JPH0682943A - Silver halide photographic sensitive material and method for forming photographic image by using same - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material capable of forming an ultrahigh-contrast image with a developing solution comparatively low in pH. CONSTITUTION:The silver halide photographic sensitive material has a silver halide emulsion layer chemically sensitized with an Se or Te compound and this emulsion layer or another hydrophilic colloidal layer containing a hydrazine derivative represented by the general formula R<1>-NHNH-G-R<2> in which R<1> is an optionally substituted aliphatic, aromatic, or heterocyclic group; G is -CO-, -SO2-, -SO-, -COCO-, thiocarbonyl, imino-methylene, or -P(O)(R<4>)-; R<2> is alkyl having the C combining with G substituted by an electron-attractive group; and R<4> is H, an aliphatic or aromatic group, alkoxy, aryloxy, or amino 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 an ultrahigh-contrast silver halide photographic light-sensitive material used for photolithography.

[0002]

The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat. No. 3,730,
No. 727 (developer combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 (silver halide) Β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for the light-sensitive material), No. 2,419,975, and The Theory of Photographic Process by Mees. Process) Third Edition (19
66) 281 pages and the like. Among these, in particular, in US Pat. No. 2,419,975, it is possible to obtain a high-tone negative image by adding a hydrazine compound.
It is disclosed. In the patent specification, a hydrazine compound was added to a silver chlorobromide emulsion to obtain a high pH of 12.8.
It is described that when developed with the developing solution of No. 2, extremely high photographic characteristics with a gamma (γ) of more than 10 can be obtained.
However, a strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use.
Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. In JP-A-1-179939 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group was used to obtain a pH of 11 A processing method of developing with a developing solution of 0.0 or less is described. However, when a compound having an adsorbing group is added to a silver halide emulsion, the photosensitivity may be impaired if the amount exceeds a certain limit.
Since it has a harmful effect of suppressing development or hindering the action of other useful adsorptive additives, the amount used is limited and sufficient contrast cannot be exhibited.

US Pat. Nos. 4,998,604 and 4,994.
No. 365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is clear from these examples, the high contrast is not sufficient, and it is difficult to obtain the high contrast and the required Dmax under practical development processing conditions. Further, the nucleating hard contrast material using a hydrazine derivative has a wide range of change in photographic property with a change in pH of the developer. The pH of the developer greatly changes due to air oxidation of the developer and increase due to concentration by evaporation of water, or decrease due to absorption of carbon dioxide in the air. Therefore, attempts have been made to reduce the dependence of photographic performance on the pH of the developer. As described above, in the conventional technique, it was not possible to obtain a light-sensitive material which exhibits sufficient contrast even when treated with a developer having a pH of less than 11 and has a small dependence of photographic performance on the pH of the developer.

[0004]

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

[0005]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the emulsion layer contains a selenium sensitizer and a tellurium sensitizer. It contains silver halide chemically sensitized by at least one of the sensitizers, and at least one of the emulsion layer and other hydrophilic colloid layers has the following general formula (VI)
It was achieved by a silver halide photographic light-sensitive material characterized by containing a hydrazine derivative represented by

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
JP-A-4-25832 and JP-A-4-109240.
It is preferable to use the compounds described in Japanese Patent Application No. 3-82929 and Japanese Patent Application No. 3-82929. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- Selenopropionic acid, 2-
(Selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium and the like. The preferred types of labile selenium compounds have been described above, but are not limiting. Speaking of unstable selenium compounds as sensitizers for photographic emulsions to those skilled in the art,
The structure of the compound is not critical as long as the selenium is unstable, and the organic portion of the selenium sensitizer molecule carries selenium and does not allow it to be present in the emulsion in an unstable form. Is generally understood to have no role. In the present invention, the labile selenium compound having such a broad concept is advantageously used. The non-unstable selenium compound used in the present invention is Japanese Patent Publication No. 46-4553.
No. 52/34 and Japanese Patent Publication No. 52-34
The compound described in No. 491 is used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (I) and (II) are preferable. General formula (I)

[0007]

[Chemical 7]

Where Z₁And Z₂Are the same
They may be different, alkyl groups (eg methyl groups,
Ethyl group, t-butyl group, adamantyl group, t-octyl
Group, alkenyl group (eg vinyl group, propenyl group)
Group), aralkyl group (eg, benzyl group, phenethyl group
Group), aryl group (eg, phenyl group, pentafluoro group)
Rophenyl group, 4-chlorophenyl group, 3-nitrofe
Nyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (eg pyridyl group, thieny)
Group, furyl group, imidazolyl group), -NR
₁(R₂), -OR₃Or-SR_FourRepresents R₁,
R₂, R₃And R_FourAre the same or different
Also, an alkyl group, an aralkyl group, an aryl group or
Represents a heterocyclic group. Alkyl group, aralkyl group, aryl
Z as a radical or heterocyclic group₁An example similar to
It However, R₁And R₂Is a hydrogen atom or an acyl group
(For example, acetyl group, propanoyl group, benzoyl
Group, heptafluorobutanoyl group, difluoroacetyl
Group, 4-nitrobenzoyl group, α-naphthoyl group, 4-
A trifluoromethylbenzoyl group). one
In general formula (I), preferably Z₁Is an alkyl group, aryl
Group or -NR₁(R₂), And Z₂Is -NR
_Five(R₆) Is represented. R₁, R₂, R_FiveAnd R ₆Haso
They may be the same or different, and may be hydrogen atoms,
Represents an alkyl group, an aryl group, or an acyl group. General formula
In (I), more preferably N, N-dialkylselenourine
Elemental, N, N, N'-trialkyl-N'-acylseleno
Urea, tetraalkyl selenourea, N, N-dialkyl
-Arylselenoamide, N-alkyl-N-aryl
-Represents an arylselenoamide. General formula (II)

[0009]

