JPH02113238A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material which is less changed in performance by a fluctuation in a processing liquid and is subjected to infrared rays sensitization by incorporating a specific hydrazine deriv., specific compd. and infrared rays sensitizing dye into emulsion layers. CONSTITUTION:The hydrazine deriv. expressed by the formula I, the compd. which has <=11.2pH and increases gamma to >=6 and the infrared rays sensitizing dye are incorporated into the emulsion layers or other hydrophilic colloidal layers. In the formula I, R1 denotes an aliphat. group or arom. group; R2 denotes a hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, etc.; G1 denotes a carbonyl group, sulfonyl group, sulfoxy group, etc.; both A1, A2 denote a hydrogen atom or one thereof denotes a hydrogen atom and the other denotes a substd. or unsubstd. alkylsulfonyl group, etc. The photosensitive material which is less changed in performance by the fluctuation in processing and is spectrally sensitized in the infrared rays region is obtd. in this way.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a silver halide photographic light-sensitive material (in % Regarding negative type), 1.
In particular, it relates to silver halide photographic materials spectrally sensitized in the infrared region.

(Prior Art) It is known that photographic images with extremely high contrast can be formed using certain silver halides, and methods for forming such photographic images are used in the field of photolithography.

Conventionally, 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 O01 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.

As a method for obtaining high contrast photographic properties using a stable developer, US Pat. /61,277, same No. ≠, 16617 Hiro 2,
Same No. 'I, J//, No. 71/, Same No. Hiroshi, 272. tit
No., μ, λ//, II No. 7, Hiroshi No. 2, 2≠3,73
There is a method using a hydrazine derivative described in No. 2 and the like. According to this method, photographic properties with ultra-high contrast and high sensitivity 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 better than that of the lithium developer. A dramatic improvement in comparison.

However, the ultra-high contrast image forming method using these hydrazine compounds strongly promotes contagious development, so when photographing text manuscripts with low contrast (thin lines of Mincho font), areas that should be thin white backgrounds are There was a problem that the text became black and the text became so black that it became unreadable. Therefore, if you reduce the exposure to match the fine lines of the Mincho typeface, the Gothic typeface will look worse.
There was a problem that the exposure latitude was narrow. A similar problem also occurs in halftone image photography, which has disadvantages in image quality in that even the parts of the halftone dots that appear as a white background are easily blackened, and the halftone gradation becomes very short.

In addition, the pH of the developer is set to 1 for practical purposes in order to obtain ultra-high contrast images.
It is necessary to increase the pH to 1.2 or higher, but at this pH, the developing agent is oxidized and deteriorates easily, and the pH changes due to absorption of carbon dioxide gas in the air, which deteriorates the performance of the photosensitive material. It also had the disadvantage of being unstable.

On the other hand, one of the exposure methods for photographic materials is to scan the original image.
A so-called scanner-only image forming method is known in which a silver halide photographic light-sensitive material is exposed to light based on the image signal to form a negative image or a positive image corresponding to the image of the original image.

There are a variety of recording devices that use a scanner-only image forming method, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, etc. have traditionally been used as recording light sources for these scanner-only recording devices. . However, all of these light sources have practical drawbacks such as low output and short lifespan. To compensate for these drawbacks, there are scanners that use a coherent laser light source such as a Ne-He laser, an argon laser, or a He-Cd laser as a one-side light source. Although these devices can provide high output, they are large and expensive, require a modulator, and use visible light, which limits the safelight of photosensitive materials and makes them difficult to handle. There are drawbacks such as.

On the other hand, semiconductor lasers have the advantage of being small, inexpensive, easy to modulate, 6D, and have a longer lifespan than the above-mentioned lasers, and a photosensitive material sensitive to the infrared region has been desired.

However, when photosensitive materials containing hydrazine derivatives are
In the ultra-high contrast image forming method in which processing is performed using two or more developing solutions, when the light-sensitive material contains an infrared sensitizing dye,
There was a drawback that the performance was likely to change greatly due to fluctuations in the developer (pH and amount of developing agent).

Furthermore, when an infrared sensitizing dye is added to a photographic material containing a hydrazine derivative, there is a drawback that the storage stability is further deteriorated.

(Objective of the Invention) The object of the present invention is to reduce performance changes due to processing liquid fluctuations.
The second object of the present invention is to provide an infrared-sensitized photographic material that has a good shelf life. A third object is to provide a silver halide photosensitive material with good reproducibility of images and halftone dots and a wide exposure latitude.

(Disclosure of the Invention) The above object is to provide a negative photographic material containing at least one silver halide emulsion layer on a support at a pH/
/, - In a black-and-white image forming method in which processing is performed with the following developer, a hydrazine derivative represented by the following general formula (I), pH/ /
This was achieved by an image forming method characterized by containing a compound having a gamma of 2 or less and a gamma of 6 or more, and an infrared sensitizing dye.

General formula (I) I A2 In the formula, R represents an aliphatic group or an aromatic group, and R2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarnebonyl group. G represents a carbonyl group, sulfonyl group, sulfoxy group, -P- group, or iminomethylene group, and Al and A2 each represent a hydrogen atom or a hydrogen atom on one side and substituted or unsubstituted alkylsulfonyl on the other. group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the present invention, nucleation development is controlled by controlling the pH of the developer to 17.2 or less. Normal pH
If it is set to /1.2 or less, the contrast will not be sufficiently sharpened, but
By using a nucleation accelerator in combination, the gradation can be made sufficiently high.

In development at this pH, contagious development is weaker and image enlargement is smaller than in development at a higher pH. Also, change the halogen composition to f3
By setting the amount to 170 molti or more, development of unexposed areas or low exposure areas adjacent to the image area is suppressed, and further,
This effect becomes noticeable when developing at p)(//, 2 or less. This is thought to be mainly due to the suppression of development due to the diffusion of Br ions generated by the development reaction to the adjacent areas of the image, and the pH//, -
In the above nucleation development, this suppression was rarely observed.

Due to this development effect, even in a backlight system using an infrared semiconductor laser, a fine white line in a blackened area and a fine black line in a white background can be reproduced satisfactorily under the same conditions.

The compound of general formula (I) used in the present invention will be explained.

General formula (I) In the formula, R1 represents an aliphatic group or an aromatic group, and R8 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarnebonyl group. ,G.

is a carbonyl group, a sulfonyl group, a sulfoxy group, A2 is both a hydrogen atom, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group represents.

In general formula (I), the aliphatic group represented by R3 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. 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,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

In the general formula (R1), the aromatic group represented by R1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. They may be combined to form a heteroaryl group.

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

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R7 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms), an alkoxy group (preferably a carbon number of 1 to 20), a substituted amino group (preferably an alkyl group having 1 to 20 carbon atoms) (amino group substituted with
), ureido group (preferably 1 to 30 carbon atoms)
) etc.

The alkyl group represented by R8 in formula -i is preferably an alkyl group having 1 to 4 carbon atoms, with substituents such as a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, and a phenyl group. It may have.

The oryl group represented by R2 is preferably a monocyclic or bicyclic ring, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, or the like.

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.

The aralkyl group is preferably a monocyclic one, and the substituent includes a halogen atom and the like.

The amino group includes an unsubstituted amino group and a carbon number of 1 to 10.
Preferred are alkylamino groups and arylamino groups, which may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, etc. The carbamoyl group is an unsubstituted carbamoyl group, and a carbamoyl group having 1 to 1 carbon atoms. An alkylcarbamoyl group or an arylcarbamoyl group of 10 is preferred, 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 1 to 10 carbon atoms, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R1, when G is a carbonyl group, preferred are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, etc.). ), aralkyl group (e.g., 0-hydroxybenzyl group, etc.)
, aryl group (e.g. phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4
-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when G is a sulfonyl group, R1 is an alkyl group (e.g., methyl group), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group, etc.) or substituted amino group (e.g.
Dimethylamino (Aonato) and the like are preferred.

