JPH0354549A - High-contrast silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high-contrast sensitive material having high sensitivity in all the blue, green and red light regions by incorporating two or more kinds of specified compds. into at least one of silver halide emulsion layers. CONSTITUTION:At least one kind of compd. represented formula I and at least one kind of compd. represented by formula III, IV or V are incorporated into at least one layer of a silver halide photographic sensitive material. In the formula I, each of R1 and R2 is H, an aliphat. or arom. group, etc., R3 is divalent arom. group, R4 is alkoxy, etc., and Y is S or O. In the formula III-V, each of R1-R4 is optionally substd. alkyl each of U, V, W and Y is H, halogen, alkoxy, etc., and X is an acid anion. A high-contrast sensitive material having high sensitivity in all the blue, green and red light regions is obtd.

Description

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

[Background of the invention]

It is known that silver halide photosensitive materials can be used to form extremely high contrast photographic images. For example, the average grain size of silver halide grains is about 0.5μ
Silver halide consisting of silver chlorobromide or silver chloroiodide emulsions with fine grains of shoulder size or smaller, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 mol% or more. A method is known in which a high-contrast halftone dot image or line image is obtained by processing a photosensitive material with an alkaline developer containing only hydroquinone as a developing agent and having a low concentration of sulfite ions.

This type of silver halide light-sensitive material is known as a lithium-type silver halide light-sensitive material, and is usually used in the photolithography process to detect changes in the continuous tone density of an original using a screen having a large and small area proportional to the density. It is used to convert to a set of points. Such conversion uses a lithium-type silver halide photographic light-sensitive material, photographs the original through a cross-line screen or a contact screen, and then processes the original with a very low sulfite ion concentration and contains only hydroquinone developing agent. The halftone dot image is shaped 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 having a high sulfite ion concentration, such as a commercially available developer for photographic paper, the gamma is at most 5 to 6, and the halftone dot shape or upper Since fringing, which must be avoided most often, occurs frequently, it is said that combination with the above-mentioned lithium type developer is essential for halftone negative/positive printing. Regarding this squirrel type developer, please refer to J.A.C Yule's Journal of the Franklin Institute (J.A.C. Yule).
: J. Franklin Institute)
Vol. 239, p. 221 (1945), this is a developing agent that essentially contains only hydroquinone as a developing agent and has a low concentration of sulfite ions that act as an antioxidant for the developing agent. It is a liquid.

Such developers have poor storage stability and are susceptible to auto-oxidation, so in order for platemakers to consistently obtain high-quality halftone negatives 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 operation 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 these days is to shorten the printing process and shorten the time, and the demand for processing speed of plate making film is increasing.

For example, Japanese Patent Application No. 59-240147 discloses 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 using the 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, 401392, 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,
Cyanine dyes and merocyanine dyes described in the specifications of U.S. Patent No. 54-34252, U.S. Patent No. 58-52574, U.S. Pat. can give.

These spectral sensitizers not only increase the sensitivity in a specific wavelength range, but also have general properties such as: (a) being affected by other additives or affecting the effectiveness of the additive (b) It does not cause changes in photographic characteristics such as a decrease in sensitivity or an increase in fog over time; and (c) It does not cause dye staining after processing. When relatively rapid development is performed, dye staining after processing becomes large, which is a big problem in practice.

In order to reduce dye staining, it is necessary to use a material that has little staining property for hydrophilic colloids such as gelatin, and that easily flows out into the processing solution.
A spectral sensitizer with high solubility may be used, and various compounds have been proposed in the past.

However, in many cases, spectral sensitizers have a large effect on the development effect that provides the extremely high contrast required for plate-making, and problems such as lower contrast occur, so it is difficult to solve dye stains in ordinary photosensitive materials. It was difficult to directly apply this method to silver halide photographic materials that undergo high contrast development.

[Purpose of the invention]

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.

[Precepts of invention]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having a support and a hydrophilic colloid layer coated on the support and comprising at least one silver halide emulsion layer. At least one layer of has the following general formula (
1 or general formula [II] and at least one compound represented by the following general formulas (I [I), (rV'l, (V)). This can be achieved by using a silver halide photographic light-sensitive material.

