JPH0619034A - Silver halide photographic sensitive material and photographic picture forming method using same material - Google Patents

Abstract

PURPOSE:To obtain sufficient high contrast with a developer at <=pH11 by incorporating a specified hydrazine derivative and a specified compd. into the photosensitive silver halide emulsion layer. CONSTITUTION:A hydrazine derivative shown by formula I and a compd. shown by formula II are incorporated into the emulsion layer or its adjacent hydrophilic layer. In formula I, R1 is aliphatic or aromatic groups and contains a partial structure such as -O-(CH2CH2O)n- and -O-(CH2CH(CH3)O)n-, a quaternay ammonium cation or -S-, G1 is -CO-, -COCO-, -CS-, etc., R2 is aliphatic and aromatic groups or hydrogen atom, and one of A1 and A2 is hydrogen atom and the other is hydrogen atom, acyl, alkyl and arylsulfonyl. In formula II, Y is a group adsorbed on silver halide, X is hydrogen atom, nitrogen atom, etc., A is a bivalent connecting group, B is an amino group, an ammonium group, etc., (m) is 1 to 3, and (n) is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an ultrahigh contrast silver halide photographic light-sensitive material used for photolithography.

[0002]

The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat. No. 3,730,
No. 727 (developer combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 (silver halide) Β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for the light-sensitive material), No. 2,419,975, and The Theory of Photographic Process by Mees. Process) Third Edition (19
66) 281 pages and the like. Among these, in particular, in US Pat. No. 2,419,975, it is possible to obtain a high-tone negative image by adding a hydrazine compound.
It is disclosed. In the patent specification, a hydrazine compound was added to a silver chlorobromide emulsion to obtain a high pH of 12.8.
It is described that when developed with the developing solution of No. 2, extremely high photographic characteristics with a gamma (γ) of more than 10 can be obtained.
However, a strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use.
Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. In JP-A-1-179939 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group was used to obtain a pH of 11 A processing method of developing with a developing solution of 0.0 or less is described. However, when a compound having an adsorbing group is added to a silver halide emulsion, the photosensitivity may be impaired if the amount exceeds a certain limit.
Since it has a harmful effect of suppressing development or hindering the action of other useful adsorptive additives, the amount used is limited and sufficient contrast cannot be exhibited. US4998604
And US Pat. No. 4,994,365 disclose hydrazine compounds having a repeating unit of ethylene oxide and hydrazine compounds having a pyridinium group. However, as is evident in these examples,
The contrast is not sufficient, and it is difficult to obtain the contrast and the required Dmax under practical development processing conditions. On the other hand, JP-A-61
-47,943 and JP-A-61-47949 disclose a sensitizing material containing a sensitizing dye selected from thiohydantoins and hydrazines. However, a light-sensitive material containing these combinations is hardened only when a high pH developer having a pH of 11 or higher is used. A developer having a low pH of 11 or less as intended in the present invention does not cause a high contrast. As described above, the conventionally known light-sensitive material was insufficient to obtain sufficient contrast with a developer having a pH of 11 or less.

[0003]

SUMMARY OF THE INVENTION Therefore, firstly, the object of the present invention is to obtain a silver halide photograph capable of obtaining a very hard negative tone photographic property with a gamma of more than 10 using a stable developing solution. To provide a light-sensitive material. A second object of the present invention is to provide a silver halide photographic light-sensitive material which can be made to have a high contrast with a developer having a pH of 11 or less.

[0004]

The above object of the present invention is to have at least one light-sensitive silver halide emulsion layer on a support, which layer and / or an adjacent hydrophilic colloid layer, This is achieved by a silver halide photographic light-sensitive material characterized by containing at least one hydrazine derivative represented by the formula (I) and at least one compound represented by the general formula (II) or the general formula (III).

[0005]

[Chemical 6]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and --O-(CH ₂ C) is used as a part of the substituent.
_{H 2 O) n -, -} O- (CH 2 CH (CH 3) O) n - or _{-O- (CH 2 CH (OH)} CH 2 O) n - moiety of (where n is an integer of 3 or more) It is a group containing a structure, a quaternary ammonium cation as a part of the substituent, or an -S- group as a part of the substituent. G ₁ is -CO- group, -COCO- group, -C
S- _{groups, -C (= NG 2 R 2} ) - group, -SO- group, -SO
₂ - group or _{-P (O) (G 2 R} 2) - represents a group. G ₂ is a simple bond, —O— group, —S— group or —N (R ₂ ) —
R ₂ represents a group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when there are plural R ₂ in the molecule, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl or arylsulfonyl group.

[0007]

[Chemical 7]

In the formula, Y represents a group adsorbing to silver halide. X is a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom,
It represents a divalent linking group consisting of an atom or a group of atoms selected from a sulfur atom. A represents a divalent linking group. B represents an amino group, an ammonium group and a nitrogen-containing heterocycle,
The amino group may be substituted. m represents 1, 2 or 3, and n represents 0 or 1.

[0009]

[Chemical 8]

In the formula, R ₁ and R ₂ each represent a hydrogen atom or an aliphatic residue. R ₁ and R ₂ may combine with each other to form a ring. R ₃ represents a divalent aliphatic group. X is nitrogen,
It represents a divalent heterocycle containing an oxygen or sulfur atom.
n represents 0 or 1. When M is a monovalent group, x =
When 1 and M are divalent groups, x = 1/2. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, or an amidino group.

