JPH0484134A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which is hard in contrast, fogs less and has good dot performance even if this material is processed with a developer of pH as low as <11 by incorporating compd. and nucleation accelerating compds. which are respectively specific. CONSTITUTION:At least one kind of the hydrazine compds. expressed by formula I and at least one kind of the nucleation accelerating compds. selected from an amine compd., hydrazine compd. and quaternary onium chloride compd. are incorporated into this photosensitive material. In the formula I, Ar denotes an aryl group; X denotes -NR1R2 or -OR3: R1, R2 denote a hydrogen atom, alkyl group, etc.; R3 denotes a hydrogen atom, alkyl group, etc.; R denotes a hydrogen atom or alkyl group; n denotes 0 or 1; m denotes integer of 1 to 3. The silver halide photographic sensitive material which has the photographic characteristic of a high contrast in spite of processing with the developer of pH <11, suppresses the fogging generated in the dot images and has the good dot performance is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photographic material having a silver halide photosensitive layer on a support, and more particularly to a silver halide photographic material capable of providing high contrast.

[Background of the invention]

The photolithography process involves converting a continuous tone original into a halftone image. In this process, contagious development has been used as a photographic technique capable of reproducing ultra-high contrast images.

The lithium-type silver halide photographic material used for infectious development has, for example, an average grain size of 0.2 μm, a narrow grain distribution and uniform grain shape, and a high silver chloride content (at least 50 mol% or more). ) Consisting of a silver chlorobromide emulsion. By processing this lithium-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, images with high contrast, high sharpness, and high resolution can be obtained.

However, these developing solutions are susceptible to air oxidation and have extremely poor storage stability, making it difficult to maintain constant development quality even during continuous use.

A method for quickly obtaining high-contrast images without using the above-mentioned Lith type developer is known.

For example, U.S. Patent No. 2,419,975, JP-A-51-
No. 16623 and No. 51-20921, No. 56-10
As seen in No. 6244, etc., a hydrazine derivative is contained in a silver halide photosensitive material.

With these methods, it is possible to maintain a high sulfite ion concentration in the developing solution, and it is possible to process with improved preservation.

However, in these methods, in order to fully exhibit the high contrast properties of hydrazine derivatives, it was necessary to process with a developer having a pH of 11 or higher.
Is a developer with a high pH of 1 or more more stable than a lithium developer, in which the developing agent tends to oxidize when exposed to air?
Due to oxidation of the developing agent, ultra-high contrast images may not be obtained.

In order to compensate for this drawback, Japanese Patent Application Laid-open No. 63-29751 and European Patent No. 333,435 and European Patent No. 345.025 disclose silver halide photographic sensitizers containing a high contrast agent that can achieve high contrast even in relatively low pH developing solutions. Materials are disclosed.

However, when silver halide photographic light-sensitive materials containing high contrast agents such as these are processed with a developer having a pH of less than 11, the present situation is that the high contrast is insufficient and satisfactory halftone dot performance cannot be obtained. .

On the other hand, European Patent No. 364166 and JP-A-62-
No. 222241, No. 60-140340, No. 62-2
No. 50439, No. 62280733, etc. describe nucleation accelerators to promote high contrast, and it is true that adding these compounds to the emulsion layer improves halftone dot performance, but It has been found that sand-like or bottle-like fog, so-called black pins, occur in the film, causing a problem in which the quality of the halftone dot image is impaired.

Therefore, there is a need for a photosensitive material using an effective contrast enhancer and nucleation accelerator that solves the above-mentioned problems.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material that has high contrast photographic properties even when processed with a developer having a pH of less than 11, and also has good halftone dot performance by suppressing fog that occurs in halftone images. There is so much to offer.

[Structure of the invention]

The above objects of the present invention have been achieved by a silver halide photographic material having the following structure.

That is, a silver halide photographic material having at least one silver halide emulsion layer contains at least one hydrazine compound represented by the following general formula [A], and contains an amine compound, a hydrazine compound, and a quaternary onium. The above object has been achieved by a silver halide photographic material containing at least one nucleation-promoting compound selected from salt compounds.

General formula (,1 O (R-(0 US ÷ "Ar-NHNH-C-C-X, where A
r represents an aryl group, and X is -NR, R2 or -0R1
, R1 and R2 are each a hydrogen atom, an alkyl group,
alkenyl group, alkynyl group, aryl group, heterocyclic group,
Hydroquinyl group, alkoxy group, alkenyloxy group,
It represents an alkynylokyne group, an aryloxy group, or a heterocyclicokyne group, and R and R2 may form a ring together with the nitrogen atom.

R3 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

R represents a hydrogen atom or an alkyl group, n represents 0 or 1, and m represents an integer of 1 to 3.

However, in the compound represented by the general formula CADI, at least one R has a group that promotes adsorption to silver halide, or
Alternatively, diffusion resistance shall be imparted as the sum of R in the molecule.

In the compound represented by the general formula [A], N1 (NH-
includes those in which at least one of H is substituted with a substituent.

To explain the general formula [A] in more detail, Ar is
Represents an aryl group (eg phenyl, naphthyl, etc.).

R1 and R2 are each a hydrogen atom, an alkyl group (e.g. methyl, ethyl, methoxyethyl, cyanethyl, hydroquinethyl, 4-(2,4-di-t-amylphenoxy)butyl, benzyl, trifluoroethyl, etc.) , alkenyl groups (e.g. allyl, butenyl, pentenyl, pentagenyl, etc.), alkynyl groups (e.g. glopargyl, butynyl, pentynyl, etc.), aryl groups (e.g. phenyl, naphthyl, /anophenyl, methoxyphenyl, etc.), heterocyclic groups (e.g. pyridine). , thiophene, 7rane or saturated heterocyclic groups such as tetrahydrofuran, sulfolane, 2,2,6,6-titramethylbiperidine), hydroxyl groups, alkoxy groups (e.g. methoxy, ethoxy , penzyluoquine, cyanomethoxy, etc.), alkenyloxy groups (e.g. allyloxy,
R1 and R2 represent nitrogen Together with the atoms, they may form a ring (eg, hahyperidine, piperazine, morpholine, etc.).

an alkyl group, an alkenyl group, an alkynyl group represented by R3,
As the aryl group and the heterocyclic group, specifically, the above-mentioned R
, and the same groups as those listed for R2.

