JPH01161340A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material which has less residual colors after development processing by incorporating a specific compd. into an emulsion layer or hydrophilic colloid layer and specifying a developing soln. CONSTITUTION:The compd. expressed by the formula I is incorporated into the emulsion layer or hydrophilic colloid layer. In the formula I, PWR denotes a group which releases (Time)t-LA when reduced; Time denotes a group which releases LA via the ensuing reaction after release as (Time)t-LA from PWR; (t) denotes 0 or 1 integer. LA has the absorption max. of light at >=310nm. The developing soln. is prepd. by using substantially only the dihydroxybenzene as a developing agent. The concn. of the free sulfite therein is >=0.8mol./l and the pH thereof is >=11.0; in addition, the developing soln. contains the compd. expressed by the formula II at >=20mg/l. In the formula II, X1 denote a nitro group, etc., X2, X3 denote an alkyl group of 1-4C, etc. The remaining colors after the development processing are thereby decreased.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for forming an ultra-high contrast negative image 1 using a halogenated trowel photographic light-sensitive material, and in particular to a silver halide photographic light-sensitive image used in a photolithography process. For more information on materials, see ultra-high contrast negative type photography suitable for photosensitive materials for bright rooms/! This invention relates to an image forming method using 8-light materials.

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

As a method for obtaining high contrast photographic properties using a stable developer, US Pat.
Same No. ≠, itr, ri No. 77, same g μ, 166.7 μλ No., same No. ≠, 3//, 7za No. 1, same No. Da, core J, 60
No. 6, No.≠, i, 2i, rs7, No. 6, Ko6ri,
A method using a hydrazine derivative gold layer is known, which is described in No. 2, No. μ, ltO, 74 (A, etc.). According to this method, ultra-high contrast and high sensitivity photographic characteristics can be obtained.
Furthermore, since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is greatly improved compared to a lithium developer.

However, although the above-mentioned image system is highly sensitive to high-contrast systems, it is a low-sensitivity light-room M&D material widely used in the turning process during the plate-making process.
r was difficult to obtain. As a method for obtaining a low-sensitivity photosensitive material for bright room use containing hydrazine, Shukai Showa 60-7≠0
No. 31, JP-A-Sho to-/622-Hiro 6, 6/-23
It is disclosed in No. 10≠R, long-awaited No. 62-1sJ//A.

Generally, in silver halide photographic light-sensitive materials, Il&l
Silver halide emulsion layers or Incorporation of light-absorbing compounds into other hydrophilic colloid layers has been practiced in the past.

In particular, silver halide photographs M&
Optical materials, more specifically photosensitive materials for bright room use, have UV and visible light absorbing dyes added to the photosensitive layer or to the layer between the light source and the photosensitive layer in order to increase safety against safelights. Ru.

It is also added to the hydrophilic colloid layer between the photosensitive silver halide emulsion layer and the support to prevent halation.

The dye used for this purpose must be decolorized during photographic processing and easily eluted from the silver halide photographic light-sensitive material to prevent substantial residual color staining caused by the dye after photographic processing. The emulsion should not have any negative effects such as fogging, smearing, or desensitization91 on the emulsion, should not be diffused from the colored layer to other layers, and should have good absorption spectrum characteristics according to its purpose of use. Furthermore, it must satisfy various conditions such as excellent stability over time in a solution or a silver halide photographic light-sensitive material, and no deterioration.

Many efforts have been made to find dyes that meet these requirements. For example, the pyrazolone oxonol dye described in British Patent No. 306°3za3, US Patent No. 3.
λ177,/27, azo dyes described in U.S. Pat. No. 2,370,707, styryl dyes described in U.S. Pat. No. 2,233,077, British Patent No. The hemioxonol dye described in U.S. Patent No. 60, U.S. Pat. The merocyanine dye described in Hiroshi J., 7 Hiroshi No. 7, US Patent No. 2. Za443. Examples include cyanine dyes described in U.S. Pat. % Gansho 61
-2 Hiroza 7/ discloses a four-chamber silver halide photographic light-sensitive material containing a dye having a λmax of less than 3 Q nm.

When the layer containing the above-mentioned dye functions as a filter layer or an antihalation layer, it is necessary to selectively color the layer so that the coloring does not substantially spread to other layers.

However, even if the above-mentioned dye is added to a layer other than the emulsion layer, it will diffuse into the emulsion layer and prevent irradiation of the exposure light in the emulsion layer. Tone controllability of dot images (In terms of A-body, it refers to the ability to make the line width slightly thicker than the original image, or to make the area slightly wider than the halftone dots of the original image. In the reversal process, the line width is exactly the same as the original image, or the line width is slightly wider than the halftone dots of the original image. In addition to the ability to reproduce halftone dot areas, when adding artistic expression, the ability to make corrections to the original image is required. There is a problem.

As a method for solving this problem, a method has been known in the past in which a so-called acid dye having a sulfo group or a carboxyl group is localized to a specific dye using a mordant.

Such mordants include those described in British Patent No. 6Jj.

≠ Ethylenically unsaturated compound polymer containing dialkylaminoalkyl ester residues described in No. 7j, No. ♂
3θ, reaction product of polyvinyl alkyl ketone and aminoguanidine described in No. 2♂/, U.S. Patent No. 2.3≠za,
3Aμ No. 2. Hirogμ.

'430, 3. /g1.01p/issue, same 3,7j6
．． Vinylpyridine polymers and vinylpyridinium cationic polymers described in the specification of No. 1/≠ are known, and in order to effectively mordant the acid dyes mentioned above, secondary and tertiary polymers are included in the polymer. Cationic mordants containing amino groups, nitrogen-containing heterocyclic groups, and quaternary cationic groups thereof are used.

However, these cationic mordants cause electrostatic interactions with gelatin, which is often used as a hydrophilic colloid, and surfactants containing alcoholade groups, carboxylade groups, sulfonate groups, and sulfate groups, which are usually used as coating aids. In some cases, it may worsen the sex.

In addition, it was said that with such a mordant, the acidic dye mentioned earlier would diffuse into other layers, and it was considered to use a large amount of mordant to eliminate the diffusion, but it was not possible to completely eliminate the diffusion. Not only is this impossible, but the thickness of the layer to be contained becomes large, resulting in the problem that the dye remains in the photosensitive material even after development.

In order to solve these drawbacks, patent application No. 12-II370
No. ≠, No. 1s2-2.2/, No. 3 discloses dyes that are prevented from diffusing into other layers and are easily desorbed. It has been discovered that, although the above-mentioned dye exhibits outstanding performance in terms of diffusion resistance and decolorization, γ is lowered, causing a deterioration in the quality of printed characters.

Substantially only dihydroxybenzene is used as a developing agent,
Image forming methods using a developing solution containing a large amount of sulfite are disclosed in U.S. Pat.
No. 732, No. 60-Tough 3≠za, No. 61-≠793/.

(Object of the invention) The first object of the invention is to develop γ of 10 using a stable developer.
An object of the present invention is to provide a halogenated scissors photographic material with extremely high contrast exceeding the above.

A second object of the present invention is to provide a photographic material for bright room use that utilizes high contrast by a hydrazine compound.

The third object of the present invention is image quality (cutting characters, tone changeability)
To provide a photographic material for bright room use, which has improved safelight properties without deteriorating the photosensitive material.

A primary object of the present invention is to provide a silver halide photographic material with less residual color after development.