General formula [I] [In the formula, R1 and R are a hydrogen atom, R is an optionally substituted aliphatic group, aromatic group or heterocyclic group, R is a divalent aromatic group, and R is a substituted Y represents a sulfur atom or an oxygen atom. ] General formula (It) K1 [wherein, R. , R and R represent a hydrogen atom, an optionally substituted aliphatic group, aromatic group, heterocyclic group, alkoxy group or aryloxy group, R1 represents a divalent aromatic group,
R represents an optionally substituted alkyl group, alkoxy group, or amino group, and Y represents a sulfur atom or an oxygen atom. ] General formula (III) (X0)I11 [wherein R. and R each represent an optionally substituted alkyl group, and at least one of R and R is a sulfoalkyl group or a carpoquinalkyl group. Z
represents an alkyl group or an aralkyl group. U, V,
W and Y each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxycarbonyl group, a carpoxyl group, or a hydroxyl group.

> (e represents an acid anion. San represents 1 or 2, and when an inner salt is formed, m is l.) General formula [■] [In the formula, R, R, and R3 are Each represents an optionally substituted alkyl group. U, V, W and Y are each a hydrogen atom, a halogen atom, a tri7fluoromethyl group, a cyano group, a carboxyl group, an alkoxy group, an alkyl group, a hydroxyl group, an acyloxy [ General formula [v] [In the formula, Rl, R2, R, and R. each represent an optionally substituted alkyl group. U, V, W, and Y
each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkoxy group, a carboxyl group, a hydroxyl group, a cyano group, or a substituted represents an optional anloxy group. Xe represents a strict anion. 12 represents 1 or 2, and Q is 1 when an inner salt is formed. ] Hereinafter, the present invention will be specifically explained.

First, general formula [1] will be explained.

In the formula, R1 and R are hydrogen atoms, optionally substituted alkyl groups (for example, methyl group, ethyl group, butyl group, 3
-aryloxybutyl group, 4-aryloxybutyl group), optionally substituted 7-enyl group, naphthyl group, cyclohexyl group, pyridyl group, and pyrrolidyl group.

R1 is preferably an aryloxyalkyl group having a substituent. Examples of the substituent include an alkyl group (preferably one having 5 to 20 carbon atoms), a ureido group, and a thioureido group.

R is preferably a hydrogen atom or an alkyl group.

R represents a divalent aromatic group (eg, phenylene group, naphthylene group), and Y represents a sulfur atom or an oxygen atom.

R, represents -NR'R'' or -oRs, R/R/
/ and R are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group), 7-enyl group (e.g. phenyl group, p-methyl 7-enyl group, p-methoxyphenyl group), naphthyl group (e.g. σ-naphthyl group, β-naphthyl group) or heterocyclic group (e.g. unsaturated heterocyclic group such as pyridine, thiophene, furan, or saturated heterocyclic group such as tetrahydrofuran, sulfolane). R' and R'' are nitrogen atoms together with a ring (e.g.
biperidine, biperazine, morpholine, etc.).

m and n represent 0 or l. R, is OR. When representing Y
preferably represents a sulfur atom.

Representative compounds represented by the above general formula (1) are shown below.

I-1 The following is all, Yuki゛ka ■ 3 I 5 ■ 6 CH, ■ 7 ■ 8 ■ 9 ■ -10 ■ -11 ■ -12 S ■ l3 S ■ -14 00 00 O0 ■ -15 ■ -16 ■ -17 H ■ -18 ■ -19 00 ■ -20 ■ 2l ■ 122 ■ =24 ■ 25 ■ 26 ■-27 I 28 ■-29 next, Compounds among the above specific compounds ■ -25 For example\ The synthesis method is shown below.

Compound ■ 25 combination schemes (A) (B) Compounds 4-nitrophenylhydrazine 153g and 500g
Mix diethyl oxalate of I112 and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 5 hours of the obtained crystals (A) were heated and dissolved in 1000 minutes of methanol, and pd/
Compound (B) is obtained by reduction under a C (palladium/carbon) catalyst in a pressurized H2 atmosphere of 50 Psi.

Add 22g of this compound (B) to acetonitrile 200+aQ
Compound (C) was dissolved in a solution of and pyridine 169 at room temperature.
A solution of 249 in acetonitrile was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and recrystallized to obtain compound (D) 31.
I got a 9.

30 g of compound (D) was hydrogenated in the same manner as above to obtain compound (
E) 20g was obtained.

