JPH03236047A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow the stable blocking of the active part of photographically useful groups at time of preservation and the release of a photographic reagent at the necessary timing at the time of processing by using a specific photographic reagent precursor. CONSTITUTION:The compd. expressed by formula I is incorporated into the above photosensitive material. In the formula, R<1>, R<2> denote H, aliphat. group, arom. group, etc.: L, Time denote a combination group; V denotes carbonyl, -CO-CO-, sulfonyl, etc.; X denotes an atom group necessary for forming a desired ring; PUG denotes a fogging preventive agent, development restrainer, development accelerator, etc. The compd. of formula II, etc., are usable as the component of the formula and may be added to emulsion layers and other hydrophilic colloidal layers. Images having a good sensitivity and gradations are obtd. without degrading a black spot characteristic if this photosensitive material is used.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide photographic light-sensitive material #+, and more specifically, to a silver halide photographic material #+, and more specifically, to The present invention relates to a silver halide photosensitive material containing silver halide and a light-sensitive material.

(Prior Art) When a photographically useful photographic reagent is added to a photographic light-sensitive material in advance to bring out its effects, it has a different effect than when it is used by containing it in a processing solution. is. As an effect, for example, it is possible to effectively utilize photographic reagents that are easily decomposed under oxidizing/reductive conditions such as acid/alkaline VH and cannot withstand long-term storage in the processing solution, and at the same time, the composition of the processing solution can be simplified. It may be easier to prepare, or it may be possible to apply the necessary photographic reagent only to the necessary location, that is, to a specific layer in the multilayer photosensitive material or to a layer in its vicinity, or to control the amount of photographic reagent present as a function of halogenation development. For example, it is possible to change the

However, if a photographic reagent is added to a photographic material in an active form, it may react with other components in the material during storage before development or decompose due to the influence of heat, oxygen, etc. As a result, the expected performance during treatment is often not achieved. One way to solve these problems is to block the active groups of photographic reagents,
There is a method of adding it to the photographic M& source material in a substantially inert form, ie, as a photographic reagent precursor. If a useful photographic reagent is an anti-capri agent or a development inhibitor, by blocking the active group, it is possible to suppress the desensitizing effect due to adsorption to photosensitive silver halide during storage and the formation of silver salts, and at the same time, it is necessary to These reagents can be released at appropriate timings. As a result, it is possible to reduce fog without compromising sensitivity, suppress image fog due to excessive dust, or display images at the required time! It has the advantage of being able to stop the When useful photographic reagents are developing agents, auxiliary developers, or fogging agents, by blocking active groups or N-absorbing groups, various photographic effects due to the formation of semiquinones and oxidants due to air oxidation during storage can be prevented. This has advantages such as preventing the generation of Capri nuclei during storage by preventing adverse effects on the silver halide or electron injection into the silver halide, and as a result, stable processing f can be realized. In the case of photographic reagents, bleaching accelerators, or bleaching/fixing accelerators, blocking their active groups prevents them from reacting with other fractions during storage and during processing. The advantage of using block groups is that the desired performance can be achieved when needed.

As mentioned above, the original use of precursors for photographic Must satisfy nV
It must be i. In other words, the contradictory requirements for the photographic reagent to exist stably under the storage conditions in the photographic light-sensitive material 1, and to release the photographic reagent quickly and efficiently by passing through the blocking group at the required timing during processing are met. It must be compatible.

There are several well-known block technologies for photographic reagents. For example, Tokko Sho μr-ta.

No. 961, % Kaisho zx-r, try No., 1tit7-l
Ko, r3μ, USA%glf3. J//, No. 4A7A,
Special Publication No. 4T7-Gμ, Roj (U.S. Patent No. 3.6/j,
Those that utilize blocking groups such as anlu group and nulfonyl group described in Japanese Patent Publication No. J/7, 36
No. 1 (U.S. Patent 3.try, T77), same j1-ta,
6ri No. 6 (U.S. Patent No. 3゜79/, 130), same jj
-jμ, Octopus No. 7 (U.S. patent≠, OORI, Q-ta No.),
Japanese Unexamined Patent Publication No. 56-77, r4tu (US IB% 4t, 3
07. /7! No.), Tatar IQj, 64t Co., Tatar i.

J, Utilizing a blocking group that releases a photographically useful reagent by the so-called reverse Michael reaction described in No.
No. t7J', No. j, ? 32, No. 4tlrO, No. 3. Tata 3. ll, No. 7, % Kaisho! 7-73j, riμ
μ issue, same! 7-/36. Tada J, 67-/36.6
4tO, which utilizes a blocking group that releases a photographically useful reagent with the production of quinone methide or quinone methide compounds through intramolecular electron transfer; JP-A-Sho! ! -!
J, No. 330, same! I% of the method utilizing the intramolecular ring-closing reaction described in Ter.
μ7 No. (USA% Xuhiro, j 3 j, -00 issue), same! 7-/36.9 Hirokata, lil? ]j7-/7ri, 1
- issue, same J-ter/37.9413, same! tar hiro0
．． Sanjyo +5, same 5ter +2/ri, 7 hiro/issue, same 10-
&/.

034 is listed in the issue! Techniques that utilize six-member ring cleavage are known as well-known techniques.

These known techniques require highly alkaline treatment with a release rate of photographic reagents of lj, tyH/2 or higher during processing if they are stable under storage conditions, or [)
Even if the release rate is sufficient in the treated solution of H-tarl-, it gradually decomposes under storage conditions, impairing its function as a precursor.

These drawbacks can be attributed to the fact that the release of useful reagents from photographic reagents is blocked by the attack of OH- ions. In other words, in the current one-stage pH control of conventional photographic materials, the difference in OH- ions during storage and processing of photographic materials is due to the fact that the pH during storage is 6-7. ,10-1
It becomes 0.

Thus, for example, a blocked photographic reagent that releases a photographically useful group with a half-life of 3 minutes (it takes 3 minutes for half of the quadrant to decompose) upon treatment at pH/0 will have a negative effect on storage ( pH=
As A], 3 minutes x 10 = 30゜000 minutes";jo
Estimated to degrade over a half-life of o hours. This means that
This means that about half of the amount of di-added 7111 decomposes after storage for about 3 weeks, which means that it is completely impractical. p
Similarly, in the treatment of H//, the blocking compound, which is released with a half-life of 3 minutes during treatment, has a half-life of decomposition during storage of approximately 30 weeks, which is approximately 10 times as long, which is a very unsatisfactory value. , it can be said that it is difficult to put it into practical use in terms of storage stability.

(Objective of the Invention) Therefore, the first object of the present invention is to provide a compound that stably blocks the active part of the photoreagent during storage and releases a photographic reagent at the required timing during processing. It is in.

A second object of the present invention is to provide a silver halide photographic material with improved image quality.

(Means for Solving the Problem) The above-mentioned object of the present invention is to provide a silver halide photographic material having at least seven silver halide emulsion layers on a support. iM was made using nine silver halide photographic materials containing gold.

General formula (1) (wherein RI B2 is a hydrogen atom, an aliphatic group,
If an aromatic group or (I purple ring group is used), R1 and R2 may be joined together to form a ring.Lll-4
A divalent linking group is used. ■ is a carbonyl 0 group. ), iminomethylene group, thiocarphonyl group. Time represents a bivalent consolidated fund. m is o
``tfc龜／'' represents an atomic group necessary to form a ring or a six-membered ring. PUG is an antifoggant, a development inhibitor, a development accelerator, a fogging agent, and a desilvering accelerator. agent, desilvering inhibitor, non-rogenation solvent, developer, auxiliary developer, fixing accelerator, fixing inhibitor, image stabilizer, coloring agent, processing-dependent contrast agent, halftone improver , dye stabilizer, surfactant, hardener, desensitizer, contrast agent, chelating agent, 1
) IR-represents hydroquinone. ) Below is the general formula (1
) will be explained in detail.

