JPH0836234A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain high-contrast photographic characteristics with a stable developer and to maintain stable photographic characteristics with a low pH developer by incorporating a compd. expressed by a specified formula into one of photographic constitution layers. CONSTITUTION:One of photographic on constitution layer contains one compd. selected from a group of compds. expressed by formula. In formula, R is a group having one thioether and having a partial structure of-(L2-Z)1-, wherein Z is an ethylene group which may have substituents and L2 is-O-, -S-, and l is an integer >=2 when L2 is -O-, and an integer >=1 when L2 is -S-. However, when L2 is-O- and Z is an ethylene group, R is -O-to couple with L1.L2 is an alkylene group or alkenylene group, Y is a bivalent aromatic group, X is a group which may have substituents, n is an integer 0-4, A1 and A2 are both hydrogen atoms or one of them is a hydrogen atom and the other is an acyl group or the like, G is a carbonyl group, sulfonyl group, or the like, and R1 is a hydrogen atom or block group.

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 a direct positive type silver halide photographic light-sensitive material having super-high contrast photographic characteristics and good image quality used in a photomechanical process. is there.

[0002]

BACKGROUND OF THE INVENTION In the process of converting a continuous tone density change of an original in a photomechanical process into a set of halftone dots having an area proportional to this density, a silver halide photographic light-sensitive material having a hard photographic property is generally used. Material is used. In order to impart a high contrast property to an image, conventionally, Japanese Patent Laid-Open No. 56-106244 and U.S. Pat.
As described in No. 7, the silver halide photographic light-sensitive material contains a contrast-increasing agent such as hydrazine, and further, silver halide grains which effectively exert the contrast-increasing characteristics of the contrast-increasing agent are used. The photographic additives were appropriately combined and adjusted to obtain a desired photographic light-sensitive material. Such a silver halide photographic light-sensitive material is stable as a light-sensitive material and a high-contrast photographic image can be obtained even if it is processed with a developing solution capable of rapid processing.

By the way, a system using the hydrazine compound as described above generally has a high pH value, for example, a pH value.
The development was performed under the condition that the value was 11.5 or more. However, such a strongly alkaline developing solution is susceptible to air oxidation, which makes it difficult to store it for a long period of time because the developing characteristics change, and also causes problems such as corrosion of the developing device, safety of work, and waste liquid. It is not preferable from the viewpoint of environmental problems.

Therefore, as a solution to the above problems, a silver halide photographic light-sensitive material is proposed in which a photographic image with high contrast can be obtained with a developer having a low pH value of 11.2 or less ( European Patent No. 2536
No. 65, No. 333435, No. 345025, No. 35
6898, U.S. Pat. Nos. 4,988,604, 4
994365 and 5041355, JP-A-6
3-223744, 63-234244, 63
-234245, 63-234246, and JP-A-2-77057).

However, the activity of the contrast-increasing agents used in these agents for marked contrast fluctuates remarkably as the pH of the developing solution changes below 11.2. Γ and sensitivity are liable to fluctuate with respect to changes, and there are drawbacks that it is stable, that good halftone dot quality and preferable black pin (sand-like or pin-like fog generated in the unexposed area) level cannot be obtained. .

Therefore, a silver halide photographic light-sensitive material which can obtain a sufficiently high contrast even with a developing solution having a low pH value and has stable photographic characteristics even if the pH changes is expected. On the other hand, as one of the methods for forming a positive image using a direct positive type silver halide photographic light-sensitive material, an unfogged internal latent image type silver halide emulsion is used, and after the image exposure, the presence of a fogging agent There is known a method in which surface development is carried out in order to obtain a positive image. Various techniques have been proposed in this technical field. For example, US Pat. No. 25
92250, 2456957, and 2497875.
No. 2,588,982, No. 3,761,266, No. 34
No. 96577, British Patent No. 1151313, Japanese Patent Publication No. 43-29405, and Japanese Patent Laid-Open No. 47-94.
No. 34, No. 47-9677, No. 47-32813,
47-32814, 48-9717, 48-
No. 9727, No. 50-8524, No. 50-38525
There is a bulletin, etc.

Hydrazine compounds are known as useful fogging agents. For example, US Pat. No. 2,563,785,
Hydrazine compounds described in US Pat. No. 2,588,982, naphthylhydrazine sulfonic acids described in US Pat. No. 2,064,700, British Patent No. 1
Sulfomethylhydrazines described in the specification of 403018 are used as fog agents. Furthermore, JP-B-41-17184 describes that a color positive image can be obtained by using a hydrazide or hydrazone compound.

However, when these compounds are used, the induction period until the start of development is long as compared with the usual development of latent image silver, and the development is considerably delayed.
Further, in the conventional techniques, when applied to a multi-layer color photographic light-sensitive material, there is a problem that non-uniformity of characteristics is likely to occur between layers and the finally obtained maximum density is low.

Further, in order to maintain a preferable fogging effect and obtain a good result, the development was conventionally carried out under the condition of a high pH value of 12 or more, which remarkably accelerates the deterioration of the developing agent, There are problems such as deterioration of film physical properties of the photographic light-sensitive material.

[0010]

DISCLOSURE OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material capable of exhibiting high-contrast photographic characteristics in a stable developing solution. The second object of the present invention is to provide a silver halide photographic light-sensitive material capable of maintaining stable photographic characteristics in a low pH developer.

A third object of the present invention is to apply it to a direct positive type silver halide photographic light-sensitive material so that a sufficiently high maximum density (Dmax) can be obtained with a developer having a low pH, and a short time is required. Even in fogging development, the maximum density is large and the minimum density (Dmi
(EN) It is intended to provide a silver halide photographic light-sensitive material capable of obtaining a good image quality with a small n) and having a minimum increase in the minimum density even after storage over time.

The above object of the present invention is characterized in that at least one of the photographic constituent layers contains at least one selected from the group of compounds represented by the following general formula [I]. It is achieved by the silver halide photographic light-sensitive material.

[0013]

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[In the above general formula [I], R contains at least one thioether, and-(L ₂ -Z)
_l- (wherein Z represents an optionally substituted ethylene group, propylene group or trimethylene group, and L ₂ is -O-,-
S- or -N (Z ₁ )-(wherein Z ₁ represents a hydrogen atom or an aliphatic group), 1 is ₂ when L ₂ is -O-.
Represents an integer greater than or equal to the above, L ₂ is -S- or -N (Z ₁ )-
Represents an integer of 1 or more). However, when L ₂ is —O— and Z is an ethylene group, R is —O— and is bonded to L ₁ . L ₁ represents an alkylene group or an alkenylene group, and Y represents a divalent aromatic group. X represents a substitutable group, and n represents an integer of 0-4. When n is 2 or more, X may be the same or different. A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and R ₁ represents a hydrogen atom or a block group. The present invention will be described in more detail below.

