JP2003114488A - Silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material which suppresses a fogging due to enhanced sensitivity while enhancing photographic sensitivity and is less liable to increase the fogging even when stored at a high temperature and a high humidity and under such severe conditions that it is exposed to harmful gas produced in combustion, such as automobile exhaust gas. SOLUTION: A silver halide emulsion containing one or more of the compounds of formulae (1)-(3) is provided. In the formula (1), Z1 is an atomic group capable of forming a 6-membered ring together with N and two C atoms of the benzene ring; R1 , R2 and RN1 are each H or a substituent; X1 is a substituent; m1 is an integer of 0-3; and L1 is a releasable group. In the formula (2), ED11 is an electron donative group; R11 , R12 , RN11 , R13 and R14 are each H or a substituent; X11 is a substituent; m11 is an integer of 0-3; L11 is a releasable group; and RN11 , R13 , R14 , X11 and ED11 may bond to each other to form a cyclic structure. In the formula (3), R22 , R23 , R21 , RN21 , Ra and Rb are each H or a substituent and L21 is a releasable group, but when RN21 is a group other then aryl, Ra and Rb bond to each other to form an aromatic ring.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to light sensitive silver halide emulsions having enhanced photographic sensitivity, and photographic elements containing same.

[0002]

Various techniques have been used to improve the photosensitivity of silver halide photographic light-sensitive materials. To increase the intrinsic sensitivity of silver halide, for example, sulfur,
Chemical sensitizers such as gold and Group VIII metal compounds have been used. Spectral sensitization with cyanines and other polymethine dyes is also a well known technique in the art. It is known as dye desensitization that the photographic sensitivity is remarkably reduced when the spectral sensitizing dye is added to the emulsion in an amount exceeding the optimum amount. As a method for improving this, a technique utilizing the supersensitizing effect of a supersensitizer is known. This is a colorless organic compound which does not exhibit a spectral sensitizing effect by itself, and acts on a sensitizing dye (or excited sensitizing dye) to exert an effect of suppressing dye desensitization.
Examples of such compounds are shown, for example, in the following patents. U.S. Pat. Nos. 2,937,089 and 3,706,6
567, 2,875,058, 3,695,8
No. 88, No. 3,457,078, No. 3,458,31
No. 8, 3, 615, 632, No. 5, 192, 654
No. 5,306,612, 2,419,975
Issue No. 5,459,052 Issue No. 4,971,890
No., European Patent No. 554856. Various electron-donating compounds are also used together with sensitizing dyes in order to increase the spectral sensitivity of silver halide photographic light-sensitive materials. Examples of these are U.S. Pat. No. 3,695,588, 3,809,5
61, British Patent Nos. 255084 and 1064193. Furthermore, compounds in which these electron-donating compounds are covalently linked to a sensitizing dye are also used. Examples of these are US Pat. Nos. 5,436,121 and 5,478,719 (compounds having an electron donating styryl base attached to a monomethine dye), US Pat. No. 4,607,006 (phenothiazine phenoxazine). , Carbazole, dibenzophenothiazine, ferrocene, an electron-donating group derived from tris-2,2'-bipyridyl-ruthenium, or a compound having a triarylamine skeleton bonded to a silver halide adsorbing group). However, even with the above measures, ideally high photographic sensitivity has not been achieved yet. In particular, it is stored under harsh conditions, such as the problem of fog that occurs with higher sensitivity, and the exposure of silver halide photographic light-sensitive materials to harmful gases such as high temperatures, high humidity, and combustion of automobile exhaust gases. At present, there are still very few compounds capable of achieving high sensitivity while being compatible with the problem of storage fog caused by the above.

On the other hand, more recently, US Pat.
7,235, 5,747,236, European Patent No. 7
86692A1 and 893731A1 and 8937
32A1, WO99 / 05570, and papers published in the American Chemical Society: "Two-Electron Sensitization: AN
ew Concept for Silver Halide Photography ", J. Am.
Chem. Soc., 122, 11934-11943 (2000), a "two-electron sensitizer" containing a compound capable of fragmenting (bond cleavage) after one-electron oxidation and releasing another electron is used. Sensitive technology has been reported. These compounds are obtained by exciting a dye hole (a sensitizing dye molecule that has lost one electron after the injection of an electron from the excited sensitizing dye into the conduction band of silver halide) or a silver halide. After being oxidized by the generated holes, another electron is released only after the fragmentation reaction, which is characterized in that it causes high sensitivity. However, even with these compounds, it has not been possible to achieve an ideal technology for increasing the sensitivity, which can provide a light-sensitive material having a high sensitivity / fogging ratio and excellent storage stability.

[0004]

SUMMARY OF THE INVENTION The present invention increases the photographic sensitivity of photographic emulsions, suppresses the fog that accompanies the increase in sensitivity, and prevents harmful effects that occur during high temperature, high humidity, and combustion of automobile exhaust gas. Another object of the present invention is to provide a silver halide photographic light-sensitive material that causes less fog increase even when stored under severe conditions such as exposure to gas.

[0005]

[Means for Solving the Problems] The above-mentioned problems are as follows.
Achieved by ~ 6. <Structure 1> A silver halide emulsion containing at least one compound represented by the following general formula (1), (2) or (3).

[0006]

[Chemical 2]

Z in the general formula (1)₁Is a nitrogen atom and
And can form a 6-membered ring with two carbon atoms of the benzene ring
Represents an atomic group₁, R₂, R_N1Are hydrogen atoms
Or represents a substituent, X₁Represents a substituent, m₁Is 0 to 3
Represents an integer, L₁Represents a leaving group. Smell of general formula (2)
ED₁₁Represents an electron-donating group, R₁₁, R₁₂, R_N11,
R₁₃, R₁₄Each represents a hydrogen atom or a substituent, X
₁₁Represents a substituent, m ₁₁Represents an integer of 0 to 3, L₁₁Is
Represents a leaving group. R_N11, R₁₃, R₁₄, X₁₁And ED₁₁
Any two groups in the above bond to each other to form a cyclic structure.
You may have. R in the general formula (3)_{twenty two}, R_{twenty three}, R
_{twenty one}, R_N21, R_a, R_bAre hydrogen atom or substituent
Represents L_{twenty one}Represents a leaving group. However, R_N21Is an aryl group
R represents a group other than_aAnd R_bAre bound together and fragranced
Form a group ring.

<Structure 2> A silver halide emulsion chemically sensitized with at least one compound represented by formula (1), (2) or (3) according to structure 1.

<Structure 3> The silver halide according to any one of Structures 1 and 2, wherein the compound according to Structure 1 is a compound having an adsorptive group for silver halide in the molecule. emulsion.

<Structure 4> The silver halide emulsion according to Structure 3, wherein the adsorptive group is a nitrogen-containing heterocyclic group substituted with two or more mercapto groups.

<Structure 5> A silver halide photographic light-sensitive material containing at least one compound described in Structures 1 to 4.

<Structure 6> A silver halide photographic light-sensitive material comprising at least one emulsion chemically sensitized with the compounds described in Structures 1 to 4.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the compound of the present invention will be described in detail. The compound of the present invention is first-electron-oxidized to a one-electron oxidant, and then, after first undergoing a bond cleavage reaction,
Further, it is a compound capable of emitting two or more electrons (preferably three or more electrons). In other words, it is a compound that can be further oxidized by 2 or more electrons (preferably 3 or more electrons). Here, the bond cleavage reaction means a cleavage reaction between L ₁ , L ₁₁ and L ₂₁ and a carbon atom in the general formula (1), (2) or (3), respectively. More specifically,
The compound of the present invention is one-electron-oxidized to a one-electron oxidant and then converted to C in the general formula (1), (2) or (3).
-L ₁ , C-L ₁₁ and C-L ₂₁ are accompanied by a bond cleavage reaction to further release one electron, and thereafter, a tautomerization reaction accompanied by spontaneous proton transfer, Alternatively, it has a structural feature that can induce a bond-forming reaction between carbon atoms and further emit one or more electrons (usually two or more electrons) therefrom. Therefore, the compound of the present invention releases two or more (preferably three or more) electrons after being subjected to one-electron oxidation.

As already mentioned in the description of the prior art, US Pat. Nos. 5,747,235 and 5,747,236.
No., European Patent Nos. 786692A1 and 893731A.
1, No. 893732A1, WO99 / 05570
Issue and a paper published in the American Chemical Society: "Two-Electro
n Sensitization: A New Concept for Silver Halide P
hotography ", J. Am. Chem. Soc., 122,11934-11943 (20
In 00), a compound that can be one-electron-oxidized and then fragmented (bond cleavage) to release another one-electron is described as a "two-electron sensitizer". This is a compound that is relatively similar in structure and function to the compound of the present invention. However, the number of electrons released after one-electron oxidation is different from that of the above-mentioned "two-electron sensitizer" in the compound of the present invention. It is clearly different and this is also the main feature of the compounds according to the invention. That is, the compound of the present invention exhibits a specific and unexpectedly high sensitization effect because the number of electrons released after one-electron oxidation is not one but two or more (preferably three or more). That is why we have newly found it.

The compound represented by formula (1), (2) or (3) of the present invention will be described in detail below. In the general formula (1), Z ₁ represents an atomic group capable of forming a 6-membered ring with a nitrogen atom and two carbon atoms of the benzene ring. The 6-membered ring formed by Z ₁ is a non-aromatic heterocycle condensed with the benzene ring of the general formula (1), and specifically,
The ring structure including a condensed benzene ring is a tetrahydroquinoline ring, a tetrahydroquinoxaline ring, or a tetrahydroquinazoline ring, which may have a substituent.

As the substituent, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom),
Alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (regardless of the substituting position), quaternary nitrogen atom-containing heterocycle Group (for example, 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, carbonimidoyl group, thiocarbamoyl group, hydroxy group,
Alkoxy groups (including groups containing repeating ethyleneoxy or propyleneoxy groups), aryloxy groups, heterocyclic oxy groups, acyloxy groups, (alkoxy or aryloxy) carbonyloxy groups, carbamoyloxy groups, sulfonyloxy groups, amino Group, (alkyl, aryl, or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thio group Semicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkenyl group) , Aryl or heterocyclic)
Thio group, (alkyl or aryl) sulfonyl group,
(Alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or a salt thereof, a group containing a phosphoric acid amide or a phosphoric acid ester structure, and the like. These substituents may be further substituted with these substituents.

In the general formula (1), R ₁ and R ₂ represent a hydrogen atom or a substituent capable of substituting for a carbon atom, and X ₁ represents a substituent. m ₁ represents an integer of 0 to 3. R ₁ , R ₂ ,
And when X ₁ represents a substituent, the substituent specifically includes, for example, a halogen atom, an alkyl group (preferably having 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms), an alkenyl group (preferably having carbon atoms). 2-18, more preferably 2-1
0), an alkynyl group (preferably having 2 to 18 carbon atoms, more preferably 2 to 10), an aryl group (preferably having 6 to 18 carbon atoms, more preferably 6 to 10), a heterocyclic group (preferably 5 to 7). Member ring, N, O, S as a hetero atom, regardless of substitution position), acyl group, alkoxycarbonyl group (preferably having 2 to 19 carbon atoms, more preferably 2 to 11), aryloxycarbonyl group (preferably Is a carbon number of 7 to 19, more preferably 7 to 19), a carbamoyl group, an oxalyl group, a cyano group, a hydroxy group,
Alkoxy group (preferably having 1 to 18 carbon atoms, more preferably 1 to 10), aryloxy group (preferably having 6 to 18 carbon atoms, more preferably 6 to 10), heterocyclic oxy group, acyloxy group, {alkoxy ( Preferably, it has 1 to 18 carbon atoms, more preferably 1 to 10) or aryloxy (preferably 6 to 18 carbon atoms, more preferably 6 carbon atoms).
-10)} carbonyloxy group, amino group, {alkyl (preferably having 1 to 18 carbon atoms, more preferably 1 to 1)
0), aryl (preferably having 6 to 18 carbon atoms, more preferably 6 to 10), or heterocycle} amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, {alkoxy (preferably carbon Number 1
18, more preferably 1 to 10) or aryloxy (preferably having 6 to 18 carbon atoms, more preferably 6 to 1)
0)} carbonylamino group, sulfamoylamino group,
Mercapto group, {alkyl (preferably having 1 to 1 carbon atoms
8, more preferably 1 to 10), aryl (preferably having 6 to 18 carbon atoms, more preferably 6 to 10), or heterocycle} thio group, {alkyl (preferably having 1 to 1 carbon atoms).
8, more preferably 1 to 10) or aryl (preferably having 6 to 18 carbon atoms, more preferably 6 to 10)} sulfonyl group, sulfamoyl group, group containing a phosphoric acid ester structure, and the like. These substituents may be further substituted with any substituent. Z is an optional substituent
_The same examples as the substituent when ₁ has a substituent can be mentioned.

In the general formula (1), R _N1 represents a substituent capable of substituting a hydrogen atom or a nitrogen atom, and examples of the substituent include the same substituents as those represented by R ₁ . When R _N1 represents a substituent, it is preferably an alkyl group, an aryl group or a heterocyclic group, which may further have a substituent, and the substituent is a substituent when Z ₁ has a substituent. The same as the example of.

In the general formula (1), L ₁ represents a leaving group, specifically a carboxy group or a salt thereof. L
_{When 1} represents a salt of a carboxy group, the counter ion forming the salt is specifically an alkali metal ion (L
i ⁺ , Na ⁺ , K ^+, etc.), alkaline earth metal ions (M
g ²⁺ , Ca ^2+, etc., heavy metal ion (Ag ⁺ , Cu ^2+, etc.), ammonium ion (tetramethylammonium ion, dimethylbenzylammonium ion, triethylhydroammonium ion, etc.), phosphonium ion (triphenylbenzylphosphonium ion) Such)
And so on.

Next, the preferred range of the compound represented by the general formula (1) will be described. Z ₁ in the general formula (1)
Preferably represents an atomic group forming a tetrahydroquinoline ring or a tetrahydroquinoxaline ring with a nitrogen atom and two carbon atoms of the benzene ring. In the general formula (1), R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group,
It is an aryl group, a hydroxy group or an alkoxy group, more preferably a hydrogen atom, an alkyl group or an alkoxy group. In formula (1), R _N1 is preferably a hydrogen atom, an alkyl group or an aryl group. More preferably, it is a hydrogen atom or an alkyl group. In the general formula (1), m ₁ is preferably 0 to 2, and more preferably 0 or 1. X
Preferably as ₁ , halogen atom, alkyl group, aryl group, acyl group, alkoxycarbonyl group, carbamoyl group, cyano group, alkoxy group, acylamino group, sulfonamide group, ureido group, thioureido group, alkylthio group, arylthio group, alkyl Examples thereof include a sulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

Next, the compound represented by the general formula (2) will be described. In the general formula (2), ED ₁₁ represents an electron donating group. Here, the electron-donating group means a hydroxy group, an alkoxy group (preferably having a carbon number of 1 to 10), a mercapto group, an alkylthio group (preferably having a carbon number of 1 to 10), an arylthio group (preferably having a carbon number of 6 to 10). , Heterocyclic thio group, sulfonamide group, acylamino group, alkylamino group (preferably having 1 to 10 carbon atoms), arylamino group (preferably having 6 to 10 carbon atoms), heterocyclic amino group, active methine group, electron excess Aromatic heterocyclic group (for example, indolyl group, pyrrolyl group, indazolyl group), nitrogen-substituted non-aromatic nitrogen-containing heterocyclic group (pyrrolidinyl group, piperidinyl group, indolinyl group, piperazinyl group, morpholino group, etc.), and An aryl group ((preferably having 1 to 10 carbon atoms, substituted with an electron donating group,
For example, p-hydroxyphenyl group, p-dialkylaminophenyl group, o, p-dialkoxyphenyl group, 4-hydroxynaphthyl group). The hydroxy group may be protected by a silyl group, for example, a trimethylsilyloxy group, t-
Examples thereof include a butyldimethylsilyloxy group, a triphenylsilyloxy group, a triethylsilyloxy group and a phenyldimethylsilyloxy group.

Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, It means a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and a carbonimidoyl group. Here, the two electron-withdrawing groups may be bonded to each other to form a cyclic structure.

The electron donating group represented by ED ₁₁ is preferably a hydroxy group, an alkoxy group, a mercapto group,
Sulfonamide group, alkylamino group, arylamino group, active methine group, aromatic heterocyclic group with electron excess, non-aromatic nitrogen-containing heterocyclic group substituted with nitrogen atom, and phenyl substituted with these electron-donating groups Group, more preferably a hydroxy group, a mercapto group, a sulfonamide group, an alkylamino group, an arylamino group, an active methine group, a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom,
And phenyl groups substituted with these electron-donating groups (for example, p-hydroxyphenyl group, p-dialkylaminophenyl group, o, p-dialkoxyphenyl group, etc.). Particularly preferred are a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an alkylamino group, an arylamino group and an active methine group.

In the general formula (2), R ₁₁ , R ₁₂ , X ₁₁ ,
R _N11 , L ₁₁ and m ₁₁ are the same groups as R ₁ , R ₂ , X ₁ , R _N1 , L ₁ and m ₁₁ in the general formula (1), respectively, and their preferable ranges are also the same. In the general formula (2), R ₁₃ and R _{14 each} represent a hydrogen atom or a substituent capable of substituting for a carbon atom, and examples of the substituent include the same as X ₁ in the general formula (1). The preferred range is also the same. In the general formula (2), R _N11 , R ₁₃ ,
Any two groups of R ₁₄ , X ₁₁ and ED ₁₁ may be bonded to each other to form a cyclic structure. Where R _N11
And a cyclic structure X _{1 1} and is formed by bonding, preferably a non-aromatic heterocyclic 5- to 7-membered condensed with a benzene ring, and specific examples thereof include a tetrahydroquinoline ring, tetrahydro Quinoxaline ring, indoline ring,
2,3-dihydro-5,6-benzo-1,4-thiazine ring and the like can be mentioned. Preferred are a tetrahydroquinoline ring, a tetrahydroquinoxaline ring and an indoline ring.

Next, the compound represented by the general formula (3) will be described. In the general formula (3), R ₂₁ is the general formula (1)
R ₁ has the same meaning as R _1, and its preferable range is also the same. In formula (3), L ₂₁ represents a leaving group, specifically a carboxy group (or a salt thereof) or a hydrogen atom.

When L ₂₁ represents a hydrogen atom, the compound represented by the general formula (3) preferably has an internal base moiety in the molecule. By the action of this base moiety, the general formula
After the compound represented by (3) is oxidized, the hydrogen atom represented by L ₂₁ is deprotonated, and electrons are further released from this. Here, the base is specifically about 1 to
It is a conjugate base of an acid showing a pKa of about 10. For example, nitrogen-containing heterocycles (pyridines, imidazoles, benzimidazoles, thiazoles, etc.), anilines, trialkylamines, amino groups, carbonic acids (active methylene anions, etc.), thioacetic acid anion, carboxylate (-
COO ⁻ ), sulfate (—SO ₃ ⁻ ), amine oxide (> N ⁺ (O ⁻ ) −) and the like. Preferably about 1
Is a conjugate base of an acid exhibiting a pKa of from about 8 and more preferably carboxylates, sulfates or amine oxides, with carboxylates being particularly preferred. When these bases have an anion, they may have a counter cation, and examples thereof include an alkali metal ion, an alkaline earth metal ion, a heavy metal ion, an ammonium ion, and a phosphonium ion. These bases are linked to the compound represented by the general formula (3) at any position. L
_{When 21} represents a hydrogen atom, it is preferable that the hydrogen atom and the base moiety are connected by an atomic group of 8 or less. Furthermore, it is more preferable that they are linked by atomic groups of 5 or more and 8 or less. Here, what is counted as a linking atomic group is an atomic group that covalently connects the central atom of the base site (that is, the atom having an anion or the atom having a lone electron pair) and the hydrogen atom, for example, carboxy. 2 atoms are counted in the case of the sulfates are S-O ^{- -} -C-O in the case of a rate is counted two atoms. The carbon atom replaced by L ₂₁ is also added to the number.

In the general formula (3), L ₂₁ is preferably a carboxy group (or a salt thereof).

In the general formula (3), R _N21 has the same meaning as R _N1 in the general formula (1), and its preferable range is also the same. R _N21 is more preferably a hydrogen atom, an alkyl group, or an aryl group (particularly a phenyl group).
Is. In the general formula (3), R ₂₂ , R ₂₃ , R _a , and R _b each represent a hydrogen atom or a substituent, and the substituent here means when X ₁ in the general formula (1) represents a substituent. Examples of the substituent include the same, and their preferable ranges are also the same. However, in the general formula (3), when R _N21 represents a group other than an aryl group, R _a and R _b are bonded to each other to form an aromatic ring. Here, the aromatic ring means an aryl group (for example, a phenyl group, a naphthyl group) and an aromatic heterocyclic group (for example, a pyridine ring group, a pyrrole ring group, a quinoline ring group, an indole ring group, etc.), and an aryl group is preferable. The aromatic ring group may have a substituent, and as the substituent, the same substituents as those mentioned when X ₁ in formula (1) represents a substituent can be mentioned, and the preferable range thereof is also included. It is the same again. In the general formula (3), R _a and R _b are preferably bonded to each other to form an aromatic ring (particularly a phenyl group).

In the general formula (3), R ₂₂ is preferably a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group, a mercapto group, an amino group or the like, and when R ₂₂ represents a hydroxy group, at the same time A case where R ₂₃ represents an electron-withdrawing group is also one of the preferable examples. Here, the electron-withdrawing group means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, a carboximide. Means an yl group, and is preferably an acyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. The structure is not limited to the structure represented by the general formula (3), and includes tautomers thereof.

