JPH0419732A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To maintain high sensitivity and high contrast and to reduce black spots by treating a silver halide emulsion with a porous adsorbent or an ion exchange resin in the manufacturing process of an emulsion layer and incorporating a hydrazine derivative in the emulsion layer or another hydrophilic colloidal layer. CONSTITUTION:The silver halide emulsion is treated with the porous adsorbent or the ion exchange resin before coating a support with it and the hydrazine derivative to be used is, preferably, represented by formula I in which R1 is an aliphatic or aromatic group; R2 is H, alkyl, amino, or hydrazino; G1 is thiocarbonyl, iminomethylene, or the like; and each of A1 and A2 is both H or one is H and the other is optionally substituted alkylsulfonyl or acyl or the like, thus permitting sensitivity, contrast, and blackening density to be enhanced, and occurrence of black spots to be reduced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is applied to silver halide photographic materials (particularly negative materials) that are used in the field of photoengraving and are capable of rapidly forming ultra-high contrast images using a highly stable processing solution. (type).

(Prior Art) In order to improve the reproduction of continuous tone images or line images using halftone images in the field of photoengraving,
There is a need for an image forming system that exhibits photographic characteristics of ultra-high contrast (especially gamma of 10 or higher).

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free FA ions is extremely low ( Usually 0°1 mol/! or less). Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

U.S. Pat. No. 4,224,401 and U.S. Pat.
, No. 168,977, No. 4,166.742, No. 4,311,781, No. 4.272.606, No. 4,221.857, No. 4,243,739 ,
There is a method using a hydrazine derivative described in 4,269,929 and the like. According to this method, photographic characteristics with ultra-high contrast and high sensitivity can be obtained, and since it is allowed to add a highly sensitive sulfite to the developer, the stability against air oxidation of the developer is better than that of the lithium developer. A dramatic improvement in comparison.

This new high-contrast negative image system can increase the maximum density by changing the amount of hydrazine derivative added and achieve a remarkable high-contrast contrast.
) may cause undesirable development.
This is a problem in the photolithography process.

A black spot is a black spot made of minute developed silver that occurs in an unexposed, non-image area.

Black spots occur frequently due to a decrease in sulfite ions, which are generally used as preservatives in developing solutions, and an increase in pH value, and this significantly reduces the commercial value of photolithographic materials. Therefore, although much effort has been made to improve the 20-black mark, the improvement of the black mark is often due to sensitivity and gamma (r).
), there has been a strong desire for a system that maintains high contrast and improves black outs. As one such method, Japanese Patent Application Laid-open No. 77274/1983 describes particle size 0.
．． A silver halide photographic material containing two types of monodispersed emulsions and a hydrazine derivative with a particle size of 5 μm or less is disclosed.

Furthermore, in the field of photolithography, in order to deal with the versatility and complexity of printed matter, there are demands for photosensitive materials with good original reproducibility, stable processing solutions, and easy replenishment.

In particular, manuscripts in the line drawing process are created by pasting typesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, a document contains images of different densities and line widths, and there is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can finish these documents with good reproduction. On the other hand, for making catalogs and large posters,
Enlarging (stretching) or reducing (shrinking) halftone photographs is widely practiced, and in platemaking that uses enlarged halftone dots, the number of lines becomes coarse and blurred dots are photographed. When reduced, the number of lines per inch is larger than that of the original, and a thinner point is photographed. Therefore, in order to maintain halftone reproducibility, an image forming method having a wider latitude is required.

A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain photographic sensitivity to these light sources, photographic materials are usually orthosensitized. However, it has been discovered that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of lenses, and as a result, image quality tends to deteriorate. Moreover, this deterioration is more noticeable for xenon lamp light sources.

The above image system has sharp halftone dot quality, processing stability,
Although it shows excellent performance in terms of speed and reproducibility of originals, there is a desire for a system with further improved reproducibility of originals in order to accommodate the diversity of printed matter in recent years.

An example of a silver halide emulsion treated with an ion exchange resin or porous adsorption during the manufacturing process is disclosed in JP-A-61-2199.
No. 48, No. 61-219949, No. 62-24095
No. 1, No. 63-40137, No. 63-40139, etc.

Examples of systems using hydrazine containing a redox compound that releases a development inhibitor when oxidized are disclosed in JP-A-61-213847 and JP-A-64-72140.

(Problems to be Solved by the Present Invention) The first object of the present invention is to provide a silver halide photographic material with high sensitivity, high contrast (for example, T of 10 or more), high blackening density, and few black spots. An object of the present invention is to provide an image forming method.

A second object of the present invention is to provide a silver halide photographic material with excellent line image quality, extremely high sensitivity and high contrast with a γ value of over 10.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer is a silver halide emulsion layer. A halogen compound containing a silver halide emulsion treated with a porous adsorbent or an ion exchange resin during the production process, and containing at least one hydrazine derivative in the emulsion layer or other hydrophilic colloid layer. This could be achieved using silver-oxide photographic materials.

Further, for the second object of the present invention, the silver halide photograph is characterized in that the emulsion layer or other hydrophilic colloid layer contains a redox compound that releases a development inhibitor upon oxidation. This was further improved by the use of photosensitive materials.

Hereinafter, a specific configuration of the present invention will be explained in detail.

In the present invention, in the process of producing a silver halide grain emulsion, the silver halide grain emulsion is treated with a porous adsorbent or an ion exchange resin before coating the silver halide grain emulsion on a support. A silver halide grain emulsion subjected to such treatment is used in the silver halide photographic light-sensitive material of the present invention.

Processing with a porous adsorbent here refers to a process in which a porous adsorbent is added to a silver halide emulsion in a batch manner, stirred and mixed, and then the porous adsorbent is removed by filtration. This refers to a process in which a silver halide emulsion is filled in a bed or an adsorption cylinder and a silver halide emulsion is passed therethrough in a continuous manner, and any of these processes can be used in the present invention.

