JPS63121838A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain such photographic characteristics as high contrast and negative gradation by forming a photosensitive silver halide emulsion layer on a support and incorporating a specified compd. into the emulsion layer or other constituent layer. CONSTITUTION:A photographic silver halide emulsion layer is formed on a support and a compd. represented by the formula is incorporated into the emulsion layer or other hydrophilic colloidal layer to obtain a silver halide photographic sensitive material. In the formula, Ar is aryl, B is formyl, acyl, alkylsulfonyl, arylsulfonyl or the like, and both of R0 and R00 are H or one of them is H and the other is alkylsulfonyl, arylsulfonyl or acyl. The amt. of the compd. added is 1X10<-5>-5X10<-2>mol, preferably 2X10<-5>-1X10<-2>mol per 1mol silver halide and the amt. is properly regulated according to the properties of the silver halide emulsion combined with the compd. Thus, such photographic characteristics as higher sensitivity and high gamma are obtd.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides extremely sharp negative images, highly sensitive negative images, and good halftone image quality... silver halide photographic materials, or direct positive photographic images. The present invention relates to a silver halide photographic light-sensitive material which forms a silver halide, and particularly relates to a photographic light-sensitive material containing a novel compound as a nucleating agent for silver halide.

(Prior Art) Adding hydrazine compounds to silver halide photographic emulsions and development sources is prohibited in the United States! Patent No. 3,730,7.27 (developer containing a combination of ascorbic acid and hydrazine) 3. Ko, 27, 31
No. 2 (using hydrazine as an auxiliary developer to directly obtain a positive color image) No. 3, 3rt, rJi (using β-mono-mono-aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials)
Contains phenylhydrazide), &/Ri, Ri No. 73, and The Theory of Photo by Mees.
It is said in oggraphicProcess 3rd edition (1997), page 21.

Among these, in particular, US Patent No. J, 4A/R.

No. 73 discloses that a high-contrast negative image can be obtained by adding a hydrazine compound.

The patent specification states that by adding a hydrazine compound to a silver chlorobromide emulsion and developing it with a high pH developer such as lco, t, extremely high-contrast photographic characteristics with a gamma (r) exceeding 10 f can be obtained. is listed. However, the pH is 7
A strong alkaline developer close to 3 is unstable and susceptible to air oxidation, and cannot withstand long-term storage or use.

Ultra-high contrast photographic characteristics with gamma exceeding IO are negative images,
Either a positive image or a halftone image (
It is extremely useful for photographic reproduction of continuous tone images or reproduction of line drawings. Conventionally, for this purpose, a silver chlorobromide photographic emulsion with a silver chloride content exceeding 30 mol%, preferably 73 mol%, is used, and the effective concentration of sulfite ions is kept extremely low (usually 0, 73 mol%).
A method of developing with a hydroquinone developer with a concentration of 1 mol/l or less was generally used. However, in this method, since the concentration of sulfite ions in the developer is low, the developer is extremely unstable and cannot be stored for more than 3 days.

Furthermore, since all of these methods require the use of silver chlorobromide emulsions with a relatively high silver chloride content, high sensitivity cannot be obtained. Therefore, there has been a strong desire to obtain ultrahigh contrast photographic characteristics useful for reproducing halftone images and line drawings by using a highly sensitive emulsion and a stable developer.

The present inventors have disclosed US Pat.
/lr, No. 977, 4t, 2413.73? No., same≠
, Co. 7 Co., J/4A No., Co. Mu, 3 Co. J., and 1r No. 13, etc., disclosed silver halide photographic emulsions that use stable developers and provide extremely high-contrast negative photographic properties. It has been found that the aclhydrazine compounds used have several drawbacks.

In other words, it is known that these conventional hydrazines generate nitrogen gas during the development process, and these gases collect in the film and form bubbles, damaging the photographic image. If it leaks into the processing solution, it may have an adverse effect on other photographic materials.

In addition, when these conventional hydrazines are required in large quantities for sensitization and high contrast, or when particularly high sensitivity is required in terms of the performance of the photosensitive material, other sensitization techniques (such as chemical sensitization) may be used. U.S. Patent Da, Ko 7 Ko, t.

When used in combination with the addition of compounds that promote a feeling of majesty, such as those described in No., Dohiro, 2≠/, /Jμ, etc., sensitization and enhancement over time may generally occur during storage. be.

Therefore, there has been a desire for a compound that can reduce the generation of bubbles and leakage into the developer, has no problems with stability over time, and can provide extremely high-contrast photographic properties with the addition of a very small amount. .

Also, U.S. Patent No. 3TJ, IOR No.

, 2t, Tako No. 2 describes that extremely sharp negative gradation photographic properties can be obtained by using hydrazines having substituents that are easily adsorbed to silver halide grains. Among the hydrazine compounds having adsorbent groups, those specifically mentioned in the above-mentioned known examples have a problem of causing desensitization over time during storage. Therefore, it was necessary to select a compound that would not cause such problems.

On the other hand, there are various direct positive photography methods, including a method in which silver halide grains that have been fogged in advance are exposed to light in the presence of a desensitizer and then developed, and a method in which photosensitive nuclei are formed inside the silver halide grains. The most useful method is to develop a silver halide emulsion in the presence of a nucleating agent after exposing it to light. The present invention relates to the latter.

Silver halide emulsions that mainly contain photosensitive nuclei inside silver halide grains and in which latent images are mainly formed inside the grains are called internal latent image type silver halide emulsions. They are distinguished from silver halide grains that form latent images.

Internal latent image type silver halide photographic emulsions A method for obtaining direct positive images by surface development in the presence of a nucleating agent and photographic emulsions or light-sensitive materials used in such a method are described, for example, in U.S. Pat. ri No. 33, same co, ≠ 27. ? 73
No., same, μ27゜17 No., same, 2. jl'r, 91
2nd issue, same, 3rd issue, 3rd issue, lto issue, same 2, 1.7! , 37
No. r, same 3゜co27. j! , No. 2, 3, 3/7, 3.
2.2, British Patent/, oii, ot, No. Z, same/, /
j/, 3z No. 3, same/, 269. A4tO, same, 2,
0/I.

3! P/, special public Akihiro 3-ta 2, ≠QJ, 4t,
L? -38', /Otsu≠No., JP-A-Shojt3-/l, Bu23
No., same/37. /No.33, same! ≠-37,732, same! ll-4tO, Otsu, No. 25', same j11--711.
! IT issue, same! Goo 7μ, 7 Kota issue, same! j-1, 2,
.

It is known for its works such as No. 33 and 3-auto O1 and aO.

In the above-mentioned method for obtaining direct positive image gold, the nucleating agent may be added to the developer, but it is also adsorbed to the surface of the silver halide grains by adding it to the photographic emulsion layer of the light-sensitive material or other suitable material. Sometimes better inversion characteristics can be obtained.

The nucleating agent used in the above method for obtaining a direct positive image includes U.S. Pat.
hydrazides and hydrazine-based compounds described in U.S. Patent J, 227.432; t/ma,
2/! No. 3,7/ri, Nuta≠ No. 3,7341,
73♂ issue, same group, 0 tag.

