JPS62265647A - Spectrally sensitized silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material ensuring high photosensitivity in the entire region of blue to red and high contrast and causing little dye stain by incorporating specified compounds into hydrophilic colloidal layers including a silver halide emulsion layer formed on a support. CONSTITUTION:A compound represented by formula I and at least one kind of compound selected among compounds represented by formulae II-IV are incorporated into hydrophilic colloidal layers including a silver halide emulsion layer formed on a support. In the formula I, Z1 is a group of nonmetallic atoms required to form an oxazole, benzoxazole or naphthoxazole ring, R<1> is alkyl, R<2> is alkoxycarbonylalkyl or other prescribed group and each of R<3> and R<4> is H, Cl, F or a prescribed group such as alkyl. In the formulae II-IV, each of Z2-Z6 is a group of atoms required to form an oxazole ring or other prescribed ring together with c and N, each of Q1-Q4 is group of atoms required to form a 4-thiazolidinone ring or other prescribed ring, each of R5-R10 is alkyl, each of L1-L3 is alkyl, aryl or H, X<1> is an anion and m=0 or 1.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material that is spectrally sensitized with a new merocyanine dye and is sensitive to all colors, particularly for green color. The present invention relates to a silver halide photographic light-sensitive material which has high light and red light sensitivity and can obtain a high-contrast halftone image even in relatively rapid development, and which has extremely little dye staining after processing.

[Conventional technology]

It is known that photographic images with extremely high contrast can be formed using silver halide photosensitive materials. For example, the average grain size of silver halide grains is approximately 0.5 μm
Silver halide consisting of a silver chlorobromide or silver chloroiodide emulsion with fine grains of m or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 mol% or more. This type of silver halide photosensitive material is known as a lithium-type silver halide photographic photosensitive material, which produces a high contrast film by processing the photosensitive material with an alkaline developer containing only hydroquinone as a developing agent and with a low concentration of sulfite ions. It is usually used in the photolithography process to convert the continuous tone density changes of an original into a set of halftone dots whose area is proportional to the density. Such conversion uses a lithium-type silver halide photographic light-sensitive material, in which the original is imaged through a cross-line screen or a contact screen, and then the sulfite ion concentration is very low and it contains only a hydroquinone developing agent. A halftone image is formed by developing with a so-called Lith type developer. Even when this lithium-type silver halide photographic light-sensitive material is processed with a normal developer with a high sulfite ion concentration, such as a commercially available developer for photographic paper, the gamma is only 5.
6 to 6, and fringes, which must be avoided the most, occur frequently in forming halftone dots. Therefore, for halftone dot negatives/positives, a combination with the above-mentioned lithium type developer is said to be indispensable. Regarding this lithium-type developer, please refer to J.N.C.Y.A.R.'s Journal of the Franklin.
Institute (J, A, CYule
: J.Franklin In5titut
e), Vol. 239, p. 221 (1945), which essentially contains only hydroquinone as a developing agent, and the sulfite ion concentration that serves as an antioxidant for the developing agent. It is a developer with a low

Such developers have poor shelf life and are susceptible to auto-oxidation, so in order for plate makers to consistently obtain high-quality halftone negative or halftone positive images, they must reduce the activity of the developer, which decreases over time. Although it is necessary to manage the developer to maintain a constant value, it is unavoidable that the scraping becomes complicated.

Furthermore, in the lithographic development process, there are two major disadvantages: in addition to the above-mentioned developer management that keeps the activity constant, the processing speed is slow.

The trend in printing plate making in recent years has been to shorten and shorten the printing process time, and there is a demand for faster processing of plate making films.

For example, Japanese Patent Application No. 59-240147 uses a silver halide photographic light-sensitive material containing a tetrazolium salt as a technique for obtaining an extremely high contrast image suitable for plate making using a developer with high stability. A method is disclosed. This method allows the use of a stable developer with a high concentration of sulfite ions, and enables rapid processing with a development time of around 30 seconds and a drying time of 90 to 100 seconds, which was not possible with conventional lithography. be.

On the other hand, silver halide photographic light-sensitive materials for use in plate making are generally required to have so-called almighty type photosensitivity, which is sensitive to green areas and sensitive to red and blue light.

Since a photosensitive silver halide emulsion alone has a narrow wavelength range of sensitivity, a spectral sensitizer is used for the purpose of expanding the wavelength range of sensitivity to longer wavelengths. For example, Japanese Patent Publications Nos. 38-7828, 40-392, and 43-10 provide sensitivity to green and red light.
No. 251, No. 43-22884, British Patent No. 815.1
No. 72, No. 955,961, No. 955,912, No. 142.228, U.S. Patent No. 1,942.854, No. 1,950,876, No. 1,957.869, No.
, 238.231, 2,521,705, 2,
No. 647,059, Special Publication No. 43-2606, No. 44-
No. 3644, No. 46-18106, No. 46-1810
No. 8, No. 48-15032, No. 49-33782,
No. 54-34252 1. No. 58-52574, U.S. Patent No. 2,839,403, U.S. Patent No. 3,567.458,
Examples include cyanine dyes and merocyanine dyes described in specifications such as No. 3,625,698.

