JPH04177336A - Silver halogenide film sensitive material - Google Patents

Abstract

PURPOSE:To improve rubbing fog and pressure sensitization generated when films are rubbed with each other, by including a specified compound in an emulsifier and/or the other formed layer. CONSTITUTION:A compound expressed by an expression I is included in an emulsifier and/or in the other formed layer. In the expression I, X1, X2 are hydroxy group that can be formed by hydrolysis, or amino group that can be substituted or not substituted, and Z is =CR2-, =N-, while R1, R2 are hydrogen atom or the difference that can be substituted, and (n) is 0-5. Blackening due to rubbing damage at the time of handling or to pressure can be improved, and a silver halogenide picture sensitive material of high sensitivity that has rapid process property can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to silver halide photographic materials, particularly X-
This relates to sensitive materials used in the fields of rays, photoengraving, micro, general amateur negatives, etc., and relates to improved silver halide photographic materials that are free from scratches and pressure sensitization that occur when films rub together. It is.

(Prior Art) In recent years, rapid processing has been rapidly progressing in the field of photosensitive materials. Speeding up exposure involves shortening exposure time (higher sensitivity),
Transportability within exposure equipment (cameras, scanners, etc.) and toughness in handling are required. In addition, to speed up the development process, high-temperature and rapid processing is carried out using automatic processing machines.
Since it can be processed in a short time, a sensitive material is required that has excellent developing properties and dries in a short time after washing with water.

Covering power (
It is essential to improve the optical density (optical density per unit silver amount), and it is known that the covering power can be improved by reducing the amount of gelatin by methods such as those described in JP-A-61-116347 and JP-A-57-182732. .

However, when the amount of gelatin relative to Ag is reduced, scratched areas tend to blacken due to rubbing between films, etc., and scratch capri is more likely to occur.

Furthermore, if tabular grains with a high aspect ratio are used as silver halide grains for the purpose of increasing sensitivity, pressure sensitization is likely to occur due to scratches or bending during handling of the sensitive material before development.

In addition, it improves the developability of photosensitive materials and the drying speed after washing with water.
If an attempt is made to reduce the amount of binder for the purpose of reducing the amount of binder, it may lead to deterioration of graininess in terms of photographic performance or worsen pressure sensitization during handling.

As a technique for achieving both scratch resistance and covering power, Japanese Patent Application Laid-Open No. 64-29834 discloses a method of incorporating water-soluble polyester into a photosensitive material, but this technique has not yet completely solved the problem. There was a need for further improved technology.

In addition, in the field of photolithographic materials, there is a system that eliminates the instability of image formation in conventional lithographic development and forms stable, rapid, ultra-high contrast negative images with a T of over 10.
U.S. Patent No. 4.166.742, U.S. Patent No. 4,168.977
No. 4,221,857, No. 4,224,401, No. 4,243゜739, No. 4,272,606,
It is described in No. 4,311.781, etc.

These systems use a hydrazine compound to increase the sensitization and contrast, and the development time is 60 to 10 minutes.
0 seconds), much faster processing (developing time 20#~30')
) was achieved. However, although high sensitivity and ultra-high contrast have been achieved, the disadvantage is that sharp capri, pressure sensitization, etc. are amplified and easily occur. In ultra-high contrast image forming systems using these hydrazine compounds, the use of hydroquinone or substituted polyhydroxybenzene as a method for improving pressure sensitization was disclosed in Japanese Patent Application Laid-Open No. 1986-62.
21143, No. 56-1936.

Further, JP-A-54-40629 discloses the use of substituted hydroquinone, particularly hydroquinone substituted with a thio group, to improve sensitivity and contrast.

These JP-A Nos. 62-21143, 59-1936, and 54-40629 all use hydroquinone derivatives, but these are compounds different from the general formula (1) of the present invention.

(Objective of the Invention) The object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a silver halide photographic material which has improved scratches during handling and blackening due to pressure, and has high sensitivity and suitability for rapid processing. It is about providing.

(Structure of the Invention) The above object is to have a surface latent image type silver halide emulsion layer on a support, and to contain a compound represented by the following general formula (1) in the emulsion layer and/or other constituent layers. This was achieved by a silver halide photographic material characterized by containing:

First, the compound of general formula (1) used in the present invention will be explained.

General formula (I) x, +c = z +x.

In the formula, X,
,,R, represents a hydrogen atom or a substitutable group, n represents 0.1.2.3.4, or 5, and when n is 2 to 5, it becomes a repeating unit (C=Z( They may be the same or different, and may form a single ring or a condensed ring.

Here, in at least one of X3, Xz, Rt, and Rt, a hydrogen atom contained in the group is substituted with a group that promotes adsorption to silver halide grains.

However, when n is 1 to 5, the repeating unit is 1+C
At least one of =Z)- is Z=N-, and when n is 0, X, , and X do not simultaneously become substituted or unsubstituted amino groups.

This will be explained in more detail below.