The aliphatic group represented by R and R2 preferably has a carbon number l
It is a substituted or unsubstituted aliphatic hydrocarbon group with ~3 co, more preferably l-co, 20 saturated or unsaturated, button-shaped or cyclic, 10 branched.

Typical examples of aliphatic groups include methyl, ethyl, propyl, /-butyl, /-butyl, /-hexyl, l-hebutyl, l-octyl, /-nonyl, l-decyl, l-
undenle, l-dodecyl, l-tridecyl, l-tetradecyl, l-pentadecyl, /-hexadecyl, /-
heptadecyl, /-octadecyl, /-nonadecyl, /
-eicosyl, -propyl, λ-butyl, coventyl, 3-inchyl, t-butyl, 1-(2-ethylhexyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, vinyl, /-butenyl, allyl, /-hexenyl, l-hexynyl group, etc., six groups.

The aromatic group represented by R and R is preferably (1 carbon number 6
~CoO, more preferably a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.

R1 and R2 make up the complex Pi;! , the group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, has a nitrogen atom as a hetero atom, and has a substituent atom or a yellow atom in #, and is substituted or substituted with nothing. , a 3- to 7-membered heterocyclic group. Representative fIj of the heterocyclic group include cobiridyl, μm pyridyl, cochenyl, -monofuryl, coimidaglyl, pyrazinyl, 2-pyriminyl, λ-indolyl, /, J, t-theanazole-coyl, benzoxanol- 2-il, Kokinoril,! , 4I-dioxo/, J-imidazolidine-y-yl, l, λ,
3-triazol-3-yl, tetrazole-! -yl group is mentioned.

Examples of the substituents for the aliphatic group, aromatic group, and heterocyclic group are: ・Loken atom (fluorine atom, chlorine atom, etc.);
Alkyl groups (methyl, ethyl, isopropyl, l-butyl, t-butyl, l-octyl, etc.), aryl groups (phenyl, p-tolyl, phenyl, ≠-ethoxyphenyl, l-naphthyl, etc.), hetero Cyclic groups (4!-pyridyl, cofuryl, etc.), hydroxyl groups, alkoxy groups (methoxy, ethoxy, /-butoxy, etc.), aryloxy groups (phenoxy, methoxyphenoxy, ≠-
Nitrophenoxy, 3-butanesulfo/amidophenoxy1. ? , j-di-t-amylphenoxy, corner 7 toxy, etc.), peterocyclic oxy group (2-furyloxy, etc.), acyloxy group (acetoxy, pivaloyl oxy 7, benzoyloxy, dodecanoyl oxy 7%), alkoxycarbonyloxy group (ethoxycarbonyloxy . , sulfamoyloxy group (rv, N-diethylsulfamoyloxy, N-
propylsulfamoyloxy, etc.), sulfonyloxy groups (methanesulfonyloxy, benzenesulfonyloxy, etc.), carboxyl groups, acyl groups (acetyl, pivaloyl, benzoyl, etc.), alkoxycarbonyl groups (ethoxycarbonyl, etc.), 7' )-ruoxycarbonyl group (
phenoxycarbonyl, etc.), carbamoyl 4 (N, N-
Dibutylcarbamoyl, heethyloctylcarbamoyl, heprobilylbamoyl, etc. 9, amine group (
amino, hemeteramino, N,N-dioctylamino, etc.), anilino group (hemethylanilino, etc.), heterocyclic amino group (syn-pyridylamino, etc.), amide group (acetamide, benzamide, etc.), urethane group (N-hexylurethane) , N, N-dibutylurethane, etc. Ureido group (N, N-dimethylureido, N-phenylureido, etc.), Nurphonamide group (phthanurbonamide, p-
toluenesulfonamide, etc.), alkylthio groups (ethylthio, octylthio, etc.), arylthio groups (phenyl f
(e, <4-dotecylphenylthio, etc.), sulfinyl groups (benzenulfinyl, etc.), sulfonyl groups (methanesulfonyl, octane-nulfonyl, p-)luenesulfonyl, etc.), sulfo groups, cyano groups, nitro groups, etc. can be mentioned. In addition, among the above, in the case of amine groups, aniI) groups, and heterocyclic amino groups, those in the form of quaternary ammonium salts,
References to carboxyl and sulfo groups include those in the form of alkali metal salts or ammonium salts.

A divalent linking group represented by L (1 IC'-C-LfV-ner ÷ Time-ner released by the hydrolysis reaction of the compound of general formula (1))' is nucleophilic to the carbonyl group of LiG. It is a group that makes it possible to cleave (Time+-PUG) by the subsequent intramolecular nucleophilic reaction triggered by the reaction of the agent, such as alkyref group, alkenylene group, arylene group, heteroarylene group ( These groups may have a substituent], and these groups and -〇--S-1- (R3 is a hydrogen atom,
Alkyl group, 3 aryl 7! k), - to;, -CO-1-8O□-, etc. can be mentioned.

Preferred examples of the divalent linking group represented by L are shown below. Here, (shan) represents the site that binds to C in general formula (1), and (shun (shun is ←Vsuichi→Timener) 'm site that binds to LJG.
n To represent a meeting.

(bud) -CH2CH2-(group (transfer), ((transfer) -CH2
CH2UH2-(to the set/2H5 'l' i me represents all divalent linking groups, time/
It may also be placed on the back of the adjustment function 1. n is 0 or /i table fumar n=0. If m, =/, 1PUG; 6E means direct introduction to V; if n=0, m=0, PUG
This means that LIG is directly connected.

The divalent linking group represented by Time is a base in which PUG is synthesized from the compound represented by the general formula (1) through one or more step reactions.

Examples of divalent linking groups mentioned in 'f ime' include, for example, U.S. Pat.
A photographically useful group (P
[JG)'; U.S. Pat. No. 4L, Jlo;
6/λ No. (% Kaishojjr-jJ, No. 330) and the same μ
,! 30, No. 6/7, etc., which releases PUG by an intramolecular ring-closing reaction after ring cleavage; U.S.A.
j, P/P issue, same person, Hiroshi≠6. λ1645, same me, ref.
3. With the formation of an acid anhydride by an intramolecular ring-closing reaction of the carboxyl group of a succinic acid monoester or its analogs as described in Japanese Patent Publication No. RI/RI, JP-A Shoj Tarco/, J21, etc.) 'LIG emitting; U.S. Pat. No. 4, aOY;
No. 323, same≠,≠ko i, r da! issue, Research Day Closure Magazine & Co/, λλF (/riri/J month),
U.S. Patent No. 76.277 (Kaisho, t7-/3
1. ri≠Reference), Kaisho! r-xo ri, No. 736, same 1
The aryloxy group xfc described in 17'-JOY, No. 731, etc. generates quinomonomethane, l, or its analogue by electron transfer via a double bond conjugated with a heterocyclic oxy group, and releases PUGi; U.S. Patent No. μ, ≠2
0°! J Hiro No. (% 17-/34, 6eO), Unexamined Japanese Patent Publication FKF97-/Jj, 4tj, z'y-iir.

No. 036, same jzaita 1,7ko 1 and same! t-co 0
PU from the 7-position of the enamine by electron transfer of the part having the enamine structure of the nitrogen-containing heterocycle described in No. 737, etc.
Kaisho is the one who emits G! No. 7-jb, No. 137, which releases PUG through an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of a nitrogen-containing heterocycle, US Pat. 7≠6,3
No. 76 (tP!f Kaishojλ-taOri No. 32), Tokukaishoyota 23. ≠4Lλ, JP-A No. 88j Turfj≠7j, etc., which release PCl and Gi with the formation of aldehydes; JP-A-Sho! /-/≠6.1ko1, same j7-/
PLJG=i is released with decarboxylation of the carboxyl group described in No. 7, b-, same tar 10 da, 6q no. Formation of carbonic acid and subsequent aldehydes′? t#riteteP
Those that release LIG; % Production of isocyanate as described in Japanese Patent Publication No. 1729/1972; Those that release PUGi accompanied by 4. Oxidation of color developers as described in U.S. Pat. No. 31/Pj, etc. P causes a coupling reaction with the body.
Examples include those that release UGt.