When G1 is a sulfoxy group, R1 is preferably a cyanobenzyl group, a methylthiobenzyl group, etc., a methoxy group,
An ethoxy group, a butoxy group, a phenoxy group, and a phenyl group are preferred, and a phenoxy group is particularly preferred.

When G is an N-file or p'fl-tA iminomethylene group, R2 is preferably a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R2, in addition to the substituents listed for R1, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, etc. can be applied.

The most preferred G in the general formula (R) is a carbonyl group.

Also, R8 splits the G, -R, part from the remaining molecule, -
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the G Rz portion, and specifically, one that can be represented by general formula (a).

General formula (a) Rs Zl In the formula, Z attacks G nucleophilically, G-R, -Z
, is a group capable of splitting the moiety from the remaining molecule, and R3 is R
When one hydrogen atom is removed from o, Zl undergoes nucleophilic attack on G, and a cyclic structure can be generated with Gl, R3, and Zl.

More specifically, 2. When the hydrazine compound of general formula (I) generates the following reaction intermediate by oxidation etc., it easily undergoes a nucleophilic reaction with G to form R, -N-N-Gl -R3-Z.

R, -N-N group can be split from G, specifically OH, SH or NHR, (I'?, is a hydrogen atom, an alkyl group, an aryl group, -COR, or -5O
tRs, where R8 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.)
It is a functional group that reacts directly with
f(, S H5N HR.

Even if -COOH is temporarily protected to generate these groups by hydrolysis with an alkali, etc., R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a hetero group). It may be a functional group that can react with G by reacting with a nucleophile such as an acid ion or a sulfite ion.

Furthermore, the ring formed by G1, R3, and Z is preferably a 5-membered or 6-membered ring, and among those represented by the general formula (al), preferred are the general formulas (b) and (
C) can be mentioned.

General formula rb) In the formula, R, l to R54 are a hydrogen atom, an alkyl 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 2 to 12 carbon atoms) 6 to 12), which may be the same or different, B is an atom necessary to complete a 5- or 6-membered ring that may contain an EI IA group, m, n is 0 or! and (n + m is 1 or 2.

Examples of the 5-membered or 6R 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).

General formula (C) Rc (−N−)T+CRc　　　R,”−)−TZ.

In the formula, Rc' and Rc'' represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom, and may be the same or different.

R6' represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

P represents 0 or l, and 9 represents 1-4.

Rc', Rc'' and R,3 may be bonded to each other to form a ring as long as the structure allows Zl to make an intramolecular nucleophilic attack on G.

Rc', R,'' is preferably a hydrogen atom, a halogen atom,
or an alkyl group, and R and s are preferably an alkyl group or an aryl group.

9 preferably represents 1 to 3, and when 9 is 1, P is! or 2, when 9 is 2, p stands for 0 or 1, when 9 is 3, p stands for 0 or l, and when 9 is 2 or 3, CR
c′ Rc ” may be the same or different.

ZI has the same meaning as general formula (a).

At and AI are hydrogen atoms, alkylsulfonyl groups and arylsulfonyl groups having a carbon IJt of 20 or less (preferably phenylsulfonyl groups or phenylsulfonyl groups substituted such that 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 modified so that the sum of Hammett's substituent constants is −0.5 or more, or a linear, branched, or cyclic unsubstituted and a substituted 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, and a sulfonic acid group)) At and Ax are most preferably hydrogen atoms. .

R1 or R1 in the general formula (+) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 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,
It can be selected from alkylphenoxy groups, etc.

It is preferable that R1 or R2 in the general formula (I) has a bracket incorporated therein to enhance adsorption to the silver halide grain surface. Examples of such adhering groups include a thiourea group, a heterocyclic thioamide group, Mercapto? ] Barocyclic groups, triazole groups, etc., U.S. Pat.
No. 59,347, JP-A No. 59-195.233, No. 5
9-200゜231, 59-201.045, 59-201.046, 59-201,047,
No. 59-201,048, No. 59-201,049, JP-A-61-170,733, No. 61-270.7
No. 44, No. 62-948, Patent Application No. 62-67.508
No. 62-67.501 and No. 62-67.510.

Specific examples of the compound represented by the -i formula (+) are shown below.
However, the present invention is not limited to the following compounds.

■-5) ■-6)! -8) ■-9) C1hCHxCHtSH H Summer-15) Ren ■-18 L17Sl'111 In addition to the above-mentioned hydrazine derivatives, RESEARCHDISCLO5URE
Item 23516 (November 1983 issue, P, 34
6) and the documents cited therein, as well as U.S. Pat.
80.207, 4,269.929, 4.27
No. 6.364, No. 4,278,748, No. 4,385
, No. 108, No. 4,459,347, No. 4,560.
No. 638, No. 4,478,928, British Patent No. 2,01
1,391B, JP-A-60-179734, JP-A-6
No. 1-170,733, No. 61-270.744, No. 62-948, EP No. 217,310, Patent Application No. 1983-
No. 175.234, No. 61-251,482, No. 61
-268,249, 61-276.283, 6
2-67.508, 62-6529, 62-6
No. 7.510, No. 62-58.513, No. 62-13
No. 0,819, No. 62-143,469, No. 62-1
66.117 can be used.

The amount of the hydrazine derivative added in the present invention is #)/×10 mol to jX/
Preferably it contains 0 mol, %1C7xl
The preferable addition amount is in the range of 0 mol to 10 mol.

In order to make G 6 or more at a pH of 2 or less, it is preferable to incorporate a compound represented by the general formula (n) or / and (I) into the light-sensitive material.

This G value measurement is based on the following equation: E)H of the developer is I)H//.

Any B/W developer having a B/W ratio of 2 or less may be used, and the development temperature and time are 31r0C for 30 seconds. G
is the difference in the amount of light applied (△lo
It is the concentration difference for g E ).

General formula (, Fl) (In the formula, Y represents a group adsorbed to silver halide. represents a valent 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 is l, λ, or 3 , n
represents O or l. ) The group represented by Y that adsorbs to silver halide includes nitrogen-containing heterocyclic compounds.

When Y represents a nitrogen-containing heterocyclic compound, the compound of general formula (n) is represented by the following general formula ([[-a).

General formula (,, I-a) In the formula, l represents O or l, m represents /, 2 or 3, and n represents O'' or l.

((X+-A-B) has the same meaning as that in the general formula (I), Q is a carbon atom, a nitrogen atom, an oxygen atom,
Composed of at least one type of sulfur atom! or represents an atomic group necessary to form a t-membered heterocycle.

Further, this heterocycle may 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, triazoles, tetrazoles, Examples include azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, and quinolines.

MVi hydrogen atom, alkali metal atom (e.g. sodium atom, potassium atom, etc.), ammonium group (e.g. trimethylammonium group, dimethylbenzylammonium group, etc.), group that can become M=H or an alkali metal atom under alkaline conditions (e.g. (acetyl group, cyanethyl group, methanesulfonylethyl group, etc.).

