JPH03168635A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance the sensitivity of a sensitive material and to improve the shelf stability of the material at high temp. and humidity and the staying property of a coating soln. by incorporating two kinds of specified compds. CONSTITUTION:This photographic sensitive material contains one or more kinds of compds. represented by formula I and one or more kinds of compds. represented by formula III. In the formulae I, III, each of Y1 and Y2 is a group of atoms required to form a desired N-contg. hetero ring, each of R1 and R2 is (un)satd. aliphatic, each of Q1 and Q2 is a group of atoms required to form a ring such as 4-thiazolidinone or 4-oxazolidinone, each of L1-L3 is (substd.) methine, each of R4 and R5 is (un)substd. alkyl, each of A1-A6 is H, alkyl, etc., each of X1<-> and X2<-> is an anion, each of n1 and n2 is 0-3 and m is 0 or 1. Compds. represented by formulae II, IV may be used as the compds. represented by the formulae I, III, respectively.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material with improved storage stability and coating solution stagnation property. [Prior Art] In recent years, demands on silver halide photographic light-sensitive materials have become increasingly strict, and there is a strong demand for the development of light-sensitive materials that are particularly sensitive and have excellent image characteristics. The technology of adding photosensitive dyes to silver halide emulsions to achieve spectral sensitization has been well known for the purpose of increasing sensitivity.
Furthermore, research on so-called supersensitization, in which extremely high sensitivity can be obtained by combinations of photosensitive dyes or special combinations of photosensitive dyes and some additives, has been actively conducted in the industry. Special Publication No. 54-34535, No. 48
There are notes regarding supersensitization in No. 42501, No. 56-38936@, etc. Although the spectral sensitivity could be improved by these combinations, the storage stability under high temperature and high humidity conditions often deteriorated, and the stagnation of the coating solution worsened. Therefore, a photosensitive material that satisfies these requirements and has high sensitivity and high performance has been desired for a long time.

[Problem to be solved by the invention 1] The present invention has been made to solve the above problems,
An object of the present invention is to provide a silver halide photographic material which is highly sensitive and has improved storage stability and coating solution stagnation at temperature B and high humidity. [Means for Solving Problem 1] The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, which is represented by the following general formula [I]. 111 of the following compounds, at least one compound represented by the following general formula [I], and at least one compound represented by the following general formula [III]. This is achieved using silver photographic materials. General formula [I] [However, in the above general formula [I], Y1 and Y2 are each 5
Represents an atomic group necessary to form a membered ring and/or a 6-membered nitrogen-containing heterocycle. R1 and R2 each represent a saturated or unsaturated aliphatic group. , Q1 and 02 are 4-thiazolidinone, 4-oxazolidinone, 4-imidazolidinone, 5-thiazolidinone, 5-oxazolidinone or 5-
Represents the atomic group necessary to form an imidazolidinone ring. L, L2 and L3 represent a methine group, a substituted methine group, or R3 I (-C~, where R3 represents an ethyl group, a methyl group, an ethoxy group, or an aryl group). Xse represents an anion. nI+02 represents an integer from 0 to 3. ] General formula [II] [wherein R4 . Rs represents a substituted or unsubstituted alkyl group; eAt to A6 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group; however, adjacent ones may form a ring. However, either one or both of A2 and A5 must be a phenyl group. The weight is 0 or 1, and is 0 when forming an inner salt. Moreover, X2e represents an anion and is the same as X+e defined in general formula [I]. 1 General formula [I[1] R, [wherein M represents a hydrogen atom, -NH4 group or an alkali metal, R6 represents a hydrogen atom, an alkyl group or an aryl group, and Z may have a substituent. Represents the atomic group necessary to form a good 5-membered heterocycle or a 5-membered heterocycle fused with a benzene ring. ] Hereinafter, the present invention will be specifically explained. The silver halide photographic light-sensitive material of the present invention is a compound represented by the general formula [I] (hereinafter also referred to as compound [I]).
