JPH0252A - High contrast image forming method - Google Patents

Abstract

PURPOSE:To rapidly and stably form the high contrast image of a photosensitive material by developing the photosensitive material having a photosensitive silver halide emulsion layer with a developer contg. a prescribed component, in the presence of a hydrazide compd. shown by the prescribed formula. CONSTITUTION:The high contrast image is rapidly and stably formed by developing the photosensitive material contg. 3-pyrazolidone compd. and/or di or trihydroxy benzene compd. with the developer contg. the di or trihydroxybenzene compd., a sulfite and an amino compd., in the presence of at least one kind of the hydrazide compd., shown by formulas I, II and III. In formula I, R1 and R2 are each aryl group, etc., R is an org. binding group, (n) is 0-6, (m) is 0 or 1, when (n) is >=2, groups R may be the same or the different with each other. In formula II, R21 is an aliphatic group, etc., R22 is hydrogen atom, etc., P1 and P2 are each hydrogen atom, etc. In formula III, Ar is an aryl group contg. at least one of an antidispersible group or a silver halide absorption promoting group, R31 is a substd. alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an image forming method, and more particularly to a silver image forming method that rapidly and stably provides a high contrast photographic image with high sensitivity.

[Conventional technology]

In general, high-contrast photographic images are used in the photolithography process to form characters and halftone-resolved photographic images, and in the ultra-precision photolithography process to form fine line images. It is known that silver halide photographic materials for this purpose can form photographic images with extremely high contrast.

Conventionally, for example, a photosensitive material made of a silver chlorobromide emulsion with an average grain size of 0.2 μm, a narrow grain distribution, a uniform grain shape, and a high silver chloride content (at least 50 mol %) was processed using sulfite ions. A method of obtaining an image with high contrast, high sharpness, and high resolution, such as a halftone dot image or a fine line image, is carried out by processing with an alkaline hydroquinone developer having a low concentration.

This type of silver halide photosensitive material is known as a lithium-type photosensitive material.

The photolithography process involves converting a continuous-tone original into a halftone image, that is, converting the continuous-tone density changes of the original into a set of halftone dots with an area proportional to the density. There is.

For this purpose, a halftone dot image is formed by using the above-mentioned lithium-type photosensitive material and photographing an original through an intersection screen or contact screen, followed by development processing.

For this purpose, a silver halide photographic light-sensitive material containing a silver halide emulsion with fine grains and uniform grain size and grain shape is used. When processed with a commercially available developer, the halftone image formation, etc., is inferior to when developed with a Lith type developer.

Therefore, it is processed with a developer called a Lith type developer, which has an extremely low sulfite ion concentration and uses hydroquinone as a single developing agent. However, Lith-type developer is susceptible to auto-oxidation and has extremely poor storage stability.
There is a strong demand for a control method that keeps development quality constant even during continuous use, and great efforts have been made to improve the retention of this developer.

As a method to improve this, we have developed a replenisher (processing fatigue replenisher) that compensates for the deterioration in activity due to development processing in order to maintain the retention of the developer, and a replenisher (processing fatigue replenisher) that compensates for oxidative deterioration over time. A so-called two-liquid separation replenishment system, in which the replenisher (replenishment due to fatigue over time) and the replenisher (replenishment due to aging) are replenished using separate replenishers, is generally widely adopted in automatic developing machines for photolithography and the like. However, the above method has the disadvantage that it is necessary to control the replenishment balance of the two liquids, which complicates the equipment and operation.

In addition, in the Lith type development, it takes a long time (induction period) until an image appears due to development, and therefore an image cannot be obtained quickly.

On the other hand, there is a known method for quickly obtaining high-contrast images without using the above-mentioned Lith type developer. For example, U.S. Patent No. 2.419.975, JP 51-1662
As seen in No. 3 and JP-A-51-20921, a hydrazine compound is contained in a silver halide photosensitive material. According to these methods, it is possible to maintain a high sulfite ion concentration in the developer, and it is possible to process with improved preservability. However, all of these methods require a fairly high pH of the developer to obtain a high-contrast image, and there is a problem in the stability of the developer as a technique for obtaining images quickly and with high sensitivity. Further, since the pH of the developing solution is high, fog is likely to occur, and in order to suppress this fog, various organic inhibitors are contained in high concentrations, resulting in a disadvantage that sensitivity is sacrificed.