In addition, these heterocycles include a nitro group, a chlorine atom (such as a chlorine atom, a bromine atom, etc.), a mercapto group, and a cyano group, each of which may be directly substituted or not substituted! It-substituted alkyl group (e.g. methyl group, ethyl group, propyl group, t-methyl group,
cyanoethyl group, methoxyethyl group, methylthioethyl group, etc.), aryl group (e.g. phenyl group, μm methanesulfonamidophenyl group, Hiro-methylphenyl x%J
+! - dicalphenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group C example: t
benzyl group, Hiro-methylbenzyl group, phenethyl group,
etc.), alkoxy groups [e.g. methoxy group, ethoxy group,
etc.], aryloxy groups [e.g. phenoxy group, Hiro-methoxyphenoxy7 group, etc.], alkylthio groups (e.g. methylthio group, ethylthio group, methoxyethylthio group),
Arylthio group (e.g. phenylthio group), sulfonyl group (e.g. t is methanesulfonyl group, ethanesulfonyl M
, p-)luenesulfonyl group, etc.), carbamoyl group (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (
sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide group (e.g. acetamide group, benzamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), acyloxy group (e.g. acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (
For example, methanesulfonyloxy 5, etc.), ureido group [
For example, unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.], thioureido group (for example, unsubstituted thioureido group, methylthioureido group, etc.), acyl group (for example, acetyl group, benzoyl group, etc.), heterocyclic groups (e.g. l-morpholino group,
l-piperidino group, copyridyl group, cupyridyl group,
2-thienyl group, /-pyrazolyl'b, /-imidazolyl group, coated 2hydrofuryl group, tetrahydrothienyl &, etc.), oxycarbonyl group (e.g. methoxycarzenyl, phenoxycarbonyl, etc.), oxycarbonylamino groups (e.g. hamethoxyluponylamino group,
phenoxycarbonylamino group, coethylhexyloxycarbonylamino group, etc.), amino group (e.g. unsubstituted amino group, dimethylamino group, methoxyethylamino group, ani IJ) group, etc.), carbon K or its salt, sulfone group. or a salt thereof, or may be substituted with a hydroxy group.

The divalent linking group represented by X is (J
u The bonding group may be bonded to Q via a linear or branched alkylene group (e.g., methylene group, ethylene group, propylene group, butylene group, hexylene group, l-methylethylene group, etc.) good. R1, 几2・R3・Bon4・
EL5, R6, 几7, R8, BON, and kLlG
is 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, λ-methyl phenyl group, 4), substituted or unsubstituted alkenyl group (e.g. proynyl group, l-
methylvinyl group, etc.), or a substituted or monosubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

A represents a divalent linking group, and the divalent linking group includes a linear or branched alkylene group (e.g., ethylene group, ethylene group, propylene group, methylene group, hexylene group, /-
methylethylene group, etc.), linear or branched alkenylene group (e.g. vinylene group, /-methylvinylene group, etc.)
, straight-chain or branched aralkylene group (e.g. benzylidene group, etc.), arylene 1 (iflJ, phenyl μ/,
naphthylene, etc.]. In the above group represented by A, X and A may be further substituted in any combination.

The substituted or unsubstituted 7-mino group of B has the general formula % formula % general formula CI-b) (wherein, R, 11, and B12 may be the same or different, and each is a hydrogen atom, substituted or unsubstituted carbon number l~
30 alkyl, alkenyl or aralkyl groups, these groups are straight-chain (e.g. methyl, ethyl, n-propyl, n-butyl, n-octyl,
Allyl group, 3-butenyl group, benzyl group, l-naphthylmethyl group, isobranched (e.g. isozolopyl group, t-octyl group, etc.), or cyclic (e.g. cyclohexyl group,
etc.), but that's fine.

In addition, 10L11 and R12 may be connected to form a ring, and a saturated heterocycle containing one or more heteroatoms (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.) Examples of substituents for B12 include carboxyl group, sulfo group, cyano group, halogen group, etc. atoms (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl group having 20 or less carbon atoms (for example, sibmethoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, penzyloxycarbonyl group, etc.), Alkoxy group with carbon number 2θ or less (
For example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), cyclic aryloxy group with about 20 carbon atoms (e.g., phenoxy group, p-) lylox group, etc.), carbon 4j, co-O The following acyloxy groups (e.g. acetyloxy group, propionyloxy group, etc.),
Acyl groups having 20 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl groups (e.g. carbamoyl group, N-dimethylcarbamoyl group, morpholinocarbonyl group, pyridinocarbonyl group, etc.), sulfamoyl group groups (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, pyridinosulfonyl group, etc.), acylamino groups having 20 or less carbon atoms (e.g. acetylamino group,
zolopionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide! (ethylsulfonamide group, p-toluenesulfonamide group, etc.), carbonamide group with carbon number of 0 or less (e.g., t is methylcarbonamide group, phenylcarbo/amide group, etc.), carbon number 20
Examples include the following ureido groups (?!l, t are methylureido groups, phenylureido groups, etc.), amino groups, and the like.

The ammonium group of B is represented by the general formula (It-C).

General formula (I[-C) 7′ N-1<　14 ■\H,15 (Zo).

(In the formula, l(, 13, R14, R15 are the above-mentioned general formula (
It is the same group as R]1 and 几12 in I[-b), and Ze represents an anion, such as a ride ion (for example, αe B, e He, etc.), a sulfonate ion (for example, trifluoromethane sulfonate), etc. p is 0 or / However, if the compound forms an inner salt, it is O.) The nitrogen-containing heterocycle of B refers to at least 7 nitrogen atoms! or jJ1 ring, and these rings may have a substituent or 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 (II), preferred are compounds represented by the following general formulas (II-m), (IF-rl), (I1F-o) or (and-p).

General formula (II-m) General formula (II-n) General formula (II-0) (X→-A-B General formula (TL-p) (wherein, (X+-A-B, Mu(, m is the general formula (Ir
- It has the same meaning as that of a). z Z and Z3Fi
1% 2 General formula (+X in 0 (Is it synonymous with A-B?
Or... rogen atom, alkoxy group having 20 or less carbon atoms (
For example, methoxy group), hydroxy group, hydroxylamide 7
group, substituted and unsubstituted amine groups, and its substituents include 几11 and 燠12 in the general formula (M-b).
can be selected from among the substituents. However, at least one of Zl, Z2 and z3 is synonymous with BeX (A-B).

Further, these +J rings may be substituted with a substituent applicable to the heterocycle of general formula (M).

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

■-2 1-μ -t anal-6 [-10 ■-7 ■-// ■-r ■-2 ■-t≠ [-I1 ]1-it ■-tA IJ-7 general formula (K> In the formula, Bl and 2 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.

Represents n1dO or l. (8) 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 R1 and R2 are preferably alkyl groups, alkenyl groups, and alkynyl groups each having carbons/~lλ, each of which may be substituted with an appropriate group. Examples of the alkyl group include methyl group, ethyl group, propyl group,
These include butyl group, hexyl group, decyl group, dodecyl group, isopropyl group, 5ec-butyl group, cyclohexyl group, and the like.

Examples of the alkenyl group include an allyl group, a coptenyl group, a λ-hexenyl group, and a coptenyl group. Examples of the alkyl group include a bronoZrugyl group and a copenyl group. Substituents include te, phenyl i, li1 substituted phenyl group, alkoxy group, alkylthio group, hydroxy group, carboxyl group, sulfo group, alkylamino group,
An amide group, etc.

When 1 and R2 form a ring, a j-membered or t-membered carbocyclic or heterocyclic ring consisting of carbon or a combination of nitrogen and boron is particularly preferred, and a saturated ring is particularly preferred.

The most preferable one for 1 and it2 is the number of carbon atoms/~
Of the alkyl groups in No. 3, an ethyl group is more preferred.

The divalent aliphatic group for R3 is -R4- or -1(,'
S- is preferred. Here, R4 is a divalent aliphatic residue, preferably a saturated or unsaturated haze of carbon number/-A, such as -0H2--CH2CH2--(CH2)3--(C
)I2)4--(OH2).

-CH (,:H=CHCH--CHc=<:cH2-, the preferred carbon number is 2 to μ, and R4 is more preferably 10) 12C) 12- and -CH2
CH2C)I2. When n of O(x) is 0, R3 represents only 4-.

The heterocycle of X includes nitrogen, oxygen or sulfur! and a 6-membered heterocycle may be fused to a benzene ring.

The heterocycle is preferably aromatic, such as tetrazole, triazole, thiadiazole, oxadiazole, imidazole, thiazo/heoxazole,
These include be/zimidazole, be/dithiazole, and benzoxazole. Among these, tetrazole and thianazole are particularly preferred.

The alkali metal of M is Na1 ( There are Li+, etc.

