JPH045651A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To absorb a safe light and to restrain fog by incorporating a specified compound in the silver halide photographic sensitive material. CONSTITUTION:The photographic sensitive material is decolored during development processing and extremely reduced in color stains due to residual dyes after processing by containing the compound represented by formula I in which each of R1 and R2 is H, halogen, alkylcarbonyl, aminosulfonyl, optionally substituted alkyl, or such aryl, and a ring may be formed by both of them; X and Y may be same or different; (n) is an integer of 0 - 6; Z is hydroxy, mercaptoxy, sulfo, aminosulfonyl, or optionally substituted alkyl or such aryl; (m) is an integer of 0 - 3; each of M1 and M2 in an alkali metal atom, each optionally same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material free from residual color stains.

[Conventional technology]

It is generally known that silver halide photographic materials contain dyes that have the function of absorbing light at specific wavelengths in order to use filters, prevent halation, prevent irradiation, or adjust the sensitivity of photographic emulsions. It is being

Dyes used for such purposes should: (1) have good spectral characteristics depending on the purpose of use;

■It is completely decolored during the development process, and there is no residual color contamination caused by the dye after the development process.■It has no negative effects such as fog or desensitization on photographic emulsions.■It has excellent stability over time in photosensitive materials. You must satisfy various conditions such as:

In the past, many studies have been attempted to satisfy the above-mentioned conditions, such as British Patent No. 506,385 and U.S. Patent No. 3,2
No. 47,127, Special Publication No. 39-22089, Special Publication No. 4
No. 3-13168, U.S. Patent No. 1,845,404, U.S. Patent No. 2,493.747, U.S. Patent No. 2,843,4
No. 86, West German Patent No. 818,007, Japanese Unexamined Patent Publication No. 1986-85
No. 130, No. 49-98620, No. 49-11442
No. 0, No. 49-129537, No. 50-28827, No. 52-108115, No. 57-185038,
Techniques related to dyes have been proposed in Japanese Patent No. 59-24845 and the like.

[Problem to be solved by the invention]

However, the reality is that no dye satisfying all of the above conditions has been obtained in any of the above conventional techniques.

Therefore, 1) the present invention 1) has good spectral characteristics, absorbs safelight light and does not cause fog, especially in photosensitive materials for printing plate making; 2) Decolors during development processing, and has extremely little residual color staining after processing. (2) The object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye that is inert to photographic emulsions.

[Means to solve the problem]

The present inventor has made extensive studies to achieve the above object, and as a result has arrived at the present invention.That is, the silver halide photographic light-sensitive material according to the present invention has at least one layer of silver halide photographic material on a support. In a silver halide photographic material having an emulsion layer, the following general formula CI
) is characterized by containing the compound represented by.

General formula (I) represents an aryl group (for example, phenyl group, etc.), and R1 and R
2 may form a ring (for example, a 5- or 6-membered ring).

X and Y are each // -0-, -9-1-5e-1-Te-
, -C-1SO2-, -N-, and X and Y may be the same or different.

In the formula, R, and R2 each represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkylcarbonyl group (
For example, methylcarbonyl group, ethylcarbonyl group, etc.),
Hydroxycarbonyl group, alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.)
, a sulfonic acid group, an aminosulfonyl group, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, etc.), or =CH-, =C-.

n represents an integer from 0 to 6.

Z is a hydroxy group, mercaptoxy group, sulfonic acid group, amino group, hydroxycarbonyl group, alkylcarbonyl group (e.g. methylcarbonyl group, ethylcarbonyl group, etc.), halogen atom (e.g. chlorine atom, bromine atom, etc.)
, an alkoxy group, an alkylthio group (eg, methylthio group, etc.), an aminosulfonyl group, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, etc.), or an aryl group (eg, phenyl group, etc.).

The number represents an integer from 0 to 3.

R3, R4 and R5 are each an alkyl group (e.g. methyl group, ethyl group etc.), an aryl group (e.g. phenyl group etc.)
, alkoxy groups (e.g. methoxy group, ethoxy group, etc.),
It represents an alkylthio group (eg, methylthio group, etc.), a trialkylsiloxy group (eg, trimethylsiloxy group, etc.), a halogen atom (eg, chlorine atom, bromine atom, etc.), and a tertiary amine group.

MIJ-2 is an alkali metal (eg, sodium, potassium, etc.), and Ml and M2 may be the same or different.

Specific examples of the compound represented by the general formula [I] are listed below, but the invention is not limited thereto.

Specific example 0aK SO, K OJ 31゜5O3K So, K 0J so* In K SO, K SO, K SO3K SO, the dye represented by the above general formula CI) may be used alone or in combination of two or more. Furthermore, the dye represented by the general formula CI) and other known dyes may be used in combination.

In the present invention, the dye represented by the general formula CI) contained in the silver halide photographic light-sensitive material may be contained in the silver halide emulsion layer.

It may also be contained in other constituent layers including hydrophilic colloid layers.

The content of the dye represented by the general formula CI) is as follows:
It is preferably 1 mg to 2 g per 41 rn', more preferably in the range of 5 g to 1 g (7).

