JPH1138544A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material high in sensitivity and small in fog even in the case of rapid processing and improved in pressure resistance and small in deterioration of performance during storage by incorporating a selenium compound and/or tellurium compound and a phosphazene compound and a specified compound. SOLUTION: This silver halide photographic sensitive material contains the selenium compound and/or the tellurium compound, and phosphazene compound and the compound represented by the formula in which each of R11 and R15 is, independently, a 1-5C optionally substituted alkyl or such alkoxy or cyano group; each of R12 -R14 is, independently, an H atom, corboxy, sulfonic, phosphoric group or an 1-4C alkyl or alkenyl group substituted by a carboxy, sulfonic acid, sulfuric or phosphoric acid, but each is not an H atom at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material. More specifically, the present invention relates to a silver halide photographic light-sensitive material having high sensitivity even with rapid processing, low fog, improved pressure resistance, and little performance deterioration during storage.

[0002]

2. Description of the Related Art In recent years, advances in electronics have dramatically shortened access times to images, and silver halide photographic materials have been required to be processed more and more rapidly. Further, a technique for improving the image quality (granularity, sharpness) of an image is desired, and further finer silver halide grains are required. Under these circumstances, a chalcogen sensitization method using a selenium or tellurium compound is widely known as one of the chemical sensitization methods for silver halide emulsions. However, while this technology can achieve high sensitivity, fogging due to external pressure is remarkable during handling and processing of photosensitive materials, and especially when a rapid processing by an automatic developing machine is performed, the roller is pressed by a transport roller. Fogging failure of streaks or black spots called marks may be caused.
Further, the silver halide emulsion or a photographic material containing the same has a drawback in that the photographic performance is remarkably changed upon storage after preparation, and improvement has been desired.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and low fog even in rapid processing, improved pressure resistance, and little deterioration in performance upon storage. It is to provide a processing method.

[0004]

The above objects of the present invention have been attained by the following constitutions.

(1) A silver halide photographic material comprising a selenium compound and / or tellurium compound, a phosphazene compound and a compound represented by the following general formula (1).

[0006]

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[Wherein, R ₁₁ and R ₁₅ each independently represent an alkyl group having 1 to 5 carbon atoms, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, or a cyano group. R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a carboxy group,
A sulfonic acid group, a phosphonic acid group, or a C1 to C4 alkyl or alkenyl group substituted with a carboxy group, a sulfonic acid group, a sulfate group, or a phosphate group.
However, R ₁₂ , R ₁₃ and R ₁₄ are not simultaneously hydrogen atoms. (2) A silver halide photographic light-sensitive material comprising a selenium compound and / or tellurium compound, a phosphazene compound and a compound represented by the following general formula (2).

[0008]

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[Wherein, R ₂₁ , R ₂₃ , R ₂₅ and R ₂₆ each independently represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group; Represents a group, a substituted aryl group, a substituted alkoxy group, a substituted aryloxy group, or a sugar residue. However, R ₂₁ , R ₂₃ , R ₂₅ and R ₂₆ are not hydrogen atoms at the same time.

R ₂₂ and R ₂₄ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, Represents an alkoxy group, a substituted aryloxy group, or a sugar residue. (3) A silver halide photographic light-sensitive material comprising a selenium compound and / or tellurium compound, a phosphazene compound and a compound represented by the following general formula (3).

[0011]

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[Wherein R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆ each independently represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group; Represents a group, a substituted aryl group, a substituted alkoxy group, a substituted aryloxy group, or a sugar residue. However, R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆ are not hydrogen atoms at the same time.

R ₃₂ and R ₃₄ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, Represents an alkoxy group, a substituted aryloxy group, or a sugar residue. (4) A silver halide photographic material comprising a selenium compound and / or tellurium compound, a phosphazene compound, and a disulfide compound having a molecular weight of 500 or more.

(5) A silver halide photographic light-sensitive material comprising a selenium compound and / or tellurium compound, a phosphazene compound and a compound represented by the following formula (5).

Formula (5) R ₅₁ -SR _{52 wherein} R ₅₁ and R ₅₂ each independently represent an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, Represents a ring group or a substituted heterocyclic group. (6) A silver halide photographic material comprising a selenium compound and / or tellurium compound, a phosphazene compound, and a compound represented by the following general formula (6).

[0016]

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Wherein R ₆₁ represents a hydrogen atom or a methyl group. R ₆₂ , R ₆₃ and R ₆₄ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxy group. Where R
_{When 62} , R ₆₃ and R ₆₄ are alkyl groups, they may be substituted with a hydroxy group, a carboxy group or a sulfo group. (7) A silver halide photographic light-sensitive material containing a selenium compound and / or tellurium compound, a phosphazene compound and a compound represented by the following general formula (7).

[0018]

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[Wherein R ₇₁ and R ₇₂ each independently represent a hydrogen atom or a methyl group. M represents a hydrogen atom, an alkali metal atom or an ammonium salt, and n represents 0, 1 or 2. However, when either or both of R ₇₁ and R ₇₂ are a methyl group, they may be substituted with —COOM or —OH. (8) A silver halide photographic light-sensitive material containing a selenium compound and / or tellurium compound, a phosphazene compound, and a compound represented by the following general formula (8).

Formula (8) (Me) n ₀ HAO ₃ [wherein Me represents a monovalent or divalent atom, and n ₀ represents Me
Is 2 when Me is monovalent, and 1 when Me is divalent. A represents an atom of Group 5B of the periodic table. However, nitrogen is excluded. (9) A silver halide photographic material comprising a selenium compound and / or tellurium compound, a phosphazene compound, and a compound represented by the following general formula (9).

Formula (9) R ₉₁ NH—OH wherein R ₉₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group or acyl group. (10) A processing method comprising subjecting the silver halide photographic light-sensitive material according to any one of the above items 1 to 9 to image processing and then photographic processing under conditions satisfying the following formula.

Le ^0.75 × t = 40 to 90 (0.7 ≦ Le ≦ 4.0) [wherein, Le is a contact point between the first roller pair at the film insertion port of the automatic processor and the last roller pair at the film drying port. Represents the length (unit: m) of the transport path to the contact point, and t is Le
Represents the time required to pass through (in seconds). The present invention will be described in more detail. The phosphazene compound used in the present invention is represented by the following general formula (11) or general formula (1)
The compound represented by 2) is preferred.

[0023]

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In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, alkoxy group, aryl group, aryloxy group, alkenyl group, alkynyl group, amino group, alkylimino group, arylimino group, alkylthio group. Represents an arylthio group, an acyl group, a cyanide group, or an azide group;
₁ and R ₂ may be the same or different. n ₁ is 1
Represents a positive integer of the above, and when n ₁ is plural, R ₁ or R ₂
May be the same or different.

[0025]

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In the formula, R ₃ and R ₄ are each represented by the general formula (1)
It represents a group having the same meaning as R ₁ and R _{2 in} 1), and R ₃ and R ₄ may be the same or different. n ₂ represents a positive integer of 3 or more, and R ₃ or R ₄ may be the same or different.

