JPH0113096B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for developing high-contrast silver halide photographic materials. More specifically, the present invention relates to a method for rapidly developing halftone photographic original plates for printing. In general, high contrast lithium-type silver halide photographic light-sensitive materials and a developer called a so-called contagious developer, which is different from a normal black-and-white developer, are used to produce halftone photographic original plates for printing. Thereby, the continuous tone density changes of the original are resolved into halftone dots and converted into area changes. The infectious developer usually contains a dihydroxybenzene-based developing agent and contains an aldehyde bisulfite alkali salt adduct as a preservative. This type of contagious developer has a low free sulfite ion concentration so that the oxidation products of the dihydroxybenzene developing agent have a long lifetime and act as a medium for contagious development. In other words, in the early stage of development, development is started by the dihydroxybenzene developing agent and its oxidized products are accumulated, and the development is contagiously activated and accumulated one after another, resulting in rapid development and contrast. It is believed that a high-quality image, that is, a good halftone image, can be obtained. A method of forming such a photographic halftone image is described in JACYule "J.Frank.
Inst.” Volume 239, page 221 (1945). As is already well known, the infectious developer contains only dihydroxybenzene as a developing agent and does not contain an auxiliary developing agent, so that the induction period of development (the time from the start of development to the appearance of photographic black density) Since the time is long, the normal development time is 100 seconds or more. The development time can be shortened by using an auxiliary developing agent to shorten the induction period of development and perform development in a short time. However, the contrast of the obtained photographic image becomes low, and therefore a good halftone dot image cannot be obtained. It has been desired for some time to rapidly carry out infectious development. As mentioned above, since the infectious developer does not contain an auxiliary developing agent, the induction period of development is long, and therefore it is difficult to carry out rapid development processing. However, it was not possible to obtain halftone dot images by performing rapid processing. The object of the invention is to obtain good halftone images with rapid processing. The present inventors conducted research on how to shorten the development time and increase the contrast of photographic images to obtain good halftone images. As a result, formaldehyde bisulfite is composed of 0.30 to 0.45 mole/carbonate, carbonate is composed of 0.28 to 0.45 mole/potassium, and more than 45 mole% of the total cation components are potassium. We have discovered a method for developing silver halide materials in 45 to 75 seconds. More preferably, a so-called infectious developer is used in which formaldehyde bisulfite is composed of 0.30 to 0.45 mol/carbonate, carbonate is composed of 0.28 to 0.45 mol/potassium, and at least 45 mol% of the total cation components are potassium. 4 per square meter
It has been found that when a lithium-type photosensitive silver halide material having a weight of less than g is developed, a halftone photographic original plate for printing with a high contrast photographic image and an extremely good halftone image can be obtained by rapid development. Specific examples of formaldehyde bisulfite used in the present invention include sodium formaldehyde bisulfite, potassium formaldehyde bisulfite, and the like. Specific examples of the carbonate used in the present invention include sodium carbonate and potassium carbonate. Specifically, the cations referred to in the present invention include:
Examples include sodium ions, potassium ions, ammonium ions, lithium ions, etc., but sodium ions and potassium ions are preferred. These cations are added to the developer in the form of formaldehyde bisulfite, carbonate, potassium halide, PH buffer, and the like. Furthermore, in the present invention, "contains substantially no auxiliary developing agent" is a condition under which the developer has an infectious developing effect, and generally does not contain an auxiliary developing agent.
It is an infectious developer containing only about 0.05g/or less. The infectious developer used in the present invention basically contains dihydroxybenzene compounds as developing agents, such as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,3 dichlorohydroquinone, and 2,5 dimethyl. Hydroquinone, etc. Among these, hydroquinone is particularly useful. These developing agents may be used alone or in combination. The amount of developing agent added is 5 to 50 g per developer, more preferably,
It is 10-30g. As a sulfite ion buffer, in addition to formaldehyde bisulfite, aldehyde bisulfite alkali adducts, ketone bisulfite alkali adducts such as acetone sodium bisulfite adduct, and carbonyl bisulfite amines such as sodium bis(2-hydroxyethyl)aminomethanesulfonate can be used. Condensation products such as ascorbic acid are also used. The alkaline agent is added to make the developer solution alkaline, preferably at pH 9 or higher. The inherent feature of infectious developers is that they have a low concentration of free sulfite ions, as indicated above, and for this reason sulfite ion buffers are generally used. Usually, an alkali sulfite salt such as sodium sulfite potassium sulfite is added to the sulfite ion buffer in an amount of 8 g or less per developer to control the concentration of free sulfite ions. In addition to the above-mentioned components, the infectious developer of the present invention may optionally contain a pH buffering agent such as a water-soluble acid, alkali, or salt, and a development control agent such as an alkali halide. Certain alkalis not only alkalinize the developer, but also act as PH buffers and development regulators.