The amount of porous adsorbent used depends on the performance of the adsorbent (e.g. type, shape, adsorption capacity, adsorption capacity, etc.) and the contents of the target silver halide emulsion (e.g. type of chemical sensitizer, amount used) etc.) can be selected as appropriate.

For example, in the case of a batch method, the amount of adsorbent used can range from 0.05 g to 100 g/kg of silver halide emulsion, and in the case of a continuous method, the adsorbent may be added in an amount of 0.05 to 100 g/kg of silver halide emulsion. Considering the amount, it can be used within the same range as the batch type.

In addition, the processing temperature is the temperature at which the silver halide emulsion becomes liquid (
The temperature may be higher than approximately 30°C, and the processing time may be as follows:
For both batch and continuous methods, an appropriate time of 1 minute or more may be used.

The timing of the treatment with the porous adsorbent in the present invention can be appropriately selected depending on the target silver halide emulsion, but it is preferably carried out after the completion of chemical ripening or immediately before coating, and most preferably carried out immediately after the completion of chemical ripening. .

The porous adsorbent used in the present invention is a porous solid adsorbent (also called an adsorbent) with a large surface area, and specifically includes activated carbon, activated alumina, activated clay, and silica-based adsorbents (water-resistant (preferably)
, Inorganic porous adsorbents such as zeolite-based adsorbents, porous glass, and porous ceramics.

Among these, activated carbon is most preferred.

The shape may be powdery, granular, fibrous, film, etc., and any shape that is easy to handle may be selected as appropriate.

Further, the size needs to be larger than the silver halide grains used in the silver halide emulsion.

This is because after a silver halide emulsion is treated with a porous adsorbent, the porous adsorbent often remains in the emulsion, and although some remain without any harmful effects, it is generally not possible to remove the porous adsorbent by filtration. This is because it is necessary to remove the porous adsorbent from the emulsion.

These porous adsorbents are commonly subjected to reprinting;
You can easily obtain the one that suits your purpose.

Next, processing of the silver halide emulsion with an ion exchange resin will be explained.

Processing a silver halide emulsion with an ion exchange resin as used herein means a process of adding an ion exchange resin to a silver halide emulsion in a batch manner, stirring and mixing, and then filtering and removing the ion exchange resin. This refers to a process in which resin is continuously filled into an adsorption bed or adsorption column, and the silver halide emulsion is passed therethrough, and either process can be used in the present invention.

The amount of ion exchange resin used depends on the performance of the resin (e.g., layer exchange capacity, type of exchange group, selectivity, etc.) and shape (resin particle size, effective surface area, etc.) and the content of the target silver halide emulsion ( For example, it can be appropriately selected depending on the type of chemical sensitizer, amount used, etc.).

For example, in the case of a batch method, the amount of adsorbent used can range from 0.1 g to 100 g per 1 kg of silver halide emulsion, and in the case of a continuous method, the amount of adsorbent can be calculated based on the total amount of silver halide emulsion passing through. If you think about it, it can be used in the same range as the batch type.

In addition, the processing temperature is the temperature at which the silver halide emulsion becomes liquid (
The temperature range may be from about 30'C) to the tolerable temperature of the resin, and the treatment time may be an appropriate time of 1 minute or more for both batch and continuous processes.

The timing of the treatment with the ion exchange resin in the present invention can be appropriately selected depending on the intended silver halide emulsion, but it is preferably carried out after the completion of chemical ripening or immediately before coating, and most preferably carried out immediately after the completion of chemical ripening.

The ion exchange resin referred to in the present invention specifically refers to a cation exchange resin (for example, the product name Amberlite IR-12
0; manufactured by Rohm and Haas Co., Ltd.), anion exchange resin (for example, product name Diaion 5A-
21A; manufactured by Mitsubishi Kasei Co., Ltd., trade name DOWEX 1×8; manufactured by Dow Chemical Company, etc.) amphoteric resins and chelate resins (for example, trade name Diamond CR)
-20; manufactured by Mitsubishi Kasei Corporation, etc.).

Many types of these ion exchange resins are available for cloth boards, and one suitable for the purpose can be easily obtained.

Among these, anion exchange resins, amphoteric resins and chelate resins are preferred, and anion exchange resins are most preferred.

As the resin material, not only synthetic resins (eg, styrene-divinylhensen copolymer, etc.) but also natural resins (eg, those based on cellulose, etc.) may be used.

The shape may be granular, powder, film, etc., and any shape that is easy to handle may be selected as appropriate.

Further, the size needs to be larger than the silver halide grains used in the silver halide emulsion.

This is because after a silver halide emulsion is treated with an ion exchange resin, ion exchange resin often remains in the emulsion, and although some residual ion exchange resin may have no harmful effects, it is generally done by filtering or other means to remove the ion exchange resin. This is because it is necessary to remove the exchange resin from the emulsion.

In the present invention, the effects of the present invention are obtained by removing part or most of the unreacted portion of the chemical sensitizer or chemical sensitization adjuvant used or other impurities.

Therefore, it can be said that this method is different from the conventional method of adding stabilizers, antifoggants, dyes, etc. to prevent the progress of chemical sensitization.

In the present invention, the method of the present invention may be used alone when producing a silver halide emulsion, but conventional stabilizers (especially 4-hydroxy-6-methyl-1,3,3a,
7-chitrazaindene), an antifoggant, a dye, etc. are preferably used in combination.

The hydrazine derivative used in the present invention has the following general formula (
Compounds represented by 1) are preferred.

General formula (1) % formula % In the formula, R represents an aliphatic group or an aromatic group, R1 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, G1 represents a -C- group, a -8O7 carbonyl group, or an iminomethylene group, and A, , A are both hydrogen atoms, or one hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted alkylsulfonyl group. Represents an arylsulfonyl group or a substituted or unsubstituted acyl group.

In general formula (I), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

The aromatic group represented by R in general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be fused with an aryl group.

Preferred as R+ is an aryl group, particularly preferably one containing a benzene ring.

