JPH0367250A - Image forming method - Google Patents

Abstract

PURPOSE:To extend exposure latitude at the time of photographing a line image and to obtain ultrahigh contrast and high resolving power by incorporating a specified compd. and a redox compd. into a photographic sensitive material and adding a nucleus forming development accelerator to a developing soln. CONSTITUTION:When an exposed silver halide photographic sensitive material is developed to form an image, a compd. represented by formula I and a redox compd. releasing a development inhibitor on being oxidized are incorporated into the sensitive material and a nucleus forming development accelerator is added to a developing soln. In the formula I, R1 is an aliphat. or arom. group, R2 is H, alkyl, aryl, etc., and each of A1 and A2 is H or one of them is H and the other is optionally substd. alkylsulfonyl, etc. A high-contrast negative image, a negative image having high sensitivity or satisfactory dot image quality is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it provides a high-contrast negative image, a high-sensitivity negative image, and a good halftone image quality. This invention relates to silver halide photographic materials.

(Prior art) In the field of photoengraving, in order to deal with the diversity and complexity of printed matter, there are demands for photosensitive materials with good original reproducibility, stable processing solutions, and easy replenishment schedules. .

Particularly in the line drawing process, manuscripts are created by pasting typesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, a document contains images of different densities and line widths, and there is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can finish these documents with good reproduction.

On the other hand, enlarging (stretching) or reducing (shrinking) net photographs is widely used in the making of catalogs and large posters.
In plate making that uses enlarged halftone dots, the number of lines becomes coarser, resulting in blurred dots. When reduced, the number of lines per inch is larger than that of the original, and a thinner point is photographed. Therefore, in order to maintain halftone reproducibility, an image forming method having a wider latitude is required.

A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain sensitivity to these light sources, photographic materials are usually orthosensitized. It has been discovered that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of the lens, and as a result, image quality is more likely to deteriorate. Moreover, this deterioration is more noticeable for xenon lamp light sources.

As a system that meets the demands for a wide latitude, a lithium-type silver halide photosensitive material made of silver chlorobromide (silver chloride content of at least 50% or more) is used, with an extremely low effective concentration of sulfite ions (usually 0.1 mol/min). 1 or less) A method is known in which a line image or halftone image with high contrast and high blackening density, in which image areas and non-image areas are clearly distinguished, is obtained by processing with a hydroquinone developer. However, due to the low concentration of sulfite in the developing solution, this method is extremely unstable to air oxidation, and various efforts and innovations have been made to keep the solution activity stable. Currently, the process is extremely slow, reducing work efficiency.

For this reason, the above development method (lith development system)
There is a need for an image forming system that eliminates the instability of developed image formation caused by the process, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics, and one example of this is U.S. Pat. No. 4,168,977, No. 4
, 221. , No. 857, No. 4,224,401, No. 4
, 243°739, 4,272,606, 4,
As seen in No. 311.781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound has been added is prepared at a pH of 11.0 to 12.3 without a sulfite preservative.
．． A system has been proposed for forming ultra-high contrast negative images with a T of more than 10 by processing with a developer containing 15 mol/1 or more and having good storage stability. This new image forming system has the feature that it can also use silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chlorobromide, which has a high silver chloride content. There is.

The above image system has sharp halftone dot quality, processing stability,
Although it shows excellent performance in terms of speed and original reproducibility, a system with further improved original reproducibility is desired in order to deal with the variety of printed matter in recent years.

On the other hand, in the work of the collection and reversing process, efforts have been made to improve work efficiency by performing the work in a brighter environment, and for this purpose it is necessary to work in an environment that can be called a bright room. Progress has been made in the development of photosensitive materials for plate making and exposure printers that can be used for printing.

The photosensitive material for bright room use described in this patent refers to a photosensitive material that can safely use light having a wavelength of 400 nm or more, which does not contain an ultraviolet component, as safelight light for a long period of time.

The photosensitive material for bright room use used in the collection and reversing processes uses a developed film on which characters or halftone images have been formed as an original, and the original and the photosensitive material for reversing are exposed in close contact to form a negative image/image. It is a photosensitive material used to perform positive image conversion or positive image/positive image conversion. Possesses the ability to convert into a positive image■ Tone adjustment of halftone images, line width of character line images! There has been a demand for a photosensitive material capable of I1m properties, and photosensitive materials for bright room reversal have been provided to meet this demand.

However, in the advanced image conversion work of forming cut-out character images by overlapping and repeating, the conventional method using a bright room reversing process using a light-sensitive material for use in a bright room is not suitable for the conventional method using a darkroom reversing process using a conventional reversing photosensitive material for darkrooms. Compared to other methods, this method has the disadvantage that the quality of the extracted character image deteriorates.

To explain in more detail the method of forming cut-out character images by overlapping, as shown in Figure 1, transparent or semi-transparent pasting bases (a) and (b) (usually polyethylene terephthalate having a thickness of about 100 μm) are used. (b) A film on which characters or line images are formed (line drawing original) (b) and a film on which a halftone dot image is formed (halftone original) (d).
The materials pasted on the original are superimposed to form an original, and the emulsion side of the return photosensitive material (E) is brought into close contact with the halftone original (D) for exposure.

After exposure, a development process is performed to form blank white portions of line drawings in the halftone image.

The important points in this method of forming a character image are:
Ideally, negative image/positive image conversion is performed according to the halftone dot area and image line of each of the halftone dot original and the line drawing original. However, as is clear from Figure 1, halftone originals are exposed in direct contact with the emulsion surface of the photosensitive material for return, whereas line drawing originals are exposed using a pasting base (c) and a halftone original (black). ) is exposed to the photosensitive material for return through the intermediate layer.

For this reason, if you apply an exposure amount that faithfully converts a halftone original from a negative image to a positive image, the line drawing original will be exposed out of focus through the spacer created by the pasting base (c) and the halftone original (d). The inside of the drawing line in the blank white part becomes narrower, which is the cause of the deterioration in the quality of the extracted character image.

In order to solve the above problems, a system using hydrazine is disclosed in Japanese Patent Application Laid-open Nos. 62-80640 and 62-235938.
However, it is not sufficient. , further improvements are desired.

For example, attempts to improve image quality include
A method is known in which a development inhibitor is released from a redox compound having a carbonyl group in the manner of a silver image, as disclosed in Japanese Patent No. 3847. However, even when these compounds are used, the halftone gradation is insufficiently extended, and the image tone control is narrower than that of the lithographic development system, making it impossible to create a high-contrast development system that can be used for halftone image photography. Composition (e.g. pH 1 sodium sulfite concentration, etc.)
The nucleating activity may be too high or insufficient depending on the change in the nucleation activity, resulting in a loss of commercial value such as unevenness of the obtained images.

Therefore, it has been desired to develop a photosensitive material that can form a high-contrast halftone image using a stable developer and that can be broadly controlled in image tone.

(Objective of the Invention) The first object of the present invention is to provide a photographic material having a wide exposure latitude in line drawing photography, ultra-high contrast (especially γ value of 10 or more), and high resolution.

A second object of the present invention is to provide an ultra-high contrast photographic material that can reproduce line drawings well and has a high background density (D wax).

A third object of the present invention is to provide an ultra-high-contrast photographic material that has a wide exposure latitude in halftone image photography, has high density, has clear outlines of halftone dots, and has excellent halftone dot quality. It is.

A fourth object of the present invention is to provide an ultra-high contrast photographic material in which the resulting image does not fluctuate even if the composition of the developing treatment solution changes.

(Groove Bottom of the Invention) An object of the present invention is to develop a silver halide photographic light-sensitive material that has been exposed to light to form an image, when the photographic light-sensitive material contains a compound represented by the following general formula (1) and an oxidized light-sensitive material. This is achieved by employing the formation of an image characterized in that the IJI image processing solution contains at least one redox compound capable of releasing a development inhibitor when the IJI image processing solution is processed. Ta.

General formula (1) In the formula, R1 represents an aliphatic group or an aromatic group, R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarbonyl group, G.

represents a carbonyl group, a sulfonyl group, a sulfoxy group, a 1-P- group, or an iminomethylene group, and A1 and 1 A are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or Represents a substituted or unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group.

The present invention will be explained specifically and in detail below.

To explain the compound of general formula (1), general formula (1)
), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. The branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms, and the alkyl group may be an aryl group, an alkoxy group, or , a sulfoxy group, a sulfonamide group, a carbonamide group, or the like.

The aromatic group represented by R6 in the general formula (1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyridine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc. Among them, those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl Examples of substituents include straight-chain, branched or Cyclic alkyl group (preferably one with 61 to 20 carbon atoms), aralkyl group (
Preferably, the alkyl moiety is a monocyclic ring having 1 to 3 carbon atoms or 2 carbon atoms.
ring), alkoxy group (preferably 1 to 20 carbon atoms)
), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (
(preferably having 2 to 3 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), Numbers 1 to 30).