[Problem that the invention seeks to solve]

, these spectral enhancers increase the sensitivity in a specific wavelength range, and at the same time have general properties such as: (a) not being affected by other additives or affecting the effectiveness of the additive; (bl) There should be no change in photographic characteristics such as a decrease in sensitivity or an increase in fog even after the passage of time (C)
Properties such as not causing dye staining after processing are required, but when the above-mentioned relatively rapid development is performed, dye staining after processing increases, which poses a serious problem in practice.

In order to reduce dye 7η staining, it is sufficient to use a highly soluble spectral enhancer that has little staining property for hydrophilic colloids such as gelatin and easily flows out into the processing solution. Proposed.

However, spectral enhancers often have a large effect on the development effect that provides the extremely high contrast required for plate making. It was difficult to directly apply this method to silver halide photographic materials that undergo high contrast development.

The object of the present invention is to solve the above-mentioned problems, and to provide high sensitivity throughout the blue, green, and red colors, and to obtain extremely high contrast through rapid processing using a common developer with a high concentration of sulfite ions. The object of the present invention is to provide a silver halide photographic material which has extremely little dye staining after processing.

[Means for solving problems]

As a result of various studies, the present inventors have found that in a silver halide photographic material having a support and a hydrophilic colloid layer coated on the support, the hydrophilic colloid layer includes a silver halide emulsion layer. A silver halide photographic photosensitive material containing a compound represented by the following general formula [I] and at least one of the compounds represented by the following general formulas (n) to (IV). It has been found that the above objects can be achieved with the help of materials.

General formula (T) Z represents an atomic group necessary to complete an oxazole nucleus, benzoxazole nucleus or naphthoxazole nucleus,
These nuclei may have substituents on carbon atoms.

Specific examples of substituents include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), unsubstituted alkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.) , an alkoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, propoxy group,
butoxy group), hydroxyl group, alkoxycarbonyl group having 2 to 6 carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), alkylcarbonyloxy group having 2 to 5 carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.) ), phenyl group, hydroxyphenyl group, etc.

Specific examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4.5-dimethyloxazole, 4-phenyloxazole, etc. as the oxazole nucleus; benzoxazole, 5-chlorobenzoxazole, etc. as the benzoxazole nucleus; 5-
Bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-acetyloxybenzoxazole, 5-phenylbenzoxazole, 6 Naphtho (1,2-
d) Nuclei such as oxazole, naphtho(2,1-d)oxazole, and naphtho(2,3-d)oxazole can be mentioned.

R' represents an unsubstituted or substituted alkyl group.

Examples of substituents include hydroxy, sulfo, and sulfonate! , carboxy group, halogen atom side (e.g. fluorine atom, chlorine atom), unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (the alkoxy group may be further substituted with a sulfo group or hydroxy group), 2 carbon atoms ~5 alkoxy groups, luponyl groups, R1-4 alkylsulfonyl groups, sulfamoyl groups, unsubstituted or substituted carbamoyl groups (including substituted carbamoyl groups substituted with alkyl groups having 1 to 4 carbon atoms), substituted phenyl groups ( Examples of the substituent include a sulfo group, a carboxy group, a hydroxy group, etc.), a vinyl group, and the like.

Specific examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of substituted alkyl groups include 2-hydroxyethyl and 3-hydroxypropyl groups as hydroxyalkyl groups, and 2-sulfoethyl and 3-hydroxypropyl groups as sulfoalkyl groups.
-Sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2
-chloro-3-sulfopropyl group, etc., carboxyalkyl group such as carboxymethyl group, carboxyethyl group, carboxypropyl group, 2.2.2-trifluoroethyl group, 2-(3-sulfopropyloxy)ethyl group, 2-(2-hydroxyethoxy)ethyl group, ethoxycarbonylethyl group, methylsulfonylethyl group, 2-sulfamoylethyl group, 2-carbamoylethyl group, 2-N,N-dimethylcarbamoylethyl group as sulfamoylalkyl group groups such as phenethyl group, p-
p as carboxyphenethyl group, sulfoaralkyl group
-sulfophenethyl group, 0-sulfophenethyl group, etc.
Examples include p-hydroxyphenethyl group, allyl group, and phenoxyethyl group.

R″ is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, a phenyl group, an alkoxyalkyl group, or a substituent + CH1hA or ÷< Ht 0
+CHrhA-. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or an alkoxy group having 1 to 8 carbon atoms, and n represents an integer value of 1 to 4.