The aliphatic group or aromatic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, Urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide Preferred substituents include alkyl groups (preferably those with 1 to 20 carbon atoms), aralkyl groups (preferably those with 7 to 30 carbon atoms), alkoxy Group (
(preferably those having 1 to 20 carbon atoms), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), anrulamino groups (preferably those having 2 to 30 carbon atoms), sulfonamides. Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30), a phosphoric acid amide group (preferably one having 1 to 30 carbon atoms), and the like.

The alkyl group represented by R2 in general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). .

1; When G1 is a -C- group, preferred among the groups represented by R2 are a hydrogen atom, an alkyl group (e.g., a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxybenzyl group, etc.), aryl group (e.g., phenyl group, 3°5-dichlorophenyl group, 0-methanesulfonamidophenyl group) , 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.),
Particularly preferred is a hydrogen atom.

R2 may be substituted, and the substituents listed for R can be used as substituents.

G in general formula (I) is most preferably a -C- group.

Also, R8 splits the G1-R7 part from the remaining molecules,
It may also be one that causes a cyclization reaction to produce a cyclic structure containing atoms of the -G, -R, moieties, such as those described in JP-A No. 63-29751, etc. Can be mentioned.

A hydrogen atom is most preferred as A1 and Ai.

R or R7 in formula (I) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group,
It can be selected from phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group, etc. Examples of the polymer include those described in JP-A No. 1-100530.

R1 or R7 in the general formula (I) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
, No. 347, JP-A No. 59-195, 233, No. 59-
200゜231, 59-201,045, 59
-201.046, 59-201.047, 5
9-201,048, 59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, patent application No. 62-67.508,
Examples include the groups described in No. 62-67.501 and No. 62-67.510.

Specific examples of the compound represented by general formula (1) are shown below.

However, the present invention is not limited to the following compounds.

■ C. H.

■-12 ■-14 ■-15 ■-18 ■-20 ■-24 ■-26 In addition to the above-mentioned hydrazine derivatives, RESEARCI (D[5CLO3URE
Item23516 (November 1983 issue, P.
346) and the references cited therein, as well as U.S. Pat.
No. 080.207, No. 4,269,929, No. 4.
No. 276.364, No. 4,278,748, No. 4,3
No. 85,108, No. 4,459,347, No. 4,56
No. 0,638, 4. 478. No. 928, British Patent No. 2,011,391B, Japanese Patent Application Publication No. 179734/1986,
No. 62-270,948, No. 63-29,751,
No. 61-170゜733, No. 61-270,744, No. 62-948, EP 217,310, or U
S4゜686.167, JP-A-62-178,246
No. 63-32,538, No. 63-104゜047
No. 63-121,838, No. 63-129.33
No. 7, No. 63-223,744, No. 63-234,2
No. 44, No. 63-234, 245, No. 63-234,
No. 246, No. 63-294 No. 552, No. 63-306
, No. 438, JP-A-1-100,530, JP-A No. 1-10
No. 5,941, No. 1-105,943, JP-A No. 1983-
No. 1O,233, Japanese Patent Application Publication No. 1-90,439, Patent Application No. 1989
No. 3-105,682, No. 63-114,118, No. 63-110,051, No. 63-114.119,
No. 63-116,239, No. 63-147.33, No. 63-179,760, No. 63-229,163
No., Japanese Patent Application No. 1-18.377, No. 1-18,378, No. 1-18379, No. 1-15,755, No. 1-
No. 16.814, No. 1-40,792, No. 1-42.
No. 615, No. 1-42, 616, No. 1-123.69
No. 3, No. 1-126,284 can be used.

The amount of the hydrazine derivative added in the present invention is 1XIO-' mole to 5XIO-' mole per mole of silver halide.
-' mol is preferable, and the addition amount is particularly preferably in the range of 1X10-' mol to 2X10-' mol.

The hydrazine derivative of the present invention may be used alone, or two
More than one type may be used in combination.

Next, the development inhibitor of the present invention is released by being oxidized. I will explain about the redox compounds that are produced.

The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones, and more preferably hydrazines.

The hydrazines used as the redox compound capable of releasing a development inhibitor upon oxidation of the present invention preferably have the following general formula (R-1), general formula (R-2), and general formula (R-3). It is expressed as A compound represented by general formula (R-1) is particularly preferred.

General formula (R-1) A, Ax General formula (R-2) General formula (R-3) In these formulas, represents an aliphatic group or an aromatic group /Gt R1 group, -C- group, -8 Represents 〇- group, -5O2- group or -P- group. G2 is just a connection G, -R.

Atte, -O--S- or -N-, RR3 represents a hydrogen atom or R1.

A, At represents a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, and may be substituted. In general formula (R-1), at least one of Ax2 is a hydrogen atom. A is synonymous with A1 or -CH,C
H-(Time), -PUGA.

represents.

A4 represents a nitro group, a cyano group, a carboxyl group, a sulfo group, or -G, -G2-R.

Time represents a divalent linking group, and t represents O or 1. PUG stands for development inhibitor.

General formulas (R-1), (R-2), and (R-3) will be explained in more detail.

In general formulas (R-1), (R-2), (R-3),
The aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

This alkyl group may have a substituent.

In general formulas (R-1), (R-2), (R-3),
The aromatic group represented by R1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group.

For example, among the benzene rings, naphthalene rings, pyridine rings, quinoline rings, isoquinoline rings, etc., those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group,
Acyl group, alkoxycarbonyl group, acyloxy group,
Examples include carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, etc. Preferred substituents include linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), aralkyl group (preferably is one having 7 to 30 carbon atoms), an alkoxy group (preferably one having 1 to 30 carbon atoms), a substituted amino group (preferably one having 1 to 30 carbon atoms),
~30 alkyl group substituted), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms)
, a ureido group (preferably one having 1 to 40 carbon atoms,
A phosphoric acid amide group (preferably a -0- group, a -8O□- group, and a -C- group is most preferable in terms of carbon number OO).

A, , At is preferably a hydrogen atom;

As hydrogen atom, CHt CH(T im e″
+-TPUG is preferred.

In general formulas (R-1), (R-2), and (R-3), T
ime represents a divalent linking group and may have a timing adjustment function.