T! 3rd issue and the same gu, //,! r,/, No. 2.2, British Patent/, No. 213.231, JP-A No. 2-3412A
No. and same! 2-A? Heterocyclic primary salt compound described in &/3, U.S. Patent No. 030.224, μ, 03/
, /Core issue, Dohiro, /3F, 3♂ issue 7, Dogu, 2μj
, No. 037, same≠, Ko3! , 3// issue and same ≠, , 2
7j, No. 34μ, British Patent, 2,072. thiourea-bonded acylphenylhydrazine compounds described in US Pat. No. 207, a compound having a heterocyclic thioamide as an adsorption group, British Patent Co., Ltd.

0//, a phenylacylhydrazine compound having a mercapto group on a polycyclic ring group as an adsorption type described in 3-7B, and has a nucleating effect as described in US Pat. No. 3,71♂, 4t70! A sensitizing dye with a compound in its molecular structure, JP-A-Sho! Tar, 200. ．． No. 230, 3 ter 2/2, 1.2
r issue, J Turco lλ, tλ r issue, Re5earch
Disclosure magazine No. +23310 (/rit3/
The hydrazinated compounds described in 1999 are known.

However, all of these compounds have insufficient activity as nucleating agents, and those with high activity have insufficient storage stability, or lose their activity after being added to the emulsion and before coating. There were drawbacks such as fluctuations in the amount of oxidation, and deterioration of film quality when added in even larger amounts.

(Objective of the Invention) Accordingly, the seventh object of the present invention is to provide a silver halide photographic light-sensitive material that can obtain photographic characteristics of an extremely sharp negative gradation with a gamma exceeding IO using a stable developer. It is to be.

A second object of the present invention is to provide a negative-working silver halide photograph containing acurvidrazine, which can provide all of the desired photographic characteristics of extremely high contrast negative gradation with a small amount of addition without adversely affecting photographic performance. Our goal is to provide all kinds of photosensitive materials.

A third object of the present invention is to provide a direct positive type silver halide photographic light-sensitive material containing a highly active nucleating agent.

The purpose of the present invention is to contain all hydrazines which are easy to synthesize, have small activity fluctuations during the production of sensitive materials, have excellent storage stability, and do not cause deterioration of film quality when added in large amounts, and which have stable stability over time. The objective is to provide good silver halide photographic materials.

-I O- (Structure of the Invention) A feature of the present invention is that in a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer, the photographic emulsion layer or at least seven other hydrophilic colloid layers This was achieved by containing at least one compound represented by the following general formula (1).

General formula (I) (wherein, Ar represents an aryl group, B represents a formyl group,
Represents an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group or a heterocyclic group; Roo are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group,
Represents an arylsulfonyl group or an acyl group. “0%
The alkylsulfonyl group, arylsulfonyl group, and acyl group represented by "00" may further have a substituent. However, B, Ro.

and the nitrogen atoms to which they are bonded may form a hydrazone partial structure -N=C,2.

Furthermore, Ar has at least 7 or more sulfonamide groups or sulfamoyl groups as a substituent.

Here, the sulfonamide group or sulfamoyl group is -N
ZSO2 or -802NZ- (Z is a hydrogen atom, a linear, branched, cyclic substituted or unsubstituted alkyl group having up to 30 carbon atoms, or a substituted or unsubstituted group having up to 30 carbon atoms) (for example, a phenyl group) or a naphthyl group.

What is the total number of Ay and B carbon atoms? / That's all. ) General formula (
Among the compounds represented by 1), those represented by the following general formula (It) or (In) are preferred.

General formula (It) General formula (III) (wherein, Ar represents a substituted phenylene group or substituted naphthylene group; A2 represents a phenyl group, naphthyl group, substituted phenyl group, or substituted naphthyl group; X is an aliphatic residue ,
Represents an aromatic residue or a heterocyclic residue; Ll and B
3 represents an n+7 valent organic group; B2 is -CO-1-8
Represents O-1 or -SO□-, and 5m is O or 1 to 3
represents an integer of , n represents an integer of / to 3; B1
"O%fLOO represents the same group as defined in the above general formula (I).

Further, X has at least one sulfonamide group (-NZ802-7Z is a group as defined above) or a sulfamoyl group (-802NZi2 is a group as defined above) as a substituent, and Z is a hydrogen atom. preferable.

Furthermore, the total number of carbon atoms in X, Ll, A, , B is 21 or more.

Among the groups represented by L□, preferred are those represented by the general formula (I
V) is a group having a carbon atom number of μθ or less.

General formula (IV) (wherein La is a group capable of bonding with X in general formula (If), a substituted or unsubstituted alkylene group having t to 30 carbon atoms, a substituted or Unsubstituted phenylene group or naphthylene group, number of carbon atoms 7
~30 substituted or unsubstituted aralkylene groups, or
Substituted or unsubstituted 3- or z-membered heterocyclic tetravalent group having carbon atoms/~30 (heteroatoms include N, 0.
Contains at least 7 of the 8 -l groups. ); Lb is 10-1-CONR-1-NRCO-1-8ONR-1-
NR8O□-1-OCO-1-COO-1-S-1-N
几-1-CO-1-SO-1-SO2-1-0COO-
1-N'fLCONfL/-1-NRCOO-1-OC
ONR-1 or -Na2O2NI(,/-, where R and R/ are independently a hydrogen atom, a linear, branched, or cyclic substituted or unsubstituted alkyl group having 30 or less carbon atoms, p represents 1 or 2, and qlr represents 0. / and λ, q%r cannot be O at the same time.

Among the groups represented by Ll, particularly preferred are those having 7 to aOO carbon atoms, and Lb is -NHCON
It represents H-.

Preferred substituents on A1 include, in addition to L□, halogen atoms, alkoxy groups having 30 or less carbon atoms (e.g., methoxy group, 7 λ-hydroxyethoxy groups, 7 2-methoxyethoxy groups, hexadecyloxy group, etc.). ), aryloxy groups (e.g. phenoxy group, goomethylphenoxy group, λ, gauge 1 ert-pentylphenoquine group, etc.) with 30 or less carbon atoms, 2 with carbon atoms 3θ or less
or a tertiary amine group (e.g. diethylamino group, di(2-
hydroxyethyl)amine group, N-methyl-N-octylamino group, morpholino group, N-methyl-N-phenylamino group, etc.), linear, branched, or cyclic alkyl groups having 30 or less carbon atoms (e.g. methyl group, tert-pentyl group, cyclohexyl group, hexadecyl group, etc.) and substituted alkyl i (Example 1-j cohydroquinethyl group, benzyl group, (2-hydroxyphenyl)methyl group, 3-acetylprobyl group, etc.) , a group represented by -CORI (
However, R represents a group synonymous with the above-mentioned alkyl group, alkoxy group, aryloxy group, or amine group), -SO□R
The group represented by 2 (wherein R2 represents a group having the same meaning as the above-mentioned alkyl group or amine group) is a hydroxy group.

BJo1 in general formulas (1), (II), and (In). . More specifically, it refers to a hydrogen atom, an alkylsulfonyl group having less than 0 carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenyl substituted such that the sum of Hahamet's substituent constants is -0.3 or more) Sulfonyl, acyl group having 30 or less carbon atoms (preferably a benzoyl group, or a sum of Hammett's substituent constants 10,
! A benzoyl group substituted as above or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (substituents include, for example, halogen, ether group, sulfonamide group, carbonamide group, hydroxyl group, carboxyl group) and sulfonic acid groups.)) 几. , 几. . A hydrogen atom is most preferred.