5.mercaptotetrazole, tetrazaindenes (e.g. 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene, etc.), preferably 1 per developer.
~10 mg, amine compounds such as alkanolamines (e.g., diethanolamine, triethanolamine, etc.), organic solvents such as triethylene glycol, dimethylformamide, methyl alcohol, cellosolve (0 to 300 ml per developer), and the like. Further, polyalkylene oxide such as polyethylene oxide having a molecular weight of 1000 to 3000 may be included as a leg cutting agent in an amount of 0.01 to 5 g/range. As the water softener used in the infectious developer of the present invention, nitrilotriacetic acid, ethylenediaminetetraacetate acid, triethylenetetraaminehexaacetate acid, diethylenetetraaminepentaacetate acid, etc. can be used. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. The fixer may also contain a complex of ethylenediaminetetraacetic acid and trivalent iron ions as an oxidizing agent. The developer of the present invention can be used in an automatic processor for development processing. At this time, the developer can be divided into two or more parts. Moreover, a replenisher can also be used to keep the developing activity constant. At this time, a method can be used in which the replenisher is divided into a replenisher for processing fatigue and a replenisher for aging fatigue. For details, see JP-A-53-
It is described in Publication No. 94926, Publication No. 53-10023, etc. The lithium-type photosensitive silver halide photographic material used in the present invention may use any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride as the silver halide. Preferred silver halide is silver chlorobromide or silver iodochlorobromide containing silver chloride of 50 mol % or more (more preferably 70 mol % or more) (silver iodide is preferably 5 mol % or less). . The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
(expressed as an average based on the projected area) is not particularly limited, but is preferably 0.6μ or less. The particle size distribution can be narrow or wide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubes and octahedrons, or irregular crystal shapes such as spherical and plate shapes. It may also have a crystalline form or a composite form of these crystalline forms.
It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is P. Glafkides
Written by Chimie et Physique Photographique (Pual
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. The soluble salts are usually removed from the emulsion after precipitation or physical ripening, and the long-known Nudel water washing method in which gelatin is gelatinized may be used as a means for this purpose. Utilizing inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flocculation) may also be used. The process of removing soluble salts may be omitted. Silver halide emulsions do not undergo chemical sensitization,
It is also possible to use so-called primitive emulsions or to chemically sensitize them. For chemical sensitization, please refer to the above-mentioned book by Glafkides or Zelikman et al. or Die Grundlagen der edited by H. Frieser.
Photographischen Prozesse mit
Silberhalogeniden (Akademische
Verlagsgesellschaft.1968) can be used. In other words, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or activated gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. Can be done. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
No. 2278947, No. 2728668, No. 3656955, No. 4032928,
The reduction sensitizers described in No. 4067740 include:
Stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in the U.S. Pat.
No. 2487850, No. 2419974, No. 2518698, No. 2983609,
It is described in No. 2983610, No. 2694637, No. 3930867, No. 4054458. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in the periodic table group such as platinum, iridium, and palladium can be used.
It is described in issues such as No. 618061. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto. Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds, e.g. Oxazolinthione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,
7) Many compounds known as antifoggants or stabilizers can be added, such as tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; etc. The silver halide material used in the present invention may contain an inorganic or organic hardening agent. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal,
glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (2,3-
dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-S-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy -S-triazine, etc.), mucohalogen acids (mucochloric acid,
mucophenoxychloric acid, etc.), etc. can be used alone or in combination. The silver halide material used in the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of the photosensitive material used in the present invention, they may be mordanted with a cationic polymer or the like. For example, British Patent No. 685475, US Patent No. 2675316, US Patent No. 2839401, US Patent No. 2882156,
No. 3048487, No. 3184309, No. 3445231, West German Patent Application (OLS) No. 1914362, Japanese Patent Application Laid-Open No. 1973-47624