Substitutable groups represented by Rt and Rz include halogen atoms (fluorine, chlorine, bromine), alkyl groups (preferably those with 1 to 20 carbon atoms), and aryl groups (preferably those with 6 to 20 carbon atoms). ), an alkoxy group (preferably one with 1 to 20 carbon atoms), an aryloxy group (preferably one with 6 to 20 carbon atoms), an alkylthio group (preferably one with 1 to 20 carbon atoms), an arylthio group (preferably one with 1 to 20 carbon atoms) 6 to 20 carbon atoms), acyl group (preferably 2 to 20 carbon atoms),
20), acylamino group (preferably carbon number 1 to
20 alkanoylamino group, benzoylamino group having 6 to 20 carbon atoms), nitro group, cyano group, oxycarbonyl group (preferably alkoxycarbonyl group having 1 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms)
, a carboxy group, a sulfo group, a hydroxy group, a ureido group (preferably an alkylureido group having 1 to 20 carbon atoms, an arylureido group having 6 to 20 carbon atoms), a sulfonamide group (preferably an alkylsulfone having 1 to 20 carbon atoms) amide group, arylsulfonamide group having 6 to 20 carbon atoms),
A sulfamoyl group (preferably an alkylsulfamoyl group having 1 to 20 carbon atoms, an arylsulfamoyl group having 6 to 20 carbon atoms), a carbamoyl group (preferably a carbon number 1 to 20),
20 alkylcarbamoyl group, arylcarbamoyl group having 6 to 20 carbon atoms), acyloxy group (preferably an alkanoyloxy group having 2 to 20 carbon atoms, 7 to 20 carbon atoms)
(benzoyloxy group), amino group (unsubstituted amino, preferably an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms)
~20 aryl group substituted secondary or tertiary amino group), carbonate group (preferably an alkyl carbonate group having 2 to 20 carbon atoms, an alkyl carbonate group having 7 to 20 carbon atoms), Sulfonyl group (preferably 1 to 2 carbon atoms)
0 alkylsulfonyl group, arylsulfonyl group having 6 to 20 carbon atoms), sulfinyl group (preferably 1 carbon number)
~20 alkylsulfinyl groups, arylsulfinyl groups having 6 to 20 carbon atoms), and heterocyclic groups (pyridyl groups, imidazolyl groups, furyl groups), and when there are two or more substituents, they may be the same. May be different.

These groups may be further substituted.

As the group that generates a hydroxyl group by hydrolysis of -In addition to hydroxybenzyloxy groups, etc.
Represents a ring-forming ring represented by a lactone ring, oxacylone ring, oxazinedione ring, etc.

When xl and The number of these substituents is more preferably one, which may be a group that forms a -NH group, but when the substituted amino group is a di-substituted amino group, the substituents may be the same or different ( , and the substituents may be linked to form a nitrogen-containing heterocycle (for example, a morpholino group, a piperidino group, a pyrrolidino group, an imidazolyl group, a piperazino group), and these substituents other than the hydroxy group are: It may be further substituted, and examples of substituents include the same as those listed as substitutable groups for R, , R,.

The compound represented by general formula (1) is Kenda 1-P
It is a compound that satisfies the elz law, and (endal P
For compounds that follow the elz rule, ↑he Theor
y of Photographic Process,
Forth Edition, pages 298-327
Page, 1977, monac*1llan Pub-1is
hing Co., Inc. ) Specifically, for example, hydroxylamines (n=0
), 3-pyrazolidones, 3-amino-2-pyrazoline IN (when n = 1), 2゜5-diaminopyrimidine N (when n = 2), 4-amino-5-hydroxypyrimidine and 5-amino-4-hydroxypyrimidine 11 (when n=3).

The adsorption promoting group to silver halide can be represented by the general formula (a).

General formula (a) χIL+.

Y is a group promoting adsorption to silver halide, and 9m, which is a divalent linking group, is O or 1. Preferred examples of the adsorption promoting group to silver halide represented by Y include a thioamide group, a mercapto group, a group having a disulfide bond, or a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by Y is a divalent group represented by -C-amino, and may be a part of a ring structure, or may be an acyclic thioamide group.
Thioamide adsorption promoting groups for Ir, for example, U.S. Pat.
No. 030,925, No. 4,031,127, No. 4,0
No. 80,207, No. 4,245,037, No. 4. 2
55. No. 511, No. 4,266.013, and No. 4
．． No. 276.364, as well as [Research Disclosure J]
re ) Magazine Volume 151 Arashi 15162 (November 1976
), and Vol. 176, No. 1?626 (January 1978)
You can choose from those disclosed in February).

Specific examples of acyclic thioamide groups include thiourido groups, thiourethane groups, dithiocarbamate groups, etc. Specific examples of cyclic thioamide groups include 4-thiazoline-2=thione, 4-imidacyline-
2-thione, 2-thiohydantoin, rhodanine, thiobarbic acid, tetrazoline-5-thione, 1.2.
4-Driazoline-3-thione, 1.3.4-thiadiazolin-2-thione, 1,3.4-oxacyapurine-
2-thousand, benzimidacillin-2-thione, benzoxazoline-2-thione and hendithiazoline-2-
Examples include thione, which may be further substituted.

The mercapto group of Y is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (if the carbon atom to which the -SH group is bonded is a nitrogen atom, it is a cyclic thioamide that has a tautomeric relationship with the nitrogen atom). group, and specific examples of this group are the same as those listed above).

5j represented by Y! The 6-membered nitrogen-containing heterocyclic group is a 5-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur and carbon.
and 6-membered nitrogen-containing heterocycles. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidapool, benzothiazole, thiazole, hendioxazole, oxazole, thiadiazole, oxadiazole, triazine and the like.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as substitutable groups for Rr and Rz.

Among those represented by Y, preferred are cyclic thioamide groups (i.e., mercapto-substituted nitrogen-containing heterocycles,
For example, 2-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptohenzuoxazole group base, etc.),
Or it is the case of a nitrogen-containing heterocyclic group (for example, a hensitriazole group, a benzimidazole group, an indazole group, etc.).

Y-(L3-, two or more groups may be substituted and may be the same or different.

The divalent linking group represented by C, N, S, ○
An atom or atomic group containing at least one of the following. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -0-1-S-1-NH-
1-N-1-CO-1-8O□- (these groups may have a substituent) alone or in combination.

Specific examples include -CONH-1-NHCON)l-1-3O,NH-1
-COO-1-NHCOO-1-CH*CHxSOJH
-, -CH, CH□CONB-, and the like.

These linking groups may be further substituted with a suitable substituent. Examples of the substituent include the same substituents as those listed as substitutable groups for Rr and Rt.

Specific examples of the compound represented by the general formula (1) include those described in JP-A-61-90153.

Preferred specific examples of the compound represented by the general formula (1) are shown next, but the scope of the present invention is not limited thereto.

