JP2824722B2 - Processing method of silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rapid processing method for a silver halide photographic light-sensitive material, and more particularly, to a processing method which is excellent in drying property, fixing property and water washing property, has little risk of environmental pollution and has high stability.

[0002]

2. Description of the Related Art In the photographic industry, rapid processing, stabilization, and reduction of pollution are important issues, and many studies have been made. Particularly in the photographic industry, in recent years, with respect to the prevention of the occurrence of environmental pollution, techniques have been developed to reduce the amount of various waste liquids generated in the development processing method of a silver halide photosensitive material (hereinafter, referred to as a light-sensitive material).

[0003] As a method for reducing the washing water, for example, Japanese Patent Application Laid-Open No. 57-8542 discloses a method of drastically reducing the washing water using an aqueous solution to which a specific antifungal agent is added.
Japanese Patent Application Laid-Open No. 7-8543 discloses a method in which a multi-stage countercurrent method is adopted and the amount of washing water is reduced by specifying a replenishing amount. Japanese Patent Application Laid-Open No. 57-15724 discloses a processing bath having a fixing ability and a washing bath. A method of providing a preliminary washing step between them to reduce the amount of washing water is disclosed. On the other hand, the replenishment amount of the developing solution has been about 50 ml per 775 cm ^{2 of the} photosensitive material so far, and it is desired to reduce this amount. However, simply reducing the development processing amount causes a problem such as softening of the image with reduced sensitivity, and it is difficult to simply reduce the liquid amount. When the replenishment amount of the developing solution is reduced, the developing solution shows a certain equilibrium state depending on the composition of the film and the composition of the replenishing solution. Therefore, this replenishment amount has a very significant effect on the composition of the processing solution.
This equilibrium state can be inferred from chemical engineering calculations. However, it is difficult to accurately know the amount of the additive released from the film to the processing solution, the amount of the composition of the processing solution adsorbed on the film, and the like. It is difficult to accurately grasp the composition of the composition, and it is difficult to know the correct equilibrium state. When the replenishment amount is reduced, there is a means for increasing the concentration of the developing agent in order to maintain the development stability. However, simply increasing the developing agent in the processing solution causes a problem that the image quality is deteriorated.

[0004] On the other hand, in order to realize rapid processing, various improvements in photosensitive materials have been studied. As a commonly used method for improving the drying property of a light-sensitive material, a sufficient amount of a hardening agent (gelatin cross-linking agent) is added in advance in a light-sensitive material coating step, and a developing-fixing-water washing step is performed. There is a method of reducing the water content in the photosensitive material before the start of drying by reducing the swelling amount of the emulsion layer or the hydrophilic colloid layer. In this method, if a large amount of a hardener is used, the drying time can be shortened accordingly. However, the reduction in the amount of swelling causes the development to be delayed, resulting in low sensitivity, softening, and a decrease in covering power. Even if the development progress can be improved, the delay in the fixing speed due to the high hard film causes problems such as residual silver, residual hypo and residual color of the sensitizing dye, which is an obstacle to shortening the processing time.

For the purpose of improving the above-mentioned viewpoint, a technique utilizing tabular grains is disclosed in US Pat. No. 4,43,43.
9, 520, 4,425, 425 and the like. Also, JP-A-63-305343, JP-A-1-77
No. 047 discloses a technique for improving the development progress and the sensitivity / fog ratio by controlling the development start point of a silver halide grain having a (111) plane to the vertex and / or ridge of the grain and the vicinity thereof. . Further, JP-A-58-11193
For No. 3, tabular particles were used and the swelling of the hydrophilic colloid layer was 20
Having a covering power of 0% or less,
A radiographic element is disclosed that does not require the addition of a dura during processing. These known techniques are excellent in improving the development progress of the light-sensitive material and have high utility values. However, development, fixing,
If the processing time of each washing step is shortened, in addition to the reduction in photographic sensitivity, the remaining silver and the remaining hypo are deteriorated due to the deterioration of fixability. Further, in the case of a light-sensitive material which has been subjected to spectral sensitization with a sensitizing dye, the problem of residual color also appears. These problems other than photographic properties are limited in improvement by modifying silver halide grains, and ultimately result in problems of film quality. That is, the thickness of the hydrophilic colloid layer determines fixing and residual color, which is an obstacle to speeding up.

In this regard, Japanese Patent Laid-Open Publication No.
3, JP-A-64-86133, JP-A-1-105524
4, JP-A-1-158435, JP-A-1-158436
For example, the amount of gelatin on the side having a hydrophilic colloid layer including a silver halide emulsion layer is adjusted to a range of 2.00 to 3.50 g / m ² , and the total processing time is reduced to 20 by combining with other technical elements. Means to achieve ultra-rapid processing in seconds to less than 60 seconds is disclosed. JP-A-2-68537 discloses a means for achieving ultra-rapid processing by adjusting the weight ratio of silver to gelatin (silver / gelatin) of the photosensitive silver halide applied to the emulsion layer to 1.5 or more. Is disclosed. Further, JP-A-63-221341 discloses that silver halide grains in an emulsion layer mainly consist of tabular grains having a grain size of 5 times or more the grain thickness, and a gelatin content of 2.00 to 3.20 g.
A means for achieving ultra-rapid processing with a total processing time of 20 seconds or more to less than 60 seconds by setting the melting time to 8 minutes or more and 45 minutes or less at / m ² is disclosed.

Furthermore, the swelling ratio in JP-A 4-194929 150 to 250% of the photosensitive material, the replenishment rate of the development processing solution is not more than the photosensitive material 1 m ² per 300 ml, and said developer is a silver halide A processing method characterized by containing a solvent is disclosed.

