JPH01147536A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the title material having the high sensitivity, the high contrast and the high blackening density by incorporating a hydrazine derivative and a compd. which does not substantially have the max. absorption at a visible region in a silver halide emulsion layer mounted on a supporting body. CONSTITUTION:The inorganic sensitive material comprises at least one layer of the silver halide emulsion layers mounted on the supporting body. The hydrazine derivative and a compd. shown by formula I are incorporated in the emulsion layer and another hydrophilic colloidal layer. In formula I, R1, R2, R3 and R4 are each hydrogen atom, hydroxy or alkoxy group. When the compd. shown by formula I, is 1,4-dihydroxybenzene, groups R1, R2, R3 and R4 are not hydrogen atom at the same time. And, the compd. which does not have substantially the max. absorption at the visible region and is shown by formula II is incorporated in the photographic sensitive material. In formula II, Z<11> and Z<12> are each a benzoxazole, a benzothiazole or a benzoselenazole nucleus, etc., R<11> and R<12> are each alkyl or aralkyl group, and at least one of the groups R<11> and R<12> is an acidic group, X is an electric charge balancing pair ion, (n) is 0 or 1.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a silver halide photographic light-sensitive material used in the field of photoengraving, which allows ultra-high contrast images to be rapidly formed using a highly stable processing solution. negative type).

<Prior Art> It is well known that certain silver halides can be used to form extremely high contrast photographic images, and methods for forming such photographic images are used in the field of photolithography.

For example, silver chlorobromide (at least the silver chloride content is jO
By processing a lithium-type silver halide photosensitive material consisting of %J or more with a hydroquinone developer in which the effective degree of sulfite ion is extremely low (usually 0.1 mol/l or less), image areas and non-image areas can be separated. Methods are known for obtaining clearly defined line or halftone dot images with high contrast and high blackening density. However, with this method, the concentration of sulfite in the developer is low, making the development extremely unstable against air oxidation.Currently, various efforts and innovations have been made to keep the solution activity stable. Met.

For this reason, the development method as described above (Lith development cystyl)
There is a demand for an image forming system that eliminates the instability of image formation caused by the oxidation process, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics. Fl'4', /
A4.7 Gu issue, same reference, /Jt, 277 issue, same reference, coco i, rz7 issue, mukai 4t.

2 Ko Hiro, Hiro O1, same 4! lλμ3.73 No., same≠,
27, tot issue, Dohiro, ii1. yri, bound for 26
Tatakota, same≠, t! As shown in 0.7≠t, a surface latent image type silver halide photographic light-sensitive material to which a specific aclhydrazine compound was added was prepared at pH //, 0-/J, and a sulfite preservative was added at pH 0.7≠t. /! A system has been proposed for forming an ultra-high contrast negative image with r exceeding io by processing with a developer having a mol/1 or more and good storage stability. This new image forming system has the feature that it can also use silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chlorobromide, which has a high silver chloride content. There is.

On the other hand, this new high-contrast negative image forming system provides a remarkable increase in high-contrast contrast and a high maximum density (Dmax), while at the same time eliminating black porosity due to contagious development.
), which is a problem in the photolithography process.

A black spot is a black spot made of minute developed silver that occurs in an unexposed, non-image area.

Black spots occur frequently due to a decrease in sulfite ions, which are generally used as preservatives in developing solutions, and an increase in pH value, and this significantly reduces the commercial value of photolithographic materials. Therefore, although great efforts are being made to improve these black spots, the improvement of black spots often involves the maximum sensitivity K (D
There has been a strong desire for a system that maintains high sensitivity contrast and improves black blemishes while reducing max) and gamma (r).

On the other hand, ultra-high contrast negative forming systems using hydrazine,
Due to the mechanism of the system, hydrazine amplifies even the slightest part of the light and makes it clear and high contrast.
Fog nuclei due to electrons generated by pressure applied from the outside and sublatent image nuclei reinforced by electrons generated due to pressure also have the disadvantage of being easily amplified.

If we look at this as a practical problem with photographic systems, we can see inconvenient areas such as linear fog caused by pressure and sensitization caused by pressure at the bottom of the image, where areas that should not be darkened in the first place are turned black. This will cause the phenomenon. Hereinafter, this phenomenon will be referred to as "pressure property." In this high-contrast negative image forming system using hydrazine, general formula (I)
Some of the compounds represented by JP-A-Shoj! -uO6
2? , 67-/934. Same 74-497! lr, same j
7-l Kota Hiroshi 74. Doyo 7-/Koku 4t33, Dojo j7-
l Kota 11. Same 7-12ri 4A3! , 61-ko 33
73 Da, Mukai T Co. L/μ3, Ko T Co. 43912, Japanese Patent Application Sho Al-iaitra, No. 61-, 24M/47, etc. The compound of general formula (n) is disclosed in Japanese Unexamined Patent Application Publication No. Shoj/
- Kota 117, Tokuhan Showa 6/-rotuo, Tokuhan ti-ix
It is described in U.S. Pat. j Gua for coloring
It is described as a fog suppressant for silver halide photographic materials.

Tokukai Sho quoted above! 6-/ri 74, for structures in which the photosensitive material contains hydroquinone and the compound of the general formula (I) of the present invention in an amount of 0°0 layer mol/Ag mol or more,
Although it is disclosed, there is no mention of a combination with a technique for improving adhesion resistance. On the other hand, unsubstituted hydroquinone and sulfo f! Although hydroquinone having a thickness of 1 m improves pressure resistance, it is stated that its drawback is that it deteriorates adhesive resistance. In the prior known documents, there is no disclosure of any technology or structure that satisfies both the pressure resistance and black spots in the combination of compound (I) and compound (n). In order to achieve the effect of -C) on improving pressure resistance, a technology for improving adhesion resistance has been long awaited.

Problems to be Solved by the Present Invention> The objects of the present invention are to provide a film with few black spots, excellent pressure resistance and adhesion resistance, high sensitivity, and high contrast (r: 10 or more).
The object of the present invention is to provide a silver halide photographic material that can provide a high degree of blackening.