The dye represented by the general formula [I] may be dissolved in a suitable solvent, such as water, alcohol such as methanol or ethanol, or a mixed solvent thereof, and added to the coating solution for the hydrophilic colloid layer.

Further, these dyes may be mordanted with a cationic polymer or the like.

The silver halide used in the silver halide photographic light-sensitive material of the present invention includes any silver halide such as silver bromide, silver cyclide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains with different internal and surface layers, with latent images forming primarily on the surface or primarily within the grain. It may be a particle that is

Any shape of silver halide grains can be used. One preferred example is a cube having a (100) plane as the crystal surface. Also, U.S. Patent No. 4,183
, No. 756, No. 4,225. GEiB issue, Japanese Unexamined Patent Publication No. 1983
-26589, Special Publication No. 55-42737, The Journal of φ Photographic Science (J, Photogr, 5ci), 21.39 (1
By the method described in the literature such as 973), octahedron, 1
Particles having shapes such as tetrahedrons and dodecahedrons can also be prepared and used. Furthermore, particles having twin planes may be used.

The silver halide grains may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and it may be an emulsion with a wide grain size distribution (polydisperse emulsion), or an emulsion with a narrow grain size distribution (monodisperse emulsion) alone or in combination. Alternatively, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

In the present invention, it is preferable to use a monodispersed emulsion.

The silver halide grains in the monodisperse emulsion have an average grain size r
It is preferable that the weight of silver halide contained within a grain size range of ±20% around , is 60% or more of the total weight of silver halide grains, particularly preferably 70% or more, and still more preferably 80% or more. .

Here, the average particle size r is the frequency n of particles having particle size ri.
It means the particle size when the product n1Xri3 of 1 and ri3 becomes maximum.

(3 significant digits, round off the smallest digit) The grain size referred to here means the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than cubic or spherical. Represents the diameter when converted to a circular image with the same area.

The particle size can be obtained, for example, by photographing the particle with an electronic m* mirror at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print. (The number of particles to be measured is assumed to be 1000 or more indiscriminately.

) In the present invention, a highly monodisperse emulsion is preferred, with a coefficient of variation (monodispersity) defined by the following formula preferably 20 or less, more preferably 15 or less.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
You can obtain it by referring to the number etc.

Silver halide emulsions can be chemically sensitized by conventional methods. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

After completion of chemical sensitization as described above, a stabilizer such as 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene can be used. Furthermore, if necessary, a silver halide solvent such as a thioether may be used, and a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be used during the formation of silver halide grains or during grain formation. It may be added and used after the completion of the treatment.

In the present invention, the silver halide grains used in the emulsion are cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, in the process of grain formation and/or grain growth. Metal ions can be added to the inside of a particle and/or on the particle surface using iron rings or complex salts thereof, and can be reduced inside the particle and/or on the particle surface by placing them in an appropriate reducing atmosphere. Can provide sensitizing nuclei.

Emulsions containing silver halide grains may have unnecessary soluble salts removed after the growth of silver halide grains has finished, or may be left in the emulsion. This can be carried out based on the method described in Disclosure No. 17843.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a sensitizing dye. Sensitizing dyes may be used alone or in combination of two or more,
A dye that does not itself have a spectral sensitizing effect together with a sensitizing dye, or a compound that does not substantially absorb visible light,
A supersensitizer that enhances the sensitizing effect of the sensitizing dye may be included in the emulsion.

Furthermore, these sensitizing dyes can be used for purposes such as gradation adjustment and development adjustment in addition to their original spectral sensitizing effect.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like can be used.

The light-sensitive material of the present invention contains at least one tetrazolium compound represented by the following general formula (II) or at least one hydrazine compound represented by the following general formula (m) in order to obtain high contrast for use in printing plate making. is preferred.

In the general formula (H), preferred examples of the substituents represented by R1 to R3 include alkyl groups (for example, methyl group, ethyl group, cyclopropyl group, propyl group, isopropyl group, cyclobutyl group, butyl group, isobutyl group, pentyl group, cyclohexyl group, etc.), amine group, acylamino group (e.g. acetylamino group), hydroxyl group,
Alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.), acyloxy groups (e.g. acetyloxy), halogen a atoms (e.g. fluorine, chlorine, bromine, etc.), carbamoyl groups, acylthio groups (e.g. acetylthio group), alkoxycarbonyl group (e.g. ethoxycarbonyl group), carboxyl group, acyl group (e.g. acetyl group), cyano group, nitro group, mercapto group.

Examples include sulfoxy group and aminosulfoxy group.

Examples of the anion represented by x0 include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, and acid groups of organic acids such as sulfonic acid and carboxylic acid. , anionic activators, specifically lower alkylbenzenesulfonic acid anions such as P-)toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, and higher alkyl sulfates such as lauryl sulfate anions. Ester anions, boric acid anions such as tetraphenylpolone, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxy sulfate anions, stearic acid anions Higher aliphatic anions such as
Examples include polymers such as polyacrylate anions with acid groups attached.

Specific examples of the compound represented by the general formula (TI) are listed below, but the invention is not limited thereto.