For specific examples of these divalent linking groups represented by Time, see %Kaisei 67-236. j≠ri issue, % Gansho +3-
It is also described in detail in yr, to3, etc.

Here, (@ is f Time − in general formula (1)) T P tJ G is Iso V where m=/
If m=o, the parts that Mf are connected are shown above. (The state (+) indicates the site where HUG binds.

A preferable example of X body as Time is Ushigan 63-211
Preferred examples of the compounds listed as T-(1) to T7 (invasion) in No. 03 are as follows.

T-(20) T-<9) T-(26) / 2H5 T-(3s2H5 Also, Ro, R2 and iTimell Sono(flc:
l! It may also incorporate pallast groups or polymers commonly used in immobile photographic additives such as J-Plur.

A palast group is an organic group that provides sufficient molecular weight to substantially prevent the compound of general formula (I) from diffusing into other layers or processing materials, such as an alkyl group, It consists of a combination of one or more of an aryl group, a heterocyclic group, an ether group, a thioether group, an abado group, a ureido group, a urethane group, a sulfonamide group, etc.

PUGi (Time+-)'U(J9tafi)'
UG includes anti-fogging agents, development inhibitors, development accelerators, fogging agents, desilvering accelerators, desilvering inhibitors, silver halide solvents, developing agents, auxiliary developers, construction accelerators, and desilvering inhibitors. Inhibitor, image stabilizer, color toning agent, processing preservation improver, halftone improver, dye stabilizer, surfactant, hardener, g-reducer, hardening agent, chelating agent , 1) IR-Hydrokino/Worokuwasu.

Since these photographically useful groups often overlap in terms of 7Pi character, typical examples are listed below with specific V.
C.Explain.

The anti-fog agent xfc, which is used in PUG, is a common development inhibitor that has a heteroatom and is bonded via the heteroatom.
Chi Mee 7 (C, E, K.

Mees) and Chee H. James (T, H.

James) [The Theory of the Photographic Process]
Photographic Processes)
J 3rd edition, /ri66 Macmillan
) Published by the company, 34 is described in Hiroshi page ~ 3q6 member, etc. Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothiadiazoles, benztriazoles, benzimidazoles, and indazoles. Examples include adenines, guanines, tetrazoles, tetraazaindenes, triazaindenes, mercaptoaryls, and the like.

The anti-fog agent xfc, represented by PUG, may be substituted with a development inhibitor. Examples of the substituent include the following, or these groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Acylamino group, sulfonylamine group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, nulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarba Nyl group,
Examples include a carbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbodiamide group, a sulfonamide group, a carboxyl group, a sulfoxy group, a phosphono group, a honufinyl group, and a phosphoamide group.

Also, antifoggant and development inhibitor are 8! After being released from the compound represented by the general formula (I) in the image processing step, it becomes a compound that has development inhibitory properties, and further changes into a compound that does not substantially have or has significantly reduced development inhibitory properties. It may be.

The main antifoggants or development inhibitors are shown below.

/Mercaptotetrazole derivative (1)/-722ru yo-mercaptotetrazole (co)/-(44-hydroxyphenyl) -S-mercaptotetrazole (J)/-(daraminophenyl)-j-mercaptotetrazole (≠ )/-(4-carboxyphenyl)-! -Mercaptotetrazole<6)/-(μm chlorophenyl)-! -Mercaptotetrazole (A)/-(Hiro-methylphenyl)-j-Mercaptotetrazole (7)/-(25μm dihydroxyphenyl)-Yo-Mercaptotetrazole (j)/-(44-Nurcoamoylphenyl)-! -mercaptotetrazole (Y)/-CJ-carboxyphenyl)-y-mercaptotetrazole (10)/-(J, j-dicarboxyphenyl)-j-mercaptotetrazole (10/-(≠-methoxyphenyl)-5- Mercaptotetrazole (/J) /-(cometquinphenol)-j-mercaptotetrazole (t3)i-(≠-(cohydro/ethoxy)phenyl-5-mercaptotetrazole(/li/-(J ,
≠-dichlorophenyl)-j-mercabutotetranol<it)/-(4t-dimethylaminophenyl)-j-
Mercaptoti, torazol (/6)/-(Hiro-nitrophenyl)-1-mercaptotetrazole (i7) i,t-bis(j-mercapto-7-tetrazolyl)benze/(it)i-(α-naphthyl)- Yo-mercaptotetrazole (/ri)/-(Hiro-sulfophenyl-5-mercaptotetrazole (X))/-(j-sulfophenyl)-j-mercaptotetrazole (,2/)/-(β-naphthyl) -j-mercaptotetrazole (=)/-methyl-! -Mercaptotetrazole (2J) /-ethyl-! -Mercactotetrazole (alcohol)/-propyl-! -Mercaptotetrazole (co)/-Octyl-yo-Mercaptotetrazole (26) /-Dodeflu! -Mercatotetrazole (core)/-, y-chlorohexyl-j-mercaptotetrazole (co)l-palmityl! -Mercaptotetrazole (n) /-Carboquinethyl-! -Mercaptotetrazole (3o)/-(co-diethoxyether)-z-mercaptotetrazole (31)/-(λ-aminoether)-! -Mercaptotetrazole hydrochloride (Ω)/-(J-diethylaminoethyl)-yo-mercaptotetrazole (33)λ-(!-mercapto-7-tetrazole)ethyltrimethylammonium chloride<1o)t-(J-phenoxycarbonylphenyl )−
! -Merkabutotetolezole <3 gradient 1-(J-maleinimidophenyl)-6-mercaptotetrazole (1) u-722-3-mercaptotriazole (co) a-phenyl-yo-methyl-3-mercaptotrianol ( J) 4A,! -diphenyl-3-mercaptotriazole (Hiro) + - (+-carboxyphenyl) -J -mercaptotriazole (j) 4t-methyl-3-mercaptotriazole<6) 4'-(λ-dimethylaminoethyl)-3-
Mercaptotriazole (7) Hiro-(α-naphthyl)-3-mercaptotriazole (1) Hiro-(Hiro-sulfophenyl)-3-mercaptotriazole (ri) Hiro-(3-nitrophenyl)-3-mercaptotriazole ( 1) /-Phenyl-co-mercaptoimidazole (λ) i,z-diphenyl-2-mercaptoimidazole (3) /-(4A-carboxyphenyl)-2-mercaptoimidazole (μ) /-(≠-hexy mercaptoimidazole (j)/-(J-nitrophenyl)-2-mercaptoimidazole (j)/-(4(-sulfophenyl)-comelcabutoimidazole (1) Thiouracil (7-mercaptoimidazole) Uracil (3) Ethylthio9racil (μ) Propylthiouracil (Rinonylthiouracil (6) Aminothiouracil (7) Hydroxythiouracil j Mercaptobenzimidazole derivative (1) Comelcabutobenzimidazole (co)!- power boxy 2
-Mercaptobenzimidazole (J)j-aminocomercaptobenzimidazole°-
(II) j-nitro-λ-mercabutobenzimitazole (B z-chlorocomercabutobenzimidazole (4)!-methoxyλ-mercabutobenzimitazole (7) λ-mercaptonaphthoimidazole ( 1) 2-Mercato!-sulfobenzimidazole (ri) /-(λ-hydroxy7ethyl)-comelcabutobenzimidazole (io) j-caproamide comelcabutobenzimidazole (10j-(J-ethylhexanoyl) Amino)-2-mercaptobenzimidazole 6 Mercaptothiasia/-ol derivative (1) j-71 tilthio-comelkabuto-7゜3
, μm thiadiazole (λ)! -ethylthiokomercap)-/.