<Means for Solving the Problems> The above object of the present invention is to have at least one silver halide emulsion layer on a support, and in the silver halide emulsion layer or other hydrophilic colloid layer, hydrazine is added. A negative type, characterized in that it contains a visiting conductor and a compound represented by the following general formula (I), and further contains a compound represented by the following general formula (n) that does not substantially have an absorption maximum in the visible range. This could be achieved using silver halide photographic materials.

General formula (I) In the formula, R1% R2, R3 and R4 are each a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a 1-layer atom, a tertiary amino group , carbonamide group, sulfonabad group, alkyl group, aryl group, at least one
0, contains S atoms! represents a membered or t-membered heterocyclic group, formyl group, keto group, sulfonic acid group, carboxylic acid group, alkylsulfonyl group, or arylsulfonyl group. However, in the case of /, Hiro-dihydroxybenzene, %R1, R2
, R3 and R4 do not have hydrogen atoms at the same time.

General formula (I1) z 11 and z12 each represent a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a selenazole nucleus, and a selenazole nucleus. Represents the nonmetallic atomic groups necessary to complete the nucleus, pyridine nucleus, benzimidazole nucleus, or quinoline nucleus.

R11 and R12 each represent an alkyl group or an aralkyl group, at least one of which has an acid group. X
is a charge balance counterion, and n represents O or l.

Next, the constituent elements of the invention will be described in more detail.

First, dihydroxybenzene represented by the general formula (2) and its derivatives will be explained.

Specific examples of these dihydroxybenzene derivatives include, for example, The Merck Index 10th
Many examples are described in U.S. Pat.

4c! No. 3, 3.227. ! T! - issue, JP-A-Sho≠2-
1063.2P issue, same to-irt, pit issue, same ta
-ioysap issue, same! 7-Coco 237, same JP-CoQ Co4LJj, same! r-/7411/ issue, Tokko Akira! 0
-, 2/J41, rt-4/Lorlr, jter 374t27, British patent 7!21 Dal, 101
No. 6201, West German Patent Publication λ, 14I5', No. 7r,
Chemical, Abstruck magazine! Volume 4Jj7h, JP-A-1
7-77 Rihiro 2, etc.

Three of these dihydroxybenzenes 913 are shown below, but the present invention is not limited thereto.

1-/l-7■-ノ
l -a -j H ■-buH H -r H ■-tati 1-1/ 1-/koH 1-/ J H O)-i 1-/j 1-77 1-
Ko101(0H 1-/rl-,2ko01(0H 1-/ta 1-230H
0H I-coo
l-co-san OH01-1 ■-coz I-co2H ■-241-10 1-core ■-J/!
-ko r l-Jko1-J z
l-jta ll
-10 1-741-4I0 1-1
1/ l-reference l-4A
Ko I-da t-4A Hiro
1-441COOC2H
s coNi1c2t15
Next, the compound represented by the general formula (If) which has substantially no absorption maximum in the visible region will be explained.

In general formula (II), the heterocycle formed by Z and z12 is preferably a benzoxazole nucleus, a benzothiazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a thiazole nucleus, or an oxazole nucleus, and more preferably a benzoxazole nucleus. The nucleus is a benzothiazole nucleus, mainly a naphthoxazole nucleus, and most preferably a benzoxazole nucleus or a naphthoxazole nucleus. In the general formula (■), the heterocycle formed by Z or z 12 may be substituted with at least one group, and the @ sandwiching group is a halogen atom (e.g. fluorine, chlorine, bromine, iodine). ), nitro group, alkyl group (preferably one having a carbon number of 1-1, such as methyl group, ethyl group, trifluoromethyl group, benzyl group, 7enethyl group), aryl group (e.g. phenyl group), alkoxy group (
Preferably, those having 1 to 1 carbon atoms (e.g., ethoxy, ethoxy, propoxy, butoxy), carboxyl, alkoxycarbonyl groups (preferably 2 to 1 carbon atoms)
Examples include ethoxy 7 carbonyl group), hydroxy 7 group, and quano group.

Regarding zll and z12 in general formula (II), examples of the benzothiazole nucleus include benzothiazole,! -Chlorobenzothiazole,! -Nido abenzothiazole,!
-Methylbenzothiazole, -bromobenzothiazole,! -Iodobenzothiazole! -Phenylbenzothiazole,! -methoxybenzothiazole, t-methoxybenzothiazole,! -Carboxybenzothiazole,! -ethoxycarbonylbenzothiazole, j-fluorobenzothiazole, j-chloro-4-methylbenzothiazole, ')! J fluoromethylbenzothiazole, etc., as the naphthothiazole nucleus, for example,
capto [λ, /-dJ thiazole, naphtho (/, code d
]thiazole, Nando[-13-d]thiazole, j-
Methoxy f7 (/.

λ-d]thiazole,! -Methoxycaft [2゜3-d
] Thiazole, etc., as a benzoselenazole nucleus, for example, benzoselenazole,! -Chlorobenzoselenazole,! -Methokikkubenzo hair nazor,! -Hydroxybenzoselenazole,! Examples of the naphthoselenazole core include naphtho[/, code d] selenazole, natu[co], and the like.

/-dJ selenazole, etc., thiazole nuclei include, for example, thiazole nucleus, goomethylthiazole nucleus, cuphenylthiazole nucleus, 4(, j-dimethylthiazole nucleus, etc.), and thiazoline nuclei, for example, thiazoline nucleus, goomethylthiazole nucleus, etc. Examples include nuclear.

