JP2005099224A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material which suppresses fogging caused by enhanced sensitivity and ensures small increase in fog even when stored under severe conditions such as high temperature and high humidity. <P>SOLUTION: The silver halide photographic sensitive material contains at least one compound selected from the following types (1)-(3); type (1): a compound which is represented by formula (1) and of which one-electron oxidized derivative produced by oxidation of a reducing group (X<SP>1</SP>) in its molecule is capable of releasing one or more electrons with nucleophilic addition reaction of a nucleophilic group (Nu) in its molecule to the one-electron oxidized derivative; type (2): a compound which is represented by formula (2) or formula (3) and of which one-electron oxidized derivative produced by one-electron oxidation of a reducing group (X<SP>2</SP>) is capable of releasing one or more electrons with desorption reaction of a desorption group (Z<SP>1</SP>) from the one-electron oxidized derivative; type (3): a compound which is represented by formula (4) and has no covalently bonded base in its molecule and of which one-electron oxidized derivative produced by one electron oxidation of the compound is capable of releasing one or more electrons with desorption of a proton from the one-electron oxidized derivative. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver halide photographic material having improved photographic sensitivity and the like.

  Various techniques are used to improve the photosensitivity of the silver halide photographic material. In order to increase the intrinsic sensitivity of silver halide, for example, chemical sensitizers such as sulfur, gold and Group VIII metal compounds are used. Spectral sensitization using cyanine and other polymethine dyes is also a well-known technique in the art.

  A phenomenon in which photographic sensitivity is markedly reduced when a spectral sensitizing dye is added to an emulsion in excess of the optimum amount is known as dye desensitization. As a method for improving this, a technique using a supersensitization effect by a supersensitizer is known. This is a normally colorless organic compound that does not itself exhibit a spectral sensitizing effect, and acts on a sensitizing dye (or an excited sensitizing dye) to exert an effect of suppressing dye desensitization.

  In order to increase the spectral sensitivity of the silver halide photographic light-sensitive material, various electron donating compounds have been used together with the sensitizing dye.

  Furthermore, compounds in which these electron donating compounds are covalently linked to a sensitizing dye are also used. Examples of these are compounds having an electron donating styryl base attached to a monomethine dye, phenothiazine, phenoxazine, carbazole, dibenzophenothiazine, ferrocene, an electron donating group derived from tris-2,2′-bipyridyl-ruthenium, or And compounds having a triarylamine skeleton bonded to a silver halide adsorbing group.

  However, even with the above-described devices, an ideally high photographic sensitivity has not yet been realized. In particular, it is stored under harsh conditions such as fogging caused by high sensitivity and silver halide photographic materials being exposed to harmful gases generated during combustion at high temperatures, high humidity, and automobile exhaust. In reality, there are still very few compounds that can achieve high sensitivity while being compatible with the problem of storage fogging.

  On the other hand, recently, sensitization techniques using fragmentable electron donating compounds have been reported (for example, see Patent Documents 1 to 6 and Non-Patent Document 1).

  These compounds are basically considered to be compounds that have been proposed in the category of supersensitizers associated with spectral sensitization techniques. However, these compounds are excited by dye holes (sensitized dye molecules that have lost one electron after being injected from the excited sensitizing dye into the silver halide conduction band) or silver halide. It is specified in the specification that another electron is emitted only after being oxidized by holes generated in this way and then undergoes a fragmentation reaction, which causes a high sensitivity. As used herein, fragmentation means a “bond cleavage reaction” caused by a radical formed during the oxidation of XY, a reaction that can be caused by another radical, a dimer compound, a deprotonation. There is a clear distinction between oxidation, hydrolysis, nucleophilic substitution and disproportionation reactions. Further, there are sensitizers that emit another electron through deprotonation (see, for example, Patent Document 7), and chemical sensitizers that take various reaction forms other than the above (for example, see Patent Documents 8 to 11). It has been reported.

However, even with these compounds, it has not been possible to achieve an ideal high-sensitivity technology that can provide a photosensitive material having a high sensitivity / fogging ratio and excellent storage stability.
US Pat. No. 5,747,235 US Pat. No. 5,747,236 European Patent Application No. 786692A1 European Patent Application No. 893731A1 European Patent Application No. 893732A1 International Publication No. WO99 / 05570 pamphlet Journal of American Chemical Society 119, 11934, (2000) US Pat. No. 5,994,051 Japanese Patent Laid-Open No. 2003-140287 JP2003-114487 Japanese Patent Laid-Open No. 2003-114488 JP 2003-75950 A

  The present invention increases the photographic sensitivity of photographic emulsions, suppresses fogging that occurs with higher sensitivity, and is exposed to harsh conditions such as being exposed to harmful gases generated during combustion at high temperatures, high humidity, and automobile exhaust. An object of the present invention is to provide a silver halide photographic light-sensitive material in which fog rises little even when stored.

  As a result of intensive studies on the performance improvement of the sensitizer described above, the present inventors have found compounds of types (1) to (3) defined in the present invention having a high sensitivity / fogging ratio and excellent in storage stability. Finally, the present invention was completed. That is, the said subject was achieved by the following structures 1-5.

(Configuration 1)
A silver halide photographic light-sensitive material comprising at least one compound of type (1), (2) or (3).

(i) Type (1)
It is represented by the general formula (1), and further emits one or more electrons with the nucleophilic addition reaction of the nucleophilic group in the molecule to the one-electron oxidant generated by oxidation of the reducing group in the molecule. Compound.

(In the formula, X ¹ represents a reducing group. Nu represents a nucleophilic group, and represents —NHR ¹ , —PR ² ₂ or —OH. Here, R ¹ represents a hydrogen atom, an alkyl group, or a heterocyclic group. , —C (═O) —R ¹³ , —C (═S) —R ¹³ or —SO ₂ —R ¹³ , wherein R ² and R ¹³ are a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group, respectively. Represents an alkoxy group, an aryloxy group or an amino group, and L ¹ represents a linking group.

(ii) Type (2)
One or more electrons are emitted with the elimination reaction of the leaving group from the one-electron oxidant represented by the general formula (2) or the general formula (3), which is generated by one-electron oxidation of the reducing group. Possible compounds.

(In the formula, X ² represents a reducing group. L ² represents a single bond or an arylene group. R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. Z ¹ represents a leaving group. A methyl group substituted with two or more aryl groups or aromatic heterocyclic groups, or a methyl group substituted with at least one hydroxy group, silyloxy group, alkoxy group, amino group, alkylamino group, acylamino group or sulfonamino group In the case where Z ¹ is a methyl group substituted with a hydroxy group or an alkoxy group, the methyl group does not have a group which can be taken as X ² as a substituent.

(In General Formula (3), Y represents an alkylamino group, an arylamino group, a heterocyclic amino group, an aromatic or non-aromatic nitrogen-containing heterocyclic group, an alkoxy group or an aryloxy group in which nitrogen is substituted. R ⁵ represents a substituent, a is an integer of 0 to 4, and when a is 2 or more, a plurality of R ⁵ may be the same or different, L ³ is —O—, -S- or -N (-R ⁶ )-, where R ⁶ represents a substituent, Z ² is a leaving group, and is a methyl group substituted with two or more aryl groups or aromatic heterocyclic groups. Represents.)

(iii) Type (3)
A compound represented by the general formula (4), which does not have a covalently bonded base in the molecule, and further includes one or more protons from the one-electron oxidant produced by one-electron oxidation. A compound that can emit electrons.

Wherein X ³ is an alkylamino group, arylamino group, heterocyclic amino group, an aromatic or non-aromatic nitrogen-containing heterocyclic group in which nitrogen is substituted, or at least one alkoxy group or aryloxy group Represents a substituted aryl group, L ⁴ represents a single bond or an arylene group, R ⁷ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group, R ⁸ represents a hydrogen atom, an alkyl group, Represents an aryl group or a heterocyclic group, wherein at least one of X ³ , L ⁴ , R ⁷ and R ⁸ is an oxiranyl group, an oxetanyl group, —OR ⁹ , —OCO ₂ R ⁹ , —CO ₂ R ⁹ , Or substituted with a substituent containing a quaternary salt structure of nitrogen or phosphorus, R ⁹ represents a substituted methyl group or t-alkyl group of two or more aryl groups or aromatic heterocyclic groups.

(Configuration 2)
The silver halide photographic light-sensitive material according to constitution 1, wherein the compounds of types (1) to (3) have an adsorbing group for silver halide in the molecule.

(Configuration 3)
The silver halide photographic light-sensitive material according to Structure 1 or 2, wherein the compounds of types (1) to (3) have a sensitizing dye structure as a partial structure in the molecule.

(Configuration 4)
A silver halide emulsion chemically sensitized with the compound according to any one of Structures 1 to 3.

(Configuration 5)
A silver halide photographic light-sensitive material comprising at least one silver halide emulsion described in Structure 4.

First, the compound represented by the general formula (1) of the present invention will be described in detail.
In the compound represented by the general formula (1), the nucleophilic group Nu existing in the molecule is nucleophilic to the one-electron oxidant (cation radical species) generated by one-electron oxidation of the reducing group X ^1. By performing an addition reaction and forming a bond between X ¹ and Nu, a new ring containing X ¹ , Nu, and a linking group L ¹ is formed, and one or more electrons are released accordingly. Compound. The nucleophilic addition reaction here refers to a reaction type in which a nucleophilic group Nu donates two electrons to a one-electron oxidant (cation radical species) and a new bond is formed between Nu and X ^1. It is different from radical reaction, which is another reaction mode of cationic radical species.

In the general formula (1), X ¹ represents a reducing group capable of producing a one-electron oxidant by oxidation, and an aryl group, aromatic or non-aromatic nitrogen-containing heterocyclic group can be used. Preferably, an aryl group substituted with at least one electron donating group (the electron donating group here means a hydroxy group, an alkoxy group, a mercapto group, a sulfonylamino group, an acylamino group, an amino group, an alkylamino group) , Arylamino group, heterocyclic amino group, active methine group, 5-membered aromatic heterocyclic group containing 1 or 2 nitrogen, oxygen or sulfur atoms (can be monocyclic or condensed), substituted with nitrogen atom Non-aromatic nitrogen-containing heterocyclic group (pyrrolidinyl group, indolinyl group, tetrahydroquinolyl group, piperidinyl group, piperazinyl group, morpholino group, etc.)), aromatic having 1 or 2 nitrogen atoms in the ring Alternatively, a non-aromatic heterocyclic group is used. X is more preferably a phenyl group substituted with at least one electron-donating group, a 5-membered aromatic heterocyclic group having one nitrogen atom in the ring (wherein examples of the heterocyclic ring include a pyrrole ring, an indole) A non-aromatic nitrogen-containing heterocyclic group having one or two nitrogen atoms in the ring (in this case, a benzo-condensed heterocyclic ring is preferred, and examples thereof include a tetrahydroquinoline ring, an indoline ring, a tetrahydro ring, and the like. A quinoxaline ring) is used.

X ¹ may have a substituent. Specific examples of the substituent include a halogen atom (fluorine atom, chloro atom, bromine atom, or iodine atom), an alkyl group (aralkyl group, cycloalkyl group, active group). Methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (regarding the position of substitution), heterocyclic group containing quaternized nitrogen atom (eg pyridinio group, imidazolio group, quinolinio group) , Isoquinolinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano Group, thiocarbamoyl group, hydroxy group, alkoxy group ( (Including groups containing repeating tyleneoxy or propyleneoxy units), aryloxy groups, heterocyclic oxy groups, acyloxy groups, (alkoxy or aryloxy) carbonyloxy groups, carbamoyloxy groups, sulfonyloxy groups, amino groups, (alkyls) , Aryl, or heterocyclic) amino group, acylamino group, sulfonamido group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino Group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, Or heterocyclic) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoric acid Examples thereof include a group containing an amide or phosphate ester structure, a silyloxy group (for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a silyl group (for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl) and the like. These substituents may be further substituted with these substituents.

Nu is a nucleophilic group and represents —NHR ¹ , —PR ² ₂ or —OH. Here, R ¹ represents a hydrogen atom, an alkyl group, a heterocyclic group, —C (═O) —R ³ , —C (═S) —R ³ , —SO ₂ —R ³ . R ² and R ³ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group. These groups may have a substituent, and the substituent is selected from the same group as that which X ¹ can take. When the nucleophilic group has a negative charge and has a counter cation, the counter cation can be a metal ion, a quaternary cation of nitrogen or phosphorus, or the like.

As Nu, more preferably, -NHR ¹ (R ¹ is a hydrogen atom, an alkyl group, a group represented by -C (= O) -R ³ , -C (= S) -R ³ ), or -OH is Used. More preferably, —NHR ¹ (R ¹ is an alkyl group, —C (═O) —R ³ , a group represented by —C (═S) —R ³ , where R ³ is a hydrogen atom, an alkyl group, or an aryl group. Group, a group represented by an amino group), or -OH.

In the general formula (1), L ¹ is a linking group, and any group can be used as long as X ¹ and Nu can be bonded by a covalent bond. Preferably, an alkylene group, an arylene group, a heterocyclic group, —O—, —S—, —NR—, —C═O—, —SO ₂ —, —SO—, —P═O—, —C≡C— , -CR = CR'- represents a group consisting of a single group or a combination thereof. Here, R and R ′ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group. More preferably as L ¹ after X ¹ and Nu has generated a bond, X ^1, L ^1, ring structure that is newly formed by connecting each unit of Nu it is preferable to form a 5- to 12-membered ring. Particularly preferably, it is composed of a combination of an alkylene group, an arylene group, an aromatic heterocyclic group, —O—, —S—, —NR—, —C═O—, —SO ₂ —, X ¹ , L ¹ , A new ring structure formed by linking each unit of Nu to form a 5- to 8-membered ring is used. L ¹ may be substituted with a substituent, and as the possible substituent, those which can be taken by X ¹ described above are used.

Particularly preferred compounds represented by the general formula (1) are those represented by the following general formulas (5) and (6).

In the general formula (5), D ¹ represents —NR ²¹ R ²² or —OR ²³ . R ²¹ , R ²² and R ²³ each independently represents an alkyl group, an aryl group or a heterocyclic group. A ¹ represents a hydrogen atom or a substituent. b is an integer of 0 to 3, and when b is 2 or more, a plurality of A ¹ may be the same or different. b is preferably an integer of 0 to 2, more preferably 0 or 1. L ¹¹ represents a linking group and is a group selected from the same range as L ¹ in the general formula (1). The substitution position of L ¹¹ is preferably the meta position or para position of D ¹ . Nu ¹ is a nucleophilic group.

When D ¹ is —NR ²¹ R ²² , R ²¹ and R ²² may be further substituted with a substituent which X ¹ in the general formula (1) can take. Further, R ²¹ and R ²² may each form a ring structure via a substituent substituted with a phenyl group substituted by D ¹ , a linking group L ¹¹ , or a nucleophilic group Nu ^1. . R ²¹ may be bonded to R ²² through a substituent or directly bonded to form a ring structure. The total number of carbon atoms of the substituents R ²¹ and R ²² on the nitrogen atom is 40 or less, preferably 30 or less, more preferably 20 or less. When D ¹ is —OR ²³ , R ²³ may be further substituted with a substituent that X ¹ in general formula (1) can take. Further, R ²³ may form a ring structure via a phenyl group substituted by D ¹ , a linking group L ¹¹ , or a nucleophilic group Nu ¹ via a substituent or directly bonded thereto. R ²³ has a total carbon number of 40 or less, preferably 30 or less, more preferably 20 or less.

When A ¹ is a substituent, it is selected from the group of substituents that X ¹ in the general formula (1) can take. Preferably alkyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, cyano group, halogen, nitro group, hydroxy group , An alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group are used. More preferably, alkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, cyano group, halogen, hydroxy group, alkoxy group, aryl An oxy group is used. A ¹ is particularly preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 alkoxycarbonyl groups, C1-C10 acylamino groups, C1-C10 sulfonylamino groups, C1-C10 carbamoyl groups, C1-C10 sulfamoyl groups, cyano groups, halogens, C1 ~ 10 alkoxy groups are used.

Nu ¹ is a group represented by -NHR ²⁴ (R ²⁴ is an alkyl group, -C (= O) -R ²⁵ , -C (= S) -R ²⁵ , where R ²⁵ is a hydrogen atom or an alkyl group. , An aryl group, an amino group, or -OH. R ²⁴ and R ²⁵ may be substituted with a substituent, and as the substituent, those selected from the substituent group which X ¹ in the general formula (1) can take are used. When R ²⁴ is an alkyl group, the carbon number thereof is 1 to 30, preferably 1 to 20, and more preferably 1 to 15. When R ²⁵ is an alkyl group, the carbon number thereof is 6 to 30, preferably 6 to 20, and more preferably 6 to 15. When R ²⁵ is an aryl group, the carbon number thereof is 6 to 30, preferably 6 to 20, and more preferably 6 to 15. Most preferably, NHR ²⁴ (wherein R ²⁴ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms) or —OH is used as Nu ¹ .

Next, general formula (6) will be described.
In the general formula (6), D ² represents —NR ²⁶ R ²⁷ or —OR ²⁸ . R ²⁶ , R ²⁷ and R ²⁸ each independently represents an alkyl group, an aryl group or a heterocyclic group. R ²⁶ , R ²⁷ and R ²⁸ may have a substituent, and the substituent is selected from the group of substituents that can be taken by X ¹ in the general formula (1). A ² represents a hydrogen atom or a substituent and has the same meaning as A ¹ in formula (5). c is an integer of 0 to 5, and when c is 2 or more, a plurality of A ² may be the same or different. c is preferably an integer of 0 to 4, more preferably an integer of 0 to 2. L ¹² represents a linking group, which is bonded to R ²⁶ , R ²⁷ or R ²⁸ as a substituent on R ²⁶ , R ²⁷ or R ²⁸ , and connects these to Nu ² , in general formula (1) a group selected from the same range as the L ^1. Nu ² is a nucleophilic group, and here is a group selected from the same range as the nucleophilic group Nu ¹ of the general formula (5).

Next, the compound represented by formula (2) or (3) will be described. The compound represented by the general formula (2) or (3) has reductive properties by elimination of a specific leaving group from a one-electron oxidant (cation radical) generated by one-electron oxidation of the compound. It is a compound that can emit one or more electrons by generating radical species. In the fragmentable electron donor (XY) described in the background art, according to the description, the leaving group is CO ₂ , Group 13 or Group 14 metal (Si, Ge, Sn, B). And a group that can be an electron-donating group X, and the leaving group of the present invention does not fall within these categories. In this respect, the compound represented by the general formula (2) or (3) of the present invention is different from the above-mentioned fragmentable electron donor.

Next, the compound represented by the general formula (2) will be described.

X ² is a reducing group, and specific examples thereof include the following groups. That is, amino group, alkylamino group (methylamino group, diethylamino group, etc.), arylamino group (represents phenylamino group, diphenylamino group, etc., and also includes N-alkyl-N-arylamino group), heterocyclic amino group (Represents benzthiazolylamino group, pyrrolylamino group, etc., including N-alkyl-N-heterocyclic amino group and N-aryl-N-heterocyclic amino group), alkylthio group (such as methylthio group), arylthio group (1 -Naphthylthio group, etc.), heterocyclic thio group (such as 2-pyridylthio group), aryloxy group (phenoxy group, etc.), aryl group (phenyl group, naphthyl group, anthryl group, etc.), aromatic or non-aromatic heterocycle Group (the heterocyclic group may be monocyclic or condensed. Specific examples of the heterocyclic ring include tetrahydroquinoline ring, tetra Droisoquinoline ring, tetrahydroquinoxaline ring, tetrahydroquinazoline ring, indoline ring, indole ring, indazole ring, carbazole ring, phenoxazine ring, phenothiazine ring, benzothiazoline ring, pyrrole ring, imidazole ring, thiazoline ring, piperidine ring, pyrrolidine ring, Morpholine ring, benzimidazole ring, benzimidazoline ring, benzoxazoline ring, 3,4-methylenedioxyphenyl ring, etc.), active methylene (meaning methylene substituted with two electron withdrawing groups) The electron withdrawing group is an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, trifluoromethyl group, cyano group, nitro group, imino group. Here, two electron-withdrawing groups may be bonded to each other to form a cyclic structure.) A group having a structure, an active methine group (a methine group substituted with two electron-withdrawing groups) The electron withdrawing group is the same as described in the description of the active methylene), and a group containing a trivalent phosphorus atom (for example, Ph ₂ P-group, (EtO) ₂ P-group, etc.) Can be mentioned.