The divalent linking group represented by Time represents a group that releases PUG from Time-PUG released from the oxidized product of the redox mother nucleus through one or more reaction steps.

As the divalent linking group represented by Time, for example, U.S. Pat.
U.S. Pat. No. 4,310,612 (JP-A-55-53,330) and U.S. Pat. Those that release PUG by an intramolecular ring-closing reaction after ring opening as described in US Pat. No. 525, etc.; US Pat.
No. 4,483,919, JP 59-121.328
U.S. Patent No. 4,40, which releases PUG with the production of an acid anhydride through an intramolecular ring-closing reaction of the carboxyl group of a succinic acid monoester or its analog described in US Patent No. 4,40.
No. 9,323, No. 4,421,845, Research Disclosure Magazine Nα21,228 (1981
February), U.S. Patent No. 4,416,977 (Japanese Unexamined Patent Publication No. 57
-135.944), JP-A No. 58-209.736, JP-A No. 58-209,738, etc., quinomonomethane is produced by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group. , or analogs thereof to release PUG; U.S. Pat. No. 4,420,
No. 554 (Japanese Patent Publication No. 57-136,640), Japanese Patent Application Publication No. 5
No. 7-135゜945, No. 57-188,035, No. 58-98.728, and No. 58-209,737, etc., by electron transfer of the moiety having an enamine structure of the nitrogen-containing heterocycle. one that releases PUG from the γ-position of Those that release PUG, U.S. Pat.
No. 8, JP-A-60-249149, which releases PUG with the production of aldehydes; JP-A-51
-146,828, 57-179.842, 5
9-104,641 which releases PUG with decarboxylation of the carboxyl group; -o-COOCR,R
, -PUG (R, , R, represents a -valent group) structure, and releases PUG with decarboxylation and subsequent generation of aldehydes; JP-A-60-7,429 Examples include those that release PUG with the production of isocyanate as described in U.S. Pat. I can do it.

For specific examples of these divalent linking groups represented by Time, see JP-A No. 61-236,549 and Japanese Patent Application No. 63-Sho.
It is also described in detail in No. 98,803.

PUG is (Time F + PUG or P
UG represents a group having a development inhibiting effect.

The development inhibitor represented by PUG or (T im e ) + PU G is a known development inhibitor having a heteroatom and bonded via a heteroatom, and these are, for example, C.E. Chee Mees (C.

E, K9Mess) and Chi H James (
T. H. James) “The Theory of the
Photographic Process (The Theory)
of Photographic Process
es) J 3rd edition, 1966 Macmi
llan), pp. 344-346.

The development inhibitor represented by PUG may be substituted. Examples of substituents include those listed as substituents for R1, and these groups may be further substituted.

Preferred substituents include a nitro group, a sulfo group, a carboxyl group, a sulfamoyl group, a phosphono group, a phosphinico group, and a sulfonamide group.

In general formulas (R-1), (R-2), and (R-3), R1 or the term PUG contains a ballast group commonly used in immobile photographic additives such as couplers. or general formula (R-1), (R-2), (R-3)
A group that promotes adsorption of the compound represented by the formula to silver halide may be incorporated.

The ballast group has the general formula (R-1), (R-2), (R-3
) is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the formula from diffusing into other layers or into the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, and an amide group. group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidacyline-2-thione, 2-thiohydantoin, rhodanine, thiobarbital acid, tetrazoline-5-thione, 1,2.4-) liazoline-3-thione, 1. 3. 4-year-old xacillin-2-thione, benzimidacillin-2-thione, benzoxazoline-2-thione, benzothiazoline-2-
Thione, thiotriazine, 1,3-imidacyline-2-
Cyclic thioamide group such as thione, chain thioamide group,
Aliphatic mercapto group, aromatic mercapto group, peterocyclic mercapto group (if the carbon atom to which the -3H group is bonded is a nitrogen atom, it has the same meaning as a cyclic thioamide group that has a tautomeric relationship with this group, and Specific examples of groups are the same as those listed above.

Groups having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxazole,
5- or 6-membered nitrogen-containing heterocyclic groups consisting of a combination of nitrogen, oxygen, sulfur, and carbon such as oxazoline, thianazole, oxathiazole, triazine, and asaindene; and heterocyclic tetracyclic groups such as benzimidazolinium. Examples include grade salt.

These may be further substituted with a suitable substituent.

Examples of the substituent include those mentioned as the substituent for R1.

Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

O = D/ In addition to the above-mentioned redox compounds used in the present invention, for example, JP-A-61-213゜847 and JP-A No. 61-213゜847,
No. 2-260,153, Patent Application No. 1-102,393,
Those described in No. 1-102.394, No. 1-102,395, and No. 1-114.455 can be used.

The method for synthesizing the redox compound used in the present invention is, for example, JP-A-61-213,847 and JP-A-62-260,15.
No. 3, U.S. Patent No. 4,684,604, Patent Application No. 1983-
98,803, U.S. Patent No. 3,379,529, U.S. Patent No. 3,620,746, U.S. Patent No. 4,377.634, U.S. Pat.
．． 332. No. 878, JP-A-49-129,536
No. 56-153,336, No. 56-153,34
It is written in No. 2, etc.

The redox compound of the present invention is preferably 1X10-' to 5X10-2 mol per mole of silver halide, more preferably 1
It is used within the molar range of Xl0-' to lXl0-'.

The redox compounds of the present invention can be used in suitable water-miscible organic solvents, such as alcohols (methanol, ethanol, propatool, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoquine, methyl cellulose. It can be used by dissolving it in, etc.

In addition, by the well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate are dissolved using oils, and auxiliary solvents such as ethyl acetate and noclohexanone are used to mechanically emulsify and disperse. You can also create and use things.

Alternatively, by a method known as solid dispersion method,
The layer containing the redox compound of the present invention may contain silver halide emulsion grains and/or hydrazine derivatives, or may contain other hydrophilic compounds. It may also be a sexual colloid layer.