Each of the above groups includes those having a substituent. For example, those in which the alkyl moiety of the above group is replaced with W by a halogen atom can also be preferably used. Examples of R1 include alkoxycarbonylalkyl groups in which each alkyl group is substituted with a halogen atom (e.g., methoxycarbonylfluoromethyl group, ethoxycarbonylfluoromethyl group, fluoroethoxycarbonylethyl group, etc.), hydroxyalkyl groups (e.g., 2-hydroxy Fluoroethyl group, 2-
hydroxyfluoropropyl group, 3-hydroxyfluoropropyl group, 2,3-dihydroxyfluoropropyl group, etc.), hydroxyalkoxyalkyl group (e.g. hydroxymethoxyfluoromethyl group, 2-(2-hydroxyfluoroethoxy)ethyl group, 2-hydroxy fluoroethoxymethyl group, etc.), carbamoyl alkyl group (N
-Alkyl-substituted, N,N-dialkyl-substituted, N-hydroxyalkyl-substituted, N-alkyl-N-hy)'0xyalkyl-substituted, N,N-di(hydroxyalkyl)-substituted carbamoyl alkyl groups and 5- and 6-membered carbamoylalkyl group alloys of cyclic amines) (e.g. 2-carbamoylchloroethyl 5.2-N-(2-hydroxyethyl)carbamoylchloroethyl group, N-hydroxyfluoroethylcarbamoylmethyl group, (2
-hydroxyfluoroethyl)carbamoylmethyl group,
2-N,N-di(2-hydroxyethyl)carbamoylchloroethyl M,N,N-dimethylcarbamoylchloromethyl group, cerfolinolylbamoylchloromethyl group, piperidinocarbamoylmethyl group, etc.), hydroxyphenyl group, carbon 7 to 9 hydroxyalkylphenyl groups (
For example, p-(2-hydroxyfluoroethyl)phenyl, m-(1-hydroxyfluoroethyl)phenyl, etc.), or a substituent +CH1hA or ÷CH
It represents t + r O÷CHz+iA. Here, A is a nitrile group, an alkylsulfonyl group, a sulfonamide group,
It represents an alkylsulfonylamino group or a lower alkoxy group, and among these, the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms (e.g., methylsulfonyl group, ethylsulfonyl group, etc.), and the sulfonamide group is , preferably a sulfonamide group having 1 to 4 carbon atoms (e.g., N-methylsulfonamide group, N,
N-dimethylsulfonylamino group, etc.), the alkylsulfonylamino group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms (for example, methylsulfonylamino group, etc.), and the lower alkoxy group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms. 1 to 4 alkoxy groups (eg, methoxy group, ethoxy group, etc.).

n represents an integer value of 1-4.

R3 and R4 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably one with 1 to 4 carbon atoms,
For example, methyl group, ethyl group, etc.), alkoxy group (preferably one having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, etc.), alkyl sulfonic acid group, sulfonic acid group, chlorine atom, fluorine atom, or carboxy group. represent.

Particularly preferred compounds of the above general formula [I] are those in which R1 represents a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a sulfo group or a carboxyl group and/or a hydroxyl group. Yes, specifically sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, carboxymethyl group, carboxyethyl group, hydroxyethyl group, 3-sulfo-2
-Hydroxypropyl group, etc.

Next, typical examples of the compound represented by the above general formula (1) used in the present invention will be given, but it goes without saying that the compounds used in the present invention are not limited to these.

(I) -2 OCR.

CI) -4 CB,SO,K CI)-15 (1)-170CHs H3 (I)-19 (I)-21 (I)-28 (I)-34 The above general formula (1) used in the present invention ) is disclosed in Japanese Patent Publication No. 46-549 and Japanese Patent Publication No. 46-18105.
No. 46-18106, No. 46-18108, No. 47-4085, No. 5B-52574, U.S. Patent 2
．． No. 839.403, No. 3.384.486, No. 3,
625.698, 3.480.439, 3.5
It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 67゜458 etc. *
,,,, -1 or less i:l: ,'-1 General formula [■] In the above general formulas (n) to (TV), Z2, z, z4, Z
s, z, and 2? combine with a carbon atom and a nitrogen atom to complete an oxazole nucleus, a thiazole nucleus, a benzoxazole nucleus, a benzthiazole nucleus, a benzselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, or a naphthoselenazole nucleus, respectively. represents the atomic group necessary for Ql and Q2, and Q3 and Q4, together with a carbon atom, each represent an atomic group necessary to complete a 4-thiazolidinone nucleus, a 5-thiazolidinone nucleus, or a 4-imidazolidinone nucleus.

Rs, R6, R? , Ra, R9 and R1° are
Each represents a substituted or unsubstituted alkyl group.

L+ 1Lt and ri each represent a substituted or unsubstituted alkyl group or aryl group. However, L+
and R2, in particular R2, can also be a hydrogen atom. X- represents an anion, and m is an integer of 0 or 1.

The above general formula (If
), (III) and (IV), Z2.1, z
Examples of nitrogen-containing heterocycles completed by 4, Z5, z, and Z include the following.