X ² is preferably an alkylamino group, an arylamino group, an aromatic amino group (aromatic or non-aromatic), an aromatic or non-aromatic nitrogen-containing heterocyclic group substituted with nitrogen, at least one alkoxy group or An aryl group substituted with an aryloxy group is used. Here, the nitrogen-substituted aromatic or non-aromatic nitrogen-containing heterocyclic group may be monocyclic or condensed, and specific examples include tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinoxaline ring, tetrahydroquinazoline ring, indoline ring. , Indole ring, indazole ring, carbazole ring, phenoxazine ring, phenothiazine ring, benzothiazoline ring, pyrrole ring, imidazole ring, thiazoline ring, piperidine ring, pyrrolidine ring, morpholine ring, benzimidazole ring, benzimidazoline ring, benzoxazoline ring Etc.

X ² is more preferably an alkylamino group, an arylamino group, a heterocyclic amino group, an aromatic or non-aromatic heterocyclic group substituted with nitrogen, or a phenyl group substituted with at least three alkoxy groups. More preferably, when L ² is a single bond, an arylamino group, an aromatic heterocyclic amino group, an aromatic or non-aromatic heterocyclic group substituted with nitrogen, or a phenyl group substituted with at least three alkoxy groups is used. When L ² is an arylene group, an alkylamino group, an arylamino group, or a non-aromatic heterocyclic group substituted with nitrogen is used. Particularly preferably, when L ² is a single bond, an arylalkylamino group or a phenyl group substituted with three alkoxy groups is used, and when L ² is an arylene group, a dialkylamino group is used.

L ² represents a single bond or an arylene group. If L ² is an arylene group, it may be one of any positional relationship between the carbon atoms which is substituted in X ² and Z ¹ is a carbon atom which is substituted by Z ¹ in the ortho or para position X ² is substituted It is preferable that The arylene group may be substituted with a substituent, and the substituent is selected from the group of substituents that X ¹ in the general formula (1) can take. As the arylene group, a phenylene group is preferably used. L ² is particularly preferably a single bond.

R ³ and R ⁴ each independently represents a hydrogen atom or a substituent, and this substituent is selected from the group of substituents that X ¹ in the general formula (1) can take. R ³ and R ⁴ are preferably hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, hydroxy groups, alkoxy groups, aryloxy groups, silyloxy groups, more preferably hydrogen atoms, An alkyl group, an aryl group, a heterocyclic group, a hydroxy group, and an alkoxy group are used, and a hydrogen atom, an alkyl group, and an aryl group are more preferably used. In the case of an alkyl group, those having 1 to 30 carbon atoms are used, preferably those having 1 to 20 carbon atoms, more preferably those having 1 to 15 carbon atoms. As the aryl group, those having a total carbon number of 6-30 are used, preferably those having a total carbon number of 6-20, and more preferably those having a total carbon number of 6-15. R ³ and R ⁴ may be further substituted with a substituent, and the substituent is selected from the group of substituents that can be taken by X ¹ in the general formula (1).

Z ¹ is a leaving group, a substituted methyl group of two or more aryl groups or aromatic heterocyclic groups, or at least one hydroxy group, silyloxy group, alkoxy group, amino group, alkylamino group, acylamino group, Represents a methyl group substituted with a sulfonamino group. Where two or more aryl groups or aromatic heterocyclic groups substituted methyl groups, or at least one hydroxy group, silyloxy group, alkoxy group, amino group, alkylamino group, acylamino group, sulfonamino group The methyl group may be substituted with an alkyl group, an aryl group or a heterocyclic group in addition to these groups. However, when Z ¹ is a methyl group substituted with a hydroxy group or an alkoxy group, the methyl group is an aryl group (an amino group, an alkylamino group, a hydroxy group, an alkoxy group or an aryloxy group is substituted), The anthryl group is not substituted with a 5-membered nitrogen-containing aromatic heterocyclic group having one nitrogen atom in the ring. Further, the group substituted with these methyl groups may further have a substituent, and as the substituent, those selected from the group of substituents which X ¹ in the general formula (1) can take are used.

A preferable range of Z ¹ will be described below. In the case of a methyl group substituted with two or more aryl groups or aromatic heterocyclic groups, preferably a diarylmethyl group or a triarylmethyl group is used, more preferably a diphenylmethyl group or a trityl group is used. A trityl group is preferably used. In the case of a methyl group substituted with at least one hydroxy group, silyloxy group, alkoxy group, amino group, alkylamino group, acylamino group, sulfoneamino group, preferably one hydroxy group, silyloxy group, alkoxy group, amino group Group, an alkylamino group, and a methyl group substituted with an acylamino group are used, more preferably one hydroxy group, a silyloxy group, an amino group, and a methyl group substituted with an alkylamino group are used, and more preferably Z ^1. Is a methyl group substituted with a hydroxy group or a silyloxy group, and substituted with an aryl group or an aromatic heterocyclic group. Particularly preferably, Z ¹ is substituted with a hydroxy group and an aryl group (carboxyl group, amide group, sulfonamido group, amino group, alkylamino group, hydroxy group, alkoxy group, mercapto group, phenylthio group not substituted with alkylthio group) Or a naphthyl group), and a methyl group substituted with a 6-membered nitrogen-containing aromatic heterocyclic group (which may be monocyclic or condensed).

Next, the compound represented by the general formula (3) will be described.

Y represents an alkylamino group, an arylamino group, a heterocyclic amino group, an aromatic or non-aromatic nitrogen-containing heterocyclic group substituted with nitrogen, an alkoxy group or an aryloxy group. Preferably, an alkylamino group, an arylamino group, a heterocyclic amino group, or a non-aromatic nitrogen-containing heterocyclic group substituted with nitrogen is used, more preferably an alkylamino group, an arylamino group, a heterocyclic amino group, or nitrogen. A non-aromatic nitrogen-containing heterocyclic group to be substituted is used, and a dialkylamino group, a diarylamino group, or an alkylarylamino group is particularly preferably used. Y may be substituted with a substituent, and the substituent is selected from the group of substituents that can be taken by X ¹ in the general formula (1).

R ⁵ represents a substituent, and this substituent is selected from the group of substituents that can be taken by X ¹ in the general formula (1). Preferably, an alkyl group, aryl group, heterocyclic group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, thiocarbamoyl group, (alkyl or aryl) sulfonyl group, sulfamoyl group are used. . These substituents may be further substituted with a substituent selected from the substituent group which X ¹ in the general formula (1) can take. a is an integer of 0 to 4, and when a is 2 or more, a plurality of R ⁵ may be the same or different. a is preferably an integer of 0 to 3, more preferably an integer of 0 to 2.

L ³ represents —O—, —S—, or —N (—R ⁶ ) —. R ⁶ represents a substituent. R ⁶ is preferably an alkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, or (alkyl or aryl) sulfonyl group. These groups may be further substituted with a substituent, and the substituent is selected from the group of substituents that X ¹ in the general formula (1) can take. The positional relationship between L ³ and Y may be any, but it is preferable that L ³ is substituted at the ortho or para position of Y. L ³ is preferably —O— or —S—, and particularly preferably —S—.

Z ² is a leaving group and represents a methyl group substituted with two or more aryl groups or aromatic heterocyclic groups. Any two groups of two or more aryl groups and aromatic heterocyclic groups substituted on a methyl group may be linked via a single bond or a divalent group such as —O—. In the case of a methyl group in which two aryl groups or aromatic heterocyclic groups are substituted, the remaining one substituent is a hydrogen atom or an alkyl group. Preferably diphenylmethyl group, di (4-methoxyphenyl) methyl group, triphenylmethyl group, tris (4-methoxyphenyl) methyl group, dibenzosuberyl group, α-naphthyldiphenylmethyl group, 9- (9-phenyl) A xanthenyl group or the like is used, and more preferably a di (4-methoxyphenyl) methyl group, a triphenylmethyl group, a tris (4-methoxyphenyl) methyl group, a dibenzosuberyl group, or a 9- (9-phenyl) xanthenyl group. Is used.

Z ² has preferably 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, still more preferably 6 to 30 carbon atoms, and particularly preferably 7 to 20 carbon atoms.

  Next, the compound represented by the general formula (4) will be described. These compounds are compounds that can further emit one or more electrons by generating a reducing carbon radical accompanying the elimination of a proton from a one-electron oxidant produced by one-electron oxidation. These compounds are characterized by having a specific substituent, whereby protons can be eliminated from the one-electron oxidant in the absence of a base covalently bonded in the molecule. In this respect, the deprotonated electron donor in which a base is covalently bonded to the molecule described in the aforementioned US Pat. No. 5,994,051 and the compound of the present invention represented by the general formula (4) are clearly shown. Are distinguished.

The compound represented by the general formula (4) will be described.

X ³ is a reducing group and can take the same group as X ² in formula (2). The preferable range of X ³ is also the same as the preferable range of X ² in the general formula (2). L ⁴ represents a single bond or an arylene group, and can take the same group as L ² in the general formula (2). The preferable range of L ⁴ is also the same as the preferable range of L ² in the general formula (2). R ⁷ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an aryloxy group. R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ⁷ and R ⁸ may be further substituted with a substituent, and the substituent is selected from the group of substituents that can be taken by X ¹ in the general formula (1). H represents a proton to be eliminated.

R ⁷ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an aryloxy group. As R ⁷ , when L ⁴ is a single bond, an alkyl group or an aryl group is preferably used, and an alkyl group is more preferably used. When L ⁴ is an arylene group, an alkoxy group, an alkyl group or an aryl group is preferably used, and an alkoxy group is more preferably used. R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. A hydrogen atom or an alkyl group is preferable, and a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferable.

At least one of X ³ , L ⁴ , R ⁷ and R ⁸ is an oxiranyl group, an oxetanyl group, a group represented by —OR ⁹ , a group represented by —OCO ₂ R ⁹ , or a group represented by —CO ₂ R ⁹ . Or a group containing a quaternary salt structure of nitrogen or phosphorus. R ⁹ represents a methyl group or a t-alkyl group substituted with two or more aryl groups or aromatic heterocyclic groups. R ⁹ is preferably a diarylmethyl group, a triarylmethyl group or a t-alkyl group, more preferably a triarylmethyl group or a t-alkyl group, particularly preferably a trityl group or a t-butyl group. Is used.

An oxiranyl group, an oxetanyl group, a group represented by —OR ⁹ , a group represented by —OCO ₂ R ⁹ , a group represented by —CO ₂ R ⁹ , or a group containing a quaternary salt structure of nitrogen or phosphorus The substituted group is preferably L ⁵ , R ⁷ or R ⁸ , more preferably R ⁷ or R ⁸ . An oxiranyl group, an oxetanyl group, a group represented by —OR ⁹ , a group represented by —OCO ₂ R ⁹ , a group represented by —CO ₂ R ⁹ , or a group containing a quaternary salt structure of nitrogen or phosphorus Among them, an oxiranyl group, a group represented by —OR ⁹ , —OCO ₂ R ⁹ , a group containing a quaternary salt structure of nitrogen or phosphorus is preferably used, and more preferably an oxiranyl group, —OCO ₂ R ⁹ , nitrogen Alternatively, a group containing a quaternary salt structure of phosphorus is used.

  When a group containing a quaternary salt structure of nitrogen or phosphorus is substituted, any counter anion may be used, but a carboxylate ion or a sulfonate ion is preferably used. As the structure of the quaternary salt of nitrogen, tetraalkylammonium or a nitrogen-containing heterocycle in which the nitrogen atom is quaternized is preferably used. As the quaternary salt structure of phosphorus, tetraalkylphosphonium and alkyltriarylphosphonium are preferably used. More preferably, a quaternary salt structure of nitrogen is used, and tetraalkylammonium (herein, the total number of carbon atoms of four alkyl groups is 20 or less), pyridinium, 4-phenylpyridinium, quinolinium, and isoquinolinium are more preferably used. It is done.

  Of the compounds of types 1, 2, and 3, preferably "a compound having an adsorbing group to silver halide in the molecule" or "a compound having a partial structure of a spectral sensitizing dye in the molecule". is there. Typical examples of the adsorptive group to silver halide are those described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. The partial structure of the spectral sensitizing dye is a structure described on page 17, right line 34 to page 18, left line 6 of the same specification.

  As the compounds of types 1, 2, and 3, more preferable are “compounds having at least one adsorptive group for silver halide in the molecule”. More preferred is “a compound having two or more adsorptive groups to silver halide in the same molecule”. When two or more adsorptive groups are present in a single molecule, these adsorptive groups may be the same or different.

  The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) or imino silver (> NAg) And a nitrogen-containing heterocyclic group having a —NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.). Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferable examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing terocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

  A quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (such as a trialkylammonio group, a dialkylaryl (or heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a quaternized nitrogen atom. A group containing a nitrogen-containing heterocyclic group containing The quaternary salt structure of phosphorus includes a phosphonio group (trialkyl phosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.) Is mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably, a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of counter anions of quaternary salts include halogen ions, carboxylate ions, sulfonate ions, sulfate ions, perchlorate ions, carbonate ions, nitrate ions, BF ₄ ⁻ , PF ₆ ⁻ , Ph ₄ B ^{− and the} like. It is done. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As the counter anion not present in the molecule, a chlorine ion, a bromo ion or a methanesulfonate ion is particularly preferable.

A preferred structure of the compound represented by types 1, 2, and 3 having a quaternary salt structure of nitrogen or phosphorus as the adsorptive group is represented by the general formula (7).

In the general formula (7), P ¹ and R ¹⁰ each independently represent a quaternary salt structure of nitrogen or phosphorus that is not a partial structure of a sensitizing dye. Q ₁ and Q ₂ each independently represent a linking group, specifically, a single bond, an alkylene group, an arylene group, a heterocyclic group, —O—, —S—, —NR _N —, —C (═O ) —, —SO ₂ —, —SO—, —P (═O) — each independently or a combination of these groups. Here, _RN represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. S ¹ is a residue obtained by removing one atom from compounds of types (1), (2), and (3). i and j are integers of 1 or more, and are selected from a range in which i + j is 2 to 6. Preferably, i is 1 to 3, and j is 1 to 2, more preferably i is 1 or 2, and j is 1, and particularly preferably i is 1 and j is 1. The compound represented by the general formula (7) preferably has a total carbon number in the range of 10 to 100. More preferably, it is 10-70, More preferably, it is 11-60, Most preferably, it is 12-50.

  Of the compounds of types 1 to 3 of the present invention, compounds of type 1 or type 2 are preferred, and compounds of type 1 are particularly preferred.

  The compounds of types 1 to 3 of the present invention are subjected to one-electron oxidation triggered by exposure of the silver halide photographic light-sensitive material using the compound, and after the subsequent reaction, one more electron or two or more electrons depending on the type Electrons are emitted and oxidized, and the oxidation potential of the first electron is preferably about 1.4 V or less, and more preferably 1.0 V or less. This oxidation potential is preferably higher than 0V, more preferably higher than 0.3V. Accordingly, the oxidation potential is preferably in the range of about 0 to about 1.4V, more preferably about 0.3 to about 1.0V.

  Here, the oxidation potential can be measured by a cyclic voltammetry technique. Specifically, a sample is dissolved in a solution of acetonitrile: water (including 0.1 M lithium perchlorate) = 80%: 20% (volume%). After bubbling nitrogen gas for 10 minutes, a glassy carbon disk was used as the working electrode, a platinum wire was used as the counter electrode, and a calomel electrode (SCE) was used as the reference electrode at 25 ° C. and 0.1 V / Measured at a potential scanning speed of seconds. The oxidation potential versus SCE is taken at the peak potential of the cyclic voltammetry wave.

  In the case where the compounds of types 1 to 3 of the present invention are one-electron oxidized and further emit one electron after the subsequent reaction, the subsequent oxidation potential is preferably −0.5 V to −2 V. More preferably, it is -0.7V-2V, More preferably, it is -0.9V--1.6V.

  In the case where the compound of types 1 to 3 of the present invention is a compound which is oxidized by one electron and emits two or more electrons after the subsequent reaction and is oxidized, there is no particular limitation on the oxidation potential of this latter stage. Absent. This is because the oxidation potential of the second electron and the oxidation potential of the third and subsequent electrons cannot be clearly distinguished, and it is often difficult to accurately measure and distinguish these actually.

Specific examples of the compounds represented by types 1 to 3 are listed below, but the present invention is not limited thereto.

Synthesis Example Synthesis of Exemplary Compound 69: Synthesis was performed according to the following scheme.

1,3-Dibromopropane was added to a mixture of Intermediate 1 (13.5 g, 0.1 mol), K ₂ CO ₃ (13.8 g, 0.1 mol), and dimethylacetamide (20 ml (hereinafter, ml is also referred to as “mL”)). (40 g, 0.2 mol) was added, and the mixture was stirred for 3 hours at 100 ° C. The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate, and the ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography. Intermediate 2 was reacted with NaH in THF and ethyl diethylphosphonoacetate, and the reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate.The ethyl acetate layer was dried and concentrated. The product was purified by silica gel column chromatography to obtain Intermediate 3 (23.4 g, 90%), which was dissolved in THF, LiAlH ₄ was added, and the disappearance of Intermediate 3 was confirmed by TLC. After that, the reaction mixture was poured into ice water and with hydrochloric acid. After extraction, the reaction mixture was concentrated, dissolved in methanol, Pd / C (10%, 2 g) was added, and hydrogenated at atmospheric pressure. 4 (18.5 g, 90%) was obtained, and a mixture of Intermediate 4 and Intermediate 5 (29.2 g, 0.1 mol), K ₂ CO ₃ (13.8 g, 0.1 mol) and dimethylacetamide (20 mL) was added at 120 ° C. The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate, and the ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 6 (16.1 g, 50%). Intermediate 6 (4.97 g, 0.01 mol) was dissolved in methanol, 5N, NaOH aqueous solution (10 mL) was added and stirred for 6 hours, the reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. Concentrate and purify by silica gel column chromatography to give Exemplified Compound 69 (2.2 g 55%).

Synthesis of Exemplary Compound 82: Synthesis was performed according to the following scheme.

Intermediate 7 (24.1 g, 0.1 mol), phenacyl bromide (20 g, 0.1 mol) K ₂ CO ₃ (13.8 g, 0.1 mol), and dimethylacetamide (20 mL) were mixed and stirred at 60 ° C. for 2 hours. The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 8 (18 g, 50%). Intermediate 8 was dissolved in methanol, NaBH ₄ (2 g) was added and stirred at room temperature for 30 minutes, and then Pd / C (10%, 2 g) and ammonium formate (10 g) were added and stirred for 2 hours. The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 9 (12.2 g, 90%). To a THF solution of intermediate 9 was added dropwise isobutyl chloroformate (12.3 g, 0.09 mol) and then triethylamine (9.1 g, 0.09 mol) at 0 ° C. Intermediate 10 (10 g, 0.09 mol) was then added and stirred at room temperature for 2 hours. The reaction mixture was added to 1N NaOH aqueous solution and stirred for 6 hours, then acidified with dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated, and purified by silica gel column chromatography to obtain Exemplified Compound 82 (6.4 g, 30%).

Synthesis of Exemplary Compound 92: Synthesis was performed according to the following scheme.

Intermediate 11 (15.3 g, 0.1 mol) and diphenylmethanol (18.4 g, 0.1 mol) were stirred in trifluoroacetic acid at room temperature for 2 hours, then the reaction mixture was poured into aqueous NaHCO ₃ solution and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain intermediate 12 (16 g, 50%). 1,3-Dibromopropane (20 g, 0.1 mol) was added to a mixture of Intermediate 12, K ₂ CO ₃ (13.8 g, 0.1 mol) and dimethylacetamide (20 mL), and the mixture was stirred at 100 ° C. for 3 hours. The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 13 (11 g, 50%). A mixture of Intermediate 13 and Intermediate 5 (7.3 g, 0.025 mol), K ₂ CO ₃ (6.8 g, 0.05 mol), dimethylacetamide (20 mL) was stirred at 120 ° C. for 5 hours, and the reaction mixture was poured into dilute hydrochloric acid. Extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain intermediate 14 (6.5 g, 40%). Intermediate 14 (6.5 g, 0.01 mol) was dissolved in methanol, 5N NaOH aqueous solution (10 mL) was added and stirred for 6 hours. The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated, and purified by silica gel column chromatography to give Exemplified Compound 92 (3.86 g, 70%).