■-1) l-2) n! -3) h □ Shu ■-4) ■-5) ■-6) ■-7) l-8) ■-9) I-11) I-12) 〇Synthesis of the compound represented by general formula (1) Vessel, Kend
a 1-Pe I A known compound according to the Iz rule and a compound known as an antifoggant are combined by devising a connecting group, or a connecting group is introduced into a reducing agent according to the Kendal-Pelz rule, and then a compound known as an antifoggant is bonded to the connecting group. It can be easily synthesized by introducing an adsorption group, specifically, according to JP-A-61-90
It can be synthesized according to the synthesis method described in No. 153.

Further, the compound represented by the general formula (1) is silver halide 1
Preferably, the content per mole ranges from lXl0-' mol to 1 x 10-1 mol, particularly from 1 x 10-' to 5 x 10
The preferable addition amount is in the range of 1 to 10 moles.

Hydrazine compounds may also be used in the present invention.

The hydrazine derivative used in the present invention has the following general formula (
Preference is given to compounds represented by II).

General formula (I [) R, -, N-N-G, -R2 A, A2 In the formula, R represents an aliphatic group or an aromatic group, and R1 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group , represents an aryloxy group, an amino group or a hydrazino group, and G1 is a 10- group, -8O! ■R.

represents an ocarbonyl group or iminomethylene group, A,
, A2 both represent a hydrogen atom, one a hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In general formula (II), 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.

In the general formula (If), 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 fused with an aryl group.

Preferred as R1 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, and 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,
Preferred substituents include an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoamide group, a diacylamino group, and an imidable substituent; 7 to 30 carbon atoms), alkoxy groups (preferably those having 1 to 20 carbon atoms), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (preferably carbon atoms) (having a carbon number of 2 to 30), a sulfonamide group (preferably having a carbon number of 1 to 30), a ureido group (preferably having a carbon number of 1 to 30), a phosphoric acid amide group (preferably having a carbon number of 1 to 30), ~30).

The alkyl group represented by R2 in general formula (n) 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). .

When G is a -C- group, preferred among the groups represented by R8 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, etc.) group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.),
Particularly preferred is a hydrogen atom.

R8 may be substituted, and the substituents listed for R1 can be used as substituents.

G in general formula (n) is most preferably a 10-group.

Also, R7 splits the G1-R2 part from the remaining molecules,
It may be one that causes a cyclization reaction to produce a cyclic structure containing the atom of the -01-R1 moiety, such as the one described in JP-A No. 63-29751. .

A hydrogen atom is most preferable as A+ and At.

R1 or R2 in the general formula (n) may have a ballast group or a 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-1-100530.

R1 or R2 in general formula (n) 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゜No. 231, No. 59-201.045, No. 59
-201.046, 59-201,047, 5
No. 9-20.1,048, No. 59-201.049,
JP-A-61-170,733, JP-A No. 61-270,74
No. 4, No. 62-948, Japanese Patent Application No. 62-67.508, No. 62-67.501, and No. 62-67.510.

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

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

I-1 I-3 l-6 f-8 l-10 ■-13 ■-14 ■-15 ■-16 I -N l-18 ■-19 ■-20 H ■-23 ■-24 ■-25 ■ -26 I In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCHDISCLO3LIRE
Item23516 (November 1983 issue, P, 3
46) and the documents cited therein, as well as U.S. Pat.
No. 76.364, No. 4,278,748, No. 4.38
No. 5,108, No. 4,459,347, No. 4,560
, No. 638, No. 4.478.928, British Patent No. 2,0
11,391B, JP-A-60-179734, JP-A No. 62
-270,948, 63-29,751, 61
-170゜733, 61-270,744, 6
No. 2-948, EP 217,310, or US 4
゜686.167, JP 62-178,246,
No. 6332,538, No. 63-104゜047, No. 63-121,838, No. 63-129.337,
No. 63-223,744, No. 63-234,244, No. 63-234,245, No. 63-234,246
No. 63-294.552, No. 63-306.43
No. 8, JP-A No. 1-100,530, 1. 105.
No. 941, No. 1-IO5,943, JP-A No. 1986-1
No. 0.233, Japanese Patent Application Publication No. 1-90,439, Patent Application No. 1983
-105,682, 63-114,118, 6
No. 3-110,051, No. 63-114.119, No. 63-116,239, No. 63-147,339,
63-179,760, 63-229,163, Japanese Patent Application No. 1-18.377, 1-18,378,
1-18.379, 1-15,755, 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 from 1X10-' mole to 5X10 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.

When these compounds of general formulas (I) and (II) are incorporated into a photographic photonic material, they may be contained in an aqueous solution if water-soluble, or as an alcohol (e.g. methanol, ethanol) ester WA (e.g. It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as ethyl acetate (ethyl acetate) ketones (for example, acetone).

When added to a silver halide emulsion solution, it can be added at any time from the start of chemical ripening to coating, but it is preferable to add it after chemical ripening, especially when the coating is prepared for coating. It is preferable to add it to the liquid.

The method for preparing the silver halide emulsion used in the present invention is described by Chimie et al.
Physique Photographique J
(Paul Monte1, 1967), G.
, F. Duffin, “Photographic Em
ulsion ChemistryJ (The F
(published by ocal Press, 1966), V, L, Z
Making and by Elilvan et al.
Coating Photographic EIII
ulsion J (The Focal Press
(1964), the conversion method described in U.S. Patent No. 2.592.250, U.S. Pat. It can be prepared using the core/shell emulsion preparation method described in et al.

As a method of reacting the water-soluble silver salt (silver nitrate aqueous solution) and the water-soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used.

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used.

Grain formation can also be carried out using so-called silver halide solvents such as ammonia, thioethers, and tetrasubstituted thioureas.

By the controlled double jet method and the grain forming method using a silver oxide solvent, it is easy to produce a silver halide emulsion with a regular crystal shape and a narrow grain size distribution.

The silver halide grains in the photographic emulsion used in the present invention may have a relatively wide grain size distribution, but preferably have a narrow grain size distribution. It is preferred that the size of the grains that account for 90% of the total in terms of number is within ±40% of the average grain size (such emulsions are generally referred to as monodisperse emulsions).

