JPS61230145A - Formation of image - Google Patents

Abstract

PURPOSE:To rapidly form an image high in contrast by processing a negative type silver halide photographic sensitive material with a developing soln. specified in compsn. contg. a dihydroxybenzene type developing agent in the presence of an amino compd. and a hydrazine compd. CONSTITUTION:The negative type silver halide photographic sensitive material is processed with a developing soln. specified in compsn. contg. a dihydroxybenzene type developing agent and a sulfite in a concn. of 0.3mol/l and in a pH of >=10, in the presence of an amino compd., preferably, represented by formula I or II, and a hydrazine compd., preferably, represented by formula III. In formulae I, II, and III, R1 is H, OH, or COOH; R2-R6 are each H or a monovalent org. group, and R3-R6 combining with N are each, preferably, a hydrophobic group having at least 3 C; A is a divalent group; R3 or R4 may combine with R5 or R6 to form a hetero ring contg. 2 N and A; R7 is a monovalent org. group; R8 IS H or acyl, and X is O or S. It is preferred to add phosphate and/or carbonate to a developing soln., and to add silver chloride to a silver halide in an amt. of about 30mol% of the total silver halide, thus permitting an image high in quality and contrast and low in fog to be formed rapidly and stably and this development process to be applied to graphic art fields, and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for forming a high-contrast silver image by processing a silver halide photographic material, and particularly to a method for forming a high-contrast silver image.

Silver halide photographic materials used in the IC Arts field (
High contrast II (hereinafter abbreviated as photosensitive material) is processed with a nine-stable developer containing a higher concentration of sulfite than the so-called IJ developer.
&1i111 formation method.

(Prior art) Lith developer contains a dihydroxybenzene compound as a developing agent, and has a pH of 9 to 11, usually 9.5 to 10.5.
It is characterized by containing, as a preservative, a low a degree sulfite (usually 0.1 mol/11 or less) and an adduct of formalin and bitonite and salt (sulfite ion buffering agent). It is.

Regarding the method of forming such a high-contrast photographic image and the Liss developer, please refer to the Journal of the Fists by J.D.
C, Yule; J, of the Frankl
inInst, ) volume 239, pages 221-230 (
(1945). Incidentally, lithographic development is sometimes called contagious development because development occurs contagiously.

When performing Lith development processing, high contrast and high quality halftone dots can be obtained, but as can be inferred from the characteristics of the Lith developer described above, there are problems with air oxidation, storage stability, and rapid processability. be. In this sense, stabilization and acceleration are old and new themes in the field of graphic arts.

The rapid processing referred to here means that the development time is less than 1 minute, usually 40
Refers to processing within seconds.

Examples of methods for rapid processing from the developer side include high pH, high temperature development, and the combination of a dihydroxybenzene-based agent and a developing agent exhibiting superadditivity (for example, a 1-phenyl-3-pyrazolidone-based developing agent). However, they are
When taken alone, either method is contradictory to stability or high contrast, and is currently the biggest problem when rapidly processing photosensitive materials.

As a method to improve the above problems, JP-A-53-177
No. 20, No. 54-92235, No. 56-106244
There are many technical disclosures such as No.

However, neither has reached a satisfactory level. In particular, JP-A-56-106244 discloses that a photosensitive material is processed in the presence of a hydrazine compound using a developer containing a dihydroxybenzene developer, a 3-pyrazolidone developer, an M salt of sulfite, and a contrast-promoting amount of an ε compound. A technique for obtaining hard WI4 images through processing has been disclosed, but when photographed using a contact screen, the halftone quality is still not at a satisfactory level.
When developing using an automatic processor or the like, the sensitivity obtained fluctuates depending on the processing equipment of the photosensitive material and the aging condition of the developing solution, which has the drawback that the processing cannot be stably controlled.

(Objective of the Invention) The present invention was made to improve these drawbacks, and the first object of the present invention is to rapidly process and process hard lN4i.
Il! A method for forming igI is provided.

A second object of the present invention is to provide a method for forming high quality halftone dots with low capri.

A third object of the present invention is to provide a stable rapid processing image forming method.

Other objects of the invention will become apparent from the description below.

(Structure of the Invention) An object of the present invention is to prepare a negative light-sensitive material in the presence of an amino compound and a hydrazine compound, a dihydroxybenzene-based developing agent, and a 10 or more compound containing a dihydroxybenzene-based developing agent and a fl. This is achieved by processing with a developer having a pH value.