Synthesis of Exemplary Compound 94: Synthesis was performed according to the following scheme.

A mixture of Intermediate 15 (35.4 g, 0.2 mol), MeI (50 mL), K ₂ CO ₃ (27.6 g, 0.25 mol), dimethylacetamide (100 mL) was stirred with heating under reflux for 5 hours, and the reaction mixture was poured into water. Poured, neutralized with hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain intermediate 16 (32.8 g, 80%). A THF solution of intermediate 16 was added dropwise to a THF solution of LiAlH ₄ (6 g, 0.16 mol). An aqueous NaOH solution was added to the reaction mixture to inactivate excess LiAlH ₄ , and then the supernatant was taken out by decantation, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 17 (14 g, 50%). Intermediate 17 was added with acetyl chloride (7.85 g, 0.1 mol) and triethylamine (10.2 g, 0.1 mol) in an ethyl acetate solvent, stirred at room temperature for 1 hour, poured into water, and the ethyl acetate layer was separated. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 18 (15.8 g, 90%). DMF (14.6 g, 0.2 mol) was added to chloroform, oxalyl chloride (25.4 g, 0.2 mol) was further added dropwise, and the mixture was stirred at room temperature for 1 hour. A chloroform solution of intermediate 18 (15.8 g, 0.072 mol) was added dropwise to the resulting solution, and the mixture was further stirred at room temperature for 4 hours. The resulting reaction mixture was poured into an aqueous sodium bicarbonate solution little by little and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 19 (13.4 g, 75%). Intermediate 19 was dissolved in acetonitrile (50 mL), water (5 mL) was added, and then NaClO (9.7 g, 0.11 mol) was added little by little. After stirring at room temperature for 5 hours, the mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 20 (2.84 g, 20%). 1N NaOH aqueous solution (20 mL) was added to the methanol solution of the intermediate 20 and stirred at room temperature for 2 hours. After concentration under reduced pressure, water was added and the mixture was extracted with hydrochloric acid, adjusted to pH 3, and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated and purified by silica gel column chromatography to obtain Intermediate 21 (1.1 g, 46%). Triethylamine (1 g, 0.01 mol) followed by Boc anhydride (2.2 g, 0.01 mol) was added to the dimethylacetamide solution of intermediate 21 and stirred at room temperature for 2 hours, and then intermediate 22 (0.91 g, 5 mmol) was added. The mixture was further stirred for 2 hours. The resulting reaction mixture was poured into an aqueous solution and extracted with ethyl acetate. The ethyl acetate layer was dried, concentrated, and purified by silica gel column chromatography to give Exemplified Compound 94 (0.48 g, 20%).

  Other exemplary compounds can also be synthesized by referring to the methods described in the literature.

  The compounds of types 1 to 3 of the present invention may be used at any time during the preparation of the emulsion and during the photosensitive material production process. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The addition position is preferably from the end of particle formation to before the desalting step, at the time of chemical sensitization (from immediately before the start of chemical sensitization to immediately after the end), and before application, more preferably at the time of chemical sensitization and before application.

  The compounds of types 1 to 3 of the present invention are preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added.

The compounds of types 1 to 3 of the present invention are preferably used in the emulsion layer, but may be added to the protective layer and intermediate layer together with the emulsion layer and diffused during coating. The timing of addition of the compound of the present invention is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 2 mol per 1 mol of silver halide, regardless of before and after the sensitizing dye. X10 ^-3 mol in a silver halide emulsion layer.

  The silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, tetrahedrons, rhombohedral dodecahedrons, and irregularities such as spheres and plates Those having an (irregular) crystal form, those having a higher-order plane ((hkl) plane), or a mixture of grains having these crystal forms, are preferably tabular grains, preferably tabular The particles are described in detail below. For particles having higher-order surfaces, Journal of Imaging Science, Vol. 30 (1986), pages 247 to 254 can be referred to.

  The light-sensitive material of the present invention preferably contains a light-sensitive silver halide emulsion composed of tabular grains (silver halide grains having two opposing parallel major planes, hereinafter referred to as “tabular grains”). The tabular grains will be described in detail below.

  The aspect ratio of the tabular grain in the present invention is obtained by dividing the equivalent circle diameter (the diameter of a circle having the same projected area as the main plane) of two opposing parallel main planes by the distance of the main plane (that is, the thickness of the grains). Defined as a value.

  The aspect ratio of the tabular grains is preferably 5 or more and 100 or less. In order to express the effect of the present invention, it is more preferably 8 or more and 60 or less, and particularly preferably 10 or more and 30 or less. If the average aspect ratio is less than 2, the merit (improvement of sensitivity and image quality) of tabular grains cannot be fully utilized, and if it exceeds 100, the pressure resistance deteriorates, which is not preferable. In the tabular grains in the present invention, the proportion of tabular grains is preferably 60% or more of the total projected area, more preferably 80% or more, and particularly preferably 90% or more. If it is less than 50%, the advantages of tabular grains cannot be fully utilized.

  The average grain thickness in the present invention is an arithmetic average of grain thicknesses of all tabular grains. The average grain thickness of the tabular grains of the present invention is preferably 0.01 to 0.3 μm, more preferably 0.01 to 0.12 μm, and particularly preferably 0.01 to 0.07 μm. If the average particle thickness is less than 0.01 μm, the pressure resistance is deteriorated, and if it exceeds 0.3 μm, it is difficult to obtain the effects of the present invention.

  In the present invention, the grain thickness and aspect ratio in the above range may be selected according to the purpose, but it is preferable to use tabular grains having a small grain thickness and a high aspect ratio.

  Although the diameter (equivalent circle diameter) of the tabular grain in the present invention can be arbitrarily selected, it is preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm. If the average equivalent circle diameter, which is the arithmetic average of the equivalent circle diameters of all tabular grains, is less than 0.3 μm, it is difficult to obtain the effect of the present invention.

  The particle diameter and particle thickness can be measured from an electron micrograph of the particles as described in US Pat. No. 4,434,226. As an example of the method for measuring the aspect ratio, there is a method of obtaining a diameter (equivalent circle diameter) and thickness of a circle having an area equal to the projected area of each particle by taking a transmission electron micrograph by a replica method. In this case, the thickness can be calculated from the length of the shadow of the replica.

  The tabular grains of the present invention are preferably monodispersed. The variation coefficient of the particle size distribution of all silver halide grains is preferably 35% or less, more preferably 25% or less, and particularly preferably 20% or less. If it exceeds 35%, it is not preferable in terms of homogeneity between particles. Here, the variation coefficient of the particle size distribution is a value obtained by multiplying the value obtained by dividing the variation (standard deviation) of the sphere equivalent diameter of each silver halide grain by the average sphere equivalent diameter by 100. The grain size distribution of a silver halide emulsion consisting of a group of grains with uniform grain morphology and small grain size variation shows a normal distribution, and the standard deviation can be easily determined.

  The preparation of monodispersed tabular grains is described in JP-A-63-111928. Monodispersed hexagonal tabular grains are described in JP-A No. 63-151618. The circular monodispersed tabular grain emulsion is described in JP-A-1-131541. In JP-A-2-838, 95% or more of the total projected area is occupied by tabular grains having two twin planes parallel to the main plane, and the size distribution of the tabular grains is monodisperse. An emulsion is disclosed. EP 514,742 A1 discloses a tabular grain emulsion prepared using a polyalkylene oxide block copolymer and having a coefficient of variation of grain size of 10% or less.

  Tabular grains having a main surface of (100) and (111) are known, and the technique of the present invention can be applied to both. The former is described in US Pat. No. 4,063,951 and JP-A-5-281640 regarding silver bromide, and in European Patent No. 534,395A1 and US Pat. No. 5,264,337 regarding silver chloride. There is a description. The latter tabular grains are grains having various shapes having one or more twin planes. Regarding silver chloride, U.S. Pat. Nos. 4,399,215, 4,983,508, No. 5,183,732, JP-A-3-137632 and JP-A-3-116113.

  Various methods can be used as the method for forming tabular grains. For example, the grain forming method described in US Pat. No. 5,494,789 can be used.

  In order to form high aspect ratio tabular grains, it is important to generate small twin nuclei. Therefore, it is preferable to perform nucleation within a short time at low temperature, high pBr, low PH, and low gelatin content. The types of gelatin are low molecular weight, low methionine content, and phthalated Etc. are preferable.

  After nucleation, only tabular grain nuclei (parallel multiple twin nuclei) are grown by physical ripening, and other normal crystal nuclei, single twin nuclei, and non-parallel multiple twin nuclei disappear and are selectively parallel multiplexed. Leaves twin nuclei. Thereafter, a soluble silver salt and a soluble halogen salt are added and grain growth is performed to prepare an emulsion composed of tabular grains.

  It is also preferable to grow the grains by supplying silver and halides by adding silver halide fine particles prepared separately in advance or simultaneously prepared in another reaction vessel.

  The tabular grains in the present invention may have dislocation lines. A dislocation line is a linear lattice defect at the boundary between a region that has already slipped and a region that has not yet slipped on the slip plane of the crystal.

  When the tabular grain in the present invention has a dislocation line, the position may be formed, for example, on a vertex part, a fringe part or a main plane of the grain. Here, the fringe portion refers to the outer periphery of the tabular grain. Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a certain point for the first time when viewed from the side is the total grain size. The point outside the point where the average silver iodide content was exceeded or below.

  When the tabular grains in the present invention have dislocation lines, the density of the dislocation lines is arbitrary, and can be 10 or more, 30 or more, 50 or more per grain, and the like. The tabular grains used in the present invention may have dislocation lines in the grains.

  Japanese Unexamined Patent Publication No. 63-220238 discloses a technique for introducing dislocations into silver halide grains under control. Tabular grains with dislocation lines introduced are more effective than tabular grains without dislocation lines in improving photographic properties such as sensitivity and reciprocity, improving storage stability, improving latent image stability, and reducing pressure fog. It has been shown to be obtained. According to the invention described in this publication, dislocations are mainly introduced into edge portions of tabular grains. Further, tabular grains in which dislocations are introduced at the center are described in US Pat. No. 5,238,796.

  Dislocation lines in silver halide grains are, for example, JF Hamilton, Photo.Sci.Eng., 11, 57 (1967) and T.Shiozawa, J.Soc.Photo.Sci.Japan, 35, 213 (1972). Can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocations from the emulsion are placed on a mesh for observation with an electron microscope, and the sample is placed to prevent damage (printout) due to electron beams. Observe by cooling method in the cooled state. At this time, the thicker the particle, the more difficult it is for the electron beam to pass through. Therefore, it is possible to observe more clearly using a high-pressure type electron microscope (200 kv or more for particles having a thickness of 0.25 μm). it can. The position and the number of dislocation lines for each particle when viewed from a plane perpendicular to the main plane can be obtained from the photograph of the particle obtained by such a method.

  As the tabular grains in the present invention, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, silver chloride, silver chloroiodobromide and the like can be used, but silver bromide, silver iodobromide, It is preferable to use silver chloroiodobromide.

  It is also preferable from the viewpoint of rapid processing suitability to use silver chlorobromide, silver chloroiodide, silver chloroiodobromide or silver chloride having an aspect ratio of 2 or more and containing 50 mol% or more of silver chloride. Although there is no restriction | limiting in particular in the upper limit of silver chloride content rate, 99.6 mol% or less is preferable.

  In the case of having a phase containing iodide or chloride, these phases may be uniformly distributed or localized in the grains. Other silver salts such as rhodium silver, silver sulfide, silver selenide, silver carbonate, silver phosphate and organic acid silver may be contained as separate grains or as part of silver halide grains.

  The preferred silver iodide content of the tabular grains in the present invention is from 0.1 to 20 mol%, more preferably from 0.1 to 15 mol%, particularly preferably from 0.2 to 10 mol%. If it is less than 0.1 mol%, it is difficult to obtain effects such as enhanced dye adsorption and an increase in intrinsic sensitivity, and if it exceeds 20 mol%, the development speed is generally delayed, such being undesirable.

  In the case of tabular grains having an aspect ratio of 2 or more containing 50 mol% or more of silver chloride, silver iodide may be contained, but the silver iodide content is preferably 6 mol% or less, more preferably 2 mol% or less. is there.

  In the present invention, the tabular grains preferably have a coefficient of variation of the inter-grain silver iodide content distribution of 30% or less, more preferably 25% or less, and particularly preferably 20% or less. If it exceeds 30%, it is not preferable in terms of homogeneity between particles. The silver iodide content of each tabular grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. Here, the variation coefficient of the silver iodide content distribution is a value obtained by dividing the standard deviation of the silver iodide content of each grain by the average silver iodide content.

  The tabular grains in the present invention may be epitaxial silver halide grains in which at least one silver salt epitaxy is formed on the surface of the host tabular grains.

  In the present invention, silver salt epitaxy may be formed at selected sites on the surface of the host tabular grains, and the corners and edges of the host tabular grains (when the tabular grains are viewed from above, the side surfaces of the grains and the sides of each side). The upper part) may be limited.

  When forming silver salt epitaxy, it is preferable to form silver salt epitaxy at selected sites on the surface of host tabular grains uniformly within and between grains. Specifically, the site direct method of silver salt epitaxy includes a spectral sensitizing dye (for example, cyanine dye) and aminoazaindenes (for example, adenine) on the host particle before silver salt epitaxy formation described in US Pat. No. 4,435,501. ) Or a method of containing silver iodide in the host grain, and these methods may be used. In addition, iodide ions may be added and deposited on the host grains before silver salt epitaxy formation. These site direct methods may be selected according to circumstances, or may be used in combination.

  When silver salt epitaxy is formed, the proportion of silver salt epitaxy occupied by the host tabular grain surface area is preferably 1 to 50%, more preferably 2 to 40%, and particularly preferably 3 to 30%. .

  When forming silver salt epitaxy, the silver amount of silver salt epitaxy is preferably 0.3 to 50 mol%, more preferably 0.3 to 25 mol%, based on the total silver amount of the silver halide tabular grains. Particularly preferred is 0.5 to 15 mol%.

  The composition of the silver salt epitaxy can be selected depending on the case, and may be a silver halide containing any one of chloride ion, bromide ion and iodide ion. Preferably there is. Since silver chloride forms the same face-centered cubic lattice structure as silver bromide and silver iodobromide, which are host tabular grains, it is easy to form epitaxy. However, there is a difference in the lattice spacing formed by the two types of silver halide, and this difference forms an epitaxy junction that contributes to an increase in photographic sensitivity.

  The silver chloride content contained in the silver halide epitaxy is preferably at least 10 mol% higher than the silver chloride content contained in the host tabular grains, more preferably 15 mol% or more, and more preferably 20 mol% or more. Particularly preferred. If the difference between the two is less than 10 mol%, it is difficult to obtain the effect, which is not preferable.

  When introducing halide ions into silver halide epitaxy, it is preferable to introduce halide ions in the order corresponding to the composition of the epitaxy in order to increase the amount of introduction. For example, in the case of forming epitaxy that contains a large amount of silver chloride inside, a large amount of silver bromide in the middle, and a large amount of silver iodide on the outside, chloride ions, bromide ions, iodide ions These halides are added in order to lower the solubility of the silver halide containing the added halide ions from that of other silver halides, precipitate the silver halide, and enrich the silver halide. Forming a layer. Silver salts other than silver halides, such as rhodium silver, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver, may be contained in the silver salt epitaxy.

  Methods for forming silver salt epitaxy include methods of adding halide ions, methods of adding silver nitrate aqueous solution and halide aqueous solution by the double jet method, methods of adding silver halide fine particles, etc. You may select it, and you may use it in combination of two or more. The temperature, pH, pAg, and the type and concentration of the protective colloid agent such as gelatin, the presence / absence of the silver halide solvent, the type and concentration, and the like can be selected widely when forming silver salt epitaxy.

  In the case of epitaxial silver halide grains, the outer region of the host tabular grains (the last sedimented part and the edge of the grains) is used to maintain the morphology of the host tabular grains or to perform site direct to the grain edge / corner of silver salt epitaxy. / Form a corner portion) is preferably at least 1 mol% higher than the silver iodide content in the central region. At that time, the silver iodide content in the outer region is preferably 1 to 20 mol%, more preferably 5 to 15 mol%. If it is less than 1 mol%, the above-mentioned effect is hardly obtained, and if it exceeds 20 mol%, the development speed is delayed, which is not preferable. In this case, the ratio of the total silver amount in the outer region containing silver iodide to the total silver amount of the host tabular grains is preferably 10 to 30%, and more preferably 10 to 25%. If it is less than 10% or exceeds 30%, it is difficult to obtain the above effect, which is not preferable. Further, the silver iodide content in the central region at that time is preferably 0 to 10 mol%, more preferably 1 to 8 mol%, and particularly preferably 1 to 6 mol%. If it exceeds 10 mol%, the development speed is delayed, which is not preferable.

  The tabular grains used in the present invention may be any ordinary dopant known to be useful for a silver halide face-centered cubic crystal lattice structure. Common dopants include Fe, Co, Ni, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Hg, Pb, Tl and the like. These dopants can be present in the host emulsion and / or the silver salt epitaxially disposed on the grain surface.

  The above emulsion in the present invention and other photographic emulsions used in combination with it are described below.

  Silver halide grains in other emulsions used in the present invention have regular crystals such as cubes, octahedrons and tetradecahedrons, and irregular crystal shapes such as spheres and plates. Those having crystal defects such as twin planes, or a composite form thereof. The grain size of the silver halide in the present invention may be fine grains of about 0.2 μm or less or large size grains having a sphere equivalent diameter of about 3 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

  Specifically, US Pat. No. 4,500,626, column 50, 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17029 (1978), No. 17643 ( (1978) 22-23, No. 18716 (1979) 648, No. 307105 (1989) 863-865, JP-A-62-253159, JP-A-64-13546, JP-A-2-13546. No. 236546, No. 3-110555 and Grafkide, “Physics and Chemistry of Photography”, published by Paul Monte (P. Glafkides, Chemie et Phisque Photographique, Paul Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, Focal Press Published (GFDuffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photogr aphic Emulusion, Focal Press, 1964) and the like.

  In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic such as grain size, grain size distribution, halogen composition, grain shape, and sensitivity of a photosensitive silver halide emulsion are mixed in the same layer. Can be used. Further, an emulsion composed of tabular grains having a silver chloride content of 50 mol% or more and an aspect ratio of 2 or more preferably used in the present invention and an emulsion different from the emulsion are used in separate layers, or mixed in the same layer. It can also be used.

  In the process of preparing the photosensitive silver halide emulsion in the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, a Nudell water washing method in which gelatin is gelled may be used, and inorganic salts (for example, sodium sulfate) composed of polyvalent anions, anionic surfactants, anionic polymers (for example, polystyrene sulfonic acid) Sodium) or a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used, and the precipitation method is most preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The addition amount, in general by the intended use, 10 per mol of silver halide ^- a 9-10 ^-3 mol. Moreover, when making it contain, particle | grains may be put uniformly and you may make it local in the inside and surface of particle | grains. Specifically, emulsions described in JP-A-2-236542 and 1-116637 are preferably used.

  In the grain formation stage of the photosensitive silver halide emulsion in the present invention, rhodan salts, ammonia, tetrasubstituted thiourea compounds, organic thioether derivatives described in JP-B-47-11386 or JP-A-53-144319 are used as silver halide solvents. Can be used.

  For other conditions, Grafkide's "Photophysics and Chemistry", published by Paul Monte (P.Glafkides, Chemie et Phisque Photographique, Paul Montel, 1967), Duffin's "Photoemulsion Chemistry", Focal Press (GFDuffin, Photographic Emulsion Chemistry, Focal Press, 1966), “Production and coating of photographic emulsions” by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photographic Emulusion, Focal Press, 1964), etc. Refer to the description. That is, any of an acidic method, a neutral method, and an ammonia method may be used, and any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used as a form for reacting a soluble silver salt and a soluble halogen salt. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used.

  A backmixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the simultaneous mixing method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is generated is kept constant can be used.