Compound (E) 109 was dissolved in 100tQ of acetonitrile, and ethyl isothiocyanate was added.3. Og was added and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) 7 was purified by recrystallization.
Obtained 0g. Compound (F) 5.09 in methanol 50+
Methylamine (40% aqueous solution 8-) was added to the mixture and stirred. After slightly concentrating the methanol, the precipitated solid was taken out and purified by recrystallization to form a compound! -25 was obtained.

The general formula (
The amount of the compound 1) is 5 x 1 per mole of silver halide contained in the silver halide photographic material of the present invention.
Preferably from 0-' to 5 x 10-' moles, more preferably from 5 x 10-' to l x 10-' moles.
Next, general formula [II] will be explained.

K3 In the formula, R,, R, 8 and R are hydrogen atoms, R-substituted alkyl groups (e.g., methyl group, ethyl group, butyl group, 3-aryloxybutyl group). Good phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group, optionally substituted alkoxy group (e.g. methoxy group, ethoxy group, butquine group) R optionally substituted aryloquine group (e.g. 7-enoxy group, 4
-notylphenoxy group).

R and R are preferably substituted alkyl groups (substituents include an alkoxy group and an aryl group).

R is preferably a hydrogen atom or an alkyl group.

R. represents a divalent aromatic group (eg, phenylene group, naphthylene group), and Y represents a sulfur atom or an oxygen atom.

R represents an optionally substituted alkyl group, alkoxy group, or amine group, and this substituent includes an alkoxy group, a cyano group,
There are aryl groups, etc.

Representative compounds represented by the above general formula [■] are shown below.

nt 11-2 n-3 ■ 4 ■ 5 H 6 ■ 7 ■ 8 ■ 9 ■ -10 ■ -11 ■ l2 ■ 13 ■ l4 ■ -15 ■ - 16 ■ l7 General formula CIII) In the formula, R1 and R represents an optionally substituted alkyl group, and at least one of R and R is a sulfoalkyl group or a carpoxyalkyl group. 2 represents an alkyl group or an aralkyl group. U, V, W
and Y are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkoxy group,
Represents a canoleboxyl group or a hydroquinl group. Xe represents an acid anion. m represents l or 2, and when an inner salt is formed, 4 is l.

Examples of substituents for the alkyl group represented by R1 and R are hydroxyl group, sulfo group, sulfonate group, sulfonato group, carpoxyl group and its salt, carboxylate group, halogen atom (e.g. fluorine atom, chlorine atom), carbon An unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (the alkoxy group may be further substituted with a sulfo group or a hydroquine group), an alkoxy carbonyl group having 2 to 5 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms , sulfamoyl group, unsubstituted or substituted rubamoyl group (including substituted rubamoyl group substituted with an alkyl group having 1 to 4 carbon atoms), substituted phenyl group (examples of substituents include sulfo group, carboxyl group, hydroxyl group) group, etc.), vinyl group, etc.

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

Examples of substituted alkyl groups include hydroxyalkyl groups such as 2-hydroquinethyl group and 3-hydroxybutypyl group, and sulfoalkyl groups such as 2-sulfoethyl group and 3-hydroxybutypyl group.
-sulfobutyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroquine-3-sulfobutyl group, 2
-Chloro-3-sulfobropinole group, etc., carboxylmethyl group, carpoxyethyl group, carboxylpropyl group, etc. as canolepoxynoleanolequinole group, 2,2
．． 2-tri7fluoroethyl group, 2-(3-sulfobyloxy)ethyl group, 2-(2-hydroxyethoxy)
Ethyl group, Etquine carponylethyl group, methylsulfonylethyl group, 2-sulfamoylethyl group, 2-carbamoylethyl group, 2-sulfamoylethyl group as sulfamoyl alkyl group,
-NN-dimethyl-rubamoylethyl group, phenethyl group, p-carpoxyphenethyl group, p-sulfophenethyl group as sulfoaralkyl group, p-sulfophenethyl group as sulfoaralkyl group, p-hydroxyphenethyl group, phenoxyethyl group, etc. Can be mentioned.

Examples of halogen atoms represented by U, V, W and Y include fluorine atom, chlorine atom, bromine atom, etc., and examples of alkyl groups include methyl group, ethyl group, proyl group, butyl group, etc. Examples of the alkoxy group include methoxy group, ethquine group, broboxy group, and putoxy group, and examples of the alkoxycarbonyl group include methoxycarbonyl group and ethoxycarbonyl group. , a hydroquinyl group, a carboxyl group, etc.