Regarding z 11 and z 12 in general formula (n),
Examples of the nzoxazole nucleus include the benzoxazole nucleus! -Chlorobenzoxazole nucleus,! -Methylbenzoxazole nucleus,! -Glomobenzoxazole nucleus, j-fluorobenzoxa! -r nucleus, r-phenylbenzoxazole nucleus,! -Methoxybenzoxazole nucleus,! -Ethoxybenzoxazole nucleus, t-trifluoromethylbenzoxazole nucleus,! -Hydroxybenzoxazole nucleus,! -Carboquinbenzoxazole [,4-methylbenzoxazole nucleus, 6-chloroabenzoxazole nucleus, t-methoxybenzoxazole nucleus, 6-hydroxy 7penzoxazole nucleus, j,7-dimethylbenzoxazole nucleus, etc.? , Naphthoxazole nucleus includes, for example, f7 oxazole nucleus, nando (/, λ-dJ oxazole nucleus, capto[
2,3-dJ oxazole nucleus,! -Methoxy6ft [/
.

code d] oxazole nucleus, etc.

Furthermore, regarding Z and ZK, examples of the oxazole nucleus include oxazole nucleus, ≠-methyloxazole nucleus, cuphenyloxazole nucleus, goumethoxyoxazole nucleus,
the law of nature,! Examples of the pyridine nucleus include -dimethyloxay-iv nucleus, z-phenyloxazole nucleus, and methoxyoxazole nucleus. -Methyl-λ-pyridine nucleus, 3-methyl-μm pyridine nucleus, etc., and as a quinoline nucleus, for example, CoΦ
Norin nucleus, Hiro-quinoline nucleus, 3-methyl-λ-Mikoto Norin nucleus,! -Ethyl-λ-quinoline nucleus, r-fluoro-quinoline nucleus, t-methoxy-quinoline nucleus, t-chloro-hiro-quinoline nucleus,! - Methylated quinoline nucleus, etc. As the benzimidazole nucleus, for example, j e &-cyclo/-ethylbenzimidazole i, a-cycloC1-/-ethyl-j-) IJ
Examples of fluoromethylbenzi include dazole nuclei.

In general formula (n), the alkyl groups represented by R11 and TL12 include unsubstituted and substituted alkyl groups, and at least one of them has an acid group such as a sulfo group or a carboxyl group. As the alkyl group substituted with 1, the number of carbon atoms is preferably /l or less, particularly r or less, such as methyl group, ethyl group, n-propyl group, n-gutyl group, n-hexyl group, n-octadecyl group. etc. Further, the substituted alkyl group is preferably one in which the number of carbon atoms in the alkyl moiety is t or less, particularly preferably one in which the number of carbon atoms is less than or equal to Hiroshi. For example, an alkyl group substituted with a sulfo group (sulfo group may be bonded via an alkoxy group, aryl group, etc. For example, haco-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, l-sulfobutyl group, λ-(3-sulfopropoquine)ethyl group, Alkyl groups substituted with J carboxy groups such as λ-[co(3-sulfopropoxy)ethoxy]ethyl, nohehydroxy-3-sulfopropyl, p-sulfophenethyl, p-sulfophenylpropyl may be bonded via an alkoxy group, an aryl group, etc.For example, a carboxymethyl group, a cocarboxyethyl group, a 3-carboxypropyl group, a μ-carboxybutyl group, etc.), a hydroxyalkyl group (for example, a cocarboxyethyl group, a hydroxyethyl group, 3-hydroxypropyl group, etc.), acrooxyalkyl group (e.g., coacetoquinethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (e.g., comethoxy7ethyl group, 3-methoxypropyl group) , etc.], alkoxycarbonylalkyl groups (e.g., comethoxylponylethyl group, 3-methoxycarbonylpropyl group, ≠-ethoxycarbonylgutyl group, etc.), vinyl group-substituted alkyl groups (e.g., allyl group), cyanoalkyl groups (e.g. cocyanoethyl group, etc.), carbamoyl alkyl group (e.g. cocarbamoylethyl group), aryloxyalkyl group (e.g. cophenoxyethyl group, 3-phenoxypropyl group, etc.), aralkyl group (e.g. cophenethyl group, 3-phenoxypropyl group, etc.)
phenylpropyl group), or aryloxyalkyl group (for example, cophenoxyethyl group, 3-phenoxypropyl group), and the like.

The charge balance counter ion n, etersulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion, etc. In this case, n
is l.

charge balance counter ion
1. When containing a free group, the salt can be in the form of a betaine, in which case no counterion is required and n is O. When R11 and R12 have anionic substituents such as two sulfoalkyl groups, X is a cationic counterion, such as an alkali metal ion (sodium ion, potassium ion, etc.) or an ammonium ion. Examples include salts (Trief/l/ammonium, etc.).

Here, a compound that "substantially does not have an absorption maximum in the visible light region" means a compound that has a color tone that is below a level that does not cause any practical problems in residual color on photographic light-sensitive materials. It is a compound whose residual color is below a level that poses no practical problem.

Preferably, the above compound has an absorption maximum of μ60 nm or less in methanol, more preferably 4'jOnm or less.

Examples of compounds represented by general formula (II) are shown below. However, the present invention is not limited to the following compounds.

11-/ ■-ko1-J ■-≠ [-j -j -r ■-ta■-lko[1-/J [1-/! [-/j 11-/A ■-77 1-/If 11-/ri■-20 1-, 2/ ■-Coco2H5 O3Na ■-1I C2H5 ■-Co is the hydrazine visiting conductor used in the present invention next. As such, those represented by the following general formula (I) are preferable.

General formula (Ill) s R6 In the formula, A represents an aliphatic group or an aromatic group, and B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxy group. Carbonita group, sulfinamoyl group, alkoxysulfonyl group, thioacyl group, thiocarbamoyl group, sulfaniyl group or heterocyclic group, ROs R1 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or R-substituted or unsubstituted arylsulfonyl group, or substituted or unsubstituted acyl group.

However, 8% R6 and the nitrogen atom to which they are bonded may form a hydrazone partial structure -=08.

Next, the general formula (lit) will be explained in detail.

In the general formula (In), the aliphatic group represented by 8 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
-CoO is a linear, branched or cyclic alkyl group. Here, the branched alkyl ih may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

For example, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group,
Examples include a tetrahydrofuryl group and a morpholino group.

The aromatic group represented by A in general formula (1) is a monocyclic or λ-ring aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

ff1lt is a benzene ring, a naphthalene ring, a pyridine ring,
BiIJ Among the hazine ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc., those containing a benzene ring are preferred.