Examples of alkaline earth metals include Ca, 8 (g+10), etc.

As the quaternary ammonium salt of M, carbon number≠~3oyj
-ra fx le ft, Ote, flJ, t 4-j' (,C
)I3) of 4N.

(C2H5)4Ne, (04H9)4N(B, C6
H3CH2Ne(CH3)3, C□6H33Ne(CH
3) 3, etc. As the quaternary phosphonium salt, (C
4H0)4Pa, C1,)i3Pe(C)I3)3
, C6H3CH2Pe (CH3), etc.

Examples of unprepared salts of the compound represented by the general formula Cm) include hydrochloride, sulfate, and phosphate; organic acid salts include acetate, propionate, and methanesulfonate.
Examples include be7zenesulfone l'12 salt and p-toluenesulfonate.

Specific ν of the compound represented by the general formula (Ill) below;
List j.

■-/ ■-j l-3 ■-t ■-! ()l(JCH2CH2) 2NC)12C1(2SH
[-y -s ■-t 1[-/r 1[-/P 1[-20 ■-tA [-/7] The optimum addition amount of these accelerators varies depending on the type of compound, but (I) X/ 0-3~o, z g/
m2 preferably j, OX/0-3~0.7g
It is desirable to use it within the range of /m2. These accelerators are oily solvents (H20, alcohols such as methanol and ethanol, acetone, dimethyl chloride, etc.).

Muamide, methylcellosolve, etc.) and added to the fabric solution.

A plurality of types of these additives may be used in combination.

The silver halide emulsion of the present invention is infrared sensitized in a wavelength range of 7jOnm or more, waiting for maximum sensitization.

Any sensitizing dye may be used for infrared sensitization, but from the viewpoint of sensitization performance and stability, tocarbocyanine dyes and/or dicarbocyanine dyes with a ≠-quinoline nucleus are particularly preferred. .

Among the tricarbocyanine dyes used in the present invention, particularly useful ones are those represented by the following general formula (IVa) or (Wb).

General formula (wa) (X)n-! General formula (ffb) (X-). -1 In the formula, [Mo and RJ2 may each be the same or different, and each represents an alkyl group (preferably number of carbon atoms/
-J', such as methyl group, ethyl group, propyl group, methyl group, pentyl group, heptyl group.

etc.), substituted alkyl groups (substituents such as carboxy group, sulfo group, anano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), droxy group, alkoxycarbonyl group (up to r carbon atoms, e.g. methoxycarbonyl group, etquin carbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (carbon a7
Hereinafter, for example, methoxy group, ethoxy group, propoxy group,
Butoxy group, (such as ndyloxy group), aryloxy group (such as phenoxy group, p-tolyloxy group, etc.),
Acyloxy group (up to 3 carbon atoms, e.g. acetyloxy, propionyloxy, etc.), afur group (up to 3 carbon atoms, e.g. acetyl, propionyl, benzoyl, menyl group, etc.), carbamoyl group (e.g. carbamoyl group) , N, N-dimethylcal/ζmoyl group,
morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group,
~, N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), aryl group (e.g. phenyl group, p-hydroquinophenyl group, p-carboxyphenyl group, p-
an alkyl group (the number of carbon atoms in the alkyl moiety is 6 or less) substituted with a sulfophenyl group, α-naphthyl group, etc.

However, this one substituent may be substituted with an alkyl group in combination of λ or more. Represents 1.

R represents a hydrogen atom, a methyl group, a methoxy group, or an ethoxy group.

1 (and R4 are each hydrogen atom, lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), lower alkoxy group (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group, benzyl group represent.

IL 5 is a hydrogen atom, a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), a lower alkoxy group (
For example, a methoxy group, an ethoxy group, a glopo group, each substituted or unsubstituted alkyl group (the number of carbon atoms in the alkyl moiety is l~
it, preferably /~hiro, such as methyl group, ethyl group,
Propyl group, butyl group, benzyl group, phenylethyl group), aryl group (e.g. phenyl group, naphthyl group, tolyl group, p-chlorophenyl group, etc.), Wl and s
Connect with V 2! or t-membered nitrogen-containing heterocycles can also be formed.

D represents a group of atoms necessary to complete a divalent ethylene bond, e.g. ethylene or triethylene; Alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl, etc.)
, a halogen atom (chlorine atom, bromine atom, etc.), or an alkoxy group (number of carbon atoms/~≠, such as a methoxy group, an ethoxy group, a propoxy group, an inpropoxy group,
butoxy group, etc.).

D and l)2 each represent a hydrogen atom. However, D
and D2 can also form a divalent ethylene bond having the same meaning as above.

2 and Zl each represent a nonmetallic atomic group necessary to complete a j-membered or 6-membered nitrogen-containing vI core, such as a thiazole nucleus [e.g., benzothiazole, ≠-chlorpentthiazole, j-chlorobenzothiazole, 6 -Chlorpentthiazole, 7-chlorobenzothiazole, ≠-methylbenzothiazole, j-methylbenzothiazole, t-
Methylbenzothiazole! -bromobenzothiazole, 6-bromobenzothiazole,! -Iodobe/sothiazole, j-phenylbenzothiazole,! -Methoxybe/Zothiazole, O-Methoxybenzothiazole, j
-Ethoxybenzothiazole,! -carboxybenzothiazole, j-ethoxycarbonylbenzof7zole,
! -7enethylbenzothiazole, j-fluorobenzothiazole, j-)lifluoromethylbenzothiazole, j.

6-dimethylbe/zothiazole, j-hydroxy-4-
, methylbenzothiazole, tetrahydrobenzothiazole, Hiro-phenylbenzothiazole, naphtho [co, /
-d) Thiazole, naphtho [/.

λ-d] thiazole, naphtho[λ, J-d) thiazole, j-methoxynaphtho(/,, 2-d) thiazole, 7
-Nitoxynaphtho(u,/-d)thiazole,! -methoxynaphtho(u,/-d)thiazole, j-methoxynaphtho[co,3-d)thiazole, etc.], zelenazole core [eg, penzozelenazole, j-chlorobenzimidazole, termethoxybenzozelenazole, yo-methylbenzoxazole, j-hydroxybenzoxazole, naphtho (J,/-d) zelenazole, naphtho (/,
-2-d) zelenazole etc.], oxazole nucleus [benzoxazole, j-chlorobenzoxazole, j-
Methylbenzoxazole! -Prombe/zooxazole, j-fluorobenzoxazole, j-phenylbenzoxazole,! -methoxybenzoxazole, j-trifluorobenzoxazole, j-hydroxybenzoxazole,! -carpoxyinzoxazole, 6-methylbenzoxazole, A-chlorobenzoxazole, t-methoxybenzoxazole,
6-Hydroxybenzoxazole, p,6-dimethylbenzoxazole, j-ethoxybenzoxazole, naph)(2,/-d]oxazole, naphtho(' +
2-d] oxazole, naphtho(x, J-d) oxazole, etc.], quinoline nucleus [e.g. λ-quinoline, 3-methyl-λ-quinoline, j-ethyl-λ-quinoline, 6-
Methyl-choquinoline! - fluorocorquinoline,
6-Medoxy 2-quinoline, 6-hydroxycorquinoline, l-chlorocorquinoline, t-fluoro-≠
-quinoline, etc.), J,J-dialkylindolenine nuclei (e.g., 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-yo-cyanoindolenine/, 33-dimethyl-yo -methoxyindolenine, J-dimethyl-y-methylindolenine, 3-dimethyl-y-chloroindolenine), imidazole core (e.g., no-methylbenzimidazole, l
-ethylbenzimidazole, /-methyl-yo-chlorobenzimidazole, /-ethyl-! -chlorbe, /shiimidazole, /-methyl-! , t-dichlorobenzimidazole, noethyl-! , 6-cyclobenzimitasole, l-alkyl-! -methoxybenzimidazole, /-methyl-cyanobenzimidazole, /
-Ethyl-! -cyanobenzimidazole, / -methyl-j-fluorobenzimidazole, / -ethyl-!
-fluorobenzimidazole, /-phenyl-j,t
-dichlorobenzimidazole, l-allyl-! , t-
Dichlorobenzimidazole, l-allyl-j-chlorobenzimidazole, l-phenylbenzimidazole, l-phenyl-y-chlorobenzimidazole, l
-methyl-j-) IJ fluoromethylbenzimidazole, /-ethyl-3-trifluoromethylbenzimidazole, /-ethylnaphtho(/,2-d)imidazole, etc.), pyridine nucleus (e.g. pyridine, j-methyl-copyridine) , 3-methyl-≠-pyridine, etc.). Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used.

