JP2704295B2 - Processing method of silver halide photographic material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution for a silver halide photographic light-sensitive material. More specifically, the present invention relates to an improved fixing solution that does not cause fluctuations in running density and does not cause residual color contamination. The present invention relates to a method for processing a silver halide photographic light-sensitive material.

[Background of the Invention]

Usually, silver halide photographic materials are developed after image formation.
Fixing → drying after washing with water, and finishing the process.

In recent years, continuous processing by an automatic developing machine has been performed for a long time due to rapid processing, and it is strongly demanded to constantly obtain a stable image.

In general, the pH of the fixing solution rises because the developing solution is carried in as the photosensitive material is continuously processed.

As a result, there is a problem that the photographic maximum density is reduced between the image obtained when the fixing solution is fresh and the image after running.

On the other hand, when using a new fixing solution, the performance does not differ between the new fixing solution and the running solution. It was inevitable.

Conventionally, the developing solution has been adapted to such new and old processing solutions, but there are very few known techniques for improving the fixing solution.

The present applicant has proposed in Japanese Patent Application No. Sho 62-230705 a fixing solution for replenishing ammonium thiosulfate, and also a fixing solution using polyhydroxyalkanes as disclosed in Japanese Patent Application No. 1-164020, but the largest among the new and old solutions has been proposed. It did not reach the point where the concentration fluctuation was resolved. Therefore, an urgent solution was strongly desired.

[Object of the invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which does not cause a decrease in the maximum image density of a light-sensitive material based on a fixing solution and has no color contamination. Other objects will be apparent from the following description.

[Configuration of the invention]

As a result of diligent studies, the present inventors have found that these objects can be more easily achieved as follows, and have accomplished the present invention.

That is, in a processing method of a silver halide photographic light-sensitive material which is processed in the order of development, fixing, washing with water and drying, it is achieved by a processing method of a silver halide photographic light-sensitive material in which a starter is added to the fixing solution.

 Hereinafter, the present invention will be described in detail.

The starter referred to in the present invention refers to an additive added to the new solution so that the development finish performance of the photosensitive material with the new solution is closer to the running state, and the additive may be a solid or a solution as long as it is soluble in the fixing solution. Preferably, the solution state is easy to use.

The starter of the present invention is characterized by containing at least one alkali agent.

The alkali agent can be advantageously selected without any particular limitation as long as it is a water-soluble compound that acts alkaline in the fixing solution.

Specific examples of the alkali agent include, for example, sodium carbonate, (including anhydrous or hydrated), sodium hydroxide, potassium hydroxide, and the like.

The amount of the alkaline agent used is not uniform depending on the type of the fixing solution or the type of the compound.
0.1 to 10 g, preferably 0.5 to 5 g.

The pH of the fixing solution is preferably in the range of 4.0 to 5.0 due to the addition of the alkali agent, and the pH difference between the new solution and the running solution is within 0.2, preferably 0.05 to 0.15.

By adding and adding potassium iodide to the starter of the present invention, the object effects of the present invention can be further enhanced.

The amount of potassium iodide added is 10-1000mg per fixer
And preferably 50 to 500 mg.

The above alkaline agent and potassium iodide may be used alone or in combination, respectively, and are added in the form of crystals or an aqueous solution to a fresh fixer or a fixer at the beginning of running.

The fixing solution composition according to the present invention may be a conventionally known fixing solution, and may contain, for example, a silver halide solvent such as sodium thiosulfate and ammonium thiosulfate, and a preservative such as sodium sulfite.

The fixing solution according to the present invention preferably contains potassium alum as an acidic hardening solution. For details of the fixer, see Basics of Photonics-Silver halide photography-33
See page 0, 1978, published by Corona.

The emulsion of the silver halide photographic light-sensitive material used in the processing method of the present invention may be any silver halide such as silver iodobromide, silver iodochloride, silver iodochlorobromide, but particularly high sensitivity Is preferred in that silver iodobromide is obtained.

The silver halide grains in the photographic emulsion are cubic, octahedral,
They may be all isotropically grown, such as tetradecahedrons, polyhedral crystals, such as spheres, twins having image defects, or mixtures or composites thereof. The size of these silver halide grains is 0.1 μm
Large particles ranging from the following fine particles to 20 μm may be used.