3. Hiro-thiadiazole (j)? -(2-dimethylaminoethylthio)-comercapto/,! , #-thiadiazole (4(,l Ji-(J-carboxypropylthio)
-λ-Mercapto/,! , 41-thiadiazole (j) J-phenoxycarbonylmethylthio-yo-mercatto/,! , 4A-Thiadiazole (1) Komelkabutobe/Zuthiazole (Co) j-Nitro Komelkabutobe/Zuthiazole (J)! -Carboki7-J-Mercaptobe/Zuteazole (1)j-Nurhokomerkabutobenzthiazole (1)! -Mercaptobenzoxazole (2)! -Nitro-comercabutobenzoxazole (j)! -Carboxycomercabutobenzoxazole (≠)j-Sulfocomercabutobenzthiazole (1) (λ) (3) (Reference) (j) (6) (7) CI) (Ri)! , 6-dimethylbenzotriazole! -Bunalbenzotriazole! -Methylbenzotriazole! -Chlorobenzotriazole! -70 mobennotriazole j, 6-chlorobenzotriazole≠, g-dichlorobenzotriazole! - Nitrobenzotriazole Reference - Nitro-6-chloropensotriazole <1o) a, s, t-trichlorobenzotriazole (ll) j-carboxine benzotriazole (/co)
! -Sulfobenztriazole %a salt (/j) j
-Methoxycarbonylbenzotriazole! -Aminobenzotriazole j-butoki 7bentriazole j-ureidobenztriazolebenzotriazole! -phenoki 7 carbonyl nizotriazole (/ri) Yo-(-, j-dichloropropyloki 7 carbonyl bentrianol 10 benzimidazole derivative (/su(muri (16) (/7) (/1) (j) z-methylbenzimidazole (6) 41-chlorobenzimidazole (7) 'r'
V Methylbenzimidazole (t) yo-nitroco-
(Trifluoromethyl-benzimidazole (1) (-2) (3) (μ) (ri (6) (7) (J') (ri) !-12loindazole 6-nitroindazole j-aminoindazole 6 -AminoindazoleIndazole 3-Ditroindazole!-Nitroj-chloroindazole3-Chloro-j-nitroindazole3-Calfoxyyom=troindazole (/) (Co) (3) CI-) Benzimidazole! -Chlorobenzimidazole - Nitrobenzimidazole j-lobetylbenzimidazole (2) j-phenyltetrazole (J) t-(j-carboxyphenyl)-tetrazole/3 Tetrazaindene rust conductor (1) ≠-Hydroxy-6-methyl-yoichinitro/,
3. Ja, 7-thitraazaindene(co)4I-mercapto-6-methyl-yo-nitro/
, J. ) can be mentioned.

- Soft type (II, 1 (+) <-k) (÷3- L 1+ L 2+, LA type "P (-113 (appetizer) < +) mark [-L (V-4- → T
ime-)-cross the bonding position @ of hem n.

Ll represents a group that can be further separated from Time during the development process. L2 is a divalent linking group and k is 01
fC is an integer of l. A is a group that substantially exhibits a fogging effect on the halogenated recording emulsion in the developer.

Preferred examples of Ll include a monocyclic oxy group, a heterocyclic oxy group, an arylthio group, an alkylthio group, a peterocyclic thio group, and an azolyl group41! You can make money.

A specific example of Ll is shown below.

Examples of (匍(chiJ(4)-b-(CH2)2-(→(viscosity) (supper)(chi)(÷)-s-(aH2)4-L2 are alkylene/, alkenylene, Arylene, covalent heterocyclic group, -Q--8-imino, -00--〇〇NH
-H to NHeO, -NHC:0O- -8ONH--CO--8O2--8O--NH302
A combination of these can be mentioned.

Preferred specific examples of A include, for example, reducing groups (e.g. hydrazi/, hydrazide, hydrazone, hydroxylamine, polyamine, enamine, hydroquino/, catechol, ρ-amino/7:r-/-, 0-amine). A group having a partial structure of phenol, aldehyde, or acetylene) or a group capable of forming a developable silver sulfide nucleus by acting on silver oxide during development (e.g., thiourea, thioamide, thiocarbamate, dithiocarbamate, thiocarbamate, etc.) Examples include groups having partial structures such as hydantoin and rhodanine) and quaternary salts (for example, pyridinium salts).

Of the groups represented by t, the groups for %KN are of the following general formula (I
V, a group represented by l.

-Soft formula (IV) In the formula, both A□ and A2 are hydrogen atoms, or 10,000 is a hydrogen atom, and the other is a nurphinic acid residue, a group, a sulfonyl group,
Represents a nulphoxy group and an oxy7 group. ) represents an iminomethylef group. Loo represents an arylene group or a divalent heterocyclic group.

14 reads 0 and l.

Specific examples of PLUG represented by general formula (III) are listed below. (+o+)(+>h -L+Vsu-f T i
The bonding position to m e n is determined.

alkenyl group, aryl group, alkoxy group, or aryloxy group, n is an integer of 6 and/or 6;

Represents Nwo. Roo represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an azo group, or a heterocyclic group. G is carbonyl (轡((trans)(@0(shun(→(state)) Examples of cases where PUG is a fogging agent include, in addition to the above, the coupler described in Japanese Patent Application Laid-Open No. 2003-120101/No. 701≠Q. The part of the leaving group that is released is more.

For example, when PUG is a silver halide solvent, %
Kaisho 60-/l,! , 0≠λ, U.S. Patent No. V, 003
, Evening No. 10, US] is also Patent No. V, 37g.

Menion compounds described in C2≠ etc., JP-A-Shoj
7-=02. There are mercaptoazoles or 1-guazolthiones having an amino group as a substituent, which are described in Japanese Patent Application Laid-open No. 61-30/36, etc. can be mentioned. Other PL) OK, please refer to 60-7/,
7AJ', US Pat. No. 1, No. 6, etc. can be referred to.

An example of a case where PUG is used as a whitening accelerator is disclosed in Japanese Patent Application Laid-open No. 6
- Ko0/, Kohiro 7 and % Gansho 62-24tt, ij
Compounds described in No. t etc. can be mentioned.

Examples of PUG i units of developer and auxiliary developer are:
For example, hydroquinones, catechols, aminophenols, p-phinidine diamines, pyrazolidones,
Examples include anucorbic acid.

In addition, PLIG is a photographic reagent that further has a redox function that releases the above photographic reagent with the development reaction of silver halide, such as color 0 for color diffusion transfer sensitive materials.
Ruiuni DIR and Idolokino group 7 golds can also be mentioned as photographic reagents for M.

Other PUGs may be listed as % Kaisho A/-230/3j, US %#+No. 1, -2gl, Ri6ko+5, etc.

The PLJG of the present invention can be used in conjunction with an antifoggant to exhibit all the effects of the compound of the present invention! #
The atomic groups necessary to form a six-membered ring include, for example, an alkylene group, an alkenylene group, an arylene group, and the like. Preferred examples of X include the following.

-CHOH--CH2(,:H2CH22) In silver halide photographic N& source materials, almost all the silver in the sensitive material is removed by the development process and subsequent processes (fixing, RI bleach-fixing, etc.) such as phosphorous ions, thiols, etc. It is dissolved by the silver solvent containing sulfur ions and flows into the processing solution.

At this time, there was a large amount of fii! (1) Ions or soluble silver complexes are generated.

At this time, if a compound represented by general formula (1) exists in the sensitive material, a reaction represented by the following scheme 1 occurs, and P
It is thought to emit UG.

scheme/.

X may further have a substituent group, and as preferred substituents, those listed as R and the substituent groups can be applied.

