JPH01179939A - Method for forming ultrahigh contrast negative image - Google Patents

Abstract

PURPOSE:To make possible to maintain ultrahigh contrast and the stability of a negative image with a developer having a low pH by using a silver halide photographic sensitive material contg. a hydrazine derivative and a specified compd. in an emulsion layer or an another hydrophilic collidal layer. CONSTITUTION:The silver halide photographic sensitive material providing a silver halide emulsion layer on a supporting body, and containing the hydrazine derivative and the compd. shown by formula I in the emulsion layer or the another hydrophilic colloidal layer, is developed with a developer having pH of 11.0.-9.6. In formula I, Y is a group capable of adsorbing silver halide, X is a divalent linking group contg. an atom. such as hydrogen or carbon atom. or its atomic group, A is a divalent linking group, B is amino or ammonium group, etc., (m) is 1-3, (n) is 0 or 1. Thus, in the photosensitive material contg. the hydrazine compd., the image having the ultrahigh contrast can be obtd. by developing the material with the developer having pH of 11.0-9.6, and the photographic performance of the photographic material can be stably maintained by using a stable developer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic material and a method for forming an ultra-high contrast image using the same. It concerns photographic materials.

(Prior Art) In the field of graphic arcs, in order to improve the reproduction of continuous tone images or line images using halftone images, i[ A II7 imaging system is required.

Traditionally, a special developer called a Lith developer has been used for this purpose. Rhys developer contains only hydroquinone as a developing agent, and in order to avoid completely inhibiting its infectious development properties, sulfite, which is a preservative, is used in the form of an adduct with total formaldehyde, and the concentration of free sulfite ions is extremely low ((usually Therefore, the Lith developer Vi has the serious disadvantage that it cannot be completely oxidized in the air and cannot be stored for more than 3 days.

As a method for obtaining high contrast photographic properties using a stable developer, US Pat.
, /lr, No. 977, same No. 4t, /At, 7412
No. 41.31! , 71! No. 1I, 272.
tOt No. 1I, 2//, No. 117, No. ≠,
There is a method using a hydrazine derivative described in Koko No. 3,73. 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. It improves dramatically in comparison.

However, in order to form ultra-high-contrast images using hydrazine derivatives, the pH must be 11.0 or higher, and as a result, the developing agent is easily oxidized, and the pH also fluctuates due to absorption of CO2 in the air. However, it has the disadvantage that it is difficult to obtain stable photographic properties. Therefore, in order to maintain the stability of the developer, a method of obtaining ultra-high contrast images in the presence of a high-d degree sulfite with p14//, 0 or less has been preferred.

There is a strong desire for a means to fully promote high contrast using hydrazine. , Japanese Unexamined Patent Application Publication No. 1986-1989/Hiro03-Hiro OK discloses an amine compound as a contrast enhancing agent. However, even when these compounds are used, it is difficult to promote high contrast at pH 7/or lower.

When trying to obtain a photosensitive material for bright room use with low sensitivity using a single-layer hydrazine compound, for example, in JP-A-6O-r3o3r and JP-A-60-/Jj, u4LA, a silver halide photosensitive material containing gold containing water-soluble rhodium salt is used. is disclosed. However, when a sufficient amount of rhodium is added to lower the sensitivity, the high contrast caused by the hydrazine compound is inhibited, and the desired sufficiently high contrast images cannot be obtained.

(Objective of the Invention) The object of the present invention is to provide a method for achieving ultra-high contrast in a system using a hydrazine compound when the pI-1 of the developer is //, 0 to 1, and The objective is to provide ultra-high contrast image formation that can maintain stable performance using a stable developer.

(Structure of the Invention) The above object of the present invention is to have at least one silver halide emulsion layer on a support, and the emulsion layer or other hydrophilic colloid layer contains at least one hydrazine derivative and the following general formula: A carbide rubber containing at least one compound represented by (I)! 4 negative silver halide photographic material at pH 11,
O-? This was achieved by a method of forming an ultra-high contrast negative image characterized by processing with a developer of .

(In the formula, Y represents a group that adsorbs to silver halide. X is selected from hydrogen atom, carbon atom, nitrogen atom, oxygen atom, and sulfur atom.
Represents the linking group of i. A represents a divalent linking group. B represents an amine group, an ammonium group, or an arsenic-containing heterocycle, and the amino group may be substituted. m represents /, ko, or 3, and n represents O or /. ) The group represented by Y that adsorbs to silver halide includes nitrogen-containing heterocyclic compounds.