In the above general formula [I], at least one R is
Thioether and-(L₂-Z)_lTogether with the partial structure of −
Represents a group having L₂Is -O-, -S- or -N (Z
₁)-(However, Z₁Is a hydrogen atom or methyl, ethyl,
Propyl, i-propyl, butyl, t-butyl, hex
Le, cyclohexyl, octyl, dodecyl, octadecyl
Alkyl groups such as vinyl, allyl, butenyl, etc.
Alkynyl such as lukenyl group and propargyl and butynyl
Represents an aliphatic group such as a group). Incidentally, Z₁Is hydrogen
Child, alkyl group having 1 to 8 carbon atoms, alke having 3 to 6 carbon atoms
A nyl group and an alkynyl group having 3 to 6 carbon atoms are preferable. Z is
Represents ethylene, propylene or trimethylene groups
However, these are suitable substituents (eg, alkyl groups,
Kenyl group, alkynyl group, aryl group, heterocyclic group,
Telocyclic onium group, amino group, ammonium group, acyl
Amino group, carbamoyl group, sulfonamide group, sulf
Amamoyl group, ureido group, alkoxy group, aryloxy group
Si group, heterocyclic oxy group, hydroxy group, urethane group,
Alkylthio group, arylthio group, heterocyclic thio group, sulfur
Rufonyl group, sulfinyl group, halogen atom, cyano
Group, sulfo group, carboxyl group, acyloxy group, acyl group
Group, alkyloxycarbonyl group, aryloxy group
Rubonyl group, nitro group, thioacyl group, thioacyl amine
Group, thioureido group, etc.). l is
L₂Represents an integer of 2 or more when -O-, L ₂Is -S-
Or -N (Z₁) -Represents an integer of 1 or more. However
Then L₂Is -O- and Z is an ethylene group, R is -O.
Via L₁Combine with.

In the general formula [I], R is the following general formula [I
The groups represented by I] and [III] are preferable. Formula (II) _{R 2 - (L 3) i} -A 3 - (L 4)
_j -S- general formula [III] _{R 3 -S- (L 5) k} -A 4 - [In these formulas, R ₂ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic radical, R ₃ represents an aliphatic group, an aromatic group or a heterocyclic group, A ₃ is-(OZ ₂ ) _l -,-
_{(Z 2 -O) l -,} - (S-Z) l -, - (Z-S) l
−, − (N (Z ₁ ) −Z) ₁ − or − (Z−N
(Z ₁ )) _l- (wherein Z ₂ represents a propylene group or a trimethylene group. Z, l and Z ₁ are Z, l in the above-mentioned (-L ₂ -Z) _1- as a partial structure of R. and for the Z wherein -N of (Z ₁₎ -. representing the Z ₁ and each synonymous group) represents, a ₄ is _{- (Z-L 2) l} - ( provided that
Z, L ₂ and l are the above-mentioned partial structures of R.
(L ₂ -Z) _1- represents the same group as each. ),
L ₃ , L ₄ and L ₅ each represent a divalent linking group, i, j,
k represents 0 or 1, respectively. A _{3 in the} general formula [II] is −
(Z ₂ —O) ₁ −, − (Z−S) ₁ − or − (Z−N
In the case of (Z ₁ )) ₁ −, j is 1. ] The aliphatic group of R ₂ is an alkyl group (for example, methyl,
Ethyl, propyl, i-propyl, butyl, t-butyl, hexyl, cyclohexyl, octyl, dodecyl,
Octadecyl etc.), an alkenyl group (eg vinyl, allyl, butenyl etc.), an alkynyl group (eg propargyl, butynyl etc.) and the like.

The aromatic group of R ₂ is a monocyclic ring (eg, phenyl group) or a condensed ring (eg, naphthyl group).
Etc. The heterocycle of R ₂ includes N, O,
5-membered ring containing at least one atom selected from the group of S and Se (for example, pyrrole, imidazole, pyrazole, thiophene, furan, isothiazole, isoxazole, triazole, tetrazole, pyrazoline,
Oxazole, thiazole, selenazole, imidazolidine, pyrazolidine, imidazoline, tetrahydrofuran, sulfolane, etc.), 6-membered ring (for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, piperidine, piperazine, morpholine, pyran, dithiin, etc.) heterocycle, And a condensed ring thereof with a suitable ring (for example, benzoxazole, benzothiazole, benzoselenazole, indole, indazole, benzimidazole, benzotriazole, quinoline, isoquinoline, quinoxaline, quinazoline, carbazole, acridine,
Benzothiophene, phenothiazine, phenoxazine,
Cyanthrene, indoline, etc.) are preferred.

As the aliphatic group, aromatic group and heterocyclic group for R ₃ , those mentioned above for R ₂ can be mentioned as preferred examples. The aliphatic group, aromatic group and heterocyclic group of R ₂ and R ₃ may be further substituted with a substituent as described above as a suitable substituent of Z. L ₃ ,
Examples of the divalent linking group represented by L ₄ and L ₅ include groups shown below, groups consisting of combinations of the groups shown below, and substituents suitable for them (as described above as suitable substituents for Z). A group having an appropriate substituent). For example, -C
_{H 2 -, - CH = CH} -, - C 6 H 4 -, pyridinediyl, -N (Z ₃₎ - (where, Z ₃ is a hydrogen atom, an alkyl group, an aryl group), - O -, - S- ,-(CO)-,-
_{(SO 2) -, - CH} = N- , and the like.

In the general formula [I], the alkylene group represented by L ₁ is an alkylene group having 1 to 10 carbon atoms,
And those having an appropriate substituent (for example, an alkyl group or an aryl group) thereto are preferable. In the general formula [I], the alkenylene group represented by L ₁ is preferably an alkenylene group having 2 to 10 carbon atoms and a substituent having an appropriate substituent (for example, an alkyl group or an aryl group).

As L ₁ , an alkylene group is preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable. Most preferably, it is a methylene group or an ethylene group. In the general formula [I], the divalent aromatic group represented by Y is a monocyclic ring (for example, benzene or the like) or a bicyclic ring (for example, naphthalene or the like).
The arylene group of is mentioned. Particularly, a phenylene group is preferable. In addition, these may be substituted with an appropriate substituent (substituent as described above as an appropriate substituent of Z).