Examples of the alkyl group represented by R include methyl, ethyl,
Six groups include propyl, butyl, benzyl and the like.

Various substituents can be introduced into the alkyl group represented by R, but
Examples of such groups include carbamoyl group, ureidocarbonyl group, oxycarbonyl group, anrulamino group, sulfonamido group, carbonyloxy group, sulfamoyl group, and the like.

A diffusion-resistant group or a silver halide adsorption-promoting group can be introduced through these substituents.

The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers.

A ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkyl 7-enyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

When there are a plurality of R-(◯)n- groups in the molecule, it is sufficient that the sum of the R groups (as a whole) imparts diffusion resistance.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385.108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

Various substituents can be introduced into the aryl group represented by Ar. Examples of substituents that can be introduced include halogen atoms, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfamoyl, acyl, amino, alkylamino, arylamino, and acylamino. , sulfonamide, arylaminothiocarbonylamino,
Examples include groups such as hydroxyl, carboxyl, sulfo, nitro, and cyano.

In the general formula [A), N1 of -NHNH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (e.g. methanesulfonyl,
(toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, ethoxycarbonyl, etc.), an oxalyl group (e.g., oxalyl, pyruvoyl, etc.); The compounds represented also include such compounds.

In the present invention, more preferred compounds (2, general formula (A
) in which at least one of R1 and R2 represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group, or an alkoxy group, or a compound in which R1 represents an alkynyl group or a saturated heterocyclic group.

Typical specific examples of the compound represented by the above general formula [A] are shown below, but the present invention is not limited thereto. The compound is described in British Patent No. 2.011.391 and US Patent No. 4.686.167.
No., European Patent No. 301,799, JP-A-62-1
It can be easily synthesized according to the synthesis method described in JP-A No. 80361, No. 62-178246, and the like.

For example, the exemplary compound (1) can be synthesized by the following method.

Compound (13) can be synthesized by the following method.

Ru. Among these, preferred compounds include (V)-1゜[
■]-II, [V)-11[,CVT)-I, (
Examples include the compounds Vl)-II and (Vl)-■.

General formula CI) Other compounds can be similarly synthesized.

In the present invention, the amine compound, hydrazine compound, and quaternary onium salt compound of the nucleation promoting compound to be used in combination with the compound represented by the general formula [A] is represented by the following general formula [I].
- [VI) Compounds are mentioned, and Rr, R2, and Rs represent a hydrogen atom or a substituent. R3R2 and R3 may be linked to each other to form a ring.

Examples of the substituents represented by R, R2, R include alkyl groups (for example, methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, etc.), alkenyl groups (for example, allyl, butenyl, etc.), alkynyl groups ( (e.g., propargyl, butynyl, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), heterocyclic groups (e.g., piperidinyl, piperazinyl, morpholinyl, pyridyl, furyl, thienyl, tetrahydrofuryl, tetrahydrothienyl, sulfolanyl, etc.) Can be mentioned.

Examples of the ring that R, , R, , R may be formed by linking each other include piperidine, morpholine, piperazine,
Examples include rings such as quinuclidine and pyridine.

The groups represented by R, R2, R, may be further substituted with a substituent (for example, a group such as hydroquine, alkoxy, aryloxy, carpoquine, sulfo, alkyl, aryl, etc.). R, , R2, R are preferably a hydrogen atom or an alkyl group.

Typical specific examples are shown below.

I-I l-2 (C2Hs)2NcH2cFlzcI (zOHC83N
)ICH2CH20HI-3l-4 (C2H5)2NC)12CH20f((CzH5)2
NCH2C1(CH20)1H I-5, 1-6 ■ (C+H*)2NcHzcHzo)l (C,H,)2NCH2CHCH20HH ■ ■ -14 ■ ■ -16 ■ ■ ■ (i-C31h)2NH ■ C+HsN (CHaCH20H) 2 ■ (Ph-CH2)2NCH2CH,OH■ (C1l)117)2NCH2CH20H■ (C+Jx,)2Nc82GHzOH General formula (II) R2-, Q-R.

I Xo Q represents N or P atom, RI+ R2+ R3+ R
4 each represents a hydrogen atom or a substitutable group. Xo represents an anion. R,, R,, R,, R, may be connected to each other to form a ring.

Examples of substitutable groups represented by R, R2, R, and R include six groups such as alkyl, alkenyl, alkyl, aryl, petero ring, and amino. ), those explained for R,, R2, R3° can be mentioned.

Rings that Rl+ R2+ Rs and Ra can form include:
Examples of the ring that can be formed by R,, R2, and R in the general formula CI) include the same rings as those described above.

Examples of the anion represented by X8 include inorganic and organic anions such as halide ions, sulfate ions, nitrate ions, acetate ions, and paratoluenesulfonbutyric ions.

Typical specific examples are shown below.