Examples of the alkyl group represented by 2 include a methyl group, ethyl group, and probyl group, and examples of the aralkyl group include a benzyl group.

Acid anions represented by xe include, for example, chloride, bromide, iodide, thionanate, sulfonate, methylsulfonate, ethylsulfonate, perc sulfate, and p-toluenesulfonate.

Compound represented by the general formula CI [[) used in the present invention General formula [rV) R3 In the formula, R, , R, and R each represent an optionally substituted alkyl group. U, V, W and Y are each a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group,
Represents a carpoxyl group, an alkoxy group, an alkoxyl group, a hydroxyl group, an acyloquine group, a hydroxyalkyl group, a hydroxyalcoquine group, or a phenyl group. Xθ represents an acid anion. n represents 1 or 2,
When an inner salt is formed, n is l.

The alkyl group represented by R, , R, and R is represented by the general formula (II
It has the same meaning as the alkyl group represented by R or R2 in I).

Examples of the alkoxy groups represented by U, V, W, and Y include methoxy, ethoxy, propoxy, and butoxy groups, and examples of the alkoxy carbonyl groups include methoxy carbonyl and ethoxy carbonyl groups. Examples of acyl group include acetyloxy group and probionyloxy group, examples of hydroxyalkyl group include hydroxymethyl group, hydroxyethyl group, hydroxybutyl group, and hydroxybutyl group. Examples of the group include hydroxymethoxy group, hydroxyethoxy group, hydroxyproboxy group, and hydroxybutoxy group.

The acid anion represented by Xe is Xe of the general formula [1111]
It is synonymous with .

Specific examples of the compound represented by the general formula (IV) used in the present invention are shown in Table 2 below.

? Lower brown, white. ＼・ ■＼． 、． ．． ．． −． ．． ．． 7, General formula (V) In the formula, R1, R! , R, and R each represent an optionally substituted alkyl group. U, V, W and Y are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkoxy group, a carboxyl group, a hydroxyl group, Represents a cyano group or an optionally substituted acyloxy group.

R. The alkyl group represented by R1 to R1 has the general formula (I[I
) is synonymous with the alkyl group represented by R1 or R, and the halogen atom, alkyl group, alkoxy group and alkoxyl group represented by Y are the same as the alkyl group represented by R1 or R, of the general formula (III). It has the same meaning as U to Y, and the acyloxy group has the same meaning as U to Y in general formula [■].

The acid anion represented by xe has the same meaning as xe in general formula (III).

Compounds represented by general formula (V) used in the present invention The sensitizing dyes represented by general formulas (1) to [v] used in the present invention are known, and can be easily synthesized by known methods. For example, F. M. 'The Cya' by Homes
nine Dyes and Related Coa
+poundsInLersciencePubli
Shers, New York (1964).

The above general formulas (l[I) to [v] used in the present invention
The dye represented by ] can be added and dispersed in a silver halide emulsion by various methods, for example, conventionally known methods. For example, Special Public Interest Publication No. 49-44895
JP-A-50-11419, a method of dispersing and adding together with a surfactant described in the specification of JP-A-50-11419;
No. 6624, No. 53-102732, No. 53-102
No. 733, U.S. Patent No. 3,469,987, U.S. Patent No. 3,67
Examples include the method of adding as a dispersion with a hydrophilic substrate as described in the specification of No. 6,147, and the method of adding 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, propanol, heptadalcohol, pyridine, etc. alone or in a mixture thereof and added to the emulsion. It may be added at any time during the emulsion manufacturing process, but preferably during or after chemical heat. The above general formula used in the present invention (
The amount of the dyes II[) to (V) to be added is the amount for spectral sensitization of the silver halide emulsion, for example, 10-' to 2 x 10-" mol per mol of silver halide, preferably IO-'
~2 x 10-' moles.

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

The average particle diameter of the silver halide grains used is preferably in the range of 0.05 to 0.5 microns.
A 40 μ course is more preferable.

The single fractionation degree S of the silver halide emulsion used in the present invention is expressed as a value obtained by dividing the standard deviation of the grain size by the average grain size r times 100, and the grain size of the silver halide grains used in the present invention is , for convenience, is expressed by the edge length of cubic grains. The value is preferably adjusted to 5-25, more preferably 8-20.

