JPH02302755A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material improved in color sensitivity, graininess, sharpness, and safelight nonsensitivity by controlling each color sensitive part so as to specify mutual relations among relative sensitivities obtained by using each color filter. CONSTITUTION:The silver halide photographic sensitive material having at least one silver halide photographic emulsion layer on a substrate is adjusted in relative sensitivities obtained by measuring the sensitivities (SB) at 430nm, (SG) at 540nm, (SR) at 700nm, respectively, by using each glass filter, so as satisfy expressions I and II, thus permitting the obtained silver halide photographic sensitive material to be used for black-and-white photosensitive materials to be printed from a light-transmission type color photosensitive material and improved in color sensitivity, graininess, sharpness, and safelight nonsensitivity.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically to a black-and-white light-sensitive material for printing printed from a color-transmitting light-sensitive material, which is characterized by its color sensitivity, graininess, This invention relates to a silver halide photographic material with improved sharpness and safelight properties.

[Background of the Invention 1 Silver halide photographic materials are used in all fields because of their useful photographic properties.

In recent years, the proportion of transparent photosensitive materials used for print production has been increasing, and in general, it is commonly printed on color vapor, but as the image quality of color negatives continues to improve, black and white photographic paper is becoming more popular. The number of cases in which prints are made from color negatives is increasing. Especially in newspapers and news agencies! l Shadow colored negative for color gravure,
Alternatively, there is a growing trend that it is more cost-effective to share them, such as for regular black and white printing, and the proportion of color negatives used is rapidly increasing.

However, when printing from a color negative onto black-and-white photographic paper, printing on conventional regular color-sensitive black-and-white photographic paper results in good sharpness but extremely poor graininess, resulting in only low-quality prints 1 to 1. This is because the color sensitivity of vapor is only in the blue-sensitive area, so only the negative yellow layer, which uses relatively large grains of silver halide, functions as a negative.

For this reason, Kodak's Panchrome Vapor was released as a black and white photographic paper that had blue, green, and red areas like color paper. In both cases, the first flight was extremely dark, making it difficult to use and difficult for workers accustomed to using ordinary black and white photographic paper. J again! The current situation is that the image quality is poor in sharpness and it is difficult to focus because information from the negative cyan layer, which has poor Y sharpness, is added.

In order to improve these defects, Fuji Film Co., Ltd. has released a photographic paper called Fuji Pro Ortho, but since this is a photographic paper that only has blue and green areas, red safelight can be used. Although it is a black and white photographic paper that can be used under light lighting and has a high image quality of #52, the cyan-blue color reproduction is unsatisfactory due to the lack of red-sensitive areas. The black and white photographic paper was not necessarily satisfactory due to its poor graininess.

[Problems to be solved by the invention] In view of these current circumstances, it is desired to develop black and white photographic paper printed from a color negative that can use bright safelight and has improved color reproduction, sharpness, and graininess. .

An object of the present invention is to provide a silver halide photographic material which is a black and white photosensitive material for printing printed from a color transmissive photosensitive material and which has improved color sensitivity, graininess, sharpness and safelight property. .

[Means for Solving Problem 1] An object of the present invention is to provide a silver halide photographic light-sensitive material in which a silver halide photographic emulsion is coated on a support with at least -FI.
(7) Sensitivity a (S B ), sensitivity at 540 nm (SG
), the relative sensitivity is 0 when the sensitivity (SR) of 700na+ is determined using colored glass filters under the conditions shown below.
This is achieved by a silver halide photographic material characterized in that the sensitivity of each color-sensitive area is adjusted so that the following relationships hold: <SB/SG≦0.8 0<SR/SG≦0.7.

However, using a tungsten light sensitometer with a sensitivity of 8B of 2854 K and 400 lux, a colored glass filter K L-43 manufactured by Toshiba Glass Co., Ltd. was inserted on the optical axis, and the sample was exposed for 1 second through an M continuous edge. Then, D-
72 developer (manufactured by Kodak) diluted 1:2 with water at 20°C for 90 seconds, then stopped and fixed using IF-5 fixer (manufactured by Kodak) at 20°C for 5 minutes. , wash with water and dry.

9 Odor sensitivity is determined from the following equation using an exposure (ff11-N lux x seconds) that gives an optical density 0.6 optical 81 degrees higher than the minimum density (1) min ).

Sensitivity -1000/t1 Sensitivity SG and sensitivity SR are colored glass filter KL-4
In place of 3, KL-54 and KL-70 filters are inserted, respectively, and the sensitivity is determined in the same manner as above.

The present invention will be explained in detail below.

The silver halide photographic material of the present invention is characterized by a blue-sensitive area,
By changing the balance of the sensitivity of the green and red areas to a large degree compared to the conventional panchromatic vapor, it is possible to improve image quality from color negatives (more contribution of yellow in color negatives to graininess, sharpness) The contribution of the cyan layer of color negatives to the color negative) is reduced, thereby achieving both sharpness and graininess, as well as improving color reproducibility by adding a red-sensitive area to orthomatic paper, and improving green-sensitivity. The aim is to improve safelight properties by lowering the sensitivity of the red-sensitive area relative to the sensitivity of the red-sensitive area.