The compound of the present invention has at least one adsorptive group which adsorbs to or promotes adsorption of silver halide at any position in the molecule, or alternatively, a portion of the spectral sensitizing dye. It preferably has a structure.

As the adsorptive group for silver halide,
Examples thereof include a thioamide group, a mercapto group, or a heterocyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom. Examples of the adsorptive group exhibiting relatively weak adsorptivity to silver halide include a sulfide group (-S-), a cationic group, and an ethynyl group.

As the thioamide-adsorptive group,

[Chemical 3]

It is a divalent group represented by and may be a part of the ring structure, and is preferably an acyclic thioamide group. Useful thioamide adsorptive groups are described, for example, in US Pat. Nos. 4,030,925 and 4,031,1.
No. 27, No. 4,080,207, No. 4,245,03
No. 7, No. 4,255,511, No. 4,266,013
And 4,276,364, and Research Disclosure 151.
Volume, November 1976, Item 15162, and Id. 176.
Volume, December 1978, Item 17626. Particularly preferred thioamide groups are those of formula (A).

[0034]

[Chemical 4]

[Wherein one of E and E'is -N (R₆₂)
Represents-, the other is -O-, -S- or -N
(R₆₂′) -Represents. R₆₁Is a hydrogen atom, an aliphatic group,
Represents a reel group or heterocyclic group, or if E
Or an E'bond to each other to form a 5- or 6-membered heterocycle
Form (ie, become a ring-forming thioamide group). R
₆₂And R ₆₂′ Is a hydrogen atom, aliphatic group, aryl
It is a group or a heterocyclic group. ].

The thioamide represented by the formula (A) is thiourea, thiourethane or dithiocarbamic acid ester. Examples of the case where E or E'and R ₆₁ are bonded to each other to form a ring include those which are seen as an acidic nucleus of a merocyanine dye, and examples thereof include 4-thiazoline-2-thione and thiazolidine-2-. Thion, 4-
Oxazoline-2-thione, oxazolidine-2-thione, 2-pyrazoline-5-thione, 4-imidazoline-
2-thione, 2-thiohydantoin, rhodanine, isorhodanine, 2-thio-2,4-oxazolidinedione, thiobarbituric acid, tetrazoline-5-thione,
1,2,4-triazoline-3-thione, 1,3,4-
Thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione and benzothiazoline-2-thione, which are further substituted. May be.

As the mercapto-adsorptive group, an aliphatic mercapto group, an aryl mercapto group, or a heterocyclic mercapto group (when a carbon atom to which the SH group is bonded is adjacent to a nitrogen atom, a ring-forming thioamide group which is a tautomer) Has already been mentioned as). Examples of the aliphatic mercapto group include a mercaptoalkyl group (for example, a mercaptoethyl group and a mercaptopropyl group), a mercaptoalkenyl group (for example, a mercaptopropenyl group) and a mercaptoalkynyl group (for example, a mercaptobutynyl group). Examples of the aryl mercapto group include a mercaptophenyl group and a mercaptonaphthyl group. The heterocyclic mercapto group is an aromatic heterocyclic mercapto group or a non-aromatic heterocyclic mercapto group, examples of which include those described in the ring-forming thioamide group, for example, 4-mercaptopyridine ring group, 5-
Mercaptoquinoline ring group, 6-mercaptobenzothiazole ring group, 2,4-dimercaptopyrimidine ring group, 2,
Examples thereof include 4-dimercaptotriazine ring group, 3,5-dimercapto-1,2,4-triazole ring group, 2,5-dimercapto-1,3-thiazole ring group, and 6-mercaptopurine ring group.

Mesoionic compounds formed by dissociation of the heterocyclic mercapto group can also be mentioned as the adsorptive group.
The meso-ionic compounds as referred to herein, the unsaturated heterocyclic ring of 5 or 6 membered a positively charged conjugated, a sulfide group (Sulfido group, -S ^- (ion)) is obtained by replacing the positive conjugated here The 5- or 6-membered unsaturated heterocycle having a charge is, for example, imidazolium, pyrazolium, oxazolium, thiazolium, triazolium, tetrazolium, thiadiazolium, oxadiazolium, thiatriazolium. , Oxatriazolium, dithianium, pyridazinium, pyrimidinium, triazinium, tetrazinium,
Examples thereof include oxathianiums, thiaziniums, oxaziniums, oxadiaziniums, thiadiaziniums and the like. A 5-membered unsaturated heterocycle is preferable, thiadiazolium compounds, oxadiazolium compounds, and triazolium compounds are preferable, and triazolium compounds are most preferable. In this case, 1,2,4-triazolium-3-thiolates are most preferable as the mesoionic compound.

The heterocyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom as an adsorptive group means a -NH- group capable of forming iminosilver (> NAg). -Containing heterocyclic group having a partial structure of, or "-S-" group, "-Se-" group, or "-Te" capable of coordinating to silver ion by a coordination bond
A heterocyclic group having a "" group or a "= N-" group as a partial structure of the heterocycle, examples of the former include a benzotriazole group, a triazole group, an indazole group, a pyrazole group, a tetrazole group, a benzimidazole group, and an imidazole group. Examples of the latter include thiophene group, thiazole group, oxazole group, benzothiazole group, benzoxazole group, thiadiazole group, oxadiazole group, triazine group, selenazole group, benzselenoazole group, tellurazole group. Group, a benztelluazole group, etc. The former is preferable.

A sulfide group as an adsorptive group means --S--
And all groups having the partial structure of are mentioned, but preferably alkyl (or alkylene) -S-alkyl (or alkylene), aryl (or arylene) -S-
A group having a partial structure of alkyl (or alkylene), aryl (or arylene) -S-aryl (or arylene). Furthermore, these sulfide groups are
It may form a cyclic structure or may be a -S-S- group. Specific examples of forming a cyclic structure include thiolane ring, dithian ring, 1,3-dithiolane ring, 1,2-dithiolane ring, thian ring, tetrahydro-
Examples include groups containing a 1,4-thiazine ring (thiomorpholine ring) and the like. The sulfide group is particularly preferably a group having a partial structure of alkyl (or alkylene) -S-alkyl (or alkylene). The cationic group as the adsorptive group means a group containing a quaternized nitrogen atom, specifically, an ammonio group or a group containing a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom. . However, the cationic group does not become a part of the atomic group (for example, cyanine chromophore) forming the dye structure.

Here, the ammonio group includes a trialkylammonio group, a dialkylarylammonio group, an alkyldiarylammonio group and the like, for example, a benzyldimethylammonio group, a trihexylammonio group, a phenyldiethylammonio group and the like. Can be mentioned. Examples of the nitrogen-containing heterocyclic group containing a quaternized nitrogen atom include a pyridinio group, a quinolinio group, an isoquinolinio group, and an imidazolio group. A pyridinio group and an imidazolio group are preferable, and a pyridinio group is particularly preferable. The nitrogen-containing heterocyclic group containing a quaternized nitrogen atom may have any substituent, but in the case of a pyridinio group and an imidazolio group, the substituent is preferably an alkyl group, an aryl group or an acylamino group. , A chloro atom, an alkoxycarbonyl group, a carbamoyl group, and the like. In the case of a pyridinio group, a phenyl group is particularly preferable as the substituent. The ethynyl group as the adsorptive group means a -C [identical to] CH group, and the hydrogen atom may be substituted.

The above adsorptive group may have an arbitrary substituent. Specific examples of the adsorptive group include those described in JP-A No. 11-95355, p4 to p7.

Preferred as the adsorptive group in the present invention is a ring-forming thioamide group (that is, a mercapto-substituted nitrogen-containing heterocyclic group such as a 2-mercaptothiadiazole group, a 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) or a nitrogen-containing heterocyclic group having an —NH— group capable of forming imino silver (> NAg) as a partial structure of the heterocycle (eg, benzotriazole group, benzimidazole group, indazole group, etc.). . Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, and most preferred are 3-mercapto-1,2,4-triazole group, and 5 A mercaptotetrazole group.

Among the compounds of the present invention, a compound having two or more mercapto groups in the molecule as a partial structure is also a particularly preferable compound. Here, the mercapto group (-S
H) may be a thione group when it can be tautomerized. As an example of such a compound, an adsorptive group having a mercapto group or a thione group as a partial structure described above (for example, a ring-forming thioamide group, an alkylmercapto group, an arylmercapto group, a heterocyclic mercapto group) is intramolecularly included. Or a compound having two or more mercapto groups or thione groups as a partial structure among the adsorptive groups (for example, a dimercapto-substituted nitrogen-containing telocyclic group), You may have one or more. Examples of the adsorptive group having two or more mercapto groups as a partial structure (dimercapto-substituted nitrogen-containing telocyclic group, etc.) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, and 3,5. -Dimercapto-1,2,4-triazole group, 2,5-dimercapto-1,3-thiazole group, 2,5-dimercapto-1,3-oxazole group, 2,7-dimercapto-
5-Methyl-s-triazolo (1,5-a) -pyrimidine, 2,6,8-trimercaptopurine, 6,8-dimercaptopurine, 3,5,7-trimercapto-s-triazolo (4. 3-a) -s-triazine, 4,6-dimercaptopyrazolo (3,4-d) -pyrimidine, 2,
5-dimercaptobenzimidazole and the like,
2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3,5-dimercapto-1,2,4
-Triazole groups are particularly preferred.

In the present invention, the groups mentioned as the adsorptive group (for example, cyclic thioamide group and nitrogen-containing heterocyclic group)
Is preferably bonded to an aryl group (eg, a phenyl group), but is formed by bonding _a benzene ring of general formula (1) or general formula (2) or R _a and R _b of general formula (3). It is preferable that the adsorptive group is not directly bonded to the benzene ring.
That is, the aryl group to which the adsorptive group is bonded and the benzene ring or R _N1 , R _N11 or R _N21 is a single bond or any divalent organic group (for example, an amide bond, a sulfonamide bond, an ether bond, an alkylene, a carbonyl group). , Imino, sulfonyl, or a divalent group formed by combining these, specifically, —NHCO—, —NHSO ₂ —, —N
HCONH- and the like) are preferred.

The partial structure of the spectral sensitizing dye is a group containing a chromophore of the spectral sensitizing dye, which is a residue obtained by removing any hydrogen atom or substituent from the spectral sensitizing dye. The position to which the spectral sensitizing dye residue is preferably bound is the same as the above-mentioned adsorptive group. Preferred spectral sensitizing dyes are spectral sensitizing dyes typically used in color sensitizing techniques, such as cyanine dyes, complex cyanine dyes, merocyanine dyes,
It includes complex merocyanine dyes, homopolar cyanine dyes, styryl dyes, and hemicyanine dyes. Typical spectral sensitizing dyes are Research Disclosure, Item 3
6544, disclosed in September 1994. Research Disclosure or FM Hamer's The Cya
nine dyes and Related Compounds (Interscience Publ
Those skilled in the art can synthesize these dyes by the procedure described in ishers, New york, 1964). Further, JP-A-11-95355 (US Pat. No. 6,054,260)
All of the dyes described in the specifications p7 to p14 of (No.) are applicable as they are.

The compound of the present invention is one-electron-oxidized by the exposure of the silver halide photographic light-sensitive material using the compound, and further two or more electrons are emitted with subsequent bond cleavage. It is oxidized, but the oxidation potential of the first electron is preferably about 1.4 V or less, and further 1.0
V or less is preferable. This oxidation potential is preferably above 0V, more preferably above 0.3V. Therefore, 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 the technique of cyclic voltammetry. Specifically, a sample is acetonitrile: water (containing 0.1 M lithium perchlorate) = 80.
%: Dissolved in 20% (volume%) solution and bubbled with nitrogen gas for 10 minutes, then use glassy carbon disk as working electrode, platinum wire as counter electrode, and see calomel electrode (SCE) Used for electrodes, at 25 ℃, 0.1
It is measured at a potential scanning speed of V / sec. The oxidation potential vs. SCE is taken at the peak potential of the cyclic voltammetry wave.

The compound of the present invention is one-electron-oxidized, and further, two or more electrons are released and oxidized with subsequent bond cleavage. Regarding the oxidation potential of the latter stage,
There is no particular limitation. 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 therefore it is often difficult to actually measure and distinguish them accurately.

The compound of the present invention is one-electron-oxidized, and further two or more electrons are released and oxidized with the subsequent bond cleavage, but preferably three or more electrons are released after the bond cleavage. And is a compound that is oxidized. Furthermore, a compound that is oxidized by releasing 3 electrons or by emitting 5 electrons after bond cleavage is particularly preferable. Specific compound examples of the present invention are listed below, but the present invention is not limited thereto.

[0051]

[Chemical 5]

[0052]

[Chemical 6]

[0053]

[Chemical 7]

[0054]

[Chemical 8]

Synthetic Example The compound of the present invention can be easily synthesized by a known method. Specific examples thereof will be described below. Synthesis of Exemplified Compound 1 Exemplified Compound 1 was synthesized according to Synthesis Scheme 1 below.

[0056]

[Chemical 9]

Synthesis of Synthetic Intermediate A-2 Compound A-1 (2
0 g), DMF (50 mL) and phosphorus oxychloride (70 g) were added, and the mixture was stirred at room temperature for 24 hours. The reaction was stopped by adding water, and after extraction and concentration, the residue was purified by column chromatography to give 12.6 g of synthetic intermediate A-2 (yield 52
%). Synthesis of Synthesis Intermediate A-3 Synthesis Intermediate A-2 in 200 mL of methylene chloride at room temperature
(12 g), acetyl chloride 8.7 g, pyridine 11.7
g was added and the mixture was stirred for 4 hours. The reaction was stopped by adding water, and after extraction and concentration, the residue was purified by column chromatography to synthesize 12.8 g of synthetic intermediate A-3 (yield: 85
%). Synthesis of Synthetic Intermediate A-4 In 200 mL of THF, 10.5 g of methoxymethyltrimethylsilane was added at -78 ° C, and sec-butyllithium (1.0 M, cyclohexane solution) was added to 118 m.
L was dropped and the temperature was raised to -25 ° C. Then synthetic intermediate A
-3 (12 g) was added dropwise and the temperature was gradually raised to room temperature. The reaction was stopped by adding a saturated aqueous solution of ammonium chloride, extracted from ether and concentrated, and the residue was purified by column chromatography to synthesize 9.9 g of synthetic intermediate A-4 (yield 7
7%).

Synthesis of Synthetic Intermediate A-5 In 50 mL of toluene, Synthetic Intermediate A-4 (9.0 g),
0.14 g of sodium tungstate dihydrate, tri (n-octyl) methylammonium sulfate 5.
8g, 30% hydrogen peroxide solution 7.0 is added, and 50 ℃
The mixture was stirred for 5 hours. After concentration, the residue was purified by column chromatography to obtain 7.7 g of synthetic intermediate A-5. (Yield 80%). Synthesis of Synthesis Intermediate A-6 Synthesis Intermediate A-5 (7.0 g) in methanol (150 mL)
And 0.5 mL of concentrated sulfuric acid was added, and the mixture was reacted under reflux for 5 hours. After cooling to room temperature and concentration, the residue was purified by column chromatography to give synthetic intermediate A-6-3.
Obtained in 8 g (yield 62%). Synthesis of Synthesis Intermediate A-7 Synthesis Intermediate A-6 (3.5 g), γ-bromobutyric acid benzyl ester 5.3 g and triethylamine 4.3 g were mixed with ethyl acetate 50 mL and stirred at 50 ° C. for 6 hours. .
After cooling to room temperature, water was added for extraction and concentration, and the residue was purified by column chromatography to give a synthetic intermediate A-7.
Was obtained in 5.5 g (yield 85%).

Synthesis of Synthetic Intermediate A-8 Synthetic Intermediate A-7 (5.2 g) was dissolved in 50 mL of isopropyl alcohol, and 1.0 g of 5% Pd / C was added.
The reaction was performed overnight under a hydrogen atmosphere at atmospheric pressure. After substituting with nitrogen,
The catalyst was filtered off using Celite, the filtrate was concentrated, and the residue was purified by column chromatography to synthesize the synthetic intermediate A-.
8 was obtained in 3.0 g (77% yield). Synthesis of Synthetic Intermediate A-10 Synthetic Intermediate A-8 (2.8 g) was added to 30 mL of methylene chloride.
Dissolved in 4.9 g of triethylamine, 2.8 g of mesyl chloride, 0.1 g of 4- (N, N-dimethylamino) pyridine were added at 0 ° C., and the mixture was stirred for 30 minutes, and then the synthetic intermediate A-9 was mixed with 3. 8 g was added slowly. After stirring at room temperature for 8 hours, the reaction was stopped by adding water, and after extraction and concentration, the residue was purified by column chromatography to obtain 2.8 g (yield 58%) of synthetic intermediate A-10. It was

Synthesis of Exemplified Compound 1 Synthesis Intermediate A-10 (2.5 g) was added to 25 mL of methanol.
Was dissolved in 3.5 mL of a 5 M aqueous sodium hydroxide solution, and the mixture was stirred at 50 ° C. for 2 hours. After cooling to room temperature, hydrochloric acid was added to acidify the mixture, and the residue was purified to obtain 1.6 g of Exemplified Compound 1 (yield 65%).

Synthesis of Exemplified Compound 11 Exemplified Compound 11 was synthesized according to Synthesis Scheme 2 below.

[0062]

[Chemical 10]

Synthesis of Synthesis Intermediate B-2 Under a nitrogen atmosphere, Synthesis Intermediate B-1 (35 g), PdCl
₂ (PPh ₃ ) ₂ 0.7 g, triphenylphosphine 1.2 g, copper iodide 6.7 g, tetrabutylammonium iodide 3.7 g, 2-methyl-3-butyn-2-ol 25.4 g were added to triethylamine. It was dissolved in 500 mL and reacted under reflux for 2 hours. Triethylamine was distilled off, ethyl acetate and water were added for extraction and concentration, and the residue was purified by column chromatography to give a synthetic intermediate B-
2 was obtained in 31 g (88% yield). Synthesis of Synthesis Intermediate B-3 Synthesis Intermediate B-2 (30 g) was dissolved in 300 mL of toluene, 1 g of sodium hydroxide was added, and the mixture was stirred under reflux for 3 hours. After cooling, toluene was distilled off and the residue was purified by column chromatography to give 21 g of synthetic intermediate B-3.
(Yield 85%). Synthesis of Synthesis Intermediate B-4 Synthesis Intermediate B-3 (20
g), 13.8 g of triethylamine, and 14.5 g of methyl iodide were added, and the mixture was stirred for 2 hours. The reaction was stopped by adding water, the mixture was extracted with ether and concentrated, and the residue was purified by column chromatography to obtain 19.3 g (yield 92%) of a synthetic intermediate B-4.

Synthesis of Synthesis Intermediate B-5 Synthesis Intermediate B-4 (19 g) was dissolved in 200 mL of methanol, 21 mL of 3M hydrochloric acid was added, and the mixture was stirred at 70 ° C. for 2 hours. After cooling, concentration and purification of the residue by column chromatography gave 13.3 g of synthetic intermediate B-5.
(Yield 81%). Synthesis of Synthesis Intermediate B-6 Synthesis Intermediate B-5 (13 g), methyl bromoacetate 11.
2 g and potassium carbonate 13.5 g were mixed in DMF200mL, and it stirred at 80 degreeC for 3 hours. After cooling, hydrochloric acid was added to neutralize the reaction, extracted from ethyl acetate, concentrated,
The residue was purified by column chromatography to obtain 12.2 g (yield 74%) of synthetic intermediate B-6. Synthesis of Synthesis Intermediate B-7 Synthesis Intermediate B-6 (12 g) was dissolved in 150 mL of isopropyl alcohol, 10% Pd / C 1.2 g was added,
The mixture was stirred overnight under a hydrogen atmosphere at atmospheric pressure. After substitution with nitrogen, the catalyst was filtered off using Celite, the filtrate was concentrated, and the residue was purified by column chromatography to give a synthetic intermediate B.
-7 was obtained in 5.9 g (66% yield). Synthesis of Exemplified Compound 11 Synthesis Intermediate B-7 (5.5 g), triethylamine 1
1.2 g, mesyl chloride 6.3 g, and 4- (N, N-dimethylamino) pyridine 0.2 g were added to methylene chloride 120.
It was dissolved in mL at 0 ° C. and stirred for 1 hour. Furthermore, the synthetic intermediate B-8 (5.8 g) was slowly added, and the mixture was stirred at room temperature for 3 hours. The reaction was stopped by adding water, extracted from ethyl acetate and concentrated. Dissolve the residue in 60 mL of methanol, 5M
16 mL of aqueous sodium hydroxide solution was added and stirred at 50 ° C. for 1 hour. After cooling, the mixture was acidified with diluted hydrochloric acid, the solvent was distilled off, and the residue was purified to give 5.1 g of Exemplified Compound 11.
(Yield 52%).

Synthesis of Exemplified Compound 31 Exemplified Compound 31 was synthesized according to Synthesis Scheme 3 below.