B in general formulas (n) and (III) is specifically a formyl group, an acyl group (acetyl group, propionyl group,
Trifluoroacetyl group, chloroacetyl group, benzoyl group, μm chlorobenzoyl group, bilboyl group, methoxalyl group, methyloxamoyl group, etc.), alkylsulfonyl group (methanesulfonyl group, cochloroethanesulfonyl group, etc.), arylsulfonyl group (benzene sulfonyl group, etc.), alkylsulfinyl group (methanesulfinyl group, etc.), 71J-Rusulfinyl group (benzenesulfinyl group, etc.), carbamoyl group (methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (dimethylsulfamoyl group, etc.) ), alkoxycarbonyl group (methoxycarbonyl group, methoxyethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxy7carbonyl group, etc.), sulfinamoyl group (methylsulfinamoyl group, etc.), alkoxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, etc.), thioacyl group (methylthiocarbonyl group, etc.), thiocarbamoyl group (methylthiocarbamoyl group, etc.), or haheterocyclic group (pyridine ring, etc.).

Particularly preferred as B is a formyl group or an acyl group, and the acyl group is aliphatic, aromatic, or heterocyclic, and may have a substituent, and the number of carbon atoms is Preferably, the number is between 30 and 30. Examples of the substituent on the anru group include a hydroxy group, an alkoxy group, a sulfonamide group, a carbonamide group, a ureido group, a hydroxyphenyl group, and an aryloxy group.

As B, formyl is most preferred.

R80 in the general formula (II) and (in) together with B and the nitrogen atom to which these are bonded together with R80 in the general formula (I The partial structure -〇-N-@ may be formed.

R In the above, R represents an alkyl group, a ring group, or a heterocyclic group. Rt't represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group 't-.

Examples of the hydrazone formed by B and L2 include acetone hydrazone, benzaldehyde hydrazone, and 0-hydroxybenzaldehyde hydrazone.

Among the groups represented by L3, preferred are groups represented by the following general formula (V) having a carbon atom number of IO to μO.

General formula (V) (L a f L b 1tL a q□ (wherein, La
S Lb represents a group as defined in the general formula <W), l is O or to, 1□ is 0 or /, 13 is / or -
represents. ) Among the groups represented by L3, particularly preferable ones have carbon atoms of IO to ≠0, and the group Lb is -
CONH-1-8O2N)i-1-NHCONH-.

Among the groups represented by L2, a particularly preferred group is -CO-
It is.

m is preferably O or /Xn is preferably /or.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited only to these.

Ichiko / − ＼ 呵
呵-+2 +2- O=○ Senkou 1vl Ball
Kenpaku handle
Mouse = 〆 jealousy
Sail”I
'i 111 Kokuken Goe
SI'II'I) Ichikotar'i f+1
jealousy
Next, typical methods for synthesizing the compound of the above general formula CI) will be explained with reference to synthetic examples.

The compound of the present invention can be synthesized with full reference to, for example, JP-A-Sho JJ-J7R, US Pat.

Synthesis example 1. Synthesis of compound (1) Synthesis of co[≠-(J-(j-nitrophenyl)ureido]phenyl]-/-formylhydrazine 4-(≠-aminophenyl)-l-formylhydrazine O1≠1 with acetonitrile Next 00ttdl and N, N-
Add and dissolve 200 ytlf of dimethylformamide, -
, t'C. Metanitrophenyl isocyanate Δj,tt was dissolved in acetonitrile λ00 and added dropwise. During this time, the liquid was hot! The mixture was stirred while cooling so as not to exceed 'Ci. Further, acetonitrile JOOrptl was added, and the mixture was stirred at o'C for 3 hours, and the resulting crystals tt were collected and washed with acetonitrile and then methanol. The obtained crystals were dissolved in 1 liter of N,N-dimethylformamide, filtered through a non-bath section t1'', and methanol was added to the F solution.
In addition, crystals were grown by cooling. The crystals were separated and washed with acetonitrile and then methanol. Yield yr, ty (2) Co[≠-[3-(j-aminophenyl)ureido]phenyl]-/-formylhydrazine synthesis iron powder/ j r r, ammonium chloride! ? , dioxane λ, μtL, and water ♂♂3 were mixed and heated and stirred on a steam bath. The nitro compound Wrff obtained in (1) was added to this, and the mixture was further refluxed for a0 minutes. Next, all insoluble matter was filtered, and after concentrating Solution F under reduced pressure, water was added. The resulting nine crystals were separated and washed with acetonitrile. Yield: 7.1 (3) Synthesis of compound / Under nitrogen atmosphere, the amine compound obtained in (2) J, /? t
-N,N-dimethylformamidota0rItI! Then, acetonitrile, O'tnl and N-methylmorpholine io,at were added and the mixture was cooled to -z'C.

To this, Hiro (9 μm G-tert-Bentyl 3
μ-phenoxy)-/-butylsulfonyl chloride≠2.
72 was added dropwise. During this time, the mixture was cooled and stirred so that the liquid temperature did not exceed 0.0 cw. After stirring at Hikitsuzu@o'c for 7 hours,
The organic layer was collected on the organic layer. After concentrating the organic layer, it was separated and purified by silica gel column chromatography. l = /
/ / 0). Yield 3kg, melting point 13ter/4tloC (decomposition) Synthesis Example 2. Synthesis of compound 3
.

Under nitrogen atmosphere, 3-(3-(co,≠-di-tert-bentylphenoxy)propylsulfamoyl)aniline j fIt=N, N-dimethylacetamide 10 m
1, then add pyridine 2,01, -z'c
It was cooled to Phenyl chloroformate, /f was added dropwise to this. During this time, the liquid was cooled and stirred so that the temperature did not exceed O'CVI. In addition, further co(≠-aminophenyl)-/-formylhydrazine, Ottl
A solution of -/0g dissolved in N,N-dimethylacetamide was added dropwise, and the mixture was heated and stirred at 0c for 3 hours. 30
After cooling to 0 C, it was poured into a mixture of 100 stl of salt e1 and 100 ml of ethyl acetate. The organic layer was separated and recrystallized from a mixed solvent of concentrated ethyl acetate and n-hexane (vol/vol=J/J).

Yield J, tf, melting point 100-1017'C (decomposition) When incorporating the compound of the present invention into the hydrophilic colloid layer, the compound of the present invention is dissolved in water or a water-miscible organic solvent (if necessary). It may be added to a hydrophilic colloid solution (for example, a silver halide emulsion, an aqueous gelatin solution, etc.) (it may be added to a hydrophilic colloid solution (for example, a silver halide emulsion, an aqueous gelatin solution, etc.) (if necessary, it may be dissolved by adding an alkali hydroxide or a tertiary amine to form a salt). (The pH may be adjusted by adding acid or alkali.)

The compounds of the present invention may be used alone or in combination of two or more. The amount of the compound of the present invention added is silver halide/-r:
: Lua fc? )/x10-5 to Jx10-2 mol, preferably 1
L, <u, zXlo-5 mol to txlo-'' mol, and an appropriate value can be selected depending on the properties of the silver halide emulsion to be combined.

