JPS6066248A - Method for developing high contrast silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a good image always repidly with a developing soln. good in storage stability by developing a photosensitive material contg. a specified amt. of polyalkylene oxide in an emulsion layer or the like contg. specified amts. of silver chloride and Rh salt or more, respectively, with a developing soln. contg. a specified amino alcohol. CONSTITUTION:The emulsion layer of a photosensitive layer contains AgCl in an amt. of 80mol% of the total silver halide and has an average grain size of <=400nm, and a water-soluble Rh salt is added in am amt. of >=1X10<-7>mol per mol of Ag salt at an optional time before the end of the first ripening stage of emulsion preparation. Polyalkylene oxide having a mol.wt. of >=600 or its deriv. is added also to another hydrophilic colloidal layer in an amt. of 1X10<-5>-1X 10<-2> mol per mol of Ag salt. This photosensitive material exposed and developed with a developing soln. contg. a dihydroxy type developing agent in an amt. of 0.05-0.5mol/l, free SO3<-2> in an amt. of >=0.25mol/l, 5- or 6-nitroindazole in an amt. of >=20mg/l, and further a compd. represented by formula I or II. As a result, a good negative image is rapidly obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for developing halogenated photographic materials.
More particularly, the present invention relates to a stable method for developing photographic materials that can be handled in an environment that can be essentially called a bright room.

(Prior art) In response to the desire to perform the contact non-light process (so-called return process) in a bright room using relatively low-sensitivity photosensitive materials in the printing plate-making process, in recent years, silver halide has been used as a photosensitive element. Photographic materials that can be handled in what can essentially be called a bright room environment have been developed.

Extremely sensitive to visible light
) This is achieved by exposing the degraded photosensitive material to a light source containing a large amount of ultraviolet rays under safe light that does not substantially contain ultraviolet rays.

On the other hand, the so-called return process involves not only a simple one-sheet contact return process, which uses a single developed film as an original, contact exposure and development of the return photosensitive material to perform negative/positive image conversion. A sophisticated image conversion process called character extraction is performed.

These cut-out characters are ink that drips into the areas in printed matter where ink is on the paper in the form of halftone dots (halftone areas and areas where ink is on the entire surface of the paper (referred to as solid areas)). It refers to the parts of characters, symbols, etc. that are not marked.If we are to specifically describe how to make cut-out characters in the photolithography process, as shown in Figure 1, a transparent or semi-transparent adhesive base 3 (usually several 100 μm thick) is used. A developed film with halftone dots (halftone original) is pasted onto a polyethylene terephthalate film (polyethylene terephthalate is used), and a film with so-called line drawing positive images such as letters and symbols formed on the pasting base l. The original is made by overlapping the developed film (?flJ image with original raco applied).

Photosensitive material for returning to the halftone image area! The emulsion surfaces of the image are brought into close contact with each other and subjected to non-light development processing to form white areas of line drawings in the halftone image. An important point in this step is that the halftone dot image and the line drawing must be subjected to negative/positive image conversion, respectively, with respect to their halftone dot area and object line It]K. For example, a halftone image with a black area of zoel has a white area of jOchi.

A line drawing with a black line width of 50 μm must be accurately converted to a white line width of 10 μm. However, as is clear from FIG. 1, the halftone dot image is brought into direct contact with the emulsion surface of the photosensitive material for return and is non-light-emitting, whereas the line image V ) and the pasting base 3 (several ioum thick) for the halftone original in the middle to expose the photosensitive material for return.In other words, the line image is exposed to light through a transparent or translucent spacer of several 1100 μm. Therefore, if a normal non-light amount (a non-light amount that faithfully converts the halftone dot area from negative to positive) is applied to the photosensitive material for return use, it will be blurred due to the effect of non-bokeh exposure. The white line width of the line image becomes thinner.On the other hand, if you reduce the amount of light to reduce the blurred shadows and faithfully convert the line width of the line image from negative to positive, the halftone dot area becomes thinner due to the lack of contrast. This phenomenon is not limited to photosensitive materials.