Silver halide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or irregular crystal structures such as spherical and plate shapes.
It may have crystals such as gular 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.

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

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

The silver halide emulsion used in the present invention may or may not be chemically sensitized, but methods of chemical sensitization include gold sensitization, gold sensitization, and sulfur sensitization, reduction sensitization, noble metal sensitization, etc. A combination of methods such as sensitization can be used.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium. A specific example is U.S. Patent No. 2.448,06
No. 0, British Patent No. 618.061, etc.

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. Specific examples are U.S. Patent Nos. 1,574,944 and 2.
, 278.947, 2,410.689, 2.
No. 728.668, No. 3,501,313, No. 3.
No. 656.955.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include U.S. Pat. No. 2,487,850,
2.518.698, 2゜983.609, 2,9
83,610 and 2°694.637.

Furthermore, this silver halide emulsion can be optically sensitized for the purpose of increasing sensitivity and imparting photosensitivity to a desired wavelength range. As a method of optical sensitization, sensitizing dyes such as cyanine dyes and merocyanine dyes are used alone or in combination.
Spectral sensitization and hyperchromatic enhancement are applied.

These techniques are described in U.S. Patent No. 2.688.54.
No. 5, No. 2,912.329, No. 3.397.0
No. 60, No. 3,615.635, No. 3,628,
No. 964, Special Publication No. 43-4936, No. 44-1403
No. 0, Japanese Unexamined Patent Publication No. 55-52050, etc.

The photographic emulsion used in the present invention may contain one or more compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as penzothiadurium salts, nitroimidazoles, nitrohenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles! ! (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines, mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindene I! (especially 4-hydroxo-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.; A number of compounds known as inhibitors or stabilizers can be added.

Among these, particularly preferred is benzotriazole I
I (e.g. 5-methylbenzotriazole) and nitroindazole! II (e.g. 5-nitroindazole)
In addition, these compounds may be included in the treatment liquid.

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, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5 -1-lyacryloyl-hexahydro-5-) riazine, 1.3
-vinylsulfonyl-2-propanol), active halogen compounds (2,4-dichloro-6-hydroxy-S
-triazine, etc.), mucohalogenic acid W4 (mucochloric acid, mucophenoxychloroic acid, etc.), 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, high contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), grindol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Active autopsy; alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkylclarins, sulfosuccinates, Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphate esters, etc. ;Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidabrilam Cationic surfactants such as heterocyclic quaternary ammonium salts such as phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

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.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g., vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylate Polymers containing a combination of acids, α, β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acids, etc. as monomer components can be used.

As the processing solution used in the present invention, a dihydroxybenzene-based developing agent is used as a developing agent, and p-
It is preferable to use an aminophenol-based developing agent or a 3-pyrazolidone-based developing agent.

Examples of dihydroxybenzene-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, and 2.3-dichlorohydroquinone.
-Dibromohydroquinone, 2,5-dimethylhydroquinone, etc., among which hydroquinone is particularly preferred.

Examples of 1-phenyl-3-pyrazolidone or its derivatives as an auxiliary developing agent include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5
Examples include -merul-3-virapriton, 1-p-aminophenyl-4,4-dimethyl-3-virapriton, and 1-p-tolyl-4,4-dimethyl-3-virapriton.

As the p-aminophenol auxiliary developing agent, N-methyl-p-aminophenol, p-aminophenol, N
-(β-hydroxyethyl>-p-aminephenol,
Examples include N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferred.

Dihydroxybenzene developing agent is usually 0.05 mol/
1-0.8 mol/7! Preferably, it is used in an amount of .

In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols, the former is added at 0.05 mol/1 to 0.5 mol/
1. It is preferable to use the latter in an amount of 0.06 mol/1 or less.

Examples of sulfite-preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfite is used at least 0.3 mol/I1, but if too large a quantity is added, it will precipitate in the developer and cause solution contamination, so the upper limit is preferably 1.2 mol/I.

The developer solution of the present invention may contain a tertiary amine compound as a development accelerator, particularly the compounds described in U.S. Pat. No. 4,269,929.

In addition, the developer of the present invention may contain pH5L, such as boric acid, borax, tribasic sodium phosphate, and tribasic potassium phosphate.
pT(I) described in JP-A No. 60-93433
I buffer agents can be used.

Development inhibitors such as potassium bromide and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve,
Organic solvents such as hexylene glycol, ethanol, and methanol; fogging agents such as indazole compounds such as 5-nitroindazole, henttriazole compounds such as sodium 2-mercaptohenraimidazole-5-sulfonate, and 5-methylbenztriazole. It may also contain an inhibitor or a black pepper inhibitor; in particular, when a compound such as 5-nitroindazole is used, it may be added in a separate area from the area containing the dihydroxyhensen developing agent or sulfite preservative. It is common to dissolve the mixture in advance, mix the image and add water before use. Furthermore, if the part where 5-nitroindazole is dissolved is made alkaline, it will be colored yellow and will be convenient to handle.

Furthermore, it may contain a toning agent, a surfactant, a water softener, a hardening agent, etc., if necessary.

As the fixing agent, one having a commonly used composition 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 fixer contains a water-soluble aluminum salt, such as aluminum sulfate, as a hardening agent.
The amount of the water-soluble aluminum salt, which may also contain aluminum salt, is usually 0 to 3.0 gA1/1. Moreover, ethylenediaminetetraacetic acid Fe(I[f) complex salt may be used as the oxidation side.

The treatment temperature is usually selected between 18°C and 50°C, but 1
The temperature may be lower than 8°C or higher than 50°C.

The effects of the present invention will be explained in more detail with reference to Examples below.

Example ~ 1 1ヱSasada 1J water contains 5g of potassium bromide, 0.05g of potassium iodide, 30g of gelatin, 1(0(C11寞)!5(CH,hS(CH,)!01) of thioether
2.5 cc of a 5% aqueous solution of No. 1 was added and kept at 73°C, and an aqueous solution of 8.33 g of silver sulfate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide were added with stirring. It was added in 45 seconds using the double jet method. Subsequently, 2.5 g of potassium bromide was added, and then an aqueous solution containing 8.33 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the beginning of the addition.

