JPS63183438A - Negative type silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an extra high contrast negative type photographic sensitive material for daylight having high covering power by incorporating silver halide (AgX) of a specified average particle size and a specified amt. of a rhodium salt into an AgX emulsion layer on a supporting body. CONSTITUTION:AgX is <=0.15mum average particle size and a rhodium salt are incorporated into at least one AgX emulsion layer formed on a supporting body. The amt. of the rhodium salt is 10<-5>-5X10<-4>mol. per 1mol. Ag. A hydrazine deriv. is preferably incorporated into the emulsion layer and/or a layer adjacent to the emulsion layer. By this structure, the contrast is increased and the sensitivity can be lowered without lowering the high contrast. The quality of white-on-black character is kept on a practically usable level with ensured safety to safelight. An extra high contrast negative type photographic sensitive material suitable for use as a daylight sensitive material is obtd. and used especially for a photomechanical process.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a halogen specific gravity photographic material and a method for forming ultra-high contrast negative images using the same, and in particular to a silver halide photographic material used in a photolithography process. The present invention relates to materials, and more specifically to ultra-high contrast negative photographic materials suitable for use in bright rooms.

(Prior art) In the field of graphic arts, in order to improve the reproduction of continuous tone images or line images using halftone images, photographic characteristics of ultra-high contrast (especially commas of 70 or more) are shown. An imaging system is required.

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde to keep the concentration of free sulfite ions extremely low (usually θ .

1 mol/l or less). Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

A method for obtaining high contrast photographic properties using a stable developer is disclosed in US Pat. No. '1. ．． 224t, 4t07 issue, same number, /! , No. 927, same No. G, /g Otsu, 74t
No. 2, No. 3, 3//, No. 77, No. 1, λ72,
6θ6, same No. g, co//, l'j No. 7, same No. 7,
．． There is a method using a hydrazine derivative described in No. 2173.739 and the like. According to this method, ultra-high contrast and high sensitivity photographic characteristics can be obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is lower than that of a lithium developer. This is a dramatic improvement compared to .

However, when creating ultra-high contrast images using these hydrazine compounds, there are problems such as a decrease in density and softening of gradation due to pH fluctuations due to processing fatigue and air fatigue, a decrease in developing agent, and accumulation of inhibitors. There is a strong desire for a means to promote high contrast with hydrazine, and phosphonium salt compounds are used in JP-A-4/-/, <7939; An amine compound is disclosed as a contrast enhancing agent in JP-A-60-/&θ3. However, even when these compounds are used, it is difficult to prevent softening during processing.

When trying to obtain a photosensitive material for bright room use with low sensitivity by partially using a hydrazine compound, for example, JP-A No. 60-303♂ and JP-A-60-0-/Otsu-2. ．． 2, discloses a silver halide photosensitive material containing a water-soluble rhodium salt. However, when a sufficient amount of rhodium is added to lower the sensitivity, the high contrast caused by the hydrazine compound is inhibited, and the desired sufficiently high contrast images cannot be obtained.

Also, Tokukai Akira! Tah/! 7. 33 contains a silver halide photograph containing a water-soluble rhodium salt in an amount of 6/θ-8 to/θ-5 mol per mol of silver halide and an organic desensitizer in which the sum of the anode potential and the cathode potential of a polarographic is positive. A method of making an emulsion is disclosed. However, although this method does lower the sensitivity, it is not possible to obtain a high-contrast image sufficient for use in the industrial field targeted by the present invention.

Also, Tokukai Akira! ≦−t2, . No. 24tj discloses a method of obtaining a high-contrast image by developing in the presence of a tetrazolium compound and suppressing development of the toe portion of the characteristic curve with the tetrazolium compound. However, silver halide photosensitive materials containing tetrazolium compounds deteriorate during storage, resulting in only soft-tone images being obtained, some reaction products from the development process of the tetrazolium compound may remain in the film, causing contamination, and development unevenness may occur. There are problems such as easy to occur.

As described above, in the high contrast method using a hydrazine compound, there is always a problem of soft contrast during running processing or when trying to obtain a low-sensitivity image using rhodium salts or organic desensitizers. occurred. It was extremely difficult to reduce the sensitivity of ultra-high contrast images using hydrazine compounds while maintaining the high contrast.

In addition, large amounts of hydrazine compounds are added to increase contrast, which weakens the strength of the emulsion film, worsens storage stability, and dissolves large amounts into the developer during thinning processing, resulting in other effects. It may affect the material.
A method of promoting high contrast using a small amount of hydrazine compound was also desired.

-Yo= As mentioned above, it is very difficult to use a hydrazine compound to reduce the sensitivity of a sensitive material that has been made high contrast while maintaining the high contrast. This is because hydrazine compounds are involved in the development process and cause nucleation and contagious development due to their electron donating properties to silver halide, resulting in high-contrast images.On the other hand, organic desensitizers and rhodium Inorganic desensitizers such as salts are photoelectron acceptors and act to reduce sensitivity by accepting photoelectrons during image exposure and preventing latent image formation. Sometimes, it also accepts electrons donated from an electron donor such as a hydrazine compound, which also prevents nucleation and contagious development, making it impossible to obtain high-contrast images. Therefore, there has been a strong desire for a method for reducing the sensitivity of high contrast photosensitive materials using hydrazine while maintaining the high contrast.

In addition, in the field of graphic arc return processes, in addition to sensitive materials with super-hard tones (more than guff θ), gamma is y~! A photosensitive material is used that exhibits photographic properties of a certain degree of gradation. During the adhesion return process, sensitive materials with such gradations have a super-hard feel due to peony holes caused by dust and blank areas called tape marks from the adhesive tape used to fix the original. Although it is smaller in size than wood, it has the disadvantage that it is inferior in sharpness of images such as letters and halftone dots. Practically speaking, it is necessary to maintain a certain degree of image sharpness, and for that purpose, the gamma must be set to 3! It needs to be around r-f. Furthermore, in order to handle it for use in a bright room, it is necessary to lower the sensitivity of the photosensitive material. Although it is possible to reduce the sensitivity by incorporating a rhodium salt into the silver rhodide grains,
A problem arises in that the gamma decreases and the image loses its sharpness. Further, when a dye is used to lower the sensitivity, there is a problem in that the irradiation prevention effect of the dye makes it difficult to adjust the tone and line width of the halftone image by adjusting the exposure amount.