Contains at least one kind of. General Formula [I] However, in the above general formula [Il, Y1 and Y2 each represent an atomic group necessary to form a 5-membered ring and/or a 6-membered nitrogen-containing heterocycle. The above heterocycles include a thiazole ring, a penzothiazole ring, a naphthothiazole ring, a selenazole ring, a penzoselenazole ring, a naphthoselenazole ring, an oxazole ring, a penzoxazole ring, a naphthoxazole ring, an imidazole ring, and a penzimidazole ring. Alternatively, there is a nitrogen-containing heterocycle such as a quinoline ring, and Y+ Y2 represents a group of nonmetallic atoms necessary to form such a heterocycle. Y1. The heterocycle formed by Y2 may have a substituent. Examples of substituents include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups such as alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, n-butyl group). base,

[-butyl group, etc.), alkoxy group, e.g., alkoxy group having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, n-
(probyloxy group, etc.), aryl group (eg, phenyl group, etc.), and the like. R1. R2 each represents a saturated or unsaturated aliphatic group, and such groups include, for example, methyl group, ethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-methoxyethyl group,
-acetoxyethyl group, canoleboxymethinole group, 2-
Kanoleboxyethinole group, 3-carpoxybrobyl group,
4-carboxybutynole group, 2-sulfoethyl group, 3-
Sulfopyl group, 3-sulfobutyl group, 4-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group,
Examples include p-sulfophenethyl group, n-probyl group, isobrobyl group, n-butyl group, phenylethyl group, and p-sulfophenylethyl group. Q1 and 02 represent an atomic group necessary to define a 4-thiazolidinone ring, a 5-buazolidinone ring, a 4-imidazolidinone ring, a 5-imidazolidinone ring, a 4-oxazolidinone ring, a 5-oxazolidinone ring, Q1 and 02
By combining these, such a ring is formed. Such a ring may have a substituent. That is, examples of substituents on the thiazolidinone ring, isotazolidinone ring, or oxazolidinone ring include alkyl groups, such as alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, 2-hydroxyethyl group, -methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carpoxyethyl group, probyl group, isoprobyl group, benzyl group, phenylethyl group, p-sulfophenyl group>, aryl group (e.g. phenyl group, 2-carpoxyethyl group), poxyphenyl group, etc.). L+, L2 .L3 represents a methine group or a substituted methine R3 l group (-C-). R3 represents an ethyl group, a methyl group, an ethoxy group, an aryl group (
For example, it represents a phenyl group, p-chlorophenyl group, p-methylphenyl group, etc.), and may be substituted. X+ 8 is an anion (e.g., chloride ion, bromide ion, iodine ion, perchloric acid, benzenesulfonate, p
(toluenesulfonate, methyl sulfate, ethyl sulfate, etc.). Next, specific examples of the compound represented by the above general formula [I] used in the present invention will be shown. However, the compounds used in the present invention are not limited to these compounds [Examples of 1: MeOH ^eaax 584 nm MeOH λax 570 nm MeOH λwax 572 ram le MeOH λwax 595 nm MeOH λax 603 nm Me OH ^- ax 600 11JI λax 598 MeOH λwax 595 n theory MeOH λax 593 +v MeOH λwax 588 nm MeOH λIIILX 595 n+s MeOH MeOH λwax 597 nm MeOH λ wax 594 nm MeOH MeOH MeOH λyear ax 680 nth floor MeOH AllIII×6630II 1 -19 C. H. C 2 H s MeOH λax 658 n (The number at the bottom right of the structural formula is the wavelength ^wax (unit: 201) at the point where the light absorption curve of the methanol solution takes the maximum value) Halogen of the present invention The silver oxide photographic light-sensitive material contains at least one compound represented by the general formula [I[] (hereinafter also referred to as compound [II]). General formula [I[] In the formula, R4 and R5 represent a substituted or unsubstituted alkyl group. A1 to A6 each represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group, but may form a ring by adjoining each other. However, either one or both of A2 and A5 must be a phenyl group. m is 0 or 1, and is O when forming an inner salt. Also X
2e is an anion, X+8 defined in general formula [I]
is the same as Specific examples of the compound represented by the general formula [I1] are given below, but the compound [II
Examples of I 1-1 11-2 n-3 n-4 1]-5 11-6 [17 ■-8 Compound [I] is preferably 1 per mole of silver halide.
mg to 2 g, more preferably 5 mg to 1 g, and compound [11] is preferably 10 to 5001 g, more preferably 20 to 250 a+ per mole of silver halide.