Particularly preferred as A is an aryl group.

The aryl group or unsaturated heterocyclic group of A may have a substituent. Typical Iti substituents include linear, branched or cyclic alkyl groups (preferably those having 7 carbon atoms), and aralkyl groups (preferably monomers having 1 to 3 carbon atoms in the alkyl moiety). a ring or two rings], an alkoxylic group (preferably one having a carbon number of 1-0), a substituted amino group (preferably a ξ substituted with an alkyl group having 7 to 20 carbon atoms), an acylamino group (preferably carbon number 2-3
Examples include a sulfonamide group (preferably one having 1 to 30 carbon atoms), a ureido group (preferably one having 1 to 30 carbon atoms), and the like.

A of the general formula (Ill) may have a ballast group, such as a coupler, commonly used in immobile photographic additives 7111 incorporated therein. The palaste group is a group having 2 or more carbon atoms and is relatively inert with respect to photographic properties,
For example, AH of the general formula (I1), which may be selected from alkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups, etc., contains a group that enhances adsorption to the silver halide grain surface. It may be a built-in one. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc. 2.
3≠No.7, Tokukai Sho! Tar/ri No. 5.233, same! Turco 00, 23/ No., J Turco 20/, Our No., J Turco 0/, 04<A No., same J Turco 20/, 0μ7 No., same J Turco 0/, 0g No., same! Tar, 2oi, Ohiro issue, Tokugan Shoj tar 3a, 'yrr issue, same 40-//4
! Examples include groups described in No. 1Y, tO-/RI No. 732, and the like.

B is a formyl group, an acyl group (acetyl group,
propionyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, Hirochlorobenzoyl group, bilboyl group, methoxalyl group, methyloxamoyl group, etc.)
, alkylsulfonyl groups (methanesulfonyl group, cochloroethanesulfonyl group, etc.), arylsulfonyl groups (
benzenesulfonyl M, etc.), alkylsulfinyl group (
methanesulfinyl Ml), arylsulfinyl group (
benzenesulfinyl Ml), carbamoyl group (methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (dimethylsulfamoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, methoxyethoxy7carbonyl group, etc.), aryloxycarbonyl group (
phenoxycarbonyl group, etc.), sulfinamoyl group (methylsulfinamoyl group, etc.), alkoxysulfonyl group (
methoxysulfonyl group, ethoxysulfonyl group, etc.),
It represents a thioacyl group (such as a methylthiocarbonyl group), a thiocarbamoyl group (such as a methylthiocarbamoyl group), or a heterocyclic group (such as a pyridine ring).

Particularly preferable B is a formyl group or an acyl group.

B in general formula (l[I) is the partial structure of hydrazone together with R6 and the nitrogen atom to which they are bonded.
7 represents an alkyl group, an aryl group, or a heterocyclic group.

R8 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

R5 and R6 are a hydrogen atom, a furkylsulfonyl group having 2Q or less carbon atoms, and an arylsulfonyl group (preferably!L<$1
a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of the substituent constants of 1 met is -0.2 or more), an acyl group having a carbon number of 0 or less (preferably a benzoyl group, or a Hammett substituent) A benzoyl group substituted so that the sum of the constants is 10,! or more, or a linear, branched, or cyclic aliphatic acyl group (for example, a halogen atom, ether group,
Examples include sulfonamide group, carbonamide group, hydroxyl group, carboxyl group, and sulfonic acid group. ].

Hydrogen atoms are most preferred as R5 and R6.

In addition to the above-mentioned hydrazine conductors used in the present invention, RESEAItC)I DISCLO8U
RETtem Ko3pit<1yri/January issue, P
.

34At) and the literature cited therein, as well as the US%
ff1A, No. 010, 207, Same, Ko6ri, 2λ2, Same≠, No. 276.3tv, Same ψ, No. 271゜7441, Same '1. Irni', lOrgo, samee, ptri, 3≠7
No., same u, zto, t3.

1t7r,? Jr No., British Patent 2,0//, 39/B
1 Japanese Patent Publication No. 60-775'774! You can use those listed in the No.

Next, compounds represented by the general formula (In) are illustrated.

m-i ) ■-2) ■-3) 111-4' ) ■-rit -C5H11 111-4J ■-r ) ■-ta) ch2cH2ch2sH 1■-1o) Ill -/ko] 1-/71 [ 1-/Dan H 1-/71 1[-/41 111-/7) 1ll-/r 1 1-/ri) 111-10) H 1-J/1 ■-here) ■-23) l1l- λμn (J CAN■-
24) 1[-+27) Nl-1N)icHO Ill-λt) 1■-Cotane 1ll-30) Circle-j/) In the present invention, the compound represented by the general formula (!), the compound represented by the general formula (II) The compound and the hydrazine derivative represented by the general formula (°■) are preferably contained in the silver halide emulsion layer, but other non-photosensitive R-colloids (e.g., protective layer, intermediate layer, filter layer, antihalation layer, etc.).

Hydrophilic colloids can be used as a medium if the compound to be used is water-soluble, or as a solution in a water-miscible organic solvent such as alcohols, esters, or ketones if the compound is poorly water-soluble. Just add it to the solution.

When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between the end of chemical ripening and before coating. In particular, it is preferable to add DO to a coating solution prepared for coating.

The groups contained in the compounds of general formulas (I), (U), and (III) of the present invention include the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the layer containing the compound, and the halogenation. It is desirable to select the optimum amount depending on the relationship of the silver emulsion, the type of antifogging compound, etc., and testing methods for selection are well known to those skilled in the art. The compound (H is usually preferably from 10-6 mol to /x10-' mol per mole of silver halide, especially !Xl0
-3 (Lua, !tX10''-2 mole range).