The compound represented by the general formula (1) of the present invention can form a high contrast negative image by using it in combination with a negative emulsion. On the other hand, it can also be used in combination with an internal latent image type silver halide emulsion. The compound represented by the general formula (1) of the present invention is preferably used in combination with a negative emulsion to form a negative image with high contrast.

When used to form a negative image with high contrast, the average grain size of the silver halide used is preferably fine (for example, 7 μm or less), particularly preferably 0.2 μm or less. There is basically no limit to the particle size distribution, but
Monodispersity is preferred. Monodisperse herein means that at least 23 particles by weight or number of particles are composed of particles having a size within ±μ04 of the average particle size.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a facet, or an irregular crystalline structure such as a spherical or plate-like structure.
It may have egular crystals or a composite of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

One or more silver halide emulsions formed separately may be used in combination.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

Silver halide particularly suitable for use in the present invention is prepared in the presence of 910-8 to 10 moles of iridium salt or a complex salt thereof per 7 moles of silver, and has a silver iodide content on the grain surface of It is silver haloiodide with a higher content than silver oxide. When such an emulsion containing gold haloiodide is used, photographic characteristics with higher sensitivity and higher gamma can be obtained.

3r - The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses all gold compounds, mainly gold complex salts. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and rhodium. Specific examples are U.S. Patent λ, Hirogu♂, oto
No., British Patent t/I.

It is described in OtI issue etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used.

In the above, it is desirable to add the iridium salt in the above amount before the completion of physical ripening in the silver halide emulsion manufacturing process, particularly during grain formation.

The iridium salt used here is a water-soluble iridium salt or an iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (In), potassium hexachloroiridate (IV),
Examples include hexachloroiridium(m)e ammonium.

In the present invention, the silver halide emulsion layer is a
It is preferable to include two types of monodisperse emulsions with different average particle sizes as disclosed in Japanese Patent Application ShotoO-, 23201t from the viewpoint of increasing the maximum density (Dmax), and small-sized monodisperse particles are chemically amplified. The chemical sensitization method is preferably sulfur sensitization. Dog-sized monodispersed emulsions do not need to be chemically sensitized, but
It may be chemically sensitized. Generally, dog-sized monodisperse particles are not chemically sensitized because black spots are likely to occur.
When chemically sensitizing, it is particularly preferable to apply the chemical sensitization shallowly to the extent that black spots do not occur. Here, "shallow application" means that chemical sensitization is performed by shortening the time, lowering the temperature, or suppressing the amount of chemical sensitizer added compared to chemical sensitization of small-sized particles. There is no particular limit to the sensitivity difference between a dog size monodisperse emulsion and a small size monodisperse emulsion, but Δ1ogE is o, i~/, 0, more preferably Oo~0°7, and the dog size monodisperse emulsion is higher. is preferable.

Here, the sensitivity of each emulsion is determined by coating it on a support containing a hydrazine derivative, sulfite ion fO, /! It is obtained when processing with a developer having a pH of 10,j to 2.3 and containing mol/1 or more.

More specifically, it follows the evaluation method described in Examples.

The average grain size of the small-sized monodisperse grains is 0% or less, preferably ro% or less, of the average grain size of dog-sized silver halide monodisperse grains.

The average grain size of the silver halide emulsion grains is preferably 0.0.2 μ to i, more preferably O0/μ to 0.0 μ.
It is preferable that the average particle size of dog-sized and small-sized monodisperse particles is included within this range of 3μ.

In the present invention, two or more types of milk of different sizes - μ /
- When used in a formulation, the amount of coated silver in a small size monodisperse emulsion is preferably 1.10 to POwt based on the total amount of coated silver.
%, more preferably 1O-IOWtfy.

In the present invention, monodispersed emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into separate layers.

When introduced in separate layers, it is preferred to have the dog size emulsion in the upper layer and the small size emulsion in the lower layer.

In addition, the total amount of coated silver is /it'/m2~r1/m
2 is preferred.

The photosensitive material used in the present invention has a Japanese Patent Application Publication (Kokai) Showa! ! -320jO No. gu! Sada~! All of the sensitizing dyes (for example, cyanine dyes, merocyanine dyes, etc.) described on page 3 can be added.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of 11 supersensitization.

Along with the sensitizing dye, 4L itself has a spectral sensitizing effect.
The emulsion may contain a color-free dye or a substance that does not substantially absorb all visible light and exhibits supersensitization.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
76 volumes/
74113 (Published in July, 2015) Page 23 ■-5
It is described in the section.

The photographic material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the photographic material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptotheadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially with hydroxyl substitution (/, J, ja, 7)
Many compounds known as antifoggants or stabilizers can be added, such as 5-benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc., such as tetrazaindenes), pentaazaindenes, etc. Among these, preferred are benzotriazoles (eg !-methyl-benzotriazole) and nitroindazoles (eg 3-nitroindazole). Further, these compounds may be included in the entire treatment solution.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts, aldehydes (formaldehyde, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), activated vinyl compounds (/, J,!
-triacryloyl-hexahydro-5-) riazine,
l,3-vinylsulfonyl-coprobanol),
Active halogen compounds (λ, dag-chloro-4-hydroxy-5-)riazine, etc.), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic agents, smoothness improvement, emulsion, dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, Various surfactants may be included for various purposes such as high contrast, sensitization, etc.

In particular, the surfactant preferably used in the present invention is Tokko Sho! ? - Molecule described in Tata≠12 publication -IJθO
These are the above polyalkylene/oyacides. When used as an antistatic agent, fluorine-containing surfactants (for details, see U.S. Pat. No. 41,207,314, JP-A-Sho-To-Roray, and JP-A No. 3-7≠j!IA) are particularly recommended. preferable.

The photographic light-sensitive material of the present invention may contain a matting agent of -μ 3 - such as phosphoric acid, magnecrum oxide, polymethyl methacrylate, etc., in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for purposes such as improving dimensional stability. For example, alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these and acrylic acid, methacrylic acid, etc. as monomer components. can be used.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the invention preferably contain all compounds having acid groups. Examples of compounds having acid groups include polymers or copolymers having repeating units of organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid. Regarding these compounds, patent application No. 0-IJ/7, same to-
6rrYJ, to-/13rjt, and toO-
/the law of nature! tj,! The description in Specification No. J can be referred to. Among these compounds, particularly preferred is ascorbic acid as a low molecular compound, and ascorbic acid as a high molecular compound, and a compound containing an acid monomer such as acrylic acid and two or more unsaturated groups such as divinylbenzene as a high molecular compound. It is a water-dispersible latex of a copolymer made of crosslinkable monomers.

In order to obtain ultra-high contrast and high-sensitivity photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or the method described in US Patent No. 2. ≠19. It is not necessary to use a highly alkaline developer with a pH close to 3 as described in the 7-year-old issue, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ion fO, /j mole/1 or more as a preservative, and p
H10, m~/, 2,3, especially pH/i, o~i, 2.
By using a developer of 0.0, it is possible to obtain a negative image with sufficient ultra-high contrast.