These emulsions can be manufactured by a known method. For example,
Research Disclosure (RD) No. 17643 (1978)
1) Emulsion manufacturing method (Emulsion Prepa)
raition and types) and (RD) No. 18716 (November 1979
Mon.), page 648.

An emulsion of a silver halide photographic light-sensitive material is, for example, THJa
"The theory of the photographic process" by mes # 4
Edition, published by Macmillan (1977), pp. 38-104,
GFDauffin, Photographic Emulsion Chemistry, Photographic emulsi
on Chemiistry ", Focal press (1966), P. Glafk
"Chemie et physique photo"
"Grahique", published by Paul Montel (1967), "Making and coating pho", by VLZelikman et al.
It is prepared by the method described in, for example, "Tographic emulsion" Focal press (1964).

That is, solution conditions such as neutral method, acidic method, ammonia method, etc., mixing conditions such as forward mixing method, back mixing method, double jet method, controlled double jet method, and particle preparation conditions such as conversion method, core / shell method, etc. And a combination thereof.

Preferred silver halide photographic materials in the processing method of the present invention include monodisperse emulsions in which silver iodide is localized inside the grains. The monodisperse emulsion as used herein means that at least 95% of the particles by number or weight are ± 40% of the average particle diameter when the average particle diameter is measured by a conventional method, for example.
%, Preferably within ± 30%. The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The crystal structure of the silver halide may be different from the silver halide composition inside and outside.

Examples of the silver halide emulsion preferably used in the processing method of the present invention include a core / shell type monodisperse emulsion having a clear two-layer structure comprising a high iodine core portion and a low iodide shell layer. .

Methods for producing such monodispersed emulsions are known, for example, J. Pho
t.Sic.12.242 to 251 (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, UK Patent
Nos. 1,413,748 and U.S. Pat. Nos. 3,574,628 and 3,655,394.

As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus is particularly preferable. As a method for obtaining a core / shell emulsion, for example, British Patent No. 1.027.146, US Patent Nos. 3,505,068 and 4,444,877
And JP-A-60-14331.

Silver halide emulsion used in the processing method of the present invention,
Tabular grains having an aspect ratio of 5 or more may be used.

The advantages of such tabular grains include, for example, improvement in spectral sensitization efficiency, improvement in graininess and sharpness of an image, and the like, for example, British Patent No. 2,122,157, U.S. Pat.
Nos. 433,048, 4.414,310, and 4,434,226.

The emulsion described above may be either a surface latent image type for forming a latent image on the grain surface, an internal latent image type for forming a latent image inside the grain, or a type for forming a latent image on the surface and inside. Good. 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 Nudel washing, flocculation sedimentation or ultrafiltration in order to remove soluble salts.
As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or a coagulated polymer agent exemplified by G3, G8 described in JP-A-63-158644, etc. The method used is a particularly preferred desalting method.

The silver halide photographic light-sensitive material to which the processing method of the present invention can be applied is not particularly limited as long as it is a chemistry to be subjected to a chemical development process, and is preferably a spectrally sensitized silver iodobromide emulsion. Is satisfied, the effect of the present invention can be exhibited more favorably.

Spectral sensitization may be any known method,
Particularly preferably, the following general formulas (I), (II) and (II)
It is preferable that the silver halide photographic material is spectrally sensitized with at least one of the cyanine dyes represented by the formula (I).

In particular, this is remarkable in the spectral sensitization method using a combination of the general formulas [I] and [II].

General formula [I] In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and at least _one of R ₁ and R ₂ is a sulfoalkyl group Or a carboxyalkyl group.

R ₃ represents an alkyl group.

 X Is an anion, Z₁And Z_TwoMay each have a substituent
Non-metallic elements necessary to complete a benzene or naphtho ring
The child group, n represents 1 or 2.

(However, when an inner salt is formed, n is 1.) In the above formula, R ₁ and R ₂ may be the same or different, and may be an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group). Group,
As a substituted alkyl group, a substituted alkyl group having 1 to 4 carbon atoms such as a halogen atom or a hydroxy group is used as a substituted alkyl group, and up to 4 carbon atoms as an alkenyl group (for example, an allyl group, 2-butenyl group and the like).