Examples of containing a hydrazine derivative in the photosensitive emulsion layer and containing the redox compound of the present invention in other hydrophilic colloid layers include Japanese Patent Application No. 1-108215 and Japanese Patent Application No. 1-24.
There are issues such as No. 0967.

At this time, the layer containing the redox compound of the present invention may be either an upper layer or a lower layer of the light-sensitive emulsion layer containing the hydrazine nucleating agent. The layer containing the redox compound of the present invention may further contain photosensitive or non-photosensitive silver halide emulsion grains between the layer containing the redox compound of the present invention and the light-sensitive emulsion layer containing a hydrazine nucleating agent. An intermediate layer comprising gelatin or synthetic polymers (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided.

The silver halide grains in the photographic emulsion used in the present invention may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape. It may have crystals or a composite of these crystal forms.

The average grain size of the silver halide grain crystals in the present invention is preferably 0.7 μm or less, more preferably 0.1 μm or less.
A particle size distribution of m to 0.5 μm is preferably monodisperse.

Monodisperse grains herein mean a silver halide emulsion having a grain size distribution with a coefficient of variation defined below of 20% or less, particularly preferably 15% or less.

Various methods known in the field of silver halide photographic materials can be used to prepare the silver halide emulsion used in the present invention. For example, Chiei by P. Glafkides.
s et Physique Photography
que (published by Pau1Monte1, 1967)
, Photographic by G.F. Duffin
Egeulsion Chemistry (T
he Focal Press, 1966) V.
Making by L. Zelikman at al.
and Coating Photography
c Emulsion (The Focal Pres.
s, 1964).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the water-soluble silver salt (silver nitrate aqueous solution) with the water-soluble halogen salt include one-sided mixing method, simultaneous mixing method,
One type of simultaneous mixing method that may use any of these combinations is a method of keeping p and Ag constant in the liquid phase in which silver halide is produced, that is, the controlled double jet method. It can also be used. Grains can also be formed using so-called silver halide solvents such as ammonia, thioethers, and tetrasubstituted thioureas.

The controlled double jet method and the grain formation method using a silver halide solvent can easily produce a silver halide emulsion with a regular crystal shape and a narrow grain size distribution, and are suitable for producing the emulsion used in the present invention. It is an effective method.

In addition, in order to make the particle size uniform, British patent 1,
No. 535,016, Special Publication No. 4B-36890, 52-
As described in No. 16364, a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, British Patent No. 4,242,445, Japanese Patent Application Laid-open No. 5
It is preferable to use a method of varying the concentration of an aqueous solution as described in Japanese Patent No. 5-158124 to grow rapidly within a range that does not exceed the critical saturation level.

The monodispersed emulsion preferably has a regular crystal shape such as a cube, an octahedron, or a dodecahedron, and a cubic or dodecahedral shape is particularly preferred.

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

There is no particular restriction on the halogen composition of the silver halide emulsion used in the present invention, and it may consist of any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, and silver iodochlorobromide. But that's fine.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodilam salt or a complex salt thereof, iridium salt or a complex salt thereof may be coexisting in the silver halide grain formation or physical ripening process. good.

In the present invention, the silver halide emulsion which is particularly suitable as a light-sensitive material for line drawing, shadowing and halftone dot creation is
This is an emulsion produced in the presence of 0-1 to 10-5 moles of iridium salt or a complex salt thereof.

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 (III), potassium hexachloroiridate (IV), ammonium hexachloroiridate (DI), etc. There is.

In the case of a light-sensitive material, its halogen composition is silver halide containing silver chloride in an amount of 90 mol% or more, particularly 95 mol% or more, and chlorobromide containing 0 to 5 mol% of silver chloride or silver bromide. Silver or silver chloroiodobromide is preferable; if the ratio of silver bromide or silver iodide increases, the safelight safety in a bright room may deteriorate or the tone may become weak, which is not preferable.

In order to contain rhodium atoms, it can be added as a metal salt in any form such as a single salt or a complex salt at the time of particle preparation.

Examples of rhodium salts include -rhodium chloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, etc., but preferably water-soluble trivalent rhodium halogen complex compounds such as hexachlororhodium (I
[I) An acid or a salt thereof (ammonium salt, sodium salt, potassium salt, etc.).

The amount of these water-soluble rhodium salts added is 1!1
It is used in a range of 1.0 x 10-'' mol to 1.0 x 10-3 mol per mole. Preferably l.

0XIO-' mol to 1.0XIO-3 mol, particularly preferably 5.0 x 10-s mol - 5.0 x 10-4 mol.

If the amount of rhodium salt is 10@-3 mol or more, it will be impossible to achieve sufficient contrast. On the other hand, if the temperature is 10'' hmol rice, it becomes impossible to achieve a low sensitivity suitable for light-sensitive materials.

The silver halide used in the light-sensitive material used in the present invention is preferably a so-called core/shell type silver halide, particularly a core/shell type silver halide in which the rhodium content of the shell is higher than that of the core.

In order to make the above-mentioned water-soluble rhodium salt exist in silver halide grains, there is a method of adding it to the water-soluble silver salt or to the halide solution when simultaneously mixing the water-soluble silver salt and the water-soluble halide solution. preferable.

Alternatively, silver halide grains may be prepared by a method of simultaneously mixing three liquids as a third solution when silver salt and hydrad solution are mixed at the same time.

The grain size of the silver halide emulsion for light-sensitive materials is 0°15μ.
or less, and more preferably a fine grain emulsion of 0.12 μ or less.

In the present invention, to prepare silver halide fine grains for light-sensitive materials, the mixing conditions include a reaction temperature of 50°C or lower, preferably 40°C or lower, more preferably 30°C or lower, and a sufficient stirring speed to ensure uniform mixing. Silver potential 100m under high conditions
V or more, preferably 150mV to 400mV, pH is 3
-8, preferably 5-7, good results can be obtained. In the case of silver chloride fine particles, due to their high solubility, particle growth may occur even during the water washing and dispersion processes. They can coexist.