[Purpose of the invention]

Therefore, a first object of the present invention is to provide an image forming method that can quickly and stably obtain a high-contrast image.

A second object of the present invention is to provide image formation in which a high-contrast image can be stably obtained with high sensitivity and little loss of sensitivity.

A third object of the present invention is to provide an image forming method that provides images with high contrast and less fog.

A fourth object of the present invention is to provide an image forming method that provides high contrast and good halftone dot quality.

Other objects of the invention will become apparent from the following description of the specification.

[Structure of the invention]

The above object of the present invention is to prepare a photosensitive material having at least one light-sensitive silver halide emulsion layer containing a 3-pyrazolidone compound and/or a di- or trihydroxybenzene compound by the following general formulas [11, [2], Achieved by an image forming method characterized by processing with a developer containing the following components (a), (b) and (c) in the presence of at least one hydrazide compound represented by [3]. Ru.

(a) Di- or trihydroxybenzene compound (b)
Sulfite (c) Amino compound general formula [N (wherein R1 and R2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n represents 0 to 6, m represents 0 or l) , when n is 2 or more, each R may be the same or different.) General formula [2] (wherein, R21 represents an aliphatic group, an aromatic group, or a heterocyclic group, Ro represents a hydrogen atom, an optionally substituted alkoxy group, a heterocyclic oxy group, an amino group, or an aryloxy group, and ol and R2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3 ] % Formula % (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R31 represents a substituted alkyl group.) The specific structure of the present invention will be described in more detail below. Explain.

General formulas [1], [2], and [3] will be specifically explained below in the margins.

General formula [1] In the formula, Ro and R8 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is O-6, and ■ is 0
or represents l.

Here, examples of the aryl group represented by R1 and R2 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group, etc., but preferred as R1 and R8. is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R3 and R3. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, impropoxy, butoxy, octyloxy, dodecyloxy, etc.), and acylamino groups. (e.g. acetylamino, pivalylamino,
Benzoylamino, tetradecanoylamino, a-<2
．． (4-di-t-amylphenoxy)butyrylamino, etc.), sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylaminohonylamino, benzenesulfonylamino, etc.), urea groups (e.g., phenylurea, ethylurea, etc.),
Thiourea groups (e.g., phenylthiourea, ethylthiourea, etc.), hydroxyl groups, amine groups, alkylamino groups (e.g., methylamino, dimethylamino, etc.)
, a carboxy group, an alkoxycarbonyl group (eg, ethoxycarbonyl), a carbamoyl group, a sulfo group, and the like. Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, trimethylene, tetramethylene, etc.), arylene groups (N,
The alkylene group may include an oxy group, a thio group, a seleno group, a carbonialyl group), a sulfonyl group, etc. in the bond. Various substituents can be introduced into the group represented by R.

Examples of substituents include -C0N11NllR4(R,
has the same meaning as R8 and R3 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

Among the compounds represented by the general formula [11, preferably R1
and R2 is a substituted or unsubstituted phenyl group, and n=
In this compound, m=1'''cR represents an alkylene group.

Representative compounds represented by the above general formula [11] are shown below.

Margin below specific compound tc. 11. + ■ =17 OC12112@n ■ ■ l tc, 11. .

11th on t =54 tC, t+,.

(2) Next, the aliphatic group represented by R21 to explain general formula [21] preferably has 6 carbon atoms.
In the above, in particular, straight chain, branched or I; having 8 to 50 carbon atoms is a cyclic alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more Hete II atoms therein.

Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, or a sulfoxy group.

The aromatic group represented by lRz+ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrorazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as Rfl is an aryl group.

The aryl group or unsaturated heterocyclic group of R21 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably an alkyl group having 1 to 20 carbon atoms). monocyclic or bicyclic), alkoxy groups (preferably those with 1 to 20 carbon atoms), substituted amine 7 groups (
(preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably substituted with an alkyl group having 2 to 30 carbon atoms)
), sulfonamide group (preferably carbon number l
~30), ureido group (preferably 1 carbon number)
~30).