Further, either R ₁ or R ₂ is a sulfoalkyl group or a carboxyalkyl group, and the sulfoalkyl group is a group having 2 to 4 carbon atoms (for example, a 2-sulfoethyl group, a 3-sulfopropyl group, A sulfobutyl group, a 4-sulfobutyl group, a 2- [3-sulfopropoxy] ethyl group, a 2-hydroxy-3-sulfopropyl group, and a 3-sulfopropoxyethoxyethyl group.

Examples of the carboxyalkyl group include (for example, a 2-carboxyethyl group, a 3-carboxypropyl group, a 4-carboxybutyl group, and a carboxymethyl group).

R ₃ is an alkyl group having 1 to 2 carbon atoms and represents a methyl group or an ethyl group.

 X Is an anion such as a halogen atom (I, Br, Cl
Etc.) in Z¹And Z^TwoIs a fused ring which may have a substituent.
Non-metallic elements necessary to form a benzene ring or naphthalene ring
Substitutable groups (for example, halogen atom, cyano
Group, alkyl group, alkoxy group, aryl group, trifluoro
Oromethyl group, alkoxycarbonyl group, acyl group
) May be substituted.

n is 1 or 2 and when the dye forms an inner salt, n
Is 1.

When R ₁ and R ₂ are sulfoalkyl groups or carboxyalkyl groups, salts may be formed in the form of R-SO ₃ M groups or R-COOM groups, respectively, where M is a hydrogen atom, an alkali metal atom. (Eg, Na, K, etc.) or an ammonium group.

 General formula (II) Where R₁And R_ThreeIs a substituted or unsubstituted alkyl
Group, R_TwoAnd R_FourEach represents an alkyl group, a hydroxyalkyl
Group, sulfoalkyl group or carboxyalkyl group, X
Is an anion, Z₁And Z_TwoIs a ben which may have a substituent
Non-metallic atoms necessary to complete the zen or naphtho ring,
n represents 1 or 2.

(However, when an inner salt is formed, n is 1.) In the above formula, R ₁ and R ₃ are an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group and the like). )
The substituted alkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, etc.) The alkyl group for R ₂ and R ₄ has 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, or butyl group). Group).

Examples of the hydroxyalkyl group include a sulfoalkyl group (for example, a 2-hydroxyethyl group and a 3-hydroxypropyl group) and a carboxyalkyl group represented by the general formula [I]:
It may have the same meaning as R ₁ and R ₂ , and may form a salt of R-SO ₃ M or R-COOM.

Z ₁ and Z ₂ are a group of nonmetallic atoms necessary for forming a benzene ring or a naphthalene ring which may have a substituent in a condensed ring, and the substituent (for example, Cl, B
r, fluoro group, etc.) trifluoromethyl group, or -C
An OOM group (R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a ventil group, and an aryl group such as a phenyl group).

 X and n have the same meanings as those in formula (I).

The dyes of the above general formulas [I] and [II] are known and described in the following patent documents.

That is, French patent 1,108,788, U.S. patent 2,503,776
No. 2,912,329, JP-B No. 47-25379, No. 47-37443
No.

Even in cases where there is no description in these documents, by referring to the cited documents, the production method can be easily clarified for those skilled in the art.

Hereinafter, specific examples of the dyes represented by the general formulas [I] and [II] are shown below.

Next, the dye represented by the general formula [III] will be described.

General formula (III) In the formula, Z ₁ and Z ₃ represent a benzothiazole nucleus optionally having a substituent, a benzoxazole nucleus, a naphthothiazole nucleus, a nonmetallic atom group necessary for forming a naphthoxazole nucleus, and R ₁ and R ₂ Represents a saturated or unsaturated aliphatic group, respectively.

Z ₂ represents a carbon atom ring 5- to 6-membered, A is Z ₂ is 6
In the case of a member, it represents a hydrogen atom. In the case of a 5-membered ring, the general formula [II
Ia].

General formula [III-a] Where A is Represents

R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and R ₅ and R ₆ each represent an alkyl group having 1 to 12 carbon atoms, R ₇ represents an alkyl group having 1 to 12 carbon atoms, an allyl group having 6 to 10 carbon atoms, or an alkoxycarbonyl having an alkoxy group having 1 to 4 carbon atoms. Represents a group.

When Z ₂ is a 6-membered ring, it is represented by the general formula [III-b].

 General formula [III-b] Where R₈Is a hydrogen atom or a methyl group, R₉Is a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms or a monocyclic allyl group. X
Represents an anion, and n represents 1 or 2 (forming an inner salt)
When n is 1, n is 1).

