EP1260858A2

EP1260858A2 - Image formation process

Info

Publication number: EP1260858A2
Application number: EP02011470A
Authority: EP
Inventors: Shoji Yasuda; Kazuki Yamazaki; Mitsunori Hirano
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Corp
Priority date: 2001-05-25
Filing date: 2002-05-24
Publication date: 2002-11-27
Also published as: JP2002351002A; EP1260858A3

Abstract

An image formation process is provided which includes developing a silver halide photographic light-sensitive material using a developing solution having a pH of 9.0 or above but less than 11.0. The silver halide photographic light-sensitive material has at least one silver halide emulsion layer on a support, and another hydrophilic colloid layer. At least one type of hydrazine derivative and at least one type of compound represented by formula (1) are contained in at least one layer of the emulsion layer and the hydrophilic colloid layer,

wherein M represents hydrogen, an alkali metal, or a protecting group that can be cleaved by an alkali, and R₁₁, R₁₂, and R₁₃ may be identical to or different from each other and independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, a nitro group, a substituted or unsubstituted alkoxy group, or a cyano group.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a silver halide photographic light-sensitive material and a process for forming an ultra high contrast negative image using same. It relates in particular to an image formation process using an ultra high contrast negative photographic light-sensitive material suitable for a silver halide light-sensitive material for photomechanical plate-making.

2. Description of the Related Art

As one method for exposing a photographic light-sensitive material to light in an image formation process there is a known method, the so-called scanner system, in which an original image is scanned and a silver halide photographic light-sensitive material is exposed to light according to the image signal so obtained to give a negative image or a positive image of the original image. There are various types of recorder utilizing an image formation process involving the scanner system, and the so-called dot generator system employing a dot generator is widely used at present. These recorders involving the scanner system use, as a light source for recording, a conventional glow lamp, xenon lamp, mercury lamp, tungsten lamp, light-emitting diode, etc. However, all of these light sources have practical defects such as low output and short lifetime. In order to compensate for these defects, there are scanners that use as a light source for the scanner system a coherent laser light source such as a He-Ne laser, an argon laser, a He-Cd laser, or a semiconductor laser. Light-sensitive materials that can be used with these scanners are required to have various characteristics and, in particular, it is essential for them to have high sensitivity and high contrast under conditions such as those where exposure is carried out using a short exposure time such as 10^-3 to 10^-8 sec. Moreover, since output of the laser tube is reduced in order to ensure a long lifetime, a light-sensitive material having a higher sensitivity is more advantageous. Furthermore, in order to obtain good dots, it is necessary to shape the laser beam using a slit, etc. and in order to compensate for a concomitant reduction in the laser output it is also necessary to use a light-sensitive material having high sensitivity.
In recent years, a nucleation system that contains a hydrazine derivative and can give ultra high contrast photographic characteristics has dominated this field in terms of high sensitivity and high contrast. In order to increase the sensitivity of a light-sensitive material, it is necessary to increase the sensitivity of the silver halide used, and the activities of a sensitizing dye and the hydrazine compound used, but this often causes degradation in the storage stability.
Moreover, in the printing industry there is a strong desire for a reduction in the amount of process effluent in terms of influence on the environment, and there is a widespread need for a reduction in the amounts of developing solution and fixing solution that are replenished. In order to meet these needs in the printing industry, there is a desire for the development of a developing solution and a fixing solution whose compositions in processing solutions vary little when the replenishment amounts are reduced, and a light-sensitive material that can suitably be used with small amounts of replenisher.

BRIEF SUMMARY OF THE INVENTION

It is a first object of the present invention to provide an image formation process using a high sensitivity and high contrast silver halide photographic light-sensitive material.
A second object of the present invention is to provide a silver halide photographic light-sensitive material that gives stable photographic characteristics even when the amount of developing solution replenished is reduced and that also has excellent storage stability, and a processing system therefor.
The above-mentioned objects have been accomplished by the invention below.
(1) An image formation process comprising a processing step in which a silver halide photographic light-sensitive material is developed using a developing solution having a pH of 9.0 or above but less than 11.0, the silver halide photographic light-sensitive material comprising a support, at least one silver halide emulsion layer on the support, and another layer comprising a hydrophilic colloid, wherein at least one type of hydrazine derivative and at least one type of compound represented by formula (1) are contained in at least one layer of the emulsion layer and the hydrophilic colloid layer.
In the formula, M represents a hydrogen atom, an alkali metal atom, or a protecting group that can be cleaved by an alkali, and R₁₁, R₁₂, and R₁₃ may be identical to or different from each other and independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, a nitro group, a substituted or unsubstituted alkoxy group, or a cyano group.
(2) The image formation process according to (1) wherein the hydrazine derivative is a compound represented by formula (2) below.
In the formula, Ar represents an aromatic group, L₂₁ represents a divalent linking group having an electron-withdrawing group, and X represents an anionic group.
(3) The image formation process according to (1) wherein the hydrazine derivative is a compound represented by formula (3) below. Formula (3) A₃₁ ― NHNH ― CO ― R₃₁ In the formula, R₃₁ represents a difluoromethyl group or a monofluoromethyl group, and A₃₁ represents an aromatic group.
(4) The image formation process according to (1) wherein the hydrazine derivative is a compound represented by formula (4) below.
In the formula, R₄₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; R₄₂ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R₄₃ represents a hydrogen atom or a blocking group; L₄₁ represents an alkylene group or an alkenylene group, provided that at least two rings, which may be bonded to each other directly and/or through an aliphatic linking group, are contained in the R₄₁-S-L₄₂ part; J₄₁ and J₄₂ each represent a linking group; n is 0 or 1; X represents an aromatic or heterocyclic residue; and A₄₁ and A₄₂ are each a hydrogen atom, or one of them is a hydrogen atom and the other one is an acyl, sulfonyl or oxalyl group.
(5) The image formation process according to (1) wherein the hydrazine derivative is a compound represented by formula (5) below.
In the formula, R₅ represents an acyl group chosen from the group consisting of COR₅₁, SO₂R₅₂, SOR₅₃, POR₅₄R₅₅, and COCOR₅₆; R₅₁ and R₅₆ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl or heteroaryl group, OR₅₇ or NR₅₈R₅₉; R₅₂ and R₅₃ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl or heteroaryl group, OR₅₇ or NR₅₈R₅₉; R₅₄ and R₅₅ independently represent one of the substituents cited for R₅₂ or together form a ring; R₅₇ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl or heteroaryl group; R₅₈ and R₅₉ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl or heteroaryl group, or together form a ring; A₅ and A₅' independently represent a hydrogen atom, an SO₂R₅₀ group, or a group that can generate hydrogen under alkaline photographic processing conditions, provided that when A₅ is SO₂R₅₀, A₅' is hydrogen and vice versa, and R₅₀ represents one of the substituents cited for R₅₂; L₅ is a divalent linking group; Q is a cationic nitrogen-containing aromatic heterocyclic ring; Y^- is a negatively charged counter ion for neutralizing the positive charge of Q; n is 0 when the compound of formula (5) is an intramolecular salt, or n is an integer that is equal to the positive charge of Q; and Z represents atoms required to form a substituted or unsubstituted aromatic or heteroaromatic ring.
(6) The image formation process according to (1) wherein the hydrazine derivative is a compound represented by formula (6) below.
In the formula, R₆ is alkyl having from 6 to 18 carbon atoms or a heterocycle having 5 or 6 ring atoms, including ring atoms of sulfur or oxygen; R₆₁ is alkyl or alkoxy having from 1 to 12 carbon atoms; X is alkyl, thioalkyl or alkoxy having from 1 to about 5 carbon atoms; halogen; or -NHCOR₆₂, -NHSO₂R₆₂, -CONR₆₂R₆₃ or -SO₂R₆₂R₆₃ where R₆₂ and R₆₃, which can be the same or different, are hydrogen or alkyl having from 1 to about 4 carbon atoms; and n is 0, 1 or 2.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 shows absorption spectra of the emulsion layer side and the back layer side of a silver halide light-sensitive material in an example of the present invention.
In FIG. 1, the ordinate denotes absorbance (interval 0.1) and the abscissa denotes wavelength from 350 to 950 nm. The solid line denotes the absorption spectrum of the emulsion layer side and the broken line denotes the absorption spectrum of the back layer side.