It-I I[-2 Ph CH2N(CHI)I CQeC161(3
1N(CIll)I Br'Ph CH2N(C
H3) 2 CQ0 Director c, 482 e CI2H250Ph CH2N(CHs) x C
(10t-9 (UzHs) 3N (H2) aN (2Hs) 32Q
'':' CH2C1(2-Ph r0 ■ CHzCOOCJ CH2Ph N) IcOcs)In ■ ■ CQe CHxCH200C(CH2)+COOCfbCHx General formula CIII) ■ (CJs)+pe CI 6H33 Br0 Br' R,, R2 represents an alkyl group, R 1 and R2 may be linked to form a ring.R1 is an alkyl group, an aryl group,
It represents a heterocyclic group, and A represents an alkylene group.

Y is 100NR, -, -0CONR, -, -NR, C0
NR4-, -NR,Coo-.

coo--oco-, ~Co-, -0COO-, -NR
, CO-, -502NR.

NRISO2-, NR45O□NR,-, -3O2-,
-3-, -0-, NR.

N= represents a group, and R4 represents a hydrogen atom or an alkyl group.

As the alkyl group represented by R8 and R2, the general formula [■
Examples include the same alkyl groups as Rl, R2, and R1 explained above, and examples of the ring that can be formed by R1 and R2 include the same alkyl groups.

Examples of the alkyl group, aryl group, and heterocyclic group represented by R3 include those similar to the alkyl group, aryl group, and heterocyclic group represented by R, , R, , R in the general formula [E].

Examples of the alkylene group represented by A include methylene,
Examples include ethylene, l-rimethylene, and tetramethylene, and examples of substituents for A include aryl groups, alkokene groups, hydroxyl groups, and halogen atoms.

The alkyl group represented by R is preferably a lower alkyl group having 1 to 5 carbon atoms or an aralkyl group (eg, benzyl group).

Typical specific examples are shown below.

■ (C2H5)2N(CH2)2NHCOC13H27(
CH3)2N(CH2)2CONHC14H29(C2
Hi)2N(CH2)3NHcONHc+28. s■-
12 cso++(t) ■ (CIHs)2N(CHz)zOcON)ICeH+
7(C,R9)2N(CH2)3NH502N(CH2
Ph).

■ (Pb-CH2)2N(CH2)30C,R9CH2)
2N((Jh)2NHs02N(CH＞'h0C1□H
2S ■ C3H7(i) R2 General formula (TV) TV-4 R,, R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and R1, R
2,E may form a ring.

E is a group containing at least one group represented by (CH2CH20i, and n represents an integer of 2 or more.

Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group represented by R, ,R, and R1゜R2,E
Examples of the ring that can be formed include R+ of general formula CI], R
2. The same ones as those explained in R3 can be mentioned.

Typical specific examples are shown below.

TV-1 TV-5 (C4)19)2N(CH2CH20)3HV-6 (C2H5)2N(CR2CH2O)~,,CH2CH
2N(C2H5)IC,R7)2N(CH,CH20)
, CI(2C82N(C3H.

TV-10 (C2Hs)2N(CH2CH20)~3zcH2cH
2N(C2Hs)2(i-C3H7)2N(CH2C
H20)~6H■-2 (C3H+)2N(CH2CH20)~scHzcH2
N(CsHy)2(CJ7)xN(CH3CH20)i
f(■ (C+H+)2N(01zC)I20)~, ,CH2
CH2N(C1l(7)2C[(: =CFIC)12
NH(CH2CH20)~1. cH2cH2NHcH2
cH=cH.

■ CI(2CC82NH(CI(2CH20)~+ *C
HzCH2NHCH2C MiCI((C3H7)2N(C
H2CH20) ~ 32CH2CH2N(C3H+)2(
CIF! 9) 2N(CH2CH20)~sC)] 2
CH2N (Ct H+ ) 2■ (C,H,)2N(CH20H20)21((C,H2N(CH2C1(20)~, ,CH2CH2N(C
,I(,)2■ (c, o, 7)2N(CH2CH2O)28■ (CHx)2cHcH*c)INH(CHzCH20)
〜+tcH2cH2NHcHct(,CH(CHx)
2(CnaHss'1zNccHzcHzo')xH■ (Ph CH2)J(CHzCHzO)J(CHx)
2CH(CH2)xcHNH(CH2CH20)〜+
a CH2CH2NHCHCH(CH2) i CH(
C83) 2■ (C4Ht)2N(CH20H20)2cHzcHzN
(CnHs)zCsH+ +NH(CH2CH20)~
, ,CHICH,NHC5H.

■ (CsH+ +)zN(CI(zcl(zo)2cHz
cH2N(Cs)It 7)2c,o,5NH(CH
2C1(20)~zCH2CH2NHC7H+i■ (HOCH2CH2)2N(CH2CH,0)2CH2
CH2N(C)1. c) I20H)! (HOCHHzCH
2) 2N (CHZCH20) ~ + IC1 (2C82N
(CI(2CH20H)2 General formula [■]-a (CI(2= CH2CH2) zN(CI(:CH2
0) 2H(CH2=CHCH2)2(CH20H20)
2CH2CH2N (CH2CH-CH2)2C6H! 1 Ca! (z COs l:H=CHC)12N (CH2CHz
O) 2 C) 12 CH2NCH2CH= CHC
H3CH,-Pb CH2-PhR,,R
2, R is an alkyl group, an alkenyl group, an alkynyl group,
Indicates an aryl group or a heterocyclic group.

However, at least one of R, R, and R3 represents an alkenyl group or an alkynyl group, or at least one of RR2 represents an aryl group or a heterocyclic group. Rr, R2, L, and Rs may form a ring. L represents a linking group.

The alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by R,, R2, and R include RItR! of the general formula [E]. The same groups as those listed for +Rs can be mentioned.

Examples of the ring that can be formed by R, , R, , L and R1 include heterocycles such as piperidine, morpholine, and pyrrolidine.

As a linking group represented by, for example, general formula (III)
-A-Y- mentioned above can be mentioned.

Typical specific examples are shown below.