Therefore, a method of reducing sensitivity without reducing gamma has been strongly desired.

The photosensitive material for reprinting is made by using a processed film as a manuscript and printing it with a Hg printer, or by using ultraviolet rays in the post-process.
Since it is printed onto a printing plate such as a printing plate, a high concentration of ultraviolet light is required, and conversely, there is a desire to reduce the amount of silver coated on the photosensitive material as much as possible in order to save resources. Therefore, there has been a strong desire for a method of obtaining high ultraviolet light density with a small amount of coated silver.

(Objective of the Invention) The first object of the present invention is to provide a means for promoting high contrast in a system using a rhodium salt or an organic desensitizer,
The second purpose is to create a system using a hydrazine compound.
The purpose of the present invention is to provide a means for promoting high contrast, and a third purpose is to provide a low-sensitivity photographic material for use in bright rooms.
The third objective is to provide a silver halide sensitive material with high covering power.

(Structure of the Invention) The above-mentioned object of the present invention is to provide a light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide in the emulsion layer has a grain size of O8/! μ or less and more than Q-5 mol of silodium salt per mol of silver,
! This was achieved by means of a negative-working silver halide photographic material characterized in that it contains less than 10-4 mol.

The average grain size of the silver halide used in the present invention is O
9/! Although it is less than μm, it is particularly preferable that O0θg~θ, 73 μm. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse here means at least 1% by weight or number of particles.
is composed of a group of particles whose size is within θ between the average particle size.

Average particle size Q used in the present invention, /! Methods for preparing silver halide with a particle size of less than μ include lowering the temperature during grain formation, adjusting the binder concentration, adjusting the addition rate and concentration of silver nitrate and halogen compounds, mercapto compounds, and azole compounds. Any method well known to those skilled in the art may be used, such as using compounds such as , imidazole compounds, triazole compounds, thiazole compounds, and azaindene compounds.

Silver halide grains in photographic emulsions may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
ular) crystals, or a composite form of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

Silver halogenide emulsions of two or more types formed separately may be mixed and used. The silver composition is preferably silver chloride or silver chlorobromide (Br/θ mol or less).

In the present invention, the average particle size is O0/! If it exceeds μm, the omission of fine lines will worsen as will be described later.

In particular, sensitive materials containing hydrazine derivatives have the disadvantage of softening gradations and deteriorating the quality of printed characters, as described below.

A rhodium salt is allowed to coexist in the silver halide emulsion of the present invention during the formation of silver halide grains or during the physical ripening process.

The rhodium salt used in the present invention may be any rhodium salt that can be incorporated into silver halide grains, such as rhodium chloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, etc., but preferably A water-soluble trivalent rhodium halide complex compound, such as hexachlororhodic (I) acid or a salt thereof (ammonium salt, sodium salt, potassium salt, etc.).

The amount of rhodium salt used in the present invention is equivalent to 1 mole of silver! 11
More than 10-5 moles (slightly more than r x 10-4 moles.

! If an amount exceeding 10@-4 mol is used, line omission becomes worse as will be described later. In particular, when used in hydrazine-containing photosensitive materials, there is a drawback that the sensitivity decreases too sharply, as will be described later.

On the other hand, if an amount less than /θ-5 is used, there will be noticeable defects such as image edges as described below, and furthermore, in the case of hydrazine-containing photosensitive materials, there will be a disadvantage that the desired low sensitivity cannot be achieved.

In the present invention, together with rhodium salt, cadmium salt,
Lead salts, thallium salts, and iridium salts can also be used in combination.

The present invention is O1/! It is characterized by using rhodium salt in an amount of more than 10-5 mol and less than 10-4 mol in an emulsion having a grain size of μm or less. The effect is especially great on wood.

The hydrazine derivative used in the present invention is preferably one represented by the following general formula (1).

General formula (1) % formula % In the formula, A represents an aliphatic group or an aromatic group, and B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or an aryl group. represents an oxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfaniyl group, or a heterocyclic group, where X and Y are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group. group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

However, B, Y, and the nitrogen atom to which they are bonded may form a hydrazone partial structure -N=(:.

Next, general formula (1) K will be explained in detail.

In the general formula (1), the aliphatic group represented by A preferably has carbon atoms/~3θ, particularly carbon atoms/~3θ.
is a straight chain, branched or cyclic alkyl group of θ. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. -! The alkyl group of the octopus may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

For example, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group,
Examples include a tetrahydrofuryl group and a morpholino group.

The aromatic group represented by A in general formula (I) 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, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Among the isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc., those containing a benzene ring are preferred.

Particularly preferred as A is an aryl group.

The aryl group or unsaturated heterocyclic group of A may have a substituent. Typical substituents include straight-chain, branched or cyclic alkyl groups (preferably those with a carbon number of ~20), aralkyl groups (preferably monocyclic or bicyclic alkyl groups with a carbon number of ~3). ), alkoxy groups (
Preferably carbon number is 7 or more. 20), substituted amine groups (
(preferably an amine group substituted with an alkyl group having a carbon number of 2 to 20), an acylamino group (preferably a carbon number of 2 to 3
Examples include those having 0), sulfonamide groups (preferably those having carbon numbers of 1 to 3Q), and ureido groups (preferably those having 1 to 30 carbon atoms).

A in the general formula (I) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group that has two or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. be able to.

A in the general formula (1) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc. as described in US Patent Nos. &, 3r! ' , /θza issue, same gu, gu!
? , 3 Gua, Tokukaisho! 2-/rij, No. 233, 69
-200.23/issue, same! ? -20/, 0g! Same issue!
Turco θ/, 0ri No. 5, same! 9-2θ/, 0g No. 2, same! 2~ko07, O Rito issue, same! Turco θ/, 0 geta issue,
Special application 1986-3 &, 7J'♂ issue, same Otsu θ-//4t! Examples thereof include groups described in No. 1, 6θ-/9732, and the like.

