has been disclosed in
It is preferable to contain the sulfinic acid salt described in No. 51237.

As a stabilizing solution, Japanese Patent Application Laid-Open No. 5-34888 can be used.
Nos. 5,348,89 and preferred are stabilizers containing N-methylolazoles and azolylmethylamines. The treatment time with water washing or a stabilizing solution is 20 seconds to 5 minutes, but 1 minute to 3 minutes is preferable from the viewpoint of achieving both rapid processing and ensuring the water washing effect. When the washing or stabilizing treatment is performed in multiple tanks, it is preferable to extend the time of the rear tank as compared with the front tank in order to enhance the washing or stabilizing effect. 30 seconds, 30 seconds,
A time configuration such as 1 minute or 30 seconds, 40 seconds, 50 seconds is preferable.

The replenishment amounts of the other processing solutions to be carried out simultaneously with the present invention are preferably in the following ranges. In the case of processing a color negative film (per 1 m ^{2 of} light-sensitive material), replenishing amount of color developing solution: 700 ml or less, preferably 600 to 2
00 ml, bleach-fixing solution replenishing amount: 300 ml or less, preferably 200 to 50 ml, fixing solution replenishing amount: 600 ml or less, preferably 500 to 200 ml, in the case of color reversal film processing (per 1 m ^{2 of} light-sensitive material), black and white developing solution replenishing Volume: 2100 ml or less, preferably 1300-60
0 ml, reversal solution replenishment amount: 1200 ml or less, preferably 800 to 200 ml, color developer replenishment amount: 2100 ml
Below, preferably 1300 to 600 ml, replenishing amount of bleach-fixing solution: 1200 ml or less, preferably 800 to 200 m
1, fixer replenishing amount: 1200 ml or less, preferably 80
0-200 ml.

The automatic developing machine for carrying out the present invention may be any one, but examples of preferable commercially available developing machines include:
Color negative film processor FP230B, FP350, FP360B, FP manufactured by Fuji Photo Film Co., Ltd.
560B, FP900, FNCP900, FNCP60
0, FNCP300, color reversal film processor F
RCP-500 is mentioned, "Photo Industry", March 1975, p. 70, April, p. 40, May, p.
6, page 41, page 41 of the same year, JP-A-4-130432, and the like. Including the bleaching solution of the present invention, the liquid surface of all processing liquid tanks should be covered as much as possible from the viewpoints of preventing evaporation of water, preventing oxidation of components of the processing liquid, and preventing absorption of carbon dioxide into the processing liquid. It is preferable that the area is reduced. Specifically, it is preferable that 60% to 90% of the liquid surface is covered with a floating lid or floating ball, particularly 70% to 90%, and further 80% to 90%. preferable.

The light-sensitive material used in the present invention has an average silver iodide content of 3 to 20 mol% in all the light-sensitive silver halides on the support, and particularly 5 to 15%. Is preferred. Examples of the silver halide include silver iodobromide, silver iodochloride and silver iodochlorobromide, with silver iodobromide being preferred. Specifically, the light-sensitive material used in the present invention is preferably a color negative film and a color reversal film for photographing. Regarding these photosensitive materials, JP-A-5-34
887, column 127, line 40 to column 135
Line 6, and JP-A-5-2251, column 12
The description from line 21 to column 25 line 5 can be cited. The silver halide emulsion used in the present invention is 1 to
It may contain 10 mol% of silver chloride. These silver halide emulsion grains are preferably tabular grains having an aspect ratio of 5 or more and double-structure grains having different halogen compositions inside and outside. Aspect ratio is especially 5
20 is preferable, and 6-12 is more preferable.

The light-sensitive material used in the present invention is preferably one having a dry film thickness of 20.0 to 12.0 .mu.m for all the constituent layers except the undercoat layer and back layer of the support, and particularly the support. Is 18.0 to 13.0μ, and further 17.0
It is preferably ˜14.0 μ. The support of the present invention may be provided with a conductive layer and a transparent magnetic layer on one side as described in JP-A-4-62543, and may be provided in International Publication Patent Publication WO90 / 04205, FIG. The magnetic recording layer described in 1A, the stripe magnetic recording layer described in JP-A-4-124628, and the protective layer on the magnetic recording layer described in JP-A-4-73737 may be provided. The light-sensitive material of the present invention can be processed into various formats for use. Specifically, in addition to those specified in Japanese Industrial Standards, JP-A-4-125558 and JP-A-4-1217.
It is also preferable to use those described in No. 39 and No. 4-1235560.