-i The alkyl group represented by Rt in formula (1) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a 1f substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, phenyl group, or sulfonyl group.

The aryl group is preferably a monocyclic or bicyclic aryl group, such as one containing a benzene ring. This end-
The group is, for example, a halogen atom, an alkyl group, a cyano group,
It may be substituted with a carboxyl group, a sulfo group, a sulfonyl group, etc.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

A monocyclic group is preferable as the aryoloxy group, and examples of the substituent include a halogen atom.

The amino group includes an unsubstituted amino group and a carbon number of 1 to 10.
An alkylamino group or an aryamino group is preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, a C1-C10 furkylcarbamoyl group, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group or an aryloxycarbonyl group having a carbon number of 1 to 1°, and may be ilFm-contained with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R2, in the case of G1 cacarponyl group, preferred are a hydrogen atom, an alkyl group (e.g.
Methyl group, trifluoromethyl group, 3-human dipropyl group, 3-methanesulfonadopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxybenzyl group, etc.), aryl group (e.g. , phenyl group, 3,5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when G1 is a sulfonyl group, R7 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group) or substituted amino group (e.g.
dimethylamino group, etc.) are preferred.

When G is a sulfoxy group, R1 is preferably a cyanobenzyl group, a methylthiobenzyl group, or the like.

When Gl is an N-substituted or unsubstituted iminomethylene group,
Preferred examples of Rt include a methyl group, an ethyl group, and a substituted or unsubstituted phenyl group.

As the substituent for R2, the substituents listed for Rt can be used.

The most preferred GI in formula (1) is a carbonyl group.

Also, Rz splits the GI-Rz part from the remaining molecules, -
Those that cause a cyclization reaction to produce a cyclic structure containing atoms of the GI-Rz moiety are preferably methoxy, ethoxy, butoxy, phenoxy, or phenyl groups, and in particular, phenyl groups may be used. Specifically, general formula (a)
It is something that can be expressed as

General formula (a) -R3-Z.

In the formula, Zl nucleophilically attacks Gl, and GI -Rz
−Z+ is a group capable of splitting from the remaining molecules, and R
3 is R2 with one hydrogen atom removed, Z, attacks G, and G +, Rs.

A cyclic structure can be generated with Zl.

More specifically, Zl easily undergoes a nucleophilic reaction with 01 when the hydrazine compound of general formula (1) generates the following reaction intermediate by oxidation etc., resulting in R1-N-N-CI -R1-ZI R , -N-N group from G, specifically OH, SH or NHR, (R is a hydrogen atom, an alkyl group, an aryl group, -CORs, or -5O,R
5, and Rs is a hydrogen atom, an alkyl group, an aryl group,
G1 such as C○○H (representing a heterocyclic group, etc.)
It may also be a functional group that directly reacts with (here, OH
, SH, NHR4゜-C○OH may be temporarily protected so that these groups are generated by hydrolysis with alkali etc.) Represents a telocyclic group 〉 is a hydroxyl ion or! It may be a functional group that can react with 61 by reacting with a nucleophile such as sulfate ion.

Furthermore, the ring formed by CI, Rs, and Z+ is preferably a 5- or 6-membered ring.

Among those represented by general formula (a), preferred are those represented by general formulas (b) and (c).

General formula (b) In the formula, Rh'-Rb'' is a hydrogen atom, an alkyl group, (
represents an alkenyl group (preferably one having 1 to 12 carbon atoms), an alkenyl group (preferably one having 2 to 12 carbon atoms), an aryl group (preferably one having 6 to 12 carbon atoms), and may be the same or different. B is a 5-membered ring or a 6-membered ring which may have a substituent
These are atoms necessary to complete a membered ring, m and n are 0 or 1, and (n+m) is 1 or 2.

Examples of the 5- or 6-membered ring formed by B include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

zl has the same meaning as in general formula (a).

-Formation CC) c +N←r→CR,'R,'')TZ In the formula, RC' and Re2 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, etc., and may be the same or different. Good too.

R and 3 represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents O or l; q represents 1-4;

Rt'5R(2 and Re3 may be bonded to each other to form a ring as long as the structure allows intramolecular nucleophilic attack of Zl to G.

Re'-, Re'' is preferably a hydrogen atom, a halogen atom, or an alkyl group, and R% is preferably an alkyl group or an alkyl group.

q preferably represents 1 to 3; when q is l, p represents 1 or 2; when q is 2, p represents O or 1; when q is 3, @p represents O or 1; CR when is 2 or 3
c′ R,” may be the same or different.

Z has the same meaning as in general formula (a).

Al5A! is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group, or a group where the sum of Hammett's substituent constants is −0
, 5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more), a benzoyl group, or a straight, branched, or cyclic unsubstituted aliphatic acyl group (substituents include, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group) )) As A3 and Al, a hydrogen atom is most preferable.

-i R1 or R1 in formula (1) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

A ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, and includes, for example, alkyl group, alkoxy group, phenyl group, althyl phenyl group, phenoxy group, alkylphenoxy group, etc. You can choose from.

R1 or R2 in the general formula (1) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Examples of 5 include thiourea group, heterocyclic thioamide group, mercapto heterocyclic group, triazole group, etc.
, No. 347, JP-A No. 59-195, 233, No. 59-
200゜231, 59-201,045, 59
-201.045, 59-201,047, 5
9-201.048, 59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, patent application No. 62-67.508,
-62-67,501 and the groups described in 162-67.510 are mentioned.

Examples of the compounds represented by the general formula (1) are shown below, however, Akira Kimi is not to be judged negatively by the following compounds.

■-1) ■-6) 1-12) -151 H 1-16) C! H3! -8) r-10) 1-11) 1-17) 1-20) H [-30) [-31) 1-32) iHs [-25) I-27) 1-28) -331 [-35 ) 1-36) ○ N ○ 1-37) r-38) 1-40) 1-45) 1-46) 1-47) 0 l-41) 1-48) -491 1-50) 1-51 ) 1-54) 1-52) 1-53) In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCHDISCLO3IJRE
I ten23516 (November 1983 issue, p. 3
46) and the documents cited therein, as well as U.S. Pat.
No. 76.364, No. 4,278,748, No. 4,38
No. 5,108, No. 4,459,347, No. 4,560
, No. 638, No. 4,478,928, British Patent No. 2,0
11,391B, JP-A-60-179734, JP-A No. 62
-270.948, 63-29.751, JP-A-61-170.733, JP-A-61-270,744,
No. 62-948, EP No. 217,310, Patent Application No. 1983
-475,234, 61-251,482, 6
1-268. , No. 249, No. 61-276゜283,
No. 62-67528, No. 62-67゜509, No. 6
2-67.510, 62-58.513, 62
-130,819, 62-143.467, 6
No. 2-166.117, or US 4,686,167
No., JP-A-62-178,246, JP-A-63-23
No. 4,244, No. 63-234,245, No. 63-2
34.246, 63-294,552, 63-
No. 306,438, Patent Application No. 166117/1986, No. 6
2-247.478, 63-105 682, 63-114,118, Giu 63-110,051, 63-11'4゜119, 63-116,23
No. 9, No. 63-147.339, No. '63-179,
No. 760, No. 63-229,163, Patent Application No. 1-18 Hei.
, No. 377, No. 1-18, 378, No. 1-18, 37
No. 9, No. 1-15 755, No. 1-16,814,
1-40,792, 1-42. No. 615, same 1
-42,616 can be used.

When incorporating the compound represented by the general formula (1) of the present invention into a photographic emulsion layer or a hydrophilic colloid layer, the compound of the present invention is dissolved in water or a water-miscible organic solvent (if necessary). It may be added to a hydrophilic colloid solution (for example, a silver halide emulsion, an aqueous gelatin solution, etc.) (it may be added to a hydrophilic colloid solution (for example, a silver halide emulsion, an aqueous gelatin solution, etc.) (at this time, an acid may be added as necessary). (The pH may be adjusted by adding an alkali.) The compound of the present invention may be used alone or in combination of two or more. The amount of the compound of the present invention added is preferably per mole of silver halide. I X 10-h to 5×10-” mol,
More preferably, it is IX10-'mol-1XIO-''mol, and an appropriate value can be selected depending on the properties of the silver halide emulsion to be combined.

Examples of useful nucleating development accelerators contained in the processing solution used in the present invention include, for example, JP-A No. 56
-106244, 61-267759, 61-
No. 230145, No. 62-211647, No. 63-5
Amine compound described in Natoni No. 0247 or JP-A No. 6
Examples include benzyl alcohol derivatives described in No. 0-200250.

Preferred compounds as nucleation development accelerators include compounds represented by the following general formula (2).

In the formula, Ro, R11% R1) are respectively HR,...
The sum of the logarithm (logP) values of n-octanol/water partition coefficients as HRig, H-R1, is 2.6 or more10.
Substituted or unsubstituted alkyl groups less than 0 represent an unsubstituted alkyl group.