The relative relationship between the color separation sensitivity 88.8G and SR determined by the color separation filter described above is 0<SB/SG≦0.
8 0<SR/SG≦0.7, preferably 0.2<SB/SG≦0.7 and 0.2<SR/SG≦0.6.

Means for adjusting the sensitivity of the blue-sensitive area, green-sensitive area, and red-sensitive area within the scope of the present invention include the grain size of silver halide grains, chemical sensitization method, type and Φ of sensitizing dye, and appropriate dominant wavelength. It is effective to add a filter dye having the following properties, and it is useful to use each dye alone or in combination.

In the photographic material used in the present invention, the halide emulsion is generally one in which silver halide grains are dispersed in a hydrophilic colloid, and the silver halide includes silver bromide, silver chlorobromide, silver iodobromide, Examples include silver chloroiodobromide or a mixture thereof.

The silver halide emulsion used in the present invention is preferably silver bromide, silver chlorobromide, or silver chloride.

Various methods can be used to prepare the silver halide emulsion used in the present invention.

For example, any of the acidic method, neutral method, alkaline method, ammonia method, etc. may be used, and the forward mixing method, back mixing method, simultaneous mixing method, pAg chondral double jet method, conversion method, etc. may be used. be able to.

The silver halide emulsion used in the present invention contains cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, or a complex salt thereof in the silver halide grain formation or physical ripening process.
Rhodium salts or lead salts thereof, iron salts or Ti salts thereof, etc. may also be avoided.

Gelatin is usually used as the binder for the silver halide emulsion used in the present invention, but in addition to gelatin, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein may be used. I can do it.

The average grain size of the silver halide grains is preferably smaller than 2 μm, more preferably 0.25 μIm to 0.35 μm in order to reduce the sensitivity of the blue sensitive area relative to the green sensitive area.
m range.

The grain size distribution may be wide or narrow, but monodisperse emulsions with a narrow distribution are useful in order to impart relatively high gradation. In this case, in order to control the gradation from highlights to shadows, methods such as mixing monodisperse emulsions or mixing monodisperse emulsions and polydisperse emulsions are useful.

The silver halide emulsion used in the present invention can be chemically sensitized with various sensitizers.

For example, sulfur sensitizers (e.g., hypo, thiourea, activated gelatin, etc.), noble metal sensitizers (e.g., gold sensitizers such as gold chloride, rhodan gold, etc., platinum salts, palladium, iridium salts, rhodium salts, ruthenium salts, etc.), Reduction sensitizers (for example, stannous chloride, thiourea dioxide, hydrazine derivatives, etc.) can be used alone or in combination.

The silver halide emulsion used in the present invention is imparted with photosensitivity in a desired wavelength range using a sensitizing dye.

Sensitizing dyes advantageously used in the present invention include methylene dyes and styryl dyes such as cyanine, merocyanine, hemicyanine, rhodacyanine, oxonol, and hemioxonol.

Typical blue-sensitive sensitizing dyes include the following.

General formula [BS-I] In the formula, Z+ and Z2 are each an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, a pyridine nucleus, a benzothiazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus,
Represents the atomic group necessary to form a benzimidazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoimidazole nucleus, or a quinoline nucleus.

R+ and R2 each represent an alkyl group, an alkenyl group or an aryl group.

Xe represents an anion, and Xe represents O or 1.

The heterocyclic nucleus represented by 21.22 is a thiazole nucleus,
A selenazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, and a naphthothiazole nucleus are preferable, a benzothiazole nucleus and a benzoselenazole nucleus are more preferable, and a benzothiazole nucleus is most preferable.

The heterocyclic nucleus represented by Z+ and Z2 may have an H substituent, and preferable substituents include a halogen atom, a hydroxyl group, a cyam L aryl group, an alkyl group, and an alkoxy group.

A particularly preferred halogen atom is a chlorine atom, and a preferred aryl group is a phenyl group. The alkyl group is preferably an IT 1-chain or branched alkyl group having 1 to 4 carbon atoms, and is particularly preferably a methyl group. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group is particularly preferable.

The groups represented by R+ and R2 are preferably alkyl groups, particularly linear or branched alkyl groups having 1 to 6 carbon atoms, and methyl, ethyl, propyl, isopropyl and the like are preferred.

These alkyl groups may be substituted, and preferred substituents include a sulfo group, a carboxylhydroxyl group, and an alkoxycarbonylkylsulfonylamino group.

The alkyl group represented by R+ and R2 is preferably an alkyl group substituted with a sulfo group or a carboxyl group. A sulfo group, a carboxyl group, etc. may form a salt with an organic cation such as a pyridinium ion or a triethylammonium ion, or an inert cation such as an ammonium ion, a sodium ion, or a potassium ion.

The anion represented by Xe is preferably a chloride ion, a bromide ion, an iodide ion, a toluenesulfonate ion, etc., and a halide salt ion is preferred. Further, when an inner salt is formed, an anion may not be included, and in that case, i does not represent O.