[Chemical 8]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -NR ₈ (R ₉ ), -SR. ₁₀ , -Se
R ₁₁ , X and hydrogen atom are represented. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. , X represents a halogen atom. In the general formula (II), Z ₃ , Z ₄ , Z ₅ , R ₇ ,
The aliphatic group represented by R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group, n-propyl group, Isopropyl group, t-butyl group,
n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group,
Allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group, phenethyl group). In the general formula (II), Z ₃ , Z ₄ ,
The aromatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, a phenyl group, a pentafluorophenyl group, a 4-chlorophenyl group, 3- Sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (II),
Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁
The heterocyclic group represented by is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom (for example, a pyridyl group, a thienyl group, a furyl group, a thiazolyl group. , An imidazolyl group, and a benzimidazolyl group). In the general formula (II), R
_The cation represented by ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In general formula (II), preferably Z
₃ , Z ₄ or Z ₅ is an aliphatic group, an aromatic group or -OR
₇ , R ₇ represents an aliphatic group or an aromatic group.
In the general formula (II), trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate is more preferable. Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0011]

[Chemical 9]

[0012]

[Chemical 10]

[0013]

[Chemical 11]

[0014]

[Chemical 12]

[0015]

[Chemical 13]

[0016]

[Chemical 14]

[0017]

[Chemical 15]

[0018]

[Chemical 16]

Examples of tellurium sensitizers used in the present invention include US Pat. Nos. 1,623,499, 3,320,069, 3,772,031 and British Patent 235. No. 211, No. 1,121,496
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, Journal of Chemical Society Chemical Communication
(J. Chem. Soc. Chem. Commun.) 635 (1980),
ibid 1102 (1979), ibid 645 (197)
9), Journal of Chemical Society
Perkin Transaction (J. Chem. Soc. Perkin Tr
ans.) 1, 191 (1980), S.I. Patay (S. Pata
i) The Chemistry of Organic Selenium and Tellurium Companies (The Chemist)
ry of Organic Selenium and Tellurium compounds),
It is preferable to use the compounds described in Vol 1 (1986) and Vol 2 (1987). Specific tellurium sensitizers include, for example, colloidal tellurium, telluroureas (eg, allyl tellurourea, N, N-dimethyl tellurourea,
Tetramethyl tellurourea, N-carboxyethyl-
N ', N'-dimethyl tellurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), isotellocyanates (for example, allyl isoterocyanate), telluroketones (for example, telluroacetophenone) , Telluroamides (eg, telluroacetamide, N, N-dimethyltellobenzamide), tellurohydrazide (eg, N, N ′, N′-tolumethyltellobenzhydrazide), telluroester (eg, t-
Butyl-t-hexyl telluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride),
Diacyl (di) tellurides (eg, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-
N-methylcarbamoyl) telluride, diethylcarbamoyltelluride, bis (ethoxycarbonyl) telluride), (di) tellurides, and other tellurium compounds (eg, negatively charged telluride ion-containing gelatin described in British Patent No. 1,295,462). , Potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, allyl tellurocyanate). Of these tellurium compounds, preferably the following general formula (III),
(IV) and (V).

[0020]

[Chemical 17]

In the above general formula (III), R ₁₁ , R ₁₂ and R
₁₃ is an aliphatic group, an aromatic group, a heterocyclic group, OR ₁₄ , NR
₁₅ (R ₁₆ ), SR ₁₇ , OSiR ₁₈ (R ₁₉ ) (R ₂₀ ), X
Or represents a hydrogen atom. R ₁₄ and R ₁₇ are aliphatic groups,
An aromatic group, a heterocyclic group, a hydrogen atom or a cation is represented, R ₁₅ and R ₁₆ are an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and R ₁₈ , R ₁₉ and R ₂₀ are an aliphatic group. And X represents a halogen atom. Next, the general formula (I
II) will be explained in detail. In the general formula (III),
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R
_The aliphatic group represented by ₁₉ and R ₂₀ is preferably one having 1 to 30 carbon atoms, and particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group, alkenyl group, alkynyl group, or aralkyl group. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl and 2-butenyl. , 3-pentenyl, propargyl, 3-pentynyl,
Examples include benzyl and phenethyl. In the general formula (III), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇
The aromatic group represented by is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. In the general formula (III), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
The heterocyclic group represented by R ₁₅ , R ₁₆ and R ₁₇ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be a single ring or may form a condensed ring with another aromatic ring or a heterocycle. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocycle,
Examples include pyridyl, furyl, thienyl, thiazolyl, imidazolyl and benzimidazolyl. General formula (I
In II), the cations represented by R ₁₄ and R ₁₇ are alkali metals and ammonium. In formula (III), the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Further, the aliphatic group, aromatic group and heterocyclic group may be substituted. The following are mentioned as a substituent. Representative substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups,
Alkoxy group, aryloxy group, amino group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group , Phosphoric acid amide group, diacylamino group, imide group, alkylthio group, arylthio group, halogen atom, cyano group, sulfo group, carboxy group, hydroxy group, phosphono group, nitro group, and heterocyclic group. These groups may be further substituted. When there are two or more substituents, they may be the same or different. R ₁₁ ,
R ₁₂ and R ₁₃ may combine with each other to form a ring together with the phosphorus atom, and R ₁₅ and R ₁₆ may combine with each other to form a nitrogen-containing heterocycle. In formula (III), preferably R ₁₁ and R
₁₂ and R ₁₃ represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group.