Among the groups represented by R11 in general formula [2], the optionally substituted alkoxy group has 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

Among the groups represented by Ro in the general formula [2], the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituents include a halogen atom alkyl group, an alkyl Among the groups represented by R2□, which include a cyan group and a cyan group, preferred are an optionally substituted alkoxy group or an amine group.

A may be a cyclic structure containing an optionally substituted alkyl group, an alkoxy group, or a 10--S--N- group bond. However, R1 is never a hydrazino group.

Rfl or R22 in general formula [21] may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a 7-ninoxy group,
It can be selected from alkylphenoxy groups, etc.

R21 or Ro in the general formula [2] may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include the groups described in US Pat. No. 4,355,105, such as thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups. Among the compounds represented by the general formula [21], the compounds represented by the following general formula [2-al] are particularly preferred.

General formula [2-al In the above general formula [2-al, R13 and R24 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, cyanoethyl group,
2-chloroethyl group), an optionally substituted phenyl group,
Naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group) group, pyrrolidyl group, 4-methyl-2
-pyrrolidyl group), R2 is a hydrogen atom or an optionally substituted benzyl group,
Alkoxy and alkyl groups (e.g. benzyl, p-
methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group), R2 and R27 represent a divalent aromatic group (e.g. phenylene group or naphthylene group),
Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -5O2CIIzCIlaNII 502
Nll, 0CII, SO*NIl, -0-CIl-
RZa represents -NR'R" or -0R2, R',
R" and RZS are a hydrogen atom, an optionally substituted alkyl group (e.g. methyl group, ethyl group, dodecyl group), a phenyl group (e.g. phenyl group, p-methylphenyl group, p-
methoxyphenyl group) or naphthyl group (e.g. α-su7tyl group, β-naphthyl group), and m and n represent 0 or.

R2, is OR,, Specific example of general formula [2] When represented, Y preferably represents a sulfur atom.

■ The above general formulas [2] and [2 A typical example represented by al. 1゛Bottom margin C=0 C.F.

■ ※→Open11CCOCII2CIl□5OzCIliCI
IzOIIfi-N11N11L;L;υji112Ul
Otori 3) UII! L; l12Ut1■ * Tatsumi NIINIIICCNIIC+ 2+l□Next, a method for synthesizing the compound 2-45°2-47 will be shown as an example from among the above-mentioned specific compounds.

Synthesis of compound 2-45 Synthesis scheme (B) (E) (A) Compounds 4-nitrophenylhydrazine 1539 and 500
Mix mQ of diethyl oxalate and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 50 of the obtained crystals (A)
9 was heated and dissolved in 100011IQ methanol, pd
Compound (B) is obtained by reduction under a /C (palladium/carbon) catalyst in a H2 atmosphere pressurized at 50 Psi.

22g of this compound (B) was added to 200m+2 of acetonitrile.
and pyridine 169 at room temperature.
4 g of acetonitrile solution was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and purified by recrystallization to obtain compound CD319.

30 g of compound (D) was hydrogenated in the same manner as above to obtain compound (
E) 20g was obtained.

Compound (E) 109 was dissolved in acetonitrile 100+oQ and ethyl inthiocyanate 3. Oy was added and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) 7 was purified by recrystallization.
．． Obtained 0g. Compound CF) 5.0g in methanol 5
Methylamine (40% aqueous solution 8 m (2
) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out, recrystallized and purified to obtain Compound 2-45.

Synthesis of Compound 2-47 Synthesis Scheme (C) (D) (E) Compound 2-47 22 g of compound (B) was dissolved in 200 ml of pyridine, and 22 g of p-nitrobenzenesulfonyl chloride was added into a stirring vessel. The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C). This compound (C) was subjected to the same reaction as compound 2-45 according to the synthesis scheme to obtain compound 2-47.

Next, general formula [31] will be explained.

General formula [31.