In the formula [I], the substitutable group represented by X is a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20) or an alkenyl group (preferably carbon). Number of 2 to 20), alkynyl group (preferably having 2 to 20 carbon atoms), aryl group (eg, phenyl, etc.), alkoxy group (preferably having 1 to 20 carbon atoms in the alkyl portion). An alkenyloxy group (eg, allyloxy, butenyloxy, etc.),
Alkynyloxy groups (eg, propargyloxy, butynyloxy, etc.), aryloxy groups (eg, phenoxy, etc.), acyloxy groups (eg, acetyloxy,
Propionyloxy, benzoyloxy, etc.), acylamino group (eg, acetylamino, propionylamino, butanoylamino, octanoylamino, benzoylamino, etc.), sulfonamide group (eg, methanesulfonamide, ethanesulfonamide, propanesulfonamide), Butanesulfonamide, hexanesulfonamide, octanesulfonamide, dodecanesulfonamide, benzenesulfonamide, etc.), ureido group (eg, methylureido, ethylureido, propylureido, butylureido, hexylureido, cyclohexylureido, octylureido, dodecylureido). , Octadecylureido, phenylureido, naphthylureido, etc.), oxamoylamino group (eg, methyloxamoylamino, ethyl Kisamoiruamino, butyl oxamoylamino, octyl oxamoylamino, phenyl oxamoylamino, etc.), hydrazinocarbonyl amino group (e.g., methyl hydrazino carbonyl amino,
Ethylhydrazinocarbonylamino, dimethylhydrazinocarbonylamino, phenylhydrazinocarbonylamino, diphenylhydrazinocarbonylamino, phenylmethylhydrazinocarbonylamino, etc.), alkylamino groups (eg methylamino, ethylamino, butylamino, octylamino) , Dodecylamino, etc.), dialkylamino group (eg, dimethylamino, diethylamino, dibutylamino, methyloctylamino, etc.), amino group, hydroxy group, halogen atom, alkylthio group (preferably having an alkyl moiety having 1 to 20 carbon atoms). ), Alkenylthio group (eg, allylthio, butenylthio, etc.), mercapto group, sulfo group, carboxyl group, thioureido group (eg, methylthioureido, ethylthioureido, butyl) Aureido, cyclohexylthioureido, octylthioureido, dodecylthioureido, phenylthioureido, etc.), cyano group, sulfonyl group (eg, methanesulfonyl etc.), sulfamoyl group (eg, methylsulfamoyl, ethylsulfamoyl, butylsulfur) Famoyl, phenylsulfamoyl, etc.), a carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl, butylcarbamoyl, octylcarbamoyl, phenylcarbamoyl, etc.) and the like. In addition, these groups may be further substituted with an appropriate substituent. For example, it may be substituted with a substituent as described above as a suitable substituent of Z.

In the general formula [I], A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (eg acetyl, trifluoroacetyl, benzoyl etc.) or a sulfonyl group (eg Methanesulfonyl, toluenesulfonyl, etc.) or oxalyl group (eg,
Etoxaryl etc.) It is preferable that both A ₁ and A ₂ are hydrogen atoms.

In the general formula [I], G is carbonyl
Group, sulfonyl group, sulfoxy group, phosphoryl group or
Represents an imino methylene group. Among them, it is a carbonyl group
Is preferred. In the general formula [I], R₁Is hydrogen
An aliphatic group as a child or blocking group (eg, methyl
Ru, ethyl, benzyl, methoxymethyl, trifluoro
Methyl, phenoxymethyl, 4-methoxybenzenesul
Fonylmethyl, 1-pyridiniomethyl, hydroxymethy
, Methylthiomethyl, phenylthiomethyl, etc.), fragrance
Group groups (eg, phenyl, hydroxymethylphenyl,
Chlorophenyl etc.), heterocyclic group (eg pyridyl,
Thienyl, furyl, N-methylpyridinio, etc.), amino
Groups (eg, methylamino, phenylamino, etc.), ar
Coroxy groups (eg methoxy, ethoxy, butoxy
Etc.), an aryloxy group (eg, phenoxy etc.),
COOR_FourGroup and -CON (R_Five) (R₆) Groups
It Incidentally, R_FourIs a hydrogen atom, an alkyl group (for example, methyl
, Ethyl, benzyl, hydroxyethyl, etc.), alk
Nyl group (eg, allyl, butenyl, etc.), alkynyl group
(Eg, propargyl, butynyl, etc.), aryl group
(Eg, phenyl, naphthyl, etc.), heterocyclic group (eg,
For example, 2,2,6,6-tetramethylpiperidinyl, N-
Ethylpiperidinyl, tetrahydrofuryl, sulfolane
Saturated heterocycles such as, pyridyl, pyrimidinyl, thie
Unsaturated heterocycles such as nyl and furyl) and the like.
Also, R_FiveAnd R₆Are a hydrogen atom and an alkyl group (for example,
For example, methyl, ethyl, benzyl, hydroxyethyl
Etc.), alkenyl groups (eg, allyl, butenyl, etc.),
An alkynyl group (eg, propargyl, butynyl, etc.),
Aryl group (eg, phenyl, naphthyl, etc.), hetero
A cyclic group (eg, 2,2,6,6-tetramethylpiperidi
Nil, N, N'-diethylpyrazolidinyl, quinuclidi
Nyl, N-ethylpiperidinyl, N-benzylpiperidi
Nyl, N-benzylpyrrolidinyl, tetrahydrofuri
Saturated ring such as sulfolane, pyridyl, pyri
Unsaturated heterocycles such as midinyl, thienyl and furyl
Etc.), hydroxyl groups, alkoxy groups (eg
Ci, ethoxy, benzyloxy, cyanomethoxy, etc.),
Alkenyloxy groups (eg allyloxy, butenyl
Oxy, etc.), alkynyloxy groups (eg, propargy
Luoxy, butynyloxy, etc.), aryloxy groups (eg
For example, phenoxy, naphthyloxy, etc.), heterocyclic oki
Si group (eg, pyridyloxy, pyrimidyloxy
Etc.), amino groups (eg, amino, methylamino, dime
Tilamino, dibenzylamino, anilino, etc.) etc.
It Incidentally, R₁Is a hydrogen atom, an aliphatic group, an aromatic group,
-COOR_FourGroup and -CON (R_Five) (R₆) Group is preferred
, Especially -COOR_FourGroup and -CON (R_Five) (R₆) Group
Is preferred. Most preferably R in the general formula [I]₁
As for -COOR_Four'Group and -CON (R _Five’) (R
₆’) Group (R_Four′ Is an alkynyl group or saturated heterocycle
Group, R_Five'Is a hydrogen atom, an alkyl group, an alkenyl group,
Rukinyl group, aryl group or heterocyclic group, R₆’Is a
Lucenyl group, alkynyl group, saturated heterocyclic group, hydroxy
Si group or alkoxy group).

Specific examples of the compound represented by the general formula [I] are shown below. The present invention is not limited to these.

[0025]

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[0026]

[Chemical 4]

[0027]

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[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

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[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

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[0037]

[Chemical 15]

[0038]

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[0039]

[Chemical 17]

[0040]

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[0041]

[Chemical 19]

[0042]

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[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24]

[0047]

[Chemical 25]

[0048]

[Chemical formula 26]

[0049]

[Chemical 27]

[0050]

[Chemical 28]

[0051]

[Chemical 29]

[0052]

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[0053]

[Chemical 31]

[0054]

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[0055]

[Chemical 33]

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

[Chemical 38]

[0061]

[Chemical Formula 39]

[0062]

[Chemical 40]

[0063]

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[0064]

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[0065]

[Chemical 43]

[0066]

[Chemical 44]

[0067]

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[0068]

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[0069]

[Chemical 47]

[0070]

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[0071]

[Chemical 49]

[0072]

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[0073]

[Chemical 51]

[0074]

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Next, a method for synthesizing the compound represented by the general formula [I] will be described. For example, compound I-1 is synthesized as follows.

[0076]

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Further, the compound I-3 is synthesized as follows by using the synthetic intermediate b of the compound I-1.

[0078]

[Chemical 54]

Next, a preferred embodiment in the case where the silver halide photographic light-sensitive material of the present invention is suitable as a light-sensitive material exhibiting high contrast photographic characteristics will be described. In the silver halide photographic light-sensitive material to which the present invention can be applied to obtain a high-contrast image, at least one of the compounds represented by the above general formula [I] is contained as a substance functioning as a contrast-increasing agent. However, the amount of the compound of the general formula [I] contained in the photographic light-sensitive material is 5 × 10 ^{−7 to} 5 × 10 ⁻¹ mol per mol of silver halide contained in the photographic light-sensitive material. preferable. In particular, it is preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide.