When Y represents a nitrogen-containing heterocyclic compound, the compound of general formula (I) is represented by the following symbol (n).

- Monna (If) QN÷M)a In the formula, l represents /, m represents /, 2 or 3, and n represents O or /.

÷(X+-A-B]m has the same meaning as in -Moreka (1) above, and Q is composed of at least one kind of atom of carbon atom, nitrogen atom, oxygen atom, and sulfur atom! or a t-membered atom. Represents a group of atoms necessary to form a heterocycle.This heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle formed by Q include substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, Examples include azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, and quinolines.

M is a hydrogen atom, an alkali metal atom (e.g. sodium atom, potassium atom, etc.), an ammonium group (e.g. trimethylammonium group, dimethylbenzylammonium group, etc.), and under alkaline conditions M=H can become an alkali metal atom. Groups (e.g. acetyl group, cyanoethyl group, methanesulfonylethyl group %!;) K Table Was.

In addition, these heterocycles include nitro groups, halogen atoms (e.g., chlorine atom, bromine atom, etc.), mercapto groups, cyano groups, and substituted or unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, etc.). , t-methyl group, cyanoethyl group, methoxyethyl group, methylthioethyl group,
etc.), aryl i (for example, phenyl silkworm, ≠-methanesulfonamidophenyl group, ≠-methylphenyl i,
j, 4'-dichlorophenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. hahenzyl group, μm methylbenzyl group, phenethyl a
, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), aryloxy groups (e.g. phenoxy group, Hiro-methoxyphenoxy group, etc.), ruthio% (L
i'Jj- is methylthio, ethylthio, methoxyethylthio group), arylthio T: (fiJ is phenylthio group), sulfonyl (=IL8i) tansulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, 4), carbamoyl group (for example, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, 4), sulfamoyl group (for example, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide groups (e.g. acetamido group, benzamide group, etc.), sulfonamide groups (e.g. methanesulfonamide group, benzenesulfonamide!)
, p-toluenesulfonamide group, etc.), alkoxy groups (e.g. acetyloxy group, penzoyloxy group,
Sulfonyloxy group (I]e: kemethanesulfonyloxy, etc.), ureido group (e.g., unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.), thioureido group (e.g., unsubstituted thioureido group, methylthioureido group, etc.), acyl group (for example, acetyl group, benzoyl group, etc.), heterocyclic group (for example, l-morpholino group, /-piperidino group, cobiridyl group, ≠-pyridyl group, 2- thienyl group, l-pyrazolyl group, l-imidazolyl group, 2-tetrahydrofuryl group, tetrahydrothienyl group, etc.), oxycarbonyl I
(for example, methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (e.g., methoxycarbonylamino group, phenoxycarbonylamino group, coethylhexyloxycarbonylamino group, etc.), amine group (e.g., swallow (amino group, dimethylamino group, methoxyethylamino group, anilino group, etc.), carbonaceous 7t may be substituted with its base, sulfone 7t may be monosubstituted with 7-salt, hydroxyl group, etc.

As a link between the two cars represented by i (For example, methylene group, ethylene group, propylene M, -y-tylene group, hexylene group, l-methylethylene group, @) may be bonded through. About 0,
R2, Ru3, Ru4, Ru5, R6, R7, R8, Rin, and Ro. represents a hydrogen atom, respectively, or an unsubstituted alkyl group (e.g. methyl group, ethyl group, propyl group,
n-butyl, n-butyl), unsubstituted or unsubstituted aryl groups (e.g., phenyl, !-methylphenyl, etc.), substituted or unsubstituted alkenyl groups (e.g., propenyl, /-methylvinyl, etc.) , na), maku is replaced or:
Aralkyl groups (NJ, benzyl, phenethyl, etc.) substituted with pAt are listed below.

A is a divalent chain group, and as a divalent chain, one straight chain is a branched alkylene group (e.g. methylene group, ethylene group, propylene group, butylene group, hexylene group, /-
Methylethylene group, etc.
Straight chain or branched aralkylene groups (e.g., benzylidene group, etc.), arylene groups (e.g., phenylene, naphthylene, etc.) and the like can be mentioned. The above valence represented by A is X
and A may be further replaced with any set of 4#.