Below, the reaction of the compound represented by formula (1) during photographic processing will be explained.

20 AgS-X-NH-R” 0 To U Here, the nucleophile is quarrel.

Below is the general formula ( ) Specific details of the compound detected by For example, The present invention is limited by these et al. It's not a thing.

00□8H37 t.

U2 10 /J: /t 7 1.2゜ <n) C1□H23 /r l　ta C2H5 −／ +22 +23 Ko Z λl Kota (n) C: H 9 2j: Kot t H3 Specific synthesis examples of the compounds of the present invention are shown below.

Synthesis example/ (Synthesis of compound t) -A! -B to r-)゛-C/- (1) Synthesis of compound r -e 1-B6/M (0,60m01)f benzene 100id
The solution was dissolved in water and dehydrated under heat reflux at the edge of the blade. Next, go to the place where stirring is refluxing - A1612? (0,10mo
9 drops of Pensef 60 wl solution of 1) were slowly added, and after the addition was completed, the mixture was refluxed for μ hours.

The reaction fik was condensed under reduced pressure (approximately 20 mmHg), and the concentrate was distilled to TFF (IA to F7 °C//mmHg fraction) to form a colorless and transparent electric material with -C.

Of (4t2./mmol) was obtained. Yield: 4-μ%/-
(2j The ashes of compound r-E 1-C4L, 001 (2/, 0m01) and Za-D
3.00f? (20, Ornmol) f methanol JO
After stirring at room temperature for an hour, 4 was further reacted at ≠O''C for an hour. After concentrating the reaction solution, silica gel column chromatography (developing solvent: methanol/chloroform=//3 vol/vol)) n
By manufacturing t-Els, ri01(/1.Jmm
ol) Obtained. Yield Tacora 1-(3) Synthesis of compound wJl I-Ej, 2cof(10, Ommoi), -Fl, 1
09 (10,2 mm 04) and Hiro-dimethylaminoviridi 70. /f (0.1 jmmol) in 20t of acetone
Dissolved in dicyclohexylcarbonimide, stirred and cooled with water. (Ko Q.

A 10xd solution of 0 mmol) in acetone was added dropwise.

After the completion of the addition, the temperature was raised to room temperature, and the mixture was stirred for an additional 758 minutes, and the precipitated solid kF was separated. After concentrating to Pg', silica gel column chromatography (developing solvent: methanol/
Chloroform = / / j (vol /vo
By refining with l) ), it becomes a colorless transparent viscous liquid r
ib, rit (I10rnmol) was obtained. Yield J/% The structure was confirmed by H-NMR spectrum and manufacturer.

Elemental analysis 1i! IC)l N S calculated value 6≠, 13% 7.32% /g, 1% 1.
66chi measurement value 6≠, 6j% 7,26% / da, μ6
Attack 6. Ichi Rf value 0.36 Synthesis example-2 (synthesis of compound/compound) 1 Co A
)> Yohi /2 -B, 2.32? (20,0
mmol) i pi, -tanol 30 resistant + 1C bath dissolved,
The mixture was stirred at room temperature for 2 hours. reaction? Because of the concentration, silica gel column chromatography (developing bath medium / /
Shi/ri.

Roholm = / / / (vo] / vo
l)) By is, V/λ-C is μ, rio
f(/za, rmmoff) was obtained. Yield dej%, 2-(2+ Synthesis of compound 12 12-Cu, ri of (/1.Irnrnol), /u-
DJ, rf (co/, jmmol) and μm dimethylaminopyridine 0. Jt (2.46 mmol) was dissolved in acetone and Od, stirred over water-cooled, and Mk dissolved in 301 nt of dicyclohexylcarbodiimide (30,/rnmol) in acetone was added dropwise. After the dropping was completed, the temperature was raised to room temperature and stirred for an additional hour.
After concentrating the F solution, silica gel column chromatography (ih bath mi methanol/chloroform=//ri(v
o 1. 'vol)) By making Ic and treetops υ
i color atq viscous t=i body/”′ to 3.17f(”, 22m
mo7i;! It was. The production yield of 4 tons was confirmed by IH-MR spectroscopy and Manunu by chromatography.

Elemental analysis value CH~S Calculated value 1.0.11% 7. 3% /6,6%
7゜11 measurement value 60.26 attack 7.2% /6.6
2% 7. Kuda whisper Rf value O1Sλ The compound of the present invention is present in a silver halide emulsion layer, in a hydrophilic colloid layer provided above or below the emulsion layer,
It can also be added to both layers of the cloth to achieve all desired purposes.

Conventional methods can be used to introduce additives into the silver halide emulsion layer and/or other hydrophilic colloid layers. That is, a compound that is soluble in water is dissolved in water, and 1 or 1
1. Adding it to gelatin water bath solution will work. Compounds that are insoluble or sparingly soluble in water can be dissolved in a water-miscible solvent and combined with an aqueous gelatin solution, for example, in US Pat.
．． 32 pieces.

The method described in No. 027 and the like is used. Examples include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phonuphat, tricresyl phonuphat, dioctyl butyl phosphate), citric acid esters (such as acetyl phosphate, tributyl acid), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl rawalyl amide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate) etc., or about the boiling point
After dissolving in a CQM solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methylinobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. , dispersed in hydrophilic colloids. The above-mentioned high-boiling point organic solvent and low-boiling point organic solvent may be used together.

The compounds of the present invention may be used alone or in combination of 12 or more. The strength of the compound of the present invention is preferably 9/X10 -/y,io'' mole, preferably 1xio' mole to jX/0 per 7 moles of halogenated compound.
-2 mol, and an appropriate value can be selected depending on the properties of the silver halide emulsion to be combined.

The light-sensitive material of the present invention can be used, for example, as a coupler-type color photographic light-sensitive material. Examples of color photosensitive materials include color negative film for photography (general use, professional use, movie use, etc.), color reversal film, color photographic paper, color reversal photographic paper, cinema positive, and the like.

The compounds of the present invention can be found in, for example, "The Theory of the Photographic Process, Chapter 7-2, Principles and Chemistry of Color Photography ■, Silver Dye Bleach Process, 1st Hong Kong Edition" (T.A. James, Macmillan, New York) (The i'heory of th
e PhotographicProcess, C
hapter/2, l'rinciplesand
Chemltry of Co1or Ph
oto-graphy lv, 5ilver Dy
e BJeachProcess, 4t the e
d, T, H, Jamesed, Macrrx an, ew York), /ri 77, 363
It is also possible to use a silver dye bleaching method as described in -366 Negative.

The present invention can also be used in black and white g-light materials. Examples of black-and-white photosensitive materials include X-ray film for direct use, polar bear film for general photography, lithium film, and scanner film.

When the present invention is applied to color diffusion transfer photography, the peeling (Beer/<-t) type or the
jl, No. 4AIr-JJ6F7, Japanese Patent Publication No. 1973-1
No. 3040 and British Patent/, 330,! Integrated type as described in No. 2μ, JP-A-7-//31IL! It is possible to adopt a structure of a film unit that does not require peeling, as described in No.

1. This invention is covered by US Patent No. 1! 00, 1.26 issue, % Kaisho 60-/3.3114 issue, same! Tar 2114
It can also be applied to heat-developable photosensitive materials that are not described in No. t4tJ, %fi No. 6O-7Y7C#, etc.

Silver rognide that can be used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. It may be n. The halogen composition within the particles may be uniform, or may have a multiple structure with different compositions on the surface and inside [% Kaisho! 7-/Bar No. 32, same! l
-101! No. 33, same! Tar≠t7! ! No., r5JJter! No. 237, U.S. Pat. No. 33,0 Dar and European Patent No. In addition, tabular grains with a grain thickness of 0.1 μm or less, a diameter of at least 0.6 μm, and an average aspect ratio of 5 or more (U.S. Patent No. 411
No. 17.310, uJ, t, 41 Tata and OLS No. 3,2/.

