JP3515603B2 - Developing agent for silver halide photographic material and method for developing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer for a silver halide photographic light-sensitive material and a method for developing the same, and more particularly to a developer for developing a black-and-white silver halide photographic light-sensitive material with a developing agent different from hydroquinone and a developer for the same. The present invention relates to the developing method used.

[0002]

2. Description of the Related Art Generally used black-and-white silver halide light-sensitive materials (for X-ray, for plate making, for micro, and for negative) have conventionally used hydroquinone as a developing agent and a 3-pyrazolidone compound or a compound as an auxiliary developing agent. After being developed with an alkaline developing solution containing an aminophenol-based compound, an image is formed by a developing treatment including steps of fixing and washing. Among them, especially the X-ray photographic light-sensitive material contains a relatively large amount of silver halide, and since these are processed rapidly, a highly active developer containing a large amount of hydroquinone as a developing agent is used. It is used. To maintain high activity, such developers have been replenished in large amounts against air oxidation. However, the toxicity and safety of hydroquinone is becoming a problem now. US Pat. No. 2,682 as a developing agent replacing hydroquinone
There are reductones known from JP-A-8-549, JP-A-3-249,756, etc., but these developing agents are used as a simple developer of one liquid, with little silver stain and per unit area of photosensitive material. A developing method for developing with a small replenishment amount has not been known. As a silver stain preventive agent used in a developing solution, Japanese Patent Publication Nos. 56-46585 and 62-4702.
Japanese Patent Publication No. 62-4703, US Pat. No. 4,254,
No. 215, No. 3,318,701, Japanese Patent Publication No. 58-20
No. 3439, No. 62-56959, No. 62-2845.
No. 9, 62-178247, and JP-A 1-20024.
No. 9, Japanese Patent Application Nos. 3-94955 and 3-112275.
No. 3-233718, EP-566,323A2
However, there is no known simple one-liquid developer using ascorbic acid and / or its derivative as a developing agent.

[0003]

The problems to be solved by the present invention are silver halide photographic light-sensitive materials (especially for black and white).
Is a simple one-component liquid developer containing a silver stain inhibitor in which ascorbic acid and / or its derivative is used instead of hydroquinone as a developing agent, and a developing method thereof. Further, the developer waste solution has a high chemical oxygen demand (so-called COD) and a high biological oxygen demand (so-called B.O.D.).
O. Since D) is included, it has been desired to reduce the replenishment amount per unit area of the silver halide photographic light-sensitive material (especially for black and white) in order to reduce the economical load of the waste liquid treatment.

[0004]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having the following composition (especially for black and white).
1-liquid developer for use, and the 1-liquid developer contained in a packaging material having an oxygen permeability of 50 ml / m ² · atm · day or less, or a black and white silver halide photographic light-sensitive material 1 m ² This is achieved by processing with a replenishing amount of 300 ml or less per unit. (a) Ascorbic acid and / or its derivative developing agent (b) Super-additive auxiliary developing agent (c) Alkaline agent necessary for at least pH 9.0 (d) The following general formula (I) Or a compound represented by the general formula (II), the general formula (I)

[0005]

[Chemical 3]

General formula (II)

[0007]

[Chemical 4]

Here, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group,
R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m is 0, 1, or 2. R ₅ represents a hydroxyl group, an amino group, or an alkyl group having 1 to 3 carbon atoms. M represents a hydrogen atom, an alkali metal atom, or an ammonium group, and X represents a hydrogen atom or a carbon number of 1 to 1.
3 represents an alkyl group, a sulfonyl group, an amino group, an acylamino group, a dimethylamino group, an alkylsulfonylamino group or an arylsulfonylamino group. Next, particularly preferred specific examples of ascorbic acid or a derivative thereof used in the present invention will be given, but the present invention is not limited thereto.

[0009]

[Chemical 5]

[0010]

[Chemical 6]

The ascorbic acids used in the present invention can also be used in the form of alkali metal salts such as lithium salt, sodium salt and potassium salt. These ascorbic acids are used in an amount of 1 to 100 g, preferably 5
It is preferable to use ˜80 g.

The auxiliary developing agent exhibiting superadditivity is 3-
As a pyrazolidone-based developing agent, 1-phenyl-3-
Pyrazolidone, 1-phenyl-4,4-dimethyl-3-
Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4
-Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4,4-dimethyl-3-pyrazolidone, 1-
p-tolyl-4-methyl-4-hydroxymethyl-3-
There is pyrazolidone. These auxiliary developing agents are 10
^-4 to 10 ^-1 mol / l is preferably used, more preferably 5 x 10 ^{-4 to} 5 x 10 ^-2 mol / l, and further preferably 10 ^{-3 to} 3 x 10 ^-2 mol / l. It is preferable.

Examples of p-aminophenol-based developing agents include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl). Glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc. are available, but among them N-methyl-p
-Aminophenol is preferred. These auxiliary developing agents are preferably used at 10 ^-4 to 10 ^-1 mol / liter, more preferably 5 × 10 ^{-4 to} 5 × 10 ^-2 mol / liter.