The exposure light source has a large contribution. That is, if the exposure light source is small enough to be called a point light source, the degree of blurring and non-lighting will be reduced. However, since the light-sensitive material for use in bright rooms, such as the one of the present invention, requires the use of an exposure device with a large field of view, the light source is much harsher than in conventional dark-room exposure devices, which causes deterioration in the quality of extracted characters.

Until now, there have been almost no reports on means to eliminate such deterioration in the quality of cut-out characters, and there have been few reports on methods for eliminating such deterioration in the quality of cut-out characters. Since the objectives were completely different from those of the Japanese government, there was no knowledge of what measures should be taken.

For silver halide photosensitive materials that can be handled in a bright room, see 1, for example, JP-A No. 4-2673, JP-A No. 4-2673;
Examples of emulsions in which grains are formed by adding a large amount of rhodium salt are described in ``A9O3O@'', ``A9O3O@'', and ``Hiro 703/,'' but these known examples do not describe any techniques for improving the quality of cut characters. It has not been. In addition, these known examples disclose that polyalkylene oxides are added to the developer, but as is clear from the results of comparative sample A listed in Examples/ ) Even if polyalkylene oxides are added only to the liquid, the quality of punched characters cannot be improved.

On the other hand, in recent years, many attempts have been made to obtain image quality comparable to lithographic processing through rapid and stable processing, but there is also a desire to perform the cutting process, which is an advanced image conversion process, using the same rapid and stable processing. The demand has become stronger.

For example, in Japanese Patent Application No. 7-72-16, the average grain size of at least rθ momole silver chloride of all halogenated grains is O0≠μm or less, and any arbitrary grain size before the end of the first ripening of emulsion production It has an emulsion layer containing a silver halide emulsion containing a water-soluble rhodium salt in an amount of @1 mole/X/(7' mole) and further in the emulsion layer or other hydrophilic colloid layer. polyalkylene oxide or a derivative thereof having a molecular weight of at least too p/xio' per mole.
A silver halide photographic light-sensitive material containing 1 to 10" moles of dihydroxybenzene-based developing agent was added to the photosensitive material after exposure to light.
Contains 02 to O,S mol/l and contains free sulfite ions of O,XS mol/l or more without substantially containing an auxiliary developing agent! Or, it contains 10 ml or more of 6-nitroindazole.

A developing method has been disclosed in which the developer is treated with a developer containing a sufficient amount of alkali to raise the pH to lθ, 5 or higher, but this method was still insufficient in terms of the stability of the developer over time. . That is, with the above developer, the photographic sensitivity decreases when the automatic processor is stopped for a long period of time. Specifically, when an automatic processor is left in a stopped state (usually for about a week) during a long summer or winter vacation, and then restarted after the vacation, the sensitivity decreases compared to the state before the vacation. It turned out to be an inconvenience.

(Object of the invention) The object of the invention is to
It is an object of the present invention to provide a developing method that provides stable photographic sensitivity without any change in lc# degree. An object of the present invention is to provide a method for quickly obtaining good cut-out character images using a stable developer.

(Components of the Invention) The above objects of the present invention are such that at least to mol of all silver halides is composed of silver chloride, the average grain size is 00 μμm or less, and Contains a silver halide emulsion containing a water-soluble rhodium salt in an amount of 1 mole of silver, p/ Polyalkylene oxide or its derivative per mole of /x/θ-5 to 1x
A silver halide photosensitive material characterized by containing IO-2 mol of a dihydroxybenzene-based developing agent is used. Oj to o, r mol/, substantially free of auxiliary developing agent, and containing a free myelite ion concentration of 70,,26 mol/! or tnitroindazole, 20
my / /, or more, and the pH of the developer is 10. This was achieved by processing with a developer containing a sufficient amount of alkali to achieve the above and further containing a compound represented by the following general formula [1) or general formula [II].