The above general formulas (11) and (12) are phosphazene derivatives whose basic skeleton is composed of P = N bonds.
In the general formula (11), n ₁ is not particularly limited as long as it is a positive integer of 1 or more, and preferably 1 to 30,000
Or less, more preferably 1 or more and 10,000 or less, and still more preferably 1 or more and 5,000 or less. In the general formula (12), n ₂ is not particularly limited as long as it is a positive integer of 3 or more.
More preferably 3 or more and 8 or less, still more preferably 3 or 4
It is.

These compounds include a high molecular weight compound in which the P = N bond is linear, a cyclic compound and a cyclic compound. The method of synthesizing these compounds is described in more detail as follows: (PNF ₂ ) ₃ , (PNF ₂ ) ₄ , (PNF ₂ ) n
And the like, in which the side group such as is a trimer, tetramer, or n-mer of an F atom, (PNCl ₂ ) ₃ , (PNCl ₂ ) ₄ , (PNCl ₂ )
Compounds in which the side group such as n (n <15) is a Cl atom trimer, tetramer, n-mer, (PNBr ₂ ) ₃ , (PNB
(Pr ₂ ) ₄ , (PNBr ₂ ) n, etc., a compound in which the side chain group is a Br atom trimer, tetramer, n-mer, (PNI ₂ ) ₃ , (PNI)
₂ ) ₄ , (PNI ₂ ) n or the like has a side chain group of a halogen atom of a trimer, tetramer, or n-mer compound of an I atom as C ₂ H ₅ ON.
a, CF ₂ HCF ₂ CH ₂ ONa, C ₂ H ₅ SNa, C ₆ H ₅
ONa, CH ₃ C ₆ H ₄ ONa, (C ₆ H ₅ O) ₂ Ca, CF
₃ reaction with metal salts of organic compounds such as CH ₂ ONa, C
An organic compound having a hydroxyl group such as ₆ H ₅ OH or C
P such as alcohol such as H ₂ (CH ₃ ) = C—COOCH ₂ CH ₂ OH, amines such as C ₆ H ₅ NH ₂ , etc.
An organic compound capable of nucleophilic substitution with a halogen atom on an atom,
Examples thereof include a method of mixing with amines such as aniline and halogen acceptor compounds such as sodium hydroxide and sodium carbonate.

The phosphazene derivative is generally synthesized in this manner.
There is no particular limitation.

Further, the combination of the side chain groups may not necessarily be composed of a single group, but may be a combination selected from a plurality of these groups. In addition, Chem. R
ev. , 1972, vol72, no. 4, 315-3
It may be a functional group contained in the compound shown in 56.

Next, specific examples of the compound represented by formula (11) or (12) are shown, but the present invention is not limited thereto. In the following specific examples, L is a chain compound,
C represents a cyclic compound, and Hy represents a cyclic compound having a structure in which the cyclic compound is further connected in a chain or network.

L-1 [NP (NCS) ₂ ] _n L-2 [NP (NCO) ₂ ] _n L-3 [NP (COCH ₃ ) ₂ ] _n L-4 [NP (COC ₁₇ H ₃₅ ) ₂ ] _n L-5 [NP (CN) ₂ ] _n L-6 [NP (OMe) ₂ ] _n L-7 [NP (OEt) ₂ ] _n L-8 [NP (OCH ₂ CF ₃ ) ₂ ] _n L- 9 [NP (OCH ₂ C ₂ F ₅ ) ₂ ] _n L-10 [NP (OCH ₂ CF ₂ CF ₂ H) ₂ ] _n L-11 [NP (OCH ₂ C ₃ H ₇ ) ₂ ] _n L-12 [NP (OCH ₂ CF ₃ ) (OCH ₂ C
_{3 F 7)] n L-} 13 [NP (OCH 2 (CF 2) 6 CF 3) 2] n L-14 [NP (OCH 2 C 2 F 5) (OCH 2 C
_{3 F 7)] n L-} 15 [NP (OCH 2 CF 2 CF 2 H) (OCH 2 C
₆ F ₁₂ H)] _n L-16 [NP (OPh) ₂ ] _n L-17 [NP (OC ₆ H ₄ F-p) ₂ ] _n L-18 [NP (OC ₆ H ₄ CF ₃ -m) ₂ ] _n L-19 [NP (OC ₆ H ₄ Cl-p) ₂ ] _n L-20 [NP (OC ₆ H ₃ Cl ₂ -2, 4) ₂ ] _n L-21 [NP (OC ₆ H _{4 CH 3 -p) 2] n L} -22 [NP (OC 6 H 4 C 6 H 5 -p) 2] n L-23 [NP (NHMe) 2] n L-24 [NP (NHEt) 2] n L-25 [NP (NHPr-n) ₂ ] _n L-26 [NP (NHBu-n) ₂ ] _n L-27 [NP (NHPh) ₂ ] _n L-28 [NP (NMe ₂ ) ₂ ] _n L −29 [NP (NC ₅ H ₁₀ ) ₂ ] _n L-30 [NP (NEt ₂ ) Cl] _n L-31 [NP (NEt ₂ ) (NH ₂ )] _n L-32 [NP (NEt ₂ ) ( NHMe)] _n L-33 _{NP (NEt 2) (NHEt)} ] n L-34 [NP (NEt 2) (NHPr-n)] n L-35 [NP (NEt 2) (NHBu-n)] n L-36 (NPPh 2) n L-37 [NP (SEt) ₂ ] _n L-38 [NP (N ₃ ) ₂ ] _n L-39 [NP (NH ₂ ) ₂ ] _n

[0033]

