CA1310533C

CA1310533C - Process for the formation of high contrast negative images and silver halide photographic element

Info

Publication number: CA1310533C
Application number: CA000529184A
Authority: CA
Inventors: Jonathan Peter Kitchin; Carlo Marchesano
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1986-02-07
Filing date: 1987-02-06
Publication date: 1992-11-24
Anticipated expiration: 2009-11-24
Also published as: AU6854087A; JPS62187340A; IT8619334A1; EP0231850B1; MX168443B; US4777118A; IT1188549B; DE3775570D1; BR8700549A; IT8619334A0; AU594999B2; EP0231850A3; EP0231850A2; AR246133A1

Abstract

Process For The Formation Of High Contrast Negative Images And Silver Halide Photographic Element ABSTRACT OF DISCLOSURE

High contrast negative images are obtained by devel-oping a silver halide photographic element, in the pres-ence of a hydrazine compound, with an alkali aqueous de-veloping solution which contains a combination of develop-ing agent comprising hydroquinone or substituted hydroqui-none and a superadditive developing agent and an antioxi-dant, wherein the developing solution has a pH lower than about 12 and wherein the silver halide photographic ele-ment comprises an emulsion layer including surf ace latent image negative type silver halide grains in reactive asso-ciation with a contrast promoting agent, preferably a di-arylcarbinol compound, more preferably a diarylmethanol compound in a quantity useful to increase contrast.

Description

~31~53~

Process For The Formation Of Hi~h Contrast Negative Images And Silver Halide Photo~raphic Element FIELD OF THE INVENTION

This invention relates to silver halide photographic light-sensitive elements and, more particularly, to silver halide photographic light-sensitive elements which provide high contrast negative images upon processing with a sta-ble developing solution.
' BACKGROUND OF THE ART

In the process for forming high contrast images by development of silver halide photographic elements neces-sary to obtain useful images for graphic arts processes, special developers known in the art as "lith" developers are used. The high contrast is achieved by means of the infectious development as described in Journal of the Franklin Institute, vol. 239, 221-230 (1945). These devel-opers exhibit an induction period prior to the development of exposed silver halides, after which the infectious de-velopment occurs, which gives rise to the high contrast.
The typical "lith" developer contains only a single developing agent of the dihydroxybenæene type, such as hydroquinone. In order to enhance the infectious develop-ment, "lith" developers contain a low contPnt of alkali sulfite. This low sulfite content renders the developer more prone to aerial oxidation, especially when it is used in combination with processing machines and, more particu-larly, with Rapid Access type processing machines, where the developer degradation is accelerated.
Moreover, the delay in start of development caused ~y the long induction period of hydroquinone developers lengthens the processing time and delays access to the finished material. While the induction period has been eliminated and proce5sing time reduced by using the so ' .-: ' . ; ~ '~ ,' ~ ~311~3~

called "Rapid Access" developers, which contain bothhydroguinone and a superadditive developing agent such as phenidone or metol, these Rapid Access developers are not useful for lithographic purposes because they cannot pro-duce the necessary high contrast. This is because Rapid Access developers have a high sulfite content which pre-vents infectious development and causes a lower contrast than "lith" developers.
Processes for obtaining a high contrast development of silver halide photographic emulsions have been dis-closed. They are based on the addition of a hydrazine com-pound to a negative surface latent image type silver ha-lide emulsion and on the development of the emulsion at a pH of about 12.8. The use of hydrazine compounds allows the use of auxiliary dèveloping agents in combination with the dihydroxybenzene developing agents in order to in-crease the developing capacity. It also allows the use of relatively high sulfite concentrations to protect the de-veloping agents against oxidation, and thereby increasing the developer stability. Anyhow, the high pH level neces-sary to obtain the high contrast from the use of hydrazine compounds makes the life of the developing solution rela-tively short.
The process which makes use of hydrazine is disclosed in US Patent Specifications 2,419,975; 4,168,977 and 4,224,401. Modifications and improvements to the hydrazine process are disclosed ~n US Patent Specifications 2,419,974; 2,410,690; ~,166,742; 4,221,857; 4,237,21~;
4,241,164; 4,311,871; 4,243,739 and 4,272,614.
Despite the improvements which have been made in the hydrazine process, a remaining inconvenience was the rela tively low stability of the developer to aerial oxidation, which is a consequence of the high pH required to achieve the desired high contrast.
Contrast promoting agents have been described in US
Patent Specification 4,269,929 and in European Patent Ap-plication S.N. 155,690 which, incorporated in the ,, ~ ~31 ~:33 developing solution, allow the photographic element, in-cluding the hydrazine compound, to reach the desired high contrast at a low pH. It would be still desirable to o~-tain a photographic element providing a high contrast upon development in the presence of a hydraæine compound with a conventional Rapid Access type developer solution, without the necessary addition to said solution of ingredients of uncommon use such as the above mentioned contrast promot-ing agents.