(Means for Solving the Problems) The above object of the present invention is to have at least seven silver halide emulsion layers on a support, and contain a hydrazine derivative in the emulsion layer or other hydrophilic colloid layer. In an image forming method in which a halogenated photosensitive material is imagewise exposed and then developed using a developer, a compound represented by the following general formula [I] is added to the emulsion layer or the hydrophilic colloid layer. Contains
And the current gI! This was achieved by an image forming method characterized in that the liquid satisfies the following conditions (1), (2), (2) and @.

General formula (])% formula%) In the formula, PWR1j: By being reduced (T i m
e+1-LAt- represents a releasing group.

Time is from PWR (Time + - LA
represents a group that releases LA through a subsequent reaction after being released as LA.

t is expressed as an integer 1 of O or l.

Conditions for LA to have a light absorption maximum of 3/Q nm or more: (1) Substantially only dihydroxybenzene must be used as a developing agent.

■ The free sulfite concentration is at least 0.7 gmol7
Must be 2 or more.

■　ph should be //, 0 or more.

(2) It contains at least i0xg/ft of the compound represented by general formula (II).

General formula (It) In the formula, X1 represents a hydrogen atom or a nitro group.

X2 and X3 each represent a hydrogen atom or an alkyl group having a carbon number of /≠.

The compound of general formula [I] used in the present invention will be explained.

First, PWH will be explained in detail.

PWR is U.S. Patent No. ≠, /3, No. 3 or U.S. Patent Ko, /3, No. 377, JP-A-Shojter/I! ;333
Even if it corresponds to a moiety containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in No. Good, US Patent≠, 23.2.1
No. 07, JP-A-5Y-IOI6 ≠ No. 07, % Kai-Sho 6
As disclosed in No. 7-11.237, the electron-accepting quinonoid center and the carbon atom linking it to the photographic reagent in a compound that eliminates the photographic reagent by an intramolecular electron transfer reaction after being reduced. It may correspond to the part that contains the part. Also, Unexamined Showa JLS-1≠,
No. 2330, U.S. Pat.

゛3 Hiroshi 3. Aryl groups substituted with electron-withdrawing groups in compounds whose single bond is cleaved after reduction to release a photographic reagent, as shown in US Pat. It also does not apply even if it corresponds to a moiety containing an atom (sulfur atom, carbon atom, or nitrogen atom) that connects it to a photographic reagent. Also, US patent≠,≠30.2
It may correspond to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom that connects the photographic reagent with the nitro group as disclosed in U.S. Pat. It corresponds to the geminal dinitro moiety in the dinitro compound that β-eliminating the photographic reagent after accepting electrons and the carbon atom-containing moiety that connects it to the photographic reagent described in No. 60, No. 670. It doesn't matter if there is. However, in order to more fully achieve the object of the present invention, the compound of general formula [I] is preferably one represented by general formula (IV).

General formula [IV] 1 /'EAG' In the general formula (V), ■ EAG corresponds to (T im e-) - LA is 几, R or EA
Combines with at least one of G.

X is an oxygen atom (-(J-), a sulfur atom (-8-), Represents a group containing a nitrogen atom (-he).

BAG has a group that accepts or accepts electrons from a reducing substance,
Bonds to nitrogen atoms. As a BAG, the following general formula (A)
or CB) is preferred.

General formula (A) General formula CB) In the general formula (A), Sub Vn' represents an atomic group forming a 3- to g-membered ring together with Zl and z2, and n' represents an integer from 3 to g, but V3 Z3-1V4 knee Z3-Z4-%v5:
Zs ”4-Zs-1■6;-23-24-25
26-1V7 * Zs -Z4 Zs -Z62
Fu -, V8: -Zs-Z4-Zs -z6-z7
-28-.

-5-1 or -802-, and 8ub represents a simple bond (7G bond), a hydrogen atom, or a substituent described below. 8ub may be the same or different. or may be bonded to each other to form a 3- to g-membered saturated or unsaturated carbocycle or heterocycle.In general formula (A), the sum of the Hammett substituent constants σp of the substituents is +0 .0 or more,
More preferably +0.3 or more, most preferably 10,
Select 8upf so that ≠j or more.

Examples when Sub is a substituent are listed below. (The number of carbon atoms is preferably Q-≠θ in each case.) Substituted or unsubstituted alkyl group (?!I, methyl group, ethyl group, 5eC-butyl group, t-octyl group, benzy/I' group, Schiff O Hexadecyl group, chloromethyl group, dimethylaminomethyl group, n-hexadecyl group, trifluoromethyl group, 3,3,3-trichloropropyl group, methoxycarbonylmethyl group, etc.), substituted or unsubstituted alkenyl groups (e.g. Vinyl group, λ-ria Robinyl group,
l-methylvinyl group, etc.), substituted or unsubstituted alkynyl groups (e.g. ethynyl group, /-buΩvinyl group, etc.)
, cyano group, nitro group, halogen atom (fluorine, chlorine,
bromine, iodine), substituted or unsubstituted hexagonal residue i<
2-pyridyl group, l-imidazolyl group, benzothiazol-2-yl group, morpholino group, benzoxazole-
2-yl group, etc.), sulfo group, carboxyl group, substituted or unsubstituted aryloxycarbonyl or alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxycarbonyl group, 2-methoxyethyl group, carbonyl group) group, phenoxycarbonyl group, tercyanophenylcarbonyl group, λ-
chlorophenoxycarbonyl group E), 11WA or at-substituted carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, methylhexadecylcarbamoyl group, methyloctadecylcarbamoyl group, phenylcarbamoyl group, -21", 6
' Lichlorophenyl group (rubamoyl group, N-ethyl-phenylcarbamoyl group, 3-hexadecylsulfamoylphenylcarbamoyl group, etc.), hydroxyl group, substituted or unsubstituted azo group (e.g. phenylazo group, p-methoxyphenylazo group) group, l-thia/-U-
methanesulfonylphenyl 7:/i, etc.), substituted or unsubstituted aryloxy or alkoxy groups (e.g. methoxy, ethoxy, dodecyloxy, benzyloxy, phenoxy, p-methoxyphenoxy,
3-acetylaminophenoxy group, 3-methoxy group, pyroxy? fs, 2-trimethylammonioethoxy group, etc.), sulfino group, sul7e7 group, mercapto group, substituted or unsubstituted acyl group (e.g. acetyl group, trifluoroacetyl group, n-butyroyl group,
t-butyroyl group, benzoyl group, 2-carpoxybenzoyl group, 3-nitrobenzoyl group, formyl group, etc.)
, substituted or unsubstituted aryl or alkylthio groups (e.g. methylthio group, ethylthio group, t-octylthio group, hexadecylthio group, phenylthio group, λ, !,
j-trica lotio group, nomethoxy-3-t-octylphenylthio group, λ-acetylaminophenylthio group, etc.), substituted or unsubstituted aryl groups (e.g., e-haphenyl group, naphthyl group, 3-sulfonate group), Phenyl group゛,≠
-methoxyphenyl group, 3-lawoylaminophenyl group), substituted or unsubstituted sulfonyl group (e.g. methylsulfonyl group, chloromethylsulfony/'!, n
-Octylsulfonyl group, n-hexadecylsulfonyl i, 5eC-octylsulfonyl group, p-toluenesulfonyl group, ≠-chlorophenylsulfonyl group, ≠-dodecylphenylsulfonyl group, Hiro-dodecyloxyphenylsulfonyl group, ≠-nitrophenylsulfonyl group groups), substituted or unsubstituted sulfinyl groups (e.g., methylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, ≠-nido a phenylsulfinyl group, etc.), substituted or unsubstituted amino groups (e.g., methylamino group, Diethylamino group, methyloctadecylamino group, phenylamino group, ethylphenylamino group, 3
-Tetradecylsulfamoylphenylamino group, acetylamino group, trifluoroacetylamino group, N-hexadecylacetylamino group, N-methylbensylamino group, methoxycarbonylami/group, phenoxycarbonylmethyl group, hemethoxyacetyl group Amino group, amidinoamino group, phenylami7carponylamino group, ≠
-cyanophenylaminocarbonylamino group, heethyl ethoxyluponylamino group, hemethyldodecylsulfonylamino group, N-(2-cyanoethyl)-p-
1-luenesulfonylamine 7 groups, -, xadecylsulfonylamino groups, trimethylammonio groups, etc. or unsubstituted sulfamoyl groups (e.g. dimethylsulfamoyl group, hexadecylsulfamoyl group, sulfamoyl group, methyloctadecyl group) sulfasoyl group,
Methylhexadecylsulfamoyl group, 2-thia/ethylhexadecylsulfamoyl group, phenylsulfamoyl group, N-(3,≠-dimethylphenyl) -N -
octylsulfamoyl group, dibutylsulfamoyl group, dioctadecylsulfamoyl group, bis(,2-methoxycarbonylethyl)sulfamoyl group, etc.), gi
Substituted or unsubstituted acyloxy groups (e.g., acetoxy, benzoyloxy, decyloxy, chloroacetoxy, etc.), substituted or unsubstituted sulfonyloxy groups (e.g., methylsulfonyloxy, p-)luenesulfonyloxy groups , p-chlorophenylsulfonyloxy group, etc.).

