JPH02839A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a stable image having high quality by incorporating a hydrazine deriv. and other specific compd. into a silver halide emulsion layer contg. silver chloride or other hydrophilic colloidal layers. CONSTITUTION:The silver halide emulsion layer contg. at least 80% silver chloride is provided and the hydrazine deriv. and the compd. expressed by formula I are incorporated into this silver halide emulsion layer or the other hydrophilic colloidal layers. In formula, Q denotes a residual heterocyclic group bonded directly or indirectly with at least one kind of hydrophilic groups; M denotes a hydrogen atom, alkali metal or quaternary phosphonium. The stable image having the high quality is obtd. in this way and the superhard negative type photographic sensitive material suitable for daylight photosensitive materials particularly for photomechanical process for printing is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an ultra-high contrast negative type photographic light-sensitive material suitable as a bright-room light-sensitive material for photolithography for printing. be.

(Prior art) In the field of graphic arcs, image formation exhibiting photographic characteristics of ultra-high contrast (especially gamma of 10 or more) is used to improve the reproduction of continuous tone images or line images using halftone images. A system is necessary.

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free sulfite ions is extremely low (usually 0). Therefore, the Lith developer has the serious disadvantage that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

U.S. Pat. No. 4,224,401 and U.S. Pat.
, 168,977, 4,166.742, 4,311.781, 4.272,606, 4.221.857, 4,243.739 There is a method using a hydrazine derivative described in et al.

According to this method, photographic properties with ultra-high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is better than that of the lithium developer. A dramatic improvement in comparison.

Furthermore, as a light-sensitive light-sensitive material produced by this method, a light-sensitive material based on a silver chloride emulsion was disclosed in Japanese Patent Application Laid-Open No. 60-140.338.
, 60-140,339, 61-238,049,
Patent application No. 60-221,498, No. 61-5715, No. 6
1-53461, 61-79,531, 61-99
．． 482, etc.

It is also known that various anti-capri agents and stabilizers are added to silver halide photographic materials in order to prevent capri during storage or photographic processing, or to stabilize photographic performance. There is.

However, if an anti-capri agent or stabilizer is used in a conventionally known combination in a photosensitive layer containing silver chloride as a main ingredient, a silver halide emulsion, and a hydrazine derivative, serious problems will occur in the production and performance of the photosensitive material. did.

In other words, a problem in the production of photosensitive materials is that precipitates are generated in the coating solution, which deteriorates the coating surface quality, and a performance disadvantage is that as the photographic processing solution becomes fatigued, the halftone dot area changes significantly. .

(Object of the Invention) As a result of intensive research, the present inventors have solved these problems and have made possible a light-sensitive material for printing photolithography that utilizes supercuring with a hydrazine derivative.

A first object of the present invention is to provide a photosensitive material for bright room reversal that provides high quality and stable images.

A second object of the present invention is to provide a photographic light-sensitive material for bright room reproduction that utilizes high contrast enhancement by a hydrazine derivative.

A third object of the present invention is to provide a photographic material for use in a bright room with high production stability.

A fourth object of the present invention is to provide a photographic material for use in a bright room with high processing stability.

(Structure of the Invention) The above object of the present invention is to have at least one silver halide photosensitive emulsion layer containing at least 80 mol % of silver chloride, and the silver halide emulsion layer or other hydrophilic colloid layer has This has been achieved by a silver halide photographic material containing at least one type of hydrazine derivative and at least one type of compound represented by the following general formula ('I).

General formula (1) In the formula, Q represents a heterocyclic residue to which at least one hydrophilic group is bonded directly or indirectly, and 0M represents a hydrogen atom, an alkali metal, or a quaternary phosphonium.

(Detailed Description of the Invention) The silver halide used in the present invention may be silver chloride, silver chlorobromide, silver chloroiodide, or silver iodide; The amount is 80 mol% or more, more preferably 90 mol% or more. When the silver chloride content decreases, the safety under bright room light, which is important for bright room photosensitive materials, deteriorates (capri occurs), so the workability of handling bright room photosensitive materials deteriorates. This results in a practical obstacle. This is because as the content of silver chloride decreases, the spectral devil of the photosensitive material extends to longer wavelengths, making it more sensitive to bright room lights that cut off ultraviolet rays, and thus reducing safety. It will be done.