That is, a thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 4.5-dimethylthiazole, 4.5-diphenylthiazole);
Benzthiazole nucleus (e.g. benzthiazole, 5-
Chlorbenzthiazole, 6-chlorpenzthiazole, 5-methylbenzthiazole, 6-methylbenzthiazole, 5゜6-dimethylbenzthiazole, 5-bromobenzthiazole, 6-bromobenzthiazole, 5
-Iodobenzthiazole, 5-phenylbenzthiazole, 5-methoxybenzthiazole, 6-methoxybenzthiazole, 5-ethoxybenzthiazole, 5-
Ethoxycarbonylbenzthiazole, 5-hydroxybenzthiazole, 5-carboxybenzthiazole,
5-fluorobenzthiazole, 5-dimethylaminobenzthiazole, 5-acetylaminobenzthiazole, 5-trifluoromethylbenzthiazole, 5-ethoxy-6-methylbenzthiazole, 5-hydroxy-6
-methyl-benzthiazole, tetrahydrobenzthiazole, etc.); naphthothiazole nuclei (e.g. naphtho(2,1-d)thiazole, naphtho(1,2-d)thiazole, naphtho(2,3-d)thiazole, 5-methoxy Naft (1
,2-d) Thiazole, 7-nitoxynaphtho(2,1-
d) Thiazole, 8-methoxynaphtho (2,1-d)
thiazole, 5-methoxynaphtho(2,3-d)thiazole, etc.); Oxazole core (e.g. oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-methyloxazole, etc.); Benzoxazole, (e.g. benzoxazole) ,
5-fluorobenzoxazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 5-methyl-6-phenylbenzoxazole, 5. 6-Simethylbenzoxazole, 5-methoxybenzoxazole, 5.6-Simethoxybenzoxazole, 5. -carboxybenzoxazole-15-methoxycarbonylbenzoxazole, 5-acetylbenzoxazole, 5-hydroxybenzoxazole, etc.); Naphthoxazole nucleus (e.g. naphtho(2,1-d)oxazole, naphtho(1,2) -d) oxazole, etc.)
; Benzselenazole core (e.g. benzselenazole, 5
- Chlorbenzselenazole, 5-phenylbenzselenazole, 5-methylbenzselenazole, 5-methoxybenzselenazole, 5-hydroxybenzselenazole, 5-ethoxy-6-methylbenzselenazole,
5,6-dimethylbenzselenazole, 5,6-simethoxybenzselenazole, 5-hydroxy-6-methylbenzselenazole, etc.); and naphthoselenazole cores (e.g. naphtho(2,1-d) selenazole, naphtho (1,2-d) selenazole, etc.).

In the above general formula, Rs, Rh, R? , Re , Rq
The unsubstituted alkyl group represented by and R1° is preferably a lower alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group, etc.). In addition, the substituted alkyl group is preferably an alkyl radical having 1 to 5 carbon atoms,
Such examples include hydroxyalkyl groups (e.g. 2-hydroxyethyl, 3-bitroxypropyl,
4-hydroxybutyl group, etc.); carboxyalkyl group (e.g. carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxypropyl group, 2-(2-carboxyethoxy)ethyl group, etc.); sulfoalkyl groups (e.g. 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-
Sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-(3-sulfopropoxy)ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2-(
3-sulfopropoxy)propyl i, 2-[(3-sulfopropoxy)ethoxyalkyl group, 2-hydroxy-
3-(3'-sulfopropoxy)propyl group, etc.);
Aralkyl group, preferably phenylalkyl group (e.g. benzyl group, phenethyl group, phenylpropyl group,
phenylbutyl group, p-)lylbropyl group, p-methoxyphenethyl group, p-chlorophenethyl group, p-carboxybenzyl group, p-sulfophenethyl group, p-sulfobenzyl group, etc.); aryloxyalkyl group, preferably phenoxy Alkyl groups (e.g. phenoxyethyl group, phenoxyprobyl group, phenoxybutyl group, p-
methylphenoxyethyl group, p-methoxyphenoxypropyl group, etc.); vinylmethyl group, etc.

Furthermore, the unsubstituted alkyl group, t, and L3 are preferably lower alkyl groups (e.g., methyl group, ethyl group, etc.); the substituted alkyl group is preferably a substituted lower alkyl group (e.g., 2-ethoxyalkyl alkoxyalkyl groups such as groups, carboxyalkyl groups such as 2-carboxyethyl groups, alkoxycarbonylethyl groups such as 2-methoxycarbonylethyl groups, aralkyl groups such as benzyl groups, phenethyl groups, etc.); or substituted or unsubstituted It may be an aryl group (eg, phenyl group, p-methoxyphenyl group, p-chlorophenyl group, 0-carboxyphenyl group, etc.). Note that one of Ll and Lz may be a hydrogen atom.

Examples of substituents that can be bonded to the nitrogen atom at the 3-position of the 4-thiazolidinone nucleus, 5-thiazolidinone nucleus or 4-imidaridinone nucleus formed by Q+ and Q2 or Q and Q4 together with a carbon atom include: Substituted or unsubstituted alkyl groups or aryl groups can be mentioned, and specific examples thereof include alkyl groups, preferably alkyl groups having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.); Allyl group; aralkyl group, preferably aralkyl group having 1 to 5 carbon atoms in the aralkyl radical, especially phenylalkyl group (e.g. benzyl group, p-carboxyphenylmethyl group, etc.); aryl group, preferably having 6 to 9 carbon atoms aryl group (e.g. phenyl group, p-carboxyphenyl group, etc.); hydroxyalkyl group, preferably a hydroxyalkyl group having 1 to 5 carbon atoms (e.g. 2-hydroxyethyl group) of an alkyl radical; carboxyalkyl group, preferably is a carboxyalkyl group having 1 to 5 carbon atoms of an alkyl radical (
Examples include carboxymethyl group); alkoxycarbonylalkyl groups, preferably alkoxycarbonylalkyl groups in which the alkyl radical has 1 to 5 carbon atoms and the alkoxy moiety has 1 to 3 carbon atoms (for example, methoxycarbonylethyl group); Can be done.

