JPS6095537A - Image forming method - Google Patents

Abstract

PURPOSE:To form an image with high sensitivity without causing fog by imagewise exposing a photosensitive material contg. a specified compound in a silver halide emulsion layer or a hydrophilic colloidal layer and by processing the material with a developing soln. contg. a specified amount of a developing agent and much alkali. CONSTITUTION:A photosensitive material having at least one silver halide emulsion layer sensitive to visible light on the support and contg. a compound represented by the general formula in the emulsion layer or other hydrophilic colloidal layer is imagewise exposed and processed with a developing soln. contg. 0.05-0.5mol/l dihydroxybenzene developing agent, 0-0.05g/l auxiliary developing agent, >=0.25mol/l free sulfite ions, >=20mg/l 5- or 6-nitroindazole and enough alkali to adjust the developing soln. to >=10.5pH.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an image forming method, and particularly to a method for quickly forming a high-sensitivity, high-contrast silver image using a stable processing liquid. .

(Prior Art) In the photoengraving process, an image forming system exhibiting ultra-high contrast photographic characteristics is required in order to achieve good continuous tone reproduction or line drawing reproduction using dot images.

Conventionally, for this purpose, it has been common to use a hydroquinone developer (infectious developer) with an extremely low effective concentration of sulfite ions (usually 0.1 mol/l or less). However, in this method, since the concentration of sulfite in the developer is low, the developer is extremely unstable and cannot be stored for more than 3 days.

On the other hand, in recent years, hydroquinone and 1-phenyl-3 of about 0.1 g/lt or more have been developed as a system for forming silver images that can be used for printing and plate-making applications through rapid and stable processing.
-Rapid using a developer containing pyrazolidones
Access systems are widespread. However, since it is difficult to obtain photographic characteristics with sufficient contrast and high sensitivity with this system, its scope of application has been limited primarily to light-sensitive materials used in the return process.

For this reason, various methods have been considered to increase sensitivity in systems that use stable developers to obtain ultra-high contrast images, but these methods tend to increase fog or soften gradations. The current situation is that this problem is still unresolved, as it is accompanied by harmful effects.

(Objective of the Invention) Therefore, the object of the present invention is to provide highly sensitive images that can rapidly obtain ultra-high contrast characteristics using a stable processing solution and that can also be used in line-taking and net-hauling processes. An object of the present invention is to provide an image forming method that can obtain an image without causing softening of the tone.

(Structure of the Invention) The object of the present invention is to have at least one silver halide emulsion layer sensitive to visible light on a support, and in the emulsion layer or other hydrophilic colloid layer, the following: After imagewise exposing a photographic light-sensitive material containing the compound represented by general formula (1), 0.05 to 0.5 mol/β of a dihydroxybenzene-based developing agent is added.
Contains 0 to 0.05 g/J of auxiliary developing agent! containing 0.25 mol/1 or more of free sulfite ions,
This was achieved by an image forming method characterized by processing with a developer containing 20 qr/# of 5- or 6-nitroindazole and a sufficient amount of alkali to raise the pH to 1005 or higher.

General Formula (1) Among the compounds represented by General Formula (1), R is preferably a hydrogen atom, an optionally substituted alkyl group having 8 or less carbon atoms, an optionally substituted phenyl group having 8 or less carbon atoms, represents an optionally substituted benzyl group having 8 or less carbon atoms; Represents a CI- group, an optionally substituted -CH=N- group, and an optionally substituted 1-C-CH2- group. However, the above substituents do not include carboxylic acid or sulfonic acid.

In particularly preferred compounds among the compounds represented by general formula (1), R is a hydrogen atom, an alkyl group having 6 or less carbon atoms,
Hydroxy-substituted alkyl group having 6 or less carbon atoms, alkoxy-substituted alkyl group having 6 or less carbon atoms, carbonamide-substituted alkyl group having 6 or less carbon atoms, sulfonamide-substituted alkyl group having 6 or less carbon atoms, amino-substituted alkyl group having 6 or less carbon atoms group, phenyl group; X is a sulfur atom or ':;N
-R'group; Z is dimethylene group, -CH-CH- group, -CH=N-
group, - to -CH, - group, or an alkyl group having 6 or less carbon atoms, an alkoxy-substituted alkyl group having 6 or less carbon atoms = 6-, an alkoxy group having 6 or less carbon atoms, an alkyl group having 6 or less carbon atoms Rethio group, phenyl group,
Represents a group substituted with a chlorine atom or a fluorine atom.

In the above, R' represents a group selected from the same range as R.

Specific examples of the compounds of the present invention are shown below.