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.
There is basically no limit to the zero particle size distribution, which is preferably 5μ or less, but monodisperse is preferable.What does monodisperse mean here? i means that at least 95% of the amount or number of particles is composed of particles having a size within ±40% of the average particle size.

Silver halide grains in photographic emulsions may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
It may have ular crystals or a composite of these crystals, but cubic shapes are particularly preferred.

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.

The silver halide emulsion used in the present invention may contain a rhodium salt or a complex salt thereof.

Examples of rhodium salts include rhodium chloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, etc., but preferably water-soluble trivalent rhodium halogenated compounds such as hexachlororhodium (m
) M or its salts (ammonium salt, sodium salt,
potassium salts, etc.).

The amount of these water-soluble rhodium salts to be added is in the range of 1.0x1O-' mol to 1.0x1O-4 mol per 1 mol of silver halide. Preferably 5゜0XIO-'mol~
5.0 x 10-' moles.

The rhodium salt is preferably added during the formation of silver halide grains during the preparation of a silver halide emulsion or during the physical ripening process.

In addition to rhodium salts, cadmium salts, sulfite salts, lead salts, thallium salts, and iridium salts can also be coexisting.

The compound represented by the general formula (1) of the present invention will be explained in detail.

In general formula (1), the hydrophilic group of Q is 505M
, -3OJHR'-NHCONHR', -NH30
□RICOJHR'N1(COR', -PO3M
, -C00M, or OH are preferred.

R1 here represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Specifically, the heterocyclic residue represented by Q in general formula (1) includes an oxazole ring, a thiazole ring, an imidazole ring,
zelenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, bentazole ring, pyrimidine ring, thiasia ring, triazine ring, thiadiazine ring, etc., or rings bonded to other carbocycles or heterocycles, such as benzothiazole ring, It represents a benzotriazole ring, benzimidazole ring, benzoxazole ring, benzoselenazole ring, naphthoxazole ring, triazaindolizine ring, diazaindolizine ring, tetrazaindolizine ring, etc.

Among the mercapto heterocyclic compounds represented by the general formula (1), particularly preferred are those represented by the general formulas (IV) and (V).

General formula (IV) RI+ General formula (V) y and z in general formula (IV) are N or CRI! (R'l
represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group) R1 is -303M
, -COOM, -SO□Nul+' -NIICON
HR'.

-NH3OtR'C0tNHR' -NHCOR
', -PO3H or OH. octadecyl group, etc.), an aryl group having 6 to 20 carbon atoms (e.g. phenyl group, naphthyl group, etc.), or a linking group composed of an alkyl group, aryl-3O□-, etc. The following groups can be mentioned.

These alkyl groups and aryl groups further include halogen atoms (F, Cj!, Br, etc.), alkoxy groups (methoxy group, methoxyethoxy group, etc.), aryloxy groups (such as phenoxy groups), alkoxy groups (where R1 is aryl), group), an aryl group (when R11 is an alkyl group),
Amide group (acetamido group, etc.), carbamoyl group (methylcarbamoyl group, etc.), sulfonamide group (methanesulfonamide group, etc.), sulfamoyl group (methylsulfamoyl group, etc.), sulfonyl group (methylsulfonyl group, etc.), sulfinyl group (such as a methylsulfinyl group), a cyano group, an alkoxycarbonyl group (such as a methoxycarbonyl group), an aryloxycarbonyl group (such as a phenoxycarbonyl group), and a nitro group.

Here, the substituents of R11 are -505M, -C00M, -5
0, II) II? '-NICONHR', -NH3OJ
'-COJI(R'NHCOR', -PO!
l'l may be the same or different when there are two or more -OH.

M has the same meaning as that expressed in general formula (1).

Next, X in general formula (V) is a sulfur atom, an oxygen atom, or RI! Represents a selenium atom or -N- (R+3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), L is -CONR14-NR
1GO-3OzNR14--NR1'SO! --OCO
--COO--5--NR14--CO--50--0
COO--NR”C0NR” --NRth COO--O
CONR14-or-NRI4SO! NR"-; Rl 4 and RI' each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group); R11 and M represent the general formula (1) and (
IV), where n represents O or 1.