In the general formula (13), n' represents an integer from / to ul; '1% U2 ; -Yl-Y2Nu3nyyl
-Y2-Y3, [,14nee Y1-Y2-Y3-Y4%
U5 knee Y1-Y2-'3 ”4 '5-1C1
6: -Y, -Y2-Y3-Y4-Y5-Y6.

Sub'Y-Y6 each represents 10-8ub', or Sub' itself represents a simple bond (σ bond, π bond) or a substituent of 8ub described in formula (A).

-For formula CB), the sum of the Hammett substituent constants σp of the substituents is +0,0 or more, more preferably 100.3
or more, most preferably 10, ≠ 8u so that it is 3 or more
Select b'.

To give a more specific example of EAG, an aryl group substituted with at least one electron-withdrawing group (9'lJeva<
z-nido-O phenyl group, λ-nitro≠-N-methyl-
he-octadecylsul 7 amoylphenyl group, 2-N,
N-dimethylsulfamoyl-goonitrophenyl group,
λ-cyanogu octadecylsulfonylphenyl group,
z,≠-dinito0 phenyl group 1,2. Hiroshi, 6-dolycyanophenyl group, 2-nitro-μm-hemethyl-he-octadecyl-rubamoylphenyl group, λ-nitro-j-octylthiophenyl group 1,2.4! -dimethanesulfonylphenyl group, 3,3-dinitrophenyl M, 1-1o
a-μm nitro-j-methylphenyl group, λ-nido O-
3. J-dimethyl-μm tetradecylsulfonylphenyl group 1.2.4t-dinito af7f group, 2-ethylcarbamoyl-≠-nitrophenyl group, 2. μm bis-dotecylsulfonyl-3-)lifluoromethylphenyl group, 2゜3, ≠, j, A-pentafluorophenyl group, λ-acetyl-t-nitrophenyl group, -z, ≠
-diacetylphenyl group, λ-nitro 17-IJ
fluoromethylphenyl group), substituted or unsubstituted bicyclic rings (e.g., λ-pyridyl group, λ-pyrazyl group, j-nitro-2-pyridi/I/ group,
! −〜−Hexadecyl Rubamoyl-Viridyl crystal,
≠-pyridyl group, 3. j-dicyano-1-pi, lysyl group, j-dodecylsulfonyl-2-pyridyl M, 3-cyano-2-biladyl group, Hiro-nitrothiophen-211yl group, j-nitro-/, --dimethylimidazole- Hiro-yl group, J, J-diacetyl-cokyridyl group, /-
dodecyl-j-rubamoylpyridinium-coyl group), substituted or unsubstituted quinones (e.g. /,!
A-benzoquinone-2-yl group, 3.3゜6-drimethyl-7, l-benzoquinone-λ-yl group, 3-methyl-
7,≠-naphthoquinone-λ-yl group, 3,6-dimethyl-j-hexadecylthio-7,4! -Benzoquinone-2
-yl group, j-pentadecyl-7, λ-benzoquinone-hiro-yl group, etc.), or in addition to the vinyllobes listed above, nitroalkyl groups (e.g. !-nido-o-2-propyl group), nitroalkenyl groups (e.g. Examples thereof include -1 ditoethenyl (l&), and a monovalent group of an α-diketo compound (for example, a λ-oxopropanoyl group).

LL, 几 and R represent a group other than a hydrogen atom or a simple bond.

H11 and RFi substituted or unsubstituted alkyl group,
Preferred are aryl groups, heterocyclic residues, acyl groups, sulfonyl groups, and the like.

R12 is preferably a substituted or S-substituted acyl group or sulfonyl group.几 , 几 and R combine with each other to j-
A 4-negative ring may be formed.

Furthermore, in order to achieve the object of the present invention, general formula (IV)
Among the compounds represented by formula [V], those represented by formula [V] are more preferred.

General Formula (V) In the general formula [■], EAG (Time-)E-LA is bonded to at least one of EAG. - Y is a divalent linking group in the moiety that is half of PW in formula (V), and is preferably -
C- or -5O2-. xFi represents the above-mentioned 几3 用(-(') -1-8-1 or -N-, but preferably represents an eR elementary atom.

H and 14 represent an atomic group that is bonded to X and Y to form a 5- to 5-membered single Ijil or condensed heterocycle including a nitrogen atom.

+ Preferable examples including the bonding position of T t me i LA will be described.

C)i=C)i20Lari2'N''11'ime represents a group that releases LA through a subsequent reaction without causing cleavage between N-X.

t represents an integer of 0 or /, and when 1=0, T i m
e represents a simple bond.

'l' i m eO example is JP-A-6/-, 231
，! ;14, those described as Time can be mentioned.

Preferred examples of Time in the present invention are specifically described below, and in the compounds of the present invention (*2 means bonding to the PWR side (*) (*l means bonding to the LA side).

+6) (9)C
H2-(*I*1 αa to D02 (to) 0 C)la (*) (c) \(331(3η C2h5 LA represents a group having an absorption maximum at 310 nm or more,
Dyes used in iron halide photographic materials, such as ary IJ dyes, styryl dyes, butadiene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, hemicyanine dyes, diarylmethane dyes, These are lylmethane dyes, azomethine dyes, azo dyes, metal chelate dyes, anthraquinone dyes, stilbene dyes, chalcone dyes, and indophenol dyes.

Specific examples of the compound represented by the general formula [I] used in the present invention are shown below. However, the present invention is not limited to these.

1-≠ 1-≠ -j C)i3 NO□ 1-za1-taCOOC2H5 1- / / 1-/, 2 1-/3 1-/! -j -/ 3 C) 1-/za1-/riji1-. 12 1-λhiro -2j ]-j/0 The compounds of the present invention emit dyes as described in the US patent≠.

13ri, 3gri, sameg, /3ri, 37ri, Tokukai Shoj
Method for synthesizing compounds disclosed in U.S. Pat. No. 232,107, U.S. Pat. %iIf≠, 3≠3゜g No. 73, rotation, 6/ri, method for synthesizing compounds disclosed in Zaza-Ki No., and furthermore, U.S. Patent≠, ≠30゜No. 2.23, μ, 10ri, 610
No., % Gansho 60-2μ Hiroza No. 73, same 6/-gza 623
It can be easily synthesized by binding to the PWR moiety with reference to the compound synthesis method disclosed in No.