[0066]

[Chemical 11]

Synthesis of Synthetic Intermediate C-2 Synthetic Intermediate C-1 (30 g) was added to 300 mL of methylene chloride.
23.8 g of thionyl chloride and 1 drop of DMF were added to 2
Stir for hours. After concentration, it was dissolved in 300 mL of methylene chloride, and 19 g of acetoacetic acid t-butyl ester, 14.3 g of magnesium chloride and 11.9 g of pyridine were added,
The mixture was stirred at 50 ° C for 5 hours. The reaction was stopped by adding water, extracted from ethyl acetate, concentrated, and the residue was purified by column chromatography to give 30 g of synthetic intermediate C-2.
(Yield 68%). Synthesis of Synthetic Intermediate C-3 Synthetic Intermediate C-2 (30 g) was dissolved in 250 mL of DMF, 9.3 g of 25% aqueous ammonia was added, and the mixture was mixed at 50 ° C. for 3 days.
Stir for hours. After cooling, the mixture was neutralized with diluted hydrochloric acid and extracted from ethyl acetate. The residue after concentration was purified by column chromatography to give the synthetic intermediate C-3.
Obtained in 9 g (44% yield). Synthesis of Synthetic Intermediate C-4 100 mL of isopropanol, 20 mL of water, 1.4 g of ammonium chloride and 14 g of reduced iron were added, and the mixture was stirred at 80 ° C. for 1 hour. After cooling, the synthetic intermediate C-3 (10
g) was added, and the mixture was stirred at 80 ° C. for 3 hours. After filtration through Celite at 60 ° C. and concentration of the filtrate, the residue was purified by column chromatography to obtain 8.6 g of synthetic intermediate C-4 (yield 93%). Synthesis of Synthetic Intermediate C-5 Synthetic Intermediate C-4 (8.5 g), methyl bromoacetate 5.
Dissolve 3 g and 6.4 g of potassium carbonate in 60 mL of DMF,
The mixture was stirred at 80 ° C for 2 hours. After cooling, water and ethyl acetate were added thereto for extraction and concentration, and the residue was purified by column chromatography to obtain 8.8 g (yield 87%) of synthetic intermediate C-5.

Synthesis of Synthetic Intermediate C-6 Synthetic Intermediate C-5 (8.0 g), methyl iodide 3.1
g, 3.8 g of potassium carbonate were dissolved in 60 mL of THF,
The mixture was stirred at room temperature for 12 hours. The reaction was stopped by adding water, the mixture was extracted with ether and concentrated, and the residue was purified by column chromatography to obtain 6.5 g of synthetic intermediate C-6 (yield 79%). Synthesis of Synthetic Intermediate C-7 Synthetic intermediate C-6 (6.0 g) was dissolved in 120 mL of isopropyl alcohol, and 10% Pd / C1.2 g was added.
The mixture was stirred overnight at room temperature under a hydrogen atmosphere at atmospheric pressure. After substituting with nitrogen, the catalyst was filtered off using Celite, the filtrate was concentrated, and the residue was purified by column chromatography to obtain 4.0 g of synthetic intermediate C-7 (yield 83%). . Synthesis of Synthetic Intermediate C-9 Synthetic intermediate C-7 (4.0 g) was added to 60 mL of methylene chloride.
, Thionyl chloride (2.6 g) and DMF (1 drop) were added.
Stir for 2 hours. After concentration, it was dissolved again in 60 mL of methylene chloride, 4.8 g of Synthetic intermediate C-8 and 2.2 g of triethylamine were added, and the mixture was stirred at room temperature for 6 hours. The residue after extraction by addition of water and concentration was purified by column chromatography to give 4.3 g of synthetic intermediate C-9 (yield 61
%). Synthesis of Exemplified Compound 31 Synthetic intermediate C-9 (4.5 g) was dissolved in 50 mL of methanol, 3.5 mL of 5 M aqueous sodium hydroxide solution was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling, the mixture was acidified with diluted hydrochloric acid, and the residue after concentration was purified to obtain 2.7 g (yield 74%) of Exemplified Compound 31.

The compounds of the present invention represented by the general formulas (1) to (3) may be used at any time during the preparation of an emulsion and the process of producing a light-sensitive material. For example, during grain formation, desalting step, during chemical sensitization, before coating and the like. It is also possible to add them in multiple times during these steps. General formula (1)-
The addition position of the compound of the present invention represented by (3) is preferably from the end of grain formation to before the desalting step, at the time of chemical sensitization (just before the start of chemical sensitization to immediately after the end), and before coating. Preferably, during chemical sensitization and before coating. The compound of the present invention is preferably added by dissolving it 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 raised or lowered may be dissolved by raising or lowering the pH and then added.

The compounds of the present invention represented by the general formulas (1) to (3) are preferably used in the emulsion layer, but they are added to the protective layer and the intermediate layer together with the emulsion layer and diffused during coating. You may let me. The compound of the present invention may be added before or after the sensitizing dye, and preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol, and more preferably 1 ×, per mol of silver halide.
10 ^{−8 to} 2 × 10 ⁻³ mol, more preferably 1 × 10 ⁻⁷ to
It is contained in the silver halide emulsion layer in a ratio of 1 × 10 ⁻³ mol.

The silver halide grains of the photographic emulsion are cubic,
Regular (regu, such as octahedron, tetradecahedron, rhombic dodecahedron)
lar) crystals, those with irregular crystal forms such as spheres, plates, etc., those with high-order planes ((hkl) planes), or those of these crystal forms Although it may consist of a mixture of grains, it is preferably tabular grains, which are described in detail below. For particles with higher surface, see the Journal of Imaging
2 pp. 247 of Science magazine, Volume 30 (1986)
See page 54.

The light-sensitive material of the present invention may contain a light-sensitive silver halide emulsion composed of tabular grains (silver halide grains having two opposing parallel principal planes, hereinafter referred to as "tabular grains"). preferable. The tabular grains will be described in detail below. The aspect ratio of the tabular grains in the present invention is obtained by dividing the equivalent circle diameter of two opposing parallel principal planes (the diameter of a circle having the same projected area as the principal planes) by the distance between the principal planes (that is, grain thickness). Defined as a value.

The aspect ratio of tabular grains is 5 or more and 100.
The following are preferred. To realize the effect of the present invention, 8
It is more preferable that it is not less than 60 and not more than 30
The following is particularly preferable. If the average aspect ratio is less than 2, the advantages of tabular grains (improvement in sensitivity and image quality) cannot be fully utilized, and if it exceeds 100, pressure resistance deteriorates, which is not preferable. Further, 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, which is not preferable. 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. When the average particle thickness is less than 0.01 μm, pressure resistance deteriorates, and 0.3 μm
If it exceeds, it becomes difficult to obtain the effects of the present invention, which is not preferable. In the present invention, the grain thickness and the aspect ratio in the above ranges 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.

The diameter (equivalent circle diameter) of the tabular grains in the present invention can be arbitrarily selected, but is preferably 0.3-.
It is 20 μm, more preferably 0.5 to 10 μm. If the average equivalent-circle diameter, which is the arithmetic mean of equivalent-circle diameters of all tabular grains, is less than 0.3 μm, the effect of the present invention is difficult to obtain.
If it exceeds μm, the pressure resistance deteriorates, which is not preferable.
Particle diameter and particle thickness are measured by US Pat. No. 4,434,22.
It can be determined from an electron micrograph of the particles as in the method described in No. 6. As an example of a method of measuring the aspect ratio, there is a method of taking a transmission electron micrograph by a replica method and obtaining the diameter (circle equivalent diameter) and thickness of a circle having an area equal to the projected area of each particle. 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 monodisperse. The variation coefficient of the grain size distribution of all silver halide grains is 3
It is preferably 5% or less, more preferably 25%
It is 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 grain size distribution is a value obtained by dividing the variation (standard deviation) of the sphere-equivalent diameters of individual silver halide grains by the average sphere-equivalent diameter and multiplying by 100. The grain size distribution of a silver halide emulsion consisting of grain groups in which the grain morphology of silver halide grains is uniform and the variation in grain size is small shows almost normal distribution, and the standard deviation can be easily obtained.
For the preparation of monodisperse tabular grains, see JP-A-63-119.
28. The monodisperse hexagonal tabular grains are described in JP-A-63-151618. Regarding the circular monodisperse tabular grain emulsion, JP-A-1-131541
There is a description in the issue. Further, 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 principal plane, and the size distribution of the tabular grains is monodisperse. An emulsion is disclosed. EP 514,742 A1 discloses tabular grain emulsions prepared with polyalkylene oxide block copolymers having a grain size variation coefficient of 10% or less.

It is known that the tabular grains have major surfaces (100) and (111), and the technique of the present invention can be applied to both. Regarding the former, regarding silver bromide, U.S. Pat. No. 4,063,951 and JP-A-5-281640.
No. 534,3 regarding silver chloride.
95A1 and US Pat. No. 5,264,337. The latter tabular grains are grains having various shapes having one or more of the above twin planes, and regarding silver chloride, US Pat. Nos. 4,399,215 and 4,983,5
08, No. 5,183,732, JP-A-3-1376.
32 and 3-116113.

Various methods can be used for forming tabular grains, and for example, US Pat. No. 5,494,7 can be used.
The particle forming method described in No. 89 can be used. To form tabular grains with a high aspect ratio, it is important to generate twin nuclei with a small size. Therefore, it is preferable to perform nucleation at low temperature, high pBr, low PH, and low gelatin amount in a short time, and the type of gelatin is low molecular weight, low methionine content, or phthalated. Are preferred. After nucleation, only tabular grain nuclei (parallel multiple twin nuclei) are grown by physical ripening, and other normal nuclei, single twin nuclei and non-parallel multiple twin nuclei are eliminated, and selective parallel multiplex is performed. Leave twin nuclei. Then, a soluble silver salt and a soluble halogen salt are added and grain growth is carried out to prepare an emulsion consisting of tabular grains. It is also preferable to add silver halide fine particles prepared separately in advance or simultaneously prepared in another reaction vessel to supply silver and halide to grow the particles.

The tabular grains in the present invention may have dislocation lines. A dislocation line is a linear lattice defect on the slip plane of a crystal at the boundary between a region that has already slipped and a region that has not slipped yet. When the tabular grain in the present invention has a dislocation line, the dislocation line may be formed at, for example, the apex portion of the grain, the fringe portion or the 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 of the tabular grain to the center, the silver iodide content at a certain point from the side is the Points outside the point where the average silver iodide content exceeds or falls below.

When the tabular grains in the present invention have dislocation lines, the density of the dislocation lines is arbitrary,
0 or more, 30 or more, 50 or more can be selected. The tabular grains used in the present invention may have dislocation lines in the grains. Regarding the technique for controlling and introducing dislocations into silver halide grains, see JP-A-63-220.
No. 238. Compared with tabular grains having no dislocation lines, tabular grains having dislocation lines are more effective in improving photographic characteristics such as sensitivity and reciprocity law, 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 the edge portions of tabular grains. The tabular grains having dislocations introduced in the center are described in US Pat. No. 5,238,796.

The dislocation line in the silver halide grain is, for example,
JF Hamilton, Photo.Sci.Eng., 11, 57 (1967) and T.Sh
It can be observed by a direct method using a transmission electron microscope at low temperature described in iozawa, J.Soc.Photo.Sci.Japan, 35, 213 (1972). That is, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation from the emulsion are placed on a mesh for electron microscope observation,
The sample is observed by a transmission method while being cooled so as to prevent damage (printout) due to an electron beam. This time,
The thicker the particles, the more difficult it is for an electron beam to pass through.
It is possible to observe more clearly by using an electron microscope (v or more). The position and the number of dislocation lines for each grain when viewed from the plane perpendicular to the main plane can be determined from the photograph of the grain obtained by such a method.

The tabular grains used in the present invention include silver bromide,
Although silver chlorobromide, silver iodobromide, silver iodochloride, silver chloride, silver chloroiodobromide, etc. can be used, it is preferable to use silver bromide, silver iodobromide, silver chloroiodobromide. Also, silver chloride is 50 mol%
The use of silver chlorobromide, silver chloroiodide, silver chloroiodobromide or silver chloride having an aspect ratio of 2 or more contained as described above is also preferable from the viewpoint of suitability for rapid processing. The upper limit of the silver chloride content is not particularly limited, but is preferably 99.6 mol% or less. When it has a phase containing iodide or chloride, these phases may be uniformly distributed in the grain or may be localized. Other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate, and silver salt of organic acid may be contained as separate grains or as a part of silver halide grains.

The range of the silver iodide content of the tabular grains used in the present invention is preferably 0.1 to 20 mol%, more preferably 0.1 to 15 mol%, and particularly preferably 0.2 to 10 mol%.
Mol%. If it is less than 0.1 mol%, the dye adsorption is enhanced,
It is difficult to obtain effects such as an increase in intrinsic sensitivity, and if it exceeds 20 mol%, the developing speed is generally delayed, which is not preferable. In the case of tabular grains containing 50 mol% or more of silver chloride and having an aspect ratio of 2 or more, silver iodide may be contained, but the silver iodide content is preferably 6 mol% or less, more preferably 2 mol% or less. is there. The variation coefficient of the intergranular silver iodide content distribution of the tabular grains in the present invention is preferably 30% or less, more preferably 25% or less, and particularly preferably 20% or less. When 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 coefficient of variation 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 having at least one kind of silver salt epitaxy formed on the surface of host tabular grains. In the present invention, silver salt epitaxy may be formed at a selected site on the surface of the host tabular grain, and the corners or edges of the host tabular grain (the side faces of the grain and the sides of each side when the tabular grain is viewed from above) are formed. It may be limited to the upper part). When silver salt epitaxy is formed, it is preferable to form silver salt epitaxy uniformly at a selected site on the surface of host tabular grains within and between grains. A specific method for site directing silver salt epitaxy is described in US Pat.
No. 5,501, a method of adsorbing a spectral sensitizing dye (for example, a cyanine dye) or an aminoazaindene (for example, adenine) on a host grain before forming a silver salt epitaxy, a method for incorporating silver iodide into the host grain, and the like. Therefore, these methods may be used. Further, iodide ions may be added and deposited on the host grains before the silver salt epitaxy is formed. These site direct methods may be selected depending on the case, and a plurality of them may be used in combination.

When silver salt epitaxy is formed, the ratio of silver salt epitaxy to the host tabular grain surface area is preferably 1 to 50%, more preferably 2 to 40%, and particularly preferably 3 to 30. %. When silver salt epitaxy is formed, the silver amount in the silver salt epitaxy is preferably 0.3 to 50 mol%, more preferably 0.3 to 2 mol% based on the total silver amount of the silver halide tabular grains.
It is 5 mol%, particularly preferably 0.5 to 15 mol%.
The composition of silver salt epitaxy can be selected depending on the case, and may be silver halide containing any of chloride ion, bromide ion, and iodide ion, but it is not limited to silver halide containing at least chloride ion. Preferably there is. Since silver chloride forms the same face-centered cubic lattice structure as the host tabular grains, silver bromide and silver iodobromide, epitaxy can be easily formed. However, there is a difference in the lattice spacing formed by the two types of silver halides, and this difference forms an epitaxial junction that contributes to an increase in photographic sensitivity. The silver chloride content in silver halide epitaxy is at least 10% higher than the silver chloride content in host tabular grains.
It is preferably high by mol%, more preferably high by 15 mol% or higher, particularly preferably high by 20 mol% or higher. 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 the halide ions in an order corresponding to the composition of epitaxy in order to increase the introduction amount. For example, in the case of forming epitaxy in which a large amount of silver chloride is contained inside, a large amount of silver bromide is contained in the middle part, and a large amount of silver iodide is contained in the outside, chloride ion, bromide ion, and iodide ion of By sequentially adding these halides, the solubility of the silver halide containing the added halide ions is made lower than the solubility of other silver halides, and the silver halides are precipitated to enrich the silver halides. Form a layer. Silver salts other than silver halide, for example, silver rhodanide, 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 a method of adding a halide ion, a method of adding a silver nitrate aqueous solution and a halide aqueous solution by a double jet method, a method of adding silver halide fine particles, and the like. It may be selected depending on the case, or a plurality of combinations may be used. The temperature of the system when forming silver salt epitaxy,
The type and concentration of the protective colloid agent such as pH, pAg and gelatin, the presence / absence of a silver halide solvent, the type and concentration thereof can be widely selected.

In the case of epitaxial silver halide grains,
In order to maintain the morphology of host tabular grains or site-direct to grain edge / corner of silver salt epitaxy,
It is preferable that the outer region of the host tabular grain (the portion which is finally precipitated and forms the edges / corners of the grain) has a silver iodide content higher than that of the central region by at least 1 mol%. . At that time, the silver iodide content of the outer region is preferably 1 to 20 mol%, more preferably 5 to 15 mol%. If it is less than 1 mol%, it is difficult to obtain the above-mentioned effects, and if it exceeds 20 mol%, the developing rate 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%, more preferably 10 to 25%. If it is less than 10% or more than 30%, it is difficult to obtain the above effects, which is not preferable. Also,
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%. When it exceeds 10 mol%, the developing rate is delayed, which is not preferable. For the tabular grains used in the present invention, any ordinary dopant known to be useful for a silver halide face centered cubic crystal lattice structure can be used. Typical dopants are Fe, Co, N
i, Ru, Rh, Pd, Re, Os, Ir, Pt, A
u, Hg, Pb, Tl and the like. These dopants can be present in the host emulsion and / or the silver salt epitaxially deposited on the grain surface.

The above emulsion in the present invention and other photographic emulsions used together therewith are described below. The silver halide grains in other emulsions used in the present invention are cubic,
Having regular crystals such as octahedron, tetradecahedron,
It may have an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, 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 grains having a sphere-equivalent diameter of about 3 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Specifically, U.S. Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17029 (1)
1978), No. 17643 (1978) 22-2
Page 3, ibid. No. 18716 (1979) page 648, ibid.
307105 (1989), pages 863-865, JP-A-62-253159, JP-A-64-13546, JP-A-2-236546, JP-A-3-110555 and Graphide, "Physics and Chemistry of Photography", Pallmonte. Published (P.
Glafkides, Chemie et Phisque Photographique, Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion
Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VLZe
likman et al., Making and Coating Photographic Emul
It can be selected from silver halide emulsions prepared by the method described in USION, Focal Press, 1964).

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic such as grain shape and sensitivity can be mixed and used in the same layer. 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, which is preferably used in the present invention, and an emulsion different therefrom are used in different layers, or mixed in the same layer. It can also be used. In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to perform so-called desalting to remove excess salt. As a means for this, the Nudel 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 (eg, 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 kinds. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When contained, the particles may be uniformly added, or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A-2-236542 and 1-116637 are preferably used. In the step of forming grains of the photosensitive silver halide emulsion in the present invention, a rhodan salt, an ammonia, a 4-substituted thiourea compound, an organic thioether derivative described in JP-B-47-11386, or a silver halide solvent as a silver halide solvent, or JP-A-53-144319. The sulfur-containing compounds described in 1) and the like can be used.

For other conditions, see Graphide, "Physics and Chemistry of Photography", published by Paul Monte (P.Glaf).
kides, Chemie et Phisque Photographique, Paul Mont
el, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chem
istry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikm).
an et al., Making and Coating Photographic Emulusi
on, Focal Press, 1964). That is, any of the acidic method, the neutral method, and the ammonia method may be used, and as the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. The double jet method is preferably used to obtain a monodisperse emulsion.

A back mixing method in which grains are formed in the presence of excess silver ions can also be used. A so-called controlled double jet method, in which pAg in the liquid phase in which silver halide is produced is kept constant, can also be used as one type of the simultaneous mixing method. Further, in order to accelerate the grain growth, the addition concentration, the addition amount, and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142).
No. 329, No. 55-158124, and U.S. Pat. No. 3,6.
50, 757). Further, the stirring method of the reaction liquid may be any known stirring method. 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 chemically sensitized (for example, after "one-electron oxidation to one-electron oxidation product defined in the present invention, a bond-cleavage reaction occurs, and further two or more electrons are included." A chemical compound capable of releasing a compound) (excluding chemical sensitization). Chemical sensitization of the light-sensitive silver halide emulsion in the present invention includes known chalcogen sensitizing methods such as sulfur sensitizing method, selenium sensitizing method, tellurium sensitizing method, gold, platinum, etc. A noble metal sensitization method using palladium or the like and a reduction sensitization method can be used alone or in combination (JP-A-3-11055).
No. 5). It is also a preferred embodiment to carry out the sensitization of the present invention by allowing the compound relating to the present invention (particularly, the compound represented by the general formula (1) or (2)) to be present during these ordinary chemical sensitizations. . In this case, the compound relating to the present invention may be added during normal chemical sensitization, immediately before chemical sensitization, or immediately after the end of chemical sensitization. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. Sho 6-62).
2-253159). Further, an antifoggant described below can be added after the completion of the chemical sensitization. Specifically, the methods described in JP-A-5-45833 and JP-A-62-40446 can be used. The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.
5, and 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 0.01 in terms of silver.
It ranges preferably to 10 g / m ^2, particularly preferably 6 g / m ² or less.