The inventors of the present invention have studied these prior arts. As a result, when the amount of gelatin is reduced or the ratio of silver / gelatin is increased while the amount of coated silver is kept constant, blackening of abrasions and roller marks are significantly deteriorated. Eventually, the level was unacceptable for practical use, and as a result, it was confirmed that the product could not be completed as a product that could be processed very quickly. Abrasion blackening refers to a phenomenon in which, when a film is handled, rubbing between the films or when the film is rubbed with another substance, abrasion-like blackening occurs after development processing. Further, the roller mark refers to a phenomenon in which when a photosensitive material is processed by an automatic developing machine, pressure is applied to the photosensitive material due to fine irregularities on the surface of a conveying roller, resulting in black spot-like density unevenness.

The present inventors have studied means for improving scratches and roller marks while reducing the amount of gelatin applied. As a result, when the amount of silver iodide contained in a silver halide emulsion is reduced, the problem tends to be solved. I found a tendency to go. JP-A-63-221341 discloses an example in which tabular grains having a silver iodide content of 0.57 mol% at the time of forming silver halide grains were used. At the time of sensitization, 0.1 mol% of potassium iodide was added, and the total silver iodide content was 0.67 mol%.
As a result of evaluating the performance of the roller mark with this emulsion, the level was not at a sufficient level.

[0010]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, a first object of the present invention is to provide a halogenated halide which has a high development processing stability even when the replenishing amount of the development processing solution is reduced and has a low environmental pollution. An object of the present invention is to provide a method for processing a silver photographic light-sensitive material. The second object of the present invention is to provide a photographic light-sensitive material which has high sensitivity even when subjected to rapid processing, has no impairment in drying property, fixing property and residual color property, and has a sufficiently practical roller mark. It is to provide a processing method.

[0011]

The above object of the present invention has been attained by the following method. (1) A method of processing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support while replenishing a developing and fixing processing solution, wherein the emulsion of the light-sensitive material is a layer is the total hydrophilic colloid layer swelling rate of the side is less 220% to 180% of the light-sensitive material
The amount of silver applied is 1.7 g / m ² or less on one side , and the silver iodide content of the silver halide contained in the emulsion layer is 0.0
5 mol% or more and 0.15 mol% or less, and the replenishment amount of the developing / fixing processing solution is 20 ml per 775 cm ^{2 of the} photosensitive material.
Below 5 ml or more, and replenisher for developing / fixing processing solution
A method for developing a silver halide photographic material, wherein the amount and the processing time satisfy the following relational expression . 300 ≦ S × T ≦ 1000 where S is the developing / fixing processing solution per 775 cm ² .
Replenishment amount (ml), T is dry from start of processing of photographic material
The time (seconds) required to complete the drying. (2) The amount of silver applied to the silver halide photographic material is one side
And 1.5 g / m ² or less.
1. The development processing method . (3) All of the silver halide grains contained in the photosensitive emulsion layer
70% or more of the total projected area of grains has an aspect ratio of 5 or less
3. The upper tabular grains as claimed in claim 1, wherein
Development processing method.

Hereinafter, the present invention will be described in detail. In the light-sensitive material of the present invention, at least one light-sensitive silver halide emulsion layer may be provided on one side of the support.
At least one layer may be provided on each side of the support. The light-sensitive material of the present invention may have a hydrophilic colloid layer in addition to the light-sensitive silver halide emulsion layer, if necessary. For example, a protective layer is preferably provided. In the light-sensitive material of the present invention, the amount of gelatin on the side having the hydrophilic colloid layer including the light-sensitive silver halide emulsion layer is 1.70 to 3.70.
It is in the range of ² g / m ² . If the photosensitive emulsion layer is present only on one side of the support, the amount of gelatin on that side needs to be within the above range, and if the photosensitive emulsion layer is present on both sides of the support, the amount of gelatin on both sides is required. The amount of gelatin must be in the above range. When there is no hydrophilic colloid layer other than the photosensitive emulsion layer, the amount of gelatin in the photosensitive emulsion layer is in the above range.

The amount of gelatin is more preferably from 1.80 to
Range of 2.8 g / m ^2, especially in the range of 2.0~2.7g / m ² is preferred. The melting time of the light-sensitive material of the present invention is 2
The time is preferably set to 0 minutes or more and 70 minutes or less.
Melting time as used in the present invention is 1cm x 2cm
When the silver halide photographic light-sensitive material cut into pieces is immersed in a 1.5% by weight aqueous solution of sodium hydroxide at 50 ° C., at least one silver halide emulsion layer constituting the silver halide photographic light-sensitive material starts to melt. Say time to

The amount of the hardening agent used is influenced by the presence of a hardening accelerator or a hardening inhibitor, but is preferably 1 × 10 ⁻⁶ mol / g. Gelatin to 1 × 10 ⁻² mol / g.・
Used in the range of gelatin. More preferably 5 × 10
^-5 mol / g · gelatin to 5 × 10 ⁻³ mol / g · gelatin.