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support. The silver halide emulsion can be coated directly on a support or can be coated through another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the emulsion layer. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer made of a hydrophilic colloid may be provided between the silver halide emulsion layers. An intermediate layer may be provided between the silver halide emulsion layer and the protective layer. That is, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, and a backing layer may be provided if necessary.

In order to incorporate the compound represented by the general formula [I] into the silver halide photographic light-sensitive material of the present invention so as to function as a contrast-increasing agent, it is preferable to incorporate it in the hydrophilic colloid layer in the light-sensitive material. Particularly preferably, it is contained in the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer. Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described. The silver halide having any composition can be used. Examples are silver chloride, silver chlorobromide, silver chloroiodide, pure silver bromide, silver iodobromide or silver chloroiodobromide. The average grain size of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, and more preferably 0.10 to 0.40 μm.

The grain size distribution of the silver halide grains used in the present invention is arbitrary, but the monodispersity value defined below is from 1 to 3
It is preferably 0, more preferably 5 to 20. Monodispersity = [(Σr−r _i ) ² n _i / Σn _i ] ^1/2 ÷ r
× 100 That is, this monodispersity is defined as a value obtained by multiplying the standard deviation of the particle size by the average particle size by 100 times. For the sake of convenience, the grain size of silver halide grains is represented by the edge length of cubic grains, and the other grains (octahedral, tetradecahedral, etc.) are calculated by the square root of the projected area.

When the present invention is carried out, for example, as the grains of silver halide, those of the type having a multilayer laminated structure of at least two layers can be used, and for example, the core portion is silver chloride or silver iodobromide. It is possible to use silver chlorobromide grains or silver chloroiodobromide grains in which the shell portion is silver bromide, the core portion is silver bromide, and the shell portion is silver chloride. At this time, iodine can be contained in any layer, but iodine is preferably within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention have a complex salt containing a cadmium salt, a zinc salt, a lead salt, a thallium salt and an iridium salt in the process of forming and / or growing the grains. ), A rhodium salt (containing complex salt), and an iron salt (containing complex salt), at least one metal ion can be added to allow these metal elements to be contained inside the particle and / or on the surface of the particle. Further, the reduction sensitizing nuclei can be imparted to the inside of the grain and / or the surface of the grain by placing in a suitable reducing atmosphere.

Furthermore, the silver halide can be sensitized with various chemical sensitizers. Examples of such sensitizers include active gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiacinate, etc.), selenium sensitizers (N, N-dimethylselenourea, selenoureas). Etc.), reduction sensitizers (triethylenetetramine, stannous chloride, etc.), such as potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloro. Various metal sensitizers represented by platinate, sodium chloroparadite and the like can be used alone or in combination of two or more. In addition, when a gold sensitizer is used, rodan ammon can be used as an auxiliary agent.

When the present invention is applied to a light-sensitive material capable of obtaining a high-contrast image, the light-sensitive material whose silver halide grains are particles having a surface sensitivity higher than the internal sensitivity, that is, silver halide grains giving a negative image. Since it can be preferably applied to, the performance can be enhanced by treating with the above chemical sensitizer. The silver halide emulsion used is a mercapto compound (1-phenyl-5).
-Stabilize or suppress fogging by using mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromobenzotriazole, 5-methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole), etc. (Note that a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener, a development accelerator and the like can be added to the silver halide emulsion used in the present invention).

When the compound of the general formula [I] according to the present invention is added to the hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but a hydrophilic colloid other than gelatin may be used. I can. In the practice of the present invention, as a support that can be used in a light-sensitive material for obtaining a high-contrast image, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate A film can be mentioned. These supports are appropriately selected according to the purpose of use of the silver halide photographic light-sensitive material.

To develop a silver halide photographic light-sensitive material capable of obtaining a high-contrast image, the following developing agents are used, for example. Typical examples of the HO- (CH = CH) _n- OH type developing agent include hydroquinone, and catechol and pyrogallol. Also, HO
Typical examples of the-(CH = CH) _n -NH ₂ type developer include ortho and para aminophenols and aminopyrazolones, and N-methyl-p-aminophenol,
N-β-hydroxyethyl-p-aminophenol, p
-Hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

Heterocyclic type developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-.
Hydroxymethyl-3-pyrazolidone, 1-phenyl-
Examples thereof include 3-pyrazolidones such as 4-methyl-4-hydroxymethyl-3-pyrazolidone.

Others, T. H. By James "The
Theory of the Photographi
c Process, Fourth Edition "
Pages 291-334 and “Journal of
the American Chemical Soci
ety ", vol. 73, page 3100 (1951), can be effectively used in the present invention. These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination (in the case of a single agent, hydroquinone,
When combined, hydroquinone and 1-phenyl-
3-pyrazolidone, hydroquinone and N-methyl-p-
A combination of aminophenols is preferred).

The effect of the present invention is not impaired even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for development. Further, hydroxylamine or a hydrazine compound may be used as a preservative. In addition, pH adjustment and buffer function with caustic alkali, alkali carbonate or amine used in black and white developers, and inorganic development inhibitors such as bromcali and organic development inhibitors such as benzotriazole, ethylenediaminetetraacetic acid, etc. Metal ion scavenger,
Development accelerators such as methanol, ethanol and benzyl alcohol, naphthol alkylaryl sulfonates, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, hardeners such as glutaraldehyde, formalin and glyoxal, sodium sulfate It is optional to add an ionic strength modifier such as

In the present invention, a light-sensitive silver halide emulsion layer, its adjacent layer or a developing solution used in the developer is used for the purpose of increasing sensitivity, increasing contrast or promoting development, an amine compound, a hydrazine compound, an onium salt compound or A polyalkylene oxide compound may be contained, and the performance of the present invention can be enhanced by using these compounds or by using these compounds in combination. Specific examples of these compounds include, for example, the nucleation promoting compound described in Japanese Patent Application No. 2-160539, and the general formula [P] = R ₁ -O- (CH ₂ CH ₂ O) in the specification. Specific examples of the compound represented by _n H include those listed above.

Next, a preferred mode of using the light-sensitive material of the present invention as a direct positive type silver halide photographic light-sensitive material will be described. In this case, the compound represented by the general formula [I] can function as a fogging agent.
Hereinafter, when the compound represented by the general formula [I] is used as a fogging agent, this is referred to as the "fogging agent of the present invention".

The fogging agent of the present invention contains at least one of them so as to fog an internal latent image type silver halide emulsion which is an emulsion which directly gives a positive type image upon development after imagewise exposure. Just go. That is, the photographic light-sensitive material having an internal latent image type silver halide emulsion may be contained in the light-sensitive material in such a form that it can be subjected to development processing in the presence of the fogging agent of the present invention after exposure. In a preferred embodiment, at least one fog agent of the present invention is incorporated in a silver halide emulsion layer or a layer adjacent thereto (for example, a silver halide photosensitive layer, an intermediate layer, a filter layer, a protective layer, an antihalation layer, etc.). It is included.