In order to provide the photosensitive silver halide used in the present invention with color sensitivity such as green sensitivity and red sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. Further, 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. Specifically, US Pat. No. 4,617,257
JP-A-59-180550 and 64-13546.
And sensitizing dyes described in JP-A Nos. 5-45828 and 5-45834. These sensitizing dyes may be used alone, or may be used in combination,
Especially, the combination of sensitizing dyes is often used for the purpose of wavelength control of supersensitization or spectral sensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself 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). , 61
5,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or in accordance with US Pat. Good. Further, these sensitizing dyes and supersensitizers may be added in a solution of an organic solvent such as methanol, a dispersion of gelatin or a solution of a surfactant. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

Further, the present invention is preferably used in combination with a technique for improving the light absorption rate with a spectral sensitizing dye. For example, by utilizing the intermolecular force, the sensitizing dye is adsorbed on the surface of the silver halide grain more than a single layer saturated adsorption (that is, one layer adsorption), or two or more sensitizing dyes are not separately conjugated but covalently bonded. Adsorbing a so-called linking dye having a linked chromophore. Among them, it is preferable to use the techniques described in the following patents together. JP 10-23978
9, JP 11-133531, JP 2000-267216, JP 200
0-275772, JP 2001-75222, JP 2001-75247, JP 2001-75221, JP 2001-75226, JP 2001-75223.
No. 2001-255615, No. 2002-23294, No. 10-
171058, JP 10-186559, JP 10-197980, JP 2000-81678, JP 2001-5132, JP 2001-166413.
No. 2002-49113, No. 64-91134, No. 10-1
10107, JP 10-171058, JP 10-226758, JP 10-307358, JP 10-307359, JP 10-31071
5, JP-A-2000-231174, JP-A-2000-231172, JP-A-200
0-231173, JP 2001-356442, European Patent 985965A
European Patent No. 985964A, European Patent No. 985966A, European Patent No. 985967A, European Patent No. 1085372A, European Patent No. 1
085373A, European Patent 1172688A, European Patent 1199595
No. A, European Patent No. 887700A1. In particular, it is preferable to use it in combination with the technique described in the following patents. Kohei
10-239789, JP 2001-75222 A, JP 10-171058 A.

The photographic additives that can be used in the present invention are described in RD, and the related descriptions are shown below. 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 enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, to page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. 5. Light absorber, pages 25-26, page 649, right column, page 873, filter dye, ~ page 650, left column, ultraviolet absorber 6. Binder page 26 page 651 left column page 873 to 874 7. Plasticizer, lubricant page 27 page 650 right column page 876 8. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 9. Static, page 27, page 650, right column, pages 876-877, inhibitor 10. Matting agent pp. 878-879

In the present invention, it is also preferable 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 at 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 substance containing a source capable of reducing silver ions. Silver salts of organic acids, especially (having 10 to 30 carbon atoms, preferably 15 to
Silver salts of long chain fatty carboxylic acids (of 28) are preferred. Complexes of organic or inorganic silver salts in which the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver-providing substance can preferably constitute about 5 to 30% by mass 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 silver salt of an aliphatic carboxylic acid 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 their derivatives can also be used.
Preferred examples of these compounds include silver salts of 3-mercapto-4-phenyl-1,2,4-triazole, 2
-Silver salt of mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2- (ethylglycolamido) benzothiazole, s-alkylthioglycolic acid (wherein the alkyl group has 12 carbon atoms).
A silver salt of thioglycolic acid, such as a silver salt of
Dithiocarboxylic acid silver salt such as dithioacetic acid silver salt, thioamide silver salt, 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine silver salt, mercaptotriazine silver salt, 2-mercaptobenzoxazole Silver salt,
Silver salts described in US Pat. No. 4,123,274, eg 3
Silver salts of 1,2,4-mercaptothiazole derivatives, such as the silver salt of -amino-5-benzylthio-1,2,4-thiazole, and 3- salts described in U.S. Pat.
Includes silver salts of thione compounds such as silver salts of (3-carboxyethyl) -4-methyl-4-thiazoline-2-thione. Furthermore, compounds 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, and US Pat. Fourth 4,220,7
No. 09, 1,2,4-triazole or 1-H-tetrazole silver salts, imidazole and imidazole derivative silver salts, and the like. Various silver acetylide compounds, such as those described in US Pat. Nos. 4,761,361 and 4,775,613, may also be used. Moreover, two or more kinds of organic silver salts may be used in combination.

In the present invention, the above-mentioned organic compound is mixed with silver nitrate in a suitable reaction medium to form a silver salt of the compound (hereinafter referred to as an organic silver salt). It is also possible to replace part of the silver nitrate with another silver ion donor (eg, silver chloride, silver acetate). The method of adding these reaction reagents is arbitrary. The compound may be placed in a reaction vessel in advance and silver nitrate may be added thereto, or conversely, silver nitrate may be placed in the reaction vessel and the compound may be added thereto. Alternatively, a part of the compound may be placed in a reaction vessel, a part of silver nitrate may be added, and then the rest of the compound and silver nitrate may be sequentially added. Further, silver nitrate and an organic compound can be added to the reaction vessel at the same time. It is preferable to stir during the reaction. The above organic compound is usually mixed with silver nitrate in a ratio of 0.8 to 100 mol with respect to 1 mol of silver, but depending on the kind of the compound, it can be used outside this range. The addition rate of silver nitrate or a compound may be adjusted so as to control the silver ion concentration during the reaction.

The above organic silver salt may be added to any layer, and may be added to one layer or a plurality of layers. Further, it is a hydrophilic colloid layer provided on the side having a silver halide emulsion layer, and 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 a support and an emulsion layer. This is also preferable in terms of storage stability improvement. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.05 to 1 mol, per 1 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, preferably 0.1~12g / m ^2, particularly preferably 6 g / m ²
That is all. Silver halide emulsion and // in the present invention
Alternatively, the organic silver salt can be protected against additional fog formation by antifoggants, stabilizers and stabilizer precursors and stabilized against variations in sensitivity during inventory storage. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are:
US Pat. Nos. 2,131,038 and 2,694,71
Thiazonium salts described in US Pat. No. 6,886,496
37 and 2,444,605, azaindene, mercury salts described in US Pat. No. 2,728,663, urazole described in US Pat. No. 3,287,135, US Pat. No. 3,235. No. 652, sulfocatechol,
Oxime, nitrone, nitroindazole described in British Patent No. 623,448 and US Pat. No. 2,839,405.
Polyvalent metal salts described in US Pat. No. 3,220,839, and thiuronium salts described in US Pat. No. 3,220,839, and US Pat.
6,263 and 2,597,915, palladium, platinum and gold salts, US Pat. No. 4,108,665.
And the halogen-substituted organic compounds described in US Pat. Nos. 4,128,557 and 4,442,202.
137,079, 4,138,365 and 4,
Examples include the triazine described in US Pat. No. 459,350 and the phosphorus compound described in US Pat. No. 4,411,985.

The antifoggant preferably used in the present invention is an organic halide, for example, JP-A-50-11.
9624, 50-120328, 51-121
No. 332, No. 54-58022, No. 56-70543.
No. 56-99335, No. 59-90842, No. 61-129642, No. 62-129845, JP-A No. 6-208191, No. 7-5621, No. 7-27.
81, 8-15809, U.S. Pat. No. 5,340,7.
No. 12, No. 5,369,000, No. 5,464,73
And compounds such as those disclosed in No. 7. The antifoggant of the present invention may be added by any method such as solution, powder and solid fine particle dispersion. Dispersion of solid fine particles is performed by a known refining 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 of the present invention may contain benzoic acids for the purpose of increasing sensitivity and preventing fog. The benzoic acids of the present invention may be any benzoic acid derivative,
An example of a preferred structure is U.S. Pat. No. 4,784,93.
No. 9, No. 4,152,160 and the like. The benzoic acid of the present invention may be added to any part of the light-sensitive material, but as an addition layer, it is preferable to add it to a layer on the side having a light-sensitive layer, and it is more preferable to add it to an organic silver salt-containing layer. . The benzoic acid of the present invention may be added at any step of the coating solution preparation, and when it is added to the organic silver salt-containing layer, it may be any step from the preparation of the organic silver salt to the preparation of the coating solution. It is preferred that the salt is prepared and immediately before coating. The benzoic acid compound of the present invention may be added by any method such as powder, solution and fine particle dispersion. Also, it may be added as a solution mixed with other additives such as a sensitizing dye and a reducing agent. The amount of the benzoic acid of the present invention to be added may be any amount, but is preferably 1 × 10 ⁻⁶ to 2 mol, and more preferably 1 × 10 ^{−3 to} 0.5 mol, per 1 mol of the photosensitive silver halide.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are used for the purpose of controlling development by suppressing or accelerating development, improving spectral sensitization efficiency, and improving storage stability before and after development. Can be included. When the mercapto compound is used in the present invention, it may have any structure, but Ar-SM, A
Those represented by r-S-S-Ar are preferable. 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 is, for example, halogen (for example, Br and Cl), hydroxy, amino, carboxy, alkyl (for example, having 1 or more carbon atoms, preferably one having 1 to 4 carbon atoms) and alkoxy ( For example, one or more carbon atoms, preferably 1 to
It may have one selected from the group of substituents consisting of (having 4 carbon atoms). As the mercapto-substituted heteroaromatic compound, 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-imidazolthiol, 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-mercaptopyrimidine 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-
Examples include mercapto-5-phenyl-1,2,4-triazole and 2-mercapto-4-phenyloxazole, but the present invention is not limited thereto. The addition amount of these mercapto compounds is preferably in the range of 0.001 to 1.0 mol per mol of photosensitive silver halide in the emulsion layer, and more preferably 0.01 to 1.0 mol per mol of photosensitive silver halide. An amount of 0.3 mol.

It is also preferable to use a silver halide solvent in the light-sensitive material of the present invention. For example, thiosulfates, sulfites, thiocyanates, thioether compounds described in JP-B-47-11386, and compounds having a 5- or 6-membered imide group such as uracil and hydantoin described in JP-A-8-179458, Compounds having a carbon-sulfur double bond described in Sho 53-144319, Analytica Chimica Acta, 248, 6
Mesoionic thiolate compounds such as trimethyltriazolium thiolate described on pages 04 to 614 (1991) are 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 the silver halide solvent contained in the photosensitive material is 0.01 to 100 mmol / m ^2.
And preferably 0.1 to 50 mmol / m ² , and more preferably 10 to 50 mmol / m ² . The molar ratio is 1/20 to 20 times, preferably 1/10 to 10 times, and more preferably 1/3 to 3 times the coating silver amount of the photosensitive silver halide of the photosensitive material. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropyl glycol or the like, or an alkaline 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 a plurality of silver halide solvents may be used in combination.

A hydrophilic binder is preferably used as the binder of the constituent layers in the light-sensitive material of the present invention. Examples thereof include the above-mentioned RD and JP-A-64-135467.
The thing described in pages 1-75 is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, for example, a protein such as gelatin, a gelatin derivative or a cellulose derivative, a natural compound such as a polysaccharide such as starch, gum arabic, dextran, pullulan, etc. and polyvinyl alcohol, a modified Polyvinyl alcohol (eg, terminal alkyl-modified Poval MP103, MP203 manufactured by Kuraray Co., Ltd.)
Etc.), polyvinylpyrrolidone, acrylamide polymer and other synthetic polymer compounds. Further, superabsorbent polymers described in U.S. Pat. No. 4,960,681, JP-A-62-245260, that is, -COOM or
A homopolymer of a vinyl monomer having SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers with each other or with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate,
Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more. A combination of gelatin and the above binder is particularly preferable. Further, the gelatin may be selected from lime-processed gelatin, acid-processed gelatin and so-called decalcified gelatin having a reduced content of calcium etc. according to various purposes, and it is also preferable to use them in combination.

It is also preferable to use a polymer latex as the binder in the present invention. Here, the polymer latex is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As the dispersed state, the polymer is emulsified in the dispersion medium,
It may be emulsion-polymerized, micelle-dispersed, or a polymer having a partially hydrophilic structure and molecular chains themselves being molecularly dispersed in the polymer molecule. For the polymer latex of the present invention, see "Synthetic Resin Emulsion".
(Edited by Tadashi Okuda and Hiroshi Inagaki, published by Kobunshi Kogakukai (1978)),
"Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, published by Polymer Publishing Society (1993))", "Chemistry of Synthetic Latex (Souichi Muroi, Published by Polymer Publishing Society (19)
70)) ”and the like.

The average particle diameter of the dispersed particles is 1 to 50000n.
m, more preferably in the range of about 5 to 1000 nm. There are no particular restrictions 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. Further, the polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more kinds of monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer.

The number average molecular weight Mn of the polymer is 0.5 to 1,000,000, preferably about 1 to 500,000. If the molecular weight is too small, the mechanical strength of the photosensitive layer is insufficient, and if it is too large, the film-forming property is poor, which is not preferable.

The polymer of the polymer latex used in the present invention has an equilibrium water content of 2% by mass at 25 ° C. and 60% RH.
The following is more preferable, and 1% by mass or less is more preferable.
The lower limit of the equilibrium water content is not particularly limited, but is preferably 0.01% by mass, more preferably 0.03% by mass.
Is. For the definition and measurement method of the equilibrium water content, for example, “Polymer Engineering Course 14, Polymer Material Testing Method (Polymer Society, edited by Jijijinkan)” can be referred to. Specifically, the equilibrium water content at 25 ° C. and 60% RH is 25
It can be expressed by the following equation using the mass W _{1 of} the polymer that has reached the humidity control equilibrium in the atmosphere of 60 ° C. RH and the mass W ₀ of the polymer in the absolutely dry state at 25 ° C. "Equilibrium moisture content at 25 ° C. 60% RH" _{= {(W 1 -W 0)} / W 0}
× 100 (mass%)

Such polymers are commercially available,
The following polymers can be used as the polymer latex. For example, as an example of acrylic resin, Sebian A-46
35, 46583, 4601 (above Daicel Chemical Industries, Ltd.), Nipol
Lx811, 814, 821, 820, 857 (Nippon Zeon Co., Ltd.)
For polyester resin such as FINETEX ES650, 61
1,675,850 (manufactured by Dainippon Ink and Chemicals, Inc.), WD-siz
e, WMS (above Eastman Chemical), polyurethane resin such as HYDRAN AP10, 20, 30, 40 (above Dainippon Ink and Chemicals, Inc.), rubber resin LACSTAR 7
310K, 3307B, 4700H, 7132C, DS206 (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol Lx416, 433, 410, 438C, 2507,
(Made by Nippon Zeon Co., Ltd.), vinyl chloride resins such as G351, G576 (Made by Nippon Zeon Co., Ltd.), and vinylidene chloride resin by L502, L513 (Made by Asahi Kasei Corporation)
Made) etc. as olefin resin, Chemipearl S120, SA1
00 (above, manufactured by Mitsui Petrochemical Co., Ltd.) and the like. These polymers may be used alone as a polymer latex, or may be used by blending two or more kinds as necessary.

As the polymer latex used in the present invention, a latex of styrene-butadiene copolymer is particularly preferable. The mass ratio of the styrene monomer unit and 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 above. The styrene-butadiene copolymer latex preferably used in the present invention is commercially available LA
CSTAR 3307B, 7132C, DS206, Nipol Lx416, Lx433 etc. are mentioned. In the present invention, the coating amount of the binder is 1
To 20 g / m ^2, preferably from 2 to 15 g / m ^2, more preferably suitably 3~12g / m ^2. Among them, gelatin can be used in a proportion of 50 to 100%, preferably 70 to 100%.

The light-sensitive material of the present invention contains a dye-forming coupler. The couplers preferably used in the present invention are compounds collectively called active methylene, 5-pyrazolone, pyrazoloazole, phenol, naphthol and pyrrolotriazole. These couplers are RD No.3
8957 (September 1996), pp. 616-624,
The compounds cited in "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.

The group acting as the anionic leaving group of the 2-equivalent coupler includes a halogen atom (eg, chlorine atom, bromine atom), an alkoxy group (eg, methoxy, ethoxy), an aryloxy group (eg, phenoxy, 4-
Cyanophenoxy, 4-alkoxycarbonylphenyl), alkylthio group (eg methylthio, ethylthio, butylthio), arylthio group (eg phenylthio, tolylthio), alkylcarbamoyl group (eg methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl). , Heterocyclic carbamoyl groups (eg piperidylcarbamoyl, morpholylcarbamoyl), arylcarbamoyl groups (eg phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), carbamoyl groups, alkylsulfamoyl groups (eg methylsulfamoyl) , Dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dib Rusurufamoiru), heterocyclic sulfamoyl group (e.g., piperidyl sulfamoyl,
Morphorylsulfamoyl), arylsulfamoyl group (eg phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), sulfamoyl group, cyano group, alkylsulfonyl group (eg methane) Sulfonyl, ethanesulfonyl), arylsulfonyl groups (eg phenylsulfonyl, 4-chlorophenylsulfonyl, p-toluenesulfonyl), alkylcarbonyloxy groups (eg acetyloxy, propionyloxy,
Butyroyloxy), an arylcarbonyloxy group (for example, benzoyloxy, toluyloxy, anisyloxy), a nitrogen-containing heterocyclic group (for example, imidazolyl, benzotriazolyl) and the like.

The group acting as the cationic leaving group of the 4-equivalent coupler includes a hydrogen atom, a formyl group, a carbamoyl group, and a methylene group having a substituent (the substituent includes an aryl group, a sulfamoyl group, a carbamoyl group, and Alkoxy group, amino group, hydroxyl group, etc., acyl group,
Examples thereof include a sulfonyl group. RD No. 38957 above
In addition to the compounds described in (1), the couplers described below can be preferably used.

EP5 is used as the active methylene coupler.
Couplers represented by formulas (I) and (II) of 02,424A; couplers represented by formulas (1) and (2) of EP 513,496A; and formula (I) of claim 1 of EP 568,037A. Couplers represented; US Pat. No. 5,
No. 066,576, column 1, lines 45 to 55, a coupler represented by formula (I); JP-A-4-274425;
No. 0008, paragraph 0008, a coupler of the general formula (I); coupler described in claim 1 on page 40 of EP 498,381A1; EP 447,969A.
A coupler represented by formula (Y) on page 4 of U.S. Pat. No. 1, U.S. Pat. No. 4,476,219, column 7, lines 36-58.
The couplers represented by I) to (IV) can be used. As a 5-pyrazolone type coupler, JP-A-57-
The compounds described in 35858 and JP-A-51-20826 are preferred.

As the pyrazoloazole-based coupler, the imidazo [1,2] described in US Pat. No. 4,500,630 can be used.
-B] pyrazoles, pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,654, and pyrazolo [[3,5,067] described in U.S. Pat. No. 3,725,067. 5,1-c] [1,2,4] triazoles are preferable, and in view of light fastness, pyrazolo [1,5]
-B] [1,2,4] triazoles are preferred. Further, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of a pyrazolotriazole group as described in JP-A-61-265245, JP-A-6-62.
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in 1-65245, JP-A-61-61
No. 147254, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group, JP-A-62-209457 or 63-30.
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in 7453 and pyrazolotriazole couplers having a carbonamide group in the molecule described in JP-A-2-201443 are also preferably used. You can

Preferable examples of the phenol-based coupler include US Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,82
No. 6,2,772,002, and the like, 2-alkylamino-5-alkylphenol-based compounds, US Pat.
No. 72,162, No. 3,758,308, No. 4,12
No. 6,396, No. 4,334,011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729, 2,5-diacylaminophenol system described in JP-A-59-166956, US Pat. No. 3,446,622,
Examples thereof include 2-phenylureido-5-acylaminophenol compounds described in No. 4,333,999, No. 4,451,559, No. 4,427,767 and the like. Preferred examples of naphthol couplers include U.S. Pat. Nos. 2,474,293, 4,052,212, 4,146,396, 4,228,233, and 4,296. 2-carbamoyl-1- as described in No. 200, etc.
Examples thereof include naphthol type and 2-carbamoyl-5-amido-1-naphthol type described in US Pat. No. 4,690,889 and the like.

Preferable examples of the pyrrolotriazole type couplers include European Patent Nos. 488,248A1 and 4
91,197A1 and 545,300. In addition, couplers having a structure such as condensed phenol, imidazole, pyrrole, 3-hydroxypyridine, active methine, 5,5-condensed heterocycle, and 5,6-condensed heterocycle can be used. As the condensed ring phenol-based coupler, there are U.S. Pat. No. 4,327,173.
No. 4,564,586, No. 4,904,575 and the like can be used.

As the imidazole couplers, the couplers described in US Pat. Nos. 4,818,672 and 5,051,347 can be used. Pyrrole couplers are disclosed in JP-A-4-188137 and JP-A-4-190347.
The couplers described in No. etc. can be used. As the 3-hydroxypyridine type coupler, couplers described in JP-A-1-315736 can be used. As the active methine couplers, US Pat. Nos. 5,104,783 and 5;
The couplers described in 162,196 and the like can be used.

As the 5,5-condensed heterocyclic type couplers, the pyrrolopyrazole type couplers described in US Pat. No. 5,164,289 and the pyrroloimidazole type couplers described in JP-A No. 4-174449 can be used. .. 5,6
-Fused-ring heterocyclic couplers include US Pat.
The pyrazolopyrimidine couplers described in JP-A No. 50,585, the pyrrolotriazine couplers described in JP-A-4-204730, and the couplers described in EP 556,700 can be used.

In the present invention, in addition to the above-mentioned coupler, West German Patent Nos. 3,819,051A and 3,823,049,
U.S. Pat. Nos. 4,840,883 and 5,024,93
No. 0, No. 5,051,347, No. 4,481,268
No., European Patent Nos. 304,856A2 and 329,03
No. 6, No. 354,549A2, No. 374,781A
No. 2, No. 379, 110A No. 2, No. 386, 930A
No. 1, JP-A-63-141055, and JP-A-64-3226.
0, 64-32261, JP-A-2-297547.
No. 2-44340, 2-110555, 3
-7938, 3-160440, 3-1728
No. 39, No. 4-172447, No. 4-179949
Nos. 4-182645, 4-184437, 4-188138, 4-188139, 4-1.
No. 94847, No. 4-204532, No. 4-2047
The couplers described in No. 31, No. 4-204732, etc. can also be used. These couplers are from 0.05
10 mmol / m ² , preferably 0.1-5 mmol /
m ² can be used.