After this, 20cc of 25% ammonia solution, 50% NH
- After adding 10 CC of NO3 and physically ripening for 20 minutes, 240 cc of IN sulfuric acid was added to neutralize it, and then an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added in a control double while maintaining the potential at pAg 8.2. It was added by jet method over 40 minutes. The flow rate at this time was accelerated so that the flow rate at the end of addition was nine times the flow rate at the start of addition. After the addition is complete, add 15 c of 2N potassium thiocyanate solution.
c, and then add 25 cc of 1% potassium iodide aqueous solution to 3
Added over 0 seconds. After that, the temperature was lowered to 35°C and soluble salts were removed by a sedimentation method, and then the temperature was raised to 40°C, 30g of gelatin and 2g of phenol were added, and the pH was adjusted to 6.40 and pAg to 8.10 with caustic soda and potassium bromide. .

After raising the temperature to 56℃, 6 aggravating dyes with the following structure were added.
00 ■ and 150 ■ of stabilizer were added.

After 10 minutes, sodium thiosulfate pentahydrate 2.4 ■ thiocyanic acid strength 140 w, chlorauric acid 2. ]■ was added to each emulsion, and after 80 minutes, it was rapidly cooled and solidified to form an emulsion. In the obtained emulsion, 98% of the total projected area of all grains are grains or lanalis with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 1.4 μm.
The standard deviation was 15%, the average thickness was 0.187 μm, and the aspect ratio was 7.5.

Sensitizing dye (CHz)! (CL) sSOi e
The following chemicals were added per mole of silver halide to the SO3Na stabilizer emulsion to prepare a coating solution.

- Gelatin was added so that the gelatin Ag/Binder ratio was 1.0.

(Binder = Gelatin + Polymer) - Water-soluble polyester WD-3TZE manufactured by Eastman Chemical Company 15. Og・Polymer latex (poly(ethyl acrylate/methacrylic acid)=97/3) 25.0g・Hardening agent 1.2-bis(sulfonylua・Compound of general formula (1) of the present invention or comparative compound Table 1 Addition amount stated: 2.6-
Bis(hydroxyamino)-4-diethylamino-1,3,5-triazine 80■ Sodium polyacrylate (average molecular weight 4,10000) 4.0g Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0g Above coating Coat the liquid with the surface protective layer coating liquid at the same time as transparent P with a thickness of 175 μm.
Coated on an ET support.

The amount of silver coated was 2.0 g/bore.

The surface protective layer was prepared so that each component was coated in the following coating amounts to form photographic materials 1 to 13 (Table 1).

1 plate m Natsuyoshi Yoshi Coating l ・Gelatin 1.15g/n (・Polyacrylamide (average molecular weight 45,000) 0.25 ・Sodium polyacrylate (average molecular weight 400,000) 0.02・pt-octylphenoxy Sodium salt of diglyceryl butyl sulfonate 0.02 ・Poly (degree of polymerization 10) Oxyethylene cetyl ether 0.035 ・Poly (degree of polymerization 10) Oxyethylene-Poly (degree of polymerization 3) Oxyglyceryl-butyl phenoxy ether 0. 01 ・CaFrtSOs!I, 0.
003Jy・CsF+? 5OJ(C)lzteτKGHz)
asOsNao, 001 CJ.

'' CsFr, 5OJ) CToCHJ cat-CH2CH
CHzO)-HO,OO3 ・Polymethyl methacrylate (average particle size 3.5 μm) 0.025・Poly (
Methyl methacrylate/methacrylate) (mole ratio 7:3, average particle size 2.5 μm) 0.020 liters Photographic materials 1 to 1 under green light with a peak at 550 nm
3 was exposed to 1/2o second using an automatic processor FPM9000 manufactured by Fuji Photo Film ■, developer RD7, and fixer Fu.
Sp treatment at 35°C using jiF (Dry to D
ry 45 seconds) was performed.

The sensitivity was determined by the reciprocal of the exposure amount that gives the density of Fog+l and Q, and the results are summarized in Table 1, with photographic material 1 set as 100.

After conditioning the humidity of photographic materials 1 to 13 with scratches for 1 hour at 25°C and 25% RH, under the same conditions, using a commercially available nylon scrubber, a load of 100 g was applied to an area of 2 x 1 cs, and 1 cs per second was applied.
I rubbed it at a speed of After performing the above automatic development process in an unexposed state, the number of blackened scratches was counted.

(Table 1) From the results in Table 1, it can be seen that the products to which the compound of the present invention (general 2N) was added had improved scratch resistance without deterioration in sensitivity.

In the samples Nll0 to 13 to which comparative compounds were added,
Although the scratches tend to improve slightly, they are accompanied by a decrease in sensitivity, which is not desirable.

Example 2 A blue colored polyethylene terephthalate base having a thickness of 175 μm was provided with an undercoat layer on both sides of the base in the following coating amount.

・Gelatin 84■/Po17■
/mt The emulsion of Example 1 was coated on both sides of this base so that the amount of silver coated on each side was 1.9 g/rr+. At this time, the compound of -a formula (1) or a comparative compound was added in an amount shown in Table 2 per mole of silver. The same coating liquid as in Example 1 was used for the surface protective layer. The amount of hardener added was changed to 15 mmol/100 g-ge1. Photographic materials 1 to 13 were thus obtained. Scratches were evaluated by the same method as in Example 1. However, the processing was changed to the same one as in the photographic performance evaluation described below.

亙　 Average Condition ■ Review 1 The same exposure as in Example 1 was given from both sides, and processing was carried out using an automatic processor using the following developer and fixer.

<Developer concentrate> Potassium hydroxide 56.6g Sodium sulfite 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbonate
16.7g Hydrolic acid
10g hydroquinone
83.3g diethylene glycol 40
g4-Hydroxymethyl-4-methyl1-phenyl-3=pyrazolidone 11.0g5-methylbenzotriazole
Adjust to 11 with 2g water (adjust to pH 10.60).