The package (Patrone) for accommodating the color negative film of the present invention may be any existing or known one, but in particular, US Pat. No. 4,834,30.
No. 6, FIG. 1-FIG. The shape described in 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. Those described in 3 are preferable. In addition, the color negative film used in the present invention is disclosed in JP-A-4-125558.
No. 14 Page Upper Left Column 1st Line to 18th Page Lower Left Column 1st
The one having the content described in the first line is preferable, and the coupler is particularly preferably a pyrazoloazole-based magenta coupler,
A 5-amide naphthol type cyan coupler is preferable.

[0072]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. Example 1 (1) Material of Support, etc. Each support used in this example was prepared by the following method. PEN: 100 parts by weight of a commercially available poly (ethylene-2,6-naphthalate) polymer corresponding to P-1 in the text and 2 parts by weight of Tinuvin P.326 (manufactured by Geigy) as an ultraviolet absorber and a conventional method. After being dried at 300 ° C, it is extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C, then laterally stretched 3.3 times at 130 ° C, and further stretched at 250 ° C by 6 times. Heat set for 2 seconds. The glass transition temperature was 120 ° C. By the above method, the thickness 125
Four types of supports of mμ, 110 mμ, 85 mμ and 60 mμ were prepared.・ 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. A 110 mμ thick layer was prepared by the above method.

(2) Coating of Undercoat Layer Each of the above supports is subjected to corona discharge treatment on both sides thereof, and then an 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 where 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 mixture 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 would be 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 of gelatin 27 parts by weight of water 60 parts by weight of methanol 2 parts by weight of resorcin 0.01 part by weight of polyoxyethylene nonylphenyl ether [Coating liquid for coating layer (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 PEN support After the undercoat layer and the back layer were applied and dried and wound by the above method, the PEN support was heat-treated at 110 ° C. for 48 hours. A light-sensitive material was prepared by coating each layer having the following composition on each support of PEN and TAC prepared by the above method. The details of the samples of the light-sensitive material are as follows. Sample 101 PEN 125mμ with heat treatment
Comparative Example Sample 102 PEN 110 mμ with heat treatment
Inventive Sample 103 PEN 85 mμ with heat treatment
Inventive Sample 104 PEN 60 mμ with heat treatment
Inventive Sample 105 PEN 85 mμ No heat treatment
Comparative Example Sample 106 TAC 110 mμ No heat treatment
Comparative Example (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: Ultraviolet absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H : Gelatin hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in 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.

First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 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-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 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 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 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-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 70

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-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0095]

[Table 1]

In Table 1, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331. (6) As described above, the average silver iodide content in all the photosensitive silver halides is 8.6 mol%.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
was μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0099]

[Chemical 7]

[0100]

[Chemical 8]

[0101]

[Chemical 9]

[0102]

[Chemical 10]

[0103]

[Chemical 11]

[0104]

[Chemical 12]

[0105]

[Chemical 13]

[0106]

[Chemical 14]

[0107]

[Chemical 15]

[0108]

[Chemical 16]

[0109]

[Chemical 17]

[0110]

[Chemical 18]

[0111]

[Chemical 19]

[0112]

[Chemical 20]

[0113]

[Chemical 21]

[0114]

[Chemical formula 22]

Photosensitive material sample 101 prepared as described above
To 106, Japanese Industrial Standard JIS. After performing processing (including perforation processing) conforming to the 135-size, 24-shot shooting format described in K7519, the camera was loaded into a camera and a standard subject was photographed. Next, in each test, the light-sensitive material was processed by the following processing method at 1.0 m ² per day for 20 days, and the pH and photographic performance of the bleaching solution after processing were comparatively evaluated.