V-a-1 (CH3)2N(CI(z)3NICONFl(CHz
)acH−CHCaH+ y■ (C21(s) 2N(CH2) xNHco(CH
2) yCH= CHCJ Iy-a (C4Hs)2N(C)h)zOcONH(CHz)s
cH=cHcsH+ 7■ (CzHs)2N(CH2)3N)ICOO(CH2)
gcH=cHcaH+ 7 ■ ■ ■ -a-8 -a ■ (CHz = CI(CH2)2N(CH2)2NH5O
2N(Ph-CH2)2-a (C4Hs)zN(CHz)3NH3O2N(CHzC
H-CHz)z-a (Ph CHz)zN(CH2)zNH5OzN(C
I(zcH=cHz)z■■ (C2H5)2N(C)12)30COC:CC6H,
3-a (C2Hs)2N(CH2)2NHCOOCH2C=C
C+H+ s■ (Ph CH2)2N (CI(2)20CONHC)
l:C-CH-a-13 (Ph C112)2N(CH2)2NHcON(C
H2CH=CI(z)2■ (Ph CHz)2N(CH2)3NHcOcmiCC
,H,3■ (Ph CH2)2N(CH2)2NHCOOC1(
2CH=CH2 and 2H5 ■ -a General formula R, , R2, R4 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and is a hydrogen atom or a substitutable group Table 1゜L is a linkage represents a group, and n represents an integer of 0 or l.

R2, R,, L, R, may be connected to form a ring.

Examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by R, , R2, and R include the same groups as explained for R1, R2+R3 in the general formula [■].

Examples of the substitutable group represented by R3 include six groups such as alkyl, alkenyl, aryl, and heterocycle, including the same groups as mentioned above.

L represents a linking group, for example -co-, -coo-CO
Represents a group such as NRs, 502, 5O2NRs-.

R6 represents a hydrogen atom or a substitutable group.

Examples of the ring that can be formed by R, , R2, R, , L and R include heterocycles such as piperidine and morpholine.

(CI(3)2NNH5O2C+6Hx+(C)Iz)
zNNH5O2(Ph C1(2)2nu-!-no■ -b -b (CH2-Ph)2NNH3O2C,H,7■ (Ph-CH2)2N-NCOC,3H2□H2-Ph -b ■ (CH2=CHCH2 )2NNH5O2CI2H2S ■ -b ■ b ■ ■ -b ■ ■ ■ General formula % Formula % R1 represents a hydrogen atom or a substituent, R2 represents 6 groups of alkyl, alkenyl, alkynyl, aryl, and heterocyclic group.L is Represents a linking group.

C,) represents a nitrogen-containing heterocycle. n represents an integer of 0 or 1. R1 is Mari! form a ring with ゛,,-,5
′ is also good.

The six groups of alkyl, alkenyl, alkynyl, aryl, and heterocycle represented by R2 include R of the general formula CI)
l+R 2+R The same groups as those explained for s can be mentioned. Examples of the substituent in the group represented by R1 include the same groups as those explained for R2 above.

As a linking group represented by, for example, the general formula CI [[)
Examples include those similar to those represented by Y in .

Typical specific examples are shown below.

-c Examples of possible heterocycles include heterocycles such as quinuclidine, piperidine, and pyrazolidine.

■ ■ ■ ■ ■ CH, CH-CH2 ■ ■ C,H.

■ ■ - ■ ■ ■ - ■ ■ -c ■ -c-31 -c-35 ■ General formula (VI) R, , R represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, R1 represents a hydrogen atom or a substituent.

R4ha ACHx CHX end Mataha (CH2CHCH2
Oi is a group containing at least one group represented by Te. R
represents a hydrogen atom or an alkyl group, and X is 0.3 or NH
Y represents a hydrogen atom or an OR group, and n represents an integer of 2 or more. R,, R2, R1, and R may be connected to form a ring.

R+, R! Alkyl group, alkenyl group represented by
Examples of the alkynyl group, aryl group, and heterocyclic group include the same groups as those explained for R, , R2, and R in general formula (I).

Examples of substituents among the groups represented by R1 include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, oxycarbonyl groups, and carbamoyl groups. Among the substituents represented by R3, alkyl groups, alkenyl groups, alkynyl groups,
As the aryl group and heterocyclic group, R□ of the general formula [■]
, R2, R, and the same groups as explained above.

Examples of the anlu group include acetyl and benzoyl, examples of the sulfonyl group include methanesulfonyl, toluenesulfonyl, etc., examples of the oxycarbonyl group include etquin carbonyl, phenoxycarbonyl, etc., and examples of the carbamoyl group include , methylcarbamoylmoyl and the like.

Examples of the ring that can be formed by R , , R 2,R , , R , include rings such as piperidine and morpholinone.

Among the groups represented by R, the alkyl group is methyl, ethyl, etc., and the methyl group is preferable.

Typical specific examples are shown below.