Compound (n) is usually used preferably in an amount of /x10@-6 mol to 1.times.10 mol, particularly /XIO mol to 1.times.10 mol, per mol of silver halide. For compound (III), it is usually preferably from /x10-6 mol to /X per mol of silver halide.
It is used in a range of 10-' mol, more preferably /X/0-5 mol to Hiroshi x 10-3 mol.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochlorobromide, etc., but silver iodobromide is preferred. The content of silver iodide is less than io morti, especially o, i~3°! Morti is preferred.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7μ or less), particularly 0.7μ or less.
．． It is preferably 2μ or less. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse herein means that at least 5% of N, ffi, or the number of particles is composed of particles having a size within aO% of the average particle size.

Silver halide grains in photographic emulsions are cubic, octahedral, /4
! Regular (regular) faces such as heptahedrons, rhomboids, dihedrons, etc.
) may have a crystalline substance, and particularly preferred are:
It is a cube and a tetradecahedron. In addition, spherical, plate-like, and irregular shapes (irregu
lar) crystals, or a composite form of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of a uniform phase or may be composed of different phases.

Formed separately. Two or more types of silver halide emulsions may be used in combination.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

Silver halide particularly suitable for use in the present invention is prepared in the presence of 10-8 to 10-5 mol of iridium salt or complex salt thereof per mol of silver, and has a silver iodide content on the grain surface of The silver iodide content is higher than that of silver iodide. When an emulsion containing such silver haloiodide is used, photographic characteristics with higher sensitivity and higher gamma can be obtained.

In the above case, it is desirable to add the above-mentioned iridium salt before the completion of physical ripening in the silver halide emulsion manufacturing process, particularly during grain formation.

The iridium salt used here is a water-bathable iridium salt or an iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (I), potassium hexachloroiridate (II/),
Examples include hexachloroiridium (In ammonium).

The silver halide emulsion in the light-sensitive material used in the present invention may be one type or two or more types (for example, those with different average grain sizes, those with different halogen compositions, those with different crystal habits, those with different chemically enhanced (those with different sensation conditions) may be used in combination.

Here, when using two types together, JP-A-Sho J/-, 2, 2
It is preferable from the viewpoint of maximum fliFK (Dmax x J Mi+, and small size It is preferable that monodisperse grains are chemically sensitized, and sulfur sensitization is the most preferable chemical sensitization method.Large size monodisperse emulsions do not need to be chemically sensitized, but they are not chemically sensitized. Since large-sized monodisperse particles generally tend to generate black spots, it is particularly preferable not to perform chemical sensitization, or when chemically sensitizing, to apply the chemical sensitization shallowly to the extent that black spots do not occur. "Construction" refers to the process of chemical sensitization by shortening the chemical sensitization time, lowering the temperature, and reducing the amount of chemical sensitizer added compared to chemical sensitization of small-sized particles.Large-sized monodisperse There is no particular limit to the sensitivity difference between the emulsion and the small-sized monodisperse emulsion, but Δlog E is preferably O. preferable.

Further, the silver halide emulsion layer may be a single layer, or may be a multilayer (two layers, 3W1, etc.). In the case of a multilayer, different silver halide emulsions may be used. ,
The same one may be used.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. Examples include gelatin conductors, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose conductors such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sodium alginate, and starch.
Single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. A wide variety of synthetic hydrophilic polymeric materials can be used. □ In addition to lime-treated gelatin, acid-treated gelatin may be used as the gelatin, and gelatin hydrolysates and gelatin enzymatically decomposed products may also be used.

The emulsion of the present invention is chemically sensitized, and known methods such as sulfur sensitization, reduction sensitization, gold sensitization, etc. can be used for chemical sensitization, and these methods can be used alone or in combination. . A preferred chemical sensitization method is sulfur sensitization.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Examples of interest are U.S. Patent/, 57 μ, Hari issue, same λ,
λ71, 2≠7, same 2. <No. 110,411, same
7Jr, 4JR, same 3. ! 0/, J/J issue, same 3.
This is what was written in the tjt, Riyo issue. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg during chemical sensitization is preferably t, 3 or less, more preferably 7.3 to t,O.

Furthermore, Mo1sar, ni1ein Ge1atine,
Proc.

The method of using polyvinylpyrrolidone and thiosulfate in combination, as reported by Symp, Cond, J(77-JQri/70) et al., also gives good results.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. M may also contain complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium.

As the reduction sensitizer, ester salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

In the present invention, sensitizing dyes having an absorption maximum in the visible region (for example, n-anine dyes, merocyanine dyes, etc.) described in JP-A No. 11-12010, pages 4Ij to 3, may be added. This makes it possible to perform spectral sensitization on the long wavelength side of the inherent sensitivity region of silver halide.

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

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, supersensitizing dye combinations, and supersensitizing substances are listed in Research Disclosure (Res.
76 volumes/7J
4<,? (Published in July 2007/J) It is described in item 5 of page 3, ■.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. Namely, azoles such as benzothiazolium salts, nitroinda/-lffl, rioopenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzoteyy-hs. , nitrobenzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (% with hydroxyl substitution (/, J@Ja17
) tetrazaindenes), interazaindenes, etc.;
Many compounds known as antifoggants or stabilizers can be used, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like. Among these, preferred are benzotriazoles (e.g., !-methyl-benzotriazole)
and nitroindazoles (eg !-nitroindazole), these compounds may also be included in the treatment solution.

The photographic light-sensitive material of the present invention may contain developing agents such as hydroquinone derivatives other than the general formula (I) and phenidone derivatives for various purposes such as stabilizers and accelerators.

The photographic light-sensitive material of the present invention may contain an inorganic hardening agent or a hardening agent (19) in the floating emulsion layer and other hydrophilic colloid layers.

For example, chromium salts (chromium alum, etc.), aldehydes, (formaldehyde, geltaraldehyde, etc.)
, hacarbamoylpyridinium salts ((l-morpholinocarbonyl-3-pyridiniothmethane sulfocate), haloamidinium salts (/ -(/-rian-/
-pyridinomethylene) pyrrolidinium, conaphthalene sulfonate, etc.), hemethylol compounds (dimethylol urinate, etc.), dioxane derivatives (co-,3-dihydroxydioxane, etc.), active vinyl compounds, active no\
Chlorogen compounds (J, <4-dichloro-6-hydroxy-s-triazinato), mucohalogen acids (such as mucochloric acid), etc. can be used alone or in combination, but activated vinyl compounds are particularly preferably used. Among them, active vinyl compounds represented by the general formula (fVJ) are preferred.