<Fixer concentrate> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid disodium dihydrate 0.10g Sodium hydroxide 24g Adjust to 11 with water (adjust pH to 5 and 10 with acetic acid).

Automatic development! LJLJ developing tank 5.51 35℃ x 12.5 seconds holding tank 6
．． 5g 35℃ x 10 seconds water washing tank 6.5z
Dry at 20℃ x 7.5 seconds *
50°C Dry to Dry processing time: 48 seconds When starting the development process, each tank was filled with the following processing solution.

Developing tank: The above developer solution S ring condensation 333d, 66 ml of water, and a starter 10 containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to IQ, 15.

Fixing tank 2: 250 ml of the above fixer concentrate and 750 ml of water The results are summarized in Table 2. The sensitivity of sample floor 1 was set to 100.

A film of 24.5 x 30.5 ca size was processed in the automatic processor as described above, and the film that came out of the drying zone was immediately touched with the hand to check whether it was dry. The results are summarized in Table-2. The evaluation criteria are as follows.

◎ ... The film that comes out is quite warm and dry enough.

O... The film that comes out is slightly warm and dry.

M... The film that comes out is damp.
Insufficient drying.

×... The film that comes out is wet, and the films are in contact with each other.

(Table 2) From the results in Table 2, it is clear that the samples using the compound of general formula (1) of the present invention have excellent drying properties in rapid processing, high sensitivity, and good scratch resistance.

Example-3 1.Made by Nasukan Emulsions A-E were prepared by the method described below.

Halloween! 1. To a container containing potassium bromide and 25 g gelatin in water 11, while maintaining pAg at 8.7, add silver nitrate aqueous solution and potassium bromide and potassium iodide aqueous solution by double jet method to obtain an average particle size of 0°. A regular octahedral silver iodobromide emulsion of 8 μm was prepared and chemically sensitized using sodium thiosulfate and chloroauric acid to give pAg8.6, p) (Ei,
4 and a regular octahedral photosensitive silver iodobromide emulsion with a normal content of 8 mol% (
A) was obtained.

1 day Halon 1 25g potassium bromide and 4.5g potassium iodide in 11 water
Into a container containing 9 cc of N potassium thiocyanate and 24 g of gelatin, a silver nitrate aqueous solution and a potassium bromide aqueous solution were added using the normal ammonia method using a double jet method to form particles with an average particle size of 1°0 μm and a relatively amorphous shape. A thick plate-shaped silver iodobromide emulsion with a nominal content of 3 mol% was prepared, and chemically sensitized using sodium thiosulfate and chloroauric acid to obtain a pA.
A photosensitive silver iodobromide emulsion (B) having a gs of 6 and a pH of 6.4 was obtained. 9 g of potassium iodide was present in the initial solution;
Grain formation and chemical sensitization were carried out in the same manner as in emulsion (B), and a photosensitive silver iodobromide emulsion (C) with a normal content of 6 mol % and an average grain size of 0.6 μm and 8 g of potassium iodide were added in the initial solution. By adding 4 g of potassium iodide to a halogen aqueous solution using a double jet method, a photosensitive silver iodobromide emulsion (D) having a normal content of 8 mol % and an average grain size of 1.0 μm was obtained.

To a container containing 5 g of potassium bromide and 30 g of gelatin in water 11, a 5% aqueous silver nitrate solution and a mixed aqueous solution of potassium bromide and potassium iodide were added while keeping the pAg at 9.5. 5% of silver nitrate was added by a single jet method, and the remaining 90% of silver nitrate aqueous solution and a mixed aqueous solution of potassium bromide and potassium iodide were added by a double jet method while maintaining PAg at 8.1. Projected area diameter 1.3 μm, standard deviation 15%, aspect ratio 6.
A tabular silver bromide emulsion of No. 5 was prepared and chemically sensitized using sodium thiosulfate and chloroauric acid to give a pAg of 8.6.
Photosensitive silver iodobromide emulsion with a legal content of 3 mol% at pH 6.4 (
E) was obtained.

1. The side coated with the emulsion made by Gobakan Hosaku was pre-undercoated, and the back side was coated with (C1,
) s 0iCHzCJO+-J (m+n=32) 101mg/rrf diacetyl cellulose 143■/n (silicon oxide
A coated sample was prepared by coating a triacetyl cellulose support coated with 5 .mu./n (2.5 mm/n) on the emulsion-coated side of the triacetyl cellulose support.

(Emulsion layer) Amount of coated silver: 3.5 g/n (Amount of gelatin: 1.5 g/Ag1g 4-hydroxy-6-methyl 1.3.3a, 7-titrazaindene) O■/Ag1g Polyethylene oxide 8■/Ag1g Polypotassium p
-Vinylbenzenesulfonate 20■/Ag1g sensitizing dye
230 1 mol AgrW The compound of general formula (1) and the comparative compound were added in amounts shown in Table 3. For the dura mater, the coated sample was heated at 25°C6.
After storage at 5% RH for 7 days, the film was immersed in distillation at 25°C for 3 minutes and adjusted with bis-(vinylsulfonylacetamido)ethane so that the film thickness was 200±10% of the dry film.

(Surface protective layer) Amount of gelatin 0.8g/Bopolipotasum P-vinylbenzenesulfonate 1*+g/Bipolymethyl methacrylate fine particles (average size 3μ) 0.13g/1 sprinkle each Prescription Metol 2g Anhydrous sodium sulfite 100g Hydroquinone
5g boric acid
Add water to 2g or more to make 1j! Make it.

(Adjust the pH to 8.7) Constant liter melon soup 1 Sodium thiosulfate 240g Anhydrous sodium sulfite 15g 28% acetic acid
48M! Boric acid
7.5g potassium alum
Add water to 15g or more to make 11.