Polymers described in No. 50-71332 and the like can be used. The lithium-type photosensitive silver halide material used in the present invention may be spectrally sensitized with methine dyes or the like. Useful sensitizing dyes are described, for example, in German patent 929080
No., U.S. Patent No. 2493748, U.S. Patent No. 2503776, U.S. Patent No.
No. 2519001, No. 3694217, No. 4025349, Tokko Akira
It is described in No. 44-14030 and No. 52-24844. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are US Patent No. 2688545, US Patent No. 2977229, US Patent No.
No. 3522052, No. 3527641, No. 3617293, No. 3522052, No. 3527641, No. 3617293, No.
No. 3666480, No. 3672898, No. 3679428, No.
No. 3703377, No. 3814609, No. 3837862, Special Publications
No. 53-12375, Japanese Patent Application Publication No. 52-110618, No. 52-
Described in No. 109925. The photographic emulsion layer of the lithium-type photosensitive silver halide material used in the present invention contains, for example, ether,
It may also include derivatives such as esters and amines, thioether compounds, thiomorpholins, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent No. 2400532, US Patent No. 2423549, US Patent No.
No. 2716062, No. 3617280, No. 3772021, No.
Those described in No. 3808003, British Patent No. 1488991, etc. can be used. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., using a variety of synthetic hydrophilic polymeric materials such as single or copolymers. be able to. In addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.JapanNo.16 30
Enzyme-treated gelatin such as that described in Page (1966) may be used, and hydrolyzed or enzymatically decomposed products of gelatin may also be used. Gelatin derivatives include gelatin, for example, acid halides, acid anhydrides,
Those obtained by reacting various compounds such as isocyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are used. A specific example is US Patent No. 2614928
No. 3132945, No. 3186846, No. 3312553,
British Patent No. 861414, British Patent No. 1033189, British Patent No. 1005784,
It is described in Special Publication No. 42-26845. The gelatin graft polymer used is gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and acrylonitrile styrene. be able to. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. Typical synthetic hydrophilic polymer substances include West German Patent Application (OLS) No. 2312708 and U.S. Patent No. 3620751.
No. 3879205 and Special Publication No. 7561 of 1973. The silver halide material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for purposes such as improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, A polymer containing a combination of methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. For example, US patent
No. 2376005, No. 2739137, No. 2853457, No. 2376005, No. 2739137, No. 2853457, No.
No. 3062674, No. 3411911, No. 3488708, No. 3488708, No. 3411911, No. 3488708, No.
No. 3607290, No. 3635715, No. 3645740, No.
Those described in British Patent No. 3525620, British Patent No. 1186699, and British Patent No. 1307373 can be used. The polyalkylene oxide or its derivative used in the lithium-type silver halide material used in the present invention has a molecular weight of at least 600 and a carbon number of 2 to 2.
a polyalkylene oxide consisting of at least 10 units of an alkylene oxide, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, preferably ethylene oxide; water, an aliphatic alcohol, an aromatic These include condensates with compounds having at least one active hydrogen atom, such as group alcohols, fatty acids, organic amines, and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. That is, as polyalkylene oxide compounds, specifically, polyalkylene glycols polyalkylene glycol alkyl ethers polyalkylene glycol aryl ethers polyalkylene glycol (alkylaryl) ethers polyalkylene glycol esters polyalkylene glycol fatty acid amides poly Alkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, etc. can be used. The number of polyalkylene oxide chains is not limited to one in the molecule, and two or more may be included. In that case, the individual polyalkylene oxide chains may consist of fewer than 10 alkylene oxide units, but
The total number of alkylene oxide units in the molecule must be at least 10. If there is more than one polyalkylene oxide chain in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention is preferably 14 or more.
Contains up to 100 alkylene oxide units. Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of the various known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, and xenon flash lamps. The exposure time can be from 1/1000 second to 1 second, or shorter than 1/1000 second, such as 1/10 ⁴ to 1/10 ⁶ seconds using a xenon flash lamp, or 1/10 4 to 1/10 6 seconds. Exposures longer than seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter.
Laser light can also be used for exposure. Examples of the present invention will be shown and specifically explained below. Example 1 Automatic processor: FG25L (manufactured by Fuji Photo Film Co., Ltd.) As a lithium-type photosensitive material, a cubic emulsion of silver chlorobromide containing 75 mol% of silver chloride with an average grain size of 0.3 μm was placed on a support of polyethylene terephthalate. A lithium-type silver halide photosensitive material coated with a silver content of 4.8 g/m ² was used as film sample 1. A lithium-type silver halide photosensitive material coated with a silver content of 3.8 g/m ² was designated as film sample 2. After passing film sample 1 and film sample 2 through a 150-line contact screen and photographing the light wedge, apply each developer A, B, C, D, E, F for 40 minutes as shown in Table 1 below.
A solution was prepared and developed.