Compound NO ]-2 r-4 II-9 knee 10 II-11 =-12 II-+3 knee 16 II-18 II-+9 ■-20 III-21 ■-22 II-25 II-26 p-C)l.

-Clls o-Cll.

-CHI p-ocll.

-OCRs o-OCII p-ocIl3 p-C, II.

m-Cllla p-C, II.

p-OC. H.

p-QC)l.

p-QC)I.

p-QC, Ii□ p-QCs It lt -n J)-C+sL*-n p-N(C!(+)t p-Nl+.

-Off -ca -Off p-Cll3 p-OCII.

-OCR3 R.

p-Cll.

m-(JT.

o-C)I.

-cos p-OCII.

m-OCtl　s -OCH3 -OCHs -CsHa m-C,H.

-CsHy p-QC, II.

p-ocIl.

p-OC. H.

p-OCII.

p-OCIH++-n 1) -C+zllzs-n p-KcHi)x p-Ni+.

-OH -CQ m-C(1 p-C11.

p-Qcll.

p-OCH! The tetrazolium compound represented by the general formula C II - (Chemical
It can be easily synthesized according to the method described in Reviews, Vol. 55, pp. 335-483.

The amount of the tetrazolium compound represented by the general formula (II) is preferably about 1 mg or more per mole of silver halide contained in the silver halide photographic material of the present invention. More preferably, it is used in a range of about 10+*g to about 2g.

The layer containing the tetrazolium compound represented by the general formula (II) is a wood-philic colloid layer, preferably a silver halide emulsion layer and/or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

In order to incorporate the tetrazolium compound represented by the general formula (rl) into the wood-philic colloid layer, the tetrazolium compound represented by the general formula (rl) can be added by dissolving both in appropriate water and/or an organic solvent, or by adding a solution dissolved in an organic solvent to gelatin or Examples include a method in which the agent is added after being dispersed in a hydrophilic colloid matrix such as a gelatin derivative, or a method in which the agent is added after being dispersed in latex.

The tetrazolium compound represented by the general formula (IT) is 1
One species may be used, or two or more species may be used in combination in an appropriate ratio.

It is also preferable to use an anion that binds to the tetrazolium compound and reduces its phylicity. Examples of such anions include the anions represented by xo described above, and these 7 anions may be mixed with a tetrazolium compound in advance and then added to the hydrophilic colloid layer, or may contain or not contain tetrazolium alone. It can be added to the silver halide emulsion layer or the woody colloid layer.

General formula (m) In the formula. R1 represents a monovalent organic residue, R2 represents a hydrogen atom or a monovalent organic residue, and Ql and Q2 represent a hydrogen atom or an alkylsulfonyl group (including those with a substituent), an arylsulfonyl group (including a substituted (including those having groups), and XI represents an oxygen atom or a sulfur atom. Among the compounds represented by the general formula (m), compounds in which xl is an oxygen atom and R2 is a hydrogen atom are more preferred.

The monovalent organic residues for R1 and R2 include aromatic residues, heterocyclic residues, and aliphatic residues.

Aromatic residues include phenyl groups, naphthyl groups, and substituents thereof (alkyl groups, alkoxy groups, acylhydrazino groups, dialkylamino groups, alkoxycarbonyl groups, cyano groups, carboxy groups, nitro groups, alkylthio groups, hydroxyl groups, sulfonyl groups, etc.) group, caroctamoyl group, halogen atom acylamino group, sulfonamide group, urea group, thiourea group, etc.). Specific examples of those with substituents include 4-methylphenyl group, 4-ethylphenyl group, 4-oxyethylphenyl group, 4-dodecylphenyl group, 4-carboxyphenyl group, 4-diethylaminophenyl group, -octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2-methylphenyl group, 4-(3-ethylthioureido)phenyl group, 4-[2-(2,4-
Examples include a tert-butylphenoxy)butyramido]phenyl group, an i,t-dibenzyl semicarbazide group, and the like.

The heterocyclic residue is a membered or six-membered monocyclic or fused ring having at least one of oxygen, nitrogen, ft yellow, or selenium atoms, which may have a substituent, specifically, for example, , biroline ring, pyridine ring, quinoline ring, indole ring.

Residues such as oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole ring, naphthoselenazole ring, etc. can be mentioned.

These heterocycles have 1 to 4 carbon atoms, such as a methyl group or an ethyl group.
Alkyl group, methoxy group, ethoxy group, etc. having 1 to 4 carbon atoms
may be substituted with an aryl group having 6 to 18 carbon atoms such as an alkoxy group or a phenyl group, a halogen atom such as chloro or bromine, an alkoxycarbonyl group, a cyano group, or an amine group.

Aliphatic residues include linear and branched alkyl groups, cycloalkyl groups, and those with substituents, as well as alkenyl and alkynyl groups.