Further, examples of the anion represented by
Examples include methyl sulfate ion and ethyl sulfate ion.

Next, the above general formulas (I[) to (I
Specific examples of the sensitizing dye represented by V) are shown below. However, the sensitizing dyes used in the present invention are not limited to these.

■-8 ■- Z-1 f-2 f-3 Ding -4 1! ? -9 II! -1O ■- 12 ■- 13 ■-16 π-17 (UFi, ), S (J:s?1 It -21 ! -22 (stingy), 10.- 1 - The above general formula used in the present invention (If)～[ko]
The aggravating pigment represented by can be synthesized according to various methods, for example, known methods.

For example, The Theory of the Photographic Ink Process, 4th edition, by T. H. James.
ry of the Photographic Pr
cess, Fourth Edition) No. 194
You can refer to pages 234 to 234.

Further, one or more of the sensitizing dyes represented by the above general formulas (Il) to (IV) are generally contained in the emulsion layer with halogenated 1!
The content is preferably 5a+g to 500 mg, more preferably 10 to 200 mg per mole. In order to incorporate these sensitizing dyes into a silver halide photographic emulsion, a known method may be followed.

The above general formulas (1) to (IV) used in the present invention
Addition and dispersion of the dye represented by the above into a silver halide emulsion can be carried out by various methods, for example, conventionally known methods. Method of dispersing and adding with a surfactant described in JP-A-53-166
No. 24, No. 53-102732, No. 53-10273
No. 3, U.S. Patent No. 3,469,987, U.S. Patent No. 3,676
Examples include a method of adding the compound as a dispersion with a hydrophilic substrate, as described in the specification of East German Patent No. 143,324, and a method of adding it as a solid solution, as described in the specification of East German Patent No. 143,324. In addition, the merocyanine dye may be dissolved in a water-soluble solvent such as water, ethanol, methanol, acetone, n-propanol, fanned alcohol, pyridine, etc. alone or in a mixture thereof and added to the emulsion. The timing may be any time during the emulsion manufacturing process, but preferably during or after chemical ripening. The above used in the present invention-
The amount of the dye of I'IQ formulas (1) to (II/) to be added is the amount for spectral sensitization of the silver halide emulsion, for example, 10-S to 2×1 O-t mol per mol of silver halide, preferably is 1
0-4 to 2 x 104 moles.

The silver halide used in the silver halide photographic light-sensitive material of the present invention can be used in any composition, but preferably silver chlorobromide or chloroiodobromide containing at least 50 mol % of silver chloride.

The average particle size of the silver halide grains used is preferably in the range of 0.05 to 0.5 μm and 0.10 to 0.4 μm.
0 μm is more preferable.

The monodispersity of the silver halide emulsion used in the present invention is expressed by the following formula (1), and the value is preferably 5 to 25, more preferably 8 to 20, at 111 g.

The grain size of the silver halide grains used in the present invention is conveniently expressed by the principal dimension of cubic grains, and the monodispersity S is the value obtained by dividing the standard deviation of the grain size by the average grain size T, as shown in the following formula (1). 100
Expressed as a multiplied value.

Further, as the silver halide that can be used in the present invention, for example, a type having a multilayer laminated structure of at least two layers can be used. Silver chloride or silver chlorobromide particles having a shell portion of silver chloride may be used. In this case, iodine can be contained in any layer within 5 mol %.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening or at the time of preparing the emulsion coating solution.

In this case, the rhodium salt may be a double salt in addition to a simple salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.

The amount of rhodium salt added can be freely changed depending on the required sensitivity and gradation, but it ranges from 10-s mol to 1 s mol per mol of silver.
A range of 0-6 moles is particularly useful.

When rhodium salts are used, other iridium-free compounds such as iridium salts, platinum salts, thallium salts, cobalt salts, gold salts, etc. may also be used together. Iridium salts are often used for the purpose of high-light special positions. , 10-1 mole per mole of silver
A range of up to 10-h moles can be preferably used.

The silver halide used in the present invention can be sensitized by various chemical sensitizers in addition to the spectral sensitization using a compound of the mm type [ethyl chloride]. Examples of thickening agents include activated gelatin, sulfuric acid sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reducing Sensitizers (triethylenetetramine, stannic chloride, etc.) 1, e.g. potassium chlorooleite, cacao-lothiocyanate, potassium chlorooleate, 2-oresulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chlorooleate Various noble metal sensitizers, such as sodium chloride and sodium chlorovaladite, can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The spectrally sensitized silver halide used in the present invention is present in the hydrophilic colloid layer, and the hydrophilic colloid particularly advantageously used in the present invention is preferably gelatin, and hydrophilic colloids other than gelatin include: For example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, such as U.S. Pat. 2nd, 52
Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in the specifications of No. 5, 753, or the specifications of U.S. Pat. Nos. 2,548,520 and 2,831,767. Examples include gelatin graft polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester, as described in Colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, interlayers, etc.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Typical examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

The light-sensitive material according to the present invention has, for example, a hydrophilic colloid layer including a silver halide emulsion layer on the support as described above, and the silver halide emulsion layer has an appropriate film thickness, that is, preferably 0.1 It is particularly preferable to have a structure in which a hydrophilic colloid layer of ~10 μm, particularly preferably 0.8 to 2 μm, is coated as a protective layer.