The general formula (1) will be described in more detail. In the general formula (1), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly 1 carbon atom
To 20 straight, branched or cyclic alkyl groups. This alkyl group has a substituent. In the general formula (1), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aliphatic group or aromatic group of R ₁ is substituted, and a typical substituent is, for example, an alkyl group,
Aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, ureido group, urethane group (alkoxycarbonylamino group, aryloxycarbonylamino group), aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, Arylthio group, sulfonyl group, sulfinyl group, hydroxy group,
Halogen atom (for example, F, Cl, Br), cyano group,-
_{SO 3 M ', - COOM'} (M ' is a hydrogen atom, an alkali metal, quaternary ammonium, alkaline earth metal), an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group , A phosphoric acid amide group and the like, and preferable substituents are a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), Alkoxy group (preferably having 1 to 30 carbon atoms), substituted amino group (preferably amino group substituted with an alkyl group having 1 to 30 carbon atoms), acylamino group (preferably having 2 to 40 carbon atoms) , Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms), phosphoric acid amide (Preferably 1 to 4 carbon atoms
0) and so on.

Some of the aliphatic groups, aromatic groups or their substituents of R ₁ are --O-(CH ₂ CH ₂ O) _n- , O.
_{(CH 2 CH (CH 3)} O) n -, or -O- (CH
_{2 CH (OCH 2 O) n} - (n is an integer of 3 or more,
3 or more and 15 or less is preferable),
Alternatively quaternary ammonium cation (fluorine ion Examples of a counter anion, chloride, bromide, iodide ion, toluenesulfonate ion, naphthalene sulfonic acid ion, examples of the anion SO ₃ ^-,
COO ^- if they contain, etc.), or -S
-Contains. R ₁ is preferably of the general formula (I
a), general formula (Ib), general formula (Ic), general formula (I
d) or general color (Ie).

[0014]

[Chemical 9]

In the formula, L ₁ and L ₂ are -CONR ₇ -groups, -NR ₇ CONR
_{It represents an 8} -group, a -SO ₂ NR ₇ -group or a -NR ₇ SO ₂ NR ₈ -group, which may be the same or different. R ₇ and R
₈ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably a hydrogen atom.
m and p are 0 or 1. R ₃ and R ₄ are a divalent aliphatic group or an aromatic group, and preferably an alkylene group, an arylene group or their groups, an —O— group, a —CO— group and a —S— group.
Group, -SO- group, -SO ₂ -group, -NR ₉ -group (R ₉ is represented by the general formula (I
a), (Ib), and (Ic) have the same meanings as R ₇ ) and are a divalent group. An alkylene group is more preferred as the aliphatic group, and an arylene group is more preferred as the aromatic group. R ₅ is an aliphatic group, an aromatic group or a combination thereof, and an alkylene group or an alkylene group with an arylene group is particularly preferable. R ₃ , R ₄ and R ₅ may be substituted, and preferable substituents include those listed as the substituents for R ₁ .

In the general formulas (Ia) and (Ib), Z ₁ represents an atomic group necessary for forming a nitrogen-containing aromatic ring.
Preferable examples of the nitrogen-containing heteroaromatic ring formed by Z ₁ and a nitrogen atom include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, a pyrrole ring, an oxazole ring, a thiazole ring and benzo-condensation thereof. Other than the ring, a pteridine ring, a naphthyridine ring and the like can be mentioned. Formulas (Ia), (Ib),
In (Ic), when p = 1, X ⁻ represents a counter anion (eg, fluorine ion, chlorine ion, bromine ion, iodine ion, toluenesulfonate ion, naphthalenesulfonate ion). When p = 0, Z ₁ or R ₆ has a SO ₃ ⁻ group or a COO ⁻ group and forms an inner salt. Formula (Ib), (Ic), (Id) or (I
R ₆ in e) represents an aliphatic group or an aromatic group.
R ₆ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The three R _{6 s} in formula (Ic) may be the same or different,
Further, they may be bonded to each other to form a ring, but preferably they do not form a ring. Z ₁ and R ₆ may be substituted, and preferable substituents include those listed as the substituents for R ₁ . In formula (Id), L ₃ is a —CH ₂ CH ₂ O— group, a —CH ₂ CH (CH ₃ ) O— group, or a —C
Represents a H ₂ CH (OH) CH ₂ O- group, and n has the same meaning as in formula (1).

G ₁ in the general formula (1) is a —CO— group,
The -SO ₂ -group is preferred, and the -CO- group is most preferred. A ₁ , A
₂ is preferably a hydrogen atom.

The alkyl group represented by R ₂ in the general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, a benzene ring). Including). G ₁
Is a -CO- group, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, Phenylsulfonylmethyl group etc.), aralkyl group (eg o-hydroxybenzyl group etc.), aryl group (eg phenyl group,
3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-
(Eg, a hydroxymethylphenyl group), and a hydrogen atom is particularly preferable. R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms Examples thereof include compound 2 in JP-A-63-29751.
Those described as 8, 37, 40 are mentioned.

R ₁ or R ₂ of the general formula (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-1005
Those described in No. 30 are mentioned.

R ₁ or R _{2 in} the general formula (I) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include U.S. Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
4,459,347, JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
No. 47, No. 59-201, No. 048, No. 59-201,
049, 61-170, 733, 61-27.
0,744, 62-948, 63-234,2.
44, 63-234, 245, 63-234,
The groups described in No. 246 are mentioned.

Of the compounds of the general formula (I) used in the present invention, particularly preferred are the compounds of the general formula (Ib) and the general formula (Ic). More preferred are compounds represented by formula (Ic).

The compounds of the general formula (I) of the present invention are disclosed, for example, in JP-A-61-213,847 and JP-A-62-260,153.
U.S. Pat. No. 4,684,604, Japanese Patent Application No. 63-9.
8,803, U.S. Pat. Nos. 3,379,529, 3,620,746, 4,377,634, 4,332,878, and JP-A-49-129,536.
No. 56-153,336, No. 56-153,34
2, U.S. Pat. Nos. 4,988,604 and 4,994.
It can be synthesized by utilizing the method described in No. 365 or the like. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

[0032]

[Chemical 19]

[0033]

[Chemical 20]

[0034]

[Chemical 21]

[0035]

[Chemical formula 22]

[0036]

[Chemical formula 23]

The addition amount of the compound of the general formula (1) of the present invention is 1 × 10 ⁻⁶ to 5 × 1 per mol of silver halide.
It is preferably contained in an amount of 0 ^-2 mol, and particularly preferably in the range of 1 x 10 ^-5 mol to 2 x 10 ^-2 mol.

