JPH02291547A - High-contrast silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a high contrast and excellent dot quality and less fogging and to attain a high sensitivity even in rapid processing by confining pAg to <=9.0 after the end of a desalting stage and incorporating specific compds. into emulsion layers. CONSTITUTION:Particles having substantially no twin plane are formed before the formation of the particles and physical maturation and the pAg is confined to <=9.0 after the end of the desalting stage; in addition, the emulsion layers contain at least one kind of the compds. expressed by formulas I to III. In the formula I, R1 and R2 denote an aryl group or heterocyclic group; R denotes an org. bond group; n denotes 0 to 6; m denotes 0 or 1. In the formula II, R21 denotes an alicyclic group, arom. group, or heterocylic group; R22 denotes a hydrogen atom, alkoxy group. etc.; P1 and P2 denote a hydrogen atom, acyl group or sulfinic acid group. In the formula III, Ar denotes an aryl group contg. at least one of a diffusion resistant group or silver halide adsorption accelerating group; R31 denotes a substd. alkyl group. Hard-contrast images are rapidly and stably obtd. in this way and the high-sensitivity, high contrast, less fogging and good dot quality are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and particularly to a high-contrast silver halide photographic light-sensitive material.

[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 certain types of 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, in order to maintain the stability of the above-mentioned Lith-type developer, there is a replenisher (processing fatigue replenisher) that compensates for the deterioration in activity due to development processing, and a replenisher (processing fatigue replenisher) that compensates for the 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. Pat.
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. Furthermore, since the pH of the developing solution is high, it is easy to cause fogging, and in order to suppress this fogging, 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 provide a silver halide photographic material having at least one silver halide photographic emulsion layer on a support, which substantially has twin planes until grain formation and physical ripening. l) after the end of the desalination process, forming no particles;
Ag is 9.0 or less, and the emulsion layer has the following general formula [1
], [2], and [3].

General formula [1] R22 represents a hydrogen atom, an optionally substituted alkoxy group, a heterocyclic oxy group, an amino group, or an aryloxy group, and P and P represent a hydrogen atom, an acyl group,
Or represents a sulfinic acid group. ) General 2 [3] I Ar NHNH C R31 (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and Ri+ represents a substituted alkyl group.) More details regarding the specific configuration (in the formula,
R0 and R represent an aryl group or a heterocyclic group, and R
represents an organic bonding group, n represents θ to 6, m represents 0 or l, and when n is 2 or more, each R may be the same or different. ) General formula [2] (wherein R!l is an aliphatic group, an aromatic group, or a hetether) The following general formula [N.[2].[3] will be specifically explained.

General formula [1] In the formula, R and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is θ ~ 6, and m is 0
or represents l.

Here, examples of the aryl group represented by R and R2 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a penzothiazolyl group, a quinolyl group, a chenyl group, etc. and R2 is preferably an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R1 and R. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., tomoxy, ethoxy, impropoxy, butoxy, octyloxy, dodecyloxy, etc.), and acylamino groups. {For example, acetylamino, bivalylamino, penzoylamino, tetradecanoylamino, α-(2
．． 4-di-t-amylphenoxy)butyrylamino, etc.}sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea groups (e.g., phenylurea, ethylurea, etc.), thiourea groups (e.g. , phenylthiourea, ethylthiourea, etc.), hydroxyl group, amino group, alkylamino group (e.g., methylamino, dimethylamino, etc.), carpoxy group, alkoxyl group (e.g., ethoxycarponyl), carbamoyl group, sulfo group Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, tolyltylene,
tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. Aralkylene groups include oxy groups, thio groups, seleno groups, carpo R3 t nyl groups, -N monogroups ( R 3 is a hydrogen atom, an alkyl group,
It may also contain a sulfonyl group (representing an aryl group). Regarding the group represented by R, various specific substituted compounds can be introduced.

Examples of substituents include -CONHNHRa (R
a has the same meaning as R and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carpoxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

Among the compounds represented by general formula (1), preferably R1
and R2 is a substituted or unsubstituted phenyl group, and n-
A compound in which R in m-1 represents an alkylene group.

