JPH046548A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enlarge a tone reproduction range in a high-contrast image forming method high in stability by incorporating a hydrazine derivative in an emulsion layer or another nonphotosensitive hydrophilic colloidal layer and a specified compound in a second emulsion layer. CONSTITUTION:The first silver halide emulsion layer formed on a support contains at least one kind of silver halide emulsion and this emulsion layer or another nonphotosensitive hydrophilic colloidal layer contains the hydrazine derivative, and the second emulsion layer contains the compound represented by formula I in which Q<1> is an atomic group necessary to from a >= 5-membered hetero ring together with the combined atoms; R1 is a group substitutable on the hydroquinone ring; B is a group for releasing PUG after being released from the hydroquinone ring; PUG is a development inhibitor group; l is 0 or 1; and each of A and A' is H or a group removable by alkali, thus permitting the tone reproduction range to be wide and an image good in dot quality to be obtained.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material and a method for forming an ultra-high contrast negative image using the same, and in particular to a silver halide photograph used in a photolithography process. The present invention relates to ultra-high contrast negative type photographic materials suitable for photosensitive materials.

(Prior Art) In the field of photoengraving, in order to deal with the diversity and complexity of printed matter, there are demands for photosensitive materials with good original reproducibility, stable processing solutions, and easy replenishment.

Particularly in the line drawing process, manuscripts are created by pasting typesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, a document contains images of different densities and line widths, and there is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can finish these documents with good reproduction.

On the other hand, enlarging (stretching) or reducing (shrinking) net photographs is widely used in the making of catalogs and large posters.
In plate making that uses enlarged halftone dots, the number of lines becomes coarser, resulting in blurred dots. When reduced, the number of lines/ink is larger than that of the original, resulting in a photograph of a thinner point. Therefore, in order to maintain halftone reproducibility, an image forming method having a wider latitude is required.

A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain sensitivity to these light sources, photographic materials are usually orthosensitized. However, it has been discovered that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of lenses, and as a result, image quality tends to deteriorate. Moreover, this deterioration is more noticeable for xenon lamp light sources.

As a system that meets the demands for wide latitude, we use a lithium-type silver halide photosensitive material made of silver chlorobromide (silver chloride content of at least 50% or more) with an extremely low effective concentration of sulfite ions (usually 0.1 mol/min). 1 or less) A method is known in which a line image or a halftone dot image with high contrast and high blackening density, in which image areas and non-image areas are clearly distinguished, is obtained by processing with a hydroquinone developer. However, due to the low concentration of sulfite in the developing solution, this method is extremely unstable to air oxidation, and various efforts and innovations have been made to keep the solution activity stable. Currently, the process is extremely slow, reducing work efficiency.

For this reason, the above development method (lith development system)
There is a need for an image forming system that eliminates the instability of image formation caused by the process, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics, and one example of this is U.S. Pat. No. 4.168.977, No. 4
．． No. 221,857, No. 4,224,401, No. 4.
No. 243739, No. 4,272,606, No. 4.31
As seen in No. 1.781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound has been added is mixed with a sulfite preservative of 0.1 at pH 11.0 to 12.3.
A system has been devised for forming ultra-high contrast negative images with a T of over 10 by processing with a developer containing 5 mol/1 or more and having 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.

The above image system has sharp halftone dot quality, processing stability,
Although it shows excellent performance in terms of speed and original reproducibility, a system with further improved original reproducibility is desired in order to deal with the variety of printed matter in recent years.

JP-A-56-153,336, JP-A No. 61-156.04
No. 3, No. 61-230, 135 and No. 62-296
, No. 138 discloses a photographic material containing a redox compound that releases a photographically useful group upon oxidation, and an attempt is made to widen the gradation reproduction range.

However, in ultra-high contrast processing systems using hydrazine derivatives, these redox compounds have the disadvantage of inhibiting high contrast, and their properties cannot be utilized.

(Object of the Invention) An object of the present invention is to provide a photosensitive material for plate making that has a wide halftone gradation reproduction range in a highly stable high contrast image creation method.

The second object is to provide a photosensitive material for plate making that has a wide halftone reproduction range and high contrast.

(Object of the invention) The object of the invention is to have a first silver halide emulsion layer containing at least one silver halide emulsion on a support, the emulsion layer or other non-photosensitive hydrophilic colloid layer. contains a hydrazine derivative and has a second silver halide emulsion layer,
This was achieved by a silver halide photographic material characterized in that the second emulsion layer contains a compound represented by general formula (1).

General formula [Ico^ In formula (1), Ql represents an atomic group containing at least one heteroatom and necessary to form a 5-membered or more heterocyclic ring with the bonding carbon atom, and R+ represents a hydroquinone mother group. B represents a group that can be substituted on the nucleus, B represents a group that releases PUG after elimination from the hydroquinone mother nucleus, and PU
G represents a development inhibitor, l represents 0 or l, A
and A' represents a hydrogen atom or a group that can be removed with an alkali.

Formula (1) will be explained below.

Formula (1) will be explained in detail below.

Ql is a divalent group containing at least one heteroatom, examples of which include amide bond, divalent amino group, ether bond, thioether bond, imino bond, sulfonyl group, carbonyl group, alkylene group , alkenylene groups, etc., and may be a group combining multiple of these, and these may further have a substituent. However, if Ql contains an ether bond, it must be a 5-membered ring. There isn't.