The present invention will be explained in detail below.

The amino compounds used in the present invention include primary, secondary, and tertiary amines and Vc quaternary ammonium compounds, but preferred compounds are represented by the following general formula [Ia] or [Ib]. .

General formula CIa] General formula (Ib) In the formula, R1 represents a hydrogen atom, a hydroxy group, or a carboxy group, and R, ·R, ·R4, R1, and R each represent a hydrogen atom or Ifi monovalent organic group. However, these may be the same or different.The organic group may be an aliphatic group, an aromatic group, or a heterocyclic group, but at least 1 of R1 to R1 bonded to the nitrogen atom must be at least 43. Preferably, it is a non-hydrophilic group having carbon atoms, such as an alkyl group such as a propyl group, a butyl group, an octyl group, a dodecyl group, an aryl group, an aralkyl group, an alkaryl group, etc. , preferably an optionally substituted organic divalent group, specifically a methylene group,
Examples include ethylene group and hydroxyethylene group. i
R, and R, may be bonded to each other, and may form a heterocycle such as piperazine together with the atom of 2(Ia), and R1 and R1 and R1 and R6 may be bonded to each other,
It may be used together with two nitrogen atoms to form a complex bridge JJI.

Typical specific examples of amine compounds are shown below, but the present invention is not limited thereto in any way.

(I-1) 2-diethylamino-1-ethanol (I-2) 2-diethylamino-1-butanol (I-3) 3-diethylamino-1,2-propanediol (i-4) 3-dimethylamino-1 , 2-propanediol Cl-5) N-butylgetanolamine Cl-6
) dimethylaminodecane-N-ammonium bromide (I-7) 6-aminohexanoic acid (I-8) 3-diethylamino-1-propatol ((-9) )liethanolamine (I-10) 3-dichloro Bilamino-1,2-propanediol (I-11) 2-dioctylamino-1-ethanol (i-2nd) 3-dodecylamino-1,2-propanediol ()-13) 3-dodecylamino-1 -Propatur (i-14) 3-amino-1,2-propanediol (I-15) 1-diethylamino-2-propanediol (I-16) Glycine (■-17) -- Menzylamine ((-18 ) Diethylamine (i-19) ) Liethylamine Cl-20) Triethylenediamine Cl-21)
1-(3-aminopropyl)piperazine (I-22) 1-(2-hydroxyethyl)-4-
(2-mercaptoethyl)-piperazine (I-ta) 11-aminocundecanoic acid Cl-24) o-7 minobenzyl alcohol (I-
25) m-phenylenediamine Cl-26) m-aminophenol These amino compounds are used in coating layers on the photosensitive layer side of photosensitive materials (e.g. /S silver halide emulsion layer, protective layer, hydrophilic colloid layer of subbing layer) ) may be contained in at least one layer and/or in the developer, and a preferred embodiment is a mode in which it is contained in the developer. The concentration of the amino compound varies depending on the object to be included, the type of amino compound, etc., but it is necessary to promote contrast, so it is usually 0.1 N per IJ of developer.
It is in the range of ~10011.

The hydrazine compound used in the present invention is preferably a compound represented by the following general formula (III).

General formula (III ■ R, -NH-NH-C-R.

In the formula, R represents a monovalent organic residue, and is particularly preferably an electron-donating group and/or a non-diffusible group. R.

represents a hydrogen atom or an acyl group, and X represents a hydrogen atom or a sulfur atom.Among the compounds represented by the general formula (I []), the compound in which X is an oxygen atom and R8 is a hydrogen atom is More preferred.

The monovalent organic residue represented by 8 above includes aromatic residues, heterocyclic residues, and aliphatic residues.

Examples of aromatic residues include phenyl groups, naphthyl groups, and substituents thereof (for example, alkyl groups, alkoxy groups,
° Acylhydrazino group, sialic amino group, alkoxycarbonyl group, cyano group, carboxyl group, nitro group, alkylthio group, human oxyi% sulfonyl group, carbamoyl group, halogen atom, acylamino group, sulfonamide group, thiourea group, etc.) Examples include those with a .

Specific examples of substituent groups include, for example, 4-methylphenyl group, 4-ethylphenyl group, 4-oxyethylphenylft, 4-)”tesylphenyl group, 4-carboxyphenyl group, 4-diethylaminophenyl group. , 4
-octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2-methylphenyl group, 4
-(3-ethylthiothurate)phenyl group, 4-[2-
(2<4-di-tert-butylphenoxy)butyramide]phenyl group, 4-C2-<2.4-didodecylphenoxy)butyramide]phenyl group, and the like.