Further, the following functional couplers may be contained. Examples of couplers in which the coloring dye has an appropriate diffusibility include U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,873B, and German Patent 3,234,533. Those described in No. 10 are preferable.
As a coupler for correcting unnecessary absorption of a color forming dye, a yellow colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 ( Especially YC on page 84
-86), the yellow colored magenta couplers ExM-7 (page 202) and EX-1 (249) described in the European patent.
Page), EX-7 (page 251), U.S. Pat. No. 4,833,0.
No. 69 magenta color cyan coupler CC-
9 (column 8), CC-13 (column 10), (2) of U.S. Pat. No. 4,837,136 (column 8), and formula (A) of claim 1 of WO 92/11575. Colorless masking couplers (especially the exemplified compounds on pages 36 to 45) are preferred.

Examples of compounds (including couplers) which release a photographically useful compound residue by reacting with an oxidized product of a developing agent include the following. Development inhibitor releasing compound: EP 378,236A1
Compounds represented by formulas (I) to (IV) described in No. 11 (preferably T-101 (page 30), T-104 (page 31),
T-113 (page 36), T-131 (page 45), T-1
44 (page 51), T-158 (page 58)), European Patent 436,938A2, page 7 (compounds of formula (I) (particularly D-49 (page 51)), European Patent 56).
Compounds represented by formula (I) of No. 8,037A (particularly (23) (page 11)), European Patent 440,195A2
Compounds represented by formulas (I), (II) and (III) described in Nos. 5-6 (in particular, I- (1) on page 29).

Bleach accelerator releasing compound: European Patent No. 31
No. 0,125A2, compounds represented by formulas (I) and (I ') on page 5 (particularly (60) and (61) on page 61) and formula (I) in claim 1 of JP-A-6-59411. Compounds (especially (7) (page 7)).

Ligand-releasing compounds: US Pat. No. 4,55
A compound represented by LIG-X according to claim 1 of 5,478 (particularly, compounds at lines 21 to 41 of column 12).

Leuco dye releasing compounds: US Pat. No. 4,7.
49, 641 columns 3-8 compounds 1-6. Fluorescent dye-releasing compounds: compounds represented by COUP-DYE in claim 1 of U.S. Pat. No. 4,774,181 (especially compounds 1-11 in columns 7-10).

Development accelerator or fogging agent releasing compound:
Formula (1) of column 3 of US Pat. No. 4,656,123,
Compounds represented by (2) and (3) (particularly (I-22) in column 25) and ExZK-2 on page 75, lines 36 to 38 of EP 450,637A2. Compounds which release a group which becomes a dye only upon leaving: Compounds represented by the formula (I) in claim 1 of U.S. Pat. No. 4,857,447 (especially Y-1 to Y-1 in columns 25 to 36)
9).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: JP-A-62-215272
No. P-3,5,16,19,25,30,42,4
9, 54, 55, 66, 81, 85, 86, 93 (14
0-144). Latex for impregnation of oil-soluble organic compounds: US Pat. No. 4,
Latex described in 199,363. Developer Oxidizer Scavenger: US Pat. No. 4,978,
No. 606 column 2, lines 54 to 62, compounds represented by formula (I) (especially I- (1), (2), (6), (12)
(Columns 4-5)), U.S. Pat. No. 4,923,787, column 2, lines 5-10 (especially compound 1 (column 3). Stain inhibitors: European Patent 298,321A, page 4, 3).
Formulas (I)-(III) on lines 0-33, especially I-47,7
2, III-1, 27 (pages 24-48). Anti-fading agent: A-6 of EP 298,321A
7, 20, 21, 23, 24, 25, 26, 30, 3
7, 40, 42, 48, 63, 90, 92, 94, 16
4 (pages 69 to 118), U.S. Pat. No. 5,122,444, columns 25 to 38, II-1 to III-23, especially III-1.
0, 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 through 48, especially A-39,42.

Materials that reduce the amount of color-enhancing agent or color-mixing inhibitor used: European Patent No. 41,132A, I-1 to II-15, especially I-46, pages 5 to 24. Formalin Scavenger: European Patent 477,932
No. A, pages 24 to 29, SCV-1 to 28, especially SCV-
8. Hardener: H-1 on page 17, JP-A-1-214845.
4,6,8,14, U.S. Pat. No. 4,618,573, compounds (H-1 to 54) represented by formulas (VII) to (XII) in columns 13 to 23, JP-A-2-214852, page 8 Compounds (H-1 to 76) represented by the formula (6) at the lower right, especially H-14, Claim 1 of US Pat. No. 3,325,287
The compound according to. Development inhibitor precursor; P-24, 37, 39 (pages 6 to 7) of JP-A-62-168139, US Pat.
019,492, claim 1, especially column 7, 28,29. Preservatives, antifungal agents: U.S. Pat. No. 4,923,790 columns 3-15, I-1 to III-43, especially II-1,9,1
0,18, III-25. Stabilizers, antifoggants: U.S. Pat. No. 4,923,793, columns 6-16, I-1 to (14), especially I-1,6.
0, (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, 15-1
A-1 to b-20 on page 8, especially a-1, 12, 18, 2
7, 35, 36, b-5, V-1 and 2 on pages 27-29
3, especially V-1, European Patent No. 445,627A 33-
F-I-1 to F-II-43 on page 55, especially F-I-1
1, F-II-8, EP457, 153A, pages 17-28, I
II-1 to 36, especially III-1,3, International Patent No. 88/0
No. 4794, pages 8 to 26, Dye-1 to 124 microcrystalline dispersion, EP 319,999A, pages 6 to 11, compounds 1 to 22, especially compound 1, EP 519,306.
Compounds D-1 to 8 represented by formulas (1) to (3) of No. A
7 (pages 3-28), compounds 1-22 of formula (I) in U.S. Pat. No. 4,268,622 (columns 3-1).
0), compounds (1) to (31) represented by formula (I) of US Pat. No. 4,923,788 (columns 2 to 9).

UV absorber: Compounds (18b) to (18r), 1 represented by the formula (1) of JP-A-46-3335.
01-427 (pages 6-9), European Patent 520,938.
Compounds (3) to (66) represented by formula (I) of No. A
(Pages 10 to 44) and the compound of formula (III) HBT-1 to 10 (page 14), European Patent No. 521,82.
Compounds (1) to (31) represented by Formula (I) of No. 3A
(Columns 2-9).

It is preferable to use such a functional coupler or additive in an amount of 0.05 to 10 times, preferably 0.1 to 5 times the molar amount of the above-mentioned coupler contributing to color development.

Hydrophobic additives such as couplers and color developing agents can be incorporated into the layer of the photographic material by known methods 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 and 4,5.
87,206, 4,555,476, 4,599,
No. 296, Japanese Patent Publication No. 3-62256, etc., a high boiling point organic solvent, if necessary, a boiling point of 50 ° C. to 160 ° C.
It can be used in combination with the low boiling point organic solvent. Two or more kinds of these dye donating couplers and high boiling point organic solvents can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, and more preferably 1 g to 0.1 g, relative to 1 g of the hydrophobic additive used. Also, 1 mL or less for 1 g of binder, further 0.5 mL
Below, 0.3 mL or less is particularly suitable.

JP-B-51-39853, JP-A-51-
The method of dispersing by a polymer described in JP-A-59943 and the method of adding it as a fine particle dispersion described in JP-A-62-30242 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-15763
No. 6, pages 37 to 38, those listed as the surfactant in RD above can be used. In addition, JP-A-7-5
The phosphate ester type surfactants described in Nos. 6267, 7-228589 and West German Laid-Open Patent No. 1,932,299A can also be used.

The light-sensitive material of the present invention can use various antifoggants or photographic stabilizers. Examples thereof include azoles and azaindenes described in RD No. 17643 (1978), pages 24 to 25, JP-A-59-16.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-8442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-87957.
The acetylene compounds and the like described in No. 1 are used. The light-sensitive material of the present invention, when a diffusion resistant reducing agent or color developing agent is used, promotes electron transfer between the diffusion resistant reducing agent or color developing agent and developable silver halide. 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 mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. 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 above-mentioned coupler, developing agent and DIR compound, color mixing inhibitor, dye and the like. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is disclosed in German Patent No. 1,121,47.
It is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in No. 0 or British Patent No. 923,045 so that the photosensitivity becomes lower toward the support. A non-photosensitive layer may be provided between the halogen emulsion layers. Also, JP-A-57-11275
No. 1, No. 62-200350, No. 62-206541.
No. 62-206543, a low-sensitivity emulsion layer can be provided on the side farther from the support and a high-sensitivity emulsion layer can be provided on the side closer to the support.

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 (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of. In addition, Japanese Examined Japanese Patent Publication Sho 55-34
As described in No. 932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, JP-A-56-25738,
No. 62-63936, from the side farthest from the support, the blue-sensitive layer / GL / RL / GH / R.
It is also possible to arrange them in the order of H.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, there may be mentioned an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same light-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. Other, high sensitivity emulsion layer / low sensitivity emulsion layer /
Medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer /
The high-sensitivity emulsion layers may be arranged in this order. Also,
Even in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproduction, US Pat. No. 4,663,271
No. 4,705,744, No. 4,707,436
JP-A-62-160448 and 63-89850.
Layer (CL) having a multilayer effect different in spectral sensitivity distribution from the main photosensitive layer such as BL, GL, RL, etc.
It is also preferred that the is disposed adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. The emulsion of the present invention can be used in any emulsion layer, but it is particularly preferably used in the high sensitivity emulsion layer.

In the present invention, the silver halide emulsion, the dye-forming coupler, the color developing agent and / or the precursor thereof may be contained in the same layer, but if they are in a reactive state, they are divided into different layers. Can also be added. For example, when the layer containing the color developing agent and the layer containing the silver halide emulsion are separated from each other, the raw storability of the light-sensitive material can be improved. The relationship between the spectral sensitivity of each layer and the hue of the coupler is arbitrary,
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, direct projection exposure can be performed on conventional color paper and the like. In the light-sensitive material, various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between the silver halide emulsion layers and in the uppermost layer and the lowermost layer. It is also possible to provide various auxiliary layers such as a back layer on the opposite side of the support.

Specifically, the layer structure as described in the above patent, the undercoat layer as described in US Pat. No. 5,051,335, JP-A-1-167838, and JP-A-61-29494.
An intermediate layer having a solid pigment as described in JP-A-3-
No. 120553, No. 5-34884, No. 2-6463
An intermediate layer having a reducing agent and a DIR compound as described in US Pat. Nos. 4,017,454 and 5,139,91.
9, an intermediate layer having an electron transfer agent as described in JP-A-2-235044, a protective layer having a reducing agent as described in JP-A-4-249245, or a layer in which these are combined can be provided. As the dye that can be used in the yellow filter layer and the antihalation layer, those that are decolorized or removed during development and do not contribute to the density after processing are preferable. When the dye in the yellow filter layer and antihalation layer is decolored or removed during development,
The amount of dye remaining after processing is 1/3 or less, preferably 1/10 or less of that at the time of application, and the dye component may be transferred from the light-sensitive material to the processing material at the time of development or may be reacted at the time of development. May be changed to a colorless compound. Specific examples thereof include dyes described in European Patent No. 549,489A and dyes ExF2 to 6 of JP-A-7-152129. It is also possible to use a solid-dispersed dye as described in JP-A-8-101487. Further, a mordant and a binder may be mordanted with a dye. In this case, as the mordant and dye, those known in the photographic field can be used, and US Pat. No. 4,500,626, Nos. 58 to 59 can be used.
Examples thereof include mordants described in the columns, JP-A-61-88256, pages 32 to 41, JP-A-62-244043 and JP-A-64-244036.

It is also possible to use a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, to release the active dye with an alkali during development, and transfer and remove it to the processing material. Specifically, U.S. Pat. Nos. 4,559,290 and 4,783,396, European Patent 220,746A2.
No. 87-6119, published technical report No. 87-6119. A decolorizing leuco dye or the like can also be used. Specifically, JP-A-1-150132 discloses a silver halide light-sensitive material containing a leuco dye which has been previously developed with a developer of an organic acid metal salt. ing. The leuco dye and the color-developing agent complex react with heat or an alkaline agent to lose the color. Known leuco dyes can be used, and Moriga and Yoshida “Dyes and Chemicals”, page 9,84 (Chemical Industry Association), “New Edition Dye Handbook”
242 (Maruzen, 1970), R. Garner "Reports on
the Progress of Appl. Chem "56, 199 (19
71), "Dyes and Chemicals", p. 19,230 (Chemical Industry Association, 1974), "Coloring Materials," p. 62,288 (198).
9), "Dyeing Industry" 32, 208, etc. As the developer, an acidic clay-based developer, a phenol formaldehyde resin, and a metal salt of an organic acid are preferably used. As the metal salt of an 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. Of the above-mentioned color developers, oil-soluble zinc salicylate salts are described in U.S. Pat. Any thing 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 and JP-A-62-24526.
1, No. 61-18942, JP-A-4-218044.
The hardeners described in JP-A-No. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type 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 to 1 g, preferably 0.001 g per 1 g of the hydrophilic binder.
5 to 0.5 g is used.

Various antifoggants or photographic stabilizers and their precursors can be used in the light-sensitive material. Specific examples thereof include RD, US Pat. Nos. 5,089,378, 4,500,627, and 4,6.
14,702, JP-A-64-13564 (7)-
Pages (9), (57) to (71) and (81) to (9
7), U.S. Pat. Nos. 4,775,610 and 4,626,
No. 500, No. 4,983,494, JP-A-62-174.
No. 747, No. 62-239148, JP-A-1-150.
No. 135, No. 2-110557, No. 2-178650
No. 17643 (1978), pages 24 to 25, and the like. The amount of these compounds is preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver,
Further, 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol is preferably used.

Various surfactants can be used in the light-sensitive material for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are known technology No. 5 (March 22, 1991, issued by Aztec Co., Ltd.), pages 136 to 138, JP-A-62-1734.
63, 62-183457 and the like.
The photosensitive material may contain an organic fluoro compound for the purpose of preventing slipperiness, preventing electrification, improving peelability and the like. As a typical example of the organic fluoro compound, Japanese Patent Publication No. 57-9053
No. 8 to 17 columns, JP-A Nos. 61-20944 and 62-62.
Examples thereof include a fluorine-based surfactant described in No. 135826 and the like, or an oily fluorine-based compound such as fluorine oil or a hydrophobic fluorine compound such as a solid fluorine compound resin such as tetrafluoroethylene resin. A fluorine-based surfactant having a hydrophilic group is also preferably used for the purpose of achieving both wettability of the light-sensitive material and antistatic property.

The light-sensitive material preferably has a slip property.
The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. The preferred sliding property is a dynamic friction coefficient of 0.
25 or less and 0.01 or more. The measurement at this time is 5 m in diameter
The value when conveyed at a rate of 60 cm / min for a stainless steel ball of m (25 ° C. 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the mating material, the values are almost the same. Usable lubricants are polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and the like, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane. ,
Polymethylphenyl siloxane or the like can be used. The addition layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and ester having a long chain alkyl group are preferable. Silicon oil and chlorinated paraffin are preferably used in order to prevent pressure fog and desensitization of silver halide.

In the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acids and carboxylates, polymers containing sulfonates,
Examples thereof include cationic polymers and ionic surfactant compounds. The most preferable antistatic agent is
_{ZnO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, Si
Particle size 0 in which at least one selected from O ₂ , MgO, BaO, MoO ₃ and V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. ．
001 to 1.0 μm crystalline metal oxide or fine particles of their composite oxide (Sb, P, B, In, S, Si, C, etc.), and further sol-like metal oxide or their composite oxide It is a fine particle. The content in the light-sensitive material is preferably 5 to 500 mg / m ² , and particularly preferably 1
It is 0 to 350 mg / m ² . The ratio of the conductive crystalline oxide or its composite oxide to the binder is 1: 300.
~ 100: 1 is preferable, and more preferably 1: 100 ~.
It is 100: 5. It is also preferable to coat the water-resistant polymer described in JP-A-8-292514 on the back surface of the support of the light-sensitive material. The composition of the light-sensitive material or the processing material described below (including the back layer) includes various polymers for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. A latex can be included. Specifically, JP-A-62-24
No. 5258, No. 62-136648, No. 62-110.
Any of the polymer latexes described in No. 066, etc. can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect is obtained. can get.

A matting agent may be used in the light-sensitive material of the present invention. The matting agent may be added either on the emulsion side or the back side, but it is preferably added to the outermost layer on the support on the emulsion side or the outermost layer on the back side. The matting agent may be soluble or insoluble in the treatment liquid, and both may be used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / 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, the particle size distribution is preferably narrow, and 90% or more of the total number of particles may be contained within 0.9 to 1.1 times the average particle size. preferable.
Further, it is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property, for example, polymethylmethacrylate (0.2 μm), poly (methylmethacrylate / methacrylic acid = 9/1 (molar ratio), 0. 3μ
m)), polystyrene particles (0.25 μm), and colloidal silica (0.03 μm). In particular,
JP-A No. 61-88256, page 29. In addition, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274.
There are compounds described in No. 944 and No. 63-274952. In addition, the compounds described in the above RD can be used. These matting agents can be used as a dispersion by dispersing them with the various binders described in the section of the binder as needed. In particular, various types of gelatin, for example, acid-treated gelatin dispersion, are easy to prepare a stable coating solution, and at this time, it is preferable to optimize pH, ionic strength, and binder concentration as necessary.

In the present invention, the support for the light-sensitive material is transparent and can withstand the processing temperature. Generally, "Basics of Photographic Engineering-Silver Salt Photo-" edited by the Photographic Society of Japan, published by Corona Publishing Co., Ltd. (1979) 2
Examples include papers described on pages 23 to 240, photographic supports such as synthetic polymers (films), and the like. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) and the like. In addition to this, JP-A-62-1
No. 253159, pages 29 to 31, JP-A-1-161236.
Nos. 14-17, JP-A-63-16848, JP-A-2-22651, JP-A-3-56955, US Pat. No. 5,001,033 and the like can be used. These supports are heat-treated (crystallinity and orientation control), uniaxially and biaxially stretched (orientation control), blends of various polymers, in order to improve optical properties and physical properties.
Surface treatment or the like can be performed. In particular, when the heat resistance and the curl characteristics are severely demanded, they are used as a support for a photosensitive material in JP-A-6-41281, JP-A-6-43581, and JP-A-6-514.
The supports described in Nos. 26, 6-51437 and 6-51442 can be preferably used.

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 the light-sensitive material other than the above, processing, cartridges and examples, refer to Kokai Giho, Jpn. 199
4.3.15. )It is described in. The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components.
Examples include-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and diols such as diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is 50 to 100 of 2,6-naphthalenedicarboxylic acid.
It is a polyester containing mol%. Among them, polyethylene-2,6-naphthalate is particularly preferable. The range of average molecular weight is about 0.5 to 200,000. The Tg of the polyester usable in the present invention is 50 ° C. or higher,
C. or higher is preferable.

Next, the polyester support has a winding tendency.
In order to make it difficult, the heat treatment temperature is 40 ° C or higher and lower than Tg,
More preferably, the heat treatment is performed at Tg of -20 ° C or higher and lower than Tg.
U The heat treatment may be performed at a constant temperature within this temperature range.
Alternatively, the heat treatment may be performed while cooling. This heat treatment time
Is 0.1 to 1500 hours, more preferably 0.5 to
200 hours. Heat treatment of the support is performed in roll form
Alternatively, it may be carried out in web form.
Yes. Giving unevenness to the surface (eg SnO₂And Sb₂O _Fiveetc
Of conductive inorganic fine particles), even if the surface condition is improved
Good. In addition, knurling is added to the end so that only the end is slightly higher.
To prevent the cut end of the winding core from appearing
It is desirable to do. These heat treatments are performed after forming the support film.
After surface treatment and back layer application (antistatic agent, slip agent
Etc.), at any stage after applying the undercoat. Good
It is preferable to apply the antistatic agent. This polyester
An ultraviolet absorber may be kneaded in. Also light pie
To prevent ping, Diaresin made by Mitsubishi Kasei and Nippon Kayaku
Dyes commercially available for polyester such as Kayaset
Alternatively, the objective can be achieved by kneading the pigment.
It is possible. To bond the support and the photosensitive material layer
It is preferable to surface-treat the support. Chemical treatment,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment,
High frequency treatment, glow discharge treatment, active plasma treatment, laser
Surface treatment such as heat treatment, mixed acid treatment, ozone oxidation treatment, etc.
There is a chemical treatment. Among the surface treatments, the preferred one is
UV irradiation treatment, flame treatment, corona treatment, glow treatment
is there.

Next, the undercoat layer will be described. The undercoat layer may be a single layer or two or more layers. Examples of the binder for the undercoat layer include vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, and a copolymer having a monomer selected from among maleic anhydride as a starting material. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, gelatin, polyvinyl alcohol and modified polymers thereof. Compounds that swell the support include resorcin and p-chlorophenol. For the undercoat layer, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4) are used as gelatin hardening agents.
-Dichloro-6-hydroxy-s-triazine etc.),
Examples thereof include epichlorohydrin resin and active vinyl sulfone compound. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent. Further, as the support, for example, JP-A-4-1246
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in Nos. 45, 5-40321, 6-35092, and 6-317875.