The method for synthesizing the above compound is disclosed in Japanese Patent Application No. 1986/A 370≠
Disclosed in the issue.

The compound of formula [I] used in the present invention can be added in a necessary amount depending on the purpose, but
It is preferable to use the starting concentration in the range of 0.03 to 3.0. The specific amount of dye varies depending on the dye, but is generally /θ-311/rr? ~3, 01p/m, especially /0-"j'/m"~/, 0ta/rr? Preferred amounts can be found in the range of .

The compound of formula [I] according to the invention can be incorporated into the hydrophilic colloid In by any known method.

For example, these compounds can be dissolved or dispersed in gelatin by dissolving them in a suitable solvent [e.g., alcohol (meth/ol, ethanol, propanol), acetone, methyl ethyl ketone, methyl cellosolve, dimethyl formamide, cyclohexanone, ethyl acetate]. Alternatively, it can be dissolved in oil with a higher boiling point to form an emulsified dispersion in the form of fine oil droplets and added to foil. As the oil, known oils such as trifle:dyl phosphate, diethyl phthalate, dibutyl phthalate, and triphenyl phosphate can be used.

The compound of the formula [I] according to the present invention can be contained in an intermediate layer, a photosensitive layer, a protective layer, an overcoat layer, etc., but is preferably outside the photosensitive layer located farthest from the support. It is preferably contained in a non-photosensitive hydrophilic colloid layer (for example, a surface protective layer) located in the support, or in a non-photosensitive hydrophilic colloid layer between the support and the photosensitive layer located closest to the support.

Next, the compound represented by the general formula (II) of the present invention will be explained.

The present invention - Among the compounds represented by the formula (ff), particularly preferred are compounds in which Xl is a hydrogen atom or a nitro group,
2 and X3 each represent a hydrogen atom, a methyl group, an ethyl group, etc., such as Intersol, j-
Nitroindazole, 6-nitroindazole, 3-methyl-j-nitroindazole, 3-methyl-6-nitroindazole, 3-methylindazole, 3-ethyl-
Examples include j-nitroindazole,
Compounds that can be used in the present invention are not limited to these.

In order to incorporate the compound represented by the general formula (It) into the developer solution, the compound represented by the formula (II) is dissolved in water or a water-miscible low boiling point organic solvent at an appropriate concentration. , added to the developer as a solution, or added as a solid to the developer.

The preferred content is /Misaki/A-/OF/A%
More preferably, it is 70×72 to 3P/2.

As the hydrazi derivative used in the present invention, a compound represented by the following formula (1) is preferable.

- Formula (II) where A1 represents an aliphatic group or an aromatic group, B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
Represents a carbamoyl group, alkoxy or aryloxycarbonyl group, sulfinamoyl group, alkoxysulfonyl group, thioacyl group, thiocarbamoyl group, sulfamoyl group, carbamoylcarbonyl group, oxycarbonylcarbonyl group or -terocyclic group, and Ro and R1 are both hydrogen. One of the atoms is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a #-substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

However, B1R1 and the nitrogen atoms to which they are bonded may form a hydrazone partial structure -N=C.

Next, general formula (1) will be explained in detail.

- In formula (1), the aliphatic group represented by A1 preferably has 1 to 30 carbon atoms, especially carbon number /
-20 linear, branched or cyclic alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

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

- In the formula ゛(■), the aromatic group represented by a human is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated -terocyclic group is a monocyclic or bicyclic aryl group. It may be condensed with an aryl group to form a -teroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Among the isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc., those containing a benzene ring are preferred.

Sometimes preferred as Al is an aryl group.

The aryl group or unsaturated heterocyclic group of A1 may have a substituent. Typical substituents include linear, branched or cyclic alkyl groups (preferably carbon number/~2Q
), aralkyl group (preferably a monocyclic or bicyclic alkyl group with 7 to 3 carbon atoms), alkoxy group (preferably 7 to 2 carbon atoms), substituted amide 7
group (preferably an amino group substituted with an alkyl group having 2 to 20 carbon atoms), an acylamino group (preferably an amino group substituted with an alkyl group having 2 to 20 carbon atoms),
Examples include those having 30 carbon atoms), sulfonamide groups (preferably those having carbon numbers of 7 to 30), and ureido groups (preferably those having 7 to 30 carbon atoms).

A1 in the general formula (1) may have a ballast group such as a coupler incorporated therein which is commonly used in processing immobile photographic foils. More carbon than ballast group ff
'fr is a relatively inert group with respect to photography,
For example, it can be selected from alkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups, and the like.

A1 in general formula (1) may have a group incorporated therein that enhances N absorption to the silver halide grain surface. Such absorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto polycyclic groups, triazole groups, etc. as described in US Patent No. 3, 3. 1OX, same≠, vjri, 3≠7, JP-A-Shojter No. 173.233, same Jterr 200.2
3/ issue, same jter 20/, 0 μj issue, 439-20/,
0≠6, same jter 20/, 0≠7, same! Tha! oi
, ottg issue, 5y-ioi, o4c issue, JP A/-/70,733, JP 6/-270, 7≠Hiroshi, 6.2-Tada g, JP 12-A7゜30g issue, same 6
It is described in No. 2-1.7.307, No. 6.2-67.37θ, etc., and examples include fc&.

B is specifically a formyl group, an acyl group (for example, an acetyl group, a bopionyl group, a trifluoroacetyl group, a chloroacetyl group, a benzoyl group, a q-chlorobenzoyl group, a pyruvoyl group, a methoxalyl group, a methyl oxamoyl group, etc.), alkylsulfonyl'M (e.g., methanesulfonyl group, 2-chloroethanesulfonyl group, etc.), arylsulfonyl group (e.g., benzenesulfonyl group, etc.)
, an alkylsulfinyl group (e.g., methanesulfinyl group, etc.), an arylsulfinyl group (e.g., benzenesulfinyl group, etc.), a carbamoyl group 1'lJ, t,
methylcarbamoyl group, phenylcarbamoyl group, etc.),
Sulfamoyl group (e.g., dimethylsulfamoyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, methoxyethoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), sulfinamoyl group (e.g., methylsulfinamoyl group, etc.), alkoxysulfonyl IIJ, methoxysulfonyl group, ethoxysulfonyl group, etc.),
thioacyl group (for example, methylthiocarbonyl group, etc.),
Thiocarbamoyl group (e.g., methylthiocarbamoyl group, etc.), sulfamoyl group (e.g., non-substituted sulfamoyl group, methylsulfamoyl group, etc.), carbamoylcarbonyl group (e.g., non-substituted carbamoylcarbonyl group, etc.), oxycarbonylcarbonyl group ( For example, methoxycarbonylcarbonyl group, phenoxycarbonylcarbonyl group, etc.), or heterocyclic group (for example, pyridine ring, etc.)
represents.

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

B in the general formula (Rin) is the partial structure of hydrazone together with Ro and the nitrogen atom to which they are bonded. In the above, R12
represents an alkyl group, an aryl group or a --terocyclic group.

R13 is a hydrogen atom, an alkyl group, an aryl group, or -.
Represents a telocyclic group.

RO% I is a hydrogen atom, a furkylsulfonyl group having up to 20 carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is 10.j or more) group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted such that the sum of Hammett's substituent constants is -0.3 or more, or a linear, branched, or cyclic Unsubstituted and substituted aliphatic acyl groups (f
Examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. )"0XR1 is most preferably a hydrogen atom.