The substituted or unsubstituted amino group of B is represented by the general formula % general formula (Vl[) r(, l l / (wherein 11 and 12 may be - or different). Often, each hydrogen atom has 7 or more carbon atoms
The argyl group and the alkenyl group in 30 are aralkyl groups, and these groups are linear groups (e.g. methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, allyl group, 3- butenyl group, bemesyl group, l-naphthylmethyl group, etc.), branched (eg, isopropyl group, t-octyl group, etc.), or cyclic (eg, cyclohexyl group, etc.).

Moreover, R11 and R-12 may be connected to form a ring,
Seven of them! The group may be cyclized to form a saturated heterocycle containing more than one heteroatom (e.g., oxygen, sulfur, hydrogen atoms, etc.), such as pyrrolidyl, piperidyl, morpholino, etc. Examples include groups. Examples of substituents for Bll and B.12 include a carboxyl group, a sulfo group, a cyano group, and a halogen atom (eg, a fluorine atom, a chlorine atom, and a bromine atom).

), hydroxyl group, cycal in alkyl having 20 or less carbon atoms
Nyl group (e.g. methoxycarzenyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group having 20 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), carbon Monocyclic aryloxy groups having 20 or less carbon atoms (e.g. phenoxy group, p-)lyloxy group, etc.), acyloxy groups having 20 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyl having 20 or less carbon atoms group (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), force k ha% (ki
(flJ, j hacarpasoyl i, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group) , piperidinocarbonyl group, etc.), acylamino group having 20 or less carbon atoms (e.g. acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide group (ethylsulfonamide group, P-)luenesulfonamide [groups]], cardanamide groups with a carbon number of 0 or less (e.g., methylcarmenamide groups, phenylcarbonamide groups, etc.), carbon e2
Examples include 0 or less ureido groups (for example, methylureido groups, phenylureido groups, etc.), amino groups (synonymous with -monna (■)), and the like.

The ammonium group of B is represented by the general formula (■).

(Zo).

(In the formula, R1B and R are the same groups as Bll and B12 in the above-mentioned general formula (■) K, and ze represents an anion, such as a halide ion (e.g., αe, Bre, etc.), a sulfonate ion, etc. ions (e.g. trifluoromethanesulfonate, paratoluenesulfonate, benzenesulfonate, trichlorobenzenesulfonate), sulfate ions (
For example, ethyl sulfate, methyl sulfate, etc.)
, nochlorate, tetrafluoroborate, and the like. p #i0 几 excludes l and is O if the compound forms an inner salt. ) The snow-containing heterocycle of B contained at least 7 or more nitrogen atoms! Or, it is a membered ring, and these rings may have a substituent or may be fused with another ring.

Examples of the nitrogen-containing heterocycle include an imidazolyl group, a pyridyl group, and a thiazolyl group.

Preferred examples of general formula (n) include compounds represented by the following formulas (II), (■), and (V).

General formula (I [I) General formula (IV) General formula (V) (X+-A-B General formula (Vl) It has the same meaning as that. Zl, "2 and Z3 have the same meaning as +XA-8 in the above-mentioned -Momona (I), or a halogen atom, an alkoxy group having 20 or less carbon atoms (for example, a methoxy group), a hydroxy group , a hydroxyamino group, a substituted and unsubstituted amine 7 group, and the substituent of 7 can be selected from the substituents of R11 and R12 in the above-mentioned - Monna (■).However, among Z Z and Z3 At least seven of the above are synonymous with MOXU-A-B.

These heterocycles may also be substituted with the substituents applicable to the heterocycles of general formula CI).

Next, examples of compounds represented by general formula (1) will be shown, but the present invention is not limited thereto.

l.

t α 10° //.

/+Z /3 1. /l /7 /Yo 20° H 2 yu 23° 2 hiro 26° z 30° t 33° 3yo H Z da O1 μl.

Hiroyu ≠ 3゜ μ Hiro ≠ ≠ 6 α
r 1chte der I) eutsch
enChemischen Ge5ellschaft
) 2r, 77 (/, r5'j), Tokukai Sho! 0-37tA
Jj issue, same! / -j JJ / No. 3, US Patent No. 2, No. 7 O, US Patent! ,! No. 74,310, Berichte der Deutschen? Hemitschengesellschaft (Berichte der 1) eutschen
Chemischen Gesellschaft)
22, ttr<irr), same 2, 24! r3(ir
yt), Journal of Chemical Society (
J, Chem, 8oc,)/rijj,/rat, Journal of the American Chemical Society (J, Am.