It is contained in the silver halide emulsion in an amount within the range of g. However, the ratio of the addition amounts of compound [I] and compound [I[] is preferably 1:3 to 3:1. Compound [I] or compound [1[] can be partitioned directly into an emulsion. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. Each of Compound [I] and Compound [I[] may be one type each, or either one or both may be used in combination of two or more types. Moreover, sensitizing dyes other than those mentioned above can also be used in combination. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content. The compound represented by general formula [I] is disclosed in Yoneda Patent 2,
No. 503,776, British Patent No. 742,112, French Patent No. 2,065,662, and Japanese Patent Publication No. 40-2346, and compounds represented by the general formula [I[] can be prepared according to known methods. Can be easily synthesized. Compound [I] or compound [II] may be added to the silver halide emulsion during or after chemical ripening. The silver halide photographic material of the present invention has the general formula [III]
Contains at least one compound represented by (hereinafter also referred to as compound [1 [1]). General formula [1 [1] In the formula, M represents a hydrogen atom, a 1N group, or an alkali metal, and R6 represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group preferably has 1 to 8 carbon atoms (for example, methyl group, ethyl group, probyl group, hexyl group, octyl group), and the aryl group preferably has 6 to 8 carbon atoms.
10 (eg phenyl group, naphthyl group). Z represents an atomic group necessary to form a 5-membered heterocycle which may have a substituent or an atomic group necessary to form a 5-membered heterocycle condensed with a benzene ring. The 5-membered heterocycle is preferably an imidazole ring, a triazole ring, a tetrazole ring, etc., and the substituent for the heterocycle is an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a probyl group,
(hexyl group, octyl group, etc.) and an aryl group having 6 to 10 carbon atoms (e.g., phenyl group, naphthyl group) are preferable. As the 5-membered heterocycle fused to the benzene ring, a penzimidazole group is preferable. General formula [nI ] The compound represented by the formula is a compound in which at least one carbon atom is a carboxyl group or a salt thereof, carbamoyl I (100NH2), a hydroxy group,
Those substituted with a sulfo group or a salt thereof, an amino group (-NH2), or a lower alkoxy group (preferably one having 1 to 3 carbon atoms, such as a methoxy group, an ethoxy group, or a broboxy group) are preferred. Among these, a carboxy group or a salt thereof, and a sulfo group or a salt thereof are particularly preferred. Among the compounds represented by the general formula [11[], compounds represented by the following general formula [IV] or general formula [VI] are particularly preferred. General formula [rV] R, in which R7 is the alkyl group described above (preferably a carbon number of 1 to
8) or the above-mentioned aryl group (preferably one having 6 to 10 carbon atoms), and is preferably substituted with a water-soluble group. As the water-soluble group, a carboxy group or a salt thereof, a carbamoyl group, a hydroxy group, a sulfo group or a salt thereof, or an amino group are preferable, and a carboxy group or a salt thereof, a sulfo group or a salt thereof are particularly preferable. General formula [V] In the formula, Ra and Rs each represent a hydrogen atom, a halogen atom, or the water-soluble group described above. However, it is preferable that at least one of R8 and Rs is a water-soluble group. Examples of the water-soluble group include a carboxy group or a salt thereof, a canoleba monole group, a hydroxy group, a snorefo group or a salt thereof, an amino group or a lower alkoxy group, and among these, a carboxy group or a salt thereof, a sulfo group or a salt thereof are particularly preferred. Among the general formulas [IV] and [v5], the effect of the compound represented by the general formula [V] is greater. Next, the compound (3
) (5) (7》 (4) (6) (8) (9) (1l) (13) (l5) H H (10) (l2) (l4) (l6) ■ H (17》 (l9) (2l) (18) (20) These compounds represented by the general formula [1
No. 0169 Publications: British Patent No. 1275701 Ming @ Hu; D. A, 3 er Qe Setal, “Journ
al or Heterocyclic Chesis
Try”, Vol. 15, p. 981 (1978): “Th
e ChelliStrl/ of Heteroc
yclic Coapounds” l midaz
ole and [)erives pa
rt Eng., pp. 336-339 and 384; E. mouthooQarth, “Journal or Chem
ical Society” 1949, 1160~
It can be easily synthesized by the method described in, for example, p. 1167, or by a method analogous thereto. The compound represented by the general formula [m1 is added to the silver halide emulsion layer or a layer adjacent thereto. The addition is preferably done before coating each layer, but it is also possible to impregnate the coated layer with a solution of the compound after coating. The compound represented by the general formula [1[1] is preferably used per mole of silver 1. OX 1 0 → mole to 6 X 10