DETAILED DESCRIPTION OF THE INVENTION

The benzotriazole compound represented by formula (1) is explained further in detail.
In the formula, M denotes a hydrogen atom, an alkali metal atom (e.g. a sodium atom, a potassium atom), or a protecting group that can be cleaved by an alkali (e.g., acetyl, propionyl, pivaloyl, stearoyl, benzyl, p-toluenesulfonyl, dodecylcarbamoyl, benzoyl, cyclohexylcarbamonyl). R₁₁, R₁₂, and R₁₃ may be identical to or different from each other and independently represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having up to 12 carbons, e.g., methyl, ethyl, propyl, hexyl, hydroxyethyl, chloropropyl, benzyl, cyanoethyl), a substituted or unsubstituted aryl group (preferably having 6 to 12 carbons, e.g., phenyl, naphthyl, p-tolyl, p-chlorophenyl), halogen atoms (e.g., chlorine, bromine), a nitro group, a substituted or unsubstituted alkoxy group (preferably having up to 12 carbons, e.g. methoxy, ethoxy, n-butoxy, dodecyloxy, hydroxyethoxy), or a cyano group.
Specific examples of the compound represented by formula (1) of the present invention are listed below, but they are not intended to limit the present invention.
Particularly preferable compounds are 5-methylbenzotriazoles.
(1) 5,6-Dimethylbenzotriazole
(2) 5-Butylbenzotriazole
(3) 5-Methylbenzotriazole
(4) 5-Chlorobenzotriazole
(5) 5-Bromobenzotriazole
(6) 5,6-Dichlorobenzotriazole
(7) 4,6-Dichlorobenzotriazole
(8) 5-Nitrobenzotriazole
(9) 4-Nitro-6-chlorobenzotriazole
(10) 4,5,6-Trichlorobenzotriazole
(11) 5-Carboxybenzotriazole
(12) 5-Sulfobenzotriazole, sodium salt
(13) 5-Methoxycarbonylbenzotriazole
(14) 5-Aminobenzotriazole
(15) 5-Butoxybenzotriazole
(16) 5-Ureidobenzotriazole
(17) Benzotriazole
The benzotriazole compound represented by formula (1) in the present invention may be added to any layer of a silver halide emulsion layer and another layer comprising a hydrophilic colloid on the silver halide emulsion layer side of the support, but it is preferably added to the silver halide emulsion layer or a hydrophilic colloid layer adjoining it.
It is also possible to use two or more types of benzotriazole compound represented by formula (1) in combination.
The amount thereof added is preferably 1 x 10^-4 to 1 x 10^-1 mol per mol of the silver halide, and particularly preferably 1 x 10^-3 to 7 x 10^-2 mol.
It should be noted that in the present invention a range such as this includes the lower figure as the minimum value and the higher figure as the maximum value.
The hydrazine derivative represented by formula (2) is explained further in detail.
In the formula, Ar represents an aromatic group, L₂₁ represents a divalent linking group having an electron-withdrawing group, and X represents an anionic group.
The hydrazine derivative represented by formula (2) is preferably a compound represented by formulae (2-a) and (2-b).
In the formulae, Ar represents an aromatic group and L₂₂ represents a fluorine-containing divalent alkylene or phenylene group. M represents a counter cation and m is an integer of 1 to 3.
The most salient feature of the compound of the present invention is the acyl moiety of the hydrazide; it has both an electron-withdrawing group and an anionic group as substituents, and as a result the high contrast nucleation properties of a nucleating agent can be enhanced, and the storage stability can also improved. These effects are not observed in a hydrazide derivative having as the acyl group a 2-carboxyethylcarbonyl group that has not been substituted with an electron-withdrawing group, which is disclosed in JP-A-63-32538 (JP-A denotes a Japanese unexamined patent application publication).
In the present invention, the anionic group includes a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group, and a salt thereof. The electron-withdrawing group is an electron-withdrawing substituent excluding these anionic groups, and it specifically means a substituent having a positive Hammett substituent constant (σm). The anionic group of the compound for use in this invention is preferably a carboxylic acid group, a sulfonic acid group, or a salt thereof, and more preferably a carboxylic acid group or a salt thereof. Examples of the preferable electron-withdrawing group in the present invention include a halogen atom, a cyano group, a nitro group, an oxycarbonyl group, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a quaternary ammonium group, a sulfonyl group, and an acyl group; a halogen atom is particularly preferred, and a fluorine atom is more preferred.
With regard to the compound represented by formula (2) of the present invention, Ar denotes an aromatic group and, more specifically, a substituted or unsubstituted phenyl group, naphthyl group or heterocyclic group. The group represented by Ar in formula (2) is preferably a substituted phenyl group, and examples of the substituent include the following groups.
The substituents in the present invention represent a halogen atom or a substituent bonded to the ring or main chain through a carbon, oxygen, nitrogen, or sulfur atom. Examples of the substituent bonded through a carbon atom include an alkyl group, alkenyl group, alkynyl group, aryl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, carboxyl group, cyano group, and heterocyclic group. Examples of the substituent bonded through an oxygen atom include a hydroxyl group, alkoxy group, aryloxy group, heterocyclyloxy group, acyloxy group, carbamoyloxy group, and sulfonyloxy group. Examples of the substituent bonded through a nitrogen atom include an acylamino group, amino group, alkylamino group, arylamino group, heterocyclylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, imido group, and heterocyclic group. Examples of the substituent bonded through a sulfur atom include an alkylthio group, arylthio group, heterocyclylthio group, sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfonyl group, sulfo group, and sulfinyl group. These groups each may be substituted with any of these substituents.
Preferable substituents in the present invention are explained in greater detail. Examples of the halogen atom include a fluorine atom, chlorine atom, and bromine atom. The alkyl group is a linear, branched, or cyclic alkyl group having from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include methyl, ethyl, isopropyl, t-butyl, benzyl, and cyclopentyl. The alkenyl group has from 2 to 16 carbon atoms, and examples thereof include vinyl, 1-propenyl, 1-hexenyl, and styryl. The alkynyl group has from 2 to 16 carbon atoms, and examples thereof include ethynyl, 1-butynyl, 1-dodecenyl, and phenylethynyl. The aryl group has from 6 to 24 carbon atoms, and examples thereof include phenyl, naphthyl, and p-methoxyphenyl.
The carbamoyl group has from 1 to 18 carbon atoms, and examples thereof include carbamoyl, N-ethylcarbamoyl, N-octylcarbamoyl, and N-phenylcarbamoyl. The alkoxycarbonyl group has from 2 to 18 carbon atoms, and examples thereof include methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has from 7 to 18 carbon atoms, and examples thereof include phenoxycarbonyl. The acyl group has from 1 to 18 carbon atoms, and examples thereof include acetyl and benzoyl. The heterocyclic group bonded through a carbon atom on the ring is a five- or six-membered, saturated or unsaturated heterocyclic group having from 1 to 5 carbon atoms and containing one or more heteroatoms of one or more elements selected from oxygen, nitrogen, and sulfur. Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyridyl, and 2-imidazolyl.
The alkoxy group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include methoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group has from 6 to 24 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy, and m-(3-hydroxypropionamido)phenoxy. The heterocyclyloxy group is one in which the heterocycle is a five- or six-membered, saturated or unsaturated heterocycle having from 1 to 5 carbon atoms and containing one or more heteroatoms of one or more elements selected from oxygen, nitrogen, and sulfur, and examples thereof include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy, and 2-pyridyloxy. The acyloxy group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include acetoxy, benzoyloxy, and 4-hydroxybutanoyloxy. The carbamoyloxy group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include N,N-dimethylcarbamoyloxy, N-hexylcarbamoyloxy, and N-phenylcarbamoyloxy. The sulfonyloxy group has from 1 to 16 carbon atoms, and examples thereof include methanesulfonyloxy and benzenesulfonyloxy.
The acylamino group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include acetamido and p-chlorobenzoylamido. The alkylamino group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include N,N-dimethylamino and N-(2-hydroxyethyl)amino. The arylamino group has from 6 to 24 carbon atoms, and examples thereof include anilino and N-methylanilino. The heterocyclylamino group is one in which the heterocycle is a five- or six-membered, saturated or unsaturated heterocycle having from 1 to 5 carbon atoms and containing one or more heteroatoms of one or more elements selected from oxygen, nitrogen, and sulfur, and examples thereof include 2-oxazolylamino, 2-tetrahydropyranylamino, and 4-pyridylamino. The ureido group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include ureido, methylureido, N,N-diethylureido, and 2-methanesulfonamidoethylureido.
The sulfamoylamino group has from 0 to 16, and preferably from 0 to 10, carbon atoms, and examples thereof include methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has from 2 to 16, and preferably from 2 to 10, carbon atoms, and examples thereof include methoxycarbonylamino. The aryloxycarbonylamino group has from 7 to 24 carbon atoms, and examples thereof include phenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino. The sulfonamido group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include methanesulfonamido and p-toluenesulfonamido. The imido group has from 4 to 16 carbon atoms, and examples thereof include N-succinimido and N-phthalimido. The heterocyclic group bonded through a nitrogen atom of the ring is a five- to six-membered heterocyclic group in which the ring includes a nitrogen atom and at least one element selected from carbon, oxygen, and sulfur, and examples thereof include pyrrolidino, morpholino, and imidazolino.
The alkylthio group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include methylthio and 2-phenoxyethylthio. The arylthio group has from 6 to 24 carbon atoms, and examples thereof include phenylthio and 2-carboxyphenylthio. The heterocyclylthio group is a five- or six-membered ring, saturated or unsaturated heterocyclylthio group having from 1 to 5 carbon atoms and the ring comprises one or more heteroatoms of one or more elements selected from oxygen, nitrogen, and sulfur, and examples thereof include 2-benzothiazolylthio and 2-pyridylthio.
The sulfamoyl group has from 0 to 16, and preferably from 0 to 10, carbon atoms, and examples thereof include sulfamoyl, methylsulfamoyl, and phenylsulfamoyl. The alkoxysulfonyl group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include methoxysulfonyl. The aryloxysulfonyl group has from 6 to 24, and preferably from 6 to 12, carbon atoms, and examples thereof include phenoxysulfonyl. The sulfonyl group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include methanesulfonyl and benzenesulfonyl. The sulfinyl group has from 1 to 16, and preferably from 1 to 10, carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.
Preferable substituents in the present invention are a halogen atom, alkyl group, aryl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, cyano group, alkoxy group, aryloxy group, carbamoyloxy group, acylamino group, ureido group, sulfamonylamino group, alkoxycarbonylamino group, sulfonamido group, sulfamoyl group, and sulfonyl group. More preferred are an alkyl group, aryl group, carbamoyl group, alkoxy group, acylamino group, ureido group, sulfonamido group, and sulfamoyl group. Particularly preferred are an acylamino group, ureido group, and sulfonamido group. The group represented by Ar in formula (2) may have as a substituent a group that accelerates adsorption onto silver halide grains. Preferable examples of the group that accelerates adsorption onto silver halide include a thioamido group, a mercapto group, and a five- or six-membered nitrogen-containing heterocyclic group. As the thioamido adsorption-accelerating group there is a divalent group represented by the formula below.
This group may be a part of a ring structure, or may preferably be an acyclic thioamido group. Useful adsorption-accelerating thioamido groups can be selected, for example, from the thioamido groups disclosed in U.S. Pat. Nos. 4,030,925, 4,031,127, 4,080,207, 4,245,037, 4,255,511, 4,266,013, and 4,276,364 and Research Disclosure, Vol. 151, No. 15162 (November 1976) and Vol. 176, No. 17626 (December 1978). Especially preferred thioamido groups are those represented by formula (A).
In the formula, one of E and E' represents -N(R₇₃)- and the other represents -O-, -S-, or -N(R₇₄)-; R₇₂ represents a hydrogen atom, an aliphatic group, or an aromatic group, or is bonded to E or E' to form a five- or six-membered heterocycle; and R₇₃ and R₇₄ represents a hydrogen atom, an aliphatic group, or an aromatic group.
Examples of the thioamide represented by formula (A) include thiourea, thiourethane, and dithiocarbamates. In the case where E or E' is bonded to R₇₂ to form a ring, examples of the structure represented by formula (A) include the acid nuclei of merocyanine dyes. Specific examples thereof include 4-thiazoline-2-thione, thiazolidine-2-thione, 4-oxazoline-2-thione, oxazolidine-2-thione, 2-pyrazoline-5-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, isorhodanine, 2-thio-2,4-oxazolidinedione, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, and benzthiazoline-2-thione. These may be further substituted.
The adsorption-accelerating mercapto group may be an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (in the case where the heterocycle contains a nitrogen atom adjacent to the SH-bonded carbon atom, this heterocycle has been described as a ring-forming thioamido group, which is a tautomer thereof). Examples of the aliphatic mercapto group include mercaptoalkyl groups (e.g., mercaptoethyl and mercaptopropyl), mercaptoalkenyl groups (e.g., mercaptopropenyl), and mercaptoalkynyl groups (e.g., mercaptobutynyl). Examples of the aromatic mercapto group include mercaptophenyl and mercaptonaphthyl. Examples of the heterocyclic mercapto group include 4-mercaptopyridyl, 5-mercaptoquinolinyl, and 6-mercaptobenzthiazolyl, in addition to the groups enumerated hereinabove with regard to the ring-forming thioamido group.
The five- or six-membered nitrogen-containing heterocyclic group which accelerates adsorption may be a five- or six-membered nitrogen-containing heterocycle comprising a combination of nitrogen and oxygen, sulfur and carbon. Preferable examples thereof include benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, and triazine. These may have one or more appropriate substituents. Preferred are benzotriazole, triazole, tetrazole, and indazole. Benzotriazole is particularly preferred.
Preferred specific examples of the nitrogen-containing heterocycle include benzotriazol-5-yl, 6-chlorobenzotriazol-5-yl, benzotriazole-5-carbonyl, 5-phenyl-1,3,4-triazol-2-yl, 4-(5-methyl-1,3,4-triazol-2-yl)benzoyl, 1 H-tetrazol-5-yl and 3-cyanoindazol-5-yl.
In the compound represented by formula (2), L₂₁ denotes a divalent linking group substituted with the electron-withdrawing group described above. Specific examples thereof include an alkylene group, an alkenylene group, an alkynylene group, an aralkylene group, an arylene group, and combinations thereof. L₂₁ is preferably an alkylene group or an arylene group, and particularly preferably an alkylene group or a phenylene group.
The compound represented by formula (2-a) or (2-b) of the present invention is now explained.
In formulae (2-a) and (2-b), Ar has the same meaning as in formula (2), and preferred examples thereof are also in the same range as for formula (2). L₂₂ represents a divalent alkylene or phenylene group partly or fully substituted with fluorine atoms. Specific examples of the group represented by L₂₂ include -CF₂CF₂-, -C₃F₆-, -CF₂CH₂-, -CFH-, -(CF₂)₄-, -(CF₂)₆-, -C₆F₄- (tetrafluorop henylene group), and -CF₂-. Especially preferred groups represented by L₂₂ are -CF₂CF₂- and -C₃F₆-.
In formula (2-b), M represents a counter cation and m represents an integer of 1 to 3. Examples of the cation represented by M include a lithium ion, a sodium ion, a potassium ion, a calcium ion, a magnesium ion, an aluminum ion, a zinc ion, a barium ion, a quaternary ammonium ion, a heterocycle containing a quaternized nitrogen atom, and a quaternary phosphonium ion. M is especially preferably a sodium ion or a potassium ion. In this case, m is 1.
The group represented by Ar in formulae (2-a) and (2-b) may contain a substituent group which accelerates adsorption onto silver halide grains.
The compound represented by formula (2) is preferably represented by the following formulae (3-a) or (3-b).
In the above formulae, L₂₂, M, and m each have the same meaning as in formulae (2-a) and (2-b). X₁ and X₂ each represent a group capable of bonding as a substituent to a benzene ring. m₁ and m₂ represent an integer of 0 to 4 and an integer of 0 to 5, respectively. When m₁ or m₂ is an integer of 2 or above, the groups represented by X₁ or X₂ may be identical to or different from each other and may be bonded to each other to form a ring. The substituent represented by X₁ has the same meaning as the substituent described hereinabove. Preferred examples of the substituent include an alkyl group, hydroxyl group, amino group, alkylamido group, arylamido group, alkylsulfonamido group, arylsulfonamido group, carboxyl group, sulfo group, salts of these groups, alkylthio group, mercapto group, acyloxy group, and heterocyclic group. Especially preferred among the compounds represented by formula (3-a) or (3-b) are those where m₁ is 0. X₂ has the same meaning as the substituent of Ar described hereinabove with regard to formula (2), and preferred examples thereof are also in the same range. The group represented by X₂ may contain a group which accelerates adsorption onto silver halide grains. m₂ is preferably 1 or 2, and more preferably 1.
Especially preferred among the compounds represented by formula (3-a) or (3-b) are those represented by the following formulae (4-a, b) to (7-a, b).
In formulae (4-a, b) to (7-a, b), X₃ and X₄ each represent a substituent, and have the same meanings as X₁ and X₂ in formulae (3-a) or (3-b). m₃ and m₄ each represent an integer of 0 to 4. J₁, J₂, J₃, and J₄ each represent a divalent linking group. Examples thereof include groups represented by -SO₂NR₇₆ -, -NR₇₆SO₂ -, -CONR₇₆ -, -NR₇₆CO-, -COO-, -O-CO-, -O-, -S-, -NR₇₆SO₂NR₇₇ -, and -NR₇₆CONR₇₇ -, wherein R₇₆ and R₇₇ each represent a hydrogen atom, an aliphatic group, or an aromatic group. p, q, r, and t each represent 1 or 2. When p, r, and t are each 2, m₄ represents an integer of 3 or smaller. s and u each represent 0 or 1.
In formula (4-a) or (4-b), R₇₅ represents a substituted or unsubstituted, branched or linear alkyl group having from 4 to 16 carbon atoms in total. When the alkyl group represented by R₇₅ has a substituent, examples of this substituent include the same groups as the aforementioned examples of the substituent of Ar in formula (2). Preferred examples of the substituent include an aryloxy group, alkoxy group (including those containing ethyleneoxy repeating units), carboxyl group, and alkoxycarbonyl group.
In formula (5-a) or (5-b), R₇₈ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R₇₉ represents a divalent aliphatic group. The total number of carbon atoms contained in R₇₈ and R₇₉ is preferably from 2 to 20. These groups may further have a substituent. Preferred examples of the substituent include an alkoxy group (including those containing ethyleneoxy repeating units), alkyl group, carboxyl group, alkoxycarbonyl group, carbamoyl group, ammonium group, amino group, hydroxyl group, and alkylthio group.
In formula (6-a) or (6-b), A represents a group which accelerates adsorption onto silver halide grains. Examples of A include the same groups as the aforementioned adsorption-accelerating substituent groups which Ar in general formula (1) may have. Preferred examples of A include an aromatic or heterocyclic group containing a mercapto group, a heterocyclic group having a mercaptoalkylene group, a thioureido group, a thiourethane group, a thioamido group, an alkyl or cycloalkyl group containing a disulfide bond, and a nitrogen-containing heterocyclic group containing two or more nitrogen atoms at least one of which is bonded to a hydrogen atom. Specific examples thereof include mercapto, mercaptophenyl, 2-mercapto-1-thia-3,4-diazolyl, 5-mercaptotetrazolyl, 2-mercapto-1,3,4-triazolyl, 2-mercaptobenzoxazolyl, 2-mercaptobenzothiazolyl, 2-mercaptopyridyl, 4-mercapto-1,3,3a,7-tetrazaindenyl, benzotriazolyl, thiatriazolyl, thioureido, N'-phenylthioureido, and phenylthiourethane.
In formula (7-a) or (7-b), B represents a cationic group and a counter anion therefor. Examples of the cationic group include a quaternary ammonium group, a nitrogen-containing heterocyclic group having a quaternized nitrogen atom, a quaternary phosphonium group, and a tertiary sulfonium group, and examples of the counter anion include a chlorine anion, bromine anion, iodine anion, and sulfo anion. The cationic group represented by B is preferably a quaternary ammonium group or a nitrogen-containing heterocyclic group having a quaternized nitrogen atom. Examples of these groups include a trialkylammonium group, pyridinium group, quinolinium group, isoquinolinium group, phenanthrenium group, triazolinium group, imidazolinium group, and benzothiazolinium group. These groups may be further substituted with a substituent. Preferred substituents include an alkyl group, aryl group, alkoxy group, alkylcarbamoyl group, amino group, ammonium group, and heterocyclic group. Especially preferred examples of the cationic group represented by B are a trialkylammonium group and a pyridinium group, and especially preferred examples of the counter ion are a chlorine anion and a bromine anion. R₈₀ represents a divalent aliphatic group, and may further have a substituent. R₈₀ is preferably an alkylene group, and especially preferably an unsubstituted, linear or branched alkylene group.
In formulae (4-a, b) to (7-a, b), M and m each have the same meaning as in formula (1).
Representative examples of the hydrazine derivative denoted by formula (2) for use in the present invention are given below, but the present invention should not be construed as being limited thereto.
The hydrazine derivative represented by formula (3) is explained further in detail.
In the formula, R₃₁ denotes a difluoromethyl group or a monofluoromethyl group, and A₃₁ denotes an aromatic group. Preferred compounds among those represented by formula (3) are represented by formula (31) below. X₃₁ ― (R₃₄)_m33 ― (L₃₂― R₃₃)_m32 ― L₃₁ ― A₃₂-NHNH ― CO ― R₃₂
In the formula, R₃₂ denotes a difluoromethyl group or a monofluoromethyl group, A₃₂ denotes a divalent aromatic group, and X₃₁ denotes a group that accelerates adsorption onto silver halide, but X₃₁ may denotes a hydrogen atom. R₃₃ and R₃₄ denote divalent aliphatic or aromatic groups, L₃₁ and L₃₂ denote divalent linking groups, and m₃₂ and m₃₃ independently denote 0 or 1. Preferred compounds among those represented by formula (31) are represented by formula (32) below.
In the formula, X₃₂, R₃₅, R₃₆, R₃₇, L₃₃, m₃₄, and m₃₅ denote the same groups as those represented by X₃₁, R₃₂, R₃₃, R₃₄, L₃₂, m₃₂, and m₃₃ respectively in formula (31), Y denotes a substituent, and n is an integer of 0 to 4.
Next, compounds represented by formula (3) are explained in detail.