In the present invention, the swelling ratio refers to the degree to which a layer which swells in a developing solution, usually a hydrophilic colloid layer of a silver halide photographic material, swells in the solution. The difference between the film thickness before swelling and the film thickness before swelling was determined, and this was divided by the film thickness before swelling and multiplied by 100. Specifically, the swelling ratio in the present invention is determined by the following step (a):
(B), (c) can be determined. (A) measuring the thickness of the hydrophilic colloid layer in the silver halide photographic light-sensitive material; (b) immersing the silver halide photographic light-sensitive material in distilled water at 25 ° C. for 3 minutes;
The percentage of the change in the thickness of the layer is determined by comparing with the thickness of the layer measured in the above. Therefore, the swelling ratio in the present invention refers to the total thickness of all the hydrophilic colloid layers (for example, silver halide emulsion layer, surface protective layer, intermediate layer) present on the side of the support on which the silver halide emulsion layer is present. Can be said to be expressed as a percentage of swelling caused by immersion in distilled water at 25 ° C. for 3 minutes.

Next, the emulsion grains used in the present invention will be described. The sphere-equivalent average particle size of the same volume as the particles is 0.
It is preferably 4 μm or more. Especially 0.5 to 2.0
μm is preferred. In the case of tabular grains, the diameter of a circle having an area equal to the projected area is preferably 0.5 to 1.5 μm. The narrower the particle size distribution, the better. The silver halide grains in the emulsion may have a regular crystal form such as cubic or octahedral, or irregular (i) such as spherical, plate-like or potato-like.
It may have a crystalline form, or may consist of a mixture of particles of various crystalline forms. The composition of silver halide is silver iodobromide because of high sensitivity. The silver iodide content of the silver halide grains of the present invention is 0.05 mol% or more based on the total silver amount as an average of various grains.
0.15 mol% or less. The silver iodide distribution between individual grains may be present or uniform. The silver halide grains of the present invention may contain a trace amount of silver chloride which does not affect photographic properties, but desirably does not.

When a monodisperse emulsion is used as an emulsion in the practice of the present invention, the rate of addition of a water-soluble silver salt and a water-soluble halide is increased with the growth of silver halide grains. It is desirable to speed it up.
By increasing the addition rate, the particle size distribution is made more monodispersed and the mixing time is shortened, which is advantageous for industrial production. It is also preferable in that the chance of forming structural defects inside the silver halide grains is reduced. As a method for increasing the rate of addition, JP-B-48-36890 and Ibid.
As described in JP-A-2-16364 and JP-A-55-142329, the addition rates of the aqueous silver salt solution and the aqueous halide solution may be increased continuously or stepwise.
The upper limit of the above-mentioned addition rate may be a flow rate just before new silver particles are generated, and the values are temperature, pH, pAg, degree of stirring, composition of silver halide particles, solubility, particle size, distance between particles, or protection. It changes depending on the type and concentration of the colloid.

The method for producing a monodisperse emulsion is known, and is described, for example, in J. Am.
Phot. Sci. 12, 242-251 (1963), JP-B-48-36890, JP-B-52-16364, JP-A-55-142329, and JP-A-57-179835. You can also use the technology that is being used. The silver halide emulsion used in the present invention may be a core-shell type monodisperse emulsion, and these core-shell emulsions are known from JP-A-54-48521.

When a polydisperse emulsion is used as an emulsion in the practice of the present invention, a known method can be used for producing the polydisperse emulsion. For example, “The Theory” by TH James
neutral method, acidic method, ammonia method, forward mixing, reverse mixing, and the like described in documents such as of the Photographic Process, 4th edition, published by Macmillan (1977) pp. 38-104.
It can be manufactured by applying a method such as a double jet method, a controlled double jet method, a conversion method, or a core / shell method.

Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention.
SEARCH DISCLOSURE Volume 225 Item 22534 p.20
Pp. 58, January, 1983, and JP-A-58-12
7921 and 58-113926). The tabular silver halide grains can be produced by appropriately combining methods known in the art.

The tabular silver halide emulsion was prepared by using Cug (Cug).
nac) and Chateau "Evolution of Morphology of Silver Bromide Crystals during Physical Ripening (Evolution of the Morphology of Silver Promide Crystals Dualing Physical Ripping)" Science・ E-Industrie Photography, 33
Vol., No. (1962) pp. 121-125, Duffin (D
uffin), "Photographic emulsion Chemistry", Focal Press, New York, 1966,
p.66-p.72, APH Trivelli, WF
Smith Photographic Journal (Photogr
aphic Journal), Vol. 80, p. 285 (1940), and the like, but are described in JP-A-58-127,921, JP-A-58-113,927, JP-A-58-113,928,
It can be easily prepared by referring to the method described in U.S. Pat. No. 4,439,520.

The above-mentioned emulsions are either emulsions of the surface latent image type in which a latent image is formed on the surface of a grain, internal latent image types in which a latent image is formed in the interior of a grain, and emulsions in which a latent image is formed on the surface and inside. You may. These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a Nudel washing method or a flocculation sedimentation method to remove soluble salts. As a preferable washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B No. 35-16086, or an agglomerated polymer agent exemplified by G3 or G8 described in JP-A-63-158644 can be used. The method used is a particularly preferred desalting method.

In the emulsion according to the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. In the present invention, there are no particular restrictions on the various additives and the like used in the photographic light-sensitive material, and for example, those described in the relevant places cited below can be used.

In the present invention, it is necessary to satisfy the relation of 300 ≦ S × T ≦ 1000 in order to stably perform rapid treatment and reduce waste liquid. Preferably 400 ≦ S × T ≦
900, particularly preferably 500 ≦ S × T ≦ 900.