The silver halide emulsion layer and hydrophilic colloid layer used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, anti-oxidants, etc., as necessary. The effect of the present invention is impaired when using staining agents, PH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed adjusters, matting agents, etc. It is preferable to develop in the presence of a compound [wherein R5I is a nitro group at the 5- or 6-position,
R5□ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion. ] Specific examples of the compound represented by the general formula (V) include 5-nitroindazole and 6-nitroindazole, but the present invention is not limited thereto in any way.

The compound represented by formula (V) may contain diethylene glycol, triethylene glycol, or ethanol. Examples of the alkanolamines mentioned above include triethanolamine jetanolamine, ethanolamine trimethylamine 2-diethylamino-1-ethanol 2-methylamino-1-ethanol 3-diethylamino-1-propanediol 3-diethylamino-1-propanol 5 -Amino-1-pentanoldiethylaminemethylaminetriethylaminedipropylaminedi-isopropylamine3.3'-diaminodipropylamine3-dimethylamino-1-propatolhydantoic acidallylamineethylaminedimethylamineethylenediamine2-dimethylaminoethanol2- Ethylaminoethanol 2-(2-aminoethylamino)ethanoltetramethylammonium acetatecholinecholine chloridehydroxylamine sulfate 2-((2-aminoethylamino)-ethylaminoco-ethanolaminoguanidine sulfate 6-aminohexanoic acid 3-amino-1 -Propatur 1-dimethylamino-2-Propatur 2-hydroxy-4-thiadodecyltrimethylammonium (pta) Pyridine glycine 0-amine benzoic acid polyethyleneimine L-(+)-cystine hydrochloride benzylamine 2-amino-1 -ethanol 4-amino-1-butanol 3-(dimethylamino)-1,2-propanediol 3-morpholino-1,2-propanediol 1,4-piperazinebis(ethanesulfonic acid)3-piperidino-1
, 2-propanediol, N-piperidine, ethanol, etc., an alkali such as sodium hydroxide, an acid such as acetic acid, etc., and the resulting solution may be added to the developer, or it may be added as is.

The compound represented by the general formula ('V'') is contained in a concentration range of preferably about 1 mg to 1.000 mg, more preferably about 50 mg to 300 mg, per 1 j! of the developer.

Examples of the developing agent for the silver halide photographic light-sensitive material of the present invention, particularly for the black-and-white photographic light-sensitive material, include the following. This developing agent can be used together with the compound represented by the above-mentioned general formula (7).

Typical examples of 110,000 CH= CI-h-OH type developing agents include hydroquinone, as well as catechol, pyrogallol and its derivatives, ascorbic acid, chlorohypyroquinone, bromohydroquinone,
Isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2.3-dibromohydroquinone, 2.5-dihydroxyacetophenone, 2.5-diethylhydroquinone, 2.5-dichlorohydroquinone -p
-Phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4-(2-hydroxybenzoyl) ) Pyrogallol, sodium ascorbic acid, etc.

In addition, ■0÷CII=CH+-N Typical Hz type developers include ortho and para aminophenols or aminopyrazolones, and 4-aminophenol, 2-amino-6-phenylphenol, 2-aminophenol, and 2-aminophenol. −
4-chloro-6-phenylphenol, 4-amino-2
-phenylphenol, 3,4-diaminophenol,
3-Methyl-4,6-diaminophenol, 2.4-cyamylsorcinol, 2.4.6-)riaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-amino Examples include phenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, and the like.

Petrocyclic type developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl-4-dimethyl-3-pyrazolidone. -4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Pyrazolidones, 1-phenyl-4-amino-5-pyrazolone, 1-<p-aminophenyl)-3-amino-
Examples include 2-barazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, and 5-aminouracil.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess.

Fourth Edition, pages 291-334 and Journal of the American Chemical Society.
an Chemical 5ociety) Volume 73,
3, p. 100 (1951) etc. can be effectively used in the silver halide photographic material of the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as potassium sulfite or ammonium sulfite is used as a preservative in the developer used for processing the photosensitive material of the present invention, the effects of the present invention will not be impaired, and the effects of the present invention will not be impaired. This can be cited as one feature.

Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. Other organic development inhibitors such as caustic alkali, alkali carbonate or abibenzotriazole used in general black and white developers, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol,
Development accelerators such as benzyl alcohol and polyalkylene oxide, surfactants such as sodium alkylarylsulfonate, natural saponins, sugars or alkyl esters of the above compounds, glutaraldehyde, formalin,
It is optional to add a hardening agent such as glyoxal, an ionic strength regulator such as sodium sulfate, etc.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the above-mentioned alkanolamine include monoethanolamine, jetanolamine, and triethanolamine, and triethanolamine is preferably used. The amount of these alkanolamines used is 1
5 to 500 g per 2 is preferable, more preferably 20 to 500 g per 2
It is 200g.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1.4-phthanediol, 1.5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols used is 5 to 500 g per 11 of the developer, preferably 2
0 to 200 g.

These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention can be developed with a developer containing the above-mentioned development inhibitor, thereby obtaining photosensitive characteristics with extremely excellent storage stability.

The pH value of the developer having the above composition is 9 to 12,
From the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 11.

The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
The temperature is preferably 0°C or lower, particularly preferably around 30°C, and the development time is generally completed within 3 minutes.
Particularly preferably within 40 seconds often brings about good results. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called early field image processing such as plate development or frame field image processing, or mechanical development such as roller development or hanger development.

〔Example〕

Examples of the present invention will be described in detail below. Note that, as a matter of course, the present invention is not limited to the embodiments described below.

A silver chlorobromide emulsion was prepared using the following solutions A, B, and C.

<Solution A> Ossein gelatin 17 g Polyisopropylene-polyethylene oxydisuccinate sodium salt 511Il! 10% ethanol solution Distilled water 1280 cc Solution B> Silver nitrate 170 g (distilled water 410++/! <Solution C> Sodium chloride 40.9 g Potassium bromide 35.7 g Polyisopropylene oxydisuccinate ester sodium salt 10
% ethanol solution 3ml ossein gelatin
11 g distilled water
After keeping 407ml of solution A at 40℃, the EAg value was 16.
Sodium chloride was added so that the voltage was 0 mV.

Next, solutions B and C were added by a double jet method using the mixer described in JP-A-57-92523 and JP-A-57-92524.

As shown in Table 1, addition was carried out by gradually increasing the addition flow rate over a total addition time of 80 minutes while keeping the EAg constant.

The EAg value was 3II11 5 minutes after the start of addition from 160 mv.
EAg value 120 using /l sodium chloride aqueous solution
mv and maintained this value thereafter until the completion of mixing.

To keep the EAg value constant, 3 mol/l of sodium chloride was added.
A metal silver electrode and a double junction type Ag/AgC1 comparison electrode were used to measure the EAg values (the electrode configuration used was the double junction disclosed in JP-A-57-197534). .

Further, a variable flow rate roller tube metering pump was used to add solutions B and C.

Furthermore, during the addition, the emulsion was sampled and observed using an electron microscope to confirm that no new particles were generated within the system.

Also, during the addition, the pH value of the system was kept constant at 3.0.
% nitric acid aqueous solution.

After addition of liquids B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, and then desalted and washed with water in a conventional manner.
600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) was added, and the emulsion was then gold-sulfur sensitized at 55°C and 6-methyl-4-
Hydroxy 1,3.3a.

7-Chitrazaindene was added. As shown in Table 2, the autopsy was divided and the compounds of general formulas (I) to (IV) according to the present invention or the following comparative dye ((1) -a) were used for comparison.
-c, (II) -a, b, (III) -a.

b, (IV)-a) were added individually or in combination at a rate of 2×10 −′ mol/Ag 1 mol. Each emulsion was then treated with 6 sodium n-dodecylbenzenesulfonates.
00 mg/1 mole of Ag, 600 mg/1 mole of 2.3.5-triphenyltetrazolium chloride, 2 g/1 mole of styrene-maleic acid copolymer, and 3.5 g of Ag on the polyethylene terephthalate film.
The coating was applied so that the amount of gelatin was 2.0 g/rd.

At that time, 1-decyl-2-(3-isopentyl)succinate 2-sulfonate sodium was added as a spreading agent at 30+ag/rd so that the gelatin amount was 1.0g/cd.
, formalin 25mg/n as a hardening agent? A multilayer protective layer containing dural membrane was applied.

Comparative sensitizing dye cm] -b ■- (rV] -a Three pieces of each sample were taken, one piece was subjected to stepwise exposure with tungsten light using an infrared photometer and an optical wedge, and the other one was One piece is contact screen GN No. 2 (150L) manufactured by Dainippon Screen Manufacturing Co., Ltd.
The shaded areas were exposed to xenon light. Further, the remaining piece was subjected to the following processing without being exposed to light.

The above sample piece was processed in an automatic developing machine with a developing tank capacity 1401 using a developer having the following formulation and a commercially available fixer.

[Development processing conditions]

(Process) (Temperature) (Time) Development 28℃
Fixing for 30 seconds Washing at 28℃ for 20 seconds Drying at 20℃ for 20 seconds 40℃ for 20 seconds [Developer composition] (Mi composition A) (Composition) When using the developer, dissolve the above composition A in the order of composition A and composition in 500 ml of pure water. , 1N and used.

For developed samples subjected to wedge exposure, draw a photographic characteristic curve and calculate the sensitivity at an optical density of 2.5 for sample N.
The relative value is calculated based on o, 1, and gamma is the optical density of 1.
．． The tana value of the straight line section from 0 to 2.5 is shown.