Further, as the silver halide that can be used in the present invention, for example, at least 211! A type having a multilayer laminated structure can be used. For example, silver chlorobromide particles may have silver chloride in the core and silver bromide in the shell, or conversely, silver bromide in the core and silver chloride in the shell.

At this time, 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 as well as a simple salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.

The amount of the dium salt added can be freely changed depending on the required sensitivity and gradation, but a range of 10-' mol to 10-' mol per 1 mol of silver is particularly useful.

Mat: When using rhodium salt, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt,
Gold salt etc. may be used together. Iridium salts are often used for the purpose of imparting high-luminance properties, ranging from 101 mole to 1 mole of silver.
It can be preferably used up to a range of 10-6 mol.

The silver halide photographic material used in the present invention can be produced by methods known in the photographic material industry. Namely, photographic emulsion preparation methods, sensitization methods, additives, hydrophilic colloids,
Binder, support, processing agent, processing method, etc.

Examples of the image agent for the black and white silver halide photographic light-sensitive material of the present invention include the following.

+10 f CH = CH Th A typical example of the OH type developing agent is hydroquinone.

Also, 80 +CH - CH jri Nll! Typical mold developers include ortho- and para-aminophenol or aminovirazolone, including 4-aminophenol, 2-amino-6-phenylphenol, and 2-aminophenol.
Amino-4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3.4-diaminophenol, 3-methyl-4.6-diaminophenol, 2
, 4-diaminoresorcinol, 2,4.6-triamino 7-enol, N-methyl-p-amino 7-enol, N
-β-hydroxyethyl p-aminophenol, p-
Examples include hydroxyphenylaminoacetic acid and 2-aminonaphthol.

Examples of the heterocyclic developer include l-7enyl-3-virazolidone, 1-phenyl-4,4-dimethyl-3-virazolidone, l-7enyl-4-methyl-4-hydroxymethyl-3-virazolidone, l- Examples include 7enyl-4-methynole-4-hydroxymethynole-3-virazolidone.

Others, T. H. James, The Theory Op.
The Photographic Process 4th Edition (The Th
eOry of the Photographic
ProcessFourth Edition) No. 29
1-334 and Journal of the American Chemical Society.
e American Chemical Society
ty) Vol. 73, p. 3.100 (1951), etc., can be effectively used in the silver halogenide photographic light-sensitive 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 present invention will not be impaired. This can be cited as one of its characteristics.

In addition, caustic alkali, alkali carbonate, or amine used in general black and white developers are used to adjust the ρH and provide a buffer function, as well as inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, and ethylene diamine. Metal ion scavengers such as tetraacetic acid,
Development accelerators such as methanol, ethanol, benzyl alcohol, and polyalkylene oxide, surfactants such as sodium alkylarylsulfonate, natural sabonin, sugars, or alkyl esters of the above compounds, and hardening agents such as glutaraldehyde, formalin, and glyoxal. agent,
It is optional to add an ionic strength adjusting agent such as sodium sulfate.

The silver halide photographic material of the present invention can achieve the objects of the present invention to a higher degree by developing it using a developer containing the above-mentioned development inhibitor.

The p1 value of the black and white developer for photosensitive materials according to the present invention is 9 to 1
A range of 3 is suitable, but a range of 10 to 12 is preferable for the pll value from the viewpoint of stability and photographic properties.

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 40°C, and the development time is generally completed within 3 minutes.
In particular, the effect of improving dye staining is remarkable in rapid development within 40 seconds. Processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening, neutralization, etc. may be optionally employed, and these may be omitted as appropriate. Furthermore, these processes include so-called manual development processes such as plate development and frame development, as well as roller development, hanger development, etc. ! Mechanical development may also be used.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A) A silver iodobromide emulsion (i1!0.5 mol % of iodide per 1 mol of silver) was prepared using the simultaneous mixing method.

The emulsion consisted of cubic grains with an average grain size of 0.15 microns. This emulsion was washed with water and desalted in a conventional manner, and then subjected to sulfur sensitization at 62°C for 90 minutes, and the I) Ag at 40°C was adjusted to 7.90 with an aqueous potassium bromide solution.