B specifically represents a formyl group, an acyl group (acetyl group,
propionyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, cuchlorobenzoyl group, pyruvoyl group, methoxalyl group, methyloxamoyl group, etc.)
, alkylsulfonyl groups (methanesulfonyl group, cochloroethanesulfonyl group, etc.), arylsulfonyl groups (
benzenesulfonyl group, etc.), alkylsulfinyl group (
Methanesulfinyl group 'J-), arylsulfinyl group (benzenesulfinyl group, etc.), carbamoyl group (methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (dimethylsulfamoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, methoxyethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), sulfinamoyl group (methylsulfinamoyl group, etc.), alkoxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, etc.)
, represents a thioacyl group (such as a methylthiocarbonyl group), a thiocarbamoyl group (such as a methylthiocarbamoyl group), or a heterocyclic group (such as a pyridine ring).

Particularly preferred as B is a formyl group or an acyl group.

In the general formula (1), B together with Y and the nitrogen atom to which they are bonded represents a hydrazone partial structure. In the above, Y2 represents an alkyl group, an aryl group, or a heterocyclic group. Y2 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

and
phenylsulfonyl group substituted with 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 10,! or more, or a linear, branched, or cyclic unsubstituted and Substituted aliphatic acyl group (substituted groups include, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group)) X and Y are most preferably hydrogen atoms.

Specific examples of the compound represented by general formula (I) are shown below.

However, the present invention is not limited to the following compounds.

■-1) ■-2) ■-3) I-<') -/,! ? - ■-ri1-, <) ■-2) ■-♂) CH2CH2CH25H 1-/θ) ■-/1) I-/3) 1-/g) 1-/<) I-/1) One piece /- ■-27) 1-J1) 1-,? O) ■-37) In addition to the above-mentioned hydrazine derivatives used in the present invention, RESERCHDISCLO8UREIt
emJjJ-/J (/973//month issue, P, 3k 2
) and the literature cited therein, as well as U.S. patents Gu, C#
0.207, same, 24, 929, same, 9.2
73.36y issue, same da, 22 and 2y♂ issue, same gu, 3
j”!, /θi No., same g, ri j9゜34t7, same g, tto, go No. 31, same, 4t7♂, No. 92!, British patent co, θ//, 39/B.

Those described in Japanese Patent Application Laid-Open No. 797341 can be used.

The compound represented by formula (I) is preferably contained in an amount of /X/(17-6 mol to !x10-2 mol, particularly /x/θ-5 mol to 2 mol per mol of silver halide).
A preferable addition amount is in the range of x10'-2 moles.

In the present invention, when a compound represented by the following general formula (II) or (I[I) is used in combination with a hydrazine derivative represented by the general formula (I), high contrast is promoted, and a decrease in gradation due to a decrease in sensitivity is prevented. Therefore, it is preferable.

General formula (II) (wherein, Y represents a group that adsorbs to silver halide. Represents a linking group. A represents a divalent linking group. B represents an amine group, an ammonium group and a nitrogen-containing heterocycle, and the amine group may be substituted. m represents /, 2 or 3; ,n
represents O or /. ) The group represented by Y that adsorbs to silver halide includes nitrogen-containing heterocyclic compounds.

When Y represents a nitrogen-containing heterocyclic compound, the general formula (ff)
The compound is represented by the following general formula (If-8).

General formula (II-a) In the formula, l represents θ or /, m represents /, 2 or 3, and n represents 0 or /.

(-(X return A-B'm has the same meaning as that in the general formula (If) above, and Q is a j or 6-membered atom consisting of at least one type of carbon atom, nitrogen atom, oxygen atom, or sulfur atom) Represents the atomic group necessary to form a heterocycle.This heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle formed by Q include substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, tri26=azoles, Tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines,
Examples include pyridines and quinolines.

M is a hydrogen atom, an alkali metal atom (e.g., sodium atom, potassium atom, etc.), an ammonium group (e.g., trimethylammonium group, dimethylbenzylammonium group, etc.), or a group that becomes M, =H or an alkali metal atom under alkaline conditions. It represents a diluent group (eg, acetyl group, cyanethyl group, methanesulfonylethyl group, etc.).

In addition, these heterocycles include a nitro group, a halogen atom (e.g., chlorine atom, bromine atom, etc.), a mercapto group, a cyan group, a substituted or unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group, a t- butyl group, cyanoethyl group, methoxyether group, methylthioethyl group, etc.), aryl group (e.g. phenyl group, goomethanesulfonamidophenyl L &-methylphenyl group, 3.<
t-dichlorophenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. evabenzyl group, goomethylbenzyl group, phenethyl group, etc.)
, alkoxy group (e.g. methoxy group, ethoxy group, etc.)
, aryloxy groups (e.g. phenoxy group, gumethoxyphenoxy group, etc.), alkylthio groups (e.g. methylthio group, ethylthio group, methoxyethylthio group), arylthio groups (e.g. phenylthio group), sulfonyl groups (
Examples Evamethanesulfonyl group, ethanesulfonyl group, p-
) luenesulfonyl group, etc.), carbamoyl group (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl L, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.) , carbonamide group (e.g. acetamide group, benzamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide L p-toluenesulfonamide group, etc.),
Acyloxy group (e.g. acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g. methanesulfonyloxy group, etc.), ureido group (e.g. unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.), thioureido groups (e.g. unsubstituted thioureido group, methylthioureido group, etc.), acyl groups (e.g. acetyl group, benzoyl group, etc.), heterocyclic groups (e.g. /-morpholino group, /-piperidino group,
Cobiridyl group, goupyridyl group, 2-chenyl group, /
-pyrazolyl group, /-imidazolyl group, 2-tetrahydrofuryl group, tetrahydrochenyl group, etc.), oxycarbonyl group (e.g. methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (e.g. methoxycarbonyl group, etc.) amino group, phenoxycarbonylamino group, coethylhexyloxycarbonylamino group, etc.), amino group (e.g. unsubstituted amino group, dimethylamino group, methoxyethylamino group, anilino group, etc.)
, carboxylic acid or its salt, sulfonic acid or its salt,
It may be substituted with a hydroxy group or the like.