1. Automatic processor used Negative film processor F made by Fuji Photo Film Co., Ltd.
The test was performed as it was, except that the capacity of the P360B bleaching bath was reduced to 2 liters. FP-360B is
In order to approximate the usage on the market, the sample was kept in a standby state or a drive state for 10 hours a day, and samples were randomly processed during this period. A pair of hard vinyl chloride nip rollers was arranged between the treatment liquid tanks to reduce the carry-in amount of the pre-treatment liquid. This nip roller is replaced with a new one at the start of each test,
The same nip pressure was adjusted to suppress variations between tests. 2. Processing specifications <Processing process><Processingtemperature><Processingtime><Replenishment amount *><Dwellingtime> Color development 38 ° C. 3 minutes 15 seconds 400 ml 29 days Bleaching 38 ° C. 50 seconds 100 ml 20 days Fixing 1 38 ° C. 50 Second-13 days Fixing 238 ° C 50 seconds 400 ml 13 days Water washing 38 ° C 30 seconds 800 ml 4 days Stable 1 38 ° C 20 seconds-6 days Stable 238 ° C 20 seconds 500 ml 6 days * per 1 m ^{2 of} photosensitive material Replenishment amount

3. Formulation of processing solution Color developing solution Tank solution (g) Replenishing solution (g) Diethylenetriaminepentaacetic acid 1.0 1.0 4,5-Dihydroxybenzene-1,3-disulfonic acid sodium salt 0.5 0.5 Sodium sulfite 3.9 5.5 Potassium bromide 1.3-Potassium iodide 0.0013-Hydroxylamine sulphate 2.4 3.5 Dinatrim-N, N-bis (sulphonatoethyl) hydroxylamine 2.0 3.0 3.0 2- Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino} aniline sulfate 4.5 6.5 Water was added to 1 liter 1 liter pH (adjusted with sulfuric acid and sodium hydroxide) 10.05 10 .20

Bleaching liquid Tank liquid (g) Replenishing liquid (g) 1,3-Diaminopropanetetraacetic acid ferric ammonium monohydrate 130 190 Ammonium bromide 70 105 Ammonium nitrate 14 21 Organic acid A 2/3 of replenishing liquid 2/3 of organic acid B replenisher described in Table 3 pH (adjusted with ammonia water) 4.5 4.0 Water added 1 liter 1 liter Fixer tank liquid (g) replenisher (g) Sub Ammonium sulfate 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water was added to 1 liter 1 liter pH (adjusted with ammonia water and acetic acid) 7.4 7.5

Rinsing water (common to tank liquid and replenisher) 20 mg of sodium chlorinated isocyanurate in tap water
/ Add liter for use. Stabilizer (tank liquid, replenisher common) Tank liquid, replenisher (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.2 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.05 In the above treatment liquid formulation, the tank liquid is It means a fresh processing liquid in the developer tank at the start of processing.

4. Evaporation correction method In some tests, the amount Q of water calculated using the following formula-5 described in the text was replenished to the color development processing tank and the bleaching processing tank every morning at the start of the operation of the developing machine. Water for replenishment was obtained from the wash replenishment tank. _{Q = (b d -a d p} ) × T d + (b s -a s p) × T s
+ (B _o −a _o p) × T _o −α (Equation-5) The following values are specifically used for the coefficients a, b, and α in Equation-5. Color developing tank to bleaching tank _{b d = 21.5 20.8 b s =} 14.3 7.3 b o = 5.1 3.5 a d = 0.15 0.15 a s = 0.14 0 .14 a _o = 0.07 0.07 α = 40 40 Further, as a correction operation method, Japanese Patent Laid-Open No. 5-181250
The method described in Japanese Patent Laid-Open Publication No. 2004-242242 was adopted. The following temperature sensors and relative humidity sensors were used outside the developing machine. Temperature sensor: Thermistor temperature sensor Relative humidity sensor: TDK CHS-GS humidity sensor

5. Evaluation method-pH of bleaching solution: The pH of the bleaching tank solution at the end of running was measured by the glass electrode method as an index for evaluating the amount of the color developing solution carried in. It is preferable that the change from the pH of the fresh bleaching solution at the start is small.・ Amount of residual silver: At the end of running, sample 10
3 was exposed to 100 CMS over the entire surface at a color temperature of 4800 K for processing, and the amount of residual silver after the processing was quantified by a fluorescent X analysis method. The upper limit of the amount of residual silver is about 5 μg / 100 cm ² , and if it is less than this value, it may have commercial value, but the lower amount is more preferable in terms of image quality such as gradation, sharpness, and color saturation. Stain: Regarding the stain, at the end of running, the sample 103 was processed without being exposed, and the minimum density of magenta was measured by an X-ray photographic densitometer and evaluated. Details of the samples used in the above tests are shown in Table 2. The test results are shown in Table 3.