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C-1 [NP (CF ₃ ) ₂ ] ₃ C-2 (NPPh ₂ ) ₃ C-3 (NPPh ₂ ) ₄ C-4 [NP (C ₆ H ₄ Cl-p) ₂ ] ₃ C- 5 [NP (OC ₆ H ₄ F-p) ₂ ] ₃ C-6 [NP (OC ₆ H ₄ F-p) ₂ ] ₄ C-7 (NPET ₂ ) ₃ C-8 (NPet ₂ ) ₄ C- 9 [NP (COCH ₃ ) ₂ ] ₃ C-10 [NP (COC ₁₇ H ₃₅ ) ₂ ] ₃ C-11 [NP (COCH ₃ ) ₂ ] ₄ C-12 [NP (COC ₁₇ H ₃₅ ) ₂ ] ₄ C-13 [NP (OCH ₂ CF ₃ ) ₂ ] ₃ C-14 [NP (OCH ₂ CF ₃ ) ₂ ] ₄ C-15 [NP (OMe ₂ ) ₂ ] ₃ C-16 [NP (OMe ₂ ) ₂ ] ₄ C-17 [NP (OEt ₂ ) ₂ ] ₃ C-18 [NP (OEt ₂ ) ₂ ] ₄ C-19 [NP (OPr-i) ₂ ] ₃ C-20 [NP (OPr-i) ₂ ] ₄ C-21 [NP (OBu-n) ₂ ] ₃ C-22 [NP (OBu-n) ₂ ] ₄ C-23 [NP (OCH ₂ Ph) ₂ ] ₃ C-24 [NP (OCH ₂ Ph) ₂ ] ₄ C-25 [NP (OPh) ₂ ] ₃ C-26 [NP (OPh) ₂ ] ₄ C-27 [NP (OC ₆ H ₄ CH ₃ -p) ₂ ] ₃ C-28 [NP (OC (OC ₆ H ₄ CH ₃ -p) ₂ ] ₄ C-29 [NP (SEt) ₂ ] ₄ C-30 [NP (SPh) ₂ ] ₃ C-31 [NP (SPh) ₂ ] ₄ C-32 [NP ( NHMe) ₂ ] ₃ C-33 [NP (NHMe) ₂ ] ₄ C-34 [NP (NHEt) ₂ ] ₃ C-35 [NP (NHEt) ₂ ] ₄ C-36 [NP (NHBu-n) ₂ ] _{3 C-37 [NP (NHBu} -n) 2] 4 C-38 [NP (NMe 2) 2] 3 C-39 [NP (NMe 2) 2] 4 C-40 [NP (NEt 2 _{2] 3 C-41 [NP} (NEt 2) 2] 4 C-42 [NP (NMePh) 2] 3 C-43 N 3 P 3 Ph 3 (NHMe) 3 (cis) C-44 N 3 P 3 Ph ₃ (NHMe) ₃ (trans) C-45 N ₃ P ₃ Ph ₃ (NHEt) ₃ (cis) C-46 N ₃ P ₃ Ph ₃ (NHEt) ₃ (trans) C-47 N ₃ P ₃ (NHEt) ₄ (OCH ₂ CF ₃ ) ₂ (g
em) C-48 N ₃ P ₃ (NHEt) ₄ (OCH ₂ CF ₃ ) ₂ (n
on-gem) C-49 N ₃ P ₃ (OC ₆ H ₅ ) ₄ (NH ₂ ) ₂ (gem) C-50 N ₃ P ₃ (OC ₆ H ₅ ) ₄ (NH ₂ ) ₂ (non-
gem) C-51 [NP (NCS) ₂ ] ₃ C-52 [NP (NCO) ₂ ] ₃ C-53 [NP (CN) ₂ ] ₃ C-54 [NP (N ₃ ) ₂ ] ₃ C-55 [NP (OPr-n) ₂ ] ₃ C-56 [NP (OCH ₂ CF ₃ ) ₂ ] ₃ C-57 [NP (SEt) ₂ ] ₃ C-58 [NP (NH ₂ ) ₂ ] ₃ C-59 [NP (CF ₃ ) ₂ ] ₄ C-60 [NP (NCS) ₂ ] ₄ C-61 [NP (NCO) ₂ ] ₄ C-62 [NP (CN) ₂ ] ₄ C-63 [NP (OPr- n) ₂ ] ₄ C-64 [NP (NH ₂ ) ₂ ] ₄ C-65 [NP (OMe) ₂ ] ₅ C-66 [NP (NMe ₂ ) ₂ ] ₅ C-67 [NP (OPh) ₂ ] _{5 C-68 N 5 P 5} (OC 6 H 5) 8 (NH 2) 2 (gem) C-69 [NP (OMe) 2] 6 C-70 [NP (NMe 2) 2] 6 C-71 [ NP (O _{h) 2] 6 C-72} N 6 P 6 (OC 6 H 5) 10 (NH 2) 2 (gem) C-73 [NP (OMe) 2] 8 C-74 [NP (NMe 2) 2] 8 C-75 [NP (OPh) ₂ ] ₈ C-76 N ₈ P ₈ (OC ₆ H ₅ ) ₁₄ (NH ₂ ) ₂ (gem)

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The compound represented by the general formula (11) or (12) of the present invention may be contained in at least one layer in any silver halide photographic light-sensitive material, and is preferably contained in a protective layer. If it is. The amount used is 100% by weight or less, preferably 50% by weight or less, more preferably 20% by weight, based on the binder of the layer containing the compound.
It is preferably at most 15% by weight or less.

Next, the compound represented by formula (1) will be described. In the general formula (1), R ₁₁ and R ₁₅
Is preferably an alkyl group having 3 or 4 carbon atoms, a substituted alkyl group, an alkoxy group, or a substituted alkoxy, respectively.

R ₁₂ , R ₁₃ and R ₁₄ represent a carboxy group,
It is preferably a sulfonic acid group or a phosphonic acid group.
More preferably, two of R ₁₂ , R ₁₃ and R ₁₄ are the above groups.

The compound represented by the general formula (1) can be synthesized by a generally known method, and its preferable addition amount is from 1 × 10 ^-6 to 1 × 10 ⁶ per mol of silver halide.
^-2 mol is preferably used. More preferably, 1 ×
It is 10 ^{-5 to} 5 × 10 ^-3 mol.

Hereinafter, specific examples of the compound represented by formula (1) of the present invention will be shown, but the invention is not limited to the following compounds.

[0047]

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[0048]

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Next, the compound represented by formula (2) will be described. In the general formula (2), R ₂₁ , R ₂₃ , R
₂₅ and R ₂₆ each independently represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group;
Represents a substituted aryl group, a substituted alkoxy group, a substituted aryloxy group, or a sugar residue. Provided that R ₂₁ , R ₂₃ , R ₂₅ and R
₂₆ cannot be a hydrogen atom at the same time. Among these substituents, preferred substituents are a hydroxy group, a methoxy group, a phenyloxy group, a hydroxy-substituted phenyl group, and a sugar residue, and particularly preferred are a hydroxy group,
It is a hydroxy-substituted phenyl group.

R ₂₂ and R ₂₄ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, Represents an alkoxy group, a substituted aryloxy group, or a sugar residue.
Preferred substituents among these substituents are a hydrogen atom and a hydroxy group.

The compound represented by the general formula (2) can be synthesized by a generally known method, and its preferable addition amount is 1 × 10 ^-6 to 1 × 10 ⁶ per mol of silver halide.
^-2 mol is preferably used. More preferably, 1 ×
It is 10 ^{-5 to} 5 × 10 ^-3 mol.

Specific examples of the compound represented by formula (2) of the present invention are shown below, but the invention is not limited to the following compounds.

[0053]

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[0054]

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[0055]

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Next, the compound represented by formula (3) will be described. In the general formula (3), R ₃₁ , R ₃₃ , R
₃₅ and R ₃₆ each independently represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group;
Represents a substituted aryl group, a substituted alkoxy group, a substituted aryl axi group, and a sugar residue. Provided that R ₃₁ , R ₃₃ , R ₃₅ and R
₃₆ cannot be a hydrogen atom at the same time. Among these substituents, preferred substituents are a hydroxy group, a methoxy group, a phenyloxy group, a hydroxy-substituted phenyl group, and a sugar residue, and particularly preferred are a hydroxy group,
It is a hydroxy-substituted phenyl group.

R ₃₂ and R ₃₄ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, Represents an alkoxy group, a substituted aryloxy group, or a sugar residue.
Preferred substituents among these substituents are a hydrogen atom and a hydroxy group.