The effect of the present invention is particularly remarkable in a system having a small coated silver amount, and is particularly effective in a system having a coated silver amount of 1.5 g / m ² or less (per one side). Item: This section 1) Chemical sensitization method: JP-A-2-68539, page 10, right upper column, line 13 to upper left column, line 16, Japanese Patent Application No. 3-105035. 2) Antifoggant JP-A-2-68539, page 10, lower left column, line 17 and stabilizers, page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left Column. 3) Color tone improver JP-A-62-276439, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94249, page 6 lower left column, line 15 Page 11, upper right column, line 19. 4) Spectral sensitizing dyes JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 5) Surfactant JP-A-2-68539, page 11, upper left column, line 14 or antistatic agent, page 12, upper left column, line 9; 6) Matting agent, slip agent JP-A-2-68539, page 12, upper left column, line 10 or plasticizer from line 10, upper right column, line 10 from line 10, lower left column, line 14 to line 1, lower right column. . 7) Hydrophilic colloid From page 11, upper right column, line 11 to lower left column, line 16 of JP-A-2-68539. 8) Hardener From page 17, lower left column, line 17 to page 13, upper right column, line 6 of JP-A-2-68539. 9) Support 10) Crossover From page 20, upper right column, line 20 of JP-A-2-264944 or from the cutting method, page 14, upper right column. 11) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9. JP-A-3-24537, page 14, lower left column to page 16, lower right column. 12) Polyhydroxyl JP-A-3-39948, from page 11, upper left column to the first benzenes, page 2, lower left column, EP Patent No. 452772A. 13) Layer structure JP-A-3-19841. Hereinafter, the present invention will be specifically described with reference to examples.

[0026]

【Example】

Example 1 (Preparation of Octahedral Particles A-1) 40 cc of an aqueous silver nitrate solution (as silver nitrate) was added to a solution in which 0.35 g of potassium bromide and 20.6 g of gelatin were added to 1 liter of water and kept at 50 ° C. while stirring. 0.28 g) and 40 cc of potassium bromide aqueous solution (0.21 g of potassium bromide) were added simultaneously by the double jet method over 10 minutes. Subsequently, 200 cc of an aqueous silver nitrate solution (1.42 g as silver nitrate) and 200 cc of an aqueous potassium bromide solution (1.06 g as potassium bromide) were simultaneously added over 8 minutes.
Thereafter, 27 cc of a potassium bromide aqueous solution (2.7 g of potassium bromide) was added. Thereafter, an aqueous silver nitrate solution and an aqueous potassium bromide solution were again added by the control double jet method. The added aqueous solution of silver nitrate was 1 liter (140 g of silver nitrate), and the flow rate was 2 cc / min at the start of the addition, and was linearly accelerated so that the addition was completed in 70 minutes. Control potential is pA
An aqueous solution of potassium bromide was added at the same time while controlling to g = 8.58. Thereafter, the temperature was lowered to 35 ° C., and soluble salts were removed by a sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrenesulfonate as a thickener were added, and the pH was adjusted to 6.0 with sodium hydroxide. Thus, monodispersed pure silver bromide octahedral particles A-1 having a diameter of 0.62 μm were obtained.
Was formed.

(Preparation of Octahedral Particles A-2) A solution of 0.35 g of potassium bromide and 20.6 g of gelatin in 1 liter of water was added to a solution kept at 50 ° C. while stirring, and 40 cc of an aqueous silver nitrate solution (as silver nitrate) was added. 0.28 g) and potassium bromide aqueous solution 4
0 cc (0.21 g of potassium bromide) was added simultaneously by the double jet method over 10 minutes. Continue with silver nitrate aqueous solution 20
0 cc (1.42 g as silver nitrate) and potassium bromide aqueous solution 20
0 cc (1.06 g as potassium bromide) was added simultaneously over 8 minutes. Thereafter, 27 cc of a potassium bromide aqueous solution (2.7 g of potassium bromide) was added. Thereafter, an aqueous silver nitrate solution and an aqueous potassium bromide solution were again added by the control double jet method. 1 liter of the added silver nitrate aqueous solution (silver nitrate 1
At the start of the addition at 40 g), the flow rate was 2 cc / min, and the addition was linearly accelerated so that the addition was completed in 70 minutes. An aqueous potassium bromide solution was added simultaneously while controlling the control potential to pAg = 8.58. (The steps in this step are the same as those in A-1.) Subsequently, a 1% aqueous KI solution was added in an amount of 0.1 mol% based on the total silver over 1 minute. Thereafter, the temperature was lowered to 35 ° C., and soluble salts were removed by a sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrenesulfonate as a thickener were added.
Adjusted to 6.0. Thus, monodispersed silver iodobromide octahedral grains A-2 having a diameter of 0.62 μm and a silver iodide content of 0.1 mol% were obtained.
Was adjusted.

(Preparation of Octahedral Particles A-3) 40 cc of an aqueous silver nitrate solution (as silver nitrate) was added to a solution of 0.35 g of potassium bromide and 20.6 g of gelatin in 1 liter of water and kept at 50 ° C. while stirring. 0.28 g) and potassium bromide aqueous solution 4
0 cc (0.21 g of potassium bromide) was added simultaneously by the double jet method over 10 minutes. Continue with silver nitrate aqueous solution 20
0 cc (1.42 g as silver nitrate) and potassium bromide aqueous solution 20
0 cc (1.06 g as potassium bromide) was added simultaneously over 8 minutes. Thereafter, 27 cc of a potassium bromide aqueous solution (2.7 g of potassium bromide) was added. (The steps so far are A-1, A
Same as -2. Thereafter, a silver nitrate aqueous solution and a mixed aqueous solution of potassium iodide and potassium bromide were added again by the control double jet method. One liter of the added silver nitrate aqueous solution (silver nitrate 140
In g), the flow rate was 2 cc / min at the start of the addition, and the addition was linearly accelerated so that the addition was completed in 70 minutes. A mixed aqueous solution of potassium iodide and potassium bromide was added simultaneously while controlling the control potential to pAg = 8.58. The amount of potassium iodide consumed here was 0.35 mol% based on the total silver amount. Subsequently, over 1 minute, a 1% aqueous KI solution was added in an amount of 0.1 mol% based on the total silver. Thereafter, the temperature was lowered to 35 ° C., and soluble salts were removed by a sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin and 2.3 of phenoxyethanol were obtained.
5 g and 0.3 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6.0 with sodium hydroxide. Thus, the diameter was 0.63 μm, and the silver iodide content was 0.45.
A mol% of monodispersed silver iodobromide octahedral grains A-3 was prepared.