In formula (3), the aromatic group represented by A₃₁ is a mono- or bi-cyclic aryl group or an aromatic heterocyclic group. Specific examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrrole ring, a furan ring, a thiophene ring, a thiazole ring, and an indole ring. A₃₁ preferably includes a benzene ring and is particularly preferably a benzene ring. A₃₁ may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, an acyloxy group, an acyl group, an oxycarbonyl group, a carbamoyl group, an N-sulfonylcarbamonyl group, a carboxyl group, a substituted amino group, an acylamino group, a sulfonamido group, a ureido group, a urethane group, a sulfonylureido group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfamoyl group, an acylsulfamoyl group, a carbamoylsulfamoyl group, a sulfo group, a cyano group, a halogen atom, a phosphinyloxy group, a phosphinylamino group, a sulfamoylamino group, and an oxyamoylamino group. These groups may further be substituted. Among these, a sulfonamido group, a ureido group, an acylamino group, a carbamoyl group, an alkoxy group, a substituted amino group, an alkyl group, a hydroxy group, a halogen atom, a carboxyl group, and an oxycarbonyl group are preferred, and a sulfonamido group and a ureido group are particularly preferred. A₃₁ may have a substituent, and at least one substituent of A₃₁ may be a group that accelerates adsorption onto silver halide.
With regard to a preferable group accelerating adsorption onto silver halide, a thioamido group, a mercapto group, a group having a disulfide group, and a five- or six-membered nitrogen-containing heterocyclic group can be cited. As the thioamido adsorption-accelerating group there is a divalent group represented by -CS-amino-, which may be a part of a ring structure, or an acyclic thioamido group. A useful thioamido adsorption-accelerating group can be chosen from those disclosed in US Pat. Nos. 4,030,925, 4,031,127, 4,080,207, 4,245,037, 4,255,511, 4,266,013, and 4,276,364, and Research Disclosure, Vol. 151, No. 15162 (Nov. 1976) and Vol. 176, No. 17626 (Dec. 1978).
Specific examples of the acyclic thioamido group include a thioureido group, a thiourethane group, and a dithiocarbamic acid ester group; and specific examples of the cyclic thioamido group include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazolin-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, and benzothiazoline-2-thione, and they may further be substituted. Examples of the mercapto group include an aliphatic mercapto group, an aromatic mercapto group, and a heterocyclic mercapto group (if a nitrogen atom is bonded to the carbon atom to which -SH is bonded, this is the same as the tautomeric cyclic thioamido group, and specific examples of this group are the same as those listed above.)
With regard to the five- or six-membered nitrogen-containing heterocyclic group, there can be cited a five- or six-membered nitrogen-containing heterocyclic group having a combination of nitrogen, oxygen, sulfur, and carbon. Preferred examples thereof include benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, and triazine. They may further be substituted with an appropriate substituent. Preferred examples of the adsorption-accelerating group include a cyclic thioamido group (that is, mercapto-substituted nitrogen-containing heterocycles such as 2-mercaptothiadiazole, 3-mercapto-1,2,4-triazole, 5-mercaptotetrazole, 2-mercapto-1,3,4-oxadiazole, and 2-mercaptobenzoxazole) and an imino silver-forming nitrogen-containing heterocyclic group (e.g., benzotriazole, benzimidazole, indazole, etc.) The adsorption-accelerating group includes a precursor thereof. The precursor referred to here means an adsorption-accelerating group having a precursor group that only releases an adsorption-accelerating group by the action of a developing solution during a development process and its decomposition is triggered by hydroxide ion or sulfite ion in the developing solution or a reaction with a developing agent. Specific examples thereof include carbamoyl, 1,3,3a,7-tetrazainden-4-yl, uracil, alkoxycarbonyl, 4-substituted-2,5-dihydroxyphenyl whose 4-position has been substituted with ureido, sulfonamido, or amido. Examples of a particularly preferable group that accelerates adsorption onto silver halide that is present in the substituent of A₃₁ in formula (3) include 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, and benzotriazole, and most preferably 3-mercapto-1,2,4-triazole and 5-mercaptotetrazole.
Among the compounds represented by formula (3), those represented by formula (31) are preferred, and are explained in detail below.
R₃₃ and R₃₄ in formula (31) denote divalent aliphatic or aromatic groups. The divalent aliphatic group includes a substituted or unsubstituted, straight, branched, or cyclic alkylene, alkenylene, or alkynylene group; and the divalent aromatic group includes a mono- or bi-cyclic arylene group. R₃₃ and R₃₄ are preferably alkylene or arylene groups, and most preferably R₃₃ is a phenylene group and R₃₄ is a phenylene group or an alkylene group. They may have a substituent such as those explained above for the substituent of A₃₁ in formula (3). Preferable examples of the substituents of R₃₃ and R₃₄ include a halogen atom, an alkyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a cyano group, an alkoxy group, an aryloxy group, a carbamoyloxy group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a sulfonamido group, a sulfamoyl group, and a sulfonyl group, and more preferably an alkyl group, an aryl group, a carbamoyl group, an alkoxy group, an acylamino group, a ureido group, a sulfonamido group, and a sulfamoyl group.
The divalent linking groups represented by L₃₁ and L₃₂ in formula (31) are -O-, -S-, -N-(RN)- (RN denotes a hydrogen atom, an alkyl group, or an aryl group), -CO-, -SO₂-, etc. either singly or in a group formed by combination thereof. The group formed by combination thereof referred to here is specifically -CON(RN)-, -SO₂N(RN)-, -COO-, -N(RN)CON(RN)-, -SO₂N(RN)CO-, -SO₂N(RN)CON(RN)-, -N(RN)COCON(RN)-, -N(RN)SO₂N(RN)-, etc. L₃₁ in formula (31) is preferably -SO₂NH-, -NHCONH-, -O-, -S-, or -N(NR)-, and most preferably -SO₂NH- or -NHCONH-. L₃₂ is preferably -CON(RN)-, -SO₂NH-_,-NHCONH-, -N(RN)CONH-, or -COO-. When L₃₂ denotes -CON(RN)- or -N(RN)CONH-, RN may denote, as a substituted alkyl group, the -R₃₄-X₃₁ group in formula (31).
The divalent aromatic group represented by A₃₂ in formula (31) is preferably a monocyclic arylene group, and more preferably a phenylene group. When A₃₂ denotes a phenylene group, it may have a substituent. With regard to the substituent of the phenylene group, those cited as the substituent of A₃₁ in formula (3) can be cited; an alkyl group, an alkoxy group, a hydroxy group, an amino group, an alkylamino group, an acylamino group, a sulfonamido group, a ureido group, a halogen atom, a carboxyl group, a sulfone group, etc. are preferred; they preferably have a total number of carbons of 1 to 12, and particularly preferably 1 to 8. Among the phenylene groups represented by A₃₂, the unsubstituted phenylene group is particularly preferred.
In formula (31), X₃₁ denotes a group accelerating adsorption onto silver halide, but X₃₁ may denotes a hydrogen atom. X₃₁ is the same as that cited for the group that accelerates adsorption onto silver halide that is present in at least one substituent of A₃₁ in formula (3), and preferable examples thereof are also the same.
Among the compounds represented by formula (31), those represented by formula (32) are preferred. A substituent represented by Y in formula (32) is the same as those cited for the substituent of A₃₂ in formula (31), and preferable examples thereof are also the same. n is preferably 0 or 1, and more preferably 0.
Representative compounds denoted by formula (3) used in the present invention are listed below, but the present invention is in no way limited thereby.
The hydrazine derivatives represented by formula (4) will now be explained in more detail.
R₄₁ represents an alkyl group (for example, methyl, ethyl, i-propyl, butyl, t-butyl, hexyl, octyl, t-octyl, decyl, dodecyl, tetradecyl, cyclohexyl, cyclohexylmethyl, or benzyl) an alkenyl group (e.g., allyl, 1-propenyl, 1,3-butadienyl, 2-butenyl, 2-pentenyl, or cinnamyl), an alkynyl group (e.g., propargyl or 2-butynyl), an aryl group (e.g., phenyl, tolyl, di-i-propylphenyl, or naphthyl), or a heterocyclic group (e.g., pyridyl, furyl, tetrahydrofuryl, thienyl, oxazolyl, benzooxazolyl, or benzothiazolyl) and these groups may be substituted with a substituent such as an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamido group or a ureido group.
L₄₁ represents an alkylene group (e.g., methylene, ethylene, trimethylene, methylmethylene, ethylmethylene, butylmethylene, hexylmethylene or decylmethlene) or an alkenylene group (e.g., propenylene or butenylene). These groups may be substituted with a substituent such as an alkyl, aryl or heterocyclic group.
The R₄₁-S-L₄₁ part contains at least two rings. These rings are aromatic rings (e.g., phenyl or naphthyl), heterocycles (e.g., piperazinyl, pyrazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl or indolyl) or aliphatic rings (e.g., cyclohexyl or cyclopropyl). The rings may be bonded to each other through a bond and/or an aliphatic group.
R₄₂ represents a hydrogen atom, an alkyl group (e.g., methyl, ethyl, methoxyethyl, or benzyl), an aryl group (e.g., phenyl, naphthyl, or methoxyphenyl) or a heterocyclic group (e.g., pyridyl, thienyl, furyl, or tetrahydrofuryl).
R₄₃ represents a hydrogen atom or a blocking group, and as specific examples of the blocking group an alkyl group (e.g., methyl, ethyl, benzyl, methoxyethyl, trifluoromethyl, phenoxymethyl, hydroxymethyl, methylthiomethyl, or phenylthiomethyl), an aryl group (e.g., phenyl, chlorophenyl, or 2-hydroxymethylphenyl), a heterocyclic group (e.g., pyridyl, thienyl or furyl), -CON(R₄₄)(R₄₅), and -COOR₄₆ are preferred.
R₄₄ and R₄₅ each represent a hydrogen atom, an alkyl group (e.g., methyl, ethyl, or benzyl), an alkenyl group (e.g., allyl or butenyl), an alkynyl group (e.g., propargyl or butynyl), an aryl group (e.g., phenyl or naphthyl), a heterocyclic group (e.g., 2,2,6,6-tetramethylpiperidinyl, N-ethyl-N'-ethylpyrazolidinyl, or pyridyl), a hydroxy group, an alkoxy group (e.g., methoxy or ethoxy) or an amino group (e.g., amino or methylamino). R₄₄ and R₄₅ may be combined with a nitrogen atom to form a ring (e.g. piperidino or morpholino). R₄₆ represents a hydrogen atom, an alkyl group (e.g., methyl, ethyl, or hydroxyethyl), an alkenyl group (e.g., allyl or butenyl), an alkynyl group (e.g., propargyl or butynyl), an aryl group (e.g., phenyl or naphthyl), or a heterocyclic group (e.g., 2,2,6,6-tetramethylpiperidinyl, N-methylpiperidinyl, or pyridyl).
J₄₁ and J₄₂ each represent a linking group, and examples of J₄₁ are listed below.
J₄₁ is -CO-, -SO₂-, -N(A₄₃)CO-, -N(A₄₃)N(A₄₄)CO-, or -CON(A₄₃)N(A₄₄)CO-, in which A₄₃ and A₄₄ each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Preferably, n is 1 and J₄₁ is -CO-.
For J₄₂ there can be specifically cited an acylamino group (e.g., benzoylamino or phenoxyacetylamino), a sulfonamido group (e.g., benzenesulfonamido or furansulfonamido), a ureido group (e.g., ureido or phenylureido), an alkylamino group (e.g., benzylamino or furfurylamino), an anilino group, an alkylideneamino group (e.g., benzylideneamino), an aryloxy group (e.g., phenoxy), an aminocarbonylalkoxy group (e.g., aminocarbonylmethoxy), a sulfonylhydrazinocarbonylamino group (e.g., benzenesulfonylhydrazinocarbonylamino), etc. J₄₂ is preferably a benzenesulfonamido group.
X represents an aromatic residue (e.g., phenylene or naphthylene, which can be substituted) or a divalent heterocyclic group (e.g., a divalent residue of pyridine, pyrazole, pyrrole, thiophene, benzothiophene, or furan, which can be substituted).
A₄₁ and A₄₂ each represent a hydrogen atom, or one of them is a hydrogen atom and the other one is a group selected from an acyl group (e.g., acetyl or trifluoroacetyl), a sulfonyl group (e.g., methanesulfonyl or toluenesulfonyl) and an oxalyl group (e.g., ethoxyoxalyl). A₄₁ and A₄₂ are preferably both hydrogen atoms.
Representative specific examples of the compound represented by formula (4) are given below, but the invention is not limited thereto.
The hydrazine derivative represented by formula (5) is now explained further in detail.
In the formula, R₅ denotes an acyl group chosen from the group consisting of COR₅₁, SO₂R₅₂, SOR₅₃, POR₅₄R₅₅, and COCOR₅₆; R₅₁ and R₅₆ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl or heteroaryl group, OR₅₇ or NR₅₈R₅₉; R₅₂ and R₅₃ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl or heteroaryl group, OR₅₇, or NR₅₈R₅₉; R₅₄ and R₅₅ independently represent one of those cited for R₅₂ or atoms required to together form a ring. R₅₇ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl or heteroaryl group; R₅₈ and R₅₉ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl or heteroaryl group, or atoms required to together form a ring.
A₅ and A₅' independently represent a hydrogen atom, an SO₂R₅₀ group, or a group that can generate hydrogen under alkaline photographic processing conditions, provided that when A₅ is SO₂R₅₀, A₅' is hydrogen and vice versa, and R₅₀ has the same meaning as R₅₂.
L₅ is a divalent linking group. Q is a cationic nitrogen-containing aromatic heterocyclic ring. Y^- is a negatively charged counter ion for neutralizing the positive charge of Q. n is 0 when the compound of formula (5) is an intramolecular salt, or n is an integer that is equal to the positive charge of Q. Z represents an atomic group necessary for forming a substituted or unsubstituted aromatic or heteroaromatic ring.
In the most preferred embodiment, Q is chosen from pyridinium, quinolinium, and isoquinolinium, and L₅ is substituted or unsubstituted ethylene.
Specific examples of compounds represented by formula (5) are listed below, but they are not intended to limit the present invention.
The hydrazine derivative represented by formula (6) is now explained further in detail.
In the formula, R₆ denotes an alkyl group having 6 to 18 carbons or a five- or six-membered heterocycle containing as a ring atom sulfur or oxygen, R₆₁ denotes an alkyl or alkoxy group having 1 to 12 carbons, X denotes alkylthio, thioalkyl or alkoxy having 1 to about 5 carbons, a halogen atom, -NHCOR₆₂, -NHSO₂R₆₂, -CONR₆₂R₆₂, or -SO₂R₆₂R₆₃ (R₆₂ and R₆₃ may be identical to or different from each other and denote hydrogen atoms or alkyl groups having 1 to about 4 carbons), and n is 0, 1, or 2.
Alkyl groups represented by R₆ can be straight or branched chain and can be substituted or unsubstituted. Substituents include alkoxy having from 1 to 4 carbon atoms, halogen atoms (e.g., chlorine and fluorine), or -NHCOR₆₂- or NHSO₂R₆₂- where R₆₂ is as defined above. Preferred R₆ alkyl groups contain from 8 to 16 carbon atoms since alkyl groups of this size impart a greater degree of insolubility to the hydrazide nucleating agents and thereby reduce the tendency during development for these agents to be leached into developer solutions from the layers in which they are coated. Heterocyclic groups represented by R₆ include thienyl and furyl, which can be substituted with alkyl having from 1 to 4 carbon atoms or with a halogen atom such as chlorine.
Alkyl or alkoxy groups represented by R₆₁ can be straight or branched chain and can be substituted or unsubstituted. Substituents on these groups can be alkoxy having from 1 to 4 carbon atoms, halogen atoms (e.g., chlorine or fluorine); or -NHCOR₆₂ or -NHSO₂R₆₂ where R₆₂ is as defined above. R₆₂ may further have a substituent. Preferred alkyl or alkoxy groups contain from 1 to 5 carbon atoms in order to impart sufficient insolubility to the hydrazide nucleating agents to reduce their tendency to be leached by a developer solution out of the layers in which they are coated.
Alkyl, thioalkyl and alkoxy groups which are represented by X contain from 1 to 5 carbon atoms and can be straight or branched chain. When X is a halogen atom, it may be chlorine, fluorine, bromine or iodine. Where more than one X is present, such substituents can be identical to or different from each other.
Specific examples of compounds represented by formula (6) are listed below, but they are not intended to limit the present invention.
The hydrazine derivative of the present invention can be synthesized by, for example, methods disclosed in JP-A-61-213847, JP-A-62-260153, US Pat. Nos. 4,648,604, 3,379,529, 3,620,746, 4,377,634, 4,332,878, JP-A-49-129536, JP-A-56-153336, JP-A-56-153342, JP-A-1-269936, US Pat. Nos. 4,988,604, 4,994,365, etc.
The hydrazine derivative for use in the present invention may be dissolved before use in an appropriate water-miscible organic solvent, such as an alcohol (e.g. methanol, ethanol, propanol, a fluorinated alcohol), a ketone (e.g. acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, or methyl cellosolve.
The hydrazine-series nucleating agent for use in the present invention may also be used as emulsion dispersion obtained by dissolving the compound according to an already well-known emulsion dispersion method using an oil, such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate; or using an auxiliary solvent, such as ethyl acetate or cyclohexanone, and mechanically processing it into an emulsion dispersion. Alternatively, the hydrazine derivative powder may be used by dispersing it in water using a ball mill, a colloid mill, or ultrasonic waves, according to a method known as a solid dispersion method.
The hydrazine nucleating agent for use in the present invention may be added to any of a silver halide emulsion layer and other hydrophilic colloid layers on the silver halide emulsion layer side of a support, but it is preferably added to the above-described silver halide emulsion layer or to a hydrophilic colloid layer adjacent thereto. It is also possible to use two or more types of hydrazine nucleating agent in combination.
The amount added of the nucleating agent for use in the present invention is preferably from 1 x 10^-5 to 1 x 10^-2 mol, more preferably from 1 x 10^-5 to 5 x 10^-3 mol, and most preferably from 2 x 10^-5 to 5 x 10^-3 mol, per mol of silver halide.
The halogen composition of the light-sensitive silver halide emulsion used in the present invention can be any chosen from silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide.
The silver halide grains may have any shape of cubic, tetradecahedral, octahedral, amorphous, and tabular forms, and cubic or tabular grains are preferred.
The photographic emulsion for use in the present invention can be prepared using methods described, for example, by P. Glafkides, in Chimie et Physique Photographique, Paul Montel (1967); by G. F. Duffin, in Photographic Emulsion Chemistry, The Focal Press (1966); and by V. L. Zelikman et al., in Making and Coating Photographic Emulsion, The Focal Press (1964).
More specifically, either an acid process or a neutral process may be used. Further, a method of reacting a soluble silver salt and a soluble halogen salt may be carried out by any of a single-sided mixing method, a simultaneous mixing method, and a combination thereof.
A method of forming grains in the presence of excess silver ion (the so-called reverse-mixing method) may also be used. As one form of the simultaneous mixing method, a method of maintaining the pAg constant in the liquid phase where silver halide is produced, namely, the so-called controlled double jet method, may be used. Further, it is preferred to form the grains using a so-called silver halide solvent, such as ammonia, a thioether, or a tetra-substituted thiourea, and more preferably using a tetra-substituted thiourea compound, and this is described in JP-A-53-82408 and JP-A-55-77737. Preferred examples of the thiourea compound include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The amount of silver halide solvent added varies depending on the kind of the compound used or the intended grain size and the intended halogen composition, but it is preferably from 10^-5 to 10^-2 mol per mol of silver halide. It is also possible to form grains in the presence of a nitrogen-containing heterocyclic compound capable of forming a complex with silver, and Compounds N-1 to N-59 described in JP-A-11-344788 are preferred. The amount of such a compound added varies depending on various conditions such as the pH, the temperature and the size of the silver halide grains, but it is preferably 10^-6 to 10^-2 mol per mol of silver halide. Such a compound can be added appropriately in any step prior to, during, or subsequent to formation of the grains, but it is preferably added during formation of the grains.
According to the controlled double jet method or the method of forming grains using a silver halide solvent, a silver halide emulsion including grains having a regular crystal form and a narrow grain size distribution can be easily prepared. These methods are useful means for preparing the silver halide emulsion for use in the present invention.
In order to render the grain size uniform, it is preferred to rapidly grow grains within the range not exceeding the critical saturation, using a method of changing the addition rate of silver nitrate or alkali halide according to the grain growth rate, as described in British Patent No. 1,535,016, JP-B-48-36890 ("JP-B" means examined Japanese patent publication), and JP-B-52-16364, or a method of changing the concentration of the aqueous solution, as described in British Patent No. 4,242,445 and JP-A-55-158124.
The emulsion for use in present invention is preferably a monodisperse emulsion having a coefficient of variation (deviation coefficient) obtained by the equation: {(standard deviation of grain size)/(average grain size)} x 100, of 20% or less, and more preferably 15% or less.
The silver halide emulsion grains preferably have an average grain size of 0.5 µm or less, and more preferably 0.1 to 0.4 µm.
The light-sensitive silver halide emulsion in the present invention can be used singly or in a combination of two or more types. When a combination of two or more types is used, the grain sizes are preferably different from each other. The difference in grain size, as the average grain length, is preferably 10% or more.
The ratio of the two or more types of silver halide emulsion used in the present invention is not particularly limited. For example, the ratio of an emulsion having a larger amount thereof is 1:1 to 1:20 on the basis of the silver present in the silver halide emulsions, and more preferably 1:1 to 1:10.
It is also preferable to mix at least two types of emulsion to which have been added different amounts of a nitrogen-containing heterocyclic compound capable of forming a complex with silver as described in sections 0020 to 0032 of Japanese patent application No. 2000-379706.
The silver halide emulsion used in the present invention can contain a metal that belongs to Group VIII of the periodic table. In order to achieve high contrast and low fog, it preferably contains a rhodium compound, an iridium compound, a ruthenium compound, a rhenium compound, a chromium compound, etc. A preferred example of these heavy metal compounds is a metal coordination complex, or a hexa-coordinate complex represented by the general formula below. [M(NY)_mL_6-m]^n-
(In the formula, M is a heavy metal chosen from the group consisting of Ir, Ru, Rh, Re, Cr and Fe. L denotes a bridging ligand. Y is oxygen or sulfur. m = 0, 1 or 2 and n = 0, 1, 2 or 3.)
With regard to preferable examples of L, halide ligands (fluoride, chloride, bromide and iodide), a cyanide ligand, a cyanate ligand, a thiocyanate ligand, a selenocyanate ligand, a tellurocyanate ligand, acid ligands, and an aquo ligand can be cited. When an aquo ligand is present, it preferably occupies one ligand or two ligands.
In order to achieve high sensitivity, it is preferable for the silver halide emulsion to contain an iron compound, and it is particularly preferable for it to contain a metal coordination complex having a cyan ligand.
These compounds are used as a solution in water or an appropriate solvent. A method that is usually employed in order to stabilize a solution of the compound, that is to say, a method in which an aqueous solution of a hydrogen halide (for example, hydrochloric acid, hydrobromic acid or hydrofluoric acid) or an alkali halide (for example, KCI, NaCI, KBr or NaBr) is added can be employed. It is also possible to add and dissolve other silver halide grains which have been doped with the above-mentioned compounds.
Specific examples of the metal coordination complex are as follows.