The general formula (II) will be described. Examples of the group represented by Y that is adsorbed on the silver halide include nitrogen-containing heterocyclic compounds. When Y represents a nitrogen-containing heterocyclic compound, the compound of general formula (II) is represented by the following general formula (II-a).

[0039]

[Chemical formula 24]

In the formula, l represents 0 or 1, m is 1,
2 or 3, and n represents 0 or 1.
[(X) _n -AB] _m has the same meaning as in formula (II) above, and Q represents a carbon atom, a nitrogen atom, an oxygen atom,
It represents a group of atoms necessary for forming a 5- or 6-membered heterocycle composed of at least one kind of sulfur atom.
The heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

The heterocycle formed by Q is, for example, a substituted or unsubstituted indazole, benzimidazole, benzotriazole, benzoxazole, benzthiazole, imidazole, thiazole, oxazole, triazole, Examples thereof include tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines and quinolines. M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammonium group (eg, trimethylammonium group, dimethylbenzylammonium group, etc.), and M = under alkaline conditions.
H or a group which can be an alkali metal atom (eg, acetyl group, cyanoethyl group, methanesulfonylethyl group,
Etc.).

Further, these heterocycles include a nitro group, a halogen atom (eg, chlorine atom, bromine atom, etc.), a mercapto group, a cyano group, and a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group). , T-butyl group, cyanoethyl group, methoxyethyl group, methylthioethyl group, etc.), aryl group (eg, phenyl group, 4-
Methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group, etc.),
Alkenyl group (eg, allyl group, etc.), aralkyl group (eg, benzyl group, 4-methylbenzyl group, phenethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group,
4-methoxyphenoxy group, etc.), alkylthio group (eg methylthio group, ethylthio group, methoxyethylthio group), arylthio group (eg phenylthio group), sulfonyl group (eg methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group) , Etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide A group (eg, acetamide group, benzamide group, etc.),
Sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group,
Benzoyloxy group, etc.), sulfonyloxy group (eg methanesulfonyloxy group, etc.), ureido group (eg unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.), thioureido group (eg nothing Substituted thioureido group, methylthioureido group, etc.), acyl group (eg acetyl group, benzoyl group, etc.), heterocyclic group (eg 1-morpholino group, 1-
Piperidino group, 2-pyridyl group, 4-pyridyl group, 2-
Thienyl group, 1-pyrazolyl group, 1-imidazolyl group,
2-tetrahydrofuryl group, tetrahydrothienyl group,
Etc.), oxycarbonyl group (eg methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group, etc.), amino group (eg Unsubstituted amino group, dimethylamino group, methoxyethylamino group, anilino group, etc.), carboxylic acid or salt thereof, sulfonic acid or salt thereof, hydroxy group and the like.

As the divalent linking group represented by X, for example,
For example, -S-, -O-, -N (R₁)-, -C (O) O-,
-OC (O)-, -C (O) N (R₂)-, -N (R₃) C
(O)-, -SO₂N (R_Four)-, -N (R_Five) SO₂-,
-N (R₆) C (O) N (R₇)-, -N (R₈) C (S) N
(R₉)-, -N (R_Ten) C (O) O-, -SO₂-,-
C (O)-,-(O) S (O) O-, -O (O) S
(O)-, etc., but these linking groups are
A linear or branched alkylene group (eg methylene
Group, ethylene group, propylene group, butylene group, hexyl group
Group, a 1-methylethylene group, etc.)
You may stay. R₁, R₂, R₃, R_Four, R_Five, R ₆, R
₇, R₈, R₉And R_TenIs a hydrogen atom,
Or unsubstituted alkyl groups (eg methyl, ethyl
Group, propyl group, n-butyl group, etc.), substituted or not
Substituted aryl groups (eg phenyl, 2-methylphene)
Nyl group, etc.), substituted or unsubstituted alkenyl group (eg
A propenyl group, a 1-methylvinyl group, etc.), or
A substituted or unsubstituted aralkyl group (eg benzyl
Group, phenethyl group, etc.).

A represents a divalent linking group, and as the divalent linking group, a linear or branched alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, Etc.), linear or branched alkenylene groups (eg vinylene group, 1-methylvinylene group, etc.), linear or branched aralkylene groups (eg benzylidene group, etc.), arylene groups (eg phenylene, naphthylene, etc.), etc. Is mentioned. In the above groups represented by A, X and A may be further substituted with any combination. The substituted or unsubstituted amino group of B is represented by the general formula (II-b).

[0045]

[Chemical 25]

In the formula, R ¹¹ and R ¹² may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group or an aralkyl group. The group is a straight chain (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, allyl group, 3-butenyl group, benzyl group, 1-naphthylmethyl group, etc.), branched (for example, iso propyl group, t
-Octyl group, etc.) or cyclic (eg cyclohexyl group, etc.).

R ¹¹ and R ¹² may be linked to each other to form a ring, which may be a saturated ring containing one or more hetero atoms (eg, oxygen atom, sulfur atom, nitrogen atom, etc.). It may be cyclized so as to form a heterocycle, and examples thereof include a pyrrolidyl group, a piperidyl group, and a morpholino group. Examples of the substituents of R ¹¹ and R ¹² include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom), a hydroxy group, an alkoxycarbonyl having 20 or less carbon atoms. Group (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group having 20 or less carbon atoms (eg, methoxy group, ethoxy group, benzyloxy group,
Phenethyloxy group, etc.), monocyclic aryloxy group having 20 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, etc.), acyloxy group having 20 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), carbon Number 20 or less acyl group (eg, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl Group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), carbon number 2
0 or less acylamino group (for example, acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide group (ethylsulfonamide group, p-toluenesulfonamide group, etc.), carbon number 20
The following carbonamide groups (eg, methylcarbonamide group, phenylcarbonamide group, etc.), ureido groups having 20 or less carbon atoms (eg, methylureido group, phenylureido group, etc.), amino groups and the like can be mentioned. The ammonium group of B is represented by the general formula (II-c).