Typical specific examples of compounds represented by the general formula [BS-IJ] are listed below, but are limited to [BS-1-I
J [I3S-1-2] [BS-1-31 [BS-1-4] [BS-1-51 [l3S-1-Gl [13S-1-7] [13S-1-9] [BS -1-1'O] [B5-1-111 [B5-1-121 [13S -1-13] [B5-1-14] [BS-[-15] [B5-1-16] [B5- 1-17] [B5-1-18] [B5-1-19] C211゜[r3 S -1-20] General formula [BS-I] In the formula, z3 is benzoxazole nucleus, benzothiazole nucleus, benzoselenium Represents an atomic group necessary to form a zole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, naphthothiazole nucleus, nara1-selenazole nucleus, naphthimidazole nucleus, pyridine nucleus, or quinoline nucleus.

Z4 is thiobarbyl acid group, barbyl acid group, 2
- Does not represent the atomic group necessary to form a thioxazolidine-2,4-dione nucleus, a 2-thioselenazolidine-2,4-dione nucleus, a rhodanine nucleus or a 2-thiohydantoin nucleus.

R3 and Rq each represent an alkyl group, an alkenyl group or an aryl group.

The heterocyclic nucleus represented by z3 is preferably a benzothiazole nucleus, a benzoselenazole nucleus, or a naphthothiazole nucleus, more preferably a benzothiazole nucleus or a benzoselenazole nucleus, and most preferably a benzothiazole nucleus.

The heterocyclic nucleus represented by Z3 may have a substituent, and preferred substituents include a halogen atom, a human myxyl group, a cyano group, an aryl group, an alkyl group, and an alkoxy group.

A particularly preferred halogen atom is a chlorine atom, and a preferred aryl group is a phenyl group. The alkyl group is preferably a straight chain or branched alkyl group having 1 to 4 carbon atoms, and among them, a methyl group is preferable. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group is particularly preferable.

The alkyl group represented by R3 has 1 to 1 carbon atoms.
A straight chain or branched alkyl group of 6 is preferable, and a methyl group, ethyl group, propyl group, isopropyl group, etc. are preferable. These alkyl groups may be substituted, and preferred substituents include a sulfo group, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, and an alkylsulfonylamino group.

The alkyl group represented by 1 (3) is preferably an alkyl group substituted with a sulfo group or a carboxyl group.The sulfo group or carboxyl group is preferably an organic cation such as a pyridinium ion or a triethylammonium ion, or an ammonium ion, or a sodium ion. A salt may be formed with an unresolved cation such as ion or potassium ion.

The alkyl group represented by R4 has 1 to 1 carbon atoms.
6 straight chain or branched alkyl groups are preferred, for example,
Examples include methyl group, ethyl group, propyl group, isopropyl group, and butyl group.

These alkyl groups may be substituted, and preferred substituents include a sulfo group, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an alkylsulfonylamino group, and an aryl group.

The alkyl group represented by R4 is preferably an alkyl group substituted with a sulfo group or a carboxyl group. Sulfo groups, carboxyl groups, etc. may form salts with organic cations such as pyridinium ions and 1-ethylammonium ions, or free cations such as ammonium ions, sodium ions, and potassium ions.

The alkenyl group represented by R3 and R+ includes an allyl group.

Examples of the aryl group represented by R3 and R4 include an engineering group and a p-tolyl group.

Typical specific examples of the compound represented by the general formula [B5-1r] are listed below, but are limited to [B5-11
-1] [B5-ll-2] [B5-11-31 [rlS-If-4] [l3S-11-5] rBs-It-6] [B5-ff-7] [B5-1-8] [B5-n-91 [13S-11-101 [B5-1-121 [BS-u-13] [B S -U -14] S O2+-1 [13S -n -15] [BS -It - 101 [B5-n-17] [r3 S-11-18] The above compounds are generally known, for example, as described in "The Cyanine Dice and Related Combines" by He 7- (Interliance Publishers). It can be easily synthesized by the method described in J.D., New York, 1969).

The blue-sensitive sensitizing dye used in the present invention is preferably 5 x 10-5 mol/2 x 1 mol of silver halide.
0-3 mol, more preferably I x 10-4 mol ~
Used at 7 x 10-4 moles of ffuE.

These sensitizing dyes may be added at any time from silver halide grain formation to coating, but it is particularly preferable to add them from the end of silver halide grain formation to coating. preferable.

These sensitizing dyes may be dispersed in a water-miscible organic solvent without being dissolved, and the dispersion may be added to a silver halide emulsion, or they may be mixed with water or water such as methanol, ethanol, acetone, dimethylformamide, etc. They may be dissolved in a miscible organic solvent alone or in a mixture and added to the silver halide emulsion.

Further, the blue-sensitive sensitizing dye according to the present invention can be used in combination with other sensitizing dyes within a range that does not impair the effects of the present invention. In this case, the two sensitizing dyes may be dissolved separately and mixed before being added, or may be added as separate solutions.

The two solutions may be added at the same time or at a predetermined time interval.

Examples of green-sensitive sensitizing dyes include the following.

General formula [GS-I] Z5 represents an atomic group necessary to complete an oxazole nucleus, benzoxazole nucleus or naphthoxazole nucleus, and these nuclei may have a substituent on a carbon atom. Specific examples of substituents include halogen atom, carbon number 1-
6 alkyl group, alkoxy group having 1 to 4 carbon atoms, human 1
]-1-C group, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylcarbonyloxy group having 2 to 5 carbon atoms, a phenyl group, a hydroxyphenyl group, and the like.