General Formula [II] In the formula, 1 represents a hydrogen atom or an optionally substituted lower alkyl group, and 2 represents an optionally substituted lower alkyl group.

Although the exact mechanism of action of these ethanolamines and propatoolamines is not known, it can be inferred from Example 1 that the pH of the developer can be lowered, which reduces silver oxidation and further improves the stability of the herbal medicine. It is considered that

The halogenated @i-1' silver halide photosensitive material used in the developing method of the present invention consists of chloride iron, chlorobromide steel, iodochloride silver, iodobromochloride chloride, and at least 10 mol of the halogenated material is from chloride steel. It is preferable that at least a molar proportion of Vc or more is composed of silver chloride, and it is preferable that at least a molar coefficient of Vc or more is composed of silver chloride.

The average grain size of silver halide is 0. It is preferably lIam or less, particularly preferably 0.3 μm or less. The average grain size is a term that is commonly used and easily understood by experts in the field of photographic science of oxidized steel. Particle size means the particle diameter in the case of particles that are spherical or can be approximated to a sphere. If the particle is cubic, the edge length x/T
Let π be the particle size. The average particle projected area is also the algebraic mean or the number 4i'
Determine by J average. Details on how to calculate the average particle size, JJ
~p,! J, (/944, published by McMillan Publishing Co., Ltd. 2).

Furthermore, so-called monodisperse halogenated steel particles are particularly preferably used.

The water-soluble rhodium salt used in the present invention is typically rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc., but complex salts can also be used. The time for adding the rhodium salt in the present invention is limited to before the end of the first ripening during emulsion production, and it is particularly desirable to add it during grain formation, and the amount added is at least 1 mol per 1 mol of complex/X/. Preferably,
Further, it is preferably 1x10 or more, and a range of jtXlo' to /xIO is particularly preferred.

The soluble silver salt and soluble halogen salt in the halogenated photographic light-sensitive material used in the development method of the present invention may be reacted by any one of a single side mixing method, a simultaneous mixing method, and a combination thereof.

It is also possible to use a method in which particles are formed under an excess of ion (a 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, 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.

Particle formation is preferably carried out under acidic conditions. In our experiments, we found that the effectiveness of the present invention decreases under neutral and alkaline conditions. The preferred p I-1 range is pH 6.
It is below j, more preferably below j.

Used as a binder in photographic emulsions or as a colloid as a binder.

Although gelatin is advantageously used, other hydrophilic colloids can also be used.

The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized. From the viewpoint of improving handling properties in a bright room, it is rather preferable that the film is not chemically sensitized. In the case of chemical sensitization, any one of ordinary sulfur sensitization, reduction sensitization, and gold sensitization or a combination thereof is used.

The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 to 3 carbon atoms, such as ethylene oxide, propylene-19,2-oxide, butylene-/, 2-oxide, etc., preferably at least 10 years unit of ethylene oxide. polyalkylene oxide consisting of, and water.

Aliphatic alcohols, aromatic alcohols, fatty acids.

It includes condensates with compounds having at least one active hydrogen atom, such as organic amines and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. That is, as the polyalkylene oxide compound, specifically, polyalkylene glyco, Q4[
4 Polyalkylene glycol alkyl ethers Polyalkylene glycol aryl ethers (Alkylene glycol ethers Polyalkylene glycol esters Polyalkylene glycol fatty acid amides Polyalkylene glycol amines Polyalkylene glycol block copolymers Polyalkylene glycol grafts Polymers etc. can be used.The molecular weight needs to be 600 or more.

The number of polyalkylene oxide chains is not limited to one in the molecule, and two or more may be included. In that case, any number of 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 more than one polyalkylene oxide chain is carried 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 /≠ to 100 alkylene oxide units.