-,29- As the covalent linking group represented by methylethylene group, etc.). R1, R2, R3, R4, R5/R6, R7
・R8, R9 and RIO each represent a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group, propyl group, n-butyl group, etc.), a substituted or unsubstituted aryl group (e.g. phenyl group, - monomethylphenyl group, etc.), substituted or unsubstituted alkenyl groups (e.g. propenyl group, /-methylvinyl group, etc.), or substituted or unsubstituted aralkyl groups (e.g. benzyl group,
phenethyl group, etc.).

Ai; j, represents a z-valent linking group, and the divalent linking group is a linear or branched alkylene group (e.g. methylene group,
ethylene group, propylene group, butylene group, hexylene group, /-methylethylene group, etc.), straight-chain or branched alkenylene group (e.g. vinylene group, /-methylvinylene group, etc.), straight-chain or branched aralkylene group ( For example, benzylidene group, etc.), arylene group (for example, phenylene group, etc.),
naphthylene, etc.). In the above group represented by A, X and A may be further substituted in any combination.

The substituted or unsubstituted amine group of B is represented by the general formula (I[-b) (wherein, R11 and R112 may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted Number of carbons/~3
0 alkyl group, alkenyl group or aralkyl group, and these groups are linear (for example, methyl group, ethyl group,
n-propyl group, n-butyl group, n-octyl group, allyl group, 3-butenyl group, benzyl group, /-naphthylmethyl group, etc.), branched (e.g. isopropyl group, t-octyl group, etc.), or cyclic (e.g. cyclohexyl group,
etc.) is also acceptable.

Further, R11 and R12 may be connected to form a ring, and a saturated heterocycle containing seven or more heteroatoms (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.) Examples thereof include a pyrrolidyl group, a lysyl group, and a morpholino group. In addition, examples of substituents for R11 and R12 include carboxyl group, sulfo group, cyano group, noherogen i
(For example, fluorine, chlorine, and bromine atoms.)
, hydroxy group, alkoxycarbonyl group having 20 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group having 2θ or less carbon number (e.g. methoxy group, ethoxy group, benzyl group) oxy group, phenethyloxy group), monocyclic aryloxy group having 20 or less carbon atoms (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy group having 2Q or less carbon atoms (e.g. acetyloxy group, propionyloxy group) ), acyl groups with a carbon number of 2θ or less (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (
Examples, tJf carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, pyharidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, Piha + ) dinosulfonyl group, etc.), acylamino groups with a carbon number of 2θ or less -33= (e.g. acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide groups (ethylsulfonamide group, p
-) luenesulfonamide group, etc.), carbonamide groups with a carbon number of less than or equal to ), amine group (synonymous with general formula (I[-b))
Examples include.

The ammonium group of B is represented by the general formula (nc).

(In the formula, R, R, and R are the same groups as R11 and R12 in the above-mentioned general formula (II-b), and zo represents an anion, such as . θ, etc.), sulfonate ions (e.g. trifluoromethanesulfona),
Examples include paratoluenesulfonate, benzenesulfonate, parachlorobenzenesulfonate, etc.), sulfato ions (eg, ethylsulfate, methylsulfate, etc.), perchlorate, and tetrafluoroborate. p represents O or /, and is θ when the compound forms an inner salt. ) The nitrogen-containing heterocycle of B contained at least 7 or more nitrogen atoms! Alternatively, the ring may be a membered ring, and the ring may have a substituent or may be fused with another ring.

Examples of the nitrogen-containing heterocycle include an imidazolyl group, a pyridyl group, and a thiazolyl group.

Among the general formulas (I[), preferred are the following general formulas (It-m), (II-n), (II-0) or (
Examples include compounds represented by I[-p).

General formula (It-m) General formula (If-n) General formula (n-0) General formula (II-p) (wherein, +XqA-B, M, and m are the same as those of the above general formula (II) Zl, Z2 and Z3 have the same meaning as ÷X)-A-B in the general formula (II), or a halogen atom, an alkoxy group having 2θ or less carbon atoms (for example, a methoxy group), a hydroxy group, It represents a hydroxyamino group, a substituted or unsubstituted amine group, and its substituent can be selected from the substituents of R and H in the general formula (I[-b)]. However, at least one of Zl, Z2 and z3 has the same meaning as +X-A-B.

Further, these heterocycles may be substituted with substituents applicable to the heterocycle of general formula (II).

Next, examples of compounds represented by the general formula (If) will be shown, but the present invention is not limited thereto.

[-/ ■-2 I[-,3 ■-gJ [-j -3! - ■-za [-7 ■-♂ [-9 [-IO ■-// ■-72 ■-73 ]1-/ Gu ■-/! , h ■-/Otsuni ■-77 ■-ri / - ■-// 1[-/ri General formula (II[) In the formula, R1 and R2 each represent a hydrogen atom or an aliphatic residue.

R1 and R2 may be bonded to each other to form a ring.

R3 represents a divalent aliphatic group.

X represents a divalent heterocycle containing a nitrogen, oxygen or sulfur atom.

4t2-n represents O or /. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, or an amidino group.

The aliphatic residues of R1 and R2 each have carbon/~7.2
The alkyl group, alkenyl group and alkynyl group of are preferably each optionally substituted with a suitable group. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, dodecyl group, isopropyl group, 5ee-butyl group, and cyclohexyl group.

Examples of the alkenyl group include allyl group, -1-butenyl group, cohexenyl group, and -1-octynyl group. Examples of the alkyl group include propargyl group and cobentinyl group. Substituents include phenyl group, alkoxy group, alkylthio group, hydroxy group, carboxyl group, sulfo group, alkylamino group, and amide group.

When R1 and R2 form a ring, it is composed of carbon or a combination of nitrogen and oxygen! A membered or di-membered carbocyclic ring or a heterocyclic ring, with saturated rings being particularly preferred.

Particularly preferred as R and R is an alkyl group having up to 3 carbon atoms, and more preferably an ethyl group.