X represents an acid anion.

nd/or λ.

Among the ψ-quinoline nucleus-containing dicarbo7anine dyes used in the present invention, those having the following general formula are particularly useful. and 117 represent the same meanings as R,1 and +(,2, respectively).

ru has the same meaning as ru. However, a8 is preferably a lower alkyl group or a benzyl group.

V is a hydrogen atom, a lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), an alkoxy group (e.g. methoxy group, nidoxy group, butoxy group, etc.), a halogen atom (
For example, fluorine atoms, chlorine atoms, etc.), substituted alkyl groups (
For example, trifluoromethyl group, carboxymethyl group, etc.)
represents.

2 represents the same meaning as 2 and Zl.

Xl represents agreement IA.

m, nl, and p each represent l or ji.

Specific examples of the sensitizing dye used in the present invention are shown below. However, the present invention is not limited to these sensitizing dyes.

1';21'15 (IT-/J) (W-"/1 to 2FI5 knee (nu-/ 6) ([7-7-7 7)C/r) r- ■- α04- (W-/ ri) (W-koO) ■- (Tr-col) 1″19shi4 U41′19 (W-2yo) ■- (I7-2bu) (Iv-27) 2H5 (#-22> ( lit-Jj) (III-1da) (III-λr) (■-λri) CllN-30) α04- ■- 2H5 (CH2)4S03- ■- tO4- <w-3i> (■-32) CM -J J ) (W-Jf) (■-32) (■-3da) (cu2)3so3- (III-J j ) (C)12)2(JH r- (i[[-J j ) ( L;?12J4iMLJ3 (■-Reference 〇) 〇2H5 Knee (III-Reference/ ) α (III-4') (C) i2) 2S (73Na Cf42CCJO- ■ α04- α04- The above red used in the present invention The external sensitizing dye is jXlo'mok to jX10-3 mol per silver halide/mo
It is preferably contained in a silver halide photographic emulsion in a ratio of 1XIO-6 moles to 1x1Q-3 moles, particularly preferably λx10' moles to tX10-4 moles.

The infrared sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution.

Ultrasonic waves can also be used for dissolution. Further, as a method of adding the above-mentioned infrared sensitizing dye, US Patent No. 3. Hiroshi62. A method of bath-dissolving a dye in a volatile organic solvent, fractionating the solution into a hydrophilic colloid, and adding this dispersion into an emulsion, as described in Japanese Patent Publication Akihiro 6.
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to the entire emulsion, as described in US Pat. No. 3,122,135, as described in -2≠/1j, etc. A method of dissolving a dye in a surfactant and adding the solution to an emulsion as described; JP-A-Sho! l-7≠t2μ
A method of dissolving a red-shifting compound and adding the solution into an emulsion as described in JP-A-Sho-to-
A method of dissolving a dye as described in No. 1, No. 1, No. 2, No. 1, No. 1, No. 2, No. 2, No. 2, No. 2, No. 2, No. 2, No. 1, No. 3, No. 2, No. 2, No. 2, No. 1, No. 2, No. 2, No. 1, No. 2, No. 1, No. 2, No. 1, No. 1, No. 1, No. 1, No. 2, No. 1, March 2006, and the like, a dye is dissolved in a substantially water-free acid, and the resulting solution is added to an emulsion. Other additions to emulsions include U.S. Pat.
Pig 6. Corfu, No. 3. ≠The method described in Kota, No. lJj, etc. can also be used. Furthermore, the infrared sensitizing dye of the above general formula (IV) may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but it is of course possible to disperse the infrared sensitizing dye in any step in the preparation of the silver halide emulsion. It can also be distributed.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. tNJ U.S. Patent No. J, 70
3.377, 2.1. It, j Hiroj No. 3,
No. 327.040, same No. J, t/j.

No. 433, No. J, No. 621.26μ, British Patent No. 1,2 Ko 2,111, No. 1.293, It- No.
Special Publication Sho≠3-μ23, Dahiro/Hiro No. 030, Guj-10773, U.S. Patent No. 3゜≠/7. Octopus No. 7,
Tokuko Sho≠3−≠! No. 730, U.S. Patent No. 3. tij, 6
/ No. 3, same No. 3. tij.

No. 432, No. 3, 1. /7. ．． 2ri No. 5, same No. 3゜4
Sensitizing dyes described in 33.7J1 and the like can be used.

In the present invention, a compound represented by the following general formula (■) can be used for the purpose of further increasing the supersensitizing effect and/or the storage stability.

General formula (V) In the formula, -person- represents all covalent aromatic residues, and these are-
803M group [where M represents a hydrogen atom or a cation (eg, sodium, potassium, etc.) that provides water solubility. ]
May contain.

-Person- is preferably selected from the following -A or -A2-, for example. However, if "9", "10% FL11 or R1□ does not include -803M, -A- is -A
Selected from the group 1-.

-A-: S(73M \ O3M 803M SOM 503M S(J3M 03M S(JMSU3M, etc.) where M represents a hydrogen atom or a cation that provides water solubility.

-A2-: Rru, IL and FL1□ are each from Mizurehara 9~
10 l 1 child, 7 hydroxy groups, lower alkyl group (the number of carbon atoms is preferably /~t. For example, methyl group, ethyl group, n-
propyl group, n-methyl group, etc.), alkoxy group (preferably 7 to g carbon atoms, e.g. methoxy group,
ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (I+! I, for example, phenoxy 7 group, naphthoxy group,
o-troxy group, p-sulfophenoxy group, etc.), halogen atoms (e.g. chlorine atom, bromine atom, etc.), heterocyclic nuclei (e.g. ), heterocyclylthio groups (such as benzothiazolylthio groups, benzimidazolyl groups, phenyltetrazolylthio groups), arylthio groups (e.g. phenylthio groups, tolylthio groups), amine groups, alkylamino groups or substituted alkyl groups. Amino group, (e.g. methylamino group, ethylamino group, propylamine group, dimethylamine group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydrokine ethylamino group,
β-hydroxyethyl)amine group, β-sulfoethylamino group), arylapino group, or substituted arylamino group (clearly anilino group, O-sulfoanilino group, m
-sulfoanilino group, p-sulfoanilino group, o-toluidino group, m-)luidino group, p-)luidino group, 0-
Carboxyanilino L m-carboxyanilino group, p
-carboxyanilino group, 0-chloroanilino group, m-
Chloroanilino group, p-chloroanilino group, p-aminoanilino group, 0-anindino group, m-anindino group, p
-anisidine 4, o-acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamino layer (for example, 2-<nzothiazolylamino group, λ-bidylylamino group, etc.), substituted or unsubstituted (f-substituted aralkylamino group (e.g., benzylamino group, 0-anisyl amino group, m-anisyl amino group, p-anisyl amino group, etc.), aryl group (e.g., phenyl group), represents mercapto 4. R3, FL4, FL5, R
6 may be the same or different from each other. -A- is-
When selected from A2-'s Gunto Tame, a RXrt
, Le, □ 9% 10
11 At least one has one or more sulfo groups (which may be free acid groups,
may form salts).

W represents -ch= or -N=, preferably -CH=
is used.