Alkali agents necessary for adjusting the pH to at least 9.0 are sodium hydroxide, potassium hydroxide,
A pH adjuster such as sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate can be used. Furthermore, in addition to these, JP-A-60-93433
The pH buffering agent described in No. 1 can be used. The compound represented by the general formula (I) or the general formula (II) that can be used in the present invention is

[0015]

[Chemical 7]

[0016]

[Chemical 8]

[0017]

[Chemical 9]

The general formula (I) and the general formula (II) of the present invention
The preferred concentration of the compound (1) in the developer (use solution) is 0.01 mmol to 50 mmol / liter, more preferably 0.05 mmol to 10 mmol / liter, and particularly preferably 0.1 mmol to 5 mmol / liter. .

The developer used in the present invention may contain an amino compound for promoting development. In particular, JP-A-50-1
06244, JP-A-61-267759, JP-A-2
The amino compound described in -208652 may be used.

Development inhibitors such as potassium bromide and potassium iodide; organic solvents such as dimethylformamide, methylcellosolve, hexylene glycol, ethanol and methanol; 5-methylbenztriazol and 5-bromobenz as benztriazole derivatives. Triazole, 5-
There are chlorobenztriazole, 5-butylbenztriazole, benztriazole and the like, but 5-methylbenztriazole is particularly preferable. Examples of the sulfite preservative that can be used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite. The sulfite content is preferably 0.01 mol / liter or more, particularly preferably 0.02 mol / liter or more. Further, the upper limit is preferably up to 2.5 mol / liter. In addition, 22 of "Photographic Processing Chemistry" by LFA Mason, published by Focal Press (1966)
Those described in pages 6 to 229, U.S. Pat. Nos. 2,193,015, 2,592,364, and JP-A-48-64933 may be used. Further, if necessary, a color tone agent, a surfactant, a water softener, a hardener and the like may be contained. As the surfactant, a phosphoric acid ester type can be used. For example, the compound represented by the general formula (III) can be preferably used. General formula (III)

[0021]

[Chemical 10]

Here, R ₆ is an aliphatic group, an alicyclic compound group,
R ₇ represents an aromatic group or a heterocycle, and R ₇ represents an aliphatic group, an alicyclic compound group, an aromatic group, a heterocycle or a group represented by —LZ. Q ₁ , Q ₂ and Q ₃ are each a single bond, an oxygen atom, a sulfur atom —N (R ₈ ) — or —N (R
₈ ) a group represented by —CO— (R ₈ is a hydrogen atom or R
Group represented by ₇ ). L represents a divalent linking group. Z represents an ionic group.

As the chelating agent in the developer, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, Diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylene Phosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1- Hosuhon'etan-2-carboxylic acid, 1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphono-1,3,
Examples thereof include 3-tricarboxylic acid, catechol-3,4-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, and particularly preferably, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanol. Tetraacetic acid, glycol ether diamine tetraacetic acid, hydroxyethyl ethylenediamine triacetic acid, 2-phosphonobutane-
1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1- Aminoethylidene
1,1-diphosphonic acid, 1-hydroxyethylidene-
There are 1,1-diphosphonic acids and their salts.

The oxygen permeability preferably used in the present invention is 50 ml / m ² · atm · day (temperature 20 ° C. relative humidity (6
5%) or less, a packaging material having a thickness of 1 mm or more may be used, but as a packaging material having a thickness of 0.5 mm or less and being flexible and easy to handle, a saponified product of ethylene-vinyl acetate copolymer and nylon At least one of
Oxygen permeability consisting of 50ml / m ² · a
A container of plastic packaging material having a tom · day (temperature of 20 ° C. and relative humidity of 65%) or less is preferable. More preferably, the oxygen permeability is 25 ml / m ² · atom · day (temperature 2
By storing in a container of plastic packaging material having a temperature of 0 ° C. and a relative humidity of 65% or less, stable photographic performance can be obtained even when the developer is stored for a long period of time. As a method for measuring oxygen permeability, N ₂ Calvano et al. O ₂ permeation o
f plastic container, Modern Packing 12/1968 12
The method described in pages 143 to 145 of the monthly issue is used.
Oxygen permeability of 50 ml / m ² · atom · day comprising at least one of saponified ethylene-vinyl acetate copolymer (trade name: EVAL) and nylon
As a plastic packaging material having a temperature of 20 ° C. and a relative humidity of 65% or less, these plastics may be used alone, for example, polyvinylidene chloride, polyvinyl alcohol (trade name: vinylon), polyvinyl chloride, aluminum foil laminated film. , A metal vapor deposition film such as aluminum can be used in combination, and a composite film obtained by laminating these onto a substrate such as polyethylene or ethylene-vinyl acetate copolymer can also be used. The shape of the container made by using these plastic packaging materials includes a bottle, a cubic type, a laminated pillow type and the like. In the case of a bottle or a cubic type, the above-mentioned material having low oxygen permeability can be used to form a laminated material by coextrusion. Nylon and a saponified product of ethylene-vinyl acetate copolymer are particularly preferable in that they have low oxygen permeability, have high strength when formed into a container, and are easy to process the material into a container.

