JPS63106648A - Spectrally sensitized silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the deterioration of the photograph characteristics during storage and to enhance the photosensitivity by spectrally sensitizing silver halide particles in a hydrophilic colloidal layer with a merocyanine dye and incorporating a specified compd. into the colloidal layer. CONSTITUTION:The silver halide particles in a hydrophilic colloidal layer are spectrally sensitized with a compd. represented by formula I and a compd. represented by formula II or III is incorporated into the colloidal layer. In the formula I-III, Z is a group of nonmetallic atoms required to form an oxazole ring, a benzoxazole ring or the like, R<1> is optionally substd. alkyl group, R<2> is alkoxycarbonylalkyl, hydroxyalkyl group or the like, each of R<3> and R<4> is hydrogen atom, alkyl group or the like, each of R<5> and R<6> is hydrogen atom, alkyl group or the like, M is hydrogen, an alkali metal atom or the like and R<7> is alkyl group. Thus, the sensitivity is enhanced and the deterioration of the photographic characteristics during storage is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a halogenated IL1# photosensitive material, and more particularly to a silver halide photographic material for plate making that is spectrally sensitized with a melonanine dye. .

[Conventional technology]

The photolithography process using silver halide photosensitive materials involves the process of converting a continuous tone original into a halftone dot image, that is, converting continuous tone density changes into a set of halftone dots having an area proportional to the density. Halftone dots ii obtained in the converting step and the interpolation step
It includes a step of converting the i-image into a halftone image with better sharpness, that is, a turning step.

It is essential that the photosensitive materials used in these processes have high contrast in order to obtain good quality.

Conventionally, a method for obtaining such characteristics has been to develop a photosensitive material made of a silver chlorobromide emulsion with relatively fine grains and a narrow particle size distribution (and a high ffi chloride content) using a flukaline hydroquinone developer with a very low sulfite ion concentration. How to process with,
A so-called Lith development method is known.

However, when this method is used, the storage stability is extremely poor because the concentration of sulfite ions in the developer is low, and because hydroquinone is used as a single main agent, the development speed is slow and rapid processing is not possible.

Therefore, the so-called PQ contains a super-additive developing agent that has good storage stability and can be processed quickly, and contains a relatively high concentration of sulfite.
It is desired to develop a new photosensitive material that can obtain high contrast by processing with a type or MQ type developer.

As one of the things related to this new photosensitive material,
-17825, 59-17818, 59-17
No. 819, No. 59-17820, No. 59-17821
No. 59-17826 and No. 59-17822 disclose silver halide photographic materials containing a tetrazolium compound.

Further, Japanese Patent Application Laid-open No. 106244/1983 discloses a silver halide photographic material using a hydracune compound.

On the other hand, silver halide photographic materials for use in plate making are generally required to have so-called Orn type photosensitivity, which is photosensitivity in the green area.

Since the photosensitive silver halide emulsion alone has a narrow photosensitive wavelength range, spectral sensitizers are used to expand the photosensitive wavelength range to longer wavelengths.For example, to increase the sensitivity to green light, As a grant, Tokuko Sho 3) 82
No. 8, No. 40-392, No. 43-10251, No. 4
3-22884, British Patent No. 815.172, British Patent No. 95
5°961, 955.912, 142,228
No. 1,942°854, U.S. Pat. No. 1,950
, No. 876, No. 1,957,869, No. 2,238゜231, No. 2,521.705, No. 2,647,0
No. 59, Special Publication No. 43/2606, No. 44-3644, No. 46-18106, No. 46-18108, No. 4
No. 8-15032, No. 49-33782, No. 54-3
No. 4252, No. 58-52574, U.S. Patent No. 2,83
9.403, 43,567.458, 3.625
Examples include cyanine dyes and merocyanine dyes described in specifications such as No. 698.

[Problem that the invention seeks to solve]

These spectral sensitizers increase the sensitivity in a specific wavelength range, and their general properties include, for example: (1) They are not affected by other additives and do not affect the effectiveness of the additives.

■ No change in photographic characteristics such as a decrease in sensitivity or an increase in capri even after time has elapsed.

■ No dye staining occurs after development.

■ High sensitivity and low capri.