[0122]

[Table 2]

[0123]

[Table 3]

Test No. No. 1 is the result of Sample 101 having a support thickness other than the present invention. However, since the amount of the color developing solution brought in was large, the pH of the bleaching solution after running increased to 5.0, and the bleaching performance also deteriorated. The residual silver amount exceeds the allowable limit of 5.0, and the stain is relatively high. On the other hand, the thickness of the support is 110 mμ and 85 m in the present invention.
μ, samples 102, 103, 104 reduced to 60 mμ
Test No. using For 2, 3, 4 and 7, the pH of the bleaching solution
Is close to 4.5 at the start, both the amount of residual silver and the stain are decreased, and the effect of the present invention is clearly shown. Test N
o. No. 5 is a content in which an organic acid was used in combination, but the results were further improved in the amount of residual silver and stain as compared with the case of using alone. In addition, the test No. In No. 6, although the bleaching solution is evaporation-corrected, it is clear that this gives the best results. Test No. 8 ~
All 10 are aspects outside the present invention. No. No. 8 is different from the present invention in that acetic acid is used as an organic acid, and has a drawback that the stain is particularly high. Further, the amount of residual silver is at a relatively high level while being within the allowable range. No. No. 9 uses the organic acid in the present invention in combination, but the total organic acid concentration exceeds the range of the present invention, which causes an increase in the residual silver amount and stain. In addition, No. 10 is T
Although AC is used as a support, the increase in pH of the bleaching solution and the consequent increase in residual silver amount and stain result in unacceptable performance.

Example 2 Samples 103, 105, and 106 produced in Example 1 were processed into 126 size (including perforation processing) defined in Japanese Industrial Standard JIS7529, and then Example 1 was performed.
Photographing exposure was performed in the camera as described in 1. Next, in each test, this light-sensitive material was processed by 5 m ² per day for 30 days by the following method, and the pH and photographic performance of the bleaching solution after processing were comparatively evaluated. 1. An automatic processor Negative film processor FNCP-40B manufactured by Fuji Photo Film Co., Ltd. was remodeled to have a bleaching solution tank capacity of 18 liters and subjected to a test. In addition, between each processing liquid tank,
A wiper blade type squeegee made of silicone rubber was provided to reduce the carry-in of the processing liquid in the previous step. Further, the color developer, the bleaching solution and the fixing solution were subjected to the same evaporation correction as described in Example 1.

2. Processing specifications Processing process <Processing process><Processingtime><Processingtemperature><Replenishmentamount><Dwellingtime> Color development 3 minutes 15 seconds 38.0 ° C 600 ml 13 days Bleaching 3 minutes 00 seconds 38.0 ° C 120 ml 30 days Washing (1) 15 seconds 24.0 ℃ From (2) to (1) 11 days countercurrent piping method Washing (2) 15 seconds 24.0 ℃ 350 ml 11 days Fixed 3 minutes 00 seconds 38.0 ℃ 400 ml 20 days Washing (3 ) 30 seconds 24.0 ℃ From (4) to (3) -Countercurrent piping system Washing (4) 30 seconds 24.0 ℃ 3000 ml-Stability 30 seconds 38.0 ℃ 400 ml 10 days Dry 4 minutes 20 seconds 55 ℃ * Replenishment The amount is a value per 1 m ² of the light-sensitive material.