[0048]

[Chemical formula 26]

Where R¹³, R¹⁴, R¹⁵Is the above general formula
R in (II-b)¹¹And R¹²Is a group similar to
Z^-Represents an anion, for example, a halide ion (for example,
If Cl ^-, Br^-, I^-Etc.), sulfonate ion
(Eg trifluoromethanesulfonate, paratoluene
Sulfonate, benzene sulfonate, parachlorobe
Benzene, etc.), sulfato ion (eg,
Ethyl sulfate, methyl sulfate, etc.), Par
Examples include chlorate and tetrafluoroborate.
It p represents 0 or 1, and the compound forms an inner salt
When it does, it is 0.

The nitrogen-containing heterocycle represented by B is a 5- or 6-membered ring containing at least one or more nitrogen atoms, and these rings may have a substituent or are condensed with another ring. May be. Examples of the nitrogen-containing heterocycle include an imidazolyl group, a pyridyl group and a thiazolyl group.

Among the general formula (II), preferred are the compounds represented by the following general formula (II-m), (II-n), (II-o) or (II-p).

[0052]

[Chemical 27]

In the formula,-(X) _n -A-B, M and m have the same meanings as those in formula (II-a). Z ₁ , Z ₂ and Z ₃ are — (X) _n —A in the general formula (II-a).
Has the same meaning as -B, or represents a halogen atom, an alkoxy group having 20 or less carbon atoms (for example, a methoxy group), a hydroxy group, a hydroxyamino group, a substituted or unsubstituted amino group, and the substituent has the above general formula. It can be selected from the substituents of R ¹¹ and R ¹² in (II-b).
However, at least one of Z ₁ , Z ₂ and Z ₃ is-
(X) has the same meaning as _n- AB. Further, these heterocycles may be substituted with a substituent applied to the heterocycle of the general formula (II). Next, examples of the compound represented by the general formula (II) are shown, but the present invention is not limited thereto.

[0054]

[Chemical 28]

[0055]

[Chemical 29]

[0056]

[Chemical 30]

[0057]

[Chemical 31]

[0058]

[Chemical 32]

In the general formula (III), R¹, R²Is
Each represents a hydrogen atom or an aliphatic residue. R¹And R²Are mutual
To form a ring. R³Is a divalent aliphatic group
Represents X is divalent containing nitrogen, oxygen or sulfur atom
Represents a heterocycle of. n represents 0 or 1. M is one
When it is a valent group, x = 1, when M is a divalent group, x =
It is 1/2. M is hydrogen atom, alkali metal, alkali
Earth metal, quaternary ammonium salt, quaternary phosphonium salt or
Represents an amidino group. R¹, R²As an aliphatic residue of
Are alkyl groups, alkenyl groups and
And alkynyl groups are preferably each substituted with a suitable group.
May be. As the alkyl group, for example, a methyl group,
Ethyl, propyl, butyl, hexyl, decyl
Group, dodecyl group, isopropyl group, sec-butyl group,
For example, a chlorhexyl group. For example, as an alkenyl group
For example, allyl group, 2-butenyl group, 2-hexenyl group, 2-
Such as an octenyl group. Examples of alkyl groups include
Examples include lopargyl group and 2-pentynyl group. With substituents
Then, a phenyl group, a substituted phenyl group, an alkoxy group,
Alkylthio group, hydroxy group, -COOM ', -SO
₃M '(M' is a hydrogen atom, an alkali metal (such as Na or K
DO), NH_Four, Alkaline earth metals), alkylamino
Groups, amide groups and the like. R¹And R²A field that forms a ring with
In total, 5 members consisting of carbon or a combination of nitrogen and oxygen
Or a 6-membered carbocyclic or heterocyclic ring, particularly a saturated ring is preferred.
, For example pyrrolidyl, piperidyl, morpholyl, pi
Perazyl, 4-methyl-piperazyl, etc. can be mentioned.
It R¹And R²Particularly preferred as is having 1 carbon atom
And an alkyl group of 3 to 3, more preferably an ethyl group. R
³The divalent aliphatic group of is -R^Four-Or-R^FourS-
preferable. Where R ^FourIs a divalent aliphatic residue, preferably
Is a saturated or unsaturated one having 1 to 6 carbon atoms, for example, -C
H₂-, -CH₂CH₂-,-(CH₂)₃-,-(CH
₂)_Four-,-(CH₂)₆-, -CH₂CH = CHCH
₂-, -CH₂C = CCH₂-, -CH₂CH (CH₃)
CH₂-And so on. R_FourThe preferred carbon number of is 2
~ 4, R^FourMore preferably as -CH₂C
H₂-And-CH₂CH₂CH₂Is. (X)_n
R when n is 0³Is -R^Four-Represents only.

The hetero ring of X may be a 5- or 6-membered hetero ring containing nitrogen, oxygen or sulfur, which may be condensed with the benzene ring. The heterocycle is preferably an aromatic one, for example, tetrazole, triazole, thiadiazole, oxadiazole, imidazole, thiazole, oxazole, benzimidazole, benzothiazole,
Benzoxazole and the like. Of these, tetrazole and thiadiazole are particularly preferable.