However, when relatively rapid development is performed as described above, dye staining after the development process becomes large;
This is a big problem in practice.

In order to reduce dye staining, it is sufficient to use a spectral sensitizer that has low dyeability to hydrophilic colloids such as gelatin (and has high solubility and is easily washed away into the processing solution). Proposed.

However, the spectral sensitizers often have a large chromatic effect on the developing effect with extremely high film resistance, which is required for plate-making, and cause problems such as a decrease in contrast, which is difficult to achieve with ordinary photographic light-sensitive materials. It was difficult to directly apply the means for solving dye staining described in 1. to silver halide photographic materials that undergo high-contrast development.

In addition, when used in combination with tetrazolium salt or hydrazine, a photographic material with very high contrast can be obtained, but the photographic performance often deteriorates over time and sufficient effects cannot be obtained.This is especially true when used in combination with hydranone. It is noticeable in

The purpose of the present invention is to solve the above-mentioned problem, to solve the problem of α, and in particular to provide a solution that has extremely little deterioration of photographic properties during storage, has high photosensitivity, and uses an ordinary developer with a high concentration of sulfite ions. It is an object of the present invention to provide a silver halide photographic light-sensitive material which can obtain extremely high contrast even through rapid development processing and has little dye staining.

[Means for solving problems]

The above object of the present invention is to provide a silver halide photographic material having a hydrophilic colloid layer including a support and at least one silver halide emulsion layer coated on the support. silver halide grains are spectrally sensitized by a compound represented by the following general formula [11], and the hydrophilic colloid layer contains a compound represented by the following general formula [11 or general formula [1111]. We have discovered that this can be achieved by using a silver halide photographic light-sensitive material.

General formula [1] Z is an oxazole nucleus, a benzoxazole nucleus, or 7
represents the atomic group necessary to complete the tooxazole nucleus, and these nuclei may have a substituent on the carbon atom, r
Specific examples of 1 substituent include halogen atom, carbon number 1-6
unsubstituted alkyl group, JXfta 1-4 alkoxy group, hydroxy group, carbon ftfi2-G furkylsulfonyl group, C2-5 furkylcarbonyloxy group,
Examples include a 7-enyl group, a hydroxyphenyl group, and the like.

Examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-tumethyloxazole, 4-phenyloxazole, etc. as oxazole nuclei; benzoxazole, 5-clobenzo as benzoxazole nuclei. Oxazole, 5-
Bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-7
Cetyloxybenzoxazole, 5-7dynylbenzoxazole, 6-methylbenzoxazole, 6-noFoxybenzoxazole, 5,6-7methylbenzoxazole, 6-chloro-5-methylbenzoxazole, etc., naphthoxazole 7 as a core [1.2-
d]oxazole, naphtho[2.1-d]oxazole, naphtho[2.3-d]oxazole, and the like.

R'j! Ki? ! r represents a substituted or substituted furkyl group,
Examples of substituents include hydroxy group, sulfo group, sulfonate group, carboxy group, halogen atom (e.g. fluorine atom, chlorine atom), unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (alkoxy group further includes sulfo group). may be substituted with a hydroxy group), charcoal! ! ! 2 to 5 furkylsulfonyl groups, JXfta 1 to 4 furkylsulfonyl groups, sulfamoyl groups, unsubstituted or substituted carbamoyl groups (including substituted carbamoyl groups substituted with alkyl groups having 1 to 4 carbon atoms) , substituted phenyl group (examples of ra substituents include sulfo group, carboxy group, hydroquine group, etc.), 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, 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-sulf77moylethyl group, 2-carbamoylethyl 1,2-N-N-tumethylcarbamoylethyl group as sulf77moylethyl group etc., 7enethyl group, p-carboxine 7enethyl group, p-sulfo7enethyl group, 0-sulfo7enethyl group, etc. as sulfoaralkyl group, p-
Examples include hydroxy 7enethyl group, allyl group, phenoxyethyl group, and the like.