The compound represented by the general formula (3) can be synthesized by a generally known method, and its preferable addition amount is 1 × 10 ^-6 to 1 × 10 ⁶ per mol of silver halide.
^-2 mol is preferably used. More preferably, 1 ×
It is 10 ^{-5 to} 5 × 10 ^-3 mol.

Specific examples of the compound represented by the general formula (3) of the present invention are shown below, but are not limited to the following compounds.

[0060]

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[0061]

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Next, the disulfide compound having a molecular weight of 500 or more of the present invention (hereinafter, also referred to as the disulfide compound of the present invention) will be described.

The disulfide compound of the present invention needs to have a molecular weight of 500 or more, but if the molecular weight is 500 or more, there are no particular restrictions on its structure and substituents.
When the molecular weight is 500 or less, the effect on photographic properties is large, and it is not suitable for practical use.

The disulfide compound of the present invention can be synthesized by a generally known method. That is, it can be obtained by oxidizing a mercapto-containing compound using an enzyme or another oxidizing agent.

The following are specific examples of the disulfide compound of the present invention, but are not limited to the following compounds.

[0066]

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Next, the compound represented by formula (5) will be described. In the general formula (5), R ₅₁ and R ₅₂ each independently represent an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, or a substituted heterocyclic group. Among them, an alkyl group, an aryl group, and a heterocyclic group having 1 to 6 carbon atoms are preferable, and a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are more preferable. Preferred substituents are a hydroxy group, a carboxy group, a sulfo group, or an alkali metal salt thereof.

The compound represented by the general formula (5) can be synthesized by a generally known method, and its preferable addition amount is from 1 × 10 ^-6 to 1 × 10 ⁶ per mol of silver halide.
^-2 mol is preferably used. More preferably, 1 ×
It is 10 ^{-5 to} 5 × 10 ^-3 mol.

Next, specific examples of the compound of the general formula (5) will be shown, but it should be understood that the present invention is not limited thereto.

[0070]

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In the general formula (6), R ₆₁ represents a hydrogen atom or a methyl group. R ₆₂ , R ₆₃ and R ₆₄ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxy group. However, when R ₆₂ , R ₆₃ and R ₆₄ are alkyl groups, they may be substituted with a hydroxy group, a carboxy group or a sulfo group. R ₆₁ is preferably a hydrogen atom. Hereinafter, specific examples of the compound of the general formula (6) are shown, but are not limited thereto.

[0072]

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The preferable addition amount of the compound represented by the general formula (6) is 1 × 10 ^-6 to 1 × per mol of silver halide.
10 ^-2 mol is preferably used. More preferably,
It is 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol.

In the general formula (7), R ₇₁ and R ₇₂ each represent a hydrogen atom or a methyl group. When either or both of them are a methyl group, they may be substituted with —COOM or —OH. R ₇₁ and R ₇₂ are preferably each a hydrogen atom. M represents a hydrogen atom, an alkali metal atom or an ammonium salt. n represents 0, 1 or 2, and 0 is preferred. Hereinafter, specific examples of the compound of the general formula (7) are shown, but are not limited thereto.

[0075]

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The preferable addition amount of the compound represented by the general formula (7) is 1 × 10 ^-6 to 1 × per mol of silver halide.
10 ^-2 mol is preferably used. More preferably,
It is 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol.

In the general formula (8), Me is monovalent or divalent.
N ₀ represents 2 when Me is monovalent, and represents 1 when Me is divalent. A represents an atom of Group 5B of the periodic table excluding nitrogen, and phosphorus is preferable. Compounds containing nitrogen are excluded because they are significantly less effective. The reason is that pπ-pπ double bond can be formed stably in nitrogen,
For atoms above phosphorus, the energy level of the 3d orbital is low and 3
This is probably because d orbitals are not used for the reaction. Hereinafter, specific examples of the compound of the general formula (8) will be shown, but the present invention is not limited thereto.

8-1 K ₂ HP 0 ₃ 8-2 Na ₂ HP 0 ₃ 8-3 MgHP 0 ₃ 8-4 K ₂ HSb 0 ₃ 8-5 Na ₂ HSb 0 ₃ 8-6 MgHSb 0 ₃ 8-7 K ₂ HBi0 ₃ 8- 8 Na ₂ HBiO ₃ 8-9 MgHBiO ₃ The preferable addition amount of the compound represented by the general formula (8) is preferably 1 × 10 ^-6 to 1 × 10 ^-2 mol per mol of silver halide. More preferably, 1 × 10 ⁻⁵ to
5 × 10 ^-3 mol.

In the general formula (9), R ₉₁ is a hydrogen atom,
Or each substituted, represents an unsubstituted alkyl group, alkenyl group, acyl group, but represents a hydrogen atom or a substituted with 1 to 4 carbon atoms, an unsubstituted alkyl group or a substituted with 2 to 4 carbon atoms, an unsubstituted alkenyl group, An acyl group is preferable, and a substituent is preferably a group selected from a hydroxyl group, a carboxyl group, an amino group, a nitro group, a sulfo group, a sulfate, and salts thereof. As R ₉₁ , an alkyl group or an alkyl group substituted with a hydroxyl group is most preferred.

Specific examples of the compound represented by formula (9) are shown below, but the present invention is not limited thereto.

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[0082]

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The amount of the compound represented by the general formula (9) is not particularly limited, but is practically 5 × 10 ^{-5 to} 5 × 10 ^-3 mol, preferably 1 ×, per mol of silver halide. 10 ^-4
１1 × 10 ⁻³ mol.

In the present invention, a selenium compound and / or tellurium compound is used as a chemical sensitizer for silver halide grains. The selenium and tellurium compounds used include a wide variety of compounds.

Examples of the selenium compound of the present invention include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), and selenoureas (eg, N, N-
Dimethylselenourea, triethyl-N, N, N'-selenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylseleno Urea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids And selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), and selenides (triphenylphosphine selenide, diethyl Selenide, diethyl diselenide, etc.). Particularly preferred selenium compounds are selenides, selenoureas,
Selenoamides and selenoketones.

The amount of the selenium compound used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 10 ^-4 per mol of silver halide.
Use about moles.

The temperature of chemical ripening using a selenium compound is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The emulsion pH was 4-9, pAg
Is preferably in the range of 6.0 to 9.5.

Hereinafter, specific examples of the selenium compound used for the chemical sensitization of the present invention will be listed, but the present invention is not limited thereto.

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[0090]

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Next, useful examples of tellurium compounds used in the present invention include telluroureas (for example, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea). , N, N'-
Dimethyl-N'phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluramides (eg, Telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like.

The technique for using the tellurium compound conforms to the technique for using the selenium compound. In the present invention, chemical sensitization may be performed by combining selenium sensitization and tellurium sensitization.

The silver halide composition of the silver halide photographic light-sensitive material according to the present invention may be arbitrarily selected, for example, silver chloride, silver iodochloride, silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide. And any other silver halide may be used. When silver iodochloride is contained, the silver iodide content is preferably from 0 to 1.5 mol% as an average silver iodide content in the whole silver halide grains, and from 0 to 1.
0 mol% is more preferred.