The method of preparing the treating agent used in the present invention is described in JP-A-61-177132 and JP-A-3-134666.
The method described in JP-A-3-67258 can be used. As the method of replenishing the developing solution as the processing method of the present invention, the method described in Japanese Patent Application No. 54131/1992 can be used.

The fixer used in the present invention is an aqueous solution containing thiosulfate, and has a pH of 3.8 or higher, preferably 4.2 to 4.2.
Has 6.0. Sodium thiosulfate as a fixing agent,
Examples include ammonium thiosulfate. The amount of the fixing agent used can be appropriately changed, and the fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum.

Tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more in the fixing solution. It is effective that these compounds contain 0.005 mol or more per 1 liter of the fixing solution, and particularly, it is preferable that the content of the compound is 0.005.
01 mol / liter to 0.03 mol / liter is particularly effective.

Preservatives (eg, sulfite, bisulfite), pH buffering agents (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having a water softening ability may be included in the fixing solution, if desired. And compounds described in JP-A-62-78551. As the processing method of the present invention, the methods described in JP-A-1-4739 and JP-A-3-101728 can be used for promoting fixing. In the processing method of the present invention, after the development and fixing steps, it is processed with washing water or a stabilizing solution and then dried.

As the automatic developing machine used in the present invention, various types such as a roller carrying type and a belt carrying type can be used, but a roller carrying type automatic developing machine is preferable. Further, by using the developing machine of the developing tank having a small opening ratio as described in JP-A-1-166040 and 1-193853, there is little air oxidation and evaporation, and the washing water is squeezed out, that is, through a squeeze roller. To be dried. It may be more preferable that the washing water used in the present invention be subjected to a pretreatment before being supplied to the washing tank through a filter member or a filter of activated carbon to remove dust and organic substances existing in the water.

Known as an anti-fungal means, Japanese Patent Laid-Open No. Sho 6
0-263939, UV irradiation method, 60-
Method using magnetic field described in No. 263940, 61-
A method for producing pure water using the ion exchange resin described in No. 131632, Japanese Patent Application Nos. 2-208638 and 2-3.
No. 03055, a method of circulating a filter and an adsorbent column while blowing ozone, Japanese Patent Application No. 3-2
Method by microbial degradation described in Japanese Patent No.
2-115154, 62-153952, 62
The methods using the antibacterial agents described in Nos. -220951 and 62-209532 can be used in combination.

Furthermore, MW Beach, "Microbiological G
rowths in Motion-picture Processing "SMPTE Journal
Vol.85 (1976), RODeegan, "Photo Processing Wash
Water Biocides "J. Imaging Tech. Vol.10, No.6
(1984) and JP-A-57-8542, 57-57.
58143, 58-105145, 57-13.
No. 2146, No. 58-18631, No. 57-9753
No. 0, No. 57-257244 and the like, antibacterial agents, antifungal agents, surfactants and the like can be used in combination as necessary.

Further, in the washing bath (or stabilizing bath), RTKreiman, J. Image. Tech. Vo.
l. 10, No. 6, p. 242 (1984), isothiazoline compounds, bromochlorodimethylhydantoin, Research Disclosure Vol. 205, No. 20.
526 (May, 1981), Vol. 228, No. 2
The isothiazoline compounds described in 2845 (April, 1983), the compounds described in JP-A-62-209532, and the like can be used in combination as a bacteriostatic agent (Microbiocide), if necessary.

In addition, "Chemistry of antibacterial and antifungal" by Hiroshi Horiguchi,
Compounds such as those described in Mitsui Shuppan (Showa 57), "Handbook of Antibacterial and Antifungal Technology", Japan Society of Antibacterial and Antifungal, Hakuhodo (Showa 61) may be included. The photographic material which has been developed, fixed and washed (or stabilized) is squeezed out of washing water, that is, dried through a squeeze roller.
Drying is performed at about 40 ° C to about 100 ° C, and the drying time is appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 seconds.
Minutes, particularly preferably at 40-80 ° C. for about 5 seconds
2 minutes.

When a dry-to-dry development process for 100 seconds or less is performed, a roller made of a rubber material as described in JP-A-63-151943 is developed in order to prevent development unevenness peculiar to rapid processing. It is applied to a roller at the outlet of a tank, the discharge flow rate for stirring a developing solution in a developing solution tank is set to 10 m / min or more, as described in JP-A-63-151944, and ,
As described in JP-A-63-264758, it is more preferable to stir more strongly than during standby at least during the development processing.