As the alkali metal of M, Na ⁺ ,
K ⁺ , Li ⁺ and the like. As an alkaline earth metal,
There are Ca ⁺⁺ , Mg ⁺⁺ , and the like. The quaternary ammonium salt of M is one having 4 to 30 carbon atoms, for example, (C
^{_{H 3) 4 N +, (}} C 2 H 5) 4 N +, (C 4 H 9) 4 N +, C
₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₃ , C ₁₆ H ₃₃ N ⁺ (CH ₃ ) ₃
And so on. Examples of the quaternary phosphonium salt include (C ₄ H ₉ ).
₄ P ⁺ , C ₁₆ H ₃ P ⁺ (CH ₃ ) ₃ , C ₆ H ₃ CH ₂ P ⁺
(CH ₃ ) and the like.

The inorganic acid salt of the compound represented by the general formula (III) includes, for example, hydrochloride, sulfate and phosphate, and the organic acid salt includes acetate, propionate, methanesulfonate and benzene. Examples include sulfonates and p-toluenesulfonates. Specific examples of the compound represented by formula (III) are shown below.

[0063]

[Chemical 33]

[0064]

[Chemical 34]

[0065]

[Chemical 35]

[0066]

[Chemical 36]

[0067]

[Chemical 37]

The optimum addition amount of these general formulas [II] and [III] is 1.0 depending on the kind of the compound.
× 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ⁻³ to
It is desirable to use it in the range of 0.3 g / m ² . These accelerators are suitable solvents (H ₂ O, alcohols such as methanol and ethanol, acetone, dimethylformamide,
Methyl cellosolve etc.) and added to the coating solution. You may use these additives together in multiple types.

Next, the sensitizing dye of the general formula (IV) will be described. General formula (IV)

[0070]

[Chemical 38]

In the formula, V ₁ and V ₃ represent hydrogen atoms or electron withdrawing groups, and V ₂ and V ₄ represent electron withdrawing groups.
R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and represent an alkyl group or an alkenyl group having a total carbon number of 10 or less, which may be substituted, and R ₁ , R ₂ , R ₃ or R 4
_At least one of ₄ is a group having a sulfo group or a carboxy group. X ₁ represents a counter ion necessary for neutralizing the charge. n represents 0 or 1, and is 0 in the case of an inner salt.

Preferred groups as the electron-withdrawing group for V ₁ , V ₃ or V ₂ , V ₄ are a halogen atom and a lower perfluoroalkyl group (more preferably a total carbon number of 5 or less, for example, a trifluoromethyl group, 2 , 2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group), acyl group (total carbon number is preferably 8 or less, for example, acetyl group, propionyl group, benzoyl group, mesityl Group, a benzenesulfonyl group), an alkylsulfamoyl group (more preferably a total carbon number of 5 or less, and examples thereof include a methylsulfamoyl group and an ethylsulfamoyl group), a carboxy group, an alkoxycarbonyl group ( The total carbon number is preferably 5 or less, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. ) And a cyano group.

The alkyl group and alkenyl group of R ₁ , R ₂ , R ₃ and R ₄ preferably have a total carbon number of 18 or less. As the substituent of the alkyl group or the alkenyl group, in addition to the sulfo group and the carboxy group, a halogen atom (eg, fluorine, chlorine, bromine), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms or an aryloxycarbonyl group (eg, methoxy group) Carbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group), monocyclic aryloxy group having 10 or less carbon atoms (eg, phenoxy group, p-tolyloxy group), acyloxy group having 3 or less carbon atoms (eg, acetyl). Group, propionyl group, benzoyl group, mesyl group), carbamoyl group (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (for example, sulfamoyl group,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), aryl groups having 10 or less carbon atoms (eg, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group), etc. Is mentioned.

At least one of R ₁ , R ₂ , R ₃ and R ₄ is an alkyl group or an alkenyl group substituted with a sulfo group or a carboxy group, more preferably a sulfoalkyl group. At least one of R ₁ , R ₂ , R ₃ and R ₄ is preferably an alkyl group substituted with an alkoxy group having 3 or less carbon atoms, and further a 2-methoxyethyl group or a 2-ethoxyethyl group. Three
-Methoxypropyl group and 3-ethoxypropyl group.

Specific examples of the sensitizing dye represented by the general formula (IV) are shown below, but the invention is not limited thereto.

[0076]

[Chemical Formula 39]

[0077]

[Chemical 40]

[0078]

[Chemical 41]

[0079]

[Chemical 42]

In the present invention, it is preferable to form an aggregate of the above-mentioned sensitizing dye, and it is particularly preferable to use a sensitizing dye that easily forms the J-aggregate among the above. Also,
For example, JP-B-49-46932 and JP-A-58-2
8738, U.S. Pat. No. 3,776,738, and other compounds that enhance J aggregates (eg, water-soluble bromide,
It is preferable to use a bispyridinium salt, a mercapto-heterocyclic sulfonated compound, an alkali metal salt) together. These compounds are used in the range of 10 ^-5 to 1 mol per mol of silver halide.

The addition amount of the sensitizing dye of the general formula (IV) used in the present invention varies depending on the shape and size of the silver halide grains, but is 4 × 10 ⁻⁶ to 8 × 1 per mol of silver halide.
It is used in the range of 0 ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−7 to} 3.5 × 10 per 1 m ² of surface area of the silver halide grain.
^-6 mol addition amount range is preferred, especially 6.5 × 10 ^-7 ~
The addition amount range of 2.0 × 10 ⁻⁶ mol is preferable.