In addition to the above-mentioned hydrazine derivatives used in the present invention, examples of hydrazine derivatives include RESE (C)I DI8CLO8URE
Item 233/lsc/9g3//month issue, P.
j! &) and the literature cited therein, as well as U.S. Patent p.
1 oza 0.207 issue, same≠, 26ri.

No. 2, same≠, 276.344, same≠, -7f,
7≠g issue, same g, 3g! , / No. 01, same gu.

Hirojri, 3≠7, 4≠, JA0.63g, same≠,≠
7g, 22g, British Patent No. 2,0//, 3ri/B, JP-A No. 60-/7273≠, No. 6/-/70.733,
Same 1. /-270,7 Hirohiro issue, 6.2-ta≠g issue, E
ll/7,310, patent application Sho 1x/-/7J, 23≠
No. 6i-rsi, μgλ No. 6/-λAff,
, 24t No. 6/-λ76, . No. 213, 1s.
, 22-1p7JO issue, same 6! -A7.30 No. 1
No. 2-67.310, No. 62-j, No. 373, No. 6/30, No. I/R, No. A, 2-/≠3. ≠No. 6, 42-/A Otsu.

Those described in No. 117 can be used.

- Among those represented by formula (1), a preferable one can be represented by general formula (Vl).

-Formula (Vl) R3-iM 02N1-1-A2-f'J -f'l
-1j 1-H2).

In the formula, G1 represents a carbonyl group, sulfonyl group) sulfoxy group, phosphoryl group, or iminomethylene group, and R
2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarbonyl group, A2 represents a phenylene group or a tyrene group, 1t3 represents an aliphatic group, Represents an aromatic group or a heterocyclic group, and 几ff1R1 is represented by the general formula (1)
and n represents/or 2. Here, R2,
At least one of R3 and A2 has a ballast group or a group that promotes adsorption to the halogenated product.

In the formula, the aliphatic group represented by R3 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R3 is a monocyclic or bicyclic aryl group, such as a phenyl group or a naphthyl group.

■ The heterocycle of t3 is a 3- to θ-membered saturated or unsaturated heterocycle containing at least one of He, 0, or S atoms, and these may be monocyclic;
Furthermore, a condensed ring may be formed with another aromatic ring or heterocycle. The heterocycle is preferably a j- to 6-membered aromatic heterocyclic group, such as a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an inquinolinyl group, a thiazolyl group, a benzthiazolyl group, etc. is preferred.

R3 may have tl replaced with a substituent. Examples of the substituent include the following. These groups may be further substituted with f.

For example, alkyl groups, aralkyl groups, alkoxy groups, aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups,
Examples include sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, and human O-oximino group.

These groups may be linked together to form IM when possible.

Among the groups represented by 几2, when G1 is a carbonyl group, preferred are a hydrogen atom, an alkyl group (e.g.
methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.),
Aralkyl group (e.g., 0-hydroxybenzyl group, etc.), aryl group (e.g., l', phenyl group, j, j-
(dichlorophenyl group, 0-methanesulfonamidophenyl group, ≠-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

When 7tcG1 is a sulfonyl group, R2 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0-hydroxyphenylmethyl group, etc.), or an i-i group (e.g., phenyl group, etc.) or a substituted amino group (eg, dimethylamino group).

When G1 is a sulfoxy group, preferable 2 is a cyanobenzyl group, methylthiobenzyl group, etc., and when G1 is a phosphoryl group, 2 is a methoxy group, ethoxy group, butoxy group, phenoxy group, or phenyl group. Preferred is a phenoxy group, particularly a phenoxy group.

When Gl is an iminomethylene group with or without substitution, R2 is preferably a methyl group or an ethyl group, and the substituted group is
t, is a substituted phenyl group.

As the substituent for R2, in addition to the substituents listed for kLl, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, etc. can be applied.

These [9!18 groups may be substituted with these substituents. Further, if possible, these groups may form a ring connected to each other.

) Ballast groups that can be substituted for R2, R3 or A2 include those explained in general formula (1), but R2
, 3 and A2 is preferably 73 or more, more preferably 2 or more.

Next, the adsorption-promoting group to silver halide that can be substituted for R2, 3 or A2 can be represented by X1+L1→-.

Here, Xl is an adsorption promoting group for halogenated molecules, and Ll
is a divalent linking group. m is O or /.

Preferred examples of the adsorption-promoting group to silver halide represented by Xl include a thioamide group, a mercapto group, a group having a disulfide bond, or a nitrogen-containing heterocyclic group having j or more members.

The thioamide adsorption promoting group represented by Xl is a divalent group represented by -C-amino, and may be a part of a ring structure, or may be an acyclic thioamide group. Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
030. ri No. 25, 4≠, 03/, /27, 4t,
Oza0. ．． No. 207, Dogu, 2gu J, No. 037, Douhiro,
233. J// issue, ψ, 21st, 0/3 issue, 27A, 36≠ issue, and “Research Disc
Losure ) Magazine Volume 13/46/! ;/12c/
(July 17, 1976), and Vol. 776, 4/7 AJA (/
77g year/, year month. You can choose from those disclosed in

Specific examples of the acyclic thioamide group include a thioaleido group, thiourethane group, and dithiocarbamate group, and specific examples of the cyclic thioamide group include, for example, goutiazoline-2-thione, Hiro-imidazoline-
Corchion, l-thiohydantoin, rhodanine, thiobarbic acid, tetrazoline-j-thione N/
s -2-tI-triazoline-3-thione, /, 3.
IA-Thiadiazoline-2-thione, l, J, II-Thiadiazoline-2-thione, benzimidacillin-2
-thione, benzoxazoline-λ-thione, and benzothiazoline-λ-thione, which may be further substituted.

The mercapto group of is synonymous with a certain bulk thioamide group, and specific examples of this group are the same as those listed above).

The j- to 6-membered nitrogen-containing heterocyclic group represented by Xl includes a j- to 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur, and charcoal. Among these, preferred are benzotriazole,
Examples include triazole, tetrazole, indanol, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, and triazine. These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for 几3.

Among those represented by group, 2-mercapto-7,3,≠-oxadiazole group, commercabutobenzoxazole group, etc.), or nitrogen-containing heterocyclic group (e.g., benzotriazole group, benzimidazole group, indazole group, etc.) It is.

Moreover, the X1+L1+ group may be substituted with two or more,
They can be the same or different.

The divalent linking group represented by Ll specifically represents an alkylene group, an arylene group, an alkynylene group, an arylene group, and one or more of these groups may be combined, or -(J+, -s.

-N) to i-1-, -C0-1-8O2- (these groups may have a substituent), etc. may be added singly or in combination. Specifically, for example, etc. may be mentioned.

These may be further substituted with a suitable substituent.

[As the substituent, those described for 6 in 几1 can be mentioned.

Approximately 0, R1 has the same meaning as the general formula (薯), and n is l or -
, R'0%''1 is most preferably a hydrogen atom, and Gl is most preferably a carbonyl group.

Among those represented by the general formula (■), particularly preferred are those represented by the general formula (Vn).

- Formula (■) In the formula) 几0嘱Rl % R2・G1. Xl and Ll are synonymous with those explained in general formulas (1) and (Vl), and Y
l has the same meaning as the substituent for R3 in general formula (Vl), n is/or λ, m is 0 or/, A is 0.
When L is 2, Yl may be the same or different.

Furthermore, preferably,
The p position is most preferred.

Specific examples of the compound represented by general formula (1) are described below.