-3 mol, particularly preferably from 5X10' mol to 5.2
×10-3 moles! ! Use in a surrounding area. Further, at least one compound having an absorption wavelength range of 400 to soon m is provided on the silver halide emulsion layer of the present invention and/or the layer. Preferably, it is added to the layer. Examples of compounds that can be advantageously used as such compounds include compounds represented by the following general formulas [VI] to [XI]. General formula (Vl) General formula [■] General formula [■] General formula ([) - Shell formula (X) - Shell formula [Punishment] General formula (XI) R2, where 2 is benzthiazole, naphthothiazole or Represents a group of nonmetallic atoms necessary to form the heterocyclic nucleus of benzoxazole. Q represents an atomic group necessary to form vilazolone, barbituric acid, thiobarbituric acid or 3-oxythionaphthene. R' is a substituted or unsubstituted alkyl group, R1R2'. R3' and R4 are each a hydrogen atom,
an alkoxy group, a dialkylamino group or a sulfone group,
R5' represents a hydrogen atom or a halogen atom. Rs' * R7' + Ra' + R9' * R
1oR++'. R+2. R+3'. R++' *
R+sR16' and R17' each represent a hydrogen atom, a chlorine atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group, or a sulfone group. However, R12' and R13' may be bonded to each other to form a benzene ring. R+a is a hydrogen atom,
Acyl group or alkoxycarbonyl group, R19' is a hydrogen atom or alkyl group, R20R21' and R22
each represents a hydrogen atom, an alkyl group or a sulfone group. M is a hydrogen atom, sodium atom or potassium atom, Xe
is an anion, m and n4 each represent 0 or 1, and n3
represents 1 or 2. However, when 1 is O, an inner salt is formed. Y represents an alkyl group or a carboxyl group. Generally, these compounds can be added to the emulsion after chemical ripening, and if added to the protective layer, they can be added at any time before coating. Further, the amount added may be 100 mg to 3.0 g in dry weight per film 112. Next, general formula [VI] to general formula [XI]
] (hereinafter referred to as compound [VI] to compound [X
A specific example of ``I'' is shown below. However, the present invention is not limited thereto. Specific example of compound [■] (Vl) -(1) [■)-(2> Specific example of compound [■] [■)-(1) [■)-(2) [■)-(3) Compound Specific examples of [■] [■)-(1) (■)-(2) [■)-(3) SO. H Compound CI! )’s costume example CI! )-(1) [l1')-(2) CI! )-(3) Cp (IM)-(4> (IM)-(6) (ff)-(7) Specific examples of compound (X) (X)-(1) (X)-(2) (X ) - (3) Prefectural example of compound [luck] [nail] - (1) [revised] 1 (2) [phantom] - (3) (XI) - (4) (XI3-(5) H [revised) -(6) (XI)-(7) Conjugate example of compound [■] [■)-(1) 0 [■)-(2) 0 (XI)-(3) 0 (XI)-(4) 0 b and 11 yen a [■) - (S) 0 The use of additives selected from compounds [V1] to [XI] reduces the sensitivity in the unnecessary photosensitive wavelength range (400 to 600 nm) and produces bright safe light. enable the use of The silver halide emulsion used in the light-sensitive material of the present invention includes:
As the silver halide, silver chlorobromide or silver chloroiodobromide containing 50 mol% or more of silver chloride is used, and more preferably silver chloride is 6 mol% or more.
0 mol% or more is used. Silver halide grains are prepared using an acid method. The particles may be obtained by either the neutral method or the ammonia method, and the particle size is preferably 0.2μ1 or more and 0.5μ1 or less. It is preferable that a water-soluble rhodium salt and a water-soluble iridium salt be added to the silver halide grains used in the emulsion according to the present invention during the process of forming the grains, and include them inside the grains and/or on the grain surfaces. The amount added is silver halide 1
10-6 to 10-9 mol per mole is preferred. The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/sil grains in which the silver halide composition differs between the inside of the grain and the surface layer. The particles may be formed on the surface or mainly inside the particles. Any shape of the silver halide grains according to the present invention can be used. One preferred example is (ioo
) plane as the crystal surface. Also, U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
737, and The Journal of Photographic Science (J. Photor.
Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared by the method described in literature such as Sci., 21.39 (1973), and used. Furthermore, particles having twin planes may be used. The silver halide grains according to the present invention 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 emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used. In the present invention, monodispersed emulsions are preferred. As single-dispersion silver halide grains in a monodispersed emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. is preferable, particularly preferably 70% or more, and still more preferably 80% or more. Here, the average particle size r is the frequency ni of particles having particle size ri.