R5 represents an alkyl group. This alkyl group includes those having a substituent, and examples of the substituent include a hydroxy group,
Sulfonate group, carboxyl group, halogen atom, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 5 carbon atoms, alkylsulfonyl group having 1 to 4 carbon atoms, sulfa7yl group, carbamoyl group (having 1 to 4 carbon atoms) 4), phenyl group, vinyl group, etc.

Specific examples of the alkyl group include methyl group, edyl group, propyl group, butyl group, and the like.

R6 is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, a fluorine group, an alkoxyalkyl group,
(CH2-+-A or (CH2-+-O+CH2+-
Represents A. Here, △ is a nitrile group, an alkylsulfonyl group, a sulfonamide group, an alkylsulfonylamino M1
or represents a lower alkoxy group having 1 to 8 carbon atoms, where n is 1
Represents an integer value of ~4.

Each of the above groups represented by R6 also includes those with substituents. For example, those in which the alkyl moiety of the above group is substituted with a halogen atom can also be preferably used.

The alkylsulfonyl group represented by A is preferably an alkylsulfonyl group having 1 to 4 carbon atoms, the sulfonamide group is preferably a sulfonamide group having 1 to 4 carbon atoms, and the alkylsulfonylamino group is Preferably it is an alkylsulfonylamino group having 1 to 4 carbon atoms, and the lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.

R7 and R8 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably one with 1 to 4 carbon atoms),
It represents an alkoxy group (preferably one having 1 to 4 carbon atoms), an alkylsulfonyl group, a sulfo group, a chlorine atom, a fluorine atom, or a carboxyl group.

Particularly preferred among the IC compounds represented by the above general formula [GS-I], R5 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. In the case,
Specifically, sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, hydroxyethyl group, 3-sulfo-2
-Hydroxypropyl U and the like.

Next, typical specific examples of the compound represented by the above general formula [GS-I] will be given, but they are limited to [GS-1-1
] [GS-1-2] [GS-1-3] ? H [GS-1-41 [GS-f-5] [GS-1-6] [G5-1-9] OH [G
S-1-101 [G5-1-12] [G5-1-131 [G5-1-141 [GS-1-15] [G5-1-17] oo.

Ward IG S -1-18J [GS-I-191 [G5-1-201 [G5-1-211 [GS-1-221 (CI!2) ff5O, N & [G5-1-23] [GS -1-24] [G5-1-251 [G S-1-26] [G S-1-27] [G5-l-281 [G S-1-29] [G S-1-30] [ G5-1-March [GS-1-:121 [GS-I-331 The compound represented by the above general formula [GS-■1] used in the present invention is □, Japanese Patent Publication No. 46-549, Same 4G-
No. 18105, No. 4G-1810G, No. 46-181
No. 08, No. 47-4085, No. 58-52574,
U.S. Patent No. 2.839.403, U.S. Patent No. 3.384.486
No. 3,625,698 @, 3.480.439
It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 3.567, No. 458, etc.

General formula tGs-1t] In the formula, R9 and Rho each represent an alkyl group that may have a substituent, and at least one of R9 and Rho is a sulboalkyl group or a carboxyalkyl group. Z6 represents an alkyl group or an aralkyl group. U,
V, ~VJ3 and Y each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl or a hydroxyl group. X (-) represents an acid anion. m represents 1 or 2, and m is 1 when an inner salt is formed.

R. Examples of substituents for the alkyl group represented by 9 and Rho include hydroxyl group, sulfo group, sulfonate group, sulfonato group, carboxyl tla3 and its salt, carboxylado group, halogen atom, alkoxy having 1 to 4 carbon atoms. group, alkoxycarbonyl group having 2 to 5 carbon atoms, alkylsulfonyl group having 1 to 4 carbon atoms, sulfamoyl group, carbamoyl group (including substituted carbamoyl group substituted with an alkyl group having 1 to 4 carbon atoms) , phenyl group, vinyl group,
etc. can be mentioned.

Specific examples of alkyl groups include methyl, ethyl, propyl, and butyl groups.

U. V. Examples of the halogen atom represented by W and Y include fluorine atom, chlorine atom, and bromine atom; examples of alkyl groups include methyl group, ethyl group, propyl group, and butyl group; and examples of alkoxy groups include Examples include methoxy group, (1) toxy group, propoxy group, 11-oxy group, etc. Examples of alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, etc. Each of these groups is a halogen atom, a sulfo group, a hydroxyl group, etc. It may be substituted with a group, a carboxyl group, etc.

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

Examples of acid anions represented by Xe include chloride, bromide, iodide, thiocyanate, sulfone-1, methylsulfonate, ethylsulfonate, verchlorate,
Examples include pt-luenesulfonate.

General formula [G5-111] represented by general formula [G5-11] used in the present invention In the formula, Rs, Rlo and R++ each do not represent an alkyl group. U, V, and Y each represent a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group, a carboxyl group,
Represents an alkoxy group, an alkoxycarbonyl group, a human Oxyl group, an acyloxy group, a hydroxyalkyl group, a hydroxyalkoxy group, or a phenyl group. Xel(tM
Represents an anion.

m represents 1 or 2, and when an inner salt is formed, I
is 1.