Chem, Soc, )7/, l/1000 (/51
'Hirori), U.S. Patent Co., ZRZ, No. 3rt, 2. ! μ
No. 7゜22, Advances in Heterocyclic ζ Chemistry (Advanceo 1nHet
erocyclic chemistry) L, /
A j (19buts), Organic Synthesis (O
rganic 5ynthesis) ■, jJri (
/rit3), Journal of the American Chemical Society (J, Am, Chem, Soc,)
Hiro! , 23riO (/ri23), Hemische. Berichte (C
Hemische Berichte) ≠4! (
/r7t), Tokko Sho ≠ o-, 2t4t ri, Tokko Shoj
No. O-19034L, U.S. Patent 3. IO≦, Hiroshi 67,
Same 3. μ20,470, same, J7/.

2 Kota issue, same! , /37. J71, same! , / Hiro r, o
tt issue, same 3. j//, tbu 3, same 3゜Obu 0.02
No. 1, same! , 27/, /J≠ issue, same J, 23/, tri7
No. 3. ! Ril, No. 122, same! , /4Llr, 06
No. 6, Special Publication Show≠3-Pi No. 131, U.S. Patent No. 3. Otsu/jo
No. 16, 3,4L Koo, tt4L, 3.07/,
II≦No.3, same.

4tt, tu, toz issue, same 2. μ Hiro≠, tobu issue, same 2 1AlAlt, t07 issue, same 2,931, 4c01
No. 1 Japanese Patent Publication No. 77-202. j No. 37, 67-/67
．． No. 023, same j7-/bu μ, No. 733, same to-to
.

Ryo No. 32, same! ♂-/12,23! No., same j7-/Hiro,
r J number, same jter/12. Hankyugo, same to-/
J O, 7J No. 7, same≦0-/31. Monthly issue 4, same jr
-r3. rz2, same 5r-it,! 2nd issue, same! Tah/! ri, No. 162, Otsu 0-2/7. JJr No., same / -I O, 2J No. 1, special public Akibu O-Koji, 3ri 0
No., Dobu Q-Kota, Jri No. 1, Dobu 0-/JJ, 0tt
No. 41-/, No. 31, etc., it can be easily synthesized.

The optimum amount of these accelerators to be added differs depending on the type of compound; i'/m2
, preferably j, l:)X/0-3~0,/9
It is preferable to use it within a range of 7m2. These accelerators are dissolved in a suitable solvent (H2O, alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcernorp, etc.) and added to the coating solution.

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

The hydrazines/derivatives used in the present invention include U.S. Pat. octopus! Examples include hydrazine derivatives having a sulfinyl group and compounds represented by the symbol (X) below.

General formula (X) R-NHN? 1-CHQ In the formula, R1 represents an aliphatic group or an aromatic group.

- In the pattern hole (X), the aliphatic group represented by Ro preferably has 7 to 3 carbon atoms, particularly carbon number/~
2Q is a straight chain, branched or cyclic alkyl group. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing seven or more heteroatoms therein. In addition, this alkyl group is an aryl group,
It may have a substituent group such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

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

- The aromatic group represented by R in the pattern (X) is a monocyclic or monocyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a single ring or a complete aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrrolidyl group, quinoline ring,
Examples include an isoquinoline ring, a penzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or aromatic group of Ro may have a substituent.

Typical substituents include straight chain, branched or cyclic alkyl groups (preferably those with 1 to 20 carbon atoms), aralkyl groups (preferably monocyclic or cocyclic alkyl groups with 1 to 3 carbon atoms in the alkyl moiety). ), alkoxy groups (preferably those having a carbon number of l-coO), substituted amine groups (preferably carbon atoms at
-2o alkyl group-substituted amino group), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 7 to 30 carbon atoms)
, a ureido group (preferably one having a carbon number of 1 to 3°)
and so on.

80 of the general formula (X) may have a pallast group, which is commonly used in immobile photographic additives such as couplers, incorporated therein. What is the ballast group? It is a relatively inert group with respect to photography having the above carbon number, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like.

RlFi of general formula (X) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Examples of such adsorption groups include groups such as a thiourea group, a heterocyclic thioamide group, a mercapto VI ring group, and a triazole group, which are described in US 1% Permit No. 31rj, No. 102.