Furthermore, compounds in which the sum of the values of ffiogP falls within the range of 3.0 or more and less than 8.0 are particularly preferred.

Next, - formation (2) will be explained in detail.

R! ＋""'R1! Examples of the substituents of the substituted alkyl group represented by include a hydroxyl group, an alkoxy group, a carboxy group, a sulfo group, an aryloxy group, and an amino group.

Note that the logarithm (log
The calculation method for the value of
Substituent Con5tantsFor
Correlation Analysis i
n Chemistry and Biology)
Handbook of Chemical Property Estimation Methods
chemical property estimation
onMethods) and is defined in the present invention. The value of logP was also determined using this method.

Typical H-R□, HRtt and H-Ruff are shown below.
The value of logp is shown.

Value of logarithm (RogP) of n-octanol/water partition coefficient of HRtt, H-R, , H-R, , H-RH, HRz
z, HR23EogP I straight H-CH2CHz
CHff 2.32HCHz
CHl CHI C) (i2, 86 R2 H-C-CH.

CH□ 2, 73 H (CHt) a CHs H-(C)f□　scHi H-(CH,), CH3 3, 40 3,94 4, 48 HCHl CHl OC4H-(n)HC,H.

HCH2CHz ○H HCHz CHt CHz OHHCHzCHt
OCHtCHzOH H-CH2CHCH,OH OH HCfhCHzCHzCHtOH 2゜l.

-01 O8 Ten.

1゜0.870 H-CfhCHCIhCHzCHzCQOOH H(CHl)&OH H(CHl)# OH HCHzCHzOCIhCHtOCHzCHzOHH-
CH, CHCH, So, e OH H-CHz CHz OCHs -4,35 1,950 3,030 -0,431 -4,16 0,66 Specific examples of the amino compound represented by general formula (2) are shown below. However, the compounds of the present invention are not limited thereto.

2-26) CHz Unlike other agono compounds, the amino compound represented by the general formula (2) significantly promotes high contrast even in a small amount, but has a weak effect as a solvent for silver halide. It has excellent performance in that it does not cause silver stains.

The amino compound represented by the general formula (2) is preferably used in an amount of 0.01 to 0.30 mol/i per developer 11, particularly 0.01 to 0.0 mol/i. It is preferably used in a range of 2 mol/l.

The amino compound represented by general formula (2) is a developer (water)
Since the solubility in -S formula (2) is relatively low, if an attempt is made to reduce the volume by concentrating the developer solution for convenience of storage and transportation, the amino compound of -S formula (2) may precipitate. . The following general formula (4) or (5)
When the compound represented by is used in combination, it is possible to prevent the occurrence of such precipitation and precipitation even if the liquid is concentrated, so it may be used.

General formula (4) %Formula% Specific examples of the compound of general formula (4) include p-)sodium toluenesulfonate, sodium benzenesulfonate,
Examples include sodium 1-hexane sulfonate. Specific examples of the compound of general formula (5) include sodium benzoate, sodium p-)ruylate, potassium isobutyrate, n
-Sodium caproate, sodium n-caprylate,
Examples include sodium n-caprate.

-a The amount of the compound represented by formula (4) or (5) varies depending on the amount of the ano compound of general formula (2) used, but it is usually 0.005 mol/j2 or more, especially 0. 0.03 mol/l to 0.1 mol/l is suitable. Also, the general formula (2
) is suitably in the range of 0.5 to 20 mol per mol of the amino compound.

General formula (5) %formula% Here, M represents a hydrogen atom, Na, or NH.

Rz4 and RH represent an alkyl group having 3 or more carbon atoms, an alkylbenzene group, or a benzene group.

The redox compound of the present invention that can release a development inhibitor when oxidized will be explained.

The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones, and more preferably hydrazines.

The hydrazines used as the redox compound capable of releasing a development inhibitor upon oxidation of the present invention preferably have the following general formula (R-1), general formula (R-2), and general formula (R-3). It is expressed as A compound represented by general formula (R-1) is particularly preferred.

General formula (R 1 1) N-N-Gl (Time), -PUGA+At General formula (R-2) R1-G2-Gl-N N-(JlzCH-(Tim
e) t-PUG^+AzAn General formula (R-3) In these formulas, R1 is an aliphatic group or an aromatic group○
It represents 0 0 II 1111. G1 represents 10- group, -C-C- group, 1 or -P- group. G2 is just a bond, G, -
R.

10--5- or -N-, R2 is water t Represents an elementary atom or R1.

A, , A represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In general formula (R-1), at least one of AA2 is a hydrogen atom. A is synonymous with A- or -GHz
Represents CH(Time)t-PtlG.

4 A4 represents a nitro group, a cyano group, a carboxyl group, a sulfo group or 10+ Gz R+.

Trme represents a divalent linking group, and t represents O or 1. PUG stands for development inhibitor.

- Form force (R-1), (R-2), and (R-3) will be explained in more detail.

In general formulas (R-1), (R-2), (R-3),
The aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. In addition, this alkyl group includes an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group,
It may have a substituent such as a carbonamide group.

In general formulas (R-1), (R-2), (R-3), R
The aromatic group represented by 1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be fused with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include an inquinoline ring, a benozigodazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R+ is an aryl group.

The aryl group or unsaturated heterocyclic group of R may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted a[ group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group,
Acyl group, alkoxycarbonyl group, acyloxy group,
Examples include carbonamide groups, sulfonamide groups, carboxyl groups, phosphoric acid amide groups, etc. Preferred ta groups include linear, branched or cyclic alkyl groups (preferably those with 1 to 20 carbon atoms), aralkyl groups ( (preferably monocyclic or bicyclic alkyl moiety having 1 to 20 carbon atoms)
, an alkoxy group (preferably one having 1 to 30 carbon atoms),
Substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms) ), ureido group (preferably one having 1 to 40 carbon atoms), phosphoric acid amide group (
Preferably, those having 1 to 40 carbon atoms are used.

For general formulas (R-1), (R-2), and (R-3), -C- group and SOz- group are preferable, and -0- group is most preferable.

A1, A! is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group, or a group where the sum of Hammett's substituent constants is −0
, 5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) group, or one sublinear, branched, or cyclic unsubstituted and substituted aliphatic acyl group (W substituents include, for example, a halogen atom, an ether group, a sulfonate group, a carbonamide group, a hydroxyl group, a carboxy group,
Examples include sulfonic acid groups. )) is preferred.

A hydrogen atom is most preferable as A+ and Ax.

A is a hydrogen atom, -CHz-Ct(-+Time
) t PUG4 is most preferred.

In general formulas (R-1), (R-2), and (R-3), T
ime represents a divalent linking group and may have a timing adjustment function. L represents O or 1.

The divalent linking group represented by Time represents a group that releases PUG from Time-PUG released from the oxidized product of the redox mother nucleus through one or more reaction steps.

As the divalent linking group represented by Time, for example, U.S. Pat.
U.S. Pat. PUG is released by an intramolecular ring-closing reaction after ring opening as described in No. 525, etc.; U.S. Pat. No. 4,330.617, U.S. Pat. 121,328 etc., which releases PUG with the production of an acid anhydride through an intramolecular ring-closing reaction of the carboxyl group of succinic acid monoester or its 11 units; US Patent No. 4,40
No. 9,323, No. 4,421,845, Research Disclosure Magazine Nα21,22B (1981
February), U.S. Patent No. 4,416.977 (Japanese Unexamined Patent Publication No.
-135□944), JP-A-58-209゜736
No. 58-209,738, etc., which generates quinomonomethane or its analogs by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group and releases PUG; U.S. Patent No. 4,420
, No. 554 (Japanese Unexamined Patent Publication No. 57-136,640), Unexamined Japanese Patent Application No. 57-135.945, No. 57-188,035,
5B-98,728 and 58-209,737
A nitrogen-containing heterocycle which releases PUG from the 7-position of the enamine by electron transfer of the moiety having an enamine structure in the nitrogen-containing heterocycle described in JP-A No. 57-56,837; PUG is formed by an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with an atom.
Those that emit: U.S. Pat.
No., JP-A-59-75475, JP-A-6024914
No. 8, JP-A-60-249149, which releases PUG with the production of aldehydes; JP-A-51
-146,828, 57-1.79,842, and 59-104,641 which release PUG with decarboxylation of carboxyl groups; -0-COOCR
-Rh-PUG (R,, R1 represents a monovalent group)
has the structure and releases PUG with decarboxylation and subsequent generation of aldehydes; JP-A-60-7-429
PUG is released with the production of isocyanate as described in US Pat. No. 4,438,193, etc.;
Examples include those that release G.

Time of general formulas (R-1), (R-2), (R-3)
The divalent group represented by is preferably represented by the following general formula (T-
1) to -formation (T-6). In these, ** represents the site where Time binds to PUG, and *
represents the other binding site.