Although there are no particular restrictions on the developing agent used in the developer used in the present invention, it is preferable that it contains all dihydroxybenzenes, as it is easy to obtain good halftone dot quality. A combination of 3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used.

The developing agent is usually preferably used in an amount of o, or morph 1-o, r mol/l. Further, when using a combination of dihydroxybenzenes and l-phenyl-3-pyrazolidones or p-amine-phenols, the former f0.
0j mol/l to 0°3 mol/l, the latter fO, Ot mol/l
It is preferable to use it in an amount of 1 or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.1.1 mol/1 or more, particularly O0j mol/1 or more.

The developing solution of the present invention contains JP-A-Sho! as a silver stain preventive agent. t-2
A compound described in μ, 3≠7 can be used. Patent application filed in 1977 as a dissolution aid added to the developer.
No. 713. Furthermore, as a pH buffering agent used in the developer, JP-A-ShozO-23. Compounds described in Kou No. 33 or patent application No. 1970/-21, 70
The compound described in 1 can be used.

The compound represented by the general formula (I) can be used in combination with a negative emulsion in a high-contrast sensitive material as described above, and can also be used in combination with an internal latent image type silver halide emulsion. state In this case, general formula (1)
The compound represented by is preferably contained in the internal latent image type silver halide emulsion layer, but may be contained in the hydrophilic colloid layer adjacent to the internal latent image type silver halide emulsion layer.

Such a layer may be any layer with all functions, such as a colorant layer, intermediate layer, filter layer, protective layer, antihalation layer, etc., as long as it does not prevent the nucleating agent from diffusing into the silver halide grains. Good too.

The content of the compound represented by the general formula (I) in the layer is such that when the internal latent image type emulsion is developed with a surface developer, a sufficient maximum density (for example, silver concentration /, 0 or more) is obtained. It is desirable that In practice, the appropriate content can vary over a wide range as it depends on the characteristics of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but internal latent image silver halide Approximately 00 ootyq to 2 per mole of silver in the emulsion
A range of about 0.00 mf/mf to about i/mf per mole of silver is preferred.

θ■. When it is contained in a hydrophilic colloid layer adjacent to an emulsion layer, the same t as above may be contained relative to the amount of silver contained in the same area of the internal latent image type emulsion layer. Regarding the definition of internal latent image type silver halide emulsion, see JP-A/Sho A/
-/70733 Publication No. 10, top column and British Patent No. 2.
Orri, O! It is described in Publication No. 7, pages 1r to 20.

In the light-sensitive material of the present invention, the internal latent image type emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine color complexes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. These sensitizing dyes include, for example, JP-A-37-4A
O, No. 631, same! ? -110. Tit issue and the same! 19
It includes cyanine dyes and merocyanine dyes described in No.-31.73P.

The light-sensitive material of the present invention may contain a color image-forming coupler as a coloring material. Alternatively, it can be developed with a developer containing a color image-forming coupler.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD)/7A 4J (/year/month J) -D
The invention is described in the patents cited in Section 1 and 1/lf7/7.

Couplers in which the color-forming dye has appropriate diffusivity, non-color-forming couplers, DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler.

In the present invention, it is preferable to use a two-equivalent yellow kazoler, and typical examples include an oxygen atom elimination type yellow coupler or a nitrogen atom elimination type yellow coupler. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

The Mai/Ta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! The -pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an aclaramino group, from the viewpoint of the hue and color density of the coloring dye.

As a leaving group for a two-equivalent 3-pyrazolone coupler, U.S. Patent No. ≠, 310. Nitrogen leaving group as described in No. A/R or US Patent No. a, 3zi.

The arylthio group described in No. 7 is particularly preferred.

Also, European Patent No. 73. It has a palust group as described in AJA issue! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. J
pyrazolobenzimidazoles as described in US Pat. No. 3,7,222, preferably pyrazolo(j,/-c) (/, 2. Research Disclosure 2172.2
Pyrazolotetrazoles and Research Disclosure, 211-2jO described in 0 (/Yru year to month)
Examples include pyrazolopyrazoles described in C/RRP year to month). Imidazo(/, 2-b) pyrazoles described in European Patent No. 1/2, No. 717/ are preferred from the viewpoint of low yellow side absorption of coloring dyes and light fastness; Pyrazolo [/.

7-b) (/, co, ge) triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers. ≠7 Hiroshi.

The naphthol couplers described in λ-Li No. 3, preferably US Pat.

/#4. jFJ No. 44. ．． Typical examples include two-equivalent naphthol couplers of the friendly oxygen atom dissociation type described in No. 2.2r, jJJ and No. 2.2r, jJJ, No. 200. Specific examples of phenolic couplers are described in U.S. Patent No. 2. JJ Ri, Takota, No. 2. ♂0/ , 177
No. 2,772, /62, No.-, r9! ,
, rzA issue, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. J, 772.0.
A phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus described in No. 02, Co! - has a diacylamino-substituted phenolic coupler and a phenylureido group at the λ-position and! These include phenolic couplers having an acylamino group at the - position.

In order to completely correct the unnecessary absorption in the short wavelength region of the dyes generated from the magenta and cyan couplers, it is preferable to use a colored coupler in combination with the color sensitive material for -3g photography.

It is possible to completely improve the graininess by using a coupler in which the coloring dye has an appropriate degree of diffusivity. Such dye-diffusive couplers are described in US Patent No. 3tA.

No. 237 and British Patent No. j, /λ! A specific example of a magenta coupler is shown in European Patent No. J+70,
! No. 70 and West German Application No. 3,23≠.

No. 433 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the above-mentioned special couplers may be entirely formed into dimers or higher polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. ≠37. The,
No. 20 and No. ≠, O♂0゜2//. Specific examples of polymerized magenta couplers are described in British Patent No. 1, IO Co., 173 and US Pat. No. 11,3t7.
, No. 21.2.

Do the various couplers used in the present invention have the characteristics required for photosensitive materials? In order to meet the requirements, two or more compounds can be used together in the same layer of the photosensitive layer, or the same compound can be introduced into two or more different layers.

Typical usage amounts for color couplers range from 0.00/ to 1 mole per mole of photosensitive silver halide, preferably from 0.0/ to 0.00/mole for yellow couplers.
3 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

In the present invention, developing agents such as hydroxybenzenes (example 1-j hydroquinones), aminophenols, 3-pyrazolidones, etc. may be contained in the emulsion or the light-sensitive material.

The photographic emulsion used in the present invention can be prepared in combination with a dye image-providing compound (coloring material) for color diffusion transfer processes which releases a diffusible dye in response to development of the silver halide. It can also be used to obtain the desired total transferred image in the image-receiving layer after processing. Many coloring materials are known for use in color diffusion transfer methods. It is preferable to use a type of coloring material that releases a diffusible dye (hereinafter abbreviated as a DRR compound). Among these, DRR compounds having an N-substituted sulfasoyl group are preferred. In particular, it is suitable for use in combination with the nucleating agent of the present invention: US Pat. , Hiroshi, 2r issue,
Same 4t, 0jt3. ．． 3/2 issue and μ, 336.3.2
DRR compounds having an 0-hydroxyarylsulfamoyl foundation such as those described in No.
7≠ is a DRR compound having a redox core as described in No. 32r. When used in combination with such an R compound, the temperature dependence particularly during treatment is significantly small.