Iris Ar NHNil CR31 In the general formula [3], Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group,
The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. I can do it.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

R3 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, and the like.

Substituents introduced into these alkyl groups include alkoxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy, p-chlorophenoxy, etc.), peterocyclic oxy (e.g., pyridyloxy, etc.), mercapto, alkylthio (methylthio), etc. , ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl ( For example, benzenesulfonyl, etc.), heterocyclic sulfonyl (for example, pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (for example, acetyl, benzoyl, etc.), cyano, chloro, bromine, alkoxycarbonyltoxycarbonyl, etc.), aryloxycarbonyl (for example, phenoxycarbonyl, etc.) ), carboxy, carbamoyl, alkylcarbamoyl (e.g., t tf., N-
methylcarbamoyl, N,N-dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-722carbamoyl, etc.), amino, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino, naphthylamino, etc.), acylamino (e.g., acetylamino, benzoylamino, etc.), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.), acyloxy (e.g., acetyloxy) , benzoyloxy, etc.), alkylaminocarbonyloxyaminocarponyloxy, etc.), arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.), aryl Examples include multiple groups such as sulfamoyl (eg, phenylsulfamoyl, etc.).

Even if the hydrogen atom of hydrazine is substituted with a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, etc.), an oxalyl group (e.g., ethoxalyl, etc.), good.

Representative compounds represented by the above general formula [3] include:
There are the following.

SuG *-NIINIICCIIzOCII2CIhOC1l
zCIlxOI1 Next, a synthesis example of compound 3-5 will be described.

Compound 3- Synthesis of 5 Synthesis scheme Compound 3 was prepared according to the synthesis method of compound 2-45. Obtained.

General formula [
The amount of the compounds 1], [2], and [3] is 5 X 10-' to 5 X 10-' per mole of silver halide contained in the silver halide photographic material of the present invention. Up to mol is preferred, more preferably in the range from 5 x 10-' to 1 x 10-'' mol.

In the method of the present invention, the hydrazide compound may be contained in the light-sensitive material and/or the developer. When incorporated into a light-sensitive material, it is on a light-sensitive silver halide emulsion layer containing a 3-pyrazolidone compound and a di- or trihydroxybenzene compound and/or on a support that can diffuse and move into the emulsion layer at least until the time of development. It may be contained in at least one of the other coating layers. When included in photosensitive materials,
The amount of hydrazide compound is lo- per mole of silver halide.
A range of 6 to 1 O-1 mole is suitable, preferably a range of 10-' to 10-' mole per mole of silver halide. The appropriate amount can be arbitrarily determined by considering the composition of silver halide, particle size, chemical ripeness, amount of hydrophilic colloid as a binder, and balance with additives such as stabilizers, suppressors, and accelerators. .

When the hydrazide compound is contained in the developer, the amount added is 10-'-10-" mol, preferably 10-4 to 10-" mol, per developer lo, and the amount of addition is 10-'-10-' mol, preferably 10-4 to 10-' mol, and coexisting amino compounds, PHN fog inhibitors, etc. The appropriate amount is determined based on the balance.

The 3-pyrazolidone compound contained in the photosensitive material used in the method of the present invention is a compound represented by the following formula.

R4+ In the formula, %R41 represents an optionally substituted aryl group, and R4! , R, and R44 each represent a hydrogen atom or an optionally substituted alkyl group. Examples of substituents for the aryl group represented by RlI include methyl group, chloro group, amino group, methylamino group, acetylamino group,
Examples of the aryl group represented by R41 include phenyl group, p-aminophenyl group, p-chlorophenyl group, p-acetamidophenyl group, and p-methoxyphenyl group. etc.

The alkyl group represented by R42+R43 and R44 is
It is a prime number of 1 to 8, and examples of its substituents include If' hydroxy group, carboxy group, and sulfo group, such as methyl group, hydroxymethyl group, ethyl group, and propyl group.

Typical specific examples of the above 3-pyrazolidone compound are shown below.