General formula (T-1) In the formula, W represents an oxygen atom, a sulfur atom or a -NR group, R8 and R1□ represent a hydrogen atom or a substituent, R11 represents a substituent, and t is 1 or 11 or 2. When t is 2, two -W-CR points represent the same thing or different things. When R11 and R11 represent a group, representative examples of R11 include R0 group, R0C○~ group, R,,SO,- group, RzNCO- group or RI% R,, NSO,- group, etc. Can be mentioned. R0RI here
5 represents an aliphatic group, an aromatic group, or a heterocyclic group, and RI5
represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.

Each of R8, R, □ and R1ff represents a divalent group,
It also includes the case where they are connected to form a cyclic structure.

Specific examples of the group represented by general formula (T-1) include the following groups.

General formula (T-2) * Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, and a snake represents an electrophilic group, and from Nu It is a group that can cleave the bond with the mark ** upon nucleophilic attack, and Li
nk represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction, and is represented by the general formula (
Specific examples of the group represented by T-2) are as follows.

-Formation (T-3) In the formula, W, R++, R1! and t have the same meaning as explained for (T-1). Specifically, the following groups may be mentioned.

- Fierce dog (T-4) General formula (T-5) 1 Q-C-** 1 S-C-** General formula (T-6) In the formula, W and R1+ are in the general formula (T-1>) It has the same meaning as explained above.-Specific examples of the group represented by fierce dog (T-6) include the following groups.

Umbrella-〇-C-Ichining 5-C-*Bear Kushi-0-CO.

Also, as Time, general formula (T-1) ~ -general formula T-
A group formed by combining two or more groups represented by 6) is also useful. Preferred specific examples thereof are shown below. umbrella,*
* has the same meaning as in general formulas (T-1) to -general formula T-6).

C,H.

Book-〇-CH2 C,H.

＼11 N-C-Umbrella car / C, H5 2H5 O.C.J.

OCH.

1 book-0-C-N(-CHd-r-N-C-ms1 ll30 OCH,O II I II Palm-0-C-0+CHt+-rN C-*Umbrella These T
For specific examples of the divalent linking group represented by ime, see JP-A-61-236,549 and JP-A-64-884.
51, Japanese Patent Application No. 63-98.803, etc., in detail.

PUG represents a group having a development inhibiting effect as (Tlmeht PUG or PUG).

PUG or (Time)-, the development inhibitor represented by PUG is a known development inhibitor that has a heteroatom and is bonded via the heteroatom, and these are, for example, C.E.K. (C, E.

K., Kawaess) and Chi. H. James (T.H.
.

James) The Theory of the Photographic Process
photographicProcesses)” 3rd
ed., published by Macmillan in 1966, pages 344 to 346. Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoikudazoles, mercaptopyridines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothiadiazoles, benztriazoles, and benzimidazoles. , indazoles, adenines, guanines, tetrazoles, tetraazaindenes, triazaindenes, mercaptoarenes, and the like.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include the following, but these groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Azyla main group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryl oxycarbonyl group,
Acyl group, alkoxycarbonyl group, acyloxy group,
These include a carbonate group, a sulfone group, a carboxyl group, a sulfoxy group, a phosphono group, a phosphinico group, and a phosphoamide group.

Preferred substituents include a nitro group, a sulfo group, a carboxyl group, a sulfamoyl group, a phosphono group, a phosphinico group, and a sulfonamide group.

The main development inhibitors are shown below.

(2) 1-(4-hydroxyphenyl)-5-mercaptotetrazole (3) 1-(4-aminophenyl)-5-mercaptotetrazole f4) 1-(4-carboxyphenyl)-5-mercaptotetrazole (5) 1-(4-chlorophenyl)-5-mercaptotetrazole (6) 1-(4-methylphenyl)-5-mercaptotetrazole (711-(2,4-dichlorophenyl) 5-mercaptotetrazole (8) 1-(4-sulfamoylphenyl)-5-mercaptotetrazole (9) 1-(3-carboxyphenyl)-5-mercaptotetrazole 0011-(3,5-dicarboxyphenyl) 5-mercaptotetrazole 01) 1-( 4-methoxyphenyl)-5-mercaptotetrazole Q2) 1-(2-methoxyphenyl)-5-mercaptotetrazole 03) 1-(4-(2-hydroxyethoxy)phenyl]-5-mercaptotetrazole 1114) 1-(
2,4-dichlorophenyl)-5-mercaptotetrazole 05) 1-(4-dimethylaminophenyl)-5-mercaptotetrazole Ge1-(4-nitrophenyl)-5-mercaptotetrazole 07) 1,4-bis(5-mercapto- 1-Tetrazolyl)benzene 08) 1-(α-naphthyl>-5-mercaptotetrazole 0'DI-(4-sulfophenyl)-5-mercaptotetrazole # 1-(3-sulfophenyl)-5-mercaptotetrazole (21 ) l-(β-naphthyl)-5-mercaptotetrazole (22) 1-methyl-5-mercaptotetrazole (23) 1-ethyl-5-mercaptotetrazole (24) 1-propyl-5-mercaptotetrazole (25) 1 -Octyl-5-mercaptotetrazole (26) 1-Dodecyl-5-mercaptotetrazole (27) 1-Cyclohexyl-5-mercaptotetrazole (28) 1-Palwara Chi-5-mercaptotetrazole (29) 1-Carboxyethyl-5 -Mercaptotetrazole (30) 1-(2,2-jethoxyethyl)-5mercaptotetrazole (31) 1-(2-aminoethyl)-5-mercaptotetrazole hydrochloride (32) 1-(2-diethylaminoethyl) -5 mercaptotetrazole (33) 2-(5-mercapto-1-tetrazolyl)ethyltrimethylammonium chloride (34) 1-(3
-phenoxycarbonylphenyl) = 5-mercaptotetrazole (35) 1-(3-maleinimidophenyl)-6-mercaptotetrazole mercap i Azole (1) 4-phenyl-3-mercaptotriacye (2)
4-phenyl-5-methyl-3-mercaptotriazole (3) 4.5-diphenyl-3-mercaptotriazole (4) 4-(4-carboxyphenyl)-3-mercaptotriazole (5) 4-methyl-3- Mercaptotriazole (6)
4-(2-dimethylaminoethyl)-3-mercaptotriazole (7) 4-(α-naphthyl)-3-mercaptotriazole (8) 4-(4-sulfophenyl)-3-mercaptotriazole (9) 4-( 3-nitrophenyl)-3-mercaptotriazole (2) 1,5-diphenyl-2-mercaptoimi 02)
5-Sulfobenzotriazole Na salt 03) 5-methoxycarbonylbenzotriazole 5-71 Nobenzotriazole 5-butoxybenzotriazole 5-ureidobenzotriazole Benzotriazole 5-phenoxycarbonylbensitriazole-J 09) 5-(2, 3-dichloropropyloxycarbonyl)benzotriazole 10 Benzimizole 1 Benzimidazole 5-chlorobenzimidazole 5-nitrobenzimidazole 5-n-butylbenzitrizodazole 5-methylbenzimidazole 4-chlorobenzimidazole 5. Methylbenzimidazole 5-nitro-2-(trifluoromethyl)benzimidazole 11 Imidazole (1) 5-nitroindazole (2) 6-nitroindazole (3) 5-aminoindazole (4) 6-aminoindazole (5 ) Indazole (6) 3-nitroindazole (7) 5-nitro-3-chloroindazole (8)
3-Chloro-5-nitroindazole (9) 3-carboxy-5-nitroindazole 12-trisol rod ゛(]) 5-(4-nitrophenyl)tetrazole (2)
5-phenyltetrazole (3) 5-(3-carboxyphenyl)-tetrazole 13-dosaine-entsu(1) 4-hydroxy-6-methyl-5-nitro 1.3
．． 3a, 7-thitraazaindene (2) 4-mercapto-6-methyl-5-nitro 13.3a, ? -tetraazaindene 14 mercapdoor -no L, i*(1) 4-nitrothiophenol (2) thiophenol (3) 2-carboxythiophenol Also, general formula (R-1), (R-, 2), ( In R-3), R, or (T im e + t P UG
contains ballast groups commonly used in immobile photographic additives such as couplers, general formulas (R-1), (R-
2), a group that promotes adsorption of the compound represented by (R-3) to silver halide may be incorporated.

The ballast group has the general formula (R-1), (R-2), (R-3
) is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the formula from diffusing into other layers or into the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, and an amide group. group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidacylin-2-thione, 2-thiohydantoin, rhodanine, thiobarbital acid, tetrazoline-5-thione, I, 2.4-) liazoline-3-thione, l, 3.4- Oxazoline-2
-thione, benzimidacillin-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, cyclic thioamide group such as 1,3-imidacillin-2-thione, linear thioa-based group , aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -3H group is bonded is a nitrogen atom, it is synonymous with a cyclic thioamide group that has a tautomeric relationship with this, Specific examples of this group are the same as those listed above), a group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxazole , 5- or 6-membered nitrogen-containing heterocyclic groups consisting of a combination of nitrogen, oxygen, sulfur and carbon such as oxaprine, thiadiazole, oxathiazole, triazine, azaindene, and heterocyclic quaternary groups such as henzimidazolinium. Examples include salt.