(Preparation of Octahedral Particles A-4) A solution of 0.35 g of potassium bromide and 20.6 g of gelatin in 1 liter of water was added to a solution kept at 50 ° C. while stirring and 40 cc of an aqueous silver nitrate solution (as silver nitrate) was added. 0.28 g) and potassium bromide aqueous solution 4
0 cc (0.21 g of potassium bromide) was added simultaneously by the double jet method over 10 minutes. Continue with silver nitrate aqueous solution 20
0 cc (1.42 g as silver nitrate) and potassium bromide aqueous solution 20
0 cc (1.06 g as potassium bromide) was added simultaneously over 8 minutes. Thereafter, 27 cc of a potassium bromide aqueous solution (2.7 g of potassium bromide) was added. (The steps so far are A-1, A
-2, same as A-3. Thereafter, a silver nitrate aqueous solution and a mixed aqueous solution of potassium iodide and potassium bromide were added again by the control double jet method. One liter of the added silver nitrate aqueous solution (silver nitrate 140
In g), the flow rate was 2 cc / min at the start of the addition, and the addition was linearly accelerated so that the addition was completed in 70 minutes. A mixed aqueous solution of potassium iodide and potassium bromide was added simultaneously while controlling the control potential to pAg = 8.58. The amount of potassium iodide consumed here was 0.6 mol% based on the total silver amount. Subsequently, over 1 minute, a 1% aqueous KI solution was added in an amount of 0.1 mol% based on the total silver. Thereafter, the temperature was lowered to 35 ° C., and soluble salts were removed by a sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin and 2.35 of phenoxyethanol were obtained.
g and 0.8 g of sodium polystyrenesulfonate as a thickener were added, and the pH was adjusted to 6.0 with sodium hydroxide. Thus, monodisperse silver iodobromide octahedral grains A-4 having a diameter of 0.63 μm and a silver iodide content of 0.7 mol% were prepared. A
-1, A-2, A-3, and A-4 were added with chloroaurate, sodium thiosulfate, and ammonium thiocyanate, respectively, and subjected to optimal gold-sulfur sensitization. , B are added in the amounts shown below, and 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene 2 ×
Stabilized at 10 ^-7 mol. Sensitizing dye A 450mg / Ag1mol

[0030]

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Sensitizing dye B 12 mg / Ag 1 mol

[0032]

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(Preparation of Emulsion Layer Coating Solution) The above-mentioned chemically sensitized emulsions A-1, A-2, A-3 and A-4 were coated by adding the following chemicals per mole of silver halide. Liquid.・ 72 mg of 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine ・ 9 g of trimethylolpropane ・ 18.5 g of dextran (average molecular weight 39,000) ・ potassium polystyrene sulfonate (average molecular weight 60) 1.8 g ・ Gelatin Adjusted to the amount and swelling ratio shown in Table-1 ・ Hardener 1,2-bis (vinylsulfonylacetamido) ethane Adjusted to the amount and swelling ratio shown in Table-1

Preparation of Coating Solution for Surface Protective Layer The surface protective layer was prepared and prepared such that each component had the following coating amount. Content of surface protective layer Coating amount ・ Gelatin 0.670 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.023

[0035]

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Polymethyl methacrylate (average particle size: 3.7 μm) 0.087 Proxel 0.0005 (adjusted to pH 7.4 with NaOH)

(Preparation of photographic material) As the polyethylene terephthalate having a thickness of 183 µm used as a support, a polyethylene terephthalate coated with an undercoat layer containing a dye having the following structure in an amount of 0.04 wt% was used.

[0038]

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An emulsion layer and a surface protective layer were coated on both sides of the transparent support by a simultaneous extrusion method. The amount of coated silver per one side was 1.7 g / m ² . Thus, Table-1
Photographic material was obtained.

(Evaluation of Photographic Performance) Photographic materials 1 to 16 were exposed to blue light for 0.1 second from both sides using a sharp cut filter SC52 manufactured by Fuji Photo Film Co., Ltd. After the exposure, an automatic developing machine treatment was performed using the following combinations of a developing solution and a fixing solution. When evaluating the sensitivity,
Each of the photographic materials 1 to 16 each having 775 cm ² was exposed to a developing rate of 35% and processed for 500 sheets, and then sensitometry was performed. The sensitivity was represented by the reciprocal of the ratio of the exposure amount giving a density of 1.0 based on the photographic material-1. Table 2 summarizes the results. Table 1 photographic material Emulsion surface protective layer swelling rate per silver iodide content one side and total gelatin in the emulsion layer 1 A-1 0 mol% 2.3g / m 2 150% 2 A-2 0.1 undefined undefined 3 A-3 0.45 〃 4 A-4 0.7 〃 5 A-10 １９０ 1906 A-2 0.1 〃 7 A-3 0.45 〃 8 A-4 0.7 〃 〃 9 A-10 〃 230 10 A-2 0.1 〃 １１ 11 A-3 0.45 〃 １２ 12 A-4 0.7 〃 １３ 13 A-10 ２６０ 260 14 A-2 0.1 〃 〃 15 A-3 0.45 〃 １６ 16 A-4 0.7 〃 〃

<Concentrate of developer> 56.6 g of potassium hydroxide 200 g of sodium sulfite 6.7 g of diethylenetriaminepentaacetic acid 6.7 g of potassium carbonate 16.7 g of boric acid 8 g of hydroquinone 83.3 g of diethylene glycol 40 g of 4-hydroxymethyl-4-methyl1-phenyl- 3-pyrazolidone 22.0 g 5-methylbenzotriazole 0.2 g Make up to 1 liter with water (adjust to pH 10.60).