There are no particular restrictions on the various additives and development processing methods used in the light-sensitive material of the present invention in addition to the above, and those described in the following sections can be preferably used. Item Relevant part 1) Silver halide emulsion and JP-A-2-97937, page 20, lower right column 12, from its production line to page 21, lower left column, line 14, JP-A-2-12236, page 7 The selenium sensitization method described in the upper right column, line 19 to the same, page 8, lower left column, line 12 and Japanese Patent Application No. 3-189532. 2) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4; and JP-A 2-103535, page 16, lower right column, line 3 to page 17 Spectral sensitizing dyes described in the lower left column, line 20, and further in JP-A Nos. 1-112235, 2-124560, 3-79928, and Japanese Patent Application Nos. 3-189532 and 3-411064. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, left lower column, line 13 to page 4, right Bottom line, line 18. 4) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A 1-23753 A thiosulfinic acid compound described in JP-B-8. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 7) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column 1, plasticizer, line 5 to page 19, upper right column, line 15 8) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 9) Dyes Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Black spot prevention agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 12) Redox compound A compound represented by the formula (I) in JP-A-2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 in JP-A 3-174143). R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 13) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 14) Dihydroxy Compounds described in JP-A-3-39948, page 11, upper left column, benzenes, page 12, lower left column, and EP452772A. 15) Developer and developing method JP-A-2-103536, page 19, upper right column, line 16 to page 21, upper left column, line 8

[0083]

The present invention will be described in detail with reference to the following examples.

Example-1 <How to make a silver halide emulsion> Emulsion-A 0.37 mol of silver nitrate aqueous solution, and (NH ₄ ) ₃ corresponding to 1.0 × 10 ⁻⁷ mol per mol of silver in the finished emulsion. RhCl
_An aqueous solution of halogen salt containing ₆ and 2 × 10 ⁻⁷ mol of K ₃ IrCl ₆ , 0.15 mol of potassium bromide and 0.23 mol of sodium chloride, sodium chloride and 1,3-dimethyl-2-imidazolidinethione. Nucleation is carried out by adding a double jet method at 45 ° C. for 12 minutes to a gelatin aqueous solution containing the above to obtain silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 60 mol%. It was Then, similarly, a 0.63 mol silver nitrate aqueous solution, a 0.25 mol potassium bromide, and a 0.41 mol sodium chloride containing halogen salt aqueous solution were added over 20 minutes by the double jet method. Thereafter, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver, conversion was carried out, and the product was washed with water by the flocculation method according to a conventional method, 40 g of gelatin was added, pH 6.5, pAg 7.5.
In addition, 7 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added per 1 mol of silver, and the mixture was heated at 60 ° C. for 45 minutes to be chemically sensitized and treated with 4-hydroxy- as a stabilizer. 150 mg of 6-methyl-1,3,3a, 7-tetrazaindene and proxel as preservative were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.28 μm and a silver chloride content of 60 mol%. (Coefficient of variation 9%)

<Preparation of Coating Sample> On a polyethylene terephthalate film (150 μm) support having an undercoat layer (0.5 μm) made of a vinylidene chloride copolymer, a layer structure of EM and PC was sequentially formed from the support side. So that
Apply sample No. 101-112 were created. The preparation method and coating amount of each layer are shown below. (Emulsion layer) The emulsion-A was dissolved together with gelatin at 40 ° C., and then the sensitizing dye S-1 was added at 3.6 × 10 ⁻⁴ mol / mol A.
g, the following compound (a) 2.5 mg / m ² , 2,6-dihydroxylamino-4-N, N diethylamino-1,3,5
-Triazine 2.0 mg / m ² , 8-chloro-5-hydroxyquinoline 5 mg / m ² , the following compound (b) 50 mg / m ² , 20 wt% polyethyl acrylate based on gelatin, 15 wt% based on gelatin The following compound (d), 3.8 wt% of the following compound (c) with respect to gelatin as a gelatin hardening agent, and the general formula (I), as shown in Table 1,
The compounds of the general formula (II) and the general formula (III) are added to
It was applied so that the coating amount would be 3.6 g / m ² . At this time, the coated gelatin amount was 1.8 g / m ² .

[0086]

[Chemical 43]

[0087]

[Table 1]

(Surface protection layer) A polymethylmethacrylate dispersion (average particle size 5 μm) and the following surfactants (e, f) were added to a gelatin solution to prepare gelatin 1.0
g / m ² , 0.5 g / m ² as polymethylmethacrylate
Was applied so that

[0089]

[Chemical 44]

The developer formulation used in this example is shown below. Developer formulation Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Ethylenediaminetetraacetic acid disodium 1.0 Sodium carbonate 11.0 Potassium bromide 10.0 5- Methylbenzotriazole 0.4 2-Mercaptobenzimidazole-5-sulphonic acid 0.3 Sodium 3- (5-mercaptotetrazole) benzene sulfonate 0.2 Sodium toluenesulfonate 8.0 1 liter with water added (pH 10 .5)

Evaluation of Photographic Properties 1. Sensitometric gradation (γ) After exposure through a filter having a color temperature of 3200 ° K and a step wedge using a tungsten sensitometer, FG-
Using a 710F automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.), development was carried out at 34 ° C. for 30 ″, followed by fixing, washing with water and drying in order. The fixing solution was GR-F manufactured by Fuji Photo Film Co., Ltd.
1 was used. Further, after the developer of the above formulation was kept in the automatic developing machine for 1 week, it was exposed and developed in the same manner as above. γ = optical density difference (3.0−0.3) ÷ ΔlogE where ΔlogE is (exposure amount (logE3.0) required to give optical density 3.0 and optical density 0.3) Means the difference in exposure dose (logE0.3) required for

2. Practical skill Dmax A manuscript containing an image with a line width of 40μ was created on a typesetting paper. The line width was measured by scanning the original in the line width direction with a reflective microdensitometer. At this time, the optical density of the line was 0.6. The line width (white clear) of this manuscript was 4 using a reflection type plate-making camera C-690 (auto companica) manufactured by Dainippon Screen Co., Ltd.
The exposure amount was adjusted so as to be 0 μ, and after photographing, the above 1.
It was developed in the same manner as in.