Straight-chain and branched alkyl groups include, for example, carbon atoms with 1
~18. Preferably it is an alkyl group of 1 to 8, and specifically, for example, a methyl group, an ethyl group, an isobutyl group, a l-
Octyl group, etc.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as cyclopropyl, cyclohexyl, adamantyl, and the like. Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkylthio groups, amide groups, acyloxy groups,
Cyano group, sulfonyl group, halogen atom (e.g. chlorine,
bromine, fluorine, iodine, etc.), aryl groups (side-light phenyl group, halogen-substituted phenyl group, alkyl-substituted phenyl group), etc. Specific examples of substituted groups include 3-methoxypropyl group, ethoxycarbonylmethyl group, etc. , 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, and p-chlorobenzyl group. In addition, examples of alkenyl groups include allyl (
Examples of the allyl) group and the alkynyl group include a propargyl group.

Preferred specific examples of the hydrazine compound are shown below.

111-1 1-formyl-2-! 4-(2-(2,4
-di-ta'rt-butylphenoxy)butyramide]
phenyl)hydrazine 111-2 1-formyl-2-C4-diethylaminopheny)hydrazine -31-pormyl-2-(p-tolyl)hydrazine 1
11-4 1-formyl-2-(4-ethyl-2-ruphenyl)
Hydrazine ■-51-Formyl-2~ (4-acetamibe 2-
methylphenyl)hydrazine N-61-formyl-2-(4-oxyethylphenyl)hydrazine II [-71-pormyl-2-(4-N N-dihydroxyethylaminophenyl)hydrazine IIT-81-formyl-2-( 4-(3-ethylthioureido)phenyl)hydrazine I [[-,91-thioformyl-2-[4-[2-(2
,4-di-tert-butylphenoxy]butylamido]phenyl)hydrazine 11-10 1-formyl-2-(4-pendylaminophenyl)hydrazine III-II 1-formyl-2-C4-octylaminophenyl)hydrazine III- 12,1-formyl-2-(4-dodecylphenyl)hydrazine l-131-acetyl-2-[4-2-2,4-diL
ert-butylphenoxy)butyramido]phenyl)
hydrazine m-144-carboxyphenylhydrazine lff-1
51-acetyl-1-(4-methylphenylsulfonyl)-2-phenylhydrazine 1-161-ethoxycarbonyl-1-(4-methylphenylsulfonyl)-hydrazine/l1l-181-(4- Acetoxyphenyl)-2-formyl 1-(4-methylphenylsulfonyl)-hydrazine/llll-191-formyl-2-(4-hexanoxyphenyl)2-(4-methylphenylsulfonyl)-hydrazine m-20lit Lumilou 2-(4-(te) rat:
dolo, -211-pyran-2-yloxy)-phenyl)-2-(4-methylphenylsulfonyl)-hydrazinell-211-formyl-2-(4-(3-hexylureidophenyl))-2-( 4-Methylphenylsulfonyl)-hydrazineIn-221-formyl-2-(4-methylphenylsulfonyl)-2-(4-(phenoxythiocarbonylamino)-phenyl)-hydrazinem-231-(4-ethoxythiocarbonyl aminophenyl)-2-formyl-1-(/l-methylphenylsulfonyl)-hydrazinell-241-formyl-2-(4-methylphenylsulfonyl)-2-(4-(3-methyl-3-7enyl) 2-Thioureido)-phenyl]-hydrazine I[1
-251-(f4i3-(4-(2,4-bis-1-amylphenoxy)-phthyl]-ureido)-phenyl+
12-Formyl-1-(4-methylphenylsulfonyl)-hydrazine ■ ]ll-31 ■ B' ■ I [1-30 ■ 11゜OC++IL+ I (shi) ■ ■ ■ -38 ■ ■ ■-48 ■ -50 C, ll□ ■ I+.

I[[-44 L-45 ■ ■ ■ ll-55 ■-56 ■-57 ■-58 CH.

The hydrazine compound represented by the general formula (III) is added to the silver halide emulsion layer and/or the non-photosensitive hydrophilic colloid layer on the side of the silver halide emulsion layer on the support. It is a silver oxide emulsion layer and/or its lower layer. The amount added is 10-5 to 10-1 mol/lF! 1 mol is preferable, more preferably 10-4~
1O-2 mol/[1 mol.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Or, during chemical ripening or at the end of chemical ripening, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance.
and/or after chemical ripening and before coating the silver halide emulsion, azoles such as benzothiazolium salts, nitroindazoles, triazoles, hensitriazoles, benzimidazoles (particularly nitro- or halogen-substituted ), peterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
, mercaptopyridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetrazaindenes (especially 4-hydroxy substituted (1,3 , 3a, ?) Tetrazaindenes),
Antifoggants or stabilizers such as benzenethiosulfonic acids, benzenesulfinic acids, etc. can be added.

An example of a compound that can be used is K. Mies (K.

The Theory of the Fists Photographic Process
Photographic Process, 3rd
(edition, 1966), with the original paper listed.

For more detailed examples and other methods of use, see, for example, U.S. Pat.
No. 82,947, No. 4,021,248 or Special Publication No. 5
The description in No. 2-28680 can be referred to.

Further, the photographic constituent layer may contain a furkylacrylate latex described in U.S. Pat. No. 3,411,911, U.S. Pat.