1.: [Rh(H₂O)Cl₅]^2-
2.: [RhCl₆]^3-
3.: [Ru(NO)Cl₅]^2-
4.: [RuCl₆]^3-
5.: [Ru(H₂O)Cl₅]^2-
6.: [Ru(NO)(H₂O)Cl₄]^-
7.: [Ru₂Cl₁₀O]^6-
8.: [Re(NO)Cl₅]^2-
9.: [Ir(NO)Cl₅]^2-
10.: [Ir(H₂O)Cl₅]^2-
11.: [Re(H₂O)Cl₅]^2-
12.: [RhBr₆]^3-
13.: [ReCl₆]^3-
14.: [IrCl₆]^3-
15.: [Re(NS)Cl₄(SeCN)]^2-
16.: [Cr(CN)₆]^3-
: 17. [Fe(CN)₆]^3-

In addition to the compounds described above, it is also possible to preferably use compounds described in sections 0027 to 0056 of Japanese patent application No. 2000-95144.
The amount of these compounds added is 1 x 10^-8 to 5 x 10^-6 mol per mol of silver in the silver halide emulsion, and preferably 5 x 10^-8 to 1 x 10^-6 mol. Furthermore, the above-mentioned heavy metals can be used in combination. The distribution of the heavy metal in the silver halide grains is not particularly limited; it can be distributed uniformly or in a core-shell form in which the distribution differs between the surface and the interior, or the distribution can be changed continuously. The addition of these compounds can be carried out appropriately in any step of the production of the silver halide emulsion grains or prior to coating the emulsion, but it is particularly preferable to add them during the emulsion formation so as to incorporate them into the silver halide grains.
In the present invention it is preferable for the light-sensitive silver halide emulsion layer or another layer comprising a hydrophilic colloid to contain solid particles that can increase the average value of the integral of the spectral reflectance in the wavelength range from 850 to 1000 nm by at least 1.5% relative to a case where they are not added. The amount thereof added is preferably at least 2% and, from the point of view of degradation of haze, at most 5%.
In the present invention, the average value of the integral of the spectral reflectance of the light-sensitive material at wavelengths of 850 to 1000 nm can be measured simply using a spectrometer. For example, it can be measured using a U3500 spectrometer manufactured by Hitachi, Ltd. with an integrating sphere placed in a light-receiving part thereof, by applying probe light to a light-sensitive material with black paper placed on its back surface, and integrating the reflected light by means of the integrating sphere.
The material for the solid particles used in the present invention that can increase the above-mentioned integral value of the reflectance is not particularly limited as long as the above-mentioned reflectance characteristics can be provided; any type including inorganic particles and a dispersion of an organic material can be used as long as the photographic characteristics are not affected, and those having a refractive index of at least 1.54 are preferred.
The refractive index referred to in the present invention denotes the refractive index relative to air. The refractive index varies slightly depending on the wavelength of the light and the temperature, and a value for nD20 that is obtained at 20°C using the Na-D line (λ = 589.3 nm) as a light source is used. In the case of a solid, since the refractive index might vary depending on the direction due to crystal anisotropy, the maximum value is used.
Various compounds can be cited as specific examples of compounds having a refractive index of at least 1.54, and include silver halides, metal oxides such as magnesium oxide, alumina, calcite, ZrO₂, SnO₂, ZnO, Al₂O₃, and TiO₂, barium sulfate, polystyrene, and a vinylidene chloride resin.
A preferable range for the refractive index is 1.60 and above, and particularly preferably 1.70 and above.
A preferable range for the particle size of the solid particles depends on the refractive index, but it is preferably 2 nm to 20 µm, and more preferably 5 nm to 10 µm. The solid particle size referred to here denotes the particle size obtained by a light scattering method, and more specifically the average particle size is measured using an ELS-800 manufactured by Otsuka Electronics Co., Ltd.
The amount of solid particles added is preferably 10 mg to 1 g/m², and particularly preferably 20 to 500 mg/m².
The position at which the solid particles is added is not particularly limited, and they can be used in an emulsion layer, between the emulsion layer and a support, in an emulsion protecting layer, in a backing layer, or in the support, but the uppermost layer on which light emitted by the infrared source of an infrared sensor directly impinges is particularly preferred.
It is necessary for these solid particles to be in a granular form in the light-sensitive material and, although it depends on the method used for dispersing fine particles, the water solubility of the solid particles is preferably low. Those having the property of dissolving in a processing solution are preferably used.
Furthermore in the present invention, among the above-mentioned solid particles, light-insensitive silver halide grains are preferably used.
The halogen composition of the light-sensitive silver halide emulsion used in the present invention can be any chosen from silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide.
The silver halide grains may have any shape of cubic, tetradecahedral, octahedral, amorphous, and tabular forms, and cubic, tetradecahedral, and tabular grains are preferred.
The light-insensitive silver halide grains for use in the present invention can be prepared using methods described, for example, by P. Glafkides, in Chimie et Physique Photographique, Paul Montel (1967); by G. F. Duffin, in Photographic Emulsion Chemistry, The Focal Press (1966); and by V. L. Zelikman et al., in Making and Coating Photographic Emulsion, The Focal Press (1964).
The light-insensitive silver halide grains of the present invention have a blue region sensitivity that is 1/10 or less of that of the light-sensitive silver halide grains used in the light-sensitive material of the present invention, and are preferably not spectrally sensitized. The light-insensitive silver halide grains of the present invention can be subjected to surface modification such as metal complex doping or chemical sensitization, described in the section above related to light-sensitive silver halides.
When the cubic or tetradecahedral grains are used, the light-insensitive silver halide is preferably in the form of monodisperse grains; its coefficient of variation obtained by the equation: {(standard deviation of grain size)/(average grain size)} x 100, is 20% or less, and preferably 15% or less. The average size of these silver halide grains is preferably at least 0.1 µm, more preferably 0.2 µm to 10 µm, and yet more preferably 0.5 µm to 1.5 µm.
The tabular silver halide grains referred to here means general silver halide grains having one twin plane or two or more parallel twin planes. The twin plane refers to a (111) plane when all lattice ions on either side of the (111) plane are in a mirror image relationship. When viewed from above, these tabular particles have a triangular, square, hexagonal or roundish circular form, and the triangular particles, the hexagonal particles, and the circular particles have respectively triangular, hexagonal, and circular external surfaces that are parallel to each other.
The light-insensitive emulsion used in the present invention preferably includes tabular grains having a thickness of 0.02 to 0.20 µm over at least 50% of the total projection area. The thickness of the grains can be easily obtained by vapor-depositing a metal both on the grains and on a reference latex from an oblique direction, measuring the length of the shadow of the grains on an electron micrograph and calculating using the length of the latex shadow as a reference.
In the present invention, all the grains of the light-insensitive emulsion preferably have a circle-equivalent diameter of less than 1.5 µ, and more preferably 0.2 to 1.2 µm. The coefficient of variation in the circle-equivalent diameter is preferably at most 40%, more preferably at most 25%, and yet more preferably 15%.
The tabular silver halide emulsion can be easily prepared by reference to methods disclosed in JP-A-58-127927, JP-A-58-113927, JP-A-58-113928, etc. Alternatively, seed crystals having at least 40 wt % of tabular particles are formed in an atmosphere having a pBr value of 1.3 or below, which is comparatively low, and the seed crystals are made to grow by simultaneously adding silver and a halogen solution while maintaining the pBr value at the same level as above. During this growth process, the silver and the halogen solution are desirably added so as to prevent growth of new crystal nuclei. The size of the tabular silver halide grains can be adjusted by controlling the temperature, the type and the amount of a solvent, and the rates of addition of a silver salt and a halide during grain growth.
The amount coated of the silver halide emulsion used in the present invention is preferably 5 g/m² or below expressed as the amount of silver in both the light-sensitive and light-insensitive emulsions, and more preferably 2.2 to 4.5 g/m². The amount of the light-sensitive emulsion is preferably 4.5 g/m² or below expressed as the amount of silver, and more preferably 2 to 4 g/m². The amount of the light-insensitive emulsion is preferably 0.5 g/m² or below expressed as the amount of silver, and more preferably 0.03 to 0.3 g/m².
The silver halide emulsion for use in the present invention is preferably subjected to chemical sensitization. The chemical sensitization may be performed using a known method, such as sulfur sensitization, selenium sensitization, tellurium sensitization, or noble metal sensitization, and these sensitization methods may be used singly or in combination. When these sensitization methods are used in combination, a combination of sulfur sensitization and gold sensitization; a combination of sulfur sensitization, selenium sensitization, and gold sensitization; and a combination of sulfur sensitization, tellurium sensitization, and gold sensitization, are preferred.
The sulfur sensitization employed in the present invention is usually carried out by adding a sulfur sensitizer to the silver halide emulsion and stirring the mixture at a high temperature, and preferably at least 40°C, for a predetermined time. The sulfur sensitizer used may be a known compound, and examples thereof include, in addition to a sulfur compound present in gelatin, various types of sulfur compound such as thiosulfates, thioureas, thiazoles or rhodanines. Furthermore, sulfur sensitizers disclosed in US Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, 3,656,955, German Patent No. 1,422,869, JP-B-56-24937, JP-A-55-45016, etc. can be used. Preferred sulfur compounds are thiosulfates and thiourea compounds.
The amount of sulfur sensitizer added varies depending on various conditions such as the pH and the temperature at the time of chemical ripening and the size of the silver halide grains, but it is preferably 10^-7 to 10^-2 mol, and more preferably 10^-5 to 10^-3 mol per mol of silver halide.
The selenium sensitizer for use in the present invention may be a known selenium compound. The selenium sensitization is generally performed by adding a labile and/or non-labile selenium compound and stirring the emulsion at a high temperature of 40°C or higher for a predetermined time. Preferable examples of the labile selenium compound include the compounds described in JP-B-44-15748, JP-B-43-13489, and JP-A-4-25832, JP-A-4-109240, JP-A-4-324855, etc. Specific examples of the labile selenium compound include isoselenocyanates (e.g. aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (e.g. 2-selenopropionic acids, 2-selenobutyric acids), selenoesters, diacylselenides (e.g. bis(3-chloro-2,6-dimethoxybenzoyl)selenide), selenophosphates, phosphine selenides, colloidal metal selenium, etc. The above-mentioned preferable types of labile selenium compound are not cited for restriction. A person skilled in the art generally understands that, with regard to a labile selenium compound as a sensitizer for a photographic emulsion, the structure of the compound is not important as long as the selenium is labile, and the organic moiety of a selenium sensitizer molecule has no function other than that of allowing selenium to be present in a labile form in an emulsion. In the present invention, a labile selenium compound defined by such a broad concept is advantageously used. With regard to the non-labile selenium compound used in the present invention, compounds described in JP-B-46-4553, JP-B-52-34492 and JP-B 52-34491 can be used. Specific examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidindione, 2-selenooxazolidinthione, and derivatives thereof. Particularly preferred are the compounds represented by formula(VIII) or (IX) of JP-A-4-324855.
Further, a low-decomposition-activity selenium compound can also be preferably used. The low-decomposition-activity selenium compound is a selenium compound such that, when a water/1,4-dioxane (1/1 by volume) mixed solution (pH: 6.3), containing 10 mmol of AgNO₃, 0.5 mmol of the selenium compound, and 40 mmol of 2-(N-morpholino)ethanesulfonic acid buffer, is reacted at 40°C, the half-life of the selenium compound is 6 hours or more. When determining the half-life, the selenium compound can be detected and analyzed using HPLC, etc. Preferred examples of the low-decomposition-activity selenium compound include Compounds SE-1 to SE-8 exemplified in JP-A-9-166841.
The tellurium sensitizer for use in the present invention is a compound for forming silver telluride, which is presumed to become a sensitization nucleus, on the surface of or inside a silver halide grain. The rate of formation of silver telluride in a silver halide emulsion can be examined according to a method described in JP-A-5-313284.
Specific examples of the tellurium sensitizer to be used include the compounds described in U.S. Pat. Nos. 1,623,499, 3,320,069, and 3,772,031, British Patent Nos. 235,211, 1,121,496, 1,295,462, and 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640, JP-A-4-271341, JP-A-4-333043, and JP-A-5-303157, J. Chem. Soc. Chem. Commun., 635(1980); ibid., 1102 (1979); ibid., 645 (1979); J. Chem. Soc. Perkin. Trans., 1, 2191 (1980); S. Patai (compiler), The Chemistry of Organic Selenium and Tellurium Compounds, Vol.1 1 (1986); and ibid., Vol. 2 (1987). The compounds represented by formulae (II), (III), and (IV) of JP-A-5-313284 are particularly preferred.
The amount to be used of the selenium sensitizer or the tellurium sensitizer for use in the present invention varies depending on the silver halide grains used, the chemical ripening conditions, etc., but it is generally in the order of 10^-8 to 10^-2 mol, and preferably from 10^-7 to 10^-3 mol, per mol of silver halide. The conditions of chemical sensitization in the present invention are not particularly restricted, but the pH is generally from 5 to 8, the pAg is generally from 6 to 11, and preferably from 7 to 10, and the temperature is generally from 40 to 95°C, and preferably from 45 to 85°C
Examples of the noble metal sensitizer for use in the present invention include gold, platinum, palladium, and iridium, and a gold sensitizer is particularly preferred. With regard to the above-mentioned gold sensitizer, its gold oxidation state may be monovalent or trivalent, and a gold compound that is normally used as a gold sensitizer can be used. Representative examples of the gold sensitizer for use in the present invention include chloroauric acid, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and gold sulfide. The gold sensitizer can be used in an amount of approximately from 10^-7 to 10^-2 mol per mol of silver halide.
In the silver halide emulsion for use in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, etc. may also be present during the formation or physical ripening of the silver halide grains.
In the present invention, reduction sensitization may be employed. Examples of the reduction sensitizer to be used include stannous salts, amines, formamidine sulfinic acid, and silane compounds.
To the silver halide emulsion for use in the present invention, a thiosulfonic acid compound may be added, according to the method described in European Unexamined Patent Publication (EP) 293,917.
With regard to the silver halide emulsion in the light-sensitive material used in the present invention, two or more types of emulsion can be used in combination in a single layer, the emulsions having different types, distributions and contents of metal complex; different crystal habits and forms; different types, amounts added and sensitization conditions of chemical sensitizer; and different types, amounts added and spectral sensitization conditions of spectral sensitizer, and, moreover, such layers can be formed into a layered structure.
The light-sensitive silver halide emulsion for use in the present invention may be spectrally sensitized to light having a comparatively long wavelength such as blue light, green light, red light, or infrared light, by a sensitizing dye, according to the purpose for which the light-sensitive material is used. Examples of the sensitizing dye that can be used include a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, and a hemioxonol dye.
Useful sensitizing dyes for use in the present invention are described, for example, in Research Disclosure, Item 17643, IV-A, page 23 (December, 1978); ibid., Item 18341 X, page 437 (August 1979), and publications cited therein.
In particular, sensitizing dyes having a spectral sensitivity suitable for the spectral characteristics of various light sources in a scanner, an image setter, or a photomechanical process camera, can be advantageously selected.
For example, A) for an argon laser light source, Compounds (I)-1 to (I)-8 described in JP-A-60-162247, Compounds I-1 to 1-28 described in JP-A-2-48653, Compounds I-1 to 1-13 described in JP-A-4-330434, Compounds of Examples 1 to 14 described in U.S. Pat. No. 2,161,331, and Compounds 1 to 7 described in West German Patent No. 936,071; B) for a helium-neon laser light source and a red laser diode light source, Compounds I-1 to 1-38 described in JP-A-54-18726, compounds I-1 to 1-35 described in JP-A-6-75322, Compounds I-1 to 1-34 described in JP-A-7-287338, and Compounds 2-1, 2-14, 3-1 to 3-14 and 4-1 to 4-6 described in JP 2822138 (JP denotes Japanese Examined Patent Publication); C) for an LED light source, Dyes 1 to 20 described in JP-B-55-39818, Compounds I-1 to 1-37 described in JP-A-62-284343, Compounds I-1 to 1-34 described in JP-A-7-287338, and Compounds 2-1 to 2-14, 3-1 to 3-14 and 4-1 to 4-6 described in JP 2822138; D) for a semiconductor laser light source, Compounds I-1 to 1-12 described in JP-A-59-191032, Compounds I-1 to 1-22 described in JP-A-60-80841, Compounds I-1 to I-29 described in JP-A-4-335342, and Compounds I-1 to I-18 described in JP-A-59-192242; and E) for a tungsten or xenon light source of a photomechanical camera, Compounds (1) to (19) represented by general formula (I) of JP-A-55-45015, Compounds 4-A to 4-S, Compounds 5-A to 5-Q, and Compounds 6-A to 6-T described in JP-A-6-242547, and Compounds I-1 to 1-97 described, in Japanese Patent Application No. 9-160185 may be advantageously selected. but the present invention is not limited thereby.
These sensitizing dyes may be used singly or in combination, and a combination of sensitizing dyes is often used for the purpose of, particularly, supersensitization. In combination with the sensitizing dye, a dye which itself has no spectral sensitization effect, or a material that adsorbs substantially no visible light, but that exhibits supersensitization, may be incorporated into the emulsion.
Useful sensitizing dyes, combinations of dyes that exhibit supersensitization, and materials that show supersensitization are described, for example, in Research Disclosure, Vol. 176, 17643, page 23, Item IV-J (December 1978); JP-B-49-25500, JP-B-43-4933, JP-A-59-19032, and JP-A-59-192242.
The sensitizing dyes for use in the present invention may be used in a combination of two or more. The sensitizing dye may be added to a silver halide emulsion by dispersing it directly in the emulsion, or by dissolving it in a single or mixed solvent of such solvents as water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol or N,N-dimethylformamide, and then adding the solution to the emulsion.
Alternatively, the sensitizing dye may be added to the emulsion by a method disclosed in U.S. Pat. No. 3,469,987, in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and the dispersion is added to the emulsion; a method disclosed, for example, in JP-B-44-23389, JP-B-44-27555, and JP-B-57-22091, in which a dye is dissolved in an acid, and the solution is added to the emulsion, or a dye is formed into an aqueous solution in the presence of an acid or base and then it is added to the emulsion; a method disclosed, for example, in U.S. Pat. Nos. 3,822,135 and 4,006,025, in which a dye is formed into an aqueous solution or a colloid dispersion in the presence of a surfactant, and the solution or dispersion is added to the emulsion; a method disclosed in JP-A-53-102733 and JP-A-58-105141, in which a dye is directly dispersed in a hydrophilic colloid, and the dispersion is added to the emulsion; or a method disclosed in JP-A-51-74624, in which a dye is dissolved using a compound capable of producing a red-shift, and the solution is added to the emulsion. Ultrasonic waves may also be used to form a solution.
The sensitizing dye for use in the present invention may be added to a silver halide emulsion for use in the present invention at any step known to be useful during the preparation of a photographic emulsion. For example, the dye may be added at a silver halide grain formation step, and/or in a period before desalting, or at a desalting step, and/or in a period after desalting and before the initiation of chemical ripening, as disclosed, for example, in U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, and 4,225,666, JP-A-58-184142, and JP-A-60-196749, or the dye may be added in any period or at any stage before coating of the emulsion, such as immediately before or during chemical ripening, or in a period after chemical ripening but before coating, as disclosed, for example, in JP-A-58-113920. Also, a single kind of compound alone, or a combination of compounds different in structure, may be added in a divided manner; for example, a part during grain formation, and the remainder during chemical ripening, or after completion of the chemical ripening; or a part before or during chemical ripening, and the remainder after completion of the chemical ripening, as disclosed, for example, in U.S. Pat. No. 4,225,666 and JP-A-58-7629. The kind of compounds added in a divided manner, or the kind of combination of compounds, may be changed.
The amount added of the sensitizing dye for use in the present invention varies depending upon the shape, size, the halogen composition of the silver halide grains, the method and degree of chemical sensitization, the kind of antifoggant, and the like, but the amount added can be from 4 x 10^-6 to 8 x 10^-3 mol per mol of silver halide. For example, when the silver halide grain size is from 0.2 to 1.3 µm, the amount added is preferably from 2.0 x 10^-7 to 3.5 x 10^-6, and more preferably from 6.5 x 10^-7 to 2.0 x 10^-6 mol, per m² of the surface area of the silver halide grains.
'Another layer comprising a hydrophilic colloid' referred to in the present invention denotes a hydrophilic colloid layer that is provided on the same side as or the opposite side to the silver halide emulsion layer relative to a water impermeable support. Examples of the former include a protecting layer and an interlayer, and examples of the latter include a backing layer.