  Further, in order to accelerate the grain growth, the addition concentration, addition amount, and addition rate of the silver salt and halogen salt to be added may be increased (Japanese Patent Laid-Open Nos. 55-142329, 55-158124, US Pat. No. 3). , 650,757 etc.). Furthermore, the stirring method of the reaction solution may be any known stirring method.

  Further, the temperature and pH of the reaction solution during the formation of silver halide grains may be selected according to the purpose. The preferred pH range is 2.2 to 7.0, more preferably 2.5 to 6.0.

  The light-sensitive silver halide emulsion is usually a silver halide emulsion which has been chemically sensitized (excluding chemical sensitization by the compounds of types (1) to (3) defined in the present invention). In the chemical sensitization of the photosensitive silver halide emulsion in the present invention, a known chalcogen sensitizing method such as sulfur sensitizing method, selenium sensitizing method, tellurium sensitizing method, gold, platinum, A noble metal sensitizing method using palladium or the like, a reduction sensitizing method, or the like can be used alone or in combination (Japanese Patent Laid-Open No. 3-110555). In carrying out these normal chemical sensitization, it is also a preferred embodiment that the compound (particularly the compound represented by the general formula (1) or (2)) related to the present invention is present to carry out the sensitization of the present invention. . In this case, the compound may be added at any time during normal chemical sensitization, immediately before chemical sensitization, or immediately after completion of chemical sensitization. Such chemical sensitization can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253159). Further, the antifoggant described later can be added after the chemical sensitization is completed. Specifically, the methods described in JP-A-5-45833 and JP-A-62-240446 can be used.

  The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 9 .0.

The coating amount of the photosensitive silver halide used in the present invention is preferably in the range of 0.01 to 10 g / m ² in terms of silver, and particularly preferably 6 g / m ² or less.

  In order to give the photosensitive silver halide used in the present invention color sensitivity such as green sensitivity and red sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes and the like. If necessary, the blue-sensitive emulsion may be spectrally sensitized in the blue region.

  The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specific examples include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828, and 5-45834. It is done.

  These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization.

  Along with the sensitizing dye, a dye which itself does not have spectral sensitizing action or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3, 615, 641, JP-A 63-23145, etc.).

These sensitizing dyes may be added to the emulsion during or after chemical ripening, or before or after nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. Good. These sensitizing dyes and supersensitizers may be added in a solution of an organic solvent such as methanol, a dispersion such as gelatin, or a surfactant solution. The addition amount is generally 1 mol of silver halide per 10 ^- 8 to 10 ^-2 moles.

  Furthermore, the present invention is preferably used in combination with a technique for improving light absorption with a spectral sensitizing dye. For example, by using intermolecular force, more sensitizing dyes can be adsorbed on the surface of silver halide grains than single-layer saturated adsorption (ie, single-layer adsorption), or two or more separate conjugated dyes can be covalently bonded. Adsorption of so-called linked dyes with linked chromophores. Among these, it is preferable to use together with the technique described in the patent shown below.

JP 10-239789, JP 11-133531, JP 2000-267216, JP 2000-275772, JP 2001-75222, JP 2001-75247, JP 2001-75221, Special JP 2001-75226, JP 2001-75223, JP 2001-255615, JP 2002-23294, JP 10-171058, JP 10-186559, JP 10-197980, JP JP 2000-81678, JP 2001-5132, JP 2001-166413, JP 2002-49113, JP 64-91134, JP 10-110107, JP 10-171058, JP JP 10-226758, JP 10-307358, JP 10-307359, JP 10-310715, JP 2000-231174, JP 2000-231172, JP 2000-231173, JP 2001 -356442, European Patent No. 985965A, European Patent No. 985964A, European Patent No. 985966A, European Patent No. 985967A, European Patent No. 1085372A, European Patent No. 1085373A, European Patent No. 1172688A, European Patent No. 1199595A No., European Patent No. 887700A1.
In particular, it is preferable to use in combination with the technology described in the following patents.
JP-A-10-239789, JP-A-2001-75222, JP-A-10-171058.

The photographic additives that can be used in the present invention are described in RD, and the following related portions are shown.
RD No.17643 No.18716 No.307105
Types of additives (December 1978) (November 1979) (November 1989)
1. Chemical sensitizer, page 23, page 648, right column, page 866, 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizer 23-24 pages 648 right column 866-868 supersensitizers 649 pages right column 4. Whitening agent 24 pages 647 right column 868 pages 5. 5. Light absorber, page 25-26, page 649, right column, page 873 Filter dye,-page 650, left column, UV absorber Binder page 26 page 651 left column page 873-874 Plasticizer, lubricant page 27 page 650 right column page 876 page 8. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surface active agent 9. Static page 27 page 650 right column page 876-877 Inhibitor
Ten. Matting agent, 878-879 pages

  In the present invention, it is also preferred to use an organic metal salt as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, organic silver salts are particularly preferably used.

  The organic silver salt that can be used in the present invention is relatively stable to light, but is 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent. It is a silver salt that forms a silver image when heated above. The organic silver salt may be any organic material containing a source capable of reducing silver ions. Silver salts of organic acids, particularly silver salts of long chain fatty carboxylic acids (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms) are preferred. Also preferred are complexes of organic or inorganic silver salts where the ligand has a complex stability constant in the range of 4.0 to 10.0. The silver-providing material can preferably constitute about 5-30% by weight of the image forming layer.

  Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the aliphatic carboxylic acid silver salt include silver behenate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, and tartaric acid. Includes silver, silver linoleate, silver butyrate and silver camphorate, mixtures thereof, and the like.

  Silver salts of compounds containing a mercapto group or a thione group and derivatives thereof can also be used. Preferred examples of these compounds include silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, 2 Silver salt of-(ethylglycolamido) benzothiazole, silver salt of thioglycolic acid such as silver salt of s-alkylthioglycolic acid (wherein the alkyl group has 12 to 22 carbon atoms), silver salt of dithioacetic acid, etc. Silver salt of dithiocarboxylic acid, silver salt of thioamide, silver salt of 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, US Pat. 4,123,274, for example, 1,2, such as silver salt of 3-amino-5-benzylthio-1,2,4-thiazole Silver of a thione compound such as a silver salt of a 4-mercaptothiazole derivative and a silver salt of 3- (3-carboxyethyl) -4-methyl-4-thiazoline-2-thione described in US Pat. No. 3,301,678 Contains salt. Furthermore, a compound containing an imino group can also be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole, US Patent 1,2,4-triazole or silver salt of 1-H-tetrazole as described in US Pat. No. 4,220,709, and silver salts of imidazole and imidazole derivatives. For example, various silver acetylide compounds as described in US Pat. Nos. 4,761,361 and 4,775,613 can also be used. Two or more organic silver salts may be used in combination.

In the present invention, the above organic compound is mixed with silver nitrate in an appropriate reaction medium to form a silver salt of the compound (hereinafter referred to as an organic silver salt). A part of silver nitrate can be replaced with another silver ion supplier (eg, silver chloride, silver acetate).
The method for adding these reaction reagents is arbitrary. The compound may be previously placed in a reaction vessel and silver nitrate may be added thereto, or conversely, silver nitrate may be placed in a reaction vessel and the compound may be added thereto. Alternatively, a part of the compound is put in a reaction vessel, and a part of silver nitrate is added, and then the remaining compound and silver nitrate are sequentially added. Furthermore, silver nitrate and an organic compound can be simultaneously added to the reaction vessel. It is preferable to stir during the reaction.

  The organic compound is usually mixed with silver nitrate at a ratio of 0.8 to 100 moles per mole of silver, but depending on the type of the compound, it can be used outside this range. The rate of silver nitrate or compound addition may be adjusted so as to control the silver ion concentration during the reaction.

  The organic silver salt may be added to any layer, and may be added to one layer or a plurality of layers. In addition, a hydrophilic colloid layer provided on the side having the silver halide emulsion layer is added to a layer not containing a photosensitive silver halide emulsion such as a protective layer, an intermediate layer, a so-called undercoat layer between the support and the emulsion layer. This is also preferable in terms of improving storage stability.

The organic silver salt can be used in an amount of 0.01 to 10 mol, preferably 0.05 to 1 mol, per mol of photosensitive silver halide. 0.02~20g / m ² in total coating amount of silver in terms of the light-sensitive silver halide and organic silver salt is preferably 0.1~12g / m ^2, particularly preferably 6 g / m ² or more.

  The silver halide emulsions and / or organic silver salts in the present invention are protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors and are sensitive to variations in sensitivity during inventory storage. Can be stabilized. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are the thiazonium salts, US Pat. Nos. 2,131,038 and 2,694,716 described in US Pat. Azaindene described in US Pat. Nos. 2,886,437 and 2,444,605, mercury salt described in US Pat. No. 2,728,663, urazole described in US Pat. No. 3,287,135, US patent Sulfocatechol described in US Pat. No. 3,235,652, oxime described in British Patent No. 623,448, nitrone, nitroindazole, polyvalent metal salt described in US Pat. No. 2,839,405, US Pat. No. 3,220,839 and palladium, platinum and gold salts described in US Pat. Nos. 2,566,263 and 2,597,915, US Pat. , 665 and 4,442,202, U.S. Pat. Nos. 4,128,557 and 4,137,079, 4,138,365 and 4,459. No. 3,350 and the phosphorus compounds described in US Pat. No. 4,411,985.

Antifoggants preferably used in the present invention are organic halides such as JP-A-50-119624, JP-A-50-120328, JP-A-51-121332, JP-A-54-58022, JP-A-56-70543, 56-99335, 59-90842, 61-129642, 62-129845, JP-A-6-208191, 7-5621, 7-27881, 8-15809, USA Examples thereof include compounds disclosed in Japanese Patent Nos. 5,340,712, 5,369,000, and 5,464,737.
The antifoggant of the present invention may be added by any method such as a solution, a powder, or a solid fine particle dispersion. The solid fine particle dispersion is performed by a known finer means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). Further, a dispersion aid may be used when dispersing the solid fine particles.

  The light-sensitive material in the present invention may contain benzoic acids for the purpose of increasing sensitivity and preventing fog. Although the benzoic acid of the present invention may be any benzoic acid derivative, examples of preferred structures include compounds described in US Pat. Nos. 4,784,939 and 4,152,160.

The benzoic acids of the present invention may be added to any part of the light-sensitive material, but the addition layer is preferably added to the layer having the photosensitive layer, and more preferably added to the organic silver salt-containing layer. . The benzoic acid of the present invention may be added at any step of preparing the coating solution, and when added to the organic silver salt-containing layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be used. It is preferable that the salt is prepared and immediately before coating. As a method for adding the benzoic acid of the present invention, any method such as powder, solution, fine particle dispersion and the like may be used. Moreover, you may add as a solution mixed with other additives, such as a sensitizing dye and a reducing agent. It may be any amount as an additive amount of the benzoic acids of the present invention but, 1 × 10 photosensitive silver halide per mole ^- 6 to 2 mol is preferable, 1 × 10 ^-3 to 0.5 mol is more preferable.

  In the present invention, a mercapto compound, a disulfide compound, and a thione compound are included for the purpose of controlling development by suppressing or promoting development, improving spectral sensitization efficiency, and improving storage stability before and after development. Can do.

  When a mercapto compound is used in the present invention, any structure may be used, but those represented by Ar-SM and Ar-SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring group or a condensed aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring can be, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms) and alkoxy ( For example, it may have one selected from a substituent group consisting of one or more carbon atoms, preferably one having 1 to 4 carbon atoms. Examples of the mercapto-substituted heteroaromatic compounds include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2, 2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6- Hydroxy-2-mercaptopi Midine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole and the like. However, the present invention is not limited to these.

  The amount of these mercapto compounds added is preferably in the range of 0.001 to 1.0 mole per mole of photosensitive silver halide in the emulsion layer, and more preferably 0.01 to 1 mole per mole of photosensitive silver halide. The amount is 0.3 mol.

  The light-sensitive material of the present invention preferably uses a silver halide solvent. For example, thiosulfate, sulfite, thiocyanate, thioether compound described in JP-B No. 47-11386, uracil described in JP-A-8-179458, compound having a 5- to 6-membered ring imide group such as hydantoin, JP A compound having a carbon-sulfur double bond described in Sho 53-144319, a meso such as trimethyltriazolium thiolate described in Analytica Chimica Acta, 248, 604-614 (1991) An ion thiolate compound is preferably used. Further, compounds capable of fixing and stabilizing silver halide described in JP-A-8-69097 can also be used as a silver halide solvent.

The amount of silver halide solvent contained in the light-sensitive material is a 0.01~100mmol / m ^2, preferably 0.1~50mmol / m ^2, more preferably 10~50mmol / m ^2. With respect to the coated silver amount of the photosensitive silver halide of the photosensitive material, the molar ratio is 1/20 to 20 times, preferably 1/10 to 10 times, and more preferably 1/3 to 3 times. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, or methylpropyl glycol, or an alkali or acidic aqueous solution, or may be dispersed in solid fine particles and added to the coating solution. The silver halide solvent may be used alone or in combination with a plurality of silver halide solvents.

In the present invention, a hydrophilic binder is preferably used as the binder of the constituent layer in the photosensitive material. Examples thereof include the above-mentioned RD and those described in JP-A No. 64-13546, pages 71-75. Specifically, transparent or translucent hydrophilic binders are preferable, for example, proteins such as gelatin and gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, polyvinyl alcohol, modified Examples thereof include synthetic polymer compounds such as polyvinyl alcohol (for example, terminal alkyl-modified POVAL MP103, MP203 manufactured by Kuraray Co., Ltd.), polyvinyl pyrrolidone, acrylamide polymer, and the like. Also, a highly water-absorbing polymer described in US Pat. No. 4,960,681, JP-A-62-245260, that is, a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal). Homopolymers or copolymers of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are also used. Two or more of these binders can be used in combination. A combination of gelatin and the above binder is particularly preferred. The gelatin may be selected from so-called demineralized gelatin with a reduced content of lime-processed gelatin, acid-processed gelatin, calcium, etc., depending on various purposes, and is preferably used in combination.

  As the binder in the present invention, it is also preferable to use a polymer latex. Here, the polymer latex is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, the emulsion is polymerized, the micelle is dispersed, or the polymer molecule has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Anything may be used. Regarding the polymer latex of the present invention, “Synthetic Resin Emulsion (Hiraku Okuda, Hiroshi Inagaki, Published by Kobunshi Publishing (1978))”, “Application of Synthetic Latex (Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, "Molecular Publications (1993))" and "Synthetic Latex Chemistry (Muroichi Muroi, published by High Polymers Publication (1970))".

The average particle size of the dispersed particles is preferably 1 to 50000 nm, more preferably about 5 to 1000 nm. There is no particular limitation on the particle size distribution of the dispersed particles. Examples of the polymer species used for the polymer latex include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, and polyolefin resin.
The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer.

  The molecular weight of the polymer is 0.5 to 1,000,000, preferably about 1 to 500,000 in terms of number average molecular weight Mn. If the molecular weight is too small, the mechanical strength of the photosensitive layer is insufficient.

The polymer latex polymer used in the present invention preferably has an equilibrium water content of 2% by mass or less, more preferably 1% by mass or less at 25 ° C. and 60% RH. Although there is no restriction | limiting in particular in the minimum of an equilibrium moisture content, Preferably it is 0.01 mass%, More preferably, it is 0.03 mass%. For the definition and measurement method of the equilibrium moisture content, for example, “Polymer Engineering Course 14, Polymer Materials Testing Method (Edited by Polymer Society, Jinshokan)” can be referred to. Specifically, the equilibrium water content at 25 ° C. and 60% RH is determined based on the mass W _{1 of} the polymer that has reached humidity control equilibrium in an atmosphere of 25 ° C. and 60% RH and the mass W _{0 of the} polymer in an absolutely dry state at 25 ° C. Can be expressed as follows.

“Equilibrium moisture content at 25 ° C. and 60% RH” = {(W ₁ −W ₀ ) / W ₀ } × 100 (mass%)
Such polymers are also commercially available, and the following polymers can be used as the polymer latex. For example, as an example of acrylic resin, Sebian A-4635, 46583, 4601 (above Daicel Chemical Industries, Ltd.), Nipol Lx811, 814, 821, 820, 857 (above made by Nippon Zeon Co., Ltd.) , FINETEX ES650, 611, 675, 850 (Dai Nippon Ink Chemical Co., Ltd.), WD-size, WMS (Eastman Chemical), etc., polyurethane resins such as HYDRAN AP10, 20, 30, 40 (more Nippon Ink Chemical Co., Ltd.) and other rubber resins such as LACSTAR 7310K, 3307B, 4700H, 7132C, DS206 (above Dainippon Ink Chemical Co., Ltd.), Nipol Lx416, 433, 410, 438C, 2507, (above Nippon Zeon Co., Ltd.), vinyl chloride resin G351, G576 (Nippon Zeon Co., Ltd.), vinylidene chloride resin L502, L513 (Asahi Kasei Kogyo Co., Ltd.), etc. Is Chemipearl S120, SA100 (Mitsui Petrochemical Co., Ltd.) You can. These polymers may be used alone as a polymer latex, or may be used by blending two or more thereof as necessary.

  The polymer latex used in the present invention is particularly preferably a styrene-butadiene copolymer latex. The mass ratio of the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene copolymer is preferably 50:50 to 95: 5. The proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is preferably 50 to 99% by mass. The preferred molecular weight range is the same as described above.

  Examples of latexes of styrene-butadiene copolymer that are preferably used in the present invention include LACSTAR 3307B, 7132C, DS206, Nipol Lx416, and Lx433, which are commercially available products.

In the present invention, the coating amount of the binder is from 1 to 20 g / m ^2, preferably from 2 to 15 g / m ^2, more preferably suitably 3~12g / m ^2. Among these, gelatin can be used in a proportion of 50 to 100%, preferably 70 to 100%.

The light-sensitive material of the present invention can contain a dye-forming coupler.
The coupler preferably used in the present invention is a compound generically called active methylene, 5-pyrazolone, pyrazoloazole, phenol, naphthol or pyrrolotriazole. As these couplers, compounds cited in RD No. 38957 (September 1996), pages 616 to 624, “X. Dye image formers and modifiers” can be preferably used.
These couplers can be divided into so-called 2-equivalent couplers and 4-equivalent couplers.

  Examples of groups that act as anionic leaving groups for 2-equivalent couplers include halogen atoms (eg, chloro and bromo atoms), alkoxy groups (eg, methoxy, ethoxy), aryloxy groups (eg, phenoxy, 4-cyanophenoxy, 4-alkoxy). Carbonylphenyl), alkylthio groups (eg methylthio, ethylthio, butylthio), arylthio groups (eg phenylthio, tolylthio), alkylcarbamoyl groups (eg methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl), heterocyclic carbamoyl groups ( For example, piperidylcarbamoyl, morpholylcarbamoyl), arylcarbamoyl groups (for example, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbyl) Moyl, benzylphenylcarbamoyl), carbamoyl group, alkylsulfamoyl group (eg methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl), heterocyclic sulfamoyl group (eg piperidyl) Sulfamoyl, morpholylsulfamoyl), arylsulfamoyl groups (eg phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), sulfamoyl groups, cyano groups, alkylsulfonyl Group (for example, methanesulfonyl, ethanesulfonyl), arylsulfonyl group (for example, phenylsulfonyl, 4-chlorophenylsulfonyl, p-toluenesulfonyl), alkylcarbonyloxy (E.g. acetyloxy, propionyloxy, butyroyloxy), an arylcarbonyloxy group (e.g., benzoyloxy, toluoyloxy, anisyloxy), nitrogen-containing Hajime Tamaki (e.g. imidazolyl, benzotriazolyl), and the like.

In addition, as a group that acts as a cationic leaving group of the 4-equivalent coupler, a hydrogen atom, a formyl group, a carbamoyl group, a methylene group having a substituent (substituents include an aryl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, Amino group, hydroxyl group and the like), acyl group, sulfonyl group and the like.
In addition to the compounds described in RD No. 38957, the couplers described below can be preferably used.