The alkyl groups represented by R9, RIO and R++ include those having substituents, and a specific example is R9 of the general formula [GS-■]
Alternatively, the same examples as the alkyl group represented by R+o can be mentioned.

Examples of the alkoxy group represented by U, V, W and Y include methoxy group, ethoxy group, butoxy group, and butoxy group, and examples of the alkoxycarbonyl group include methoxycarbonyl group and 11-oxycarbonyl group. , Examples of the acyloxy group include acedeloxy group,
Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Examples of the hydroxyalkoxy group include a hydroxymethoxy group, a hydroxyalkyl group, and a hydroxypropoxy group. group, hydroxybutoxy group, etc.

The acid anion represented by Xe is X of the general formula [GS-II]
The same thing as in e can be mentioned.

General formula [GS-IV] represented by general formula [O8-111] used in the present invention In the formula, R3, Rho, R+1 and RI2 each represent an alkyl group which may have a substituent, tJ, V.

W and Y each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, or an acyloxy group, including those having a substituent. y is 1 or 2
and l is 1 when forming an inner salt.

The alkyl group represented by R9 to R+2 has the general formula [GS
The halogen atom, alkyl group, alkoxy group and alkoxycarbonyl group represented by J, V, W or Y are of the general formula [GS-IF] The acyloxy group has the same meaning as in the mouth to Y, and the acyloxy group is represented by the general formula [G5-111
] has the same meaning as in Y.

The acid anion represented by Xe is X of the general formula [GS-II]
It is synonymous with adding 1 to e.

Specific examples of the compound represented by the general formula [GS-IV] used in the present invention are shown below.

The sensitizing dyes represented by the general formulas [GS-If] to [GSIV] of the present invention are known and can be easily synthesized by known methods, such as F, M
, by Homes” 7' he (:, yanin
e D yes and Re1ated Comp
ounds”[intersciencePublish
ers, New York (19G4).

The above general formula [GS-■] to [
The dye represented by G S -IV ] is prepared by adding molecules 1. can do.

The above general formulas [GS-I] to [GS
-rV] is used to spectral sensitize the silver halide emulsion, for example, 10-rV per mole of silver halide.
5-2X10-2 mol, preferably 10→-2X10-2
It is 3 moles.

Examples of red-sensitive sensitizing dyes include the following.

General formula [R8-I] (Xe)1-1 General formula [R3-If] (Xe)1-. In the formula, RI3 represents a hydrogen atom or an alkyl group, and RI
4 to R+7 each represent an alkyl group or an aryl group, Ze, Z7, Zs t3 -UZ+a represents an atomic group necessary to form a benzene ring or naphthalene ring condensed to a hasolesolethiazole ring or selenazole ring, and Z8 represents Hydrocarbon atoms n necessary to form a 6-membered ring
represents Y, Z represents a sulfur atom or a lerene atom, and X
e represents an anion. ri represents 1 or 2, and when forming an inner salt! is 1.

[R8-1ff] In the formula, R+8 and R+s each represent an alkyl group, an aryl group, or an allyl group, and at least one of R+a and RI9 represents an alkyl group containing a sulfo group or an alkyl group containing a carboxyl group. R20 and R2+ each represent an alkyl group. Zt+ represents a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic nucleus.

In the general formulas [R8-4] and [R8-II], R
13 is preferably a hydrogen atom, a methyl group, or an ethyl group, particularly preferably a hydrogen atom or an ethyl group.

Further, R1→, R+s, R16 and RI7 are each preferably a straight chain or branched alkyl group having 1 to 6 carbon atoms, and this alkyl group may have a substituent.

Examples of the ra substituent include an alkoxy group, an aryl group, a halogen atom, a hydroxyl group, and a carboxyl sulfo group. Further, the aryl group (for example, a phenyl group) represented by 17 in R H'~1 may have a substituent such as a carboxyl group or a sulfo group. Zs, Z7
, Z9 and ,7+o may have a substituent, and preferable substituents are a halogen atom, an aryl group, an alkyl group, or an alkoxy group, and further a halogen atom (e.g. (chlorine atom), phenyl group, and methoxy group are preferred.

The anion represented by Xe is, for example, C. f. , Br
.

C2 Hs 804 etc.

In the general formula [RS-1[[], the alkyl groups represented by R+a and R+s have 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. The alkyl group includes those having substituents, and this device 13! Examples of the group include a sulfo group, a hydroxy group, an ace]hexy group, an alkonitocy group, a sulfoaryl group, an alkoxyaryl group,
These include a halogen-substituted aryl group, an aryloxy group, an alkyl- or alkoxy-substituted aryloxy group, and the like. R
The aryl group represented by 5 and R6 preferably has 4 to 15 carbon atoms, such as phenyl group and pyridyl group. The aryl group includes those having a substituent, and the same substituents as those of the substituted alkyl group are used.

At least one of R+a and R+s represents an alkyl group containing a sulfo group or an alkyl group containing a carboxyl group.

The alkyl group represented by R20 and R2+ has 1 to 1 carbon atoms.
5 is preferable, such as methyl group, ethyl group, propyl group, etc.