(A-1) (A-2) (A-33 (A-4) (A-5) (A-6) l-phenyl-3-pyrazolidone l-7enyl-4,4-dimethyl-3-pyrazolidone 1 -722-4-methyl-4-hydroxymethyl-3
-pyrazolidone 1-phenyl-4,4-di(hydroxymethyl)-3-
Pyrazolidone l-phenyl-5-methyl-3-pyrazolidone 1-7 22-4,4-dimethyl-3-pyrazolidone [A-7) t-p-aminophenyl-4-methyl-4propyl-3
- Pyrazolidone may be linear, branched, or cyclic, preferably carbon (A-
8) t-p-chlorophenyl-4-methyl-4ethyl-3-
Pyrazolidone (A-9) 1-p-acetamidophenyl-4,
4-diethyl-3-pyrazolidone (A-10) 1-p-methoxyphenyl-4,
4-Diethyl-3-pyrazolidone The present compound is preferably present in a light-sensitive silver halide emulsion layer, but it may be present in a non-emulsion layer such as a protective film layer, intermediate layer, subbing layer or backing layer. I don't mind. Generally, this compound can be added by dissolving it in an organic solvent, and the amount added is 10-' to 10-' mol per 1 mol of silver halide, but the best range is lo-4 to 1 O-2 mol. Show the results.

The di- or trihydroxybenzene compound contained in the photosensitive material and developer used in the image forming method of the present invention is a compound represented by the following formula.

H In the above formula, Rs, , R, 2 and R53 are each a hydrogen atom, a halogen atom, an alkyl group (including a substituted alkyl group), an aryl group (including a substituted aryl group)
, heterocyclic group (including substituted heterocyclic group), -0-
Represents R, 4 or -3R54. R represents a hydrogen atom, an alkyl group (including substituted alkyl groups), an aryl group (including substituted aryl groups), or a heterocyclic group (including substituted heterocyclic groups). n represents 0 or 1.

Specific main compounds of the above di- or trihydroxybenzene compounds are shown below.

(B=1) Hydroquinone CB-2) Chlorohydroquinone [B-31 Bromohydroquinone CB-4,) Methylhydroquinone (:B-5)
2.3-dichlorohydroquinone CB-6)
2.5-dibenzoylaminohydroquinone CB-7) Gallic acid butyl ester CB-8)
Ethyl gallic acid ester This compound is preferably present in the light-sensitive silver halide emulsion layer, but it may also be present in non-emulsion layers such as a protective film layer, intermediate layer, subbing layer or backing layer. do not have. Generally, this compound can be added by dissolving it in water or an organic solvent such as alcohols such as methanol or ethanol, glycols such as diethylene glycol or triethylene glycol, or ketones such as acetone, and the amount of silver halide added is determined. 0.001-0.1 per mole
0 mol is added, preferably 0.005 to 0.03
It is a mole.

The dihydroxybenzene compound contained in the developer used in the method of the present invention is most preferably hydroquinone, which is a developing agent widely used in photographic processing, and the amount added is usually 0.05 to 0.5 mol/Q. It is.

As the sulfite contained in the developer used in the method of the present invention, those commonly used in the developer of silver halide photographic light-sensitive materials can be used, and specific examples include sodium sulfite, potassium sulfite, sulfite, etc. Examples include lithium, ammonium sulfite 17 sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Its concentration protects the developer from air oxidation,
The concentration may be as long as it can provide a sufficient sulfite ion concentration to change stable photographic performance, and the amount added should be 0.05 mol/Q or more, but preferably 0.15 mol/Q or more. be.

Furthermore, the amino compound contained in the developer used in the method of the present invention is used for the purpose of promoting high contrast, and particularly to produce a strong effect even at a relatively low pH level of the developer.

Amino compounds useful in this invention include both inorganic and organic amines. The organic amine can be an aliphatic amine, an aromatic amine, a cyclic amine, a mixed aliphatic-aromatic amine or a heterocyclic amine. 1st. Second
and tertiary amines and quaternary ammonium compounds were all found to be effective.