The photosensitive material may contain the following various additives, namely:
As thickeners or plasticizers, e.g. U.S. Pat.
No. 04, Special Publication No. 43-4139, West-German Application Publication 1,
No. 904,804, JP-A-48-83715, Belgian Patent No. 782,833, U.S. Patent No. 3,787,41
0, Belgian Patent No. 588,143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde, epoxy, and ethyleneimine hardeners. ,
Various hardeners such as active halogen type, vinyl sulfone type, incyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, and acyloyl type; UV absorbers include, for example, US Pat. No. 3,253,921, UK Compounds described in the specifications of Patent No. 1,309,349, especially 2-(2'-hydroxy-5-tertiary butylphenyl)hencytriazole, 2-(2'-hydroxy-3', 5 '-Di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3'-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy3',5 '-di-tertiary butylphenyl)-5-chlorobenzotriazole and the like can be mentioned. Furthermore, coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent Nos. 548,532 and 1.
, 218,389, US Pat. No. 2.02Ei, 202, US Pat.
No. 3-3186, No. 49-20785, French Patent No. 20
Anionic, cationic, nonionic or amphoteric compounds described in No. 2,588, Belgian Patent No. 773,459, JP-A-48-101118, etc. can be used, but among these, Particularly preferred are anionic surfactants having a sulfonic group, such as succinic acid ester sulfonates, alkylbenzene sulfonates, etc.
In addition, as antistatic agents, Japanese Patent Publication No. 4B-24159, Japanese Patent Application Laid-Open No. 48-89979, and U.S. Patent No. 2,882,157
issue.

No. 2,972,535, Japanese Unexamined Patent Publication No. 48-20785,
No. 48-43130, No. 48-90391, Special Publication No. 4B-24159, No. 4B-39312, No. 48-
There are compounds described in JP-A-43809 and JP-A-47-33827.

The constituent layers of the photosensitive material include matting agents, such as Swiss Patent No. 33.
Silica as described in No. 0,158, Buddhist Patent No. 1,298.9
Glass powder described in No. 95, British Patent No. 1,173,181
Inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; US Pat. No. 2,322.03
The starch described in No. 7, the starch derivative described in Belgian Patent No. 825,451 or British Patent No. 981,198,
Polyvinyl alcohol described in Japanese Patent Publication No. 44-3843, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158, US$ 3,
Organic particles such as the polyacrylonitrile described in US Pat. No. 079,257 and the polycarbonate described in US Pat. The average particle diameter of the mer and torment agents is preferably 2 to 8 final layers.

A slippery agent is added to the constituent layers of the photosensitive material, such as U.S. Pat.
Higher aliphatic higher alcohol esters described in No. 88,758 and No. 3,121,080, US Pat. No. 3,295
．． Casein described in No. 979, British Patent No. 1,283,7
Higher aliphatic calcium salts described in No. 22, British Patent No. 1,
313.384, U.S. Pat. No. 3,042,522, and U.S. Pat. No. 3,4H,587.

Dispersions of liquid paraffin and the like can also be used for this purpose.

The photosensitive material may further contain various additives depending on the purpose. These additives, including those mentioned above, are described in more detail in Research Disclosure No. 178@I.
tem 17843 (December 1978) and 18
It is described in Volume 7, Item 18716 (November 1979), and the relevant sections are summarized in the table below.

1. Chemical sensitizer 2. Sensitivity enhancer 3. Spectral sensitizer Super sensitizer 4. Brightener 5. Antifogging agent and stabilizer Anti-stain agent Dye image stabilizer Hardener Binder Plasticizer/lubricant Coating aid・23 pages 23-24 pages 24 pages 24-25 pages 25 right column 25 pages 26 pages 26 pages 27 pages 28-27 pages 648 right column Same as above page 648 right column - 649 right column 649 pages right column Page 650 Left to right columns Page 651 Left column Same as above Page 650 Right column Same as above Surface active agent 12, anti-stain agent Page 27 Same as above The pH of the coating solution for the constituent layers of the photosensitive material must be in the range of 5.3 to 7.5. In the case of multi-layer coating, it is preferable that p)l of the coating liquid obtained by mixing the coating liquids of each layer in the ratio of coating lrJ amount is in the range of 5.3 to 7.5.
If H is less than 5.3, the progress of hardening may be slow, which is undesirable, and if pH is greater than 7.5, it may have an adverse effect on photographic performance, which is not preferred.

Gelatin is usually used as a binder for silver halide emulsions, but if necessary, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic woody polymeric substances such as copolymers can also be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin, and Bull, Soc, Sci, Phot, Japan.
No.

Oxygen-treated gelatin as described on page 16.30 (198B) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin conductors include various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds. The product obtained by reacting is used. Specific examples include U.S. Pat. 033j No. 89,
It is described in Japanese Patent Publication No. 1,005,784, Japanese Patent Publication No. 42-26845, etc.

Examples of proteins include albumin and casein; examples of cellulose conductors include hydroxyethylcellulose, carboxymethylcellulose, and sulfuric acid esters of cellulose; and examples of sugar derivatives include sodium alginate and starch derivatives, which may be used in combination with the gelatin.