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

Polyalkylene oxide compound example l1l-/HO(CH2CH20)90H[1-,2
C48g0(CH2CH20)15HJll-3Ctz
HzsO(CH2CH20)tsHIn-4'Cts
H370(CH2C)lzc))xsHm' C15
Ha 70(CH2CH20)4oHl-4C3H
1□C)l=cHcgH□60(CH2CH2(υ□5
H1[-10C11H23COO(CH2Cl-120
)B(,HIII-//C11H23C00(CH2
C1-120) 240CC1□H23■-/3 C11
H23CONH(CH2CH20)15HIll”
C14H29N (CH2ba cH2ci-i2o)24n
111-/7 H(CH2CH2U) a (CH2H20) b (C
H2CH20) , H anzu H3 a + L) + c = j O b: a + c = 10: ri111-/ff l1l -/ri1ll-2/ HO(CH2CJJ 20) a (CH2CH3CH
2CH20) b(CH2CH20), l-1a+c
=30, b=/ ≠ 1[-22 b" l a+c=!O ll-2J 11[-2≠ ■-2yo HU+CH2Cl-120-jrrH Others, JP-A Showjθ-1rt≠, No. 23, JP-A Showa 12-
Polyalkylene oxide compounds described in No. 101/, No. 30 Oyo and JP-A-33-32/7 can also be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

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

The polyalkylenoxide compound used in the present invention is
Halogenated 01 mole/×10' mole/x
A range of 10 moles is desirable.

In addition, in the present invention, it has been discovered that the quality of extracted characters can be further improved when a benzotriazole compound and/or a mercapto compound, which are commonly used as anti-capri agents, are used in combination. These compounds were effective only when included in photosensitive materials. This effect was not simply an effect of preventing fogging, nor was it an effect of making the special curves sharper, but rather improving the quality of the drawn characters. One of the preferred compounds includes one or more substituents selected from alkyl groups (methyl, ethyl, heptyl, etc., alkoxy groups, halogen atoms, acyl groups, acylamino groups, carbamoyl groups, sulfamoyl groups, aryl groups, etc.). Benzo which may be substituted with a group) IJ azole compound, @
An alkyl-substituted benzotriazole having up to 3 carbon atoms was effective for this purpose.

And the range of its addition amount is (111 mol/gixio'
to 1×10 mol, particularly preferably jx/
θ to jXlo moles.

Other preferable compounds (l'':) have the following general formula (%), where M represents a hydrogen atom, -NH4 group, or an alkali metal atom.

X represents -NR group, sulfur atom, and oxygen atom.

RVi hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, a zHt-membered heterocycle (e.g., tetrazole, triazole, imidazole, thiadiazole), or a j-membered heterocycle fused to a benzene ring Indicates the atomic groups necessary to form a heterocycle (eg, penzimidaso-rubenzthiazole, pensuoxasol), and these heterocycles are alkyl groups.

It may be substituted with an alkoxy group, a carboxy group, a sulfo group, a hydroxyfur group, an amine group, a nitro group, a halogen atom, a carbaceyl group, an alkylthio group, a mercapto group, or the like. Among these, 2 is preferred as tetrazole, triazole, thiadiazole, benzimidazole, and penzthiazo.

69. Most preferred are tetrazole compounds. Specific examples of preferred compounds are shown below.

21 2 The effective addition range of the compound is J'X1 per mole of iron.
0' No! It was in the range of ×10 mol.

The photographic emulsion used in the developing method of 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, steryl dyes, merocyanine dyes, cyanine dyes and azo dyes.

Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The photographic emulsion used in the developing method of the present invention has no F.
A″!, it may contain a hardening agent for heavy machinery, such as chromium salts (chromium alum, chromium acetate, etc.).

Aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urine, methyloldimethylhydantoin, etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.), activated vinyl compounds (/, J, triacryloyl-hekizahi)"os-) riazine,
Bis(hinyl sulfonyl la methyl ether, N, N'-
Methylenebis-[β-(hynylsulfonylphurobionamide], etc.), active halogen compounds (2,11,-dichloro-6-hydroxy-8-triazine fz, mucohalogen acids (mucochloric acid, mucophenoxychloric acid) finoxazoles, dialdehyde starch, etc.
-Chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.