It is defined as the grain size ri when the product nix ri3 of nix ri3 is maximum. (3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when converted to a circular image with the same area. The particle size can be obtained, for example, by photographing the particles with an electron microscope 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 grains to be measured shall be 1,000 or more under thermal discrimination.) In the present invention, particularly preferred highly monodispersed emulsions are those with a monodispersity of 20 or less, more preferably 15 or less. Here, the average grain size and grain size standard deviation shall be determined from ri defined above.
No. 1, No. 58-49938 and No. 60-122935
It can be obtained by referring to Publications No. 4, etc. Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, the G larkides or z
elikman et al. or H. F rtese
Die Grundlagen der Photo
ographischenP rozesse wit
Silberhalooeniden, A ka
demicche Verlagsgesellsch
aft, 1968) can be used. That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and a noble metal sensitization method using gold or other noble metal compounds can be used. Thiosulfur is a sulfur sensitizer!
Salts, thioureas, thiazoles, O-danines, and other compounds can be used, and specific examples thereof include U.S. Pat.
It is described in No. 2,278,947, No. 2,728,668, and No. 3,656,955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamide disulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. No. 2,487,85.
0@, No. 2,419,974, No. 2,518,698
No. 2,983,609@, No. 2,983,610, and No. 2,694,637. For noble metal sensitization, in addition to gold salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used. Specific examples thereof are described in U.S. Pat. No. 448,060, British Patent No. 618,061, etc. In the present invention, these methods can be used in combination. In addition, the conditions such as pt-+, pAa, m degree, etc. during chemical sensitization are not particularly limited to III, but the DH value is 4 to 9, especially 5 to
8 is preferable, and the I) AiJ value is 5 to 11, especially 7.
It is preferable to keep it at 9. Also, the temperature is 40 to 90
℃, especially 45 to 75℃ is preferred. When carrying out the present invention, for example, 4-hydroxy-6-methyl-1.3,
Various stabilizers can also be used, including 3a,7-tetrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like. Furthermore, if necessary, a silver halide solvent such as a thioether, or a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used. In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure 1 764
This can be carried out based on the method described in No. 3. In the present invention, the above emulsion may be used alone as the silver halide emulsion, or two or more emulsions may be used in combination. Various compounds can be added to the above-mentioned silver halide emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic material. That is, azoles such as penzothiazolium salts,
Nitroindazoles, triazoles, penzotriazoles, penzimidazoles (especially nitro or halogen substituted), heterocyclic mercabut compounds such as mercaptothiazoles, menolecabutobenzimidazoles, mercabutthiazoles, mercabutotetrazole (especially 1-phenyl-5-merkabutotetrazole), merkabutopyridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thiol compounds such as oxazolinthione, Azaindenes such as tetraazaindenes (especially 4)
Many compounds known as stabilizers can be added, such as -hydroxy-substituted (1.3.3a.7) tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc. An example of a compound that can be used is }(, Mees, The Theory of the Photographic Process (Th
e Theory or the Photographer
aphic process, 3rd edition, 1966). 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. 2-28660 can be referred to. Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included. The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.
No. 15, Belgian Patent No. 762,833, U.S. Patent No. 3,767,410, Belgian Patent No. 588,
Substances described in the various books of Ill. No. 143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde, eboxy, ethyleneimine, active halogen, and vinyl sulfone. , isocyanate type, sulfonic acid ester type,
Examples of various hardening agents and ultraviolet absorbers such as carbodiimide, mucochloric acid, and acyloyl-based agents include those described in U.S. Pat.
