JPS63163336A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the processing stability of the titled material and to obtain the high sensitivity and the high contrast of the titled material by developing a specific photographic sensitive material in the presence of a hydrazine compd. CONSTITUTION:The titled material comprises a silver halide photographic emulsion layer provided on a substrate. Said emulsion layer is composed of the core/shell type silver iodobromide crystal, and has a thickness of the shell part of 0.0015-0.025mum, and the iodine content of the core part higher than that of the shell part, and is effected iodine conversion on the surface of the silver iodobromide emulsion crystal. The titled material is developed in the presence of the compd. shown by formula I, where Ar is aryl group, R is hydrogen atom, aryl or alkyl group. Thus, the titled material having the improved processing stability and the high sensitivity and contrast is obtd.

Description

Detailed Description of the Invention (A) Industrial Application Field The present invention relates to a method of forming a photographic image using a silver halide photographic light-sensitive material, and relates to a method of forming an ultra-high contrast image using a hydrazine compound. It is something.

(B) Problems with the Prior Art When the continuous gradation of a normal photograph or the contrast (shading) of an original is expressed in a printed matter, this must be replaced by the size of halftone dots. The size of one halftone dot is therefore as small as 100 microns, and there are several hundred halftone dots per inch. Moreover, these halftone dots are required to be as sharp as possible.

Therefore, in the field of printing, a special effect called the contagious development effect (Lith effect) is used to obtain ultra-high contrast images by combining a Lith type photosensitive material and a Lith developer.

Processing is carried out using a special developer called an infectious developer (Lith developer), which has a different composition from that of general photographic developers.

However, this Lith developer has a sulfite ion concentration of 0.
It is necessary to keep the amount below 1%, and it is not possible to add multi-generation sulfite ions as a preservative like in general developer solutions, resulting in extremely poor preservation of the developer against air oxidation.

In addition, the lithium-type photosensitive material is easily affected by the concentration of the developing agent and the i degree of Br ions in the developer, making it extremely difficult to obtain halftone images of stable quality. In actual printing development, a cumbersome management system is required that checks the performance of the developer every few hours and makes adjustments using replenisher.

Further, in order to obtain a halftone image of sufficient quality using a lith film, a relatively long development time of 1 minute to 2 minutes is required at a development temperature of 25° C. to 35° C.

In order to solve these problems, a method has been introduced in which a photographic emulsion is developed in the presence of a hydrazine compound to quickly obtain a negative image with high contrast and high sensitivity. (@Open/Open 53-16623, Open/Open 53 However, in the above system, it cannot be said that sufficiently high contrast characteristics can be obtained.

(C) Object of the Invention An object of the present invention is to provide a method for developing a silver halide photographic material having high processing stability, high sensitivity, and high contrast characteristics.

CD) Structure of the Invention The present inventors have conducted extensive studies and found that the thickness of the shell portion of the core/shell type silver iodobromide crystal is 0.0015 μm or more and 0.02 μm or more.
5 μm or less, and has at least one silver halide photographic emulsion layer on the support in which iodine conversion has been performed on the surface of a silver iodobromide emulsion crystal in which the iodine content in the core portion is higher than that in the shell portion. It has been discovered that the above object can be achieved by developing a photographic material in the presence of a compound represented by the following general formula (1).

General formula (1) %Formula % The core/shell type silver iodobromide crystal used in the present invention can be prepared by a mild method. For example, a method is used in which a core is formed by a single jet method or a double jet method, and a shell is further formed on the core by a double jet method.

The iodine content of the core/shell type silver iodobromide used in the present invention is from 1 to 10 molty in the core, and from θ to 10 molty in the shell, and more preferably from 0 to 3 molty. It is necessary that the iodine content of the shell portion be higher than that of the shell portion, but it is preferably about 1 or more iodine higher than that of the shell portion.

Also, the thickness of the shell part is 0.0015μm or more and 0.025μm
m or less. If the thickness is greater than this, undesirable results such as decreased sensitivity will result.

Iodine convergence can be applied at any time after grain formation by adding a water-soluble iodide, such as an aqueous potassium iodide solution. Iodine salt is 0.1 mole or more per mole of silver1
．． It is preferable to add so that the amount is 0 molt or less.

The hydrazine compound used in the present invention has the following general formula C
I).