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

厘-7 C)i2C)i2C)i2SH 1g ■-Tase-lpi■-76 Seal-77 5fl1 for t 1-/♂ 1-/ri1-. 20 1-λ3 ■-,2≠ ■-2j 1-J♂ tC5)ill In the present invention, when the compound represented by formula (1) is contained in a photographic light-sensitive material, it is contained in the silver halide emulsion layer. However, it is preferable to include other non-photosensitive hydrophilic colloid layers (e.g., protective layers, intermediate layers, filter layers, etc.).
(antihalation layer, etc.) may contain K. Specifically, if the compound used is water-soluble, it can be prepared as an aqueous solution.
If the colloid is poorly water-soluble, it may be added to the hydrophilic colloid solution as a solution of a water-miscible organic solvent such as alcohols, esters, or esters. 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 best to add it to the coating liquid prepared for application.

The content of the compound represented by the general formula (1) 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 antifogging compound, etc., and testing methods for selection are well known to those skilled in the art. Usually and preferably from 10-6 mol per mol of silver halide to /X/
It is used in the range of 0"-" mol, especially lo-5 to ≠×10-2 mol.

The silver halide emulsion used in the present invention is a silver halide consisting of iron chloride or more, and the bromide image is 0-j
Silver chlorobromide or silver chloroiodobromide containing malt is preferred. If the ratio of silver bromide or silver iodide increases, the safelight safety in a bright room will deteriorate or the brightness will become weak, which is undesirable. 'The emulsion of the present invention preferably contains rhodium atoms, which can be added in the form of a metal salt in any form such as a single salt or a complex salt when preparing the grains.

Examples of rhodium salts include -rhodium chloride, rhodium dichloride, rhodium trichloride, ammonium hexachloride acid, etc., but preferably water-soluble trivalent rhodium halide complex compounds, such as hexachlororhodium (
I'll acid or its salts (ammonium salt, sodium salt, potassium salt, etc.).

The rhodium salt used in the present invention is 1x per mole of silver.
1O-8 molar mass (! x/ 0-' molar mass is low.

Preferably, to-5 molar positions are higher and Jx/0 molar positions are lower. Niji preferably jXlo 'Morue lot! xtO'Molnigi small omission becomes worse. In particular, when used in hydrazine-containing photosensitive materials, there is a drawback that the sensitivity decreases too much, as will be described later.

On the other hand, if it is less than 10, it will not be possible to achieve a low sensitivity suitable for bright room photosensitive materials.

The silver halide used in the present invention is preferably a so-called core/shell type silver halide, particularly a core/shell type silver halide in which the shell has a higher rhodium content than the core.

In order to make the above-mentioned water-soluble rhodium salt exist in silver halide grains, when simultaneously mixing the water-soluble silver salt and the water-soluble halide solution, it is cooled in the water-soluble silver salt or in the halide solution. is preferred.

Alternatively, when silver salt and halide solutions are mixed simultaneously, silver halide grains may be prepared by a method of simultaneous mixing of the three solutions as a third solution.

The grain size of the silver halide emulsion of the present invention is Q.

/jμ or less is preferable, more preferably O, OS to 0.
It is a fine grain emulsion of 10μ or less.

In order to prepare silver halide fine particles in the present invention, the mixing conditions are such that the reaction temperature is 30°C or lower, preferably 0°C or lower, more preferably 30°C or lower, and the stirring rate is sufficiently high to ensure uniform mixing. Potential 100mV or more, -
Preferably ljOm■~ta o o m-V, p)l
Good results can be obtained when the amount is 3 to 7 g, preferably j to 7. In the case of silver chloride fine particles, due to their high solubility, particle growth may occur during the water washing and dispersion processes, and the temperature is below 33 °C, or when using nucleic acids, mercapto compounds, or tetrazaindenization to suppress particle growth.
Things can coexist.

The particle size distribution is basically not limited, but it is preferable that it be monodisperse. Monodisperse here means that at least 3% of the weight or number of particles is ±≠θ% of the average particle size.
It is composed of a group of particles having a size within 20 cm, and more preferably within 20 cm.

The silver halide grains of the present invention preferably have regular crystal bodies such as cubes and octahedrons, and cubic shapes are particularly preferred.

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

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 or gold compound as raw material. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium. A specific example is a US patent! ,≠μg,06
No. 0, British Patent No. 67g, obi No.

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.

The halogenated photographic material of the present invention may contain an organic desensitizer. The organic desensitizer preferably has at least one water-soluble group or an ano-potash dissociating group.

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

A polarographic method for measuring redox potential is described, for example, in US Pat. No. 3.30/307.

Specific examples of the at least seven water-soluble groups present in the organic desensitizer include sulfonic acid groups, carboxylic acid groups, and phosphonic acid groups. piperidine, morpholine, etc.) TFC may form a salt with an alkali metal (eg, sodium, potassium, etc.).

The alkali-dissociable group refers to the pH of the developing solution (usually pH ~
p) in the range of i/3, but other than this p)lt
- There may also be processing solutions that show. ) or below, a substituent that undergoes a deprotonation reaction and becomes anionic. Specifically, substituted/unsubstituted sulfamoyl groups, substituted/unsubstituted sulfamoyl groups,
Substituents in which there are at least 7 hydrogen atoms bonded to a nitrogen atom by substituting 1, such as an unsubstituted carbamoyl group, a sulfonamide group, an acylamino group, a substituted or unsubstituted waleido group, and a hydroxy group. Point.

Also included in the alkali-dissociable group is a heterocyclic group in which a hydrogen atom is removed on the nitrogen atom constituting the heterocycle of a nitrogen-containing heterocycle.

These water bathing groups and alkali dissociable groups may be connected to any part of the organic desensitizer, and may have 2a or more at the same time.

Preferred specific examples of the organic desensitizer used in the present invention include %
Gansho 1. It is described in /-20ri/6ri issue, but some examples are given below.

(J2N How many desensitizers are used in the halogenated emulsion layer/-0X10-8
~/, 0x10 'mol/rr? , especially l.

O×l0-7~/, 0x10-5 mol/lr? It is preferable to make it exist.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye at the same time as the compound of formula (1) as a filter dye or for irradiation prevention and other purposes. .

Filter dyes include dyes for further lowering photographic sensitivity, preferably ultraviolet absorbers having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and safety against safelight z when handled as bright room photosensitive materials. In order to increase
ノ/rrl~/P/n? It is added within the range of Preferably it is 10 to 10 ortq7.

Specific examples of dyes are described in detail in %Gan No. 6/1980-209/6, and some are listed below.

803K 803 to 803a The above dye can be dissolved in a suitable solvent [e.g., water, alcohol (e.g. methanol, ethanol, propatool, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] to form a non-inventive, non-photosensitive dye. It is added to the coating solution for the hydrophilic colloid layer.

Gelatin is most commonly used as the binder or stabilizing colloid for 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: hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters, sugar derivatives such as sozoalginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl Synthetic hydrophilic commercial molecular materials such as single or copolymers of imidazole, polyvinylpyrazole, etc. can be used.

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.

Although a known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention, it is preferable not to add it.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. Namely, the nine azoles are benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, and nido-O. benzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thiol compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially those with hydroxyl substitution (i + 3+ 3a
+7) Tetrazaindenes), pentaazaindene, etc.; many compounds known as antifoggants, hydroquinone at or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added. Among these, preferred are benzotriazoles (eg j-methyl-benzotriazole), hydroquinones and nitroindazoles (eg 3-nitroindazole). Further, a compound capable of releasing a development inhibitor during processing as described in JP-A-62-302≠3 can be included.