The graft polymers of gelatin and other polymers include gelatin, conductors such as acrylic acid, methacrylic acid, their esters and amides, and single (homo) or copolymers of vinyl monomers such as acrylonitrile and styrene. can be used. Particularly preferred are graft polymers of gelatin with polymers which are compatible to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates, examples of which are described in U.S. Pat.
No. 83,825, No. 2,831,767, No. 2.95
No. 6,884, etc.

In a light-sensitive material, for example, a silver halide emulsion layer and other layers can be formed by coating on one or both sides of a flexible support commonly used in photographic light-sensitive materials. The amount of gelatin on the silver halide emulsion layer side is preferably 10 g or less per 1 m'.

Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers, or α-olefins. Examples include paper coated or laminated with a polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using a dye or pigment,
The surface of these supports, which may be colored blue for the purpose of blocking light, is generally subjected to an undercoat treatment to improve adhesion with silver halide emulsion layers and the like.

The undercoating treatment is as per JP-A-52-104913 and JP-A-59-1.
No. 8949, No. 59-19940, No. 59-1894
The treatments described in each publication No. 9 are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In light-sensitive materials, photographic emulsion layers and other wood-philic colloid layers can be coated on the support or on other layers by various coating methods. Application methods include dip application method, roller application method,
A curtain coating method, an extrusion coating method, etc. can be used.

The photosensitive material preferably has an antistatic layer, such antistatic layer preferably comprising a conductive polymer or a metal oxide.

When carrying out the present invention, the positive g? An organic desensitizer in which the sum of the li position and the cathode potential is positive can also be used.

The photosensitive material of the present invention can be exposed using an ITT magnetic wave in a spectral region to which the emulsion layer constituting the photosensitive material is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, quartz light sources, carbon arc lamps, xenon fuller lamps, cathode ray tubes,
Various types of laser beams, single emission, electron beams, X-rays, gamma rays,
Any known light source can be used, such as light emitted from a phosphor excited by alpha rays or the like.

Mata Unexamined Patent Publication No. 62-210458 etc. (7) 3 for UV light source
U is equipped with an absorption filter that absorbs wavelengths of 70 nm or less, or has a main wavelength of 370 nm to 420 nm.
A V light source may also be used.

The exposure time may be 1 millisecond to 1 second, but it may be shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond using a cathode ray tube or xenon flash tube, or it may be longer than 1 second. These exposures may be performed continuously or intermittently.

The present invention can be applied to various photosensitive materials such as those for printing, X-ray, general negative, general reversal, general positive, and direct positive.

In the present invention, various types of development processing such as black and white, color, and reversal processing using known methods can be used to develop the photosensitive material, but this method is particularly effective when processing for printing photosensitive materials that provide high contrast. .

After the photosensitive material of the present invention is developed and fixed, it is washed with water and/or stabilized.

A combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is preferred as a developing agent used in a developer, especially a black and white developer, since it is easy to obtain good performance. May include.

The above dihydroxybenzene developing agents include /hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, 2.5-dichlorohydroquinone, 2.3-dibromohydroquinone, 2
, 5-dimethylhydroquinone, etc., and hydroquinone is particularly preferred.

The developing agent for the above 1-phenyl-3-pyrazolidone or its derivative is 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl 4.
Examples include 4-dihydroxymethyl-3-pyrazolidone.

The p-7 minophenol-based developing agents include N-methyl-p-7 minophenol, p-aminephenol, N
-(β-hydroxyethyl)-p-aminephenol,
N-(4-hydroxyphenyl)glycine 2-methyl-
Examples include p-7 minophenol and P-benzylaminophenol, among which N-methyl-p-aminephenol is preferred.

The developing agent is preferably used in an amount of usually 0.01 mol/kg to 1.2 mol/ml.

Sulfites are used as preservatives in developing solutions, and examples of such sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, and 1! ! These include sodium sulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The amount of sulfite is preferably 0.2 mol/liter or more, particularly 0.4 mol/liter or more, and the upper limit is preferably 2.5 mol/liter.

The p)I of the developer is preferably in the range from 9 to 13, more preferably from p)110 to 12. P.H.
Alkaline agents used for adjustment include sodium hydroxide,
JP-A-61-28708 (Borate), JP-A-93439 (Borates), including pH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate. For example, buffers such as sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol; l-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain an antifoggant such as a mercapto compound, an intazole compound such as 5-nitroindazole, or a benztriazole compound such as 5-methylbenztriazole, and may further contain a color toning agent, a surfactant, and an antifoaming agent as necessary. , hard water softener, JP-A-1987-
It may also contain the amino compounds described in No. 108244.

In the present invention, a silver stain preventive agent 1 such as the compound described in JP-A-56-24347, JP-A-58-1
Amino compounds such as flukanolamine described in No. 06244 can be used.

In addition, F. A. Menn [Photography 7 Book Processing and Chemistry], published by Focal Press (1
9 [18], pages 226-229, U.S. Patent No. 2,19
No. 3.015, No. 2,592,384, Japanese Unexamined Patent Publication No. 1973-
Those described in No. 84933 may also be used.