Next, specific examples of compounds included in general formula (IV) used in the present invention will be given. However, the present invention is not limited only to these compounds.

(V-/) Hiroshi, μ′-bis[μ,6-di(penzothiazolyllucochio)pyrimidine-koylamino]stilbene-2,-′-disulfonic acid disodium salt (V--2) 4', μ'-bis[Hiroshi, t-di(penzothiazolyl-co-amino)pyrimidine-coylamino)]]stilbene-2,2'-disulfonic acid disodium salt V-3) 4c, l- Bis(p,G-di(f7thyl-cooxy)pyrimidin-2-ylamino)stilbeneco,co'-disulfonic acid disodium salt (■-μ)tI+V'-bis[Hiroshi, t-di(naphthyl-
4-oxy)pyrimidine-koylamino]bibenzyl-21λ'-disulfonic acid disodium salt (V-t) lI, Hiro'-bis(4L, 4-dianilinopyrimidine-koylamino)stilbeneco, λ'-disulfone Acid disodium salt (V-g)p, ≠'-bis[Hiro-chloro-6-(cornaphthyl-oxy)pyrimidin-2-ylaminocobiphenyl-2゜2'-disulfonic acid disodium salt (V-7 ) ILt, 4c'-bis(p, +-di(/
-Phenyltetrazolyl-jthio)pyrimidine-co-ylamino]stilbene-,21λ'-disulfonic acid disodium salt (V-za) ≠ 1,1/-bis[≠, 6-? Di(penzimidazolylucochio)pyrimidine-λ-ylamino]stilbene-2,2'-disulfonic acid disodium (■-ta) 4L, u/-bis(lI, g-diphenoxypyrimidin-2-ylamino) Stilbene-cot 2'-disulfonic acid disodium salt 4c/-bis(≠, 6-cyphenylthiopyrimidine--ylamino) Stilbeneco, λ'-disulfonic acid disodium salt, ≠'-bis(≠, 6-dimerkabutovirimidi/-koylamino) biphenyl-x, ,2/-,) sulfonic acid disodium salt, bis'-bis(dow 6-dianilitriazine-koylamino) stilbene-,22/- Disulfonic acid disodium salt (7-z3) μ, μ′-bis(guanilino-6(
V"-#') (V-//) (r-/co)-hydrokyltriazin-2-ylamino)stilbeneco, 2'-disulfonic acid disodium salt (V-hat) u,p'-bis[ Gunaphthylamino-t-anilino-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium Among these specific examples, (V-/) to (V-/co) are preferred, particularly C" l-/), (V-J), (T-3),
(V-4'), <v-r>, and (V-7) are preferred.

The compounds of general formula (T) are advantageously used in amounts of from about 0.0/gram of silium per mole of silver halide in the emulsion.

The ratio (weight ratio) between the infrared sensitizing dye of the present invention and the compound represented by the general formula <V> is as follows: infrared sensitizing color chart/compound represented by the general formula (l=l//- The range //100 is advantageously used, especially the range //100 to 17jo.

The compounds represented by the general formula CV) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (such as methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or It can also be dissolved in a mixed solvent of these and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes. Also, Tokukai ShojO
They can also be dispersed and added into the emulsion by the method described in the Roil publication.

In the present invention, compounds of the following general formula (Vl) can be further used in combination.

General formula (Vl) In the formula, z3 is a j-membered or 6-membered nitrogen-containing heterocyclic metal atom necessary for the formation of a nonmetallic atom. j-methylbenzothiazolium, j-chlorobenzothiazolium, j-methoxybenzothiazolium, t-methylbenzothiazolium, t-methoxybenzothiazolium, naphtho(/, 2-d)thiazolium,
naphtho(J,/-d)thiazolium, etc.), oxacilliums (e.g. oxacillium, ≠-methyloxacillium, benzoxacillium, 1-chlorobenzoxacilium, j-phenylbenzoxacilium, j-methyl( 1, imidazoliums (e.g. l-methylbenzothiazolium, t--Propyru-1-chloropenzimidazolium, l-ethyl-yo, 6 -cyclopenzimidazolium, l-allyl-j-)dichloromethyl-6-chloro-benzimidazolium, etc.), selenazoliums [e.g. benzoselenazolium, !-chlorobenzoselenaturium, !-methylbenzoselenazolium , j-methoxybenzoselenazolium, nut (/,
, 2-d) selenazolium, etc.]. ”13
represents a hydrogen atom, an alkyl group (a carbon atom or less, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.), or an alkenyl group (such as an allyl group). "14 represents a hydrogen atom or a lower alkyl group (methyl group, ethyl group, etc.). X2 represents an acid anion (e.g. α-Br-I-1αU4p-toluenesulfonic acid, etc.)
, Z3, thiazoliums are preferably used. More preferably, a-substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used.

The specific interest rate of the compound represented by the general formula (Vl) is shown below. However, the present invention is not limited to only these compounds.

(Vl-/) ■-λ (M-J) (M-≠) (M-1) , ('J-t (M-ti (yl-/2) (M-/J (M-A) CH2- CF(=CF(2 (M-7) CH-CH=CH2 <VI-4) 2H5 (M-ta) (M-/≠) (M-/j) <■-1t 2H5 (M-/7) (M-/J') The compound represented by the above general formula (M) is advantageously used in an amount of from about 0.07 grams to !durams per mole of silver halide in the emulsion.

The ratio (weight ratio) of the above-mentioned infrared sensitizing dye of the present invention to the compound represented by the general formula (M) is the infrared sensitizing dye of the present invention/-the compound represented by the general formula (Vl)*- +m=l/l
A range of ~//300 is advantageously used, in particular //2 ~
//! A range of Q is advantageously used.

The compound represented by the general formula (l) used in the present invention is
It can be directly dispersed in an emulsion, or it can be dissolved in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propatool, methyl cellosolve, acetone, etc.) or a mixed solvent containing multiple of these solvents to form an emulsion. It can also be added inside. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes.

The compound represented by the general formula (M) may be added to the emulsion before or after the addition of the infrared sensitizing dye of the invention described above.

Alternatively, the compound of general formula (■) and the infrared sensitizing dye may be dissolved separately and added to the emulsion separately and at the same time, or they may be mixed and then added to the emulsion.

The silver halide used in the present invention is, for example, T, H
, by James @The Theory of the
Phtographic Process, 1st edition, Ma
Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, Chondral-double jet method, core-shell method described in the literature by Zar-ioti Tei et al. published by cmiIfan (1977) Manufactured by methods such as

If necessary, grain size, grain formation, distribution, etc. can be controlled by using silver halide solvents such as thioethers and thioureas.

Although there are no particular limitations on the grain size, grain size distribution, crystal habit, form (normal crystal, twin crystal, etc.) of the silver halide grains, silver halide grains having a relatively uniform grain size of o, or to 0, rμ are preferable.

In addition, the particle size distribution is preferably monodispersed, and monodisperse means that 3% of the particles have a size within ±i,0% of the number average particle size, preferably within ±0% of the number average particle size. Preferably, it is a dispersion system that falls within the range.

The crystal habit, shape, etc. of silver halide are not particularly limited as mentioned above, but cubic, octahedral, dodecahedral, or a mixture thereof are preferred, and octahedral and dodecahedral are particularly preferred.

The halogen composition includes silver bromide, silver iodobromide, silver chlorobromide,
Any of silver chloroiodobromide, silver chloride, etc. may be used, but it is preferable that the bromine content is 30 mole or more.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

In particular, iridium salts are lo-8 to 10-5 mol/Ag1 mol, and rhodium salts are io-1o-' mol/Ag1
Preferably, it is added in moles.

These silver halides may be chemically sensitized after forming grains and undergoing a desalting step, or may be used without chemical sensitization.