Specific examples of DfLR compounds include those described in the above-mentioned patent specifications, and magenta dye image-forming substances such as /-hydroxy-cochitramethylenesulfamoyl-
≠−[3′-methyl-μ/, −(2〃-hydroxy-μ
“-Methyl-3”-hexadenyloxyphenylsulfamoyl)-phinylazocnaphthalene, yellow dye image-forming substance /-phenyl-3-cyano-μ+
2'//, μ''''-di-tert-pentylphenoxyacetaminophenylsulfamoyl]phenylaso)-3 pyrazolone, and the like.

A photosensitive material using the internal latent image type emulsion of the present invention can be directly developed into a positive image by developing it using a surface developer. A surface developer is one in which the development process is substantially induced by latent images or fog nuclei on the surface of silver halide grains. Although it is preferable not to include a silver halide solubilizer in the developer, as long as the internal latent image does not substantially contribute to the completion of development by the surface development centers of the silver halide grains, the Q1 silver halide solubilizer (e.g. sulfite It may contain some amount of salt.

In order to completely develop the light-sensitive material using the internal latent image type emulsion of the present invention, known developing agents can be used.

Examples of the present invention are shown below, but the present invention is not limited thereto.

-, tr- (Example) The present invention will be explained in detail below with reference to Examples.

Example 1 Emulsions (A), CB) as shown below! e-prepared.

[Emulsion A]

per mole of silver in an aqueous gelatin solution maintained at to'c ≠
In the presence of 0-7 mol of iridium chloride and ammonia, a silver nitrate aqueous solution and potassium iodide, potassium bromide aqueous solutions were added at the same time during rp-needle to pAgt-
A cubic monodisperse emulsion having an average grain size of 0.3 μm and an average silver iodide content of 1 mol % was prepared by maintaining the grain size at 7.r.

[Emulsion B]

The amounts of potassium iodide and ammonia were adjusted in the same manner as in Emulsion A to obtain an average grain size of 0,022μ and an average silver iodide content of 0.
1 molten cubic monodispersed emulsion gold-tone yoshitomo. Emulsion AX B
Both samples were desalted by the 70 curation method.

Emulsion B was then subjected to sulfur sensitization using hypo to prepare a cubic monodisperse sulfur sensitized emulsion with an average grain size of 0022 .mu.m and an average silver iodide content of o, i mol.

As a sensitizing dye in these silver iodobromide emulsions! .

Sodium salt of 3'-cycloterethyl-3,3/-bis(3-sulfoglovir)oxacarbocyanine, cyclohydroxy-t-methyl-/, J as a stabilizer,
Ja, 7-chitrazaindene, aqueous latex (a) represented by the following structural formula, aqueous latex (a) dispersion of polyethyl acrylate, l,3-divinylsulfonyl-coprononol, emulsion A, '
Bl silver halide weight ratio /: After mixing so that the ratio is 4t, and further adding the compound of general formula (I) of the present invention as shown in Table 1 per 1 mole of silver, it is mixed on a polyethylene terephthalate film. Coating was carried out so that the silver amount J was 097 m. Each sample was fully exposed and developed, and its photographic properties were measured.

The results are shown in Table 1.

Note that a developer having the following formulation was used.

Developer formulation Hydroquinone daj, 0fN-methyl-p-aminophenol //, disulfate o, re sodium hydroxide /r, 09 potassium hydroxide
jrj, Of! -Sulfosalicylic acid
Hiro! , 0? Boric acid
, 21.0? Potassium sulfite /10.
Of゛Pa...12, Ethylenediaminetetraacetic acid disu”,
, thorium salt 7.02 Odor resistance, lithium t,
ot3-methylbenzotriazole ・211.1.
o, a tn-butyldiethanolamine g t'-'= n /
! , Add water/Ji'% 1) H=//
, A OK combination cell.

-Bu-1 The unit of the amount added is 1 mol Ag.

++ r is (3,o-o,3)/(log(concentration 3
．． It represents the value of (exposure amount that gives 0°) - 1ag (@exposure amount that gives 0 degrees 3) l.

■Blue Halftone quality! The quality is visually evaluated in stages, with "ma" representing the best quality and "/" representing the worst quality.

As a halftone original plate for plate making, halftone dot quality "3" and "ri" are practical, "3" is poor but barely practical, and "ko" and "/" are halftone dots of impractical quality. It is.

Comparative Compounds From the above results, the compounds of the present invention are comparative compounds a,
It can be seen that with a smaller amount than b, it gives a sharp tone and has excellent halftone dot quality.

Example 2 [Preparation of Emulsion C] Silver nitrate aqueous solution and sodium chloride aqueous solution containing 1 mole of silver υJf x 10' mole of ammonium hexachloride rhodium(III) were prepared by total double jet method≠o6C
A monodisperse silver chloride emulsion with an average grain size of 0.2 microns was prepared by mixing in a gelatin solution while controlling the total pH to 2.3.

After particle formation, all soluble salts were removed by a flocculation method well known in the art, and stabilizers such as g-hydroxy-t-methyl-, 3°3a, 7-titraazaindene and l-phenyl-! -Mercaptotetrazole was added. The gelatin contained in emulsion/4 is j
, tf, and the trowel were 10zy.

One-two! - Dye compound C Using emulsion Cy<, the compounds of the present invention shown in Table 2 and the above dye compound C (/30 mg/m2) were added, and further, as a hardening agent, co-, goudichlor-monohydroxy-/
, j, j) Add riazine sodium salt to 7 m2 F) 3.3? The entire silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the silver amount was , and then a gelatin layer was coated as a protective layer on top of the silver halide emulsion layer to give sample numbers (,2-/) to (,2-10). A photosensitive material was prepared.

Dainippon Screen P-1/7DQ type printer (light source 100cm, l) through each photosensitive material IRf-optical wedge
Exposure with a kW quartz halogen lamp) and! : 4
- Later, 3♂c'020 was developed using a developer with the same composition as in Example 1.
It was developed for seconds, then fixed, washed with water, and dried in a conventional manner.

The density of each developed sample was measured, and the relative value of the exposure amount that gave the density O was determined.

Each of the photosensitive materials with sample numbers (Call) to (λ-10) was illuminated with a Toshiba anti-fade light (FLI) as safelight light.
After leaving it for 0 minutes to 0 minutes under the brightness of -〇〇 lux of 2000W-DL-X N07M), it was developed for J r'c2θ seconds with a developer having the same composition as in Example/, and fixed.
Washed with water and dried.

The concentration of each sample obtained was measured, and the critical irradiation time at which the fog density of each sample began to increase was determined.

(The time limit was set as the time for the turnip concentration to increase by 0.0.) The results obtained are shown in Table 2.

From the results in Table 2, the sample number according to the present invention (,2-μ)
The photosensitive materials of ~(, z-io) have a sensitivity that allows practical exposure and printing with a /kW quartz halogen lamp, and are excellent in safelight safety under ultraviolet light-cut silicon lamps.

Curvature 1 Density μ, Of Reciprocal of exposure amount Total sample number (2
-/ ) is expressed as a relative value with 100.

Supper 2 Anti-fading Kei Gento made by Toshiba ■ (FLRgO8W-D
L-X-N07M) When left under 200 lux, the fog density increased within +0.01 and showed a critical irradiation time.