Representative compounds represented by the above general formula (1) ■ l -12 -14 l -17 ■ ? C1■H■1n l l =19 l 2l l l l l l =33 l l l -34 l l l l l l -46 l -53 l -54 tcsH+ 1 l Next, general formula [2] will be explained. Do R! The aliphatic group represented by l preferably has 6 carbon atoms.
Among the above, it is particularly a linear, branched or cyclic alkyl group having 8 to 50 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated betaro ring containing one or more helaro 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 R,1 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.

For example, benzene ring, naphthalene ring, pyridine ring, birimidine ring, imidazole ring, pyrorazole ring, quinoline ring, isoquinoline ring, penzimidazole ring, thiazole ring, penzothiazole ring, etc. Among these, those containing a benzene ring are preferred.

Particularly preferred as R2l is an aryl group.

R. The aryl group or unsaturated heterocyclic group in l may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably a monocyclic alkyl group having 1 to 20 carbon atoms). or two rings), alkoxy groups (
(preferably one having 1 to 20 carbon atoms), substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably one having 2 to 30 carbon atoms), sulfonamide Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30).

R of general formula [2]. Among the groups represented by the above, 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 R2■ in general formula [2], the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituent is a halogen atom alkyl group or an alkoxy group. , cyano group, etc. Among the groups represented by, preferred are an optionally substituted alkoxy group or an amino group.

A2 may be an optionally substituted alkyl group, an alkoxy group, or a cyclic structure containing a 10-1S-1N bond. However, R. is never a hydrazino group.

R21 or R22 in general formula [11] may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

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

R2 or R'22 in general formula [2] may have a group incorporated therein that enhances 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 [2], the compounds represented by the following general formula [2-al] are particularly preferred.

General formula [2-a] In the above general formula [2-a], R! 3 and R! 4 is a hydrogen atom, an alkyl group that may be substituted (e.g., methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypuchyl group, 2-cyanoethyl group, 2-chloroethyl group), or an optionally substituted alkyl group Phenyl group, naphthyl group, cyclohexyl group, pyridyl group, birrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, α-hydroxyna 7-tyl group, cyclohexyl group, p-methylcyclohexyl group, biridyl group, 4- proyl 2-pyridyl group, pyrrolidyl group, 4-methyl-2
-pyrrolidyl group), R. is a hydrogen atom or an optionally substituted benzyl group, alkoxy group and alkyl group (e.g. benzyl group, p-methylbenzyl group, methoxy group, ethoxy group, ethyl group,
butyl group), and R2. and R27 represents a divalent aromatic group (e.g. 7-enylene group or naphthylene group), and Y
represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -SOzCJCHJi{ S02NH,
OCH2SO2NH, O--CH-N-), R2m represents -R/R// or -OR,, R',
R'' and R,. are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl, ethyl, dodecyl), phenyl groups (e.g. phenyl, p-methylphenyl, p-
methoxyphenyl group), naphthyl group (e.g. α-naphthyl group, β-na7thyl group), or heterocyclic group (e.g. pyridine, thiophene, furan-like unsaturated heterocyclic group, tetrahydrofuran, sulfolane), ), and R' and R'' together with the nitrogen atom represent a ring (e.g.
piperidine, piperazine, morpholine, etc.).

m and n represent 0 or l. When R26 represents OR, , Y preferably represents a sulfur atom.

Representative general formulas [2] and (2-a) represented by the above general formulas [2] and (2-a)
Specific example of 21 l3 =15 CL 2l -22 -23 ■ *-NHNHCCOCH2CH. SO2CFl. CH,
O}l*-NHNHCCOCH2CH,SCH,C}1
, OFICH. CIllH11fl =20 -25 =26 S b b O0 O0 O0 -33 H tI3 * ■ Il1 -NHNHCCNHC+ 2H2 s q 113L; Next, compound 2 -45.2- of the above specific compounds
Taking No. 47 as an example, its synthesis method will be shown.

Synthesis of compound 2-45 Synthesis scheme (B) (E) (A) Compound '111 4-nitrophenylhydrazine 1539
and 500 mQ of diethyl oxalate and refluxed 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, 509 of the obtained crystals (A) were heated and dissolved in 1000 methanol of methanol,
Compound (B) is obtained by reduction under pd/C (palladium/carbon) catalyst in H atmosphere under pressure of 50 Psi.