R2 is an alkoxycarbonylalkyl group, a hydroquinylalkyl group, a hydroxyalkoxyfurkyl group, a carbamoylfurkyl group, a hydroxy7enyl group, a hydroxyfurkylphenyl group, a 7enyl group, an alkoxyfurkyl group, or a substituted Base "T CII a ↑"^ or T
CII 2'rfr''OtCH2-1°, where A is a nitrile group, an alkylsulfonyl group, a sulfonamide group, an alkylsulfonylamide 7 group, or a carbon 1
It represents an alkoxy group of 1 to 8, 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 a halogen atom can also be preferably used. Examples of R2 include those in which each alkyl group is substituted with a halogen atom. Alkoxycarbonylalkyl group, hydroxyalkyl group, hydroxyalkoxyalkyl group, carbamoylalkyl group (N-
Alkyl-substituted, N-N-dialkyl-substituted, N-hydroxyalkyl-substituted, N-furkyl-N-hydroxyalkyl-substituted, N-N-)(hydroxyalkyl)-substituted carbamoyl alkyl groups and cyclic amines with 5 and 6 shell rings. carbamoylalkyl group f) (M, tlr2-carbamoylchloroethyl!, 2-N-(2-hydroxyethyl)carbamoylchloroethyl M, N-hydroxyfluoroethylcarbamoylmethyl group, N-N-(2
-hydroxyfluoroethyl)carbamoylmethyl group,
2-N-N-(2-hydroxyethyl)carbamoylchloroethyl u, N-N-trimethylcarbamoylchloromethyl group, cerfolinolupamoylchloromethyl group,
piperidinocarbamoylmethyl group, etc.), hydroxyphenyl group, hydroxyalkylphenyl group having 7 to 9 carbon atoms, or substituent 1C112 Amahachi or MCII
2 r represents OiCII 2 constant^. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfamide group, an alkylsulfonylamide group, or a lower alkoxy group, and among these, the alkylsulfonyl group is preferably a furkylsulfonyl group having 1 to 4 carbon atoms! (e.g., methylsulfonyl group, ethylsulfonyl group, etc.), and the sulfamide group is preferably a sulfonamide group having 2111 to 4 carbon atoms (e.g., N-methylsulfonyl group, N, N-7 methylsulfonyl group, etc.). and alkylsulfonyl 7
The mino group is preferably a 7-furkylsulfonylamine group having 1 to 4 carbon atoms (for example, 7 methylsulfonylamine groups), and the lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms (for example, ethoxy group, ethoxy group, etc.), and n represents an integer value of 1 to 4.

R3 and R4 may be the same or different, and each represents a hydrogen atom, a furkyl group (preferably one with 11 to 4 carbon atoms,
(e.g., methyl group, ethyl group, etc.), alkoxy group (preferably one having 1 to 4 carbon atoms, e.g., methoxy group, ethoxy group, etc.), alkyl sulfone group, sulfone group, chlorine atom, 7 2 i atoms, or carboxyne group represents.

Particularly preferred in the compound represented by the general formula [N] is a case where RI represents a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a sulfo group, a carboxyl group, and/or a human myxyl group. , formally, sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, carboxymethyl group, carboxynethyl group, hydroxyethyl group, 3-sulfo-2-
Examples include hydroxyprobyl group.

Next, typical specific examples of the compound represented by the above general formula [1] used in the present invention will be given, but the compounds used in the present invention are limited to these: The above general formula used in the present invention [The compound represented by 11 is
No. 6-549, No. 46-18105, No. 46-181
No. 06, No. 46-18108, No. 4), No. 4085,
No. 58-52574, U.S. Patent 2,8:49,403
No. 3,384.486, No. 3.625.698, No. 3,480.439, No. 3,567.458, etc. be able to.

Adding and dispersing the norocyanine dye represented by the above general formula [11] used in the present invention into a silver herodenide emulsion can be carried out by various methods, for example, conventionally known methods. -44895
No. 50-11419, a method of dispersing and adding with a surfactant described in the specification of JP-A-50-11419, JP-A-53-16
No. 624, No. 53-102732, No. 53-1027
No. 33, U.S. Patent No. 3,469,987, U.S. Patent No. 3,676
．． The method of adding it as a dispersion with a hydrophilic substrate described in the specification of No. 147;
Examples include the method of adding as a solid solution as described in . Other water-soluble solvents for merocyanine dyes, such as water, ethanol, methanol, 7setone, n-propanol, 77
Hydrogenated alcohol, pyridine, etc. may be added to the emulsion either alone or as a mixture thereof dissolved in melted wax.The addition may be made at any time during the emulsion manufacturing process, but during chemical ripening or chemical ripening. The amount of the merocyanine dye used in the present invention is preferably 0.) 10 The amount for spectral sensitization of the silver denride emulsion, for example, 7% I per mole of silver lodenide.
X 10-' -2X 10-''-1: mol, preferably 1X10-' to 2X10-' mol.