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

For example, active vinyl compounds (/, 3.3-1-lyacryloyl-xahydro-5-) riazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-[β-(vinylsulfonyl)propionamide], etc.) , active halogenated @proboscis (,21μm dichloro-6-hydroxy-s-triazine etc.), mucohalogen [M(
mucochloric acid, etc.), haloamidinium salts ((/-molpoly)carbonyl-3-pyridinio) methanesulfonate, etc.), haloamidinium salts (/-
(/-diO-low/-pyridinomethylene)pyrrolidinium, -naphthalenesulfonate, etc.) can be used alone or in combination.

Among them, JP-A-33-'712.20. same! r3-!
;7237, same jter/12 bow, mukai tog.

+Activated vinyl compound according to r≠6 and rice l@Patent 3
, 3, 23.2g No. 7 is preferred.

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

For example, saponins (steroids), alkylene oxide 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 aA, E) (alkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Ionic surfactant;
Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfones [1, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, heacyl-alkylta-9 phosphorus, sulfosuccinates, sulfoalkyl poly Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, WCfl ester groups, phosphate ester groups, etc., such as oxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, diamino acids, Ampholytic surfactants such as aminoalkyl sulfonic acids, amyl/alky IL/sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides: alkylamine salts, aliphatic or aromatic ammonium salts, pyridinium, imidazolium Cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, in the present invention, a polyalkylene oxide compound having a molecular weight of 6,100 or more can be used for the purpose of further increasing the image quality to 1.

The polyalkylene oxide compound used in the present invention is an alkylene oxide having a carbon number of λ to t, such as ethylene oxide, propylene-/, 2-oxide, butylene-71,2-oxide, etc., preferably at least 410 units of ethylene oxide. A condensate of a base polyalkylene oxide and a compound having at least/an active hydrogen atom such as water, an aliphatic alcohol, an aromatic alcohol, a fatty acid, an organic amine, a hexitol derivative, or a block of two or more polyalkylene oxides. Including copolymers and the like. That is, as polyalkylene oxide compounds, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers (alkylaryl), ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides d? Realkylene glycol amines polyalkylene glycols
Block copolymers, polyalkylene glycol graft polymers, and the like can be used. It is necessary that the molecular weight is 600 or more.

The polyalkylene oxide is not limited to one, but may be contained two or more in the molecule. In that case, the individual polyalkylene oxides may be composed of fewer than IO alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least IO. When the molecule has two or more polyalkylene oxides, each of them has a different alkylene oxide unit,
For example, it may consist of ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention preferably contains at least /q and up to 100 alkylene oxide units.

Specific examples of the polyalkylene oxide compounds used in the present invention are as follows.

Examples of polyalkylene oxide compounds/ki() (CH2CH20) 9o) f,
2 C4Hg0(CH2C)120)15h301□
H2i) (CH2CH20) 15) 1≠ C, 8)
1370 (C)12C)120)ts)IJ
C18113, (J(C)12C)f2(J)4o)1
6 CBH1□C)1=C)1c8)i160(C
) 12C) 120), 5) 110 011) 123c
00(C)*2C)izO)80)111 Cyu□8
2. ,C00(C)i2cH20)240CC111i
□3/3 C1□H23C(-)NH
(CH2CM20) 151-1/j c14H
! to 9 (C) 12)CCH2C)izO)z4H17,
e) i2-0-CM-C) 120C11) i23H(O
Ch2C)i2)140-Ch-Oh-C)i-(CH
20H20) 14H (QCI food 2 CH20) 1aH /7) 1(C) 12cHzr)) 1(eHcH20
)b(C)12C)120)c)1C)i3 a+b+c=t.

b:a+c=10:ri,20 MO(CH2CH20)a(CH2CH2C)izO)
t20)b(C:M2C)t20). ) ta+c==j
(lit, b=i xib=za, a+c=30 2co.2≠)io+CH2C) i20 increase etc.
0-/36≠, polyalkylene oxide compounds described in No. 23, JP-A-32-101/30 and JP-A-33-32/7 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

When these polyalkylene oxide compounds are cooled into a halogenated bride emulsion, they are dissolved in an aqueous solution of an appropriate concentration or dissolved in a low boiling point organic solvent that is miscible with water.
It can be added to the emulsion at any suitable time before coating, preferably after chemical ripening. It may be added to non-photosensitive hydrophilic colloid layers, such as intermediate layers, protective layers, filter layers, etc., without being added to the emulsion. Further, the light-sensitive material of the present invention, which may contain these compounds in the processing solution, can be entirely made to contain a polymer latex such as polyalkyl acrylate for dimensional stability.

Supports for the photosensitive material of the present invention include cellulose triacetate, cellumise diacetate, nitrocellulose,
Polystyrene, polyethylene terephthalate, baryta paper, polyethylene-coated paper, etc. can be used.

Suitable development accelerators or nucleating and contagious development accelerators for use in the present invention include JP-A Nos. 3-77616, 4 (-3773λ), 3-/37/33, 6
In addition to the compounds disclosed in No. 0-lda 03ψO, No. 60-/11-93, etc., compounds of various types containing an atom or an S atom are effective.

Next, specific examples are listed.

ki H (C2Hs)2 to C) 12C) l-C) 120) 1n-
C4)1. N (C2)14C)i)2 The optimum addition amount of these accelerators differs depending on the type of compound, but /, 0
'pC10-3~0. Jf/1, preferably j, O×
l0-3~0. /l/rr? - It is preferable to use the range. These promoters are added to the coating solution after being dissolved in a suitable solvent (120), an alcohol such as methanol or ethanol, acetone, dimethylformate, methylcellosolve, etc.

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

In order to obtain the photographic characteristics of a super hard portrait using the halogenated sickle photosensitive material of the present invention, it is necessary to use a conventional infectious developer or the U.S. Pat.
Therefore, it is not necessary to use a highly alkaline developer similar to PA73 published in No. 273, and a stable developer can be used.

That is, the halogenated fa photosensitive material of the present invention contains sulfite ions t-0, /g mol/°C or more as a preservative,
p) il/, O-7,2,3, especially p) i//, 3~/
, 2.0, a sufficiently high contrast negative image can be obtained.

The developer used in the present invention does not contain any auxiliary developing agent (e.g. evanophenyl-3-pyrazolidones or p-aminophenol@) or contains only 0°031/L or less, and contains dihydroxybenzene as the main developing agent. 0. O.J.
NO, 3 mol/12 (especially 0.7-Q, μmol/A)
A developing solution containing free sulfite ions with a degree of o
, ir mol/i or more, - 20 k/L of the compound of formula (1) (preferably j- or 6-nitroindazole)
or more, and the pH is //, '0 or more (particularly l/, 3
Sufficient amount of Alka IJ to
'? This is a developer containing gold. Among these, it is preferable to use dihydroxybenzenes (especially hydroquinone) alone, which do not contain an auxiliary developing main system.

This developing solution enables the use of the light-sensitive material of the present invention to meet all the photographic properties of extremely high contrast, and is extremely stable because it can develop with a large amount of sulfite ions.

In the above, as dihydroxybenzene-based drugs, Shio Rie uses hydroquinone, chlorohydroquinone,
70 mohydroquinone, isopropylhydroquinone,
Toluhydrohydroquinone, methylhydroquinone 1.
2.3-dichlorohydroquinone, λ,j-dimethylhydroquinone, etc., l-phenyl-3-pyrazolidone-based drugs include /-phenyl-3-pyrazolidone, q,t-dimethyl-7-phenyl -3-pyrazolidone, t-hydroxymethyl-≠-methyl-/-phenyl-3-pyrazolidone, t,≠-dihydroxymethyl-7-phenyl-3-pyrazolidone, and p-aminophenol-based developing agents include p- Aminophenol, hemethyl-p-aminophenol, etc. are used.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, formaldehyde sodium bisulfite, which provides almost no free sulfite ions in the developer, may be used.