Furthermore, RI! , R13, R14, and the alkyl group and aryl group represented by RI' may be substituted with the substituents listed for R11.

Specific examples of preferred compounds represented by the general formula H) used in the present invention are listed below. .

CH2CHz CHI SOx Na CHi CH! ○H CHffi COOH Hs The compound represented by the general formula (1) can be synthesized by the method described in the following literature.

U.S. Patent No. 2,585,388, 2.541.92
No. 4, Special Publication No. 42-21,842, Japanese Patent Publication No. 53-50
, 169, British Patent No. 1,275.701, D. A. Berges et, aj! , +
Journal ofHeterocyc)ic C
hemistry” Volume 15, No. 981 (No. 1978)
, “The Chemistry of Heter
Cyclic Chemistry”I
m1dazola and Derivatives
part L 3 3 pages 6-9, Che
mical Abstract, No. 58.7921 (1
963), p. 394.

E. Hoggartb Journal
of Chemical Society
'1160-7 (1949), and S, R, 5an
dier + W, Karo l “Organic Fu
ctioner Group Preparation
nwAcademic Press, pp. 312-5 (1
968).

1, 1. Kovtunouskaya Levsh
ine, Tr, Ukr, In5t.

Eksperim Endokrinol * 18
jL 345 pages (196l).

M., Chamdon, et al., Bull, Che.
+m, Fr, + 723 (1954).

D, A, 5hirley, D, W,
Alley, J., Amer.

Chem, Soc,, 19. 4922 (1954
) A, l1chl J, Marchwald,, Be
r, (Journal of the German Chemical Society).

Volume 22, page 568 (1889) Praphalla Chandra Guha,
J,Awer,Chem,Soc,.

11.1502-10 (1922) U.S. Patent No. 3,017,270, British Patent No. 940.
No. 169, Japanese Patent Publication No. 49-8, 334, Japanese Patent Publication No. 55-59
, 463, Advanced in Heterocyclic
Che+m1stry+ '1 165~209 (
196B) Khim, Geterotsikl
.

5 oedin, 7 (7) 905~9° West German Patent No. 2,716.707 The Chemistry of Heteroc
yclic compoundsis+1dazole
and Derivatives+Vol 1+ 3
84 pages, Org, 5ynth, rV,, 569
(1963) L, B, 5ebre11. C,E,
Booed, J., Ataer.

CheIIl, Soc, +±5.2390 (192
3), JP-A-50-89,034, JP-A-53-28.4
26, 55-21.007, 57-202531,
57-116340, Japanese Patent Publication No. 40-28,496 The amount of the compound represented by the general formula (1) of the present invention is il
1.0×10-S mole-5゜0×1O-f per mole
fi mol, preferably lXl0-' mol to 5X10-
These compounds can be added in aqueous solutions or as solutions in organic solvents such as alcohols (e.g. methanol, ethanol), ketones (e.g. acetone), esters (e.g. ethyl acetate). These compounds are added during the production of the halogenated emulsion (for example, added during emulsion grain formation or during post-ripening) or added to a coating solution prepared for coating.

There are various known hydrazine derivatives used in the present invention. In addition to the hydrazine compounds described in the numerous patents listed in the (Prior Art) section above, U.S. Pat.
3. U.S. Patent No. 4.323.643, Japanese Unexamined Patent Publication No. 57-9
9,635, 60-179,734, 62-948
, 61-270,744, 62-160,438,
Patent application No. 61-21, 199, No. 61-175, 234,
61-251,482, 61-276゜283, 62-58,513, 62-67゜509, 62-
67.510. 62-130°819, 62-14
3,469 can be used.

Particularly preferred hydrazine derivatives are those having a ureido group represented by the following general formula (n).

General formula (II) In the formula, R1 and R4 may be the same or different and each represents a hydrogen atom, an aliphatic residue, an aromatic residue, or a heterocyclic group, and Rs is a hydrogen atom, or It represents an aliphatic residue, and X represents a divalent aromatic residue.