This compound (B) 229 was mixed with acetonitrile 200+iQ
and pyridine 169 at room temperature.
24 g of acetonitrile solution was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and recrystallized to obtain compound (D) 31.
I got g.

Compound (D) 309 was hydrogenated in the same manner as above to obtain compound (
E) 209 was obtained.

10 g of compound (E) was dissolved in 100 mQ of acetonitrile, 3.0 g of ethyl inthiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) 7 was purified by recrystallization.
I got 09. Compound (F) 5.0g in methanol 50g
The mixture was dissolved in mQ, and methylamine (40% aqueous solution 8.a) was added and stirred. Add methanol. After drying and concentration, the precipitated solid was taken out and purified by recrystallization to obtain Compound 2-45.

Synthesis of Compound 2-47 Synthesis Scheme (B) CD) (E) Compound 2-47 Compound (B) 229 was dissolved in 200 ml of pyridine, and 22 g of p-nitrobenzenesulfonyl chlorite was added into a stirring vessel. The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound CC"). Compound 2-47 was obtained by reacting this compound (C) in the same manner as compound 2-45 according to the synthesis scheme.

Next, general formula [3] will be explained.

General formula [3].

Ar NHNH-CRs+ In the general formula [3], Ar represents an aryl group containing at least one diffusion-resistant group or a halogenated (C) silver adsorption promoting group; Ballast groups commonly used in additives are preferred. A 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,
It can be selected from phenyl groups, alkylphenyl groups, phenoxy groups, alkyl 7-enoxy groups, and the like.

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.

R31 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-chloro7-enoxy, etc.), heterocyclic oxy (e.g., biridyloxy, etc.), mercapto, alkylthio (methylthio), etc. , ethylthio, etc.), arylthio (e.g., phenylthio, p-chlor7enylthio, etc.), peterocyclicthio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl ( (e.g., benzenesulfonyl, etc.), peterocyclic sulfonyl (e.g., biridylsulfonyl, morpholinosulfonyl, etc.), acyl (e.g., acetyl, benzoyl, etc.), cyano, chlor, bromine, alkoxyl (e.g., ethoxyl, methoxyl, etc.), Aryloxycarbonyl (e.g. phenoxycarbonyl), carpoxy, carbamoyl, alkylcarbamoyl (e.g. N-methylcarbamoyl, N,N-
dimethyl-rubamoyl, etc.), aryl-rubamoyl (e.g., N-7-phenylcarpamoyl, etc.), amino, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino,
naphthylamino, etc.), acylamino (e.g., acetylamino, penzoylamino, etc.), alkoxycarponylamino (e.g., ethoxyluponylamino, etc.), aryloxyluponylamino (e.g., 7-enoxyluponylamino, etc.), acylamino (e.g., acetyloxy, penzoyl), oxy, etc.), alkylaminoluponyloxy (e.g., methylaminoluponyloxy, etc.), arylaminoluponyloxy (e.g., phenylaminoluponyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.), Examples include various groups such as arylsul-7-amoyl (eg, 7-enylsulfamoyl, etc.).

Even if the hydrogen atoms of hydrazine are substituted with substituents such as sulfonyl groups (e.g., methanesulfonyl, toluenesulfonyl, etc.), acyl groups (e.g., acetyl, trifluoroacetyl, etc.), oxalyl groups (e.g., ethoxalyl, etc.), etc. good.

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

Reshirishi k3 -25 q *-NFINHCCHzOCHzCH20(JlzCH
*OH=28 =38 =32 -35 4l Next, a synthesis example of compound 3-5 will be described.

Synthesis of Compound 3-5 Synthesis scheme Compound 3-5 was obtained according to the synthesis method of Compound 2-45.
child .