Zt+ represents a nonmetal atom if necessary to form a 5- or 6-membered nitrogen heterocyclic nucleus with a nitrogen atom, and examples of the heterocyclic nucleus include a thiazole nucleus, a selenazole nucleus,
Examples include oxazole nucleus, quinoline nucleus, 3,3-dialkylindolenine nucleus, imidazole nucleus, and lysine nucleus. Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably benzodeazole nucleus, Nara 1 to thiazole nucleus, naphthooxy)
Long sol cores are advantageously used.

General formula [RS-I], [RS-II] used in the present invention
The Sarel sensitizing dyes represented by ]a and [Rs-1]r are known, for example, as described in The Chemistry of Heterophysics by F.M. Palmer (
T be C hemistry of H ete
rocyclic compounds)
Volume 1 8, 1F ・The Qyan is and related combinations
ine Dyes and RelatedComp
ounds) (A. Weissberger o
d.

Published by Interscience, New York
It can be easily synthesized by the method described in (1964).

Typical specific examples of the sensitizing dyes used in the present invention are shown below, but the compounds that can be used in the present invention are not limited to these.

RS-I Rs-2 Rs-3 Rs-4 RS-5 RS-6 rO RS-7 RS-8 Rs-9 R3-10 R3-II S-20 RS-21 S-23 R3-24 RS-25 RS -35 s-39 R5-40 RS -41 fn of the sensitizing dyes of the general formulas [R3-II, [I<S-II] and [R8-I[1] is not particularly limited, but halogenated It is preferable to use 2X10-6 mol to I X 10-3 mol per mole of silver, more preferably 5X
Preferably, from 10@-6 moles to 5.times.10@-" moles are used.

The above-mentioned sensitizing dye can be added to the emulsion in the same manner as the blue-sensitive sensitizing dye and the green-sensitive sensitizing dye described above.

Moreover, general formula [R8-II, [RS-II] J3
The sensitizing dyes represented by [R8-I[1] and [R8-I[1] can also be used in combination with other sensitizing dyes as various supersensitizing combinations μ. In this case, the respective sensitizing dyes may be dissolved in the same or different solvents, and these solutions may be mixed or added separately prior to addition to the emulsion. When adding them separately, the order and time interval can be arbitrarily determined depending on the purpose.

Furthermore, the general formula [R8-■], [R
At least one of each of the sensitizing dyes shown in Table 4 in [3-II] J5 and [R8-111] can be used in combination.

430 nm of silver halide photographic light-sensitive materials as in the present invention.
Sensitivity (SB), Sensitivity (SG) of 540nm, 700n
The relative sensitivity when the sensitivity (SR) of m is determined using a colored glass filter is within the range of the present invention, that is, 0<SB/SG≦
0.8 In order to satisfy 0<SR/SG≦0.7, any of the blue-sensitive sensitizing dyes, green-sensitive sensitizing dyes, and red-sensitive sensitizing dyes selected from the group of sensitizing dyes described above must be used. For example, a method using a combination of B5-1-17 as a blue-sensitive sensitizing dye, G5-1-34 as a green-sensitive sensitizing dye, and R8-2 as a red-sensitive sensitizing dye is effective.
It is determined by experimentally determining the change in relative sensitivity by adding various amounts of 0 to the emulsion. These can be easily determined by those skilled in the art. Temporarily, SB/SG.

If one of SR/SG is within the range of the present invention and the other is outside the range, adjust the sensitivity by increasing or decreasing the sensitizing dye, or if the adjustment is not effective with the amount of sensitizing dye, remove it. If the tonality changes or the fog is high (F1'J), it is also possible to selectively increase or decrease the sensitivity of a desired part of the color sensitive area by selecting the filter dye described later and adding an appropriate amount. . Furthermore, since photographic sensitivity can generally be adjusted by changing the size of silver halide grains, it is also possible to adjust the sensitivity by arbitrarily changing the grain size. In particular, when using a sensitizing dye with high color sensitization efficiency, the gradation often changes depending on m, so it may be effective to adjust the particle size of the filter dye or silver halide grain. There are many. In any case, SB, SG,
Those skilled in the art can easily adjust the sensitivity of each SR color area.

The filter dye used in the present invention is not particularly limited, but cyan dyes, azo dyes, etc. can be used.
Preferably it is a water-soluble dye.

The layer to which the filter dye is added may be either an emulsion layer or a non-emulsion layer. The period of addition is determined as appropriate, but for example, when selecting a filter dye that has a main peak in the blue or red sensitive area, the relative sensitivity of each color sensitive area should be within the range of the present invention. Just adjust the amount of addition. Further, a filter dye having a main peak in the range of 590 nm to 610 tv is useful for improving safelight properties, and is preferably added in the present invention.

Specific examples of preferred dyes are shown below.
1L-L 502K S tJ3 to 5
LJ :+ +VIa N H25O3K
Examples of the support used in the photographic material of the present invention for SO3 include paper,
Supports such as glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, polypropylene, etc., or a laminate of two or more substrates such as a laminate of paper and polyolefin (e.g. polyethylene, polypropylene, etc.), etc. However, from the viewpoint of cost etc., a laminate of paper and polyolefin is preferable.

A hardening agent can be used in the photographic material of the present invention,
For example, vinyl sulfone, cyanuric chloride,
Organic hardeners such as acryloyl-based and ethyleneimine-based hardeners or non-stainless hardeners such as chromium alum and potassium alum can be used alone or in combination of two or more.