<Fixing Solution Concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (adjusted to pH 5.10 with acetic acid). When the developing process was started, each tank of the automatic developing machine was filled with a processing solution having the following composition. Development tank and replenisher: 333 ml of the above-mentioned developer concentrate,
The pH was adjusted to 10.25 by adding 667 ml of water and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid. Fixing tank and replenisher: 200 ml of the above-mentioned fixing solution concentrate and 800 ml of water. As an automatic developing machine, FP manufactured by Fuji Photo Film Co., Ltd. is used.
Modified M2000 to speed up film transport,
The processing time of Dry to Dry was set to 60 seconds. Rinse water was flowed at a rate of 3 liters per minute only while the film was passing, and stopped at other times. The replenishment and processing temperatures of the developing solution and the fixing solution were as follows: temperature replenisher solution 35 ° C. 12.5 ml / 775 cm ² fixed 32 ° C. 15 ml / 775 cm ² water washing 20 ° C. 3 liters / one minute drying 60 ° C. S × T defined in the present invention is: current: 12.5 × 60 = 750, fixed: 15 × 60 = 900.

(Evaluation of Roller Mark) Photographic Materials 1-1
Sample No. 6 was uniformly exposed so as to have a density of 1.0 at a size of four pieces, and then processed under the same conditions as in the evaluation of photographic performance. However, the transport roller in the developing tank and the crossover roller from development to fixing used at this time were rollers that were intentionally fatigued. The surface of the roller had irregularities as large as ± 10 μm. The processed photographic material had many fine spots due to the unevenness of the roller depending on the photographic material. The state was sensory evaluated in the following four stages. Table 2 summarizes the evaluation results. ◎: Almost no spots were observed. …: A level where slight spots are generated, but not practically bothersome. Δ: Spots are generated but not normally generated with the roller. Acceptable level. X: Spots are frequent, and even a normal roller is not practical.

(Evaluation of Drying Property) After processing 500 sheets of each photographic material, 4 pieces of photographic material were processed under the same conditions as those for evaluating photographic performance.
The dryness of the film when each of the cut photographic materials was continuously processed was organoleptically evaluated by touch. The film was continuously processed with the short side in the transport direction. Table-Results
2 ◎ Even on the 30th sheet, the film comes out warm and dry. No problem at all. ○ Even on the 30th sheet, the film is completely dry. The temperature when touched was similar to that of the film left at room temperature. Δ On the 30th sheet, the film was slightly cold, but the continuously processed film did not adhere and was practically at an acceptable level × the 30th sheet, and the film was wet and undried. The films adhere to each other.

(Evaluation of Fixability) After processing 500 sheets of each photographic material, each photographic material was processed in an automatic developing machine under the above-mentioned conditions without exposure, and observed under a fluorescent lamp. It was evaluated whether or not it was established for the time being. The photographic material in which the turbid portion was also a little was regarded as having poor fixability. Needless to say, even if there is no problem in this evaluation, a problem may occur in image storability due to residual silver or residual hypo. Table 2 summarizes the results.

From the results in Table 2, it can be seen that when the swelling ratio is smaller than the range of the swelling ratio of the present invention, the fixing property cannot be practically endured, and when the swelling ratio is large, the drying property cannot be practically endured. I understand. Further, silver iodobromide has higher sensitivity than pure silver bromide, but the sensitivity is rather lowered when the content of silver iodide exceeds the range of the present invention. It is clear that

Example 2 The same evaluation as in Example 1 was performed using the photographic material 6 in Example 1. However, the following processing conditions were used. Table 3 Processing Conditions Developing Solution Fixing Solution From Insertion to Drying Developing / Fixing Replenishing Solution Replenishing Solution S × T A 45 45 60 2700 B 25 25 60 1500 C 15 15 60 900 D 10 10 60 600 E 7.5 7.5 60 450 F 4.5 4.5 60 270 G 7.5 7.5 90 675 H 7.5 7.5 120 900 I 7.5 7.5 150 1125 J 15 15 45 675 K 15 15 30 450 L 15 15 20 300 M 15 15 75 1125 The evaluation results are summarized in Table-4. Table-4 Processing conditions Fixing property Drying property Sensitivity S × TA (comparison) Possible ○ 105 2700 B (〃) 〃 105 1500 C (the present invention) 〃 100 900 D (〃) 〃 95 600 E ( 〃) 〃 ７０ 70 450 F (comparison) not possible △ 50 300 G (〃) possible ◎ 90 675 H (〃) 〃 １００ 100 900 I (〃) 〃 105 1125 J (the present invention) 〃 95 675 K (〃) 〃 △ 85 450 L (〃) 〃 △ 45 300 M (〃) ◎ ◎ 105 1125

From the comparison of the processing conditions A to F, when the replenisher amount was reduced, the developing and fixing replenisher solutions of the present invention did not greatly affect the fixing property, drying property and sensitivity until S × T was 2700 to 600. It can be seen that the amount of the developing and fixing waste liquid which has an adverse effect on the environment can be significantly reduced. S × T
However, when the value is 300, the sensitivity is significantly reduced, which is an allowable limit for the system. Further, comparison between E and GI, C and J to M
The effect of the present invention is also apparent from the comparison of. S × T is 10
If the value is larger than 00, unnecessary waste liquid flows out to the environment or unnecessary processing time is wasted, which is not preferable for the original purpose of automatic development.