, 253,921, British Patent No. 1, 309, 349
Compounds described in each specification etc. of No. 21, especially
'-Hydroxy-5-tertiary butylphenyl〉penzotriazole, 2-(2'-hydroxy-3'.5'
- Tertiary butylphenyl penzotriazole, 2
-(2-hydroxy-3'-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2
'-Hydroxy-3'5'-di-tertiary butylphenyl)-5-chlorobenzotriazole and the like can be mentioned. Further, as coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials, British Patent No. 548,532, No. 1,216,389, U.S. Patent No. 2,026,202, U.S. Patent No. 3,514,293,
Special Publication No. 44-26580, No. 43-17922, No. 43-17926, No. 43-3166, No. 48-2
It is possible to use anionic, cationic, nonionic or amphoteric compounds described in No. 0785, French Patent No. 202,588, Belgian Patent No. 773,459, JP-A-48-101118, etc. However, among these, it is particularly preferable to use anionic surfactants having a sulfone group, such as succinic acid ester sulfonates, alkylbenzene sulfonates, and the like. In addition, as an antistatic agent, Japanese Patent Publication No. 4G-24159, Japanese Patent Publication No. 4 G-24159,
No. 8-89979, U.S. Pat. No. 2,882,157, U.S. Pat. No. 46-39312, No. 48
There are compounds described in JP-A-43809 and JP-A-47-33627. In the present invention, it is preferable that the p value of the coating liquid is in the range of 5.3 to 7.5. In the case of multi-layer coating, it is preferable that the p ratio of the coating solution obtained by mixing the coating solutions for each layer in the ratio of coating amounts is in the above range of 5.3 to 7.5. If the pH is less than 5.3, the progress of hardening will be slow, which is undesirable, and if the pH is more than 1.5, it will have an adverse effect on photographic performance, which is not preferred. In the light-sensitive material of the present invention, the constituent layers include matting agents such as silica as described in Swiss Patent No. 330,158, glass powder as described in French Patent No. 1,296,995, and matting agent as described in British Patent No. 1,173,181. Inorganic particles such as alkaline earth metals or carbonates such as cadmium, zinc, etc.: starch as described in US Pat. No. 2,322,037, Belgian Patent No. 6
Starch derivatives described in No. 25,451 or British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158, U.S. patent Organic particles such as polyacrylonitrile as described in US Pat. No. 3,079,257 and polycarbonate as described in US Pat. No. 3,022,169 can be included. In the photosensitive material of the present invention, the constituent layers include slipping agents, such as those described in US Pat. No. 2,588,756 and US Pat.
higher alcohol esters of higher aliphatics as described in US Pat. No. 3,295,979, casein as described in US Pat. Patent 3,042
, No. 522, No. 3, 489, 567, etc. may also be included. Dispersions of liquid paraffin and the like can also be used for this purpose. The silver halide photographic material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176 1 tea 17643 (1
December 978) and Volume 187 1 teg+ 18
716 (November 1979),
The relevant locations are summarized in the table below. Additive type 1. Chemical sensitizer 2. Sensitivity enhancer 3. Spectral sensitizer Super sensitizer 4. Brightener 5. Antifoggants and stabilizers6. Light absorbers, filter dyes, ultraviolet absorbers, stain inhibitors, dye image stabilizers, hardeners, binders, lubricants, ram agents, coating aids/surfactants, static inhibitors, R D 17643, 23 pages, 23-24 pages, 24 pages, 24- 25 pages 25-26 pages 25 right column 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 pages R D 1B716 648 right column Same as above page 648 right column ~ 649 right column 649 pages right column 649 page right column ~ Page 650 Left column Page 650 Left to right column Page 651 Left column Same as above Page 650 Right column Same as above Same as above In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers are commonly used in photographic light-sensitive materials. It can be constructed by coating on one or both sides of a flexible support. 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. Bolimar (
Examples include paper coated or laminated with polyethylene, polypropylene, ethylene/butene copolymer, etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating treatment is as per JP-A-52-104913 and JP-A-52-104913.
No. 9-18949, No. 59-19940, No. 59-1
The treatments described in each publication of No. 1941 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 the silver halide photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. The photographic processing of the silver halide photographic material of the present invention is not particularly limited, and various methods can be used. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or higher than 50°C. In the present invention, dihydro-oxybenzenes (e.g., hydro-quinone), 3-virazolidones (e.g., 1-
phenyl-3-virazolidone), aminophenols (
For example, N-methyl-101 aminophenol) can be used alone or in combination. In the photographic processing of the silver halide photographic light-sensitive material of the present invention, processing can also be carried out using a developer containing imidazoles as a silver halide solvent. It is also possible to process with a developer containing a silver halide solvent and an additive such as indazole or triazole. Developers generally contain various preservatives, alkaline agents, pH! l! Contains i-agent, anti-fogging agent, etc., and further contains solubilizing agent, color toning agent, development accelerator, surfactant, antifoaming agent, water softener, hardening agent, viscosity imparting agent, etc. as necessary. Also good. Furthermore, so-called "squirrel-type" development processing can be performed. As a special type of development processing, a method may be used in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is treated with an aqueous alkaline solution to perform development. Research Disclosure 1 for hydrophobic developing agents
It can be included in the emulsion layer by the method described in No. 69 et al. Such a development process involves ammonium chloride using thiocyanate. It may also be combined with standardization processing. As the fixer, one having a commonly used composition can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. Exposure for the photosensitive material of the present invention varies depending on the state of chemical sensitization, purpose of use, etc., but may include tungsten, fluorescent lamp, arc lamp, mercury lamp, xenon sunlight, xenon flash, cathode ray tube flying spot, laser light, electron beam, etc.