With regard to the support used in the present invention, for example, baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, a polyester film such as polyethylene terephthalate, a support made of a styrene system polymer having a syndiotactic structure described in JP-A-7-234478 or US Pat. No. 5,558,979, and a support, described in JP-A-64-538 or US Pat. Nos. 4,645,731, 4,933,267 or 4,954,430 formed by coating a polyester film with a vinylidene chloride copolymer can be cited. These supports are chosen as appropriate according to the purpose for which the silver halide photographic light-sensitive material is used.
As a binder for the silver halide emulsion layer and another hydrophilic colloid layer of the present invention, gelatin is preferably used, but it is also possible to use a polymer described in paragraph 0025 of JP-A-10-268464. The amount of binder present in the whole hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g/m² or less (preferably 1.0 to 3.0 g/m²), and the total amount of binder present in the whole hydrophilic colloid layer on the side having the silver halide emulsion layer and the whole hydrophilic colloid layer on the opposite side is 7.0 g/m² or less, and preferably 2.0 to 7.0 g/m².
In the present invention, in order to control the surface roughness of the outermost layers of the silver halide light-sensitive material, inorganic and/or organic polymer fine particles (hereinafter, called a matting agent) are used in a hydrophilic colloid layer. The surface roughness of the outermost layer on the side having the silver halide emulsion layer of the light-sensitive material and the surface roughness of the outermost layer on the opposite side can be controlled by variously changing the average particle size of the matting agent and the amount thereof added. The layer to which the matting agent is added can be any of the light-sensitive material forming layers, but with regard to the side having the silver halide emulsion layer, it is preferable to add it to a layer positioned far from the support in order to prevent pinholes, and the outermost layer is particularly preferred.
The matting agent used in the present invention can be of any type of solid particles as long as it does not adversely affect the various photographic characteristics. Specific examples include those described in paragraph Nos. 0009 to 0013 of JP-A-10-268464.
The average particle size of the matting agent used in the present invention is preferably 20 µm or less, and particularly preferably in the range of 1 to 10 µm. The amount of matting agent added is preferably 5 to 400 mg/m², and particularly preferably 10 to 200 mg/m².
With regard to the surface roughness of the light-sensitive material of the present invention, at least one of the outermost surfaces of the side having the emulsion layer, and the side opposite thereto, and preferably both surfaces, have a Bekk smoothness of 4000 s or less, and preferably 10 to 4000 s. The Bekk smoothness can be easily determined in accordance with JIS P8119 and TAPPI T479.
In the present invention, in order to improve settling of the matting agent when coating and drying the silver halide light-sensitive material and improve pressure induced sensitivity modification, curl balance, abrasion resistance and adhesion resistance during automatic transfer, exposure, development, etc., colloidal inorganic particles can be used in the silver halide emulsion layer, a middle layer, a protective layer, a back layer, a back protective layer, etc. Preferable examples of the colloidal inorganic particles include elongated silica particles described in paragraphs 0008 to 0014 of JP-A-10-268464, colloidal silica, and the pearl-like (pearl necklace form) colloidal silica 'Snowtex PS' manufactured by Nissan Chemical Industries, Ltd.
The amount of colloidal inorganic particles used in the present invention is 0.01 to 2.0 as a ratio by dry weight relative to the binder (e.g. gelatin) that is present in the layer to which they are to be added, and preferably 0.1 to 0.6.
In the present invention in order to improve the pressure induced sensitivity modification, etc., it is preferable to use the polyhydroxybenzene compounds described on page 10, lower right, line 11 to page 12, lower left, line 5 of JP-A-3-39948. More specifically, compounds (III)-1 to (III)-25 in the above specification can be cited.
In the present invention, in order to improve brittleness, dimensional stability, pressure induced sensitivity modification, etc. a polymer latex can be used. With regard to examples of the polymer latex, there are polymer latexes formed from various types of monomer such as an alkyl acrylate and an alkyl methacrylate described in US Pat. Nos. 2,763,652 and 2,852,382, JP-A-64-538, JP-A-62-115152, JP-A-5-66512 and JP-A-5-80449, JP-B-60-15935, 6-64048 and 5-45014, etc. and polymer latexes formed by copolymerizing a monomer having an activated methylene group and a monomer such as an alkyl acrylate described in JP-B-45-5819 and JP-B-46-22507, JP-A-50-73625, JP-A-7-152112 and JP-A-8-137060, etc. Particularly preferred are polymer latexes having a core/shell structure, the shell structure having a repeating unit formed from an ethylenically unsaturated monomer containing an active methylene group, described in JP-A-8-248548, JP-A-8-208767 and JP-A-8-220669, etc. These core/shell structure polymer latexes having an active methylene group in the shell part can improve properties such as brittleness, dimensional stability and adhesion resistance between photographic light-sensitive materials without degrading the wet film strength of the light-sensitive material, and the shear stability of the latexes themselves can also be enhanced.
The amount of polymer latex used is 0.01 to 4.0 as a ratio by dry weight relative to the binder (e.g. gelatin) that is present in the layer to which the latex is added, and preferably 0.1 to 2.0.
In the present invention, in order to decrease the pH of the coated film for the purpose of improving the storage stability, pressure induced sensitivity modification, etc. of the silver halide light-sensitive material, it is preferable to use an acidic polymer latex described on page 14, left column, line 1 to right column, line 30 of JP-A-7-104413. More specifically, compounds II-1) to II-9) described on page 15 of the above specification and compounds having an acid group described on page 18, lower right, line 6 to page 19, upper left, line 1 of JP-A-2-103536 can be cited.
The pH of the coated film on the side having the silver halide emulsion layer is preferably 6 to 4.
At least one of the layers forming the silver halide light-sensitive material of the present invention can be an electrically conductive layer having a surface resistivity at 25°C and 25 %RH of 10¹² Ω or less.
With regard to an electrically conductive material that is present in the electrically conductive layer used in the present invention, there are the electrically conductive materials described on page 2, lower left, line 13 to page 3, upper right, line 7 of JP-A-2-18542. More specifically, metal oxides described on page 2, lower right, line 2 to line 10 of the above specification, electrically conductive macromolecular compounds P-1 to P-7 described in the above specification, and acicular metal oxides described in US Pat. No. 5,575,957, paragraphs 0034 to 0043 of JP-A-10-142738 and paragraphs 0013 to 0019 of JP-A-11-23901 can be used.
In the present invention, in addition to the above-mentioned electrically conductive material, the fluorine-containing surfactants described on page 4, upper right, line 2 to page 4, lower right, line 3 from the bottom of JP-A-2-18542 and page 12, lower left, line 6 to page 13, lower right, line 5 of JP-A-3-39948 can be used, thereby further improving the antistatic properties
The silver halide emulsion layer or another hydrophilic colloid layer of the present invention can contain a coating aid, a dispersing and solubilizing agent for additives and various types of surfactant in order to enhance lubrication, prevent adhesion, improve the photographic characteristics (for example, development acceleration, hard gradation enhancement, sensitization, storage stability), etc. For example, there are surfactants described on page 9, upper right, line 7 to lower right, line 3 of JP-A-2-12236, PEG system surfactants described in page 18, lower left, lines 4 to 7 of JP-A-2-103536 and, more specifically, Compounds VI-1 to VI-15 described in the above specification, and fluorine-containing surfactants described on page 4, upper right, line 2 to lower right, line 3 from the bottom of JP-A-2-18542 and on page 12, lower left, line 6 to page 13, lower right, line 5 of JP-A-3-39948.
Furthermore, various types of slip agent can be used in the present invention in order to improve abrasion resistance, pressure induced sensitivity modification and transport performance of the silver halide light-sensitive material in an automatic transporter. For example, slip agents described on page 19, upper left, line 15 to upper right, line 15 of JP-A-2-103536 and in paragraphs 0006 to 0031 of JP-A-4-214551 can be cited.
With regard to a plasticizer for a coated film of the silver halide light-sensitive material of the present invention, Compounds described on page 19, upper left, line 12 to upper right, line 15 of JP-A-2-103536 can be used.
With regard to a cross-linking agent for the hydrophilic binders used in the emulsion layer and the protective layer, compounds described on page 18, upper right, line 5 to line 17 of JP-A-2-103536 and paragraphs 0008 to 0011 of JP-A-5-297508 can be used.
The percentage swelling of the hydrophilic colloid layers including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is preferably in the range of 50 to 200%, and more preferably in the range of 70 to 180%. The percentage swelling of hydrophilic colloid layers is determined by measuring the thickness (d0) of the hydrophilic colloid layers including the emulsion layer and the protective layer in the silver halide photographic light-sensitive material, immersing the silver halide photographic light-sensitive material in distilled water at 25°C for 1 minute, measuring the thickness increase (Δd) and calculating the percentage swelling (%) using the formula (Δd/d0) x 100.
The process, environment, and heat treatment for post-coating drying of the silver halide light-sensitive material of the present invention and winding up into roll form after drying are determined according to the method described in paragraphs 0026 to 0032 of JP-A-10-268464.
The light-sensitive material of the present invention is preferably subjected to a heat treatment at any time after coating and prior to development. The heat treatment can be carried out immediately after coating or after a certain period has passed, but it is preferably carried out after a short time, for example, within 1 day. The heat treatment is carried out mainly in order to promote hardening so as to make the film strength sufficient to withstand development. The heat treatment conditions should be determined appropriately according to the type of hardening agent, the amount thereof added, the pH of the film, the required film strength, etc. The heat treatment is preferably carried out at 30 to 60°C, and more preferably 35 to 50°C, preferably for 30 minutes to 10 days.
It is preferable for the light-sensitive material of the present invention to contain as a nucleation accelerator an amine derivative, an onium salt, a disulfide derivative, or a hydroxymethyl derivative. As examples of the nucleation accelerators used in the present invention there can be cited: compounds described on page 48, lines 2 to 37 of JP-A-7-77783; and more specifically, Compounds A-1) to A-73) described on pages 49 to 58; compounds represented by (Chemical formula 21), (Chemical formula 22), and (Chemical formula 23) described in JP-A-7-84331; specifically, compounds described on pages 6 to 8 of the specification; compounds represented by formulae (Na) and (Nb) described in JP-A-7-104426; specifically, Compounds Na-1 to Na-22 and Compounds Nb-1 to Nb-12 described on pages 16 to 20 of the specification; compounds represented by general formulae (1), (2), (3), (4), (5), (6) and (7) described in JP-A-8-272023 and, more specifically, Compounds 1-1 to 1-19, Compounds 2-1 to 2-22, Compounds 3-1 to 3-36, Compounds 4-1 to 4-5, Compounds 5-1 to 5-41, Compounds 6-1 to 6-58 and Compounds 7-1 to 7-38 described in the above specification; and nucleation accelerators described on page 55, column 108, line 8 to page 69, column 136, line 44 of JP-A-9-297377.
Specific examples of the nucleation accelerator for use in the present invention are illustrated below, but it is not intended to restrict the scope of the invention to them.
The nucleation accelerator for use in the present invention may be dissolved in an appropriate water-miscible organic solvent before use, and examples of the solvent include an alcohol (e.g. methanol, ethanol, propanol, a fluorinated alcohol), a ketone (e.g. acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, or methyl cellosolve.
The nucleation accelerator may be used as an emulsion dispersion obtained by dissolving the compound according to an already well-known emulsion dispersion method, using an oil, such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate, or using an auxiliary solvent, such as ethyl acetate or cyclohexanone, and mechanically processing it into an emulsion dispersion. Alternatively, the nucleation accelerator powder may be used by dispersing it in water using a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.
The nucleation accelerator for use in the present invention may be added to any of a silver halide emulsion layer and other hydrophilic colloid layers on the silver halide emulsion layer side of the support, but it is preferably added to the silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto.
The nucleation accelerator for use in the present invention is preferably added in an amount of from 1 x 10^-6 to 2 x 10^-2 mol, more preferably from 1 x 10^-5 to 2 x 10^-2 mol, and most preferably from 2 x 10^-5 to 1 x 10^-2 mol, per mol of silver halide. It is also possible to use two or more types of nucleation accelerator in combination.
Various additives can be used in the light-sensitive material of the present invention and are not particularly restricted, and, for example, those described in the following passages may be preferably used:
Polyhydroxybenzene compounds described in JP-A-3-39948, from page 10, lower right column, line 11, to page 12, lower left column, line 5, and more specifically, Compounds (III)-1 to (III)-25 described in the above specification;
Compounds described in JP-A-1-118832 represented by formula (I) and having substantially no absorption maximum in the visible region, and more specifically, Compounds I-1 to 1-26 described in the above specification;
Antifogging agents described in JP-A-2-103536, page 17, lower right column, line 19, to page 18, upper right column, line 4;
Polymer latexes described on page 18, lower left, line 12 to line 20 of JP-A-2-103536; polymer latexes described in JP-A-9-179228 having an active methylene group represented by general formula (I); more specifically, Compounds I-1 to 1-16 described in the above specification; polymer latexes having a core-shell structure described in JP-A-9-179228; more specifically, Compounds P-1 to P-55 described in the above specification; acidic polymer latexes described on page 14, left column, line 1 to right column, line 30 of JP-A-7-104413; more specifically, Compounds II-1) to II-9) described on page 15 of the above specification;
Matting agents, slip agents, and plasticizers described in JP-A-2-103536, page 19, from upper left column, line 15, to upper right column, line 15;
Hardening agents described in JP-A-2-103536, page 18, upper right column, lines 5 to 17;
Compounds having an acid group described in JP-A-2-103536, from page 18, lower right column, line 6, to page 19, upper left column, line 1;
Electrically conductive materials described in JP-A-2-18542, from page 2, lower left column, line 13, to page 3, upper right column, line 7; specifically, metal oxides described in the above specification, page 2, lower right column, lines 2 to 10, and the electrically conductive high-molecular compounds of Compounds P-1 to P-7 described in the above specification;
Water-soluble dyes described in JP-A-2-103536, page 17, lower left column, line 1 to lower right, line 18;
Solid disperse dyes described in JP-A-9-179243 represented by general formulae (FA), (FA1), (FA2) and (FA3); more specifically, Compounds F1 to F34 described in the above specification, Compounds (11-2) to (II-24) described in JP-A-7-152112, Compounds (III-5) to (III-18) described in JP-A-7-152112; Compounds (IV-2) to (IV-7) in JP-A-7-152112; solid disperse dyes described in JP-A-2-294638 and JP-A-5-11382;
Surfactants described in JP-A-2-12236, from page 9, upper right column, line 7 to page 9, lower right column, line 3; PEG-series surfactants described in JP-A-2-103536, page 18, lower left column, lines 4 to 7; fluorinated surfactants described in JP-A-3-39948, from page 12, lower left column, line 6, to page 13, lower right column, line 5 and, more specifically, Compounds IV-1 to VI-15 described in the specification;
Redox compounds described in JP-A-5-274816 capable of releasing a development inhibitor when oxidized, preferably redox compounds represented by formulae (R-1), (R-2), and (R-3) described in the specification and, more specifically, Compounds R-1 to R-68 described in the specification; and
Binders described on page 3, lower right, line 1 to line 20 of JP-A-2-18542.
The processing agents, such as the developing solution and a fixing solution, and the processing method for use in the present invention are described below, but it is not intended to restrict the scope of the invention thereto.
The development process used in the present invention may be performed by any known method, and a known developing solution may be used.
A developing agent used in the developing solution (hereinafter, a developer starter solution and a developer replenisher are together called a developing solution) used in the present invention is not particularly limited, but it preferably contains a dihydroxybenzene, an ascorbic acid derivative or a hydroquinone monosulfonate, which may be used singly or in combination. It is particularly preferable to use a dihydroxybenzene system developing agent and an auxiliary developing agent that shows superadditivity therewith. A combination of a dihydroxybenzene or an ascorbic acid derivative with a 1-phenyl-3-pyrazolidone, a combination of a dihydroxybenzene or an ascorbic acid derivative with a p-aminophenol, etc. can be cited.
With regard to the developing agent used in the present invention, hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, etc. can be cited as the dihydroxybenzene developing agent, and hydroquinone is particularly preferred. With regard to the ascorbic acid derivative developing agent, there are ascorbic acid, isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred in terms of material cost.
With regard to 1-phenyl-3-pyrazolidone developing agents and derivatives thereof used in the present invention, there are 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.
With regard to the p-aminophenol system developing agents used in the present invention, there are N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyphenyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, o-methoxy-p-(N,N-dimethylamino)phenol, o-methoxy-p-(N-methylamino)phenol, etc. and, in particular, N-methyl-p-aminophenol and aminophenols described in JP-A-9-297377 and JP-A-9-297378 are preferred.
The dihydroxybenzene-series developing agent is preferably used in an amount of generally from 0.05 to 0.8 mol/L. When a dihydroxybenzene compound and a 1-phenyl-3-pyrazolidone compound or a p-aminophenol compound are used in combination, the former is preferably used in an amount of from 0.05 to 0.6 mol/L, and more preferably from 0.10 to 0.5 mol/L, and the latter is preferably used in an amount of 0.06 mol/L or less, and more preferably from 0.003 to 0.03 mol/L.
The ascorbic acid derivative developing agent is preferably used in an amount of 0.01 to 0.5 mol/L, and more preferably 0.05 to 0.3 mol/L. When using an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone or a p-aminophenol in combination, it is preferable to use 0.01 to 0.5 mol/L of the ascorbic acid derivative and 0.005 to 0.2 mol/L of the 1-phenyl-3-pyrazolidone or p-aminophenol.
The developing solution used in processing the light-sensitive material of the present invention may contain an additive (e.g. a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent) that is commonly used. Specific examples thereof are described below, but the present invention is by no means limited thereto.
Examples of the buffer for use in the developing solution used in processing the light-sensitive material of the present invention include carbonates, boric acids described in JP-A-62-186259, saccharides (e.g. saccharose) described in JP-A-60-93433, oximes (e.g. acetoxime), phenols (e.g. 5-sulfosalicylic acid), and tertiary phosphates (e.g. sodium salt and potassium salt), with carbonates and boric acids being preferred. The buffer, particularly the carbonate, is preferably used in an amount of 0.05 mol/L or more, particularly preferably from 0.08 to 1.0 mol/L.
In the present invention, both the developer starter solution and the developer replenisher preferably have the property that, when 0.1 mol of sodium hydroxide is added to 1 L thereof, the increase in the range of 0.2 to 1.5. With regard to a method for confirming that the developer starter solution or the developer replenisher that is used has the above-mentioned property, the pH of the developer starter solution or the developer replenisher that is to be tested is adjusted to 10.5, 0.1 mol of sodium hydroxide is added to 1 L of the liquid, the pH of the mixture is measured, and it is determined that the solution or the replenisher has the above-mentioned property if the increase in pH is no greater than 0.5. In the present invention, it is particularly preferable to use a developer starter solution or a developer replenisher that shows an increase in pH of no greater than 0.4 in the above-mentioned test.
Examples of the preservative for use in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde-sodium bisulfite. The sulfite is used in an amount of preferably 0.2 mol/L or more, and particularly preferably 0.3 mol/L or more, but if too much is added, silver staining in the developing solution is caused. Accordingly, the upper limit is preferably 1.2 mol/L. The amount is particularly preferably from 0.35 to 0.7 mol/L.
As a preservative for the dihydroxybenzene system developing agent, a small amount of the above-mentioned ascorbic acid derivative can be used in combination with the sulfite. It is preferable to use sodium erythorbate in terms of material cost. The amount added is preferably in the range of 0.03 to 0.12 as a molar ratio relative to the dihydroxybenzene system developing agent, and particularly preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as the preservative, the developing solution preferably does not contain a boron compound.