General formula [
I
Per mole, the hydrazide compound is preferably 5 X 10-' to 5 X to-' mole, more preferably 5 X 10-' or more per mole. . When incorporated in a light-sensitive material, it is on a light-sensitive silver halide emulsion layer containing a 3-virazolidone 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 a photosensitive material, the amount of hydrazide compound is 1 mole of silver halide.
A range of 0-' to io-' moles is suitable, preferably a range of 10-' to 10-2 moles 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 a hydrazide compound is contained in the developer, the amount added is 10-' to 1O-2 mol, preferably IO-4 to 1O-3 mol, per 112 of the developer, and the amount of addition is 10-' to 1O-2 mol, preferably IO-4 to 1O-3 mol, and coexisting amino compounds, pHt fog inhibitors, etc. The appropriate amount is determined based on the balance.

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

In the formula, R4l represents an optionally substituted aryl group, and R4! ．． R43 and R44 each represent a hydrogen atom or an optionally substituted alkyl group. Examples of substituents for the aryl group represented by R,1 include methyl group, chloro group, amine group, methylamino group, acetylamino group,
Groups such as methoxy and methylsulfonamidoethyl groups may be mentioned, R4. Examples of the aryl group represented by the formula include phenyl group, p-amino7enyl group, p-chlorophenyl group, p-acetamidophenyl group, p-methoxyphenyl group, and the like.

R,! , R as and R44 may be linear, branched, or cyclic, and preferably have 1 to 8 carbon atoms, and examples of the substituents thereof include a hydroxy group, a carpoxy group, a sulfo group, etc. Examples include methyl group, hydroxymethyl group, ethyl group, and proyl group.

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

(A-1) (A-2) (A-3) (A-4) [A 5] (A-63 [A 7] (A-8) 1-phenyl-3-virazolidone l-phenyl-4,4 -dimethyl-3-virazolidone l-phenyl-4,-methyl-4-hydroxymethyl l-phenyl-4,4-di(hydroxymethyl)-3-
Virazolidone l-phenyl-5-methyl-3-vilazolidone l-722-4,4-dimethyl-3-virazolidone l-P-chloro7enyl-4-methyl-4-probyl
3-Vyrazolidone IP-chlorophenyl-4-methyl-4 (A-9)
iP-acetamidophenyl-4.4-diethyl-3-virazolidone CA-10)
1-P-Methoxyphenyl-4,4-diethyl-3-viladridone The present compound is preferably present in the light-sensitive silver halide emulsion layer, but it is preferably present in the protective film layer, intermediate layer, undercoat layer, or backing layer. It may be present in a non-emulsion layer such as a sublayer. The compound can generally be added by dissolving it in an organic solvent, and the amount added is from io-' to 10-1 mole per mole of silver halide, but the best range is from lO-4 to 10-' mole. 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.

0l υ■ In the above equation, R, . ,R. '． and Rs! are hydrogen atoms, halogen atoms, alkyl groups (including substituted alkyl groups), aryl groups (including substituted aryl groups), hetero-reducing groups (including substituted hetero-reducing groups), -0
-Rs4 or -S-R,4. 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 examples of the above di- or trihydroxybenzene compounds are shown below.

CB-1) Hydroquinone (B-2) Chlorohydroquinone (B-3)
Promhydroquinone CB-4) Methylhydroquinone CB-5) 2,3-dichlorohydroquinone CB-6) 2,5-dibenzoylaminohydroquinone CB-7) Gallic acid butyl ester (B-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, the 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 Ascent, and the amount of addition is limited to 0.001 to 1 mole of silveride
0. 1O mol is added, preferably 0.005 to 0
．． 03 moles.

The dihydroxybenzene compound contained in the developer used in the method of the present invention is most preferably nohydroquinone, which is a developing agent widely used in photographic processing, and the amount added is usually 0.05 to 0.5 mol. /12.

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, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite, and the like. The concentration should be such that it protects the developer from air oxidation and stabilizes it; it can provide a sufficient sulfite ion concentration to change photographic performance, and the amount added is 0.05 mol/Q or more. is required, but preferably 0.15 mol/Q or more.

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, an aliphatic monoaromatic mixed amine or a heterocyclic amine. 1st, 2nd
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:

\R6, In the above formula, R61 is a hydroxyalkyl group having 2 to 10 carbon atoms, and R. , and R63 are each a hydrogen atom, l −10
an alkyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, a benzyl group or a group of the formula: /X -Cnl{. n-tJ\Y, where n in the above formula is an integer of 1 to 10, and X and Y are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 to A hydroxyalkyl group having IO carbon atoms.