The silver halide grains used in the present invention preferably have an average particle size of 0.15 to 5.0 μm.
It is more preferably from 0.2 to 3.0 μm, most preferably from 0.2 to 2.0 μm.

The crystal habit of the silver halide grains may be any crystal habit such as a cubic, octahedral, or twinned crystal, but tabular silver halide grains are preferred.

Tabular silver halide grains refer to grains having two opposing parallel main planes, and those which can be used in the present invention include those having a (111) plane as the main plane (1).
The (00) plane may be either a main plane or either plane.

In the tabular silver halide grains preferably used in the present invention, the ratio of the grain size to the grain thickness (hereinafter referred to as aspect ratio) is 2 or more, and preferably 2.0 to 2.0.
15.0. Particularly, 3 to 10 are preferable. Here, the grain size is an average projected area diameter (hereinafter, referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (of a circle having the same projected area as the silver halide grains). (Diameter), and thickness refers to the distance between two parallel major planes forming tabular silver halide grains.

When tabular silver halide grains are used in the present invention, the average grain thickness is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.60 μm.
μm, and more preferably 0.05 to 0.50 μm.
The average particle size is preferably from 0.15 to 5.0 μm, more preferably from 0.4 to 3.0 μm, most preferably from 0.4 to 2.0 μm. The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution, specifically, (standard deviation of grain size / average grain size) × 100 = width (%) of grain size distribution. Is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

When tabular silver halide grains are used in the present invention, they can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei with low pCl in the presence of iodine ions under conditions that facilitate formation of the (100) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution.

In the process of forming and / or growing the tabular silver halide grains, a cadmium salt,
Metal ions are added using at least one selected from a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt), and an iron salt (including a complex salt). These metal elements can also be contained on the particle surface.

In the present invention, it is also preferable to use reduction sensitization in combination. The reduction sensitization is preferably performed during the growth of silver halide grains. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. It also includes a method of growing the perceived silver halide grains.

In the present invention, chemical sensitization with a noble metal salt such as a sulfur compound or a gold salt can also be performed, and chemical sensitization can be performed by combining these sensitization methods with the above-described chalcogen sensitization method.

Specific examples of the sulfur sensitizer applicable to the present invention include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea and 1-ethyl-3- (2-thiazolyl) thiourea, and rhodanine derivatives. , Dithiacarbamic acids, polysulfide organic compounds, elemental sulfur and the like are preferred examples. In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable.

As gold sensitizers, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The method of adding the sulfur sensitizer and the gold sensitizer may be such that they are dissolved in water or alcohols or other inorganic or organic solvents, and added in the form of a solution. It may be added in the form of a dispersion obtained by emulsifying and dispersing using such a medium. Both sulfur sensitization and gold sensitization may be performed simultaneously or separately and stepwise. In the latter case, favorable results may be obtained if gold sensitization is performed after or during sulfur sensitization appropriately.

The reduction sensitization is performed by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion so that the reduction sensitization is performed during the growth of the silver halide grains of the silver halide emulsion. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof.
Other preferable reducing agents include polyamines such as hydrazine and diethylenetriamine, dimethylamineboranes, sulfites and the like.

The silver halide grains used in the present invention are:
It must be spectrally sensitized by methine dyes and the like. As the sensitizing dye used in the light-sensitive material of the present invention, cyanine, merocyanine, composite cyanine, composite merocyanine, holopolar, hemicyanine, styryl, and hemioxonol dyes can be used. Particularly useful dyes are those belonging to cyanines, merocyanines and complex merocyanines.

As these dyes, any of the nuclei usually used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenine nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine or complex merocyanine includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus and a 2-thiooxazolidine-nucleus as nuclei having a ketomethine structure.
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, it may contain an aminostilbene compound substituted with a nitrogen-containing heterocyclic nucleus group, an aromatic organic acid formaldehyde condensate, a cadmium salt, an azaindene compound, or the like.

It is preferable to add the spectral sensitizing dye as a dispersion of solid fine particles rather than as a solution of an organic solvent. In particular, it is preferable to disperse in a water system substantially free of an organic solvent and / or a surfactant, and to add in a state of a solid fine particle dispersion substantially insoluble in water. The particle size after dispersion is preferably 1 μm or less.

In the emulsion used in the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, Research Disclosure (RD) N
o. 17643 (December 1978), (RD) No.
18716 (November 1979) and (RD) No. 3
Various compounds described in 08119 (December 1989) can be used.

The method for developing a silver halide photographic light-sensitive material according to the present invention is processed by an automatic developing machine, and is completed through the steps of development, fixing, washing and drying.

In the present invention, the length Le of the transport path for processing is in the range of 0.7 to 4.0 (unit m). Le
Is 0.7 or less, each processing step becomes small, and sensitivity and contrast are reduced. Further, since the number of transport rollers is reduced, transportability is deteriorated. Also, Le is 4.0.
In the case described above, the conveying speed becomes too fast, and the photosensitive material is undesirably scratched.

The product of Le ^0.75 and t is 40 to 90. If this value is less than 40, problems such as a decrease in sensitivity and contrast or poor drying are not preferred. On the other hand, if this value exceeds 90, it is contrary to the current situation where rapid processing is desired, which is not preferable.

In the processing method of the present invention, processing may be carried out by using a replenisher for both the developing solution and the fixing solution. The amount of replenishment is not particularly limited, but may be from 6 to 90 ml per quarter of the photosensitive material, preferably from 6 to 4 for both the developing solution and the fixing solution.
A refill volume of 0 ml is sufficient.

In the present invention, examples of a developer for a silver halide photographic light-sensitive material include dihydroxybenzenes (such as hydroquinone), 3-pyrazolidones (such as 1-phenyl-3-pyrazolidone), and aminophenols (such as N-methyl-amino). Phenol, etc.) or reductones or the like can be used alone or in combination. As a preservative, an organic reducing agent can be used as a preservative in addition to the sulfite described in JP-A-6-138592.
Bisulfite adducts of chelating agents and hardening agents described in 138,591 can be used. Also, Japanese Patent Application Laid-Open No. 5-289
It is also preferable to add silver sludge inhibitors described in JP-A Nos. 255 and 6-308680, cyclodextrin compounds described in JP-A-1-124852, and amine compounds described in U.S. Pat. No. 4,269,929.

It is necessary to use a buffer for the developer.
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium borate, o-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, and hydrazines. , A mesoionic compound, an ionic compound, imidazoles and the like can be added as necessary.

As antifoggants, alkali metal halides such as potassium iodide and benzotriazole;
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole,
Organic antifoggants such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be used.

Further, the developer composition includes methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, JP-B-47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent, and other stain preventing agents, sludge preventing agents and layering effect promoters can also be used.

Known compounds such as a fixing agent, a chelating agent, a pH buffer and a preservative can be used in the fixing solution. For example, those described in JP-A-4-242246 or 5-113632 can be used. it can.

As the fixing agent, thiosulfate, thiocyanate and the like are used, and may further contain a preservative, a pH adjuster, a water softener and the like.

An advantageous method for processing the silver halide photographic light-sensitive material of the present invention is to use an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.