The amount of the fogging agent used in the present invention can be varied over a wide range depending on the characteristics of the silver halide emulsion used, the type of the fogging agent and the developing conditions, but a photographic material having an internal latent image type silver halide emulsion is used. After the image exposure, the amount may be such as to give a fogging effect so as to obtain a positive image by developing with a surface developing solution. It is preferable that the amount provides a sufficient maximum density after development, for example, 2.0 or more.

To add the fog-inhibiting agent of the present invention to a silver halide emulsion, the fog-inhibiting agent is added in an amount of about 10 ^{-5 to} 5 × 10 ^-1 mol per mol of the silver halide at an appropriate time after the completion of ripening. It is preferable to include it. In the practice of the present invention, silver halide developers that can be used in the development processing include hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines. , Or a mixture thereof. These developing agents may be incorporated in the emulsion in advance so that they act on the silver halide during immersion in a high pH aqueous solution.

In the practice of the present invention, the developing composition used for the development processing of the direct positive type silver halide photographic light-sensitive material may further contain a specific antifoggant and development inhibitor. Alternatively, their composition may be optionally incorporated in the layer of the silver halide photographic light-sensitive material. Commonly useful inhibitors include, for example, benzotriazoles, benzothiazoles such as 5-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole, benzotriazoles such as 5-methylbenzotriazole, 1-methyl. The polycyclic thiones such as -2-tetrazoline-5-thione and the like, aromatic and aliphatic mercapto compounds and the like are included.

When the present invention is applied to a direct positive type silver halide photographic light-sensitive material, the silver halide emulsion is an internal latent image type silver halide emulsion, that is, a latent image is mainly formed inside the silver halide grains. , An emulsion having silver halide grains having most of the photosensitive nuclei inside the grains. The silver halide for forming this emulsion contains any silver halide such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide.

Particularly preferably, the emulsion used in this case comprises about 1 part of a sample obtained by coating the emulsion on a transparent support.
Development at 20 ° C. for 4 minutes using the following surface developing solution A, which is exposed to a light intensity scale for a predetermined time of up to 2 seconds and develops only a surface image of grains which does not substantially contain a silver halide solvent. When developed, another part of the same emulsion sample is similarly exposed and the image of the grain is developed. It is not more than ⅕ of the maximum density obtained when developed at 20 ° C. for 4 minutes with the following internal developer B. It shows the maximum concentration. Preferably, the maximum densities obtained with surface developer A are no greater than 1/10 of the maximum densities obtained with internal developers.

[Surface developer A] Metol 1.5 g L-ascorbic acid 10 g NaBO ₂ .4H ₂ O 20 g KBr 1 g Water was added 1 l [Internal developer B] Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate hydrate 52.5 g KBr 5.0 g KI 0.5 g Water was added 1 l Further, the internal latent image type silver halide emulsion includes those prepared by various methods. For example, US Pat. No. 2,592.
A conversion type silver halide emulsion described in US Pat. No. 250,250, or US Pat.
No. 3,137,322, No. 3,367,778, Japanese Patent Publication No. 4
No. 3-29405, and silver halide emulsions having internally chemically sensitized silver halide grains, or the multivalent compounds described in U.S. Pat. Nos. 3,271,157, 3,447,927 and 3,531,291. A silver halide emulsion having silver halide grains having metal ions incorporated therein, or a silver halide emulsion comprising grains having a laminated structure described in JP-A-50-8524.
Alternatively, it is a silver halide emulsion containing silver iodide prepared by the ammonia method described in Japanese Patent Application No. 51-74062.

Further, the internal latent image type silver halide emulsion used contains 1 mg to 10 g of a compound having an azaindene ring, a nitrogen-containing heterocyclic compound having a mercapto group, etc. per 1 mol of silver halide. ,
More stable results can be given with lower minimum concentrations. 4- as a compound having an azaindene ring
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is preferred. As the nitrogen-containing heterocyclic compound having a mercapto group, a pyrazole ring, 1,2,4-triazole ring, 1,2,3-triazole ring, 1,3,4-
Thiadiazole ring, 1,2,3-thiadiazole ring,
1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,2,3,4-tetrazole ring, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring, these rings are 2 to
Three condensed rings, for example, triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring, etc., phthalazinone ring,
Although it has an indazole ring and the like, 1-phenyl-5-mercaptotetrazole is preferable.

The silver halide photographic light-sensitive material of the present invention may be a black-and-white photographic light-sensitive material, a single color photographic material or a multi-color photographic light-sensitive material, particularly when it is applied to a positive type light-sensitive material. In the case of a full-color light-sensitive material, it is preferable to have a blue light-sensitive layer, a green light-sensitive layer and a red light-sensitive layer. In this case, a photographic light-sensitive material is usually prepared from a blue light-sensitive silver halide emulsion layer containing a yellow coupler, a green light-sensitive silver halide emulsion layer containing a magenta coupler, and a red light-sensitive silver halide emulsion layer containing a cyan coupler. It is formed.

In one preferred embodiment, a blue photosensitive layer, a green photosensitive layer and a red photosensitive layer are layered in this order from the side farther from the support, and a non-photosensitive layer is provided between the blue photosensitive layer and the green photosensitive layer. (Yellow filter layer) is provided. As the yellow coupler, a known acylacetanilide type coupler can be preferably used, and among these, benzoylacetanilide type compounds and pivaloylacetanilide type compounds are preferable.

As the magenta coupler, a 5-pyrazolone type coupler, a pyrazoloazole type coupler and an open chain acylacetanilide type coupler can be used. As the cyan coupler, a naphthol type coupler and a phenol type coupler can also be preferably used. In addition to the above-mentioned support, a light-sensitive silver halide emulsion layer or a non-light-sensitive layer to be a yellow filter layer can be provided on the support, and an intermediate layer, a protective layer, an undercoat layer, a backcoat layer, an antihalation layer. It is possible to provide a large number of various photographic constituent layers such as. As a coating method for these, a dip coating method, an air doctor coating method, an extrusion coating method, a slide hopper coating method, a curtain flow coating method and the like can be applied.

In the case of a direct positive silver halide photographic light-sensitive material, the support may be, for example, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, a polypropylene film, a cellulose acetate film, a glass or a baryter which is optionally undercoated. Examples include paper and polyethylene laminated paper.

The support may be opaque or transparent and can be selected depending on the intended light-sensitive material.
Various photographic additives such as a wetting agent, a film physical property improving agent and a coating aid can be added to the silver halide emulsion of the light-sensitive material according to the purpose. In addition, as other photographic additives, gelatin plasticizers, surfactants, UV absorbers, pH
It is also possible to use a preparation agent, an antioxidant, an antistatic agent, a thickening agent, a graininess improving agent, a dye, a moldant, a whitening agent, a developing speed adjusting agent, a matting agent and the like.

Further, in order to prevent fading of the dye image due to the actinic rays having a short wavelength, an ultraviolet absorber such as thiazolidone,
It is useful to use a benzotriazole, acrylonitrile, or benzophenone compound. In the silver halide emulsion layer, as a protective colloid or a binder (binder), gelatin or other suitable gelatin derivative can be used depending on the purpose, and other hydrophilic binder (binder) can be used according to the purpose. ) Can be included. As the photographic light-sensitive material, it can be added to a photographic constituent layer such as an emulsion layer or an intermediate layer, a protective layer, a filter layer and a backing layer according to the purpose. Further, the hydrophilic binder is appropriately plasticized according to the purpose. Agents, wetting agents and the like can be included.