Examples of chemical sensitizers include sulfur sensitizers such as sodium thiosulfate and thiourea; noble metal sensitizers such as gold sensitizers; specifically, chlorauric acid salts, gold trichloride, etc.; palladium sensitizers, specifically Is chloride/? Palladium chloride palladate, etc., platinum compounds, iridium compounds, etc.; Selenium sensitizers, such as selenite, selenourea, etc.; Reduction sensitizers, such as stannous chloride, polyamines such as diethylenetriamine, sulfites, silver nitrate, etc. Chemical sensitization can be achieved by using a sensitizer alone or in combination.

The light-sensitive material used in the present invention contains dyes for use as filter dyes, irradiation prevention, and other purposes.
May contain water-soluble dyes. Such dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, anionine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and benzylidene dyes are useful. Specific examples of dyes that can be used are British patented! Hiro, tori issue, same/, /77, Hirokota issue, Tokukai Sho at-
rzlso issue, same≠7-? 6.20, the same μter//
ll-1f20, jJ-201r22, jP-/
j4t44JP, IP-201!441. U.S. Patent Co., Core≠17t Co., Co., jJ3, ≠72, Same λ
,the law of nature! l,, No. 179, 3. iar.

/Ir No. 7, 3. /77.071, same 3. Kohiro 7.
No. 127, same J,! ll-0, No. 1117, same 3゜! 71.70≠No., same J, 61! , No. 2or, J, 7111. It is described in No. t/-27.

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, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, promobenzibadazoles, butothiazoles.

Mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles,
nitrobenzotriazoles, etc.; mercaptopyridazines; mercaptotriazines; thioketo compounds, such as oxazolinthion; azaindenes, such as triazaindenes, tetraazaindenes (particularly hiro-hydroxy [conversion (l+3t3a,' ) tetrazaindenes), pentaazaindenes, etc.; benzenethiosulfone & many compounds known as antifoggants or stabilizers such as benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, etc. can be added. Among these, preferred are benzotriazoles (eg !-methylbenzotriazole) and nitroindazoles (eg yo-nitroindazole), hydroquinone derivatives (eg hydroquinone, methylhydroquinone). Further, these compounds may be included in the entire treatment solution.

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, active vinyl compounds ('+3*yo-triacryloyl-hexahydro-s-triazine, /, 3-vinylsulfonyl-coprobanol, etc.), active halogen compounds (co,≠-dichloro-6-hydro-?'/ -5-
) riazine, etc.), mucohalogen acids, etc. can be used alone or in combination. Among them, Tokukai Akira!
3-≠/λ-/, same j3-472!7, same 162
! Preferred are the active vinyl compounds described in Hiro 6, AO-ROT, and the active halides described in US Pat.

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, high contrast, and sensitization.

In particular, the surfactant preferably used in the present invention has a molecular weight of 60 and is described in Japanese Patent Publication No. 5R-51'Hiro/λ.
0 or more polyalkylene oxides.

When used as an antistatic agent, a fluorine-containing surfactant (for example, U.S. Patent No. 2.2oi, rt
No. 6, JP-A-Shoto-Rorttt'p) is particularly preferred.

The light-sensitive material used in the present invention may contain a dispersion of a water-soluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, a polymer containing alkoxy(meth)acrylate, alkoxyalkyl(meth)acrylate, glycidyl(meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. as a monomer component may be used. Can be done.

The photographic light-sensitive material of the present invention contains a hydroquinone impregnator (so-called DIR-1) which releases a development inhibitor in the photographic emulsion layer and other hydrophilic colloid layers in accordance with the density of the image during development.
hydroquinone).

It is preferable that the silver halide emulsion layer and other layers 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, a special patent application was filed in 1986! No. 617, 6O-
AIr No. 73, AIr to-it3rz No. 6, and AIr 6O-
The description in IP1611 can be referred to. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and acid monomers such as acrylic acid and crosslinkable polymers having two or more unsaturated groups such as divinylpene as high molecular compounds. It is a water-dispersible latex of copolymer consisting of

Binders or protective colloids used in photosensitive materials include:
It is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used. Specifically, research
Disclosure (RESEARCH DISCLO8
URE) Volume 77, ya/74≠3(/ri7 7-
Month) is listed in ■ section.

In addition to the silver halide emulsion layer, the photosensitive material used in the present invention can be provided with hydrophilic colloid layers such as a surface protective layer, an intermediate layer, a filter layer, and an antihalation layer.

In addition, the photosensitive material used in the present invention has front and back distinguishability,
The back layer (
Hereinafter, this will be referred to as the back layer. ) can be provided. The back layer used in the present invention preferably contains a matting agent having a relatively large average particle size, especially from the viewpoint of adhesion resistance. The preferred average particle size is i,oμm%/0μ
m1 is particularly preferably 0 μm to 6.0 μm.

In addition, the surface protective layer contains polymethyl methacrylate homopolymer, methyl methacrylate and methacrylic acid copolymer, magnesium oxide, etc. as matting agents. 'itD
U.S. patent 3. ≠t ri, j7 number, 4≠, Oda 7
．． The silicone compound described in No. 161, Japanese Patent Publication No. 11. −
In addition to the colloidal silica described in No. 23132, Nohiro rough-in wax, higher fatty acid esters, starch, etc. can be used.

Furthermore, polyols such as trimethylolpronone, intanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer.

In order to obtain ultra-high contrast and high-sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use the conventional infectious developer or the US Pat. Hiro ri, ri 7! It is not necessary to use a highly alkaline developer having a pH close to the pH/j described in the above issue, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at O0/! It is preferable that the developer contains mol/1 or more and the pH of the developer is mol/1.2 or less. More preferably //, 0-2°! It is good to be.

If the pH of the developer is higher than J, the pH will not fluctuate easily due to Co2 in the air, and the developer will also be easily oxidized and colored. If the pH is below 5', it is difficult to obtain high contrast, and clear image quality cannot be improved.

There are no particular restrictions on the developing agent used in the developer used in the present invention, but it is preferable to include dihydroxybenzenes because it is easy to obtain good halftone dot quality, and dihydroxybenzenes are preferred from the viewpoint of developing ability! A combination of :/-phenyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols is preferred.

Dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, etc.
Hydroquinone is particularly preferred as the developing agent for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention, such as 1-phenyl-3-pyrazolidone! -phenyl-4.4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and the like.

Examples of p-7 minophenol-based developing agents used in the present invention include N-methyl-p-aminophenol, p-7 minophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl). ) glycine, among others, N-methyl-p-aminephenol is preferred.

The developing agent is usually 0.05 mol/1. It is preferably used in an amount of ~0.8 mol/2, and dihydroxybenzenes and 1-phenyl-3-pyrazolidones or P-
When using a combination of aminophenols, the former is 0.
It is preferable to use 0.05 mol/N-0.5 mol/l, the latter at 0.0 G mol/l or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. Sulfite is used at least 0.25 mol/1, especially at least 0.3 mol/2, but if too much M is added, it will precipitate in the developer and cause solution contamination, so the upper limit is 1.2 mol/1. It is desirable to do so.

As the alkaline agent used for setting the pH, ordinary water-soluble inorganic alkali metal salts (eg, sodium hydroxide, sodium carbonate, etc.) can be used.

The developer used in the present invention includes boric acid described in Japanese Patent Application No. 61-28708 as a slowing agent, and Japanese Patent Application Laid-open No. 60-934.
Sugars (e.g. sucrose), oximes (e.g. acetoxime), phenols (e.g. 5-
sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), etc., and preferably boric acid is used.

to the developer (preferably 1X10” to 3×IQ-1
buffering agent (having an acid dissociation constant of 2) at O, 1 mol/2 or more;
In particular, 0.2 mol/l-1 mol/β can be added. By adding these compounds, regardless of the amount of silver or blackening rate of the photosensitive material being developed, the
It becomes possible to stably obtain the effects of increasing contrast and sensitivity even when using an automatic processor. Incidentally, the acid dissociation constant herein means a compound having an acid dissociation constant of IXIO" to 3X10-13, regardless of the first, second, third, etc.