These may be further substituted with a suitable substituent.

Examples of the f substituent include those described as the substituent for R1.

Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

3-1゜3-2゜3-3゜3-4゜3-6゜NO□ 3-5゜3 8゜9゜10゜czot(n) 3-1 1゜3-12゜3-21゜0 3-25゜3-26゜3-27゜3-22゜3-23゜3-24゜3-28゜3-29゜3-30゜3-38゜3-39゜3-40゜3 -42゜NO□ 3-43゜3-44゜3-45゜3-49゜3-50゜0311a 3-46゜3-47゜-48゜-51 2 -53 54 5 -59 0 -61 C , H CbH+s Ot 6 7- -62 3 4 N=co=→N 3-65 3-66 -68 9 O Of -71 In addition to the above-mentioned redox compounds used in the present invention, for example, 61-213゜847, same 6
No. 2-260,153, Patent Application No. 1-102,393,
Those described in No. 1-102,394, No. 1-102,395, and No. 1-114,455 can be used.

The method for synthesizing the redox compound used in the present invention is, for example, JP-A-61-213,847 and JP-A-62-260,15.
No. 3, U.S. Patent No. 4,684,604, Patent Application No. 1983-
98,803, U.S. Patent No. 3,379,529, U.S. Patent No. 3,620.746, U.S. Patent No. 4,377.634, U.S. Pat.
, No. 332,878, JP-A-49-129,536,
It is described in No. 56-153,336, No. 56-153,342, etc.

The redox compound of the present invention is used in an amount of IX10-' to 5X10-'' mol, more preferably 1X10-' to IX10-'' mol per mole of silver halide.

The redox compounds of the present invention can be dissolved in suitable water-miscible organic solvents, such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be used after being dissolved.

In addition, by the well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and then mechanically emulsified and dispersed. You can also create and use things.

Alternatively, by a method known as solid dispersion method,
The powder of the redox compound can also be dispersed in water using a ball mill, a colloid mill, or an ultrasonic wave.

General formula (1> and general formula (R-1) of the present invention, (R-
The compound represented by 2) or (R-3) can form a negative image with high coi last when used in combination with a negative emulsion.

On the other hand, it can also be used in combination with an internal latent image type silver halide emulsion. General formula (1) and general formula (R-
The compound represented by 1), (R-2) or (R-3) is preferably used in combination with a negative emulsion to form a high contrast negative image! Yes.

When used to form a high-contrast negative image, the average grain size of the silver halide used is preferably fine (for example, 0.7μ or less), particularly preferably o, rμ or less. There is basically no limit to the particle size distribution, but
Monodisperse is better! Yes. Monodisperse herein means that at least one can is composed of particles having a size within 0% of the average particle size in terms of weight or number of particles.

Silver halide grains in photographic emulsions are cubic, hemispherical, and rhombic.
dihedron, /4 is poorly regular like an interior body
) crystals, irregular crystals such as spherical or tabular crystals, or a composite of these crystal shapes.

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

The silver halide emulsion used in the present invention includes cadmium salts, sulfites, lead salts, thallium salts, rhodium salts or complex salts thereof, iridium salts or their A complex salt or the like may also be present.

The silver halide used in the present invention is equivalent to 7 moles of silver.
It is a silver haloiodide prepared in the presence of 10 to 10 moles of iridium salt or a complex salt thereof, and the iodide-containing wheel in the grain table is larger than the average silver iodide content of the grains. When an emulsion containing such silver haloiodide is used, photographic properties with much higher sensitivity and higher gamma can be obtained.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. As methods for chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization, and noble metal sensitization are known. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical one, and uses gold compounds, mainly total complex salts. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and rhodium. A specific example is U.S. Patent No. 2,4tψ,r,
oto, British Patent No. 6II, 0/. Contains gelatin as a sulfur enhancer! Various sulfur compounds such as thiosulfate, thiourea, thiazoles, rhodanines, etc. can be used.

Regarding IIQ, it is preferable to apply an iridium salt or a rhodium salt during grain formation immediately before the completion of physical ripening in the silver halide emulsion manufacturing process.

In the present invention, the silver halide emulsion layer is manufactured by patent application Sho go-t4.
It is preferable to include two types of phosphor-dispersed emulsions with different average particle sizes, as disclosed in No. Liqy, Japanese Patent Application No. 60-23201, in terms of increasing the maximum fDmax), and small size particles. It is preferable that the dispersed particles be chemically sensitized! Therefore, sulfur sensitization is the most preferable chemical sensitization method.

The dog size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Generally, dog-sized monodisperse particles are not subjected to chemical sensitization because they tend to generate black bubbles, but when chemical sensitization is carried out, it is especially preferable to apply the chemical sensitization shallowly to the extent that black bubbles do not occur. Here, "shallow application" means that compared to chemical sensitization of small-sized particles, chemical sensitization is performed for a shorter time, at a lower degree, or by reducing the amount of chemical sensitizer added. It is. There is no particular limit to the difference in density between dog-sized monodispersed emulsions and small-sized monodispersed emulsions, but ΔlogE
As 0, /~/, 01 yo Shikodanshi〈 is 0,2~6.7
The higher the Inusuizu cliff dispersion emulsion, the better.

Here, the sensitivity of each emulsion is determined by coating it on a support containing a hydrazine derivative and adding sulfite ions to 0. /! pH10,j~/2. containing mol/1 or more. This is obtained when the developer of J is used for processing.

The average grain size of small-sized monodisperse grains is less than or equal to the average size of dog-sized silver halide emulsion grains,
What do you like? The width is less than or equal to O. The average grain size of the silver halide emulsion grains is preferably o, oiμ~i, oμ, more preferably fio, /μ~O0! It is preferable that the average particle size of dog-sized and small-sized monodisperse particles is included in this range for μ.

In the present invention, when two or more emulsions of different sizes are used, what is the amount of silver coated in the small-sized fluorescent dispersion emulsion? : Relative to the amount of coated tatami mats, the ratio is 0 to 10 wt%, and the ratio is 10 wt%.

In the present invention, monodisperse emulsions having different grain sizes may be introduced into the same emulsion or into separate layers.

When introduced in separate layers, it is preferable to have the dog-sized emulsion in the upper layer and the small-sized emulsion in the lower layer.

Among them, the total amount of silver coated is 15'/m2~? t/yr
12 is a good number.

The photosensitive material used in the present invention includes Japanese Patent Application Laid-open Showa J-! 20! No. 0 page ~! A sensitizing dye (for example, cyanine dye, merocyanine dye, etc.) described on page 3 can be added. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of sensitizing residual color. Along with the sensitizing dye, the emulsion may contain a vlJ substance which itself has a spectral sensitizing effect or which is a substance that does not substantially absorb visible light and exhibits residual color sensitization. Useful increasing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitivity are listed in Research Disclosure/7
Volume 1/7AIAJ (Published in December) Page 13■
It is stated in Section 1.

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. Namely, azole bases such as benzothiazolium salts, nitroindazole systems, chlorobenzimidazoles, promobe/zimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminodriazoles, benzothiazoles, mercaptopyrimidi/s; mercaptotriazines; thioketo compounds such as oxacyl/thiones; azaindenes, such as triazaindenes, tetraazaindenes (particularly ψ-hydroxy-substituted t, 3.ja,
7) Antifoggants such as tetrazaindene, pentaazainde, benzene/thiosulfonic acid, thiosulfonic acid, benzenesulfonic acid amide, etc.! Many compounds known as stabilizers or stabilizers can be added. Preferred among these are benzotriazoles (e.g. !-methyl-benzotriazole) and nidroi/dazoles (e.g. nidroi/dazoles).
Dazol). ! In addition, these compounds may be included in the heat treatment solution.

Examples of promoters of image formation or promoters of nucleation and infection that are suitable for use in the present invention include JP-A No. 3-77B/B, JP-A No. 74T-37732, and JP-A No. J-/37/B. JJ issue, same t
O-/1403410, same 6゜-/ψri! In addition to the compounds disclosed in No. 1, various compounds containing N or S atoms are effective.

The optimum amount of these accelerators to be added differs depending on the type of compound, but it is desirable to use them in the range of 0x10'' to 0.7m2, preferably 0x10-3 to 0.7m2. Deshii.

The uninvented four-light material may contain a desensitizer in the photographic emulsion layer or other hydrophilic colloid layer.

The organic desensitizer used in Taibimei is defined by its polarographic half-wave potential, that is, the redox potential determined by polarography, and the sum of the polarographic anode potential and cathode potential is positive.

For a method of measuring redox potential using polarography, see, for example, US Patent No. J,! 0/, No. 307.