R8 is a hydrogen atom or an alkyl group (1 to 3 carbon atoms)
, or a phenyl group. The phenyl group may have the same substituents as above.

More specifically, the aliphatic residues represented by R3 and R4 include straight chain and branched alkyl groups, cycloalkyl groups, and those with substituents, as well as straight chain and branched alkyl groups, and alkenyl groups and alkynyl groups. Examples of chain and branched alkyl groups include alkyl groups having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and specific examples include methyl groups, ethyl groups,
Examples include isobutyl group and l-octyl group.

Moreover, as a cycloalkyl group, for example, carbon number 3-1
0, specifically, for example, a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. Examples of substituents include alkoxy groups (e.g., methoxy, ethoxy, propoxy, butoxy, etc.), aryloxy groups (e.g., phenoxy, naphthyloxy, etc.), halogen atoms (e.g., chlorine, bromine, fluorine, iodine, etc.). ), alkoxycarbonyl group, aryl group (e.g. phenyl group, halogen-substituted phenyl group, alkoxyphenyl group, alkylphenyl group), hydroxy group, cyano group, sulfonyl group, etc. Specific examples of substituted groups include 3-methoxy Propyl group, 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl L p-chlorobenzyl group, 2.
Examples include 4-dimethylamylphenoxyprobyl group. Further, examples of the alkenyl group include an allyl group, and examples of the alkynyl group include a propargyl group.

On the other hand, the aromatic residues represented by R' and R' are:
Phenyl group, naphthyl group and substituents thereof (for example, alkyl group, alkoxy group, acylhydrazino group, dialkylamino group, alkoxycarbonyl group, cyano group, carboxyl group, nitro group, alkylthio group, hydroxy group, sulfonyl group, carbamoyl group, Specific examples of those with substituents, including those with a halogen atom, etc., include p-methoxyphenyl group, 0-methoxyphenyl group, tolyl group, p-formylhydrazino group,
-chlorophenyl group, m-fluorophenyl group, etc.

The heterocyclic residue represented by R3 or R' is a three- or six-membered monocyclic ring or fused ring having at least one of oxygen, nitrogen, sulfur, or selenium atoms, even if a substituent is attached thereto. Good, specifically, for example, pyrroline ring,
Pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring,
Examples include residues such as a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring, and a naphthoselenazole ring.

These heterocycles have 1 to 4 carbon atoms, such as a methyl group or an ethyl group.
Alkyl group, methoxy group, ethoxy group, etc. having 1 to 4 carbon atoms
may be substituted with an alkoxy group, a teryl group having 6 to 1 B carbon atoms such as a phenyl group, a halogen atom such as chloro or bromine, an alkoxycarbonyl group, a cyano group, an amide group, or the like.

It is preferable that either one of R3 and R4 is a hydrogen atom.

Aliphatic residues represented by RS include straight-chain or branched alkyl groups, cycloalkyl groups, or those with substituents, and straight-chain or branched alkyl groups including alkenyl groups and alkynyl groups. , for example, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, an isopropyl group, etc. Examples of the cycloalkyl group include those having 3 to 1 o carbon atoms, specifically cyclopentyl group, cyclohexyl group, and the like. Examples of substituents include alkoxy groups (for example, methoxy groups, ethoxy groups, etc.), alkoxycarbonyl groups, aryl groups (for example, phenyl groups, halogen-substituted phenyl groups, alkoxyphenyl groups, alkylphenyl groups, etc.), amide groups, acyloxy base, etc. Specific examples of substituted groups include 3-methoxypropyl group, penzyl group, p-chlorobenzyl group, p-methoxybenzi/
L4, p-methylbenzyl group, etc. can be mentioned.

The alkenyl group has 3 to 12 carbon atoms, such as allyl group and 2-butenyl group.

RS is preferably a hydrogen atom.

X represents a divalent aromatic residue, specifically, for example, a phenylene group, naphthylene! (1,2-11゜4-12.3
-11.5-11.8-, etc.) and those having substituents.