In the past, 3 units were expressed as the number of moles per 7 moles of silver.

Cloudy 4 γ represents the gradation of the characteristic curve as defined in Examples.

5 3rc with a developer of the same composition as the coating sample All Examples/
After developing for 20 seconds, fixing, washing with water, drying, re-swelling with water, press a sapphire ball with a diameter of o and am onto the film surface with a needle glued to the tip, and move it at a speed of 1 mm in 7 seconds to the needle. It is expressed as the load (f) at which the membrane breaks (scratches occur) by changing the load continuously.

Screen 6 Comparative compounds a and b are the same compounds as in Example 1.

Of particular note is that the compounds of the invention are comparable to comparative compound a
, b, the emulsion containing a large amount of Rh:i has a remarkable contrast-enhancing effect and a strong film strength.

Example 3 A photosensitive element was prepared by coating each layer on a polyethylene terephthalate transparent support in the following order.

(1) U.S. Patent No. 3,191.0? The following repeating unit in the copolymer listed in No. r? A mordant layer containing a polymer (3,0517 m ) x:y = O:30 and gelatin (3,097 m ) in the following proportions.

(2) Titanium oxide 20 di'/m2 and gelatin λ.

0? A white reflective layer containing / m.

(3) Carbon black 2.70? /m and gelatin λ. 7of! A light shielding layer containing /rn'c.

(4) The following magenta DRR compound (o, g!1/m2
), diethyl laurylamide (0,109/m2), co,j-di-t-butylhydroquinone (0,0074t
t/m ), and a layer containing gelatin (0,7Δ?/m2).

H (5) Internal latent image type emulsion (silver content: 17 m2 Green sensitizing dye (/, mg/m2) containing the nucleating agent shown in Table 3 and!-pentadecyl-hydroquinone-cosulfone A green-sensitive internal latent image type direct positive silver iodobromide emulsion (silver iodide comol %) layer containing sodium chloride (o, / / f/m2).

(6) A layer containing gelatin (Ol Rihiro Y/m)k.

Processing was carried out by combining the above photosensitive elements 1 to 2 with the following elements.

Processing liquids Processing liquids fO and If having the above compositions were each filled into a "container breakable by pressure."

Cover sheet Polyacrylic acid (viscosity approximately 7,000 Cp in 10% by weight aqueous solution) 1197 m2 as an acidic polymer layer (neutralization layer) on a polyethylene terephthalate support and acetyl cellulose (100 f acetyl cellulose) as a neutralization timing layer thereon. Hydrolyzes to generate 3 and 3 acetyl groups)! , If/m and copolymer of styrene and maleic anhydride (composition (mole) ratio, styrene:
Maleic anhydride = approx. to', tito, molecular weight approx. 30,000)
o.

A cover sheet was prepared by applying 217 m2.

Forced deterioration conditions for the above photosensitive elements/~? A total of 2 sets are prepared, and 7 sets are kept in the refrigerator (j'
c), and the remaining 7 sets were stored at a temperature of 3je'C and a relative humidity of ♂0.
% and left for several days.

Processing process The above cover sheet and the above photosensitive sheet are overlapped, and the color test chart from one rule of the cover sheet - 7g - After full exposure, the above processing solution is applied between both sheets. μ
(Development was carried out with the help of a pressure roller for 9 times) to a thickness of . The treatment was carried out at Koj0C. After processing, the green density of the image produced in the image-receiving layer was measured through the transparent support of the photosensitive notebook with a Macbeth reflection densitometer after processing/time.

The results are shown in Table 3.

DF: Maximum density ax of the positive image area of the product stored in the refrigerator 8F: Relative sensitivity of the positive image area of the product stored in the refrigerator at density 04 (when the photosensitive element is 8t-100) BW: J4''C relative humidity! θ% Density of the positive image area of the sample left for Koichi 0.1 (D relative sensitivity (when taken as 8'f100 of the photosensitive element) Nucleating agent A-1 A-2 As is clear from the above results, Photosensitive elements 3- and 2 to which the uninvented nucleating agent was added had higher Dmax than photosensitive elements made by conventional methods at the same additive amount, and photosensitive elements 3 to 1 had a higher Dmax than l. It can be seen that there is little change in sensitivity when the material is completely aged.

Example 4 (1) Preparation of hydrazine compound solution Solution A: Compound 1 was dissolved in methanol containing 105 g of water so that the concentration was O8t%. Solution B: Compound 3 was dissolved in methanol containing 105g of water so that the concentration was O1r%. 10 to
Dissolved in methanol containing % water.

Solution C: Compound ≠ was added to 70% so that the concentration was o, r%.
Dissolved in methanol containing % water.

Solution D: Compound 2 in an equimolar amount of 0. /After the normal sodium hydroxide aqueous solution was completely dissolved, a methanol solution containing 70% water was added to adjust the concentration of compound t to 0.02%.

Solution E: Compound 7 was dissolved in methanol to a concentration of 0.7%.

Solution F: Comparative compounds were dissolved in methanol so that the total concentration was 2%.

Comparative compound a (2) Preparation of light-sensitive material sample A cubic monodisperse silver iodobromide emulsion with an average grain size of 0.3 μm (
Silver iodide content λmolde) was prepared, washed with water in a conventional manner to remove all soluble salts, and then chemically sensitized by adding sodium thiosulfate and potassium chloroaurate. This emulsion contained gelatin in an amount such that the gelatin/silver nitrate (weight ratio) was 0.30. This emulsion contains anhydro-j, j'-cyclorotaethyl-3,! as a sensitizing dye.
'-Bis-(3-sulfopropyl)oxacarbocyanine human, oxacarbocyanine salt was added, and x-(N-methyl-N-
Add oleoylamino)ethanesulfonic acid sodium salt, and then add any of the above solutions A to E so that the amount of each hydrazine compound is 0 x 10' mole per mole of silver. , the amount of the compound compared with solution F is μ per mole of silver.

After preparing the total amount of 1 × 10 mol of polyethyl acrylate, and then adding the dispersion of polyethyl acrylate to each, either immediately or after stirring with 3IrOC for 4 hours, cohydroxyl≠, ≦-dichloro-/,J,/-add sodium salt of triazine and coated silver amount 3 on polyethylene terephthalate film.
．． It was coated at At/m2. At this time, a protective layer was applied at the same time.

(3) Evaluation method Each sample was subjected to sensitometry for 7 seconds under a light wedge to evaluate sensitivity and gamma.

The processing was carried out by developing F)31r''C,J (7 seconds) using the following developer, stopping, fixing, washing with water, and drying.

Developer Hydroquinone μ0.02≠,≠
-dimethyl-/-)dinyl-3-pyrazolidone o, tt, y sodium hydroxide /3. Of anhydrous potassium sulfite tao, oy potassium triphosphate 7g, 77g' disodium ethylenediaminetetraacetate /, O? Potassium bromide t, Of! -methylbenzotriazole o, ty/-diethylamino-λ,
3-dihydroxypropane /7. Add water of /I (pH with potassium hydroxide//.

Adjust to J] The results are shown in Table μ.