Particularly preferred alkanolamines for the purposes of the present invention are represented by the formula:

aX In the above formula, R6+ is a hydroxyalkyl group having 2 to 10 carbon atoms, and Ra2 and R1 are respectively a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 2 to 10 carbon atoms. A hydroxyalkyl group having IO carbon atoms, a benzyl group or a group of the following formula: (1) where n in the above formula is an integer from 1 to 10, and X and Y are each a hydrogen atom. , an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 2 to 10 carbon atoms.

Another preferred class of amino compounds is the alkylamines, especially those represented by the formula:

In the above formula, R6 is an alkyl group having 1 to 10 carbon atoms, and R, s and Raa are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. be.

Among the many amino compounds that can be used in carrying out the present invention, particularly representative examples are listed below.

(C-1) Triethanolamine (C-2)
Jetanolamine (C-3) Ethanolamine (C-4) 2-diethylamino-1-ethanol (C-5) 2-methylamino-1-ethanol (
c-6) 3-diethylamino-1-propatol 5-amino-1-pentanoldiethylamine triethylamine diisopropylamine 2-dibutylaminoethanol 14-cyclohexane bis(methylamine) (C-7) (C-8) (C- 9) (C-10) CC-11) (C-12) 0-Aminoandochoic acid aminobutanidine sal 7ate 4-amino-1-butanol 3-pyrrolidino-1,2propanediol 3-(dimethylamino) -1,2-propanediol 1,4-piperazinobis(ethanesulfonic acid) 3-piperidino-1,2-propanediol Note that the amount of the amino compound used in the present invention added is 0.
01 to 1.0 mol/a, preferably 0, O
It is 1 to 0.04 mol/Q.

The developer used in the method of the present invention preferably contains 5 (or 6)-nitroindazole. This is effective in preventing fog, and high sensitivity and high contrast are maintained. The amount added is 0.0001 to 0.0001 per developer N2.
A range of 0.1 mole is suitable.

Note that (C-1
8) (C-17) (C-19) (C-13) (C-14) (C-15) (C-16) is used as a developer in addition to dihydroxybenzene compounds.
-Pyrazolidone compounds or ortho or p-aminophenol compounds may be included.

The pH of the developer is preferably 10 to 12, but in order to maintain this pH, an alkali metal hydroxide or carbonate can be added as an alkali agent. Furthermore, inorganic inhibitors such as potassium bromide, triazole compounds such as 5-methylbenzotriazole, 5-chlorobenzotriazole, 2-mercaptobenzimidazole, l-phenyl-5- Organic antifoggants such as mercapto compounds such as mercaptotetrazole can be used.

Further, in addition to the above-mentioned components, arbitrary additives can be used in the developer used in the method of the present invention depending on the purpose. Examples include solvents, buffers, sequestering agents, development accelerators, viscosity agents, and emulsion layer swelling inhibitors.

The development process in the method of the present invention can be carried out under various conditions, but the development temperature is preferably 50°C or lower, particularly around 40°C, and the development time is generally completed within 3 minutes. However, preferably within 2 minutes often brings about good results. As treatment steps other than development, for example, steps such as washing with water, stopping, stabilizing, fixing, and further, if necessary, prehardening and neutralization may optionally be employed, and these may be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

Various types of silver halide can be used in the 7% silver halide emulsion of the light-sensitive material used in the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. The effect of the present invention is particularly remarkable for silver bromide and silver iodobromide, and is particularly effective for high-sensitivity light-sensitive materials containing little silver iodide (Agl 5 mol % or less).

The silver halide emulsion used in the method of the present invention may be prepared by suspending the silver halide emulsion in a hydrophilic colloid by a known method, such as a neutral method, a single jet method using an ammonia method, or a double jet method. An emulsion preparation method such as a method is used.

The average grain size of the silver halogenide contained in the silver halogenide emulsion layer of the photographic material used in the present invention is 0.1.
"LOp m, particularly preferably from 0.1 to 0.Lum and at least 75% of the total particle number, particularly preferably 8
Preferably, 0% or more contains silver halide having a grain size of 0.7 to 1.3 times the average grain size.