Examples of additives that can be used other than those described above include a development inhibitor, such as sodium bromide or potassium bromide; an organic solvent, such as ethylene glycol, diethylene glycol, triethylene glycol, or dimethylformamide; a development accelerator, such as an alkanolamine like diethanolamine or triethanolamine, or an imidazole or a derivative thereof; and a physical development unevenness inhibitor, such as a heterocyclic mercapto compound (e.g. sodium 3-(5-mercaptotetrazol-1-yl)benzene sulfonate, 1-phenyl-5-mercaptotetrazole) or the compounds described in JP-A-62-212651.
Further, a mercapto-series compound, an indazole-series compound, a benzotriazole-series compound, or a benzimidazole-series compound may be added as an antifoggant or a black spot (black pepper) inhibitor. Specific examples thereof include 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl)thio)butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount thereof added is generally from 0.01 to 10 mmol, preferably from 0.1 to 2 mmol, per L of the developing solution.
Further, various kinds of organic or inorganic chelating agents can be used individually or in combination in the developing solution for use in the present invention.
Examples of the inorganic chelating agent include sodium tetrapolyphosphate and sodium hexametaphosphate.
Examples of the organic chelating agent mainly include an organic carboxylic acid, an aminopolycarboxylic acid, an organic phosphonic acid, an aminophosphonic acid, and an organic phosphonocarboxylic acid.
Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, itaconic acid, malic acid, citric acid, and tartaric acid.
Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycolethertetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycoletherdiaminetetraacetic acid, and compounds described in JP-A-52-25632, JP-A-55-67747, JP-A-57-102624 and JP-B-53-40900.
Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acids, described in U.S. Pat. Nos. 3,214,454 and 3,794,591 and West German Patent Publication (OLS) No. 2,227,369, and the compounds described in Research Disclosure, Vol. 181, Item 18170 (May 1979).
Examples of the aminophosphonic acid include aminotris(methylenephosphonic acid), ethylenediamine tetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the compounds described in Research Disclosure, No. 18170 (supra), JP-A-57-208554, JP-A-54-61125, JP-A-55-29883, and JP-A-56-97347.
Examples of the organic phosphonocarboxylic acid include the compounds described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-4024, JP-A-55-4025, JP-A-55-126241, JP-A-55-65955, JP-A-55-65956, and Research Disclosure, No. 18170 (supra).
The organic and/or inorganic chelating agents are not limited to those described above. The organic and/or inorganic chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The amount of the chelating agent added is preferably from 1 x 10^-4 to 1 x 10^-1 mol, and more preferably from 1 x 10^-3 to 1 x 10^-2 mol, per L of the developing solution.
Examples of a silver stain inhibitor added to the developing solution include the compounds described in JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, JP-A-4-362942, and JP-A-8-6215; triazines having one or more mercapto groups (for example, the compounds described in JP-B-6-23830, JP-A-3-282457, and JP-A-7-175178); pyrimidines having one or more mercapto groups (e.g. 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4,6-trimercaptopyrimidine, compounds described in JP-A-9-274289); pyridines having one or more mercapto groups (e.g. 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, compounds described in JP-A-7-248587); pyrazines having one or more mercapto groups (e.g. 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine); pyridazines having one or more mercapto groups (e.g. 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine); the compounds described in JP-A-7-175177,and polyoxyalkylphosphates described in U.S. Pat. No. 5,457,011. These silver stain inhibitors may be used individually or in a combination of two or more.
The amount thereof added is preferably from 0.05 to 10 mmol, and more preferably from 0.1 to 5 mmol, per L of the developing solution.
The developing solution may contain a compound described in JP-A-61-267759, as a dissolution aid.
Further, the developing solution may contain a color toner, a surfactant, an antifoaming agent, or a hardening agent, if necessary.
The pH of the developing solution is preferably in the range of 9.0 to 11.0, particularly preferably 9.6 to 11.0. The alkali agent used for adjusting the pH may be a usual water-soluble inorganic alkali metal salt (e.g. sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate).
When the specific gravity of the developing solution is too high, there is a tendency for the density of blackened areas of the exposed light-sensitive material to be low. The specific gravity of the developing solution used is preferably 1.100 or below, more preferably 1.020 to 1.100, and yet more preferably 1.040 to 1.100.
With respect to cations of the developing solution, potassium ions do not inhibit development compared with sodium ions and the indentations on the periphery of the blackened portion, called a fringe, are smaller. When the developing solution is stored as a concentrated solution, a potassium salt is generally preferred because of its higher solubility. However, since, in the fixing solution, the potassium ions cause fixing inhibition at the same level as is caused by silver ions, if the developing solution has a high potassium ion concentration the developing solution is carried over by the light-sensitive material to disadvantageously increase the potassium ion concentration in the fixing solution. Accordingly, the molar ratio of potassium ion to sodium ion in the developing solution is preferably between 20:80 and 80:20. The ratio of potassium ion to sodium ion can be freely controlled within the above-described range by a counter cation such as a pH buffer, a pH-adjusting agent, a preservative, or a chelating agent.
In the continuous development processing of the present invention, the amount of the developing solution that is replenished is generally 390 ml or less, preferably from 30 to 325 ml, more preferably from 120 to 250 ml, per m² of the light-sensitive material. The developer replenisher may have the same composition and/or concentration as the developer starter solution, or it may have a different composition and/or concentration from the starter solution.
Examples of a fixing agent in a fixing solution for use in the present invention include ammonium thiosulfate, sodium thiosulfate, and ammonium sodium thiosulfate. The amount of the fixing agent used may be varied appropriately, but it is generally from about 0.7 to about 3.0 mol/L.
The fixing solution for use in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt, which acts as a hardening agent, and of these salts, a water-soluble aluminum salt is preferred. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, ammonium aluminum sulfate, aluminum nitrate, and aluminum lactate. These are each preferably contained, in terms of an aluminum ion concentration in the solution used, in an amount of from 0.01 to 0.15 mol/L.
When the fixing solution is stored as a concentrated solution or a solid agent, it may be constituted by a plurality of parts, preparing the hardening agent or the like as a separate part, or it may be constituted as a one-part agent containing all components.
The fixing solution can contain, as desired, a preservative (for example, a sulfite, a bisulfite, a metabisulfite, etc. at 0.015 mol/L or more, and preferably 0.02 to 0.3 mol/L), a pH buffer solution (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc. at 0.1 to 1 mol/L, and preferably 0.2 to 0.7 mol/L), and a compound having an ability to stabilize aluminum or an ability to soften hard water (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, Tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediamine tetraacetic acid, nitrilotriacetic acid, derivatives thereof, salts thereof, saccharides, etc. at 0.001 mol/L to 0.5 mol/L, and more preferably 0.005 mol/L to 0.3 mol/L), and in terms of recent concerns related to protection of the environment it is preferable for the fixing solution not to contain a boron system compound.
In addition, the fixing solution may contain a compound described in JP-A-62-78551, a pH-adjusting agent (e.g. sodium hydroxide, ammonia, sulfuric acid), a surfactant, a wetting agent, or a fixing accelerator. Examples of the surfactant include anionic surfactants, such as sulfated products and sulfonated products; polyethylene-series surfactants, and amphoteric surfactants described in JP-A-57-6840. A known antifoaming agent may also be used. Examples of the wetting agent include alkanolamines and alkylene glycols. Examples of the fixing accelerator include alkyl- or aryl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681; thiourea derivatives described in JP-B-45-35754, JP-B-58-122535, and JP-B-58-122536; alcohols having a triple bond within the molecule; thioether compounds described in U.S. Pat. No. 4,126,459; mercapto compounds described in JP-A-64-4739, JP-A-1-4739, JP-A-1-159645, and JP-A-3-101728; and thiocyanates and meso-ionic compounds described in JP-A-4-170539.
The fixing solution for use in the present invention preferably has a pH of 4.0 or above, and more preferably from 4.5 to 6.0. The pH of the fixing solution increases due to mingling of the developing solution upon processing and, in this case, a hardening fixing solution has a pH of 6.0 or less, and preferably 5.7 or below, and a non-hardening fixing solution has a pH of 7.0 or below, and preferably 6.7 or below.
The amount of the fixing solution replenished is 500 ml or less, preferably 390 ml or less, and more preferably from 80 to 320 ml, per m² of the light-sensitive material. The replenisher may have the same composition and/or concentration as the starter solution, or it may have a composition and/or a concentration different from the starter solution.
The fixing solution may be regenerated and reused using a known fixing solution regenerating method, such as electrolytic silver recovery. An example of the regenerator includes model FS-2000 manufactured by Fuji Photo Film, Co., Ltd.
It is also preferred to remove dyes or the like by the use of an adsorption filter, such as activated carbon.
When the developing and fixing solutions used in the present invention are in liquid form, they are preferably stored using a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. When these liquids are in the form of a concentrated liquid, 1 part of the concentrated liquid is diluted with 0.2 to 3 parts of water so as to achieve a predetermined concentration before use.
Use of a developer and a fixer in solid form in the present invention can give the same results as those with the solutions. The solid processing agents are described below.
The solid agents used in the present invention can be in any known form (powder, grain, granule, lump, tablet, compactor, briquette, tabular, rod, paste, etc.). These solid agents can be coated with a water-soluble coating agent or film in order to separate components that react with each other on contact, or may have a multi-layer structure so as to separate components that react with each other, or the two methods can be employed in combination.
With regard to a coating agent and a granulation aid, a known material can be used, but it is preferable to use polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid or a vinyl series compound. In addition, that described in column 2, line 48 to column 3, line 13 of JP-A-5-45805 can be referred to.
In the case of a multi-layer structure, components that do not react with each other on contact may be sandwiched between components that react with each other, and they are then formed into tablets, briquettes, etc. Alternatively, components in a known form may be formed into a similar layer structure and then packaged. These methods are described in JP-A-61-259921, JP-A-4-16841, JP-A-4-78848, JP-A-5-93991, etc.
The bulk density of the solid processing agents is preferably 0.5 to 6.0 g/cm³, and particularly preferably 1.0 to 5.0 g/cm³ for tablets and 0.5 to 1.5 g/cm³ for granules.
With regard to a method for producing the solid processing agents used in the present invention, any known method can be employed. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, JP-A-4-78848, JP-A-5-93991, JP-A-4-85533, JP-A-4-85534, JP-A-4-85535, JP-A-5-134362, JP-A-5-197070, JP-A-5-204098, JP-A-5-224361, JP-A-6-138604, JP-A-6-138605, JP-A-8-286329, etc. can be referred to.
More specifically, a rolling granulation method, an extrusion granulation method, a compression granulation method, a crushing granulation method, a stirring granulation method, a spray drying method, a dissolution-solidification method, a briquetting method, a roller compacting method, etc. can be employed.
The solubility of the solid agents used in the present invention can be controlled by varying the surface state (smoothness, porosity, etc.) or the partial thickness or by making a hollow doughnut form. Furthermore, it is possible to introduce different solubilities to a plurality of granulated materials or employ a plurality of forms so as to adjust the degree of solubility of materials having different solubilities. Moreover, multi-layered granules having different compositions for their surface and interior may be used.
The solid agents are preferably packaged using a material having low oxygen and moisture permeability, and the packaging material can be in any known form such as a bag, a tube, or a box. It is also preferable to make a foldable form as disclosed in JP-A-6-242585 to JP-A-6-242588, JP-A-6-247432, JP-A-6-247448, JP-A-6-301189, JP-A-7-5664 and JP-A-7-5666 to JP-A-7-5669 in terms of saving storage space for waste packaging materials. These packaging materials may have a screw cap, a pull top or an aluminum seal in an outlet through which the processing agent is taken out, and the packaging materials may be heat-sealed; it is also possible to employ other known materials, and they are not particularly limited. The waste packaging materials are preferably recycled or reused from the viewpoint of environmental protection.
The method for dissolving and replenishing the solid processing agents of the present invention is not particularly limited, and a known method can be employed. Examples of such a method include a method involving dissolving a predetermined amount of a solid processing agent using a dissolution device having a stirring function and replenishing it, a method involving dissolving a solid processing agent in a dissolution device having a dissolution section and a stock section for a finished solution as described in JP-A-9-80718 and replenishing the solution from the stock section, a method for dissolution and replenishment involving charging a processing agent into a circulation system of an automatic processor as described in JP-A-5-119454, JP-A-6-19102 and JP-A-7-261357, a method involving charging a processing agent into an automatic processor with a built-in dissolution bath as the processing of a light-sensitive material progresses so as to dissolve the agent, and any other known methods can be used. The charging of the processing agent can be carried out manually or using a dissolution device having an unsealing mechanism as described in JP-A-9-138495 or an automatic processor for automatic unsealing and automatic charging, and the use of the latter devices is preferred in terms of the working environment. More specifically, there are methods in which the inlet is pierced, peeled off, cut out or pushed in, methods described in JP-A- 6-19102 and JP-A-6-95331, etc.
The light-sensitive material processed through development and fixing is then subjected to water-washing or stabilization (hereinafter, unless otherwise specified, water-washing includes stabilization, and the solution for use therein is called water or washing water). The water for use in water-washing may be tap water, ion exchanged water, distilled water, or a stabilizing solution. The amount of the washing water replenished is generally from about 8 to about 17 L per m² of the light-sensitive material, but an amount lower than the above-described range may also be used. In particular, when the amount replenished is 3 L or less (including 0, namely, standing water washing), not only can the processing achieve water savings, it can also dispense with piping for installation of an automatic developing machine. When water-washing is performed with a small amount of water replenished, a rinsing tank of a squeeze roller or a crossover roller, described in JP-A-63-18350 and JP-A-62-287252, is preferably provided. Alternatively, addition of various oxidizing agents (e.g. ozone, hydrogen peroxide, sodium hypochlorite, an active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide salt) or filtration may be combined, so as to reduce the pollution load, which is a problem incurred in the case of water-washing with a small amount of water, or for preventing water scale.
As the method for reducing the amount of washing water replenished, a multi-stage countercurrent system (for example, two or three stages) has been known for a long time, and the amount of washing water replenished is preferably from 50 to 200 ml per m² of the light-sensitive material. This effect can also be obtained similarly in the case of an independent multi-stage system (a method not using a countercurrent system but supplying a new solution individually to the multi-stage water-washing tanks).
In the method in the present invention, a means for preventing water scale may be provided in the water-washing step. The water-scale-preventing means is not particularly restricted, and a known means may be used. Examples thereof include a method of adding a fungicide (a so-called water scale inhibitor), a method of passing electricity, a method of irradiating with ultraviolet rays, infrared rays, or far infrared rays; a method of applying a magnetic field, a method of treating with ultrasonic waves, a method of applying heat, and a method of emptying the tank on standing. The water-scale-preventing means may be applied according to the processing of the light-sensitive material; it may be applied at a predetermined interval irrespective of the state of use, or it may be applied only during a non-processing period, such as nighttime. Further, the washing water may be pretreated with a water-scale-preventing means and then replenished. Further, in view of preventing the generation of resistant microbes, it is preferred to employ different water-scale-preventing means at predetermined intervals.
It is possible to employ a combination of a water-saving water-scale-preventing machine model AC-1000 manufactured by Fuji Photo Film, Co., Ltd. and a water-scale-preventing agent AB-5 manufactured by Fuji Photo Film, Co., Ltd., and a method described in JP-A-11-231485 can be used.
he fungicide is not particularly restricted, and a known fungicide may be used. Examples thereof include, in addition to the above-described oxidizing agents, glutaraldehyde; a chelating agent, such as aminopolycarboxylic acid; a cationic surfactant; and a mercaptopyridine oxide (e.g. 2-mercaptopyridine-N-oxide), and a sole fungicide may be used, or a plurality of fungicides may be used in combination.
The electricity may be passed according to the method described in JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, or JP-A-4-18980.
In addition, a known water-soluble surfactant or antifoaming agent may be added, so as to prevent uneven processing due to bubbling, or to prevent stain transfer. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the water-washing system, so as to prevent stains due to a dye dissolved out from the light-sensitive material.
The overflow solution from the water-washing step may be partly or wholly used by mixing it with a processing solution having fixing ability, as described in JP-A-60-235133. It is also preferred, from the viewpoint of conservation of the natural environment, to reduce the biochemical oxygen demand (BOD), chemical oxygen demand (COD), or iodine consumption before discharge, by subjecting the solution to a microorganism treatment (for example, sulfur oxidizing bacteria or activated sludge treatment, or treatment with a filter having a porous carrier, such as activated carbon or a ceramic carrying microorganisms thereon) or oxidation treatment with an oxidizing agent or electrification, or to reduce the silver concentration in waste water by passing the solution through a filter, using a polymer having affinity for silver, or by adding a compound that forms a hardly soluble silver complex, such as trimercaptotriazine, to precipitate silver, and then passing the solution through a filter.
In some cases, stabilization may be performed subsequent to the water-washing, and as one example, a bath containing a compound described in JP-A-2-201357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446 may be used as a final bath for the light-sensitive material. This stabilization bath may also contain, if desired, an ammonium compound, a metal compound, such as Bi or Al, a fluorescent whitening agent, various chelating agents, a film pH-adjusting agent, a hardening agent, a bactericide, a fungicide, an alkanolamine, or a surfactant.
The additives, such as the fungicide and the stabilizing agent added to the water-washing or stabilization bath, may be formed into a solid agent, similarly to the above-described developing and fixing processing agents.
Wastewater of the developing solution, the fixing solution, the washing water, or the stabilizing solution for use in the present invention, is preferably burned for disposal. The wastewater can also be formed into a concentrated solution or a solid by a concentrating apparatus, as described, for example, in JP-B-7-83867 and U.S. Pat. No. 5,439,560, and then disposed of.
When the amount of the processing agent replenished is reduced, it is preferred to prevent evaporation or air oxidation of the solution by reducing the contact area of the processing tank with air. A roller transportation-type automatic-developing machine is described, for example, in U.S. Pat. Nos. 3,025,779 and 3,545,971, and in the present specification, it is simply referred to as a roller transportation-type automatic processor. This automatic processor includes four steps of development, fixing, water-washing, and drying, and it is most preferred to follow this four-step processing also in the present invention, though other steps (e.g. a stopping step) are not excluded. Further, a rinsing bath may be provided between development and fixing, and/or between fixing and water-washing.
In the development processing in the present invention, the dry-to-dry time is preferably from 25 to 160 seconds, the development and fixing time is 40 seconds or less, preferably from 6 to 35 seconds, and the temperature of each solution is preferably from 25 to 50°C, and more preferably from 30 to 40°C. The temperature and the time of water-washing are preferably from 0 to 50°C and 40 seconds or less, respectively. According to the method in the present invention, the light-sensitive material after development, fixing, and water-washing may be passed through squeeze rollers, for squeezing out the washing water, and then dried. The drying is generally performed at a temperature of from about 40°C to about 100°C. The drying time may be appropriately varied depending upon the ambient conditions. The drying method is not particularly restricted, and any known method may be used, but hot-air drying, and drying by far infrared rays or a heat roller as described in JP-A-4-15534, JP-A-5-2256, and JP-A-5-289294 may be used, and a plurality of drying methods may also be used in combination.