General formula (fV) Ch2=CH8O2-A-8O2CH=CH2A is a monovalent linking group, and alkylene group or substituted alkylene group (
The substituent may be a halogen, hydroxyl group, hydroxyalkyl group, or amino group, and may have an amide linkage, ether linkage, or thioether linkage between the substituents.

Examples of compounds represented by general formula (N) are shown below.

■-/ CH2-cttsoz CH2802CM-CH2■-
2 CH2-C1-1802 (CI-12)2 SO2CH
-CH2■-J CH2-C)1302 (C)12)45O2CH-
C1-12■-CH2-Ct-1s (J2 C1-120cH2802
Cti-C)i2■-5 CH2-CH8O2(C1櫨2)20(CH2)2
SO2CH-CI-12■-t' CH2-CI(SC12CH2CHC1(2SO
2Ct-1-CH2■-7 0H・-ct-tso 2°H2°0Nl(]■-r 0H・-〇H80・0H・C0N)11 Addition mtit of gelatin hardening agent depends on the type of hardening agent and gelatin content. It is desirable to select the optimum amount depending on the type, etc., and 0.1-10 x 10-3 mol per toog gelatin is appropriate, preferably λ to coxi o mol.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide conductors (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers M or F-1 polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters) , polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol enzyme conductors (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters such as;
Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyl f7 talenes 7-onates, alkyl sulfates, alkyl phosphates, heacyl--alkyl taurines, sulfosuccinates, sulfoalkylpolyoxy Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phosphoric acid groups, sulfuric acid ester groups, and phosphoric acid ester groups, such as ethylene alkylphenyl ethers and polyoxyethylene alkyl phosphoric esters; amino acids, Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfur or phosphate esters, alkyl betaines, aquine oxides: alkylamine salts,
Cationic surfactants such as aliphatic or aromatic class a ammonium salts, heterocyclic tertiary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, the surfactant preferably used in the present invention has a molecular weight x o described in Japanese Patent Publication No. Sho JR-917/2
o or more polyalkylene oxides.

Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in Japanese Patent Application Laid-Open No. 2003-120000-ROT.

The photographic light-sensitive material of the present invention contains a hydroquinone fatty conductor (so-called DIR) which releases a development inhibitor in the photographic emulsion layer and other hydrophilic colloid layers in accordance with the density of the image during development.
hydroquinone).

Examples of such structures are U.S. Pat. No. 3.37 and 322, U.S. Pat.

777, AJv No., U.S. Patent No. 33, Ryr No. 1, Unexamined Japanese Patent Application Publication No. 1999-1999,! No. 36, JP-A-Shoje-t7. da/
P issue, Tokukai Akira! t-/j-3,336, JP-A-74-
/j3.3172, Tokukai Sho! Turcoa r, rjj issue,
Same jter 20 hiro 3! issue, same t yoait issue, same 5y
Examples include compounds described in No.-7irror.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, a polymer containing alkyl (meth)acrylate, alkoxy acrylate (methanoacrylate, glycidyl (meth)acrylate, etc.) alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. as a single component may be used. Can be done.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of compounds having acid groups include polymers or copolymers having organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid as repeating units. Regarding these compounds, see JP-A-A/-J, 2jrJ4! No., TL-Coco Rhiro No. 37, TL-Coco No. 217171, and TL-! ! You can refer to the record in the T.G. No. 2 Specification. Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene are particularly preferred. It is a copolymer water-dispersible latex.

In order to obtain ultra-high contrast and high-sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or an American special liver No. λ, 4/L/RI, 7! It is not necessary to use a highly alkaline developer close to the pH/l described in the above issue, and a stable developer can be used.

However, sulfite ions as a preservative are added to the silver halide photosensitive material of the present invention in an amount of 0.0%. /j mol/contains 1 or more, pl
(/0, !-/2, J, especially p)i//,
Sufficiently ultra-high contrast negative images can be obtained with a developer of 0-/0,0.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and /-phenyl- A combination of 3-pyrazolidones or a combination of dihydroxybenzenes and p-acinoenols may be used. The dihydroxybenzene developing crude drugs used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, and methyl. Hydroquinone, co, 3-dichlorohydroquinone, co, j-
Dichlorohydroquinone, ko, J-diglome hydroquinone, ko,! -dimethylhydroquinone, etc., and hydroquinone is particularly preferred.

As the developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention, l-phenyl-3-pyrazolidone, l-phenyl-μ, +-dimethyl-goupyrazolidone, l-phenyl-hiro-methyl- ≠-Hydroxymethyl-3-pyrazolidone, l-phenyl-4! , 4cm
Dihydroxymethyl-3-birasoliton, l-phenyl-5-methyl-3-pyrazolidone%' D-aminophenyl-a, 4t-dimethyl-3-pyrazolidone, /
-p-tolyl-Hiroshi, 3-dimethyl-3-pyrazolidone, and the like.

Examples of p-aminophenol-based developing agents used in the present invention include hemomethyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl-p-aminophenol, N-(4<-human-roxyphenyl) Examples include glycine, co-methyl-p-aminophenol, and p-benzylaminophenol, among which he-methyl-p-aminophenol is preferred.

The developing agent is usually 0.0! Mol/l-0. Preferably it is used in an amount of r mol/l. In addition, when using a combination of dihydroxybenzenes and l-phenyl-3-birasolitons or p-amino-phenols, the former is o,
or mol/l-0゜j mol/l, the latter as o, ot mol/l
It is preferable to use it at tl of 1 or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde heavy sodium mkf thorium. The sulfite is preferably O, a mol/l or more and %yco, r mol/1 or more. Further, the upper limit is preferably 2.5 mol/it.