Additives that may be used in addition to the above ingredients include pH agents such as potassium hydroxide and sodium carbonate; development inhibitors such as sodium bromide and potassium bromide; ethylene glycol, ethylene glycol, triethylene glycol, and dimethylformamide. Organic solvent layers such as; phenolamines such as jetanolamine and triethanolamine; development accelerators such as imidazur or its derivatives; mercapto compounds such as l-phenyl-5-mercaptotetrazole; indazole compounds such as 5-nitroindazole compound, a benztriazole compound such as 5-methylbenztriazole with an antifoggant or black
pepper) as an inhibitor, and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, etc., if necessary.

The fixing agent contains a thiosulfate such as sodium thiosulfate or ammonium thiosulfate as an essential component, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.The amount of the fixing agent used can be changed as appropriate; Approximately O11~
It is about 5 mol/i.

Examples of acidic hardeners in the fixing solution in the present invention include water-soluble aluminum salts, chromium salts, and ethylenediaminetetraacetic acid complexes using trivalent iron compounds as oxidizing agents. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate, and potassium alum.

The amount added is preferably 0.01 mol to 0.2 mol/2, more preferably 0.03 to 0.08 mol/l.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. These compounds are used in fixer 11
It is effective to contain at least 0.0 mol per mol, especially 0.0 mol or more.
Particularly effective is 1 to 0.03 mol/2 morph.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, potassium aluminum tartrate,
Potassium antimonyl tartrate, sodium antimonyl tartrate, lithium hydrogen tartrate, lithium tartrate, magnesium hydrogen tartrate, potassium boron tartrate, potassium lithium tartrate, etc.

Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution may optionally contain preservatives (e.g. sulfites, bisulfates), pH buffers (e.g. acetic acid, boric acid), pn
Modifiers (eg, sulfuric acid), chelating agents (described above) may be included. Here, since the pH of the developer is high, the pn buffer is preferably IO-Hog/l, more preferably 1t-2tg/l.
Use about 1.

The fixing temperature and time are the same as for developing, approximately 20°.
C to about 5oC and io seconds to 1 minute is preferred.

Next, the present invention will be explained with reference to examples.

In addition, the following formulation was used as a developer.

Processing liquid formulation (I) (2
) Hydroquinone jO,0gN methyl-
pAminophenol O,jg-l 14 sulfate Sodium hydroxide /I, Og! -Sulfosalicylic acid j! , 0g potassium sulfite
/10.0g ethylenediaminetetraacetic acid di /,0
g sodium potassium bromide! -Methylbenzotriazole comercaptobenzimidazole! -Sodium sulfonic acid 3-(!-mercaptotetrazole)benzenesulfonate N -N-ButyljetanolamineSodium toluenesulfonate Add water to pH Treatment solution formulation Hydroquino/Hiro-Methyl-≠-Hydroxymethyl-7-phenyl= 3-pyrazolidone io,og O99g 0.3g 0.2g 1s,og r,og /l 17.6 2yo,Og O,jg //,3 Potassium sulfite ta0. Og 1 ethylene diamide/tetraacetic acid dichloride Qg 1 sodium potassium bromide 5.0 g Ij-Methylbencitriazo 0.2 g 1-l λ-merkabutobenzi 0.3 g g Dacil! - Sodium carbonate sulfonate jO, Og I (Add sodium hydroxide to adjust pH to 10.t) Add water and l1 pH 10,71
0, IIL Comparative Example to Aqueous gelatin solution maintained at 0C was subjected to a control double jet in the presence of ammonia) 4, AgNO
3 solution and a KBr solution containing an Ir salt were simultaneously added for 60 minutes and maintained at a potential of f + j j m V during the period, thereby reducing the average particle size to 0. A cubic monodisperse emulsion of JOμ was prepared, and after grain formation, the emulsion was washed with water and dispersed. (Emulsion a) In this emulsion, ≠-hydroxy-6-methyl/.

J, Ja, 7-chitrazai/de/, a dispersion of polyethyl acrylate, /, J-divinylsulfonylcoprobanol was added as a hardening agent.

Furthermore, the hydrazine compound l-27 of the present invention is added to
t-m and coated silver amount on polyethylene terephthalate film 3. Ig/m2, and a gelatin protective layer was applied thereon.

For the protective layer, gelatin, dodecylbenzenesulfone, soda, and fluorine surfactant (C3H1□502N(
C31-17) CH2COOK), colloidal silica,
An aqueous gelatin solution consisting of a dispersion of polyethyl acrylate, a matting agent of polymethyl methacrylate, and a thickener of sodium polystyrene sulfonate was adjusted to have a gelatin coating amount of 7 g/rn2. Let this sample be A.

■-2, ■-i<, 1'l in the emulsion layer of sample A, respectively.
/-7 sensitizing dye ≠, jX10' mol 1 mol Ag
In addition, they were designated as B, C, and D, respectively.

This sample was subjected to sensitometry using a photosensitive needle having a light source with a color temperature of 21j410 and a dark red filter (SC-72) manufactured by Fuji Photo Film Co., Ltd. attached to the light source.

After exposure, using the above developer (I) (2), 3≠'Cj
The film was developed for 0 seconds, fixed, washed with water, and dried, and the sensitivity change (ΔSfog+1.5) of the fatigue solution with respect to the Fr solution was examined.

A l-27 B V-2CV-+ V-7 -o, io /J -0,Ij /≠ -0,20/Hiro-o, ir i3 The presence of the sensitizing dye reduces the pH dependence of the processing solution. , you can see that it's getting bigger.

Example 1 The hydrazine compound 1-27 4AJ9 of Sample A%B, C, and D prepared in the comparative example was adjusted to 2θ~/m, and the compound ■-ta of general formula (If) was further added to 1ooq/m2. In addition, samples A', B'C/, and D/ were prepared.

After these samples were exposed in the same manner as in the comparative example, they were developed with Jr0C for 30 seconds using the above-mentioned developing solutions (3) and (4), fixed, washed with water, and dried.
The change in sensitivity to

Hydrazine compound Nucleation accelerator Sensitizing dye GO03-
1,01-27I [-PI3 V-λ /3 ■-Otsu 13 ■-772 ΔS 1.5 -0.01 -0.03 -0.0≠ -0,02 Sensitizing dye and nucleation accelerator It can be seen that in the system used in combination, high contrast was obtained despite the low pH of the developer, and the sensitivity was stable against fluctuations in the pH of the developer.

Example λ Sample A%B%C%D 'l'00c7! %RH 3-day glycerin thermotest was carried out, and treated with developer (I) in the same manner as in the comparative example. Sample A'B', C'
, D' similarly uo 0c7! %I'tHj day glycerin thermotest was carried out and treated with developer (3) in the same manner as in Example. Determine the difference in sensitivity between before and after the thermo test for each sample.

Sample Developer A (I) A' (31 B'C'D' Sensitivity change for Fresh (Δ5) -0, / ! 10, Hiro Q -0, jλ 10, ≠5 -0, / 0 -0 .0≠10, 0j -0,01 It can be seen that the storage stability is significantly improved when the sensitizing dye and the compound of general formula (II) are used together.

Claims (1)

[Scope of Claims] A black-and-white image forming method in which a negative photographic light-sensitive material having at least one silver halide emulsion layer on a support is treated with a developer having a pH of 11.2 or less after image exposure, wherein the emulsion layer or In other hydrophilic colloid layers, the following general formula (I)
An image forming method comprising: a hydrazine derivative represented by the following formula; a compound that makes gamma 6 or more at pH 11.2 or less; and an infrared sensitizing dye. General formula (I) ▲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, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarnebonyl group; G_1 is a carbonyl group;
Represents a sulfonyl group, sulfoxy group, ▲ mathematical formula, chemical formula, table, etc. group, or iminomethylene group, A_1
, A_2 both represent a hydrogen atom, one hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.