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

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

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)
Diethanolamine (C-3) Ethanolamine (C-4) 2-diethylamino-l-ethanol (C-5) 2-methylamino-l-ethanol [
C-6) 3-diethylamino l-propanol 5-amino l-pentanol diethylamine triethylamine diisopropylamine 2-dibutylaminoethanol i4-cyclohexane bis(methynoleamine) (C-7) [C-8] (C-9 ) (C-10) (C-11) (C-12) 0-Aminebenzoic acid aminopanidine sulfite 4-amino-1-butanol 3-pyrrolidino-1.2 Propanediol 3-(dimethylamino)-1. 2 Propanediol 1,4-biverazinobis(ethanesulfonic acid) 3-biperidino-1,2-propanediol Note that the amount of the amino compound used in the present invention added is 0.
The range is from Ol to 1.0 mol/Q, preferably 0.0
It is 1 to 0.04 mol/12.

It is preferred that the developer used in the method of the present invention contains 5 (or 6) ditroindazole. This is effective in preventing capri, and high sensitivity and high contrast are maintained. The amount added is 0.000 per 112 of the developer.
A range of 1 to 0.1 mol is suitable.

In addition, in the developer used in the method of the present invention, 19] [C (C-17) (C-18) (c-13) (C-14) (C-15] (c-16) is dihydroxy 3 as a developer in addition to benzene compounds
-virazolidone compounds or ortho or p-aminophenol compounds may be included.

The po of the developer is preferably 10 to 12, but in order to maintain the pEI, 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-chloropenzotriazole, 2-mercaptobenzimitasole, 1-phenyl-5- Organic anti-brittle agents 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, warming agents, sequestering agents, development accelerators, viscosity agents, and emulsion layer swelling inhibitors.

Examples of the development accelerator used in the present invention include compounds represented by the following general formula [4].

General formula [4] R , -0 +C H . C.H. O+n H [
In the formula, R represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n represents an integer from lo to 200. ] Specific examples more preferable than the compound represented by the general formula [4] will be given, but the invention is not limited thereto.

HO(CH,CH,O)nH H0 (CH2CH20)nI{
}10(CI,CH20)nH H O (C H 2 C H 2 0 ) n H
}IP(CH,CB.O)n}I HO(CH,CH.O)11}1 n=lO n-3o n=5o n=7o n==150 J7 Gate・. These compounds are commercially available and can be easily obtained. These compounds have a content of 0.0% per mole of silver halide. It is preferable to add 4.0 mol of Ol<0.02
-2 mol is more preferred.

Further, two or more types of compounds having different values of n may be included.

The silver halide emulsion of the light-sensitive material used in the present invention includes:
Various silver halides can be used. 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 with a small amount of silver iodide (Ag1 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 silver halide contained in the silver halide emulsion layer of the light-sensitive material used in the present invention has an average grain size of 0.1 to 1
．． 0 μrtr, particularly preferably from 0.1 to 0.7 μa+ 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.

In the present invention, particles having substantially no twin planes are defined as
A particle in which all or a majority of its surfaces are (100) planes.

Moreover, the pAg to be adjusted after desalting is preferably in the range of 9.0 to 6.5, more preferably 9.0 to 8.0.

Potassium bromide and potassium iodide are used to adjust pAg, and potassium iodide is more preferred.

Furthermore, polyvalent metal ions (e.g. iridium, rhodium, etc.)
U.S. Patent No. 3 as a silver halide emulsion occluded with
．． No. 271.157, 3,447. No. 927, same 3
, 531.291 can also be used. Silver halide emulsions can be chemically sensitized using conventional sulfur compounds, gold compounds such as chlorauric acid salts, gold trichloride, and the like.

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 disclosed in U.S. Pat. No. 2,742.833 and U.S. Pat.
No. 56,148, No. 3,567.458, No. 3,61
No. 5.517, No. 3,615.519, No. 3,632
．． No. 3.40, No. 3,155,519, No. 3,384
, No. 485, No. 4,232,115, No. 3,796.
No. 580, No. 4,028,110, No. 3,752.6
Reference may be made to the descriptions in No. 73, JP-A-55-45015, and the like.