There are no particular restrictions on the photographic light-sensitive material used in the development processing method of the light-sensitive material of the present invention, and general black-and-white light-sensitive materials are mainly used. In particular, it is used for photographic materials for laser light sources, printing sensitive materials, medical direct photographing X-ray sensitive materials, medical indirect photographing X-ray sensitive materials, CRT image recording sensitive materials, microfilm, general photographing sensitive materials and the like. You can also

Next, the emulsion grains in the silver halide photosensitive material used in the present invention will be described. The diameter of a sphere having the same volume as the emulsion grains (hereinafter referred to as sphere-equivalent average grain size) is 0.2 μm.
m or more and less than 2.0 μm, and in particular, 0.
It is preferably 5 or more and less than 1.5 μm. The particle size distribution should be narrow. The silver halide grains in the emulsion may have a regular crystal form such as a cube, octahedron or tetrahedron, or may have an irregular crystal form such as a sphere, a plate or a potato. Good. It may consist of a mixture of particles of various crystal forms. Further, tabular grains having a grain size 5 times or more the grain thickness are preferably used in the present invention. (For details, see RESEARCH DISCLOSURE 225
Volume Item 22534 p. 20-p. 58, January issue, 1
983 and JP-A-58-127921 and 58-1.
It is described in Japanese Patent No. 13926. ) As a method for producing tabular silver halide grains, a method known in the art is appropriately used.
It can be achieved by combining them. Tabular silver halide emulsions are disclosed in JP-A-58-127,921 and JP-A-58-11.
It can be easily prepared by referring to the methods described in 3,927, JP-A-58-113,928 and US Pat. No. 4,439,520. The projected area diameter of the tabular emulsion of the present invention is preferably 0.3 to 2.0 μm, and particularly preferably 0.5 to 1.2 μm. The distance between parallel planes (particle thickness) is 0.05 μm to 0.3 μm, and particularly 0.1 to 0.25.
The thickness is preferably μm, and the aspect ratio is preferably 3 or more and less than 20, particularly preferably 4 or more and less than 8. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 2 or more are present in an amount of 50% (projected area) or more, especially 70% or more of all grains, and the average aspect ratio of the tabular grains is It is preferably 3 or more, and particularly preferably 4 to 8.

In order to effectively use the effects of the present invention,
As the selenium sensitizer, the selenium compounds disclosed in conventionally known patents can be used. The non-unstable selenium compound used in the present invention is Japanese Patent Publication No. 46-45.
No. 53, Japanese Patent Publication No. 52-34492 and Japanese Patent Publication No. 52-
The compound described in 34491 is used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

As the silver halide solvent which can be used in the present invention, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54- (A) Organic thioethers described in 1019, 54-158917 and the like, JP-A-53-82.
(B) thiourea derivatives described in JP-A No. 408, 55-77737, 55-2982 and the like, JP-A-53-1.
No. 44319, (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A No. 54-100717, ( Examples thereof include e) sulfite and (f) thiocyanate. Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide. The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US Patent No. 1,5
74,944, 2,410,689, 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but it is 1 × 10 ⁻⁷ mol or more per 5 mol of silver halide and 5 × 10 ^−4. It is preferably not more than mol.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide.

In order to effectively use the effects of the present invention,
During chemical sensitization during the emulsion preparation process as described in JP-A-2-68539, it is preferable that 0.5 mmol or more of a silver halide-adsorptive substance be present per mol of silver halide. This silver halide-adsorptive substance may be added at any time during grain formation, immediately after grain formation, or before and after the start of post-ripening, but a chemical sensitizer (for example, gold or sulfur sensitizer) is added. It is preferable to be added before or at the same time as the chemical sensitizer, and it must be present at least in the process of progress of chemical sensitization. As a condition for adding the silver halide adsorbing substance, the temperature may be any temperature from 30 ° C. to 80 ° C., but the range of 50 ° C. to 80 ° C. is preferable for the purpose of enhancing the adsorbability. The pH and pAg may be arbitrary, but at the time of chemical sensitization, it is preferably pH 5 to 10 and pAg 7 to 9.

Here, the silver halide adsorbing material means a class of sensitizing dyes or photographic performance stabilizers. That is, azoles {eg benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds {eg mercaptothiazoles, Mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc .; for example, oxadrinthione Thioketo compounds; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) Tiger aza indene), pentaazaindenes such like); known as antifoggants or stabilizers, such as, a number of compounds may be mentioned as the silver halide adsorptive materials. Further, purines or nucleic acids, or polymer compounds described in JP-B-61-36213, JP-A-59-90844 and the like are also adsorbable substances that can be used.

As a silver halide adsorbing substance, a sensitizing dye can realize a preferable effect. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, U.S. Pat. Nos. 3,522,052 and 3,619,197.
Issue 3, Issue 3,713,828, Issue 3,615,643
Issue No. 3,615,632 Issue 3,617,293
No. 3,628,964, 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,312,349, No. 3,677,765
Nos. 3,770,449, 3,770,440
Issue No. 3,769,025 Issue No. 3,745,014
Issue 3, Issue 3,713,828, Issue 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration) , Hardener, sensitization) and various other surfactants may be included.