Next, the fixing solution is an aqueous solution containing thiosulfate and has a pH of 3.
, 8 or higher, more preferably pH 4.2 to 5.
It is 5.

Examples of the fixing agent include sodium periosulfate and ammonium thiosulfate, but those containing thiosulfate ions and ammonium ions are preferred, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.

The amount of fixing agent used can be changed as appropriate, and is generally about 0.
．． 1 to about 6 mol/vert.

6i for fixer! It may also contain water-soluble aluminum salts 1 that act as membrane agents, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

Tartaric acid, citric acid, or their derivatives can be used alone or in combination of two or more kinds in the fixer.

It is effective to use these compounds in an amount of 0.005 mol or more per fixer 11, and particularly in a range of 0.01 mol/l to 0.03 mol/l.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution may optionally contain a preservative (e.g. sulfite, bisulfite), a pH buffer (e.g. acetic acid, nitric acid),
It can contain a pH adjuster (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in JP-A-80-213562.

The fixing temperature and time are preferably 6 seconds to 1 minute at about 20°C to about 50°C, more preferably 6 seconds to 30 seconds at 30°C to 40°C, and even more preferably 6 seconds at 30°C to 40°C. ~15
Seconds.

For washing and stabilization treatment after fixing, any method known in the art can be applied, and water containing various additives known in the art can also be used as a submergence solution or a stabilizing solution. By using anti-piping water as the washing water or stabilizing liquid, not only is it possible to save water by reducing the amount of replenishment to less than 3 centimeters per 1 m of photosensitive material, but also eliminates the need for piping for installing an automatic processing machine. This makes it possible to further reduce the number of stock tanks.In other words, the developer and fixer dilution water, washing water, or stabilizing solution can be supplied from a common stock tank, making the automatic processor more compact. It becomes possible.

When water treated with piping prevention means is used in combination with washing water or stabilizing liquid, the formation of limescale etc. can be effectively prevented.
Water saving treatment of 0 to 3 sentences per rn', preferably 0 to 14 Q, can be performed.

Here, when the replenishment amount is 0, no replenishment is performed at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservoir" is essentially not refilled. Refers to cases in which a processing method is used.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time.

When washing with a small amount of water, patent application 1729/1980
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Furthermore, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with water treated with anti-piping means, according to the treatment is disclosed in Japanese Patent Application Laid-open No. 60-2.
As described in Japanese Patent No. 35133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that.

〔Example〕

Although specific examples of the present invention are shown below, it goes without saying that the present invention is not limited to these examples.

Example 1 In a container heated to 40°C containing gelatin, sodium chloride and water, a solution of silver nitrate and 4 mols of silver halide were added.
X Silver chlorobromide particles (with a distribution of 9% width, cubic crystal, grain size 0
．． 25ua+) was maintained at p)l 3.0 and pAg 7.7, vR was adjusted, p)l was returned to 5.9, and then desalted in a conventional manner.

After gold and sulfur sensitization of this emulsion, 70111 g of 1-phenyl-5-mercaptotetrasol, 4-hydroxy-6-methyl! ,3
,3a,? - After adding 500 mg of tetrazaindene and gelatin to stop the ripening, further add 4 g of hydroquinone per mole of silver halide, 3 g of potassium bromide, 5 g of saponin, 28 g of styrene-maleic acid polymer, After adding 3 g of ethyl acrylate polymer latex, 10 g of (^) as a bactericide, 300 mg of (T) as a tetrazolium compound, and glyoxal and formalin as hardening agents, an antistatic layer was added. Silver content of 3.5 g/rn' on coated and subbed polyethylene terephthalate support, and maintained! l! Potassium bromide in an aqueous solution of 500 g of gelatin as log, 1-
Decyl-2-(3-impentyl)succinate-2-
4 g of sodium sulfonate was added, IOg of amorphous silica having an average particle size of 5 μm was added and dispersed, the dye of the present invention and the dye for comparison were added as shown in Table 1, and the gelatin was 1.
The emulsion layer and the protective layer were coated simultaneously at 0 g/m'.

The backing layer on the opposite side to the above coated side is gelatin 3
Add 1.6 g of (C-1) and 1.6 g of (C-2) to an 8 g aqueous solution.
8g of saponin, 5g of (C-3) were added, 2g of styrene-maleic acid polymer was added to adjust the viscosity FA, and the pH was adjusted to 5.4 with citric acid, and the reaction product of polyglycerol and epichlorohydrin was added. 100mg
In addition, a coating solution to which 140 mg of glyoxal was added was finally applied, and the coating was dried so that the amount of gelatin applied was 2.0 g/m'.

At the same time, as a backing protective layer, 50 g gelatin aqueous solution, 340 mg 2-sulfonate-succinic acid bis(2ethylhexyl) ester sodium salt, 3 g sodium chloride, 500 + sg mucochloric acid, and 500 mg spherical polymethyl methacrylate with an average weight of 4 gm as a matting agent.
In addition, a coating solution to which 1 g of glyoxal was added was coated and dried at the same time as the backing layer so that the gelatin coverage was 'i, og/d.