The divalent aliphatic group for R3 is -R4- or -R'S-
is preferred. Here, R4 is a divalent aliphatic residue, preferably a saturated or unsaturated residue having 7 to 7 carbon atoms, such as -
CH2-1-CH2CH2-1-(CH2)3-1-(
CH2)4-1-(CH2)6-1-CH2CH=CH
CH2-1-CH2C=:CCH2-5-CH2CH2
H2- etc.

CH3 R4 preferably has 2 to 3 carbon atoms, and R4 is more preferably -CH2CH2- and -CH2C
It is H2CH2. Note that R3 when n of (X)n is 0
represents only -R4-.

The heterocycle of X includes nitrogen, oxygen or sulfur! and may be fused to a benzene ring with a -membered heterocycle.

Preferable heterocycles include aromatic ones such as tetrazole, triazole, thiadiazole, oxadiazole, imidazole, thiazole, oxazole, benzimidazole, benzothiazole, and benzoxazole. Among these, tetrazole and thiadiazole are particularly preferred.

The alkali metals for M include Na%, K%+ There are Li, etc.

++ Examples of alkaline earth metals include Ca, Mg, etc.

Examples of the quaternary ammonium salt of M include carbon atoms having a carbon number of 7 to 30, such as (CH3)4N@, (C2H5)4
N, (C4H9)4N■, C6H3CH2NΦ(C
Ha)a, CtsH33NO(CH3)a1'.

As quaternary phosphonium salts, (C4H9)4P■, C
16H3P■(CH3)3, -G S-C6H5CH2P■(CHa), etc.

Examples of inorganic acid salts of the compound represented by formula (If) include hydrochloride, sulfate, and phosphate; organic acid salts include acetate, propionate, methanesulfonate, and benzenesulfonic acid. salt, p-toluenesulfonate, etc.

Specific examples of the compound represented by the general formula (n[) are listed below.

■-/ ■-2 [[-3 ■-Goo Gu ni - lll-5 ■-6 lll-7 [1-/ (HOCH2CH2)2NCH2CH2SH[1-9 [1-/ θ ■-// ■-72 ■ -73 ■-/ri■-/yoSH [1-/go■-77 [1-/♂ ■-79 -ri 9- ■-27 The present invention is particularly applicable to photographic systems using organic desensitizers. It is valid.

The organic desensitizer used in the present invention preferably has at least seven water-soluble groups or alkali-dissociable groups. The present inventors have discovered for the first time that when these organic desensitizers are used in a high contrast sensitive material containing a hydrazine compound, the sensitivity can be effectively lowered without interfering with high contrast. Specific examples of the at least seven water-soluble groups present in such an organic desensitizer include sulfonic acid groups, carboxylic acid groups, and phosphonic acid groups, and these groups can be combined with organic bases (for example -!
(O- ammonia, pyridine, triethylamine, piperidine, morpholine, etc.) or an alkali metal (eg, sodium, potassium, etc.).

The alkali-dissociable group refers to the pH of the developing solution (usually pH 9 to
The pH is in the range of 73, but treatment solutions with pH other than this are also acceptable. ) or below, a substituent that undergoes a deprotonation reaction and becomes anionic. Specifically, at least 7 hydrogen atoms are bonded to a nitrogen atom by a substituent such as a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbamoyl group, a sulfonamide group, an acylamino group, or a substituted or unsubstituted ureido group. Refers to substituents and hydroxy groups that are present.

Further, a hetem group having a hydrogen atom on the nitrogen atom constituting the heterocycle of the nitrogen-containing heterocycle is also included in the alkali-dissociable group.

These water-soluble groups and alkali-dissociable groups may be connected to any part of the organic desensitizer, and more than one type may be present at the same time.

Preferred organic desensitizers used in the present invention are represented by the general formulas 1) to -Vl) listed above.

General Formula (IV) In the formula, zl represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and this ring may further have a substituent.

T is an alkyl group, cycloalkyl group, alkenyl group, halogen atom, cyan group, trifluoromethyl group, alkoxy group, aryloxy group, hydroxy group, alkoxycarbonyl group, carboxyl group, carbamoyl group, sulfamoyl group, aryl group, acylamino group, a sulfonamide group, a sulfo group, or a benzo-fused ring, which may further have a substituent.

q represents /, ko or 3; r represents O1/or 2;

General formula (V) In the formula, P and Q may be the same or different from each other, and include a cyan group, an acyl group, a thioacyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and a substituted or unsubstituted sulfamoyl group. , represents a substituted or unsubstituted carbamoyl group, a nitro group, or a substituted or unsubstituted aryl group.

n represents /, ko, and 3.

Ts 1% Q has the same meaning as explained in general formula NV).

In the general formula (M) j 3, Z2 is a ketomethylene ring, such as a pyrazolone ring, isoxacilone ring, oxindole ring, barbyl ring, thiobarbyl ring, rhodanine ring, imidazo [/
, 2-a] pyridone ring, -1thioco, cuoxazolidinedione ring, 2~thioco,! -thiazolidinedione ring, thiazolidone ring, 9-thiazolone ring, λ-iminoco, teroxacillinone fB, 2,4'-imidasylinedione ring (hydantoin ring), coachiohydantoin ring,! -Represents a group of nonmetallic atoms necessary to complete an imidacylon ring, etc.

m represents /, 2.3.

T%"%q has the same meaning as explained in general formula (It1).

The organic desensitizer in the present invention is contained in the silver chloride emulsion layer /, 0x70-8 to /, 0x10-4 mol/12, especially /, θx10-7 to /, 0x10-5 Preferably, it is present in an amount of mol/12.

Next, specific examples of compounds represented by general formulas (IV) to (M) are described below. However, this invention is the best! It is not limited to Gu et al.

(IV-1) (W-3) (N-4t) Ear (Ill'-1> (IV-, <) (IV-7) ■ (IV-,!') (IV-9) (■-/ θ) (■-/1) -yo 7- NV-/, 2) (N-/3) (IV-74t> NV-/l) 〇SZ- (■-/ni) (IV-/7) ( IV-/9) (IV-,20) (N-21) (IV-,2,2) (IV-,23) (V-1) (■-2) (V-,?) -Otsu / - (V-ri) (V,t) (■-go) (Vl-1) -go (M-,2) (■-j) (■-g) (Vl-!> (■-6) ( M-7) CH2CH20CCH 2CH20 CH3 (/1) The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Filter dyes include dyes to further reduce photographic sensitivity;
Preferably, a UV absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide or a substantial amount of light mainly in the 3101rn-600nm region to increase safety against safelight light when handled as a light-sensitive material. Dyes with absorption are used.