Each constituent layer can be hardened with any appropriate hardener. Further, the photosensitive material contains A
An S agent (antistain agent) can be used. Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

[0109]

【Example】

[Example 1] [Preparation of silver halide emulsion A] A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by the simultaneous mixing method. At the time of this mixing, K ₂ IrCl ₆ was added at 8 × per mol of silver.
10 ⁻⁷ mol was added. The obtained emulsion has an average grain size of 0.2.
The emulsion consisted of 0 μm cubic monodisperse grains (coefficient of variation 9.5%). 6.5 ml per mole of silver in this emulsion
1% potassium iodide aqueous solution was added, and then modified gelatin (Exemplified Compound G- of Japanese Patent Application No. 1-180787)
8) was added, and the mixture was washed with water and desalted in the same manner as in Example 1 of Japanese Patent Application No. 1-180787. The pAg at 40 ° C. after desalting was 8.0. Further, a mixture of the following compounds [A], [B] and [C] was added as an antibacterial agent at the time of redispersion.

[0110]

[Chemical 55]

[Preparation of silver halide photographic light-sensitive material] A polyethylene terephthalate film having a thickness of 100 μm having an undercoat layer having a thickness of 0.1 μm (see Example 1 of JP-A-59-19941) on both sides On one of the undercoat layers, a silver halide emulsion layer having the following formulation (1) was used with a gelatin content of 2.
It is coated so that the amount of silver is 0 g / m ² and the amount of silver is 3.2 g / m ^2, and an emulsion protective layer having the following formulation (2) is further coated thereon so that the amount of gelatin is 1.0 g / m ^2. On the other undercoat layer on the opposite side, a backing layer of the following formulation (3) was applied so that the amount of gelatin would be 2.4 g / m ² , and the following formulation ( The backing protective layer of 4) was applied so that the amount of gelatin would be 1.0 g / m ² , and samples 1 to 20 were obtained.

[Formulation (1) Silver Halide Emulsion Layer Composition]

[0113]

[Chemical 56]

[0114]

[Chemical 57]

[Formulation (2) Composition of emulsion protective layer]

[0116]

Embedded image

[Formulation (3) Backing Layer Composition]

[0118]

Embedded image

[Formulation (4) Backing Protective Layer Composition] Gelatin 1 g / m ² matting agent (polymethyl methacrylate having an average particle size of 3.0 to 5.0 μm) 15 g / m ² Surfactant (S-2) 10 g / m ² Hardener (glyoxal) 25 mg / m ² Hardener (H-1) 35 mg / m ^{2 The} obtained sample was subjected to a halftone dot quality test by the following method.

[Dot quality test method] A stepped wedge was partially provided with a reticulated screen (150 lines / inch) having a dot area of 50%, a sample was brought into close contact with the step wedge, and exposed for 5 seconds with a xenon light source. This sample was developed under the following conditions with an automatic processor for rapid processing in which the following developing solution and the following fixing solution were added, and the halftone quality of the sample was observed with a 100 times magnifying glass. Was designated as "5", and the following "4", "3", "2", and "1" were evaluated in 5 grades. The ranks "1" and "2" are levels that are not practically preferable.

[Developer Solution Formulation] Hydroquinone 45.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 18.0 g Potassium hydroxide 55.0 g 2-Sulfosalicylic acid 45.0 g Boric acid 25 0.0 g Potassium sulfite 111.0 g Ethylenediaminetetraacetic acid sodium salt 1.0 g Potassium bromide 6.0 g 5-Methylbenzotriazole 0.6 g n-Butylethanolamine 15.0 g Water was added to adjust pH with sulfuric acid pH 11.2 (Developer 1) pH 11.0 (Developer 2) pH 10.8 (Developer 3) pH 10.5 (Developer 4) [Fixer formulation] [Composition A] Ammonium thiosulfate (72.5 w / v% aqueous solution) 240 ml Sodium sulfite 17.0 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Que Acid sodium dihydrate 2.0g [Composition B] Pure water (ion-exchanged water) 17 ml sulfuric acid (50 w / v% aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ in terms of content 8.1w / v% aqueous solution) 26 0.5 g When using the fixing solution, the above composition A and composition B were added to 500 ml of water.
Were melted in this order and finished to 1 l for use. P of this fixer
H was adjusted to 4.8 with acetic acid.

[Development Processing Conditions] (Process) (Temperature) (Time) Development 40 ° C. 15 seconds Fixing 35 ° C. 15 seconds Water washing 30 ° C. 10 seconds Drying 50 ° C. 10 seconds Incidentally, in the silver halide emulsion layer in the formulation (1). The following compounds (a), (b) and (c) were used as the comparative compounds of the added hydrazine derivative of the present invention.

[0123]

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Table 1 (however, using Developer 3) No. Hydrazine halftone dot quality Black pin 1 a 3.5 3.5 Comparative example 2 b 3.5 3.5 Comparative example 3 c 3.5 3 Comparative example 4 I-1 5 5 Invention 5 I-3 5 5 Invention 6 I-5 4 5 Invention 7 I-7 5 4.5 Invention 8 I-9 5 4.5 Invention 9 I-10 4.5 5 Invention 10 I-13 4.5 5 Invention 11 I -17 4.5 4.5 Invention 12 I-18 45 Invention 13 I-23 5 4.5 Invention 14 I-26 4.5 4.5 Invention 15 I-28 4.5 4.5 Invention 16 I-34 45 Invention 17 I-36 4.5 3.5 Invention 18 I-39 4 4 Invention 19 I-41 4.5 3.5 Invention 20 I-42 4.5 3 .5 present invention Table 2-1 No. Hydrazine Halftone Quality Developer 1 Developer 2 Developer 3 Developer 4 1 a 2 4 3.5 3 Comparative Example 2 b 3 4 3.5 2.5 2.5 Comparative Example 3 c 2.5 3 3.5 3.5 2.5 Comparative Example 4 I-1 4.5 5 5 4.5 Invention 5 I-3 4.5 5 5 4.5 Invention 7 I-7 4 5 5 4.5 Invention 8 I-9 4 4.5 5 4.5 Invention 9 I-10 4 5 4.5 4 Invention 10 I-13 4.5 5 4.5 4 Invention 11 I-17 4 5 4.5 3.5 3.5 Invention 13 I-23 4 4.5 5 4.5 Invention 15 I-28 4 5 4.5 4 Invention 17 I-36 3.5 4.5 4.5 3.5 3.5 Invention 18 I-39 4 4.5 4 3 .5 present invention Table 2-2 No. Hydrazine black pin Developer 1 Developer 2 Developer 3 Developer 4 1 a 2 2.5 3.5 3.5 3.5 Comparative example 2 b 2 2.5 3.5 4 Comparative example 3 c 2 2.5 3 3. 5 Comparative Example 4 I-1 4 4.5 5 5 Invention 5 I-3 4.5 4.5 5 5 Invention 7 I-7 3.5 4 4.5 4.5 Invention 8 I-9 4 4 4.5 5 Invention 9 I-10 4 4.5 5 5 Invention 10 I-13 4.5 4.5 5 5 Invention 11 I-17 4 4.5 4.5 5 5 Invention 13 I- 23 4 4 4.5 5 Invention 15 I-28 4 4.5 4.5 5 Invention 17 I-36 3 3.5 3.5 3.5 Invention 18 I-39 3.5 4 4 4.5 Invention From Table 1, it can be seen that the one according to the present invention has a better comprehensive evaluation of halftone dot quality and black pin as compared with the comparative example. Further, it can be seen from Table 2 that stable halftone dot quality and a more preferable black pin level can be obtained with respect to pH fluctuation of the developer in a relatively low pH range of pH 10.5 to 11.2.