Sensitomet 1- Coated samples 1 to 25 were stored at 25° C. and 65% RH for 7 days. After exposure for 1/100 seconds using a filter with a wavelength distribution equivalent to sunlight, it was heated to 20℃ using a developer.
It was developed for 7 minutes, fixed with a fixer, washed with water, and dried. Sensitivity measurements were performed on the processed samples at a fog+density of 0.3.

The sensitivity of each emulsion A to E was compared relative to the sensitivity of each blank as 100.

Amount of scratches: Scratches were made using a nylon scrubber in the same manner as in Example-1. After this sample was subjected to a development treatment similar to sensitometry, the number of blackened scratches was counted in the same manner as in Example-1.

OiI Force 11 Sensitometry was performed on coated samples stored at a temperature and humidity of 25° C. and 65% RH, and those stored at a temperature and humidity of 40° C. and 75% RH for 10 days, respectively, and the fog density was compared. The fogging value of the latter was higher than that of the former, and the difference is recorded in Table 3 as the fog over time.

From Table 3, it is clear that samples Nos. 1 to 25 using the compound of general formula (1) of the present invention have improved scratch resistance without impairing sensitivity, and have little increase in fog over time.

In addition, in the sample of the present invention, high contrast in the toe portion (so-called toe breakage) was observed in sensitometry, and furthermore, a development accelerating effect was observed in areas where the development time was short.

Example-4 Coating samples 1 to 11 were prepared with the following layer configurations.

First layer gelatin o, 6 g/m polybotacium p-vinylbenzenesulfonate 9/M second layer gelatin 1.0 g/n? Hz
CHzSOJ CHzCHzSOJ26■/
ICHzCLSO3KCJbCHzSOsK16■/n(H(1! 0.11■
/ Po 3rd layer Gelatin o, 4 g/n (Polybutonium p-vinylbenzenesulfonate 5 ■/Bo 4th layer
Silver amount using emulsion C: 1.36 g/rd Gelatin 2. 0g/rr14
5th layer
Silver amount 4.6 g/bogelatin amount 7.0 g/m 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 41 ■/M polyethylene oxide 23 ■/d polypotasium p
- Vinyl henzene sulfonate 88■ / top layer gelatin 0.8g / resistance 13■,
/r+(Polymethyl methacrylate-11 particles (average particle size 3μ) 0.13■/ri(Polypotassium p-vinylhenzenesulfonate 6■/M42■/
, I C+sHs+C00C+Js*5
0■/dc,p,,so□-N-CH2COOKC3L
1. 8 g/n (dural film was formed at 25°C after storing the coated sample at 25°C and 65% Rh temperature and humidity for 7 days.
The film thickness after immersion in Karu water for 3 minutes is 300% of the dry thickness.
%±10 was adjusted with bis-(vinylsulfonylacetamido)ethane.

To emulsions (C) and (D), 230 μm/Ag mole of the same dye as in Example 3 was added before post-ripening.

The amount of the compound of the general formula (+) of the present invention and the added layer are shown in Table 4.

Sensitometry, scratch resistance, and fogging over time were evaluated in the same manner as in Example 3, and the results are listed in Table 4.

From Table 4, it is clear that Samples 7 to 11 of the present invention are effective in improving scratch resistance and capri over time no matter which layer they are added to.

Example-5 An aqueous solution of silver nitrate, potassium bromide, and potassium iodide was mixed by a double jet method in the presence of ammonia while maintaining pAg at 7.9, and monodisperse cubes with an average particle size of 0.2 microns were obtained. A silver iodobromide emulsion (silver iodide 2.0 mol%, silver bromide 98.0 mol%) was prepared.

This silver iodide emulsion was subjected to sulfur sensitization by adding 1 mol of sodium thiosulfate (3×10 -' mols) of Ag for chemical ripening.

The sensitizing dye r5,5'-dichloro-3,3'
-di(3-sulfopropyl)-9-ethyl-oxacarbocyanine sodium salt" at 6X10 per mole of silver.
Spectral sensitization was performed by adding -' moles.

Furthermore, as a stable side, 4-hydroxy-6-methyl-1,
C+, Hs3CON-CH
zCH2SO3NaCH3 As a vinyl sulfone curing agent, CHz=(JISOtCHxCONH(CTo), 1
NHCOCHzSOzCH=CL (n=2.3), sodium polystyrene sulfonate as a thickener, 0.30 g/rd of a dispersion of polystylacrylate as a latex polymer, and 0.40 g/rd of the following compound:
It was added so that -

CH3 (CH, C8←,.(CHzC? 3゜COOII
C00C,H,OOC-(CCH2L ■ CH3 Furthermore, 0.1 g of 1-phenylmercabutotetrasol was added as an antifoggant per mole of silver, and then the following compound was added as a hydrazine compound at 6.0×10
-'1 mole of Ag was added.

Furthermore, the compound of general formula (1) was added in the amount shown in Table 5.

Furthermore, as a comparative sample, an emulsion was also prepared in which hydroquinone was added instead of the compound of general formula (1).

The protective layer includes gelatin, sodium dodecylbenzenesulfonate, silicone oil, fluorosurfactant, colloidal silica, polyethyl acrylate dispersion, polymethyl methacrylate (particle size 2.5μ) cloak agent, and sodium polystyrene sulfonate. The coating amount of gelatin is 1.6 g/rrr for gelatin aqueous solution consisting of thickener.
Also, the emulsion was coated with a silver amount of 3.6 g/r.
The emulsion layer and the protective layer were coated at the same time so that rr was obtained.

Two samples were each prepared, and one sample was ground with a load of 2.4, 6, 8.10 g applied to a sapphire needle of 0.025 mφ for the purpose of testing pressure aggravation. The other sheet was prepared without any sandpaper for the purpose of measuring the sensitivity of sensitometry, γ.

These two samples were exposed to tungsten light at 3200' for 5 seconds through an optical wedge for sensitometry, then developed for 30 seconds at 38 DEG C. with a developer having the following composition, fixed, washed with water, and dried. (For the development process, an automatic processor FG-660F manufactured by Fuji Photo Film Co., Ltd. was used.) The results are shown in Table 5.