R1 is a group that can be substituted with hydroquinone, specifically, a hydrogen atom, a monosubstituted or unsubstituted alkyl group (preferably carbon number/~30, examples include methyl, ethyl, t- butyl, t-octyl, dimethylaminemethyl, n-antaddenyl, etc.), substituted or unsubstituted aryl groups (preferably carbon atoms t to 30, such as phenyl, p-tolyl), substituted or unsubstituted alkylthio groups (preferably carbon number/~30, examples include n-butylthio,
n-octylthio, 5ec-octylthio, tetradenruthio, λ-dimethylaminoethylthio, etc.), 1-substituted,
Unsubstituted arylthio group (preferably carbon number t to 30, examples include phenylthio, 2-hydroxyphenylthio, p-chlorophenylthio, carbonylthio-1-1-octylphenyl+, t, j-methoxy) Carbonylphenylthio, etc., halogen (F, Q!
, Br, I), a hydroquine group, a substituted or unsubstituted alkoxy group (preferably carbon number/~30, and as a Fll, metquine, etkyne, penzyluoquine, octyloxy, dodenluoquine, etc.), a substituted or unsubstituted aryl group/ group (preferably has a carbon number of A to 30, examples include 7dinoxy, goukalzoquinofenoquine, etc.), substituted or unsubstituted a/l groups (preferably has a carbon number of 7 to 30, examples include acetyl, furohionyl, <nsoyl, chloroacetyl, 3-carboxypropionyl, octadecyloyl, etc.), substituted or unsubstituted alkoxycarbonyl groups (preferably having 2 to 30 carbon atoms, examples include methoxycarbonyl, ethoxycarbonyl, fenoquine carbonyl, octadenroquine carbonyl, methoxyethoxy7carbonyl), substituted or unsubstituted amide groups (preferably carbon number/~30, examples include acetamide, propionamide, 3-carboxyl), propionamide group, lauroylamide, etc.), substituted or unsubstituted sulfonamide group (preferably has 7 to 30 carbon atoms, examples include methanesulfonamide, p-toluenesulfonamide, etc.)
"j), a substituted or unsubstituted carbamoyl group (preferably carbon number/~30), examples include carbamoyl, N-butylcal/zemoyl, N-(r-methmonoethyl)carbamoyl , N-octyl ξmoyl, picolidinocarbonyl, morpholinocarbonyl, N-hexadelene carbonyl), unsubstituted sulfamoyl group (preferably ('': carbon number O to 30, e.g. sulfamoyl, dibutylsulfamoyl, etc.)
, substituted, non-WPO sulfonyl group (preferably carbon is /~
30, methanesulfonyl, benzenesulfonyl,
p-dodenlebenzenesulfonyl, etc.), fCa
5fl Group f Examples are 1-tetranoryl, -1-bennomyl, 7-noryl, etc.)? represent.

In formula CI), when A and A' are a group that can be removed by an alkali (hereinafter referred to as a precursor group), it is preferably an anru group, an alnia/carbonyl group, an aryloquine group, , carbamoyl group, imidoyl group, oxanolyl group, sulfonyl group 7-.

Which cutting edge water-decomposable group, U.S. Pat.
Reverse Michael reaction described in issue 2? Zolecursor groups of the type utilized, U.S. Pat.
Atr No., J, 932゜G No. 10 or No. 3. Tata 3. a precursor group in which the anion described in tt1 transfers electrons via a conjugated system and thereby causes a cleavage reaction;
Precursor group that causes a cleavage reaction by electron transfer of the anion reacted after ring cleavage as described in U.S. Patent No. ≠, 336,200;
Same a, <ilo, imidomethyl group of notation V in tie number? One example is a preliminary car that was used.

In the group represented by B in formula [I], after the hydroquinone core is converted into a quino-7 form by an oxidized developing agent during development, 0
+B+, a divalent group that releases PUG k and can subsequently release PUGk? It may have a timing adjustment function, or it may be an oxidation-reduction group that reacts with the oxidized herbal drug of the molecule to release PUGi.Here, when l is O, ,PUG
means the case where is directly bonded to the hydroquinone mother nucleus, and when l is 2 or more, 2 of the same or different B
Represents a combination of two or more.

When B is a divalent linking group having a timing adjustment function, examples thereof include the following.

(1) Groups that utilize the cleavage reaction of hemiacetal, such as U.S. Special Review No.
It is a group represented by the following general formula and is described in No. tyit, No. tr. Here, the * mark represents the bonding position on the left side in formula [I],
** mark is 2 in formula CI) and the bonding position on the right side! represents.

General formula (T-/) In the formula, W represents a boron atom, a sulfur atom or an IrXN-R67 group, R65 and R66 represent a hydrogen atom or a substituent, R67 represents all substituents, and t/or ,
2 is displayed. When t is 2, two -W-C- represent the same or different things. When R65 and R66 represent a substituent, and in a representative example of R67, R6
9 groups, R69C〇- group, R69So2- group, R69N
G O- group and R70R70 such as R69NS02- group are included. Here, R69 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R70 represents an aliphatic radical, an aromatic radical, or a heterocyclic group (represents a hydrogen atom). The case where each monovalent group is fully represented and connected to form a cyclic structure is also included.Specific examples of the group represented by the general formula (T-/) include the following groups.

H3 (2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction Examples include timing groups described in US Pat. It can be expressed by the following general formula.

General formula (T-λn *-O *-Nu-L i n k-E -**In the formula, the * mark represents all positions bonded to the left side in formula CI), and the ** mark represents all positions bonded to the left side in formula CI). Represents the position to join the tree, Nu
represents a cedar group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, and E represents an electrophilic group, which is a group that can cleave the bond with the mark ** upon receiving a nucleophilic attack from Nu. Link
represents a linked introduction group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction.

Specific examples of the group represented by general formula (T-2) are as follows.

*-〇*-0 (3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system.

For example, U.S. Special Forces No. 3, No. 3-3,
≠27. t≠! It is a group described in No. 1 and represented by the following general formula.