The particle size distribution is basically not limited, but it is preferable that it be monodisperse. Monodisperse herein means that at least 95% of the particles by weight or number of particles are comprised of particles having a size within ±40% of the average particle size, and more preferably within ±20%.

In addition to rhodium salts, cadmium salts, lead salts, thallium salts, and iridium salts can also be coexisting.

The emulsion of the present invention may not be chemically sensitized, but may be chemically sensitized. As a chemical sensitization method, known methods such as sulfur sensitization, reduction sensitization, gold sensitization, etc. can be used, and these methods are used alone or in combination. A preferred chemical sensitization method is sulfur sensitization.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Preferred sulfur compounds are thiosulfates and 1,000 urea compounds, and the OPAg during chemical sensitization is preferably 8.3 or less, more preferably in the range of 7.3 to 8.0.

Furthermore, Mo1sar, Klein Gelatine,
Proc, Symp, 2nd.

A method of using polyvinylpyrrolidone and thiosulfate in combination as reported by 301-309 (1970) et al. also gives good results.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The silver halide emulsion in the light-sensitive material used in the present invention is
One type may be used alone, or two or more types (for example, those with different average particle sizes, those with different halogen compositions, those with different crystal habits, and those with different chemical sensitization conditions) may be used in combination.

In the present invention, the silver halide emulsion layer is
It is preferable to include two types of monodisperse emulsions with different average particle sizes as disclosed in No. 3734 and No. 62-90646 from the viewpoint of increasing the maximum density (Dmax), and small-sized monodisperse particles are chemically sensitized. The method of chemical sensitization is preferably sulfur sensitization, and large-sized monodisperse emulsions do not need to be chemically sensitized, but
It may be chemically sensitized. Large-sized monodisperse particles generally tend to generate black spots, so chemical sensitization should not be performed.
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 large size monodisperse emulsion and a small size monodisperse emulsion, but ΔfogE is 0°1-1.0, more preferably 0.2-0.7,
It is preferable that the large size monodisperse emulsion is high.

Here, the sensitivity of each emulsion is determined by coating it on a support containing a hydrazine derivative and adding sulfite ions to 0. It is obtained when processing using a developer having a pH of 10.5 to 12.3 and containing 15 mol/1 or more.

More specifically, the evaluation method described in Example 1 was followed.

The average grain size of the small monodisperse grains is 90% or less, preferably 80% or less, of the average grain size of the large monodisperse silver halide grains.

The average grain size of the silver halide emulsion grains is preferably 0.02μ to 1.0μ, more preferably 0.1μ to 0.5μ.
It is preferable that the average particle size of large size and small size monodisperse particles is included in this range.

In the present invention, when two or more emulsions of different sizes are used, the coating silver amount of the small-sized monodisperse emulsion is preferably 40 to 90 wt%, more preferably 50 to 80 wt%, based on the total coating silver amount. be.

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 that the large emulsion be in the upper layer and the small emulsion in the lower layer.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

Sensitizing dyes (e.g., cyanine dyes, merocyanine dyes, etc.) described in JP-A No. 55-52050, pages 45 to 53, can be added to the light-sensitive material used in the present invention for the purpose of increasing sensitivity. .

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

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may be contained in the milkweed.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
176 volumes 176
43 (published in December 1978) Page 23 (■) Section J is described.

The light-sensitive 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 light-sensitive material. Among these, preferred are benzotriazoles (e.g., 5-methyl-benzotriazole) and nitroindazoles (e.g., 5-nitroindazole), and these compounds may also be included in the treatment liquid. A compound that releases an inhibitor during development as described in JP-A No. 62-30243 may be included for the purpose of stabilizing or preventing black spots.

The photographic material of the present invention may contain developing agents such as hydroquinone derivatives and phenidone derivatives for various purposes such as stabilizers and accelerators.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.
For example, active vinyl compounds (1°3.5-)lyacryloyl-hexahydro-S-triazine, l,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy -5-) riazine), mucohalogenic acid 1f (mucochloric acid), 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 properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and aggravation.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more and described in Japanese Patent Publication No. 5B-9412.

Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80849.

The photographic light-sensitive material of the present invention contains hydroquinone derivatives (so-called DIR-
hydroquinone).

Specific examples thereof include U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620.746, and U.S. Pat.
No. 4, U.S. Patent No. 4,332,878, Japanese Unexamined Patent Publication No. 49-1
29.536, JP 54-67.419, JP 56-153,336, JP 56-153.342
No., JP-A No. 59-278,853, JP-A No. 59-9043
Examples include compounds described in No. 5, No. 59-90436, and No. 59-138808.

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

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these acrylic acid, methacrylic acid, etc. is used. be able to.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of compounds having acid groups include polymers or copolymers containing organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid as repeating units.

Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene are particularly preferred. It is a copolymer water-dispersible latex.

In order to obtain photographic characteristics of high contrast and high sensitivity using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer with a pH close to 13 as described in U.S. Pat. No. 2,419,975. It is not necessary to use a stable developer, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.15 mol/1 or more of sulfite ion as a preservative, and has a pH of
By using a developer having a pH of 10.5 to 12.3, particularly 11.0 to 12.0, a sufficiently high contrast negative image can be obtained.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it is preferable that it contains dihydroxybenzenes, since it is easy to obtain a good quality award. - A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used.

Hydroquinone is particularly preferred as the dihydroxybenzene developing agent used in the present invention.

Examples of developing agents for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention include 1-phenyl-3-pyrazolidone and 1-phenyl-4,4=dimethyl-4-pyrazolidone.

As the p-aminophenol developing agent used in the present invention, N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.05 mol/E to 0.8 mol/2. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or P-amino-phenols, the former is 0.
05 mol/l to 0°5 mol/2, the latter 0.06 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 0.15 mol/e or more, particularly 0.5 mol/e or more. Also, the upper limit is 2.5 mol/! It is preferable to set it up to.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulators and buffers. The pH of the developer is 10.5-1
It is set between 2.3.