These dyes may be added to the emulsion layer depending on the purpose, or may be added to the upper part of the silver halide emulsion layer, that is, with respect to the support. - It is preferable to use it by adding it together with a mordant to the photosensitive hydrophilic colloid layer and fixing it.

It varies depending on the molar absorption coefficient of the ultraviolet absorber, but usually /θ
It is added in a range of -2g/m2 to /g/m2. Preferably it is 50 mg - 300 mg/m2.

The above ultraviolet absorber can be used in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, propatool, etc.)].
, acetone, methyl cellosolve, etc., or a mixed solvent thereof] and added to the coating solution.

As the ultraviolet absorber, for example, a benzotriazole compound substituted with an aryl group, a goutiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used.

Specific examples of ultraviolet absorbers are described in U.S. Patent No. 3,633°794.
No. 3, 3/4t, 7 tag No. 3, 3! Ko, ≦za 7, JP-A-Shogu g-27 zari, US time -6 ≦ - 3.70! ,Iθ! No. 3.707.376, same, 04t! , No. 2.22, 3, 700, 4t
! ! No. 3. ¥99.7 Go No. 2, West German patent application publication/
,! 4t7. It is written in J”t3 etc.

Examples of compounds of the ultraviolet absorber of the present invention are shown below, but the present invention is not limited to these compounds.

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

Specifically, pyrazolone oxonol dye, sheer g
9-Lyl azo dyes, styryl dyes, butadienyl dyes, merocyanine dyes, merocyanine dyes, oxonol dyes, and enamine hemioxonol dyes are used.

More specific examples of dyes that can be used in the present invention include dyes represented by the following general formulas (■) to (X[I).

General formula ■ General formula ■ General formula ■ o=c-' General formula

Q is pyrazolone, barbylic acid, thiobarbylic acid, isoxacilone, 3-oxythionaphthene or/
, represents the atomic group necessary to form 3-indandione. R is a substituted or unsubstituted alkyl group, R1, R2,
R3 and R4 are a hydrogen atom, an alkoxy group, a dialkylamino group or a sulfone group, R5 is a hydrogen atom or a halogen atom, M is a hydrogen atom, a sodium atom or a potassium atom, X is an anion y''% nl and R3 are/or 2 (However, when m is /, an inner salt is formed.) General formula
R7\ R8\ R9% R10% R1
1% R12, R15, R14\R15\R16 and R17 represent a hydrogen atom, an alkyl group, a hydroxyl group, an amine group, an acylamino group, a carboxyl group or a sulfone group. However, R12 and R15 may be combined with each other to form a benzene ring. ) Among the dyes of general formulas (■) to (X[l), dyes with acidic groups (sulfone group, carboxyl group, etc.) are preferred.

A specific example is shown below.

-7 Goo These dyes can also be used in combination.

The dyes of the invention are used in amounts necessary to enable bright room handling.

The specific amount of dye used is generally 10-3g/m2~/
Preferred amounts can be found in the range from /θ-3 g/m2 to O0J-g/m2.

Gelatin is advantageously used as the binder or protective colloid in the photographic emulsion of the invention, but other hydrophilic colloids can also be used.

For example, cellulose derivatives such as carboxymethylcellulose, dextran, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly(+)-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, etc., singly or in combination. A wide variety of synthetic hydrophilic polymeric materials such as polymers can be used.

As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (especially g-hydroxy-substituted (/, 3, 3a, 7) tetrazaindenes) ), hentaazaindenes, etc.; many compounds known as anticapri agents or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Among these, preferred are benzotriazoles (eg !-methyl-benzo) IJ thiazoles and nitroindazoles (eg !-nitroindazole). Moreover, -7- these compounds may be included in the treatment liquid.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts, aldehydes (formaldehyde, geltaraldehyde, etc.), N-methylol compounds, activated vinyl compounds (/.

3,! -) Liacryloyl-hexahydro-8-triazine, /, 3-vinylsulfonyl-cofluoro7? active halogen compounds (X, <-cyclo-6
-hydroxy-5-) riazine, etc.), mucohalogen acids, epoxy compounds, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyethylene alkylphenylethyls, polyoxyethylene alkyl phosphates, etc.
Anionic surfactant diamino acids containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups,
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; complexes such as alkyl amine salts, aliphatic or aromatic 9th-class ammonium salts, pyridinium, and imidazolium; Cationic surfactants such as cyclic 9th ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, the surfactant preferably used in the present invention is Tokko Sho! ! - Polyalkylene oxides having a molecular weight of 6θO or more described in Wag No. 72. Additionally, a polymer latex such as polyalkyl acrylate may be included for dimensional stability.

In order to obtain ultra-high contrast photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developing solution or US Pat. G/
Therefore, it is not necessary to use a highly alkaline developer with a pH close to 3 as described in No. 9Zt, and a -♂/- stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative in O9/! Contains mol/1 or more, p
H/θ,! ~/2.3, especially pH//, θ~/2. By using the θ developer, it is possible to obtain a negative image with sufficient ultra-high contrast.

There are no particular limitations on the developing agents that can be used in the method of the present invention, such as dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, /-phenyl-3-pyrazolidone, y).

Goodimethyl-/-phenyl-3-pyrazolidone), amine phenols (for example, N-methyl-p-amine phenol), etc. can be used alone or in combination.

In particular, the silver halide photosensitive material of the present invention contains dihydroxybenzenes as a main developing agent and 3-3 as an auxiliary developing agent.
Suitable for processing with developers containing pyrazolidones or aminone enols. Preferably, in this developer, dihydroxybenzenes θ, O! ~θ, t mol/1% 3-P♂colanridones or aminophenols are used in combination within the range of O8θ6 mol/l or less.