EXAMPLES

The present invention will be described in more detail with reference to the following examples, but the invention should not be construed as being limited thereto.

Example 1

Preparation of Emulsion A

Solution 1
Water	750 ml
Gelatin	20 g
Sodium chloride	3 g
1,3-Dimethylimidazolidine-2-thione	20 mg
Sodium benzenethiosulfonate	10 mg
Citric acid	0.7 g

Solution 2
Water	300 ml
Silver nitrate	150 g

Solution 3
Water	300 ml
Sodium chloride	38 g
Potassium bromide	32 g
Potassium hexachloroiridate (III)(0.005% in 20% aqueous KCI solution)	5 ml
Ammonium hexachlororhodate(0.001% in 20% aqueous NaCI solution)	7 ml

The potassium hexachloroiridate (III) (0.005% in 20% aqueous KCI solution) and ammonium hexachlororhodate (0.001% in 20% aqueous NaCI solution) used in Solution 3 were prepared by dissolving powders thereof in a 20% aqueous solution of KCI and a 20% aqueous solution of NaCI respectively and heating the solutions at 40°C for 120 minutes.
90% of each of Solution 2 and Solution 3 were simultaneously added over 20 minutes while stirring to Solution 1 that was maintained at 38°C with a pH of 4.5 so as to form grain nuclei having a size of 0.16 µm. Subsequently, Solution 4 and Solution 5 below were added to the above-mentioned mixture over 8 minutes, and the remaining 10 % of each of Solution 2 and Solution 3 were further added thereto over 2 minutes, thereby growing the grains to 0.21 µm. Moreover, 0.15 g of potassium iodide was added thereto and the mixture was ripened for 5 minutes, and the grain formation was thus completed.

Solution 4

Water 100 ml

Silver nitrate 50 g

Solution 5

Water 100 ml

Sodium chloride 13 g

Potassium bromide 11 g

Potassium ferrocyanide 5 mg
Thereafter, the emulsion was washed with water by flocculation according to a standard method. More specifically, the temperature was decreased to 35°C, 3 g of an anionic precipitating agent -1 below was added, and the pH was decreased using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.2 ± 0.2). About 3 L of the supernatant was then removed (first water washing). A further 3 L of distilled water was added to the mixture, and sulfuric acid was added until silver halide precipitated. 3 L of the supernatant was again removed (second water washing). The operational procedure of the second water washing was repeated once more (third water washing), and water-washing and desalting steps were thus completed. After the water-washing and desalting, 45 g of gelatin was added to the emulsion so as to adjust the pH and the pAg to 5.6 and 7.5 respectively. Thereto, 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate, and 10 mg of chloroauric acid were added, and the mixture was thus subjected to chemical sensitization to give it an optimal sensitivity at 55°C. Then, 100 mg of 4-hydroxy-6-metyl-1,3,3a,7-tetrazaindene as a stabilizing agent, and 100 mg of Proxel (trade name, manufactured by ICI Co., Ltd.) as an antiseptic were added.
Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol % of silver chloride and 0.08 mol % of silver iodide and having an average grain size of 0.22 µm and a coefficient of variation of 9% was obtained (the final emulsion had a pH of 5.7, a pAg of 7.5, an electrical conductivity of 40 µS/m, a density of 1.2 x 10^-3 kg/m³, and a viscosity of 50 mPa· s).

Preparation of Emulsion B

Solution 1
Water	750 ml
Gelatin	20 g
Sodium chloride	1 g
1,3-Dimethylimidazolidine-2-thione	20 mg
Sodium benzenethiosulfonate	10 mg
Citric acid	0.7g

Solution 2
Water	300 ml
Silver nitrate	150 g

Solution 3
Water	300 ml
Sodium chloride	38 g
Potassium bromide	32 g
Potassium hexachloroiridate (III) (0.005% in 20% aqueous KCI solution)	5 ml
Ammonium hexachlororhodate (0.001% in 20% aqueous NaCI solution)	15 ml

The potassium hexachloroiridate (III) (0.005% in 20% aqueous KCI solution) and ammonium hexachlororhodate (0.001% in 20% aqueous NaCI solution) used in Solution 3 were prepared by dissolving powders thereof in a 20% aqueous solution of KCI and a 20% aqueous solution of NaCI respectively and heating the solutions at 40°C for 120 minutes.
90% of each of Solution 2 and Solution 3 were simultaneously added over 20 minutes while stirring to Solution 1 that was maintained at 38°C with a pH of 4.5 so as to form grain nuclei having a size of 0.16 µm. Subsequently, 500 mg of 4-hydroxy-6-metyl-1,3,3a,7-tetrazaindene was added to the above-mentioned mixture, Solution 4 and Solution 5 below were then added to the above-mentioned mixture over 8 minutes, and the remaining 10 % of each of Solution 2 and Solution 3 were further added thereto over 2 minutes, thereby growing the grains to 0.18 µm. Moreover, 0.15 g of potassium iodide was added thereto and the mixture was ripened for 5 minutes, and the grain formation was thus completed.

Solution 4

Water 100 ml

Silver nitrate 50 g

Solution 5

Water 100 ml

Sodium chloride 13 g

Potassium bromide 11 g

Potassium ferrocyanide 2 mg
Thereafter, the emulsion was washed with water by flocculation according to a standard method. More specifically, the temperature was decreased to 35°C, 3 g of the anionic precipitating agent -1 below was added, and the pH was decreased using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.2 ± 0.2). About 3 L of the supernatant was then removed (first water washing). A further 3 L of distilled water was added to the mixture, and sulfuric acid was added until silver halide precipitated. 3 L of the supernatant was again removed (second water washing). The operational procedure of the second water washing was repeated once more (third water washing), and water-washing and desalting steps were thus completed. After the water-washing and desalting, 45 g of gelatin was added to the emulsion so as to adjust the pH and the pAg to 5.6 and 7.5 respectively. Thereto, 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 2 mg of triphenylphosphine selenide, and 1 mg of chloroauric acid were added, and the mixture was thus subjected to chemical sensitization to give it an optimal sensitivity at 55°C. Then, 100 mg of 4-hydroxy-6-metyl-1,3,3a,7-tetrazaindene as a stabilizing agent, and 100 mg of Proxel as an antiseptic were added.
Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol % of silver chloride and 0.08 mol % of silver iodide and having an average particle size of 0.18 µm and a coefficient of variation of 10% was obtained (the final emulsion had a pH of 5.7, a pAg of 7.5, an electrical conductivity of 40 µS/m, a density of 1.2 x 10^-3 kg/m³, and a viscosity of 50 mPa· s).

Formulation of light-insensitive silver halide grains 1

Solution 1
Water	1 L
Gelatin	20 g
Potassium bromide	0.9 g
Citric acid	0.2 g
Ammonium nitrate	20 g
Hydrogen peroxide	3.5 g
Sodium benzenethiosulfonate	15 mg

Solution 2
Water	400 ml
Silver nitrate	200 g

Solution 3
Water	400 ml
Potassium bromide	140.0 g
Potassium hexachloroiridate (III) (0.001% aqueous solution)	4000 ml

40 ml of NaOH (1N) was added with stirring to solution 1 maintained at 60°C, and 0.7 g of an aqueous solution of silver nitrate was further added thereto. After that, one half each of solution 2 and solution 3 were added over 20 minutes to the mixture by the controlled double jet method while maintaining the silver potential at +24 mV, the mixture was physically aged for 2 minutes, and the remaining half of each of solution 2 and solution 3 was added over 20 minutes to the mixture by the same controlled double jet method to form grains.
Thereafter, the emulsion was washed with water by flocculation according to a standard method. More specifically, the temperature was decreased to 35°C, 3 g of the anionic precipitating agent -1 below was added, and the pH was decreased using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.1 ± 0.2). About 3 L of the supernatant was then removed (first water washing). A further 3 L of distilled water was added to the mixture, and sulfuric acid was added until silver halide precipitated. 3 L of the supernatant was again removed (second water washing). The operational procedure of the second water washing was repeated once more (third water washing), and water-washing and desalting steps were thus completed. After the water-washing and desalting, 45 g of gelatin was added to the emulsion so as to adjust the pH and the pAg to 5.7 and 7.5 respectively. As an antiseptic, phenoxyethanol was added and Dispersion 1 of a non post-ripened silver iodochlorobromide tetradecahedral grain emulsion 3 containing on average 30 mol % of silver chloride and 0.08 mol % of silver iodide and having an average grain size of 0.8 µm and a coefficient of variation of 10% was obtained (the final emulsion had a pH of 5.7, a pAg of 7.5, an electrical conductivity of 40 µS/m, a density of 1.3 x 10^-3 kg/m³, and a viscosity of 30 mPa· s).
Grains were formed by adding to the aqueous solutions X-1 to X-4 below potassium hexachlororhodium (III) in an amount corresponding to 1 x 10^-5 mol per mole of KBr.

Formulation of light-insensitive silver halide grains 2

Solution 1
Water	1 L
Gelatin	20 g
Sodium chloride	3.0 g
1,3-Dimethylimidazolidine-2-thione	20 mg
Sodium benzenethiosulfonate	8 mg

Solution 2
Water	400 ml
Silver nitrate	100 g

Solution 3
Water	400 ml
Sodium chloride	13.5 g
Potassium bromide	45.0 g
Potassium hexachloroiridate (III) (0.001% aqueous solution)	860 ml

Solution 1, Solution 2 and Solution 3 that were maintained at 70°C with a pH of 4.5 were simultaneously added together over 15 minutes while stirring so as to form grain nuclei. Subsequently, Solution 4 and Solution 5 above were added to the above-mentioned mixture over 15 minutes. Moreover, 0.15 g of potassium iodide was added thereto, and the grain formation was thus completed.
Thereafter, the emulsion was washed with water by flocculation according to a standard method. More specifically, the temperature was decreased to 35°C, 3 g of the anionic precipitating agent -1 below was added, and the pH was decreased using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.2 ± 0.2). About 3 L of the supernatant was then removed (first water washing). A further 3 L of distilled water was added to the mixture, and sulfuric acid was added until silver halide precipitated. 3 L of the supernatant was again removed (second water washing). The operational procedure of the second water washing was repeated once more (third water washing), and water-washing and desalting steps were thus completed. After the water-washing and desalting, 45 g of gelatin was added to the emulsion so as to adjust the pH and the pAg to 5.7 and 7.5 respectively. As an antiseptic, phenoxyethanol was added and Dispersion 1 of a non post-ripened silver iodochlorobromide cubic grain emulsion 2 containing on average 30 mol % of silver chloride and 0.08 mol % of silver iodide and having an average grain size of 0.45 µm and a coefficient of variation of 10% was obtained (the final emulsion had a pH of 5.7, a pAg of 7.5, an electrical conductivity of 40 µS/m, a density of a density of 1.3 x 10³ to 1.35 x 10³ kg/m³, and a viscosity of 50 mPa· s).

Preparation of light-insensitive silver halide grains 3

Preparation of 1st solution

1300 mL of an aqueous solution containing 0.6 g of KBr and 1.1 g of gelatin having an average molecular weight of 15,000 was stirred at 35°C.

Addition 1

24 mL of an Ag-1 aqueous solution (containing 4.9 g of AgNO₃ in 100 mL), 24 mL of an X-1 aqueous solution (containing 4.1 g of KBr in 100 mL), and 24 mL of a G-1 aqueous solution (containing 1.8 g of gelatin having an average molecular weight of 15,000 in 100 mL) were added over 30 seconds at a constant flow rate by a triple jet method.
After that, 1.3 g of KBr was added, and the temperature was raised to 75°C. After the temperature rise, the mixture was aged for 12 minutes and then mixed with 300 mL of a G-2 aqueous solution (containing 12.7 g of gelatin in 100 mL, the gelatin being obtained by reacting an alkali-treated ossein gelatin with trimellitic acid anhydride at 50°C and a pH of 9.0, then removing the residual trimellitic acid), and 2.1 g of disodium 4,5-dihydroxy-1,3-disulfonate hydrate and 0.002 g of thiourea dioxide were then added in succession at a time interval of 1 minute.

Addition 2

Next, 157 mL of an Ag-2 aqueous solution (containing 22.1 g of AgNO₃ in 100 mL) and an X-2 aqueous solution (containing 15.5 g of KBr in 100 mL) were added over 14 minutes by the double jet method. At this point, the A-2 aqueous solution was added while accelerating the flow rate so that the final flow rate became 3.4 times the initial flow rate, and the X-2 aqueous solution was added so as to maintain the pAg of the bulk emulsion in the reactor at 8.3.

Addition 3

Next, 329 mL of an Ag-3 aqueous solution (containing 32.0 g of AgNO₃ in 100 mL) and an X-3 aqueous solution (containing 21.5 g of KBr and 1.6 g of KI in 100 mL) were added over 27 minutes by the double jet method. At this point, the A-3 aqueous solution was added while accelerating the flow rate so that the final flow rate became 1.6 times the initial flow rate, and the X-3 aqueous solution was added so as to maintain the pAg of the bulk emulsion in the reactor at 8.3.

Addition 4

Next, 156 mL of an Ag-4 aqueous solution (containing 32.0 g of AgNO₃ in 100 mL) and an X-4 aqueous solution (containing 22.4 g of KBr in 100 mL) were added over 17 minutes by the double jet method. At this point, the A-4 aqueous solution was added at a constant flow rate, and the X-4 aqueous solution was added so as to maintain the pAg of the bulk emulsion in the reactor at 8.3.
After that, 0.0025 g of sodium benzenethiosulfonate and 125 mL of a G-3 aqueous solution (containing 12.0 g of the alkali-treated ossein gelatin in 100 mL) were added in succession to the mixture at a time interval of 1 minute.
Next, 43.7 g of KBr was added, the pAg of the bulk emulsion in the reactor was adjusted to 9.0, and 73.9 g of Agl fine particles (containing 13.0 g of Agl fine particles having an average particle size of 0.047 µm in 100 g) was then added.

Addition 5

2 minutes later, 249 mL of the Ag-4 aqueous solution and the X-4 aqueous solution were added by the double jet method. At this point, the Ag-4 aqueous solution was added over 16 minutes at a constant flow rate, and the X-4 aqueous solution was added so as to maintain the pAg at 9.10.

Addition 6

For the following 10 minutes, addition was carried out so as to keep the pAg of the bulk emulsion in the reactor adjusted to 7.5.
The salts were then removed by a standard flocculation method, and water, NaOH, and the alkali-treated ossein gelatin were added so as to adjust the pH and pAg at 56°C to 5.8 and 8.9, respectively.
The grains so obtained comprised tabular silver halide grains having a circle-equivalent diameter of 1.0 µm, a grain thickness of 0.10 µm, an average Agl content of 3.94 mol %, a (111) plane as the parallel principal plane, and a coefficient of variation of the circle-equivalent diameter for all the grains of 24%.
Average molecular weight 120,000

Preparation of coated sample

A sample was prepared by coating the materials on a polyethylene terephthalate film support, which will be described below, having on both its surfaces a moisture-resistant undercoat layer containing vinylidene chloride so as to give a layer structure comprising UL layer/emulsion layer/lower protective layer/upper protective layer.
The methods of preparation, amounts coated and coating methods for each of the layers are explained below.

Emulsion Layer

Emulsion A and Emulsion B were mixed at a ratio of 1:2, and 5.7 x 10^-4 mol/mol Ag of a sensitizing dye (SD-1) was added to the mixture so as to carry out spectral sensitization.

KBr	3.4 x 10^-4 mol/mol Ag
Compound (Cpd-1)	2.0 x 10^-4 mol/mol Ag
Compound (Cpd-2)	2.0 x 10^-4 mol/mol Ag
Compound (Cpd-3)	8.0 x 10^-4 mol/mol Ag
4-hydroxy-6-metyl-1,3,3a,7-tetrazaindene	1.2 x 10^-4 mol/mol Ag
Hydroquinone	1.2 x 10^-2 mol/mol Ag
Citric acid	3.0 x 10^-4 mol/mol Ag
Hydrazine derivative (as shown in Table 18)	1.5 x 10^-4 mol/mol Ag
Nucleation-accelerator (Cpd-4)	6.0 x 10^-4 mol/mol Ag
Compounds represented by general formula (I) (as shown in Table 18)

Sodium 2,4-dichloro-6-hydroxy-1,3,5-triazine	90 mg/m²
Colloidal silica (having a particle size of 10 µm)	15 wt % relative to the gelatin
Aqueous latex (aqL-6)	100 mg/m²
Polyethylacrylate latex	150 mg/m²
Latex copolymer of methyl acrylate, sodium 2-acrylamido-2 methylpropanesulfonate, and 2-acetoxyethyl methacrylate (ratios by weight 88:5:7)	150 mg/m²a
Core-shell type latex (core: styrene/butadiene copolymer (ratio by weight 37/63)	150 mg/m²
Compound (Cpd-7)	4wt % relative to the gelatin

were added to the mixture, and the pH of the coating solution so obtained was adjusted to 5.6 using citric acid. The emulsion layer coating solution thus prepared was coated on the support below so that the amount of Ag was 3.0 g/m² and the amount of gelatin was 1.3 g/m².

Upper protective layer
Gelatin	0.3 g/m²
Amorphous silica matting agent of av. 3.5 µm	25 mg/m²
Compound (Cpd-7) (gelatin dispersion)	20 mg/m²
Colloidal silica having a particle size of 10 to 20 µm	30 mg/m²
(Snowtex C, manufactured by Nissan Chemical Industries, Ltd.)
Compound (Cpd-8)	50 mg/m²
Sodium dodecylbenzenesulfonate	20 mg/m²
Compound (Cpd-9)	20 mg/m²
Compound (Cpd-10)	20 mg/m²
Antiseptic (Proxel, manufactured by ICI Co., Ltd.)	1 mg/m²

Lower protective layer
Gelatin	0.5 g/m²
Light-insensitive silver halide grains	0.1 g/m²
Compound (Cpd-11)	15 mg/m ²
1,5-Dihydroxy-2-benzaldoxime	10 mg/m²
Polyethyl acrylate latex	150 mg/m²
Compound (Cpd-12)	3 mg/m²
Antiseptic (Proxel)	1.5 mg/m²

UL layer
Gelatin	0.5 g/m²
Light-insensitive silver halide grains (as shown in Table 18)	0.3 g/m²
Polyethyl acrylate latex	150 mg/m²
Compounds represented by general formula (I) (as shown in Table 18)

	Ref. Table 18
Compound (Cpd-6)	40 mg/m²
Compound (Cpd-13)	10 mg/m²
Antiseptic (Proxel)	1.5 mg/m²

The viscosity of each of the coating solutions for the respective layers was adjusted by adding a viscosity increasing agent represented by structure (Z) below. Viscosity-increasing agent

Further, the samples used in the present invention had a back layer and an electrically conductive layer having the following compositions.