General formula CI-j) In the formula, *, **, W, R65, R66 and t have the same meaning as explained for (T-/). Specifically, the following groups may be mentioned.

(4) A group that utilizes a cleavage reaction due to ester hydrolysis.

For example, the linking groups described in West German Published Patent Application No. J, Akoz, 3/Y include the following groups.

The * and ** marks in the formula have the same meaning as explained for the formula (T-/).

General formula (T-Hiroshi) General formula (T-j) S I II*-o-c
-** *-5-c-**(5) Imi7
A group that utilizes the catalytic cleavage reaction.

For example, US Patent No. 1t! 4t, No. 073, and is a group represented by the following formula.

General formula (TA) In the formula, *, ** and W have the same meaning as explained in formula (T-/), and Ft6a has the same meaning as R67. Specific examples of the group represented by formula (T-&) include the following groups.

When the group represented by B in general formula (1) represents a group that becomes a redox group by cleavage from the hydroquinone core,
It is preferably represented by the following general formula (R-1).

General formula (R-1> *-P-(X=Y), -Q-A In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and n X and Y
At least one of represents a methine group having -PUG as a substituent, the other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n is 1 to 3
represents an integer of n X and n Y represent the same or different), A represents a hydrogen atom or a group that can be removed by an alkali, and has the same meaning as A in formula (1), Here, the case where any two substituents of P, X, Y, Q and A become divalent groups and connect to form a cyclic structure is also included. This is the case when forming a ring or the like.

When P and Q represent a substituted or unsubstituted imino group, preferably an imino group substituted with a sulfonyl group or an acyl group.

At this time, P and Q are expressed as follows.

General formula (N-1) General formula (N-2) sow
-c o-G Here, the * mark represents the bonding position with A, and the ** mark indicates -(
X=Y), represents the bonding position with one of the free bonds of -.

In the formula, the group represented by G is a straight chain or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (for example, methyl, ethyl, benzyl, phenoxybutyl, isopropyl), a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (e.g. phenyl group, 4-methylphenyl group, 1-naphthyl group, 4-dodecyloxyphenyl group, etc.), or hetero A 4- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom, or an oxygen atom (e.g., 2-pyridyl group, 1-phenyl-4-imidazolyl group, 2-furyl group, benzothienyl group, etc.) This is a preferable example.

-a In formula (R-1), P and Q are preferably each independently an oxygen atom or a group represented by general formula (Nl).

In general formula (R-1), preferably P represents an oxygen atom and A represents a hydrogen atom.

More preferably in general formula (R-1), except when X and Y are methine groups having PUG as a substituent, the other X and Y are substituted or unsubstituted methine groups.

Among the groups represented by the general formula (R-1), particularly preferred groups are those represented by the following general formula (R-2) or (R-3).

General Formula (R-2) General Formula (R-3) In the formula, this mark represents the position where it binds to the hydroquinone core, and this mark represents the position where it binds to PUG.

R44 represents a substituent, q represents an integer of 0, 1 to 3, when q is 2 or more, two or more Ra4 may be the same or different, and two Rh4 are substituted on adjacent carbons. When it is a group, it also includes the case where each becomes a divalent group and is connected to represent a cyclic structure. In that case, a benzene condensed ring is formed, such as a ring structure such as naphthalenes, benzonorbornenes, chromans, indoles, benzothiophenes, quinolines, benzofuran l[, 2,3-dihydrobenzofurans, indanes, or indenes. and these may further have one or more substituents, examples of preferred substituents when these fused rings have a substituent, and preferred examples of Rba when Rba does not form a fused ring Examples are listed below.

That is, alkoxy groups (for example, methoxy groups, ethoxy groups, etc.), acylamino groups (for example, acedoamide groups, benzamide groups, etc.), sulfonamide groups (for example, methanesulfonamide groups, benzenesulfonamide groups, etc.),
Alkylthio groups (e.g., methylthio group, ethylthio group, etc.), carbamoyl groups (e.g., N-propylcarbamoyl group, N-t-butylcarbamoyl group, N-1-propylcarbamoyl group, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, propoxycarbonyl group, etc.) carbonyl group,
), aliphatic groups (e.g. methyl group, t-butyl group, etc.), halogen atoms (e.g. fluoro group, chloro group, etc.)
, sulfamoyl group (e.g. N-propylsulfamoyl group, sulfamoyl group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.), hydroxyl group, carboxyl group, or heterocyclic thio group (e.g. 1-phenyltetrazolyl group). -5-thio group, 1-ethyltetrazolyl-
Groups such as a 5-thio group (represented by PUG, which will be described later) can be mentioned. In addition, a typical example of a case where two R64s are linked to form a cyclic structure is this-〇 (this mark and ** mark represent the same meaning as explained in general formula (R-3)). It will be done.

In the general formula (1), the group represented by PLIG represents a development inhibitor, specifically a tetrazolylthio group, a benzimidazolylthio group, a benzothiadiazolylthio group, a hendioxazolylthio group, a henzytriazolyl group, a penzoindazoylthio group. a lyl group, a triazolylthio group, an oxadiazolylthio group, an imidazolylthio group, a thiadiazolylthio group, a thioether-substituted triazolyl group (for example, the development inhibitor described in U.S. Pat. No. 4,579,816), or an oxazolylthio group; may have a substituent as appropriate, and preferred substituents include the following. That is, R7 is a group, RyeO- group, R7q
S- group, R,,0CO- group, R? ? OS O - group,
Halogen atoms, cyano groups, nitro groups, R-attached SO! - group,
RtmCO- group, RvyCOO- group, RytSOgN-
group, ts Ry*NSOg- group, RtsNCO- group, R? drop
R'9R7! R? f RtmNCON- group, Rt, So, o- group, or Ry
*Rs.