l-a-1 (C)Is)zNN)l(CHzCHzO)~, Hl-a-2 CH2-Ph (CH3)2N-N(CltaC)120), HI-a
-3 (CH3)2NNH(CH2CH20)~racH2
cHzNHN(C)lx)2l-a-4 (CJh)tNN[((C)lzcHzo)~. CH2
-Ph■ a-5 ■ l2 C2H, C2+'+5 CC2H,)2N? (CH2CH20) ~3■CH2CH2NN(C2}
15) 2■ a-5 (Ph CH2)2NNH(CH2CH20)~, ,CH2C
H2NHN(CH2Ph)2 ■ a-7 S02CH3 S02CH3 (Ph-CH2)2N? (CI{2CH■O)〜3■CH 2C}I 2NN
(CH2 Ph). ■ ■ l4 CI{2 ph (Ph CH2)2N N(CH2CH20) ~,, CH2 ph ■ l5 COOC 2 H 6 COOC . H 5 (Ph CH2)2N N(CH2CH20)-30C82C82N N(C
H2Ph)2 COCH. COCH 3 ■ l6 (i-C3H7)2N-N(C}l, CH, O) ~ Ir
CH2CHyN N(C3H7!)x(Ph
CH2)2NNH (CHzCH20)zcH2cH2N
[{N(CHzph) 2 ■ (Pb CHx)2NNHCCH2CHxO)-3o
HVl-a l8 (CHz=CHC[{z)2N N(CH2CHzO
)-30CH2CH2N N (CH2CH=CH2)
2CH3 (CH3)2NNH(CH2CHO)-+oH■ a -19 Vl-a CH3 CH3 (Ph CH2)2NNH(CH2CI{2NH)~
16F+(CH3)2NNH(CH2CHO)~6CH
2CHNHN(CH3)2■ ■ a-20 CH2-Ph (Ph CH.)2N N((CH2Cl42NH)~6H]2(CH3)2N N(CH2CHCH20)~6H ■ a-28 0H (CH3)2NNH(CH2CH2S) 6CH2CH2
NHN(CH3)2■ a-21 Vl-a CH3 CQCH3 COCH 3 (CH3)2NNFI(CH,CHO)~l 2(CH
2CHCl{20)~6H(Ph CH2)2N
N(CH2CH2S)~6CH2Cl{2N N(C
H2 Ph) 20H ■ a-30 C2H5 CH3 VI-a-22 (Ph CH2)2N N(CH2CHC}120
)~+o(CHzCHO)-+oH(Ph CHz)
,NNH(CHzCHCHzO)~1480H 0H VI-a 3l ■ a-23 CH2 Ph CH2 ph H(OCR2CF+2)~14N N(CH2CH20)~l,H ■ CH3 CH3 ■ a-24 Ph CH2(OCH2CH2)-+oNN (C.I. {
2CH20)-10CH2 Ph(CH3)2N
N [(CH2CH20)-+oH)z ■ a-33 ■ a-25 COCH s COCH 3 (c2H6)2N? H(CH2CH2NH)-■oH (CH3)28 N(CH2CH20)~32CH2
CH2N N(CH3)2■ ■ a-42 COC: li 5 COC2H5 COCH 3 (Ph CH2)zN N(cCH2ch2o)~,,CH. CH2NN(CH2ph)2 (Ph-CH,). N-N(CH2CH2CH20)
−, 8 (CH.CHC}1.0) −1. 8 ■ 0H COCH 3 ■ a-43 (Ph CH.)2N N (CH2CH20) ~3
3CH2-PhCH2 ph CH2-Ph (Ph CH2)2N N(CH2CHpCHzO)-acHzcHzcH2N
N(Cl2 Ph)2 ■ a-44 COCH, COCH, (CH3)2N-N(C}12CI{2CH20)-
．． ．． CH2CH2CI{2NN(Ct{+)+ General formula [VI) b ■ (CH3)2NNH(CH2CH2CH20) ~8HR
l and R 2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R , , R 2, and T may form a ring.

0H ■ (C4H 9 ) 2NNH(CH2C}l 2CH2
0)-2 0CH2CH 2CH2NHN(C4H
s) 2T is RACHz-CH-X} and 1:l. -{CH2-CH
-CH. -03y "'Q Table Y ■ COCH3 A group containing at least one COCH3 group.

(C2H5)2N-N(CH2CH2CFI20)~8
CH2CH2CH2N N(C2H5)2R represents a hydrogen atom or an alkyl group, X represents an 0 S or NH group, Y represents a hydrogen atom or an OH group, and n represents an integer of 2 or more.

however, R or hydrogen field When I was a child, X is S or It represents an NH group.

Among the groups represented by Rl and R2, the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group include R + . R2. The same groups as those explained for R h can be mentioned.

Rings that can be formed with R l, R 2 T include piperidine CH, CH, morpholine, quinuclidine, virazolidine, etc.
II INH(CH2CHO)-1. CH2CHNH
Examples include heterocycles of CSH and 1.

■ b The alkyl group represented by R is methyl, ethyl CH3 CI{3 Le et al. Methyl group is preferred.

(CH2 = CHCH2)zN(CH2CHO)-ec
HzcHN (CHzCH=CH2)2 Representative examples are shown below.

■ b ■ ■−b CH, (C3}1,). N(CH2CFIO)~6H■ b CH+ CH. (C=HJ2N(CHzCHO),■ (CaH+ v)xNccHxcHo)zH■ b-3 CH. Cl3 ■ b l0 (CJs)2N(CHzCHO)〜+ *CH2CHN
(C2Ha)2CH, CH, (Ph CH2)zN(CHzCHO)2cH2cH
N(CH2Ph)2 ■ b ■ C51(,,NH(CH2CHCI(20)~128H ■ CH3 ■ ■ ■ (C2H5)2N(CF]2CHCH,O)~8HH ■ (CaH+ 7)2N(CH3CHO)120)~ 14
8H ■ (CH2-CHCH2) zNccH2cHcfho)
-+ oHH Vl-b-22 (Ph CHz) 2N (CH2CHCHzO) ~ 3H
H VT-b-29 CH.

(Ct89)zN(CH3COO)-a(CHzCHC
HzO)-1oFIH VI-b-30 Vl-b-31 CH.

(C12 CHCH2>tNccH2cHcH,o), -1, (C
)12c)10)-,oHH ■-b-32 CH3 CmH+tNHCCHtCHO')-3-CCHxCH
CHzO)-zaHH vr-b-33 Vl-b-34 ■ b ■ (C41(ri2N(CH2C)12NH)~14'1■ (CH,=CHC)12)2N(CH2C)12NH)
~2゜H Hl ■ ■ Call□NH (CH2C82CH) ~+6H■ Vl-b-45 ■ ■ ■ (Cx1(y)2N(C4C)lzs) ~5cH2cF
lzN(C3H+)iv+-b C,H% C,H.