Examples of 4I fragmentation residues include five- or six-membered single or condensed rings having at least one of oxygen, nitrogen, sulfur, or selenium atoms, with substituents attached thereto. Can be mentioned. Specifically, for example, pyrroline ring, pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoselenazole ring,
Examples include residues such as an imidazole ring, a benzimidazole ring, a thiazoline ring, a thiazole ring, a benzothiazole ring, a nathothiazole ring, a selenazole ring, a benzoselenacy h-ring, and a naphthoselenazole ring.

These heterocycles include argyl groups such as methyl, ethyl, and dodecyl groups, alkoxy groups such as methoxy and ethoxy groups, aryl groups having 6 to 18 carbon atoms such as phenyl, and halogen atoms such as chlorine and bromine. , alkoxycarbonyl group,
It may be substituted with a cyano group, an amide group, etc. Aliphatic residues include linear and branched alkyl groups, cycloalkyl groups, and their friends with substituents, as well as alkenyl and alkynyl groups.

Straight-chain and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
Specific examples of the 18 alkyl groups include a methyl group, an ethyl group, an isobutyl group, and a dodecyl group.

The cycloalkyl group has 3 to 10 carbon atoms, and specific examples thereof include a cycloprobyl group, a cyclohenocyl group, and an adamantyl group.

Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (for example, methoxy, methoxy, propoxy, butoxy groups, etc.), alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkyl groups, amide groups, and acyloxy groups. groups, cyano groups, sulfonyl groups, halogen atoms (chlorine, fluoride, fluorine, iodine, etc.), aryl groups (e.g., phenyl groups, hao/y-substituted enyl groups, alkyl-substituted phenyl groups), etc. As a result, specific examples of substituted groups include 3-methoxyglobyl group, ethoxycarbonylmethyl group, 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, p-chlorobenzyl group, etc. be able to.

In addition, as an alkenyl group, allyl (all, y
As the group l) and the alkynyl group, a gropinyl group can be mentioned.

Preferred specific examples of the hydrazine compounds of the present invention are shown below, but the present invention is not limited thereto in any way.

(II-1) 1-formyl-2-(4-(2-(2
,4-di-tart-butylphenoxy)butylobado]zenyl)hydrazine (II-2) 1-formyl-2-(4-diethylaminophenyl)hydrazine (If-3) 1-formyl-2-(p-tolyl) Hydrazine (n-4) 1-formyl-2-(4-ethylphenyl)hydrazine (II-5) 1-formyl-2-(4-acetamido-2-methylphenyl)hydrazine (n-6) 1-formyl-2-(4-ethylphenyl)hydrazine (II-5) 2-(4-oxyethylphenyl)hydrazine (n-7) 1-formyl-2-(4-N,N-dihydroxyethylaminophenyl) hydrazine (II-8) 1-formyl-2-[4- (3-ethylthioureido)phenyl]hydrazine([-9) 1-thioformyl-2-(4-(2-(
2,4-di-tart-butylphenoxy)butyramido]phenyl) hydrazine (If-10) 1-formyl-2-(4-benzylaminophenyl)hydrazine (II-11) 1-formyl-2-(4-didodecyl aminophenyl)hydrazine (n -2nd) 1-Hor is 2-(4-dodecylphenyl)hydrazine ([-13) 1-acetyl-2-(4-(2-(2)
, 4-di-tart-butylphenoxy)butyramide]phenyl) hydrazine ([-14) 1-thioformyl-4-carboxyphenylhydrazine The addition position of the hydrazine compound is the silver halide hole □Silver halide on the agent layer and/or support It is a non-photosensitive layer on the emulsion layer side, preferably the Noshima silver halide emulsion layer and/or its lower layer. The addition interval is 10-・～10-
i mol/silver 1 mol is preferred, more preferably 10-4
~101 mol/mol of silver.

Examples of the dihydroxype/zene herbal medicine used in the developer of the present invention include hydroquinone, chlorohydroquinone, and methylhydroquinone, and hydroquinone is preferred. Normally, one developer is used every time! 1 hit
~6oII.