, 6, 6A/etc.), or monodisperse emulsions with a nearly uniform particle size distribution (% Kaisho! 7-/71λ3!, 5r-
yoorat, J-1'-/4 #29, International Publication r37o23Jrhi, European Patent No. 6, 4 (/J
Silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions, etc. may also be used in combination. The gradation can also be adjusted by mixing two or more types of monodispersed emulsions with different grain sizes.

The grain size of the silver halide used in the present invention preferably has an average grain size of o, ooi μm to io μm;
A value of 0.00/μm to Jpm is more preferable. These silver halide emulsions may be prepared by any of the acid method, neutral method, l or ammonia method, and the reaction method of soluble silver salt and soluble halide salt may be one-sided mixing method or simultaneous mixing method. 1, or a combination thereof. The back-mixing method in which particles are formed under an excess of silver ions, and also the pA
The Chondral double jet method, which keeps g constant, can also be used. In addition, in order to accelerate grain growth, the concentration of silver salt and halogen to be added, the amount of addition l, or the acceleration #
You can raise it completely (% Kaisho 1!-/Teiko 3λri issue, I
j, 1tt-/jl/Koda issue, US% fraud No. 3,6!0,
7j No. 7, etc.).

Epitaxially bonded silver halide grains can also be used (%8Sho!6-/6/Co4L, US Pat. No. 09, Hiroshi, btxt).

In the stage of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent.
M-thioethyl derivatives described in /3116 or JP-A-Sho! The sulfur-containing compounds described in No. 3-/≠4A3/R can be used.

In the particle form i''tfc, cadmium salt, zinc salt, lead salt, thallium salt, etc. may coexist during the physical ripening process.

For the purpose of improving high-light failure and low-light failure, water-soluble iridium salts such as iridium chloride (In, IV) and ammonium hexachloroiridate, and water-soluble rhodium salts such as rhodium chloride can be used. 1. The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and therefore the Tardel water washing method or the precipitation method can be applied.

Haloke/silver oxide emulsions may be used unripely, but they are usually chemically sensitized before use. Known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, etc. for conventional light-sensitive material raw emulsion kl/L
It depends on whether you use them alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing cyclized compound (% Kaisho! I-/26126, 68'-27j6u)
No.l1).

The silver halide emulsion used in the present invention may be of the hexagonal latent image type, in which a latent image is formed on the surface of the grains, or may be of the internal latent image type, in which latent images are formed inside the grains. It is also possible to use a direct reversal emulsion that combines an internal latent image type emulsion and a nucleating agent. An internal latent image emulsion suitable for this purpose contains 1% of the total amount of rice.

2jO issue, 3.76/, 276, Monokoaki! r-
It is described in No. srJ da and JP-A No. 7-364μ/.

The inventive dyes may be spectrally sensitized by other dyes. The pigments used include cyanine pigments, merocyania pigments, complex cyanine pigments, and ? Included are merocyanic dyes, holopolaric dyes, hemicyanian dyes, steryl dyes, and hemioxonol dyes. Particularly suitable dyes for M are cyanine dyes, merocyania dyes, and dyes belonging to the compound merocyania chromophore. For the pigments of t'L et al., any of the nuclei commonly used in cyania pigments can be used as the basic heterocyclic nucleus. That is, pylori/nucleus, oxazoline nucleus, thiazolidine, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine/nucleus, etc.; nucleus in which alicyclic hydrocarbon hydrogen rings of these nuclei are fused; and nuclei in which aromatic hydrocarbon ring is fused to these nuclei, i.e. chi , i/dreni/nucleus, be/zui/dreni/nucleus, inodole nucleus, be/dioxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, be/zoselenazole nucleus, pe/zimidazole nucleus, quinori/nucleus etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dye or (I) merocyanine dye has ketomethylene/WI as the nucleus to form pyrazoli/-!-
O/nucleus, thiohydantoin nucleus, λ-thioxasilicia J, 41! J to 6 negative heterocyclic nuclei such as -geo/nuclear, thiazolidi/-2, dagio/machine, rhodani heptad, thiobarbyl acid radical, etc. can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are particularly used for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible 5t and exhibits supersensitization.

The surfactant may be added alone or in combination to the photographic emulsion used in the present invention.

Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, improvement of sensitization properties, antistatic properties, and antiadhesion. These surfactants include natural surfactants such as Saboni, alkylene oxide-based, glycerin-based, glycidol-based, etc.) niobium/surfactants, higher alkylamides class 7, primary ammonium salts, viridi/others. heterocycles, cationic/surfactants such as phosphonium or sulfoniums, anionic/surfactants containing acidic groups such as carbonic acid, sulfonate groups, phosphoric acid, sulfuric ester groups, phosphoric ester groups, amino acids, It can be divided into ampholytic surfactants such as aminosulfo/rItLs, sulfuric acid or phosphoric acid esters of amino alcohols, etc.It is used as an antistatic agent. *It is preferable to use a fluorine-containing surfactant. .

The photographic emulsion used in the present invention contains numerous compounds for the purpose of preventing fog during sensitivity, material manufacturing processes, storage, or photographic processing, or for stabilizing overall photographic performance. You can do it. i.e. azoles, such as habe/notiasorium salts, nitroimidazoles, nitrobe/zimitazoles, chlorobe/zimitano.”
IJ Azoles, Be/Citriazoles, Nitrobennodriazole mercaptothiazoles (%/-phenyl-!-mercaptotetrazole)
mercaptopyrimine/class; mercaptopyrimine/
Class i Thioketo compounds such as oxanolyl/thio/;
, Ja, 7-chitraazai/de/class], Ba/taazai/
Addition of many compounds known as antifoggants or stabilizers such as be/ze/thionulfo/acid, be/ze/sulfo/rRamide, etc. be able to.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, thioether compounds, thiomorpholides, quaternary a/monyl 9
It may also include diam salt compounds, urethane/derivatives, urea derivatives, imidazole visiters, 3-pyrazolidoes, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or bath-soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (methane acrylate, alkoxyalkyl (methane acrylate, azilonitrile, olefin/, styrene/, etc.) alone or in combination, or a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid/#R, etc. A polymer as a monomer component can be used.

Binders that can be used in the emulsion layer and auxiliary I#I (for example, storage layer, intermediate Ni) of the light-sensitive material of the present invention include:
Hydrophilic colloids are preferred, particularly gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin, casei, etc.; cellulose derivatives such as hydrophone ether cellulose, carboxydimethyl cellulose, cellulose sulfate esters, alkyl/acid soda, Sugar derivatives such as starch derivatives; single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, polyhevinyl biloride/polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. A wide variety of synthetic hydrophilic polymeric materials can be used. In addition, lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, etc. can be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer and other water-absorbing colloid layers.

For example, chromium salts (chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), hemethylolated derivatives (
dimethylol urea, methylol dimethyl hydride/toy/, etc.), dioxa/enzyme conductors (J, J-dihydroxydioxa 7, etc.), active vinyl compounds (/, !, !-triacryloyl-hexahydro-8-) riazi/, /, J-vinylsulfonyl-2-propatur, etc.), active halogs/compounds (2,≠-dichloro-6-hydroxy-S-triasif, etc.), mucochloric acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. t alone 1fc can be used in combination.

Akira Motoba's silver halide photographic materials contain many other weighting agents. For example, brighteners, dyes, desensitizers, coating aids, antistatic agents, plasticizers, numbing agents, matting agents, development accelerators, mordants, ultraviolet absorbers, antifading agents, antifogging agents, etc.

Regarding the A and VP agents of Kokura, specifically Lipuchi Daynu Closure (RESEA 几CHL) ISCLO8
URE) No. 776, pp. 12-3 (RD-/76'4
A, 3) (Llec, /27g, etc.) can be used.