Substituents for divalent aromatic residues include, for example, carbon atoms of 1 to
20 alkyl groups (which may be branched), aralkyl groups whose alkyl moiety has 1 to 3 carbon atoms, alkoxy groups (preferably 1 to 20 carbon atoms), substituted alkoxy groups (preferably 1 to 20 carbon atoms), 20), alkyl group or substituted alkyl group (
A mono- or di-substituted amino group with 1 to 20 carbon atoms, an aliphatic acylamino group (preferably 2 to 21 carbon atoms)
), an aromatic acylamino group, an alkylthio group, a hydroxy group, a halogen atom (for example, chlorine, etc.), and the like.

More preferred as X is a phenylene group.

Specific examples of preferred hydrazine derivatives are shown below.

■-1) ■-5) ■-2) ■-6) ■-3) ■-8) ■-4) ■-9) H3 ! l-10) n-14) n-11) I[-Is) I[-12) n-16) CH.

n-17) I[-15) II-18) In the present invention, when a compound represented by the -ship formula (ff) is contained in a photographic light-sensitive material, any one or more of the compounds in the light-sensitive material It can be included in the hydrophilic colloid layer. The compound represented by the general formula (n) is preferably contained in the surface latent image type silver halide photographic emulsion layer, but it can also be contained in other non-irradiation layers, such as protective layers, intermediate layers, filter layers, antihalation layers, etc. In layers such as layers,
Specifically, it may be a solution of a water-miscible solvent such as alcohols (e.g. methanol, ethanol), esters (e.g. ethyl acetate), ketones (e.g. acetone), or a water-soluble solvent. If the compound is hydrophobic, it can be added as an aqueous solution to a hydrophilic colloid solution, or if it is hydrophobic, it can be added as an emulsion or solid dispersion in an aqueous gelatin solution or another hydrophilic polymer aqueous solution.

When added to a photographic emulsion, it may be added at any time from after emulsion grain preparation to before coating, but it is preferably added to a coating solution prepared for coating.

The compound represented by the general formula (II) of the present invention is preferably used in an amount of 10-mol to 1-mol per mol of halogenated primate.
It is preferable to contain 10-' mol of X, especially 10-'
The content of the compound is preferably S mol to 4 x 10-'' mol, but the content of the compound depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the containing layer and the photographic emulsion layer, It is desirable to select the optimum amount depending on the type of antifoggant compound.

The compound represented by the general formula (II) of the present invention can also be used in combination with conventionally known hydrazine compounds. Various hydrazine compounds can be used in combination, but
Specific examples include JP-A-53-20921 and JP-A-53-20921;
No. 3-16.623, No. 55-52050, No. 55-
No. 90940, No. 55-174985, No. 59-36
No. 788, No. 61-270744, No. 61-2119
You can use the ones listed in No. 9 etc.

The molar ratio of the compound used in combination is 0.01 to 100 times, preferably 0.1 to 10 times, relative to the compound of formula (II) -a.

The silver halide photographic material of the present invention may contain an organic desensitizer. The organic desensitizer preferably has at least one water-soluble group or alkali dissociable group.

The organic desensitizer used in the present invention is defined by its polarographic half-wave potential, that is, the redox potential determined by polarography, and the sum of polarographic anodic potential and cathodic potential is positive.

For example, there is a US patent on the polarographic method for measuring redox potential! ,! 0/, No. 307. Specific examples of the water-soluble group present at least one in the organic desensitizer include a sulfonic acid group, a carzene acid group, and a phosphonic acid group. , biridine, morpholine, etc.) or an alkali metal (eg, sodium, potassium, etc.).

The alkali-dissociable group refers to the pH of the current treatment solution (usually pH
-pH/3, but treatment liquids with other pH values may also be used. ) Refers to a substituent that undergoes a deprotonation reaction at a pH of t or lower and becomes anionic. Specific KFi At least one hydrogen atom bonded to a nitrogen atom with a substituent such as a substituted/unsubstituted sulfamoyl group, a substituted/unsubstituted carbamoyl group, a sulfonamide group, an acylamino group, a substituted/unsubstituted ureido group, etc. Refers to substituents and hydroxy groups present.