The magnetic recording layer is formed by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder. Magnetic particles, GanmaFe ferromagnetic iron oxide such as ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide,
Ferromagnetic metals, ferromagnetic alloys, hexagonal Ba ferrite,
Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co-deposited ferromagnetic iron oxide such as Co-deposited γFe ₂ O ₃ is preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. S in specific surface area
_{The BET} is preferably 20 m ² / g or more, particularly preferably 30 m ² / g or more. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. m. The ferromagnetic particles may be surface-treated with silica and / or alumina or an organic material. Further, the magnetic particles may be surface-treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. In addition, JP-A-4-259911
No. 5,815,652, magnetic particles having a surface coated with an inorganic or organic substance 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 described in JP-A-4-219569, a natural product polymer ( Cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin
Is -40 to 300 ° C, and the mass average molecular weight is 0.2 to 100
In many cases. Specific examples include vinyl-based copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose derivatives such as cellulose tripropionate, acrylic resins, polyvinyl acetal resins, and gelatin. Is also preferable. Cellulose di (tri) acetate is particularly preferable.

The binder may be hardened by adding an epoxy, aziridine or isocyanate crosslinking agent. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, reaction products of these isocyanates with polyalcohols (for example, reaction products of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and condensation products of these isocyanates. Examples of the polyisocyanate include those described in JP-A-6-5935.
No. 7. As the method of dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. Japanese Patent Laid-Open No. 5-
The dispersant described in No. 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 to 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 0.01.
˜2 g / m ² , more preferably 0.02 to 0.5 g /
m ² . The transmission yellow density of the magnetic recording layer is 0.0
1 to 0.50 is preferable, 0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.

The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in the form of a stripe. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss,
Cast, spray, dip, bar, extrusion and the like can be used, and the coating liquids described in JP-A-5-341436 and the like are preferable.

In the magnetic recording layer, improvement of lubricity, curl adjustment,
It may have functions such as antistatic, adhesion prevention, and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are 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 preferably the same binder as that of the magnetic recording layer is used. For a photosensitive material having a magnetic recording layer, see US Pat. No. 5,336,589.
No. 5,250,404, No. 5,229,259, No. 5,215,874, and European Patent No. 466,130.

Next, a film cartridge which can be loaded with a light-sensitive 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, such as carbon black, metal oxide particles, nonion,
Anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A 1-312537,
No. 1-312538. Especially at 25 ℃ 2
The resistance at 5% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured by using a plastic in which carbon black, a pigment and the like are kneaded in order to impart a light shielding property. The size of the patrone may be the same as the current 135 size, or the size of the current 13
It is also effective to set the diameter of the 5 size 25 mm cartridge to 22 mm or less. The volume of the case of the cartridge is 30 cm ³ or less, preferably 25 cm ³ or less. The mass of the plastic used for the cartridge and cartridge case is preferably 5 to 15 g. Further, a patrone that rotates the spool to feed the film may be used. Further, the film tip may be housed in the cartridge body, and the film tip may be sent to the outside from the port section of the cartridge by rotating the spool shaft in the film feeding direction. These are US Pat. No. 4,8
34,306 and 5,226,613.

The light-sensitive material of the present invention described above is disclosed in Japanese Patent Publication No.
The film unit with a lens described in JP-A-32615 and Jpn. Pat. Appln. A film unit with a lens is a method unit in which an unexposed color photosensitive material is stored directly or in a container in a packaging unit body, which is equipped with a photographing lens and a shutter, directly or in a container, and light-tightly bonded. That is, the outer packaging is used. Further, the packaging case body is provided with a finder, a frame feeding mechanism for the photosensitive material, a mechanism for storing and taking out the photographed color photosensitive material, a parallax correcting support for the finder, and a photographing mechanism such as, for example, the actual flat plate 1 -93
No. 723, No. 1-57738, No. 1-57740,
The auxiliary illumination mechanism described in JP-A-1-93723 and JP-A-1-152437 can be provided.

Since the packaging unit main body of the present invention contains the photosensitive material, the humidity inside the packaging unit is 2%.
Relative humidity at 5 ° C 40-70%, preferably 50-
It is desirable to control the humidity to 65%. The exterior material may be a moisture impermeable material or, for example, ASTM test method D
It is preferable to use 0.1% or less of non-water-absorbent material at -570, and particularly aluminum foil laminated sheet or aluminum foil. The storage container for the photographed light-sensitive material provided in the main body of the packaging unit is a cartridge for exterior unit, a patrone commonly used, for example, JP-A-54-54.
111822, 63-194255, and U.S. Pat. Nos. 4,832,275 and 4,834,306 are used. Examples of the film of the photosensitive material used include 110 size, 135 size, half size and 126 size thereof. The plastic material used for the construction of the packaging unit in the present invention includes non-polymerizable olefins having a carbon-carbon double bond, ring-opening polymerization of small ring compounds, and polycondensation (condensation polymerization) of two or more polyfunctional compounds. ), Polyaddition and addition condensation of a phenol derivative, a urea derivative, a melamine derivative and a compound having an aldehyde.

The light-sensitive material of the present invention is RD No. 17 described above.
643, pages 28-29, No. 18716, 651 left column to right column, and No. 307105, page 880-881. 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, known technology No. 6 (April 1, 1991), page 1, lines 5 to 1 of Aztec Co., Ltd.
It is described in detail on page 0, line 5 and page 15, line 8 to page 24, line 2, and all the contents can be preferably applied. Preferable development processing including the above contents is 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 form an image by being subjected to activator processing and development with a processing solution containing a developing agent / base. The activator processing refers to a processing method in which a color developing agent is contained in a light-sensitive material and development processing is performed with a processing solution containing no color developing agent. The processing liquid in this case is characterized in that it does not contain the color developing agent contained in the usual developing processing liquid components, and may contain other components (for example, alkali, auxiliary developing agent, etc.). Regarding the activator process, European Patent No. 5
45,491A1 and 565,165A1.

The light-sensitive material of the present invention is also preferably image-formed by heat development after imagewise exposure. The heat treatment of a light-sensitive material is known in the art. For the heat-developable light-sensitive material and its process, see, for example, Fundamentals of Photographic Engineering (1970, published by Corona Co.), pages 553 to 555,
40-page video information published in April 1978, Nabletts Handboo
k of Photography and Reprography 7th Ed. (Vna Nostr
and and Reinhold Company) 32 to 33, U.S. Pat.Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075, and British Patent No. No. 1,131,108, No. 1,167,777 and RD No. 17029 (1978), pages 9 to 15. The heating temperature in the heat development step is about 50 to 250.
C., but 60 to 180.degree. C. is particularly useful. The heating method in the developing step may include contact with a heated block or plate, contact with a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared and far-infrared lamp heater or the like. There is a method of passing through the atmosphere. Any of various heat developing devices can be used for processing the light-sensitive material of the present invention. For example, JP-A-59-75247 and JP-A-59-17754.
No. 7, No. 59-181353, No. 60-18951.
The apparatus described in Japanese Utility Model Publication No. 62-25944 and the like are preferably used.

Next, the processing materials and processing methods used in the case of the heat development processing in the present invention 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 dye forming reaction. Examples of the base precursor include salts of an organic acid and a base that are decarboxylated by heat, a compound that releases amines by intramolecular nucleophilic substitution reaction, Rossen transfer or Beckmann transfer. A specific example is U.S. Pat. No. 4,
No. 514,493, No. 4,657,848 and Known Technology No. 5 (March 22, 1991, issued by Aztec Co., Ltd.), pp. 55-86. Also, European Patent No. 210,660 and US Patent No. 4,740,445.
As described in No. 1, a combination of a poorly water-soluble basic metal compound and a compound capable of complex-forming reaction with a metal ion constituting the basic metal compound and water as a medium (referred to as complex-forming compound). May be generated. The amount of base or base precursor used is 0.1 to 20 g /
m ² , preferably 1 to 10 g / m ² . A treatment member having a treatment layer containing a base or a base precursor can be used to supply the base. In addition to this, the processing member blocks air during heat development, prevents the evaporation of materials from the photosensitive material, supplies processing materials other than bases to the photosensitive material, and eliminates the need for photosensitive materials after development. The material (YF dye, AH dye, etc.) inside or a function of removing unnecessary components generated during development may be provided. As the support and binder of the processing member, the same material as the light-sensitive material can be used. A mordant may be added to the processing 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, and US Pat. No. 4,50,626, columns 58 to 59 and JP-A-61-8 can be used.
8256, pages 32 to 41, JP-A-62-244043.
And mordants described in JP-A Nos. 62-244036 and the like. Further, a dye-receptive polymer compound described in US Pat. No. 4,463,079 may be used. Moreover, you may contain the below-mentioned thermal solvent.

It is also preferable to use a small amount of water for the purpose of accelerating the development, accelerating the transfer of the processing material and accelerating the diffusion of the unwanted substances in the heat development using the processing member. Specifically, US Pat. Nos. 4,704,245 and 4,470,4
45, JP-A-61-238056 and the like. The water may contain an inorganic alkali metal salt, an organic base, a low boiling point solvent, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, a fungicide, and a fungicide. Any commonly used water may be used as the water. Specifically, distilled water, tap water, well water, mineral water or the like can be used. Further, in the heat developing apparatus using the light-sensitive material and the processing member of the present invention, water may be used up, or may be circulated for repeated use. In the latter case, water containing the components eluted from the material will be used. Further, JP-A-63-144354 and JP-A-63-1434
144355, 62-38460, JP-A-3-2.
You may use the apparatus and water described in No. 10555 etc. Water may be applied to the light-sensitive material, the processing member, or both. The amount used is preferably 1/10 to 1 times the amount required for maximum swelling of the entire coating film (excluding the back layer) of the light-sensitive material and the processing member. As a method of applying this water, for example, Japanese Patent Laid-Open No.
The method described in JP-A No. 2-253159, page 5, JP-A-63-85544, etc. is preferably used. It is also possible to enclose the solvent in microcapsules or to preliminarily incorporate the solvent in the form of a hydrate into the light-sensitive material or the processing member or both. The temperature of the water to be applied is as described in JP-A-63-8.
As described in No. 5544, etc., about 30 to 60 ° C. is preferable.

When thermal development is carried out in the presence of a small amount of water, EP 210660 and US Pat. No. 4,740,445 are used.
As described in No. 3, a basic metal compound that is poorly soluble in water and a combination of a metal ion that composes the basic metal compound and a compound that can undergo a complex formation reaction in water as a medium (referred to as complex forming compound) are used. It is effective to adopt the method of generating. In this case, it is desirable from the viewpoint of storage stability of the light-sensitive material to add a basic metal compound that is poorly soluble in water to the light-sensitive material and a complex-forming compound to the processing member.

A method of superposing a light-sensitive material and a processing member so that the light-sensitive layer and the processing layer face each other is disclosed in JP-A-62-2531.
The methods described in No. 59, No. 61-147244, page 27 can be applied. The heating temperature is preferably 70 to 100 ° C., and the heating time is preferably 5 to 60 seconds. The light-sensitive material and / or the processing sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development. The heat generating element for this heat generation is disclosed in JP-A-61-145.
No. 544 and the like can be used.

A heat solvent may be added to the light-sensitive material of the present invention for the purpose of promoting heat development. Here, the thermal solvent is a solid at ambient temperature, but it shows a mixed melting point together with other components at the heat treatment temperature used or at a temperature lower than that, and it liquefies during thermal development and thermal transfer of thermal development or dye transfer. It is an organic material that has the action of promoting The thermal solvent includes a compound that can be a solvent for a developing agent, a compound that is known to accelerate physical development of a silver salt with a substance having a high dielectric constant, and a compound that is compatible with the binder and has a function of swelling the binder. It is useful.

The hot solvent which can be used in the present invention includes, for example, US Pat. Nos. 3,347,675 and 3,667,
959, 3,438,776, 3,666,4
77, RD No. 17,643, JP-A-51-195.
No. 25, No. 53-24829, No. 53-60223.
No. 58, No. 58-118640, No. 58-198038.
No. 59-229556, 59-68730,
59-84236, 60-191251, 6
0-232547, 60-60241, 61-
No. 52643, No. 62-78554, No. 62-421.
No. 53, No. 62-44737, No. 63-53548.
No. 63-161446, JP-A No. 1-224751.
No. 2, No. 2-863, No. 2-120739, No. 2-1
The compounds described in each publication such as No. 23354 may be mentioned. Specifically, urea derivatives (phenylmethylurea etc.), amide derivatives (eg acetamide, stearylamide, p-toluamide, p-propanoyloxyethoxybenzamide etc.), sulfonamide derivatives (eg p-toluenesulfonamide etc.) From the polyhydric alcohols (for example, high molecular weight polyethylene glycol, etc.), it is possible to select and use a material having low water solubility which is preferable for fine crystal dispersion. The water solubility of the hot solvent used in the present invention is 1 g / m in order to improve the dispersion stability of the fine crystal dispersion.
It is preferably cubic meters or less, more preferably 10 ⁻³ g / cubic meter or less. The amount of the thermal solvent used in the present invention is appropriately 1 to 200% by mass, preferably 5 to 50% by mass based on the coating amount of the binder. The layer to be added may be either a photosensitive layer or a non-photosensitive layer depending on the purpose. Specific examples of the thermal solvent that can be used in the present invention will be shown, but the present invention is not limited to these specific examples.

[0168]

[Chemical 12]

[0169]

[Chemical 13]

In the present invention, the image information can be taken in without removing the developed silver and the undeveloped silver halide produced by the development, but the image can also be taken in after the removal. In the latter case, a means for removing these at the same time as or after the development can be applied.
To remove developed silver in the light-sensitive member at the same time as development, or to complex or solubilize silver halide, act as a oxidant or rehalogenating agent or a fixing agent for silver that acts as a bleaching agent on the processing member. If a silver halide solvent is added, these reactions can occur during thermal development. Further, after the development of the image formation is completed, a second member containing a silver oxidizing agent, a rehalogenating agent or a silver halide solvent is attached to the light-sensitive material to remove the developed silver or complex the silver halide. Solution can also occur. In the present invention, it is preferable to perform these processes to the extent that they do not hinder the reading of image information after photographing and subsequent image formation and development. In particular, undeveloped silver halide causes high haze in the gelatin film and increases the background density of the image. Therefore, the haze can be reduced or solubilized in the film by using a complexing agent as described above. It is preferable to remove the whole amount or a part thereof.
Further, it is also preferable to use tabular grains having a high aspect ratio or tabular grains having a high silver chloride content for the purpose of reducing the haze of silver halide itself.

As the bleaching agent which can be used in the processing member of the present invention, any commonly used silver bleaching agent can be used. Such bleaching agents are described in U.S. Pat. Nos. 1,315,464 and 1,946,640 and Photographic Chemi.
stry, vol.2, chapter30, Foundation Press, London,
It is described in England. These bleaches effectively oxidize and solubilize photographic silver images. Examples of useful silver bleaches are alkali metal dichromates, alkali metal ferricyanides. Preferred bleaches are water-soluble and include ninhydrin, indandione, hexaketocyclohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid, 2,5-dinitrobenzoic acid. There are also metal-organic complexes such as ferric salts of cyclohexyldialkylaminotetraacetic acid, ferric salts of ethylenediaminetetraacetic acid and ferric salts of citric acid. As the fixing agent, a silver halide solvent that can be contained in the processing member (first processing member) for developing the photosensitive member can be used. Regarding the binder, support and other additives that can be used in the second processing member, the same materials as in the first processing member can be used. 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 is 0.01 to 10 mol / mol of the coating amount of the photosensitive silver halide per unit area of the photosensitive member.
Used in a range of photosensitive members. The amount is preferably 0.1 to 3 mol / silver coated on the photosensitive member, and more preferably 0.1 to 2 mol / silver coated on the photosensitive member.

In the present invention, it is also preferable that the image formed on the photosensitive material by thermal development is photoelectrically read and converted into a digital signal. As the image reading device, a generally known image input device can be used. The details of the image input device are described in "Basics of Digital Image Input" by Takao Ando et al., Corona Publishing Co., Ltd. (1998), pp. 58-98.
It is described on the page. The image input device needs to take in a huge amount of image information efficiently, and it is roughly classified 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 it is necessary to scan either the sensitive material side or the sensor side in order to capture a planar image. Therefore, it takes a little time to read, but there is an advantage that the sensor can be manufactured at low cost. In the case of an area sensor, it is basically possible to read without scanning the sensitive material or sensor, so reading is fast, but a large sensor must be used, so the cost is high. These sensors can be used properly according to the purpose, and both can be used preferably.

The types of sensors include an electron tube type such as an image pickup tube and an image tube, and a solid-state image pickup system such as a CCD type and a MOS type. preferable. As a device 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 the Nikon film scanner LS-1000 that uses a linear CCD, the Agfa Duoscan HiD, and the Imacon FlexTight Photo, and the Kodak RFS that uses an area CCD.
3570 and the like can be preferably used. Further, an image input device using an area CCD mounted on the frontier of the digital printing system 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, pp. 35-41 realizes high-speed and high-quality reading while using a linear CCD sensor. It is particularly suitable for reading the sensitive material of the invention.

The following image processing methods can be preferably used in the image forming method of the present invention. In Japanese Patent Laid-Open No. 6-139323, a subject image is formed on a color negative, the image is converted into corresponding image data by a scanner or the like, and then the same color as the subject is output from demodulated color information. An image processing system and an image processing method capable of faithfully reproducing are described, and this may be used. Further, as an image processing method for suppressing graininess or noise of a digitized image and enhancing sharpness, Japanese Patent Application Laid-Open No. 10-
No. 243238, a method of performing weighting and subdivision processing on edges and noises based on sharpness-emphasized image data, smoothed image data, and edge detection data,
Alternatively, an image processing method described in Japanese Patent Laid-Open No. 10-243239 may be used in which edge components are obtained based on sharpness-emphasized image data and smoothed image data, and weighting and subdivision processing is performed. Further, in order to correct a variation in color reproducibility in the final print due to a difference in storage condition, development condition, etc. of the photographic material in the digital color printing system, unexposed material of the photographic material described in JP-A-10-255037. 4 steps or 4 or more color patches are exposed on the area, the patch density is measured after development, the look-up table and color conversion matrix required for correction are obtained, and the look-up table conversion and matrix operation are used to obtain the photographic image. A method of performing color correction can be used.

As a method of converting the color gamut of image data, for example, a color described in JP-A-10-229502, which becomes a color visually recognized as a neutral color when the numerical values of respective components are aligned For the image data represented by the signal,
It is possible to use a method in which a color signal is separated into a chromatic color component and an achromatic color component, and each of them is individually processed. Further, as an image processing method for removing image quality deterioration such as an aberration and a decrease in peripheral light amount due to a camera lens in an image captured by a camera, a method described in JP-A No. 11-69277 is disclosed.
A grid-shaped correction pattern for creating correction data for image deterioration is recorded on the film in advance, and after shooting, the image and the correction pattern are read with a film scanner, etc.
An image processing method and apparatus may be used in which data for correcting a deterioration factor based on a lens of a camera is created, and the image deterioration correction data is used to correct digital image data.

If the sharpness of the skin color and the blue sky is emphasized too much, the graininess (noise) is emphasized to give an unpleasant impression. Therefore, it is desirable to suppress the degree of sharpness enhancement for the skin color and the blue sky. For example, in the sharpness enhancement processing using unsharp masking (USM) described in Japanese Patent Laid-Open No. 11-103393, a method of using a USM coefficient as a function of (BA) (RA) is used. May be. In addition, flesh color, grass green, and blue sky are called important colors for color reproduction, and selective color reproduction processing is required. Of these, it is said that it is visually preferable to reproduce the lightness so that the skin color is bright and the blue sky is dark. As a method of reproducing the important color to a visually preferable brightness, for example, in Japanese Patent Laid-Open No. 11-177835, a color signal for each pixel is represented by a corresponding hue such as (RG) or (RB). A method is described in which a coefficient that takes a small value when the color is yellow-red and a large value when the color is cyan blue is used for conversion, and this may be adopted. As a method of compressing a color signal, for example, Japanese Patent Laid-Open No. 11-113023.
The color signal for each pixel described in No. 1 is separated into a lightness component and a chromaticity component, and a template whose numerical value pattern is most suitable for the chromaticity component is prepared from among a plurality of prepared hue templates. A method of encoding the hue information by selecting may be used. In addition, when processing such as increasing the saturation or sharpness, it is possible to suppress the occurrence of defects such as color blindness, highlight jumps, and crushing of high-density areas, and the occurrence of data outside the defined range, and perform natural emphasis processing. Is
Image processing described in JP-A No. 11-177832, in which each color density data of color image data is used as exposure density data by using a characteristic curve, image processing including color enhancement is performed, and density data is obtained by the characteristic curve. Methods and devices can be used.

[0177]

EXAMPLES Examples of the present invention will be shown below. However, the present invention is not limited to this embodiment. (Example 1) A silver halide emulsion Em- was prepared by the following method.
A1 to A20 were prepared. (Em-A1) 31.7 g of phthalated low molecular weight gelatin having a molecular weight of 15,000 and phthalated with 97%, KBr3
42.2 L of an aqueous solution containing 1.7 g was kept at 35 ° C. and vigorously stirred. Aqueous solution containing AgNO ₃ , 316.7 g 15
83 mL, and 1583 mL of an aqueous solution containing 221.5 g of KBr and 52.7 g of low molecular weight gelatin having a molecular weight of 15,000 were added over 1 minute by the double jet method. After the addition is complete
Immediately after adding 52.8 g of KBr, AgNO ₃ , 39
2485 mL of an aqueous solution containing 8.2 g and KBr, 291.1
2581 mL of an aqueous solution containing g was added by the double jet method over 2 minutes. KBr, 47.8 immediately after addition
g was added. Then, the temperature was raised to 40 ° C., and aging was performed sufficiently. After completion of ripening, 923 g of phthalated gelatin having a phthalation ratio of 97% and a molecular weight of 100,000 and KBr, 79.2.
g, and an aqueous solution containing AgNO ₃ , 5103 g 15
947 mL and an aqueous KBr solution were added by a double jet method over 12 minutes while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate. At this time, the silver potential was kept at -60 mV against the saturated calomel electrode. After washing with water, gelatin was added to pH, 5.7, pAg, 8.8, mass of silver equivalent per emulsion of 1 kg 131.8 g, gelatin mass of 64.1 g
To prepare a seed emulsion.