Furthermore, various surfactants can be used in the photographic material of the present invention.

For example, nonionic surfactants such as saponin and polyalkylene glycol ether, and anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, and sulbosuccinates can be used.

Various other photographic additives may be used in the photographic material of the present invention, if necessary.

For example, stabilizers, coating aids, film property improvers, ultraviolet i absorbers, optical brighteners, antioxidants, stain inhibitors, metal ion sequestrants, thickeners, matting agents, developing agents, and the like can be used.

As the developing agent used in developing the silver halide photographic light-sensitive material of the present invention, various arbitrary ones can be mentioned depending on the specifically produced light-sensitive material.

For example, HO-(cH-CH)n-OH type (hydroquinone, etc.), HO-(CH-CH)n-NH2 type (ortho and rose amine phenols or aminopyrazolones, etc.), and 82N-(CH- CH) n-NH2 type (4
-amino-2-methyl N, N-diethylaniline, etc.).

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
eory or the Photoaraphic
Process, Fourth Edition) No. 2!, pages 31-334 and Journal of the American Chemical Society (Journal or
tt+c American Chemical 5oc
73, p. 3, 100 (1951) can be effectively used in 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.

Furthermore, even if a sulfite salt such as IaM soda or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired. Furthermore, hydroxyamine and hydrazide compounds may be used as preservatives. In addition, adjusting PL-1 and providing a buffer function with caustic alkali, alkali carbonate, or amines used in general black-and-white developers, inorganic development inhibitors such as bromokali, organic development inhibitors such as benzotriazole, and nibrendiamine. Metal ion scavengers such as tetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, sodium alkylarylsulfonate, natural ribonin,
Surfactants such as saccharides or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxazole, l1ii! l! It is optional to add an ionic strength adjusting agent such as 2s-1-lium.

The developer used in the present invention may contain alkanolamines or glycols as a paid solvent.

The I)H value of the developer having the above composition is preferably 9 to 13, but from the viewpoint of storage stability and photographic properties, the I)H value is 10 to 1.
A range of 2 is preferred.

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 in the range of 30°C to 40°C, and the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, which often brings about good effects. .

Furthermore, it is optional to employ processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual image processing such as plate development or frame development, or mechanical development such as roller development or hanger development.

[Examples] The present invention will be described in detail below, but the present invention is not limited to these Examples.

Example-1 Emulsions A to C below were prepared.

[Emulsion A] Solution ■ Gelatin 20 g Water
400 solution H
AgN0a 60g water
250 ammonia water (28%) 40112 solution II [KBr
42 (1 water)
300 dai solution IV O,5
% K2 [1r (IV) Cff1e ]0.75
d Water 36.75
0.251Q from the mixture of solution IV into 112 solution ■
(The iridium salt addition m is 2 per mole of silver halide.
．． 9×10 −7 mol) was taken and added.

Next, the solution solution was heated to 35°C, and while stirring vigorously, solutions ① and ② were added simultaneously for 1 minute, and after aging at that temperature for another 5 minutes, vinegar M (20% ), the pi-1 was lowered to 5.8 and the liquid temperature was raised to 40°C.

In the desalination process, Demol N (manufactured by Kao (1)) and fil
Desalting was performed using magnesium, and additional gelatin was added to redisperse.

The resulting emulsion was a cubic monodisperse emulsion with a grain size of 0.3 μm.

[Emulsion B] Emulsion B was prepared in the same manner as Emulsion Δ except that the ripening temperature was 40°C.

The resulting emulsion was a cubic monodisperse emulsion with a grain size of 0.42 μm.

[Emulsion C] Emulsion C was prepared in the same manner as Emulsion A except that the ripening temperature was 35° C. and the ripening time was 20 minutes.

The resulting emulsion was a cubic polydisperse emulsion with a grain size of 0.45 μm.

Sodium thiosulfate was added to these emulsions for optimal chemical sensitization, and then lower °2 inhibitor 5B-1 was added to stop the chemical sensitization. Then, the following sensitizing dye A and sensitizing dye B
5B-1 Sensitizing dye Δ An emulsion layer and a protective layer were simultaneously coated according to the following formulation on a paper support laminated on both sides with polyethylene (<11 mm, 200 μm) as shown in Table 1, and a sample was prepared. was created.

(Emulsion layer) Binder: Gelatin 2.817/l' Coated silver m: 1.4 (1/l'
Optical brightener: 50mg/ly Coating aid: 1-lium dodecylbenzenesulfonate 10mΩ/1
2 (Protective layer) Binder: Gelatin 1.5Q/*' Coating aid Sodium nidodecylbenzenesulfonate 50mg/It Hardener: These samples were stored for 4 days at 40°C and 80% RH, and the following Evaluation was made using the method shown below.

(1) Evaluation of color reproducibility The Macbeth color chart is printed using a large color negative, and the degree of reproduction of each color (shade as a silver image) is visually evaluated.

O: Each color on the chart has been sufficiently reproduced.

△...Not all colors are reproduced (), but within the acceptable range.

×...The colors on the chart cannot be reproduced at all.