Further, a heterocyclic group having a hydrogen atom on the nitrogen atom constituting the nitrogen-containing heterocycle is also included in the alkali dissociable group.

These water-soluble groups and alkali-dissociable groups may be connected to any part of the organic desensitizer, and two or more types may be present at all times.

Preferred specific examples of the organic desensitizer used in the present invention are described in No. 脣 Gansho &/-2O9ItW, and some examples are listed below.

The organic desensitizer is contained in the silver halide emulsion layer in 1. Ox/0
-8~/, 0X10-'moni/ln2, especially l.

OX/0-7~/, OX/0-'' morph m2 is preferably present.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Filter dyes include dyes for further lowering photographic sensitivity, preferably ultraviolet absorbers having a spectral absorption maximum in the inherent sensitivity range of silver halide, and dyes for safelight sources when handled as bright room photosensitive materials. In order to increase safety, dyes that have subtense light absorption mainly in the region of Jj (7 mm to AOO nm) are used.

These dyes may be added to the emulsion layer depending on the purpose, or they may be added together with a mordant to the top of the silver halide emulsion layer, i.e., to a non-If & original hydrophilic colloid layer far from the silver halide emulsion layer with respect to the support. It is preferable to use it by adding it and fixing it.

Although it depends on the molar extinction coefficient of the dye, it is usually 1O-2t.
It is added in a range of 7 m'' to 7 m2, preferably 10 g/m2 to 100 g/m2.

Specific examples of dyes! #Ganshobu/-2OP/It is detailed in the first issue, but Rika will be placed next in SO3.

5 (33K S U a N a S (J a N a ) The above dyes can be used in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, prononol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof. ]K is dissolved and added to the coating solution for the non-photosensitive hydrophilic colloid of the present invention.

It is also possible to use a combination of two or more of these dyes Fiλ.

The dyes of the invention are used in the amount necessary to enable bright room handling.

The specific amount of dye used is generally 1O-3f/m2 to 1
t/m2,%/0'f7m2~o.

It is possible to find a suitable quantity in the range KIE of j9/m.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, 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; diethylcellulose in hydrolyzate,
Carboxymethyl cellulose, cellulose derivatives such as cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl vicritone, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, etc. A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of acrylamide, 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 decomposition 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 are known methods for chemically sensitizing silver halide emulsions, and any of these methods may 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 pure metals, such as platinum, nocerazicum, and iridium. A specific example is U.S. Patent J, 4<4S,
It is described in British patents t/r, o4i, 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, 7-ran 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 completely preventing capri or stabilizing the photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, guamobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. Mercaptopyrimidines; Mercaptotriazines; Teocto compounds such as oxazolinthione; Azaindenes, such as triazaindenes, tetraazaindenes (especially ≠-hydroxy substituted (/, J, Ja, 7) tetra A number of compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfo/rR amide, etc. Among these, preferred are benzotriazoles (eg !-methyl-benzotriazole) and nitroindazoles (eg !-nitroindazole). Further, these compounds may be included in the treatment liquid.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, the active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-5-)riazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-(
β-(vinylsulfonyl)propionamide], etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-3-triazine, etc.), mucohalogen Mi (mucochlorate, N-carbamoylpyrodinium IN ((
1-morpholy)carbonyl-3-pyridinio)methanesulfonate, etc.), heroamidinium salts (1-(1-
1:) rho-1-pyridinomethylene) pyrrolidinium,
2-naphthalenesulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-412
20. Preferred are the active vinyl compounds described in US Pat. No. 53-57257, US Pat. No. 59-162546, US Pat.

The supports used in the present invention include glass, cellulose acetate film, polyethylene terephthalate film,
Examples include baryta coated paper, polyolefin (eg, polyethylene, polypropylene, etc.) laminate, polystyrene film, polycarbonate film, and metal plates such as aluminum.

These supports may be corona treated by a known method, and may also be undercoated by a known method if necessary.