1-/ ■-2 -J 1- ■-μ -j -t ■-7 9- -r ■-ta■-IO -ii 10- 1-/2 S 1-/ J 1-/≠ -is 1 -/7 1-/7 1-/r By introducing the compound represented by the general formula (1) into the emulsion layer or other hydrophilic colloid layer, when processed with the developer of the present invention described below, Highly sensitive images can be obtained without impairing the characteristics of low fogging and ultra-high contrast.

The amount of the compound represented by the general formula (I) added is preferably 10 to 10@-1 mol, particularly 10 to 10@-3 mol, per 811 mol of halogenation.

Most of the compounds represented by the general formula (I) are known, and others can be easily synthesized by known methods, and examples of their synthesis will be shown below.

Synthesis Example Synthesis of Compound 1-8 27 g of 2-bromoethanol and 50 mj+ of N,N-dimethylformamide were added to 16 g of l-methylimidazole, and the mixture was heated and stirred on a steam bath for 3 hours.

250 ml of ethyl acetate was added and the mixture was cooled with stirring, and the resulting solid was collected by filtration to obtain 31 g of 3-(2-hydroxyethyl)-1-methylimidazolium bromide as a deliquescent solid. To 30 g of this compound were added 250 ml of 13-methanol, 5 g of sulfur powder, and 15 g of potassium carbonate, and the mixture was heated under reflux for 1.5 hours. After removing insoluble matter by filtration and concentrating the filtrate, add 200ml of ethanol.
J+ was added to remove insoluble matter, the filtrate was concentrated, and the residue was purified by silica gel column chromatography. The obtained crystals were recrystallized from methanol containing water. Yield 3.5
g Melting point 84-85°C.

The silver halide in the silver halide photosensitive material used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodobromochloride, etc., but 40 mol% is composed of silver chloride. More preferably, 70 mol% or more of silver chloride is present.

The content of silver iodide is 5 mol% or less, more preferably 1 mol% or less.

In the present invention, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

Formation of particles under excess silver ions=14= A method (so-called back-mixing method) can also be used.

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, the so-called Chondrald double jet method. According to this method, the crystal form is regular and A silver halide emulsion with nearly uniform grain size can be obtained.

The silver halide grains in the photographic emulsion used in the present invention are
Although it is possible to have a relatively wide grain size distribution, it is preferable to have a narrow grain size distribution, especially when the size of grains that account for 90% of the total weight or number of silver halide grains is within 140% of the average grain size. (Such emulsions are generally called monodisperse emulsions).

The silver halide grains used in the present invention are fine grains (for example, 0
．． 7μ or less) is more preferable, and particularly preferably 0°4μ or less.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
urar) crystals, or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms.

The interior and surface layers of the silver halide grains may consist of a uniform phase or may have different phases.

2F formed separately! The above silver halide emulsions may be mixed and used.

The silver halide emulsion used in the present invention contains more than 10 moles of cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, or a complex salt thereof per mole of silver halide during the formation of silver halide grains or during physical ripening. Rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may also be present.

The soluble salts are usually removed from the emulsion after precipitation or physical ripening, and the long-known Tardel water washing method, which involves gelatinizing gelatin, may be used 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.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but is preferably chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too. Regarding these, see the above-mentioned book by Glafkldes or Zalikman et al. or H0Frleser.
Edited by Die Grundlagander Photog
RaphischsnProzesse mit Silberhalogenlden (Akademische 17- Verlagsgesellschaft, 1968)
It is described in.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. A specific example is U.S. Patent 2,448.06
No. 0, British Patent No. 618.061, etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Specific examples are U.S. Patent Nos. 1,574,944 and 2.
, No. 278.947, No. 2,410,689, No. 2.
No. 728.668, No. 3,501,313, No. 3.
656. It is described in No. 955.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include U.S. Pat. No. 2,487,850,
2.518,698, 2゜-18-1983.609, 2,983.610, 2゜694
, No. 637.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used quasi-independently, but combinations thereof may also be used, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
176 volume 17643 (197
(Published in December 2013) Page 23, Section 5.

In any case, in C, the photographic emulsion of the present invention is visible light (400n
It has photosensitivity to light with a wavelength of 700 nm to 700 nm, and cannot be handled in a bright room. □ Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, as gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used (4), and gelatin hydrolysates and gelatin enzymatically decomposed products may also be used.

In the present invention, a polyalkylene oxide compound having a molecule of 160012 Jl can be used as ζ for the purpose of improving halftone dot quality.