As the binder or protective colloid which can be used in the emulsion layer, intermediate layer and surface protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin.
Other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, dextran and starch derivatives; polyvinyl. Use various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. be able to. As the gelatin, acid-treated gelatin or enzyme-treated gelatin may be used in addition to lime-treated gelatin, and a hydrolyzed product or an enzymatically-decomposed product of gelatin may also be used. Among these, gelatin has an average molecular weight of 5
It is preferable to use not more than 10,000 dextran and polyacrylamide in combination. JP-A-63-68837, also 6
The method described in JP-A-3-149641 is also effective in the present invention.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis-
[Β- (vinylsulfonyl) propionamide], etc.,
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazine Nilated gelatin and the like can be used alone or in combination. Among them, JP-A-53-4122
1, No. 53-57257, No. 59-162546.
Nos. 60-80846 and the active halides described in U.S. Pat. No. 3,325,287 are preferred.

The hydrophilic colloid layer in the photographic light-sensitive material of the present invention is preferably hardened with these hardeners so that the swelling ratio in water is 280% or less. The swelling ratio in water in the present invention is measured by the freeze-drying method. That is, the swelling ratio of the hydrophilic colloid layer is measured when the photographic material is aged for 7 days under the condition of 25 ° C. and 60% RH. The dry thickness (a) is determined by a scanning electron microscope of the section. Swelling membrane layer (b)
Is determined by immersing the photographic material in distilled water at 21 ° C. for 3 minutes, freeze-drying it with liquid nitrogen, and then observing it with a scanning electron microscope. The swelling ratio is a value (%) obtained by dividing the value of {(b)-(a)} by (a) and multiplying the value by 100.

The emulsion layer of the photographic light-sensitive material of the present invention may contain a plasticizer such as a polymer or an emulsion in order to improve pressure characteristics. For example, British Patent No. 738,61
No. 8 is a heterocyclic compound, Nos. 738,637 is an alkyl phthalate, Nos. 738,639 is an alkyl ester, and US Pat. No. 2,960,404 is a polyhydric alcohol. No. 121,060 discloses carboxyalkyl cellulose, JP-A-49-5017 discloses paraffin and carboxylate, and JP-A-53-28086 discloses method using alkyl acrylate and organic acid. . The other constitution of the emulsion layer of the silver halide photographic light-sensitive material of the present invention is not particularly limited, and various additives can be used if necessary. For example, Rese
arch Disclosure 176, 22-28 (1978 1
The binders, surfactants, other dyes, coating aids, thickeners, etc. described in (February) can be used.

Incidentally, in a silver halide photographic light-sensitive material having photographic emulsion layers on both sides, there is a problem that deterioration of image quality is likely to occur due to crossover light. The crossover light is emitted from the respective intensifying screens arranged on both sides of the photosensitive material, passes through the support of the photosensitive material (usually a thick one of about 170 to 180 μm is used), and is exposed on the opposite side. Visible light that reaches a layer, and is light that causes deterioration of image quality (particularly sharpness). The less crossover, the sharper the image can be obtained. There are various methods for reducing crossover, but the most preferable method is to fix a decolorizable dye between the support and the photosensitive layer by a development treatment. U.S. Pat. No. 4,80
The use of microcrystalline dyes taught in US Pat. No. 3,150 has good immobilization and good decolorizing property, and can contain a large amount of dyes, which is very effective in reducing crossover. preferable. According to this method, there is no desensitization due to improper fixation, and it is possible to decolorize the dye in 90 seconds of treatment, and the crossover can be made 15% or less. A more preferable dye layer for reducing crossover is one in which dyes are arranged in the highest density possible. It is preferable to reduce the coating amount of gelatin used as a binder so that the film thickness of the dye layer is 0.5 μm or less. However, extremely thin layers tend to cause poor adhesion, and the most preferable thickness of the dye layer is 0.05 μm to 0.3 μm.

The size distribution of silver halide grains may be wide or narrow, but so-called monodisperse emulsions are better in terms of photographic characteristics such as latent image stability and pressure resistance, and processing stability such as developer pH dependency. preferable. The value S / d obtained by dividing the standard deviation S of the diameter distribution when the projected area of silver halide grains is converted into a circle by the average diameter is preferably 20% or less, more preferably 15% or less. The silver chloride, silver chlorobromide or silver chloroiodobromide emulsion used in the present invention is described in "Photochemistry and Physics" by P. Glafkides (Graphkide) (Paul Montel, Inc.,
1967), "The Chemistry of Photographic Emulsions" by GF Duffin, Focal Press, 1966, V.
It can be prepared by applying the method described in "Preparation and Coating of Photographic Emulsion" (Focal Press Co., 1964) by L. Zelikman et al. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, but the acidic method and the neutral method are particularly preferable in the present invention in terms of reducing fog. In order to obtain a silver halide emulsion by reacting a soluble silver salt with a soluble halogen salt, any one of so-called one-side mixing method, simultaneous mixing method or a combination thereof may be used. It is also possible to use a so-called reverse mixing method in which grains are formed under the condition of excess silver ions.
In order to obtain the monodisperse grain emulsion preferred in the present invention, it is preferable to use the simultaneous mixing method. As one form of the simultaneous mixing method, it is more preferable to use a method of keeping the silver ion concentration in the liquid phase where silver halide is produced constant, that is, a so-called controlled double jet method. By using this method, a silver halide emulsion having a regular silver halide crystal shape and a narrow grain size distribution can be obtained. To form high silver chloride grains, JP-A-2-32 and 3-
137,632, 4-6546, Japanese Patent Application No. 3-3
Nos. 6,632 and 3-236,880, and the like using a bispyridinium compound, and JP-A-62-29.
3,536, JP-A-1-155332, JP-A-63.
The methods described in Nos. 2,043, 63-25,643, U.S. Pat. Nos. 4,400,463, 5,061,617 and the like can be preferably used.