Compound (A) Compound (T) (C-1) (C-2) (C-3) Q Comparative dye ([) Comparative dye (II) (1) The sample obtained as above was Using the following developing solution and fixing solution, processing was carried out under the following conditions in an ordinary roller type automatic developing machine, and residual color was visually evaluated.

Processing conditions (process) (temperature) (time) Development
Fixing at 35°C for 12 seconds Washing at 34°C for 12 seconds Drying at room temperature for 10 seconds Developing solution formulation (composition A) Pure water (ion-exchanged water)! 501
1 sentence Ethylenediaminetetraacetic acid disodium 112 2g
Diethylene glycol 50g Potassium sulfite (55% W/V aqueous solution) 10011 Potassium carbonate 50g Hydroquinone 15g 5-Methylbenzotriazole 200mg 1~Phenyl-
5-mercaptotetrazole 30+ag potassium bromide
4.5g potassium hydroxide, amount to make p)I 10.4 after use (composition) Pure water (ion-exchanged water) 3rn diethylene glycol 50g ethylenediaminetetraacetic acid disodium fj 325mg acetic acid (90
% aqueous solution) 0.3+J15---
)! =+Indacy JL/llo
+ag1-phenyl-3-pyrazolidone 70
When using a 0 mg developer, the above composition A was dissolved in 500 ffi of water in the order of composition A and composition 11 was used.

Dinghang liquid summer soup (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 240m 7g 6.5g 8g 2g 13.6m Sodium sulfite Sodium acetate trihydrate [Acid sodium citrate dihydrate Acetic acid (90% W/V aqueous solution) (Composition) Pure water (ion exchange water) 17m sulfuric acid sulfuric acid resistant 0% W/V aqueous solution) 4.7g
Aluminum sulfate (A/V aqueous solution with a content of 8.1% in terms of A-03) 26.
When using 5g of fixer, the above composition A was dissolved in 500ml of water in the order of composition A and the composition was finished to 1M before use. This fixer p
H was approximately 4.3.

Note that the residual color level was evaluated in 10 steps.

5 or above 2 usable level (10: best) 1-4: Unusable The results are shown in Table 1.

(2) Safelight property test A safelight test was conducted by irradiating the emulsion layer side of each sample for 30 minutes at an illuminance of 400 Lux using a 40W anti-fading lamp manufactured by Toshiba.

The film was developed under the above conditions and fog was measured. The lower the fog value, the better the safelight property. The results are shown in Table 1.

(3) Test for aging To investigate the effect of aging on photographic performance, thermo processing was performed.

In the thermo-treatment, an unexposed sample was heated at 50° C. for 3 days to obtain an aging sample.

Each sample obtained was exposed to light using a bright room printer using a yotz quartz light source, and after development under the above conditions, the sensitivity and capri of the unexposed area were measured. At the same time, residual color was also measured using the method described above.

For photographic sensitivity, set the value of sample No. 3 before thermosetting to 100.
Expressed as a relative value.

The above results are shown in Table 1.

From Table 1, it can be seen that the samples of the present invention have a better residual color level and extremely good safelight properties than the comparative samples.

The sample of the present invention after thermo-treatment has higher sensitivity and better sensitivity than before thermo-treatment.
It can be seen that the fog is almost the same, there is little change in photographic performance over time, and the level of residual color is also very good.

Example 2 Similar evaluations were performed using the following hydrazine compound in place of compound (T) in Example 1, and similar results were obtained.

〔Effect of the invention〕

According to the present invention, the following effects are achieved.

(2) Absorbs safelight light and does not cause fog, especially in photosensitive materials for printing plate making, which have good spectral characteristics.

■During the development process, the color is decolored and there is very little residual color staining after processing.

(2) It is possible to provide a light-sensitive material containing dye 4 which has properties of being inert to photographic emulsions.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide photographic emulsion layer on a support, characterized in that it contains a compound represented by the following general formula [I]. Silver chemical photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are each a hydrogen atom, a halogen atom, an alkylcarbonyl group, a hydroxycarbonyl group, an alkoxycarbonyl group, a sulfonic acid group, an aminosulfonyl group, It represents a substituted or unsubstituted alkyl group or aryl group, and R_1 and R_2 may form a ring. X and Y are respectively -O-, -S-, -Se-, -Te-, ▲
There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X and Y can be the same or different. L represents -CH_2CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼. K represents =CH-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼. n represents an integer from 0 to 6. Z represents a hydroxy group, a mercaptoxy group, a sulfonic acid group, an amino group, a hydroxycarbonyl group, an alkylcarbonyl group, a halogen atom, an alkoxy group, an alkylthio group, an aminosulfonyl group, a substituted or unsubstituted alkyl group, or an aryl group. m represents an integer of 0 to 3. R_3, R_4 and R_5 each represent an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a trialkylsiloxy group, a halogen atom, or a tertiary amino group. M_1 and M_2 are alkali metals, and M_1 and M_2 may be the same or different. ]