Phthalated gelatin 46 having a phthalation ratio of 97%
g, and 1211 mL of an aqueous solution containing KBr 1.7 g were kept at 75 ° C. and vigorously stirred. After adding 9.9 g of the seed emulsion described above, modified silicone oil (product of Nippon Unicar Co., Ltd.,
L7602) 0.3g was added. After H ₂ SO ₄ was added to adjust the pH to 5.5, 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and the KBr aqueous solution were treated by the double jet method so that the final flow rate was 5.1 times the initial flow rate. Thus, the flow rate was accelerated and added over 6 minutes. At this time, the silver potential was kept at -20 mV against the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate, AgN
An aqueous solution containing 144.5 g of O ₃ , 410 mL and KI of 7
A mixed aqueous solution of KBr and KI containing mol% was added over a period of 56 minutes by accelerating the flow rate by the double jet method so that the final flow rate was 3.7 times the initial flow rate. At this time, the silver potential was kept at -30 mV against the saturated calomel electrode. AgNO
_3, were added over 22 minutes by the double jet method aqueous 121.3mL of KBr aqueous solution containing 45.6 g. At this time, the silver potential was kept at +20 mV against the saturated calomel electrode. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −8.
After adjusting to 0 mV, A with a particle size of 0.037 μm
6.33 g of gI fine grain emulsion was added in terms of KI mass.
Immediately after the addition was completed, 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 initial stage of the addition.

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

[0180]

[Chemical 14]

[0181]

[Chemical 15]

[0182]

[Chemical 16]

[0183]

[Chemical 17]

[0184]

[Chemical 18]

[0185]

[Chemical 19]

[0186]

[Chemical 20]

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 3 of Example 3).
It was shown to. )

(Em-A2 to A7) At the time of chemical sensitization, before adding the compounds 11 and 12 (addition pattern A)
Emulsions Em-A2 to A-A in the same manner as in (Em-A1) except that the compound of the present invention or the compound of Comparative Example was added so that the content was as shown in Table 1 with respect to the amount of silver in the emulsion.
Got 7.

(Em-A8 to A13) After the completion of chemical sensitization,
Except that the compound of the present invention or the compound of the comparative example was added before the addition of the compounds 13 and 14 (referred to as addition pattern B) so that the content was as shown in Table 1 with respect to the amount of silver in the emulsion. Emulsion Em-A in the same manner as (Em-A1)
8 to A13 were obtained.

(Em-A14 to A20) After the compounds 13 and 14 were added, the temperature of the chemically sensitized emulsion was lowered to 40 ° C. (the addition pattern C), and then the compound of the present invention or the comparative compound was added. For the amount of silver in the emulsion (Table 1)
(Em-A
Emulsions Em-A14 to A20 were obtained in the same manner as in 1).

[0191]

[Table 1-1]

Emulsions A1 to A20 were coated on a cellulose triacetate film support having an undercoat layer under the coating conditions shown in Table A below to prepare samples 101 to 120.

[0193]

[Table 1-2]

These samples were hardened for 14 hours under the conditions of 40 ° C. and 70% relative humidity. Then, the film was exposed for 1/100 seconds through a continuous wedge and a gelatin filter SC-39 (a long wavelength light transmission filter having a cutoff wavelength of 390 nm) manufactured by FUJIFILM Corporation, and the sample subjected to the developing treatment described below was subjected to a green filter. The photographic performance was evaluated by measuring the density with. In addition, each sample is 5
The same treatment was carried out for those aged for 3 days under the condition of 0 ° C. and 80% RH.

Using the negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., the treatment was carried out by the following method (until the cumulative replenishment amount of the liquid became 3 times the capacity of the mother liquor tank). (Processing method) Process Processing time Processing temperature Replenishment amount Color development 2 minutes 45 seconds 38 ° C. 45 mL Bleaching 1 minute 00 seconds 38 ° C. 20 mL Bleaching solution overflow flows into bleach-fixing tank 3 minutes 15 seconds 38 ° C. 30 mL Washing with water (1) 40 seconds 35 ° C (2) to (1) counter-current piping system Washing with water (2) 1 minute 00 seconds 35 ° C 30mL stability 40 seconds 38 ° C 20mL dry 1 minute 15 seconds 55 ° C * 35mm width 1.1m per length (24Ex. 1 piece equivalent)

Next, the composition of the processing liquid will be described.   (Color developer) Tank liquid (g) Replenisher (g)     Diethylenetriamine pentaacetic 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 1.5 mg-     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) Tank Solution and Replenishing Solution Common (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching added accelerator 0.005 mole _{(CH 3) 2 N-CH} 2 -CH 2 -S-S-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 mL water 1.0 L pH (adjusted with ammonia water and nitric acid) 6.3

[0198]   (Bleach-fixing solution) Tank solution (g) Replenishing solution (g)     Ethylenediaminetetraacetic acid ferric 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)                                             240.0 mL 400.0 mL     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 Solution) Tank water and replenisher common tap water are H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through a mixed bed column filled with to treat calcium and magnesium ions at a concentration of 3 mg / L or less, and subsequently, 20 mg / L of sodium diisocyanurate dichloride and 0.15 g / L of sodium sulfate were added. The pH of this solution is 6.5
It was in the range of 7.5.

[0200]   (Stabilizer) Common for tank liquid and replenisher (unit: g)     Sodium p-toluenesulfinate 0.03     Polyoxyethylene-p-monononylphenyl ether       (Average degree of polymerization 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     1.0L with water added     pH 8.5

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

[0202]

[Table 2]

It can be seen from Table 2 that the compound of the present invention has a large effect of increasing the sensitivity in any of the addition patterns of A, B and C, and the density (fog) of the unexposed portion, compared to the comparative compound. It turns out that is low. Also, 50 ℃
It can be seen that also in the sample that has been aged for 3 days under the condition of 80% RH, the compound of the present invention has a smaller decrease in sensitivity after raw storage and a lower fog than the comparative compound.

(Example 2) Silver halide emulsions Em-Q1 to Q15 were prepared by the following production method. (Em-Q1) Molecular weight 100,000 with phthalation rate of 97%
Phthalated gelatin, 0.38g, KBr, 0.99g
1,200 mL of an aqueous solution containing the above was maintained at 60 ° C., the pH was adjusted to 2, and the mixture was vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and an aqueous solution containing 1.97 g of KBr and 0.172 g of KI were added by the double jet method over 30 seconds.
After completion of the ripening, 12.8 g of trimellited gelatin in which an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per 1 g was chemically modified with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99
g, 6.2 g of NaCl were added. AgNO ₃ , 27.
60.7 mL of an aqueous solution containing 3 g and a KBr aqueous solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at -50 mV against the saturated calomel electrode. AgN
An aqueous solution containing 65.6 g of O ₃ and an aqueous KBr solution were added by the double jet method over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate. At this time, Em
The AgI fine grain emulsion used in the preparation of -A1 was simultaneously added while accelerating the flow rate so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV. AgN
132 mL of an aqueous solution containing 41.8 g of O ₃ and a KBr aqueous 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. Sodium benzenethiosulfonate,
After adding 2 mg, KBr was added to adjust the silver potential to -10.
It was adjusted to 0 mV. 6.2 g of the above AgI fine grain emulsion was added in terms of KI mass. AgNO immediately after addition
₃ were added over a solution 300mL containing 88.5g to 8 minutes. K so that the potential at the end of addition is +60 mV
It was adjusted by adding a Br aqueous solution. After washing with water, gelatin was added and the pH was adjusted to 6.5, pAg, and 8.2 at 40 ° C. After adding the compounds 11 and 12, the temperature was raised to 61 ° C. After adding the sensitizing dyes 15, 16 and 17, K
₂ IrCl _6, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, was optimally chemically sensitized by adding N- dimethylselenourea. Compounds 13 and 14 were added at the end of the chemical sensitization.

[0205]

[Chemical 21]

[0206]

[Chemical formula 22]

[0207]

[Chemical formula 23]

(Em-Q2 to Q15) Compounds 13 and 1
After the addition of 4, the temperature of the chemically sensitized emulsion was lowered to 40 ° C. (the addition pattern C was set as in Example 1), and then the compound of the present invention or the comparative example compound was added to the amount of silver in the emulsion. (Table 3) except that the content was added as shown in
Emulsions Em-Q2 to Q15 were obtained in the same manner as (Em-Q1). (The characteristics of the obtained silver halide emulsions Em-Q1 to Q15 are shown in Table 3 of Example 3.)

[0209]

[Table 3]

Emulsions Q1 to Q1 of the previous period were prepared in the same manner as in Example 1.
5 was applied to prepare samples 201 to 215. These samples were hardened for 14 hours under the conditions of 40 ° C. and 70% relative humidity. After that, 1/100 through a continuous wedge with gelatin filter SC-50 (long wavelength light transmission filter with a cut-off wavelength of 500 nm) manufactured by FUJIFILM Corporation
The photographic performance was evaluated by exposing the sample for a second and developing the sample in the same manner as in Example 1 by measuring the density with a green filter. Also, the same treatment was applied to each sample that had been aged for 3 days under the condition of 50 ° C. and 80% RH. The photographic performance results are shown in Table 4 below. The sensitivity was represented by the relative value of the logarithm of the reciprocal of the exposure amount required to reach the density of fog plus 0.2.
And).

[0211]

[Table 4]

From Table 4, even in the green-sensitive silver halide photographic emulsion, the compound of the present invention has a large effect of increasing the sensitivity and has a low density (fog) in the unexposed area as compared with the comparative compound, despite the small amount used. I understand. Also, 50 ℃ 8
It can be seen that also in the sample that has been aged for 3 days under the condition of 0% RH, the compound of the present invention has a smaller decrease in sensitivity after raw storage and a lower fog than the comparative compound.

(Example 3) (Em-A1) (Emulsion for high-sensitivity blue sensitive layer) It was 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 0.9 g of KBr was kept at 40 ° C and vigorously stirred. A
37.5 mL of an aqueous solution containing 1.49 g of gNO ₃ and KBr
37.5 mL of an aqueous solution containing 1.5 g of was added by the double jet method over 30 seconds. After 1.2 g of KBr was added, the temperature was raised to 75 ° C. for aging. After aging sufficiently, the amino group was chemically modified with trimellitic acid to give a molecular weight of 100,000.
Add 30 g of trimellitated gelatin and adjust the pH to 7
Adjusted to. 6 mg of thiourea dioxide was added. AgN
116 mL of an aqueous solution containing 29 g of O ₃ and a KBr aqueous solution were added by a double jet method while accelerating the flow rate so that the final flow rate was 3 times the initial flow rate. At this time, the silver potential was kept at -20 mV against the saturated calomel electrode. AgNO ₃ , 11
440.6 mL of an aqueous solution containing 0.2 g and a KBr aqueous solution were added by a double jet method over 30 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. This time,
The AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added while accelerating the flow rate 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. 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 −.
Adjusted to 90 mV. The AgI fine grain emulsion described above was converted into KI
8.5 g was added in terms of mass. Ag immediately after addition
228 mL of an aqueous solution containing 57 g of NO ₃ was added over 5 minutes. At this time, an aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. It was washed with water and chemically sensitized in the same manner as Em-A1.

(Em-C) (Emulsion for low-sensitivity blue-sensitive layer) 1192 mL of an aqueous solution containing 1.02 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation ratio of 97% and containing 35 μmol of methionine per 1 g of 0.97 g of KBr.
Was kept at 35 ° C. and stirred vigorously. AgNO ₃ , 4.4
An aqueous solution containing 7 g, 42 mL and KBr, an aqueous solution containing 3.16 g, 42 mL were added by the double jet method over 9 seconds. After 2.6 g of KBr was added, the temperature was raised to 66 ° C. and aged sufficiently. After ripening, 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, dimethylamine borane, 8 mg was added.
203 mL of an aqueous solution containing 26 g of AgNO ₃ and a KBr aqueous solution were added by the 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 against the saturated calomel electrode. AgNO ₃ , 11
440.6 mL of an aqueous solution containing 0.2 g and a KBr aqueous solution were added by a double jet method over 24 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. This time,
The AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added while accelerating the flow rate so that the silver iodide content was 2.3 mol%, and the silver potential was changed with respect to the saturated calomel electrode.
It was kept at 20 mV. 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 KBr aqueous solution were added over 2 minutes and 30 seconds by the double jet method. At this time, set the silver potential to 1
It was kept at 0 mV. The aqueous solution of KBr is added to adjust the silver potential to -7.
It was adjusted to 0 mV. The AgI fine grain emulsion described above was added in an amount of 6.4 g in terms of KI mass. AgN immediately after addition
404 mL of an aqueous solution containing 57 g of O ₃ was added over 45 minutes. At this time, an aqueous KBr solution was adjusted so that the potential at the end of the addition was −30 mV. It was washed with water and chemically sensitized in the same manner as Em-A1.

(Em-D) (Low Sensitivity Blue Sensitive Layer Emulsion) In the preparation of Em-C, the amount of AgNO ₃ added during nucleation was changed to 2.0 times. And the final AgNO ₃ , 57
The potential at the end of addition of 404 mL of an aqueous solution containing g is +90 m
It was changed to adjust to V with an aqueous KBr solution. Otherwise, it was prepared in substantially the same manner as Em-C.

(Em-E) (magenta color-developing layer having a spectral sensitivity peak at 480 to 550 nm) (Layer which gives a multi-layer effect to the red-sensitive layer) Low molecular weight gelatin having a molecular weight of 15,000, 0.71 g, KBr, 0.92 g,
Modified silicone oil 0.2 used in the preparation of Em-A1
1,200 mL of an aqueous solution containing g was kept at 39 ° C., and the pH was 1.
It was adjusted to 8 and stirred vigorously. An aqueous solution containing 0.45 g of AgNO ₃ and an aqueous KBr solution containing 1.5 mol% of KI were added over 17 seconds by the double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 56 ° C. and aging was carried out. After sufficiently ripening, 20 g of phthalated gelatin containing 35 μmol of methionine per 1 g and having a phthalation ratio of 97% with a molecular weight of 100,000 was added. After adjusting the pH to 5.9, KBr, 2.9 g was added. A
288 mL of an aqueous solution containing 28.8 g of gNO ₃ and an aqueous KBr solution were added by the double jet method over 53 minutes. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was added at the same time so that the silver iodide content was 4.1 mol%, and the silver potential was -60 m with respect to the saturated calomel electrode.
Kept at V. After adding 2.5 g of KBr, AgNO
_An aqueous solution containing 3,87.7 g and an aqueous KBr solution were added by the double jet method over 63 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the silver iodide content of the above AgI fine grain emulsion was 10.5 mol%.
Flow rate was accelerated at the same time so that the silver potential was increased, and the silver potential was maintained 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. KB so that the potential at the end of addition is +20 mV
The addition of the aqueous solution was adjusted. 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, the above AgI fine grain emulsion was converted to 5.73 in terms of KI mass.
g was added. Immediately after the addition was completed, AgNO ₃ , 66.4
609 mL of an aqueous solution containing g was added over 10 minutes. During the initial 6 minutes of the addition, the silver potential was maintained at -70 mV with a KBr aqueous solution. After washing with water, add gelatin and pH at 40 ℃
Adjusted to 6.5, pAg, 8.2. After adding the compounds 11 and 12, the temperature was raised to 56 ° C. AgI mentioned above
After adding 0.0004 mol of the fine grain emulsion to 1 mol of silver, sensitizing dyes 13 and 14 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate, N,
Optimal chemical sensitization was performed by adding N-dimethylselenourea. Compounds 13 and 14 were added at the end of the chemical sensitization.

[0217]

[Chemical formula 24]

[0218]

[Chemical 25]

(Em-F) (Emulsion for Medium-Sensitivity Green Sensitive Layer) 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 in the preparation of Em-E. did. However, Em-E sensitizing dyes are used as sensitizing dyes 15 and 16
And changed to 17.

[0220]

[Chemical formula 26]

[0221]

[Chemical 27]

[0222]

[Chemical 28]

(Em-G) (Emulsion for low sensitivity green sensitive layer) 0.70 g of low molecular weight gelatin having a molecular weight of 15,000, KB
r, 0.9 g, KI, 0.175 g, an aqueous solution 1 containing 0.2 g of the modified silicone oil used in the preparation of Em-A1
200 mL was maintained at 33 ° C., pH was adjusted to 1.8 and vigorously stirred. An aqueous solution containing 1.8 g of AgNO ₃ and 3.2
An aqueous KBr solution containing mol% of KI was added over 9 seconds by the double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 69 ° C. for aging. After aging,
27.8 g of trimellitated gelatin in which an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per 1 g was chemically modified with trimellitic acid was added. pH
Was adjusted to 6.3 and KBr, 2.9 g was added.
270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and KB
The aqueous r solution was added by the double jet method over 37 minutes. At this time, a low molecular weight gelatin aqueous solution having a molecular weight of 15,000, an AgNO ₃ aqueous solution and a KI aqueous solution were prepared as described in JP-A-10-43.
No. 570, a AgI fine grain emulsion having a grain size of 0.008 μm prepared by mixing just before addition in another chamber having a magnetic coupling induction stirrer so that the silver iodide content is 4.1 mol%. And the silver potential was kept at -60 mV against saturated calomel electrode. After adding 2.6 g of KBr, AgNO ₃ , 8
An aqueous solution containing 7.7 g and an aqueous KBr solution were added by a double jet method over 49 minutes while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time, the AgI fine grain emulsion prepared by mixing just before the addition was accelerated at the same time so that the silver iodide content was 7.9 mol%, and the silver potential was kept at -70 mV. Thiourea dioxide, 1m
After adding g, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added by the double jet method over 20 minutes. 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. Ag used in the preparation of Em-A1
5.73 g of I fine grain emulsion in terms of KI mass was added. Immediately after the addition was completed, 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 initial stage of the addition. Em-F
It was washed with water and chemically sensitized in the same manner as in.

(Em-H) (Emulsion for low-sensitivity green-sensitive layer) Ion-exchanged gelatin having a molecular weight of 100,000 17.8
An aqueous solution containing g, KBr, 6.2 g, KI, 0.46 g was kept at 45 ° C. and vigorously stirred. AgNO ₃ , 11.8
An aqueous solution containing 5 g and an aqueous solution containing 3.8 g of KBr were added by the double jet method over 47 seconds. Gelatin 2 with a molecular weight of 100,000 was ion-exchanged after heating to 63 ° C.
4.1 g was added and aged. AgN after fully aged
An aqueous solution containing 133.4 g of O ₃ and an aqueous KBr solution were added by a double jet method over 20 minutes so that the final flow rate was 2.6 times the initial flow rate. At this time, the silver potential was kept at +40 mV against the saturated calomel electrode. 10 minutes after the start of addition, 0.1 mg of K ₂ IrCl ₆ was added. Na
After adding 7 g of Cl, an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added by the double jet method over 12 minutes. At this time, the silver potential was maintained 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 the addition. After adding 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 was completed, 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. This time,
The silver potential was kept at +90 mV. It was washed with water and chemically sensitized in the same manner as Em-F.

(Em-I) (Emulsion for Low Sensitivity Green Sensitive Layer) The emulsion was prepared in the same manner as in Em-H except that the temperature at the nucleation was changed to 38 ° C.

(Em-J1) (Emulsion for high-sensitivity red-sensitive layer) Aqueous solution 1 containing phthalated gelatin having a phthalation ratio of 97% and a molecular weight of 100,000, 0.38 g, KBr, and 0.99 g.
200 mL was maintained at 60 ° C., pH was adjusted to 2, and the mixture was vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and KBr,
An aqueous solution containing 1.97 g, KI, and 0.172 g was added over 30 seconds by the double jet method. After aging, 1
Molecular weight 1 containing 35 μmol methionine per g
12.8 g of trimellited gelatin in which the amino group of 00000 was chemically modified with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g, NaCl
6.2 g was added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were mixed by a double jet method to 3
Added over 5 minutes. At this time, the silver potential was kept at -50 mV against the saturated calomel electrode. AgNO ₃ , 65.
The aqueous solution containing 6 g and the KBr aqueous solution were accelerated by the double jet method so that the final flow rate was 2.1 times the initial flow rate, and added over 37 minutes. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 had a silver iodide content of 6.5.
At the same time, the flow rate was accelerated so that the amount became mol%, and the addition was performed, and the silver potential was maintained at -50 mV. Thiourea dioxide, 1.5
After adding mg, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added by the double jet method over 13 minutes. 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. A above
6.2 g of gI fine grain emulsion was added in terms of KI mass. Immediately after the addition was completed, 300 mL of an aqueous solution containing 88.5 g of AgNO ₃ was added over 8 minutes. The potential was adjusted to +60 mV by the addition of an aqueous KBr solution at the end of the addition. After washing with water, gelatin was added and the pH was adjusted to 6.
It was adjusted to 5, pAg, 8.2. Compounds 11 and 12
After adding, the temperature was raised to 61 ° C. Sensitizing dye 18, 1
After adding 9, 20, 21 and 22, K ₂ IrC
Optimum chemical sensitization was carried out by adding l ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea. Compounds 13 and 14 at the end of chemical sensitization
Was added.