[0022]

[Chemical 18]

In the above general formula (IV), R_{twenty one}Is an aliphatic group, aromatic
Group, heterocyclic group or -NR_{twenty three}(R _{twenty four}), And R_{twenty two}
Is -NR_{twenty five}(R₂₆), -N (R₂₇) N (R₂₈) R₂₉Also
Is -OR₃₀Represents R_{twenty three}, R_{twenty four}, R_{twenty five}, R₂₆, R₂₇,
R₂₈, R₂₉And R₃₀Is hydrogen atom, aliphatic group, aromatic
Represents a group, a heterocyclic group or an acyl group. Where R_{twenty one}And R
_{twenty five}, R_{twenty one}And R₂₇, R_{twenty one}And R₂₈, R_{twenty one}And R₃₀, R_{twenty three}When
R_{twenty five}, R_{twenty three}And R₂₇, R_{twenty three}And R ₂₈And R_{twenty three}And R₃₀Is a bond
To form a ring. Details of general formula (IV)
Explained. In the general formula (IV), R_{twenty one}, R_{twenty two}, R_{twenty three},
R_{twenty four}, R_{twenty five}, R₂₆, R₂₇, R₂₈, R ₂₉And R₃₀Represented by
The aliphatic group, aromatic group and heterocyclic group represented by the general formula (II
It has the same meaning as I). In the general formula (IV), R_{twenty three}, R
_{twenty four}, R_{twenty five}, R₂₆, R₂₇, R₂₈, R₂₉And R₃₀Represented by
The acyl group shown is preferably one having 1 to 30 carbon atoms.
In particular, a linear or branched acyl group having 1 to 20 carbon atoms
, Eg acetyl, benzoyl, formyl, pivalo
Ill and decanoyl. Where R_{twenty one}And R_{twenty five}, R
_{twenty one}And R₂₇, R_{twenty one}And R₂₈, R_{twenty one}And R₃₀, R_{twenty three}And R_{twenty five}, R_{twenty three}
And R₂₇, R_{twenty three}And R₂₈And R_{twenty three}And R₃₀Combine to form a ring
When it is formed, for example, alkylene group, arylene group, ara
Examples thereof include a alkylene group and an alkenylene group. Well
In addition, this aliphatic group, aromatic group, and heterocyclic group have the general formula
It may be substituted with the substituents mentioned in (III). General formula
In (IV), preferably R_{twenty one}Is an aliphatic group, an aromatic group or-
NR_{twenty three}(R_{twenty four}), And R_{twenty two}Is -NR_{twenty five}(R₂₆) Table
Forget R_{twenty three}, R_{twenty four}, R_{twenty five}And R₂₆Is an aliphatic group or
Represents an aromatic group. In the general formula (IV), more preferably R_{twenty one}Is
Aromatic group or -NR_{twenty three}(R_{twenty four}), And R_{twenty two}Is -N
R_{twenty five}(R₂₆) Is represented. R_{twenty three}, R_{twenty four}, R_{twenty five}And R₂₆Is
Represents an alkyl group or aromatic group. Where R_{twenty one}And R
_{twenty five}And R_{twenty three}And R_{twenty five}Is an alkylene group, an arylene group,
Form a ring via a ralkyren or alkenylene group
Is more preferable.

[0024]

[Chemical 19]

In the above general formula (V), R₃₁And R₃₂Is the same
Same or different, aliphatic group, aromatic group
Group, heterocyclic group,-(C = Y ')-R₃₃Represents R₃₃Is
Hydrogen atom, aliphatic group, aromatic group, heterocyclic group, NR₃₄(R
₃₅), OR₃₆Or SR₃₇And Y'is an oxygen atom,
Sulfur atom or NR₃₈Represents R₃₄, R₃₅, R₃₆, R
₃₇And R₃₈Is a hydrogen atom, an aliphatic group, an aromatic group or
Represents a prime ring group, and n represents 1 or 2. Then the general formula
(V) will be described in detail. In general formula (V)
R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇And R₃₈
The aliphatic group, aromatic group or heterocyclic group represented by
It has the same meaning as each of formula (III). Also, R₃₁, R₃₂,
R₃₃, R₃₄, R₃₅, R₃₆, R₃₇And R₃₈Represented by
The aliphatic group, aromatic group and heterocyclic group have the general formula (III)
It may be substituted with a substituted substituent. Where R₃₁And R
₃₂And R₃₄And R₃₅May combine to form a ring. one
In general formula (V), preferably R₃₁And R₃₂Is a heterocyclic group
Or-(C = Y ')-R₃₃Represents R₃₃Is NR₃₄(R
₃₅) Or OR₃₆And Y'represents an oxygen atom.
R₃₄, R₃₅And R₃₆Is an aliphatic group, aromatic group or hetero group
Represents a ring group. In the general formula (V), more preferably R₃₁Oh
And R₃₂Is-(C = Y ')-R₃₃Represents R₃₃Is NR
₃₄(R₃₅) And Y'represents an oxygen atom. R₃₄Oh
And R ₃₅Represents an aliphatic group, an aromatic group or a heterocyclic group.
You The following formulas 20 to 34 are represented by the general formulas (III) and (IV) of the present invention.
Specific examples of the compounds represented by and (V) are shown below.
Ming is not limited to this.

[0026]

[Chemical 20]

[0027]

[Chemical 21]

[0028]

[Chemical formula 22]

[0029]

[Chemical formula 23]

[0030]

[Chemical formula 24]

[0031]

[Chemical 25]

[0032]

[Chemical formula 26]

[0033]

[Chemical 27]

[0034]

[Chemical 28]

[0035]

[Chemical 29]

[0036]

[Chemical 30]

[0037]

[Chemical 31]

[0038]

[Chemical 32]

[0039]

[Chemical 33]

[0040]

[Chemical 34]