Here, the developer used for print production was D-72 (manufactured by Kodak), developed at 20°C for 90 seconds, and stopped with glacial acetic acid 1.5
% solution, 20℃ 15 seconds, fixing is F-5 (manufactured by Kodak)
It was fixed at 20° C. for 5 minutes, washed with water, and dried. This method was used to process the phenomena in the following evaluations as well.

(2) Evaluation of image quality Images were photographed using a Konica Color GX-400 (Konica (-!FJ)), printed on coated samples through the color negative obtained through color negative processing, and evaluated for sharpness and graininess. .

O: There is no problem in practical use.

△...No practical problem, but slightly inferior.

×...It is a practical problem.

(3) Safelight safety A Konica Safelight Glass No. 9B (Konica) was placed on a 100V-40W incandescent light bulb. , Development processing was performed in the same manner as in (1), and the presence or absence of fogging was evaluated.

○...Fog occurs and is sweet.

X: Fog occurs.

(4) Evaluation of sensitivity Sensitivity at 430 nm (S B ), sensitivity at 540 nm (
SG) and sensitivity (SR) at 700 nm are then determined using colored glass filters under poly conditions.

[Sensitivity 88.8G for each color separation exposure, how to find SR] Sensitivity SB is 2854K, using a 400 lux tungsten light sensitometer, inserting a colored glass filter KL-43 manufactured by Toshiba Glass Co., Ltd. on the optical axis, The sample is exposed through a continuous wedge for 1 second. Next, development was performed at 20°C for 90 seconds using a developer prepared by diluting D-72 developer (Kodak 'It) with water at a ratio of 1:2, and after stopping, development was performed at 20°C using F-5 fixer (manufactured by Kodak). Perform fixing for 5 minutes, wash with water, and dry.

Photographic sensitivity is 0.6 optical 11 from the minimum density (Dmin)
Exposure ffl+-1 (lux x
It is calculated from the following formula using

Sensitivity -1000/l-1 Sensitivity SG and SR are obtained by inserting KL-54 and KL-70 filters in place of the colored glass filter Km-43 and using the same method as above. do.

Relative sensitivity ratios SS/SG and SR/SG were determined for each coated sample from the sensitivity JUSB, SG, and SR determined above.

As is clear from Table 1, relative sensitivity SS/SG, SR
It can be seen that when /SG is in the gloss of the present invention, color reproducibility, sharpness, graininess and safelight properties are all excellent. On the other hand, if either 813/SG or SR/SG is outside the scope of the present invention, one of the above performances is unsatisfactory.

Also, since emulsion B has larger grains than emulsion A, SB/
Even if SG and SR/SG are within the range of the present invention, the graininess is slightly inferior compared to Emulsion A, and since Emulsion C is a polydisperse emulsion, the graininess is also slightly inferior. From the above, it was found that Emulsion A was particularly excellent overall.

Example 2 Ripening was carried out under the same conditions as Emulsion A in Example 1 except that the ripening temperature was changed to 37 DEG C. to obtain a 0.35 .mu.m cubic monodisperse emulsion.

After adding sodium thiosulfate to this emulsion and optimally chemically sensitizing it, the above-mentioned inhibitor 5s-i was added to stop the chemical sensitization. Next, the following sensitizing dye C and sensitizing dye
Color sensitization was performed by adding the tm shown in the table.

Sensitizing dye C Sensitizing dye D The obtained emulsion was coated on a paper support laminated on both sides with polyethylene in the same manner as in Example-1.

At that time, the following filter dyes were added to the emulsion layer as shown in Table 2 Filter dye A Filter dye +3 Filter dye C The obtained coating sample was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2. show.

As is clear from Table 2, by adjusting the amount of sensitizing dye and adding filter dye, the relative sensitivity SS/SG, SR
The sample of the present invention, in which /SG was adjusted to fall within the range of the present invention, reproduces Example 1 and has improved color reproducibility, sharpness, graininess, and safelight property. In particular, the addition of a dye such as filter dye B improved safelight properties and was useful.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material comprising at least one layer of silver halide photographic emulsion coated on a support, wherein the sensitivity at 430 nm (SB) of the silver halide photographic light-sensitive material is 540.
When the sensitivity at nm (SG) and the sensitivity at 700 nm (SR) are determined using colored glass filters under the conditions shown below, the relative sensitivity is 0<SB/SG≦0.8 and 0<SR/SG≦0.7. A silver halide photographic material characterized in that the sensitivity of each color-sensitive part is adjusted so that the following is achieved. [However, using a tungsten light sensitometer with a sensitivity SB of 2854K and 400 lux, a colored glass filter KL-43 manufactured by Toshiba Glass Co., Ltd. was inserted on the optical axis, the sample was exposed to light for 1 second through a continuous wedge, and then, Developed at 20°C for 90 seconds using D-72 developer (manufactured by Kodak) diluted 1:2 with water, and then fixed for 5 minutes at 20°C with F-5 fixer (manufactured by Kodak). Process, wash with water, and dry. The photographic sensitivity is determined from the following formula using the exposure amount H (lux x seconds) that provides an optical density 0.6 optical density higher than the minimum density (Dmin). Sensitivity = 1000/H Sensitivity SG and sensitivity SR are colored glass filter KL-4
In place of 3, KL-54 and KL-70 filters are inserted, respectively, and the sensitivity is determined in the same manner as above. ]