As the processing agent supply means, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Application Publication No.
No. 97522, Japanese Utility Model Laid-Open No. 1-85732, etc., and in the case of granules or powder, Japanese Utility Model Application Laid-Open No. 62-81
964, 63-84151, JP-A 1-2923
No. 75, etc.
Nos. 59 and 63-195345, etc. can be referred to. The place where the solid processing agent is charged is in the processing tank, but it is preferably in communication with the processing section for processing the photosensitive material, where the processing liquid is flowing between the processing section and the processing section. A preferred structure is one in which there is a constant processing solution circulation amount and the dissolved components move to the processing section. Further, it is preferable that the solid processing agent is introduced into a processing liquid whose temperature is controlled.

In the processing method of the present invention, a preferable processing temperature is a developing temperature of 25 to 50 ° C. (more preferably 30 to 40 ° C.).
℃), fixing temperature 20-50 ℃ (further 30-40 ℃),
A washing temperature of 0 to 50 ° C (more preferably 15 to 40 ° C) and a drying temperature of 35 to 100 ° C (more preferably 40 to 80 ° C) are preferable.

Examples of the support used in the silver halide photographic light-sensitive material of the present invention include those described in the above-mentioned RD. A suitable support is a polyethylene terephthalate film or the like, and the surface of the support is coated. In order to improve the adhesiveness of the layer, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied.

[0131]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of Seed Emulsion EM-T) <Solution A ₁ > Ossein Gelatin 37.5 g KI 0.625 g NaCl 16.5 g Make up to 7500 ml with distilled water <Solution B ₁ > Silver nitrate 1500 g with distilled water and 2500ml in <solution C _1> KI and 684ml with 4g NaCl 140 g of distilled water <solution D _1> 40 ° C. to 1816ml with NaCl 375 g of distilled water, the solution a in the mixing stirrer described in JP-B-58-58288 _To 684 ml of solution B ₁ and solution C ₁
Was added over 1 minute. Adjust the EAg to 149MV, and the remaining total amount and the total amount of solution D ₁ of the solution A ₁ was added over 40 minutes after Ostwald ripening for 20 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after completion of the addition, desalting and washing were performed to obtain a tabular seed emulsion EM-T. The resulting seed emulsion was composed of tabular grains having at least 60% of the total projected area of the silver halide grains having the (100) plane as a main plane, an average thickness of 0.07 μm,
Electron microscope observation revealed that the average diameter was 0.5 μm and the coefficient of variation was 25%.

(Preparation of Emulsion EM-1) A tabular high silver chloride emulsion EM-1 was prepared using the following four kinds of solutions.

<Solution A ₂ > Ossein Gelatin 29.4 g HO (CH ₂ CH ₂ O) _n (CH [CH ₃ ] CH ₂ O) ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5 to 7) 10% methanol aqueous solution 1.25 ml seed emulsion EM-T equivalent to 0.98 mol Equivalent to 3000 ml with distilled water <Solution B ₂ > 3.50 N AgNO ₃ aqueous solution 2240 ml <Solution C ₂ > 455 g NaCl Make up to 2240 ml with distilled water <Solution> D ₂ > 1.75 N NaCl aqueous solution At the following silver potential control amount of 40 ° C., using a mixing stirrer described in JP-B-58-58288, the whole amount of solution B ₂ and solution C ₂ was simultaneously mixed with solution A ₂ by a simultaneous mixing method ( Addition growth was performed for 110 minutes by a double jet method so that the flow rate at the end of the addition was three times the flow rate at the start of the addition.

[0136] During this time of the silver potential by using the solution D ₂ +12
It controlled so that it might be set to 0 mV. After completion of the addition, precipitation and desalting were performed by the method described below to remove excess salts.

The mixed solution was heated to 40 ° C., 20 g / AgX (1 mol) of modified phenylcarbamoyl-modified (90% substitution) gelatin was added, and 56 wt% acetic acid was added to lower the pH to 4.30. Let stand and decant.

1.8 liters of pure water at 40 ° C./AgX1
After adding mol and stirring for 10 minutes, the mixture is left standing and decanted.

The above step 2 is repeated once.

Subsequently, 15 g / AgX1 mol of gelatin, sodium carbonate and water were added thereto to adjust the pH to 6.0, and the mixture was dispersed and finished to 450 ml / AgX1 mol.

When about 3,000 silver halide grains of the obtained emulsion EM-1 were observed and measured by an electron microscope to analyze the shape, 80% or more of the total projected area had the (100) plane as the main plane. Average diameter 1.17 μm, average thickness 0.
These were tabular grains having a size of 12 μm and had a coefficient of variation of 24%.

(Chemical sensitization of emulsion)
M-1 was brought to 55C. Next, as shown below, a predetermined amount of silver iodide fine grains and spectral sensitizing dyes (1) and (2) were added as a dispersion of solid fine grains. Thereafter, a sulfur sensitizer, a selenium sensitizer, and a gold sensitizer are further added, and ripening is performed for a total of 90 minutes. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7- is used as a stabilizer. Tetrazaindene (TAI) was added.

Silver iodide fine grain emulsion (*) Equivalent to 5 mmol Spectral sensitizing dye (1) 300 mg Spectral sensitizing dye (2) 30 mg Sulfur sensitizer 2.0 mg Gold sensitizer 1.0 mg Selenium sensitizer (triphenyl) (Phosphine selenide) 1.0 mg Stabilizer (TAI) 50 mg (*) 5.0% by weight containing 0.06 mol of potassium iodide
2 liters of an aqueous solution containing 7.06 moles of silver nitrate and 7.06 moles of potassium iodide were added to 6.64 liters of the gelatin aqueous solution over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

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The spectral sensitizing dye was prepared as a solid fine particle dispersion according to the method described in JP-A-5-297496. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used at 3,500 rpm.
m for 30-120 minutes.

The dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.
Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was 0.3 wt.
% While removing the ethyl acetate while stirring. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of Emulsions EM-2 to -4) After the steps of grain formation, washing and dispersion were carried out in the same manner as in Emulsion EM-1, before chemical sensitization was started, specifically after the temperature was raised to 55 ° C. Before adding the sensitizing dye, the compound represented by the general formula (1), specifically, (1-
Emulsions EM-2 and EM-3 were obtained by adding 1), (1-3), and (1-5) at 1 × 10 ⁻³ mol / mol Ag, respectively.
And EM-4. Addition of sensitizing dye and chemical sensitization are EM
Performed similarly to -1.

(Preparation of Subbed Support) (Dispersion of Conductive Particles P1) Stannous Chloride Hydrate 65 g
Was dissolved in 2000 cc of an aqueous solution to obtain a homogeneous solution. Then, this was boiled to obtain a coprecipitate. The formed precipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed to confirm that there is no reaction of chloride ions. The precipitate was added to 1000 cc of distilled water and dispersed.
c. Further, add 40cc of 30% ammonia water,
When heated in a water bath, a SnO ₂ sol solution is formed.