■ CH2-C)1cH2N(CH3CO,S)~1°CH
2C82C)12cl(-CH2(C)1.CH=CI
(C1(2)2N(CH2CH2■■-b C,I(,,N)1(C)12cI(2S)~l□CH
2CH2NHC,H,.

v+-b VI-b-57 ■-b-51 ■ (C4H,)2N(CH2C82C)1,0)~, HV
l-b-59 ■ (CH2-CI(CHz)zN(C)lzcHzcHz
o) ~1°Ht-b C,H.

CI(;CC1(,N(CI(2CO,CH,O)~1
4H ■-b-61 ■ C3H.

■ CH=CC)12N1((CI(2CH2S)-2°C
H2CH2NHCH2C=CHC0,= CHCH,N
(CH, CH2C82C) ~+ *(C)IxCHCH
*O)~1゜HH VT-b-62 C,H,,N1((CHICI(,CH20)~12H
Vl-b-63 General formula (Vl) -c ■ ■ Vl-b-66 Vl-b-67 ■ t13 (C2H8)2N(CH,CH2CH,0)-2oCH
2CH2CH,N(C2H6)2R+, R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R1, R2, and G may form a ring.

G contains at least one group represented by -(CI(2CH20)E-) and has a hydrophobic substituent constant π value of -0,5 to
It shall contain at least two substituents of −1,0 or at least one substituent whose π value is smaller than 1,0. n represents an integer of 2 or more.

Among the groups represented by R and R2, the six groups of alkyl, alkenyl, alkynyl, aryl, and heterocycle include the same groups as explained for Rl and R2+Rh in the general formula [■].

Examples of the ring that can be formed by R, , R2, and G include rings such as piperidine, quinuclidine, and morpholine.

The hydrophobic substituent constant π is described in Structure-Activation Relationship of Drugs (Nankodo), pp. 79-103 (1978).

Examples of substituents with a π value of -0,5 to -1,0 include -
Examples of substituents smaller than 1,0 include -coNH2゜C0NHOH, ""C0NHCH3, -NHffi, -
NHCONHz, NHC5NH2゜NHSO, CF
I3. -N"(CI(3)3.-Oe, -0CONH
2,-3O3”.

-5OzNL, -5OCI (3,5OzCHx, -C
Examples include groups such as OO6.

Typical specific examples are shown below.

Vl-c~1 (i C5H7)zN(CHzCFIzO)sctl
*cONH*Vl-c~2 (i-C,H,), N(CH2CH2,0)3CH,C
OONaI-c-3 CCxHs)xNccfh(JbO)scONHz1-
c-4 (HOCHzCJCHz)zN(CH2CH2O)s)
II-c-5 ■ ■ T-c ■ ■ C) 12=CHC82NH (CH2CH20) ~ 6CH
,C00K(CI(-iiCCH2)2N(C)12C
H20)~, C) 12CONI(2C, H7 CH2= CHCI(2N(CH2CH20)~, C
H, C0NHCH.

C.F.I.

(CHz -COCH2)2N(CH2CH20)-6
CH, CONH2 ■ ■ ■ ■ I-c ■ ■ ■ ■ (HOC82CH2) 2N (CH2CH20) ~ l 4
CH2CH2N(CH2CH,0H)2 ■ ■ ■ ■ ■ Vl-c-35 ■ ■ Silver halide photographic materials capable of obtaining high-contrast images to which the present invention is applied include the above general formula [A
] and at least one hydrazine compound represented by [
(2) At least one nucleation-promoting compound represented by ~CVI'l is contained, but the amount of the compound of general formula (A) and [I] ~CVI) contained in the photographic light-sensitive material is 5X per mole of silver halide contained in the light-sensitive material
Preferably, it is between 10-' mol and 5XIO-' mol.

In particular, it is preferably in the range of 5 x 10-' moles to I x 10-' moles.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support.

Then, this silver halide emulsion can be coated directly on the support, or it can be coated via another layer such as a hydrophilic colloid layer that does not contain the silver halide emulsion.
Furthermore, a hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Further, the silver halide emulsion layer may be coated separately into silver halide emulsion layers having different sensitivities, for example, high-sensitivity and low-sensitivity silver halide emulsion layers. In this case, an intermediate layer may be provided between each silver halide emulsion layer.

That is, an intermediate layer made of hydrophilic colloid may be provided if necessary. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, or a backing layer may be provided between the silver halide emulsion layer and the protective layer.

The compounds represented by formulas (A), CI) to CVI) are contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention. .

Next, the silver halide used in the silver halide photographic material of the present invention will be explained. The silver halide is silver chloroiodobromide or silver iodobromide containing 4 mol % or less of silver iodide, preferably 3 mol % or less of silver iodide. The average diameter of the silver halide particles is preferably in the range of 0.05 to 0.5 μm, particularly 0.05 to 0.5 μm. lO~0.
40pm is preferred.

Although the particle size distribution of the silver halide grains used in the present invention is arbitrary, it is preferably adjusted so that the monodispersity value defined below is in the range of 1 to 20%, and more preferably in the range of 5 to 15%. do.

Here, the monodispersity is defined as a value (%) obtained by multiplying by 100 the value obtained by dividing the standard deviation of particle diameter by the average particle diameter (coefficient of variation). For convenience, the grain size of silver halide grains is expressed by the edge length in the case of cubic grains, and is expressed by the edge length for other grains (8
(Hedron, Tetrahedron, etc.) are calculated by the square root of the projected area.