Regarding the present invention, as a current herbal medicine, L.F.N. Mason's photographic processing
Chemistry (L, F, person, Mason; Photo
Graphic Processing Chemi
stry) 2nd edition.

N-methyl-p-1 minophenol, p-1 minophenol, described on pages 19-23 (1975)
Although it is possible to use aminophenols such as 2,4-diaminophenol in combination, it is preferable to use dihydroxype/zene-based herbal medicines alone.

The sulfite a2 salt used in the present invention may be anything as long as it liberates sulfite ion (80%) in the developer. Examples include sodium sulfite, potassium sulfite, potassium bisulfite, and the like. The concentration range of sulfite ions in the developer is the developer l! It is sufficient if it is 0.3 mol or more, but 1.2 mol/l or more is not practical for manufacturing. From the manufacturing point of view, the preferred value is 0.4 to 0.7 mol/l. .

The pH value of the developing solution in the present invention may be at least 10, but it is practically preferably up to about 13, more preferably in the range of 11 to the second range, and below 10, a sufficiently high-contrast image cannot be obtained. do not have.

In a particularly preferred embodiment of the present invention, the developer contains a phosphate salt. 0.05 mol or more, more preferably 0
．． It is contained at 2 to 1 mole at a time. More preferably, the treatment is carried out in the presence of an organic anti-capri agent. Another preferred embodiment is an embodiment in which an antioxidant is further used in addition to sulfite, and still another preferred embodiment is an embodiment in which the degree of sodium ion in the developer is higher than the degree of potassium ion. be.

When an acidic hardening fixer is used as a fixer in the present invention, 98% carbonate is added to the developer as a buffering agent at 0.05%.
It is preferable to contain 1 mole or more, preferably 0.2 mole or more.

Further, a preferred embodiment of the present invention includes an embodiment in which processing is carried out with the developer of the present invention in the presence of a polyalkylene oxide compound (this meaning is the same as in the case of the amino compound).

Specific examples of the polyalkylene oxide compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.

(III-1) Ha(co, co, 0)nH[n=
35] (III-2) C, H, o (co, cH, o
)nH[n=20](III-3) CaHsyO(
CHmCHto)nH[”=30](l[I −4)
c,,H,,o(OH,CH,o)nH[” =3
0](III-7) C4H,8(C)1. C.I.
(,0)n(XJCf(,CB,C0OH[n=50(
[-8) 80(OH,OH,0)j(”y)m(
CHtCHtO)neOcI(,C1(,000B [
Il'-1-n=70, m=5]ch.

[J + n = ts, m = t7] [z + n - 30, m - 35] C goose H1 ] U - "=" = "1 [1 + n = 30, m = 15 ] 11g1, 15
) HO(CH,CH,0)Il(CB,CH,CH
tCHtO)m(CHmCHto)nH[Jl+n=feather, m===21] m+16>HU(C)(,CH,O),g(C
H,OH,CH,CH,0)m(OH,CH,0)nH
[J+tt=A, m=15] [n=Ako [J+n=15. m=15] (III -20) 0118m1C00 (CHI
C) (10) nH [11-25] The amount of the polyalkylene oxide compound optionally used in the present invention is developer 1! 0.01~40 per hit
11 is preferable, and more preferably 0.1 to 5 g.

The addition method may be by dissolving it in water or triethylene glycol, etc., or adding it as it is. When adding a polyalkylene oxide compound to a light-sensitive material, the amount is 0.01 per mole of silver halide. -10.9 is preferable, and the range of 0.1-3Ii is more preferable.

The addition position may be either the silver halide emulsion layer and/or the non-photosensitive layer, but preferably the silver halide emulsion layer and/or the layer below it.

The silver halide emulsion of the light-sensitive material used in the present invention includes:
Any silver halide used in conventional silver/10 emulsions can be used, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Particularly favorable results are obtained with silver chlorobromide, silver chloroiodide, silver chloroiodobromide or silver chloride.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after the grains have been prepared. The method for producing 1 m particles and the method for growing them may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. In addition, considering the critical growth rate of /S silver halide crystals, norogenide ions and silver ions are simultaneously added to p)1 and/or hapAgt in a mixed pot in sequence while controlling. Silver halogenide grains having a regular crystal shape and a nearly uniform grain size can be obtained by the method described above.