Synthesis methods for these compounds are described in JP-A No. 13-202-1,
Same j3-λ0222, Same 63-J4732, Same 73
-20311 etc.

In the present invention, when the compound represented by -pattern (X) is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but it is preferably contained in a non-photosensitive hydrophilic colloid layer (e.g. protective layer, intermediate layer, filter layer,
It may be included for halation prevention/if, etc.). Specifically, when the compound used is water-soluble, it is prepared as an aqueous solution, and when it is poorly water-soluble, it is prepared as a solution of water-miscible organic solvents such as alcohols, esters, and ketones, and as a hydrophilic colloid solution. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between after the end of chemical ripening and before coating. In particular, it is preferable to add it to a coating solution prepared for coating.

The content of the compound represented by the general formula (X) of the present invention is determined by the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, and the relationship between the layer containing the compound and the silver halide emulsion layer. It is desirable to select the optimum amount depending on the type of antifoggant compound, etc., and testing methods for selection are well known to those skilled in the art. Usually and preferably from to-6 mol to/x10-/x10-/mol silver halide.
''moles, especially in the range from 10 to 110 mol.

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

However, the present invention is not limited to the following compounds.

×-3 X-Hiroshi ×-! ×-4 tC5H1, / 21-15 on Meno O X-// ×-72 X-/3 X-/j ■ C. i-1 3 ×-77 CH2CH2CH2SH X-/J’ %-t X-2.

×-27 ×-22 ×-23 C(JC)i3 Mae 2 Hiro 0 ×−koj (JCH3 ×-27 -2t Sue 22 ×-30 ×-32 ×-33 X-3@ et al., U.S. Patent No. 1771. As stated in PJt issue and so on.

In the present invention, particularly preferred compounds of general formula (X) are:
It is preferable that R1 incorporates a group that enhances adsorption to the silver halide grain surface. Such adsorption groups include:
Thiourea, heterocyclic thioamide group, mercapto heterocyclic group,
U.S. Patent No. V, 3ts, io for triazole groups etc.
Examples include the groups listed in item r. Further, the substituent of the aryl group or aromatic group of R1 is preferably an amide group, a ureido group, or a thiourea group, and particularly preferably a sulfonamide group.

The compound of general formula (I) used in the present invention is jmy/
m2 to 300 my/m2 is preferable, especially 70 m2
~-210■/m2 is good. In addition, the compound of Monna (X) preferably has /~300 mq/fi2, particularly 2~200 mq
/m2 is good. Furthermore, in those in which R1 is incorporated with a group that enhances adsorption to the silver halide grain surface, 2 to
lOOki/fi2 is good.

In the photographic emulsion of the present invention, a combination of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide, and silver chloride may be used as silver halides. It is preferable that the amount of silver is equal to or more than jO molar width.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions are cubic, octahedral, l
Regular like μ-hedron, rhomboid heptahedron
It may have a regular crystalline form, or it may have an irregular crystalline shape such as a spherical shape or a plate-like shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

Further, the grain size distribution of silver halide grains in the photographic emulsion is arbitrary, and may be monodisperse.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Further, the amount of these additives may be small or large depending on the intended photosensitive material.

In addition, depending on the purpose, known silver halide solvents (for example, ammonia, Rodankali, U.S. Patent No. 3, etc.) may be used.
27/, No. 117, JP-A-1231,0, JP-A-J3-t21AOr, JP-A-33-/μ-H3/RI, JP-A-4L-100777, JP-A- /j
thioethers and thione compounds described in jF21r, etc.)
can be used.

The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, active gelatin and compounds containing sulfuric acid that can react with silver (e.g., thiosulfates, thioureas,
Mercapto compounds, rhodanines) - Sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds): Noble metal compounds ( for example,
In addition to total complex salts, a noble metal sensitization method using complex salts of metals in group 1 of the periodic table such as Pt, Ir, and Pd can be used alone or in combination.

The photographic emulsion of the present invention can contain all of various compounds for the purpose of preventing fogging during storage or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto; Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially nophenyl-mercaptotetrazole), mercaptopyrimidines The above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a dicarboxyl group or a sulfonic group: thioketo compounds Oxazolinthione: Azaindenes such as tetraazaindenes (particularly gu-hydroxy-substituted (/, 3.Ja, 7) tetraazaindenes):
Many compounds known as anti-caking agents or stabilizers can be added, such as benzenethiosulfonic acids; benzenesulfinic acids, etc.