In the course of such grain formation or physical ripening of silver halide, a cadmium salt, a zinc salt, a lead salt, a thallium salt, or the iridium salt or its complex salt, a rhodium salt or its complex salt, an iron salt as described above. Alternatively, its complex salt may coexist. During or after grain formation silver halide solvents (eg, as known, ammonia, thiocyanates, U.S. Pat. No. 3,271,1).
57, JP-A-51-12360, JP-A-53-82.
408, JP-A-53-144319, JP-A-54-
No. 100717 or thioethers and thione compounds described in JP-A No. 54-155828, etc. may be used. When used in combination with the above-mentioned method, silver halide has a regular silver halide crystal shape and a narrow grain size distribution. An emulsion can be obtained.

The black-and-white photographic light-sensitive material produced by using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

As the support of the photographic light-sensitive material of the present invention,
It must have a thickness of 150-250 μm. This is essential from the viewpoint of handleability when observing on a medical Schaukasten. Further, the material is preferably a polyethylene terephthalate film, and particularly preferably colored blue. The support is preferably subjected to a corona discharge treatment, a glow discharge treatment, or an ultraviolet irradiation treatment for improving the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene-butadiene-based latex, vinylidene chloride-based latex or the like may be provided, and a gelatin layer may be further provided thereon. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrocolloid layer can be further improved.

As the various additives and the like used in the photographic light-sensitive material of the present invention, those described in the following relevant parts can be used.

[0054]         Item This location 1) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13                         From the 16th line in the upper left column, Japanese Patent Application No. 3-105035.

[0055] 2) Antifoggant, stable JP-A-2-68539, page 10, lower left column, line 17     From the agent, page 11, upper left column, line 7 and page 3, lower left column, line 2                         From the eyes, page 4, lower left column.

[0056] 3) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7                         To page 10, lower left column, line 20, JP-A-3-9424.                         No. 9, page 6, lower left column, line 15 to page 11, upper right column 1                         Line 9

[0057] 4) Surfactant, antistatic JP-A-2-68539, page 11, upper left column, line 14     From the stoppage, page 12, upper left column, line 9 of the same.

[0058] 5) Matting agent, slip agent, JP-A-2-68539, page 12, upper left column, line 10     From plasticizer, line 10 on the upper right column, line 10 on the lower left column on the same page 14                         From the same right lower column first line.

[0059] 6) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11                         To the same, lower left column, line 16.

[0060] 7) Hardener JP-A-2-68539, page 12, lower left column, line 17                         To page 13, upper right column, line 6.

[0061] 8) Polyhydroxy ester JP-A-3-39948, page 11, upper left column     Nzens, page 12, lower left column, EP Patent No. 452772A.

[0062] 9) Layer structure JP-A-3-198041.

Next, the present invention will be described in more detail by way of examples, but the embodiments of the present invention are not limited thereto.

[0064]

【Example】

Example 1 1. Preparation of Emulsion 1200 ml of gelatin aqueous solution (containing 18 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g, pH 4.3) was put in a reaction vessel, and while maintaining the temperature at 43 ° C., Ag-1 solution (100 ml). AgNO ₃ 20 in
g, 0.8 g of the gelatin, 0.2 ml of HNO ₃ 1N solution) and X-1 solution (6.9 g of NaCl in 100 ml, 0.8 g of the gelatin, 0.3 ml of 1N NaOH solution).
Simultaneous addition of only 12 ml at 4 ml / min. After stirring for 2 minutes, Ag-2 solution (containing 2 g of AgNO ₃ in 100 ml, 0.8 g of the gelatin and 0.2 ml of HNO ₃ 1N solution) and X-2 solution (1.4 g of KBr in 100 ml, 31 ml of containing 0.8 g of gelatin and 0.2 ml of NaOH 1N solution)
Only 19 ml of the mixture was added at the same time. After stirring for 2 minutes,
The Ag-1 solution and the X-1 solution were simultaneously mixed and added at 36 ml at 48 ml / min. NaCl-1 solution (100 ml of NaCl
20 ml (including 10 g) was added to adjust the pH to 4.8 and the temperature was raised to 75 ° C. After aging for 20 minutes, the temperature is adjusted to 60
After lowering the temperature to ℃ and adjusting the pH to 5.0, A at a silver potential of 130 mV
g-3 solution (containing 10 g of AgNO _{3 in} 100 ml) and X
-3 solution (containing 3.6 g of NaCl in 100 ml)
CDJ (controlled double jet) was added. The flow rate at the start of addition was 7 ml / min, and the flow rate was accelerated at 0.1 ml / min per minute, and 400 ml of Ag-3 solution was added.