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 (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1.3.5-triacryloylhexahydro S-triazine, bis(vinylsulfonyl) methyl ether, etc.), active halides (2,4-
Dichloro-6-hydroxy-S-}riazine, etc.) can be used alone or in combination, and commonly used thickeners, matting agents, coating aids, etc. can be used. Further, as the binder, a commonly used hydrophilic binder having protective colloidal properties can be used.

Furthermore, according to the purpose of the present invention, commonly used couplers, ultraviolet absorbers, optical brighteners, image stabilizers, antioxidants, lubricants, sequestering agents, emulsifying dispersants, etc. may be added to the photosensitive material. can do.

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 coating layer on the support to improve the dimensional stability of the photographic material. It 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 anti-capri in photosensitive silver halide emulsions.
Many compounds including tetrazaindene, ■-phenyl-5-mercaptotetrazole, resorcinol oxime, and hydroquinone aldoxime were added in amounts of IO-4 to IO-1 mol per mol of silver halide. Examples will be described, but the embodiments of the present invention are not limited thereto.

Example I (Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 0.1 μm on both sides (JP-A-59-1994
A silver halide emulsion layer having the following formulation (1) with a gelatin amount of 2.0 was applied on one of the undercoating layers of a 100 μm thick polyethylene tereftate film coated with Example 1 of No. 1.
g/m', silver amount is 3.5 g/m', and on top of that, a protective layer of the following formulation (2) is applied with a gelatin amount of 1.
．． 0g/+", and on the other undercoat layer on the opposite side, apply a packing layer according to the following recipe (3) so that the gelatin amount is 3.5g/m". , and then on top of that a protective layer of the following formulation (4) with an amount of gelatin of 1 g.
/+'' to obtain sample No. 1-16.

Prescription (l) (Silver halide emulsion layer composition) Gelatin
2.0 g/m' Also, after the desalination was completed, pAg was raised from 7.7 to 8.8 with potassium iodide.
. ) 3.5g/m2 *Anti-fogging agent 10mg/Agmff Silver halide emulsion A 3.5g/+” Antifoggant: Hydroquinone stabilizer 4-methyl-6-hydroxy-1.3.3a.7-tetrazaindene interface Activator: sabonin promoter exemplified compound 4-4 Latex polymer: 25 mg/m2 30+119/112 0.1 g/m''100+119/I1' Compound according to the present invention or comparative compound Silver iodobromide emulsion (average grain size 0.20 μm1 Silver iodide 2 mol%
, amount shown in Table 1 Sensitizing dye S: (a) Prescription (2) [Emulsion protective layer composition] Gelatin 1.5 g/+*''
Matting agent: Polymethyl methacrylate with an average particle size of 3.0 to 5.0 µI 0.05 g/+*"Colloidal silicone strength 0.029/lm" Surfactant S: (b) So, Na 0. Olg/m” Hardener: (CHI・CI{SOxCHx)0
0-10g/@” Prescription (3) (Packing layer composition) (c) SO, Na Gelatin 2.7g/-2 Surfactant: Saponin 0.Ig/s' Hardener: Glyoxal 0-1g/m! Sodium dodecylbenzenesulfonate 0.019/m Beating recipe (4) [Packing protective layer composition] Gelatin Ig/m" Matting agent: Polymethyl methacrylate with an average particle size of 3.0 to 5.0μ haze 0.05g/a "Surfactant: Hardener: Glyoxal 0-01g/m"
The resulting sample was subjected to a halftone quality test using the method described below.

(Testing method for halftone dot quality) A halftone screen (150 lines/inch) with a halftone dot area of 50% is attached to a step wedge, and the sample is placed in close contact with this screen and exposed for 5 seconds to a xenon light source. The sample was developed under the following conditions in an automatic processing machine for quick processing using the developer and fixer listed below, and the quality of the halftone dots on the sample was observed with a 100x magnifying glass. "
5" rank, followed by "4", "3", "2", "l"
5 ranks.