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, improved smearability, emulsification dispersion, anti-adhesion, and improved photographic properties (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 1.tr realkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters of sugars;
Alkylamine salts Alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate ester, alkyl phosphate ester L N-acyl-N-alkyl taurine, sulfosuccinate ester, sulfoalkyl polyoxyethylene Carboxy groups such as 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 phosphates, alkyl betaines, and amine oxides; complexes such as alkyl amine salts, aliphatic or aromatic μ-class ammonium salts, pyridinium, and imidazolium. Cationic surfactants such as ring μ-grade ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

Surfactant Fi particularly preferably used in the present invention
w Kosho tr-5>≠Molecular weight tO stated in the l co-issue publication
It is a polyalkylene oxide of O or more. Additionally, a polymer latex such as polyalkyl acrylate may be included for dimensional stability.

As a development accelerator or a nucleating infectious development accelerator suitable for use in the present invention, JP-A-33-777/7. Same 3
μm37732, 13-/37°133, tO-/
410,3g01 sametO-/≠ri! In addition to the compounds disclosed in, et al., various compounds containing N or S atoms are effective.

Next, all specific examples will be listed.

The optimum addition amount of these accelerators varies depending on the type of compound;
It is desirable to use it within the range of . These promoters are dissolved in a suitable solvent (H2O, 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 the conventional infectious developer, the U.S. Patent Co., Ltd.
It is not necessary to use a highly alkaline developer with a pH close to 3 as described in R.I. No. 7J, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ion fO,/1 mole/1 or more as a preservative, and has a pH of
/ 0, j''/ko, 3, especially pH //, 0-/2.
A sufficiently ultra-high contrast negative image can be obtained using a developer of 0.

There are no particular limitations on the developing agent that can be used in the method of the present invention, such as dihydroxybenzenes (eg, hydroquinone), 3-pyrazolide yQ (eg, l-phenyl-3-pyrazolidone, ≠).

Dimethyl-7-7enyl-3-pyrazolidone), amine phenols (for example, N-methyl-p-amine phenol), etc. can be used alone or in combination.

In particular, the silver halide g-optical 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, the content of dihydroxybenzenes in this developer is 0. OJ~0. j mol/113-Pyrazolidones or aminophenols are used together in a range of 0.01 mole/1 or more.

Further, as described in US Pat. No. 4, F9-T, by adding amines to the developer, it is possible to increase the overall development speed and shorten the development time.

Other developer aids include alkali metal sulfites, carbonates,
pH buffering agents such as borates and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic anticaprilants (preferably nitroindazoles or benzotriazoles for lf!f), etc. can include. 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 -- mercaptobenzimidazole sulfonic acids, etc.)'f: May be included.

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.

Processing temperatures in the method of the invention are generally from tr''c to
“Chosen between c.

It is preferable to use an automatic processor for photographic processing, but 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 is set to 20 sheets/20 seconds. Even with high contrast, it is possible to obtain photographic characteristics with sufficient ultra-high contrast and negative gradation.

The developing solution of the present invention contains JP-A-Sho! as a silver stain preventive agent. t-2
The compounds described in Hiroshi, No. 3≠7 can be used. Patent application filed in 1977 as a dissolution aid added to the developer.
Compounds described in No. 74Lj can be used. Furthermore, as a pH buffering agent used in the developer,
The compound or compound described in No. 4133 ζ1-x97
All of the chemical compounds described in Q8 can be used.

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

In the Examples, a developer having the following formulation was used.

Developer Hydroquinone ≠! ,OfN・Methyl P・Aminophenol//Cosulfate o,rt Sodium hydroxide ir,oy Potassium hydroxide
! ! , Of! -Sulfosalicyl@
≠! , O2 houffl
Jj, Of potassium sulfite ltO
,0? Ethylenediaminetetraacetic acid disodium salt / Of Komelkabutobenzimidazole J sulfonic acid 0.3? Potassium Bromide Of! Methylbenzotriazole o, ttn/butyljetanolamine /! , Of water, Float
11 (pH=//, &) [Comparative Example-l] Add @1 mol of Shiba oy to an aqueous gelatin solution maintained at μO@C.
, io-' moles of NH4Rhα6) and a silver nitrate aqueous solution in the presence of NH4Rhα6).
Using methods well known in the art, gelatin is added after removal of soluble salts and λ is added as a stabilizer without chemical ripening.
-Methyl-guhydroxy/, J, Ja, 7-titraazaindene was added. This emulsion was a cubic monodisperse emulsion with an average grain size of o,t5μ. The following hydrazine compound was added to this emulsion at 31 μ/m' 1-phenyl-5-mercaptotetrazole 2°6 μ/
d1 and polyethyl acrylate latex were added in a solid content of 3Qwt% based on gelatin, and as a hardening agent, 1,3
-vinylsulfonyl-2-propanol was added and coated on a polyester support to give an Ag content of 3.8 g/nl. Gelatin was 1.8 g/m. A protective layer containing 1.5 g/m of gelatin as a protective layer and the following surfactants, stabilizers, and pine additives as coating aids was coated thereon and dried.