Furthermore, polyvalent metal ions (e.g. iridium, rhodium, etc.)
U.S. Patent No. 3 as a silver halide emulsion occluded with
, 271.157, 3,447.927, and 3.531.291 can also be used. No.10
The silver generator emulsion can be sensitized by chemical sensitization using a sulfur compound, a gold compound such as chloroauric acid salt, gold trichloride, etc., which is commonly performed.

The silver halide emulsion to which the present invention is applied can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye.

As the sensitizing dye, commonly used ones such as methine dyes and styryl dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxanol, and hemioxonol can be used.

The above dye is US Pat. No. 2.742.833, US Pat.
No. 56,148, No. 3,567.458, No. 3,61
No. 5,517, No. 3,615゜519, No. 3,632
．． 340, 3,155.519, 3,384°485, 4,232.115, 3,796.5
No. 80, No. 4,028° No. 110, No. 3,752.67
No. 3, JP-A-55-45015, etc. can be referred to.

The silver halide photographic emulsion of the light-sensitive material used in the present invention contains aldehydes (formaldehyde, glyoxal, glutaraldehyde,
mucochloric acid, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5-triacryloyl-hexahydro-S triazine, bis(vinylsulfonyl) methyl ether, etc.), active halides (2,4-dichloro-6-hydroxy-s-tria-zine, etc.), etc. can be used alone or in combination, and thickeners, matte Commonly used agents, coating aids, etc. can be used. Further, as the binder, a commonly used hydrophilic binder having protective colloidal properties can be used.

Furthermore, the present invention can contain coupler ultraviolet absorbers, optical brighteners, image stabilizers, antioxidants, lubricants,
Those commonly used as metal ion sequestering agents, emulsifying and dispersing agents, etc. can be added.

The light-sensitive materials used in the method of the present invention include layers other than the silver halide emulsion layer, such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a subbing layer, an auxiliary layer, an anti-irradiation layer, and a backing layer. The support to be used may be appropriately selected from baryta paper, polyethylene-coated paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc., depending on the intended use of the photosensitive material.

A polymer latex consisting of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. is applied to the photosensitive silver halide emulsion layer or other coated layer on the support to improve the dimensional stability of the photographic material. , may be included for the purpose of improving the physical properties of the film.

4-Hydroxy-6-methyl-1,3°3a,7 as a stabilizer or antifoggant in a photosensitive silver halide emulsion
-Titrazaindene, l-phenyl-5-mercaptotetrazole, resorcinol oxime, hydroquinone aldoxime, and many other compounds can be added in an amount of 10-4 to 10-1 mole per mole of silver halide.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Silver iodobromide grains containing 1.5 mol % of silver iodide were prepared.

The particles were cubic with an average particle size of 0.30 μm. After gold sensitization and sulfur sensitization, sensitizing dye and stabilizer 4
-Hydroxy-6-methyl-1,3,3a.

7-chitrazaindene was added thereto, and the mixture was divided into 13 pieces each containing 1 mole of silver halide. A 3-pyrazolidone compound and a di- or trihydroxybenzene compound of the type and amount shown in Table 1 were added to these emulsions, and saponin, formalin and glyoxal were further added,
These emulsions were coated on a polyethylene terephthalate support with a silver content of 4.5 g/m2, and a protective layer was coated on top of this emulsion layer with a gelatin content of 1.8 g/m2, dried, and exposed to light. A sample of the material was obtained.

Cut these samples into small pieces and place a negative contact screen (100 lines/inch) on one side of the step wedge.
was attached and exposed to tungsten light for 20 seconds. This sample was placed in a Konica automatic processor GR containing the following developer and fixer.
-27 (manufactured by Konica Corporation) was used for development at 35° C. for 30 seconds.

The sample obtained in this way was
Measured with DP-65, and shows the relative sensitivity with the sensitivity of sample No. 1 at a concentration of 3.0 as 100, and the sensitivity at a concentration of 0.3.
Gamma is expressed with the tangent of and 3.0. In addition, to evaluate the quality of halftone dots, visually observe them using a 100x magnifying glass.
The rough edges with many fringes are ranked as 1.
It was expressed as a grade using the 1O step method.