X-ray, Xlin! Various types of light sources such as fluorescent screens can be used as appropriate. In addition to normal exposure of 171,000 to 100 seconds, the exposure time for xenon flash, cathode ray tube, and laser light is 1.
A short exposure of /10-4 to 1/10-9 seconds can be applied. [Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto. Example 1 (Preparation of coating solution for emulsion layer) Production Δ Water
9.72 Sodium chloride
20 Q Gelatin 105
G-san Yeongdan water
3.81 Sodium chloride
380 1;1 gelatin
94 1J potassium bromide 42
0 (0.01% aqueous solution of J hexacro-iridate potassium salt 2812 0.01% aqueous solution of hexab O morodate potassium salt 5.0 [Solution C Water
3.82 nitrate S silver
i, 700 g of the above solution A kept at 40°C, pH 3, 1) While keeping Ag at 7.7, add the above solution B and solution C simultaneously functionally over 90 minutes, and add 1
After stirring for 0 minutes, dilute with aqueous sodium carbonate solution
was adjusted to 6.0, and 2o% magnesium Ta acid aqueous solution 2 was added.
2 and a 5% aqueous solution of polynaphthalene sulfonic acid 2.55
1 was added, and the emulsion was flocculated at 35°C, decanted and washed with water to remove excess salt from the aqueous solution. Next, add 3.7 liters of water to it and disperse it.
0.9 i of a 20% aqueous magnesium sulfate solution was added again to remove excess salt in the aqueous solution. 3.72 g of water and 141 g of gelatin were added thereto, and the mixture was allowed to ferment at 55° C. for 30 minutes. As a result, particles having 35 mol % of silver bromide, 65 mol % of silver chloride, an average particle size of 0.35 μm, and a monodispersity of 9 were obtained. Add 120 u of 1% citric acid aqueous solution and 5% to each emulsion.
Add potassium bromide aqueous solution 120 iR and p day 5.5, p
After adjusting the Ag to 7, 120 d of a 0.1% aqueous sodium thiosulfate solution and 80 d of a 0.2% aqueous solution of chloroauric acid were added and aged at 60° C. to obtain the highest sensitivity. The above emulsion was divided into equal parts as required, and each was divided into 4-hydroxy-6-methyl-1.3.3a and 4-hydroxy-6-methyl-1.3.3a as a stabilizer.
After adding 180n12 of a 1% solution of 7-tetrazaindene and 4001Q of a 10% aqueous solution of gelatin to stop the ripening, compounds of general formula [I] [II] [III] were added as shown in Table 1, respectively. Furthermore, 10% hydroginone solution (5012) and 5% potassium bromide solution (501J2) were added as antifoggants, 20% sabonin aqueous solution (1912) was added as a spreading agent, and 4% aqueous solution of styrene-maleic acid copolymer (501J2) was added as a thickener. , polymeric polymer latex of ethyl acrylate at 0.8 (J/f
, formalin and 1-hydroxy-3, as WIl agents.
5-dichlorotriazine sodium salt was added. (Preparation of sample) A polyethylene terephthalate support coated with the above emulsion layer coating solution and coated with an antihalation layer has a silver circumference of 4.2 (J/f) and a gelatin temperature of 1.7.
! II/f, and as a protective film, add 10% potassium bromide aqueous solution 100% to gelatin soog aqueous solution.
A 1% aqueous solution of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate (4001N) was added to reduce the average particle size to 3. 2001m each of matting agents of amorphous silica with a Qμ of 1 and polymethyl methacrylate with an average particle size of 5μ! J/f, 50 W
The addition amount was changed to IQ/f, and the gelatin was 0.8.
The emulsion layer and the protective film layer were simultaneously coated one hour after preparation of the coating solution so as to achieve Q/f. In addition, in Example @1, a compound (
Iχ-2) to 150+g/f. A sample was also prepared with the addition of (Evaluation of sample) The sample thus obtained was exposed to light through a Facsimile I (PT-503) manufactured by Matsushita Electric Transmission Co., Ltd. equipped with an LED light source, and then a conventional roller-type The samples were processed under the following conditions using an automatic processor to evaluate sensitivity and safelight resistance.