Furthermore, as described in U.S. Pat.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or anti-capri agents such as bromides, iodides, and organic anti-capri agents (particularly preferably nitroindazoles or benzotriazoles). be able to.

If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, and film silver stain preventive agents may be added. (eg, Komelkabutobenzimidazole sulfonic acids, etc.).

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.

The processing temperature in the method of the present invention is usually from /, r0c!
It is selected between θ0C.

It is preferable to use an automatic processor for photographic processing, but according to the method of the present invention, the total processing time from when the photosensitive material is put into the automatic processor until it comes out is set to 90 seconds to 20 seconds. Also, it is possible to obtain photographic characteristics of sufficiently ultra-high contrast negative gradation.

The developing solution of the present invention contains JP-A-Sho! as a silver stain preventive agent. t-2
Compounds described in No. 41,317 can be used.

Patent application Sho 6θ-109 as a dissolution aid added to the developer
, 7<tJ can be used. In addition, as a pH buffering agent used in the developer,
, No. 4t33 or the compound described in Kentoku No. 4tt3/ can be used.

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

In the examples, a developer having the following formulation was used.

Developer Hydroquinone! , OgN・Methyl p・Aminophenol//λ Sulfate 0.7g Sodium hydroxide 72.0g Potassium hydroxide
! j, Og!・Sulfosalicylic acid
76.0g boric acid 2
! ,0g potassium sulfite //θ,og
Ethylenediaminetetraacetic acid disodium salt /, 0g potassium bromide Otsu, θ3! -Methylbenzotriazole θ, 6gn・butyl・getanolamine /j, 0g water added /1 (pH=//, 4
) [Example/] Silver per mole of silver/× in gelatin aqueous solution kept at 300C
Existence of 10-5 mol of (NH4)3RhC1s! - Silver chloride particles are prepared by simultaneously mixing an aqueous solution of silver nitrate under a cloth, and after removing the soluble salts by methods well known in the art, gelatin is added and the particles are prepared without chemical ripening. As a stabilizer, λ-methyl-guhydroxy/,3.3a,7-thitraazaindene was added. This emulsion was a cubic monodisperse emulsion with an average grain size of 0.02 microns. This emulsion was designated as ■.

Add 20mg/hydrazine compound 1-30 to this emulsion
m2, nucleation accelerator II -/ was added at jOmg/m2, polyethyl acrylate latex was added in a solid content of 3θwt% of gelatin, and as a hardening agent, /, 3-
Vinylsulfonyl-coprobanol was added and coated onto a polyester support at a silver level of 3 DEG/m@2. The amount of gelatin in the emulsion layer was /2g7m2, and a layer of gelatin /2g/m2 was coated thereon as a protective layer, and this sample was designated as /-A.

Furthermore, as shown in Table -/, emulsions @, θ, and ■ were prepared in which only the amount of (NH4)3Rhα6 was changed, and were the same as /A? Go
- Samples/■~10 were prepared in the same manner.

(Preparation of comparative sample) Add p/p/mole of silver to an aqueous gelatin solution kept at temperature
, /X/0' mol tD (NH4)3
Silver chloride particles were prepared by simultaneously mixing an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of Rbcls (7), and after removing the soluble salts by a method well known in the art, gelatin was added to the particles without chemical ripening. , comethyl-guhydroxy/3,3a,7-titraazaindene was added as a stabilizer. This emulsion has an average grain size of 0.
/1. The emulsion was a monodisperse emulsion with a cubic crystal structure of μ. This emulsion is called Emulsion-4.

A sample was prepared in the same manner as /A using the milk Qi○ with
This was designated as /a. Furthermore, as shown in Table 7, (NH4
) Samples were made in the same manner as in /a using emulsions ■, ■, ■, [phase], and ■ in which the addition amount of 3Rh in 6 was changed, and these were added to /b to /d and /, respectively, as shown in Table -/. m and n.

In addition, emulsions (■) and (■) were prepared using the emulsion used in Example / by changing only the amount of (NH4)3Rhc16 added, and samples were prepared in the same manner as /A as shown in Table -/. 7M, /
N, /L.

This sample is Dainippon Screen Seimei-shitsu Printer P
107, the film was exposed to light through an optical wedge, developed for 3 times at 0C3θ seconds using the developer formulation described above, fixed, washed with water, and dried. The photographic results obtained are shown in Table 1. Also, using these photosensitive materials, a positive original film with Mincho characters of grade 6 size was passed through two sheets of transparent stamped bases (PET bases) with a thickness of /θ0μ, and then the film was printed on PETθ7. Contact printing was performed using a printer at an exposure amount such that the halftone dot area in contact exposure was /:/, and the same processing as above was performed, and the quality of the cut-out characters on the obtained negative film was evaluated. The evaluation was rated as ○ if the 3rd grade letter was missing, △ if the letter was missing but was acceptable for practical use, and × if the letter was not missing in practice.

In addition, the sensitivity is concentration /,! It is expressed as the difference in sensitivity points. Also d
From the above results, it can be seen that within the average particle size and Rh range of the present invention, a large reduction in sensitivity, high G, and character quality can be achieved at the same time.

[Example]

Similar to emulsion ① prepared at 3θ0C in Example/, only the temperature at the time of grain formation was 3r'C,<to'C1<ts
Instead of 0c, three types of emulsions (■, ■, and ■) with different grain sizes were made. Using these emulsions and using a hydrazine compound and nucleation accelerator in the same manner as /A, sample 2A1 was prepared.
Samples of CoB,...:zC were prepared.

In addition, samples 2A, 2B, and 2C were prepared by changing only the amount of Rh in the emulsion as shown in the table below.
, IC.

This was evaluated by sensitometry and practical skills in the same manner as in Example 1, and the results are shown in Table 2.

With the average particle size and Rh content of the present invention, there is a significant decrease in sensitivity,
It can be seen that high G and character quality are achieved at the same time.

one'? 2- [Example 3] tXl per mole of silver in an aqueous gelatin solution maintained at 2j0C
Silver chloride particles were prepared by simultaneously mixing an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of o 'mol (D(NH4)3RhC1e), and after removing the soluble salts by methods well known in the art, gelatin was prepared. In addition, comethyl-co-hydroxy-7,!, as a stabilizer without chemical ripening.
3a,7-thitraazaindene was added. This emulsion was a monodispersed cubic emulsion with an average grain size of 0.0 μ.