The following general formulas [11] and [1111] will be specifically explained.

General formula [111 General formula [1!11] In general formula [11], [Il[], R% and R" are respectively a water atom, an alkyl group, -C00M, -5
03M, -01l, -CO old IR', or -NICO
Rte represents each group, but a small number of R%, R. (one of them is -C00N, -5OJ, -011, -C0NHR) or -NIICOR1 group.0M is a hydrogen atom, an alkali metal atom, or - N1(, represents a group, and R7 represents an alkyl group.

Y is oxygen atom, sulfur atom, selenium atom or ■ -N- group.

Next, specific examples of the compounds represented by the general formulas [11] and [1111] are shown below, but the compounds are not limited thereto.

The following margin [Exemplified Compound 1 General Formula] Day [Exemplified Compound 1 General Formula [1・Indazole and Derivatives (TI+e chelistry orlle
terocyclic eoa+pounds 1
m1dazole and Deriva-tiv
es) Vol., I P , 384 or according to the method described therein.

General formula [
1 of the compound 11 or [I[[] is preferably in the range of 1X10-' to 1X10-' mol per mol of silver halide contained in the silver halide photographic light-sensitive material of the invention, and more preferably in the range of 1X10-' It is preferable to set it in the range of ~lXl0-2.

The silver halide photographic material of the present invention comprises a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer coated on the support, and this silver halide emulsion is directly coated on the support. Coating or coating via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid layer as a protective layer on the silver halide emulsion layer. ! In addition, the silver halide emulsion layer may be divided into silver halide emulsion layers of different sensitivities, such as high sensitivity and V low sensitivity. In this case, the silver halide emulsion layer has a An intermediate layer of a hydrophilic colloid layer may be provided between the debris, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer.

The layer containing the compound of general formula [11] and the compound of general formula [111 or [I] of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or
Or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

In order to incorporate the compound of the general formula [U] or [lff1 of the present invention into the wood-philic colloid layer, the compound of the general formula [■] or [I[[] is dissolved in an appropriate water and/or organic solvent. Examples include a method in which the axilla is dissolved in an organic solvent and then added after being dispersed in a hydrophilic colloid matrix of gelatin or a gelatin derivative, or a method in which it is added after being dispersed in latex.

The silver halide used in the silver halide photographic light-sensitive material of the present invention is a silver halide of any composition, and the average grain size of the silver halide grains used is in the range of 0.05 to 0.5 μm. It is preferably 0.10 to 0.40 μm, and more preferably 0.10 to 0.40 μm.

Regarding the monodispersity of the silver halide grains used in the present invention, the value is preferably 5 to 25, more preferably 8 to 2.
The grain size of the silver halide grains used in the present invention is conveniently expressed by the ridge of a cubic grain,
The monodispersity S is the standard deviation of the particle size divided by the average particle size, which is 1.
It is expressed as a value multiplied by 00.

Further, as the silver halide that can be used in the present invention, for example, a type having a multi-M lamination structure of at least 2N can be used. Silver bromide particles may be silver chlorobromide particles in which the shell portion is silver chloride.

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 addition, when using rhodium salts, inorganic compounds such as iridium salts, platinum salts, thallium salts, cobalt salts, salts, etc. may be used in combination.Iridium salts are often used for the purpose of imparting high-light characteristics. 10-8 mole to 1 mole of silver
It can be preferably used in a range of 0 to 6 moles.

The halogenated ffi used in the present invention has the general formula [
In addition to the spectral sensitization using the compound No. 11, sensitization can be performed using various chemical sensitizers known in the photographic material industry.