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide emulsion grain. The following tests can be conducted for the rate of silver telluride formation in a silver halide emulsion. When a large amount is added (for example, 1 × 10 ⁻³ mol / mol Ag), the formed silver telluride has absorption in the visible region. Therefore, regarding sulfur sensitizers, E. Moisar
Is Journal of Photographic Science, Volume 14, 181
Page (1966), 16 volumes, 102 pages (1968).
Year) can be applied. The amount of silver sulfide formed in a silver halide emulsion can be determined from the infinite reflectivity of the emulsion in the visible range (520 nm) by Kubelka-M
The relative silver telluride formation rate can be easily obtained by the same method as that obtained using the unk equation. Also,
Since this reaction is apparently close to the first-order reaction, the pseudo-first-order reaction rate constant can also be obtained. For example, an average particle size of 0.
5 μm silver bromide octahedral emulsion (AgBr0.
75 mol, containing 80 g of gelatin) pH = 6.3, p
While keeping Ag = 8.3, the temperature is kept at 50 ° C., and a tellurium compound dissolved in an organic solvent (methanol or the like) is added at 1 × 10 ⁻³ mol / mol Ag. 1cm with spectrophotometer with integrating sphere
The emulsion is placed in a cell having a thickness, and the reflectance (R) at 520 nm is measured with time with reference to the blank emulsion. Substituting the reflectance into the Kubelka-Munk equation (1-R) ² / 2R and changing the value, the pseudo first-order reaction rate constant k (min
^-1 ). R = if no silver telluride is produced
Because it is 1, the value of Kubelka-Munk remains the same as 0 without tellurium compound. The apparent first-order reaction rate constant k is 1 × 10 ⁻⁸ to 1 × 10 under exactly the same conditions as this test method.
Compounds at ⁰ min ^-1 are preferred. Further, in a smaller addition amount range where absorption in the visible region is difficult to detect, the produced silver telluride can be separated from the unreacted tellurium sensitizer and quantified. For example, after separation by immersion in an aqueous solution of a halogen salt or an aqueous solution of a water-soluble mercapto compound, a trace amount of Te is quantitatively analyzed by an atomic absorption method or the like. The reaction rate greatly varies within a range of several digits depending on the type of compound, the silver halide composition of the emulsion to be tested, the temperature to be tested, pAg, pH and the like. The tellurium sensitizer preferably used in the present invention is a compound capable of forming silver telluride with respect to a specific silver halide emulsion having a halogen composition and a crystal habit to be used. Generally speaking, the temperature is 40 to 95 ° C., the pH is 3 to 10, or the pAg is 6 to 11 with respect to the silver bromide emulsion.
A compound capable of forming silver telluride is preferably used in the present invention in any of the above ranges, and in this range, the pseudo first-order reaction rate constant k according to the above test method is 1 × 10 ⁻⁷ to 1
A compound falling within the range of × 10 ^-1 min ^-1 is more preferable as the tellurium sensitizer.

General formulas (III), (IV) and (V) of the present invention
The compound represented by can be synthesized according to a known method. For example, Journal of Chemical Society (J. Chem. Soc. (A)) 1969, 29.
27; Journal of Organometallic Chemistry (J. Organomet. Chem.) 4,320 (196).
5); ibid, 1,200 (1963); ibid, 113,
C35 (1976); Phosphorus Sulfur (Pho
Sphorus Sulfur 15,155 (1983); Chemist Ber. 109, 2996 (197).
6); Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Com
mun.) 635 (1980); ibid, 1102 (197).
9); ibid, 645 (1979); ibid, 820 (19
87); Journal of Chemical Society
Perkin Transaction (J. Chem. Soc. Perkin. T
rans.) 1, 191 (1980); Patay (S. Pata
i) Ed., The Chemistry of Organo Selenium and Tellurium Companies (The Chemistry
of Organo Selenium and Tellurium Compounds, Volume 2 216-267 (1987), Tetrahedron Letters 31, 3587 (199)
0), Journal of Chemical Research, J. Chem. Res., Synopses 2,56 (199).
0), Bulletin of the Chemical Society
Of Japan (Bull. Chem. Soc. Japan) 62, 211
7 (1989), ibid, 60, 771 (1987), Journal of Organometallic Chemistry.
(J. Organometallic Chem.) 338, 9 (1988),
ibid, 306, C36 (1986), Journal of the Chemical Society of Japan 7
Vol. 1475 (1987), Zeitschrift Chemie 26, 179 (19).
86), Chemistry Letters
3,475 (1987), Indian Journal
Indian Chemistry, Chemistry, Se
ction A) 25A, 57 (1986), Angewandte Chemie 97, 1051 (198)
5), Spectrochimica Acta
a, Part A) 38A, 185 (1982), Organic Preparations and Procedures I
nternational) 10,289 (1978), Organometallics 1,470 (1982)
Can be synthesized by the method described in.

The amounts of these selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ^{−7 to} 5 × 10
^Use about ^-3 mol.

The conditions for the chemical sensitization in the present invention are:
Although not particularly limited, the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. In particular, it is preferable to use a gold sensitizer, and specific examples thereof include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, etc., and 10 ⁻ per mol of silver halide. ^{About 7} to 10 ^-2 mol can be used.

In the present invention, it is also preferable to use a sulfur sensitizer together. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylurea, allylthiourea), and rhodanines. 1 mol of silver halide About 10 ^-7 to 10 ^-2 mol can be used per unit.

Next, the hydrazine derivative represented by the general formula (VI) will be described. General formula (VI)

[0048]

[Chemical 35]

R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, which may be substituted. G ¹ is -CO-
Group, -SO ₂ - group, -SO- group, -COCO- group, a thiocarbonyl group, an iminomethylene group or -P (O) (R
⁴ ) -group, and R ² represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron-withdrawing group.

Next, the compound represented by the general formula (VI) will be described in more detail. In the general formula (VI), the aliphatic group represented by R ¹ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R ¹ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.
The hetero ring of R ¹ is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group, a benzthiazolyl group. Those are preferable. Preferred as R ¹ are aromatic groups, nitrogen-containing heterocycles and groups represented by the general formula (b). General formula (b)

[0051]

[Chemical 36]

(Where X is_bIs an aromatic group or nitrogen-containing complex
Represents a ring group, R_b ¹~ R_b ^FourAre hydrogen atom and halogen
Represents an alkyl atom or an alkyl group, X_bAnd R_b ¹
~ R _b ^FourMay have a substituent if possible.
r and s represent 0 or 1. ) R¹Is more preferably an aromatic group, especially aryl.
Group is preferred. R¹May be substituted with a substituent
Yes. Examples of the substituent include, for example, an alkyl group and aralkyl.
Group, alkenyl group, alkynyl group, alkoxy group,
Reel group, substituted amino group, aryloxy group, sulfa
Moyl group, carbamoyl group, alkylthio group, aryl
Thio group, sulfonyl group, sulfinyl group, hydroxy
Groups, halogen atoms, cyano groups, sulfo groups and carboxyls
Groups, alkyl and aryloxycarbonyl groups, acyl
Group, alkoxycarbonyl group, acyloxy group, cal
Bonamide group, sulfonamide group, nitro group, alkyl
In addition to a thio group, an arylthio group, etc., the following general formula (c)
And a group represented by. General formula (c)

[0053]

[Chemical 37]

In the formula (c), Yc is --CO-- or --SO.
₂-, -P (O) (R_C3)-(Wherein R _C3Is alkoxy
Represents a group or an aryloxy group. ) Or -O
P (O) (R_C3)-, L is a single bond, -O-,-
S- or -NR_C4-(In the formula, R _C4Is a hydrogen atom, Archi
Represents an aryl group or an aryl group. ) Is represented. R_C1And R
_C2Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
I can be the same or different, and bond to each other
To form a ring. Also R¹Is one general formula (c)
Alternatively, a plurality of them can be included.