To this emulsion, select the compounds shown in Table 3 from hydrazine compounds (general formula (■)) and nucleation accelerators (general formulas (n), (■)), and add 3A to 3■ in the same manner as /A. A sample was prepared and evaluated in the same manner as in Example.

It can be seen that the nucleating agent of the present invention changes the target G and character quality, and the nucleation accelerator further improves the character quality.

= 9 Goo [Example G] 5×1 per mole of silver in an aqueous gelatin solution kept at 300C
Silver chloride particles were prepared by simultaneously mixing an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of 0-5 moles of CNH4)6Rh (26), and after removing the soluble salts by methods well known in the art, gelatin was prepared. and comethyl-co-hydroxy-/, 3.3 &
,? - Tetraazaindene was added. I took this milk and medicine.

Three types of silver chlorobromide emulsions (■@■) with different halogen compositions were prepared as shown in the table below, using a mixture of sodium chloride and potassium bromide instead of an aqueous sodium chloride solution.

These emulsions were cubic monodisperse emulsions with an average grain size of 0.02μ.

Using these emulsions, coating samples 4tA, 4tB, 4tC, and GD were prepared in the same manner as in Example 1/A.

In order to investigate the safelight safety of this sample, it was irradiated with 20-tater-θ flux for 3θ minutes under a Toshiba UV-cut fluorescent lamp NU/M, and then treated with the same treatment solution as in Example/1. The value was measured. and that f
The practical applicability of the og value was evaluated.

From the results of Table 1, it can be seen that the composition of the present invention can be used practically.

〔Example! ]

3 mg/m2 of the compound of ■-2 was added to the formulation of sample 4tA prepared in Example G, and sample! A was created. Similarly, IV-71', ■-37, V-/, ■-1 are each 3 m long.
g/m2 added and many types of samples! B, IC, evening, tE
It was created.

These were subjected to sensitometry in the same manner as in Example/.
Furthermore, in order to investigate safelight safety, after irradiating at 110θlux for 7 hours under Toshiba UV-cut fluorescent lamp NU/M, sensitometric exposure was performed, and the change in sensitivity was measured by processing with the processing solution of Example/ did.

Furthermore, the quality of extracted characters was evaluated in the same manner as in Example.

It can be seen that the compounds of the present invention (general formulas (1), (2), and (2)) reduce sensitivity and improve safelight safety. It can be seen that the character quality is maintained at a practically usable level while ensuring safelight safety.

■ Sensitivity difference before and after safelight irradiation [Example B] Emulsion prepared in Example / ■, @, 0, O, ■, ■, ■,
And to the emulsions ①, ②, and ② prepared in Example 2, polyethyl acrylate latex was added at a solid content of 30w to gelatin.
t% added and /, 3-vinylsulfonyl-copropanol as a hardening agent, and 3.
It was applied so that the amount of silver was 2g7m2. The gelatin in the emulsion layer is /.

zg/m2 and gelatin/on top of this as a protective layer.

A layer of Og/m2 was applied and the sample was coated with
Otsu-B1 Otsu-C, t-D, Go-M, t-N.

They were named Otsu-L, Otsu-a, Otsu-b, and g-C.

This sample is Dainippon Screen Seimei-shitsu Printer P
It was exposed to light through an optical wedge at TO7, developed with the above developer formulation for 3z0c3o seconds, fixed, washed with water, and dried.

The photographic results obtained are shown in Table-g.

Also, using these photosensitive materials, a 10θμ thin line positive film (/θθμ PET base) was pasted on the transparent pasting paste, and this was used as a manuscript to create a 700μ thick transparent pasting paste (PET base). Using a P<07 printer, two sheets were printed in close contact at an exposure amount such that the halftone dot area at close exposure was /, /, and the same process as above was performed to eliminate the collapse of fine lines in the resulting negative film. The extent of the damage and the edge marks on the manuscript were evaluated.

The evaluation was rated as ○ if the thin line was missing, △ if the thin line was missing or bad, and × if the line was not missing. In addition, the edge marks were evaluated, and those with no marks were marked as ○, those with marks were marked as △, and those with scratches (white spots) were marked as ×. Sensitivity and G were evaluated in the same manner as in Example.

-110/--70+21 It can be seen that in the rhodium (Rh) of the present invention, in the average particle size range, both the performance of removing fine lines and the performance of eliminating edge marks are compatible.

Preferred embodiments of the present invention are as follows.

1) Claims characterized in that the hydrazine derivative is a compound represented by the general formula (I) described in the main text (
2) Sensitive material.

2) The photosensitive material described in 1) above, which contains at least seven compounds represented by the general formulas (If) and (I[I) described in the text.

3) The light-sensitive material according to 1) or 2) above, which contains at least seven compounds represented by the general formulas (IV), (v) and (■) described in the text.

ri) 1) above, where the silver halide is silver chloride or silver chlorobromide
~3) Sensitive material.

A photosensitive material of the above 1) to G) containing at least seven of the dyes represented by the general formulas (■) to (X[[) described in the main text.

g) The photosensitive materials 1) to j) above are photosensitive materials that can be handled in a bright room.

2) After imagewise exposing the photosensitive materials of 1) to 6) above, sulfite ions are added to θ, /! Contains mol/no or more, pH/θ, s~72
．． A method of forming ultra-high contrast images using the developer described in step 3.

Patent applicant: Fuji Photo Film Co., Ltd.-/　θ　y-

Claims (1)

[Scope of Claims] 1) A light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide in the emulsion layer is
The average particle size is 0.15 μm or less, and the rhodium salt is more than 10^-^5 moles per mole of silver, and 5 × 1
Negative-working silver halide photographic material characterized by containing less than 0^-^4 moles 2) In claim 1), the hydrazine derivative is contained in the silver halide emulsion layer and/or its adjacent layer. Negative silver halide photosensitive material characterized by