When used as a coating solution, the sol solution is concentrated to about 8% while blowing ammonia into the sol solution. Regarding the volume resistivity of the particles contained in this sol solution, a thin film was formed on silica glass using the sol solution, and the value measured by the four probe method was defined as the volume resistivity of the particles. The measured volume resistivity is 3.4 × 10 ⁴
Ωcm.

(Preparation of support for silver halide photographic light-sensitive material) (Support 1) After biaxial stretching and heat fixing, a thickness of 175 μm and a density of 0.15 were applied to both sides of a polyethylene terephthalate film colored blue at 8 W / min. subjected to corona discharge treatment in m ^2, an undercoat layer so that the following subbing coating liquid B-1 on a dry film thickness of 0.8μm as one surface in JP 59-19941 JP B-1 And dried at 100 ° C. for 1 minute. Also, the surface of the polyethylene terephthalate film opposite to the undercoat layer B-1 is disclosed in JP-A-59-77.
As described in JP-A-439-439, the following undercoating coating solution B-2 was applied as an undercoating layer B-2, and dried at 110 ° C for 1 minute.

Undercoating First Layer (Undercoating Coating Solution B-1) A copolymer latex containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate. Mixture (solid content 30%) 270 g Compound A 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 liter with water.

(Undercoat Coating Solution B-2) 23 g of a copolymer latex liquid (solid content 30%) of 40% by weight of butyl acrylate, 20% by weight of styrene and 40% by weight of glycidyl acrylate 415g of conductive P1 dispersion liquid Polyethylene glycol (molecular weight 600) 0.00012 g Water 568 g Subbing second layer 8 W min / m on the subbing layers B-1 and B-2
² was subjected to corona discharge, and the following coating solution B-3 was applied so as to have a dry film thickness of 0.1 μm, and dried at 100 ° C. for 1 minute.

(Undercoat Coating Solution B-3) Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle diameter of 3 μm 0.1 g Finished to 1 liter with water.

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(Preparation and Coating of Coating Solution) Next, a cross-over of the following first layer was applied to both sides of a polyethylene terephthalate film base (thickness: 175 μm) for X-ray, which was colored blue to a concentration of 0.15 and undercoated. Using a support on which a cut layer was previously coated, the following emulsion layer and protective layer were simultaneously coated on both surfaces from below so as to have the following predetermined coating amounts, and dried. 1-8 were obtained. The additives used for each coating solution are as follows. The amount of addition is shown per 1 m ^{2 on} one side of the photosensitive material.

First Layer (Crossover Cut Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (silver halide emulsion layer) Emulsion obtained above The following various additives were added.

Compound of general formula (1) shown in Table 1 1.0 × 10 ⁻⁵ mol / m ² Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino −1 5,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-mercaptobenzimidazole-5-sulfone sodium 5 mg / m ² compound (H) 0 _{^{5mg / m 2 n-C 4}} H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2 Compound (P) 0.2g / m ² Compound (Q) 0.2g / m ² Latex (L) 0.3 g / m ² However, the gelatin was adjusted to 0.8 g / m ² .

Third layer (protective layer) Gelatin 0.6 g / m ² Polymethyl methacrylate matting agent (area average particle size 7.0 μm) 50 mg / m ² 2,4-dichloro-6-hydroxy-1,3 2,5-Triazine sodium salt 10 mg / m ² bis-vinylsulfonyl methyl ether 36 mg / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50 mg / m ² Compound (S-2) 5 mg / M ² C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2 mg / m ² _{C 8 F 17 SO 2 N- (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 SO 3 Na 1mg / m 2 hardener (B) 60mg / m ² Latex (L) 0. 3 g / m ² phosphazene compound of the present invention Amount shown in Table 1

[0159]

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[0160]

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[0161]

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It should be noted that the amount of the above-mentioned material is one side,
The coating amount of the emulsion layer was adjusted so that the amount of silver per side was 1.3 g / m ² . The obtained samples were evaluated as described below, and the results are shown in Table 1.

<Evaluation of sensitometry (photographic performance)>
Each of the obtained samples was intensified with two intensifying screens (Konica Corporation)
Manufactured by SRO-250), a tube voltage of 60 kVp, a tube current of 100 mA, and an X for 0.05 second through an aluminum wedge.
The line was irradiated.

Next, a developing process described later was performed, and each obtained sample was evaluated.

The sensitivity is represented by the reciprocal of the exposure amount giving a density of fog + 1.0. The relative sensitivities are shown assuming that the sensitivity of 1 is 100.

<Evaluation of pressure fog (roller mark)>
In this evaluation, each sample was subjected to the following treatment after X-ray exposure so that the concentration was 1.2 ± 0.5. However, the developing rack of the automatic developing machine used and the transition rack from development to fixing were those which were intentionally fatigued. That is, due to the fatigue of the rollers of each rack, irregularities of about 10 μm were formed on the entire surface. A large number of fine spot-like density unevenness was generated in the sample having poor pressure resistance due to the pressure caused by the unevenness in the sample after the treatment. This level was visually evaluated according to the following criteria.

A: No spots were generated. B: Small spots were generated. C: Many spots were generated. <Evaluation of storage stability (sensitivity / fog)>
40% RH at 55 ° C. for 3 days, and 80% RH, 23
After storage at 3 ° C. for 3 days, the sensitivity and fogging were measured and evaluated in the same manner as in the evaluation of sensitometry.

The developing process was performed using a developing solution and a fixing solution having the following formulation using an automatic developing machine SRX501 (manufactured by Konica Corporation). The transport path L of the SRX 501 is 1.95 m.

Developer Formulation Part A (for 12 liter finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriaminepentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercaptotetrazole 0 0.2 g Hydroquinone 340 g Add water to make 5000 ml Part B (for finishing 12 L) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-2-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water Fixing solution formulation Part A (for finishing 18 liters) Ammonium thiosulfate 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 45 g 50 g sodium citrate 70 g gluconic acid 70 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g PartB (for finishing 18 liters) 800 g aluminum sulfate To prepare a developer, add PartA and PartB to about 5 liters of water Then, water was added to the mixture while stirring and dissolving to make 12 liters, and the pH was adjusted to 10.40 with glacial acetic acid. The above-mentioned starter is added to 1 liter of the developing replenisher at 20 ml / l, and the pH is adjusted to 10.26.

The fixer was prepared by adding Part A, P to about 5 l of water.
artB was added at the same time, and water was added while stirring and dissolving.
Finished to 81 and adjusted the pH to 4.4 with sulfuric acid and NaOH. This is used as a fixing replenisher.

The processing temperature was 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for washing, 50 ° C. for drying, and the processing time was Dry
45 seconds for to Dry.

[0172]

[Table 1]

Example 2 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (2), specifically (2-1), (2-3) and (2-7) was used. Sample No. 1 was prepared in the same manner as in Example 1 except that emulsions EM-5, EM-6 and EM-7 were respectively added with 1 × 10 ⁻³ mol / mol Ag. 9 to 14 were prepared and evaluated in the same manner as in Example 1. Table 2 shows the obtained results.
Shown in

[0174]

[Table 2]

Example 3 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (3), specifically (3-1), (3-2) and (3-4) was used. Sample No. 1 was prepared in the same manner as in Example 1 except that emulsions EM-8, EM-9, and EM-10 were added to each of which 1 × 10 ⁻³ mol / mol Ag was added. 15-20
Was prepared and evaluated in the same manner as in Example 1. Table 3 shows the obtained results.