The spectrally sensitized silver halide and the compound represented by the general formula [U] or [1111 used in the present invention are present in a hydrophilic colloid layer known in the photographic material industry, such as gelatin. Hydrophilic colloids can also be applied to layers that do not contain silver halide, such as halide prevention layers, protective layers, intermediate layers, etc.

As the support used in the present invention, supports known in the photographic material industry, such as polyester film, can be used.

The light-sensitive material of the present invention contains, for example, a compound represented by the general formula [11] of the present invention in a hydrophilic colloid layer comprising at least one silver halide emulsion layer on a support as described above. However, it has a structure in which a hydrophilic colloid layer having an appropriate rQ thickness, preferably 0.1 to 10 μl and preferably 0.8 to 2 μl is coated as a protective layer on the silver halide emulsion layer. It is particularly preferable.

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 not impaired by staining agents, pn adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, morgunton, brighteners, development speed adjusters, matting agents, etc. It can be used within the range.

In a preferred embodiment, a silver halide photographic material containing a compound of the general formula [1] of the present invention in a silver halide emulsion layer and/or another hydrophilic colloid layer is added with the following general formula [V] or [Vll]. It can contain a compound represented by:

General formula [V] 314. Ill and fin are each a hydrogen atom or r! i represents a substituent, and xe represents an anion.

In the general formula [Vll, RIff, RIl, RIs and t7R'' each represent a hydrogen atom or an organic group, and this organic group is a hydrocarbon group such as an alkyl group, a 7-aryl group, an aralkyl group, an alkaryl group, and an N-cyclic group. represents a hydrocarbon group substituted with a substituent such as an oxy group, a thio group, an alkoxy group, a carboxy group, a sul7one-7mido group, and a halogen atom.

Compounds [V] and [Vll will be discussed in more detail below.

In the general formula [V], Rz, Ras to R11
Preferred examples of the substituent represented by 1 include a furkyl group, an amino group, an acylamino group, a hydroxyl group, an alkoxy group,
Acyloxy group, halogen atom, carbamoyl group, acylthio group, alkoxycarbonyl group, carboxyl group,
Examples include groups such as an acyl group, a cyano group, a nitro group, a norcapto group, a sulfoxy group, and an aminosulfoxy group.

Examples of the anion represented by Xe include halogen ions such as chloride ion, bromide ion, and iodide ion, wl of inorganic acids such as nitric acid, sulfuric acid, and perchlorine Fll,! r
1. Acid radicals of organic acids such as sulfonic acids and carboxylic acids, anionic activators, specifically P-) lower alkylbenzenesulfonate anions such as luenesulfonate anions, 1
)-Higher alkylbenzenesulfonic acid anions such as dodecylbenzenesulfonic acid anions, higher alkyl sulfate ester anions such as lauryl sulfate anions, rM acid anions such as tetraphenylboron, dialkyl such as di-2-ethylhexylsulfosuccinate anions, etc. Polyether alcohol sulfate ester anions such as sul7-osuccinate anions, cetyl polyethenoxysul7ate anions, high alpha fatty acid anions such as stearate 7-anions, and polymers with 1112 roots such as polyacrylic acid anions. can be mentioned.

Hereinafter, the general formula [
Specific examples of the compound represented by V] will be given below.

[V] The tetrazolium compound used in combination with the present invention is described in, for example, Chemical Review (Chemical Review).
s) No. 558, p. 335, -483T1.

The tetrazolium compound represented by the general formula [V] may be used in an amount of about 1 zg or more per mole of silver halide contained in the silver halide photographic material of the present invention. It is preferable to use soil, preferably in a range of about 10 B or more up to about 2 g.

Among the compounds represented by the above general formula [W], compounds represented by the following general formula [■1] are particularly preferred.

General formula [■] R"NllNlICOR" In the formula, R21 and R22 each represent an optionally substituted aryl group or an optionally substituted furkyl group, and the 8-unit also represents a hydrogen atom.

The aryl group represented by 121 and [22 contains a benzene ring or a 7talene ring, and this ring may be substituted with various substituents, and preferred substituents include a straight chain or branched alkyl group (preferably C1-C20 groups such as methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.), alkoxy groups (preferably C1-C20 groups e.g. nodoxy group, ethoxy group!!9), aliphatic acylamide 7 Group (preferably one with a furkyl group having 2 to 21 carbon atoms, such as 7cetylamino group, heptyl7mi7 group, etc.)
, aromatic acylami 7 groups, ami 7 groups, etc. In addition to these, -CONI+- includes substituted or unsubstituted aromatic ring groups, heterocyclic groups, alkyl groups, etc. as described above.