In the general formula (c), the aliphatic group represented by R _C1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _C1 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocycle of R _C1 is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable. R _C1 may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example, alkyl group, aralkyl group, alkenyl group,
Alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group , Halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group and an arylthio group. When possible, these groups may be linked to each other to form a ring.

The aliphatic group represented by R _C2 in the general formula (c) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _C2 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _C2 may be substituted with a substituent. Examples of the substituent include those listed as R _C1 in the general formula (c) and the substituent. If possible, R _C1 and R _C2 may be linked to each other to form a ring. A hydrogen atom is more preferable as R _C2 .

Y _C in the general formula (c) is -CO.
-, - SO ₂ - is particularly preferred, L is a single bond and -N
R _C4 − is preferred. The aliphatic group represented by R _C4 in the general formula (c) is a linear, branched or cyclic alkyl group,
It is an alkenyl group or an alkynyl group. The aromatic group represented by R _C4 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _C4 may be substituted with a substituent. Examples of the substituent include those enumerated as the substituents of R _C1 in the general formula (c). A hydrogen atom is more preferable as R _C4 .

As G in the general formula (VI), a -CO- group is most preferable. R ^{2 in the} general formula (VI) represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group, preferably 2 electron withdrawing groups, particularly preferably 3 electron withdrawing groups. Represents a substituted alkyl group substituted with a group.

The electron withdrawing group for substituting the carbon atom substituted with G in R ² preferably has a δ _p value of 0.2 or more and a δ _m value of 0.3 or more, and examples thereof include halogen, cyano, nitro, and Nitroso, polyhaloalkyl, polyhaloaryl,
An alkyl or aryl carbonyl group, a formyl group,
Alkyl or aryloxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkyl or arylsulfonyloxy group, sulfamoyl group, phosphino group, phosphine oxide group, phosphonate group, phosphone It represents an acid amide group, an arylazo group, an amidino group, an ammonio group, a sulfonio group, and an electron-deficient heterocyclic group. General formula (VI)
R ² in R ² particularly preferably represents a trifluoromethyl group.

R ¹ and R ^{2 in} the general formula (VI) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-100530
The items described in No.

R ¹ and R ^{2 in} the general formula (VI) may be those in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group, which are disclosed in U.S. Pat. Nos. 4,385,108, 4,459,347, and JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
No. 47, No. 59-201, No. 048, No. 59-201,
049, 61-170, 733, 61-27.
0,744, 62-948, 63-234,2.
44, 63-234, 245, 63-234,
The groups described in No. 246 are mentioned. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0062]

[Chemical 38]

[0063]

[Chemical Formula 39]

[0064]

[Chemical 40]

[0065]

[Chemical 41]

[0066]

[Chemical 42]

[0067]

[Chemical 43]

[0068]

[Chemical 44]

[0069]

[Chemical formula 45]

[0070]

[Chemical formula 46]

The hydrazine derivative of the present invention is prepared by reacting the corresponding hydrazine with a corresponding carboxylic acid in the presence of a condensing agent such as dicyclohexylcarbodiimide, or by reacting with an acid halide such as sulfonyl chloride or acyl chloride or an acid anhydride or active ester. It was synthesized by reacting with. Furthermore, when EWG is R ₃ SO ₂ —, the corresponding haloacetylhydrazide derivative and R ₃ SO 2
A method of reacting ₂ H in the presence of a base was also used. A specific example is shown below.

Synthetic Example: Synthesis of Exemplified Compound 16 Under a nitrogen atmosphere, triethylamine (15.3 ml) was added to a mixed solution of the starting compound A (63.2 g) and tetrahydrofuran (200 ml), and the mixed solution was cooled to 5 ° C. ,
Trifluoroacetic anhydride (16.9 ml) was added and stirred overnight at room temperature. The reaction solution was poured into 0.1N HCl aqueous solution and extracted with ethyl acetate, and the organic layer was washed with saturated saline. It was dried over anhydrous magnesium sulfate, ethyl acetate was distilled off, and the product was isolated and purified by silica gel chromatography to obtain the desired product (52.1 g). The structure of the compound was confirmed by nmr spectrum and ir spectrum. The structure of the raw material compound A is shown below.

[0073]

[Chemical 47]

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

The compounds of general formula (VI) of the present invention are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethylformamide, It can be used by dissolving in dimethyl sulfoxide, methyl cellosolve and the like. Further, by well-known emulsion dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It is also possible to dissolve it using an auxiliary solvent such as ethyl acetate or cyclohexanone and mechanically prepare an emulsified dispersion for use. Alternatively, by a method known as a solid dispersion method, the redox compound powder is ball-milled in water,
A colloid mill or ultrasonic waves may be used for dispersion.

The halogen composition of the silver halide emulsion used in the present invention may be any composition, but silver chloride, silver chlorobromide, silver bromide and silver iodobromide are preferred. More preferred is silver chlorobromide having a silver chloride content of 50 mol% or more. As a method for preparing the silver halide emulsion used in the present invention, various methods known in the field of silver halide photographic light-sensitive materials are used. For example, P. Glafkides'"Shimmy
E Physiq Photographic (Chimie et Physiq
ue Photograhique) ”(Paul Montel
l) Published in 1967), G.F.Duffin (GFDu
ffin) “Photographic Emulsion Chemistry (The Focal Press) (1966),
VLZelikman et al, “Making and Coating Photographi
c Emulsion ”(The Focal Press)
Press) 1964) and the like. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 20% or less, particularly preferably 15%.
It is the following. Here, the coefficient of variation is defined as the following (formula 1).