  As active methylene couplers, couplers represented by formulas (I) and (II) of EP502,424A; couplers represented by formulas (1) and (2) of EP513,496A; claims of European Patent No. 568,037A 1 coupler (1); US Pat. No. 5,066,576, column 1, line 45-55, coupler represented by formula (I); JP-A-4-274425, paragraph number 0008 A coupler represented by general formula (I); a coupler described in claim 1 on page 40 of European Patent No. 498,381A1; a coupler represented by formula (Y) on page 4 of European Patent No. 447,969A1; a US patent A coupler represented by the formulas (II) to (IV) on lines 36 to 58 of column 4,476,219, column 7 can be used.

  As the 5-pyrazolone couplers, compounds described in JP-A-57-35858 and JP-A-51-20826 are preferable.

  Examples of pyrazoloazole couplers include imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 and pyrazolo [1,5-b described in U.S. Pat. No. 4,540,654. ] [1,2,4] triazoles, pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067 are preferred, and in terms of light fastness, Of these, pyrazolo [1,5-b] [1,2,4] triazoles are preferred.

  Further, a pyrazoloazole coupler in which a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2, 3, or 6-position of a pyrazolotriazole group, described in JP-A-61-65245, A pyrazoloazole coupler having a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A No. 61-147254, JP-A No. 62-209457 or 63- Pyrazolotriazole couplers having an alkoxy group or aryloxy group at the 6-position described in No. 307453 and pyrazolotriazole couplers having a carbonamide group in the molecule described in JP-A-2-201443 are also preferably used. Can do.

  Preferred examples of the phenolic coupler include U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162, 2,895,826, and 3, No. 772,002, etc., U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4, No. 334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, Japanese Patent Application Laid-Open No. 59-166958, etc., US Pat. Examples include 2-phenylureido-5-acylaminophenol and the like described in 446,622, 4,333,999, 4,451,559, 4,427,767, etc. Can do.

  Preferred examples of the naphthol coupler include U.S. Pat. Nos. 2,474,293, 4,052,212, 4,146,396, 4,228,233, and 4,296. And 2-carbamoyl-1-naphthol series described in U.S. Pat. No. 4,200, and 2-carbamoyl-5-amido-1-naphthol series described in U.S. Pat. No. 4,690,889.

  Preferable examples of pyrrolotriazole couplers include couplers described in European Patent Nos. 488,248A1, 491,197A1, and 545,300.

In addition, couplers having a structure such as fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle can be used.
As the condensed phenol type couplers, couplers described in U.S. Pat. Nos. 4,327,173, 4,564,586, 4,904,575 and the like can be used.

As the imidazole couplers, couplers described in U.S. Pat. Nos. 4,818,672 and 5,051,347 can be used.
As the pyrrole couplers, couplers described in JP-A-4-188137 and JP-A-4-190347 can be used.
As the 3-hydroxypyridine couplers, couplers described in JP-A-1-315736 can be used.
As the active methine couplers, those described in US Pat. Nos. 5,104,783 and 5,162,196 can be used.

As the 5,5-fused heterocyclic coupler, a pyrrolopyrazole coupler described in US Pat. No. 5,164,289, a pyrroloimidazole coupler described in JP-A-4-174429, and the like can be used.
Examples of the 5,6-fused heterocyclic coupler include pyrazolopyrimidine couplers described in US Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, European Patent 556, The couplers described in No. 700 can be used.

  In addition to the couplers described above, the present invention includes West German Patents 3,819,051A, 3,823,049, U.S. Pat. Nos. 4,840,883, 5,024,930, 5,051,347, 4,481,268, European Patents 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2 No. 386,930A1, JP-A-63-141055, JP-A-64-32260, JP-A-64-32261, JP-A-2-297547, JP-A-2-44340, JP-A-2-110555, JP-A-3. -7938, 3-160440, 3-17239, 4-172447, 4-179949, 4-182645, 4-184437, 4-188138, 4-18813 No., the 4-194847 Patent, the 4-204532 Patent, the 4-204731 Patent, couplers as described in the 4-204732 Patent like can be used.

These couplers can use 0.05-10 mmol / m < ² > of each color, Preferably 0.1-5 mmol / m < ² >.

Moreover, you may contain the following functional couplers.
Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,873B, German Patent No. 3,234,533. Are preferred.

  As a coupler for correcting the unnecessary absorption of the coloring dye, a yellow colored cyan coupler represented by the formulas (CI), (CII), (CIII), and (CIV) described in European Patent No. 456,257A1 page 5 ( In particular, YC-86 on page 84), yellow colored magenta coupler ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251) described in the European patent, US Pat. No. 4,833, No. 069, magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10), US Pat. No. 4,837,136 (2) (column 8), International Patent No. 92/11575 A colorless masking coupler represented by the formula (A) in claim 1 (particularly, exemplified compounds on pages 36 to 45) is preferable.

Examples of the compounds (including couplers) that react with oxidized developing agent to release a photographically useful compound residue include the following.
Development inhibitor releasing compounds: compounds represented by formulas (I) to (IV) described on page 11 of European Patent No. 378,236A1 (especially T-101 (page 30), T-104 (page 31), T- 113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), European Patent No. 436,938A2, page 7 and represented by formula (I) Compounds (especially D-49 (page 51)), compounds of formula (I) of European Patent 568,037A (especially (23) (page 11)), European Patent 440,195A2 pages 5-6 (I- (1) on page 29) represented by the formulas (I), (II) and (III) described in 1.

  Bleach accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) of European Patent No. 310,125A2 page 5 (especially (60) and (61) on page 61) and JP-A-6-59411 Compound represented by formula (I) of Item 1 (particularly (7) (page 7)).

Ligand-releasing compound: a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (particularly, a compound in columns 12 to 41 in column 12).
Leuco dye-releasing compound: Compounds 1-6 in columns 3-8 of US Pat. No. 4,749,641.
Fluorescent dye releasing compound: a compound represented by COUP-DYE of claim 1 of US Pat. No. 4,774,181 (particularly, compounds 1 to 11 in columns 7 to 10).

Development accelerator or fogging agent releasing compound: U.S. Pat. No. 4,656,123 column 3, compounds of formula (1), (2), (3) (particularly column 25 (I-22)) and Europe Patent No. 450,637A2, page 75, lines 36 to 38, ExZK-2.
A compound that releases a group that becomes a dye only after leaving: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (particularly, Y-1 to Y-19 in columns 25 to 36).

As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 of JP-A-62-215272 (140- 144).
Latex for impregnation with oil-soluble organic compound: Latex described in US Pat. No. 4,199,363.
Oxidized developer scavenger: US Pat. No. 4,978,606, column 2, lines 54 to 62, the compound represented by formula (I) (particularly I- (1), (2), (6), (12) (Columns 4-5)), U.S. Pat. No. 4,923,787, column 2, lines 5-10 (particularly compound 1 (column 3).
Stain inhibitor: European Patent No. 298,321, page 4, lines 30 to 33, formulas (I) to (III), especially I-47, 72, III-1, 27 (pages 24 to 48).
Antifading agent: A-6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164 of European Patent No. 298,321A ( 69-118), US Pat. No. 5,122,444, columns 25-38, II-1 to III-23, especially III-10, EP471,347A, pages 8-12, I-1 to III-4, especially II. -2, U.S. Pat. No. 5,139,931, columns 32-40, A-1 to 48, especially A-39,42.

Materials that reduce the amount of color-enhancing agent or color mixing inhibitor used: European Patent 41,132A, pages 5-24, I-1 to II-15, especially I-46.
Formalin scavenger: European Patent 477,932A, pages 24-29, SCV-1 to 28, in particular SCV-8.
Hardener: represented by formulas (VII) to (XII) in columns 13 to 23 of H-1,4,6,8,14, U.S. Pat. No. 4,618,573, page 17 of JP-A-1-214845 Compound (H-1 to 54), compound (H-1 to 76) represented by formula (6) at the lower right of JP-A-2-214852, page 8, particularly H-14, US Pat. No. 3,325,287 A compound according to claim 1.
Development inhibitor precursor; P-24, 37, 39 (pages 6 to 7) of JP-A-62-168139, compounds described in claim 1 of US Pat. No. 5,019,492, 29.
Preservatives, fungicides: U.S. Pat. No. 4,923,790, columns 1 to 3, I-1 to III-43, especially II-1, 9, 10, 18, III-25.
Stabilizer, antifoggant: U.S. Pat. No. 4,923,793 I-1 to (14) in columns 6 to 16, especially I-1,60, (2), (13), U.S. Pat. No. 4,952 , 483 columns 25-32, compounds 1-65, especially 36.
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324.

  Dyes: JP-A-3-156450, pages 15 to 18, a-1 to b-20, especially a-1, 12, 18, 27, 35, 36, b-5, pages 27 to 29, V-1 to 23 , In particular V-1, EP No. 445,627A, pages 33-55, FI-1 to F-II-43, especially FI-11, F-II-8, EP457, 153A, pages 17-28. III-1 to 36, especially III-1 and 3, fine crystal dispersion of Dye-1 to 124 of International Patent No. 88/04794, pages 8 to 26, compound 1 of European Patent No. 319,999A, pages 6 to 11 -22, especially compound 1, compounds D-1 to 87 (pages 3 to 28) represented by formulas (1) to (3) of EP 519,306A, formulas of US Pat. No. 4,268,622 Compounds 1-22 (columns 3-10) represented by (I), in formula (I) of US Pat. No. 4,923,788 I the compounds (1) to (31) (columns 2-9).

  UV absorbers: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) in JP-A No. 46-3335, and formula (I) of European Patent No. 520,938A Compounds (3) to (66) (pages 10 to 44) represented by formula (III) and compounds HBT-1 to 10 (page 14) represented by formula (III), represented by formula (I) of European Patent No. 521,823A (1) to (31) (columns 2 to 9).

  Such functional couplers and additives are preferably used in an amount of 0.05 to 10 times mol, preferably 0.1 to 5 times mol of the coupler contributing to color development described above.

  Hydrophobic additives such as couplers and color developing agents can be introduced into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476, High-boiling organic solvents such as those described in No. 599,296, JP-B-3-62256 and the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C. to 160 ° C. as necessary. Two or more of these dye-donating couplers and high-boiling organic solvents can be used in combination.

  The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g based on 1 g of the hydrophobic additive used. In addition, 1 mL or less, further 0.5 mL or less, particularly 0.3 mL or less is appropriate for 1 g of the binder.

A dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 and a method of adding a fine particle dispersion described in JP-A-62-230242 can also be used.
In the case of a compound that is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder other than the above method.

  In dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants described in JP-A No. 59-157636, pages 37 to 38, the above-mentioned RD can be used. Further, phosphate ester type surfactants described in JP-A-7-56267, JP-A-7-228589, and West German Patent 1,932,299A can also be used.

In the light-sensitive material of the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD No. 17643 (1978) pages 24 to 25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A No. 59-168442, or JP-A No. 59-111636. The described mercapto compounds and metal salts thereof, and acetylene compounds described in JP-A No. 62-87957 are used.
The light-sensitive material of the present invention promotes electron transfer between a diffusion-resistant reducing agent or color developing agent and developable silver halide when a diffusion-resistant reducing agent or color developing agent is used. Further, if necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination. It is desirable that the electron transfer agent or its precursor has a higher mobility than the non-diffusible reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

  In the light-sensitive material of the present invention, it is sufficient that at least one light-sensitive layer is provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain the aforementioned couplers, developing agents and DIR compounds, color mixing inhibitors, dyes and the like. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion as described in German Patent 1,121,470 or British Patent 923,045. It is preferable to arrange the two layers so that the photosensitivity decreases sequentially toward the support. A non-photosensitive layer may be provided between the halogen emulsion layers. Further, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer on the side away from the support and the side close to the support A high-sensitivity emulsion layer can also be provided.

  As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of.

  Further, as described in JP-B-55-34932, it can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A Nos. 56-25738 and 62-63936, they can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

  In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low photosensitivity is arranged, and an arrangement composed of three layers having different photosensitivities in which the photosensitivity is gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitive emulsion layer / a high-sensitivity layer from the side away from the support in the same photosensitive layer. They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer. In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer. Further, the arrangement may be changed as described above even when there are four or more layers.

In order to improve color reproducibility, U.S. Pat. Nos. 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, and 63-89850 are disclosed. It is also preferable to dispose a donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specification, adjacent to or close to the main photosensitive layer.
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

  The emulsion of the present invention can be used in any emulsion layer, but is particularly preferably used in a high-sensitivity emulsion layer.

  In the present invention, the silver halide emulsion, the dye-forming coupler, the color developing agent and / or its precursor may be contained in the same layer, but if they are in a reactive state, they are added separately in separate layers. You can also. For example, if the layer containing the color developing agent and the layer containing the silver halide emulsion are separated, the raw storability of the light-sensitive material can be improved.

  The spectral sensitivity of each layer and the hue of the coupler are arbitrary. However, when a cyan coupler is used for the red photosensitive layer, a magenta coupler is used for the green photosensitive layer, and a yellow coupler is used for the blue photosensitive layer, it can be directly applied to conventional color paper. Projection exposure is possible.

  The light-sensitive material is provided with various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer between and above the silver halide emulsion layers. In addition, various auxiliary layers such as a back layer can be provided on the opposite side of the support.

  Specifically, a layer structure as described in the above patent, an undercoat layer as described in US Pat. No. 5,051,335, a solid pigment as described in JP-A 1-167838 and JP-A 61-20943. An intermediate layer having a reducing agent or a DIR compound as described in JP-A Nos. 1-120553, 5-34884, and 2-64634, U.S. Pat. Nos. 5,017,454, 5, 139,919, an intermediate layer having an electron transfer agent as described in JP-A-2-235444, a protective layer having a reducing agent as described in JP-A-4-249245, or a combination of these may be provided. it can.

As the dye that can be used in the yellow filter layer and the antihalation layer, those that are decolored or removed during development and do not contribute to the density after processing are preferable.
The fact that the dyes in the yellow filter layer and the antihalation layer are decolored or removed during development means that the amount of dye remaining after processing is 1/3 or less, preferably 1/10 or less of that applied. Sometimes the dye component may be transferred from the light-sensitive material to the processing material, or it may react during development to turn into a colorless compound.

  Specific examples include dyes described in European Patent No. 549,489A and ExF2-6 dyes described in JP-A-7-152129. A solid dispersed dye as described in JP-A-8-101487 can also be used.

  In addition, a mordant and a binder can be mordanted. In this case, mordants and dyes which are known in the field of photography can be used. US Pat. No. 4,500,626, columns 58 to 59, JP-A 61-88256, pages 32 to 41, JP-A 62 Examples thereof include mordants described in Nos. -244043 and 62-244036.

  Alternatively, a compound capable of reacting with a reducing agent to release a diffusible dye and a reducing agent can be used to release the movable dye with an alkali during development and transfer and remove it to the processing material. Specifically, it is described in U.S. Pat. Nos. 4,559,290, 4,783,396, European Patent No. 220,746 A2, and published technical report 87-6119.

  A decolorizing leuco dye or the like can also be used. Specifically, JP-A-1-150132 discloses a silver halide photosensitive material containing a leuco dye that has been developed in advance with a developer of an organic acid metal salt. ing. The leuco dye and the developer complex are decolored by reaction with heat or an alkali agent.

  As leuco dyes, known ones can be used. Moriga, Yoshida “Dyes and Drugs”, pages 9, 84 (Chemicals and Chemicals Industries Association), “New Edition Dye Handbook”, page 242 (Maruzen, 1970), R. Garner “Reports on The Progress of Appl. Chem, 56, 199 (1971), “Dye and Chemicals”, 19,230 (Chemicals and Chemicals Industries Association, 1974), “Coloring Materials”, 62, 288 (1989), “Dyeing Industry” 32 208, etc.

  As the developer, an acidic clay developer, a phenol formaldehyde resin, or a metal salt of an organic acid is preferably used. As the metal salt of the organic acid, a metal salt of salicylic acid, a metal salt of phenol-salicylic acid-formaldehyde resin, a rhodan salt, a metal salt of xanthate, and the like are useful, and zinc is particularly preferable as the metal. Among the above developers, oil-soluble zinc salicylate is described in U.S. Pat. Nos. 3,864,146 and 4,046,941 and Japanese Patent Publication No. 52-1327. Things can be used.

The coating layer of the light-sensitive material of the present invention is preferably hardened with a hardener.
Examples of hardeners include U.S. Pat. No. 4,678,739, column 41, 4,791,042, JP-A-59-116655, JP-A-62-245261, JP-A-61-18942, Examples of the hardening agent described in Japanese Patent No. 4-218044. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N′-ethylene-bis (vinylsulfonylacetamide) Ethane), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid or polymer hardeners (compounds described in JP-A-62-234157).
These hardeners are used in an amount of 0.001-1 g, preferably 0.005-0.5 g, per 1 g of hydrophilic binder.

Various antifoggants or photographic stabilizers and precursors thereof can be used in the light-sensitive material. Specific examples thereof include RD, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A Nos. 64-13564 (7) to (9). , (57) to (71) and (81) to (97), U.S. Pat. Nos. 4,775,610, 4,626,500, 4,983,494, JP-A-62-2 174747, 62-239148, JP-A-1-150135, 2-1105557, 2-178650, RD No. 17643 (1978) 24-25, and the like.
These compounds are preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, per mol of silver.

In the light-sensitive material, various surfactants can be used for the purpose of coating aid, peelability improvement, smoothness improvement, antistatic, development promotion and the like. Specific examples of the surfactant are described in publicly known technology No. 5 (March 22, 1991, issued by Aztec Co., Ltd.), pages 136 to 138, JP-A Nos. 62-173463 and 62-183457.
The photosensitive material may contain an organic fluoro compound for the purpose of preventing slipping, preventing static charge, improving peelability and the like. Representative examples of organic fluoro compounds include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, 62-135826, and fluorine oil. And hydrophobic fluorine compounds such as oily fluorine compounds or solid fluorine compound resins such as tetrafluoroethylene resin. For the purpose of achieving both wettability and antistatic property of the photosensitive material, a fluorine-based surfactant having a hydrophilic group is also preferably used.

  The photosensitive material is preferably slippery. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is 0.25 or less and 0.01 or more in terms of dynamic friction coefficient. The measurement at this time represents a value when transported at 60 cm / min with respect to a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.

  Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, and polystyrylmethylsiloxane. Polymethylphenylsiloxane and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred. Silicon oil and chlorinated paraffin are preferably used in order to prevent pressure fogging and desensitization of silver halide.

  In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include polymers containing carboxylic acids and carboxylates and sulfonates, cationic polymers, and ionic surfactant compounds.

Most preferred as the antistatic agent is at least one selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O _5. The volume resistivity of the seed is 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. The particle size is 0.001 to 1.0 μm Crystalline metal oxide or a composite oxide thereof (Sb, P, B, In, S, Si, C, etc.), and also sol-like metal oxides or composite oxides thereof. Preferably 5 to 500 mg / m ² as the content of the sensitive material, particularly preferably from 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1: 300 to 100: 1, more preferably 1: 100 to 100: 5. It is also preferable to apply a water-resistant polymer described in JP-A-8-292514 to the back surface of the support of the photosensitive material.

  The composition of the photosensitive material or the processing material described later (including the back layer) includes various polymers for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, film cracking prevention and pressure increase / decrease prevention. Latex can be included. Specifically, any of polymer latexes described in JP-A Nos. 62-245258, 62-136648, and 62-110066 can be used. In particular, if a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordanting layer, cracking of the mordanting layer can be prevented, and if a polymer latex having a high glass transition point is used for the back layer, an anti-curling effect can be obtained. can get.

  A matting agent can also be used in the light-sensitive material of the present invention. The matting agent may be added to either the emulsion surface or the back surface, but it is preferably added to the outermost layer of the emulsion surface or the outermost layer of the back surface on the support. The matting agent may be soluble or insoluble in the treatment solution, and both may be used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 to 5/5 (molar ratio)), polystyrene particles, and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and 90% or more of the total number of particles may be contained between 0.9 and 1.1 times the average particle size. preferable. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve matting properties. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 3 μm)), polystyrene particles (0.25 μm), colloidal silica (0.03 μm).

  Specifically, it is described in JP-A 61-88256, page 29. In addition, there are compounds described in JP-A-63-274944 and 63-274922, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads. In addition, the compounds described in RD can be used.

  These matting agents can be used as a dispersion by being dispersed with various binders described in the section of the binder as necessary. In particular, various gelatins such as acid-treated gelatin dispersions are easy to prepare a stable coating solution. At this time, it is preferable to optimize pH, ionic strength, and binder concentration as necessary.