【table】

【table】 The results obtained are shown in Table 2.

[Table] The halftone quality was visually evaluated in five stages. A halftone dot quality of 5 indicates a good halftone dot, and a halftone dot quality of 1 indicates a bad halftone dot. A halftone dot quality of 3 indicates a practically usable halftone dot, and a halftone dot quality of 2 indicates a practically unsatisfactory halftone dot quality. As shown in the results in Table 2, when film sample 1 is used, practical halftone dot quality is obtained with developer A for a development time of 100 seconds, but the halftone dot quality deteriorates when the development time is 60 seconds. However, in the developer of the present invention, developer C, which contains 0.36 mol of formaldehyde bisulfite, 0.36 mol of carbonate, and 52 mol% of potassium in the total cations, has a practical halftone quality even after a development time of 60 seconds. Obtained.
Developers B, D, E, and F used for comparison did not provide a practically usable halftone quality. On the other hand, for film sample 2 with a coated silver amount of 3.8 g/m ² , practically acceptable halftone dot quality can be obtained with any developer, but it can be seen that particularly good halftone dot quality can be obtained with developer C of the present invention. . Example 2

[Table] The formulation after the start of development (commonly known as mother liquor) shown in Table 3,
The processing replenisher formulation and the aging replenisher formulation are concentrated liquid formulations. When using these, Part.Y167ml
Water was added to 167 ml of Part.Z to make each working solution 1. 40 each of the starting solutions of developer G and H were prepared and processed using an automatic processor FG25L at a developing temperature of 32° C. and a developing time of 60 seconds. By developing 40 full-size films every day and adding 80 ml of processing replenisher per film, the developer sensitivity could be kept constant.
On the other hand, the aging replenisher was replenished at 250 ml every two hours while the automatic developing machine was in operation, and at 140 ml per two hours while the automatic developing machine was stopped, and was replenished when the automatic developing machine was restarted. Developing a total of 40 films per day was repeated for 10 days. Sensitometry was performed every day using Film Sample 1 and Film Sample 2 used in Example 1 as films for sensitometry. There was no change in halftone dot quality between the new solution at the start of development and the 10th day. The results obtained are shown in Table 4.

【table】

[Table] As shown in the results in Table 4, processing replenisher formulations and aging replenisher formulations are incorporated to compensate for changes in the composition of the development starting solution. The same halftone quality as the starting solution can be obtained. When film sample 1 is used, developer G can only give a practically unsatisfactory halftone dot quality, but if developer H of the present invention is used, a practically acceptable halftone quality can be obtained. Furthermore, the amount of coated silver is 3.8
It can be seen that extremely good halftone dot quality can be obtained with film sample 2 of g/m ² .

Claims (1)

[Claims] 1 Formaldehyde bisulfite is 0.30~
Consisting of 0.45 mol/carbonate and 0.28 to 0.45 mol/
A lithium-type silver halide material is prepared by using an infectious developer containing only a dihydroxybenzene compound as a developing agent and containing substantially no auxiliary developing agent. A developing processing method characterized by developing in seconds to 75 seconds.