From the results in Table 1, when the compound of the general formula (I) is used alone, as the Fresh performance, the gradation becomes harder by increasing the addition amount, and the Dm is high and the performance is good. . However, after 1 week (fatigue liquid), the tone becomes soft and the Dm also decreases, and particularly in the sample containing the compound of the general formula (I), black spots often occur, resulting in impractical performance. On the other hand, samples 103 and 10 of the present invention
In Nos. 6, 109 and 112, high contrast and high Dm were obtained with a small addition amount of the compound of the general formula (I), and even when treated with a fatigue liquid, the high contrast and high Dm could be maintained, and black spots were few and good performance was obtained. It is well understood that

Example-2 <Preparation of coating sample> The types and addition amounts of the compounds of formulas (I), (II) and (III) in the emulsion layer of Example-1 are shown in the table.
Samples 201 to 215 were prepared in exactly the same manner as in Example-1 except that the changes were made as shown in FIG. The comparative compounds used in this example are shown below.

[0095]

[Table 2]

[0096]

[Chemical formula 45]

From the results in Table 2, sample No. 210 and 2
In No. 11, the effect of freshening the contrast of the fresh image is small, and it is sensitized by the fatigue solution and becomes soft. Sample No. In 214 and 215, the freshness and hardness of both 1 week and Dm are high, but the fatigue fluid (1
Greater sensitization in week). Sample No. of the present invention 202-2
It can be seen that in Sample No. 09, both Fresh and 1 week maintain high contrast and high Dm, the sensitivity change in the fatigue solution is small, and the stability is good.

Example-3 Example-1 and Example-1 except that the compound species of the general formulas (I), (II) and (III) and the addition amount in the emulsion layer of Example-1 were changed as shown in Table 3. Similarly, samples 301 to
313 was produced. The evaluation was performed in the same manner as in Example-1.

[0099]

[Table 3]

From the results of Table 3, sample numbers 302 and 30
No sufficient hardness can be obtained with Nos. 5 and 311. However, it can be seen that all the samples of the present invention have a high contrast and a high practical skill Dmax, and there are few black spots in the fatigue liquid.

Example 4 (Preparation of Emulsion) A 0.13 M silver nitrate aqueous solution and K ₂ Rh (H) corresponding to 1.5 × 10 ⁻⁷ mol per mol of silver were prepared.
₂ O) Cl ₅ and K ₃ Ir equivalent to 2 × 10 ⁻⁷ mol
Contains Cl ₆ , 0.04M potassium bromide and 0.09M
The aqueous solution of halogen salt containing sodium chloride in a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolinethione at 12 ° C with stirring at 38 ° C.
Nucleation was performed by adding by a double jet method for a minute to obtain silver chlorobromide grains having an average grain size of 0.14 μm and a silver chloride content of 70 mol%. Then similarly,
A 0.87 M silver nitrate aqueous solution and a halogen salt aqueous solution containing 0.26 M potassium bromide and 0.65 M sodium chloride were added by the double jet method over 20 minutes, and then a 1 × 10 ⁻³ mol KI aqueous solution was added. Was added for conversion. Subsequently, a copolymer of isobutene and monosodium maleate was used as a precipitant and washed with water by a flocculation method. Then, 40 g of gelatin was added per mol of silver, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid, 200 mg of potassium thiocyanate and 5 mg of sodium thiosulfate were added per mol of silver, and the mixture was heated at 60 ° C. for 45 minutes. , Chemically sensitized. Next, 4-hydroxy-1,3,3a, 7-tetrazaindene 150m as a stabilizer
g, and then 100 mg of proxel as a preservative. The resulting emulsion has an average grain size of 0.25 μm,
It was a silver iodochlorobromide cubic grain having a silver chloride content of 69.9 mol% (variation coefficient of grain size: 10%).

(Preparation of coating sample) (Emulsion layer) The above silver halide emulsion was mixed with gelatin in 4 parts.
After dissolution at 0 ° C., sensitizing dyes were added as shown in Table 4. Then, compound (a) 1.1 × 10 ⁻⁵ mol / m ² , compound (b) 1.0 × 10 ⁻⁵ mol / m ² , compound (c)
5.0 × 10 ^-6 mol / m ² , hydroquinone 25 mg /
m ² , compound (d) 8.9 × 10 ^-6 mol / m ² , hydrazine compound of general formula (I) shown in Table 4 2 × 10 ^-5 mol / m ²
m ² and the compound of the general formula (II) or (III) of the present invention, sodium dodecylbenzenesulfonate 3 mg
/ M ² , compound (e) 10 mg / m ² , water-soluble latex of compound (f) 600 mg / m ² , methyl acrylate, 2-acrylamido-2-methylprobansulfonic acid sodium salt and acetoacetoxyethylmethacrylate latex copolymerization Combined (Polymerization ratio 88: 5: 7) 200
mg / m ² , and further 3% by weight of the compound (g) as a hardening agent to gelatin and 1% by weight of bis-vinylsulfonylmethane to gelatin were added. The pH of the solution was adjusted to 5.8. This solution was applied onto a polyethylene terephthalate film (thickness 150 μm) support having an undercoat layer (0.5 μm) made of a vinylidene chloride copolymer,
The amount of silver was 3.2 g / m ² , and the amount of gelatin was 2.0 g / m ² .

[0103]

[Chemical formula 46]

On these emulsion layers, as a protective layer, 1.0 mg / m ^{2 of} gelatin, 40 mg / m ^{2 of} amorphous silicon dioxide matting agent having an average particle size of 3.5 μm, 0.1 g / m ^{2 of} methanol silica, Polyacrylamide 100 mg
/ M ² , hydroquinone 150 mg / m ² , silicone oil 20 mg / m ² , and a coating solution containing 5 mg / m ² of the compound (h) as a coating aid and 25 mg / m ^{2 of} sodium dodecylbenzenesulfonate, and Table 4 A sample as shown in was prepared.