SUMMARY OF THE ~NV~NTION

This invention refers to a silver halide photographic element to be used with a high speed, Rapid Access devel-oper formulation having an improved resistance to air oxi-dation and producing a high contrast neyative image suit-able for lithographic purposes. Advantages such as reduced dwell time in developer baths, reduced concentrations of ingredients in baths, reduced developer bath costs, and reduced concentrations of environmentally sensitive mate-rials in wastes may be achievable by using silver halide emulsions having a contrast increasing effective amount of contrast promoting agents in reactive association with negative-acting surface latent image-type silver halide grains prior to image-wise exposure of the grains (i.e., development sensitizing exposure of the grains). Unique advantages such as high speed, high productivity, high degree of stability and high contrast can be achieved by developing a silver halide photographic element in the presence o~ a hydrazine compound with an aqueous alkaline developing solution which contains a combination of de-veloping agents comprising h~droquinone or substituted hydroquinone and at least one superadditive developing agent and a useful amount of an antioxidant (such as a sulfite compound), wherein the developing solution has a pH of less than about 12 and wherein the silver halide photographic element comprises at least one silver halide . .

131~33 ` . ~

emulsion layer including negative acting surface latent image-type silver halide grains in reactive association with a diarylcarbinol compound, preferably a diarylmethanol compound, ln a quantity useful to increase contrast.
Ac~ording to one aspect of the present invention there is provided a process for forming a high contrast neyative photo-graphic image by development of a silver halide photographic element, including at least a negative acting surface latent image--type silver halide emulsion layer, with an aqueous alkaline developing solution containing a dihydroxybenzene developing agent, a superadditive developing agent and an antioxidant at a pH
lower ~h~n 12 in the presence of a hydrazine compound, wherein at least one layer of said silver halide photographic element com-prises, prior to being contacted with said developing solution, a useful contrast promoting amount of a contrast promoting agent.
According to a further aspect of the present inventlon there is provided a silver halide photographic element which has not undergone development sensitizing exposure to actinic radia-tion, including at least one negative acting surface latent image-type silver halide emulsion layer and a contrast promoting hydra-zine compound, said element being characterized by the presence of a contrast promoting amount of a contrast promoting agent in reactive association with said silver halide emulsion layer.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with this invention, a silver halide photographic element is described ~or use in a process for obtaining a high contrast negative image by development of the exposed element, in the presence oE a hydrazine compound, with an A

3 ~
- 4a - 60557-3169 aqueous alkaline developing solution containing a dihydroxybenzene developing agent a superadditive developing agent and an an~ioxi-dant at a pH lower than 12, wherein the silver halide photographic element comprises at least one emulsion layer including negative aeting surface latent image-type silver halide grains in reactive association with a contrast promoting agen~ present in an amount effective to increase contrast. A "contrast promoting agent" is defined according t,o the present invention as a compound which when added to test developer (A) at a quantity of 10 grams per llter ~or in an amount sufficient to give a saturated solution if this is less than 10 ~rams per liter) results in an increase in contrast of at least 20% (preferably 30%, more preferably at least 50%) when test ~ilm (B) is processed in test developer (A) for 80 seconds at 30C, compared with the contrast when test developer (A) is used under the same conditions without any further addi-tions. The contrast is measured between densities of 0.5 and 1.5.

, " ~31~33 Test DeveloPer ~

water 750 cm3 Potassium hydroxide 32 g Sodium sulfite 92 g Ortho phosphoric acid 85% 1.5 cm3 Ethylenediamine tetracetic acid disodium salt 1.0 g Sodium bromide 3 g Hydroquinone 30 g l-Phenyl-4 methyl-3-pyrazolidone 0.4 g 5-methylbenzotriazole 0.8 g Water to make 1,000 cm3 adjust pH to 11.6 finally and after any addition of CPA.
Test Film (B) -Test film (B) comprises a silver halide coating of the "hydrazine infectious development" type (described for example in U.S. Patent 4,168,977~ prepared as follows:

A cubic monodisperse emulsion of average graln size ~e-tween 0.2 ~ and 0.3 ~ is precipitated by the conventional double jet procedure. The halide composition is Br 70%, Cl 28% and I 2%. The emulsion is desalted and coated at 3.5 g of silver per square meter and 3.0 g gelatin/m2 on poly-ester base wlth the following additions.
- Sensitizing dye:
Anhydro 5,5'-dichloro-9-ethyl-3,3'-bis-(3-sulfopropyl)-oxacarbocyanine hydroxide sodium salt200 mg/mole silver - Hydra~ine derivative:
l-phenyl-2-formylhydrazine3.0 g/mole silver - Wetting agent:
polyoxyethylene(20)cetyl ether1 g/mole silver - Hardener:
2-hydroxy-~,6-dichlorotriazine0.4 g/mole silver pH adjusted to 5~0.