Represents an aliphatic group, aromatic group or heterocyclic group, R□, R
? ? and R,. represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. -Rffff, R'a, in the molecule
R? ? and when there are two or more R8゜s, these may be linked to form a ring (for example, a benzene ring). Here, an aliphatic group is a saturated or unsaturated group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. , branched or straight chain, chain or cyclic, substituted or unsubstituted aliphatic hydrocarbon group. The aromatic group is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. The heterocyclic group has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and the hetero atom is selected from a nitrogen atom, a sulfur atom, or an oxygen atom. A saturated or unsaturated, substituted or unsubstituted heterocyclic group, preferably 4
It is a heterocyclic group having 8- to 8-membered rings. These aliphatic groups,
When the aromatic group and the heterocyclic group have a substituent, examples of the substituent include the heterocyclic thio group listed as an example of the development inhibitor or the substituents listed as optional substituents of the heterocyclic group. can be mentioned.

Particularly preferred development inhibitors in general formula (1) are compounds that have development inhibitory properties when cleaved, but do not substantially affect photographic properties after flowing out into the color developer. It is a development inhibitor that has the property of being decomposed (or changed) into

For example, U.S. Pat.
No. 218644, No. 60-221750, No. 60-2
Examples thereof include development inhibitors described in No. 33650 and No. 61-11743.

In formula [1], Ql is preferably represented by N-Co-Q"-, and examples of Q"+71 include a divalent amino group, an ether bond, a thioether bond, an alkylene group, an ethylene bond, an imino bond, and a sulfonyl group. basis,
Examples thereof include a carbonyl group, an arylene group, a divalent heterocyclic group, and a combination of a plurality of these groups.

RB is a hydrogen atom, an alkyl group (including those having a substituent, preferably having 1 to 10 carbon atoms; for example, methyl, ethyl, isopropyl, butyl, cyclohexyl, 2-methoxyethyl, benzyl, aryl), an aryl group (N Including those with substituents.

R1O preferably represents a carbon number of 6 to 120 (for example, phenyl, P-tolyl) or a heterocycle (including those having substituents, preferably 3 to 10 carbon atoms, for example, 2-pyridyl, 2-imidazolyl, 2-furyl) The preferred one is a hydrogen atom.

R1 is preferably a hydrogen atom or a substituent whose Hammett's substituent constant σp is 0 or more, and examples thereof include a halogen atom, substituted or unsubstituted acyl, and group, alkoxycarbonyl group, amide group, sulfonamide group, carbamoyl group,
Examples thereof include a sulfamoyl group, a sulfonyl group, a formyl group, a cyano group, a substituted methyl group (eg, chloromethyl, trifluoromethyl, hydroxymethyl, benzyl, etc.), and a heterocyclic residue.

The number of ring members of the heterocycle containing Q' is preferably 5 to 7 members, and among these, the compound represented by the following formula (If) is more preferred.

In formula [n], Q8 has the same meaning as above, and R'
, A, A', B, PUG and l have the same meaning as in formula [1].

Specific examples of the compounds used in the present invention are listed below, but the present invention is not limited thereto.

H C.B.

NO! Nu! 0■ H H H H COOCsHtn tHs Specific synthesis examples of compounds are shown below, but the compounds used in the present invention can be easily synthesized by a similar method.

Synthesis example (synthesis of exemplified compound (1)) (1-A) (1-B) (1-C) (1-D) (1-E) (1-F) (1-G) (1-H ) □ Synthesis of Exemplary Compound 1) (1-A) 2.5-dimethoxyaniline 31 (g) and pyridine 17
(+d) was added to 350 (m) of acetonitrile, and a solution of methylmalonylchloride'20 (Nl) in 50 (m) of acetonitrile was added dropwise thereto. After stirring at room temperature for 5 hours, water was added, extracted with ethyl acetate, washed with water, and dried.
'I4 contracted. The residue was crystallized from a mixed solvent of ethyl acetate and n-hexane to obtain the title compound 31 (g).

2) (1-B) Synthesis 50 (ad) of methanol was added to 5.0 (g) of (1-A) obtained above, and further 3.8 (g) of a 28% methanol solution of rhodium methoxide was added. .

After stirring for 10 minutes at room temperature, n-dodecyl bromide 4.9
The reaction mixture to which (g) was added dropwise was stirred at 45° C. for 3 hours, left to cool, and then poured into water, and the precipitated crystals were separated by filtration, washed with water, and dried. This was recrystallized from methanol to obtain the title compound 1.
9 (g) was obtained.

3) Synthesis of (1-C) 30 (m) of 5% aqueous sodium hydroxide solution and 10 (m) of methanol were added to 1.8 (g) of (1-B) obtained above, and the mixture was heated to 70-75°C. The mixture was stirred for 2.5 hours. After cooling,
The reaction mixture was poured into an aqueous hydrochloric acid solution, and the precipitated crystals were separated by filtration.
After washing with water and drying, 1.7 (g) of the title compound was obtained.

4) Synthesis of (1-D) Phosphorous oxychloride 15 (M&) was added to 3.0 (g) of (1-C) obtained by the above method, and the mixture was heated under reflux for 1 hour. After cooling, the reaction mixture was gradually poured into water, and the precipitated crystals were separated by filtration, washed with water, and dried. This was recrystallized from methanol to obtain the title compound 2. 0 (g) was obtained.

5) Synthesis of (1-E) To (1-D>2.5 (g) obtained by the above method, 30 (-) of isopropyl alcohol and 10 (-) of water were added, and further 5 (-) of concentrated sulfuric acid was added. After adding, the reaction mixture was heated under reflux for 8.5 hours. After cooling, the reaction mixture was poured into water, and the precipitated crystals were separated by filtration, washed with water, and dried to obtain 2.0 (g) of the title compound.
I got it.