  In the present invention, the support for the photosensitive material is transparent and can withstand the processing temperature. Generally, photographs such as paper and synthetic polymers (films) described in “Photographic Engineering Basics-Silver Salt Photography Edition” edited by the Japan Photography Society, Corona Co., Ltd. (Showa 54) pp. 223-240 For example. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose).

  In addition, JP-A-62-253159, pages 29-31, JP-A-1-161236, pages 14-17, JP-A-63-316848, JP-A-2-22651, JP-A-3-56955, US patent The support described in No. 5,001,033 or the like can be used. These supports are subjected to heat treatment (crystallinity and orientation control), uniaxial and biaxial stretching (orientation control), blending of various polymers, surface treatment, etc., in order to improve optical and physical properties. Can do.

  In particular, when the requirements for heat resistance and curl characteristics are strict, it is described in Japanese Patent Application Laid-Open Nos. 6-41281, 6-43581, 6-51426, 6-51437, and 6-51442 as photosensitive material supports. The support can be preferably used.

  Further, a support which is a styrene polymer mainly having a syndiotactic structure can also be preferably used. The thickness of the support is preferably 5 to 200 μm, more preferably 40 to 120 μm.

  Next, the polyester support preferably used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples other than those described above, please refer to the published technical bulletin, public technical number 94-6023 (Invention Association; 1994. 3.15.). The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid as aromatic dicarboxylic acid Examples of isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight range is about 0.5 to 200,000. The Tg of the polyester that can be used in the present invention is 50 ° C or higher, and more preferably 90 ° C or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg, in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. The surface may be improved by providing irregularities on the surface (for example, applying conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ). Further, it is desirable to devise such as preventing knurling of the core part by imparting knurling to the end part and slightly raising only the end part. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent.

  This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading commercially available dyes or pigments for polyester, such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayaset.

  In order to adhere the support and the light-sensitive material constituting layer, the support is preferably surface-treated. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the undercoat layer will be described. The undercoat layer may be a single layer or two or more layers. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, gelatin, polyvinyl alcohol, and modified polymers thereof. Examples of compounds that swell the support include resorcin and p-chlorophenol. As the gelatin hardener for the undercoat layer, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ , TiO ₂ , inorganic fine particles, or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

  Further, for example, using a support having a magnetic recording layer described in JP-A-4-124645, JP-A-5-40321, JP-A-6-35092, and JP-A-6-317875, recording photographing information and the like. Is preferred.

The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.
Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal crystal systems Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide such as Co-coated γFe ₂ O ₃ is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent on the surface thereof as described in JP-A-6-161032. Moreover, the magnetic particle which coat | covered the surface of inorganic and organic substance as described in Unexamined-Japanese-Patent No. 4-259911 and 5-81652 can also be used.

The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural polymer (described in JP-A-4-219469). Cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The resin has a Tg of −40 to 300 ° C. and a mass average molecular weight of 0.2 to 1,000,000.
Specific examples include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate, cellulose tripropionate, acrylic resin, and polyvinyl acetal resin. Gelatin Is also preferable. Cellulose di (tri) acetate is particularly preferable.

  The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohol (for example, tolylene diene). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane) and polyisocyanates formed by condensation of these isocyanates are mentioned, for example, as described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferable, as in the method described in JP-A-6-35092. A dispersant described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 to 10 μm, preferably 0.2 to 5 μm, more preferably 0.3 to 3 μm. The mass ratio of the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ^2, preferably not 0.01 to 2 g / m ^2, more preferably at 0.02 to 0.5 g / m ^2. The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15.

The magnetic recording layer can be provided on the entire back surface or stripe shape by coating or printing on the back surface of the photographic support. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extraction, etc. can be used. A coating solution described in No. 341436 is preferable.
The magnetic recording layer may have functions such as lubricity improvement, curl adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. An abrasive of non-spherical inorganic particles in which at least one kind of particles has a Mohs hardness of 5 or more is preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as that for the magnetic recording layer is preferable. For the light-sensitive material having a magnetic recording layer, U.S. Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874, and European Patent 466,130. In the issue.

Next, a film cartridge that can be loaded with a photosensitive material will be described.
The main material of the cartridge used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. In particular, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding. The size of the patrone may be the current 135 size, and it is also effective to reduce the diameter of a 25 mm cartridge of the current 135 size to 22 mm or less in order to reduce the size of the camera. The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The mass of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.

  Further, a cartridge that feeds a film by rotating a spool may be used. Alternatively, the film leading end may be housed in the cartridge main body, and the film leading end may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feeding direction. These are disclosed in U.S. Pat. Nos. 4,834,306 and 5,226,613.

  The above-described light-sensitive material of the present invention can be preferably used for the lens-attached film unit described in JP-B-2-32615 and JP-B-3-39784.

  A lens-equipped film unit is a method unit in which an unexposed color photosensitive material is stored in a sheet or roll form, either directly or in a container, in a packaging unit body that is preliminarily provided with a photographing lens and a shutter, and is light-tightly bonded. And what is further packaged.

  Further, the packaging case body is provided with a finder, a photosensitive material frame feed mechanism, a storage and taking-out mechanism for a color photographic material that has been photographed, and the finder has a parallax correction support. -93723, 1-57381, 1-57740, JP-A-1-93723 and 1-152437 can be provided.

  Since the photosensitive material is accommodated in the packaging unit main body in the present invention, it is desirable to adjust the humidity so that the humidity in the packaging unit is 40 to 70%, preferably 50 to 65% relative humidity at 25 ° C. For the exterior material, it is preferable to use a moisture-impermeable material or, for example, a non-water-absorbing material of 0.1% or less according to ASTM test method D-570, particularly an aluminum foil laminate sheet or aluminum foil.

A container for a photographed photosensitive material provided in the packaging unit main body is a cartridge for an exterior unit, a conventional cartridge, such as JP-A Nos. 54-111822, 63-194255, and U.S. Pat. No. 4,832,275. No. 4,834,306 is used.
Examples of the photosensitive material film to be used include 110 size, 135 size, half size and 126 size.

  The plastic material used for the construction of the packaging unit in the present invention includes non-polymerization of an olefin having a carbon-carbon double bond, ring-opening polymerization of a small ring compound, and polycondensation (condensation polymerization) of two or more polyfunctional compounds. ), Polyaddition and addition of phenol derivatives, urea derivatives, melamine derivatives and aldehyde-containing compounds.

  The light-sensitive material of the present invention is processed by the usual methods described in RD No. 17643, pages 28 to 29, No. 18716, 651, left column to right column, and No. 307105, pages 880 to 881. can do. Examples of the development processing for the color negative film used in the present invention include C-41 processing by Eastman Kodak Company and CN-16 processing by Fuji Photo Film Co., Ltd. Regarding the development processing for the color reversal film used in the present invention, publicly known technology No. 6 (April 1, 1991) published by Aztec Co., Ltd., page 1, line 5 to page 10, line 5 and page 15, page 8 Line to page 24, line 2 in detail, any of which can be preferably applied. Examples of preferable development processing including the above contents include E-6 processing by Eastman Kodak Company and CR-56 processing by Fuji Photo Film Co., Ltd.

  The light-sensitive material of the present invention can also form an image by developing with an activator process and a processing solution containing a developing agent / base. Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material, and development processing is performed with a processing solution that does not contain a color developing agent. The processing liquid in this case is characterized by not containing the color developing agent contained in the usual developing processing solution components, and may contain other components (for example, alkali, auxiliary developing agent, etc.). The activator treatment is exemplified in known documents such as European Patent Nos. 545,491A1 and 565,165A1.

The light-sensitive material of the present invention preferably forms an image by heat development after image exposure.
The heat treatment of the photosensitive material is well known in the art. For example, the photothermographic material and the process thereof are disclosed in, for example, the basics of photographic engineering (1970, issued by Corona), pages 553 to 555, issued in April 1978. Video information 40 pages, Nabletts Handbook of Photography and Reprography 7th Ed. (Vna Nostrand and Reinhold Company) 32 to 33, US Pat. Nos. 3,152,904, 3,301,678, 3,392, No. 020, No. 3,457,075, British Patent No. 1,131,108, No. 1,167,777 and RD No. 17029 (1978), pages 9-15.
The heating temperature in the heat development step is about 50 to 250 ° C, but 60 to 180 ° C is particularly useful.

  Heating methods in the development process include contact with heated blocks and plates, contact with hot plates, hot presses, heat rollers, heat drums, halogen lamp heaters, infrared and far infrared lamp heaters, etc. There is a method of passing through the atmosphere.

  Any of various heat developing apparatuses can be used for processing the light-sensitive material of the present invention. For example, devices described in JP-A Nos. 59-75247, 59-177547, 59-181353, 60-18951, and Japanese Utility Model Laid-Open No. 62-25944 are preferably used.

Next, in the present invention, a processing material and a processing method used in the case of heat development processing will be described in detail.
In the light-sensitive material of the present invention, a base or a base precursor can be used for the purpose of promoting silver development and a dye-forming reaction. Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Lossen transfer or Beckmann transfer. Specific examples thereof are described in U.S. Pat. Nos. 4,514,493 and 4,657,848 and publicly known technology No. 5 (published on March 22, 1991, Aztec Co., Ltd.), pages 55 to 86, etc. ing. Further, as described in European Patent No. 210,660 and US Pat. No. 4,740,445, a basic metal compound hardly soluble in water and a metal ion and water constituting the basic metal compound are used. A method of generating a base by a combination of compounds capable of complex-forming reaction (referred to as complex-forming compounds) as a medium may be used. The amount of base or base precursor used is 0.1 to 20 g / m ² , preferably 1 to 10 g / m ² .

  In order to supply the base, a processing member having a processing layer containing a base or a base precursor can be used. In addition to this, the processing member shuts off air during heat development, prevents volatilization of the material from the photosensitive material, supplies processing materials other than the base to the photosensitive material, and becomes unnecessary after development. It may be provided with a function of removing the raw materials (YF dye, AH dye, etc.) or unnecessary components generated during development. As the support and binder for the processing member, the same materials as the photosensitive material can be used. A mordant may be added to the treatment member for the purpose of removing the above-mentioned dye and other purposes. As the mordant, those known in the photographic field can be used. U.S. Pat. No. 4,50,626, columns 58 to 59, JP-A 61-88256, pages 32 to 41, JP-A 62-244043, Examples thereof include mordants described in JP-A-62-244036. Further, a dye-accepting polymer compound described in US Pat. No. 4,463,079 may be used. Moreover, you may contain the below-mentioned thermal solvent.

  In heat development using the processing member, it is also preferable to use a small amount of water for the purpose of accelerating development, accelerating the transfer of the processing material, or accelerating the diffusion of unnecessary materials. Specific examples are described in U.S. Pat. Nos. 4,704,245, 4,470,445, and JP-A-61-238056. Water may contain an inorganic alkali metal salt or organic base, a low-boiling solvent, a surfactant, an antifoggant, a complex-forming compound with a hardly soluble metal salt, an antifungal agent, or an antibacterial agent. Any water can be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water, or the like can be used. In the heat development apparatus using the photosensitive material and the processing member of the present invention, water may be used up or it may be circulated and used repeatedly. In the latter case, water containing components eluted from the material is used. Further, the apparatus and water described in JP-A Nos. 63-144354, 63-144355, 62-38460, and JP-A-3-210555 may be used. Water can be applied to the photosensitive material, the processing member, or both. The amount used is preferably an amount corresponding to 1/10 to 1 times the amount required to swell the entire coating film (excluding the back layer) of the photosensitive material and processing member. As a method for applying this water, for example, methods described in JP-A-62-253159, page 5, JP-A-63-85544 are preferably used. Further, the solvent can be confined in a microcapsule, or the photosensitive material or the processing member or both of them can be incorporated in advance in the form of a hydrate. The temperature of water to be applied is preferably about 30 to 60 ° C. as described in JP-A-63-85544.

  When heat development is carried out in the presence of a small amount of water, as described in European Patent No. 210660 and US Pat. No. 4,740,445, a basic metal compound hardly soluble in water and the basic metal It is effective to employ a method in which a base is generated by a combination of a metal ion constituting the compound and a compound capable of complex-forming reaction using water as a medium (referred to as a complex-forming compound). In this case, it is desirable from the viewpoint of storage stability of the photosensitive material that the basic metal compound hardly soluble in water is added to the photosensitive material and the complex-forming compound is added to the processing member.

  The method described in JP-A Nos. 62-253159 and 61-147244, page 27 can be applied as a method of superposing the photosensitive material and the processing member so that the photosensitive layer and the processing layer face each other. The heating temperature is preferably 70 to 100 ° C., and the heating time is preferably 5 to 60 seconds.

  The photosensitive material and / or processing sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development. As the heat generating element of this heat generation, those described in JP-A No. 61-145544 can be used.

  A thermal solvent can be added to the light-sensitive material of the present invention for the purpose of promoting thermal development.

  Here, the thermal solvent is solid at ambient temperature, but shows a mixed melting point together with other components at the heat treatment temperature used or lower, and is liquefied at the time of heat development and heat development or thermal transfer of dyes. It is an organic material having an action of promoting the above. Thermal solvents include compounds that can serve as solvents for developers, compounds that are known to promote physical development of silver salts with high dielectric constant materials, and compounds that are compatible with binders and have the action of swelling binders. Useful.

Examples of the thermal solvent that can be used in the present invention include US Pat. Nos. 3,347,675, 3,667,959, 3,438,776, 3,666,477, RD No. 17, No. 643, JP-A-51-19525, 53-24829, 53-60223, 58-118640, 58-198038, 59-229556, 59-68730, 59- No. 84236, No. 60-191251, No. 60-232547, No. 60-14241, No. 61-52643, No. 62-78554, No. 62-42153, No. 62-44737, No. 63-53548 63-161446, JP-A 1-222451, JP-A-2-863, JP-A-2-12039, JP-A-2-123354, etc. Compound may be mentioned. Specifically, urea derivatives (such as phenylmethylurea), amide derivatives (such as acetamide, stearylamide, p-toluamide, p-propanoyloxyethoxybenzamide), sulfonamide derivatives (such as p-toluenesulfonamide) From a polyhydric alcohol (for example, a high molecular weight polyethylene glycol), it is possible to select and use a low water-soluble material preferable for fine crystal dispersion. The water solubility of the thermal solvent used in the present invention is preferably 1 g / cubic meter or less, and more preferably 10 ⁻³ g / cubic meter or less, in order to enhance the dispersion stability of the microcrystalline dispersion. As a usage-amount of the thermal solvent used for this invention, 1-200 mass% of the application quantity of a binder is suitable, and 5-50 mass% is preferable. The layer to be added may be either a photosensitive layer or a non-photosensitive layer depending on the purpose.
Although the specific example of the thermal solvent which can be used for this invention is shown, this invention is not limited by these specific examples.

In the present invention, image information can be captured without removing developed silver and undeveloped silver halide produced by development, but an image can also be captured after removal. In the latter case, means for removing these can be applied at the same time as or after development.
Simultaneously with development, to remove developed silver in the photosensitive member and to complex or solubilize silver halide, it acts as a silver oxidizing agent, rehalogenating agent, or fixing agent that acts as a bleaching agent on the processing member. These silver halide solvents can be contained, and these reactions can be caused during heat development. After the development of image formation, a second member containing a silver oxidizing agent, a rehalogenating agent or a silver halide solvent is bonded to the photosensitive material to remove the developed silver or to complex or allow silver halide. Solubilization can also occur. In the present invention, it is preferable to carry out these processes to the extent that there is no obstacle to reading image information after shooting and subsequent image formation and development. In particular, undeveloped silver halide produces high haze in the gelatin film and increases the background density of the image. Therefore, the haze can be reduced or solubilized with the complexing agent as described above, and It is preferable to remove the whole amount or a part thereof. It is also preferable to use high aspect ratio tabular grains or tabular grains having a high silver chloride content for the purpose of reducing the haze of the silver halide itself.

  As a bleaching agent that can be used in the processing member of the present invention, a commonly used silver bleaching agent can be arbitrarily used. Such bleaching agents are described in US Pat. Nos. 1,315,464 and 1,946,640 and Photographic Chemistry, vol. 2, chapter 30, Foundation Press, London, England. These bleaches effectively oxidize and solubilize photographic silver images. Examples of useful silver bleaches include alkali metal dichromates and alkali metal ferricyanides. Preferred bleaching agents are those that are soluble in water and include ninhydrin, indandione, hexaketo chlorohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid, 2,5-dinitrobenzoic acid. Also, there are metal organic complexes such as ferric salt of cyclohexyldialkylaminotetraacetic acid, ferric salt of ethylenediaminetetraacetic acid, and ferric salt of citric acid. As the fixing agent, a silver halide solvent which can be contained in a processing member (first processing member) for developing the photosensitive member can be used. The same thing as a 1st processing member can be used also regarding the binder, support body, and other additive which can be used for a 2nd processing member. The coating amount of the bleaching agent should be changed according to the amount of silver contained in the photosensitive member to be laminated, but the coating amount of photosensitive silver halide per unit area of the photosensitive member is 0.01 to 10 mol / photosensitive. Used in a range of parts. Preferably, it is 0.1-3 mol / silver mole of coated photosensitive member, and more preferably 0.1-2 mol / silver mole of coated photosensitive member.

  In the present invention, it is also preferable to photoelectrically read an image formed on the photosensitive material by heat development and convert it into a digital signal. A generally known image input device can be used as the image reading apparatus. Details of the image input device are described in Takao Ando et al., “Basics of Digital Image Input”, Corona (1998), pages 58-98.

  An image input device needs to capture a large amount of image information efficiently, and is divided roughly into a linear sensor and an area sensor in the arrangement of minute point sensors. In the former, a large number of point sensors are arranged on a line, and in order to capture a planar image, it is necessary to scan either the photosensitive material side or the sensor side. For this reason, it takes a little time to read, but there is an advantage that a sensor can be made at low cost. In the case of an area sensor, since it can basically be read without scanning the photosensitive material or sensor, the reading is fast, but it is necessary to use a large sensor, so the cost is high. These sensors can be used properly according to the purpose, and both can be preferably used.

  Sensor types include an electron tube type such as an imaging tube and an image tube, and a solid-state imaging system such as a CCD type and a MOS type, but a solid-state imaging system, particularly a CCD type is preferable because of cost and ease of handling.

  As devices equipped with these image input devices, commercially available digital still cameras, drum scanners, flatbed scanners, film scanners, etc. can be used, but in order to easily read high-quality images, It is preferable to use a film scanner.

  Typical commercially available film scanners include Nikon film scanner LS-1000 using linear CCD, Agfa Duoscan HiD, Imacone FlexTight Photo, and Kodak RFS3570 using area CCD are preferred. Can be used.

  In addition, an image input device using an area CCD mounted in a digital print system frontier of Fuji Photo Film can be preferably used. Furthermore, the frontier F350 image input device described in Yoshio Ozawa et al., Fuji Photo Film Research Report No. 45, pages 35-41, achieves high-speed and high-quality reading using a linear CCD sensor. It is particularly suitable for reading the photosensitive material of the invention.

  Examples of the image processing method that can be preferably used in the image forming method of the present invention include the following.

  In JP-A-6-139323, an object image is formed on a color negative, the image is converted into corresponding image data by a scanner or the like, and the same color as the object is output from the demodulated color information. An image processing system and an image processing method capable of faithfully reproducing the image are described, and these may be used.

  Further, as an image processing method for suppressing graininess or noise of a digitized image and enhancing sharpness, sharpness enhanced image data, smoothed image data, and edge detection data described in JP-A-10-243238 are disclosed. A method for weighting and subdividing edges and noise based on the above, or an edge component based on sharpness-enhanced image data and smoothed image data described in JP-A-10-243239. An image processing method for performing a digitization process or the like may be used.

  In addition, in order to correct a change in color reproducibility in the final print due to a difference in storage conditions, development conditions, and the like of the photographic material, the unexposed photographic material described in JP-A-10-255037 can be used. 4 sections or 4 or more color patches are exposed on the part, after development, the patch density is measured, the lookup table and color conversion matrix required for correction are obtained, and the photographic image is obtained using lookup table conversion and matrix calculation. A method of performing color correction can be used.