, ~0~33 Unique properties and capabilities are achieved in the film and processes of the present invention when the contrast promoting agent comprises a diarylcarbinol com-pound, preferably a diarylmethanol compound, in a quantity useful to increase contrast.
Preferably, according to the present invention, the silver halide emulsion layer is reactively associated with a diarylcarbinol compound of formula (I) or (II):
RlR2R3COH (I) RlR2R3C(CH2)nOH (II) wherein Rl and R2 represent a substituted or unsubstituted aromatic group, R3 represents a hydrogen atom, a substi-tuted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group and n represents a positive integer from O to 4 wherein Rl, R2 and R3 are bonded to the carbon atom in the formulae.
More preferably, according to the present invention, the silver halide emulsion layer is reactively associated with a diarylmethanol compound of formula (III):
RlR2OE1H (III) wherein Rl and R2 represent a substituted or unsubstituted aromatic group bonded to the carbon atom in formula (III).
More preferably, the a~ueous alkaline developing so-lution according to the present invention has a pH lower than about 12, ~or example in the range from 9.50 to 12.00 or preferably from lO.oO to 11.50.
Still more preferably, the dihydroxybenzene develop-ing agent is hydro~uinone.
Most preferably, the superadditive developing agent is a 3-pyrazolidone compound, in particular a 1-phenyl-3-pyrazolidone. Still most preferably, the hydrazine com-pound is incorporated in the silver halide photographic element and preerably corresponds to the formula (IV):
R4-NHNH-C-H (IV) wherein R4 represents a substituted or unsubstituted aro-matic group.

~31~33 The addltion of the contrast promoting agents directly to the emulsion may enable reduction of the concentratlon of contrast promoting agents ln the ~eveloping solutions wlth attendant reduct lons in cost an~ environmental impact. The use o~
the uni~ue class of diarylcarbinols and diarylmethanols can even eliminate the need for additional contrast promotlny agents in the developer solutions. These carbinol classes of compounds can also reduce the dwell time necessary ln developer baths and enable the film to perform well at lower pH levels than fllms without these contrast promoting agents present in the film prior to contact with the developer solutions. The addition of the contrast promoting agents dlrectly to the fllm has surprisin~ly not been found to adversely affect the sensitometry or characterlstics of the film (e.g., graininess, sharpness, speed, Dmin, etc.).
The silver halide emulsions for use ln the present ln-vention may be silver chloride, silver chloro-bromide, silver lodo-bromide, sllver lodo-chloride, silver iodochloro-bromlde or any mixture thereof. Generally, the lodide content of the silver halide emulsions is less than about 10~ silver iodide moles, sald content being based on the total sllver hallde. The sllver hallde emulsions are usually monodispersed or narrow graln size distribution emulslons, as descrlbed for example in US Patent Specifications 4,166,742; 4,168,977; 4,224,401; 4,237,214;

4,241,164; 4,272,614 and 4,311,871. The silver hallde emulslons may comprlse mixtures of emuls.lons havlng different grain comblna-tions, for example a comblnation of an emulslon having a mean grain size below 0.4 ~ wlth an emulslon havlng a mean grain size above 0.7 y, or a combination of two emulslons, both having a grain size below 0.4 ~, such as for example a first silver halide emulsion havlng a mean grain slze from 0.1 to 0.4 ~ and a second silver halide emulsion with particles having a mean graln volume lower than one half the particles of the 'C ~ -: :
- :

"` ~310i33 first emulsion.
The silver halide grains of the emulsions of the present invention are capable o~ forming a surface latent image, as opposed to those emulsions forming an internal latent image. Surface latent image-forming silver halide grains are most employed in negative type silver halide emulsions, whilè internal latent latent image-forming sil-ver halide grains, though capable of forming a negative image when developed in an internal developer, are usually employed with surface developers to form direct-positive images. The distinction between surface latent image and internal latent image-forming silver halide grains is well-known in the art. Generally, some additional ingredi-ents or steps are required in the preparation of silver halide grains capable o~ preferentially forming an inter-nal latent image instead of a surface latent image.
In the silver halide emulsions of the present inven-tion, the precipitation or the growth of the silver halide grains may be carried out in the presence of metal sal~s or complex salts thereof, such as rhodium and iridium salts or complex salts thereof. According to the present inventiQn, it has been found, anyhow, that the presence o rhodium or iridium is not necessary to obtain the high contrasts. Silver halide grains ~ree of rhodium or iridi-um, as well as those formed or ripened in the presence of rhodium or iridium may be used to the purposes of the present invention.
The silver halide emulsions o~ the present invention may not be chemically sensitized, but are preferably chem-ically sensitized~ As chemical sensitization methods for silver halide emulsions, the known sulfur sensitization employing sul~ur compounds, the reduction sensitization employing mild reducing agents and the noble metal sensi-tization can be used, either alone or in combination.
The silver halide emulsions can be speatrally sensi-tized with dyes from a variety of classes, including the polymethine dye alass, such as cyanines, meroayanines, .