The emulsion used in the developing method of the present invention may contain various known surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties. good.

For example, saponins (steroids), polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (for example, alkenylcono-phosphate polyglycerides, alkylphenol polyglycerides, fatty acid esters of polyhydric alcohols).

Sugar alkyl esters, nonionic surfactants such as urethanes or ethers; triterpenoid saponins, alkyl carboxylates, alkyl sulfones ff[, alkylbenzenesulfonic acid groups, alkylnafculensulfonate salts.

Alkyl sulfates, alkyl phosphates,
Carboxy groups, sulfo groups, phosphor groups, sulfuric acid esters such as N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylholoxyethene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. anionic surfactants containing acidic groups such as phosphoric acid groups, phosphoric acid ester groups, etc.; artistic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine imides, amine oxides; Use of cationic surfactants such as alkylamine salts, aliphatic or aromatic 7th class ammonium salts, heterocyclic tertiary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles. I can do it.

The photographic emulsion used in the developing method of 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 (meta)
Acrylate, alkoxyacrylic (methacrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, A polymer containing a combination of α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The photographic emulsion used in the developing method of the present invention may contain a compound represented by the following general formula for the purpose of increasing contrast.

NHNHCO几2 (In the formula, R1 represents an aryl group. R2 represents a hydrogen atom, a phenyl group, or an unsubstituted alkyl group having 1 to 3 carbon atoms. Specifically, JP-A No. 6-763336 , the same j
7-Tata t3! Same issue! 7-/2? ≠3≠No.1. same! ≠
-≠Q6λri issue, same j ter jλO ta O issue, same! ! -tao
Rihiro O, 56-67g≠3, 13-776/l
, No., Same Ta 3-♂ Gua 1≠ No., Same J'3-/J7/,?
J issue, same! J-/66) No. 3, same! 3-10ri 2/issue,
same! Compounds of hydrazine fat conductors described in 3-Hirohiro Kota and others can be used.

The developer of the present invention (1) contains θ, or to o, r mol/of a dihydroxybenzene-based developing agent (
2) Substantially does not contain any auxiliary phenomenon 1 crude drug (3) Contains free sulfite ions of θ5.2 tamol/1 or more (4
j! or (5) contains a sufficient amount of alkali to raise the pH to 10.5 or more; (6) is represented by the following general formula (1) or general formula [11]; Contains the indicated alkanolamines.

General formula 13 As the dihydrogycybenzene type developing agent, f+1 eff hydroquinone, chlorohydroquinone, glomohydroginone, isopropylhydro-1'/n, toluhydrohydroquinone, methylhydroquinone, 2.
Examples include J-dichlorohydroquinone and 2゜j-dimethylhydroquinone.

Also, it does not substantially contain an auxiliary developing agent.

Specifically, the content is θ, Oj f / as follows:
uni, o, oiy7 means the following.

Compounds 1 that provide free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, are added to the developer as a preservative. In the case of an infectious developer, polyaldehyde sodium bisulfite may be used, which provides almost no free sulfite ions in the developer. At this time, free sulfite ions are 0.
It is 21 mol/l or more, preferably 0.2 tal/l mol/l.

j or t nitroindazole Id20vty in developer
/1 or more, but preferably λO-≠00■/l.

As the alkaline agent for adjusting the pH of the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, etc. are used.

The pH is preferably 10. j~/, 2. j, particularly preferably /l-/, 2. ! It is.

In the aforementioned general formula [1] and general formula [[1], I(
, 1 represents a hydrogen atom or a lower alkyl group that may be detected by M (for example, a methyl group, an ether group, a propyl group, a hydroxyethyl group, a hydrothousandimethyl group, etc.), and R2
It represents a lower alkyl group which may be substituted (for example, a methyl group, an ethyl group, a hydroxyethyl group, etc.).