Example 3 (Preparation of Tabular Particles T-1 of the Present Invention) In a container kept at 55 ° C., 4.5 g of potassium bromide and 6 g of lime-processed gelatin having an average molecular weight of 20,000 were added to 1 liter of water. While stirring, 37 cc of an aqueous solution of silver nitrate (3.43 g of silver nitrate) and 33 cc of an aqueous solution containing 3.3 g of potassium bromide were added over 37 seconds by the double jet method. Next, an aqueous solution of 0.9 g of potassium bromide was added, and the temperature was raised to 70 ° C.
cc (4.90 g of silver nitrate) was added over 13 minutes. Here, 15 cc of a 25% aqueous ammonia solution was added, the mixture was physically aged at the same temperature for 20 minutes, and then 14 cc of a 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by a control double jet method while maintaining the pAg at 8.5. Next, 10 cc of a 2N potassium thiocyanate solution and AgI fine particles having a diameter of 0.03 μm were added to 0.1% of the total silver amount.
5 mol% was added. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35 ° C. Thus, the total silver iodide content was 0.15 mol%, the average projected area diameter was 0.85 μm,
Monodispersed tabular grains having a thickness of 0.135 μm and a variation coefficient of diameter of 18.5% were obtained.

Thereafter, soluble salts were removed by a sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the mixture was adjusted to pH 5.90 and pAg 8.25 with sodium hydroxide and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. while stirring. First, 0.043 mg of thiourea dioxide was added and held for 22 minutes to effect reduction sensitization. Then 4
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (20 mg) and sensitizing dye A43 used in Example 1
0 mg was added. Furthermore, calcium chloride aqueous solution 1.1g
Was added. Subsequently, 2.5 mg of sodium thiosulfate, 2.5 mg of a selenium sensitizer having the following structure, and 2.6 mg of chloroauric acid
And 60 mg of potassium thiocyanate were added, and after 40 minutes, the mixture was cooled to 35 ° C.

[0051]

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Thus, the preparation of the tabular grains T-1 of the present invention was completed.

(Preparation of Tabular Particles T-2 of the Present Invention) Water 1
4.5 g potassium bromide, 20.6 gelatin in liter
g, _2.5 cc of a 5% aqueous solution of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH was added, and 37 cc of an aqueous silver nitrate solution (silver nitrate 3. 33 g), 2.97 g of potassium bromide, and 33 cc of an aqueous solution containing 0.363 g of potassium iodide were added over 37 seconds by the double jet method. Next, an aqueous solution of 0.9 g of potassium bromide was added, and the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (silver nitrate 4.90) was added.
g) was added over 13 minutes. Here, 15 cc of a 25% aqueous ammonia solution was added, the mixture was physically aged at the same temperature for 20 minutes, and then 14 cc of a 100% acetic acid solution was added.
(The steps so far are the same as in T-1.)

Subsequently, an aqueous solution of 133.3 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added to pAg8.
The mixture was added over 35 minutes by the control double jet method while maintaining the value of 1. The potassium iodide consumed here was 0.1 mol% based on the total silver content of the final grains. Then 2
10cc of N potassium thiocyanate solution and 0.03μ diameter
mI AgI fine particles were added in an amount of 0.1 mol% based on the total silver. After physical aging at the same temperature for 5 minutes, 35 ° C
The temperature was lowered. Thus, the total silver iodide content was 0.46.
Mol%, average projected area diameter 0.84 μm, thickness 0.13
Monodisperse tabular grains having a diameter of 3 μm and a coefficient of variation of diameter of 20.5% were obtained. Thereafter, soluble salts were removed by a sedimentation method.
The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrenesulfonate as a thickener were added, and the mixture was adjusted to pH 5.90 and pAg 8.25 with sodium hydroxide and silver nitrate solution. This emulsion was subjected to exactly the same chemical sensitization as the above-mentioned tabular grains T-1. Thus, the preparation of the tabular grains T-2 of the present invention was completed.

(Preparation of Comparative Tabular Particles T-3) T-2
And were prepared exactly the same except for the following. T-2
The addition amount of the 0.03 μm AgI fine particles added in the above was changed to 0.2 mol% with respect to the total silver amount. Thus, monodispersed tabular grains having a total silver iodide content of 0.56 mol% were obtained.

Preparation of Coating Samples The following chemicals were added per mole of silver halides T-1 to T-3 to prepare coating solutions. • 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg • Gelatin The amount of gelatin applied to the emulsion layer was 1. Adjusted to 7 g / m ²・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Hardener 1,2-bis ( Vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling ratio becomes the value shown in Table-5

[0057]

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Preparation of Coating Solution for Surface Protective Layer The surface protective layer was prepared and prepared so that each component had the following coating amount. Content of surface protective layer Coating amount ・ Gelatin 0.75 g / m ²・ Sodium polyacrylate (average molecular weight: 400,000) 0.023 ・ 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0 .015

[0059]

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Polymethyl methacrylate (average particle size: 3.7 μm) 0.087 Proxel 0.0005 (adjusted to pH 7.4 with NaOH)

Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dyes were ball-milled by the method described in JP-A-63-197943.