The organic desensitizer preferably contains at least one water-soluble atom, and specific examples include sulfone groups, carboxylic acid groups, and sulfonic acid groups.
For example, it may form a salt with ammonia, pyridine, triethylamine, pyfolidine, morpholine, etc.) or an alkali metal R (eg, sodium, potassium, etc.).

As organic desensitizers, compounds of the general formula (II[l~(V
) is often used.

The organic desensitizer according to the present invention is contained in the silver halide emulsion layer.
, 0X10-8~/, θxio' mol/m2, especially/, 0xIO-7~/, Ox10-5 mol/m2
It is preferable to allow z to exist.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain water-soluble dyes as filter dyes, for preventing irradiation, and for various other purposes. Filter dyes include dyes for further lowering the photographic 4 degrees, preferably ultraviolet absorbers that have a maximum spectral absorption in the specific wavelength range of silver halide, and dyes that are used as light-sensitive materials. As the emperor to increase safety against safelight light! A dye having substantial light absorption in the region of IONm-1θonm is used.

These dyes may be added to the emulsion layer depending on the purpose, or they may be added together with a mordant to the top of the silver halide emulsion layer, that is, to a non-hygroscopic water-competitive colloid layer that is far from the silver halide emulsion layer with respect to the support. It is preferable to use it by adding it and fixing it.

Although the molar extinction coefficient of the UV absorber varies, it is usually
It is added in the range of 0''97m2~/17m2. Preferably it is !Om9~j00m9/mz.

The above ultraviolet absorber Fi is dissolved in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, furopanol, etc.), acetone, methylcerone rub, etc., or a mixed solvent thereof] and added to the coating solution. can do.

As the ultraviolet absorber, for example, a benzoxazole compound substituted with an aryl group, a <-thiazolidone compound, a benzophenone compound, a katara acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used.

Specific examples of ultraviolet absorbers can be found in U.S. Patent J,! 33゜79ψ
No. 3I3/ψ, 72φ, No. 3,3!2.61/No., JP-A No. 2711A, U.S. Patent J, 701.1
0! No. J, 707, 37! No., same ψ, 01Aj, 2
No. 2, J, 700. ψ! ! No. 3,4t 7,7
≦No. 2, German Patent Application Publication i, rψ7. It is described in ♂z issue 3 etc.

Filter dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, citanine dyes) and azo dyes. In order to reduce residual color after development, dyes that are water-soluble or decolorized by alkali or mutual sulfate ions are preferred.

Specifically, for example, pyrazolone oxonol dyes described in U.S. Pat. No. 2.27'A, 7r2, U.S. Pat.
the law of nature! t, 179, and the diarylazo dyes described in U.S. Pat. styryl dyes and butadienyl dyes described in ψ23,207, ψg3,31←, ψr7; ! Melon anine dye described in US Pat.
ur4t, No. Mg2,7/r, merocyanine dyes and oquinol dyes described in U72, US Patent No. 3.27
6゜Enaminohemioxonol dyes described in JJ/No. and British Patent No.! rφ, isori number, same number 1. /77.
No. 12, JP-A No. 141-11130, same ψ Tata 9
t20, φφ10, U.S. Patent No. 2. !
33, 1A72, same no. j, /ur.

No. 117, H3, /77, o7r, No. 3゜244
7.127, same No. J, J-IA0,117, same No. f,
3. #7! , No. 70u, No. 3,613. Ta Oj,
The dye described in is used.

For each dye, use a suitable solvent [e.g. water, alcohol (e.g. methanol, ethanol, propanol, etc.), acetone,
methyl cellosolve, etc., or a mixed solvent thereof] and added to the non-photosensitive hydrophilic colloid layer suspension coating solution of the present invention.

The specific amount of dye used per month is generally 10 S'/m2
~177m2, especially / 0-35' 77712~0
.

Preferred amounts can be found in the range from j 9 / to 2.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer and other water-competitive colloid layers.

For example, chromium salts and aldehydes.

(formaldehyde, geltaraldehyde, etc.), N
- Methylol compounds (such as dimethylol urea), active vinyl compounds (/, J, r-triacryloyl-hexahydro-5-triazine, /, J-vinylsulfonyl-2
-propanolnato), active halogen compound 'Fk (2
, ψ-dichloro-6-hydroki'y-s-) riazine, etc.), mucono-rogenic acids, etc. alone! or in combination.

Photographic emulsion layer of light-sensitive material made using the present invention! or other water-competitive colloid layers, coating aids, antistatic properties, smoothness improvement, emulsification dispersion, 9N prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization. In particular, the surfactant that is used favorably in terms of non-invention is Tokukosho! ! - Polyalkylene oxides in which the molecule i≦OO or more is described in Japanese Patent No. φ12. When used as an antistatic agent, a fluorine-containing surfactant (see US Pat. No. 4!
20/, No. 114, JP-A-Sho+or.

No. 1419, same! Day 7ψ! ! ψ) is particularly cunning.

The photographic light-sensitive material of the invention can contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other colloid layers for the purpose of preventing adhesion.

The photographic emulsion of the present invention has improved dimensional stability, etc., and is water insoluble! or a dispersion of a turf-soluble synthetic polymer. For example, alkyl (meth) acrylate, alkoxy acrylic (meth) acrylate, glycidyl (meth) acrylate, etc. alone or in combination! Polymers containing a combination of these and acrylic acid, methacrylic acid, etc. as molding components can be used.

It is preferable that the silver halide emulsion layer and the other layer of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of compounds having acid groups include polymers or copolymers having repeating units of organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid. Regarding these compounds, %Kansho≦0-Bubu/7ri No., same to-
trr No. 73, tO-/13rjt, and tO-
/9! T! You can refer to the description in the specification. Among these compounds, particularly preferred are ascorbic acid as a low-molecular compound, and acid monomers such as acrylic acid and crosslinkable compounds having two or more unplated groups such as divinylbenzene as high-molecular compounds. It is a water-dispersible latex of copolymers made of monomers.

In order to obtain custom-made ultra-high-contrast, high-sensitivity photographs using the halogenated @photosensitive material of the present invention, it is necessary to use the conventional contagious image liquid or US Patent No. 2.4L19. Ri7! It is not necessary to use a high alkaline developer close to the pHIJ described in the above issue, and a stable developer can be used.

In other words, the uninvented silver halide dairy material contains sulfite ions as a preservative at O1/! Contains mol/1 or more, p
H10,r~/2.3, especially l) H//, 0-/2,0
A sufficiently high contrast negative image can be obtained using this developer.

The developing agent used in the developer used in the present invention is not particularly limited by photography, but it is preferable to include dihydroxybenzenes, since it is easy to obtain good halftone dot quality, and dihydroxybenzene a/- Some names use a combination of phenyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols. The developing agent is usually o, o
r mol/l-0. Preferably, it is used in an amount of t mol/l. ! dihydroxybenzene /-722-3
- When using a combination with pyrazolidones or p-amino-phenols, the former is 0.0! Mol/l~o,r
mol/711 The latter is preferably used in an amount of not more than o, at mol/j.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, meta-X strained potassium sulfate,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.4 L mol/1 or more, particularly 0.5 mol/1 or more.

In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
Compounds described in No. 4,347 can be used. JP-A-61-2677 as a dissolution aid added to the developer
Compounds described in No. 59 can be used. Furthermore, as a pH buffering agent for use in developing solutions, JP-A-60-93,43
Compounds described in No. 3 or JP-A-62-186259
Compounds described in this issue can be used.

-i The compounds represented by the formula (1) and the general formula (3) can be used in high contrast sensitive materials in combination with negative emulsions as described above, and can also be used in combination with internal latent image type silver halide emulsions. It is possible, but the BH will be described below. In this case, the compound represented by the -S formula (1) and the general formula (3) is preferably contained in the internal latent image type silver halide emulsion layer, but the hydrophilic compound adjacent to the internal latent image type silver halide emulsion layer is The nucleating agent may be included in the sexual colloid layer, but such layers, such as coloring material layers, intermediate layers, filter layers, protective layers, and anti-halation 957 layers, cannot prevent the nucleating agent from diffusing into the silver halide grains. The layer may have any function as long as it has the same function.

The content of the compounds represented by formulas (1) and (3) in the layer depends on the characteristics of the silver halide emulsion used;
Depending on the chemical structure of the nucleating agent and the development conditions, the appropriate content can vary over a wide range, but the appropriate content of the nucleating agent in the internal latent image type silver halide emulsion! ! Approximately 0.005 per mole
A range of from 1 to 500 mg is practically useful, and preferably from about 0.01 mg to about 100 mg per mole of silver. Regarding the definition of an internal latent image type silver halide emulsion, in which the same amount of silver as above is contained in the same area of the layer, see JP-A-61-170733.
Publication No. 10 page 1 and British Patent No. 2,089,057
It is described on pages 18 to 20 of the publication.