In particular, R1 and L7 are a hydrogen atom and an optionally substituted alkyl group having 7 to ≠ carbon atoms (4'5 is preferably a methyl group, ether group, or hydroxyethyl group), and R2 is
An alkyl group having 1 to 3 carbon atoms is preferred.

As the compound represented by general formula [1] or [1],
Specifically, 2-methylaminoethanol.

Koxymethylaminoethanol, methylethylamineethanol, 2methyldiethanolamine, λetheramineethanol, 2diethylaminoethanol, conityljetanolamine, 3methylaminopropanol, 3
Examples include dimethylaminopropanol, methylethylaminopropanol, methylhydroxyethylaminopropanol, 3ethylaminopropanol, 3diethylaminopropanol, ethylhydroxyethylaminopropanol, and the like.

The compound represented by general formula (1) or (II) is.

Usually evening ~ 300? /l, preferably 10-1009/l
It is used to a certain extent.

The developer may contain, in addition to nitroindazole, an organic compound known as an antifoggant or an 'il image inhibitor. Examples include azoles such as benzothiazolium salts, nitrobenzimidazoles, chlorobenzimidazoles, promobe/zimidazoles, mercaptothiazoles.

Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles.

Nitrobenzotriazoles, mercaptotetrazole a (% l-phenyl-!-mercaptotetrazole 2
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes.

For example, triazaindenes, tetraazaindenes (
Especially Hiro-hydroxy substitution (/, 3, Ja).

7) Tetrazaindenes), pentaazaindene; henzenetheosulfonic acid, benzenesulfinic acid,
Benzene sulfonic acid amide, Komelkabutobenzimidazole! -Sulfonic acid) l) Rum etc. It is preferable that these compounds are used usually in an amount of 1 to 10ooy/18 degrees.

When creating cut-out characters using the developing method of the present invention, it is possible to quickly form a return image with excellent cut-out character quality, and it is extremely effective because it can contain a large amount of hypoxic acid ions. It is stable.

The developer VC 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, molecular weight too.

~10000 polyethylene oxide etc. O0/,
It can be contained within a range of 109/l.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, 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 thiomenzuka and thiocyanate, organic yellow compounds known to be effective as fixing agents can be used.

The fixer may contain a water-disintegrable 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 processing temperature and processing time are determined as appropriate, but usually /r0
A processing temperature of 0 to ro0c is suitable, while the so-called automatic group I#! It is preferable to carry out rapid processing using a machine for 75 to 120 seconds.

The present method of the present invention has the excellent advantage that it can be used for a long period of time because the cut-out character image with poor image quality is stable.

Hereinafter, the present invention will be explained in detail with reference to Examples.

(Example Example 1゜Liquid: Water 10100O gelatin, 20fip)] 2a, O■Liquid: AgNO
3xooy Water AOOmO Liquid III: KBr II-, 29 LL h C/! a-〇-beating Na (SO 7.ff/Water 600 + ml ≠ evening') Liquids 11 and 111 were simultaneously added at a constant rate for 30 minutes to the aqueous gelatin solution of Liquid (2) that was maintained at CK.

After removing soluble salts from this emulsion using a conventional method well known in the art, gelatin is added as a stabilizer without chemical ripening.
-Methyl-Hydroxy-/, 3゜33.7-Tetra-hydrozaindene added 1. The average grain size of this emulsion is 0.21 μm and the yield of the emulsion is 1, so the amount of gelatin it contains is 70? Met. This emulsion was coated with hardeners λ-hydroxyak, 6-dichloro0-/, J,j-triazine,
After adding the sodium salt, the amount of silver per 7 m2 on polyethylene terephthalate film,! It was applied so that it became 2. The film sample prepared in this manner is referred to as film A.