[0176]

[Table 3]

Example 4 A compound having a molecular weight of 5 was substituted for the compound of the formula (1) in Example 1.
00 or more disulfide compounds, specifically (4-1)
Sample No. 1 was prepared in the same manner as in Example 1 except that emulsions EM-11 and EM-12 were respectively added with 1 × 10 ⁻³ mol / mol Ag of (4-4). 21 to 24 were prepared and evaluated in the same manner as in Example 1. Table 4 shows the obtained results.

[0178]

[Table 4]

Example 5 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (5), specifically, (5-1) and (5-1)
Sample No. 0) was added in the same manner as in Example 1 except that emulsions EM-13 and EM-14 were respectively added with 1 × 10 ⁻³ mol / mol Ag. 25 to 28 were prepared and evaluated in the same manner as in Example 1. Table 5 shows the obtained results.

[0180]

[Table 5]

Example 6 Instead of the compound of the general formula (1) in Example 1, the compound of the general formula (6), specifically, (6-1), (6-3) and (6-5) was used. Emulsions EM-15, EM-16 and EM-17 to which 1 × 10 ⁻³ mol / mol Ag was added, respectively.
Except that the sample No. was used in the same manner as in Example 1, 29-
34 were prepared and evaluated in the same manner as in Example 1. Table 6 shows the obtained results.

[0182]

[Table 6]

Example 7 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (7), specifically, (7-1), (7-2) and (7-5) was used. Emulsions EM-18, EM-19 and EM-20 to which 1 × 10 ⁻³ mol / mol Ag was added, respectively.
Except that the sample No. was used in the same manner as in Example 1, 35 ~
40 were prepared and evaluated in the same manner as in Example 1. Table 7 shows the obtained results.

[0184]

[Table 7]

Example 8 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (8), specifically, (8-2) and (8-3)
Was used in the same manner as in Example 1 except that emulsions EM-21 and EM-22 were respectively added with 1 × 10 ⁻³ mol / mol Ag. 41 to 44 were prepared and evaluated in the same manner as in Example 1. Table 8 shows the obtained results.

[0186]

[Table 8]

Example 9 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (9), specifically, (9-2), (9-3) and (9-10) were used. Emulsions EM-23, EM-24 and EM-2 to which 1 × 10 ⁻³ mol / mol Ag was added, respectively.
Sample No. 5 was prepared in the same manner as in Example 1 except that Sample No. 5 was used. 45
To 50 were prepared and evaluated in the same manner as in Example 1. Table 9 shows the obtained results.

[0188]

[Table 9]

As can be seen from Tables 1 to 9, the sample of the present invention is a silver halide photographic light-sensitive material having high sensitivity even with rapid processing, low fog, improved pressure resistance, and little deterioration in storage performance. I understand.

[0190]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has high sensitivity even in rapid processing, has little fog, has improved pressure resistance, and has little performance deterioration upon storage, and a processing method therefor. did it.

Claims (10)

[Claims] 1. A selenium compound and / or a tellurium compound,
And a phosphazene compound, and a compound represented by the following general formula (1). Embedded image [Wherein, R ₁₁ and R ₁₅ each independently represent an alkyl group having 1 to 5 carbon atoms, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, or a cyano group. R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a carboxy group, a sulfonic acid group, a phosphonic acid group, or a carbon number substituted with a carboxy group, a sulfonic acid group, a sulfate group, or a phosphate group. 1 to
4 represents an alkyl group or an alkenyl group. However,
R ₁₂ , R ₁₃ and R ₁₄ are not hydrogen atoms at the same time. ] 2. A selenium compound and / or a tellurium compound,
And a phosphazene compound, and a compound represented by the following general formula (2). Embedded image [Wherein, R ₂₁ , R ₂₃ , R ₂₅ and R ₂₆ each independently represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Alternatively, it represents a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, a substituted aryloxy group, or a sugar residue. However, R ₂₁ , R ₂₃ , R ₂₅ and R ₂₆ are not hydrogen atoms at the same time. R ₂₂ and R ₂₄ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, Represents a substituted aryloxy group or a sugar residue. ] 3. A selenium compound and / or a tellurium compound,
And a phosphazene compound, and a compound represented by the following general formula (3). Embedded image [Wherein, R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆ each independently represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Alternatively, it represents a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, a substituted aryloxy group, or a sugar residue. However, R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆ are not hydrogen atoms at the same time. R ₃₂ and R ₃₄ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, Represents a substituted aryloxy group or a sugar residue. ] 4. A selenium compound and / or a tellurium compound,
And a phosphazene compound and a disulfide compound having a molecular weight of 500 or more. 5. A selenium compound and / or a tellurium compound,
And a phosphazene compound, and a compound represented by the following general formula (5). Formula (5): R ₅₁ -SR ₅₂ [wherein, R ₅₁ and R ₅₂ each independently represent an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, Represents a substituted heterocyclic group. ] 6. A selenium compound and / or a tellurium compound,
And a phosphazene compound, and a compound represented by the following general formula (6). Embedded image Wherein R ₆₁ represents a hydrogen atom or a methyl group. R ₆₂ , R
₆₃ and R ₆₄ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxy group. However, R ₆₂ , R ₆₃ , R
_{When 64} is an alkyl group, a hydroxy group, a carboxy group,
It may be substituted with a sulfo group. ] 7. A selenium compound and / or a tellurium compound,
And a phosphazene compound, and a compound represented by the following general formula (7). Embedded image [Wherein, R ₇₁ and R ₇₂ each independently represent a hydrogen atom or a methyl group. M represents a hydrogen atom, an alkali metal atom or an ammonium salt, and n represents 0, 1 or 2. Where R
_When either or both of ₇₁ and R ₇₂ are methyl groups,
It may be substituted with OOM or -OH. ] 8. A selenium compound and / or a tellurium compound,
And a phosphazene compound, and a compound represented by the following general formula (8). General formula (8) (Me) n ₀ HAO ₃ [wherein Me represents a monovalent or divalent atom, and n ₀ represents Me
Is 2 when Me is monovalent, and 1 when Me is divalent. A represents an atom of Group 5B of the periodic table. However, nitrogen is excluded. ] 9. A selenium compound and / or a tellurium compound,
And a phosphazene compound and a compound represented by the following general formula (9). Formula (9) R ₉₁ NH—OH wherein R ₉₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group, or acyl group. ] 10. A processing method, comprising subjecting the silver halide photographic light-sensitive material according to claim 1 to image-wise exposure and then photographic processing under conditions satisfying the following formula. Le ^0.75 × t = 40-90 (0.7 ≦ Le ≦ 4.0) [wherein, Le is from the contact point of the first roller pair at the film insertion port of the automatic processor to the contact point of the last roller pair at the film drying port] Represents the length (unit: m) of the transfer path of t, where t is Le
Represents the time required to pass through (in seconds). ]