As is clear from Table .mu., when all the comparative compounds were added (A4-J), the sensitivity and gamma decreased significantly over time of the coating solution after addition compared to -r/-. In contrast, the samples of the present invention (Mu≠-7 to 4l-7) showed good sensitivity and gamma both when added immediately before coating and when added 6 hours before coating. That is, it can be seen that the compounds of the present invention have excellent stability over time when added to photographic emulsions.

-r, 2- Example 5 Preparation of emulsion An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous gelatin solution with vigorous stirring for about ≠0 minutes at It'C, and the average particle size was An octahedral monodisperse silver bromide emulsion with O1≠μm was obtained. To this emulsion was added 1 t each of sodium thiosulfate and chloroauric acid (≠ hydrate) per mole of silver.
- Chemical sensitization treatment was performed by heating at 73°C for jO minutes. Using the thus obtained silver bromide grains as cores, they were further grown by further treatment for aO minutes in the same precipitation environment as the first time, and finally the average grain size was o, tμ.
An octahedral monodisperse core/shell silver bromide emulsion of m was obtained. After washing with water and desalting, a free amount of sodium thiosulfate and O per mole of silver were added to this emulsion and heated at tjc'c for to minutes to perform chemical sensitization treatment to obtain a silver halide emulsion with an internal latent image pot. Ta.

A multilayer color photographic paper having the layer structure shown in Table 3 was prepared using a core/shell type autopositive emulsion on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

Preparation of first layer coating solution: 10 tons of yellow coupler (a) and color image stabilizer (b)2. Ethyl acetate 10WLl and solvent (e)≠d were added and dissolved in JP, and this solution was emulsified and dispersed in Oat, a 70% gelatin aqueous solution containing 10% sodium dodecylbenzenesulfonate 3-.

On the other hand, in the above silver bromide emulsion (containing Ag70P/#), the blue-sensitive dye shown below was added in an amount of λ per mole of silver bromide.

A blue-sensitive emulsion with 0xlO mole added! I created POff. The emulsified dispersion and the emulsion were mixed and dissolved, and the concentration was adjusted with gelatin so as to have the composition shown in Table 3, and a nucleating agent was added in the amount shown in Table 3 to prepare a coating solution for the first layer.

The coating liquids for the λth layer to the seventh layer were also prepared in the same manner as the first layer coating liquid. l-oxy-3 as gelatin hardening agent in each layer
，! -dichloro5-) riazine sodium salt was used.

−? 3- The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer; Green-sensitive emulsion layer; Red-sensitive emulsion layer; The following dyes were used as irradiation prevention dyes in each emulsion layer.

The structural formulas of the compounds used in this example, such as green-sensitive emulsion layer; red-sensitive emulsion layer; coupler, are as follows.

t　　　　　　　　 Engineering 0:i 10 ( /-1;- Engineering Engineering ○=Q °　1 Engineering Ga -no @All...Ya \　Naka　　　　　　　　　　　Q Q Q (m) Solvent (n) Nucleating agent: The number is shown in the table.

(0) Nucleation accelerator The entire multilayer silver halogenide color photographic material can be prepared by simultaneously coating the coating solutions of the first to seventh layers after adjusting the balance of surface tension and viscosity.

In this way, the samples shown in Table 6 were prepared.

These samples were subjected to full gradation exposure for sensitometry using an enlarger (Fuji Color Head, manufactured by Fuji Photo Film Co., Ltd.), and then developed using the following processing steps.

Processing process Temperature Time Developing solution 33°C 3.3 minutes Bleach-fixing solution 33e'c /, Washing with water
, 2r ~! ! 'Cj, 0 minute developer nitrilotriacetic acid/JNa -2, Of?
Benzyl alcohol 13-diethylene glycol ゛ 10rttlNa28
03 s, ofKBr
O, jf hydroxylamine sulfate J, Off guamino-3-methyl-
N-ethyl-N-(β-(methanesulfonamido)ethyl)-p-fuynylenediamine sulfate! , 0? Na2C0
3 (/water salt) 30? Add water to make /l (pH 10, /) Bleach-fix solution Ammonium thiosulfate (70 wt%) /m0rtteN
a2803/! ? N H4(F
e (ED'LA)) j!
S'EDTA0.2Na lA
? From the results in Table 1, the compounds of the present invention produce better color images when combined with an autopositive emulsion as shown in this example, compared to comparative compounds with similar structures. It is clear that the forming function is excellent.

Example 6 7 moles of silver per aqueous gelatin solution maintained at ao 0c F)!
, in the presence of 0x10''-6 mol of NH4Rhα6, an aqueous silver nitrate solution and an aqueous sodium chloride solution were simultaneously mixed, and after all soluble salts were removed by a method well known in the art, gelatin was added and chemically ripened. 2-methyl-μm hydroxy-/, J, Ja, 7-titraazaindene was added as a stabilizer without using any of the above emulsions.The emulsion was a cubic monodisperse emulsion with an average grain size of 0.2 μm. .

The compound of general formula (I) of the present invention was added to this emulsion in the amount shown in Table 1, and a desensitizer and a nucleation accelerator were added as shown below.

-Ta! − to evil
exhausted
Daughter T- After all of the above compounds were added, polyethyl acrylate latex was added in a solid content of J Ow t% to gelatin, and l,3-vinylsulfonyl-λ-propertool was added as a hardening agent, and a polyester support was added. 3.117m above
It was coated so that the amount of Ag was as follows. Gelatin is /, ♂2/m
It was 2. Gelatin i, zy as protection 1- on this
A layer of 7'm was applied.

This sample is Dainippon Screen Seimei-shitsu printer p
- At t07, expose through the Kyugaku wedge to 3tr'c, 3
The film was subjected to o-second development (the developer formulation was the same as in Examples), fixed, washed with water, and dried.

The photographic properties obtained are shown in Table 7.

As is clear from Table 7, compared to comparative compounds a and b, the compounds of the present invention provide images with lower sensitivity and significantly higher contrast in emulsions containing all the desensitizers.

Yellow 1 Comparative compounds a and b are the same compounds as in Example/.

Cloudy 2 Sensitivity (logE) of sample number t-2 is shown as a difference from 7z standard. Therefore, for example, -/, 0 means that the feeling is /, 0 lower in logE than the blank, that is, the feeling is 10 times lower.

Bud 3 This is the slope of the straight line connecting the point of density 0.3 and the point of density 3.0 on the characteristic curve. The larger the value, the higher the contrast.

Patent applicant: Fuji Photo Film Co., Ltd. - Tata

Claims (1)

[Scope of Claims] At least one photosensitive silver halide emulsion layer is provided on a support, and at least one of the emulsion layer and one or other constituent layers is formed by the following general formula (I). A silver halide photographic material containing at least one of the compounds shown below. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group, B represents a formyl group,
represents an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group or a heterocyclic group, R_o, Both R_o_o represent a hydrogen atom, one hydrogen atom and the other an alkylsulfonyl group, or one hydrogen atom and the other an arylsulfonyl group or an acyl group. However, B, R_o
_o and the nitrogen atoms bonded thereto may form a hydrazone partial structure (-N=C<). Further, Ar has at least one group selected from a sulfonamide group and a sulfamoyl group as a substituent via a linking group, and the total number of carbon atoms of Ar and B is 21 or more. )