The quality of the formed mesh (dot quality) was evaluated for those that were photographed using xenon light and a camera for printing plate making.

For dot quality, for so-called 50% dots where the area of the halftone area and the clear area are equal, the state of the fringe (blur) that occurs around the halftone dot is visually judged, and the smaller fringe is evaluated as 5.
Evaluation was made on a five-point scale.

That is, "5" is excellent, and "1" is extremely bad. If the 50% dot quality is less than '3'', this is generally unacceptable.

In addition, for samples processed without exposure, 4 films were stacked and the residual color of the film was visually evaluated and evaluated on a 5-point scale, with "5" being colorless and "1" being a strong orange residual color. Indicated.

For general plate making, residual color below "3" is at a level that is considered a major drawback.

These results are shown in Table 3.

27 Contains the compound represented by the general formula [I] according to the present invention as shown in Table 3, and also contains at least one of the compounds represented by the general formulas (n) to (rV) The sample is
The relative sensitivity is high, the gamma is 16 to 20, and the contrast is extremely high, and both the dot quality rank and the residual color rank are superior to the comparative samples, indicating that the sample has little residual color.

〔Effect of the invention〕

The silver halide photographic window optical material of the present invention has high sensitivity throughout the blue, green, and red regions, and extremely high contrast can be obtained by rapid processing using a common developer with a high sulfite ion concentration. Patent specializing in the effect of extremely little pigment staining Applicant: Konishiroku Photo Industry Co., Ltd. Agent Patent Attorney Hirate Hirate Takatsuki and Nefit Sho 4 (spontaneous) 1, Incident Indication 1988 Patent Application No. 109021 2. Name of the invention Spectral sensitized silver halide photographic light-sensitive material 3. Relationship to the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent Address: 506 Dia Palace Niban-cho, 11-9 Niban-cho, Chiyoda-ku, Tokyo 102 FAX: 03 (221) +9245, Date of Amendment Order: Voluntary Issue 7, Amendment Contents As shown in the attached sheet (1) In the specification, "sulponamide group" in the second to bottom line of the second page is amended to "sulfamoyl group."

(2) "Alkylsulfonyl group," on page 3, lines 3 to 4, is corrected to "sulfoalkyl group."

(3) Page 15, line 16 and page 18, lines 3 to 4, line 1
"Sulfonamide group" in line 8 of the same page and lines 9 to 10 of the same page are respectively corrected to "sulfamoyl group."

(4) "(e.g. N-methylsulfonamide group, N,N-dimethylsulfonamide group, etc.)" on page 18, lines 10 to 11 of the same page is replaced with "(e.g. N-methylsulfamoyl group,
(N,N-dimethylsulfamoyl group, etc.)".

(5) "Ar-1-lsulfonic acid group, sulfonic acid group," in lines 2 to 3 of the same paragraph 19 is corrected to "sulfoalkyl group, sulfo group."

(6) The structural formula of r (I)-(a)J on page 83 of the same is corrected as follows.

(1) - (a) that's all

Claims (1)

[Scope of Claims] A silver halide photographic material having a hydrophilic colloid layer including a support and a silver halide emulsion layer coated on the support, wherein the hydrophilic colloid layer has the following general formula [ I], and the hydrophilic colloid layer contains a compound represented by the following general formulas [II] to [
A silver halide photographic material containing at least one of the compounds represented by IV]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z_1 represents a group of nonmetallic atoms necessary to form an oxazole nucleus, benzoxazole nucleus, or naphthoxazole nucleus. R^1 represents an unsubstituted or substituted alkyl group. R^2 is an alkoxycarbonylalkyl group,
hydroxyalkyl group, hydroxyalkoxyalkyl group, carbamoylalkyl group, hydroxyphenyl group,
Hydroxyalkylphenyl group, phenyl group, alkoxyalkyl group, or substituent -(CH_2)-_nA or -(CH_2)-_nO-(CH_2)-_nA
represents. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or an alkoxy group, and n represents an integer value of 1 to 4. R^3 and R^4 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylsulfonyl group, a sulfo group, a chlorine atom, a fluorine atom, or a carboxy group. ] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] [In the above formula, Z_2, Z_3, Z_4, Z_5, Z_6 and Z_7 together with carbon and nitrogen atoms complete an oxazole nucleus, thiazole nucleus, benzoxazole nucleus, benzthiazole nucleus, benzselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, or naphthoselenazole nucleus, respectively represents the atomic group necessary to Q_1 and Q_2 and Q_3 and Q_4 are respectively combined with carbon atoms to form a 4-thiazolidinone nucleus, 5
- R_5, R_6, R representing the atomic group necessary to complete the thiazolidinone nucleus or 4-imidazolidinone nucleus
_7, R_8, R_9 and R_1_0 are respectively,
Represents a substituted or unsubstituted alkyl group. L_1, L
_2 and L_3 each represent a substituted or unsubstituted alkyl group or aryl group. However, L_1 and L
One of _2 can also be a hydrogen atom. X^- represents an anion, and m is an integer of 0 or 1. ]