[0077]

[Equation 1]

The average grain size of the grains in the monodisperse silver halide emulsion is 0.5 μm or less, particularly preferably 0.
It is 1 μm to 0.4 μm. As a method for reacting the water-soluble silver salt (silver nitrate aqueous solution) with the water-soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. Tetrasubstituted thiourea compounds are more preferred, and JP-A-53-82408 and JP-A-55-77 are preferred.
No. 737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The control double jet method and the grain forming method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool. Monodisperse emulsion is a cube,
It preferably has a regular crystal form such as an octahedron or a tetradecahedron, and a cube is particularly preferable. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Even if a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof are allowed to coexist in the silver halide emulsion used in the present invention in the process of formation or physical ripening of silver halide grains. Good.

In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is silver 1
It is an emulsion produced in the presence of 10 ⁻⁸ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol. In the above, it is desirable to add the above-mentioned amount of iridium salt before the physical ripening in the production process of the silver halide emulsion, especially at the time of grain formation. The iridium salt used here is a water-soluble iridium salt or iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), hexachloroiridium (I
V) potassium, ammonium hexachloroiridium (III), and the like.

In order to obtain ultrahigh contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, the conventional infectious developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, the silver halide light-sensitive material of the present invention has a sulfite ion as a preservative of 0.
A developer containing 15 mol / liter or more and having a pH of 9.6 to 11.0 can sufficiently obtain a super-high contrast negative image. There is no particular limitation on the developing agent used in the developer used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
There are 5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable. 1-phenyl-3-used in the present invention
As a developing agent for pyrazolidone or its derivative, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1- Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
Examples include -p-aminophenyl-4,4-dimethyl-3-pyrazolidone and 1-p-tolyl-4,4-dimethyl-3-pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. Also, dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p
-When the combination with amino-phenols is used, the former is 0.05 mol / liter to 0.5 mol / liter,
It is preferable to use the latter in an amount of 0.06 mol / liter or less.

As the preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably 0.15 mol / liter or more, and particularly preferably 0.3 mol / liter or more. The upper limit is 2.
It is preferably up to 5 mol / liter. The alkaline agent used for setting the pH includes a pH adjusting agent and a buffering agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate. The pH of the developer is set between 9.6 and 11.0. As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, toluethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 5-
An indazole compound such as nitroindazole, an antifoggant such as 5-methylbenztriazole or a benztriazole compound such as a benztriazole compound or a black pepper inhibitor: may be contained, and if necessary, a toning agent and a surfactant. , Antifoaming agent, water softener, hardener, JP-A-56-10
The amino compound described in No. 6244 may be included.

The compounds described in JP-A-56-24347 can be used in the developer of the present invention as a silver stain preventing agent. Japanese Patent Application No. Sho 6 as a dissolution aid added to the developer.
The compounds described in 0-109,743 can be used. Further, as a pH buffering agent used in a developing solution, Japanese Patent Laid-Open No.
No. 0-93,433 or Japanese Patent Application No.
The compounds described in -28708 can be used.
As the fixing agent, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, light vane, etc.) as a hardening agent. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g-Al / liter. Furthermore, a trivalent iron compound can be used as a complex with ethylenediaminetetraacetic acid as an oxidizing agent. The developing treatment temperature is usually selected from 18 ° C to 50 ° C, more preferably 25 ° C to 43 ° C.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item This section 1) Nucleation accelerator Japanese Unexamined Patent Publication (Kokai) No. 2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) ) And compound examples II-1 to II-22, and the compounds described in JP-A-1-179939. 2) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Spectral sensitizing dyes described in column 20, line 20 and JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and Japanese Patent Application Nos. 3-189532 and 3-411064. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, left lower column, line 13 to 4 Lower right column, line 18 4) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; further JP-A 1-237538 Thiosulfinic acid compounds described in the public notice. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 7) Matting agent, slipping agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 8) Hardeners, JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 9) Dyes: Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compound A compound represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 in JP-A No. 3-174143). R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 13) Monomethine compound Compounds of the general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 14) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to genus, page 12, lower left column, and EP452772A.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[0085]

【Example】

Example 1 (Comparative emulsion preparation) Emulsion A: 0.37 M silver nitrate aqueous solution and (NH ₄ ) ₃ RhCl ₆ and 2 corresponding to 1 × 10 ⁻⁷ mol per mol of silver.
0.1M including K ₃ IrCl ₆ corresponding to × 10 ^-7 mol
Halogen salt solution containing potassium bromide and 0.22M sodium chloride of 0.08M sodium chloride, 1,
2 containing 3-dimethyl-2-imidazolidinethione
% Gelatin aqueous solution with stirring at 38 ° C. for 12 minutes by the double jet method to give an average particle size of 0.20.
Nucleation was performed by obtaining silver chlorobromide grains having a particle size of 70 μm and a silver chloride content of 70 mol%. Then, similarly, a 0.63 M silver nitrate aqueous solution, 0.19 M potassium bromide, and 0.4
An aqueous solution of halogen salt containing 6M sodium chloride was added by the double jet method over 20 minutes. Then 1
A KI solution of × 10 ^-3 mol was added for conversion, followed by washing with water by a flocculation method according to a conventional method, 40 g of gelatin was added to adjust pH to 6.5 and pAg to 7.5, and further 5 mg of sodium thiosulfate per mol of silver. Then, 8 mg of chloroauric acid was added, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.27 μ0 and a silver chloride content of 70 mol%.
(Coefficient of variation 10%).