6) Synthesis of (1-F) 3.5 (g) of (1-E) obtained by the above method, 110 (1d) of isopropyl alcohol, 0.3 (g) of sodium hydroxide, 10 (d) of water. Add a solution containing 10% palladium on carbon and add 1. After adding 0 (g) of hydrogen, the mixture was stirred at 80 to 85°C for 7.5 hours under 20 (■/cd) of hydrogen.

After cooling, the catalyst was removed by filtration, and the filtrate was subjected to fM condensation. Water was poured into the residue, and the precipitated crystals were separated by filtration, washed with water, and dried to obtain 2.7 (g) of the title compound.

7) Synthesis of (1-G) 47% hydrobromic acid 40 (IRl) was added to 2.6 (g) of (1-F) obtained above, and heated under reflux for 3.5 hours. After cooling, water was added, extracted with ethyl acetate, washed with water, dried, and concentrated. The residue was crystallized from acetonitrile to obtain 2.1 (g) of the title compound.

8) Synthesis of (1-H) Add 150 (d) of ethyl acetate to 2.0 (g) of (1-G) obtained above and 6.0 (g) of manganese dioxide,
Stirred at room temperature for 1.5 hours. After removing the insoluble matter by filtration, the filtrate was concentrated to obtain 1.9 (g) of the title compound.

9) Synthesis of Exemplified Compound (1) 50 (sd) of methylene chloride was added to 1.8 (g) of (1-H) obtained above, and 5-mercap)-1-(
1.23 g of 4-nitrophenyl)-tetrazole and p-
) Luenesulfonic acid-hydrate o.

After adding 1 (g), the mixture was stirred at room temperature for 1 hour.

The precipitated crystals were separated by filtration, washed with acetonitrile, and dried to obtain 1.3 g of the title compound.

The compound of general formula (1) of the present invention is 1.0×10-7 to
1, OX 10-" mol/rd, preferably 1.0XIO-' to 1.OXI O-' mol/rd
Used within the range of rrr.

The compounds of the invention can be prepared in a suitable water-miscible organic solvent, e.g.
alcohol! ! (methanol, ethanol, propatool, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. for use.

In addition, using the well-known emulsifying dispersion power, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate can be dissolved in oil using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified. A dispersion can also be prepared and used. (1) can also be used by dispersing the powder of the compound in water using a ball mill, a coid mill, or an ultrasonic wave, by a method known as a solid dispersion method.

The hydrazine derivative used in the present invention has the following general formula (
Preference is given to compounds represented by IV).

General formula (IV’) R, -N-N-G, -R.

A, At In the formula, R2 represents an aliphatic group or an aromatic group, R1 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amine group, or a hydrazino group, and G1 represents a 10-group. ,-S.O.

II 1111 represents a monogroup, -80- group, -P- group, -C-C- group, thiocarbonyl group, or iminomethylene group, and AI and A2 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or It represents an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (rt/), the aliphatic group represented by R preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

This alkyl group may have a substituent.

In the general formula (IV), the aromatic group represented by R1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be fused with an aryl group.

Preferred as R1 is an aryl group, particularly preferably one containing a benzene ring.

The aliphatic group or aromatic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, Urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide Preferred substituents include alkyl groups (preferably those with 1 to 20 carbon atoms), aralkyl groups (preferably those with 7 to 30 carbon atoms), and alkoxy groups. Group (
(preferably one having 1 to 20 carbon atoms), substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably one having 2 to 30 carbon atoms), sulfonamide Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30), a phosphoric acid amide group (preferably one having 1 to 30 carbon atoms), and the like.

The alkyl group represented by Rt in general formula (IV) is preferably an alkyl group having 1 to 4 carbon atoms,
The aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring).

When IG is a -C- group, preferred among the groups represented by R2 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxybenzyl group, etc.), aryl group (e.g., phenyl group, 3°5-dichlorophenyl group, 0-methanesulfonamidophenyl group) , 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.),
Particularly preferred is a hydrogen atom.

R2 may be substituted (as the substituent, the substituents listed for R1 can be applied).

○ I G in general formula (IV) is most preferably a -C- group.

Also, R8 splits the G1 R1 part from the remaining molecules,
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the G+ Rt moiety, and examples thereof include those described in JP-A-63-29751.

A hydrogen atom is most preferable as A+ and At.

R1 or R1 in the general formula (IV) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. I can do it. Examples of the polymer include those described in JP-A-1-100530.

R3 or R2 in the general formula (■) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
, No. 347, JP-A No. 59-195, 233, No. 59-
200° No. 231, No. 59 = No. 201,045, No. 59
-201.046, 59-201,047, 5
9-201,048, 59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, patent application No. 62-67.508,
Examples include the groups described in No. 62-67.501 and No. 62-67.510.

Specific examples of the compound represented by the general formula (R') are shown below. However, the present invention is not limited to the following compounds.