During the grain formation and/or growth process, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts. It is possible to add metal ions using at least one selected from (including complex salts) to contain these metal elements inside the particles and/or on the surface of the particles, and to place them in an appropriate reducing atmosphere. By this, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

The silver halide emulsion may be freed of unnecessary soluble salts after the growth of the silver nologonide grains is completed, or may be left containing unnecessary soluble salts. Dis
Closure (hereinafter abbreviated as FRD) can be carried out based on the method described in No. 17F543, Item (2).

Silver halide grains may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical or plate shapes. In the particles, any ratio of the (100) plane to the (1111 plane) can be used. Also, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

Silver halide emulsion has an average grain size of 0.05 to 1.5 μm
5) Preferably, a monodisperse emulsion of 1 to 0.8 μm is preferable.A monodisperse emulsion as referred to herein means a value of 0.20 when the standard deviation of the grain size distribution is divided by the average grain size. Refers to the following.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
Metal sensitization methods using gold and other precious metal compounds m6! ji or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. This is good.

As a sensitizing color chart, cyanine dye, merocyanine dye 1
．． Complex cyanine dyes, complex merocyanine dyes, holobolar cyanide/dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, silver halide emulsion 1 may be used during chemical ripening, at the end of chemical ripening, and/or after chemical ripening for the purpose of preventing fog during photographic processing or maintaining stable photographic performance.
:a! Prior to fabrication, compounds known in the photographic industry as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material used in the present invention are coated with hardener T-1 or 211, which crosslinks binder (or protective colloid) molecules and increases film strength.
By using the above, hardening can be achieved. The hardening agent can be added to the processing solution in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the 1 g Korin material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, section (■).

A dispersion (latex) of a water-insoluble or -soluble synthetic polymer can be contained in the photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material for the purpose of improving stability.

In the light-sensitive material used in the present invention, the silver content of the emulsion layer is usually 0.111 to 10 g/ze, preferably IIi to 51 g/ze. In that case, gelatin as a preferred hydrophilic colloid has a ratio of 0.1.9 to 101/
rrl is preferred, particularly preferably IN~51/
It is rrl.

The photosensitive material used in the present invention is coated on a suitable photographic support. Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polyglobylene synthetic paper, glass plate, cellulose acetate, etc. Typical examples include cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polyglobylene films, polycarbonate films, polystyrene films, etc., and these supports are used for photosensitive materials. It is selected as appropriate depending on the purpose.

The photosensitive material used in the present invention typically has at least one hydrophilic colloid layer tm containing the silver halide according to the present invention on a support. A protective layer having an appropriate thickness, preferably 0.1 to 10 μm, particularly preferably 0.8 to 2 μm.
Preferably, a gelatin protective layer of .mu.m is coated.

In addition to the above-mentioned materials, the developer according to the present invention includes solvents such as triethylene glycol, diethylene glycol, ethanol, benzyl alcohol, dimethyl sulfoxide,
dimethylformamide, etc., inorganic inhibitors such as potassium bromide and potassium iodide as inhibitors, silica III salts, boron fR salts, sodium hydroxide, as alkaline agents and buffer agents;
Salts such as potassium hydroxide, sodium chloride, sodium sulfate, acetate, citrate, water softeners such as ethylenediamine sodium acetate, nitrilotriacetic acid,
A hardening agent such as glutaraldehyde, a development accelerator such as methyl imidazoline, methyl imidazole, and quaternary ammonium chloride may be added.

(Implementation Series) The present invention will be specifically described below with reference to implementation sequences, but the embodiments of the present invention are not limited thereto.

Example 1 A cubic monodisperse silver iodobromide emulsion with an average grain size of 0.2 μm was prepared according to a conventional method, sensitized with sulfur, and anhydro-5,5'-dichloro-9-ethyl-3 was added as a color sensitizer. ,3'-
Nacarbocyanine hydroxide sodium salt in bis(3-sulfopropyl) solution (250 Da/silver 1 mole), 2tisaponin as a coating aid, polyethyl acrylate (150wt*/Gel) as a softener, Polyflu #7 Compound c(III-1) (320 Da/mol of silver), 2-methyl-4-human O=? as a stabilizer. sea 1
,3,3a,7-tetrazaindene<3. I/1 mole of silver) and hydrazine compound (I[-1) (1,!
Ml/silver 1 mol) 1 was added and simultaneously coated on a polyethylene terephthalate base with the following protective layer solution to form a circle.
At this time, the amount of gelatin attached to the emulsion layer was 1.51/m, and the amount of silver was 31/rrl.