The infrared sensitizing dye represented by the general formula [III], which can be preferably used in the present invention, will be described.

In the general formula (III), Z ₁ and Z ₃ represent a benzothiazole nucleus which may have a substituent, a benzoxazole nucleus, a naphthothiazole nucleus, and a nonmetallic atom group necessary for forming a naphthoxazole nucleus. Examples of the group include a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

R ₁ and R ₂ each represent a saturated or unsaturated aliphatic group (for example, a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-acetoxyethyl group, a carboxymethyl group, a 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-
Sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, p-sulfophenethyl group, n-propyl group, isopropyl group, n-butyl group, etc.).

Z ₂ represents a carbon atom ring 5- to 6-membered, A is Z ₂ is 6
In the case of a member, it represents a hydrogen atom. In the case of a 5-membered ring, the general formula [II
Ia].

In the general formula (III-a), R ₃ and R ₄ are each a hydrogen atom,
C1-C4 alkyl group, halogen atom, C1-C1
4 represents an alkoxy group, and R ₅ and R ₆ each have 1 to 1 carbon atoms
12 alkyl groups, alkoxycarbonylalkyl groups (e.g., methoxycarbonylmethyl group, ethoxycarbonylethyl group, etc.), and optionally substituted allyl groups (e.g., phenyl group, m-tolyl group, p-tolyl group, m- A chlorophenyl group, a p-chlorophenyl group, an m-, p-alkoxyphenyl group having an alkoxy group having 1 to 4 carbon atoms, etc.)
Wherein R ₇ is an alkyl group having 1 to 12 carbon atoms, 6 to 10 carbon atoms.
And an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms.

When Z ₂ has 6 members, it is represented by the general formula [III-b].

 In the general formula [III-b], R₈Is a hydrogen atom or methyl
Group, R₉Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Represents an allyl group. X Represents an anion. (Eg chlorine
Ion, bromide ion, iodine ion, perchloric acid, benze
Sulfonate, p-toluenesulfonate, methylsa
Rulfate, ethyl sulfate, tetrafluoroboric acid
etc).

n represents 1 or 2 (n is 1 when an inner salt is formed).

Next, typical specific examples of the compound represented by the general formula [III] will be described.

Specific examples of general formula (III) These dyes of the present invention are described in U.S. Pat.Nos. 2,734,900 and 3,4,900.
Compounds can be easily synthesized according to the methods described in Nos. 82,978 and 3,758,461.

The dyes of the above general formulas [I], [II] and [III] can be directly dispersed in an emulsion. They can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a complex solvent thereof, and added to the emulsion in the form of a solution.

In the above-mentioned silver halide emulsion, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, Research
Day closure No-17643 (December 1978) and N
o-18716 (November 1979). The following table shows the types and locations of the compounds shown in these two research disclosures.

Examples of the support which can be used for the light-sensitive material include those described in the above-mentioned RD-17643, page 28 and RD-18716, page 647, left column.

As a suitable support, a plastic film or the like may be used, and the surface of the support may be generally provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. Then, the above-mentioned emulsion can be coated on one side or both sides of the support thus treated.

The processing method of the present invention can be applied to all silver halide photographic materials, but is particularly suitable for high-sensitivity black-and-white photographic materials.

The silver halide photographic light-sensitive material processed according to the present invention can be subjected to development processing by a commonly used known method. Black-and-white developers are commonly used developers such as hydroquinone, 1-phenyl-3-pyrazolidone, N-
Those containing a single substance such as methyl-p-aminophenol or p-phenylenediamine or a combination of two or more thereof are used, and conventional additives can be used.

A developer containing an aldehyde type hardener can also be used in the silver halide photographic light-sensitive material according to the present invention. For example, dialdehydes such as maleic dialdehyde or glutaraldehyde and sodium bisulfite thereof are used. A well-known developer can be used in the field of photography containing the same.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

Example 1 A silver iodobromide emulsion having an iodizing agent of 2 mol% and an average grain size of 0.6 μm was subjected to chemical ripening by an optimal gold and sulfur sensitization method.
Each of the exemplified spectral sensitizing dyes (I-4) and (II-6) was orthosensitized by adding 600 mg and 12 mg per mol of silver halide, respectively.