The coating layer on the back surface of the support was as shown below. (Back Layer Formulation) Gelatin 3 g / m ² Polyeryl acrylate latex 2 g / m ² sodium p-dodecylbenzenesulfonate 40 mg / m ² Compound (f) 3 wt% SnO ₂ / Sb (weight ratio 90) based on gelatin / 10, average particle size 0.20 μm) 200 mg / m ² dye (a) 50 mg / m ² dye (b) 100 mg / m ² dye (c) 50 mg / m ²

[0106]

[Chemical 47]

(Back protective layer) Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate Na salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

Performance Evaluation 1. Sensitometry Sensitivity, Gradation (γ) Exposure and development were performed in the same manner as in the sensitometric gradation evaluation method of Example-1. The sensitivity was represented by the relative value of the exposure amount that gives a density of 1.5. The larger the value, the higher the sensitivity. γ has the same definition as in Example-1. 2. Practical skill Dmax Evaluation was carried out in the same manner as in Example-1. 3. Safelight Property Using No. 40 manufactured by Fuji Photo Film Co., Ltd. using a tungsten 40W incandescent lamp. 5 from the sample through 6 filters
After performing 0 to 30 spectral irradiation from 0 cm away,
Development processing was performed under the same conditions as in the sensitometry, and the comparison between the safelight light irradiation time and the time at which the fog rise started was examined, and the evaluation was made in the following five grades. Fog is generated by light irradiation within 5 minutes is 1, fog is generated by light irradiation of 5 to 10 minutes is 2, fog is generated by light irradiation of 10 to 20 minutes is 3, 20 to 25 Fog was generated by light irradiation for 4 minutes, and 4 was not fogged by light irradiation for 25 minutes or more. The results are shown in Table 4.

[0109]

[Table 4]

[0110]

[Chemical 48]

From the results shown in Table 4, it is understood that all the samples of the present invention have a gradation of 15 or more and are in a high contrast, and the practical skill Dmax is sufficiently high. Among them, sample numbers 410, 412, 41
4 and 416 have γ of 20 or more and high Dmax,
It can be seen that the safelight property is better than that of sample numbers 404, 406, and 408.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 20, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0109

[Correction method] Change

[Correction content]

[0109]

[Table 4]

Claims (5)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer, and at least one of the hydrazine derivatives represented by the general formula (I) in the layer and / or the adjacent hydrophilic colloid layer. One and general formula (II) or general formula
A silver halide photographic light-sensitive material containing at least one compound represented by formula (III). [Chemical 1] In the formula, R ₁ represents an aliphatic group or an aromatic group, and as a part of the substituent, —O— (CH ₂ CH ₂ O).
_{n -, - O- (CH 2} CH (CH 3) O) n - or -O
_{- (CH 2 CH (OH)} CH 2 O) n - ( wherein n is 3
Whether it contains a partial structure of (the above integer) or contains a quaternary ammonium cation as a part of the substituent,
Alternatively, it is a group containing an -S- group as a part of the substituent. G ₁ is a -CO- group, a -COCO- group, a -CS- group,
_{-C (= NG 2 R 2)} - represents the group - group, -SO- group, -SO ₂ - group or _{-P (O) (G 2 R} 2). G ₂ is a single bond, -O- group, -S- group, or -N (R ₂₎ - represents a group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, a plurality in the molecule R _{If two} are present they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl or arylsulfonyl group. [Chemical 2] In the formula, Y represents a group adsorbed on silver halide. X represents a divalent linking group consisting of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. A represents a divalent linking group. B represents an amino group, an ammonium group and a nitrogen-containing heterocycle, and the amino group may be substituted. m represents 1, 2 or 3, and n represents 0 or 1. [Chemical 3] In the formula, R ₁ and R ₂ each represent a hydrogen atom or an aliphatic residue. R ₁ and R ₂ may combine with each other to form a ring. R
₃ represents a divalent aliphatic group. X represents a divalent heterocycle containing a nitrogen, oxygen or sulfur atom. n represents 0 or 1. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, or an amidino group. 2. A photographic image forming method, which comprises subjecting the silver halide photographic light-sensitive material of claim 1 to development processing using a developer having a pH of 9.6 to 11.0. 3. A photographic image forming method, which comprises subjecting the silver halide photographic light-sensitive material of claim 1 to development processing using a developing solution containing no amine compound and having a pH of 9.6 to 11.0. 4. R of the general formula (I)₁Is the general formula (Ib)
Or a compound represented by formula (Ic)
Item 1. A silver halide photographic light-sensitive material of item 1. [Chemical 4]Where L₁, L₂Is -CONR₇-Group, -NR₇CON
R₈-Group, -SO₂NR₇-Group or -NR₇SO₂N
R₈Represents a group, each of which is the same or different
May be. R₇And R₈Is a hydrogen atom or 1 to 1 carbon atoms
Represents an alkyl group having 6 or an aryl group having 6 to 10 carbon atoms
However, a hydrogen atom is preferable. m is 0 or 1.
R₃, R_Four, R_FiveIs a divalent aliphatic group or aromatic group
It Z in the general formula (Ib)₁Forms a nitrogen-containing aromatic ring
Represents a group of atoms required for formation. X ^-Is a counter anion
Or, when forming an intramolecular salt, it represents a counter anion moiety.
You R₆Represents an aliphatic group or an aromatic group. General formula
Three Rs in (Ic)₆Are the same
May be different from each other, or may be bonded to each other to form a ring.
May be. 5. A silver halide emulsion having the following general formula (IV):
2. The silver halide photographic light-sensitive material according to claim 1, which is spectrally sensitized with the dye. General formula (IV): In the formula, V ₁ and V ₃ represent hydrogen atoms or electron withdrawing groups, and V ₂ and V ₄ represent electron withdrawing groups. R ₁ , R ₂ ,
R ₃ and R ₄ may be the same or different and each represents an alkyl group or an alkenyl group having a total carbon number of 10 or less, and at least one of R ₁ , R ₂ , R _{3 and} R ₄ is a sulfo group. A group having a group or a carboxy group. X ₁ represents a counter ion necessary for neutralizing the charge. n represents 0 or 1, and is 0 in the case of an inner salt.