(Developer prescription) ○ Method for evaluating sensitivity Sensitivity was read from the exposure amount at the point of fog+tM degree 1.5 on the characteristic curve.

○ Evaluation method of γ From the point of fog + 4 degrees 0.3 on the characteristic curve, fog + density 3
．． The γ value was determined by connecting the 0 points with a straight line and using the slope of this straight line.

In other words, 3.0-0.3 Bog (fog + exposure amount at density 0.3) γ
corresponds to the surface quality and is preferably 10 or more.

Method for evaluating O ground-kiss sensitization: The degree of ground-kiss sensitization was visually observed and evaluated in a portion having a slight huck ground density corresponding to the toe of sensitometry.

As the load of the needle applying the pickpocket was increased, the load at which the worsening of the pickpocket began to be observed was recorded. The larger this value is, the stronger the resistance to scratches is, and it is preferably 6 g or more.

From the results shown in Table 5, it can be seen that the samples using the compounds of the present invention showed almost no decrease in sensitivity or T, and the ground-kiss sensitization was extremely improved.

In addition, as a comparative compound, hydroquinone was used with the general formula (1)
It can be seen that the sample used in place of the compound of the present invention showed a smaller degree of aggravation and improvement of scratches and a lower sensitivity than the sample of the present invention, and that the compound of the present invention was superior.

Example 6 A silver chloroiodobromide emulsion (silver iodide 0.00%) was prepared using the double jet method.
1 mol %, silver bromide 30 mol %). This silver chloroiodobromide emulsion contains (NH4)3RhC as a rhodium salt.
1b was added to the aqueous halogen solution so as to contain 1 mole of Ag (I x 10 -' mol), and at the same time, KzlrC16 was added as an iridium salt to the aqueous halogen solution so as to contain 4 x 10 -7 mole/1 mole of Ag. The halogen aqueous solution and the a2 silver nitrate aqueous solution were mixed at 45° C. for 60 minutes to prepare a monodisperse cubic emulsion with an average grain size of 0.25 μm.

After washing and desalting this emulsion, sodium thiosulfate 5 x 10-5
After sulfur sensitization was carried out by adding 1 mol of Ag, gold sensitization was carried out by adding 1 mol of potassium chloroaurate (4×10 -' mol of Ag).

This emulsion was added as a sensitizing dye to 1-(2-hydroxyethoxyethyl)-3-(pyridin-2-yl)-5-((
3-sulfobutyl-5-chloro-2-penzooxazolinidene)ethylidene]-2-thiohydantoin potassium salt at 3X10-' mol/Ag 1 mol, 4- as a stabilizer.
Hydroxy-6-methyl-1,3,3a, 7-chitrazaindene t-1,5g, resorcinaldoxime 2g,
0.1 g of 1-phenyl-5-mercaptotetrazole
Each was added per mole of silver.

Furthermore, the following compounds and saponin are used as coating aids. C+ tH33cON-C) IzCHzSO3Na heat CH.

As a vinyl sulfone curing agent cut=cnso□C)IzCONH(CHz)llN
HCOCHzSO□cn=cnz (n=2.3), sodium polystyrene sulfonate as a thickener, and a dispersion of polyethyl acrylate as a latex polymer were added.

Furthermore, as a hydrazine compound Js 1.2 x 10-' mol of 1 mol Ag was added.

Furthermore, the compound of general formula (1) or hydroquinone was added in the amount shown in Table 6.

For the protective layer, gelatin, sodium dodecylbenzenesulfonate, silicone oil, fluorine surfactant, color silicone, polyethyl acrylate dispersion, polyacrylamide (molecular weight = 5000), polymethyl methacrylate (particle size 2.5μ) were used. ) The aqueous gelatin solution consisting of a matting agent and a thickener of sodium polystyrene sulfonate was applied to the emulsion layer so that the gelatin coating amount was 1.6 g/rrr, and the emulsion was coated with a silver coating amount of 3.6 g/n. A protective layer was applied at the same time.

These samples were polished in the same manner as in Example-5, exposed and developed, and then evaluated in the same manner as in Example-5.

The results are shown in Table-6.

From the results shown in Table 6, it can be seen that even on the back side of sulfur-containing sensitized silver chloroiodobromide, the sample using the compound of the present invention has extremely improved aggravation of scratches without impairing the sensitivity or γ.

Furthermore, the compound of general formula (1) of the present invention exhibits less decrease in sensitivity and T, and has improved abrasion resistance than hydroquinone, which is a comparative compound.

Claims (2)

[Claims] (1) It has a surface latent image type silver halide emulsion layer on a support, and the emulsion layer and/or other constituent layers have the following general formula (
A silver halide photographic material containing a compound represented by I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X_1 and X_2 each represent a hydroxy group that may be generated by hydrolysis, or a substituted or unsubstituted amino group, and Z is =CR_2- , =N-, R_1 and R_2 represent a hydrogen atom or a substitutable group, n represents 0, 1, 2, 3, 4, or 5, and when n is 2 to 5, it becomes a repeating unit. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ may be the same or different, and may form a single ring or a fused ring. Here, in at least one of X_1, X_2, R_1, and R_2, a hydrogen atom contained in the group is substituted with a group that promotes adsorption to silver halide grains. However, when n is 1 to 5, at least one of the repeating units ▲mathematical formula, chemical formula, table, etc.▼ is Z=N
- and when n is 0, X_1 and X_2 cannot be substituted or unsubstituted amino groups at the same time. (2) The silver halide photographic material according to claim (1), which contains a compound represented by the following general formula (II) in the emulsion layer and/or other constituent layers. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic group or an aromatic group, and R_
2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydrazino group, and G_1 is a ▲ group with a mathematical formula, chemical formula, table, etc.;
-SO_2- group, -SO- group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups,
Represents a thiocarbonyl group or iminomethylene group, A_
1 and A_2 both represent a hydrogen atom, one hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.