[0227]

[Chemical 29]

[0228]

[Chemical 30]

[0229]

[Chemical 31]

[0230]

[Chemical 32]

(Em-K) (Emulsion for Medium Sensitive Red Sensitive Layer) Low molecular weight gelatin having a molecular weight of 15,000, 4.9 g, KB
1200 mL of an aqueous solution containing r and 5.3 g was kept at 60 ° C. and vigorously stirred. Aqueous solution 2 containing 8.75 g of AgNO ₃ .
36 mL of an aqueous solution containing 7 mL and 6.45 g of KBr was added by the 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 to 2.5
Added over minutes. NH ₄ NO ₃ , 26g, 1N, Na
After OH and 56 mL were sequentially added, the mixture was aged. After the aging, the pH was adjusted to 4.8. Aqueous solution 438 mL containing 141 g of AgNO ₃ and aqueous solution 4 containing 102.6 g of KBr 4
58 mL was added by the double jet method so that the final flow rate was 4 times the initial flow rate. After cooling to 55 ° C, AgNO
240 mL of an aqueous solution containing ₃ , 7.1 g and 6.46 g of KI
The containing aqueous solution was added by the double jet method over 5 minutes. After adding 7.1 g of KBr, sodium benzenethiosulfonate, 4 mg and K ₂ IrCl ₆ , 0.05 mg
Was added. 177 m of an aqueous solution containing 57.2 g of AgNO ₃ .
223 mL of an aqueous solution containing 40.2 g of L and KBr was added by the double jet method over 8 minutes. It was washed with water and chemically sensitized in the same manner as Em-J1.

(Em-L) (Emulsion for Medium-Sensitivity Red-Sensitive Layer) The emulsion was prepared in the same manner as in Em-K except that the temperature at the nucleation was changed to 42 ° C.

(Em-M, N, O) (Emulsion for low-sensitivity red-sensitive layer) It was prepared in substantially the same manner as Em-H or Em-I. However, the chemical sensitization was performed by a method similar to that of Em-J1.

(Em-P1) (Emulsion for high-sensitivity green-sensitive layer) Em-P1 was obtained by optimally performing chemical sensitization by changing the sensitizing dyes to 15, 16 and 17 for Em-J1. It was The characteristics of the silver halide emulsions Em-A1 to Q15 thus obtained are shown in (Table 5).

[0235]

[Table 5]

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

1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by mass and Tinuvin P.O. as an ultraviolet absorber. Three
26 (manufactured by Ciba-Geigy Ciba-Geigy Co.) and 2 parts by mass are melted, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C., and subsequently 130 ° C. Transversely stretched 3.3 times at 250 ° C
After heat fixing for 6 seconds, a PEN (polyethylene naphthalate) film having a thickness of 90 μm was obtained. The PEN film contains a blue dye, a magenta dye, and a yellow dye (I-1 described in the publication technique: Japanese Patent No. 94-6023,
I-4, I-6, I-24, I-26, I-27, II-
5) was added in an appropriate amount. Furthermore, the support was wound around a stainless steel core having a diameter of 20 cm and subjected to a heat history at 110 ° C. for 48 hours to obtain a support having less curling tendency.

2) Coating of Undercoat Layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and Soudium α-on each side. Sulfodi-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
20.12 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² An undercoat liquid was applied (10 m
L / m ² , using a bar coater), an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 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 surface of the support after undercoating. 3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, and a dispersion of fine particle powder (secondary aggregate particle diameter of about 0.08 μm) is 0. .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 N
HCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
m ² and resorcinol. 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, Long axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 Am ²
/ Kg, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide silicon oxide at 2% by mass of iron oxide) 0.0
6 g / m ² of diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed by an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H) as a curing agent
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. As a matting agent, silica particles (0.3 μm) and 3-
Aluminum oxide (0.15 μm) as an abrasive treated and coated with poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) was added in an amount of 10 mg / each.
It was added so as to be m ² . Drying was carried out at 115 ° C for 6 minutes (all the rollers and conveying devices in the drying zone are 115
C). The color density increase of D ^B of the magnetic recording layer by the X-light (blue filter) was about 0.1, the saturation magnetization moment of the magnetic recording layer was 4.2 Am ² / kg, and the coercive force was 7.3.
It was × 10 ⁴ A / m and the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (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. In addition, this mixture is xylene / propylene monomethyl ether (1 /
In 1), the mixture was melted at 105 ° C., poured into and dispersed in propylene monomethyl ether (10 times amount) at room temperature to prepare a dispersion (average particle diameter 0.01 μm) in acetone, and then added. 15 mg / m of aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as an abrasive.
^It was added to be ² . Drying was carried out at 115 ° C for 6 minutes (all the rollers and conveying devices in the drying zone were 115
C). The sliding layer had a dynamic friction coefficient of 0.06 (5 mmφ stainless hard ball, load 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clip method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later was 0.12. It had excellent characteristics.

4) Coating of Photosensitive Layer Next, each layer having the following composition was multilayer coated on the side opposite to the back layer obtained above to obtain a sample 30 which is a color negative photosensitive material.
Created 1. Samples in which the emulsion A1 is replaced with A2 to A20 are referred to as Samples 302 to 320, respectively. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent (specific compounds are given below, numerical values are given after the symbols, and chemical formulas are listed after them) The numbers corresponding to each component are the coating amounts expressed in g / m ² units. For silver halide, the coating amount in terms of silver is shown.

[0242]   First layer (first antihalation layer)     Black colloidal silver 0.155     Surface fog of 0.07 μm 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

[0244]   Third layer (middle 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

[0245]   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

[0246]   Fifth layer (medium speed 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

[0247]   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.

[0248]   7th layer (middle layer)     Cpd-1 0.089     Solid disperse dye ExF-4 0.030     HBS-1 0.050     Polyethyl acrylate latex 0.83     Gelatin 0.84

[0249]   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

[0250]   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

Tenth Layer (Medium Sensitivity 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-80 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

[0252]   11th layer (high sensitivity green emulsion layer)     Silver iodobromide emulsion P1 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.

[0253]   12th layer (yellow filter layer)     Yellow colloidal 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

Thirteenth 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-10 .24 gelatin 1.41

Fourteenth 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 1.0x10 ^-3 HBS-1 0.10 Gelatin 0.91

Fifteenth 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-30 .05 S-1 0.20 gelatin 0.75

Further, in each layer, storability, processability, pressure resistance, antifungal and antibacterial properties, B-4 to B-6, F-1 to F-18, iron salt, lead salt and gold salt are appropriately added. , Platinum salt, palladium salt, iridium salt, ruthenium salt, rhodium salt are contained. Further, the coating solution for the eighth layer was 8.5 × 10 ⁻³ g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 1.
0 ^-3 grams of calcium was added at calcium nitrate solution, to prepare a sample. Further, at least one kind of W-1, W-6, W-7 and W-8 is contained for improving antistatic property, and at least one kind of W-2 and W-5 is contained for improving coatability. Contains.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 mL and 5% aqueous solution of p-octylphenoxyethoxyethoxyethaneethanesulfonate 3 mL and 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) 0.5 g were put in a 700 mL pot mill, and dye ExF was added. -2 and 5.0 g of zirconium oxide beads (1 mm in diameter) 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, take out the contents and take 12.5
% Gelatin aqueous solution and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.

[0260] In the same manner, a solid dispersion of ExF-4 was obtained. The average particle size of the dye fine particles was 0.45 μm. E
xF-3 is European Patent Application Publication (EP) 549,489.
Microprecipitation (Microp) described in Example 1 of A specification.
It was dispersed by a reciprocation) dispersion method.
The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method. ExF-6 wet cake containing 18% water 2
To 800 g, 4000 g of water and a 3% solution of W-2 37
6 g was added and stirred to obtain a slurry having a concentration of ExF-6 of 32%. Next, 1700 mL of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultra Visco Mill (UVM-2) manufactured by IMEX Co., Ltd., and the peripheral speed was about 10 m through the slurry.
/ Sec and discharge rate 0.5 L / min for 8 hours.
The compounds used to form each of the above layers are as shown below.

[0262]

[Chemical 33]

[0263]

[Chemical 34]

[0264]

[Chemical 35]

[0265]

[Chemical 36]

[0266]

[Chemical 37]

[0267]

[Chemical 38]

[0268]

[Chemical Formula 39]

[0269]

[Chemical 40]

[0270]

[Chemical 41]

[0271]

[Chemical 42]

[0272]

[Chemical 43]

[0273]

[Chemical 44]

[0274]

[Chemical formula 45]

[0275]

[Chemical formula 46]

The evaluation method of the sample is as follows. It was exposed for 1/100 seconds through a continuous wedge with a gelatin filter SC-39 manufactured by FUJIFILM Corporation (a long wavelength light transmission filter having a cutoff wavelength of 390 nm). Development was carried out by the following using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. Incidentally, the overflow solution of the bleaching bath was modified so that the overflow liquid was discharged into the waste liquid tank without flowing into the post-bath. This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992.

The processing steps and processing liquid compositions are shown below. (Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5L Bleach 50 seconds 38.0 ℃ 5 mL 5L Fixing (1) 50 seconds 38.0 ℃ -5L Fixing (2) 50 S 38.0 ℃ 8 mL 5 L water wash 30 s 38.0 ℃ 17 mL 3 L stable (1) 20 s 38.0 ℃ −3 L stable (2) 20 s 38.0 ℃ 15 mL 3 L dry 1 min 30 s 60.0 ℃ * Replenishment amount 35 mm width per 1.1 m (corresponding to 24 Ex. 1 line) The stabilizing solution and the fixing solution were in the countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath (2). The amount of developing solution brought into the bleaching step, 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, for each 35 mm width of the photosensitive material of 1.1 m width. It was 2.0 mL. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. 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 liquid (g) Replenisher (g)   Diethylenetriamine pentaacetic 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-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3 mg-   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

[0279]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-Diaminopropanetetraacetic acid secondary     Ammonium iron 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 ammonia water] 4.6 4.0

[0280]   (Fixing (1) Tank liquid)   5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid   (PH 6.8)

[0281]   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240mL 720mL   (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 was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH type strongly basic anion exchange resin (the same Amberlite IR-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 m.
g / L or less, followed by 20 mg / L sodium diisocyanurate dichloride and 150 mg / L sodium sulfate
Was added. The pH of this liquid was in the range of 6.5 to 7.5.

[0283]   (Stabilizing liquid) Common for tank liquid and replenishing liquid (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether 0.2     (Average degree of polymerization 10)   1,2-benzisothiazolin-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   1.0L with water added   pH 8.5

The above processing was applied to the samples 301 to 320. The same treatment was also applied to the sample that had been aged for 3 days under the conditions of 50 ° C. and 80% RH. The 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 the standard: 100)

[Table 6]

From Table 6, even in the full-color silver halide photographic material, the compound of the present invention has a large effect of increasing the sensitivity in any of A, B, and C addition patterns, in comparison with the comparative compound, even though the addition amount is small. It can be seen that the density (fog) of the unexposed area is low. Further, it can be seen that also in the sample aged for 3 days under the condition of 50 ° C. and 80% RH, the compound of the present invention has a smaller decrease in sensitivity after raw storage and a lower fog than the comparative compound. From the above results, it is understood that by using the compound of the present invention, a silver halide photographic light-sensitive material having high sensitivity and low fog, less desensitization after raw storage, and less increase in fog can be obtained.

Example 4 Silver halide emulsions Em-R1 to R8 were prepared by the following production method.

(Em-R1) Emulsion Em-R1 was prepared by making the following changes to Emulsion 1-G described in Example 1 of JP-A 2001-228572.
Was prepared. The sensitizing dye is changed to sensitizing dye 11 and sensitizing dye 23. Compound 15 was used instead of chloroauric acid in the chemical sensitization.
1,3-Dimethyl-1,3-dicarboxymethylthiourea is used instead of sodium thiosulfate.

[0288]

[Chemical 47]

[0289]

[Chemical 48]

Emulsion Em-R1 was prepared according to Example 1 of JP-A-2001-228572.
Similarly to Emulsion 1-G described in 1. above, the average equivalent-circle diameter was 1.28 μm, the average grain thickness was 0.088 μm, and the average aspect ratio was 14.5. Also, 50% or more of the total projected area is equivalent to a circle
The grain size was 1.0 μm or more and the grain thickness was 0.10 μm or less, and each grain fringe portion was occupied by grains having 30 or more dislocation lines.

(Em-R2 to R8) After the compounds MER-1 and MER-2 were added, the temperature of the chemically sensitized emulsion was lowered to 40 ° C., and then the compound of the present invention or the comparative example compound was added to silver in the emulsion. Emulsions Em-R2 to R8 were obtained in the same manner as in (Em-R1), except that the content was added as shown in (Table 7).

[0292]

[Chemical 49]

In the same manner as in Example 1, the above-mentioned emulsions Em-R1.
R8 was applied to prepare samples 401 to 408. These samples were hardened for 14 hours under the conditions of 40 ° C. and 70% relative humidity. After that, through Fuji Film Co., Ltd. gelatin filter SC-39 (long wavelength light transmission filter with cutoff wavelength of 390 nm) and continuous wedge, 1
The photographic performance was evaluated by exposing the sample for 100 seconds and developing the sample in the same manner as in Example 1 by measuring the density with a green filter. In addition, each sample is 50 ℃ 80% R
The same treatment was carried out for those aged under the condition of H for 3 days. The photographic performance results are shown in Table 7 below. The sensitivity was represented by the relative value of the logarithm of the reciprocal of the exposure amount required to reach the density of fog plus 0.2. (Sample 401 was set as the standard: 100)

[Table 7]

From Table 7, in the silver halide photographic emulsion produced by grain growth by adding silver halide fine grains prepared by a mixer provided outside the reaction vessel, the compound of the present invention is less than the comparative compound. It can be seen that the sensitivity increasing effect is large regardless of the amount used and the density (fog) in the unexposed portion is low. Further, it can be seen that also in the sample aged for 3 days under the condition of 50 ° C. and 80% RH, the compound of the present invention has a smaller decrease in sensitivity after raw storage and a lower fog than the comparative compound.

(Example 5) Silver halide emulsions Em-S1 to S11 were prepared by the following production method. (Em-S1) Emulsion b described in Example 1 of JP-A-2001-159799.
On the other hand, the following changes were made to prepare an emulsion Em-S1. The sensitizing dye is changed to sensitizing dye 11. Compound 15 was used instead of chloroauric acid in the chemical sensitization.
1,3,3-Trimethyl-1-carboxymethylthiourea is used instead of sodium thiosulfate. Emulsion Em-S1 is JP200
Similar to Emulsion b described in Example 1 of 1-159799, average circle equivalent diameter 4.1 μm, variation coefficient of circle equivalent system 21%, average thickness 0.090
It was a tabular grain having a μm and an average aspect ratio of 46. Also,
70% or more of the total projected area was occupied by grains having an equivalent circle diameter of 4.1 μm or more and a grain thickness of 0.090 μm or less.

(Em-S2 to S7) After completion of the chemical sensitization, the temperature of the emulsion was lowered to 40 ° C., and then the compound of the present invention or the comparative example compound was added to the amount of silver in the emulsion as shown in (Table 8). Emulsions Em-S2 to S7 were obtained in the same manner as in (Em-S1) except that the amounts were added. (Em-S8 to S11) Except that the compound of the present invention or the compound of Comparative Example was added before the addition of the sensitizing dye so that the content was as shown in Table 8 with respect to the amount of silver in the emulsion, (Em-S8 to S11). Emulsions Em-S8 to S11 were obtained in the same manner as in S1). The emulsions Em-S1 to S11 were coated in the same manner as in Example 1 to prepare samples 501 to 511.

Each of these samples was subjected to a hardening treatment for 14 hours under the conditions of 40 ° C. and 70% relative humidity. Then, the film was exposed for 1/100 seconds through a continuous wedge and a gelatin filter SC-39 (long wavelength light transmission filter having a cutoff wavelength of 390 nm) manufactured by Fuji Film Co., Ltd.
The photographic performance was evaluated by measuring the density of a sample which had been subjected to the same development process as in 1. above with a green filter. Also,
The same treatment was applied to each sample which had been aged for 3 days under the condition of 50 ° C. and 80% RH.

The photographic performance results are shown in Table 8 below. The sensitivity was expressed as the relative value of the logarithm of the reciprocal of the exposure required to reach the density of fog plus 0.2.
Was set to 100).

[0299]

[Table 8]

From Table 8, the compound of the present invention is added to the silver halide photographic emulsion produced by adding iodide ions by adding fine silver iodide particles prepared by a mixer provided outside the reaction vessel. Despite this, it can be seen that the effect of increasing the sensitivity is greater than that of the comparative compound and the density (fog) of the unexposed area is low. Further, it can be seen that also in the sample aged for 3 days under the condition of 50 ° C. and 80% RH, the compound of the present invention has a smaller decrease in sensitivity after raw storage and a lower fog than the comparative compound.

(Example 6) Silver halide emulsions Em-T1 to T9 were prepared by the following method. (Em-T1) Emulsion Em-T1 prepared by epitaxially depositing the host emulsion e described in Example 1 of JP-A-2001-235821 by the epitaxial deposition method described in Example 1 of the same patent, and making the following modifications. Was prepared. The sensitizing dyes used in the epitaxial deposition are changed to sensitizing dyes 11 and 23. Emulsion Em-T1 is disclosed in JP 2001-235A.
Host particles similar to those in Emulsion e described in Example 1 of 821, that is, the average equivalent circle diameter is 4.2 μm, and the variation coefficient of the equivalent circle diameter is 19
%, The average grain thickness was 0.062 μm, and the average aspect ratio was 68. Further, 90% or more of the total projected area was occupied by hexagonal tabular grains having a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 1.4 or less. The epitaxially deposited emulsion had an average silver iodide content of 4.5 mol% and an average silver chloride content of 1.2 mol%.

(Em-T2 to T9) After completion of the chemical sensitization, the temperature of the emulsion was lowered to 40 ° C., and then the compound of the present invention or the comparative example compound was added as shown in Table 9 to the amount of silver in the emulsion. Emulsions Em-T2 to T9 were obtained in the same manner as in (Em-T1) except that the amounts were added. The above emulsions Em-T1 to T9 were coated in the same manner as in Example 1 to prepare samples 601 to 609.

These samples were hardened for 14 hours under the conditions of 40 ° C. and 70% relative humidity. Then, the film was exposed for 1/100 seconds through a continuous wedge and a gelatin filter SC-39 (long wavelength light transmission filter having a cutoff wavelength of 390 nm) manufactured by Fuji Film Co., Ltd.
The photographic performance was evaluated by measuring the density of a sample which had been subjected to the same development process as in 1. above with a green filter. Also,
The same treatment was applied to each sample which had been aged for 3 days under the condition of 50 ° C. and 80% RH. The photographic performance results are shown in Table 9 below. The sensitivity was represented by the relative value of the logarithm of the reciprocal of the exposure amount required to reach the density of fog plus 0.2. (Sample 601 was set as the standard: 100)

[Table 9]

From Table 9, it can be seen that even in the emulsion composed of tabular grains having an epitaxial junction, the compound of the present invention has a greater effect of increasing the sensitivity than the comparative compound and has a low density (fog) in the unexposed area. Also, 50 ° C 80% R
It can be seen that also in the sample aged for 3 days under the condition of H, the compound of the present invention has a smaller decrease in sensitivity after raw storage and a lower fog than the comparative compound.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Naoki Asanuma             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H023 CA01

Claims (6)

[Claims] 1. The following general formula (1), (2) or (3):
Characterized by containing at least one compound represented by
Silver halide emulsion. [Chemical 1] Z in the general formula (1)₁Is a nitrogen atom and a benzene ring
Represents an atomic group capable of forming a 6-membered ring with two carbon atoms of
And R₁, R₂, R_N1Are hydrogen atoms or substituents, respectively
Represent, X₁Represents a substituent, m₁Represents an integer of 0 to 3,
L₁Represents a leaving group. ED in the general formula (2)₁₁Is electric
Represents a child-providing group, R₁₁, R₁₂, R_N11, R₁₃, R₁₄Is
Each represents a hydrogen atom or a substituent, X₁₁Is a substituent
Represents, m ₁₁Represents an integer of 0 to 3, L₁₁Represents a leaving group
You R_N11, R₁₃, R₁₄, X₁₁And ED₁₁One of
The two groups may be bonded to each other to form a cyclic structure.
Good. R in the general formula (3)_{twenty two}, R_{twenty three}, R_{twenty one},
R_N21, R_a, R_bAre hydrogen atoms or substituents, respectively.
Then L_{twenty one}Represents a leaving group. However, R_N21Is other than an aryl group
When R represents a group of_aAnd R_bAre bonded together to form an aromatic ring
To form. 2. The general formula (1) according to claim 1,
A silver halide emulsion chemically sensitized with at least one compound represented by (2) or (3). 3. The silver halide according to claim 1, wherein the compound according to claim 1 is a compound having an adsorptive group for silver halide in the molecule. emulsion. 4. The silver halide emulsion according to claim 3, wherein the adsorptive group is a nitrogen-containing heterocyclic group substituted with two or more mercapto groups. 5. A silver halide photographic light-sensitive material comprising at least one of the compounds according to claim 1, 3 or 4. 6. A silver halide photographic light-sensitive material comprising at least one emulsion chemically sensitized with the compound according to claim 1.