General formula CI) ArNHNHCR In the formula, Ar represents an aryl group (eg, phenyl group, naphthyl group, etc.). However, the aryl group may be substituted, and examples of substituents include alkyl groups, aralkyl groups, alkoxy groups, aryloxy groups, amino groups, aliphatic acylamide groups, aromatic acylamide groups, aliphatic sulfonamide groups, and aromatic sulfone groups. Amide group, alkoxycarbonyl group, halogen atom, nitro group, carboxyl group, sulfo group, cyano group, carbamoyl group, sulfamoyl group,
semicarbazide group, thiosemicarbazide group, thioureido group, ureido group, alkylthio group, arylthio group,
An aliphatic thioacylamide group, an aromatic thioacylamide group, a polyether group, etc. can be used.几represents a hydrogen atom, an aryl group (eg, phenyl group, etc.), or an alkyl group (eg, methyl convex ether group, etc.).

Specific examples of the hydrazine compound used in the present invention are described below, but the present invention is not limited thereto.

C3H11 CH.

CH5 The amount of the hydrazine compound used in the present invention is 10"' to 10-1 mol/1°, more preferably 5X10-' to 5X10-' mol/l when mixed in the developer. When mixed in the photographic emulsion. In this case, 10-2 to 10-t mole of Ag is preferred.These are preferably selected depending on the type of silver halide photographic emulsion, the amount of the amino compound, the anti-capri agent, etc.

Development in the present invention can be carried out in the presence of a polyalkylene oxide derivative.

The polyalkylene oxide that can be used in the present invention has a molecular weight of at least 600 and may be added to the silver halide emulsion layer or to the developer.

The polyalkylene oxide compound that can be used in the present invention is a polyalkylene oxide consisting of at least 10 units of an alkylene oxide having 2 to 4 carbon atoms (however, these may be branched) or a monoalkylene oxide of these Block copolymers and aliphatic alcohols, aromatic alcohols, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, aromatic tears, etc. Examples of polyalkylene oxide compounds that can be used in the present invention are shown below.

2, C18Hs, 0(CH2CH20) 15H
3. C18H5,0 (CH2CH20) 4. H6,
C11H23COO(CH2CH20)61)H7,C
1,H2,C0NH(C)420H20),5H9,C
H20CH2CH20C1, H23H(OCH2CH2
), a 0CHCHCH2(CH2CH20), a
H0(CH2CH20), aH The amount of the polyalkylene oxide compound that can be used in the present invention is preferably 5 x 10-' to 5 f1 mol AgX when mixed in to neutralize the photographic emulsion, and is mixed in the developer. If so, it is 10 to 20 t/L.

Development in the present invention can be carried out in the presence of an amine compound, preferably an alkanolamine compound.

The alkanolamine preferably used in the present invention is a primary, secondary or tertiary amine compound having at least one hydroxyalkyl group. The alkanolamine contains a compound represented by the following general formula.

The alkanolamines that can be used in the present invention are shown below, but the present invention is limited to ethanolamine jetanolamine triethanolamine diimpropanolamine N-methylethanolamine N-7 mi/ethylethanolamine N,N -diethylethanolamine N,N-dimethylethanolamine N-methylgetanolamine N-ethylgetanolamine 3-aminopropanol 3-diethylamino-1,2-propanediol 1-amino-propan-2-ol 4-amino Butanol 5-amino-pentan-1-ol 3.3'-iminopropanol N-n-butyljetanolamine, N-ethyl-2
,2'-iminodiethanolamine 2-amino-2-(
Hydroxymethyl)prono-1,3-diol 2-amino-2-methylpropane-1,3-diol The alkanolamines that can be used in the present invention are preferably 5X10-' to 1 mol/L1, and more preferably 1
X10-2 to 5X10' mol/l.

The aqueous alkaline developer used in the present invention preferably contains an organic anti-capri agent necessary to minimize the formation of capri and to obtain favorable halftone dot quality. Preference is given to using benzotriazole anticapryants, more preferably 5-methylbenzotriazole.

The aqueous alkaline developer used in the invention preferably has a pH value of 11-12.

Alkali metal hydroxides, carbonates or phosphates, etc. can be used to obtain this pH value.

The aqueous alkaline developer used in the present invention contains sulfite in order to enhance its preservability. It is sufficient that the concentration of the sulfite used is about 0.1 mole/or more. Examples of the sulfite used include sodium sulfite and potassium sulfite.The aqueous alkaline developer used in the present invention contains dihydroxybenzenes as a developing agent.