complex cyanines and merocyanines (i.e., tri-, tetra- and poly-nuclear cyanines and merocyanines), oxonols, hemi-oxonols, styryls, merostyryls and streptocyanines.
The binder or protective colloid for the silver ha-lide layer and the layers of the photographic element is preferably gelatin, but other hydrophilic colloids or syn-thetic water insoluble polymers in the form of latexes can be used to partially or completely replace gelatin.
In addition, the photographic elements of the present invention may also contain any photographic additives known in the art, such as for example stabilizers, anti-~oggants, hardeners, plasticizers, development accelera-tors, gelatln extenders, matting agents and the like.
To achieve the bene~its of this invention, a hydra-zine compound has to be present during development of the exposed element and the element must contain a diarylcar-binol compound prior to the contact with the whole devel-oper solution. By "contact with the whole developer solu-tion" is meant that the exposed element is placed into contact with all of the required developer ingredients.
The hydrazine compound can be incorporated in the photographic element or in the developing solution or both in the developing solution and in the photographic ele-ment.
Hydrazine and any water soluble hydrazine derivatives are ef~ective to increase contrast when incorporated in the developing solution in combination with the diarylme-thanol compound incorporated in the photographic element.
Preferred hydrazine derivatives to be used in the develop-ing solution of this invention include compounds of ~ormu-la:
R5 ~ / R6 / N-N \

wherein R5 is an organic radical and R6, R7 and R8 each are hydrogen or an organic radical. Organic radicals rep-resented by R5, R6, R7 and R8 include hydrocarbon groups, , .

,~ .

.

13~33 such as an alkyl group, an aryl group, an aralkyl group and an alicyclic group and such groups can be substituted with substituents such as alkoxy groups, carboxy groups, sulfonamido groups and halogen atoms.
Other examples of hydrazine derivatives, which can be incorporated in the developing solutions, are hydrazides, acyl hydrazines, semicarbazides, carbohydrazides and ami-nobiuret compounds.
Specific examples of hydrazine derivatives, which can be incorporated in the developing solutions of the present invention, are disclosed in US Patent Specification 2,419,575.
In a preferred form of this invention, the hydrazine compound is incorporated in the photographic element, for example in a silver halide emulsion layer or in a hydro-philic colloidal layer, preferably a hydrophilic colloidal layer adjacent to the emulsion layer in which the effects of the hydrazine compound are desired. It can, of course, be present in the photographic element distributed between the emulsion and the hydrophilic colloidal layers, such as a subbing layer, interlayers and protective layers.
Hydrazine compounds suitable to be incorporated into the photographic element according to the present inven-tion are disclosed in GB Patent Specification 598,108 and in US Patent Specification 2,419,974; they include the water soluble alkyl, aryl and heterocyclic hydrazine com-pounds, as well as the hydrazide, semicarbazide and amino-biuret compounds.
Particularly preferred hydrazine compounds, for use according to this invention incorporated in the photo-graphic element, are the formylhydrazine compounds corre-sponding to the formula (IV):
R4-NHNH-C-H ( IV) wherein R4 represents a substituted or unsubstituted aro-matic group. Examples of aromatic groups represented by R4 include a phenyl group and a naphthyl group. Such aromatic ,:

.

',- . ' :
,' '' ' ' '' ~ ':

~ 3 ~

groups may be substituted with one or more substituents which are not electron attracting, such as straight or branched-chain alkyl groups ~e.g. methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-ottyl, n-hexyl, tert.-octyl, n-decyl, n-dodecyl, etc.), aralkyl groups (e.g.
benzyl, phenethyl, etc.), alkoxy groups (e.g. methoxy, ethoxy, 2-methyl-propyloxy, etc.), amino groups which are mono- or disubstituted with alkyl groups, acylaminoali-phatic groups (e.g. acetylamino, benzoylamino, etc.), etc., as disclosed in US Patent Specification 4,168,977 and in CA Patent Specification 1,146,001. Such aromatic groups may also be substituted with a ureido group of ~or-mula:

Rg-N-C-N-Rlo Rll wherein R9 and Rlo (which may be same or different) each represents hydrogen, an aliphatic group Isuch as a straight or branched-chain alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group and an alkynyl group), an aromatic group (such as a phenyl group and a naphthyl group) or a heterocyclic group; Rll represents hydrogen or an aliphatic group (such as those listed above) as described in US Patent Specification 4,323,643.
Other hydrazine compounds, for use according to this invention incorporated in the photographic element, are those represented by the formula:
R12-NHNH-~ R13 wherein R12 represents the same aromatic group of the for-mula above and R13 represents an alkyl group having 1 to 3 carbon atoms, which may be a straight or branched-chain alkyl (e.g. methyl, ethyl, n-propyl and isopropyl) or a phenyl group. The phenyl group may be substituted with one or more substituents which preferably are electron at-tracting groups, such as halogen atoms (chlorine, bromine, , , ... . .

etc.), a cyano groUp, a trifluoromethyl group, a carboxy group or a sulfo group, etc. Specific examples o~ hydra~
zine compounds represented by the formula above are dis-closed in US Patent Specification 4,224,401.
Still other examples o~ hydrazine compounds, for use according to this invention incorporated in the photo-graphic element, are those corresponding to the formula:

~ =N ( Y ) mX-NHNH_c_Rl 5 "-N O

wherein R14 represents hydrogen, an aliphatic group which may be substituted; Y represents a divalent linking group;
m represents 0 or 1; X represents a divalent aromatic group (such as for example a phenylene group, a naphthyl-ene group and the analogous substituted groups thereof);
R15 represents a hydrogen atom, an aliphatic group which may be substituted and Z represents a non metallic atom groups necessary to form a 5- or a 6-membered heterocyclic ring. Specific examples of hydrazine compounds represented by the formula above are disclosed in US Patent Specifica-tion 4,272,614.
In one particular pre~erred form, the hydrazine com-pound to be incorporated in the photographic element is substituted with ballasting groups, such as the ballasting groups of incorporated color couplers and other non-dif-fusing photographic emulsion addenda. Said ballasting groups contain at least 8 carbon atoms and can be selected ~rom the relatively non-reactive aliphatic and aromatic groups, such as alkyl, alkoxy, alkylphenyl, phenoxy, al-kylphenoxy groups and the like.
Such hydrazine compounds can be incorporated in the photographic element using various methods well-known in the photographic art, the most common being the method of dissolving the hydrazine derivatives in a high boiling crystalloidal solvent and dispersing the mixture in the emulsion, as described for example in US Patent Specification 2,322,027.
Hydrazine compounds incorporated in the developing solution in the practice of this invention are efEective at very low levels of concentration. For example, hydra-zine compounds give useful results in the developing solu-tion in a quantity o~ about 0.001 moles per liter to about 0.1 moles per liter, more preferably in a quantity from about 0.002 to about 0.01 moles per liter. Hydrazine com-pounds incorporated in the photographic element are typi-cally employed in a concentration ranging from about 5 x 10 4 to about 5 x 10 2 moles per mole oE silver and pref-erably in a quantity from about 8 x 10 4 to about 5 x 10 3 moles per mole of silver.
The diarylcarbinol compounds, preferably the diaryl-methanol compounds above, are incorporated into the photo-graphic element prior to the contact with the whole devel-oper solution and preferably prior to the exposure of the photographic element itself, such as for example when the diarylcarbinol compound is introduced into the element prior to the coating of the emulsion layer. For example they can be incorporated in the silver halide emulslon layer of the element or in a hydrophilic colloidal layer of the element, particularly a hydrophilic colloidal layer adjacent to the emulsion layer in which the effects of the diarylcarbinol compounds are desired. They can, for in-stance, be present in the photographic element distributed between th0 emulsion and the hydrophilic colloidal layers, such as for instance a subbing layer, interlayers and pro-tective layers~
The aromatic groups represented by Rl, R2 and R3 of formulas (I), (II) and (III) above include a naphthyl group and, preferably, a phenyl group. The alkyl groups represented by R3 of formulas (I) and (II) above include branched or straight-chain alkyl groups, preferably low alkyl groups (having from 1 to 5 carbon atoms). Such groups may contain substituents, such substituents being chosen in nature and size as not to negatively affect . . . ~

`` ~3~ 3~

their behaviour according to the present invention. For what concern their nature, such substituents include for example an alkyl group, an alkoxy group, a cyano group, a dialkylamino group, an alkoxycarbonyl group, a carboxy group, a nitro group, an alkylthio group, a hydroxy group, a sulf oxyl group, a carbamoyl group, a sulf amoyl group, a halogen atom, etc. For what concerns their size, s~ch sub-stituents are preferred to have from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms.
Parameters to take into proper account are solubility and boiling point of the diarylcarbinol compounds of the present invention. Said compounds are to be substantially soluble in water or soluble in water miscible solvents (by "substantially soluble" in water it is meant that they are to be soluble in water in a quantity of at least 1% by weight and by "soluble" in water-miscible solvents it is meant that they are to be soluble in water miscihle sol-vents in a quantity of at least 5% by weight) in order to introduce them into the aqueous coating compositions used to form the layers of the photographic elements according to the present invention. Said diarylcarbinol compounds are re~uired to have a sufficiently high boiling point not to evaporate during drying of the layer forming coat-ing composition. Said boiling points are preferably higher than 150C, more preferably higher than 200C.
Specific examples of diarylcarbinol compounds ac-cording to this invention include the following:
1) diphenylmethanol (benzhydrol) 2) 4,4l-dimethoxydiphenylmethanol 3) 4,4'-dimethyldiphenylmethanol 4) 2,2'-dibromodiphenylmethanol 5) 4,4'-dibromodiphenylmethanol 6) 2,2'-dinitrodiphenylmethanol 7) 4,4'-dinitrodiphenylmethanol 8) 2,3'-dimethoxydiphenylmethanol ..

.. .