The alkaline agents used to set the PI include pH adjusters and buffers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.Developer The pH of is 10.j-
/2.3.

Additives used in addition to the above components include compounds such as boric acid and borax; development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosol; Organic baths such as hexylene glycol, ethanol, methanol, and indazole compounds such as de/-phenyl-mercaptotetrazole, j-nitroindazole,! - May contain an antifoggant such as a penztriazole compound such as methylbenztriazole or black pepper, and may further contain a color toning agent, a surfactant, an antifoaming agent, a water softener, and a hardening film as necessary. agent, JP-A-74-106
The compound described in No. 21747 may also be included.

The developing solution of the present invention contains an anti-silver staining agent as described in Japanese Patent Application Laid-open No.
≠, 3≠Compounds described in No. 7 can be used. As a solubilizing agent added to the developer, JP-A-Sho J/-2677J
Compounds described in No. 1 can be used. Furthermore, as a pi-1 buffering agent used in the developer,
Compound or special 1 Sho A/-λ170 described in No. 33
The compound described in No. 1 can be used.

As the fixing agent, those having commonly used compositions can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain water-bathable aluminum salts (for example, aluminum sulfate, light bread, etc.) as a hardening agent.
fl-kl/l. Furthermore, a trivalent iron compound can also be used as an oxidizing agent in the form of a complex with ethylenediamine/acetic acid.

The development processing temperature is usually selected between /r'c and zo0c, but more preferably co! The temperature ranges from 0C to 3°C.

The present invention will be specifically explained below based on examples.

<Example 1> II per mole of silver was added to a gelatin bath solution maintained at zo 0c.
In the presence of ×10 moles of potassium iridium chloride (Ill) and ammonia, a silver nitrate aqueous solution and an aqueous solution of potassium iodide and potassium bromide were simultaneously added over a period of 60 minutes, during which time the pAg was reduced to 7. The average particle size o
A MO63 molar cubic monodisperse emulsion containing average silver iodide was prepared at . This emulsion was subjected to the flocculane method, desalted, and then ≠ op.
After adding inert gelatin of
Bis-(3-sulfobropyl)oxacarbocyanine (comparative compound a) was added to a solution of IO moles of Kl per 7 moles of silver, and after 11 minutes the temperature was lowered. This emulsion was redissolved and at 4 to 0C, the compounds represented by the general formulas (I) and (n) of the present invention and the hydrazine derivative lt in the amounts shown in Table 7 were added to i, axio moh7hg mohy4- i4tyo.

Add jXlo %le/Ag mole and more! Methylbenztriazole, Hirohydroxy-1,3゜3a,7-
A dispersion of chitrazaindene, the following compounds (a) and (b), and polyethyl acrylate, and compound (i)-3'4r as a gelatin hardening agent were added and coated on a polyethylene terephthalate film. Coating was carried out to obtain Hiro 1/L2. On top of this, as a protective layer, gelatin 1.1 g 7 m
Particle size! μ polymethyl methacrylate IOIQ7
m2 methanol, irg7m As a coating aid, a layer containing a fluorine-based surfactant adhesive represented by the following structural formula, CBFL7SO2NCt12COOKC3t+7, and sodium dotecylbenzenesulfonate was simultaneously coated. Each sample was exposed to light, developed, and subjected to a pressure test according to the method described at the end to evaluate its photographic properties.

From Table 7, it can be seen that the configuration of the present invention achieves all photographic characteristics to a satisfactory level.

Comparative compound (al Comparative compound (b) Comparative compound (C1 h <Example 2> Particle size O
6λμ cubic monodisperse silver chloroiodobromide emulsion (coefficient of variation 0.1
A solution of 0.1 mol of silver iodide and 30 mol % of silver bromide was prepared.

This silver chloroiodobromide emulsion contains (NH4)3FLhC1s at 1
xIO mol/Ag mol to 3IrC/! 4 to uxio-'
Mole/Ag was added to contain mole/Ag. This emulsion was desalted in a conventional manner, sensitized with gold and sulfur in a conventional manner, maintained at jOoC, added with a sensitizing dye and Kl in the same manner as in Example 1, and re-sensitized. After dissolution, the same additive chemicals as in Example 1 were applied to the gelatin, except that gelatin hardening ax 1 was changed to ■-μ (see Table-C for compounds represented by general formulas (I) and (n)), and then applied. , conducted similar tests and evaluations. The results are shown in Table-C.

From Table λ, it can be seen that even in this example, the configuration of the present invention can satisfy all photographic characteristics.

-Description of test method- Pressure test> A diamond record stylus with a diameter of ioμm was applied a load of iog and scanned in contact with the surface of the emulsion film, and then developed under the same conditions as the sensitometry evaluation. A sensory evaluation was conducted based on the frequency, thickness, and density of linear fog that occurs in the area.

j2 No occurrence 4I: Slightly visible occurrence 3: Practical limit Koni cannot be used Koni cannot be used (conspicuously thick in percentage) Kunin cytometry conditions> Step 0. / exposed through an optical wedge, Fuji "4'J"
It was developed for 30 seconds at 0C using developer solution GRD 1 for GRAIN DEX system manufactured by Film ■.

Evaluation of black spots> For evaluation of black spots, use the above developer at IO%KOr+@g,
It was developed using a solution with a higher pi-1 level than Oll, and visually evaluated using a magnification of 23 times. (j: No occurrence 3: Limit ko, l:
], and r is 3.0 from the optical density O0l. ! The sensitivity was set at 100, which is the level without additives, and expressed as a relative value of the reciprocal of the exposure amount (the larger the number, the higher the sensitivity).

(Adhesion resistance test) (4) Adhesion resistance Cut each sample into μcm x Hiroshicm and bind two sheets together as a set 3
j'CrO%R) 1 (relative humidity) for 2≠ hours by contacting the non-photosensitive top layer with the backing layer of a set of samples / under a load of Kp j j0c10%R)i''
'cJ# hours. Next, the load was removed and the area of the peeled and bonded part between the backing layer and the non-photosensitive upper layer (the part colored by the dye transferred from the backing layer in the non-photosensitive upper layer) was calculated. . The evaluation criteria for adhesion resistance were as follows.