The present invention can be applied to various halogenated photosensitive TL sensitizers. Examples are given below - For example, the compounds of the invention contain at least 60% silver chloride.
Wait for silver chlorobromide emulsion or iodine bromide emulsion containing 0-J-% of iodized bride (milk axe may be monodisperse), and polyalkylene/oxides. Contains A
It is effective in improving the quality of halogen/kamei photosensitive materials for plate making, and it is possible to improve the breakage of the legs without deteriorating the quality of halftone dots.

In these cases, the compound of the invention @ preferably contains v1×10 −7 mol P−/×l0−1 mol per mole of silver halide,
It is used in the range of %I/C/ji10'A-/X10'' moles.

Furthermore, the polyalkylene/oxide compound used here may be added with either a silver halide photographic light-sensitive material, a developer, or both a developer of silver halide photographic II and the original material.

The polyalkylene/oxide compound is an alkyle/oxide having a carbon number of 0 to 1, such as ethyle/oxide, propylea/, 2-oxide, butyle/-/, 2-oxide, etc., preferably at least 10 JI of ethele/oxide.
A condensation product of a polyalkylene oxide consisting of L position and a compound having at least/an active hydrogen atom such as water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine, power/toll derivative, etc. These include block copolymers of polyalkylene oxide, etc.

That is, examples of polyalkylene oxide compounds include polyalkylene/glycols, polyalkylene/glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol (alkylaryl) esters, polyalkylene glycol esters, and polyalkylene/glycols. Fatty acid amides, polyalkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene/glycol craft polymers, and the like can be used.

As for the molecular weight, those having a molecular weight of soo or 1 oooo are preferably used.

These polyalkylene/oxides are great! tJ may be used only in 1st class, or in combination with 21!1 or more.

When the above polyalkylene/oxide compound is added to a halogenated photographic light-sensitive material, 1 mole of halogenated chloride is added! x10 range, preferably 1x
io? It can be added to the photosensitive material in a range of 1 to 1/l. 1. When the above-mentioned polyalkylene/oxide compound is added to the developer, 0.0. /f
It can be added to the visual liquid in a range of 1 to ioy.

Also, the unexploded BA is US Patent≠, Coco≠, Hiro 0/No. 4
<, /+6Jr, 5'77 issue, same 4 (, 21/, /A reference same da, 31/, 71/ issue, same worry, ko7ko, 606
Effects of hydrazi/derivatives as described in No. 12, No. 117, No. 3, No. 73, No. 73, No. 27, No. 6/μ, No. 1, -62, Tata No., etc. More stable current i
11. It is effective in improving the black spots of photographic materials having a monodisperse silver halide emulsion layer that can form ultra-high contrast dark images in liquid form. This black part has a non-image area (
For example, black paper, which refers to nubot-like black spots that occur between halftone dots), is caused by the developer becoming fatigued over a long period of time and containing less sulfite ions, which are generally used as a preservative. It occurs noticeably when the pH becomes high,
This will damage the quality of the restoration. In the above, the stable developing solution contains at least o, is mol/1 M of sulfite ion gold as a preservative, and the developing solution has a pH of io, o~/-03.
Refers to liquid. Since this developing solution may contain a large amount of preservative, it is common to use normal Lith development W1. It is more stable and solid than the sulfite ion all-pole (which can contain only a small amount), and has a relatively low pH. Developer solution of the forming system (pH=/2
．． It is less susceptible to air oxidation and more stable than 1). this*
In this case, the compound of general formula (I) of the present invention is i'LJ
G preferably has a development inhibitor, preferably per mole of silver halide/X10 to io
It is required to be in a molar range, especially in the range of /XIQ-5 to /xlO molar.

In the present invention, when the hydrazine derivative is contained in the photosensitive material 1, it is preferable to add the content to the silver halide milk layer, but other non-photosensitive hydrophilic It may be contained in a sexual colloid layer (for example, in a protective layer, an intermediate layer, a filter layer, and an anti-haline layer). Specifically f
If the compound is water-bathable, it can be used as a water bath solution, or for poorly water-soluble compounds, it can be used as a hydrophilic colloid solution, such as a solution of alcohols, ethers, ketones, etc. All you have to do is pay. When adding an additive to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to the coating stage, but it is preferably added between the end of chemical ripening and before coating. In particular, it is best to apply it to the skin in a coating solution prepared for application.

The content of these hydrazine derivatives depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, the type of antifogging compound, etc. It is desirable to select the optimal amount depending on the amount, and those skilled in the art are familiar with the testing methods for this selection. Usually, it is preferably used in a range of 10 mol to /X10 mol, particularly lo-5 to ≠xlO mol, per mol of silver halide.

The present invention provides at least λ different spectra/L on a support.
It can be applied to winter multicolor photographic materials having [[], mainly for the purpose of preventing fogging, adjusting the level, reducing color re-dusting, and increasing sensitivity. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected depending on the 8-tatami mat.

The preferred order of increase is red sensitivity, green sensitivity, and red sensitivity from the support side.
Blue sensitivity 17' (blue sensitivity, red sensitivity, and green sensitivity are output from the support side. Also, each of the above emulsion layers may be composed of two or more emulsion layers with different M degrees, and four-sensitivity A non-photosensitive columnar layer may be present between one or more emulsion layers.

Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but a different combination may be used depending on the case. can.

There are no particular restrictions on the couplers that can be used, and hunger is a magenta coupler! - Pyrazolo/Coupler Biranlotriazole cuffler Pyrazolobenzimidazole coupler There are cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilide, piparoylacetanilides), etc. Couplers include naphthol couplers, hypophenol couplers, and the like. Further, as shea/couplers, there are also ureidocyan couplers such as diacylaminophenol cutler. These couplers are non-diffusible and have a hydrophobic group called a 2-unit group in their molecules.
It is preferable to use a polymerized material. The coupler may be μ-equivalent or λ-equivalent to iron ions. Also, colored couplers that have a color correction effect or couplers that release a development inhibitor L or development accelerator during development (so-called LIIR cyan coupler L) AR
coupler).

In addition to DIR couplers, there are also colorless DIR couplers in which the coupling reaction product is colorless and releases a development inhibitor.
It may also include a coupling agent.

In addition to the LAIR coupler, the light-sensitive material may contain a compound that releases a '#L image inhibitor upon development.

It is of course possible to use two or more of the above couplers in the same layer in order to satisfy the characteristics required of a photosensitive material, and it is also possible to use the same coupler in different co-layers. do not have.

The compound of the present invention can be used in combination with a coupler, added to the same emulsion layer as the coupler, or added as an independent emulsified dispersion to a photographic auxiliary layer such as an interlayer.

The ghost of the present invention is applied to couplers in each photosensitive layer, such as the yellow coupler in the blue sensitive layer, the mi/takagura ruru in the green M layer, or the 7 uncoupler in the plus sensitive layer in a color photosensitive material. t'Lf:rto.

/-jO mol%, preferably 0.3 to /j mol%. In addition, /x10-S mol to l'X10-2 mol, %/X
/Q'Morun! Preferably, X10" moles are used.

In photosensitive materials made using the invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer,
They may also be mordanted with a cationic polymer or the like.

The M&base material produced using the present invention may contain hydroquino/derivatives, aminophenol derivatives, gallic acid derivatives, ascorbyl/eIk derivatives, etc. as color antifoggants.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, tabe/citriazole compounds substituted with an aryl group (such as those described in U.S. Pat.
Hiro-thiazolides/compounds (e.g. U.S. Patent 3.Co/M'
, 7ritei no., Mukaij, 362.

611 (for example, those described in %Kaisho Jlb-2711I-), etc. may be used. These ultraviolet absorbers may be mordanted in a specific layer.