Preparation of film B: When preparing a sample in the same manner as film A, polyalkylene oxide compound example III -/
A film sample containing 1 mol Ag of λXIO 7 was prepared and designated as film B.

After exposure using a P-607 printer manufactured by Inuroki Screen, using a manuscript having the structure shown in FIG.

F G , 2 , lt with 71 kinds of developing solutions with the following compositions
Developed, fixed, washed, and dried using an RA automatic developing machine (manufactured by Nagisa Photo Film Co., Ltd.). After being left in the bag for 4 days, it was developed using the same film and printer.

The appropriate development time here is at a development temperature of 3.2°C.
Developing time in seconds means the developing time that provides the best cutout character image quality for the combination of developer and film.

What we mean here is the character image quality! What is the attached figure - using a manuscript like /! This refers to the image quality in which a character of 30 μmlJ is reproduced when light is applied at an appropriate thickness so that the halftone dot area of the θ ratio becomes a halftone dot area of 10 inches on the photosensitive material for return.This is a very good cutout character image quality.

The cutout character image quality is 60 μm when given the same appropriate exposure as 3°λ.

This refers to the image quality at which characters with a width of 90 μm or 20 μm are reproduced. In addition, the cut-out character image quality l refers to the image quality that can only reproduce characters of medium/J'O μm or more when the same appropriate μ light is applied.

As mentioned above, the sensitivity when milled for 3 days is expressed by comparing the exposure time required to provide appropriate island light with the non-light time required when using a new solution.

As is clear from Table 1, with film A (comparison sample), good cutout character image quality could not be obtained with any of the developers.On the other hand, with film B, the current 1#' It is clear that the image quality of the cut-out characters is inferior to that of the developing solution containing l-phenyl-3-pyrazolidone as an auxiliary agent at 0, 2y/l. Also, developer solution 2.2
Since the sulfite ion concentration is low, the sensitivity of the developing solution decreases greatly when left for a day, and a stable developing solution cannot be obtained. Development with high sulfite ion concentration 1fL3,7. //It sensitivity decreases after aging for more than g days. Current gI liquid i.

This method requires 60 seconds of development time and cannot be done quickly, and the image quality of cut-out characters is also poor.

Furthermore, with developer/l! - instead of nitroindazole! - When methylbenzotriazole is used, the character image quality is 3. Gu,! , it is not as good as Party B. Therefore, it provides good cutout character image quality in a short development time, and is a stable developer. .

It is clear from Table 1 that a favorable result is obtained for Vc% in case of B.

Example 2 Films C, Film 1) and Film E were prepared as photographic emulsions used in the developing method of the present invention, and the developing solution used in Example 1 was used as a developer.
2 was tested in the same manner as in Example 1.

Creation of film C: When creating sample e in the same manner as film A, polyalkylene oxide compound @jll-/7
A film sample containing 2×10 mol of Ag and 3×10 mol of rubensotriazole and 1 mol of Ag was prepared and designated as film C.

Preparation of film D: When preparing all the samples in the same manner as film A, polyalkylene oxide ° Compound example [1-/7
5xio-4 mol 1 mol Ag and l-phenyl-j-
Mercaptotetrazole ≠ × 10' mol 1 mol Ag
A film sample containing the above was prepared and designated as film D.

Preparation of film E: When preparing a sample in the same manner as film A, use polyalkylene oxide ° compound/l: +l
III/l'y moj v//) '-1-l 1 mol Ag and! -Metelbentriazole Ex1
0 mol 1 mol Ag and l-7 ale! -Mercaptotetrazole≠x10' A cetafilm sample containing 1 mol of Ag was prepared and designated as Film E.

As is clear from Table 2, films C, 1), and E exhibit all the more preferred embodiments, and film B and p of Example 1 also provide more preferred cutout character image quality. Especially the current @likhiro, j, t
It is clear that this provides very good cut-out character image quality for K. It is clear that when O6λy7 is added to l-phenyl-3-pyrazolidone as an auxiliary developing agent, the character image quality is inferior.Developer 2
．． Since the concentration of sulfite ions is low, the sensitivity of the developer decreases greatly when left for r days, and a stable developer cannot be obtained.