Then, known stabilizers, antifoggants, coating aids, hardeners and the like added on both sides of the base of polyethylene terephthalate blue colored 50 mg / dm ² emulsion as silver amount,
And a protective layer of the following composition on top of which 1.5 mg / dm.
² to obtain a sample as a high-sensitivity X-ray photosensitive material.

One set of the obtained samples was inserted into an intensifying screen for ortho, and X-rays were emitted through an aluminum wedge at a tube voltage of 90 KVP and a tube current of 100 mA to obtain a maximum concentration evaluation sample. For the evaluation of the residual color property, the following processing according to the present invention was performed using each of the unexposed samples.

 Developing solution XD-SR (Konica Corporation) Fixing solution Fixing solution Konica automatic developing machine SRX-501 (35 ° C 90 seconds) Fixing solution composition Ammonium thiosulfate 150 g Sodium sulfite 15 g EDTA 0.2 g Citric acid 2 g Ho Acid 8 g Sodium acetate trihydrate 28 g Glacial acetic acid 7 g Sulfuric acid 1 g Add water to make 1

Protective layer liquid composition (per coating liquid) The fixing solution was divided into nine parts, aluminum sulfate was added as a hardening agent in the following amounts, and the pH was adjusted using sulfuric acid.

<Fixing solution> pH aluminum sulfate (g /) No.1 3.60 2.5 2 4.10 2.5 3 3.60 5.0 4 3.90 5.0 5 4.10 5.0 6 4.30 5.0 7 3.60 7.5 8 4.10 7.5 9 4.70 5.0 Next, these fixing solutions (new solution) Then, the starter shown in Table 1 was added in an amount to reach the set pH, and 500 pieces of a four-cut film were run at 35 ° C.4 with an SRX-501 (automatic developing machine manufactured by Konica Corporation).
This was performed for 5 seconds.

The unexposed sample for evaluation of residual color and the sample for maximum density evaluation were passed through at the time of a new solution and at the end of running. The evaluation of the residual color was evaluated in the following five steps.

A. No residual color B. Slight residual color but good C. There is residual color but no problem in use D. Remaining color is unusually unusable E. Level that residual color is not enough to see The results are shown in Table 1 below.

In addition, the evaluation of the maximum concentration fluctuation was performed in the following five steps.

Xx The maximum concentration difference between the new solution and the running solution is 0.30 or more (very poor) x The maximum concentration difference between the new solution and the running solution is 0.15 to 0.30 (poor) △ The maximum concentration difference between the new solution and the running solution is 0.10 to 0.15 (There is no problem in practical use) ○ The maximum concentration difference between the new solution and the running solution is 0.05 to 0.10 (good) ◎ The maximum concentration difference between the new solution and the running solution is within 0.05 (very good) The results obtained are shown in the following table. It is shown in FIG.

As apparent from Table 1, according to the processing method of the present invention,
It can be seen that there is no deterioration of the residual color with the new liquid and the maximum density fluctuation during running is small.

Example 2 As an unchemically ripened emulsion, the average particle size was 1.0 μm,
An emulsion was prepared in which (average direct) / (thickness) was 13.5 and grains having (average direct) / (thickness) of 5 or more accounted for 80% or more of the total silver halide grain projected area.

After the emulsion was optimally subjected to chemical ripening, 20-9 mg of each of the exemplified spectral sensitizing dyes III-9 and III-20 was added per mol of silver halide to give infrared sensitivity. Next, a sample was prepared by preparing an emulsion containing the same additives as in Example 1 and a coating solution for a protective layer.

The sample thus obtained was cut into a 3.5 cm width, and a wedge image was printed in ^10-5 seconds using a xenon flash light source through an interference filter of 820 nm. After the exposure, development was carried out in the same manner as in Example 1, and using a fixing solution having the contents shown in Table 2 below, the residual color and the fluctuation of the maximum density in the new solution and the running solution were evaluated.

 The results obtained are shown in Table 2 below.

[Effects of the Invention] According to the present invention, the processing variability on the photosensitive material between a new fixing solution and a running solution can be improved.

That is, a fixing solution was obtained which prevented a decrease in the maximum density of the running solution and obtained an image with less color contamination at the time of the new solution.

Claims (1)

(57) [Claims] 1. A method for processing a silver halide photographic material which is processed in the order of development, fixing, washing with water and drying, wherein a starter is added to the fixing solution. Processing method.