Add a precipitating agent, lower the temperature to 30 ° C., and settle
After washing with precipitation, an aqueous gelatin solution was added, and the pH was adjusted to 6.
2, adjusted to pCl 3.0. Collect a part of the emulsion
Then, a transmission electron micrograph image of a replica of the particle (hereinafter
The "TEM image" is observed. Shape characteristic value of the particle
Was as follows: (Aspect ratio of 2 or more ((10
0) Total projected area of tabular grains / projected area of all AgX grains
Sum) = a₁= 0.91, aspect ratio 2 or more (10
0) Average aspect ratio of tabular grains (average diameter / average thickness)
Sa) = a₂= 3.4, aspect ratio 2 or more (100)
Average diameter of tabular grains = a₃= 1.0 μm, (twin crystals
(100) flat plate with total projected area / aspect ratio of 2 or more
Total projected area of particles) = a_Four= 0, (aspect ratio 2 or more
Projection of (100) tabular grains with an edge ratio of 1 to 1.4
Area sum / sum of projected areas of all AgX particles) = a_Five= 0.8
6, large (100) tabular grains with an aspect ratio of 2 or more
When you take out up to 70% of the total projected area from the
Variation coefficient of the particle diameter distribution of a) = a ₆= 0.059, flat
Uniform thickness = a₇= 0.29 μm

Thereafter, this emulsion was heated to 60 ° C., sodium thiosulfate was added, 2 minutes after that, chloroauric acid and potassium thiocyanate were added, and 65 minutes later, 4-hydroxy-
Emulsion A was prepared by adding methyl-1,3,3a, 7-tetrazaindene and then rapidly cooling to solidify. Emulsion A is AgB
A high silver chloride (100) tabular emulsion containing 0.76 mol% of r.

2. Preparation of emulsion coating liquid The following chemicals were added to Emulsion A per mol of silver halide to prepare an emulsion coating liquid.

[0068]   I. Spectral sensitizing dye [I] 138 mg   B. Polyacrylamide (molecular weight 40,000) 8.54g   C. Trimethylolpropane 1.2g   D. Sodium polystyrene sulfonate (average molecular weight 600,000) 0.46g   E. Latex of poly (ethyl acrylate / metal acrylic acid) 32.8g   F. 1,2-bis (vinylsulfonylacetamide) ethane 2 g Spectral sensitizing dye [I]

[0069]

[Chemical 11]

3. Preparation of coating solution for surface protection of emulsion layer A container was heated to 40 ° C and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12.3 g c. Sodium polystyrene sulfonate (average molecular weight 600,000) 0.6 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.7 g e. Sodium polyacrylate 3.7 g f. Sodium t-octylphenoxyethoxyethane sulfonate 1.5 g. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.3 g h. C ₈ H ₁₇ SO ₃ K 84 mg Re. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 84mg j. 0.2 g of NaOH. Methanol 78cc. 1,2-Bis (vinylsulfonylacetamide) ethane Adjusted to a swelling amount of 8 μm. Compound [II] 52 mg

[0071]

[Chemical 12]

4. A container for preparing the back layer coating solution was heated to 40 ° C., and the following chemicals were added to prepare a back layer coating solution. I. Gelatin amount 100 g b. Dye [I] 2.39 g

[0073]

[Chemical 13]

[0074]   C. Sodium polystyrene sulfonate 1.1g   D. Phosphoric acid 0.55g   E. Poly (ethyl acrylate / methacrylic acid) latex 2.9g   F. Compound [II] 46 mg   G. Oil dispersion of dye [II] described in JP-A-61-285445       246mg as dye itself Dye (II)

[0075]

[Chemical 14]

[0076]   J. Oil dispersion of dye [III] described in JP-A-61-285445.       46 mg as dye itself Dye (III)

[0077]

[Chemical 15]

5. A container for preparing the surface protection coating solution for the bag was heated to 40 ° C., and the following chemicals were added to prepare a coating solution.

B. Gelatin 100 g b. Sodium polystyrene sulfonate 0.3 g c. Polymethylmethacrylate fine particles (average particle size 3.5 μm) 4.3 g d. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g e. Sodium polyacrylate 1.7 g f. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.6 g g. C ₈ H ₁₇ SO ₃ K 268 mg Chi. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 45 mg. NaOH 0.3 g Nu. 131 mg of methanol Prepare so that the amount of 1,2-bis (vinylsulfonylacetamide) ethane back layer and its surface protective layer is 2.2% by weight based on the total amount of gelatin. Compound [II] 45 mg

6. Preparation of coating sample The coating solution for the back layer together with the coating solution for the surface protective layer of the back layer was coated on one side of a polyethylene terephthalate support colored blue with a gelatin coating amount of 2.6 for the back layer.
9 g / m ^2, a gelatin coating amount of the surface protective layer of the back layer was coated to a 1.3 g / m ^2. Following this, the emulsion coating liquid and the surface protective layer coating liquid described above were provided on the opposite side of the support, the Ag amount in the emulsion layer was 2.4 g / m ² , and the gelatin amount was 1.
8 g / m ² , the amount of gelatin in the surface protective layer was 1.2 g / m ² , the emulsion surface dry film thickness was 3.4 μm, and the emulsion surface side swelling amount was 8 μm.