In the photographic material of the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. Specific examples of spectral sensitizing dyes include Baegura 7
Written by Glafkides [Chimie Photographique
)J (2nd edition, /P77: Bauml Montel, )Guri (Paul Montel, Paris)) iJj
Chapter ~44/Chapter and F. M. Hamer [The Cyanine and Related Connoisseurs]
The Cyanine and RelatedC
yx (Inter
-science)”), and U.S. Patent No. 2,103,
No. 776, 3. ≠No. 19,113, 3. /77゜2
IQ issue, Research Disclosure
ch Disclosure) / Volume 7A / 7A Hiro J (/
7, published in December 2017), Section 23 (■), Section 5, etc.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye for certain purposes such as prevention of irradiation and various other purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes;
Hemioxonol dyes and merocyanine dyes are useful.

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, activated vinyl compounds (/, j.

j-) Liacryloyl-hexane-drawn 5-triazine, 1,3-vinylsulfonyl-copecononol, etc.), active halogen compounds (2, Hiro-dichloro-t-hydroxy-8-triazine, etc.), etc. alone or Can be used in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., enhancement of current density, dulling, sensitization, etc.). ) Various surfactants may be used for various purposes.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates,
polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkyl succinic acid) Nonionic surfactants such as polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of H; alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates , alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl betaines, amine oxides amphoteric surfactants such as alkyl amine salts, aliphatic or aromatic μ-class ammonium salts, heterocyclic primary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or aromatic rings. Cationic surfactants can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains flJ j for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain derivatives such as hapolyalkylene oxide or its ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, hydrophilic polymeric substances such as polyvinyl alcohol, polyvinyl alcohol acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, and dextran can be used.

In order to obtain ultra-high contrast photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developing solution or US Pat. t
A/? It is not necessary to use a highly alkaline developer with p)l/3 as described in No. 973, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative in an amount of o, it mol/or more, and has a pH of
A sufficiently high-contrast negative image can be obtained with a developer having a rating of //, 0 to 0, especially //, 0 to IQ, 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-pyrazolidones (eg, tiJ'/-phenyl-3-pyrazolidone, Hiroshi).

(gudimethyl-l-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. can be used alone or in combination.

In particular, the silver halide light-sensitive material of the present invention uses dihydroxy(benzenes) as the main developing agent and 3-
Suitable for processing with developers containing pyrazolidones or amine phenols. Preferably, in this developer, dihydroxybenzenes are contained in an amount of o, o to o, z mol/113-pyrazolidones or aminephenols.
o.

6 mol/are used together in the following range.

Furthermore, as described in US Pat.

The solution also contains pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, bromides,
It may contain a development inhibitor or an antifoggant such as an iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles). 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, λ-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 present invention is usually from /r0C to jO
Selected during oC.

It is preferable to use an automatic developing machine 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 developing machine until it comes out is set to f90 seconds to /0 seconds. Also, it is possible to obtain photographic characteristics of sufficiently ultra-high contrast negative gradation.

In the developing solution of the present invention, JP-A-54-2 is used as a silver stain preventive agent.
The compound Kongo described in 14.3 Ko No. 7 can be used.

Patent application Shoto-io2 as a dissolution aid added to the developer
．． Compounds described in No. 7μ3 can be used. Furthermore, as a pH buffering agent used in the developer, JP-A-6O-PJ,
The compounds described in No. 4tJJ or the compounds described in Kentokuko 43/ can be used.

Example/A silver chloroiodobromide emulsion (silver iodide 0
．． 1 molar ratio and 30 molar ratio of silver bromide) were prepared. This silver chloroiodobromide emulsion contains (NH4)3Rhα as a rhodium salt.
6! An aqueous halogen solution was added to give a ratio of X10' mol/Ag mol. At the same time, as an iridium salt,
K3 IrCl6 t"≠xio mol/Ag mol... rogen aqueous solution was added.