[Example 2] [Preparation of emulsion A] A monodisperse silver bromide emulsion was prepared in the following manner. That is, an aqueous solution containing ossein gelatin is
An aqueous solution of silver nitrate and an aqueous solution of potassium bromide were simultaneously added to the solution at 0 ° C. under vigorous stirring by the control double jet method to obtain a regular octahedron emulsion having an average particle size of 0.4 μm. To this emulsion, 5 mg of sodium thiosulfate and 6 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 75 ° C. for 80 minutes for chemical ripening to obtain a silver bromide core emulsion. An octahedral monodisperse core / shell salt having an average particle size of 0.7 μm was grown by adding an aqueous solution of silver nitrate, an aqueous solution containing potassium bromide and sodium chloride (molar ratio of 50:50) to the core emulsion thus obtained. A silver bromide emulsion was obtained. After desalting with water, 1.3 mg of each sodium thiosulfate and chloroauric acid (tetrahydrate) were added to this emulsion, and each emulsion was heated at 60 ° C. for 70 minutes to carry out chemical sensitization treatment. An image type silver halide emulsion was obtained.

[Preparation of Sample] Sample 21 was prepared by preparing a color photographic light-sensitive material having the following layer structure on a paper support laminated on both sides with polyethylene. [Seventh layer (protective layer)] Gelatin 12.3 mg / dm ² [Sixth layer (infrared absorbing layer)] Gelatin 5.4 mg / dm ² Infrared absorbing agent (UV-1) 1.0 mg / dm ² Infrared absorbing agent (UV-2) 2.8 mg / dm ² solvent (SO-3) 1.2 mg / dm ² [fifth layer (blue photosensitive layer)] Emulsion A (including sensitizing dye BD-1) 5.0 mg / dm ² Gelatin 13.5 mg / dm ² Yellow coupler (YC-1) 8.4 mg / dm ² Image stabilizer (AO-3) 3.0 mg / dm ² Solvent (SO-1) 5.2 mg / dm ² Compound (d ) 5 × 10 ⁻³ mol / mol Ag [Fourth layer (yellow filter layer)] Gelatin 4.2 mg / dm ² Yellow colloidal silver 1.0 mg / dm ² Infrared absorber (UV-1) 0.5 mg / dm ² Infrared absorber (UV-2) 1.4mg / dm ² Color mixture prevention Stopper (AS-1) 0.4 mg / dm ² Solvent (SO-3) 0.8 mg / dm ² [Third layer (green photosensitive layer)] Emulsion A (including sensitizing dye GD-1) 2.7 mg / Dm ² gelatin 13.0 mg / dm ² magenta coupler (MC-1) 2.4 mg / dm ² image stabilizer (AO-1) 2.0 mg / dm ² solvent (SO-4) 3.15 mg / dm ² compound (D) 5 × 10 ⁻³ mol / mol Ag [second layer (color mixing prevention layer)] Gelatin 7.5 mg / dm ² Color mixing inhibitor (AS-1) 0.55 mg / dm ² Solvent (SO-2) 0 .72 mg / dm ² [First layer (red photosensitive layer)] Emulsion A (including sensitizing dyes RD-1 and RD-2) 4.0 mg / dm ² gelatin 13.8 mg / dm ² cyan coupler (CC-1) ) 2.1mg / dm ² cyan coupler (CC-2) 2.1mg / dm 2 image weaker Agent (AO-3) 2.2mg / dm 2 solvent (SO-1) 3.3mg / dm 2 Compound (d) 5 × 10 ^-3 mol / mol Ag Incidentally, SA-1, SA-2 as a coating aid And HA-2 was used as a hardening agent.

The compounds used in each of the above layers are shown below.

[0128]

[Chemical formula 61]

[0129]

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[0130]

[Chemical formula 63]

[0131]

[Chemical 64]

[0132]

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On the other hand, sample No. No. 21, except that the compound (d) in each layer was replaced with the compound (e) and the fog agent represented by the general formula [I] of the present invention shown in Table 3, the sample No. 22-30 were obtained. The structures of the compounds (d) and (e) used as comparative fog agents are shown below.

[0134]

[Chemical formula 66]

Each of the obtained samples was exposed through a photo wedge using a sensitometer and processed in the processing steps shown below. [Treatment-1] Treatment step Time Temperature Color development 2 minutes 33 ° C Bleach-fixing 40 seconds 33 ° C Stability 20 seconds three times 33 ° C Dry 30 seconds 60-80 ° C [Coloring developer-1] Diethylenetriamine pentaacetic acid 2.0 g Benzyl Alcohol 12.8 g Diethylene glycol 3.4 g Sodium sulfite 2.0 g Sodium bromide 0.5 g Hydroxylamine sulfate 2.6 g Sodium chloride 3.2 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamide Ethyl) aniline 4.25 g Potassium carbonate 30.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Water was added to 1 l pH (adjusted with potassium hydroxide and sulfuric acid) 10.5 [ Bleach-fix solution] Ammonium thiosulfate (54 wt%) 150 ml Sodium sulfite 15 g Iron ethylenediaminetetraacetate 55 g (III) Ammonium ethylenediaminetetraacetate (dihydrate) 4 g Glacial acetic acid 8.61 g Water was added 1 l pH (adjusted with ammonia water or hydrochloric acid) 5.4 [Stabilizer] 1-hydroxyethylidene 1,1'-Diphosphonic acid (60%) 1.6 ml Bismuth chloride 0.35 g Polyvinylpyrrolidone 0.25 g Ammonia water 2.5 ml Nitrilotriacetic acid / 3Na 1.0 g 5-Chloro-2-methyl-4-inch azirine -3-one 50 mg 2-octyl-4-isothiazolin-3-one 50 mg Fluorescent brightener (4,4'-diaminostilbene type) 1.0 g Water was added 1 l pH (adjusted with potassium hydroxide or hydrochloric acid) 7 .5 [Treatment-2] Same as Treatment-1 except that the pH of the color developer was adjusted to 11.0. It is.