  As a method for converting the color gamut of image data, for example, a color signal described in Japanese Patent Laid-Open No. 10-229502 is expressed by a color signal that is visually recognized as a neutral color when the numerical values of each component are obtained. It is possible to use a method of separating the color signal into a chromatic color component and an achromatic color component and processing each separately for the processed image data.

  In addition, as an image processing method for removing image quality degradation such as aberration caused by a camera lens and a decrease in peripheral light amount in an image photographed by a camera, the image degradation described in JP-A-11-69277 is previously performed. Record a grid-like correction pattern to create correction data, read the image and correction pattern with a film scanner after shooting, create data to correct the deterioration factor based on the camera lens, and then image degradation You may use the image processing method and apparatus which correct | amend digital image data using correction data.

  In addition, if skin tone and blue sky enhance sharpness too much, graininess (noise) is emphasized and gives an unpleasant impression, so it is desirable to suppress the degree of sharpness enhancement for skin color and blue sky. For example, in the sharpness enhancement processing using unsharp masking (USM) described in JP-A-11-103393, a method in which the USM coefficient is a function of (B−A) (R−A) may be used. .

  Skin color, grass green, and blue sky are called important colors for color reproduction, and selective color reproduction processing is required. Of these, regarding lightness reproduction, it is said that it is visually preferable that the skin color is bright and the blue sky is dark. As a method for reproducing an important color to a visually preferable brightness, for example, in Japanese Patent Laid-Open No. 11-177835, a color signal for each pixel is changed to a corresponding hue such as (RG) or (RB). A method is described in which conversion is performed using a coefficient that takes a small value when yellow is red and takes a large value when cyan blue, and this may be adopted.

  Further, as a method for compressing a color signal, for example, a color signal for each pixel described in JP-A No. 11-113023 is separated into a lightness component and a chromaticity component, and a color signal is prepared in advance. Alternatively, a method of encoding hue information may be used by selecting a template having the best numerical pattern from a plurality of hue templates.

  In addition, when performing processing such as increasing saturation or sharpness, it is possible to perform natural enhancement processing by suppressing defects such as color blurring, highlight skipping, collapse of high-density areas, and out-of-definition data. In Japanese Patent Application Laid-Open No. 11-177732, each color density data of color image data is used as exposure density data using a characteristic curve, image processing including color enhancement is performed on this, and density data is further formed using a characteristic curve. An image processing method and apparatus can be used.

Examples of the present invention are shown below. However, the present invention is not limited to this example.
(Example 1)
Silver halide emulsions Em-A1 to A16 were prepared by the following production method.

(Em-A1)
42.2 L of an aqueous solution containing 31.7 g of phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15000 and 31.7 g of KBr was kept at 35 ° C. and stirred vigorously. 1583 mL of an aqueous solution containing 316.7 g of AgNO ₃ and 1583 mL of an aqueous solution containing 52.7 g of low molecular weight gelatin having a molecular weight of 15000 and KBr, 221.5 g, were added over 1 minute by the double jet method. Immediately after the addition, 52.8 g of KBr was added, and 2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and 2581 mL of an aqueous solution containing 291.1 g of KBr were added over 2 minutes by the double jet method. Immediately after the addition, 47.8 g of KBr was added. Then, it heated up to 40 degreeC and fully matured. After the ripening, phthalic ratio of 97 percent phthalated molecular weight of 100,000 gelatin 923g of KBr, it was added 79.2 g, final flow rate of an aqueous solution 15947mL and KBr aqueous solution containing AgNO _3, 5103g by the double jet method is the initial flow rate The flow rate was accelerated to 1.4 times and added over 12 minutes. At this time, the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added to adjust the pH to 5.7, pAg, 8.8, 131.8 g in terms of silver per kg of emulsion, and 64.1 g of gelatin to make a seed emulsion.

1211 mL of an aqueous solution containing 46 g of phthalated gelatin having a phthalation rate of 97% and 1.7 g of KBr was kept at 75 ° C. and stirred vigorously. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (product of Nippon Unicar Co., Ltd., L7602) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate is 5.1 times the initial flow rate by double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and KBr aqueous solution. The flow rate was accelerated and added over 6 minutes. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate, an aqueous solution containing 144.5 g of AgNO ₃ , a mixed solution of KBr and KI containing 410 mL and 7 mol% of KI is 3.7 times the final flow rate by the double jet method. The flow rate was accelerated so as to be added over 56 minutes. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then 6.33 g of an AgI fine grain emulsion having a grain size of 0.037 μm was added in terms of KI mass. Immediately after the addition, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. The silver potential was kept at −80 mV with an aqueous KBr solution for 5 minutes at the beginning of the addition.

After washing with water, when measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added and adjusted to pH, 5.8, pAg, 8.7 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 60 ° C. After addition of sensitizing dyes 11 and 12, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 13 and Compound 14 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound were selected from an addition amount range of 10 ⁻¹ to 10 ⁻⁸ mol per mol of silver halide.

As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the periphery of the particles.
(The characteristics of the obtained silver halide emulsions Em-A1 to A20 are shown in Table 5 of Example 3).

(Em-A2 to A16)
At the time of chemical sensitization, after adding compounds 13 and 14, the temperature of the chemically sensitized emulsion was lowered to 40 ° C., and then the electron-emitting compounds of the present invention and the comparative example were compared with the amount of silver in the emulsion (Table 1). Emulsions Em-A2 to A16 were obtained in the same manner as (Em-A1) except that they were added so as to have a content of

The emulsions A1 to A16 were coated on the cellulose triacetate film support provided with the undercoat layer under the coating conditions shown in Table A below to prepare Samples 101 to 116.

  These samples were subjected to hardening for 14 hours under conditions of 40 ° C. and 70% relative humidity. Then, the sample was subjected to 1/100 second exposure through a gelatin filter SC-39 (long wavelength light transmission filter with a cut-off wavelength of 390 nm) and a continuous wedge manufactured by FUJIFILM Corporation. The photographic performance was evaluated by measuring the density. In addition, the same treatment was applied to samples that were aged for 3 days at 50 ° C. and 80% RH.

Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., the treatment was carried out by the method described below (until the cumulative replenishment amount of the liquid became three times the mother liquid tank capacity).
(Processing method)
Process Processing time Processing temperature Replenishment amount Color development 2 minutes 45 seconds 38 ° C 45 mL
White drift 1 minute 00 seconds 38 ℃ 20mL
Bleach solution overflow
Full flow into the bleach-fixing tank Bleach-fixing 3 minutes 15 seconds 38 ° C 30 mL
Flushing (1) 40 seconds From 35 ℃ (2) to (1)
Counterflow piping system Flushing (2) 1 min 00 sec 35 ° C 30 mL
Stable 40 seconds 38 ° C 20 mL
Drying 1 min 15 sec 55 ° C
* Replenishment amount is 35mm width per 1.1m length (equivalent to 24Ex.1)

Next, the composition of the treatment liquid will be described.
(Color developer) Tank solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 1.0 1.1
1-hydroxyethylidene-1,1-diphosphonic acid
2.0 2.0
Sodium sulfite 4.0 4.4
Potassium carbonate 30.0 37.0
Potassium bromide 1.4 0.7
Potassium iodide 1.5mg −
Hydroxylamine sulfate 2.4 2.8
4- [N-ethyl-N- (β-hydroxyethyl) amino]
-2-Methylaniline sulfate 4.5 5.5
Add water 1.0L 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.10

(Bleaching solution) Common for tank solution and replenisher solution (Unit: g)
Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0
Ethylenediaminetetraacetic acid disodium salt 10.0
Ammonium bromide 100.0
Ammonium nitrate 10.0
Bleach accelerator 0.005 mol
(CH ₃ ) ₂ N—CH ₂ —CH ₂ —S—S—CH ₂ —CH ₂ —N (CH ₃ ) ₂ · 2HCl
Ammonia water (27%) 15.0 mL
Add water and add 1.0L
pH (adjusted with ammonia water and nitric acid) 6.3

(Bleaching fixer) Tank solution (g) Replenisher (g)
Ethylenediaminetetraacetic acid ferric ammonium ammonium dihydrate
50.0-
Ethylenediaminetetraacetic acid disodium salt 5.0 2.0
Sodium sulfite 12.0 20.0
Ammonium thiosulfate aqueous solution (700 g / L)
240.0mL 400.0mL
Ammonia water (27%) 6.0 mL −
Add water 1.0L 1.0L
pH (adjusted with aqueous ammonia and acetic acid) 7.2 7.3

(Washing liquid) Tank liquid and replenisher common Tap water was charged with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400). Water was passed through a mixed bed column to treat the calcium and magnesium ion concentrations to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 0.15 g / L were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether (average polymerization degree 10) 0.2
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5

The photographic performance results are shown in Table 2 below. Sensitivity was expressed as a relative value of the logarithm of the reciprocal of the exposure amount necessary to reach a fog density plus 0.2 (sample 101 was set as 100).

  From Table 2, it can be seen that the emulsion to which the electron-emitting compound of the present invention was added had a greater sensitivity increasing effect and the density (coverage) of the unexposed area was lower than that of the emulsion to which the electron-emitting compound of the comparative example was added. The emulsion to which the electron emitting compound of the present invention was added maintained the merit of increasing the sensitivity, while overcoming the high demerit of the emulsion like the emulsion to which the electron emitting compound of the comparative example was added. In addition, with respect to a sample that had been aged for 3 days under the conditions of 50 ° C. and 80% RH, the emulsion to which the electron-emitting compound of the present invention was added had a smaller decrease in sensitivity after raw storage than the emulsion to which the electron-emitting compound of the comparative example was added. It can be seen that the cover is low.

(Example 2)
Silver halide emulsions Em-Q1 to Q16 were prepared by the following production method.
(Em-Q1)
1200 mL of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g and KBr, 0.99 g was maintained at 60 ° C., the pH was adjusted to 2, and vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and an aqueous solution containing KBr, 1.97 g and KI, 0.172 g were added over 30 seconds by the double jet method. After completion of ripening, 12.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g, and NaCl 6.2 g were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at −50 mV with respect to the saturated calomel electrode. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at a flow rate acceleration so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV. 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV.

After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -100 mV. 6.2 g of the above-mentioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 300 mL of an aqueous solution containing 88.5 g of AgNO ₃ was added over 8 minutes. Adjustment was made by adding an aqueous KBr solution so that the potential at the end of the addition was +60 mV. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 61 ° C. After addition of sensitizing dyes 15, 16 and 17, K ₂ IrCl ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 13 and 14 were added at the end of chemical sensitization.

(Em-Q2 to Q16)
At the time of chemical sensitization, the compounds 13 and 14 were added to the electron-emitting compounds of the present invention and comparative examples, the temperature of the chemically sensitized emulsion was lowered to 40 ° C., and then the amount of silver in the emulsion (Table 3) Emulsions Em-Q2 to Q16 were obtained in the same manner as (Em-Q1) except that the contents were added so as to obtain the following contents.

(The characteristics of the obtained silver halide emulsions Em-Q1 to Q16 are shown in Table 5 of Example 3)

  In the same manner as in Example 1, the previous emulsions Q1 to Q16 were applied to prepare Samples 201 to 216.

These samples were subjected to hardening for 14 hours under conditions of 40 ° C. and 70% relative humidity. Thereafter, exposure was carried out for 1/100 second through a gelatin filter SC-50 (long wavelength light transmission filter with a cutoff wavelength of 500 nm) manufactured by FUJIFILM Corporation and a continuous wedge, and the same development processing as in Example 1 was performed. Photographic performance was evaluated by measuring the density of the sample with a green filter. In addition, the same treatment was applied to samples that were aged for 3 days at 50 ° C. and 80% RH.
The photographic performance results are shown in Table 4 below. The sensitivity was expressed as a relative value of the logarithm of the reciprocal of the exposure amount necessary to reach the fog density plus 0.2 (sample 201 was set as 100).

  From Table 4, also in the green-sensitive silver halide photographic emulsion, the emulsion added with the electron-emitting compound of the present invention has a greater sensitivity increasing effect than the emulsion added with the electron-emitting compound of the comparative example, and the density of the unexposed area. It can be seen that the (cover) is low. The emulsion to which the electron emitting compound of the present invention was added maintained the merit of increasing the sensitivity, while overcoming the high demerit of the emulsion like the emulsion to which the electron emitting compound of the comparative example was added. In addition, with respect to a sample that had been aged for 3 days under the conditions of 50 ° C. and 80% RH, the emulsion to which the electron-emitting compound of the present invention was added had a smaller decrease in sensitivity after raw storage than the emulsion to which the electron-emitting compound of the comparative example was added. It can be seen that the cover is low.

(Example 3)
(Em-A1) (Emulsion for high-sensitivity blue-sensitive layer) Prepared in Example 1.
(Em-B) (Emulsion for low sensitivity blue-sensitive layer)
1192 mL of an aqueous solution containing 0.96 g of low molecular weight gelatin and KBr, 0.9 g was kept at 40 ° C. and stirred vigorously. 37.5 mL of an aqueous solution containing 1.49 g of AgNO ₃ and 37.5 mL of an aqueous solution containing 1.5 g of KBr were added over 30 seconds by the double jet method. After adding 1.2 g of KBr, the mixture was heated to 75 ° C. and aged. After sufficiently ripening, 30 g of trimellitated gelatin having a molecular weight of 100000 having a chemically modified amino group with trimellitic acid was added to adjust the pH to 7. 6 mg of thiourea dioxide was added. 116 mL of an aqueous solution containing 29 g of AgNO ₃ and an aqueous KBr solution were added at a flow rate acceleration by a double jet method so that the final flow rate was three times the initial flow rate. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over 30 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method.

At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at a flow rate acceleration so that the silver iodide content was 15.8 mol%, and the silver potential was kept at 0 mV with respect to the saturated calomel electrode. It was. 96.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added over 3 minutes by the double jet method. At this time, the silver potential was kept at 0 mV. After adding 26 mg of sodium ethylthiosulfonate, the temperature was lowered to 55 ° C., and an aqueous KBr solution was added to adjust the silver potential to −90 mV. 8.5 g of the aforementioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 228 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 5 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be + 20mV. It was washed with water in the same manner as Em-A1, and chemically sensitized.

(Em-C) (low-sensitivity blue-sensitive emulsion)
1192 mL of an aqueous solution containing 1.02 g of phthalated gelatin having a molecular weight of 100,000 and 97% phthalation containing 35 μmol of methionine per gram and 0.97 g of KBr was kept at 35 ° C. and stirred vigorously. An aqueous solution containing 4.47 g of AgNO ₃ , 42 mL and KBr, an aqueous solution containing 3.16 g, and 42 mL were added over 9 seconds by the double jet method. After adding 2.6 g of KBr, the temperature was raised to 66 ° C. and fully aged. After completion of aging, 41.2 g of trimellitated gelatin having a molecular weight of 100,000 used in the preparation of Em-B and NaCl, 18.5 g were added. After adjusting the pH to 7.2, 8 mg of dimethylamine borane was added. 203 mL of an aqueous solution containing 26 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode.

440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over 24 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was added at an accelerated flow rate so that the silver iodide content was 2.3 mol%, and the silver potential was -20 mV to the saturated calomel electrode. Kept. After adding 10.7 mL of 1N potassium thiocyanate aqueous solution, 153.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added over 2 minutes and 30 seconds by the double jet method. At this time, the silver potential was kept at 10 mV. An aqueous KBr solution was added to adjust the silver potential to -70 mV. 6.4 g of the aforementioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 404 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 45 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be -30mV. It was washed with water in the same manner as Em-A1, and chemically sensitized.

(Em-D) (Low-sensitivity blue-sensitive emulsion)
In the preparation of Em-C, the amount of AgNO ₃ added during nucleation was changed to 2.0 times. Then, the addition at the end of the potential of the aqueous solution 404mL, including the final AgNO _3, 57 g was changed to adjust an aqueous KBr solution to be + 90 mV. Otherwise, it was prepared in substantially the same manner as Em-C.

(Em-E) (magenta coloring layer having a spectral sensitivity peak at 480 to 550 nm)
(Layer that gives the red-sensitive layer a multi-layer effect)
1200 mL of an aqueous solution containing 0.2 g of modified silicone oil used in the preparation of low molecular weight gelatin having a molecular weight of 15000, 0.71 g, KBr, 0.92 g, and Em-A1 is kept at 39 ° C., and the pH is adjusted to 1.8 vigorously. Stir. An aqueous solution containing 0.45 g of AgNO ₃ and an aqueous KBr solution containing 1.5 mol% KI were added over 17 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 56 ° C. and aging was performed. After fully ripening, 20 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol of methionine per gram was added. After adjusting the pH to 5.9, KBr, 2.9 g was added. 288 mL of an aqueous solution containing 28.8 g of AgNO ₃ and an aqueous KBr solution were added over 53 minutes by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added so that the silver iodide content was 4.1 mol%, and the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After adding KBr, 2.5 g, an aqueous solution containing 87.7 g of AgNO ₃ and an aqueous KBr solution are accelerated over a period of 63 minutes by the double jet method so that the final flow rate is 1.2 times the initial flow rate. did. At this time, the above-mentioned AgI fine grain emulsion was added at the same time with the flow rate accelerated so that the silver iodide content was 10.5 mol%, and the silver potential was kept at -70 mV.

After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 25 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, the pH was adjusted to 7.3. After KBr was added to adjust the silver potential to -70 mV, 5.73 g of the above AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 609 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 10 minutes. During the initial 6 minutes of addition, the silver potential was kept at -70 mV with an aqueous KBr solution. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 56 ° C. After adding 0.0004 mol of the above AgI fine grain emulsion to 1 mol of silver, sensitizing dyes 13 and 14 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 13 and 14 were added at the end of chemical sensitization.

(Em-F) (Emulsion for medium sensitivity green sensitive layer)
Em-E was prepared in substantially the same manner as Em-E, except that the amount of AgNO ₃ added during nucleation was changed to 3.1 times. However, the sensitizing dye of Em-E was changed to sensitizing dyes 15, 16 and 17.

(Em-G) (Low-sensitivity green sensitive layer emulsion)
1,200 mL of an aqueous solution containing 0.70 g of low molecular weight gelatin having a molecular weight of 15000, KBr, 0.9 g, KI, 0.175 g, and 0.2 g of modified silicone oil used in the preparation of Em-A1, was maintained at 33 ° C., and the pH was adjusted to 1. 8 and stirred vigorously. An aqueous solution containing 1.8 g of AgNO ₃ and an aqueous KBr solution containing 3.2 mol% KI were added over 9 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 69 ° C. and aging was performed. After completion of ripening, 27.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 6.3, KBr, 2.9 g was added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes by the double jet method. At this time, particles prepared by mixing a low molecular weight gelatin aqueous solution having a molecular weight of 15000, an AgNO ₃ aqueous solution, and a KI aqueous solution immediately before addition in another chamber having a magnetic coupling induction stirrer described in JP-A-10-43570 An AgI fine grain emulsion having a size of 0.008 μm was simultaneously added so that the silver iodide content was 4.1 mol%, and the silver potential was kept at −60 mV to the saturated calomel electrode. After adding KBr, 2.6 g, an aqueous solution containing 87.7 g of AgNO ₃ and an aqueous KBr solution are accelerated over a period of 49 minutes by the double jet method so that the final flow rate is 3.1 times the initial flow rate. did. At this time, the AgI fine grain emulsion prepared by mixing immediately before the above addition was simultaneously accelerated so that the silver iodide content was 7.9 mol%, and the silver potential was kept at -70 mV.

After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After raising the temperature to 78 ° C. and adjusting the pH to 9.1, KBr was added to bring the potential to −60 mV. 5.73 g of the AgI fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition, 321 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 4 minutes. The silver potential was kept at −60 mV with an aqueous KBr solution for 2 minutes at the beginning of the addition. It was washed with water in the same manner as Em-F and chemically sensitized.