Preferred internal latent image emulsions that can be used in the present invention include:
JP-A-63-108336 specification No. 2 from page lψ line ~
Favorable non-logenated particles are described on page 3, line 2 of the same specification, page 31, line 3 to page 32, line 2.

The internal latent image emulsion of the light-sensitive material of the present invention uses a sensitizing dye to produce relatively long-wavelength blue, green, and red light! Alternatively, it may be spectrally sensitized to infrared light. Examples of fI-enhancing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. . These sensitizing dyes include, for example, JP-A-Sho! 7-ao, t3 number, same jr9-140. Tit issue and the same! Cyanine dyes and merocyanine dyes described in No. 9-31, 7j5' are included.

The light-sensitive material of the present invention may contain a color image-forming coupler as a coloring material. Alternatively, twin imaging can be achieved using a developer containing a color image-forming coupler.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention can be found in Research Disclosure CFLD) t7tt, t3 (iq7r/February) -
It is described in the patents cited in Section D F. and Iry/y (17/17).

A coupler in which the coloring dye has appropriate diffusivity, a non-coloring coupler! Alternatively, DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected type azila heptamide coupler.

In the present invention, it is preferable to use a two-equivalent yellow coupler, and typical examples include an oxygen atom elimination type yellow coupler or a nitrogen atom elimination type yellow coupler. The α-pi・ζroyl-7-anito-IJ do coupler has excellent color fastness, especially light fastness, while α-
Benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected type, indacylon type or cyanoacetyl type! Examples include pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles. A certain pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group in view of the hue of the coloring dye and the torsion point of coloring.

Two equivalents! -U.S. Patent No. ψ,! as a leaving group for pyrazolone couplers! 10. The nitrogen atom detachment type case described in No. 6/9 or the US patent fable φ, 3! /.

The arylthio group described in No. 127 is particularly suitable.

It also has a ballast group as described in European Patents G7J and 4JG! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, US patent 'tE
Pyrazolo (r, 1-c) (/, 2.a) described in No. 3,72!, Obu No. 7; ) Triazoles, Research Disclosure 2ψ, 2
Pyrazolotetrazoles and Research Disclosure xix3o (LTPR)
Examples include the pyrazolopyrazoles described in tprψ, 2010). The imidazo C' + 2- b) pyrazoles described in European Patent No. 1/2, 7ψ/ are preferable in terms of low yellow side absorption of coloring dyes) and light fastness; Pyrazolo (/) described in No. 140.

J-bl(:/, ko, ψ) triazole is particularly cunning.

Cyan couplers that can be used in the present invention include oil-protected naphthol group) and phenolic couplers, such as U.S. Patent Houkiko, 4!7ψ.

The 7-tall coupler described in No. 2-3, preferably US Pat.

/ψt, jet issue, dotomiψ, Koi! Typical examples include two-equivalent naphthol couplers of the oxygen atom dissociation type described in No. 233) and No. 296,200. Further, specific examples of phenolic couplers are shown in U.S. Pat.
, 3rd, 5F2, same No., , Z, fO/, 171, same No. 2,772. /No. 61, No. 2. I? ! , No. 12, etc. Humidity and temperature robust cyan couplers are utilized in the present invention and are typically described in U.S. Pat. No. 3,772. 2. Phenolic cyan coupler containing an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in No. oo2. ! −
It has a diacylamino-substituted phenolic cabbage and a phenylureido group at the 2-position and! These include phenolic couplers having an acylamino group at the - position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta (magenta) and cyan couplers, it is wise to use a colored coupler together with color sensitive materials for photography.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in US Pat. No. ψ, J4J.

No. 137 and British Patent No. 2. /2! ,! Specific examples of magenta couplers are given in European Patent No. 70, 170
No. 3, 23ψ.

No. 133 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the above-mentioned special couplers may form dimers or higher polymers. A typical example of a polymerized dye-forming coupler is U.S. Patent G3+ 4161.
．． No. 120 button and No. xi, oro.

It is described in issue 2//. Specific examples of polymerized magenta couplers are disclosed in National Patent No. 2,102. /73) and U.S. Patent H1,t, Jt7. , No. 212.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the customization required for photosensitive materials. It can also be introduced into

Typical amounts of color couplers used range from Ho, ooi to 1 mole per 7 moles of photosensitive silver halide, and for yellow couplers, the typical amount ranges from o, oi to 0.
0.01 mole, and 0.003 to 0.01 mole for magenta couplers.
3 moles, and cyan couplers o, oox to 0.
It is 3 moles.

In the present invention, developing agents such as hydroxybe/zenes (eg, hydroquinones), aminophenols, 3-pyrazolidones, etc. may be contained in the emulsion or the light-sensitive material.

The photographic emulsion used in the present invention can be prepared in combination with a dye image-providing compound (C colorant) for color mineral transfer processes which releases a diffusible dye in response to the silver halide image. It can also be used to obtain a desired transferred image on the image-receiving layer after development. Many coloring materials are known for such color diffusion transfer methods, and among them, although they are initially non-diffusible, they undergo redox reactions with the oxidation products of the yuzoujikuri (or electron transfer agent). It is preferable to use a type of coloring material (hereinafter abbreviated as a DRR compound) that is cleaved by the dye to release a diffusible dye. Among them, N-(D having a sulfamoyl group)
The RR compound is cunning. In particular, the US patent confectionery tA, orr, 1. L2
E issue, same! , 013. J/2, same ψ, JJt, 322
DRR compounds having an 0-hydroxyarylsulfamoyl group such as those described in JP-A-Sho! 3-/
←Ri.

It is a DRR compound having a redox core as described in No. 321. When used in combination with such an RR compound, the degree dependence during treatment is particularly small.

Specific examples of DRR compounds include those listed in the above patent specifications, as well as magenta dye image-forming substances such as /
-Hydroxy-1-tetramethylenesulfamoyl-φ
−[3“′-Methyl−ψ′−(2”−Hydroxy−φ“
-Methyl-! “-hexatecyloxyphenylsul7-amoyl)-phenylazotunaphthalene, as a yellow dye image-forming substance /-phenyl-3-cyano-ψ-(
ko″≠“′-di-tert-pentylphenoxyacetamino)-phenylsulfamoyl]phenylaso)-
! - Examples include pyrazolone.

Details of color couplers that can be preferably used in the present invention are described on page 33, line lr to page ψO, end line of the same specification.

After imagewise exposure using the light-sensitive material of the present invention, after or during oxidation treatment with light or a nucleating agent, an aromatic primary amine color developing agent is added to pH//! It is preferable to form a direct positive color image by color development, bleaching and fixing treatment using the following surface developing solution. The pH of this Yuzo liquid is ii.

More preferably, it is in the range of O to io, o.

The fogging process used in the present invention is the so-called "light fogging method".
Either of the method of subjecting the photosensitive layer to continuous light exposure, called the "chemical Kabushi method", or the method of attenuating image processing in the presence of a nucleating agent, called the "chemical Kabushi method", may be used. Development may be carried out in the presence of a nucleating agent and fog light. Alternatively, a light-sensitive material containing a nucleating agent may be subjected to overlapping exposure.

Regarding the Hikari Kabushi method, the above-mentioned %Gan 67-1!371
Issue specification calculation ψ7 page ψ line ~ ψ page! Regarding the nucleating agent that can be used in the present invention, please refer to page z of the same specification.
line to page 67, especially the general formula CN-/
) and CN-x) are recommended.

Specific examples of these are given in the same specification No.! CN-1-/] to (:N-l-10] described on page 2-2 and (N4-/) to CN-I[-12 described on pages 63 to 66 of the same specification.
] is preferred.

Regarding the nucleation promoter included in the present invention, see the same specification No. 6.
It is described in page r, line 1 to page 7, line 3, and as a specific example, (A-/) to page 6 of the same page to page 70 are described.
The use of (A-/j) is preferred.

The color developing solution used in the development of the light-sensitive material of the present invention is described in the same specification, page 77, line ψ to page 72, especially for aromatic primary amine color developing solutions. As a specific example of the drug, p-phenylenediamine compounds are preferred, and representative examples thereof include 3-methyl-ψ-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 3-methyl-← -Ami/-N-Ethyl-N
-Cβ-hydroxyethyl)aniline, j-meru-k-amino-N-ethyl-N-methoxyethylaniline, and salts thereof such as sulfates and hydrochlorides.

In order to form a positive color image using the color diffusion transfer method using the light-sensitive material of the present invention, in addition to the amber color development described above, a black and white developer such as a funinidone derivative can also be used.

After color development, the photographic emulsion layer is usually bleached.