-s-, -o-, -so□Nl+-, -NlIC0NI
+-.

C112CII N-N II CS N II-
It also includes those that are bonded with a linking group such as.

The above hydranone compound can be synthesized by referring to the description in US Pat. No. 4,269,929.

The following general formula [
■Specific examples of the compound represented by l are given below.

General formula [■] R"NHNHCOR" The hydrazine compound represented by general formula [VI] is preferably contained in an amount of about 112 to about 50 g per mol of silver halide contained in the silver halide photographic material of the present invention. It is preferable that the amount is within a range of about 5 g to about 5 g.

For the development process of the present invention, please contact the photographic material industry.
Various known developing agents can be used. For example, T. II. James, The Theory Op.
Photographic Process 4th Edition (TI+c The
ory of LI+e I'l+oLograpl+
ic I'rocc! 3sFourtl+ EJiLi
on) m291-:L14iSj and Journal of the American Chemical Society (Jour
nal of the American Cbemi
cal 5ociety) Volume 13, No. 3,100 (1
951) and the like can be effectively used in the silver halide photographic light-sensitive material of the present invention.

These developers may be used in early autumn or in combinations of 2Ff1 or more, but it is preferable to use two or more types in combination.

Also, the developer used for processing the photosensitive material of the present invention! Even if a sulfite salt such as potassium sulfite or ammonium sulfite is used as a preservative, the effects of the present invention are not impaired, and this can be cited as one of the features of the present invention. Hydroxylamine or hydrazide compounds may also be used as preservatives, such as mushroom alkali, charcoal or amines used in general black and white developers. PLL adjustment and buffer 7-function,
and inorganic development inhibitors such as brompotali and organic development inhibitors such as benzotriazole, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, and polyalkylene oxide,
7. Sodium rukylarylsulfonate, natural saponin, surfactant M such as alkyl esters of tliM or 1 profile compounds, grugulaldehyde, formalin,
It is optional to add a hardening agent such as glyoxal, ionic strength adjustment W'1 such as sodium sulfate, etc.

The developer used in the present invention may contain alkanolamines or glycol chloride as an organic solution W.

By developing the silver halide photographic material of the present invention using a developer containing the above-mentioned development inhibitor, a photographic material having extremely excellent storage stability can be obtained.

The pH value of the developer having the above composition is 9 to 12,
The pH value is preferably in the range of 10 to 11 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 after 30''C@, and the development time is generally completed within 3 minutes, particularly preferably within 40 seconds, which often brings about good effects. Processing steps other than development, such as washing, stopping,
Stability, establishment, sai.

It is optional to adopt steps such as preduralization and neutralization as necessary, and these steps can be omitted as appropriate. Furthermore, these processes may be so-called manual development processes such as plate development and frame development, or R machine development processes such as roller development and hanger development.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 A silver chlorobromide emulsion (containing 65 mol% silver chloride and 3 mol% silver bromide) was prepared by an acidic method.

These silver halide grains are monodisperse grains having a cubic crystal structure and an average grain size of 0.25 μm, with 90% or more of the total grains having a size ranging from 0.7 times to 1.3 times the average grain size.

For this silver chlorobromide emulsion, a temperature of 60°C, a pH of 6.0
and sulfur-containing sensitization at an EA of 170 mV,
6-methyl-4-hydroxy-1,3,l as a stabilizer
a. Added tutetrazaindene. Divide the emulsion into m1
As shown in the table, the compound of the general formula Ill according to the present invention or the comparative compounds [A], [B], and [C] were each added at 250 B per mole of silver halide to carry out dye sensitization,
Further, to each emulsion, a compound of the general formula [■J or [I] shown in Table 1 or a comparative compound [D] was added in an amount of Oxg per mole of silver halide.