(Preparation of silver halide photographic light-sensitive material) An undercoat layer with a thickness of 0.1μ on both sides (Japanese Patent Laid-Open No. 59-1994
On one undercoat layer of a polyethylene tereftate film with a thickness of 100 μm (see Example 1 of No. 1), a silver halide emulsion layer having the following formulation (1) was applied with a gelatin amount of 2.5 μm. O
g/+", silver amount is 3.5 g/g", and on top of that, a protective layer of the following formulation (2) is applied with a gelatin amount of 1.
．． 5 g/+s", and on the other undercoat layer on the opposite side, apply a packing layer according to the following recipe (3) so that the amount of gelatin is 2.7 g/7 m", Furthermore, on top of that, a protective layer of the following formulation (4) is applied with a gelatin amount of 1.
．． Sample No. l~44
I got it.

Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0 g/m'' Silver Halide Emulsion A Silver amount 3.5 g/m' Antifoggant: Hydroquinone 251 g/, x Stabilizer 4-methyl-6-
Hydroxy-1,3.3a,7-tetrazaindene 30m9
/m” Surfactant: Saponin 0.lg/
m" Compound according to the present invention or comparative compound in the amount shown in Table 1 or Table 2 Sensitizing dye: Il10,c')υ,Na Prescription (2) (Emulsion protective layer composition) Gelatin 1.5 g/m" Matting agent: Silica 0.0 with an average particle size of 3.0 to 5.0 μg
3g/gc' Colloidal silica 0.02g/m" Surfactant S: CH*COOCHxCH(Ctl{.)C*HsW Hardener: (CH,=CHSO,CH!Tsuco0 0.lOg/m" Prescription (3) (Banoking layer composition) (a) (b) (c) SO3Na Gelatin surfactant: Sabonin hardening agent: Glyoxaltotecylbenzenesulfonic acid sodium 2.7g/m"0.1g/a' 0- 01g/a" Thorium 0.019/■2 Prescription (4) (Packing protective layer composition) Gelatin Ig/s" Matting agent: Polymethyl methacrylate with average particle size 3.0-5.0μ 0.05g/ ■2 Surfactant S: CHzCOOCHzCH(CtHs)C*Hs Hardener:
Glyoxal 0.01 g/m'' The obtained sample was divided into two pieces, and one piece was subjected to a halftone quality test according to the method described below.

(Dot quality test method) A halftone screen (150 lines/inch) with a halftone dot area of 50% is attached to a step wedge, and the sample is placed in close contact with this and exposed for 5 seconds to a xenon light source. /' This sample was developed under the following conditions using an automatic developing machine for rapid processing using the following developer and fixer, and the dot quality of the sample was evaluated. For evaluation, fringes (blur) that occur around the halftone dots are observed using a 100x magnifying glass, and those with high don't quality are ranked "5".
There were five ranks: ``3'', ``2'', and ``l''. Note that the rank rlJ is extremely poor, and if it is less than "3", it is generally at a level that is not desirable for practical purposes.

(Residual color test) The other film was subjected to the same process as above without being exposed, and the remaining color of the film was visually evaluated in 5 stages.
] had an attractive color, and [1] had a strong orange residual color. For general plate making, residual color below [3] is considered to be a major drawback.

In addition, the obtained sample was measured using a Konica digital densitometer PDP-65.
The sensitivity at the concentration of sample No. 3.0 is 10
The relative sensitivity is expressed as 0, and the gamma is expressed as the tangent between the densities 0.3 and 3.0.

Developer recipe Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Hydroquinone 5-amino l-pentanol Potassium bromide 5-methylbenzotriazole l-7enyl-3-vilazolidone Add water to make lQ, adjust sodium hydroxide to 11.5 do.

Fixer formulation (A) Ammonium thiosulfate (72.5% V/V sodium sulfite, sodium acetate, trihydrate, boric acid, sodium citrate, dihydrate (B) Pure water (ion exchange water) 1g 60g 35g 50g 2.5g o.39 0.2g pH at um (aqueous solution) 240m<2 17g 6.5g 68 2g 17mQ Sulfuric acid (50% v/w aqueous solution) 4.7g
Aluminum sulfate (aqueous solution with AI2203 equivalent content of 8.1% w/v) 2
6.5g When using a fixer, the above composition A and composition B were dissolved in 500 m+2 of water in that order, and finished to Iff and used. The pl1 of this fixer was adjusted to 6 with acetic acid.