, 70%R. mouth. The sensitivity was also measured immediately after 48 hours of release. However, the sensitivity is expressed as a relative sensitivity when the same-day sensitivity of sample No. 1 is set as 100. In addition, the safelight test was conducted using Konica Safelight Glass No. 5 c and elect 0・
Zero fog using a combination of luminescent light sources
．． The safelight time under 11 to increase by 01 (logE) was determined. Also, apply. The liquid stagnation property was determined by allowing the coating liquid to stagnate at 38° C. for 12 hours, then applying it in the same manner as above, and measuring the sensitivity in the same manner, and expressed as relative sensitivity. The results are shown in Table-1. W Riou 1 Developing +ffi 38℃ 13 seconds fixing time
36℃ 13 seconds Washing time Room temperature 10 seconds Drying time 50℃ 10 seconds Developer formulation Pure water (ion exchange water) a o o
1p disodium ethylenediaminetetraacetate 2g diethylene glycol 259 potassium sulfite (55% w/v aqueous solution) 60n potassium carbonate
15 g hydroquinone
20 (15-methylbenzotriazole 300mg1-phenyl-5-menorecabutotetrazole 60
mg potassium hydroxide 10.5 g
Ouka potassium 3.5g was used when using 1-phenyl-4.4-dimethyl-3-virazolidone developer. P port was 10. Ammonium thioVA acid (72.5% W/V 300 mg) Added pure water to make 1 liter. Sodium sulfite sodium acetate trihydrate 111 M Sodium citrate・Dihydrate acetic acid (90% w/w aqueous solution) (group B) Pure water (ion exchange water) Sulfur @ (50% w/w aqueous solution) Aluminum sulfate (Afl203 equivalent content is aqueous solution) 240112 17 (1 6 .5g 6g 2g 13.hR 8.1% w/w aqueous solution) 26.5 0 When using the fixer, add the above groups A and 17 in water soo12.
1Q 4.7g Components B were dissolved in the order of 1 and 2 and used. The p value of this fixer was about 4.1. Compound a Compound b As is clear from Table 1, the samples of the present invention showed excellent coating solution stagnation properties and also obtained excellent sensitivity after storage under high temperature and high humidity conditions. Furthermore, in Example 1, when the rX-2 dye was added to the protective film layer on the emulsion layer side at a concentration of 150 mg/1*, the sample of the present invention exhibited less sensitivity loss and improved safelight time. I understand. [Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material having high sensitivity, good coating solution stagnation properties, and excellent storage stability.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, comprising at least one compound represented by the following general formula [I] and the following general formula [I]. A silver halide photographic material comprising at least one compound represented by formula [II] and at least one compound represented by the following general formula [III]. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above general formula [I], Y_1 and Y_2 are
Each represents an atomic group necessary to form a 5-membered ring and/or a 6-membered nitrogen-containing heterocycle. R_1 and R_2 each represent a saturated or unsaturated aliphatic group. Q_1 and Q_2 are 4
- Represents an atomic group necessary to form a thiazolidinone, 4-oxazolidinone, 4-imidazolidinone, 5-thiazolidinone, 5-oxazolidinone or 5-imidazolidinone ring. L_1, L_2 and L_3 represent a methine group, a substituted methine group (▲numerical formula, chemical formula, table, etc.▼, where R_3 represents an ethyl group, a methyl group, an ethoxy group, or an aryl group). X_1^■ represents an anion. n_1, n_2 are 0
Represents an integer from ~3. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_4 and R_5 represent substituted or unsubstituted alkyl groups. A_1 to A_6 are hydrogen atoms, alkyl groups,
It represents an alkoxy group, a halogen atom, or a phenyl group, but adjacent groups may form a ring. However, A_2 or A_
Either one or both of 5 must be a phenyl group. m is 0 or 1, and is 0 when forming an inner salt. Also, X_2^■ represents an anion,
It is the same as X_1^■ defined in the general formula [I]. ] General formula [III] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, M represents a hydrogen atom, -NH_4 group, or an alkali metal, R_6 represents a hydrogen atom, an alkyl group, or an aryl group, and Z represents a substituted Represents an atomic group necessary to form a 5-membered heterocycle which may have a group or a 5-membered heterocycle fused with a benzene ring. ]