N-1 ■-3 V-5 V-1 ■-12 ■-13 ■-14 V-6 ■-10 V-1 V-16 q kidney ■-18 ■-20 ■-25 ■-26 ■-23 ■-24 In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCH DISCLOSURE
Item23516 (November 1983 issue, P, 34
6) and the documents cited therein, as well as U.S. Pat.
No. 80.207, No. 4,269,929, No. 4.27
No. 6.364, No. 4,278,748, No. 4,385
, No. 108, No. 4,459,347, No. 4,560,
No. 638, 4.478. No. 928, British Patent 2,0
11,391B, JP-A-60-179734, JP-A No. 62
-270,948, 63-29,751, 61
-170゜733, 61-270,744, 6
No. 2-948, EP No. 217,310, or US Pat. No. 63-129.337,
No. 63-223,744, No. 63-234,244, No. 63-234,245, No. 63-234,246
No. 63-294.552, No. 63-306, 43
No. 8, JP-A No. 1-100,530, 1. 105.
No. 941, No. 1-105,943, JP-A-64-1
No. 0.233, Japanese Patent Application Publication No. 1-90,439, Patent Application No. 1983
-105,682, 63-114,118, 6
No. 3-110,051, No. 63-114.119, No. 63-116,239, No. 63-147,339,
63-”179.760, 63-229,163
No., Japanese Patent Application No. 1-18.377, No. 1-18,378, No. 1-IL379, No. 1-15,755, No. 1-
No. 16.814, No. 1-40,792, No. 1-42.
No. 615, No. 1-42, 616, No. 1-123.69
No. 3, No. 1-126,284 can be used.

The amount of the hydrazine derivative added in the present invention is from 1X10-' mole to 5X10 mole per mole of silver halide.
-'' mol is preferable, and a particularly preferable addition amount is in the range of 1X10-' mol to 2X10-2 mol.

The first and second silver halide emulsion layers may be coated on the support in any order. For example, the second silver halide emulsion layer and the first silver halide emulsion layer may be placed on the support in this order, or vice versa. Further, another hydrophilic colloid layer may be provided between these layers. The second silver halide emulsion layer and/or the hydrophilic colloid layer or other adjacent hydrophilic colloid layer may contain a hydrazine derivative.

The first emulsion layer preferably has a coated silver amount of 0°01 to 2
．． 0g/rd, preferably 0.05-1.0g/r
rr, the amount of coated silver in the second emulsion layer is 0°5 to 7.5 g/
rri, preferably 1.0 to 6.0 g/i is appropriate.

The aforementioned hydrophilic colloid layer contains gelatin or a synthetic polymer (polyvinyl acetate, polyacrylamide, polyvinyl alcohol, etc.) and has a thickness of 0.1 to 5°0μ, preferably
A suitable value is 0.2 to 4.0μ.

The silver halide emulsions used in the first and second silver halide emulsion layers of the present invention include silver chloride, silver chlorobromide, silver iodobromide,
Any composition such as silver iodochlorobromide or silver bromide may be used.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less.
It is preferably 5μ or less. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse herein means that at least 95% of the particles by weight or number of particles is composed of particles having a size within ±40% of the average particle size.

The silver halide grains in the photographic emulsion may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape.
ular) crystals, or a composite form of these crystal forms.

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

Two or more silver halide emulsions formed separately 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.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a dye as a filter dye or for various purposes such as preventing irradiation. Filter dyes include dyes to further reduce photographic sensitivity;
Preferably, an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, or a UV absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, or a UV absorber mainly in the region of 350 nm to 600 nm to increase safety against safelight light when handled as a bright room photosensitive material is preferably used. Dyes with high light absorption are used.

These dyes are added to the emulsion layer depending on the purpose, or they are added together with a mordant to the upper part of the silver halide emulsion layer, that is, to the non-light-sensitive hydrophilic colloid layer which is further away from the silver halide emulsion layer with respect to the support. It is preferable to use it by fixing it.

It varies depending on the molar extinction coefficient of the dye, but usually 10-2 g.
/rd~1g/rr? It is added within the range of Preferably it is 50 to 500 μ/d.

The dyes used are disclosed in various known patents. For example, JP 55-155,350, JP 55-15
5.351, 52-92716, 56-12639
, No. 63-27838, U.S. Pat. No. 4,276,373, WO
28104794.

Additionally, known water-soluble dyes can also be used.

Here are some examples:

0sNa 0sNa As binder or protective colloid for photographic emulsions, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein: hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, acetal of polyvinyl alcohol moiety, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. A specific example is U.S. Patent No. 2,448,06
No. 0, British Patent No. 618.061, etc.

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.

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

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

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. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines: thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7) tetrazaindenes); A number of compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.), pentaazaindenes, etc.; Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be included in the treatment liquid.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, etc.), aldehydes, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, activated vinyl compounds (1,3,5-triacryloyl-hexahydro-5- triazine, l,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,
4-dichloro-6-hydroxy-5-triazine, etc.)
, mucohalogen acids, etc. can be used alone or in combination.

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, high contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkyl esters such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids;
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or sulfates, alkyl betaines, and amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium, etc. Cationic surfactants such as heterocyclic quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in Japanese Patent Publication No. 58-9412. Additionally, a polymer latex such as polyalkyl acrylate may be included for dimensional stability.

Development accelerators or nucleating and infectious development accelerators suitable for use in the present invention include JP-A-53-77616 and JP-A-53-77616;
4-37732, 53-137゜133, 60-1
In addition to the compounds disclosed in US Pat. No. 40,340, No. 60-14959, etc., various compounds containing N or S atoms are effective.

Next, specific examples are listed.

2C1@(CrHs)! NCH2CHCH20H,0H n-C+HeN(CtH+0H)z S CkhCkhN combtHs)z The optimum addition amount of these accelerators varies depending on the type of compound, but 1. o
xlo-'~o, 5g/rr? , preferably 5.0Xl
It is desirable to use it in the range of O-' to 0.1 g/m. These promoters are dissolved in a suitable solvent (H, O, alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

A plurality of types of these additives may be used in combination.

In order to obtain ultra-high contrast photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or U.S. Pat.
It is not necessary to use a highly alkaline developer with a pH close to 13 as described in No. 9,975, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.15 mol/1 or more of sulfite ion as a preservative, and has a pH of
By using a developer having a pH of 10.5 to 12.3, particularly 11.0 to 12.0, a sufficiently high contrast negative image can be obtained.