3. Treatment liquid formulation The composition of the treatment liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.2 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.0 4.8 Potassium carbonate 30.0 39.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 3.1 4 (N-ethyl-N-β-hydroxyethylamino) -2 -Methylaniline sulfate 4.5 6.0 Add water 1 liter 1 liter pH 10.05 10.15

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ferric Acid Ammonium Monohydrate 24.0 36.0 N- (2-Carboxyphenyl) iminodiacetic Acid No. Diiron complex salt pentahydrate 20.0 30.0 Sodium bromide 40.0 g 60.0 g Sodium nitrate 30.0 g 45.0 g Malonic acid (Specific example I-2) 0.07 mol 0.1 mol Glutaric acid (specific Example I-4) 0.3 mol 0.5 mol Succinic acid (Specific example I-3) 0.1 mol 0.16 mol Water was added to 1 liter 1 liter pH (adjusted with NaOH and nitric acid) 4.3 3.8

(Fixer) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 100.0 ml 130.0 ml (750 g / l) Sodium thiosulfate 100.0 130.0 Sodium sulfite 12.0 16.0 Ammonium methanethiosulfonate 15.0 20.0 1,3-Diaminopropanetetraacetic acid 5.0 7.0 Acetic acid (90%) 3.0 4.0 Add water 1 liter 1 liter pH (to NaOH and acetic acid Adjustment) 6.7 6.8

(Stabilizing Solution) Tank Solution / Replenishing Solution Common (g) p-Nonylphenoxypolyglycidol (Glycidol Average Degree of Polymerization 10) 0.2 Ethylenediaminetetraacetic Acid 0.05 1,2,4-Triazole 1.3 1, 4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 glycolic acid 0.02 gentamicin 0.01 hydroxyethyl cellulose 0.1 (Daicel Chemistry HEC SP-200) 1,2-benzisothiazoline-3 -ON 0.05 Water added 1 liter pH (adjusted with ammonia water and nitric acid) 8.5

4. Evaluation method-pH of bleaching solution: In the same manner as in Example 1, the pH of the bleaching tank solution at the end of running was measured. -Amount of residual silver: In the same manner as in Example 1, the sample 103 was subjected to 100 CMS overall exposure at a color temperature of 4800 K at the end of the running, processed, and measured by a fluorescent X-ray analysis method. Stain: In the same manner as in Example 1, the sample 103 was processed without being exposed at the end of the running, and the magenta was measured. The results of the above tests are shown in Table 4.

[0132]

[Table 4]

As shown in Table 4, the test No.
In 11, the pH was maintained in a fresh tank liquid state, the residual silver amount was small, and the stain was suppressed,
Good photographic performance is maintained. On the other hand, in the comparative example, the pH was increased, the bleaching performance was deteriorated, and the stain was increased to impair the photographic performance as seen in the increase in the residual silver amount.

[0134]

In carrying out the processing with a reduced replenishing amount of the bleaching solution, the replenishing solution of the bleaching solution may contain 0.1 to 1 mol / liter of a dicarboxylic acid compound to obtain a thick support as a support of a light-sensitive material to be processed. A poly (alkylene aromatic dicarboxylate) polymer having a size of 60 to 120 mμ and a temperature of 40 ° C.
As described above, when the heat-treated product was used at a temperature lower than the glass transition point, the pH of the bleaching solution during running could be properly maintained, and good bleaching performance could be exhibited, and at the same time, an increase in stain could be suppressed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/00 530 7/42

Claims (2)

[Claims] 1. A processing solution is replenished with an automatic processor for a silver halide color photographic light-sensitive material having an average silver iodide content of 3 to 20 mol% in all light-sensitive silver halides on a support. In the method of processing with a bleaching solution while replenishing 50 to 200 ml of a bleaching solution per 1 m ^{2 of the} light-sensitive material immediately after color development, the replenishing solution of the bleaching solution contains 0% of the dicarboxylic acid compound. 1 to 1 mol / liter, and the support of the photosensitive material has a thickness of 60 μm to 12
It is made of a poly (alkylene aromatic dicarboxylate) polymer having a glass transition temperature of 50 to 200 ° C., and the support is used after molding, before applying the undercoat layer or after applying the undercoat layer. A method for processing a silver halide color photographic light-sensitive material, characterized in that it is heat-treated at a temperature of 40 ° C. or higher and lower than the glass transition temperature before the coating of the functional layer. 2. The halogenation according to claim 1, wherein the bleaching solution tank of the automatic processor is supplemented with an amount of water calculated using the following (1) to (3) for processing. Processing method of silver color photographic light-sensitive material. (1) Evaporation rate of water from the bleaching solution tank measured in advance for each operating state of the developing machine (2) Accumulated time for each operating state of the developing machine (3) Temperature and humidity outside the developing machine