The bleaching treatment may be carried out simultaneously with the fixing treatment in a single bath bleach-fixing process, or may be carried out separately. Furthermore, in order to speed up the processing, a method may be employed in which bleaching is carried out after heat treatment, followed by bleaching and fixing, or a method in which bleaching and fixing are carried out after fixing. An aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or bleach-fixing solution of the present invention. Additives used in the bleaching solution or bleach-fixing solution of the present invention include those described in Japanese Patent Application No. Sho A/-3244J2, pages 11 to 3.
A variety of compounds described on page 0 can be used. After the demolding process (bleach-fixing or constant N), treatments such as water washing and/or stabilization are performed. It is a trick to use water that has undergone water softening treatment for the washing water or stabilizing liquid, and the b0 water softening treatment method is special @ShoA/-1Je&! Examples include a method using an ion exchange resin or a reverse osmosis device described in the specification of No. 2. These specific methods are described in the patent application 1986.
It is preferable to carry out the method described in Japanese Patent No.-131612.

Further, as additives used in the water washing and stabilization steps, various compounds described in Japanese Patent Application No. 47-324 LA2, pages 3θ to 36 can be used.

It is preferable that the amount of optic liquid in each treatment step be small. The amount of liquid to be filled is preferably o, 1-to times the amount of pre-bath carried in (per unit area of the photosensitive material), and more preferably 3 times.
~30 times.

Example 1 (Preparation of photosensitive emulsion) 4×10 mol of silver per mole of silver was added to an aqueous gelatin solution kept at 50°C.
In the presence of -' moles of potassium iridium hexachloride (IIF) and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added for 60 minutes, during which p,
By keeping Ag at 7.8, the average particle size is 0.2
8. A cubic monodisperse emulsion having an average silver iodide content of 0.3 mol % was prepared. This emulsion was desalted by the flocculesigon method, and after that, 40 g of inert gelatin per mole of silver was added and kept at 50°C, and 5
'-Dichloro-9-ethyl-3,3'-bis(3-sulfobrovir)oxacarbocyanine was added to a 10@-3 mole of Kl/silver solution and allowed to warm for 15 minutes.

(Coating of photosensitive emulsion layer) This emulsion was redissolved and the following hydrazine derivative was added at 40'C to form CHz=CH5OzCHzCHCHtS (hcH=CH
2.0 wt% based on gelatin (coating of protective layer) On top of this, as a protective layer, 1.5 g/rrr of gelatin and 0.0 wt% of polymethyl methacrylate particles (average particle size 2.5 μ)
3 g/nf was applied using the following surfactants.

Furthermore, the redox compounds shown in Table 1 were added, and 5-methylbenztriazole, 4-hydroxy 1.3.3a,
7-chitrazaindene and 30 wt for gelatin
% of polyethyl acrylate and the following compound as a gelatin hardening agent to give a silver amount of 3.8 g/rrf on a polyethylene terephthalate film (150μ) having an undercoat layer (0°5μ) made of vinylidene chloride copolymer. It was coated like this.

CHzCOOCJ+I CHCOOC6Hls 03Na Can +? C31 (performance evaluation) to 5OtNcHzcOo These samples were exposed to an optical wedge and a contact screen (Fuji Film, 1
After exposure at a rate of 37 .mu./rr1 2.5 .mu./rTf through a 50 L chain dot type), the film was developed with the developer shown in Table 2 for 34 DEG C. 3 o seconds, fixed, washed with water, and dried.

Table 3 shows the measurement results of the halftone dot quality and halftone gradation of the obtained sample. The halftone gradation is expressed by the following formula.

(G): Concentration 0. This is the slope of the straight line connecting the points 3 and 3.0. The larger the value, the higher the contrast.

Table 1 Halftone quality was visually evaluated on a five-level scale. The 5-level evaluation is
"5" indicates the best quality, and rl indicates the worst quality. As halftone dot original plates for plate making, "5" and "4" are practical, and "5" and "4" are practical.
5J is the practical limit level, r2. , "1" is of impractical quality.

The results are shown in Table 1.

From Table 3, it can be seen that the examples of the present invention are excellent in all aspects of high contrast, halftone gradation, and halftone dot quality.

Example 2 5.0X per mole of silver in an aqueous gelatin solution kept at 50°C
After simultaneously mixing an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of IO-' moles of (liH,) 2-Methyl-4-hydroxy-1,3,3a,7-titraazaindene was added as a stabilizer without ripening. This emulsion was a cubic monodisperse emulsion with an average grain size of 0.15 microns.

To this emulsion was added the following hydrazine compound, 49 μ/po, and the redox compound of the present invention shown in Table 4, and 30 wt % of polyethyl acrylate latex based on gelatin was added as a hardening agent. .3-vinylsulfonyl-2-propanol was added and coated on a polyester support to give an Ag amount of 3.8 g/bo. The gelatin content was 1.8 g/rd. On top of this, 1.5g 10f of gelatin was added as a protective layer, and 0.3g/0.3g of polymethyl methacrylate particles (average particle size 2.5μ) were added as a matting agent.
Then, a protective layer containing the following surfactant, stabilizer, and ultraviolet absorbing dye as coating aids was coated and dried.

Surfactant CH1COOC&)+13 CHCOOC&+(+s 03Na C,H,,SO□NCHzcOOK C3H? 37■/rrf 2.5■/Pot stabilizer Thioctic acid 2,1■/Bo Ultraviolet absorbing dye 5OzN (C411Jz 100■/Po In this sample, Dainippon Screen Seimei-shitsu Printer P
-607, image exposure was carried out through the original as shown in FIG. 1, and the image was developed at 38° C. for 20 seconds, fixed, washed with water, and dried. After that, the cutout character image quality was evaluated.

The developing solutions were the same as in Example 1, the comparative developing solution and the developing solutions I~■
was used.

Extracted character image quality 5 means that characters with a width of 30 μm are reproduced when a document as shown in Figure 1 is used and exposed appropriately so that 50% of the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return. In terms of image quality, the image quality is very good. -Excellent character image quality 1
is an image quality that can only reproduce characters with a width of 150 μm or more when given the same appropriate exposure, and is considered poor character extraction quality, and is ranked between 5 and 1 with a sensory evaluation of 4 to 2. A score of 3 or higher is a practical level.

The results are shown in Table 4. It can be seen that the image quality is significantly superior when the photosensitive material and developer of the present invention are used.

[Brief explanation of drawings]

FIG. 1 shows the configuration at the time of exposure in the case of forming a high-quality cut-out character image by repeating overlapping, and each symbol indicates the following. (B) Transparent or semi-transparent pasting base (B) Line drawing original (black areas indicate line drawings) (C) Transparent or semi-transparent pasting base (2) Halftone dot original (black areas indicate line drawings) (N) Photosensitive material for use (the shaded area indicates the photosensitive layer)

Claims (4)

[Claims] (1) A method of developing an exposed silver halide photographic material to form an image, in which the photographic material releases a compound represented by the following general formula (1) and a development inhibitor upon oxidation. 1. An image forming method comprising at least one type of redox compound and a nucleating development accelerator in the development processing solution. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic group or an aromatic group, and R_
2 represents a hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, amino group, carbamoyl group, or oxycarbonyl group, G_1 represents a carbonyl group, sulfonyl group, sulfoxy group, ▲ Numerical formula, chemical formula, table, etc. ▼ group or iminomethylene group, A_1,
Both A_2 represent a hydrogen atom, one of which is a hydrogen atom, and the other of which is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. (2) The image forming method according to claim (1), wherein the nucleating development accelerator is represented by the following general formula (2). General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_2_1, R_2_2, and R_2_3 are the logarithm (logP) of the n-octanol/water partition coefficient as H-R_2_1, H-R_2_2, and H-R_2_3, respectively.
represents a substituted or unsubstituted alkyl group in which the sum of the values is in the range of 2.6 or more and less than 10.0. (3) The redox compound has the following general formula (R-1), (R
The silver halide photographic material according to claim 1, which is at least one compound selected from the compounds represented by -2) and (R-3). General formula (R-1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (R-2) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (R-3) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In these formulas, R^1 represents an aliphatic group or an aromatic group ▲ Numerical formulas, chemical formulas, tables, etc. are available. G_1 has ▲mathematical formulas, chemical formulas, tables, etc.▼
There are groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, -SO- groups, -SO_2- groups, or ▲ mathematical formulas , chemical formula, table, etc. ▼ Represents a group. G
_2 represents a simple bond, -O-, -S-, or ▲a numerical formula, chemical formula, table, etc.▼, and R_2 represents a hydrogen atom or R_1. A_1 and A_2 represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, and may be substituted. In general formula (R-1), at least one of A_1 and A_2 is a hydrogen atom. A_3 has the same meaning as A_1 or represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼. A_4 represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G_1-G_2-R_1. Time represents a divalent linking group, and t represents 0 or 1. PUG stands for development inhibitor. (4) The image forming method according to claim (1), wherein the redox compound capable of releasing a development inhibitor upon oxidation is represented by the following general formula (R-1). General formula (R-1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, A_1, A_2, G_1 are general formula (1)
Synonymous with. Time represents a divalent linking group, and t represents 0 or 1. PUG stands for development inhibitor.