The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, etc., preferably at least 10 units of ethylene oxide. A condensate of a polyalkylene oxide consisting of a polyalkylene oxide and a compound having at least one active hydrogen atom such as water, an aliphatic alcohol, an aromatic alcohol, a fatty acid, an organic amine, a hexitol derivative, or a polyalkylene of two or more types. Includes oxide block copolymers, etc. Specifically, specific examples of polyalkylene oxide compounds include polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers (alkylaryl), ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, and polyalkylene glycols. Amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, and the like can be used. The molecular weight needs to be 600 or more.

The number of polyalkylene oxide compounds is not limited to one in the molecule, and two or more may be included in the molecule. In that case, the individual polyalkylene oxide units may consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. When there is more than one polyalkylene oxide unit 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 preferably contains from 14 to 100 alkylene oxide units.

22- Specific examples of the polyalkylene oxide compounds used in the present invention are as follows.

Polyalkylene oxide compound example 1 [-/HO(CHzCHgO)eoH■-λ C4
HgO(CH2CH20)1sHM-j C1zHzs
O(CH2CH20)1sHII-4' C1aHay
O(CH2CH20)xsHII-j C1aHstO
(CH2CH2O)4oH■-≦C8H1ycH=c
HcaHtgo(CH2CH20) 1sH1-IOC
11H23COO(CH2CH20)aoHy-//
C11H 3COO (CH2CH20)g+Occxt
Hga11-/J CC11H2zCONH(CH2C
H20) 1sH-/j C14HC14H25IN(C
H2) (CH2CH20)24HCH℃Sweat-C)T20
C11H2゜Todoroki ■-7j 1 ((OCH2QT2h4α()℃sho℃))
-(CHg mark 20) tJ0((?H2QTgO)14H y -/ 7 H(C,'Hz(-')TzO)g((
,'H(,'H20)l)(OI20I20)cH Todoroki(,'H3 a+b+c-4゜1): 9-4-C=IO:Taichi j- ■-/? -JO HO(LHgC)T2O) B (Q(2(,TT2C
H2 mark zO)l) (C)T2O(20)cH1+C=
jO, b=ia ■−Col Jj − ■−22 1[−,2j U−2μ HO+CHz CHz O dog 14H, etc.
The polyalkylene oxide compounds described in ILJ No. /JO and JP-A-33-3217 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

When these polyalkylene oxide compounds are added to a 10-silver-genide emulsion, they are dissolved in an aqueous solution of an appropriate concentration or in a water-miscible low boiling point organic solvent, and then added at an appropriate time before coating. Preferably, it can be added to the emulsion after chemical ripening. It may be added to non-photosensitive hydrophilic colloid layers, such as intermediate layers, protective layers, filter layers, etc., instead of being added to the emulsion.

The polyalkylene oxide compound used in the present invention is
1 x 10-5 mol to 1 x per mol of silver halide
A range of 10 moles is desirable.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercap I thiazole, mercaptobenzothiazoles, mercaptobenzimidazoles.
28-, mercaptothiadiazoles, aminotriazoles, benzotthiazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (], 3,3a, 7); Many compounds known as antifoggants or stabilizers can be added, such as tetrazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.

The photosensitive materials used in the present invention include, for example, water-soluble dyes (for filter or irradiation prevention purposes, such as oxonol dyes, hemioxonol dyes, merocyanine dyes, etc.), hardeners (such as chromium salts, aldehyde dyes, etc.), and hardeners (for example, chromium salts, aldehyde (N-methylol compounds, dioquinone conductors, active and 29-yl compounds, active halogen compounds, etc.), surfactants (
For example, various known nonionic, anionic, cationic, and amphoteric surfactants) can be included.

The developer used in the present invention contains an auxiliary developing agent (e.g. 1-
Phenyl-3-pyrazolidones or p-aminophenols) are not contained at all or are suppressed to 0.05 g/12 or less, and dihydroxybenzenes are used as the main developing agent at 0.05 g/12 or less.
05-0.5 mol/7! (especially 0.1 to 0.4 mol/1
), which has a free sulfite ion concentration of 0.25 mol/i or more, contains 5- or 6-nitroindazole 20 mol/i or more, and has a pH of 10.5 or more (particularly 11 This is a developing solution containing a sufficient amount of alkali to make it .5 or more -L). Among these, dihydroxybenzenes (especially hydroquinone) that do not contain auxiliary developing agents
Use alone is preferred.

This developing solution makes it possible to quickly obtain high-sensitivity, high-contrast photographic properties using the light-sensitive material of the present invention, and is extremely stable at 30-30° C. since it can develop with a large amount of sulfite ions.