(Em-H) (Low-sensitivity green sensitive layer emulsion)
An aqueous solution containing 17.8 g of ion-exchanged gelatin having a molecular weight of 100,000, KBr, 6.2 g, KI, and 0.46 g was kept at 45 ° C. and stirred vigorously. An aqueous solution containing 11.85 g of AgNO ₃ and an aqueous solution containing 3.8 g of KBr were added over 47 seconds by the double jet method. After raising the temperature to 63 ° C., 24.1 g of ion-exchanged gelatin having a molecular weight of 100,000 was added and aged. After fully aging, an aqueous solution containing 133.4 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes so that the final flow rate was 2.6 times the initial flow rate by the double jet method. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. In addition, 0.1 mg of K ₂ IrCl ₆ was added 10 minutes after the start of the addition. After adding 7 g of NaCl, an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 12 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of addition. After the addition of 14.4 g of KBr, 6.3 g of the AgI fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added over 11 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. It was washed with water in the same manner as Em-F and chemically sensitized.

(Em-I) (Emulsion for low sensitivity green sensitive layer)
Em-H was prepared in substantially the same manner except that the temperature during nucleation was changed to 38 ° C.

(Em-J1) (Emulsion for high-sensitivity red-sensitive layer)
1200 mL of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g, KBr, and 0.99 g was maintained at 60 ° C., adjusted to pH 2 and vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and an aqueous solution containing KBr, 1.97 g, KI, and 0.172 g were added over 30 seconds by the double jet method. After completion of ripening, 12.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g and NaCl 6.2 g were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at −50 mV with respect to the saturated calomel electrode. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at a flow rate acceleration so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV.

After adding 1.5 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -100 mV. 6.2 g of the above-mentioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 300 mL of an aqueous solution containing 88.5 g of AgNO ₃ was added over 8 minutes. Adjustment was made by adding an aqueous KBr solution so that the potential at the end of the addition was +60 mV. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 61 ° C. After the addition of sensitizing dyes 18, 19, 20, 21 and 22, K ₂ IrCl ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea was added for optimum chemical sensitization. . Compounds 13 and 14 were added at the end of chemical sensitization.

(Em-K) (Emulsion for medium sensitivity red sensitive layer)
1200 mL of an aqueous solution containing 4.9 g of low molecular weight gelatin having a molecular weight of 15000 and 5.3 g of KBr was kept at 60 ° C. and stirred vigorously. 27 mL of an aqueous solution containing 8.75 g of AgNO ₃ and 36 mL of an aqueous solution containing 6.45 g of KBr were added by a double jet method over 1 minute. After the temperature was raised to 77 ° C., 21 mL of an aqueous solution containing 6.9 g of AgNO ₃ was added over 2.5 minutes. NH ₄ NO ₃ , 26 g, 1N, NaOH, and 56 mL were sequentially added, followed by aging. After completion of aging, the pH was adjusted to 4.8. 438 mL of an aqueous solution containing 141 g of AgNO ₃ and 458 mL of an aqueous solution containing 102.6 g of KBr were added by the double jet method so that the final flow rate was four times the initial flow rate. After the temperature was lowered to 55 ° C., 240 mL of an aqueous solution containing 7.1 g of AgNO ₃ and an aqueous solution containing 6.46 g of KI were added over 5 minutes by the double jet method. After adding 7.1 g of KBr, 4 mg of sodium benzenethiosulfonate and 0.05 mg of K ₂ IrCl ₆ were added. 177 mL of an aqueous solution containing 57.2 g of AgNO ₃ and 223 mL of an aqueous solution containing 40.2 g of KBr were added by the double jet method over 8 minutes. It was washed with water in the same manner as Em-J1, and chemically sensitized.

(Em-L) (Emulsion for medium sensitivity red sensitive layer)
The Em-K was prepared in substantially the same manner except that the temperature during nucleation was changed to 42 ° C.
(Em-M, N, O) (Low-sensitivity red-sensitive emulsion)
Prepared in substantially the same manner as Em-H or Em-I. However, chemical sensitization was carried out in substantially the same manner as Em-J1.
(Em-Q1) (Emulsion for high sensitivity green sensitive layer)
As described in Example 2.

The characteristics of the thus obtained silver halide emulsions Em-A1 to Q16 are shown in Table 5.

Moreover, the outline of preparation formulation of the emulsion of this invention is shown below.
A 10% gelatin solution containing a coupler dissolved in ethyl acetate, a high-boiling organic solvent, and a surfactant are added and emulsified using a mixed homogenizer (Nippon Seiki) to obtain an emulsion.

1) Support The support used in this example was prepared by the following method.
100 parts by mass of polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Ciba-Geigy Ciba-Geigy) was dried, melted at 300 ° C., extruded from a T-shaped die, and stretched 3.3 times at 140 ° C., followed by 130 ° C. The film was stretched by 3.3 times and further heat-fixed at 250 ° C. for 6 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye, and a yellow dye (public techniques: I-1, I-4, I-6, I-24, I-26, I-27 described in public technical number 94-6023). II-5) was added in an appropriate amount. Further, it was wound around a stainless steel core having a diameter of 20 cm to give a thermal history of 110 ° C. and 48 hours, thereby providing a support that is difficult to curl.

2) Coating of subbing layer The support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides, and then gelatin 0.1 g / m ² and sodium α-sulfo di- 2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² , (CH ₂ ═CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² An undercoat solution of polyamide-epichlorohydrin polycondensate 0.02 g / m ² was applied (10 mL / m ² , using a bar coater), and an undercoat layer was provided on the high-temperature surface side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were coated as a back layer on one side of the support after the undercoating.
3-1) Coating of antistatic layer The specific resistance of the tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm is 0 of a dispersion of fine powder of 5 Ω · cm (secondary aggregated particle diameter of about 0.08 μm). .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02g / m 2, poly (polymerization degree 10) oxyethylene -p- nonylphenol 0. 005 g / m ² and resorcin.
3-2) Coating of magnetic recording layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) (specific surface area 43 m ² / g, (Major axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89Am ² / kg, Fe ⁺² / Fe ⁺³ = 6/94, surface is treated with 2% by mass of iron oxide with silicon oxide oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. 10 mg each of abrasive aluminum oxide (0.15 μm) treated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) as a matting agent / M ² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and transporting devices in the drying zone were 115 ° C.). X- light (blue filter) saturation magnetization moment of about 0.1, and the magnetic recording layer is color density increment of D ^B of the magnetic recording layer of the 4.2Am ² / kg, a coercive force 7.3 × 10 ⁴ A / m, the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. This mixture was prepared by melting at 105 ° C. in xylene / propylene monomethyl ether (1/1) and pouring and dispersing in propylene monomethyl ether at room temperature (10 times the amount). The average particle size was 0.01 μm) and then added. 15 mg / m each of aluminum particles (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as a matting agent It added so that it might become ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ stainless hard balls, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clipping method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later is 0.12. Excellent characteristics.

4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a sample 301 as a color negative photosensitive material. Samples obtained by replacing emulsion A1 with A2 to A16 are referred to as samples 302 to 316, respectively.

(Composition of photosensitive layer)
The main materials used in each layer are classified as follows:
ExC: Cyan coupler UV: Ultraviolet absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardener (Specific compounds are described below, followed by a numerical value, followed by a symbol, The chemical formula is mentioned)
The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.

First layer (first antihalation layer)
Black colloidal silver Silver 0.155
0.07 μm surface fogging AgBrI (2) Silver 0.01
Gelatin 0.87
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
HBS-1 0.004
HBS-2 0.002

Second layer (second antihalation layer)
Black colloidal silver Silver 0.066
Gelatin 0.407
ExM-1 0.050
ExF-1 2.0 × 10 ⁻³
HBS-1 0.074
Solid disperse dye ExF-2 0.015
Solid disperse dye ExF-3 0.020

Third layer (intermediate layer)
0.07 μm AgBrI (2) 0.020
ExC-2 0.022
HBS-1 0.068
Cpd-1 0.075
Polyethyl acrylate latex 0.085
Gelatin 0.294

4th layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide emulsion M Silver 0.065
Silver iodobromide emulsion N Silver 0.100
Silver iodobromide emulsion O Silver 0.158
ExC-1 0.109
ExC-3 0.044
ExC-4 0.072
ExC-5 0.011
ExC-6 0.003
ExC-8 0.052
Cpd-2 0.025
Cpd-4 0.025
HBS-1 0.17
Gelatin 0.80

5th layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion K Silver 0.21
Silver iodobromide emulsion L Silver 0.62
ExC-1 0.14
ExC-2 0.026
ExC-3 0.020
ExC-4 0.12
ExC-5 0.016
ExC-6 0.007
ExC-8 0.007
Cpd-2 0.036
Cpd-4 0.028
HBS-1 0.16
Gelatin 1.18

6th layer (high-sensitivity red-sensitive emulsion layer)
Silver iodobromide emulsion J1 Silver 1.67
ExC-1 0.18
ExC-3 0.07
ExC-6 0.047
Cpd-2 0.046
Cpd-4 0.077
HBS-1 0.25
HBS-2 0.12
Gelatin 2.12

7th layer (intermediate layer)
Cpd-1 0.089
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.83
Gelatin 0.84

Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))
Silver iodobromide emulsion E Silver 0.560
Cpd-4 0.030
ExM-2 0.096
ExM-3 0.028
ExY-1 0.031
ExG-1 0.006
HBS-1 0.085
HBS-3 0.003
Gelatin 0.58

9th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion G Silver 0.39
Silver iodobromide emulsion H Silver 0.28
Silver iodobromide emulsion I Silver 0.35
ExM-2 0.36
ExM-3 0.045
ExC-9 0.008
ExG-1 0.005
HBS-1 0.28
HBS-3 0.01
HBS-4 0.27
Gelatin 1.39

10th layer (medium sensitive green sensitive emulsion layer)
Silver iodobromide emulsion F Silver 0.20
Silver iodobromide emulsion G Silver 0.25
ExC-6 0.005
ExC-9 0.004
ExC-8 0.005
ExM-2 0.031
ExM-3 0.029
ExY-1 0.006
ExM-4 0.028
ExG-1 0.005
HBS-1 0.064
HBS-3 2.1 × 10 ^-3
Gelatin 0.44

11th layer (high sensitivity green emulsion layer)
Emulsion Q1 of Example 2 Silver 1.200
ExC-6 0.003
ExC-9 0.002
ExC-8 0.007
ExM-1 0.016
ExM-3 0.036
ExM-4 0.020
ExM-5 0.004
ExY-5 0.008
ExM-2 0.013
Cpd-4 0.007
HBS-1 0.18
Polyethyl acrylate latex 0.099
Gelatin 1.11

12th layer (yellow filter layer)
Yellow colloidal silver Silver 0.047
Cpd-1 0.16
Dye ExF-5 0.010
Solid disperse dye ExF-6 0.010
HBS-1 0.082
Gelatin 1.057

13th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion B Silver 0.18
Silver iodobromide emulsion C Silver 0.20
Silver iodobromide emulsion D Silver 0.07
ExC-1 0.041
ExC-7 0.012
ExY-1 0.035
ExY-2 0.71
ExY-3 0.10
ExY-4 0.005
Cpd-2 0.10
Cpd-3 4.0 × 10 ⁻³
HBS-1 0.24
Gelatin 1.41

14th layer (high sensitivity blue-sensitive emulsion layer)
Emulsion A1 of Example 1 Silver 0.75
ExC-1 0.013
ExY-2 0.31
ExY-3 0.05
ExY-6 0.062
Cpd-2 0.075
Cpd-3 1.0 × 10 ⁻³
HBS-1 0.10
Gelatin 0.91

15th layer (first protective layer)
0.07 μm AgBrI (2) Silver 0.30
UV-1 0.21
UV-2 0.10
UV-3 0.18
UV-4 0.025
UV-5 0.07
F-18 0.009
F-19 0.005
HBS-1 0.12
HBS-4 5.0 × 10 ^-2
Gelatin 2.3

16th layer (second protective layer)
H-1 0.40
B-1 (diameter 1.7 μm) 5.0 × 10 ⁻²
B-2 (diameter 1.7 μm) 0.15
B-3 0.05
S-1 0.20
Gelatin 0.75

Furthermore, storage stability, processability, pressure resistance, antifungal and antibacterial properties, B-4 to B-6, F-1 to F-18, and iron salts, lead salts, gold salts, platinum salts, as appropriate for each layer , Palladium salts, iridium salts, ruthenium salts and rhodium salts. Further, 8.5 × 10 ⁻³ gram per mole of silver halide was added to the eighth layer coating solution and 7.9 × 10 ⁻³ gram calcium was added to the eleventh layer with a calcium nitrate aqueous solution to prepare a sample. . Further, at least one of W-1, W-6, W-7 and W-8 is contained for improving the antistatic property, and at least one of W-2 and W-5 is used for improving the coating property. Contains.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 below was dispersed by the following method. That is, 21.7 mL of water and 3 mL of 5% aqueous p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 mL pot mill. Then, 5.0 g of dye ExF-2 and 500 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, the contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle diameter of the dye fine particles was 0.44 μm.

  Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the dye fine particles was 0.45 μm. ExF-3 was dispersed by a microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method.
To 2800 g of ExF-6 wet cake containing 18% of water, 376 g of 4000 g of water and a 3% solution of W-2 was added and stirred to obtain a slurry of ExF-6 having a concentration of 32%. Next, 1700 mL of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultra Viscomill (UVM-2) manufactured by Imex Co., Ltd., and pulverized for 8 hours through the slurry at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min. did.
The compounds used for forming each of the above layers are as shown below.

  The sample evaluation method is as follows. The film was exposed for 1/100 second through a gelatin filter SC-39 (long wavelength light transmission filter having a cut-off wavelength of 390 nm) and a continuous wedge manufactured by FUJIFILM Corporation. Development was performed as follows using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. In addition, the overflow solution of the bleaching bath was remodeled so as not to flow to the rear bath but to discharge all to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992.

The treatment process and the treatment liquid composition are shown below.
(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5L
Whitening 50 seconds 38.0 ℃ 5 mL 5L
Fixing (1) 50 seconds 38.0 ℃ -5L
Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L
Wash with water 30 seconds 38.0 ℃ 17 mL 3L
Stable (1) 20 seconds 38.0 ℃ -3L
Stable (2) 20 seconds 38.0 ℃ 15 mL 3L
Dry 1 min 30 sec 60.0 ° C
* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1)

The stabilizing solution and the fixing solution were counter-current from (2) to (1), and all the overflow solution of the washing water was introduced into the fixing bath (2). The amount of developer brought into the bleaching process, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 mL and 2.0 mL, respectively, per photosensitive material 35 mm width 1.1 m, 2.0 mL. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the treatment liquid is shown below.
(Color developer) Tank solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 3.0 3.0
Catechol-3,5-disulfonic acid disodium 0.3 0.3
Sodium sulfite 3.9 5.3
Potassium carbonate 39.0 39.0
Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 1.5 2.0
Potassium bromide 1.3 0.3
Potassium iodide 1.3mg −
4-hydroxy-6-methyl-1,3
3a, 7-tetrazaindene 0.05-
Hydroxylamine sulfate 2.4 3.3
2-Methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino]
Aniline sulfate 4.5 6.5
Add water 1.0L 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenisher solution (g)
1,3-diaminopropanetetraacetic acid ferric ammonium monohydrate 113 170
Ammonium bromide 70 105
Ammonium nitrate 14 21
Succinic acid 34 51
Maleic acid 28 42
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia] 4.6 4.0

(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution (pH 6.8)

(Fixing (2)) Tank liquid (g) Replenisher (g)
Ammonium thiosulfate aqueous solution 240 mL 720 mL
(750g / L)
Imidazole 7 21
Ammonium methanethiosulfonate 5 15
Ammonium methanesulfinate 10 30
Ethylenediaminetetraacetic acid 13 39
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water)
Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 150 mg / L were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-3-one sodium 0.10
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5

The said process was given with respect to the samples 301-316. Further, the same treatment was applied to a sample which was aged for 3 days under the conditions of 50 ° C. and 80% RH. Photographic performance was evaluated by measuring the density of the processed sample with a blue filter. The obtained results are shown in (Table 6). The obtained results are shown in (Table 6) (sample 301 was set as a reference: 100).

  From Table 6, also in the full-color silver halide photographic material, the emulsion to which the electron-emitting compound of the present invention was added had a greater sensitivity increasing effect than the emulsion to which the electron-emitting compound of the comparative example was added, and the density ( It can be seen that the covering is low. The emulsion to which the electron emitting compound of the present invention was added maintained the merit of increasing the sensitivity, while overcoming the high demerit of the emulsion like the emulsion to which the electron emitting compound of the comparative example was added. In addition, with respect to a sample that had been aged for 3 days under the conditions of 50 ° C. and 80% RH, the emulsion to which the electron-emitting compound of the present invention was added had a smaller decrease in sensitivity after raw storage than the emulsion to which the electron-emitting compound of the comparative example was added. It can be seen that the cover is low.

  From the above results, it can be seen that by using the compound of the present invention, a silver halide photographic light-sensitive material having high sensitivity and low fog, little desensitization after raw storage, and little increase in covering can be obtained.

Claims (5)

A silver halide photographic light-sensitive material containing at least one selected from compounds of type (1), (2) or (3).
(i) Type (1)
It is represented by the general formula (1), and further emits one or more electrons with the nucleophilic addition reaction of the nucleophilic group in the molecule to the one-electron oxidant generated by oxidation of the reducing group in the molecule. Compound.

(In the formula, X ¹ represents a reducing group. Nu represents a nucleophilic group, and represents —NHR ¹ , —PR ² ₂ or —OH. Here, R ¹ represents a hydrogen atom, an alkyl group, or a heterocyclic group. , —C (═O) —R ¹³ , —C (═S) —R ¹³ or —SO ₂ —R ¹³ , wherein R ² and R ¹³ are a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group, respectively. Represents an alkoxy group, an aryloxy group or an amino group, and L ¹ represents a linking group.)
(ii) Type (2)
One or more electrons are emitted with the elimination reaction of the leaving group from the one-electron oxidant represented by the general formula (2) or the general formula (3), which is generated by one-electron oxidation of the reducing group. Possible compounds.

(In the formula, X ² represents a reducing group. L ² represents a single bond or an arylene group. R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. Z ¹ represents a leaving group. A methyl group substituted with two or more aryl groups or aromatic heterocyclic groups, or a methyl group substituted with at least one hydroxy group, silyloxy group, alkoxy group, amino group, alkylamino group, acylamino group or sulfonamino group (However, when Z ¹ is a methyl group substituted with a hydroxy group or an alkoxy group, the methyl group does not have a group which can be taken as X ² as a substituent.)

(In general formula (3), Y represents an alkylamino group, an arylamino group, a heterocyclic amino group, an aromatic or non-aromatic nitrogen-containing heterocyclic group in which nitrogen is substituted, an alkoxy group, or an aryloxy group. R ⁵ represents a substituent, a is an integer of 0 to 4, and when a is 2 or more, a plurality of R ⁵ may be the same or different, L ³ is —O—, -S- or -N (-R ⁶ )-, where R ⁶ represents a substituent, Z ² is a leaving group, and is a methyl group substituted with two or more aryl groups or aromatic heterocyclic groups. Represents.)
(iii) Type (3)
A compound represented by the general formula (4), which does not have a covalently bonded base in the molecule, and further includes one or more protons from the one-electron oxidant produced by one-electron oxidation. A compound that can emit electrons.

Wherein X ³ is an alkylamino group, arylamino group, heterocyclic amino group, an aromatic or non-aromatic nitrogen-containing heterocyclic group in which nitrogen is substituted, or at least one alkoxy group or aryloxy group Represents a substituted aryl group, L ⁴ represents a single bond or an arylene group, R ⁷ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group, R ⁸ represents a hydrogen atom, an alkyl group, Represents an aryl group or a heterocyclic group, wherein at least one of X ³ , L ⁴ , R ⁷ and R ⁸ is an oxiranyl group, an oxetanyl group, —OR ⁹ , —OCO ₂ R ⁹ , —CO ₂ R ⁹ , Or substituted with a substituent containing a quaternary salt structure of nitrogen or phosphorus, R ⁹ represents a substituted methyl group or t-alkyl group of two or more aryl groups or aromatic heterocyclic groups.   2. The silver halide photographic light-sensitive material according to claim 1, wherein the compounds of types (1) to (3) have an adsorptive group to silver halide in the molecule.   The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the compounds of types (1) to (3) have a sensitizing dye structure as a partial structure in the molecule.   A silver halide emulsion chemically sensitized with a compound of any one of types (1) to (3) according to any one of claims 1 to 3.   A silver halide photographic light-sensitive material comprising at least one silver halide emulsion according to claim 4.