When carrying out the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, silver iodobromide in the core and bromide in the shell. Those consisting of silver iodobromide grains, which are silver, can be used. At this time, iodine can be contained in any layer within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including # salt), Metal ions can be added using at least one selected from rhodium salts (including complex salts) and iron salts (including complex salts) to contain these metal elements inside the particles and/or on the surface of the particles, Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Additionally, silver halide can be sensitized by various chemical sensitizers. Examples of the sensitizer include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacinate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.) ), reduction sensitizers (triethylenetetramine, tin silver chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate Various noble metal sensitizers typified by sodium chloride, sodium chlorovaladite, etc. can be used alone or in combination of two or more.

When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains whose surface sensitivity is higher than their internal sensitivity, so-called silver halide grains that give negative images. can be increased.

Further, the silver halide emulsion used in the present invention contains mercapto compounds (l-phenyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole), benzotriazoles (5-bromobenzotriazole 5-methylbenzotriazole (6-nidropenzimidazole), etc.) can be used to stabilize or suppress fog.

The photosensitive silver halide emulsion layer or its adjacent layer may contain a Research Disclosure (Research Disclosure) for the purpose of increasing sensitivity, increasing contrast, or promoting development.
Compounds described in Section XXI B-D of No. 17463 can be added.

Further, it is preferable to add a compound represented by the following general formula CP).

General formula [P] R1-0 CH2CH20H [In the formula, R1 represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n represents an integer from 1O to 200. ] First, specific examples more preferable than the compound represented by the general formula (P) will be given. The molecular weight is preferably 1500 or more, but is not limited thereto.

P l 80(CH,CHzC)nH
n=lOP2HO(CHxCLO
) nH n-30P 3 HO (
HzCH20)n)l n□50P 4
HO(CHzC)120)nH
n=70P − 5 HO (CH2Cl.O)
nl( n=150P 6 HO(
CHzCH20) nl (n=200 These compounds are commercially available and can be easily obtained.
It is preferable to add up to 4.0 mol, more preferably 0.02 to 2 mol. It is also preferable to include it in the emulsion layer. Further, two or more types of compounds having different values of n may be included.

The silver halide emulsion used in the present invention includes a sensitizing dye,
Plasticizers, antistatic agents, surfactants, hardeners, etc. can also be added. General formula (A), [I) to [
When the compound (2) is added to a hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, or hydrophilic colloids other than gelatin can also be used.

These hydrophilic binders are coated on each side of the support.
It is preferable to apply the coating at 0 g/m2 or less.

Supports that can be used in the practice of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

For developing the silver halide photographic material of the present invention, the following developing agents are used, for example.

Typical developing agents for HO-(CH=CI()n''O)l include hydroquinone, and others include catechol and pyrogallol.

In addition, typical examples of HO(CH-CH)n NH2 type developers include ortho and para aminophenol or aminopyrazolone, N-methyl-p-aminophenol, N-β-hydroquinethyl- Examples include p-aminephenol, p-hydroquinphenylaminoacetic acid, and 2-aminonaphthol.

Examples of petrocyclic type developers include 1-phenyl-3-pyrazolidone, ■-phenyl-44-dimethyl-3-pyrazolidone, ■-phenyl-4-methyl-4-hydroquinemethyl-3-pyrazolidone, and l-phenyl-4-methyl-3-pyrazolidone. 4
Examples include 3-pyrazolidones such as -hydroquinemethyl-3-pyrazolidone.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Pbotographic P
rocessFourth Edition) No. 291
~334 pages and Journal of the American Chemical Society.
American Chemical 5ociety
), Vol. 73, p. 3.100 (1951), can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination.

Furthermore, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired.

Additionally, hydroquinemethylane or hydrazide compounds may be used as preservatives.

In addition, pH adjustment and a buffer function can be provided using caustic alkali, carbonate alkali, or amine, which are used in general black and white developers.

The developing solution used in the present invention is characterized in that a pF111 non-vortexed developer can be used. In addition, the developer contains an inorganic development inhibitor such as brompotash, 5-methylbenzotriazole, 5
-Organic development inhibitors such as methylbenzimidazole, 5-nitroindazole, adenine, guanine, ■-phenyl-5-mercaptotetrazole, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol, benzyl alcohol, polyalkylene oxide, etc. Development accelerators, sodium alkylarylsulfonates, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, ionic strength R adjusters such as sodium sulfate, etc. The addition of is optional.

The developer used in the present invention includes organic solvents such as alkanolamines such as jetanolamine and triethanolamine, glycols such as diethylene glycol-4,1-') ethylene glycol, and stylamino-1,2- Alkylamino alcohols such as propanediol and butylamitubrobanol may also be included.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using a simultaneous mixing method. During this mixing, X21rC4,
was added at 8X 10-' moles per mole of silver.

The obtained emulsion was an emulsion consisting of cubic monodisperse grains (coefficient of variation 9.5%) with an average grain size of 0.20 μm.

After adding 6.5 m12 of a 1% potassium iodide aqueous solution per mole of silver to this emulsion, modified gelatin (patent application) -
By adding exemplified compound G-8) of No. 180787,
It was washed with water and desalted in the same manner as in Example 1 of No.-1890787. The pAg at 40°C after desalting was 8.0.

Furthermore, the following compounds [A] and [B] can be used as antibacterial agents during redispersion.
, [C] was added.

CA3 (B) (C) Coat a king layer with a gelatin amount of 2.4 g/m2, and then apply a banking protective layer with the following formulation (4) on top of it with a gelatin amount of 1.0 g/m2. Sample No. t~3
I got 0.

Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0 g/m2 Silver halide emulsion A (silver amount) 3.2 g/m2 Sensitizing dye: (Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 0.1 μm on both sides (Unexamined Japanese Patent Application Publication No. 1983-1982) 1994
A silver halide emulsion layer having the following formulation (1) with a gelatin amount of 2.0 was applied on one undercoat layer of a polyethylene tereftate film having a thickness of 100 μm (see Example 1 of No. 1).
g/m2, coating so that the silver amount is 3.2 g/m2,
Furthermore, an emulsion protective layer having the following formulation (2) was coated thereon so that the amount of gelatin was 1.0 g/m2. Also, on the other undercoat layer on the opposite side, apply a bulk stabilizer of the following formulation (3): 4
-Methyl-6-hydroxy 1.3.3a, 7-chitrazaindene Antifoggant: Adenine Surfactant: Saponin 30 mg/m" 10 mg/m! 0.1 g/m2 Surfactant, 5-1 8, Qmg/ff12 CI(zcQo(Cth)set(3 Na03S CHCOO(CHz)zCH(COx)
zHydranon derivative according to the present invention Nucleation promoting compound according to the present invention Latex polymer: 30+ng/m"100+ng/m"1g/m" Matting agent: Solica hardener with an average particle size of 3.5 μm: Formalin surfactant: S-3 NaO3S-CI (COOCH2(CF2), HCI(
2COOC)I2(CF2)sH3mg/m" 30mg/m2 10mg/m2 Prescription (3) (Banking layer composition) m: n -50: 50 Polyethylene glycol molecular weight 4000 0.1g/m
2 Hardener: H-1 CH2So, H Prescription (2) (Emulsion protective layer composition) Gelatin 0.9 g/m2 Surfactant: S So, Na O3Na Gelatin 2.4 g/m'' Surfactant: Saponin 0. 1g/+n": S-1 6111g/II+" Prescription (4) (Banking protective layer composition) Gelatin 1g/l 112 Matting agent: Polymethyl methacrylate with average particle size of 3.0 to 5.0 μm 15+ng/m2 Surfactant : S-
210mg/m2 Hardener: Glyoxal
25mg/m2": H135mg/+a2 The resulting sample was subjected to a halftone quality test using the method described below.

(Half dot quality test method) A part of the step wedge is attached with a halftone screen (150 lines/inch) with a halftone dot area of 50%, and the sample is placed in close contact with this and exposed to a xenon light source for 5 seconds. The sample was developed under the following conditions using an automatic processing machine for rapid processing using the following developer and fixer, and the halftone quality of the sample was reduced to 1.
Observe with a 00x magnifying glass and rate the one with high halftone quality as "5"
Ranked below as "4", "3", "2", "1",
The ranking was lowered in order for evaluation. Incidentally, ranks "1" and "2" are levels that are practically unfavorable.

Fog in the halftone dots is evaluated in the same way, and the highest rank is "5" when no black pins occur in the halftone dots, and the rank is "5" depending on the degree of occurrence of black pins in the halftone dots. 4", "
The evaluation was made in descending order of rank: "3", "2", and "1". Incidentally, in ranks rl+ and "2", the black pins are also large and are at a practically unfavorable level.

Developer prescription Developer solution 1
Developer 2 Ethylenediaminetetraacetic acid sodium salt
1g 1g sodium sulfite
60g 60g trisodium phosphate (1
dihydrate) 75g Boric acid -40g Hydroquinone 22.5
g 35g sodium hydroxide
8g 8g Sodium Bromide
3g 3g5-Methylbenzotriazole 0.25g 0.2g
1-phenyl-5-mercaptotetrazole 0.
08g 0.08g1-phenyl-4-methyl-4-
Hydroxymethyl -0,2g3-Vyrazolidonemethol 0.25g
Phenethylpicolinium bromide -2,5
g Add water 112
Adjust pH with sodium 12 hydroxide
pH-10,8pH=1O,8 Fixer formulation (composition A) Ammonium thiosulfate C72,5w/v% water soluble)
240m12 Sodium sulfite
17g Sodium acetate trihydrate
6.5μm 1m
6g Sodium citrate dihydrate
2g (composition) Pure water (ion exchange water) 17mΩ Sulfuric acid (50% W/V aqueous solution)
4.7g aluminum sulfate
26.5 g (an aqueous solution with an AI220s equivalent content of 8.1 w/v %) When using a fixer, the above composition A1 was dissolved in 500 mff of water and finished to 112 before use. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
406CI5 second swimsuit 35
Extract washed at 15°C and dried for 10 seconds at 300°C.
Drying at 50° C. for 10 seconds. Comparison compounds of the hydrazine derivative according to the present invention added to the silver halide emulsion layer in formulation (1) include the following (
Compounds a) and (b) were added.

Compound (a) (a) As is clear from Table 1, the samples according to the present invention have better halftone dot quality and black pins than the comparison.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic light-sensitive material that has high contrast, less fog, and good halftone dot performance even when processed with a low-pi developer having a pH of less than 11.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer, containing at least one hydrazine compound represented by the following general formula [A], and containing an amine compound, a hydrazine compound A silver halide photographic light-sensitive material comprising at least one nucleation-promoting compound selected from , quaternary onium salt compounds. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Ar represents an aryl group, and X is -NR_1R_
2 or -OR_3, R_1 and R_2 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group,
It represents an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group, and R_1 and R_2 may form a ring together with a nitrogen atom. R_3 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. R represents a hydrogen atom or an alkyl group, n represents 0 or 1, and m represents an integer of 1 to 3. However, in the compound represented by the general formula [A], at least one R has a group that promotes adsorption to silver halide, or the sum of R in the molecule imparts diffusion resistance. The compound represented by the general formula [A] includes -NHNH in the formula
- includes those in which at least one of H is substituted with a substituent. ]