(Development processing conditions) (Process) (@ degrees) (Time) Development
40'0 Fixed for 15 seconds
35°0 15 seconds water wash
Dry at 30°C for 10 seconds. Dry at 50°C for 10 seconds.
As comparative compounds added to the silver halide emulsion layer in 1), the following compounds (a) to (c) and comparative sensitizing dyes were used.

I-a Comparative sensitizing dye m-b Comparative sensitizing dye IV-a ■ b The results of the above examples are shown in Tables 3 and 4.

As is clear from Tables 3 and 4, the samples according to the present invention have higher sensitivity than the comparison, have high contrast, and have halftone dots. Example 2 The same procedure as in Example 1 was carried out except that the silver halide emulsion was changed to Emulsion B below and the process was carried out using a developer having the following formulation. The results are shown in Tables 5 and 6.

(Preparation of Silver Halide Emulsion B) A silver iodobromide emulsion (0.5 mol % of silver iodide per mol of silver) was prepared by a simultaneous mixing method. The obtained emulsion was an emulsion consisting of cubic grains with an average grain size of 0.15 pm.
;. After washing and desalting this emulsion with water according to a conventional method, ii! E yellow sensitization was performed at 62°C for 90 minutes, and the pAg at 40°C was adjusted to 7.90 with an aqueous potassium iodide solution.

Developer formulation Hydroquinone 22.59 methol 0.25g Ethylenediaminetetraacetic acid 1,0g Sodium sulfite 75.0g Sodium hydroxide
7.9g trisodium phosphate (dodecahydrate) 75.0g 5-methylbenzotriazole
0.25gN,N-diethylethanolamine
! Added 2.5wff water to complete the IQ, and adjusted the I)H to 11.6. Tables 5 and 6 show the results of the above examples.
It was shown to.

As is clear from the results in Tables 5 and 6, the samples according to the present invention, like Example 1, have higher sensitivity, higher contrast, and better halftone dot quality and residual color rank than the comparison.

Table 5 (General formula [I]) [Effects of the invention] The silver halide photographic light-sensitive material of the present invention has high sensitivity throughout the blue, green, and red regions, and can be quickly processed using an ordinary developer with a high sulfite ion concentration. Even through processing, it is possible to provide a silver halide photographic material with extremely high contrast, excellent halftone dot quality, very little fogging and dye staining after processing, and high sensitivity.

Claims (2)

[Claims] (1) In a silver halide photographic light-sensitive material having a hydrophilic colloid layer including a support and at least one silver halide emulsion layer coated on the support, at least one layer of the silver halide emulsion layer is provided. is represented by the following general formula [I] and at least one compound represented by the following general formula [III], [IV]
, and at least one compound represented by [V]. (2) The silver halide photographic material according to claim 1, which contains at least one compound represented by the following general formula [II] in place of the general formula [I]. material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. R_4 represents an optionally substituted alkoxy group or amino group, and Y represents a sulfur atom or an oxygen atom. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1, R_2 and R_3 are hydrogen atoms, optionally substituted aliphatic groups, aromatic groups, heterocyclic groups, alkoxy groups, or aryl R_4 represents a divalent aromatic group; R_5 represents an optionally substituted alkyl group, alkoxy group, or amino group; Y represents a sulfur atom or an oxygen atom. [In the formula, R_1 and R_2 each represent an optionally substituted alkyl group, and at least one of R_1 and R_2 is a sulfoalkyl group or a carboxyalkyl group. It is. Z represents an alkyl group or an aralkyl group. U,
V, W and Y each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxycarbonyl group, a carboxyl group or a hydroxyl group. X^■ represents an acid anion. m represents 1 or 2, and m is 1 when an inner salt is formed. ] General formula [I
V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2 and R_3 each represent an optionally substituted alkyl group. U, V, W and Y each represent a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, a hydroxyalkyl group, a hydroxyalkoxy group or a phenyl group. represent. X^■ represents an acid anion. n represents 1 or 2, and n is 1 when an inner salt is formed. ] General formula [V] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1, R_2, R_3 and R_4 each represent an optionally substituted alkyl group. U, V, W and Y are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group,
Represents an optionally substituted alkoxycarbonyl group, carboxyl group, hydroxyl group, cyano group, or optionally substituted acyloxy group. X^■ represents an acid anion. 1 represents 1 or 2, and 1 is 1 when an inner salt is formed. ]