The preservation liquid contains gelatin, co/sulfuric acid octyl ester as a coating aid, silica with a particle size of 4 μm as a matting agent,
As a hardening agent, 2-hydroxy-4゜6-dichloro-1
, 3, 5-) A layer of gelatin, such as lyazine sodium salt, was coated on the emulsion layer at a thickness of 21/m'' and dried.

The above sample was cut into an appropriate size, exposed to light through a wedge using a plate-making camera, and developed with a developer having the composition shown below. When evaluating halftone dot quality, exposure was further performed using a commonly used contact screen. The developing conditions were 3B'C for 20 seconds, using an automatic developing machine.

For fixing, an ordinary fixer containing an acidic hardener was used.

Developer (11 Hydroquinone 2511 Diethylene Glycol 40.9 Potassium Sulfite
0.6-T-L Sodium Carbonate
・0.3 mol potassium bromide
3I5-Methylbenztriazole
0.3N Sodium Ethylene Tetraacetate 21
1 amino compound Cl-3) I with 15N water
J [Finish.

Adjust the pH to 11.5 with sodium hydroxide or boric acid.

Developer (2) 1-phinyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone t-Developer (
Same composition as 1).

Developer (31 Same composition as developer (1) except that 3Ii # of N-methyl-p-aminophenol was added.

Developer (4) Same composition as developer (1) except that Cl-5) was added in place of the amino compound (I-3).

Developer (5) 1-phenyl-4-methyl-4-hydroxymethyl-3
-Developer (4) except that 0.31 pyrazolidone was added
Same composition as.

Developer (6) Same composition as developer (4) except that 3JF of N-methyl-p-aminophenol was added.

Same composition as developer (1) except that (i-2) was added instead of developer (η amino compound Cl-3).

The results are shown in Table 1. In Table 1, the sensitivity was evaluated based on the point showing the degree of 3.0 on the indication curve, and is expressed in relative terms. In Capri, the 0 gradation, which is displayed including the pace density, is displayed using the slope of the straight line on the indication curve. The halftone dot quality was measured using a 100x magnifier. ), especially samples (1), (41, and (7)) provide excellent images with little deterioration in halftone dot quality due to aging of the developing solution in an automatic processing machine and little change in equipment.

Example row 2 Cubic silver chloroiodobromide (AgCJ) with an average grain size of 0.26 μm
:Person gBr :Person gI=80 : 19.7 : 0.
3 C molar ratio]) After sulfur sensitization of the emulsion, 2-methyl-4-
Hydroxy-163m 3as 7-titrazaindene (1,5Ii/1 mole of silver) and 5-methylbenztriazole (200 Da/1 mole of silver) were added, and 1-(β-hydroxyethyl)-3 was added as a color sensitizer. -pyridyl-5-((3-r-sulfopropyl-2#penzoxazoliedene)-ethylidenecothiohydantoin (300
115i1/silver 1 mole), hydrazine compound (n-11
) (300 m9/mol of silver), 3% saponin as a coating aid, methyl allerylate as a softening agent, a ternary copolymer of 2-acrylamide, 2-methylpropanesulfonic acid and 2-acetoacetoxyethyl methacrylate ( 100wtl/gelatin), polyalkylene compound ll-7) (aooap/1 mole of silver), and emulsion layer with gelatin 21Xm/, silver with 13.81/
Gelatin was added so as to give a protective layer solution as described below on a polyester base, and the mixture was coated in multiple layers at the same time and dried.

The protective layer liquid consists of gelatin (11/m2), saponin 31 as a coating aid, and bis(vinylsulfonyl) methyl ether as a hardening agent.

The above photosensitive material was processed in the same manner as in Example 1 using the following developer. However, for fixing, a normal fixing solution containing no acid hardener such as LE8 ion was used.

Developer (8) Hydroquinone 351 Sodium Bromide 3I5-Methylbenz) I
J Azole 0.4. f amino compound (I-3
) 15. ! iF sodium sulfite
0.7mol sodium phosphate
0.5M ethylenediamine/sodium tetraacetate 2.9 Finish with 11vc water.

Adjust the pH to 11.5 with sodium hydroxide.

Developer (9) 1-phenyl-4-methyl-4-hydroxymethyl-3
- Developer solution (except for adding 0.3 II pyrazolidone
Same composition as 8).

Developer (10) Same composition as developer (8) except that 31115 N-methyl-p-aminephenol was added.