`` ~3~5~3 9) 2,4'-dihydroxydiphenylmethanol 10) 4-methyldiphenylmethanol 11) 4-ethyldiphenylmethanol 12) 2,2',4,4'-tetramethyldiphenylmethanol.
The diarylcarbinol compounds are used to the purposes of the present invention incorporated into the photograph-ic element in amount from about 10 4 to about 10 1 mole per mole of silver, more preferably in an amount from about 10 3 to about 5 x 10 2 mole per mole of silver.
According to the process of the present invention, the image-wise exposed silver halide photographic element can be processed with a stable aqueous alkaline developing solution to produce a high contrast negative image. This contrast is the slope of the straight line portion of the characteristic sensitometric curve (referred to as "aver-age contrast") and is measured between two polnts located at ~ensities of 0.10 and 2.50 above fog. Averages contrast higher than 10 can be obtained according to this invention by developing an image-wise exposed element comprising the diarylcarbinol compound, in the presence of a hydrazine compound, at a pH lower than the pH necessary to obtain the high contrast with the use of the hydrazine compound alone. As a consequence of the lower pH in the developer bath and the presence of the diarylcarbinol compound in the element, the process can be carried out to obtain the desired high contrast characteristics by using a conven-tional Rapid Access type developing solution stable during the time to the aerial oxidation ~the higher the pH the lower being the stability of the developing solution, as known to the skilled in the art) independently from the presence of contrast promoting agents in the developing solution of the type described in the above mentioned US
Patent Specification 4,269,929 and European Patent Appli-cation 155,690.

1310~33 The dihydroxybenzene developing agents employed in the aqueous alkaline developing solution for use in the practice of this invention are well-known and widely used in photographic processings. The preferred developing agent of this class is hydro~uinone. Other useful di-hydroxybenzene developing agents include chlorohydroqui-none, bromohydro~uinone, isopropylhydroquinone, tolyl-hydroquinone, methylhydroquinone, 2,3-dichlorohydroqui-none, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 1,4-dihydroxy-2-acetophenone-2,5-dimethylhydroquinone, 2,5-diethylhydroquinone, 2,S-di-p-phenethylhydroquinone, 2,5-dibenzoylhydroquinone, 2,5-diacetaminohydra~uinone and the like.
The 3-pyrazolidone developing agents employed in the aqueous alkaline developing solution for use in the prac-tice of this invention are also well known and widely used in photographic processings. The most commonly used devel-oping agents of this class are l-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidane, 1-phen~1-4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl-4,4-dihydroxy-methyl-3--pyrazolidone. Other useful 3-pyrazolidone devel-oping agents include: l-phenyl-S-methyl-3-pyrazolidone, l-p-aminophenyl-4-methyl-4-propyl-3-pyrazolidone, l-p-chlorophenyl-4-methyl-4-ethyl-3-pyrazolidone, l-p-acet~
amidophenyl-4,4-diethyl-3-pyrazolidone, l-p-~-hydroxy-ethylphenyl-4,4-dimethyl-3-pyrazolidone, l-p-hydroxy-phenyl-4,4-dimethyl-3-pyrazolidone, l-p-methoxyphenyl-4,4-diethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyr-azolidone, and the like.
The aqueous alkallne photographic developing composi-tion ror use in the practice of this invention contains a sulfite preservative at a level suicient to protect the developing agents against the aerial oxidation and thereby assure good stability characteristics. Useful sulfit~

.

-,:
i . , , '. . .:

,' -.

1310~33 preservatives include sulfites, bisulfites, metabisulfites and carbonyl bisul~ite adducts. Typical ~xamples of sul-fite preservatives include sodium sulfite, potassium sul-fite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde bisulfite salt and the like. Also ascorbic acid is a known preserva-tive agent against aerial oxidation of the developer for use in thc bath according to this invention.
The aqueous alkaline developing solutions ~cr use in the practice of this invention can vary widely with re-spect to the concentration of the various ingredients in-cluded therein. Typically, the dihydroxybenzene developing agent is used in an amount of from 0.040 to about 0.70 moles per liter, more preferably in an amount of from 0.08 to about 0.40 moles per liter; the 3-pyrazolidone develop-ing agent is used in an amount of from about 0.001 to about 0.05 moles per liter, more preferably in an amount of from about 0.005 to about O.Ol moles per liter; the sulfite preservative is used in an amount from about 0.03 to about l.O moles per liter, more preferably in an amount from about 0.10 to about 0.70 moles per liter.
In contrast with "lith" developers which require a low level of sulfite ions, the developing solutions of thi~ invention can utilize higher levels of sulfite ions, and thereby achieve the advantages of increased stability, since a higher level of sulfite ions provides increased protection against aerial oxidation.
In carrying out the method of this invention, it is preferred to use an organic antifogging agent to minimize fog formation in the processed element. The organic anti-fogging agent can be incorporated in the photographic ele-ment or can be added to the developing solution or can be both incorporated in the photographic element and added to the developing solution. According to the present inven-tion, it has been found that more preferred organic anti-fogging agents for specific use in the developing solu-tiors ~ benzo~riazole a~d/or a benzimidazole antiiogglng ' ' : . ' ' ' ' , i~10~33 agents, which proved to have beneficial effects on in-creasing contrast. Useful compounds are both substituted and unsubstituted benzotriazole and benzimidazole com-pounds, with the proviso that electron withdrawing substi-tuents at least as strong as nitro groups are excluded. As a matter of fact, nitro substituted benzotriazole and ben-zimidazole compounds, although goo~ to prevent fog, do not provide beneficial effects with reference to contrast in-crease. Benzimidazoles and benzotriazoles, as a class, are believed to be useful in the practice of this invention.
Anyhow, as indicated, difficulties in obtaining signifi-cantly improved performance with benzotriazoles and benzi-midazoles having strong electron withdrawing groups have been encountered. Benzotriazoles and benzimidazoles are therefore preferred not to have any substituents on the aromatic rings which are electron attracting groups as strong as or stronger than a nitro group. Other substi-tuents known in the art such as lower alkyl groups (having 1 to 5 carbon atoms) and halogen substituents (chlorine) proved to be substituents good to the purposes of the in-vention. Said benzotriazole and benzimidazole antifog~ing and contrast promoting agents are normally used in amounts effective to prevent fog, although quantity can be opti-mized to get the best results from the contrast point of view. Use~ul quantities, when they are included in the emulsion, may var~ from 1 to 100 milligr~s per 100 grams of emulsion and, when included in the developing bath, as~
preferred, may vary from 0.01 to 5 grams per liter.
In addition to the essential components speciied hereinabove, the developing solutions can optionally con-tain any of a wide variety of addenda, as known, useful in photographic developing solutions. For example, they can contain solvents, buf~ers, se~uestering agents, develop-ment accelerators, agents to reduce swelling of the emul-sion layers, and the like.
The invention is further illustrated by the following examples.