Developer formulation Ethylenediaminetetraacetic acid disodium salt 1g Sodium sulfite 60g Hydroquinone 35g 5-amino-1-
Pentanol 50g Sodium Bromide
2.5 g 5-methylbenzotriazole 0.3 g 1-phenyl-3-pyrazolidone 0.2 g Add water to make tc, and adjust to pnll and 5 with sodium hydroxide.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 2
40mff sodium sulfite
17g Sodium acetate trihydrate 6.5
g Boric acid
6゜Sodium citrate dihydrate
2g (composition) Pure water (ion exchange water) 17Illff Sulfuric acid (50% W/V aqueous solution) 4.
7g aluminum sulfate CkQ, O, aqueous solution with a converted content of 8.1% W/V)
When using a 26.5 g fixer, it was dissolved in 500 mQ of water in the order of the above composition A1 and finished to 1Q. The pn of this fixer was adjusted to 6 with acetic acid.

As is clear from Table 1, it can be seen that high-contrast, high-quality halftone dots can be formed using the compounds of the present invention.

Example 2 Silver bromide content is 6 mol%, rhodium is 1X per mol of silver
A silver chlorobromide emulsion containing 10-' moles was prepared. The particles were cubic with an average particle size of 0.22 μm. This is 4
-Hydroxy-6-methyl-1,3,3a.

After sulfur sensitization in the presence of 7-chitrazaindene, 1 mol of Ig/AgX of the compound D-10 of the present invention was added, and 4-hydroxy-6-methyl-1,3,
3a, 7-chitrazaindene and 5-mercaptotetrazole were added to 11
Divided into pieces. To these emulsions were added 3-pyrazolidone compound, di- or trihydroxybenzene compound in the amounts shown in Table 2, saponin and mucochloric acid were added and these emulsions were deposited on a polyethylene terephthalate support at 3.5 g/i of silver. Further, a protective layer was coated on the emulsion layer to give a gelatin content of 1.5 g/'m'' and dried to obtain a photosensitive material sample.

These samples were cut into small pieces, attached with a step wedge and exposed to tungsten light for 30 seconds. This sample was developed at 35° C. for 30 seconds using a Konica automatic processor GR-27 (manufactured by Konica Corporation) containing the following developer. In addition, sample No. 3 to No. 0.6 and No. 8 to N
For samples No. 1 and 11, a developer was used in which l-7 di-5-mercaptotetrazole was further added in the amount shown in Table 2.

The sample thus obtained was evaluated in the same manner as in Example 1.

Developer formulation Ethylenediaminetetraacetic acid disodium salt 1g Sodium sulfite 60g Hydroquinone 25g 1-phenyl-4-
Methyl-4hydroxymethyl-3-pyrazolidone
0.3g 5-methylbenzotriazole Potassium bromide 2g Triethanolamine 40g Add water to 1
a and adjust the pH to 1'2.3 with potassium hydroxide.

As is clear from Table 2, it can be seen that when the human land compound of the present invention is used, photographic characteristics with high contrast and high sensitivity can be obtained.

〔Effect of the invention〕

By the method of the present invention, it is possible to quickly and stably obtain a high-contrast image with little fog and an image with good halftone dot quality.

Claims (1)

[Scope of Claims] A photosensitive material having at least one photosensitive silver halide emulsion layer containing a 3-pyrazolidone compound and/or a di- or trihydroxybenzene compound is prepared by the following general formulas [1], [2], An image forming method comprising processing with a developer containing the following components (a), (b) and (c) in the presence of at least one hydrazide compound represented by [3]. (a) Di- or trihydroxybenzene compounds (b) Sulfites (c) Amino compounds General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R_1 and R_2 represent an aryl group or a heterocyclic group. , R represents an organic bonding group, n is 0 to 6, m is 0
or 1, and when n is 2 or more, each R may be the same or different. ) General formula [2] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_2_1 is an aliphatic group, aromatic group, or heterocyclic group, R_2_2 is a hydrogen atom, an optionally substituted alkoxy group, a heterocyclic group, etc.) Represents an oxy group, an amino group, or an aryloxy group, and P_1 and P_2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R_3_1 represents a substituted alkyl group.)