There are no particular limitations on the developing agents used in the method of the present invention, such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 4゜4-dimethyl-1-phenyl- 3-pyrazolidone), aminophenols (e.g. N
-methyl-p-aminophenol), etc. can be used alone or in combination.

In particular, the silver halide light-sensitive material of the present invention contains dihydroxybenzenes as a main developing agent and 3-3 as an auxiliary developing agent.
Suitable for processing with developers containing pyrazolidones or aminophenols. Preferably, in this developer, dihydroxybenzenes are used in an amount of 0.05 to 0.5 mol/l, and 3-pyrazolidones or aminephenols are used in an amount of 0.06 mol/l or less.

Further, as described in US Pat. No. 4,269,929, the development speed can be increased and the development time can be shortened by adding amines to the developer.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). I can do it.

If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, and film silver stain preventive agents may be added. (for example, 2-mercaptobenzimidazole sulfonic acids, etc.).

As the fixer, one having a commonly used composition 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 a water-soluble aluminum salt or the like as a hardening agent.

The processing temperature in the method of the invention is usually from 18°C to 50°C.
selected between.

Although it is preferable to use an automatic processor for photographic processing, according to the method of the present invention, the total processing time from the time the photosensitive material is put into the automatic processor until it comes out can be set to 60 seconds to 120 seconds. , sufficiently ultra-high contrast negative gradation photographic characteristics can be obtained.

In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
The compounds described in No. 4,347 can be used. Patent application 1986-109 as a solubilizing agent added to the developer.
The compounds described in No. 743 can also be used. Furthermore, as a pH buffering agent for use in developing solutions, JP-A-60-93,4
Compounds described in No. 33 or Japanese Patent Application No. 18625/1986
9 can be used.

The present invention will be explained in detail below with reference to Examples.

Example 1 (Preparation of photosensitive emulsion) Emulsion-A 4X1 per mole of silver was added to an aqueous gelatin solution kept at 50°C.
In the presence of 0-' mole of potassium iridium(II[) chloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added for 60 minutes while p
By keeping Ag at 7.8, the average particle size is 0.2
8μ, average silver iodide content 0. A 3 mol % cubic monodisperse emulsion was prepared. This emulsion was desalted by the flocculation method, and then 40 g of inert ceratin per mole of silver was added and kept at 50°C as a sensitizing dye, 5,5'-dichloro-9-ethyl-3, 3' screw (3-
sulfopropyl)oxacarbocyanine and a Kl solution of lO-1 mole per mole of silver were added, and the mixture was allowed to stand for 15 minutes, and then the temperature was lowered.

Emulsion-B In a gelatin aqueous solution with pH=4.0 kept at 50°C, a silver nitrate aqueous solution and 1.4 x 10-7 mol of 6 per mol of silver were added.
ammonium rhodium(III) chloride and 4×10−
A mixed aqueous solution of sodium chloride and potassium bromide containing 1 mol of potassium hexachloroiridium(III) acid was added simultaneously at a constant rate for 30 minutes to obtain an average particle size of 0.23.
A silver chlorobromide monodisperse emulsion (C1 composition: 70 mol %) of μ was prepared.

This emulsion was washed with water in a conventional manner to remove soluble salts, and then chemical sensitization was performed by adding sodium thiosulfate and potassium chloroaurate. Furthermore, a potassium iodide solution corresponding to 0.1 mol % per 111 mol was added to convert the particle surface.

Furthermore, after this, the following compound was added as a sensitizing dye at 50 DEG C. at 2.7.times.10@-' mol/Ag mol, and after standing for 15 minutes, the temperature was lowered and stored.

(Preparation of coating sample) Support: Undercoat layer made of vinylidene chloride copolymer (0,
Polynylene terephthalate film (5μ) with
150μ) On the support, UL, ML,
It was applied so that it had a layer structure of OL and PC. The preparation method and coating amount of each layer are shown below.

(UL) After dissolving the emulsion-B together with gelatin at 40°C,
5-methylbenztriazole, 85/d, 4-hydroxy-1,3,3a, 7-tetrazaindene 12/d
Go, add the following compounds (a), (b), (c) and gelatin to 30 wt% polyethyl acrylate and the following compound (d) as a gelatin hardening agent, Ag3.6
g/m, hydrazine compound shown in Table-1 2.8X10
-'mol/m, and Seratin was applied at a concentration of 1.9 g/m.

Compound (b) C1e 15■/d Compound (c) CaHlt CH=CH+CHt+yCON CH
tCHzSOJaCH.

50■/Go compound (d) H CH2= CH30tCHzCHC)lxsOtcH=
CH! 2.0 wt% based on gelatin (ML) 10 g of gelatin, 2.0 wt% of the above compound (d) based on gelatin were added, and water was added to make a final amount of 250 - to prepare gelatin 1. It was applied at a concentration of 5 g/d.

(OL) The above emulsion-A was dissolved at 40°C, and 5-methylbenztriazole 3/rd, 4-hydroxy-1,3,3
a, 7-chitrazaindene, the compound of general formula (I) of the present invention shown in Table 1 4.3X10-'mol/rd, compound (A) 0. 4tuz/m, (b) 1.5+og/
rrr.
It was prepared by adding wt%. It was applied so that Ag was 0.4 g/rd.

(P C) A polymethyl methacrylate dispersion (average particle size 5.0 μm) and the following surfactant were added to the gelatin solution, and the gelatin was 1.5 g/m and the polymethyl methacrylate was 0.5 g/m.
It was coated at a concentration of 3 g/rrf.

surfactant developer CHCOOC, H.