Additives used in addition to the above components include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , organic solvents such as hexylene glycol, ethanol, and methanol; antifoggants such as indazole compounds such as 1-phenyl-5-mercaptotetrazole and 5-nitroindazole; and penttriazole compounds such as 5-methylbenztriazole; or black It may also contain a black pepper inhibitor, and if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and JP-A-56-10
6244 and the amino compounds described in JP-A-1-29418.

The developing solution of the present invention contains a silver stain preventive agent.
, No. 347 can be used. Patent application 1986-109.74 as a solubilizing agent added to the developer.
Compounds described in No. 3 can be used. Furthermore, as a PAL buffer agent used in developing solutions, JP-A-60-93.433
It is possible to use the compounds described in JP-A-62-186259.

As the fixing agent, those having commonly used compositions can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain water-soluble aluminum (e.g. aluminum sulfate, light bread, etc.) as a hardening agent, where the amount of water-soluble aluminum salt is usually 0.4 to 2.0.
g-Aj! /J! It is. Furthermore, a trivalent iron compound can be used as a complex with ethylenediaminetetraacetic acid as the oxidizing side.

The development temperature is usually selected between 18°C and 50°C, more preferably between 25°C and 43°C.

Since the silver halide photographic light-sensitive material of the present invention provides a high Dmax, it maintains a high density even if the halftone dot area is reduced when subjected to power reduction treatment after image formation.

(Example) In the example, developers A, B, and C having the following formulations were used.

At this time, add potassium hydroxide, pH=11° Match.

Match.

in developer time, Add potassium hydroxide H 1゜ Match.

(Example 1) Emulsions (A) and (B) were prepared by the following method.

[Emulsion A] 0.37 mol of silver nitrate aqueous solution and 1Xl per mol of silver
(NH=)sRhcj2b and 2X corresponding to 0-' mole
10-' moles of KslrCj! a, an aqueous halogen salt solution containing 0.11-r potassium bromide and 0.27 mol of sodium chloride is added to an aqueous gelatin solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione with stirring. Nucleation was performed by adding by double jet method at 45° C. for 12 minutes to obtain silver chlorobromide particles having an average particle size of 0.20 μm and a silver chloride content of 70 mol %. Subsequently, a halogen salt aqueous solution containing 0.63 mol of silver nitrate aqueous solution, 0.19 mol of potassium bromide, and 0.47 mol of sodium chloride was similarly added over 20 minutes by the double jet method.

After that, conversion was performed by adding 1X10-3 mol of KI solution, washing with water by the flocculation method according to a conventional method, adding 40 g of gelatin, pH 6.5, PAg 7.
．． 5, and further added 7 ■ sodium benzenethiosulfonate and 5 ■ sodium thiosulfate per 111 moles.
The mixture was heated at 60 DEG C. for 45 minutes to undergo chemical sensitization, and 150 .mu. of 1.3.3a, 7-titrazaindene as a stabilizer and Proxel as a preservative were added. The obtained particles have an average particle size of 0. 28μ
m, silver chlorobromide cubic grains with a silver chloride content of 70 mol%. (Coefficient of variation 9%) (Emulsion B) When applying chemical sensitization to Emulsion A, all of the emulsions except for the chloroauric acid were removed (in the same way, the average grain size was 0.28 μm,
Silver chlorobromide cubic particles having a silver chloride content of 70 mol % were prepared. (Coefficient of variation 9%) Next, emulsions A and B were cooled to 40°C and divided into silver halide holes 'lf4100.
After adding porous adsorbent (activated carbon) or ion exchange resin per g as shown in Table 1 and stirring for 10 minutes,
Immediately, activated carbon or ion exchange resin was removed from the silver halide emulsions by filtration three times with a microfilter to obtain emulsions A-1 to A-9 and B-1 to B-6.

(Table 1) As a sensitizing dye, 5- (3-(4-sulfobutyl)
-5-chloro-2-oxazolidylidene]-1-hydroxyethyl-3-(2-pyridyl)-2-thiohydantoin was added, and an additional 2 x 10-4 moles of 1-phenyl-
5-mercaptotetrazole, 5 x 10-' moles of a short-wave cyanine dye represented by the following structural formula (a), a dispersion of a polymer represented by (b) (2001 g/rTf) and polyethyl acrylate (200 g/rrf) hard As a film agent, l 3-divinyl-sulfonyl-2-propanol (200 μ/f) and the hydrazine compound of the present invention were added as shown in Table 2, and coated on a polyethylene terephthalate film at a silver concentration of 3.8 g/rrr. did. (2 g of gelatin/box) Compound (a) Compound (b) C1h COOHC00CJiOOC +C-C1,÷L On top of this, 1.2 g/m of gelatin was added as a protective layer, and amorphous Sin with a particle size of about 3μ, matte 4011 g/I ,
Methanol silica 0°1 g/nf, polyacrylamide 100 g/nf, hydroquinone 200 g/nf, silicone oil, Proxel and phenoxyethanol as preservatives, and fluorosurfactant C* F I represented by the following structural formula as coating aid. ? S Oz N CHt
COOKC, H.

A layer containing sodium dodecylbenzenesulfonate was simultaneously coated to prepare samples as shown in Table 2.

The back layer was coated using the following recipe.

[Back layer formulation] Gelatin matte polymethyl methacrylate (particle size 3.0-4.Op) 1 Latex Polyethyl acrylate surfactant Sodium p-dodecylbenbensulfonate 4 Fluorine surfactant C, F, ? SO, NCH, C00K CsH'r Gelatin hardener 4g/Bo0■/Bo2g/Bo011g/Bo5■/Bo dye Dye (a), Dye [a) Dye [b] Dye (C) 110■/rrr Mixture of (b) and [c] 50 g/100 g/50 g/Dye (a) Dye (b) Dye (c) Proxel and phenoxyethanol were added as preservatives to the back layer coating solution.

In addition, the following test method was used for evaluation in each example.

Test method 1. Evaluation of image quality (1) Creation of manuscript Monochrome scanner 5CA manufactured by Fuji Photo Film Co., Ltd.
Using NART30 and special photosensitive material 5F-100, a transparent image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed in stages were created. At this time, the number of screen lines was 150 lines/inch.