(Preparation of Emulsion of the Present Invention) Emulsion B: Grain formation, washing with water and addition of gelatin in the same manner as in Emulsion A, pH 5.9 and pAg 7.3 were adjusted, and 5 mg of chloroauric acid and 1 mol of silver per mol of silver were prepared. Compound (I-4) (5 mg) was added as a selenium sensitizer of the invention, and the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization, and then a stabilizer and a preservative were added as in Emulsion A. (Variation coefficient 10%)

Emulsion C: Grain formation, washing with water and addition of gelatin were carried out in exactly the same manner as in Emulsion A, pH was adjusted to 5.9 and pAg was adjusted to 7.3, and further 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid and chloride were added per mol of silver. Auric acid 5m
g, and the compound (IV-3 as the tellurium sensitizer of the present invention.
9) 5 mg was added, and after chemically sensitizing by heating at 60 ° C. for 45 minutes, a stabilizer and a preservative were added as in Emulsion A.
(Variation coefficient 10%)

Emulsion D: Just as in Emulsion A, grain formation, washing with water and addition of gelatin were performed, pH was adjusted to 5.9 and pAg was adjusted to 7.3, and 5 mg of chloroauric acid, 3 mg of sodium thiosulfate and 1 mol of silver were added. Compound (I-4) (2.0 mg) was added as a selenium sensitizer, the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization, and then a stabilizer and a preservative were added as in Emulsion A. (Variation coefficient 10%)

Emulsion E: Grain formation, washing with water, addition of gelatin, adjustment to pH 5.9 and pAg 7.3 in exactly the same manner as in Emulsion A, and further 5 mg of chloroauric acid, 3 mg of sodium thiosulfate and 1 mg of silver per mol of silver. Compound (IV-39) (2.0 mg) was added as a tellurium sensitizer, the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization, and then a stabilizer and a preservative were added as in Emulsion A. (Variation coefficient 10%)

(Preparation of Comparative Emulsion) Emulsion F: 1 mol of silver nitrate aqueous solution in the presence of 1,3-dimethyl-2-imidazolidinethione salt in a gelatin aqueous solution kept at 50 ° C. and 1.2 × 10 ⁻ per mol of silver. ⁷ moles of K ₂
An aqueous solution of potassium iodide containing Ru (NO) Cl ₆ and an aqueous solution of potassium bromide were added simultaneously for 60 minutes, and the pAg during that period was adjusted to 7.
A cubic monodisperse emulsion having an average particle size of 0.25 μm and an average silver iodide content of 1 mol% was prepared by keeping the ratio at 8, desalting was performed by the flocculation method, and 40 g of gelatin was added to pH.
= 6.0 pAg = 8.5, sodium thiosulfate 5 mg and chloroauric acid 6 mg were added, and the mixture was heated at 60 ° C. for 60 minutes to be chemically sensitized, and 4-hydroxy-6-methyl was used as a stabilizer. -1,3,3a, 7-Tetrazaindene 1
50 mg was added. (Coefficient of variation 9%)

(Preparation of Emulsion of the Present Invention) Emulsion G: Grain formation, washing with water and addition of gelatin in the same manner as Emulsion F, pH 5.5 and pAg 7.3 were adjusted, and further 6 mg of chloroauric acid per 1 mol of silver and thio 3 mg of sodium sulfate and 2 mg of compound (I-4) as a selenium sensitizer of the present invention
Is added and heated at 60 ° C. for 45 minutes for chemical sensitization,
Stabilizers and preservatives were added as in Emulsion F. (Variation coefficient 10%)

Emulsion H: Grain formation, washing with water, addition of gelatin, adjustment to pH 5.5 and pAg 7.3 in exactly the same manner as in Emulsion F, and further 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid per 1 mol of silver, chloride Auric acid 6m
g, 3 mg of sodium thiosulfate and 2 mg of compound (IV-39) as a tellurium sensitizer of the present invention were added, and the mixture was stirred at 60 ° C. for 45 minutes.
After heating for a minute for chemical sensitization, a stabilizer and a preservative were added in the same manner as in Emulsion F. (Variation coefficient 10%)

Table 1 shows the halogen compositions and the chemical sensitization methods of Emulsions A to H thus obtained.

[0094]

[Table 1]

(Preparation of Coating Samples) As shown in Table 2, hydrazine derivatives were added to these emulsions. The following compounds were used as comparative compounds of the hydrazine derivative of the present invention.

[0096]

[Chemical 48]

Further, a compound of the following structural formula (S) was added to silver 1
3.4 × 10 ⁻⁴ mol, 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 5 × 10 ⁻⁴ mol of a short-wave cyanine dye represented by the following structural formula (a), and (b). Water-soluble latex represented by (200 mg /
m ² ), polyethyl acrylate dispersion (200 mg /
m ² ), and 1,3-divinylsulfonyl-2-propanol (200 mg / m ² ) as a hardener.

[0098]

[Chemical 49]

An amine compound (20 mg / m ² ) represented by the following structural formula was added as a nucleation accelerator.

[0100]

[Chemical 50]

Gelatin as protective layer 1.0 g / m²,particle
Amorphous SiO about size 3.5μ ₂Matting agent 40mg /
m², Methanol silica 0.1g / m², Polyacrylic
100 mg / m², Hydroquinone 200mg / m², Silico
As the coating oil and coating aid, the flux represented by the following structural formula
Fluorine surfactant and sodium dodecylbenzene sulfonate
The layer containing the coating was coated simultaneously with the emulsion layer.

[0102]

[Chemical 51]

The back layer and the back layer protective layer were coated by the following formulation. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Gelatin hardener

[0104]

[Chemical 52]

Dye Mixture of Dyes [a], [b], and [c]

[0106]

[Chemical 53]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μ) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² Dodecylbenzenesulfonic acid sodium salt 15 mg / m ² sodium acetate 40 mg / m ²

(Evaluation of Photographic Properties) These samples were tested for 32
After exposing through optical wedges or optical wedges and contact screens (Fujifilm, 150L chain dot type) with tungsten light of 00 ° K, 38 with the next developer 1.
It was developed at 30 ° C. for 30 seconds, fixed, washed with water and dried. As the fixing solution, GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used.

Developer 1 Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Ethylenediaminetetraacetic acid disodium 1.0 Potassium bromide 10.0 5-Methylbenzo Triazole 0.4 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 3- (5-Mercaptotetrazole) benzene sodium sulfonate 0.2 Sodium toluene sulfonate 8.0 Water is added to 1 liter pH 10.6 Match

Further, the same developing treatment was carried out using a developer 2 in which a potassium hydroxide solution was added to the developer 1 to adjust the pH to 10.8 and a developer 3 in which acetic acid was added to the developer 1 to adjust the pH to 10.4. went.