37■/rd S Os Na (Performance evaluation) After exposing these samples to tungsten light at 3200° through an optical wedge or an optical wedge and a contact screen (Fuji Film, 150L chained soto type), the following It was developed with a developer for 30 seconds at 34°C, fixed, washed with water, and dried.

As a fixer, Fuji Photo Film (!@, GR-
Fl was used.

The results obtained are shown in Table 1.

The gradation (γ) is a characteristic curve with a density of 0° It is the slope of the straight line connecting the 0 points.

3 point and 3° The halftone gradation is expressed by the following formula.

*Hatton gradation = Exposure amount that gives a dot area ratio of 95% (fog
The exposure amount (log E
5%) The halftone dot quality was visually evaluated on a five-level scale. The 5-level evaluation is
"5" indicates the best quality and "1" indicates the worst quality. As halftone dot originals for plate making, "5" and "4" are practical, and "
3" is the practical limit level, and "2" and "l" are impractical quality.

of From the results in Table-1, High, #I4 gradation is wide, I understand that it can be done.

Table 1 Samples of the present invention T gave images with good halftone quality
2-
(5-nitro-2-indazolyl)hydroquinone Example 2 (Preparation of photosensitive emulsion C) 3.0X per mole of silver was added to an aqueous gelatin solution kept at 50°C.
After simultaneously mixing an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of 10-'' moles of (NH4)sRhC,
After removal of soluble salts, gelatin is added as a stabilizing agent without chemical ripening using methods well known in the art.
-Methyl-4-hydroxy-1,3,3a,7-chitrazaindene was added. This emulsion has an average size of 0.1
It was a monodisperse emulsion with a cubic crystal shape of 5μ.

(Coating of photosensitive emulsion layer) Hydrazine compound rV-8 (25 μ/r
ri, 5-methylhencytriazole (5×1 (I
3 mol/Agen O1), polyethyl acrylate latex (30 wt% to gelatin), and 13-divinylsulfonyl-2-propanol (2°Qwt% to gelatin) were added. The coating amount was 3.5 g/rd.

Second layer gelatin (1.0 g/a) Third layer Same as photosensitive emulsion C except that 6.0 x 10-' mol of (N
Emulsion D (coated silver amount: 0.4 g/nf) prepared in the presence of Ha) JhC, 5-methylbenzotriazole (5X 10-' mol/Ag mol), polyethyl acrylate latex (30 wt% to gelatin) , 1,3-divinylsulfonyl-2-propatol (
2 wt % to gelatin) and the compound of general formula (I) of the present invention shown in Table 2 were added.

Fourth layer gelatin 1.5g/n (and as a cloak agent, polymethyl methacrylate particles (average particle size 2.5μ) 0.3g/n
rd, and the following surfactants and stabilizers as coating aids:
and a protective layer containing ultraviolet absorbing dye was applied and dried.

Surfactant CHiCOOCJrs CHCOOC6HI3 SO,Na 37■/m C,F,,So□NCFlzCOOK CsHq 2. 5■/Bostabilizer Thioctic Acid UV Absorber 2, 1■/d This sample was used with Dainippon Screen ■Meisho Printer p
-607, image exposure was carried out through the original as shown in FIG. 1, and the image was developed at 38° C. for 20 seconds, fixed, washed with water, and dried. After that, the image quality of cut-out characters was evaluated.

Extracted character image quality 5 means that characters with a width of 30 μm are reproduced when a document as shown in Figure 1 is used and exposed appropriately so that 50% of the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return. In terms of image quality, the image quality is very good. -Effortless character stroke t1
"N quality" means that only characters with a width of 150 μm or more can be reproduced when the same appropriate exposure is given, and it is poor character extraction quality, and a sensory evaluation of 4 to 20 ranks was set between 5 and 1. A level of 3 or higher is a practical level.

The results are shown in Table 2. The sample of the present invention has excellent cut-out character image quality.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the configuration during exposure when forming a character image by overlapping and repeating, and each reference numeral indicates the following. (b) Transparent or semi-transparent pasting base (b) Line drawing original (black parts indicate line drawings) (c) i3 bright or semi-transparent pasting base (d) w 4-point original (black parts are halftone dots) ) (e) Glowing material for return (the shaded area indicates the glistening layer) Patent applicant: Fuji Photo Film Co., Ltd. Procedural Amendment of the Claimed Invention of the 1゜2゜ Incident, Z, 1990 Title: 1990 Japanese Patent Application No. 108048 Silver Halide Photographic Light-sensitive Material 3 Relationship with the Amendment Person Case

Claims (1)

[Scope of Claims] 1) A first silver halide emulsion layer containing at least one type of silver halide emulsion is provided on a support, and a hydrazine derivative is included in the emulsion layer or other non-photosensitive hydrophilic colloid layer. 1. A silver halide photographic material comprising a second silver halide emulsion layer, the second emulsion layer containing a compound represented by formula (I). General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), Q^1 contains at least one hetero atom and is necessary to form a 5-membered or more heterocyclic ring with the bonding carbon atom. R_1 represents a group capable of substituting into the hydroquinone core, B represents a group that releases PUG after elimination from the hydroquinone core, and P
UG represents a development inhibitor, l represents 0 or 1,
A and A' represent a hydrogen atom or a group that can be removed with an alkali. 2) The silver halide photographic material according to claim (1), wherein the hydrazine derivative is represented by the following general formula (IV). General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic group or an aromatic group, and R_
2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydrazino group, and G_1 is a ▲ group with a mathematical formula, chemical formula, table, etc.;
-SO_2- group, -SO- group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups,
Represents a thiocarbonyl group or iminomethylene group, A_
1 and A_2 both represent a hydrogen atom, one hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.