Furthermore, 300zy of sodium p-dodecylbenzenesulfonate per 11 moles of halogenated ff, Exemplary Compound [V]
-2 was added, 2 g of styrene-maleic acid copolymer polymer, and 15 g of styrene-butyl acrylate-acrylic acid copolymer latex (average particle size approximately 0.25 μz) were added, Ag amount was 3.5 g/z. , gelatin amount 2,007
This photographic emulsion layer was processed into Japanese Patent Application Laid-open No. 59 (1986).
It was coated on a polyethylene terephthalate (polyethylene terephthalate) film base subjected to undercoating as described in Example (1) of Publication No. 19941. At that time, the amount of gelatin is 1. Oy/a2, as a spreading agent;
1-decyl-2-(3-inpentyl)succinee)-
A protective layer containing 30 g/z'' of sodium 2-sulfonate and 25 g/z'' of formalin as a hardening agent was simultaneously coated.

The samples obtained in the manner described above are shown in Table 1.

Each of the obtained samples was divided into two parts, and the other half was conditioned at 23°C and 48% relative humidity to evaluate the stability of performance over time, and then sealed and packaged with a moisture-proofing agent at 55°C. 3
Six samples subjected to daily heat treatment were exposed to light using a tungsten light source using an optical unit.

The above test sample was processed using a developing solution and a fixing solution according to the following formulation in an automatic processing machine for rapid processing.

[Development processing conditions] (Process) (Temperature) (Time) Development 28℃ 15 seconds fixation
Wash with water at 28℃ for about 10 seconds
Dry at room temperature for about 10 seconds
50°C 15 seconds [Developer composition] (11 compositions A) (11 tons) When using the developer, add one group of the above composition J to 500ziJ of water.
& n, and finished to 11 and used.

[Fixer Prescription] (Composition A) (Composition B) When using a fixer, the above group t, A, and composition were dissolved in 500M1 of water in that order, and the composition was finished to 11. The p of this fixer was approximately 4.3.

The photographic characteristic curves of the developed samples were measured for sensitivity, capri density, and residual color at the legs of the characteristic curves. The sensitivity was determined from the reciprocal of the exposure amount required to form an optical density of 2.5, and expressed as relative sensitivity with Sample No. 21 set as 100. The contrast is optical density 0.2 and 1.
It is expressed as a comma value for the exposure amount that gives a value of 5.

In addition, for samples that were processed without exposure, we stacked four films and visually evaluated the residual color of the film, and evaluated it on a five-point scale, with '5'' being colorless and '1'' being a strong orange residual color. Indicated.

For general plate making, residual color below "3" is considered to be a major drawback.

These results are shown in the ff12 table.

Comparative Compound (A) Comparative Compound (I3) Table 1: White Comparative Compound (C) Comparative Compound (D) As shown in Table 1 and Table 2, the sample of the present invention can reduce fog without impairing sensitivity. , extremely high contrast can be obtained by rapid processing using a normal developer with a high concentration of sulfite ions, and there is very little dye staining after processing.
It can be seen that the performance over time is also stable.

Example 2 Using the emulsion obtained in Example 1, tjS was applied in the same manner as in Example 1.
As shown in Table 3, 250 ifI of the compound of the general formula (11) was added per mole of silver, and the same ()Oxg of the compound of the general formula [111 or [I] was added.

Next, exemplified compound [VI]-2 was used instead of exemplified compound [V]-2.
]-9 at 250B per mole of halogenated ai,
Otherwise, the sample 26 was coated by the same method as in Example 1.
~33 was obtained.

The obtained sample was processed in the same manner as in Example 1, and its photographic properties were evaluated. However, the sensitivity is shown assuming that the unprocessed photographic sensitivity of sample No. 32 is 100.

As shown in Table 3 and Table 4, even if a hydranone compound is used instead of a tetrazolium salt, capri can be reduced without impairing sensitivity, extremely high contrast can be obtained, and there is very little dye staining after processing, resulting in excellent performance over time. It can be seen that it is also stable.

Example 3 A highly monodisperse silver iodobromide emulsion was prepared by simultaneously adding 91 g of a silver nitrate aqueous solution and a mixed aqueous solution of potassium iodide and potassium bromide to a gelatin aqueous solution kept at 50° C. while keeping the concentration at 7.5 by the Gupurnoet method. (Silver iodide 5 mol%, silver bromide 95 mol%
) was adjusted.