Developer (11) Same composition as developer (8) except that the amino compound Cl-5) was added instead of the amino compound Cl-3).

Development @ (2nd) Same composition as developer (8) except that (I-13) was added instead of amino compound (I-3).

Developer (13) Same composition as developer (8) except that Cl-4) was added instead of the amino compound Cl-3).

Developer (14) Same composition as developer (8) except that (I-9) was added instead of amino compound (i-3).

Developer (15) Instead of amino compound Cl-3) (I-14) Table -
2 From Table 2, samples (8), (10), (11) according to the present invention
), (2nd), (13), (14) and (15), especially samples (8), (11), (2nd), (13), (14)
It can be seen that in cases of (15) and (15), there is little deterioration in halftone dot quality and little change in sensitivity over time on an automatic processor.

Implementation row 3 Monodisperse silver chlorobromide (AgCJ: A
gBr-99: 1 (molar ratio)) emulsion was prepared in the presence of rhodium chloride (10°4 mol/61% l) and after sulfur sensitization, 2-methyl-4-hydroxy-1,3°3a,
7-chitrazaindene <21/mole of silver), 1-phenyl-5-mercaptotetrazole (150 Da/mole of silver), hydrazine compound (II-1) (400"9/mole of silver), 2 as coating aid Tisabonin, polyethyl acrylate (100 wt 9G/gelatin) as a softening agent, and gelatin were added to the emulsion layer so that the gelatin-coated layer was 111.8 II/m", and the following ff1 was added to the polyester paste. A single layer and a multilayer coating were applied at the same time and dried.

11114 layer solution is made of gelatin, heptalated gelatin, di-naponine, 3μ polymethyl methacrylate, 2-hydroxy-4,6-dichloro-1,3,,5-triazine sodium salt, etc., with gelatin. Amount 2117
It was simultaneously coated on the emulsion layer so as to have a thickness of 1.

The above photosensitive material was processed using the above developer solution (8), (9) and (11).
) was processed. The results are shown in Table-3. Note that the halftone dot quality is the reverse halftone dot quality, not the camera-photographed halftone dot quality. Exposure was performed using a bright room printer.

Table 3 From Table 3, it is clear that samples (16) and (18) of the present invention are superior.

Claims (10)

[Claims] (1) In the presence of an amino compound and a hydrazine compound,
1. An image forming method comprising processing a negative silver halide photographic material with a developer containing a dihydroxybenzene developing agent and a sulfite of 0.3 mol/l or more and having a pH value of 10 or more. (2) Claim 1, wherein the amino compound is a compound represented by the following general formula [I a] or [I b]
Image forming method described in section. General formula [Ia] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [I b] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents a hydrogen atom, hydroxy group, or carboxy group, R_2, R_3, R_4, R_5 and R_6 each represent a hydrogen atom or a monovalent organic group, and A
represents a divalent group, and R_3 and R_5 are bonded to each other,
Together with two carbon atoms and A, a heterocycle may be formed, and R_2 and R_5 and R_4 and R_6 may be bonded to each other to form a heterobridged ring together with two nitrogen atoms and A. ] (3) Claim 2, wherein the group bonded to the N atom of the compound represented by the general formula [I a] or [I b] is a non-hydrophilic group having at least 3 carbon atoms. image forming method. (4) The image forming method according to claim 1, wherein the hydrazine compound is a compound represented by the following general formula [II]. General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_7 represents a monovalent organic residue, and R_8 represents a hydrogen atom or an acyl group. X represents an oxygen atom or a sulfur atom. ] (5) The image forming method according to claim 1, 2, 3, or 4, wherein the negative silver halide photographic light-sensitive material contains a developing agent. (6) The composition of the silver halide is at least 30% silver chloride.
The image forming method according to claim 1, 2, 3, 4, or 5, wherein the amount is mol%. (7) The image forming method according to claim 1, 2, 3, 4, 5, or 6, wherein the developer contains phosphate and/or carbonate. . (8) Claims 1, 2, and 3, wherein the photosensitive material is developed in the presence of a benzotriazole.
The image forming method according to item 4, 5, 6, or 7. (9) Claims 1, 2, 3, 4, 5, 6, and 7, wherein the photosensitive material is developed in the presence of a polyalkylene oxide compound. or the 8th
Image forming method described in section. (10) The image forming method according to any one of claims 1 to 8 or 9, wherein the developer has a pH of 11 or more.