The photographic characteristics obtained are shown in Table 2. Where G
Is defined by Equation 2.

[0112]

[Equation 2]

S _1.5 , which represents the sensitivity, is the logarithmic value of the exposure amount that gives a density of 1.5.

As shown in Table 2, the samples of the present invention have p
It can be seen that even when processed with a developing solution of less than H11, a high-contrast image is provided, and the change in photographic sensitivity with respect to the pH change of the developing solution is small.

[0115]

[Table 2]

Example 2 The same procedure as in Example 1 was carried out except that the coated sample shown in Table 1 was developed with the following developing solution 4.

Developer 4 Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Ethylenediaminetetraacetic acid disodium 1.0 Potassium bromide 10.0 5-Methylbenzo Triazole 0.4 5-Mercaptobenzimidazole-5-sulphonic acid 0.3 3- (5-Mercaptotetrazole) benzene sodium sulfonate 0.2 Sodium toluene sulfonate 8.0 N-Dimethyl-n-hexanolamine 5. 0 Add water to adjust to 1 liter pH 10.2.

Even when the sample of the present invention was treated with the developer whose pH was further lowered by adding the amine compound to the developer, the sample of the present invention gave a high contrast image as in Example 1 and the pH fluctuation of the developer. The change in photographic sensitivity to is small.

Claims (3)

[Claims] 1. Halogenation of at least one layer on a support
In a silver halide photographic light-sensitive material having a silver emulsion layer,
Compounds represented by the following general formulas (I) to (V) are added to the emulsion layer.
Halogenation chemically sensitized by at least one
It contains silver and is less than the emulsion layer or other hydrophilic colloid layer.
At least one layer of hydrazine represented by the following general formula (VI)
Photographic image of silver halide characterized by containing a derivative
Light material. General formula (I)Where Z₁And Z₂Are the same or different
Also, an alkyl group, an alkenyl group, an aralkyl group, an
Reel group, heterocyclic group, -NR₁(R₂), -OR₃Also
Is -SR_FourRepresents R₁, R₂, R₃And R_FourHaso
They may be the same or different, and may be an alkyl group or ara.
It represents a alkyl group, an aryl group or a heterocyclic group. Archi
Group, aralkyl group, aryl group or heterocyclic group
Is Z₁An example similar to is given. However, R₁And R
₂May be a hydrogen atom or an acyl group. General formula (I
I) [Chemical 2]Where Z₃, Z_FourAnd Z_FiveAre the same or different
Optionally, an aliphatic group, an aromatic group, a heterocyclic group, -OR
₇, -NR₈(R₉), -SR_Ten, -SeR₁₁, X, water
Represents an elementary atom. R₇, R_TenAnd R₁₁Is an aliphatic group
Represents an aromatic group, a heterocyclic group, a hydrogen atom or a cation,
R₈And R₉Is an aliphatic group, aromatic group, heterocyclic group or
Represents a hydrogen atom, and X represents a halogen atom. General formula
(III) [Chemical Formula 3]In the above general formula (III), R₁₁, R₁₂And R₁₃Is aliphatic
Group, aromatic group, heterocyclic group, OR₁₄, NR₁₅(R₁₆), S
R₁₇, OSiR₁₈(R₁₉) (R₂₀), X or hydrogen atom
Represents R₁₄And R₁₇Is an aliphatic group, aromatic group, or hetero group
Represents a ring group, a hydrogen atom or a cation, and R₁₅And R
₁₆Represents an aliphatic group, aromatic group, heterocyclic group or hydrogen atom.
I, R₁₈, R₁₉And R₂₀Represents an aliphatic group, and X represents
Represents a halogen atom. General formula (IV):In the above general formula (IV), R_{twenty one}Is an aliphatic group, aromatic group, or heterocycle
Group or -NR_{twenty three}(R _{twenty four}), And R_{twenty two}Is -NR
_{twenty five}(R₂₆), -N (R₂₇) N (R₂₈) R₂₉Or -OR
₃₀Represents R_{twenty three}, R_{twenty four}, R_{twenty five}, R₂₆, R₂₇, R₂₈, R
₂₉And R₃₀Is hydrogen atom, aliphatic group, aromatic group, heterocycle
Represents a group or an acyl group. Where R_{twenty one}And R _{twenty five}, R_{twenty one}When
R₂₇, R_{twenty one}And R₂₈, R_{twenty one}And R₃₀, R_{twenty three}And R_{twenty five}, R_{twenty three}And R
₂₇, R_{twenty three}And R ₂₈And R_{twenty three}And R₃₀Combine to form a ring
May be. General formula (V)In the above general formula (V), R₃₁And R₃₂Are the same
May be different, aliphatic group, aromatic group, heterocyclic group,
-(C = Y ')-R₃₃Represents R₃₃Is hydrogen atom, fat
Group, aromatic group, heterocyclic group, NR₃₄(R₃₅), OR₃₆Well
Or SR₃₇And Y'is an oxygen atom, a sulfur atom or
NR₃₈Represents R₃₄, R₃₅, R₃₆, R ₃₇And R₃₈Is
Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group
And n represents 1 or 2. General formula (VI)R¹Represents an aliphatic group, an aromatic group or a heterocyclic group,
It may be replaced. G is a -CO- group, -SO₂-Base,
-SO- group, -COCO- group, thiocarbonyl group, imine
Nomethylene group or -P (O) (R^Four) -Represents a group,
R²Is an electron having at least one carbon atom substituted with G
Represents a substituted alkyl group substituted with an attractive group. R^FourIs water
Elementary atoms, aliphatic groups, aromatic groups, alkoxy groups, aryl
Represents an oxy group or an amino group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide in the emulsion layer is a silver halide having a silver chloride content of 50 mol% or more. 3. A photographic image forming method, which comprises developing the silver halide photographic light-sensitive material according to claim 1 or 2 with a developer having a pH of 9.0 or more and less than 11.0.