As the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, jetanolamine, triethanolamine, etc. are used.

It is preferable that the developer that can be used in the present invention contains the same type of polyalkylene oxide as described above as a development inhibitor. For example, the molecule 'tlioo.

~/0000 polyethylene oxide etc. O17
~10f/1. It can be contained within the range of.

Furthermore, the amine compounds described in US Pat.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraamine hexaacetic acid, diethylenetetraamine pentaacetic acid, etc. as a water softener to the developer that can be used in the present invention.

As the fixer, one having a commonly used composition can be used.

As a fixing agent, in addition to thiosulfate and thiocyanate tR salt,
Organic sulfur compounds known for their effectiveness as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The fixer may also contain a complex of ethylenediaminetetraacetic acid and trivalent iron ions as an oxidizing agent.

Processing source! g and processing time will be set as appropriate, but it is normal / g℃～
A processing temperature of 30 DEG C. is suitable, while rapid processing of fclj to 7.20 seconds is preferably carried out using a so-called automatic processor.

The present invention will be explained in more detail below using Examples.

(Example 1) Silver nitrate aqueous solution and i
X/0-5 mol O(Nl-14)3 Rh C1
A 6F-containing sodium chloride aqueous solution was simultaneously added during the io sorting, and the potential during that time was controlled to +somV, so that monodisperse cubic silver chloride particles with an average particle size of 0.2 μm were placed in A-pack. After removing the town salt by a conventional method, gelatin was added.

After adding the hydrazine compound of general formula (1) to this emulsion as shown in coating/, the following nucleation accelerator ■ is added at 30 kg/-1 desensitizer ■ is added to Misaki/rr? , ■ compound, 20■/r
r? In addition, polyethyl acrylate latex was added in a solid content of J Owt% based on gelatin, J-bis(vinylsulfonylacetamido)ethane was added as a hardening agent, and an iron amount of J and 6P/d was added to the polyethylene terephthalate support N body. It was applied so that Gelatin is /, 7P/lri
Met.

On top of this, gelatin I, sp/i particle size 2.
0β polymethyl methacrylate jO'Iv/-, Teocto fR &"j'/m', hydroquinone 30M9/
At the same time, a layer containing dodecylbenzene sulfate *7ef thorium and the ultraviolet light absorbing compound 1-/yellow compound J-j of the general formula (1) of the present invention as shown in Table 7 was added as a coating agent. Samples ① to ① as shown in Table 7 were prepared.

The sample thus obtained was exposed through a source wedge using Dainippon Screen Co., Ltd.'s Shimei-shitsu Printer P-607, developed with the developer shown in Tatsuko for 3g C.lambda.O seconds, fixed, washed with water, and dried. (Automatic development i#! Iso FG-AAOF) Furthermore, these samples were developed in the same manner and compared with respect to the image quality of extracted characters and fog after safelight irradiation. The results are shown in Table 1. As is clear from Table 1, the configuration of the present invention (Test 7I6u, /l) has good image quality and safelight property.

/) Relative sensitivity: Let ioo be the reciprocal of the exposure amount that gives the density i, s, sample/.

2) γ: C3,0-0,3)/-(log(concentration 0.
3) - 1 og (exposure amount to give 11 degrees 3 degrees 0★) 1 3) Extracted character image quality; Paste base/mesh image di Film with image formed ← line drawing original) / pasting base / film with halftone image formed (halftone original) When placed in close contact so that they overlap face-to-face, and given appropriate exposure such that 30% halftone dot area becomes 30% halftone [ffi product] on the film sample, and when processed as described above, 30 μm of line drawing original Let j be the character that can reproduce the width, and / be the character that can only reproduce the width of ljOμm or more, and! Sensory evaluation between and / ≠, 3
．． ．． 2 ranks are provided. 2 is the barely practical limit.

≠) Capri after safelight irradiation; Toshiba white fluorescent lamp (El≠OSW) J 0ftux
.

(Example λ) After 30 minutes of irradiation under
/θ-4 moles of (to) 14) A sodium chloride aqueous solution containing 3B and hα6 was simultaneously added for 10 minutes, and the potential during that time was controlled at 200 mV to form monodisperse silver chloride cubes with an average particle size of 0.02μ. Particles were prepared. After removing soluble salts by a conventional method, gelatin was added. (Unripened emulsion) This emulsion contains hydrazine of the general formula CIII) and J x 10' mol of 1 mol of Ag as shown in 41.
A hydrazine compound represented by is added, and then the following nucleation accelerator ■ is added at 30 kg/W? , Dye■30m9/n? ,/-
Phenyl-j-mercaptotrazole 10~/rr
l ■ Polyethyl acrylate latex was added to gelatin in a solid content of 3Qwt% as a hardener, and 3-divinyl-
Sulfonyl-2-propanol was added and coated onto a polyester support in an amount of 3497. Gelatin is /, GL! /d.

On top of this is gelatin/, 3jl/rr? as a retention layer. ,
Particle size 3. θμ polymethyl methacrylate j OJlj
l/go, tiocto l[■/rr? , sodium dodecylbensulfonate as a coating agent and the general formula (1
) All samples 6 to 9 were prepared by simultaneously applying a layer in which the compound represented by the formula was added as shown in Table 3.

The sample thus obtained was developed in the same manner as in Example. The results are shown in Table 3.

As is clear from Table 3, the configuration of the present invention (Test/16
≠, 7) has good cutout character image quality and safelight property.

(Example 3) The emulsion used in Example C and a similar weighting agent, as well as the compound (1) of the present invention/gold foil, preferably 3 x 10-3 mol 1 mol kg) Amount of silver 3, AP /rr? I applied it as desired.

On top of this emulsion layer, gelatin, surfactants A and B, mordant C, and a dye compound were added to water and applied as a protective layer so that the dyes shown in Table 1 were coated.
/I was created. At this time, the amount of gelatin applied and the mordant applied t were respectively /, (N!/lri'').The sample using this mordant and sample 7 prepared in Example λ were compared to Example -
After exposure in the same manner as above, the film was developed with developer B, and the results are shown in Table 1. Fourth! As is clear from the table, compared to the samples of the present invention, the comparative samples have insufficient character strokes and inferior 07 transparency.

Surfactant A Surfactant B Mordant C Comparative dye D Procedural amendment

Claims (1)

[Scope of Claims] After imagewise exposure of a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer or other hydrophilic colloid layer In an image forming method using a developing solution, the emulsion layer or hydrophilic colloid layer is formed by the following general formula [I
1. An image forming method comprising a compound represented by the following formula, and wherein the developing solution satisfies the following conditions (a), (b), (c) and (d). General formula [I] PWR■Time■_tLA In the formula, PWR represents a group that releases (Time■_tLA) upon reduction. Time represents a group that releases (Time■_tLA) from PWR and then initiates the subsequent reaction. t represents an integer of 0 or 1. Conditions in which LA has a light absorption maximum at 310 nm or more: (a) Substantially only dihydroxybenzene is used as a developing agent. ( b) The free sulfite concentration is at least 0.18 mol/l. (c) The pH is 11.0 or more. (d) The compound represented by formula (II) is at least 2 mol/l.
Contains 0mg/l or more. General formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, X_1 represents a hydrogen atom or a nitro group. X_2 and X_3 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.