(2) Photography by Dainippon Screen ■ The original was set on a plate-making camera C-440 so that the magnification was equal to 1:1, and then the evaluation sample was exposed to light by irradiating it with a Xe lamp.

At this time, exposure was performed so that 95% of the step wedge of the original was exposed to 5%.

(3) Small dot side (highlight area) with exposure adjusted as in evaluation (2)
A five-grade evaluation (from 5 to 1) was performed in descending order of the gradation reproducibility (difficulty of halftone dot collapse) in the shadow areas of the samples, which combined the halftone dot percentages.

2. Copy dot evaluation (1) Manuscript creation Monochrome scanner 5CA manufactured by Fuji Photo Film Co., Ltd.
A step wedge in which the mesh percentage was changed in stages was created using NART30 and a dedicated vapor SP-1oowp. The number of screen lines during exposure was 150 lines and 1 inch.

(2) Photography The above manuscript and sample were set in predetermined positions in a Dainippon Screen ■ plate-making camera C-690 (Auto Companica), and a Xe lamp was irradiated onto the reflective manuscript to take a photograph.

At this time, the exposure time is 80% of the step wedge on the original.
It was adjusted so that the portion was 10% on the sample.

(3) Tone reproducibility of the shadow area of the sample with a dot side halftone percentage of 10% by adjusting the exposure time as described in Evaluation (2) (
Relative evaluation was performed on a five-level scale, with 5 being good and 1 being bad in terms of halftone dot shift difficulty.

The obtained sample was exposed to light using a xenon light source, and a developing solution and a fixing solution were added to the developer formulation, GR-F 1 manufactured by Fuji Photo Film, and an automatic developing machine FC-71.
Using 0F, development was carried out at 34°C for 30 seconds, and the eye stretching performance and copy dot performance were evaluated.

Here, the sensitivity is a relative value of the reciprocal of the exposure amount that gives a density of 1.5 when developed at 34° C. for 30 seconds, and the value of Sample 1-1 was set as 100.

Dmax is expressed as a concentration corresponding to Dax in practical skill.

(On the characteristic curve, j!og for the sensitivity point of density 0.1
The results are shown in Table 2. As is clear from Table 2, compared to the comparative samples, the samples of the present invention have higher or equal sensitivity, T, and maximum density -ax, have better black obscurities, and have improved image quality.

(Example 2) In Example 1, I-
When Example 7 and Example 1-19 were used in combination, the structure of the present invention showed excellent characteristics similar to Example 1.

(Example 3) Emulsion C was prepared as follows.

[Emulsion C]

Silver nitrate aqueous solution and silver 1 in gelatin aqueous solution kept at 50℃
4X10-' moles of KsIrCj per mole! A monodisperse silver iodobromide emulsion (average grain size 0.28μ, silver iodide amount 0.4 mol%).

This emulsion was washed with water according to a conventional method to remove soluble salts, and then potassium iodide was added to the emulsion to convert the grain surface, so that the grain average silver iodide content/grain surface silver iodide content = 1/ A silver iodobromide emulsion of No. 3 was obtained. Phenoxyethanol was added to this as a preservative.

This emulsion C was treated with a porous adsorption side (activated carbon) or an ion exchange resin in the same manner as in Example 1, as shown in Table 3, to obtain emulsions C-1 to C-5.

(Table 3) *g/100g of emulsion 3X10 per mole of silver was added to these emulsions as a sensitizing dye.
-'moles of 5.5'-dichloro-9-ethyl-3,3'
-Bis(3-sulfobrovir)oxacarbocyanine was added, and the following compounds (a) and (b) were added as stabilizers: 4-hydroxy-6-methyl-1,3,3a, 7tetrazaindene, 5-methylbenzotriazole, ) were added so as to be coated at 5 μ/cm each.

(a) 0IO (b) 1-19 or I-7 was added as a hydrazine compound as shown in Table 3. Furthermore, polyethylene glycol with an average molecular weight of 600 was added at a ratio of 75 cm/bo, and a dispersion of polyethyl acrylate was added at a solid content ratio of 30 w to gelatin.
t%, 13-divinylsulfonyl-2-propanol was added as a hardening layer, and it was coated on a polyethylene terephthalate film at a silver concentration of 3.5 g/n (gelatin 2.
g/po] A protective layer was applied thereon in the same manner as in Example 1 to prepare samples as shown in Table 3.

Further, the back layer was also coated using the same recipe as in Example 1.

The sample thus obtained was evaluated in the same manner as in Example 1. For sensitivity, the value of sample 3-1 was set at 100.

The results are shown in Table 4. As is clear from Table 4, the samples of the present invention have higher or equal sensitivity, T, and maximum density Dmax, better black porosity, and better image quality than the comparative samples. .

(Example 4) Emulsions A-3, A-6, 8-3, and C-3 used in Example 1
The compound of the general formula (II) of the present invention was added to the sample as shown in Table 5, and the same compound as in Example 1 was further added and coated to prepare a sample. These samples were evaluated in the same manner as in Example 1. For sensitivity, the value of sample 4-1 was set as 100.

The results are shown in Table 5.

As is clear from the table, the presence of the compound of general formula (II) of the present invention further improves the image quality.

Example 5 In Examples 1 to 4, when developer B or C was used instead of developer A, the samples of the present invention showed excellent characteristics similar to Examples 1 to 4.

Patent applicant: Fuji Photo Film Co., Ltd. February 1991 lf day

Claims (2)

[Claims] (1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, the emulsion layer is treated with a porous adsorbent or an ion exchange resin during the production process of the silver halide emulsion. 1. A silver halide photographic material comprising a treated silver halide emulsion and containing at least one hydrazine derivative in the emulsion layer or other hydrophilic colloid layer. (2) The silver halide photographic material according to claim 1, wherein the emulsion layer or other hydrophilic colloid layer contains a redox compound that releases a development inhibitor upon oxidation.