Developer solution with high concentration of nitrate ions 3.7. // also causes a decrease in sensitivity when left for r days. On the other hand, if the developer used in the developing method of the present invention≠5.6! It is clear that the sensitivity is excellent even when aged over a day. Developer l/ Now! - instead of nitroindazole! - When methylbenzotriazole is used, the character image quality is not as good as that of developer 3, ≠, j, and O. In the developer solution IO, the pH of the developer solution is as low as IO0, so the appropriate development time is 1 liter.
/1moI)-t-1IinM L l 2 :Yu1/-
h L r L - At φ No. mol
1) Dihydroxybenzene-based developing agent at 0.01 to O
1j′mol/2) Substantially no auxiliary developing agent (3) Free yr = sulfite ion θ, lt
Contains mol/1 or more 41. or 6-nitroindazole, l Omy / 1 or more (sl p )
Contains an alkaline agent in an amount sufficient to make i 10.5 or more; (6) General formula [1) or general formula [``
] A phenomenon liquid that satisfies the constituent requirements of containing the compound shown in ! .

It is clear from the table that the most favorable result is given in case B.

[Brief explanation of the drawing]

Part 1v is a drawing showing the relationship between the manuscript used for cutting out characters and the photosensitive material for return. 1 in the figure. J is paste hese 1.2
1 indicates a film on which a line drawing positive image is formed (line drawing original), μ indicates a film on which a halftone dot artist is formed (halftone dot original), and y indicates a photosensitive material for reversal. Patent Applicant A± Photographic Film Co., Ltd. No. 1 Figure 9 54 = 2 = Nico Procedural Amendment Showa! On the 7th day of 2015, Mr. Commissioner of the Japan Patent Office, 1. Indication of the case, Showa SR, Japanese Patent Application No. 77μ276, 2.
Title of the invention Developing method 3 for high-contrast silver halide photographic light-sensitive materials and its relationship to 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. Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the specification and the "Detailed Description of the Invention" section of the Statement of Contents of Amendment A shall be amended as follows. . fil page 77, line 1 r C14H29N(CH2) (CH2CH20)
r 24HJ C14H29N(CH3) (CH2C
H20) Corrected to 24HJ. (2) No. λ page! Correct "carbamoyl group J" in line 1 to "carbamoyl group". (3) Correct "1/lJ" on page 36, line 10 to "m9/l". (4) Correct the "sensitivity" of the 4th page l≠ line to [sensitivity decrease 1].

Claims (1)

[Scope of Claims] At least 10 moles of the total silver halide consist of silver chloride, the average grain size is less than 01 μm, and at any time before the end of the first ripening of the emulsion production, per mole of silver/x1
A silver halide emulsion layer containing more than 0 mol of a water-soluble rhodium salt, and further containing a polyalkylene oxide having a molecular weight of at least 100 or a wire conductor thereof in the emulsion layer or other hydrophilic colloid layer with 1 mol of silver. Win/×io
After processing a silver 5 halogen photographic light-sensitive material containing 10-2 to 10-2 moles of halogen, (1) a dihydroxybenzene-based developing agent was added to 117. o
2) contains substantially no auxiliary active ingredient; (3) contains 0.21 mol/or more of free sulfite ion; 4) contains 20 η of J or T nitroindazole. / 5) Contains an alkaline agent in an amount sufficient to make the pH io, 5 or more 6) A developer containing a compound represented by the following general formula (1) or general formula ([1)] A method for developing a high-contrast silver halide photographic light-sensitive material, which is characterized by processing with. General formula [■] (In the formula, R1 represents a hydrogen atom or an optionally substituted lower alkyl group, and R2 represents an optionally substituted lower alkyl group.)