Back layer
Gelatin	3.3 g/m²
Light-insensitive silver halide grains (as shown in Table 18)	0.3 g/m²
Compound (Cpd-14)	40 mg/m²
Compound (Cpd-15)	20 mg/m²
Compound (Cpd-16)	90 mg/m²
Compound (Cpd-17)	40 mg/m²
Compound (Cpd-18)	26 mg/m²
Compound (Cpd-19)	5 mg/m ²
1,3-Divinylsulfonyl-2-propanol	60 mg/m²
Fine grains of polymethyl methacrylate	30 mg/m²
(average grain size 6.5 µm)
Liquid paraffin	78 mg/m²
Compound (Cpd-6)	120 mg/m²
Calcium nitrate	20 mg/m²
Antiseptic (Proxel)	12 mg/m²

Electrically conductive layer
Gelatin	0.1 g/m²
Sodium dodecylbenzenesulfonate	20 mg/m²
SnO₂/Sb	200 mg/m²
(9/1 ratio by weight, average grain size 0.25 µm)
Antiseptic (Proxel)	0.3 mg/m²

Support

First and second undercoat layers having the compositions below were coated in that order on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness 100 µm).

First undercoat layer
Core-shell type vinylidene chloride copolymer 1	15 g
2,4-Dichloro-6-hydroxy-s-triazine	0.25 g
Fine polystyrene particles (average particle size 3 µm)	0.05 g
Compound (Cpd-20)	0.20 g
Colloidal silica (Snowtex ZL: particle size 70 to 100 µm, manufactured by Nissan Chemical Industries, Ltd.)	0.12 g
Water	100g

The pH of the coating solution was adjusted to 6 using a 10 wt % aqueous KOH solution and the coating solution was coated on both surfaces of the support and dried at 180°C for 2 minutes to give a dry thickness of 0.9 µm.

Second undercoat layer
Gelatin	1 g
Methyl cellulose	0.05 g
Compound (Cpd-21)	0.02 g
C₁₂H₂₅O(CH₂CH₂O)₁₀H	0.03 g
Proxel	3.5 x 10^-3 g
Acetic acid	0.2 g
Water	100g

The coating solution was coated on the first undercoat layers and dried at 170°C for 2 minutes to give a dry thickness of 0.1 µm.

Coating method

On the support on which the above-mentioned undercoat layers had been coated, four layers comprising a UL layer, an emulsion layer, a lower protective layer and an upper protective layer were coated on the support in that order as the emulsion layer side by simultaneous multilayer coating by a slide bead coater method at 35°C while adding a hardening agent, and the sample was passed through a cold air setting zone (5°C). Subsequently, on the side of the support opposite to the emulsion layer side, an electrically conductive layer and a back layer were coated in that order by simultaneous multilayer coating by a curtain coater method while adding a hardening agent, and the sample was passed through a cold air setting zone (5°C). At the points when the sample had passed the respective setting zones the coating solutions had set adequately. Subsequently, both surfaces were simultaneously dried in a drying zone under the drying conditions below. After coating the back layer side, the sample was transported without making contact with any material, including rollers, until it was wound up. The coating speed at this time was 200 m/min.

Drying conditions

After the layers had set, the sample was dried with dry air at 30°C until the ratio by weight of water to gelatin became 800% and then with dry air at 35°C/30% until it changed from 800% to 200%; the application of the dry air was continued. 30 seconds after the surface temperature became 34°C, the sample was dried with air at 48°C/2% for 1 minute. The drying time was 50 seconds from the start of drying to the water to gelatin ratio becoming 800%, 35 seconds for the ratio changing from 800% to 200%, and 5 seconds from the ratio being 200% to the completion of drying.
This sensitive material was rewound at 25°C and 55% RH and subjected to a thermal treatment at 35°C and 30% RH for 72 hours. Subsequently, it was cut at 25°C and 55% RH, conditioned at 25°C and 50% RH for 8 hours in a barrier bag that had been conditioned for 6 hours, and then hermetically sealed together with cardboard that had been conditioned at 25°C and 50% RH for 2 hours, thereby giving the samples shown in Table 18. For comparison, samples that has not been subjected to the thermal treatment after rewinding were prepared.
The humidity within the barrier bag was measured and found to be 45% RH. The pH of the film surface on the emulsion layer side of the sample so obtained was 5.5 to 5.8, and the pH of the film surface on the back layer side was 6.0 to 6.5. The absorption spectra of the emulsion layer side and the back layer side were as shown in FIG. 1. Measurement of the absorption spectra was carried out using a model U-3500 spectrophotometer manufactured by Hitachi, Ltd. by removing the coating of a sample on the side opposite to the side that was to be measured and placing the sample in a 200 mm integrating sphere arranged in a sample chamber.
Evaluation was carried out as follows.

Evaluation of photographic characteristics

The samples so obtained were exposed to xenon flash light for a radiation time of 10^-6 s via an interference filter having a peak at 667 nm and a step wedge.

The sample was then processed using an automatic processor model FG-680A (manufactured by Fuji Photo Film Co., Ltd.) with developing solution A and fixing solution B having the formulations below under development conditions of 35°C and 30 s.

Formulation of Developing solution A
1 L of concentrated developing solution A
Water	600ml
Potassium hydroxide	105.0 g
Diethylenetriaminepentaacetic acid	6.0 g
Potassium carbonate	120.0 g
Sodium metabisulfite	120.0 g
Potassium bromide	9.0 g
Hydroquinone	75.0 g
5-Methylbenzotriazole	0.24 g
4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone	1.35 g
Sodium 2-mercaptobenzimidazole-5-sulfonate	0.432 g
4-(N-carboxymethyl-N-methylamino-2,6-dimercaptopyrimidine	0.18 g
2-(N-carboxymethyl-N-methylamino-4,6-dimercaptopyrimidine	0.06 g
Sodium erythorbate	9.0 g
Diethylene glycol	60.0 g

The pH was adjusted to 10.7 by adding potassium hydroxide and water to make 1 L.

The starting solution was prepared by mixing the above-mentioned solution and water at 1:3 (the pH was 10.40). The replenisher was prepared by mixing the above-mentioned solution and water at 1:2 (the pH was 10.45). The amount of replenisher was 100 ml per full size sheet (50.8 x 61.0 cm), or 323 ml per m².

Formulation of fixing solution B
1 L of concentrated fixing solution B
Ammonium thiosulfate	360 g
Disodium ethylenediaminetetraacetate dihydrate	0.09 g
Sodium thiosulfate pentahydrate	33.0 g
Sodium metabisulfite	57.0 g
Sodium hydroxide	37.2 g
Acetic acid (100%)	90 g
Tartaric acid	8.7 g
Sodium gluconate	5.1 g
Aluminum sulfate	25.2 g
pH	4.85

When the fixing solution was used, 1 part of the above-mentioned concentrated solution was diluted with 2 parts of water. The pH of the solution used was 4.8.
The sensitivity was expressed as the reciprocal of the light exposure which gave a density of fog +1.5, and a relative sensitivity was obtained using the value for Sample No. 1 shown in Table 18 as 100. The larger the value, the higher the sensitivity.

Storage stability of light-sensitive material

The samples prepared as shown in Table 18 were stored at 50°C and 45% RH for 5 days as an accelerated storage test, the sensitometry was evaluated, and the sensitivity S1.5 (thermo) was obtained. The sensitivity variation (ΔS1.5) relative to the Fr sample (S1.5(Fr)) (not subjected to the accelerated test) was obtained on a percentage basis using the equation below. Sensitivity variation (ΔS1.5) = (S1.5 (thermo) - S1.5(Fr)) / S1.5(Fr) x 100
When the sensitivity increased, the value was positive, whereas when the sensitivity decreased, the value was negative. A smaller value is preferred, and it is necessary for the absolute value to be within 25%, and more preferably within 10%.

Evaluation of practical density

Test steps at 175 lines/inch were output using an RC5600V image setter manufactured by Fuji Photo Film Co., Ltd. while changing the light intensity, and developed under the above-mentioned processing conditions, and as a practical density a D_max area was measured when light was exposed at an LV value at which the intermediate halftone dot became 50%. The screen % and the practical density were measured using a Macbeth TD904.

Evaluation of photographic characteristics using exhausted developing solution

The above-mentioned developing solution (A) was used to process 80% blackened film samples using 300 full size sheets (50.8 x 61 cm) per day while replenishing 50 ml per sheet for four consecutive days. The pH of the developing solution decreased to 10.2 after processing a large amount of film, and the Br ion concentration increased.

The exhausted developing solution thus obtained was used for evaluation of the above-mentioned practical density. Exposure to light was carried out at the same LV value as that used for the developing solution (A), and the change in practical density was evaluated.

Samp.	Hydrazine derivative	Compound of formula (1)	Light-insensitive silver halide emulsion
No.	Type	Type	Layer added to	Amount (mol/mol Ag)
1	Compound 11 in Table 2	-	-	-	3
2	"	5-Methylbenzotriazole	Emulsion layer	0.3 x 10^-2	"
3	"	Benzotriazole	"	"	"
4	"	5-Methylbenzotriazole	UL layer	1.0x10^-2	"
5	"	"	"	"	1
6	"	"	"	"	2
7	Compound 1 in Table 1	-	-	-	3
8	"	5-Methylbenzotriazole	UL layer	1.0x10^-2	"
9	Compound 1 in Table 9	-	-	-	"
10	"	Benzotriazole	Emulsion layer	0.3 x 10^-2	"
11	Compound 1-95 Chem. 46	-	-	-	"
12	"	5-Methylbenzotriazole	UL layer	1.0 x 10^-2	"
13	"	"	"	"	1
14	Compound N-XIX Chem. 55	-	-	-	3
15	"	5-Methylbenzotriazole	UL layer	1.0 x 10^-2	"
16	"	"	"	"	2
17	Compound N3 Chem. 56	-	-	-	3
18	"	5-Methylbenzotriazole	UL layer	1.0x10^-2	"
19	"	"	"	"	2

Samp.	Sensitivity	Storage stability	Practical density	Notes
No.		Sensitivity variation (ΔS1.5)	Developing solution (A)	Exhausted developing solution
1	100	+40%	4.1	3.3	Comp. Ex.
2	105	+10%	4.6	4.4	Example
3	103	+15%	4.3	4.0	"
4	105	+8%	4.6	4.5	"
5	104	+10%	4.4	4.1	"
6	106	+12%	4.4	4.0	"
7	101	+38%	3.8	3.1	Comp. Ex.
8	104	+10%	4.3	4.0	Example
9	101	+45%	3.7	3.0	Comp. Ex.
10	104	+20%	4.2	4.0	Example
11	95	+50%	3.6	3.0	Comp. Ex.
12	104	+15%	4.3	4.0	Example
13	102	+18%	4.2	4.0	"
14	90	+55%	3.7	3.0	Comp. Ex.
15	100	+18%	4.2	4.0	Example
16	105	+20%	4.1	4.0	"
17	102	+40%	4.0	3.0	Comp. Ex.
18	104	+10%	4.5	4.1	Example
19	103	+15%	4.3	4.0	"

It was found from the results in Table 18 that the samples of the present invention had excellent storage stability, showed only a small decrease in the practical density when processed using the exhausted developing solution, and had good processing stability.

Example 2

The same experiment as in Example 1 was carried out using a solid developer (C) and a solid fixer {D) that had been closely packed in polyethylene containers with the layer orders below according to the formulation of Example 1 for the developer, and the samples having the constitution of the present invention showed the same good performance as in Example 1.

Formulation of solid developer (C)
First layer	Hydroquinone
Second layer	Other components
Third layer	KBr
Fourth layer	Na₂S₂O₅
Fifth layer	Potassium carbonate
Sixth layer	KOH pellets

The fixer was formed by packing the formulation below in the same manner as for the developer.

Formulation of solid fixer (D)
First layer	(NH₄)₂S₂O₃/Na₂S₂O₃/SS	160.0 g
Second layer	Na₂S₂O₅	15.0 g
Third layer	Anhydrous sodium acetate	32.7 g
Fourth layer	Ethylenediaminetetraacetic acid	0.03 g
	Succinic acid	3.3 g
	Tartaric acid	3.0 g
	Sodium gluconate	1.8 g
Fifth layer	Ammonium aluminum sulfate	23.0 g
pH when made up to 1 L of solution	4.80

Example 3

The same experiment as in Example 1 was carried out using the developing solution (E) below instead of the developing solution (A) of Example 1, and the samples having the constitution of the present invention showed the same good performance as in Example 1.

Formulation of Developing solution E
1 L of concentrated developing solution E
Water	600ml
Potassium hydroxide	96.0 g
Diethylenetriaminepentaacetic acid	6.0 g
Potassium carbonate	48.0 g
Sodium metabisulfite	120.0 g
Potassium bromide	9.0 g
Hydroquinone	70.0 g
5-Methylbenzotriazole	0.24 g
1-phenyl-3-pyrazolidone	1.7 g
2-mercaptobenzimidazole	0.18 g
1-phenyl-5-mercaptotetrazole	0.06 g
Sodium erythorbate	9.0 g
Diethylene glycol	60.0 g

The pH was adjusted to 10.8 by adding potassium hydroxide and water to make 1 L.
A solution for use was prepared by mixing the above-mentioned solution and water at 1:2 (the pH was 10.45). The amount of replenisher was 100 ml per full size sheet (50.8 x 61.0 cm), or 323 ml per m².

Example 4

Processing was carried out as in Examples 1 to 3 except that the development temperature was 38°C, the fixation temperature was 37°C, and the development time was 20 sec, the same results as in Examples 1 to 3 were obtained, and the effect of the present invention was not lost.

Example 5

The procedures of Examples 1 to 4 were repeated except that an FG-680AS automatic developing machine manufactured by Fuji Photo Film Co., Ltd. was used with a linear material transport speed of 1500 mm/min, and the same results were obtained.

Example 6

Evaluation was carried out in the same manner as in Examples 1 to 5 except that one type of machine chosen from an FT-R5055 imagesetter manufactured by Dainippon Screen Manufacturing Co., Ltd., a SelectSet 5000, Avantra 25, or AccuSet 1000 manufactured by Agfa-Gevaert Group, a Dolev 450 or Dolev 800 manufactured by Scitex Corporation Ltd., a Lino 630, Quasar, Hercules Elite, or Signasetter manufactured by Heidelberg, a Luxel F-9000 manufactured by Fuji Photo Film Co., Ltd., and a Panther Pro 62 manufactured by PrePress Solutions Inc. was used instead of the LuxSetter RC-5600V manufactured by Fuji Photo Film Co., Ltd., and the same effects were obtained using the samples of the present invention.

Claims

An image formation process comprising:

a processing step for developing a silver halide photographic light-sensitive material using a developing solution having a pH of 9.0 or above but less than 11.0, the silver halide photographic light-sensitive material comprising a support, at least one silver halide emulsion layer on the support, and another layer comprising a hydrophilic colloid, wherein at least one type of hydrazine derivative and at least one type of compound represented by formula (1) are contained in at least one layer of the emulsion layer and the hydrophilic colloid layer,

wherein M represents a hydrogen atom, an alkali metal atom, or a protecting group that can be cleaved by an alkali, and R₁₁, R₁₂, and R₁₃ may be identical to or different from each other and independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, a nitro group, a substituted or unsubstituted alkoxy group, or a cyano group.
The image formation process according to Claim 1 wherein the hydrazine derivative is a compound represented by formula (2) below,
wherein Ar represents an aromatic group, L₂₁ represents a divalent linking group having an electron-withdrawing group, and X represents an anionic group.
The image formation process according to Claim 1 wherein the hydrazine derivative is a compound represented by formula (3) below,
wherein R₃₁ represents a difluoromethyl group or a monofluoromethyl group, and A₃₁ represents an aromatic group.
The image formation process according to Claim 1 wherein the hydrazine derivative is a compound represented by formula (4) below,
Formula (4)
wherein R₄₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; R₄₂ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R₄₃ represents a hydrogen atom or a blocking group; L₄₁ represents an alkylene group or an alkenylene group, provided that at least two rings, which may be bonded to each other directly and/or through an aliphatic linking group, are contained in the R₄₁-S-L₄₁ part; J₄₁ and J₄₂ each represent a linking group; n is 0 or 1; X represents an aromatic or heterocyclic residue; and A₄₁ and A₄₂ are each a hydrogen atom, or one of them is a hydrogen atom and the other one is an acyl, sulfonyl or oxalyl group.
The image formation process according to Claim 1 wherein the hydrazine derivative is a compound represented by formula (5) below,
Formula (5)
wherein R₅ represents an acyl group chosen from the group consisting of COR₅₁, SO₂R₅₂, SOR₅₃, POR₅₄R₅₅, and COCOR₅₆; R₅₁ and R₅₆ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl or heteroaryl group, OR₅₇, or NR₅₈R₅₉; R₅₂ and R₅₃ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl or heteroaryl group, OR₅₇, or NR₅₈R₅₉; R₅₄ and R₅₅ independently represent one of the substituents cited for R₅₂ or together form a ring; R₅₇ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl or heteroaryl group; R₅₈ and R₅₉ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl or heteroaryl group, or together form a ring; A₅ and A₅' independently represent a hydrogen atom, an SO₂R₅₀ group, or a group that can generate hydrogen under alkaline photographic processing conditions, provided that when A₅ is SO₂R₅₀, A₅' is hydrogen and vice versa, and R₅₀ represents one of the substituents cited for R₅₂; L₅ is a divalent linking group; Q is a cationic nitrogen-containing aromatic heterocyclic ring; Y^- is a negatively charged counter ion for neutralizing the positive charge of Q; n is 0 when the compound of formula (5) is an intramolecular salt, or n is an integer that is equal to the positive charge of Q; and Z represents atoms required to form a substituted or unsubstituted aromatic or heteroaromatic ring.
The image formation process according to Claim 1 wherein the hydrazine derivative is a compound represented by the formula (6) below,
wherein R₆ is alkyl having from 6 to 18 carbon atoms or a heterocyclic ring having 5 or 6 ring atoms, including ring atoms of sulfur or oxygen; R₆₁ is alkyl or alkoxy having from 1 to 12 carbon atoms; X is alkyl, thioalkyl or alkoxy having from 1 to about 5 carbon atoms; halogen; or -NHCOR₆₂, -NHSO₂R₆₂, - CONR₆₂R₆₃ or -SO₂R₆₂R₆₃ where R₆₂ and R₆₃, which can be the same or different, are hydrogen or alkyl having from 1 to about 4 carbon atoms; and n is 0, 1 or 2.
The image formation process according to any one of Claim 1 to 6, wherein the compound represented by formula (1) is 5-methylbenzotriazole.
The image formation process according to any one of Claim 1 to 7, wherein the silver halide photographic light-sensitive material comprises, in the light-sensitive silver halide emulsion layer or the hydrophilic colloid layer, solid particles that can increase the average value of the integral of the spectral reflectance in the wavelength range from 850 to 1000 nm by at least 1.5% relative to a case where they are not added.
The image formation process according to Claim 8 wherein the solid particles have a particle size of 2 nm to 20 µm.
The image formation process according to any one of Claim 8 to 9, wherein the solid particles are light-insensitive silver halide grains.