These halogenated particles are cubic and have an average particle size of 0.25.
These are monodisperse particles in which 90% or more of the total particles are 0.7 to 1.3 times the average particle diameter in μ.

This silver iodobromide emulsion was subjected to gold sulfur sensitization in the same manner as in Example 1, and 6-methyl-4-hydroxy-1 was used as a stabilizer.
=L]a-7-tetrazaindene was added.

This emulsion was divided and the general formula [! ] 25011F per mole of silver, and the same compound (70 mg) of general formula [11] or [111] was added.

Subsequently, in place of the exemplified compound [Vl-2, exemplified compound [VI]-9 was added at 2,501 mol per 1 mole of halogenation.
Coated samples 34 to 41 were obtained in the same manner as in Example 1 except that 2 was added.

The obtained sample was processed in the same manner as in Example 1, and its photographic properties were evaluated. However, the sensitivity is shown assuming that the unprocessed photographic sensitivity of sample 40 is 100.

The results are shown in the PAG table.

Table 5 As a result, even when silver iodobromide holes M are used, capri can be reduced without impairing sensitivity, extremely high hunst resistance can be obtained, and J! ! ! It can be seen that the subsequent dye staining is extremely small and the performance over time is stable.

Example 4 Using a silver chlorobromide emulsion prepared by the acidic method as in Example 1, first, as shown in Section 7a, a compound of the general formula [nl, [1111] or a comparative compound according to the present invention was added per mole of Wi halide. 70 mg was added. Next, the temperature is 60℃, p
u, o, gold sulfur sensitization at EAg 170 mV,
As a stabilizer, 6-methyl-4-hydroxy-1,3,
3a,7-tetrazaindene was added.

This emulsion was divided into silver halide 1 as shown in Table 7.
250 JIF of the compound of the general formula [11 according to the present invention or a comparative compound was added per mole, and further 19 JIF of the exemplified compound [V]-2 was added and coated in the same manner as in Example 1.
I got 49.

The obtained sample was processed in the same manner as in Example 1, and its photographic properties were evaluated. In this case, the unprocessed photographic sensitivity of sample 48 was set at 100, and other specific sensitivities were expressed.

The results are shown in Table 8.

As shown in Table 7 and Table 8, even if a compound represented by the general formula [111 or [1111] is added before chemical sensitization, the capri can be reduced without impairing the sensitivity, and extremely high mountability can be achieved. obtained, and with extremely little dye staining after processing (
It can be seen that the performance over time is also stable.

〔Effect of the invention〕

As explained in detail in the above embodiments, according to the present invention,
A silver halide silver halide with high sensitivity, minimal deterioration of photographic properties during storage, extremely high contrast obtained through rapid processing using a normal developer with a high concentration of sulfite ions, and minimal dye staining. Xiaomi is able to provide photographic materials.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material comprising a support and a hydrophilic colloid layer coated on the support, including at least one silver halide emulsion layer, wherein the hydrophilic colloid contained in the hydrophilic colloid layer The silver halide grains are spectrally sensitized by a compound represented by the following general formula [I], and the hydrophilic colloid layer contains a compound represented by the following general formula [II] or general formula [III]. Characteristic silver halide photographic material. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Z 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 represents an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group,
Represents a carbamoyl alkyl group, hydroxyphenyl group, hydroxyalkylphenyl group, phenyl group, alkoxyalkyl group, or a substituent -(CH_2)-_nA or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here A
represents a nitrile group, an alkylsulfonyl group, a sulfamide 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] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [III
]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^5 and R^6 are hydrogen atoms, alkyl groups, -COOM, -SO_3M, -OH, -CONH, respectively.
Each group represented by R^7 or -NHCOR^7 is represented by R^
5. At least one of R^6 is -COOM, -S
O_3M, -OH, -CONHR^7 or -NH
There are 7 COR^ groups. M represents a hydrogen atom, an alkali metal atom or a -NH_4 group, and R^7 represents an alkyl group. Y is an oxygen atom, a sulfur atom, a selenium atom, or a formula,
There are chemical formulas, tables, etc. ▼ Represents a group. ]