In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,
There are 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc., and 1-phenyl-3-pyrazolidone type developing agents include 1-phenyl-3-pyrazolidone,
4.4-dimethyl-1-phenyl-3-pyrazolidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, etc. p-aminophenol developing agents include p-aminophenol, N-
Methyl-p-aminophenol and the like are used.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, sodium formaldehyde bisulfite may be used, which provides almost no free sulfite ions in the developer.

As the alkaline agent for the current solution used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, jetanolamine, I.jetanolamine, etc. are used.

The developer that can be used in the present invention preferably contains the same type of polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide with a molecular weight of 1000-1000 is 0°1-10g/j! It can be contained within the range of.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic azide, triethylenetetraamine hexaacetic acid, diethylenetetraamine pentaacetic acid, etc. as a water softener to the developer that can be used in the present invention.

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.

Processing temperature and processing time are set appropriately, but usually 18℃~5
A processing temperature of 0 DEG C. is suitable, while rapid processing of 15 to 120 seconds using a so-called automatic processor is preferred.

The present invention will be explained in more detail with reference to Examples below.

Example 1 A silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to a gelatin aqueous solution with a pH of 4.0 kept at 50°C to create a 0.3μ silver chlorobromide emulsion. (B r 30 mol %) was prepared.

33- After washing this emulsion with water in a conventional manner to remove soluble salts, sodium thiosulfate and potassium chloroole-1.
was added for chemical sensitization.

This silver chlorobromide emulsion was divided, and additives were added to each as shown in Table 1 (addition amount = 3 per mole of silver halide).
X10' moles), sensitizing dyes of the following formula were added, and 4-hydroxy-6-methyl-1,3,3a, ? - dispersion of tetraazaindene, polyethyl acrylate,
2-hydroxy-4,6-cyclo-1,3,5--
) After adding riazine sodium salt, it was applied to a cellulose triacetate film at a tin content of 4 g/rd.

Sensitizing Dye 34 - These films were subjected to tip exposure via a step wedge, and then each was subjected to the following three types of development processing.

Development Process A (Invention) A developer I having the following composition was placed in an automatic processor FG-25RA manufactured by Fuji Photo Film Co., Ltd., and processed at the optimum development time (38° C., 20 seconds).

(Developer I) Potassium bromide 2.0g Potassium hydroxide 20g Potassium carbonate 35g Potassium sulfite 80g Hydroquinone 20g Triethylene glycol aog Polyethylene glycol (molecular weight 4000) 2.0g 5-Nitroindazole 0.1g Add water 11 (pH 11) , 7) Development processing B (comparison) 35- Fuji Photo Film Co., Ltd. Risu developer H8-1 was used as FG-25.
1. Put it in an automatic developing machine and develop it for 1 time (27℃, 1
minutes and 40 seconds).

Development processing C (comparison) RAS developer LI)-835 manufactured by Fuji Photo Film Co., Ltd.
Put it in the G-25RA automatic processor and set it to the optimum development time (38℃)
, 20 seconds).

The results are shown in Table 1. However, in Table 0, the sensitivity is the reciprocal of the exposure amount that gives a density of 1.5, and is a relative value when Film B in each process is taken as 100.

0 Also, gamma is calculated using the following formula.

-(Ilog (exposure amount giving density 0.3) -Ilog
(Exposure amount to give a density of 3)) The comparative compound for the 0 film Na2 is a compound of the following formula which is known to exhibit an effect of increasing sensitivity in lithographic development.

As is clear from Table 1, the comparative compounds exhibiting a high sensitization effect in lithographic development show a softening in the rapid processing using the stable developer of the present invention and cannot be used. In contrast, the compounds of the present invention greatly increase sensitivity without causing softening.

This effect is a unique effect that cannot be achieved in lithographic development or rapid access processing.

Patent Applicant: Fuji Photo Film Co., Ltd. 38- Procedural Amendment to the Commissioner of the Patent Office■, Case Description Showa SR Year Patent Application No. 20 μm No. 91 2,
Title of the invention Image forming method 3, relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. 4. Statement of the subject of amendment 5. We will submit a revised copy of the statement of contents of the amendment (no changes to the contents).

Claims (1)

[Scope of Claims] At least one silver halide emulsion layer sensitive to visible light is provided on a support, and in the emulsion layer or other hydrophilic colloid layer, a compound represented by the following general formula (1) is provided. After imagewise exposing a photographic light-sensitive material containing a compound represented by
Contains 0 to 0.05 g/J of an auxiliary developing agent,
Contains 0.25 mol/1 or more of free sulfite ions, 5
- or 6-nitroindazole at 20/1 or more, and a developing solution containing sufficient alkali to raise the pH to 10.5 or more. General formula (I)