In addition, as an auxiliary developer for dihydroxybenzenes, 1-phenyl-3-pyrazolidone and its derivatives,
Alternatively, it may contain N-methyl-p-aminophenol and its derivatives.

The halide particles used in the present invention are preferably monodisperse, and have an average particle size of 1 μm or less and 0.05 μm or more, more preferably 0.5 μm or more and 0.1 μm or more.

The emulsion according to the invention can contain various additives. For example, chemical sensitizers (for example, sulfur sensitizers such as thiourea and hypo, noble metal sensitizers such as gold, platinum, and iridium compounds, and reduction sensitizers) can also be used in combination. In addition, spectral sensitizers, supersensitizers, stabilizers, anti-capri agents, surfactants, developers, development accelerators, hardeners, hardening accelerators, couplers, desilvering accelerators, dye extraction improvers. Agents, brighteners, thickeners, breaker thereof, and the like can also be used.

Protective colloids for the silver halide emulsion used in the present invention include gelatin, modified gelatin, albumin, agar,
Examples include natural products such as gum arabic and alginic acid, and water-soluble synthetic resins such as polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of acrylamide, acrylic acid, and vinylimidazole.

The emulsions used in the present invention are coated onto a suitable support such as glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin (e.g. polyethylene, polypropylene, etc.) coated paper. .

These supports may be corona treated by a known method, and may also be undercoated by a known method if necessary.

The constituent layers used in the present invention include compounds well known in the Todoroki industry, such as hardeners, matting agents, optical brighteners, antistatic agents, thickeners, physical development nuclei, anti-capri agents, spectral sensitizers, and ultraviolet rays. Absorbent, anti-halation color = 4, fogger, developing agent,
These precursors and the like can be added.

The silver halide photographic emulsion according to the present invention is coated with a protective layer, an intermediate layer, an ultraviolet absorbing layer, an undercoat layer or other silver halide emulsions, if necessary.

(E) Examples [Preparation of emulsion A] Potassium bromide/potassium iodide aqueous solution and silver nitrate aqueous solution with a molar ratio of bromine to iodine of 9723 were mixed by the Chondrold double jet method, and washed again with water by a conventional method. After dissolution, sulfur sensitization was carried out, spectral sensitization was carried out by adding an aqueous solution of potassium iodide in an amount of 0.4 mol per 1 mol of silver, and compound (13) of general formula (1) was added to 1 mol of silver. Emulsion A was prepared by adding 3.4×10 −3 mol to the emulsion A.

[Preparation of emulsion BD]

A potassium bromide/potassium iodide aqueous solution with a molar ratio of bromine to iodine of 97=3 and a silver nitrate aqueous solution were mixed by the Chondrold double jet method to form a core part, and further a core part was formed with a molar ratio of bromine to iodine of 99:1. Form a shell part with a potassium bromide/potassium iodide aqueous solution and a silver nitrate aqueous solution to the thickness shown in the table below.
The rest was treated in the same manner as Emulsion A, and this was designated as Emulsion BD.

[Preparation of emulsion E-F]

Emulsion f was prepared in the same manner as emulsions B and C, except that the sulfur-sensitized aqueous potassium solution was not added, and these were designated as emulsion E%F.

These emulsions had a coating weight of 3.7 mm and a thickness of 100 μm.
It was coated on a polyester film of 10.m, subjected to wedge exposure, and developed for 30 days at 38°C with a developer (A) as shown below.

Developer (A) The results are shown below.

a) Sensitivity is expressed as relative sensitivity when that of sample 1 is set as 1.00.

b) γ was determined from the slope of the characteristic curve between two points at concentrations of 1.0 and 2.0.

As shown above, it can be seen that sample 2.3 coated with emulsions B and C of the present invention exhibits sufficiently high sensitivity compared to the comparison.

CF) Effects of the Invention It was possible to provide a method for developing a silver halide photographic material having high processing stability, high sensitivity, and high contrast characteristics.

Claims (1)

[Claims] (1) The thickness of the shell part of the core/shell type silver iodobromide crystal is 0.0015 μm or more and 0.025 μm or less, and the iodine content in the core part is higher than that in the shell part. Halogenation characterized by developing a photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support that has been subjected to iodine conversion in the presence of a compound represented by the following general formula (I). Processing method for silver photographic materials. General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Ar represents an aryl group, and R represents a hydrogen atom, an aryl group, or an alkyl group. ]