A photosensitive material made using non-explosion BA' may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of preventing/preventing run-off or other purposes. Such dyes include oquinol dye, hemioquinol dye, styryl aggregate, merocyanine dye 1,
Included are cyanine dyes and chlorine #+. Among them, oquinol dyes; hemioxonol dyes and merocyanine dyes are suitable for M.

When carrying out the present invention, the following known antifading agents may be used in combination, and two or more color image stabilizers used in the present invention may be used alone or in combination. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oquinphenol derivatives, and bisphenols.

For photographic processing of uninvented light-sensitive materials, known methods [
can also be used, and known treatment liquids can be used. Also, the processing temperature is usually chosen between /1r0C and to'c, but lower t
A#1fcttlzo ``The temperature may exceed Cp.Depending on the purpose, either a development process that forms a silver image (#1 Hakuyo Seikori) or a color photographic process that consists of a development process that forms a dye image. Also, heat development may be applied.

The black-and-white liquid contains dihydroxybenzenes (for example, hydroquino/) and 3-pyrazolidones (for example, fP!
Known developing agents such as -phenyl-3-pyrazoli)''/) and 7-minophenol (e.g. /fiN-methyl-p-aminophenol) can be used alone or in combination.

Color dust image axes generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenyl/diamines (e.g., amino-, N-diethylaniline, 3-methyl-
μmamino-N,N-diethylanili/,≠-amino-N-ethyl-β-hydroquinethylaniline, 3-
Menalu Hiro-amino-ethyl-β-hydroquine-ethylaniline, 3-methyl-Hiro-amino-ethyl-N-β-methanesulfamide ethylaniline, Hiro-amino-3-methyl-N-ethyl -N-β-methoxyetheraniline, etc.) may be used.

In addition, F. A. Meso/Author "Photographic Brosse/Chemistry" published by Focal Press (/
(1966), page -26~ko, U.S. Patent Co., 7?3.
01j issue, same, 3?2゜36≠ issue, Tokukai Sho! j−6μ
Those described in No. 233 may also be used.

After development, known processes such as fixing, bleaching, stabilization, bleach-fixing, stopping, and stabilization by water washing are performed.Here, washing with water, stabilization, etc. may also be used.

(Implementation flJ) Next, the present invention will be explained based on Example V.

Example 1 Gelate kept at a temperature of 1 t/mole of silver in water
r, ox t o-6molno(NH4)3khC
/Nitsu@catfish water solution and sodium chloride water@liquid in the presence of 6?
After mixing at the same time, in a well-known legend in the industry,
After removal of soluble salts, gerana was added as a stabilizer without chemical ripening.
3.3a, 7-thitraazai/thene was added. This emulsion was a cubic monodisperse emulsion with an average grain size of 0.2 microns.

After adding Compound A, Compound ≠ of the present invention, 24I-, and Comparative Compound as bsc' in the amounts shown in the first coating, polyethyl acrylate latex was added to the emulsion in an amount of 7 JOwt% based on solid content of gelatin. and dura uJ toshimata/, 3-vinylsulfonyl-copro/ζnor tl
-Additionally 3.1? on a polyester support. A of /m
It was especially applied to become a lid. Gelatin is i, try7m2
I failed. Add gelate as a layer on top of this:／／、
3 W/m ON& was applied.

Konosu/Puru ni Dainippon Scree 7t'J4L Akinoshiro Puri/
(For M machine desensitizer Vinyl/Blue A, the following developer solution was used: The film was fixed, washed with water, and dried for 30 seconds.

Development associate hydroquino/≠3.09 hemethyl-p-aξnophenol ν sulfate. ,,,l sword (sodium oxide / 1,09 potassium hydroxide! 3.01! - Sulfosalicyl #
k Reference J, Ofboric acid
Ko! , 0? Potassium sulfite /
10.0? Ethylenediamine/disodium tetraacetic acid salt /, Of potassium bromide 6.02! -Meterbe/Sotriazole 0.62n-butyl-jetanol-ami7/j, Of 7JI] of water/l(
+)H=//,,! ,) Photographic properties (-Evaluated as follows, and the results obtained are shown in the first column as total photographic properties-/.

3 times to O relative sensitivity Density in 0C3o second development /, j
The value of sample/ was set to 100 as the relative value of the reciprocal of the exposure amount giving .

0 black spots are evaluated as J grade by microscopic observation [
jJ is the best < r/j or i & ◆ represents poor quality. "
! '' or ``Hiroshi'' can be used, ``3'' is poor but barely usable, and ``-'' or ``/'' is impractical. Items between “3” and “≠” are evaluated as “3.j”, and “Hiro” and “≠” are evaluated as “3.j”.
! ” was evaluated as “4t,j”.

The evaluation of 0 black spots is the result of development at 3roC≠θ seconds.

0 gradation (γ): point of density 0.3 and 3.0 on the characteristic curve
It is determined by the slope of the @ line connecting the points.

The higher the value, the stronger the contrast. represents.

l, each untreated sample! 0°C relative humidity 7! After being left for 3 days under the conditions described above, the photographic property was determined in the same manner and was shown in the first photo as photographic property -2.

Compound A: Comparative compound a: Comparative compound b: H (U.S. Patent No. 3 ! 7j.

Comparative Compound C: As is clear from No. 1, samples (1) and (-2) that do not use the uninvented compound exhibit excellent sensitivity and gradation, but black Bad drop characteristics.

On the other hand, the IQ of the comparative sample based on Comparative Compound A had good black spot characteristics, but the sensitivity was low and the tone became soft. On the other hand, in the comparative samples // and /co, the comparative compound was extremely unstable, and the sensitivity and gradation decreased significantly, especially in the forced deterioration test (
Resurrection characteristics - 1) are remarkable.

On the other hand, samples 3 to 1 to which the compound represented by the general formula (1) of the present invention was added showed excellent sensitivity and gradation, as well as excellent black spot characteristics. Furthermore, Samples 3 to t exhibited excellent sensitivity and gradation even when subjected to a forced deterioration test.

(Effects of the Invention) According to the present invention, good sensitivity can be achieved without deteriorating black spot characteristics. A photographic image showing i could be obtained.

Furthermore, the present invention maintains a good g# even when subjected to forced deterioration tests.
, floor! l showed.

Claims (3)

[Claims] (1) A silver halide photographic material having at least one silver halide emulsion layer on a support, characterized in that it contains a compound represented by the following general formula (I): . General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 and R^2 are hydrogen atoms, aliphatic groups,
Represents an aromatic group or a heterocyclic group. However, R^1 and R^2 may be combined with each other to form a ring. L represents a divalent linking group. V is carbonyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, sulfonyl group, sulfoxy group, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_0 represents an alkoxy group or an aryloxy group), iminomethylene group, and thiocarbonyl group. Time represents a divalent linking group. m represents 0 or 1. n represents 0 or 1. X represents an atomic group necessary to form a 5-membered ring or a 6-membered ring by linking with ▲There are mathematical formulas, chemical formulas, tables, etc.▼. PUG is an antifoggant, a development inhibitor, a development accelerator, a fogging agent, a desilvering accelerator, a desilvering inhibitor, a silver halide solvent,
Developers, auxiliary developers, fixing accelerators, fixing inhibitors, image stabilizers, color toning agents, processing dependency improvers, halftone dot improvers, dye stabilizers, surfactants, hardeners, thinning agents Represents a sensitizer, contrast agent, chelating agent, and DIR-hydroquinone. (2) The ▲mathematical formula, chemical formula, table, etc.▼ produced by the hydrolysis reaction of the compound of general formula (I) causes a nucleophilic addition reaction with a nucleophile to the carbonyl group, followed by an intramolecular nucleophilic reaction. By reaction, ▲mathematical formula, chemical formula,
▼The silver halide photographic material according to claim (1), which is characterized by being cleaved. (3) The silver halide photographic material according to claim (1), wherein PUG in the compound of general formula (I) is an antifoggant or a development inhibitor.