! The area ratio of the bonded part is O-CoO%μ
J/-san〇%J
4(/~60%ko 4/-
10%l The area ratio of the adhesive part is r/% or more.Dm
How to evaluate ax: The long horizontal line of the Mincho font grade 7 character "±" printed using manual phototypesetting using 1per PL-10OWP (manufactured by Fuji Photo Film ■) was scanned vertically with a microdensitometer. , optical density of reflected light □.

It was confirmed that the line width (black part) at t was ≠θμ. Using this as a manuscript, I used a reflective plate-making camera DSC-Jz.
The sample described here was photographed using a microdensitometer (manufactured by Dainippon Screen ■), and the same part of the resulting fuka film was photographed using a microdensitometer. Scan the bay overlight optics@g
A sample exposed to light such that the line width (white blank portion) at o and r becomes 4 toμ is referred to as the l:/return condition. Macbeth I!4 pointer TD-j is the optical density of the part on the negative film corresponding to the white background part of the original (black solid part J) under this l:l return condition.

The value measured at Hiro is evaluated as the actual Dmax. - In general, the laugh technique Dmaxtx J, j is rigged at the very limit of practical use. ! It is preferable that there be more than one.

Evaluation method for residual color: A sample was separately developed for 1r0c for 20 seconds, and the color of the unexposed area was visually evaluated. rjJ is the best quality and r/J is the worst quality.

Example-λ Sample-2 of Example-1 was processed with the following developer, and the photographic performance was excellent as in Example-1.

Patent applicant: Fuji Photo Film Co., Ltd. 1. Display of case Long-awaited application No. 307/14/' of the Showa period 2, Title of invention Silver halide photographic light-sensitive material 3, Person making amendment Relationship to case Patent applicant envoy Office 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture , Subject of correction Akira
The description in Column 5 of "Detailed Description of the Invention" in the "Detailed Description of the Invention" section of the Declaration of Contents of the Amendment is amended as follows.

1) No.≠page 7th line "Stell" "Stem)" and correct it.

2) μth page l entry "Douhiro 26 Tata 22" "Same group, 26 ri, ri λ ri" and correct it.

3) ≠ page/jth line "Specific acylhydrazine compounds" "Hydrazine rust conductor" and correct it.

4) Page j, line λ "Nariwa" "In the tribe system" and correct it.

5) Page j, line j “Hard tone” "Super hard contrast" and correct it.

6) No. 6! 1st line of page "Improving system" money "How to improve" and correct it.

7) Page 13, line 13 “Hard tone” "Super hard contrast" and correct it.

8) Page 7, line O r(la-cl r(I)J and correct it.

9) Line 11 on page 11 "Chemical, Abstruck" "Chemical Abstruck" and correct it.

10) 4th ct page/1st line "It's better to use" "By using" and correct it.

11) No. 1! The full text of the page is corrected as shown in Attachment l.

12) The entire text of page 57 has been amended as shown in attached document C.

13) Page 67, line 7 "methacrylic acid" "Methacrylic acid" and correct it.

14) Put No. 6 on the first line of the page. rK/J "Potassium iodide" and correct it.

1s) Page 72, line 7 rKaIrcJ+J'(r "K3Irα6" and correct it.

16) Page 7.2, line l/ rK/J "Potassium iodide solution" and correct it.

Attachment-1 General formula (■) CH2=CH8O2-A-8o2CH=CH2 is a divalent linking group, and alkylene group or substituted alkylene group (
Examples of the II substituent include ).rogen, hydroxyl group, hydroxyalkyl group, and amino group, which may have an amide linkage, ether linkage, or thioether linkage in between.

Specific examples of the compound represented by general formula (IV) are shown below.

F/-/ CH2=CH3O2CH25O2CH=CH2■-2 CH2=CH8O2(CH2) 2802 CH=CH
2CH2=CH8O, (CH2) 48o2CH=CH
2-p CH2=CH3O2CH20CH2SO2CH=CH2
y-t CH2=CH8Oz(CH2)zo(CHz)zs(h
cH=cHzJ Attachment-2 W-4 CH2=CH3O2CH2CHCH2so2CH=CH
2■-7 11/-r The amount of gelatin hardener added is determined by the hardening agent ff[! l:li
It is desirable to select the optimum amount depending on the type of gelatin, etc., and vO,j~jOx10 per 100t gelatin.
"Mole is appropriate, preferably 2 to 0
It is a mole.

Claims (1)

[Scope of Claims] At least one silver halide emulsion layer is provided on a support, and in the silver halide emulsion layer or other hydrophilic colloid layer, a hydrazine derivative and the following general formula (I) are present.
Contains a compound represented by the following general formula (II)
1. A negative-working silver halide photographic material characterized by containing a compound represented by the formula having substantially no absorption maximum in the visible region. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1, R^2, R^3, and R^4 are hydrogen atoms, hydroxy groups, alkoxy groups, aryloxy groups, and alkylthio groups, respectively. , arylthio group, halogen atom,
1-, 2- or tertiary amino group, carbonamide group, sulfonamide group, alkyl group, aryl group, 5- or 6-membered heterocyclic group containing at least one N, O, S atom, formyl group, keto group, sulfonic acid group, carboxylic acid group, alkylsulfonyl group, or arylsulfonyl group. However, in the case of 1,4-dihydroxybenzene, R^1
, R^2, R^3, and R^4 do not take hydrogen atoms at the same time. General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Z^1^1 and Z^1^2 are benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphtho, respectively. Represents a group of nonmetallic atoms necessary to complete a selenazole nucleus, thiazole nucleus, thiazoline nucleus, oxazole nucleus, selenazole nucleus, selenazoline nucleus, pyridine nucleus, benzimidazole nucleus, or quinoline nucleus. R^1^1 and R^1^2 each represent an alkyl group or an aralkyl group, at least one of which has an acid group. X is a charge balance counterion and n is 0 or 1
represents.