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1:31~33 A cubic silver chlorobromide emulsion AgO 15Clo 85 f narrow grain size distribution and mean grain size of 0.23 was prepared by the conventional double jet procedure.
The emulsion was then coagulated and washed in the con-ventional manner and reconstituted to give a final gelatin to silver ratio of 100 g gelatin/silver mole. A coating composition was prepared by mixing this emulsion with:
- a wetting agent, - 2-hydroxy-4,6-dichloro~1,3,5-triazine hardener ~0.4 g/mole Ag), - anhydrous 5,5'-dichloro-9-ethyl-3,3'-bis-(3-sulphopro-pyl) oxacarbocyanine hydroxide sodium salt green sensi-tizing dye (0.2 g/moIe Ag) and - l-formyl-2-{4-[2-t2,4-di-t-pentylphenoxy)-butyramido]-phenyl}-hydrazide compound (1 g/mole Ag~.
A comparison coating (Sample 1) was then prepared by the application of the described mixture onto a subbed polyester base~ at a silver coverage of 3.8 g/m2. A second coating according the invention (Sample 2) was prepared using a similar coating composition but with ~urther addi-tion of benzydrol comPound (lg/mole Ag). Strips of samples 1 and 2 were exposed ~in a sensitometer consisting of a 500 watt tungsten filament light source at~enuated by a 0-4 continuous neutral density wedge in contact with the film sample. The strips were then developed for 80 seconds at z8C in a developer of the Eollowing compositioA:

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~3t~533 - Potassium hydroxide ~3 g/l - Sodium sulphite 90 g/l - Ethylene diaminotetraacetic acid disodium salt 1 g/l - Sodium bromide 3 g/l - Hydro~uinone 30 g/l - 4-methyl-1-phenyl-3-pyrazolidone0.4 g/l - 5-methylbenzotriazole 0.8 g/l - pH adjusted to 11.50 The strips were then fixed, washed and dried. ?
Densitrometric evaluation of the strips showed the charac-teristics listed in the f ollowing Table 1:
Table 1 Sample Speed Average Contrast Toe Contrast * ** ***
___________________________________._____ _______________ 1 1.0 2.8 3.2 2 1.~ 15.6 9.7 * Relative Log Sensitivity at density 0.2 above fog;
** Contrast measured between density 0.1 and 2.5 above fog;
*** Contrast measured between density 0.07 and 0.17 above fog.

The addition of the diarylcarbinol compound according : to the invention promotes the high contrast effect of the h~drazide at a development pH below that which would oth-erwise be required.
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Two silver halide emulsions were prepared having the following characteristics:
g l0.28BrO.70Io,02 with mean grain size of 0.23 Emulsion 2: AgClO 98Io 2 with mean grain size of 0.10 ,. . .
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The emulsion were mixed in molar ratio of emulsion l:emulsion 2 = 1:4. The mixed emulsions were coated as described in Example 1 (Sample 1) however replacing the hydrazide with a 1-formyl-2-[4-(4'-phenylureido)~phenyl]-hydrazide compound (3g/mole Ag) and a total silver coating weight of 2 g/m2 was used ~comparison coating Sample 3).
A second coating according the invention (Sample 4) was prepared using a similar coating composition but with the further addition of benzhydrol compound (1 g/mole Ag).
A third coating according to the invention (Sample 5) was prepared using a coating composition similar to sample 3 but with the further addition of 4,4'-dimethoxydi-phenylmethanol compound ~1 g/mole Ag).
A fourth coating (comparison coating sample 6) wasprepared using a coating composition similar to sample 3 but with the further addition of benzyl alcohol (1 g/mole Ag).
A fifth coating (comparison coating sample 7) was prepared using a coating composition similar to sample 3 but with the further addition of phenylmethylcarbinol (1 g/mole Ag).
The coatings were exposed and processed as described in example 1, with the exception that pH was 11.00. Densi-tometric characteristics of the strips are listed in the following Table 2:

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Table 2 Sample D.Max Speed Average Toe contrast contrast ______________________________________________________ 3 0.4 0.4 - 0~2 4 4.2 1.2 13.5 3.5 4.2 1.2 13.8 3.7 6 0.4 0.4 - 0.3 7 0.4 0.4 - 0.3 The results show that in the absence of the diaryl-carbinol compounds or in the presence of benzyl alcohol or aralkyl alcohols very low contrast and maximum density are achieved under these development conditions. On the con-trary, the coatings made with the addition of the diaryl-carbinol compounds of~the present invention showed very high contrast and maximum density values.
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Claims

1. A process for forming a high contrast negative photographic image by development of a silver halide pho-tographic element, including at least a negative acting surface latent image-type silver halide emulsion layer, with an aqueous alkaline developing solution containing a dihydroxybenzene developing agent, a superadditive devel-oping agent and an antioxidant at a pH lower than 12 in the presence of a hydrazine compound, wherein at least one layer of said silver halide photographic element compris-es, prior to being contacted with said developing solu-tion, a useful contrast promoting amount of a contrast promoting agent.

2. The process of claim 1 wherein said contrast pro-moting agent is present in said at least one layer of said silver halide photographic element prior to development sensitizing exposure of said silver halide emulsion layer.

3. The process of claim 1 wherein said contrast pro-moting agent is a diarylcarbinol compound.

4. The process of claim 3, wherein the diarylcarbinol compound is a diarylmethanol compound.

5. The process of claim 3, wherein the diarylcarbinol compound has the formula (I) or (II):
R1R2R3COH (I) R1R2R3C(CH2)nOH (II) wherein R1 and R2 each represent a substituted or unsub-stituted aromatic group, R3 represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group and n represents a positive integer from 0 to 4.

6. The process of claim 3, wherein the diarylcarbinol compound has the formula (III):
R1R2CHOH (III) wherein R1 and R2 each represent a substituted or unsub-stituted aromatic group.

7. The process of claim 1 wherein the hydrazine com-pound is included in the silver halide emulsion layer.

8. The process of claim 1 wherein the developing so-lution has a pH in the range from 10.50 to 11.50.

9. The process of claim 1 wherein the hydroxybenzene developing agent is hydroquinone.

10. The process of claim 1 wherein the superadditive developing agent is a 3-pyrazolidone compound.

11. The process of claim 1 wherein the antioxidant is a sulfite compound.

12. The process of claim 1 wherein said developing solution comprises an organic antifogging agent selected within the class including a benzotriazole compound and a benzimidazole compound.

13. The process of claim 12 wherein said benzotri-azole compound and said benzimidazole compound are without electron-attracting substituents as strong as or stronger than a nitro group.

14. A silver halide photographic element which has not undergone development sensitizing exposure to actinic radiation, including at least one negative acting surface latent image-type silver halide emulsion layer and a contrast promoting hydrazine compound, said element being characterized by the presence of a contrast promoting amount of a contrast promoting agent in reactive associa-tion with said silver halide emulsion layer.

15. The element of claim 14 wherein said contrast promoting agent comprises a diarylcarbinol compound.

16. The element of claim 15 wherein said contrast promoting agent comprises a diarylmethanol compound.

17. The silver halide photographic element of claim 14, wherein the diarylcarbinol compound has the formula (I) or (II):
R1R2R3COH (I) R1R2R3C(CH2)nOH (II) wherein R1 and R2 each represent a substituted or unsub-stituted aromatic group, R3 represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group and n represents a posi-tive integer from 0 to 4.

18. The silver halide photographic element of claim 14, wherein the diarylcarbinol compound has the formula (III):
R1R2CHOH (III) wherein R1 and R2 each represent a substituted or unsub-stituted aromatic group.

19. The silver halide photographic element of claim 14 wherein said compound is incorporated in the silver halide emulsion layer.

20. The silver halide photographic element of claim 14 wherein said compound is incorporated in an amount from about 10-4 to 10-1 mole per mole of silver halide.

21. The silver halide photographic element of claim 14 wherein a hydrazine compound is incorporated.

22. The silver halide photographic element of claim 14 wherein a hydrazine compound is incorporated corre-sponding to the formula:
R4-NHNH-?-H

wherein R4 represents a substituted or unsubstituted aro-matic group.

23. The silver halide photographic element of claim 14 wherein a hydrazine compound is incorporated in an amount from about 5 x 10-4 to 5 x 10-2 mole per mole of silver halide.