Sensitometry was performed on the obtained image and the maximum density D _max and the minimum density D _min of the magenta image were evaluated. The results are shown in Table 3. Table 3 No. Hydrazine Magenta Image Processing-1 Processing-2 21 d Dmax 1.69 2.01 Comparative Example Dmin 0.16 0.21 22 e Dmax 1.53 1.95 Comparative Example Dmin 0.15 0.19 23 I-1 Dmax 1.97 2.20 Invention Dmin 0.13 0.16 24 I-3 Dmax 2.01 2.23 Invention Dmin 0.13 0.17 25 I-7 Dmax 2.02 2.19 Invention Dmin 0 .14 0.18 26 I-9 Dmax 1.99 2.17 Present invention Dmin 0.14 0.17 27 I-13 Dmax 1.98 2.10 Present invention Dmin 0.12 0.15 28 I-17 Dmax 2.00 2.19 Invention Dmin 0.13 0.17 29 I-19 Dmax 1.97 2.12 Invention Dmin 0.12 0.16 30 I-38 Dmax 1.90 2.07 Invention Dmin 0 .15 0.18 Table 3 As is clear from the above, sample No. 1 containing the fog agent of the present invention. Nos. 23 to 30 are sample Nos. It can be seen that even in the low pH treatment, the maximum density is large and the minimum density is small as compared with those of Nos. 21 and 22, and a good positive image is obtained.

Example 3 The procedure of Example 2 was repeated except that the compounds shown in Table 4 were used as the fogging agent. 31-39 were produced. These samples were exposed as in Example 3 and processed in Process-1. The minimum density of the obtained magenta image is D _min .

On the other hand, a raw sample (sample before exposure and development) was stored under conditions of a temperature of 50 ° C. and a humidity of 80% RH for 3 days, forcibly deteriorated, and exposed and processed in the same manner as described above. The minimum density of the magenta image at this time is D _min '. D _min and D
The values of _min 'are shown in Table 4. Table 4 No. Hydrazine Dmin (Dmin) '31 d 0.16 0.31 Comparative Example 32 e 0.15 0.27 Comparative Example 33 I-1 0.13 0.20 Invention 34 I-3 0.13 0.19 Invention 35 I-6 0.14 0.21 Invention 36 I-9 0.14 0.23 Invention 37 I-18 0.13 0.20 Invention 38 I-23 0.14 0.22 Invention 39 I -38 0.15 0.24 The present invention As is clear from Table 4, the sample No. containing the fog agent of the present invention. Nos. 33 to 39 are sample Nos. Containing a fog agent as a comparative example. It can be seen that, as compared with those of Nos. 31 and 32, the minimum concentration did not increase even after storage with time and the stability with time was excellent.

[0139]

[Effect] According to the present invention, even if a low pH developer is used for processing,
It was possible to provide a silver halide photographic light-sensitive material having a high contrast, little fog, and stable halftone quality, which is stable even when the development pH changes. Further, by directly applying the present invention to a positive silver halide photographic light-sensitive material, a high maximum density can be obtained even when developed with a developing solution having a low pH, and the maximum density can be obtained by fog development in a relatively short time. And a low minimum density, a good positive image can be obtained, and a minimum increase in minimum density even after storage with time can be provided.

[0140]

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[Name of item to be corrected] 0032

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[Correction content]

[0032]

[Chemical 10]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

[0033]

[Chemical 11]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[0034]

[Chemical 12]

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

[0035]

[Chemical 13]

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

[0036]

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[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

[0037]

[Chemical 15]

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038]

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[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

[0039]

[Chemical 17]

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

[0040]

Embedded image

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

[Chemical 19]

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042]

Embedded image

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043]

[Chemical 21]

[Procedure amendment 20]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

[0044]

[Chemical formula 22]

[Procedure correction 21]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

[0045]

[Chemical formula 23]

[Procedure correction 22]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046]

[Chemical formula 24]

[Procedure amendment 23]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

[0047]

[Chemical 25]

[Procedure correction 24]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048]

[Chemical formula 26]

[Procedure correction 25]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[0049]

[Chemical 27]

[Procedure Amendment 26]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050]

[Chemical 28]

[Procedure Amendment 27]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

[0051]

[Chemical 29]

[Procedure correction 28]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

[0052]

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[Procedure correction 29]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

[0053]

[Chemical 31]

[Procedure amendment 30]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

[0054]

Embedded image

[Procedure correction 31]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

[0055]

[Chemical 33]

[Procedure correction 32]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

[0056]

Embedded image

[Procedure amendment 33]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

[0057]

Embedded image

[Procedure amendment 34]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

[0058]

Embedded image

[Procedure amendment 35]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

[0059]

Embedded image

[Procedure correction 36]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

[0060]

[Chemical 38]

[Procedure amendment 37]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

[0061]

[Chemical Formula 39]

[Procedure amendment 38]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction content]

[0062]

[Chemical 40]

[Procedure amendment 39]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

[0063]

Embedded image

[Procedure amendment 40]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

[0064]

Embedded image

[Procedure Amendment 41]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction content]

[0065]

[Chemical 43]

[Procedure amendment 42]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction content]

[0066]

[Chemical 44]

[Procedure amendment 43]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

[0067]

Embedded image

[Procedure correction 44]

[Document name to be amended] Statement

[Correction target item name] 0068

[Correction method] Change

[Correction content]

[0068]

Embedded image

[Procedure amendment 45]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

[0069]

[Chemical 47]

[Procedure correction 46]

[Document name to be amended] Statement

[Name of item to be corrected] 0070

[Correction method] Change

[Correction content]

[0070]

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[Procedure amendment 47]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

[0071]

[Chemical 49]

[Procedure correction 48]

[Document name to be amended] Statement

[Name of item to be corrected] 0072

[Correction method] Change

[Correction content]

[0072]

Embedded image

[Procedure correction 49]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction content]

[0073]

[Chemical 51]

[Procedure amendment 50]

[Document name to be amended] Statement

[Correction target item name] 0074

[Correction method] Change

[Correction content]

[0074]

Embedded image

[Procedure correction 51]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction content]

[0076]

Embedded image

[Procedure amendment 52]

[Document name to be amended] Statement

[Correction target item name] 0078

[Correction method] Change

[Correction content]

[0078]

[Chemical 54]

[Procedure amendment 53]

[Document name to be amended] Statement

[Name of item to be corrected] 0123

[Correction method] Change

[Correction content]

[0123]

Embedded image

[Procedure Amendment 54]

[Document name to be amended] Statement

[Correction target item name] 0134

[Correction method] Change

[Correction content]

[0134]

[Chemical formula 66]

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one selected from the group of compounds represented by the following general formula [I] in at least one of the photographic constituent layers. material. Embedded image [In the above general formula [I], R contains at least one thioether, and-(L ₂ -Z) _1- (provided that
Z represents an optionally substituted ethylene group, a propylene group or a trimethylene group, and L ₂ is -O-, -S- or-.
N (Z ₁ )-(wherein Z ₁ represents a hydrogen atom or an aliphatic group), l represents an integer of 2 or more when L ₂ is -O-, and L ₂ is -S- or -N. (Z ₁ ) -represents a group having a partial structure of 1 or more). However, when L ₂ is —O— and Z is an ethylene group, R is —O.
It connects with L ₁ by-. L ₁ represents an alkylene group or an alkenylene group, and Y represents a divalent aromatic group. X represents a substitutable group, and n represents an integer of 0-4. When n is 2 or more, X may be the same or different. A
₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom,
The other represents an acyl group, a sulfonyl group or an oxalyl group. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and R ₁
Represents a hydrogen atom or a block group. ]