This halogen aqueous solution, silver nitrate aqueous solution and t-Hiroj0060
The mixture was mixed for 1 minute to prepare a monodisperse cubic emulsion with an average grain size of 0.2 μm. After washing and desalting with water, this emulsion was added with sodium thiosulfate f/10-5 mol/Ag mol, and potassium chloroaurate was added to give a metallic effect/X10' mol/Ag mol. These emulsions are used as sensitizing dyes/-
(λ-hydroxyethoxyethyl)-3-(pyridine-coyl)-6-((j-sulfobutyl-yo-chloro-
2-penzoxazolinidene) ethylidene 2-thiohydantone potassium salt fJ x 10' mol/Ag 1 mol,
f constant agent and hydroxy-6-methyl-/3.
Ja, 7-chitrazaindene/, jt1 hydroquinone f2 f, resorcinaldoxime 2? , l-phenyl-yo-mercaptotetrazole at 0. /f were each added per mole of silver.

Furthermore, as a coating aid, the following compound and saponin were used as C17H33CON-CH2CH2803NaCH3 as a hardening agent, CH2= CH802CH2C0NH(CH2)n N
Sodium polystyrene sulfonate was added using HCOCH2802CH=CH2 (n=2.3) as a thickener, and a dispersion of polyethyl acrylate was added as a latex polymer.

Furthermore, as a hydrazine compound, from -Momonana (X), respectively X-ta, X-3/, X-λo1X-32, X-J Hiromu, 1-it2 was added as shown in Table-/.

As the M retention layer, an aqueous gelatin solution consisting of gelatin, sodium dodecylbenzenesulfonate, colloidal silica, a dispersion of polyethyl acrylate, a matting agent of polymethyl methacrylate, and a thickener of sodium polystyrene sulfonate, and a coating amount of chilatin were used. 1.697 m2, and the emulsion was coated with a silver amount of 3.6 f/m2.
The emulsion layer and capture layer were coated at the same time.

Each of these samples was exposed to tungsten light at 32,000 ℃ for 11 seconds through an optical wedge for sensitometry, and then developed with developers (A) and (B) having the following compositions at 3r0C for 30 seconds, fixed, washed with water, and dried. did.

(For the developing process, use the automatic developing machine FG manufactured by Fuji Photo Film ■.
-460F was used. ) [Developer (A) formulation] Hydroquinone JJr, 09N-
Methyl-p-aminophenol//λ sulfate o,ry Sodium hydroxide 7.0? Potassium triphosphate 7≠, O? potassium sulfite
90.0? Ethylenediaminetetraacetic acid disodium salt /, 09 Potassium bromide 3.01 methylbenzotriazole 0. Otsu? 3-diethylamino-l-propatool l, add C1 water /1 (pH, -7),
4) As a developer, by adding acetic acid to the developer (A), the pH was lowered by 2 to 10. ≠ All prepared solutions (D) were developed in the same manner.

The full results table is shown in /. Then, the G value was measured.

Further, developer solutions (A) and (D) were added to beakers containing 1/l and left for a week, and then treated with these solutions in the same manner as above, and Gi measurement was performed.

It can be seen that by using the compound of general formula (I) of the present invention, G can be maintained at 10 or more even at low pH values, and the solution is stable over time.

Example λ The film layer prepared in Example/, the same liquid as Example/ except for the pH value (B'), (C), (D), (E)
, (F), and (G) were all prepared and developed in the same manner as in Example 1, and G was measured. Also shown are the results of processing after putting the developing solutions (A) to (G) into a /l beaker and leaving them for one week.

It can be seen that by using the compound of the present invention, it is possible to maintain ultrahigh contrast of 110 or more, and stable Gi is maintained in the pH range of the present invention.

Example 3 When producing the filmta of Example 1, nucleation accelerator 1-i
Ni/6 and Ni λ/l- were added in the same manner instead of s, and films ① and ＠) were prepared. Processed in the same manner as Example/G
t-measured.

It can be seen that the compound of the present invention maintains ultra-high contrast of G10 or higher and stability in a low pH working solution.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Claims] (1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing at least one kind of hydrazine derivative in the emulsion layer or other hydrophilic colloid layer is treated with a high pH developer. In the ultra-high contrast negative image forming method in which the emulsion layer or other hydrophilic colloid layer contains at least one compound represented by the following general formula (I), the pH value of the developer is 11.0 to 9.
6. A method for forming an ultra-high contrast negative image. General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, Y represents a group that adsorbs to silver halide, and A represents a divalent connecting group, B represents an amino group, an ammonium group, or a nitrogen-containing heterocycle, m represents 1, 2,
or 3, and n represents 0 or 1. )