Note that ranks "l" and ",2" are levels that are not desirable in practical terms.

In addition, black spots in the halftone dots are evaluated in the same way, and the highest rank is ``5'' when there are no black spots in the halftone dots, and ranks are determined according to the degree of occurrence of black spots in the halftone dots. 4",
The evaluation was performed by lowering the ranks sequentially from "3" to "2" to rlJ. Note that the ranks "l" and "2" have large black spots, which are at a level that is not practical.

In addition, the obtained sample was measured using a Konica digital densitometer PDP-65.
The sensitivity at the concentration of sample No. 3.0 was set to 10.
The relative sensitivity is expressed as 0, and the gamma is expressed as the tangent between the densities 0.3 and 3.0.

Developer recipe Ethylenediaminetetraacetic acid disodium salt 1g Sodium sulfite 60g Hydroquinone 35g 5-Aminol
-Pentanol Potassium bromide 5-methylbenzotriazole 1-7enyl-3-vilazolodone Add water to make 1Q and adjust sodium hydroxide to 11.5.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w/v 2.5g 0.3g 0.2g pH in lium aqueous solution) 240m4 17g 6.5g 2g Sodium sulfite Sodium acetate trihydrate Borate Sodium citrate・Dihydrate (composition B) Pure water (ion exchange water) Sulfuric acid (50% w/w aqueous solution) Aluminum sulfate (Affi.OS equivalent content 8.1% w/w aqueous solution)
17 UQ Q 4.7g 26.5g When using a fixer, the above composition A and composition B were dissolved in 500 ml of water in that order, and finished to IQ. The pH of this fixer was adjusted to 6 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
Fix at 40℃ for 15 seconds
35℃ lO second water wash
Dry at 30°C for 10 seconds 5
0° C. 10 seconds The following compounds (a) to (c) were used as comparative compounds added to the silver halide emulsion layer in formulation (1).

The results of the above examples are shown in Table 1.

As is clear from Table 1, the samples according to the present invention have higher sensitivity, higher contrast, and lower dot quality and black spots than the comparison. Everything else was carried out in the same manner as in Example 1.

The results are shown in Table 2.

Developer formulation Hydroquinone 22.59 Methol 0.25g Ethylenediaminetetraacetic acid 1.09 Sodium sulfite 75.09 Sodium hydroxide
7.9g trisodium phosphate (decahydrate) 75.0g 5-methylbenzotriazole
0.259N,N-diethylethanolamine
Add l2.5■a water to make it 1a, and adjust the pH to 11.
．． Adjusted to 6.

The results of the above examples are shown in Table 2.

As is clear from the results in Table 2, the sample according to the present invention, like Example 1, has higher sensitivity, higher contrast, and better halftone dot quality and black spots than the comparison.

/ /: ...1 or less, lower margin Example 3 Contains 0.3 mg of potassium hexacroiridate per mole of silver halide with an average grain size of 0.22 μm, dispersion rate of 21%, silver iodide content of 2% Silver iodobromide grains were sulfur-sensitized according to a conventional method. Then, as a stabilizer, 6-methyl-
4-hydroxy-1. 3. 3a. 7-tetrazaindene was added, the mixture was divided as shown in Table 3, a hydrazine compound was added, and coating was carried out using the same formulation as in Example 1. The resulting sample was exposed to light for IO-6 seconds, and then subjected to optical analysis according to Example 1. The results are shown in Table 3.

As is clear from the results in Table 3, the samples of the present invention also exhibit excellent performance in terms of high illumination characteristics.

[Effects of the Invention] According to the present invention, it was possible to provide an image forming method of a silver halide photographic light-sensitive material that has high contrast, excellent halftone dot quality, little capri, and high sensitivity even through rapid processing.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, the grains have substantially no twin planes until grain formation and physical ripening. After the formation and desalting step, the pAg is set to 9.0 or less, and the emulsion layer contains at least one of the compounds represented by the following general formulas [1], [2], and [3]. Characteristic silver halide photographic materials. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (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] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2_1 is an aliphatic group, aromatic group, or heterocyclic group, and R_2_2 is a hydrogen atom, an optionally substituted alkoxy group, or a heterocyclic group. It 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.)