[0062]

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[0063] 6.7% aqueous solution 791ml water 434ml and Triton X-200 ^R surfactant (TX-200 ^R)
Were placed in a 2 liter ball mill. 20 g of the dye were added to this solution. 400 ml (2 mm diameter) beads of zirconium oxide (ZrO) were added and the contents were ground for 4 days. Thereafter, 160 g of 12.5% gelatin was added.
After defoaming, the ZrO beads were removed by filtration. Observation of the obtained dye dispersion showed that the particle size of the pulverized dye had a wide field ranging from 0.05 to 1.15 μm in diameter, and the average particle size was 0.37 μm. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus, Dye Dispersion D-1
I got

(2) Preparation of Support A corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a heat of 183 μm, and a first undercoating liquid having the following composition was applied at a coating amount of 5.1 cc / m ² . It was applied by a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite side. The polyethylene terephthalate used contained a dye having the following structure at 0.04% by weight.

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Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79cc 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5cc distillation 900.5 cc of water A second undercoating layer having the following composition is coated on the first undercoating layer on both sides by a wire bar coater method on each side such that the coating amount is as described below. 150 ° C
And dried.・ Gelatin 80 mg / m ²・ Dye dispersion D-1 (26 mg / m ² as a dye solid component)

[0067]

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Matting agent Polymethyl methacrylate having an average particle size of 2.5 μm 2.5 mg / m ²

Preparation of photographic material On the prepared support, the emulsion layer and the surface protective layer were coated on both sides by a simultaneous extrusion method. The coated silver amount per one side was as shown in Table-5. The swelling ratio was adjusted according to the amount of gelatin and the amount of hardener added to the emulsion layer and set as shown in Table-5. Thus, photographic materials 17 to 31 were obtained. Table 5 Photographic materials Milk agent Silver iodide content Silver coating amount Swelling ratio (mol%) (g / m ² per side) (%) 17 T-1 0.15 1.7 260 18 T-2 0.46 mm １９ 19 T-3 0.56 〃 20 T-1 0.15 1.7 220 21 T-2 0.46 〃 22 T-3 0.56 〃 23 T-1 0.15 1.7 190 24 T-2 0.46 〃 25 T-3 0.56 〃 26 T-1 0.15 1.4 220 27 T-2 0.46 〃 28 T-3 0.56 〃 29 T- 1 0.15 1.4 190 30 T-2 0.46 1.4 ３１ 31 T-3 0.56 1.4 の Evaluation of photographic performance Each sample of the photographic material was evaluated by X manufactured by Fuji Photo Film Co., Ltd. 0.0% from both sides using Ray Orthoscreen HR-8
Exposure was given for 5 seconds, and the sensitivity was evaluated. After exposure,
The following processing was performed. The sensitivity was expressed as the ratio of the reciprocal of the exposure amount giving a density of 1.0 based on the photographic material 17.
Fixing properties and drying properties were compared in the same manner as in Example 1.

Automatic developing machine: The drive motor and gears of the FPM2000 were modified to increase the transport speed. (Developer and Fixer) <Developer Concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriaminepentaacetic acid 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83.3 g Diethylene glycol 40 g 4-hydroxymethyl-4-methyl 1-phenyl-3-pyrazolidone 22.0 g 5-methylbenzotriazole 0.2 g

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Make up to 1 liter with water (adjust to pH 10.6). <Fixing solution concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (adjusted to pH 5.10 with acetic acid). When the developing process was started, each tank of the automatic developing machine was filled with the following processing solution. Developing tank: 333 ml of the above developer concentrate, 667 ml of water and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.25. Fixing tank: 200 ml of the above fixing solution concentrate and 800 ml of water Processing speed: Dry to Dry 50 seconds Developing temperature: 35 ° C. Fixing temperature: 32 ° C. Drying temperature: 55 ° C. Replenishment amount: Developing solution 12.5 ml / 775 cm ² Fixing solution 12. 5ml / 775cm ²

Table 6 shows the obtained results.

Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI G03C 5/395 G03C 5/395 (58) Investigated field (Int.Cl. ⁶ , DB name) G03C 5/31 G03C 1/035 G03C 1 / 047 G03C 1/74 G03C 5/395

Claims (3)

(57) [Claims] 1. A method for processing a silver halide photographic light-sensitive material comprising at least one light-sensitive silver halide emulsion layer on a support while replenishing a developing and fixing processing solution. a emulsion layer swelling rate of all the hydrophilic colloid layers on the side is not more than 220% to 180% the sense
When the coated silver amount of the optical material is 1.7 g / m ² or less on one side
The silver iodide content of the silver halide contained in the emulsion layer is 0.05 mol% or more and 0.15 mol% or less, and the replenishment amount of the developing / fixing processing solution is 20 ml or less per 775 cm ^{2 of the} light-sensitive material. 5 ml or more and a developing / fixing processing solution
Wherein the amount of replenisher and the processing time satisfy the following relational expression . 300 ≦ S × T ≦ 1000 where S is the developing / fixing processing solution per 775 cm ² .
Replenishment amount (ml), T is dry from start of processing of photographic material
The time (seconds) required to complete the drying. 2. The silver halide photographic light-sensitive material has a coating silver amount of
1.5 g / m ² or less per side
The development processing method according to claim 1 . 3. Silver halide contained in a photosensitive emulsion layer
Aspect is 70% or more of the total projected area of all particles
A tabular grain having a grain ratio of 5 or more.
1 or 2.