7. Preparation of developer Developer A   Potassium sulfite 30.0g   55.2g potassium carbonate   Diethylene glycol 10.0g   Diethylenetriamine pentaacetic acid 2.0 g   Sodium bromide 3.0g   5-methyl-benztriazole 0.1 g   4-hydroxymethyl-4-methyl-1-phenyl-3-     Pyrazolidone 2.0g   L-ascorbic acid 43.2 g   Surfactant [I] 0.1 g   Adjust the pH to 9.5 by adding sodium hydroxide.     300 ml with water                                                   Use 1 liter of liquid Surfactant [I]

[0082]

[Chemical 16]

Developer B A solution prepared by adding 0.40 g of compound 8-5 to developer A. Developer C Hydroquinone 27.L-ascorbic acid of Developer A was used.
The one changed to 0g. Developer D Developer C with 0.40 g of compound 8-5 added. As the fixing solution, SR-F1 manufactured by Fuji Photo Film Co., Ltd. was used. CEP manufactured by Fuji Photo Film Co., Ltd.
Use ROS-M to set the development temperature and fixing temperature to 35 ° C, and then dry to
Dry Processed for 47 seconds. 200 ml per 1 m ^{2 of} film sample
Each of them was subjected to a running process of 10 m ² per day for 2 weeks while replenishing the developing solution. The results obtained are shown in Table 1.

[0084]

[Table 1]

Here, the sensitivity means a blackening density of 1.0 with the developer A.
The reciprocal number is shown as a relative value, with the exposure amount required to obtain ## EQU1 ## as 100. As for the silver stain, the state where no silver stain is generated on the wall of the developing tank is set to "5", and the state where the silver stain is black on the entire surface of the wall of the developing tank and the developing tank needs to be washed is set to "1". It was evaluated in 5 levels. As is clear from the results of Table 1, compound 8 was used as the developing agent with L-ascorbin.
In the case of the developer B using -5, good results were obtained in which no silver stain was generated on the wall of the developing tank.

Example 2 As a packaging material Y for a developer, it is a foldable and flexible flexible layer composed of two layers of 75 μl nylon and 175 μm polyethylene and has an oxygen permeability of 20 ml / m ² · atom · day.
10 liters of the developing solution B and the developing solution D of Example 1 were prepared and put into a cubic type 10 liter container (at a temperature of 20 ° C. and a relative humidity of 65%). Further developer packaging material Z
As a foldable and flexible container consisting of 250μ of polyethylene vinyl acetate copolymer, a developer B is placed in a cubic type 10 liter container having an oxygen permeability of 100 ml / m ² · atom · day (temperature 20 ° C., relative humidity 65%). Then, 10 liter of the developer D was prepared and added. Each of these was stored at 50 ° C. for 8 weeks, and the remaining amount of compound 8-5 was examined at that time. The results shown in Table 2 were obtained.

[0087]

[Table 2]

[0088] high developer compound 8-5 residual ratio upon storage in an oxygen permeability of less Do <br/> have packaging material Y as shown by the results in Table 2. Particularly in the case of the developer B containing L-ascorbic acid as a developing agent, the residual rate is 98%, which is extremely high .
If Save This has the oxygen permeability of less Do have packaging material in one-<br/> liquid developer to the developing agent of the L- ascorbic acid, long-term compound 8-5 is stably present, use It is suggested that the effect of preventing silver stain at the time is excellent .

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 5/26

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material having the following composition :
One-component liquid developer for materials with oxygen permeability of 50 ml / m ² · at
Packaging materials with m · day (temperature 20 ℃, relative humidity 65%) or less
Silver halide photographic light-sensitive material characterized by being included in the material
A method for storing a one-pack type liquid developer for materials. (a) a developing agent of ascorbic acid and / or a derivative thereof (b) an auxiliary developing agent exhibiting superadditivity (c) an alkaline agent necessary for at least adjusting the pH to 9.0 (d) the following general formula ( I) or a compound represented by the general formula (II): General formula (II) Where R ₁ , R ₂ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m is 0, 1, or 2. R ₅ represents a hydroxyl group, an amino group, or an alkyl group having 1 to 3 carbon atoms. M represents a hydrogen atom, an alkali metal atom or an ammonium group, and X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a sulfonyl group, an amino group, an acylamino group, a dimethylamino group, an alkylsulfonylamino group or an arylsulfonylamino. Represents a group. 2. The method according to claim 1, wherein the black and white silver halide photographic light-sensitive material is stored at a ratio of 300 ml or less per 1 m ^2.
A developing method comprising replenishing an existing developing agent with an automatic developing machine.