CHx C00Ch H+5 CHC○0CiH+z SO*Na Cm F,yS Ox N CHzC3H? 0OK 37■/rd 2.5■/d Thioctic acid 2.1■/Resistance upper nail polymethyl methacrylate (average particle size 2.5μ) 9.0
Acceptable/d Silica (average particle size 4.θμ) 9.0■/Dainippon Screen Co., Ltd. Meishuku printer p-607, exposed through an optical wedge, developed at 38°C for 30 seconds, fixed,
Washed with water and dried. As a developing solution, in addition to fresh solution, Table 1
Two fatigue solutions were used as described in .

The photographic properties obtained are shown in Table 1.

From Table 1, it can be seen that the samples of the present invention have a small window degree when treated with a fatigue solution. 1! It can be seen that the samples of the present invention have the great feature that constant performance is always obtained when the developer is used continuously for a long period of time.

[Example-1] Comparative Example N-1 was carried out in the same manner as Comparative Example-1 except that the compound of the present invention was used in place of ■-phenyl-5-mercaptotetrazole.

The types and amounts of the compounds used are shown in Table-1.

An example of overlapping this sample with a manuscript with a halftone dot area of 50% -
2 When coating the samples in Comparative Example-1 and Example-1, coating was performed under the following two conditions.

They are indicated as Comparative Example-2 and Example-2. ) A coating solution for the fish stopper photosensitive emulsion layer, which should be applied immediately (within one hour at the most) after the additives have been added.

Rule 1 Add a hardener and additives other than polyethyl acrylate to the coating solution for the light-sensitive emulsion layer, let it stand at 40°C for 24 hours, then add the hardener and polyethyl acrylate and coat immediately. .

The photographic properties were evaluated in the same manner as in Example-1, and the results are shown in Table-2.

It can be seen that the samples of the present invention show little change in performance even when the coating liquid ages.

The filterability of the coating solution was also tested. The test method and results are shown in Table 2. From Table 2, the comparative example shows that as the coating solution ages, precipitates form in the solution, which clogs the filter and makes filtration impossible. It can be seen that the sample of the invention does not occur.

As described above, the samples of the present invention are suitable for stably producing photosensitive materials with little fluctuation in performance.

Example-3 In Example-1, a hydrazine derivative and -S formula (1)
Samples were prepared using the types of compounds shown in Table 3.

As can be seen from Table 3, all of the samples of the present invention have little clogging of the filtration, little change in photographic properties, and extremely excellent manufacturing stability.

Claims (2)

[Claims] (1) having at least one silver halide photosensitive emulsion layer containing at least 80 mol% of silver chloride, and containing at least one type of hydrazine derivative in the silver halide emulsion layer or other hydrophilic colloid layer; The following general formula ( I
1. A silver halide photographic material comprising at least one compound represented by: General Formula (I) Q-SM In the formula, Q represents a heterocyclic residue to which at least one hydrophilic group is bonded directly or indirectly. M represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium. (2) The silver halide photographic material according to claim 1, wherein the hydrazine derivative is selected from compounds represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) In the formula, R^3 and R^4 may be the same or different, and each represents a hydrogen atom, an aliphatic residue, an aromatic residue, or a hetero R^5 represents a hydrogen atom or an aliphatic residue; X represents a divalent aromatic residue; R^2 is a hydrogen atom or an alkyl group (1 to 3 carbon atoms)
) or a phenyl group, the phenyl group may have the same substituents as above.